Paint and Coating Testing Manual (IRAN)

MNL17-EB/Jun.
1995
Author Index
A G P
Ashton, Harry E., 696 Gale, Frances, 725 Pellowe, Don, 53

Athey, Robert D. Jr., 415 Gavett, Benjamin, 706 Perera, Dan Y., 585
Austin, M. Jay, 238 Gu6vin, Paul R. Jr., 555, 600 Petraitis, D. J., 95
Aviles, Julio I., 507 Price, Martin B., 717
Pulley, David F., 683
H
B Hacker, Larry R., 741 R

Hammond, Harry K. III, 447, 470
Bauer, Ronald S., 74 Hansen, Charles M., 383 Ralston, Henry P., 217
Bierwagen, Gordon P., 369 Hartshorn, Jack H., 826 Reiger, Carl J., 229
Billmeyer, Fred W. Jr., 447 Heitkamp, A1 53 Ryntz, Rose A., 711
Brandau, Alan H., 662 Hegedus, Charles R., 683
Braun, Juergen H., 159 Hicks, Lon S., 619
Brezinski, Darlene, 753 Hill, Loren W., 534
Hirst, Donald J., 683 S
Brezinski, J. John, 3
Broekhaus, Raymond D., 289 Santer, J. Owen, 60
Burns, Richard J., 99 Scarborough, Victoria, 748
K
Schaeffer, Leonard, 481
Kight, Robert W., 85 Schmitt, Thomas M., 835
C Kigle-Boeckler, Gabriele, 470 Schnall, Marvin J., 30
King, Vanja M., 261 Shay, Gregory D., 268
Campbell, David L., 654 Koleske, Joseph V., xi, xiii, 26, 89, 108, Sheehan, John G., 815
Carlozzo, Ben J., 15 252 Sherbondy, Valerie D., 643
Crewdson, Michael J., 619 Krauskopf, Leonard G., 115 Siegmund, A1, 731
Curtis, L. G., 23 Sliva, Thomas J., 439, 725, 748
Smyrl, William H., 609
L Snider, A. Monroe, Jr., 871
Spadafora, Stephen J., 683
D
Lewis, Peter A., 190, 209 Spindel, Saul, 735
Spinelli, Frank R., 179
Domingo, Rolando, 789
M
T
E Marx, Edward J., 74
Mills, George D., 305, 767, 865 Tan, Peter, 115
Eley, Richard R., 333 Miranda, Thomas J., 407
Ellis, Wayne, 667, 677, 891 Morse, Mark P., 525, 547
Eng, Anthony T., 683 W
Eppler, Richard A., 68, 214
N
Watkins, Michael J., 74
Neag, C. Michael, 841 Weldon, Dwight G., 783
F Nelson, Gordon L., 5~13 Wenzler, C. M., 424
Ferguson, Russell L., 223

Fletcher, J. F., 424 O Y
Friel, John M., 39
Fry, John S., 79 Odell, Loren B., 731 Yuhas, Stephen A. Jr., 125
899
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Paint and Coating
Testing Manual
Fourteenth Edition of the
Gardner-Sward Handbook
Joseph V. Koleske, Editor
ASTM Manual Series: MNL 17

ASTM Publication Code Number (PCN)
28-017095-14
1916 Race Street, Philadelphia, PA 19103
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Library of Congress Cataloging-in-Publication Data
Paint and coating testing manual: fourteenth edition of the Gardner-Sward handbook/Joseph V.
Koleske, editor.
p. cm.--(ASTM manual series; MNL 17)
Rev. ed. of: Paint testing manual. 13th ed. 1972.
"ASTM publication code number (PCN) 28-017095-14."
includes bibliographical references and index.
ISBN 0-8031-2060-5
1. Paint materials--Testing. 2. Paint materials--Analysis.
I. Koleske, J. V., 1930- . II. Paint testing manual. III. Series.
TP936.5.P34 1995
667'.6--dc20 95-10632
CIP
Copyright 9 1995 AMERICAN SOCIETY FOR TESTING AND MATERIALS, Philadelphia, PA.
All rights reserved. This material may not be reproduced or copied, in whole or in part, in any
printed, mechanical, electronic, film, or other distribution and storage media, without the written
consent of the publisher.
Photocopy Rights
Authorization to photocopy items for internal or personal use, or the internal or personal
use of specific clients, is granted by the AMERICAN SOCIETY FOR TESTING AND MATE-
RIALS for users registered with the Copyright Clearance Center (CCC)Transactional
Reporting Service, provided that the base fee of $2,50 per copy, plus $0.50 per page is paid
directly to CCC, 222 Rosewood Dr., Danvers, MA 01923; Phone: (508) 750-8400; Fax:
(508) 750-4744. For those organizations that have been granted a photocopy license by
CCC, a separate system of payment has been arranged. The fee code for users of the
Transactional Reporting Service is 0-8031-2060-5-95 $2.50 + .50.
NOTE: This manual does not purport to address (all of) the safety problems associated with its
use. It is the responsibility of the user of this manual to establish appropriate safety and health
practices and determine the applicability of regulatory limitations prior to use.
Printed in Ann Arbor, MI

June 1995
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Foreword
THIS PUBLICATION, Paint and Coating Testing Manual: Fourteenth Edition of the
Gardner-Sward Handbook, was sponsored by Committee D- 1 on Paint and Related
Coatings, Materials, and Applications. The editor was Joseph V. Koleske. This is
Manual 17 in ASTM's manual series.
III
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Acknowledgments
ASTM WOULDLIKE TO EXPRESS its gratitude to the authors of the previous 13

editions of this publication. These publications made significant .contributions to
the technology; therefore, ASTM, in its goal to publish books of technical signifi-
cance, called upon current experts in the field to revise and update this important
publication to reflect the changes and advancements that have taken place since
the last edition, which was published in 1972.
iv
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Preface
AT A JANUARY1967 MEETINGOF ASTM COMMITTEED-1 held in Washington, DC, ASTM

(American Society for Testing and Materials) accepted ownership of the Gardner-Sward
Handbook from the Gardner Laboratory. It was through this laboratory that Dr. Henry
A. Gardner published the previous twelve editions of the manual. Acceptance of this
ownership gave ASTM an assumed responsibility for revising, editing, and publishing
future editions of this well-known, respected manual. The undertaking was assigned to
Committee D-1 on Paint and Related Coatings, Materials, and Applications. This com-
mittee established a permanent subcommittee, D01.19 on Gardner-Sward Handbook,
chaired by John C. Weaver, to provide technical, editorial, and general policy guidance
for preparation of the 13th and subsequent editions of the Gardner-Sward Handbook.
The 13th edition was published in 1972 as the Paint Testing Manual (STP 500) with Mr.
G. G. Sward as editor. The manual has served the industry well for the past two decades;
it contains useful information that cannot be found elsewhere. However, the passage of
more than 20 years since its publication is readily apparent in many and perhaps most
chapters of the manual.
Although updating the manual was discussed through the years, a variety of reasons
prevented this task from being accomplished. Feasibility of updating the manual was
not realized until mid-1989 when Dr. John J. Brezinski, Union Carbide (retired), and
Mrs. Kathleen A. Dernoga, Manager of Acquisitions and Review of ASTM Technical
Books and Journals, discussed the matter and the 14th edition was conceived. Between
then and the spring of 1990 an outline for the 14th edition was developed and was
approved by members of Subcommittee DO1.19. Almost five years later the manual was
completed--no wonder such a long period elapsed between editions!
The scope of the new edition is in keeping with the stated scope of Subcommittee
D01.19:
"To provide technical, editorial, and general policy guidance for preparation of the
Fourteenth and subsequent editions of the Gardner-Sward Handbook. The hand-
book is intended for review of both new and experienced paint technologists and
the past, present, and foreseeable trends in all kinds of testing within the scope of
Committee D-1. It supplements, but does not replace, the pertinent parts of the
Society's Book of Standards. It describes briefly and critically all Test Methods
believed to have significance in the world of paint technology, whether or not these
tests have been adopted officially by the society."
In this new edition, ASTM standard methods are described by minimal detail with the
various volumes of the ASTM Book of Standards remaining the primary source of such
information. An effort was made to include references in the absence of ASTM informa-
tion concerning industrial, other society, national, and international test methods. For
the most part, the manual contains either new chapters or the old topics/chapters in
rewritten form. In a few cases, the old manual was merely updated, attesting to either
the quality of the earlier writing, the lack of development in the area, or the apparent
waning of interest in the topic. A variety of modern topics has been included. Individual
authors, experts in their various fields, were given a great deal of freedom in expressing
information about their topics.
Many things have changed through the years. The chemical emphasis has shifted
from natural products to synthetic products, so this edition of the manual contains
chapters that deal with a large number of synthetic polymers used in the coating
industry. Instrumentation has undergone a marked change with innovative electronics
providing the key to many changes. An effort was made to include chapters dealing with
a broad variety of instruments.
xi
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xii PREFACE
To the authors, a warm, heart-felt "thank you." You put your talents to work and
sacrificed much personal time to make the manual a success. A "thank you" is also due
the reviewers, who are a special lot. They must be critical, yet carry out their task in a
constructive manner. Because of the customary anonymity accorded reviewers, they
should know that some authors made a special effort to express their appreciation for
the review comments that they felt strengthened their manuscripts. Those organiza-
tions who permitted authors' time, use of support staff, and supplies are truly appreci-
ated. Works such as this manual could not be completed without their generosity--may
they prosper. The staff at ASTM is distinctive--they were interested and smilingly
helpful to the authors, reviewers, Subcommittee DO1.19, and the editor as they guided
us through the maze of the publication assembly process (though they may have gritted
their teeth at times). A very special thanks to Monica Siperko of ASTM, who worked
closely with the editor in dealing with authors, reviewers, ASTM staff, and manuscripts.
Her invaluable, cheerful assistance is appreciated. And last, but certainly not least, the
contributions of Maureen Quinn and David Jones of the ASTM editing staff are ac-
knowledged. Their able assistance ensured that the manual was uniform in style and
grammar.
Joseph K Koleske
Editor
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MNLI7-EB/Jun. 1995
Subject Index
A Wolf abrasion method, 529 automotive products, 714

Abrasion testing, can coatings, 722-723 can coatings, 722
A-A-1555, 726, 727-729, 729 Absorption testing to chalky surfaces, architectural
AAMA 801.1,739 architectural coatings, 699-700 coatings, 705
AAMA 802.3,739 masonry, 725 chemical, 514-515
AAMA 803.3, 739 Acetylacetone, antimicrobial agents that combination of phenomena, 515
AAMA 804.1,739 react with, 263, 265 concepts, 513
AAMA 805.2, 739 Acid-base adhesion, 515 diffusion theory, 514
AAMA 806.1,739 Acidity direct tensile testing, 519-523
AAMA 807.1,739 plasticizers, 115 electrostatic, 515
AAMA 808.3, 739 solvents, 152 fracture theory, 513-514
AAMA 809.2, 739 Acid resistance, 664-665 ISO 4624, 521-522
AASHTO M-247, 745 Acids, used in alkyd manufacture, 56 mechanical, 515
AASHTO T 250, 744, 745 Acid spot test, metallic pigments, 226 peel adhesion testing on plastic
AASHTO T 259, 750 Acid value, alkyds, 57 substrates, 517-518
Ablative coatings, testing, 675 Acid wash color, solvents, 152 peel angle and rate, 519
Abrasion, mechanism, 526 Acrylic emulsion polymers, 46-51 sealants, 737
Abrasion resistance architectural coatings, 46-49 versus stress, 594, 596
air blast abrasive, 527-528 exterior coatings applications, 48-49 substrate effects, 515-516
architectural coatings, 703 industrial coatings, 49-51 surface modification techniques, 5 ! 6
balanced beam tester, 531-532 interior coatings applications, 47-48 tape test, 517-519, 688
maintenance coatings, 49 controversy, 518
Bell Laboratory Rotating Disk
nonreactive emulsions, 49-50 test methods, 517
Abrasion Test, 528
properties, 50 visual assessment, 519
camp abrasion tester, 529
resistance characteristics, 51 weak boundary layer theory, 514
coin mar test, 532
thermosetting emulsions, 50-51 wet, architectural coatings, 704
comparison of wear abrasion testers, Acrylic latex sealants, 736 wetting-contact theory, 514
531 Acrylic/MF clearcoat, dynamic work of, 513
correlation with end-use performance, properties, 539-540 Adhesive shear strength, pavement
525-526 Acrylic polymers, as coatings binders, marking tape, 745
definitions, 525 39-51 Adhesive strength, 515
falling abrasive test, 526-527 acrylic emulsion polymers, 39-40 ADL Ball Rebound Apparatus, 578-579
FDC wear test, 529-530 (see also Acrylic emulsion polymers; Adsorption chromatography, 790
fingernail test, 532" Acrylic solution polymers) Aerosol beam generator and detection
gloss reduction test, 527 Acrylic solution polymers, 39-46 mechanism, 316
gravel projecting machine, 528-529 acid-functional acrylics cross-linked Aerosol spray paints, VOC standards, 8
impinging abrasive method, 532 with epoxy resins, 43-44 Aerospace and aircraft coatings, 683-694
less well-known tests, 532-533 cross-linked with amino resins, 43-45 accelerated conditions, 685
pebble abrasion wear test, 527 isocyanate-reactive acrylics, 45-46 accelerated weathering, 691-692
PEI abrasion tester, 533 thermoplastic resins, 40-42 adhesion, 688-689
Peters abrasion block, 533 thermosetting acrylic resins, 42-46 chemical analysis, 684-685
Princeton scratch tester, 532 Acrylic solvent release sealants, 735 cleanability, 693-694
rain or water erosion, 532 Additives corrosion inhibition, 690-691
RCA tape tester, 531 failure modes associated with, 772- density, 684
relation to hardness, elasticity, and 773 drying time, 686
tensile strength, 525 identification, paint analysis, 763 film thickness, 686-687
Roberts jet abrader, 527-528 Adhesion, 513-523 fineness of grind and coarse particles,
Schiefer abrasion testing machine, acid-base, 515 684
529-530 aerospace and aircraft coatings, 688- flash point, 685-686
straight-line reciprocating machines, 689 flexibility, 689
531 architectural coatings, 703-704 fluid resistance, 692-693
Taber Abraser, 530 artists' paints, 708 hardness, 690
mar test, 532 ASTM D 2197, 522-523 heat resistance, 692-693
traffic marking materials, 744 ASTM D 4541, 519-522 humidity, 692
traffic paint tests, 532 ASTM D 5179, 519-520 mar resistance, 690
901
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902 P A I N T A N D COATING T E S T I N G M A N U A L
optical properties, 687-688 in water-reducible coatings, 393, 397 exterior coatings, 697
outdoor exposure, 691 Amine value, traffic marking materials, gloss, 702-703
pigment concentration, 684 743 hiding power, 703
pot life, 686 Aminoethylpiperazine, 85 high performance, 697
storage stability, 685 Aminoplast cross-linking resins, 77 interior coatings, 697
strippability, 693 Amino resins, 60-67 properties
total solids content, 684 combining ratios, 63-64 exterior coatings, 705
viscosity, 683-684 cross-linked with acrylic polymers, 43- interior and exterior, 703-704
volatile concentration, 684 45 interior finishes, 704-705
wear resistance, 689-690 cure reactions, 64-65 reflectance, 702
Aging, effects on flexibility and definition and description, 60 roller application, 702
toughness, 554 degradation, 65-66 scope, 696-697
Air blast end uses, 66 service location, 698
abrasive, 527-528 environmental/toxicity, 66-67 spray application, 702
aerospace and aircraft coatings, 690 free formaldehyde, 64 substrate
Aircraft (see Aerospace and aircraft high-performance liquid conditions, 697
coatings) chromatography, 62-63 types, 697
Air pollutants high-solids, 61-62 test selection, 698
hazardous, in paints and coatings, 10 history, 60 touch-up uniformity, 702
volatile organic compounds, physical properties, 64 value judgments, 698
regulations, 3-12 size exclusion chromatography, 62-63 Arco microknife, aerospace and aircraft
Air toxics program, Clean Air Act, 10 solids content, 62 coatings, 690
Alcohols solvent tolerance, 62 Array method, using optical microscope,
soluble phenolic resins, 82 structure/property variations, 61-62 particle-size measurements, 319
as solvents, 129-130 surface tension, 64 Arrhenius expression, 845
Algae synthesis, 61 Articulated-strut meters, 605
associated with paint films, 656 uses, 60-61 Artists' paints, 706-710
determining presence on paint films, viscosity, 62, 64 film properties, 708-709
656 weathering, 65-66 safety and compliance, 709-710
Algicides, 261-267, 657 Analogue electromagnetic thickness storage stability, 706-707
analysis and decontamination, 265- gages, 432-433 working properties, 707-708
266 Angstrom particle sizing, 329 Asbeck-Van Loo method, critical pigment
definition of terms, 261 Anhydrides, used in alkyd manufacture, volume determination, 254-255
methods for determination of efficacy, 56 Ash (see Pigment content)
267 Aniline point, solvents, 132-133 Asphalt emulsions, 17
mode of action, 262-265 Anionic emulsions, bituminous coatings, Asphalts, 15-16
strategies for minimizing resistant 21 Associative thickeners, 348-349
strains, 265 Anodic dissolution, 610-611 ASTM, specifications, 891-893
Alkalinity, solvents, 152 Anodic passivation, inorganic anti- ASTM A 754, 886
Alkali resistance, 664-665 corrosive pigments, 239-240 ASTM B 117, 639
masonry, 727-728 ANSI/AWWA C203, 733 accelerated weathering, 650
Alkali-swellable/soluble emulsions, 277- ANSI/AWWA C210, 733 aerospace and aircraft coatings, 690
278 ANSI/AWWA C214, 733 automotive products, 715
Alkyds, 53-58 ANSI/AWWA C215, 733 bituminous coatings, 20
acid value, 57 ANSI/AWWA C217, 733 chemical resistance, 666
classification, 57-58 Anthraquinone red, 194 inorganic binders, 771-772
color, 56 Anti-corrosive pigments (see Inorganic water-resistance testing, 678
density, 56 anti-corrosive pigments ASTM B 533, 523
drying properties, 56 Antifouling paint films, structure, ASTM B 537, 613
fusion process, 54 electron microscopy, 824 ASTM B 568, 886
higher solids, 57-58 Antimicrobial agents, 656-657 ASTM B 571,523
history, 53 cationic agents, 265 ASTM C 31,729
hydroxyl value, 57 factors impacting efficacy, 266 ASTM C 43, 725, 729
nonvolatile content, 55-56 future development, 267 ASTM C 67, 725-726, 729, 750
processing, 53-54 metal chelating, 265 ASTM C 97, 725, 729
raw materials, 55-56 reacting with ASTM C 119, 725, 729
resins, gas chromatography, 806-807 acetylacetone, 263, 265 ASTM C 125, 725, 729
solvent reflux process, 54-55 nucleophilic groups, 265 ASTM C 140, 725, 727, 729
viscosity, 55 Antithixotropy, 341 ASTM C 192 729
water-borne, 57-58 API gravity, definitions, 146 ASTM C 267 750
Allen-Bradley sonic sifter, 317-318 API RP 5L2, 733 ASTM C 270 725, 729
z~ltek Mobility/Lubricity Tester, 722 API RP 5L7, 733 ASTM C 282 70-71
Alumina trihydrate, 220 Appearance ASTM C 283 70-71
A]umlnum artists' paints, 706-707 ASTM C 285 71
corroeion, 613 automotive products, 714 ASTM C 313 523
flake, 244-245 Application life, sealants, 736 ASTM C 346 71
pigment~ Aqueous solutions, corrosion in, 609-611 ASTM C 372 69
grade classification,224 Architectural coatings, 696-705 ASTM C 374 71
properties, 223-224 acrylic emulsion polymers, 46-49 ASTM C 385 71
Aluminumtriphosphate, 243 ASTM guides, 697 ASTM C 424 69
AmericanArchitecturalManufacturers brush application, 701-702 ASTM C 448 533
Association, 892-893 color, 702 ASTM C 510 738
Amines differences, 702 ASTM C 536 70-71
polyfunctional,in polyurethane definitions, 696 ASTM C 537 71
coatings, 91 dry film appearance, 702-703 ASTM C 538 70-71
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SUBJECT I N D E X 903
A S T M C 5 3 9 69,71 A S T M C 1034, 69 ASTM D 332, 170, 508

A S T M C 554 69 A S T M C 1070,216 ASTM D 335, 96
A S T M C 556 69 A S T M C 1083,738 ASTM D 344, 502, 703
A S T M C 5 7 0 737,738 A S T M C 1085, 737-738 ASTM D 365, 462
A S T M C 584 69 A S T M C 1087, 738 ASTM D 387
A S T M C 603 738 A S T M C 1109, 788 black pigments, 189
A S T M C 609 69 A S T M C 1111, 788 ceramic pigments, 216
A S T M C 6 1 4 70-71 A S T M C 1193, 738 colored organic pigments, 207
A S T M C 633 72 A S T M D 12,28 pigment dispersion, 508-509
A S T M C 63~ 738 A S T M D 21,604 ASTM D 402, 20
A S T M C 642, 725, 729 A S T M D 4, 15, 19, 733 A S T M D 412, 97, 536, 543
A S T M C 650, 69 A S T M D 5, 19, 733 A S T M D 445, 118, 133, 363
A S T M C 661, 738 A S T M D 26, 692 A S T M D 449, 19
A S T M C 666, 750 A S T M D 36, 19, 733, 745 A S T M D 450, 19
A S T M C 669, 737, 738 ASTM D 41, 20 A S T M D 466, 21
A S T M C 672, 750 ASTM D 43, 20-21, 20 A S T M D 476, 174, 176
A S T M C 675 71 ASTM D 56, 755 A S T M D 480,226
A S T M C 676 71 aerospace a n d aircraft coatings, 686 A S T M D 520,226
A S T M C 679 738 can coatings, 720 A S T M D 521,226
A S T M C 681 738 plasficizers, 117 A S T M D 522, 548-550, 771
A S T M C 690 216 so~ents, 142 aerospace and aircraft coatings, 689
A S T M C 703 71 wate~repellent coatings, 748 a r c h i t e c t u r ~ coatings, 704
A S T M C 711 738 ASTM D 61, 19 artist's paints, 709
A S T M C 712 738 ASTM D 70, 19 bituminous coatings, 20
A S T M C 713 738 ASTMD71,19,733 natural weathering, 642
A S T M C 717 738 A S T M D 86, 116, 140-141 stress-strain analysis, 544
A S T M C 718 738 A S T M D 88, 19 A S T M D 523, 471,473-474, 771
A S T M C 719 738 A S T M D 92, 19, 117 aerospace and aircra~ coatings, 688
A S T M C 724 71 A S T M D 93,755 a r c h i t e c t u r ~ coatings, 702-703
A S T M C 731 738 aerospace and aircra~ coatings, 686 can coatings, 723
A S T M C 732 738 architectural coatings, 699 natural weathering, 641
A S T M C 733, 738 plasticizers, 117 white pigments, 173
A S T M C 734, 738 so~ents, 143 A S T M D 529, 19, 20, 21
A S T M C 735,71 ASTMD 95,19,226 A S T M D 546, 317
A S T M C 736, 738 A S T M D 115, 362 A S T M D 555, 20, 29
A S T M C 738, 69 A S T M D 130, 116, 153 A S T M D 562 20, 273, 683,743
A S T M C 741,738 A S T M D 140, 19 A S T M D 570 771
A S T M C 742, 738 A S T M D 153 A S T M D 600 33
ASTMC 743,70-71 colored organic pigments, 208 A S T M D 601 28
A S T M C 756, 70-71 extender pigrnents, 221 A S T M D 602 221
A S T M C 765, 738 solids, 301-302 A S T M D 603 221
A S T M C 766, 738 traffic marking materials, 745 A S T M D 604 221
A S T M C 771,738 A S T M D 154, 743 A S T M D 6 0 5 221
A S T M C 772, 738 A S T M D 156, 149, 462 A S T M D 607 221
A S T M C 777, 71 A S T M D 185 A S T M D 609 20, 677, 774
A S T M C 780, 727, 729 aerospace and aircraft pigments, 684 A S T M D 610, 20, 641,771
A S T M C 782, 738 architectural coatings, 698 A S T M D 624, 97
A S T M C 792, 738 artist's paints, 707 A S T M D 638, 536-537, 543,745
A S T M C 793, 738 ceramic pigments, 216 A S T M D 658
A S T M C 794, 738 metallic pigments, 226 abrasion testing, 526-528
A S T M C 797, 738 A S T M D 212, 720 aerospace a n d ~ r c r a f t coatings, 690
A S T M C 824, 71 A S T M D 233 127 architectural coatings, 703
A S T M C 834, 738 A S T M D 234 2 8 , 2 5 2 - 2 5 3 wear abrasion, 531
A S T M C 836, 738 A S T M D 235 126,153, 226 A S T M D 6 6 0 641,771
A S T M C 839 71 A S T M D 255 20 ASTM D 661 6 4 1 , 6 8 0 , 7 4 9 , 7 7 1
A S T M C 8 7 2 70-71 A S T M D 256 745 ASTM D 662 20, 6 4 1 , 6 8 0 , 7 7 1
A S T M C 879 738 A S T M D 257 733 ASTM D 673 532,581
A S T M C 895 69 A S T M D 262 5O8 ASTM D 695 733
A S T M C 898 738 A S T M D 267 226 ASTM D 711 444,743, 747
A S T M C 907 738 A S T M D 269 428 ASTM D 713 746-747
A S T M C 908 738 A S T M D 270 294 ASTM D 714 2 0 , 6 4 1 , 7 7 1
A S T M C 910 738 A S T M D 281 ASTM D 715 221
A S T M C 919 738 ceramic pigments, 216 ASTM D 716 221
A S T M C 9 2 0 737-738 colored organic pigments, 207 ASTM D 717 221
A S T M C 927, 71 extender pigments, 221 ASTM D 718 221
A S T M C 957, 737-738 oil absorption, 253 ASTM D 719 221
A S T M C 961,738 white pigments, 169 ASTM D 740 128
A S T M C 972, 738 ASTM D 287, 146 ASTM D 746 120
A S T M C 981,738 ASTM D 312, 19 ASTM D 772 641,771
A S T M C 988, 523 ASTM D 319, 130 ASTM D 792 9 8 , 2 9 7 , 3 0 2
A S T M C 1016,738 ASTM D 323, 135 ASTM D 801 127
A S T M C 1021, 738 ASTM D 329, 128 ASTM D 802 127-128
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904 PAINT AND COATING TESTING MANUAL
ASTM D 816, 362 ASTM D 1217, 147 ASTMD 1614, 152

ASTM D 817, 24-25 ASTM D I218, 117, 149 ASTMD 1617, 117, 129, 151
ASTM D 821,747 ASTM D 1227, 20-21 ASTMD 1620, 188
ASTM D 822, 207, 728-729, 865 ASTM D 1250, 147 ASTMD 1630, 602
ASTM D 823 ASTM D 1259, 55, 87, 756 ASTMD 1638, 362
film preparation, 415, 419, 421 ASTM D 126, 743 ASTMD 1639,57
free film samples, 538-539 ASTM D 1260, 720 ASTMD 1640
water-resistance testing, 677 ASTM D 1266, 153 aerospace and aircraft coatings, 686
ASTM D 832 419 ASTM D 1270, 172 alkyds, 56
ASTMD 847 152 ASTM D 1286, 362 artist's paint, 708
ASTMD 848 152 ASTM D 1296, 117, 149, 699 bituminous coatings, 20
ASTMD 849 116,153 ASTM D 1298, 146 driers, 32
ASTMD 850 140-141 ASTM D 1308 drying oils, 28
ASTMD 868 743 architectural coatings, 704 drying time, 439--440
ASTMD 869 701,707,743,771 artist's paint, 709 hardness, 573
ASTMD 870 677, 774 automotive products, 715 water-repellent coatings, 748
ASTMD 871 24 chemical resistance, 662, 664-665 ASTMD 1644, 20, 34
ASTMD 882 536,543 ASTM D 1309 743 ASTMD 1647, 665
ASTMD 883 536 ASTMD 1310 142, 755 ASTMD 1652, 109, 743
ASTMD 891 118, 146-147 ASTMD 1319 150,791 ASTMD 1653, 771
ASTMD 907 513 ASTMD 1328 19 aerospace and aircraft coatings, 692
ASTM D 913 747 ASTMD 1337 362 masonry, 728-729
ASTM D 936 150-151 ASTMD 1338 362 water-repellent coatings, 750
ASTM D 941 147 ASTMD 1347 302 ASTMD 1654, 20, 641,771
ASTMD 960 28 ASTMD 1353 152 ASTMD 1669, 19
ASTMD 968 771 ASTMD 1364 118, 154 ASTMD 1718, 129
abrasion resistance, 526-527, 531 ASTMD 1366 216, 221 ASTMD 1719, 130
architectural coatings, 703 ASTMD 1370 19 ASTMD 1720, 132-133
traffic marking materials, 744 ASTMD 1392 28 ASTMD 1722, 154
ASTMD 969, 743 ASTMD 1394 168,743,763 ASTMD 1725, 133, 361
ASTMD 996, 677 ASTMD 1398 805-806 ASTMD 1729, 465, 744
ASTMD 1002, 733 ASTMD 1400 426, 434, 771 architectural coatings, 702
ASTMD 1005 415, 426, 538 ASTMD 1417 362 artist's paint, 709
ASTMD 1006 774 ASTMD 1439 277, 302,362 natural weathering, 641
ASTMD 1007 130 ASTMD 1462 28 ASTMD 1730, 677, 774
ASTMD 1014 771 ASTMD 1474 ASTM D 1734,418, 677,729
ASTMD 1044 581,733 bituminous coatings, 20 ASTM D 1735678
ASTMD 1045 117 acrylic polymers, 42 ASTM D 1737 722
ASTMD 1076 362 can coatings, 720 ASTM D 1795 839
ASTMD 1078 116, 140-141 cure testing, 412 ASTM D 1824 362
ASTMD 1079 16, 19 hardness, 564, 567, 569-571 ASTM D 1849 20, 685, 701, 748
ASTMD 1084 97, 362 ASTM D 1474A, 714 ASTM D 1856 19
ASTMD 1125 714 ASTM D 1475, 7, 299, 771 ASTM D 1894 603-604
ASTMD 1131 361 architectural coatings, 698 ASTM D 1955 28
ASTMD 1133 132 automotive products, 714 ASTM D 1963 755
ASTMD 1150 774 bituminous coatings, 20 ASTM D 1983 743, 804, 806
ASTMD 1152 130 density, 755 ASTM D 2042 19
ASTMD 1153 128 traffic marking materials, 743 ASTM D 2047 600,603-604
ASTMD 1155 745 water-repellent coatings, 748 ASTM D 2073 86
ASTMD 1159 153 ASTMD 1476 154 ASTM D 2074 743
ASTMD 1186 429,771, ASTMD 1483 169,221,252-253 ASTM D 2076 86
automotive )roducts, 714 ASTMD 1492 153 ASTM D 2090 34
can coatings, 721 ASTMD 1500 462 ASTM D 2091 3 2 , 4 2 , 4 1 1 , 5 7 3
natural weathering, 642 ASTMD 1505 302 ASTM D 2124 100
thickness gages, 432 ASTMD 1513 188 ASTM D 2134, 412, 575-576
ASTM D 1187, 21 ASTMD 1526 556 ASTM D 2192, 150
ASTM D 1199, 221 ASTMD 1535 457 ASTM D 2196, 273, 341,362, 771
ASTM D 1200, 359, 771 ASTMD 1540 20,662 aerospace and aircraft coatings, 683
aerospace and aircraft coatings, 683 ASTMD 1542 20 architectural coatings, 701
can coatings, 720 ASTMD 1544 artist's paint, 708
water-repellent coatings, 748 alkyds, 56 automotive products, 714
ASTM D 1208, 755 driers, 34-35 can coatings, 720
ASTM D 1209, 115, 148-149, 462 polyamides, 87 polyamides, 87
ASTM D 1210, 771 plasticizers, 116 water-repellent coatings, 748
aerospace and aircraft coatings, 684 scales for liquids, 462 ASTM D 2197
architectural coatings, 699 ASTM D 1545, 361 aerospace and aircraft coatings, 688,
artist's paint, 708 alkyds, 55 690
extender pigments, 221 amino resins, 62 adhesion, 522-523
particle-size measurement, 327 driers, 34-35 architectural coatings, 703
traffic marking materials, 743 polyamides, 87 mar resistance, 532, 579-580
ASTM D 1211, 554, 667 solvents, 133 ASTM D 2200, 435
ASTM D 1212, 20, 424, 504, 687 ASTM D 1555, 147, 297 ASTM D 2202, 738
ASTM D 1214, 745 ASTM D 1613, 115, 152 ASTM D 2203, 738
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SUBJECT I N D E X 905
ASTM D 2240, 97 nonvolatile content, 756 b i t u m i n o u s coatings, 20

ASTM D 2243, 20, 685,748 VOC, 8 can coatings, 722
ASTM D 2244, 465, 771 A S T M D 2698, 684, 879 natural weathering, 642
aerospace and aircraft coatings, 687 A S T M D 2704, 642 peel adhesion, 517-518
archictectural coatings, 702 A S T M D 2710, 153 ASTM D 3360, 221, 321
artist's paint, 708-709 A S T M D 2743, 804, 809 ASTM D 3361, 728-729
traffic marking materials, 744 A S T M D 2745, 171,508 ASTM D 3362, 804
natural weathering, 641 A S T M D 2764, 19 ASTM D 3363, 771
ASTM D 2245 743, 804, 806 A S T M D 279, 207, 708 aerospace and aircraft coatings, 690
A S T M D 2247 20, 692,714 A S T M D 2792, 663 can coatings, 721
A S T M D 2248 43,532 A S T M D 2794, 42, 412, 553, 689 cure, 412
A S T M D 2249 738 A S T M D 2799, 723 driers, 32
A S T M D 2268 151 A S T M D 2800, 743, 804 hardness, 559-560, 564
A S T M D 2288 97 A S T M D 2801, 358 natural weathering, 642
A S T M D 2306 151,804 A S T M D 2804, 128, 151,685, 804 ASTM D 3423, 20
A S T M D 2318 19 A S T M D 2805 ASTM D 3432, 685, 804
A S T M D 2319 19 aerospace and aircraft coatings, 687 ASTM D 3447, 151
A S T M D 2320 19, 301 a r c h i t e c t u r ~ coatings, 703 ASTM D 3450, 704, 705
A S T M D 2348, 763 automotive products, 713 ASTM D 3456, 267, 659
A S T M D 2360, 152,804 hiding power, 491,502, 504 ASTM D 3457, 804
A S T M D 2363, 277, 302 ~affic marking ma~rials, 743 ASTM D 3459, 680
A S T M D 2364, 276, 362 white pigments, 171 ASTM D 3461, 19
ASTM D 2369, 5 - 7 A S T M D 2823, 20 ASTM D 3465, 117
aerospace and aircraft coatings, 684 A S T M D 2824 20 ASTM D 3468, 21
amino resins, 62 A S T M D 2832 20, 756 ASTM D 3505, 148, 299
architectural coatings, 713 A S T M D 2849 116 A S T M D 3506, 130
bituminous coatings, 20 A S T M D 2857 839 A S T M D 3536, 838
can coatings, 720 A S T M D 2863 668-670 A S T M D 3539 135
nonvolatile content, 756 A S T M D 2879 116, 135 A S T M D 3540 129
traffic marking materials, 743 A S T M D 2916 128 A S T M D 3545 129, 151,804
water-repellent coatings, 748 A S T M D 2917 128 A S T M D 3593 838
ASTM D 2370, 733 A S T M D 2921 680 A S T M D 3619 221
bituminous coatings, 20 A S T M D 2935 148,297 A S T M D 3622 130
dynamic mechanical properties, 536 A S T M D 2939 21 A S T M D 3624 787
tensile properties, 543 A S T M D 2962 19 A S T M D 3626 804
aerospace and aircraft coatings, 664 A S T M D 2963 21 A S T M D 3698 130
architectural coatings, 704 A S T M D 2965 296 A S T M D 3717 787
ASTM D 2371, 743, 879 A S T M D 3002 774 A S T M D 3718 685,787
A S T M D 2372 684, 756 A S T M D 3008 804 A S T M D 3719 705
A S T M D 2373 35 A S T M D 3009 151,804 A S T M D 3720 1 6 4 , 7 6 3 , 8 8 0
A S T M D 2374 35 A S T M D 3037 188 A S T M D 3723 7 4 3 , 7 5 6 , 8 7 9
A S T M D 2375 35 A S T M D 3054 151,804 A S T M D 3728 129
A S T M D 2376 738 A S T M D 3055 127 A S T M D 3730 420, 523,697
A S T M D 2377 738 A S T M D 3104 19 A S T M D 3735 126
A S T M D 2393 362 A S T M D 3105 20 A S T M D 3742 151
A S T M D 2414 188 A S T M D 3128 129 A S T M D 3760 151,804
A S T M D 2 4 1 5 19, 733 A S T M D 3130 129 A S T M D 3792 6 - 7 , 7 5 5 , 8 0 4
A S T M D 2416 19 A S T M D 3131 129 A S T M D 3797 151, 8O4
A S T M D 2444 723 A S T M D 3132 134 A S T M D 3798 151,804
A S T M D 2448 221 A S T M D 3134 465-466 A S T M D 3804 35
A S T M D 2450 738 A S T M D 3143 733 A S T M D 3805 2O
A S T M D 2451, 738 A S T M D 3170 20,528, 642, 714 A S T M D 3806 670-672
A S T M D 2452, 738 A S T M D 3257 151,804 A S T M D 3893 128, 151, 804
A S T M D 2453, 738 A S T M D 3258 704 A S T M D 3894 674-675
A S T M D 2455, 804 A S T M D 3260 664 A S T M D 3925 753-754, 774
A S T M D 2456, 804 A S T M D 3265 188-189 A S T M D 3928 702
A S T M D 2485, 667 A S T M D 3271 7 6 4 , 7 9 7 , 8 0 4 A S T M D 3934 144
A S T M D 2486, 705 A S T M D 3272 756-757 A S T M D 3941 143
A S T M D 2503, 836 A S T M D 3273 267, 658-659 ASTM D 3960 6, 8, 774
A S T M D 2521, 19 A S T M D 3274 641,656 aerospace and aircraft coatings, 684
A S T M D 2556, 362 ASTM D 3278 755 architectural coatings, 699
A S T M D 2569, 19 aerospace a n d aircraft coatings, 686 automotive products, 714
A S T M D 2571, 662 architectural coatings, 699 bituminous coatings, 20
ASTMD 2574,267,657 bituminous coatings, 56 can coatings, 720
A S T M D 2613,35 can coatings, 720 chromatography, 809
A S T M D 2616,465 plasticizers, 117 gas chromatography, 804
A S T M D 2621, 100, 743,771 solvents, 143 water-repellent coatings, 748
A S T M D 2627, 128 ASTM D 3281, 523, 552-553 ASTM D 3961, 154
A S T M D 2634, 129 ASTM D 3320, 20-21 ASTM D 3964, 464, 702
A S T M D 2635,130 ASTM D 3329, 128, 151,804 ASTM D 3969, 35
A S T M D 2669, 362 ASTM D 3335, 6 8 5 , 7 8 7 , 8 8 6 ASTM D 3970, 34
A S T M D 2697, 771 ASTM D 3359, 778 ASTM D 3988, 35
aerospace and aircraft coatings, 684 aerospace and aircraft coatings, 688 ASTM D 3989, 35
automotive products, 713 architectural coatings, 703-704 ASTM D 4001, 836-837
displacement, 302 artist's paint, 708 ASTM D 4017, 6-7, 226, 685, 755
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ASTM D 4052, 118, 147, 755 ASTM D 4715, 19 ASTM E 176, 667
ASTM D 4060 526, 771 ASTM D 4735, 8O4 ASTM E t97, 463
aerospace and aircraft coatings, 690 ASTM D 4746, 19 ASTM E 201, 148
architectural coatings, 703 ASTM D 4752, 411,664 ASTM E 202, 151
automotive products, 714 ASTM D 4758, 756 ASTM E 260, 150, 764, 796, 809
can coatings, 722 ASTM D 4764, 762 ASTM E 275, 867-869
natural weathering, 642 ASTM D 4773, 129, 151 ASTM E 276, 317
wear abrasion, 530-531 ASTM D 4796, 745 ASTM E 284, 447, 449, 452, 507
ASTM D 4061 449, 744 ASTM D 4797, 744 directionality, 470-471
ASTMD 4062 274, 358,701 ASTM D 4798, 19 pearlescent pigment, 232
ASTMD 4072 19 ASTM D 4799, 19 ASTM E 300, 117, 754
ASTMD 4079 130 ASTM D 4828, 705 ASTM E 303, 603, 604, 745
ASTMD 4080 130 ASTM D 4834, 762 ASTM E 308, 453-454, 456, 462
ASTMD 4081 130 ASTM D 4835, 129 traffic marking materials, 744
ASTMD 4086 452 ASTM D 4836, 129 tristimulus values, 463
ASTMD 4126 130 ASTM D 4837, 129 ASTM E 313 461-462
ASTMD 4138 429 ASTM D 4838, 508, 708 ASTM E 346 130, 151
ASTMD 4139 221 ASTM D 4866, 20 ASTM E 355 150, 796, 809
ASTMD 4141 ASTM D 4875, 109 ASTM E 413 641
accelerated weathering, 651 ASTM D 4883, 302 ASTM E 430 477
masonry, 728-729 ASTM D 4890, 109 ASTM E 450 462
natural weathering, 638, 640 ASTM D 4892, 19, 302 ASTM E 514 728-729
water-repellent coatings, 749 ASTM D 4893, 19 ASTM E 516 798, 809
ASTM D 4145 523, 722 ASTM D 4941, 707 ASTM E 594 798, 809
ASTMD 4146 523, 552 ASTM D 4946, 42, 704 ASTM E 595 97
ASTMD 4210 757 ASTM D 4951, 788 ASTM E 603 674-675
ASTMD 4212 683, 714, 771 ASTM D 4958, 274, 702 ASTM E 663 788
ASTMD 4213 531, 705 ASTM D 4960, 744 ASTM E 682 809
ASTMD 4214 641,771 ASTM D 4989, 19 ASTM E 685 793, 809
ASTMD 4236 710 ASTM D 5008, 130 ASTM E 697 798, 809
ASTMD 4260 727 ASTM D 5018, 20 ASTM E 782 639
ASTMD 4261 727 ASTM D 5031, 680, 865 ASTM E 805 464
ASTMD 4262 726-727, 729 ASTM D 5066, 8 ASTM E 808 449
ASTMD 4274 109 ASTM D 5095, 8, 748 ASTM E 811 449
ASTMD 4287 274, 701-702 ASTM D 5098, 707, 708 ASTM E 840 809
ASTMD 4302 708 ASTM D 5107, 727, 729 ASTM E 991 449, 462
ASTMD 4303 709 ASTM D 5135, 804 ASTM E 1064, I54
ASTMD 4304 709 ASTM D 5137, 129 ASTM E 1100, 151
ASTMD 4312 19 ASTM D 5146, 696, 697 ASTM E 1131, 675
ASTMD 4360 128 ASTM D 5150, 503, 703 ASTM E 1140, 798, 809
ASTMD 4366 32, 412, 574 ASTM D 5162, 774 ASTM E 1151, 809
ASTMD 4367 152, 804 ASTM D 5178, 580 ASTM E 1164, 448, 463-464, 508
ASTMD 4368 100 ASTM D 5179, 519-520, 771 ASTM E 1247, 449
ASTMD 4400 274, 354,418, 771 ASTM D 5200, 8 ASTM E 1303, 793, 809
ASTMD 4402 19 ASTM D 5201, 8, 710 ASTM E 1331, 449, 463-464
ASTMD 4414 425, 774 ASTM D 5286, 8 ASTM E 1341, 463
ASTMD 4417 771 ASTM D 5324, 696, 697 ASTM E 1345, 464
ASTMD 4446 749 ASTM D 5325 8 ASTM E 1347, 449, 463, 688, 702
ASTMD 4449 472 ASTM D 5326 700 ASTM E 1348, 449, 463-464
ASTMD 4451 743 ASTM D 5327 8 ASTM E 1349, 449, 463-464
ASTMD 4457 6-7, 764, 797, 804 ASTM D 5328 9 ASTM E 1360, 460-461
ASTMD 4479 20 ASTM D 5383 709 ASTM E 1455, 463
ASTMD 4492 151, 804 ASTM D 5398 709 ASTM E 1499, 465, 468
ASTMD 4518 601,603 ASTM D 5401 749 ASTM E 1501, 449
ASTMD 4534 152, 804 ASTM D 5403 9 ASTM E 1541, 460
ASTMD4541 519-522, 704, 77l ASTM D 5478 363 ASTM E 1544, 748
ASTMD 4563 762 ASTM D 5531 464 ASTM F 462, 604
ASTMD 4584 714 ASTM E 11,317 ASTM F 489, 604
ASTMD 4585 679-680, 715 ASTM E 12, 145 ASTM F 518, 523
ASTMD 4587 680, 728-729, 865 ASTM E 20, 318-319 ASTM F 609, 602-604
ASTMD 4603 839 ASTM E 70, 221, 714, 748 ASTM F 692, 523
ASTM D 4610 656 ASTM E 84, 670, 672-674 ASTM F 923, 449
ASTM D 4613 82 ASTM E 96, 19, 728-729, 750 ASTM G 6, 20, 733
ASTM D 4614 129 ASTM E 97, 463, 744 ASTM G 7, 728-729
ASTM D 4615 129 ASTM E 100, 297 ASTM G 8, 733, 771
ASTMD 4616 19 ASTM E 102, 19 ASTM G 9, 733
ASTMD 4640 80 ASTM E 119, 675 ASTM G 11,733
ASTMD 4701 130 ASTM E 161,317 ASTM G 13, 733
ASTMD 4707 702 ASTM E 162, 670, 672, 674 ASTM G 14, 553, 733, 771
ASTMD 4708 416, 538-539, 774 ASTM E 167, 474, 688 ASTM G 17, 733
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SUBJECT INDEX 907
ASTM G 19, 733 Barrier coatings, 238-239 Blue pigments, 197-198

ASTM G 20, 733 Basecoat, automotive products, 713 inorganic, 210-211
ASTM G 26, 648, 680 Basic calcium zinc molybdate, 242 BN 8-4, 579
ASTM G 42, 771 Basic calcium zinc molybdate/zinc Boiling point, solvents, 137, 139-140
ASTM G 50, 613 phosphate, 242 Bond strength, thermoplastic marking
ASTM G 53, 774 Basic lead silicochromate, 242 materials, 745
aerospace and aircraft coatings, 692 Basic zinc molybdate, 242 Bone blacks, 179
automotive products, 715 Basic zinc molybdate/phosphate, 242 BON maroon, 192
accelerated weathering, 649-650 Battelle chemical resistance cell, 663 BON reds, 192
water-repellent coatings, 749 Beading, water-repellent coatings, 749 Borates, inorganic anti-corrosive
ASTM G 85, 690 Beer's law, 785 pigments, 240-241
ASTM G 90, 639-640, 652 Bell Laboratory Rotating Disk Abrasion Bourger-Beer law, 869
ASTM G 95, 771 Test, 528 Bragg equation, 872
ASTM G 104, 613 Bell Telephone Laboratories Indenting Bratt conductivity cell, 663-664
ASTM gage, particle-size measurements, Rheometer, 565 Breakthrough time, effects of molecular
327-329 Belt Buckle Test, 582 size and affinity, 401-402
Atmospheric corrosion, metals, 611-612 Bentonite clays, 282 Bridges, sealants, 737
Atmospheric exposure testing, inorganic Benzene, solvent content, 152 Brightness, 507
anti-corrosive pigments, 248-249 Benzimidazolone-based reds, 195-196 Brightwell method, 428
Atomic absorption spectroscopy, 784- Benzimidazolone orange, 203 Brinell Indentation Hardness Tester, 566
786 Benzimidazolone yellows, 199, 201 Brominated pyranthrone red, 194-195
applications, 787-788 Benzoguanamine, 66 Brooldield and Stormer viscometers, 683
background correction, 786-787 Bierbaum Microcharacter, 556 Brooklield CAP 2000 viscometer, 363
coating failure analysis, 779 Binders Brookfield Digital Viscometer Model
cold vapor technique, 786 effect on stress in organic coatings, KU-1,360
flame characteristics, 785 594 Brooldield Synchro-Lectric viscometer,
graphite furnace, 786 role in hiding power, 483 362-363
pigment identification, 762 Biocidal efficacy, microorganisms, 262 Brooklield viscometers, 362-363
sources of interference, 786-787 Biological deterioration, 654-661 Brown magnetite iron oxide, 212
Atomic emission spectroscopy, 786 antimicrobial agents, 656-657 Brown pigment, inorganic, 212
applications, 787-788 bacterial resistance, liquid paints, 657 Brunauer-Emmett-Teller method, 313
background correction, 786-787 description of problem, 654-655 Brush application, architectural coatings,
sources of interference, 786-787 determining presence of fungal or 701-702
Attapulgite clays, 281-282 algal growth, 656 Brush drag, architectural coatings, 701-
Attenuated total reflectance, 829 effect on natural weathering, 627-629 702
Automobile industry, VOC standards, 8 fungal resistance, paint films, 657-659 Brushing characteristics, artists' paints,
Automotive products, 711-716 insect-resistant paints, 659-661 707-708
coatings, 554 Biopolymers, thickeners and rheology Brushouts, 485
hiding power, 713 modifiers, 277 BS 1006, 207
identification, 711-713 Bismuth vanadate/molybdate yellow, BS 2662, 207
material requirements, 713-714 211-212 BS 3900, 441-442, 504, 561
paints, waterborne amino resins, 66 Bisphenol-A based epoxides (see Epoxy El, 550
pearlescent pigments, 230-231 resins) E4, 551
performance requirements, 714-715 Bitumens, history and background, 15- BTL Balanced Beam Mar Tester, 579-
pretreatments, 711 16 580
primer, 711-712 Bituminous coatings, 15-21 Buchholz Indentation Hardness Tester,
process requirements, 715-716 ASTM definitions, 15 566
surface cleaners, 711 general tests for, 20 Bulk modulus, 573
topcoats, 712-713 for paving, 18 Buoyancy-hydrometers, 297-298
viscosity, 714-715 resin modified, 21 Burgers model, 348-349
Azam method, oil absorption roof coatings, 16-18 Butyl alcohols, 129
determination, 253 solvent-thinned or cut-back, 20-21 Butyl sealants, 735
Azo-based oranges, 200-201,203-204 specialty paints and coatings, 16 BYK-Gardner cupping tester, 551-552
tests on, 18-20
types, 16-18
B waterproofing membranes, 18
Black box, 634-636
Bacteria accelerated natural weathering, 638 Cadmium mercury orange, 212
associated with paint, 654-655 Black panel thermometer, 633 Cadmium orange, 212
resistance of liquid paints, 657 Black pigments Cadmium red, 210
Bactericides, 261-267, 657 carbonaceous pigments, 179 Cadmium sulfide yellow, 211
analysis and decontamination, 265- classification, 180 Cadmium zinc yellow, 211
266 iron oxide blacks, 179 Caframo REAX 2 rotating mixer, 416-
definition of terms, 261 (see also Ceramic coatings) 417
methods for determination of efficacy, Bleeding Calcium borosilicate, 243-244
267 artists' paints, 708 Calcium carbonate, 176-177, 217
mode of action, 262-265 traffic marking materials, 743 California, smog, 3-4
reactive with acetylacetone, 263,265 Bleed test, colored organic pigments, 207 Camp abrasion tester, 529
strategies for minimizing resistant Blister formation, osmotic, 768 Can, production processes, 717-720
strains, 265 Block copolymer sealant, 735 can end preparation, 719
Bake latitude, automotive products, 715 Block resistance three-piece can, 718-719
Balanced beam tester, abrasion architectural coatings, 704 two-piece can, 717-718
resistance, 531-532 artists' paints, 708-709 Can coatings, 717-723
Barium metaborate, 240 can coatings, 723 industry, 717
Barium sulfate, 219-220 Blue-green pigments, 214 tests
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on cured surfaces, 721-723 Chemically reactive cross-linking Cleanability, aerospace and aircraft
on liquid paint, 720-721 binders, coating failure analysis, coatings, 693-694
ultraviolet cured, 719-720 770-771 Clean Air Act, 3-5
Cantilever (beam) method, stress in Chemical resistance, 662-666 Amendments of 1977, 5
organic coatings, 589-590 acid resistance, 664-665 Amendments of 1990, 9-12
Capillary forces, 355 alkali and detergent resistance, 664- Title I, 9
Capillary rise, 374 665 Title III, 10
Capillary rise method, contact angle artists' paints, 709 Title V, 10
measurements, 378 household, architectural coatings, 704 Title VI, 11
Capillary viscometers, 363-364 salt fog test, 664, 666 Title VII, 11
Capillary waves, 377 solvent/fuel resistance, 663-664 Cleaning, surface pH after, masonry, 727
Carbazole violet, 198 staining, 662-663 Cleansability, architectural coatings,
Carbonaceous pigments, 179 treated masonry, 750 704-705
Carbon arc lamps, 644-645, 648-649 water and moisture resistance, 666 Clearcoat
Carbon blacks, 179-189 Chemical testing, pearlescent pigments, automotive products, 713
channel process, 181 - 182 235 crack formation, 598
dispersion quality, 186-187 Chloride, effect on atmospheric Clemen Scratch Hardness Tester, 556
formation, 179-180 corrosion, 6l 1-612 Climatology, 628-635
furnace process blacks, 181, 183 Chlorinated hydrocarbons, solvents, 130 desert, 629-630
gloss, 186, 189 Chlorine exposure effects, 630-631
jetness, 183, 185, 188 detection in plasticizers, 119 extreme cold, 629, 631
lampblack process, 180-182 effect on atmospheric corrosion, 611- instrumentation, 632-635
measuring appearance properties, 188- 612 marine, 629-630
189 Chroma, 507 subtropical climate, 629-630
mechanisms of interaction with light, Chromates, inorganic anti-corrosive temperate with pollution, 629, 631-632
181-182, 184 pigments, 241 Coal tar enamels, 731
opacity, 183 Chromaticity coordinates and diagram, Coal tar epoxides, 732
optical function, 179-182 454-456 Coal tar mastic, 732
parameters affecting optical function, Chromatic paints, tinting strength, 508 Coat tar urethane, 732
182-183, 185-186 Chromatography, 789-8 l0 Coated paper techniques, for obtaining
preferred form, 186 adsorption, 790 free films, 416
selecting a grade, 187-188 "classical column," 791 Coating consistency, thickeners and
tinting strength, 183, 185, 189 displacement analysis, 790 rheology modifiers, 273-274
undertone, 185-186, 188-189 elution analysis, 790 Coating failure
Carbon dioxide, supercritical, as frontal analysis, 790 analysis, 767-779
solvents, 131 high pressure liquid, 779, 792-793 application of coating, 775-777
application techniques and
Casson viscosity, 337 liquid (see Liquid chromatography)
equipment, 776-777
Castor oil, 27 paper, 793-794
background information, 777
Catalyzed cross-linking partition, 790-791 determination if specified coating is
phenolics, 410-411 principles, 789 used, 773
silicones, 411 size exclusion, 837-839 electron microscopy, 822-823
Cathodic passivation, inorganic anti- thin-layer, 794-796 evidence collection, 777-779
corrosive pigments, 239-240 (see also Gas chromatography; High field investigation, 778
Cationic agents, as sanitizing agents, 265 performance liquid generic type of coating, 769-772
Caulks, oil-based, in sealants, 735 chromatography) hypothesis testing, 779
CDIC Hardness Penetrometer, 566-567 Chrome-doped futile, 214 identification of system, 768-774
Cellulose acetate butyrate, 25 Chrome green, 212 inorganic binders, 771-772
Cellulose acetate propionate, 25 Chrome orange, 212 laboratory investigation, 778-779
Cellulose esters, 23-25 Chrome yellow, 211 metallic coatings, 772
coating applications, 23-24 Chromium oxide green, 212 modes associated with pigment
production, 23 Chrysler MS-PPI-1,713 system, carrier system, or additive
testing, 24 C.I.E. L * a * b *, artists' paints, 708 package, 772-773
types, 23 CIELAB space, 456-457, 465 organic resin binders, 769-771
Cellulosics, 275-277 C1ELUV space, 457 proper formulation and
hydrophobe modified, 280 CIE system, 452-457, 507 manufacture, 773-774
Centrifugal sedimentation, 321-324 blackbody locus, 455-456 purpose of coating, 774-775
Ceramic black, 215 chromaticity coordinates and diagram, reporting findings, 779
Ceramic coatings, 68-72 454-456 specification preparation and follow
application processes, 72 color temperature, 456 through, 775-776
composition, 69 complementary wavelength, 455 surface/substrate preparation, 776
glass enamels, 71 dominant wavelength, 455 third party inspection, 777
glazes, 68-69 purity, 455 definition, 768
porcelain enamels, 69-71 standard observers, 453, 455 Coating films, 110
refractory coatings, 71-72 standard sources and illuminants, 452- Coatings
Ceramic pigments, 214-216 454 anti-corrosion, 238-239
properties, 215 tristimulus values, calculation, 453- cleaning and pretreatment, 380
testing, 216 454 dry, on substrates, 417-418
CGSB I-GP-71,504 uniform color spaces, 456-457 flexibility, 542
Chalky surfaces, adhesion to, Circular drying-time recorder, 443-444 high solids, xv
architectural coatings, 705 Circulation stability, automotive new technologies, xv-xvi
Channel process, carbon blacks, 181-182 products, 716 performance, properties affecting,
Chemical adhesion, 514-515 Clarion red, 203 547-548
Chemical analysis, traffic marking Clay stabilized emulsions, bituminous processes, extensional viscosity, 350
materials, 743 coatings, 21 strength, 507
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SUBJECT INDEX 909
Cobalt blue pigments, 214-215 violets, 210 Contrast ratio, 481-482

Cobalt phosphate violet, 215 yellows, 211-212 aerospace and aircraft coatings, 687
Code of Federal Regulations, subchapter Colored organic pigments, 190-208 specified spreading rate, 493
topics, 11 bleed test, 207 Control technique guidelines, 5-6, 11
Coefficient of friction, 600 blues, 197-198 VOC content determination, 6-7
Canadian government standards, 603, classification, by chemistry, 191 Copper corrosion, plasticizers, 116
605 color and tint strength, 207 Copper phthalocyanine blue, 197-198
concept of, 601 Colour Index, 190 Copper phthalocyanine green, 203-204,
determination, 601-602 exposure testing, 207-208 206
determination methods, 603-605 fastness tests, 207 Copper strip corrosion, solvents, 153
measurement, 604-605 greens, 203-204, 206-207 CoRI stressmeter, 590-591
Coefficient-of-Friction Mar Test, 582 health and environmental concerns, Corrosion
Coefficient of thermal expansion, 853- 204-206 accelerated testing, 248-249
854 oil absorption, 207 in aqueous solutions, 609-611
Cohesion, versus stress, 594, 596 oranges, 200-201,203-205 atmospheric, 611-612
Cohesion energy, 385 reds, 191-197 copper, plasticizers, 116
Cohesive energy density, hydrocarbons, high performance, 194-196 copper strip, solvents, 153
389 metallized azo, 191-192 definition, 238
Coin mar test, 532, 582 non-metallized azo, 192-194 inhibition, aerospace and aircraft
Cold checking resistance, automotive novel high-performance, 196-197 coatings, 690-691
products, 715 specific gravity, 208 metals, prevention (see Protective
Cold crack resistance tests, 554 testing, 206-208 overlayers)
Cold vapor technique, atomic absorption yellows, 198-203 resistance, automotive products, 715
spectroscopy, 786 benzimidazolone, 199, 201 thin films, 612-615
Cold weather, extreme, 629 diarylide, 199-201 Cost factor, weighted, traffic marking
Cole method, critical pigment volume heterocyclic, 199-200, 202-203 materials, 747
determination, 255 monoarylide, 198-199 Cottonseed oil, 27
Colligative properties analyses, 836 Colored pigments, 484 Coulometry, trace sulfur by, 154
Color hiding power, 487 Coulter principle, 316-317
aerospace and aircraft coatings, 687 Colorimeters, 687 Crater resistance, automotive products,
architectural coatings, 702 pearlescent pigments, 231 716
automotive products, 714 tristimulus, 463 Crevice corrosion, 610
change Colorimetry, definition, 452 Critical pigment volume, 303
artists' paints, 707 Color-matching booths, 448 Asbeck-Van Loo method, 254-255
sealants, 737 Color order systems, 457-462 Cole method, 255
colored organic pigments, 207 colorcurve system, 460 Pierce-Holsworth method, 255-256
compatibility, architectural coatings, cylindrical systems, 451 Critical pigment volume concentration
700 DIN system, 459-460 effect on stress in organic coatings,
constancy, 451 ISCC-NBS system, 458 591-595
feasibility, automotive products, 715 Munsell system, 457-458 oil absorption and, 256-257
industrial measurement, 462-465 natural color system, 459, 461 Crock resistance, automotive products,
commercial instruments, 464-465 opponent systems, 451-452 715
instrument selection and calibration, OSA-UCS system, 459-461 Cross-link density, 587
463-464 Ostwald system, 459 determination, 541-542
instruments using eye as detector, printed systems, 460 Cryogenic scanning electron microscopy,
462 scales for liquids, 462 820-821
spectrophotometers, 462-463 universal color language, 458 Cryptometers, Pfund, 486-488
tristimulus colorimeters, 463 whiteness indices, 461-462 Crystal, size, white hiding pigment, 500
liquid, mixing time, 510 yellowness indices, 462 CS 19.1-M87, 739
matching, 467-468 Colour Index, 190, 507 CS 19.2-M87, 739
measurement, can coatings, 723 Combustibility, tests for, 668-670 CS 19.6-M87, 739
metamerism, 451-452 Commercial Standard 98, Section 6.6, CS 19.13-M87, 739
mixing, 466-467 707-708 CS 19.18-M87, 739
perceived, variables, 451-452 Compartment fire tests, full-scale, 674- CS 19.20-M87, 739
temperature, 456 675 CS 19.24-M80, 739
terminology, 447 Compatibility, titanium dioxide CS 19-GP-5M, 739
tolerances, 465-466 pigments, 174 CS 19-GP-14M, 739
traffic marking materials, 743-747 Condensation CS 19-GP-17M, 739
uniform spaces, 456-457 controlled testing, 679 CS 19-GP-22M, 739
variation, artists' paints, 708 effect on natural weathering, 627-628 Cup viscometers, 683
(see also CIE system) Conductivity, automotive products, 714 Cure, 407-414
Colorcurve system, 460 Conical Mandrel tests, 548-549 adequacy of, automotive products, 714
Color differences Consistency concept and illustrations, 407-408
calculations, 465 architectural coatings, 700-701 measurement, 411-414
instrumental measurements, artists' paints, 707 dynamic mechanical analysis, 413
architectural coatings, 702 Constant depth gage, particle-size evaporative rate analysis, 413
visual comparison, architectural measurements, 328 hardness measurements, 411-413
coatings, 702 Construction Criteria Base, 892-893 impedance measurements, 413
Colored inorganic pigments, 209-212 Contact angle, 372-373, 514 solvent rubs, 411
blues, 210-211 measurement, 378 thermal analysis, 412-413
browns, 212 Contaminants, titanium dioxide torsion pendulum, 413
classification, by chemistry, 209-210 pigments, 169 mechanisms, 408-411
greens, 212 Continuous flow method, particle-size radiation (see Radiation curing)
oranges, 212 measurements, 313 reactions, amino resins, 64-65
reds, 209-210 Contrast, visual observations, 482 speed, can coatings, 720-721
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Curing agents, epoxy resins, 74-75 Diethylenetriamine, 85-86 Driers, 30-35

Current, thermally stimulated, 855 Difference spectroscopy, 830-832 function, 30-31
Curtain coating, surface energetics, 379 Differential scanning calorimetry, 759, levels in coatings, 32
Curvature, effects on film thickness 761, 842-845 liquid paint
measurement, 435 coatings characterization, 846-847 specifications, 33-34
Cycle testing, water resistance, 679-680 epoxy-amine reaction kinetics, 845- testing, 34-35
Cycloaliphatic epoxides, 109-110 846 metals, description, 31
films, tensile properties, 545 glass transition temperatures, 843-844 miscellaneous, 31-32
Cyclohexane, 127 purge gas, 846 recommendations, 33
Cylindrical Mandrel bend tests, 549-550 sample preparation, 846 testing of drying efficiency, 32-33
Differential thermal analysis, 759, 761 Drop weight, 374
Diffusion theory, 514 Dry film
D Digital electromagnetic thickness gages, appearance, m-chitectural coatings,
432-433 702-703
Damping, hardness, (see Pendulum- Dilatancy, 339-34l printing, vinyl resins, 105
rocker hardness) Dilatometry, 853 Drying oils. 26-29
Dantuma Scratch Tester, 556-557 Diluent dilution ratio, solvents, 133 classification by iodine value, 26
Database sources, specifications, 892- Diluents, 131-132 physical characteristics, 26, 28
893 Dilution limit, solvents, 133 Drying time, 439-444
Data processing, infrared spectroscopy, Dilution stability, architectural coatings, aerospace and aircraft coatings, 686
829 699 artists' paints, 708
Daylight, natural and artificial, 447, 453 Dimensional stability, water-repellent ASTM D 1640, 439-440
Deadhesion, organic coatings, 616 coatings, 749 B.S. 3900, 441-442
Deborah number, 348 Dime scrape, automotive products, 715 circular drying-time recorder, 443-444
Debye-Scherrer small angle X-ray DIN 33 157, 574 DIN 53 150, 442
scattering technique, particle-size DIN 35 152, 550 environment, 439
measurements, 325 DIN 50 101,551 Federal Test Method Standard 141C,
Debye-Sherrer camera, 872-873 DIN 50 102, 551 Method 4061.2, 440-441
Deformation, definition, 334-335 DIN 53 150, 442 I.C.I. drying time recorder, 444
Degradation, 631 DIN 53 153, 563 ISO 9117, 441
amino resins, 65-66 DIN 53 162, 505 no pick-up lime traffic paint roller, 444
test, metallic pigments, 227 Dinitroaniline orange, 200 specimen preparation, 439
Deleveling, 357 DIN system, 459-460 straight line drying time recorder, 444
Density, 289-303 Dip coating, 421-422 Dry-powder pulse jet disperser, 315-316
aerospace and aircraft coatings, 684 surface energetics, 379
Dry to-recoat, aerospace and aircraft
alkyds, 56 Dipentene, 127
coatings, 686
apparent, 290 DIPPR database, 390
Du Nuoy ring, 374-375
solids, 302 Directionality, gloss, 471-472
Du Pont Scratch Testing Machine, 557
architectural coatings, 698 Direct tensile testing, adhesion, 519-523
automotive products, 714 Dirt pickup, architectural coatings, 705 Durability
bulk, 296 Disazo condensation reds, 196 sealants, 737
can coatings, 720 Disbonding method, 560 testing, titanium dioxide pigments in
concern for, 289 Disk centrifuge, 321-323 coatings, 173
definitions, 145-146, 289-291 Dispersibility, titanium dioxide pigments, traffic marking materials, 747
dynamic model, 290 171-172 Dynamic coefficient of friction, 600
liquids, 297-301 Dispersion Dynamic mechanical analysis, 842, 847-
determination methods, 297-298 carbon blacks, 186-187 850
fluid exWrnal media, 297-298 fineness of applications, 847
fluid internal media, 298-299 aerospace and aircraft coatings, 684 automated instruments, 538
sonic frequency shifts, 299-301 architectural coatings, 698-699 coatings characterization, 848, 850
measurement systems, 296 artists' paints, 708 cure, 413
plasticizers, 117-118 can coatings, 720 studies, 858-860
relative; 290 traffic marking materials, 743 description, 538-539
skeletal, 296 interactions, 385 glass transitions, 847
solids, 301-302 pigments, 508-509 heating rate, 848
solvents, 144-148 rheology, 351-352 plot interpretation, 539-541
static model, 289-290 solubility parameter, 387, 389-391 sample preparation, 848
Density gradient column systems, 301- white hiding pigment, 500 synthetic variables and morphological
302 Displacement analysis, chromatography, character, 847-849
Desert, 629-630 790 Dynamic mechanical and tensile
Detergent resistance, 665 Displacement technique, 294-295 properties, 534-545
Deterioration, biological, (see Biological Dissolution cross-link density, determination, 541-
deterioration) anodic, 610-61 l 542
Dial gages, 426, 428 microwave, 757 definitions, 534-536
Dianisidine orange, 201 Distillation dynamic property relation to other
Diarylide yellows, 199-201 plasticizers, 116-117 mechanical properties, 542
Diatomaceous solid support materials, range, solvents, 137, 139-140 free film sample preparation, 537-538
799-800 Distinctness of image, automotive stress-strain curves, interpretation,
Dielectric analysis, 842, 855-857 products, 714 543-544
film formation, 855-856, 858 Doctor Test, 153 tensile properties, 543-545
frequency selection, 856-857 Drainage equation, 353-354 relation to other mechanical
heating rate, 857 Drawdown, thin-film, oversize particles, properties, 544-545
powder coatings, 855-856 326-327 tensile versus shear tests, 534-535
resin, 855, 857 Drawdown bars, 418-420 Dynamic mechanical thermal analyzer,
sample preparation, 856 Drier acids, description, 31 548
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SUBJECT INDEX 911
E cover coat, 70 colored organic pigments, 207-208

ground coat, 70 scum on panels, 830-831
Eddy current thickness gages, 434, 436 End group analysis, molecular weight, Extender pigments, 217-222, 484
Efflorescence 835 alumina trihydrate, 220
masonry, 726 Energetic deposition techniques, 615 barium sulfate, 219-220
treated masonry, 750 Energy dispersive spectrometer, 817-818 calcium carbonate, 217
Efflux devices, 359-360 Energy dispersive X-ray, coating failure inorganic anti-corrosive pigments, 247
Elasticity, relation to abrasion resistance, analysis, 768, 778 kaolin, 217-218
525 Energy of vaporization, for straight mica, 219
Elastic liquids, 344-350 chain hydrocarbons, 389 nepheline syenite, 220
viscoelastic models, 346~348 Engine oils, aerospace and aircraft physical properties, 220-222
viscoelastic parameters, '345-346 coatings resistance, 692-693 silica, 218-219
Elastic modulus, 577, 591 Environmental impact sodium aluminosilicates, 220
Elcometer I01,431 amino resins, 66-67 talc, 218
Elcometer dial gage, 426, 428 colored organic pigments, 204-206 test standards, 221-222
Elcometer magnetic coating thickness inorganic anti-corrosive pigments, 245 wollastonite, 220
gage 211,430 pearlescent pigments, 235-236 Extenders, 483
Elcometer pull off gage 157, 430 polyamides, 87-88 X-ray diffraction, 875-877
Electrical resistance, particle-size Environmental Protection Agency Exterior coatings, architectural coatings,
measurements, 316-317 federal environmental laws 697
Electrical resistivity, solvents, 149-150 administered by, 3 Extraction testing, can coatings, 723
Electrical resistivity/conductivity, regional offices, 11 Extrusion rate, sealants, 736
metallic pigments, 227 Environmental scanning electron Eye, 450-452
Electrochemical analysis, aerospace and microscopy, 821
aircraft coatings, 691 Envirotest, 651
Electrochemical impedance Epoxides
spectroscopy, aerospace and coal tar, 732
aircraft coatings, 691 coating failure analysis, 770 Falling abrasive test, 526-527
Electrochemical methods, monitoring fusion bond, 732 Falling ball viscometer, 361
atmospheric corrosion, 612 Epoxy Falling curtain, 377
Electrodeposition coatings, epoxy resins, reactive crosslinking, 410 Falling meniscus method, 377
77 traffic marking materials, 741 Falling-needle viscometer, 363
Electromagnetic radiation, 783-784, 866 Epoxy/acrylic copolymers, dynamic Falling weight impact tests, 542
Electromagnetic spectrum, 644 mechanical properties, 847, 849 Fastness tests, colored organic pigments,
Electromagnetic thickness gages, 432- Epoxy-amine reaction kinetics, 845-846 207
434 Epoxy polyester powder coating, cure, Fatigue tests, aerospace and aircraft
Electromotive radiation, 865 859-861 coatings, 689
Electron beam excited X-ray Epoxy resins, 74-78 Fatty acids
spectroscopy, 882-883 coatings, 75 tall oil, 85
Electron beam X-ray analysis, 759 cross-linked with acid-functional unsaturated, in drying oils, 26-27
Electron guns, scanning electron acrylics, 43 FDC Fine Scratch Test, 582
microscopy, 818-819 curing agents, 74-75 FDC wear test, 529-530
Electron microscopy, 761, 815-824 electrodeposition coatings, 77 Federal Hazardous Substances Act,
antifouling paint film structure, 824 ester, ambient cure coatings, 76 artists' paints, 710
failures and defects, 822-823 heat-cured solvent-borne coatings, 76- Federal Reference Method 24, 5-8, 720
film thickness measurements, 822-823 77 Federal Test Method 4287, 362
latex coalescence and adhesion, 824 heat-cured waterborne coatings, 77 Federal Test Method Standard 141
pigment powder coatings, 78 Method 2051,729
identification, 823-824 properties, 75 Method 2112, 702
particle sizing, 823-824 reactions with polyamides, 87 Method 2131, 702
signal types, 815-816 two-package, ambient-cure coatings, Method 2141, 701
(see also Scanning electron 75-76 Method 3011.2, 685
microscopy; Transmission electron types, 74-75 Method 3019.1, 685
microscopy) Equivalent circle diameter, 310-311 Method 3021.1,685
ElectronToptical column, transmission Equivalent spherical diameter, 310 Method 3022.1,685
ele'ctron microscopy, 822-823 Erichsen cupping tester, 551 Method 4021 684
Electron probe microanalysis, 761 Erichsen Hardness Tester, 557-558 Method 4121 489
Electron spectroscopy for chemical Erichsen Lacquer Testing Instrument, Method 4203 699
analysis, 760 723 Method 4208 685
Electron spin resonance spectroscopy, Erichsen Scar-Resistance Tester, 581- Method 4401 699
ultrafast weathering, 652 582 Method 4421 700
Electrostatic adhesion, 515 Esters, 128 Method 4541 701
Electrostatic spray, surface energetics, purity, 151 Method 6192 530
379-380 Ester value, plasticizers, 117 Method 6211 573
Elution analysis, chromatography, 790 Ethoxylate urethanes, hydrophobe- Method 6261 700
Elutriation, particle-size measurements, modified, 278 Method 6271 658
314-315 Ethyl alcohol, 129 Method 6301 704-705
Emulsion coatings, bituminous coatings, Ethyl hydroxyethyl cellulose, 277 Federal Test Method Standard 141A,
21 hydrophobe-modified, 280-281 Method 4271, 361
Emulsion particles, soap titration, 313- Evaporation rate Federal Test Method Standard 141B,
314 analysis, cure, 413 Method 6226, 689
Emulsions, cure mechanisms, 408 solvents, 135-139 Federal Test Method Standard 141C,
EN-71-3:1988, 710 Everhart-Thornley detector, 816, 818 726, 728-729
Enamels Exposure frames, 634-636 Method 2051,729
coal tar, 731 Exposure testing Method 4061.2, 440-441
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Method 6141, 531 Flame ionization detectors, 797-798 Four acrylic copolymers, glass transition
Method 6193, 526, 528 Flame retardance, 667-676 temperatures, 843-845
Method 6226, 553 ASTM D 1360, 670 Fourier transform infrared analysis,
Federal Test Method Standard 406, ASTM D 2863, 668-670 coating failure analysis, 773
Method 1093, 532, 581 ASTM D 3806, 670-672 Fracture energy, 513
Federal Test Method Standard 501a, 604 ASTM D 3894, 674-675 Fracture stress, 513
Fell equation, 488-489 ASTM E 84, 670, 672-674 Fracture theory, 513-514
Felvation, particle-size measurements, ASTM E 119, 675 Freeze/thaw resistance, treated masonry,
315 ASTM E 136, 668 750
Feret's diameter, 310-311 ASTM E 162, 670, 672, 674 Freeze-thaw stability, artists' paints, 707
Filed testing, coating failure analysis, ASTM E 603, 674-675 Fresnell equation of reflectivity, 484
778 ASTM E 1131, 675 Fresnel reflector, 651-652
Filiform corrosion, aerospace and historical methods, 675-676 concentration, accelerated natural
aircraft coatings, 691 terminology, 667-668 weathering, 639-640
Filler particles, cathodic reaction test selection rationales, 668 Friction, 600
inhibition, 616 Flame spread, tests for, 670-675 Frontal analysis, chromatography, 790
Film Flame-spread index, 670, 672 Fuel resistance, 663-664
continuity, can coatings, 72 l Flammability, automotive products, 713 Fume resistance, architectural coatings,
formation Flash point 705
dielectric analysis, 855-856, 858 aerospace and aircraft coatings, 685- Fungal resistance, paint films, 657-659
stress in organic coatings, 585-586 686 Fungicides, 261-267, 657
free, casting techniques, 415-417 architectural coatings, 699 analysis and decontamination, 265-
hardness, development, 32-33 artists' paints, 709 266
opaque, transparent, and translucent, can coatings, 720 definition of terms, 261
448-449 paint, 755 methods for determination of efficacy,
paint (see Biological deterioration) plasticizers, 117 267
porosity solvents, 140-144 mode of action, 262-265
architectural coatings, 704 Flexibility, 547-554 strategies for minimizing resistant
white hiding pigment, 500-501 aerospace and aircraft coatings, 689 strains, 265
preparation, for coating tests, 415-423 aging and weathering effects, 554 Fungus
dip coating, 421-422 architectural coatings, 704 associated with paint, 654-655
drawdown bars, 418-420 artists' paints, 709 determining presence on paint films,
film casting techniques, 415-418 automotive products, 715 656
spin coating, 422 can coatings, 722-723 discoloration of paint films, 654
spray outs, 421 cold crack resistance tests, 554 disfigurement of paint films, 655-656
wire-wound rods, 420-421 Furnace process blacks, carbon blacks,
cupping tests, 551-552
test requirements, 415 181, 183
effect on coating performance, 547-
pavement marking tape, 745 Furniture finishes, staining resistance,
548
thin, corrosion, 612-615 662-663
transparent, subtractive mixing, 466- forming tests, 552-553
Fusion bond epoxides, 732
467 humidity effects, 548
Fusion process, alkyds, 54
types, 408 impact resistance tests, 553-554
wet, 418 interpretation, 547
thickness, 424-427 Mandrel bend tests, 548-550 G
Film casting knife, 419 strain rate effects, 548
Film thickness t-bend tests, 550-551 Gallon weight cups, 294
aerospace and aircraft coatings, 686- temperature effects, 548 Galvanic cells, 612
687 Flocculation Gardner Carboloy drill thickness gage,
automotive products, 714 artists' paints, 707 426
can coatings, 721 mechanisms, thickeners and rheology Gardner-Coleman method, oil absorption
measurement, 424-438 modifiers, 271-272 determination, 252-254
hiding power, 482 Flory-Huggins limiting chi parameter, Gardner contrast hiding power board,
curvature effects, 435 386 485
electron microscopy, 822-823 Flowability, thermoplastic marking Gardner gage stand, 428
dry film materials, 745 Gardner-Holdt bubble tubes, 361
destructive methods, 426, 428-429 Fluid resistance Gardner impact, 412
nondestructive methods, 429-434 aerospace and aircraft coatings, 692- Gardner micro-depth gage, 428
statistics, 437-438 693 Gardner needle thickness gage, 426
substrate composition effects, 435, automotive products, 715 Gas chromatography, 758, 796-810
437 Fluids apparatus and technique, 797-798
surface finish effects, 435, 437 Newtonian and non-Newtonian, 336 applications, 803-804
wet film, 424-427 shear-thickening, 339-341 area normalization, 802
X-ray fluorescence, 438 shear-thinning, 339 chromatogram interpretation, 801-803
relationship between wet-film and dry- time-dependent, 341-343 column efficiency, 800-801
film, 418 Fluorescence, materials, 449 columns, 798-799
Fineness-of-dispersion gages, particle- Fluorescent light sources, 447-448, 453 detector, 797-798
size measurements, 327-329 UV/condensation lamp, 649-650 gas-solid chromatography, 808-809
Fingernail Mar Test, 582 UV lamps, 646 glossary, 808-810
Fire-retardant coatings, testing, 675 Food processing, can coatings stability, HETP, 800-801
Fischerscope Microhardness Tester, 566, 722 high-performance detectors, 797-798
568 Formaldehyde internal standardization, 802
Fisher subsieve sizer, 311-312 as biocide, 263, 265 oils, 805-806
Fish oils, 27-28 free, amino resins, 64 plasticizers, 119, 807
Flame characteristics, atomic absorption Forming tests, flexibility and toughness, programmed temperature, 798
spectroscopy, 785 552-553 pyrolysis, 806-807
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SUBJECT INDEX 913
qualitative analysis, 801-802 reflection haze, measurement, 474, Herschel-Bulkley equation, 337-338
quantitative analysis, 802-803 476-477 Heterocyclic yellows, 199-200, 202-203
resins, 806 sheen, 471 Heterogeneous surfaces, corrosion, 610
retention parameters, 801-802 specular, 470-471 HEURASE polymers, 280
solid support, 799-800 measurement, 472-473 Hexa(methoxymethyl)melamine, 63-64,
solvent identification, 764 visual evaluation, 472-473 409
solvents, 149-151,803, 805 waviness, 471 Hexamethylene diisocyanate, 45
stationary liquid phase, 800 measurement, 477,479 Hiding power, 481-505
robing materials, 799 Gloss meter, 473-474 aerospace and aircraft coatings, 687
weaknesses, 801 Glycol ethers, 128-129 architectural coatings, 703
Gas chromatography-mass spectrometry, Glycoluril, 66 ASTM methods, 502-503
solvent identification, 764-765 GM9150P, 579 automotive products, 713
Gases, 293-294 Gold bronze pigments BSI 3900, 504
adsorption, particle-size grade classification, 224 CGSB 1-GP-71,504
measurements, 313 properties, 224 colored pigments, 484, 487
as concrete materials, 295-296 Goniophotometry, 474-475 contrast, visual observations, 482
displacement, 302 Goniospectrophotometers, pearlescent contrast design and visual sensitivity,
supercritical, as solvents, 400-401 pigments, 232-236 485-486
Gas phase dipole moment, 392 Gooden-Smith method, particle-size contrast ratio, 481-482
Gassing test, metallic pigments, 227-228 measurements, 314 definition, 482-483
Gas-solid chromatography, 790, 808- 1-GP-71,891 early photometric methods, 487-489
809 1-GP-192, 605 early visual hiding power methods,
Gavarti Gv Cat Test Unit, 722-723 1-GP-200, 605 485-487
Gearhart-Ball solvent resistance, 663- Graharn-Linton Hardness Tester, 557- extender pigments, 484
664 558 Federal Test for Dry Opacity, 489
Gel coat, thixotropy, 343 Graphite furnace, atomic absorption Federal Test Method Std. 141,503
General Electric Impact Flexibility Tool, spectroscopy, 786 Fell equation, use, 488-489
553 Gravelometer, automotive products, 714 film application, 489
General Electric Indention Tester, 566 Gravimetric method, particle-size film thickness, 482
Gibbs equation, liquids, 370 measurements, 313 determination, 489-490
Gibbs free energy, 609 Gravity sedimentation, 321 French Standards Association, 504
liquids, 370 Green pigments, 203-204, 206-207 German standards, 505
Glass inorganic, 212 Hallet hidimeter, 487
beads Grind (see Dispersion, fineness of, 743) Hanstock method, 487
adhesion, pavement marking tape, incomplete, 481
745 ISO methods, 503-504
H Krebs method, 485-486
traff marking materials, 742
New York Paint Club method, 489
bonding, automotive products, 715
Hallet hidimeter, 487 Pfund cwptometers, 486-487
enamels, 71 photometric end-point, 483
Hansa yellow G, 198-199
insulating, sealants, 737 Hansa yellow 10G, 199 photometric measurements, 490
panels, as hiding power test substrate, Hansen solubility parameters, 384-385 pigment role, 483-484
490 liquids, 394, 397 relative, determination from tinting
Glass transitions surface energy/contact angle data, 499
dynamic mechanical analysis, 847 characterizations, 401 relative dry, 485-486
temperature Hanstock method, hiding power, 487 spreading rate, 482
differential scanning calorimetry, Hardness, 555-582 determination, 489-490
843-844 aerospace and aircraft coatings, 690 standard test substrates, 481
thermoplastic acrylic resins, 40-42 automotive products, 714 terminology, 481
Glazes can coatings, 721 test substrates, 490
ceramic, 68-69 mar resistance testing, 579-582 early, 485
lead-containing, 69 measurements, 411-413 titanium dioxide pigments, 170-171
leadless, 68-69 pendulum-rocker, 573-578 traffic marking materials, 743
matte, 69 rebound, 578-579 Van Eyken-Anderson method, 489
satin, 69 relation to abrasion resistance, 525 visual end-point, 483
Gloss, 470-479 sealants, 736 white
aerospace and aircraft coatings, 688 Tukon, thermoplastic acrylic resins, 42 factors affecting, 499-501
architectural coatings, 702-703 (see also Indentation hardness; Scratch hiding pigments, 484
artists' paints, 709 hardness) (see also Kubelka-Munk two-constant
automotive products, 714 Haze, 471 theory)
can coatings, 723 Heat-activated binders, coating failure High performance architectural coating,
carbon blacks, 186, 189 analysis, 771 697
definition, 470 Heat aging, effects on sealants, 736 High performance liquid
directionality, 471-472 Heated Black Box Test, 638 chromatography, 758
goniophotometry, 474-475 Heat of mixing, 384 additive identification, 763
haze, 471 Heat resistance, 667 amino resins, 62-63
image clarity, 471 aerospace and aircraft coatings, 692- applications, 793
measurement, 477-478 693 size exclusion chromatography, 837-
Landolt ring use, 472-473 Heat stability, architectural coatings, 701 838
orange peel HEEASE polymers, 280 High pressure liquid chromatography,
measurement, 477 Hegman gage, 327-328 792-793
visual evaluation, 473 Helium gas pycnometer, 297, 302 coating failure analysis, 779
percentage, 581 Hencky strain rate, 350 High-shear capillary rheometry, 364
pigment effects on, 173-174 Heptane Miscibility Test, solvents, 154 Highways, sealants, 737
reduction test, 527 Herbert Pendulum Tester, 573 Hildebrand parameters, 384
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Hoffman Scratch Tester, 557-558, 580 water resistance, 677-678 application and protective coating
Holmium glass, spectrum, 867, 869 Impact resistance, 547 performance, 247-248
Hopeite, X-ray diffraction, 880-881 thermoplastic marking materials, 745 atmospheric exposure testing, 248-249
Hot stamp transfer, vinyl resins, 105 tests borates, 240-241
Household chemicals aerospace and aircraft coatings, 689 cathodic and anodic passivation, 239-
resistance, architectural coatings, 704 flexibility and toughness, 553-554 240
staining from, 662 Impedance measurements, cure, 413 chromates, 241
Hue, 507 Impinging abrasive method, 532, 581 environmental considerations, 245
Humidity Imprint resistance, indentation hardness, extender pigments, 247
absolute, 625 572-573 formulation and performance, 245-247
aerospace and aircraft coatings, 692 Incandescent light sources, 447, 453 inhibitor loading levels, 246-247
effect on flexibility and toughness, 548 Indanthrone blue, 198 ion exchange pigment, 244
relative Indentation hardness, 563-573 leads, 241-242
atmospheric corrosion, 611 Bell Telephone Laboratories Indenting micaceous iron oxide, 245
effect on natural weathering, 625- Rheometer, 565 molybdates, 242
627 Brinell Indentation Hardness Tester, neutralization, 239
100% testing, 678-679 566 new product development, 249
variation and stress in organic Buchholz Indentation Hardness Tester, oxidative passivation, 239
coatings, 587 566 phosphates, 242-243
Hutchinson method, 658 categories, 563 phosphites, 243
Hutto-Davis method, particle-size CDIC Hardness Penetrometer, 566-567 pigment volume concentration, 245-
measurements, 314 Fischerscope Microhardness Tester, 246
Hydrated chromium oxide green, 212 566, 568 reactivity and solubility, 247
Hydraulic fluids, aerospace and aircraft General Electric Indention Tester, 566 silicates, 243-244
coatings resistance, 692-693 ICI Pneumatic Microindenter, 566-568 statistical analysis, 249
Hydride generation, atomic absorption imprint resistance, 572-573 steel flake, 245
spectroscopy, 786 Knoop Indenter, 567-569 substrate selection, 248
Hydrocarbons Pfund Hardness Tester, 569 zinc, in primers, 244
chlorinated, 130 Rockwell Hardness Tester, 571 zinc oxide, 244
cohesive energy density, 389 Twisting Cork Tester, 573 Inorganic binders, coating failure
nitrated, 130 Wallace Microhardness Tester H-7, analysis, 771-772
nonaromatic, in aromatic solvents, 152 571-572 Inorganic coating, low-energy, 615
processes that produce, 4 Wilson/Tukon Hardness Tester, 571- Inorganic pigments, (see Inorganic anti-
solvents, 125-128 572 corrosive pigments; Colored
aliphatic, 125-126 Indentation method, 560 inorganic pigments)
aromatic, 126-127 Inductively coupled argon plasma Inorganic sol-gel films, 615
naphthenic, 127 spectroscopy, 759 Insect-resistant paints, 659-661
terpenes, 128 pigment identification, 761-762 Inspector's Dur-O-Test Pocket Size
Hydrodynamic chromatography, particle- Inductively coupled plasma spectroscopy, Hardness Tester, 558-559
size measurements, 329 787 Interface, diffuse and sharp, 516
Hydrodynamic mechanism, thickeners Industrial coatings, pearlescent Interfacial thickness, 514
and rheology modifiers, 271 pigments, 230 Interferometry, 827-828
Hydrogen, active sources, in Information Handling Services, 892-893 Interior coatings, architectural coatings,
polyurethane coatings, 91 Infrared analysis, 759 697
Hydrogen bonding, 385 Infrared radiation, 449 Intumescent coatings, testing, 675
solubility parameter, 392 Infrared spectrophotometry, plasticizers, Ion chromatography, 759
temperature effects, 397 118-119 Ion exchange pigment, 244
Hydrometer methods, solvents, 146-147 Infrared spectroscopy, 758, 826-833 Ion scattering spectrometry, 759-760
Hydrophobe modified alkali-swellable/ additive identification, 763 Iron blue, 210-211
soluble emulsions, 279-280 applications, 829-831 Iron oxide blacks, 179
Hydrophobe modified nonionic data processing, 829 Iron oxide reds, 209
synthetics, 278-279 difference spectroscopy, 830-832 Iron oxide yellows, 211
Hydroxyethyl acrylate, 44-45 dispersive instrumentation, 826-827 ISCC-NBS system, 458
Hydroxyethyl cellulose, 47-48, 275-276 Fourier transform infrared ISO 1518, 557, 561
hydrophobe-modified, 280 spectroscopy, 827-828 ISO 1519 550
Hydroxyethyl methacrylate, 44-45 infrared absorption, 826 ISO 1522 574
Hydroxyl value, alkyds, 57 pigment identification, 761 ISO 2813 474
Hydroxypropyl guar, 277 quality assurance, 832-833 ISO 3904 504
Hydroxypropyl methyl cellulose, 276-277 sample preparation, 828-829 ISO 3905 503-504
sampling accessories, 829 ISO 3906 504
spectral searching, 831-833 ISO 4624 521-522
time lapse spectroscopy, 832 ISO 6504 504
vehicle identification, 760-761 ISO 6860 550
ICI cone and plate viscometer, 363 Inhibitor loading levels, inorganic anti- ISO 6927 739
ICI drying time recorder, 444 corrosive pigments, 246-247 ISO 7389 739
ICI Pneumatic Microindenter, 566-568 Inks ISO 8339 739
ICI Rotothinner, 360 particle-size measurements, 328 ISO 8340 739
Image clarity, 471 pearlescent pigments, 230 ISO 8394 739
measurement, 477-478 vinyl resins, 105 ISO 8503 435
Immersion testing VOC standards, 9 ISO 9000 329
aerospace and aircraft coatings, 691, Inmont wet film gage, 424-425 ISO 9046 739
693 Inorganic anti-corrosive pigments, 238- ISO 9047 739
automotive products, 715 250 ISO 9048 739
cyclic, accelerated weathering, 650- accelerated corrosion testing, 248-249 ISO 9117 441
651 aluminum flake, 244-245 Isocyanate-reactive acrylics, 45-46
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SUBJECT INDEX 915
Isocyanates coalescence and adhesion, electron Liquid phase, stationary, gas

in polyurethane coatings, 90-91 microscopy, 824 chromatography, 800
reactive cross-linking, 410 film, drying, 408 Liquid pycnometers, 294, 298
ISO/DIN 3494, 530 glass transition, 843-844 Liquids, 293-294
ISO/DIN 4496, 749 gloss and semigloss, 47 as concrete materials, 295-296
ISO/DIN 4584, 530 Laurie-Baily Hardness Tester, 558-559 density, 297-301
ISO TC 35, 551 Leveling, 354-358 displacement, 297-299, 301-302
architectural coatings, 701 dynamic properties, 373
measures, 358 Hansen solubility parameters, 394, 397
J mechanics, 355-356 surface tension measurement, 373-378
thickeners and rheology modifiers, surface thermodynamics, 370-372
Jetness, carbon blacks, 183, 185, 188 274-275 (see also Elastic liquids)
Judd graph, 493-495 Leveling rate, 358 Liquid-solid chromatography, 790
Library, sources of specifications, 893 Liquid/solid interfaces, thermodynamics,
Light, 644-647 372-373
K additive mixing, 466-467 Lithol reds, 191-192
CIE standard sources and illuminants, Lithol rubine red, 192
Kaolin, 217-218 452-454 Loss tangent
electron microscopy, 823-824 colored, 451 shear, 536
Karl Fischer reagent method, solvents, color-matching booths, 448 tensile, 535
154 electromagnetic spectrum, 448 Lubricants, slip resistance, 603
Katharometers, 797 enclosed carbon arc, 644-645
Kauri-Butanol value, solvents, 132 fluorescent UV lamps, 646
Kelvin-Voigt model, 347-348 interaction mechanisms, carbon M
Ketimine, curing agents, 76 blacks, 181-184, 184
Ketones, 128 lamp stability, 646-647 Magne-gage, 429-430
purity, 150-151 open-flame carbon arc, 645 Magnetic recording media, vinyl resins,
Kinetic stability, 610 reflection and transmission, 448-449 106
Knife scrape, automotive products, 715 fluorescence, 449 Magneto resistor, 431-432
Knoop hardness number, 412, 564, 567 opaque, transparent, and translucent Maintenance coatings, acrylic emulsion
Knoop Indenter, 567-569 film, 448-449 polymers, 49
Krebs diamond-stripe hiding power retroreflection, 449 Mandrel bend tests, 542, 548-550
chart, 485-486 ultraviolet and infrared spectral can coatings, 722
Krebs method, hiding power, 485-486 regions, 449 aerospace and aircraft coatings, 689
Krebs-Stormer viscometer, 683-684 sources, 447-448 Manganese-doped ruffle, 214
Krieger-Dougherty model, 351-352 spectrum, Fresnel-reflector testing Marangoni effect, 357-358
Kubelka-Munk equations, 170-171 devices, 652 Marine atmosphere, 629-630
Kubelka-Munk relation, 467 terminology, 447 Marine finishes, vinyl resins, I05-I06
Kubelka-Munk two-constant theory, 491- xenon arc, 645-646 Mark-Houwink equation, 41,839
499 Mar resistance testing, 579-582
Light absorption, 481 aerospace and aircraft coatings, 690
equation symbols, 491-492 Lightfastness, artists' paints, 709
hiding power impinging abrasive method, 581
Lightness, 507 scuffing methods, 581-582
calculation from tinting data, 498- Light scattering, 481
499 single scratch methods, 579-580
molecular weight determination, 836- Martin's diameter, 309, 311
general method, 492-493 837
relative, untinted white paints from Masonry, 725-730
techniques, particle-size absorption testing, 725
tinting data, 499 measurements, 323-325 alkali resistance, 727-728
results, 495-496, 498 d-Limonene, 127 application, 727
Judd graph, 493-495 Linseed oil, 27 artificial weathering tests, 728
Mitton graph and table, 495-497 Liquid chromatography, 791-792 coatings, 726-727
original equations, 492 applications, 791-792 definition, 725
scattering coefficient and scattering coating failure analysis, 779 efflorescence, 726
power, 492 plasticizers, 119 field testing, 728
theoretical problems and practical solvents, 150 moisture in, 727
considerations, 496-498 Liquid coatings performance tests, 727-729
Laboratory testing coarse particles in, 698 pH, 726
coating failure analysis, 778-779 color compatibility, 700 porosity, 725
traffic marking materials, 743-746 density, 698 resistance to wind driven rain, 728
Lab roller mill, 416 dilution stability, 699 selection, 729
Lacquers fineness of dispersion, 698-699 solvent-borne coatings, 727
coating failure analysis, 769 flash point, 699 specimens, 729
cure mechanisms, 408 odor, 699 surface
penetration, 699-600 finish, 726
properties, 698-701 pH after cleaning, 727
theology, 700-701 preparation, 727
traffic marking materials, 741 treatments, VOC standards, 8
Lambert's law, 785 laboratory testing, 743 water-reducible coatings, 726-727
Lampblack process, carbon blacks, 180- volatile organic compound, 699 water-repellent coatings, 749-750
182 Liquid paint water vapor permeability, 728
Landolt rings, 472-473 bacterial resistance, 657 Mass, 291
Laplace equation, for potential, 614 can coatings tests, 720-721 Mass color, definitions, 507
Laser light, diffraction, particle-size driers Mass spectrometry, 758
measurements, 325-326 specifications, 33-34 Masstone, 507
Latex testing, 34-35 Mastic, coal tar, 732
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"Matrix flushing" method, X-ray Microbiological resistance, determining, National Association of Corrosion
diffraction, 878 657-661 Engineers, 892
Maximum bubble pressure methods, Micrometers, 426, 428 National Cooperative Highway Research
375-377 Microorganisms, associated with paint, Program Report 244, 750
Maxwell model, 537 654-656 National Standards Association, 893
elastic liquids, 346-348 Microprocessor electromagnetic Natural color system, 459, 461
Maxwell relaxation time, leveling rate thickness gages, 432, 434 Natural iron oxides, 212
dependence, 349 Microscopy, 428 NBS Technical Note 883, 726, 750
McArdle-Robertson evaporation index, film thickness, 428-429 Needle micrometer, 425-427
140 particle-size measurements, 318-320 NEN 5336, 561
Measurement systems, density, 296 Microstructures, corrosion, 612-615 Nepheline syenite, 220
Mebon Prohesion Cabinet, 650 Microvoids, white hiding power, 501 New York Paint Club method, hiding
Mechanical adhesion, 515 Microwave dissolution, 757 power, 489
Mechanical properties, dynamic (see also MIL-C-27227, 563 NFT 30-016, 574
Dynamic mechanical and tensile MIL-C-81945B, 693 NFT 30-019, 551
properties) MIL-C-83286, 691 NFT 30-075, 504
Media mills, laboratory miniature, 509- MIL-C-85285, 692-693 NFT 30-076, 504
510 MIL-C-85570, 694 Nickel
MEK resistance, 664 MIL-D-23003A, 604 doped ruffle, 214
Melamine resins, 61 MIL-D-24483A, 605 pigments, properties, 224
end uses, 66 MIL-H-83282, 693 powder and flake, grade classification,
reactive crosslinking, 409 MIL-I-46058C, 97, 110 225
Mercury arc emission spectrum, 868 MIL-L-23699, 693 Nitrated hydrocarbons, solvents, 130
Mercury cadmium red, 210 MIL-P-23377, 694 Nitrogen, detection in plasticizers, 119
Metallic coatings, 110-111 MIL-R-81294, 693 Nitrogen dioxide, standard, 5
coating failure analysis, 772 MIL-STD-810, 693 Nongaseous molecules, adsorption,
scanning electron microscopy, 819- Mineral blacks, 179 particle-size measurements, 313-
820 Mineral spirits, 126 314
Metallic pigments, 223-228 Miscibility, polymers, 400-401 Non-ionic emulsions, bituminous
acid spot test, 226 Mitton graph and table, 495-497 coatings, 21
aesthetic properties, 227 Mixing time, liquid colors, 510 Nonionic nonurethanes, hydrophobe-
ASTM test methods, 226 Mobility/lubricity, can coatings, 722 modified, 278-279
degradation test, 227 Modified zinc phosphates, 243 Non-metallized azo reds, 192-194
economics of use, 225 Modulus, definition, 336 Non-Newtonian behavior, modified
electrical resistivity/conductivity, 227 Mohs scale, 555 static, 377-378
formulation, 225 Moisture Non-Newtonian materials, rheological
gassing test, 227-228 content, thermogravimetry, 850 properties, 701
history, 223 effect on coatings, 677 Nonthermal, high-energy-cured binders,
manufacture, 223 effect on natural weathering, 625-628, coating failure analysis, 771
market applications, 225 647 Nonvolatile residue, solvents, 152
particle-size analysis, 226 condensation, 627-628 No pick-up time traffic paint roller, 444
pH measurement, 227 rainfall, 626-627 Normal Incidence Pyranometer, 632
properties, 223-224 relative humidity, 625-627 Notch gages, 425, 427
water coverage, 226-227 Moisture-cured binders, coating failure NOx, sources, 4
Metallic soaps, 30-35 analysis, 770 NPIRI grindometer, particle-size
as bodying and flatting agents, 30 Moisture resistance, 666 measurements, 328
coatings applications, 30 Moisture vapor transmission, treated Nuclear magnetic resonance, 758
Metallized azo reds, 191-192 masonry, 750 vehicle identification, 761
Metals Mold, resistance to, interior coatings, Nucleophilic groups, antimicrobial
antimicrobial agents that chelate, 265 658-659 agents that react with, 265
atmospheric corrosion, 611-612 Molecular weight, definitions, 835 Nuodex method, 658
corrosion, prevention (see Protective Molybdate orange, 209 NWMA-M-2-81, 749
overlayers) Molybdates, inorganic anti-corrosive
drier, 31 pigments, 242
oxide film on surface, 516 Monk cup, 299 0
panels, painted, as hiding power test Monoarylide yellows, 198-199
substrate, 490 Monochromator, 463 Object colors
pretreatment, X-ray diffraction, 880- Monocoat, automotive products, 712- cylindrical systems, 451
881 713 opponent systems, 451-452
thin films and microstructures, Muller Obstructed-flow devices, 360-361
corrosion, 612-615 automatic, 509-510 Odor
Metamerism, 451-452 spatula or hand, 509 architectural coatings, 699
indices, 466 Munsell system, 457-458 artists' paints, 708
Methanol, 129 Murphy equation, 356 automotive products, 713
Methyl ethyl ketone, solvent rubs, 411 plasticizers, 117
Mica, 219 solvents, 149
Micaceous iron oxide, 245 N Ohmic drop, 611
Micelles, 372 Oil
Microbial problems, in-can preservation, NACE RP T-10D, 733 absorption
261-262 Naphthas, 126, 132 colored organic pigments, 207
Microbicides Doctor Test, 153 titanium dioxide pigments, 169
in coatings industry, 265 Naphthenic hydrocarbon solvents, 127 pigments, 252-258
mode of action, 262-265 Naphthol orange, 201,203 characterization of dispersions at oil
nitrogen and/or sulfur-containing, 264 Naphthol reds, 193 absorption point, 257-258
in paints and coatings, 263 NASA SP 5014, 675 critical pigment volume, 253-256
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SUBJECT INDEX 917
Asbeck-Van Loo method, 254-255 stratospheric protection, 11 electrical resistance, 316-317

Cole method, 255 by elutriation, 314-315
Pierce-Holsworth method, 255-256 felvation, 315
critical pigment volume fineness-of-dispersion gages, 327-329
concentration and, 256-257 gas adsorption, 313
determination methods, 252-255 Package integrity, artists' paints, 707 gravity sedimentation, 321
mechanism, 252 Package stability, architectural coatings, history, 305-306
gas chromatography, 805-806 701 hydrodynamic chromatography, 329
vegetable, used in alkyd manufacture, Packaging, vinyl resins, 105 importance, 306-307
56 Paint individual particle sensing, 315-317
(see also Drying oils) analysis, 753-765 light-scattering techniques, 323-325
Oiticica oil, 27 additive identification, 763-764 metallic pigments, 226
Olefins, in solvents, 153 analytical data, 757 nongaseous molecule adsorption, 313-
Opacity, 481 density, 755 314
aerospace and aircraft coatings, 687 flash point, 755 permeation through packed powders,
artists' paints, 708 inorganic structural analysis, 759- 314
carbon blacks, 183 760 reference test material, 329-330
dry, Federal Test, 489 laboratory protocol, 754 roller particle-size analyzer, 315
titanium dioxide pigments, 170-171 nonvolatile content by volume, 756 sampling techniques, 307-308
Optical density, carbon blacks, 183 nonvolatile content by weight, 755- by sedimentation, 319-323
Optical measurement methods, contact 756 by sieving, 317-319
angles, 378 organic structural analysis, 758-759 spectrophotometric techniques, 323-
Optical properties pigment content, 756 324
aerospace and aircraft coatings, 687- pigment identification, 761-763 Stokes' law, 320-321
688 quality assurance, 754 from surface area, 311-314
pearlescent pigments, 230 sample preparation, 757 thin-film drawdown for oversize
Orange peel sampling, 753-754 particles, 326-327
measurement, 477 solvent identification, 764-765 time of flight from light blockage, 315-
visual evaluation, 473 solvent separation, 756-757 316
Orange pigments, 200-201,203-205 structural analysis, 757-760 total light scattering, 325, 327
inorganic, 212 testing, 754-755 X-ray microradiography techniques,
Orchard equation, 356 trace analysis, 765 328-329
Organic coatings vehicle identification, 760-761 X-ray scattering, 325
deadhesion, 616 vehicle separation, 756 Partition chromatography, 790-791
drying time, 439-440 water content, 755 Parylene coatings, 111
on plastics, pull strength, 521 deterioration, 631 Pasteurization, can coatings stability, 722
resistance to rapid deformation effects, films (see also Biological deterioration) Pavement marking tape, 742
412 durability, pigment effects, 172-174 special considerations, 747
structural analysis, 758-759 fungal resistance, 657-659 Paving
(see also Architectural coatings; stress-strain curves, 306 bituminous coatings, 18
Protective overlayers; Stress) X-ray diffraction, 875-876 sealers, bituminous coatings, 20
Organic paints, ceramic pigments, 214- gloss and semigloss, 47 Pearlescent pigments, 229-236
215 material "floating" in can, 829-830 automotive coatings, 230-231
Organic pigments (see Colored organic white, untinted, relative hiding power chemical testing, 235
pigments) from tinting data, 499 color measurement, 231-236
Organic solvent resistance, aerospace volume solids, 303 composition, 229-230
and aircraft coatings, 692 Paintability, water-repellent coatings, 749 health and environmental
Organoclays, 282 Paintbinders, suppliers and trademarks, considerations, 235-236
Organosilica, as thickeners and rheology 399 history, 229
modifiers, 282-283 Painted metal panels, as hiding power industrial coatings, 230
Organosols, 104-105 test substrate, 490 manufacturing, 229-230
Orifice cups, 359-360 Pall glass mill, 510 optical properties, 230
Orthonitroniline orange, 200 Paperboard charts, as hiding power test particle size, 234-235
OSA-UCS system, 459-461 substrate, 490 powder coatings, 231
Oscillating jet, 376-377 Paper chromatography, 793-794 water-based coatings, 231
Osmometry, vapor pressure, 836 applications, 794 weatherability testing, 232, 234
Ostwald-deWaele model, 337 Para reds, 193 Pebble abrasion wear test, 527
Ostwald system, 459 Parker-Siddle Scratch Tester, 559 Peel, sealants, 737
Outdoor exposure, aerospace and aircraft Particles Peel test
coatings, 691 coarse aerospace and aircraft coatings, 688
Oxidative binders, coating failure in aerospace and aircraft coatings, plastic substrates, 517-518
analysis, 769-770 684 PEI abrasion tester, 533
Oxidative cross-linking, polymers, 408- in architectural coatings, 698 Pencil hardness, 412, 542
409 oversize, thin-film drawdown, 326-327 aerospace and aircraft coatings, 690
Oxidative drying, theory of, 30-31 shapes, definitions, 309-311 can coatings, 721
Oxidative passivation, inorganic anti- size versus Vickers hardness, 565
corrosive pigments, 239 definitions, 309-311 Pencil Hardness Tester, 559-560
Oxygen, weathering effect, 647-648 pearlescent pigments, 234-235 Pendant drop shape method, 375-376
Oxygenated solvents, 127-130 pigment, white hiding, 499-500 Pendulum damping, 412
Ozone Particle-size measurements, 305-330 Pendulum-rocker hardness, 573-578
control in atmosphere, 9 centrifugal sedimentation, 321-324 K6nig pendulum, 574
effect on copper and silver corrosion, comparison methods, 311 Persoz pendulum, 574-575
612 diffraction of laser light, 325-326 Rolling Ball Hardness Tester, 574-575
nonattainment areas, 9 direct microscopic measurement, 318- Sward Rocker Hardness Tester, 575-
standard, 5 320 578
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Pendulum-type COF devices, 605 stability, solubility parameter distillation range, 116-117
Penetration, architectural coatings, 699- relations, 399-400 ester value, 117
700 techniques, 509-510 flash point, 117
Penetration rate, contact angle effect on stress in organic coatings, gas chromatography, 119, 807
measurements, 378 591-595 grade classification, 224-225
Pensky-Martens Closed-Cup Tester, 143, extender, 217-222 identification methods, 118-120
145,685-686 failure modes associated with, 772- infrared spectrophotometry, 118-119
Perception, of objects and colors, 450 /773 instrumental methods, 118
Permanent dipole interactions, 385 fUl~Ction, 160-161 isolation, 118
Permanent magnet thickness gages, 429- hiding, 483 liquid chromatography, 119
432 identification, electron microscopy, low-temperature properties, 120-121
Permanent red 2B, 192 823-824 permanence, 120
Permeability, automotive products, 715 iron oxide blacks, 179 pour point, 117
Permeation, 296 metallic, 223-228 properties, 118-119
Persoz pendulum, 574-575 mixing of colors, 467 qualitative methods, 119-120
Perylene reds, 195 oil absorption, 252-258 refractive index, 117
Peters abrasion block, 533 particle sizing, electron microscopy, residual water, 118
Pfund cryptometers, 420, 486-487 823-824 sampling, 117
hiding power, 713 plasticizer absorption, 253,256 specific gravity, 117-118
Pfund Hardness Number, 568, 570 quantitation by X-ray diffraction, 879 vinyl resins, 102-104
Pfund Hardness Tester, 569 role in hiding power, 483-484 viscosity, 118
Pfund precision cryptometer, 487-488 sacrificial, 238 Plastics
Pfund wet film gage, 424-426 solute adsorption, 313 peel adhesion testing, 517-518
pH void, 177-178 pull strength of organic coatings, 521
automotive products, 714 volume concentration, inorganic anti- Plastisols
masonry, 726 corrosive pigments, 245-246 primers, 104-105
measurement, metallic pigments, 227 wetting/suspension characteristics, 401 vinyl resins, 104
rainfall, 629, 632 white, hiding power, 483 Platinum-cobalt scale, solvents, 148-149
Phase shift, ideal viscous and elastic white hiding (see White hiding Polar solubility parameter, 390, 392
bodies, 345 pigments) Pollution, effect on natural weathering,
Phenolics, 79-84 X-ray diffraction, 875-877 627
acid catalyst, 80, 82 (see also Carbon blacks; Colored Polyacrylates, properties, 39
alcohol-soluble resins, 82 organic pigments; Inorganic anti- Polyalcohols, 108-109
base catalyst, 79-81 corrosive pigments; Pearlescent Polyamides, 85-88
catalyzed cross-linking, 410-411 pigments; White pigments) acids, 85
chemistry, 79 Pigment orange 38, 193
amines, 85
as cross-linking agents for other Pigment orange 60, 203
Pigment orange 62, 203 chemical properties, 86-87
polymers, 82-83 curing agents, 76
Pigment red 5, 193
definition, 79
Pigment red 7, 193 environmental~toxicity, 87-88
first coatings, 79 history, 86
Pigment red 22, 193
heat-reactive aromatic soluble resins, Pigment red 122, 193 imidazoline content, 86-87
82-83 physical properties, 87
Pigment red 146, 193
intermediate pH catalysis, 80 Pigment red 170, 193 reaction with epoxy resins, 87
nonheat-reactive resins, 83 Pigment red 187, 193 synthesis, 86
raw materials, 79-80 Pigment red 188, 193 Polyamine adducts, 76
testing, 80, 82 Pigment yellow 65, 199 Polyesters
varnish resins, 83-84 Pigment yellow 73, 199 history, 53
Phenoxy, 111 Pigment yellow 74, 199 resins, gas chromatography, 806
Phosphates, inorganic anti-corrosive Pigment yellow 75, 199 saturated, 57-58
pigments, 242-243 Pigment yellow 97, 199 silicone-modified, 58-59
Phosphites, inorganic anti-corrosive Pigment yellow 99, 199 traffic marking materials, 741
pigments, 243 Pigment yellow 116, 199 Polyethylene, pipeline coatings, 732
Phosphorus, detection in plasticizers, Pine oil, 127 Polyhydric alcohols, used in alkyd
119 Pipeline coatings, 731-733 manufacture, 56
Phosphosilicates, 244 application techniques, 732-733 Polymer, 407
Photometric measurements, hiding coal tar mastic, 732 addition, 407
power, 490 external coatings, 731-732 coatings, 615
Phthalates, detection in plasticizers, 119- failure, 773 condensation, 407
120 internal protection systems, 732 miscibility, 400-401
Pierce-Holsworth method, critical market, 731 mixtures, solubility relations, 400
pigment volume determination, product design, 733 molecular weight, 835-839
255-256 quality control, 733 colligative properties analyses, 836
Pigment usage, 731 definitions, 835
carbonaceous, 179 Plastic behavior, non-Newtonian end group analysis, 835-836
cathodic reaction inhibition, 616 behavior, 343-344 by light scattering, 836-837
colored inorganic, 209-212 Plastic film, clear, as hiding power test size exclusion chromatography, 837-
concentration, 510 substrate, 490 839
aerospace and aircraft coatings, 684 Plasticizers, 115-121 viscometry, 839
content absorption by pigments, 253, 256 noncarbon, coating failure analysis,
paint, 756 acidity, 115 771-772
traffic marking materials, 743 color, 115-116 organic resin binders, 769-771
critical volumes, 303 compatibility, 120-121 oxidative cross-linking, 408-409
definition, 190 copper corrosion, I 16 packings, gas-solid chromatography,
dispersion, 508-509 density, 117-118 808
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SUBJECT INDEX 919
phenolics as cross-linking agents, 82- infrared spectroscopy, 832-833 Reynolds number, 320
83 paint analysis, 754 Rhamsan gum, 277
reactive cross-linking, 409-410 Quality control Rheology and viscometry, 333-365
solubility parameters, 393, 398-399 instruments, theology and viscometry, architectural coatings, 700-701
solutions viscosity, 350-351 359-361 definitions, 334-336
used in sealants, 735-736 pipeline coatings, 733 dispersion rheology, 351-352
viscoelasticity, 572-573 X-ray fluorescence spectroscopy, 885- extensional rheology, 350
viscosity, 547 886 instrumentation, 358-359
Polymerization Quinacridone reds, 194 leveling, 354-358
emulsion, vinyl resins, 100 QUV/HO, 651 modifiers
post processing, vinyl resins, 100 definition, 269
suspension, vinyl resins, 100 (see also Thickeners and rheology
Polymethacrylates, properties, 39 R modifiers)
Polyols, 108-109 molecular weight determination, 839
Polysulfides, 111 Radiant power, 868 Newtonion fluids, 336
sealants, 736 Radiation nomenclature, 333
Polyurethane coatings, 89-94 curable polyurethane coatings, 93 non-Newtonian behavior, 336-350
catalysts, 91 curing, xiv-xv elastic liquids, 344-350
chemistry, 90-93 electromagnetic, 783-784 plastic behavior, 343-344
definitions, 89-90 safety, X-ray analysis, 871 shear-dependent viscosity, 337-339
markets, 93-94 Radiometers, 646-647 shear-thickening fluids, 339-341
powder coatings, 93 Rainfall shear-thinning fluids, 339-340
radiation-curable, 93 duration sensor, 633-634 time-dependent fluids, 341-343
raw materials, 90-91 effect on natural weathering, 626-627 yield behavior, practical aspects, 344
reactions, 91-92 erosion non-Newtonian fluids, 336
thermoplastic, 92-93 abrasion resistance, 532 polymer melt and solution rheology,
water-borne, 93 aerospace and aircraft coatings, 690 350-351
Polyurethane sealants, 736 wind driven, masonry resistance, 728 quality control instruments, 359-361
Porcelain enamels, 69-71 Rain gage, 634 recurrent failing in testing, 334
Porosity, masonry, 725 Raman spectroscopy, 758 relative viscosity, 351
Position-sensitive detector, 872 Rank pulse shearometer, 364-365 research rheometers/viscometers, 361-
Pot life, aerospace and aircraft coatings, RCA tape tester, 531 365
686 Reaction kinetics, 845-847 Brookfield CAP 2000 viscometer, 363
Pour point, plasticizers, 117 Reactive crosslinking, polymers, 409-410 Brooldield viscometers, 362-363
Powder coatings, xiii-xiv Rebound hardness testing, 578-579 capillary viscometers, 363-364
dielectric analysis, 855-856 Red lead, 241-242 ICI cone and plate viscometer, 363
epoxy polyester, cure, 859-861 RED numbers, 387, 399-400 rank pulse shearometer, 364-365
epoxy resins, 78 Red pigments rotational instruments, 361-362
pearlescent pigments, 231 inorganic, 209-210 vendors, 365-366
polyurethane coatings, 93 (see also Colored organic pigments, sagging, 352-345
vinyl resins, 106 reds, 191) sealants, 736
Power law, 337 Reference intensity, 879 time-dependent effects, 356-357
Precision Spectral Pyranometer, 632 Reflectance Rising-bubble viscometers, 361
Preservation, in-can, 261-262 aerospace and aircraft coatings, 688 Roberts jet abrader, 527-528
Pretreatments, automotive products, 711 directional, architectural coatings, 702 Rockwell Hardness Tester, 571
Primer, automotive products, 711-712 pavement marking tape, 745 Rods, wire-wound, 420-421
conductive, 712 traffic marking materials, 744 Roller application, architectural coatings,
electrodeposited, 711-712 Reflection, light, 448-449 702
nonconductive, 712 Reflectivity Roller mill, laboratory, 510
weatherable, 712 determination, 492-493 Roller particle-size analyzer, 315
Princeton scratch tester, 532, 580 Fresnefl equation, 484 Roller spatter, architectural coatings, 702
Print resistance, 572-573 Refraction, Snell's law, 483 Rolling Ball Hardness Tester, 574-575
architectural coatings, 704 Refractive index, 837-838 Rolling friction, coefficient, 576
Protective overlayers, 609-616 glass beads, 746 Rondeau Scratch Tester, 560-561,580
corrosion control, 615-616 hiding power, 483-484 Roof coatings, bituminous coatings, 16-
thin metal films and microstructures, plasticizers, 117 18, 20
612-615 solvents, 149 Ro-tap sieve shaker, 317-318
Pseudoplastic, 339 Refractory coatings, 71-72 Rotating cell holder centrifuge, 323-324
Pull strength, organic coatings on Regulations Rotational casting, 416-417
plastics, 521 concerns about density, 289 Rotational viscometers, 361-352
Purge gas, differential scanning volatile organic compound emissions, Rotothinner, 360
calorimetry, 846 3-12 Rutile, in titanium dioxide pigments,
Putrefaction, artists' paints, 707 Relaxation behavior, 547-548 164, 167-168
PVC latex, vinyl resins, 106 Relaxation map analysis, 855
Pycnometers Resilience, 578
helium gas, 297, 302 Resin
liquid, 298 cloud, 831-833
methods, solvents, 147-148 dielectric analysis, 855, 857 Saberg drill, 429
solid density, 301 gas chromatography, 806 SAE J2020, 715
Pyrazolone orange, 200-201 gel coat, cross-linking reaction, 858 SAE J400, 528, 714
Resistivity, automotive products, 714 SAE J861, 715
Retroreflectance Safflower oil, 27
O pavement marking tape, 745 Sagging
traffic marking materials, 744, 747 films, 420
Quality assurance Retroreflection, 449 measures, 354-355
www.iran-mavad.com

resistance, architectural coatings, 701 ISO standards, 739 Slumping, 353

sealants, 736 polymers used in, 735-736 Smog, 3-4
test film casters, 420 sources of specifications, 739-740 Smoke characteristics, automotive
thickeners and rheology modifiers, test procedures, 736-737 products, 713
274-275 Secondary ion mass spectrometry, 759- Snell's law of refraction, 483
Salt spray/fog testing 760 SNV 37 112, 574
accelerated weathering, 639, 650 Sedimentation, particle-size Soap titration, emulsion particles, 313-
aerospace and aircraft coatings, 690- measurements, 319-323 314
691 Sedimentation E. S. D., 310 Sodium aluminosflicates, 220
automotive products, 715 Seeding, artists' paints, 707 Sodium carboxymethyl cellulose, 277
chemical resistance, 664, 666 Sensor materials, 602-603 Softening point
Sampling, paint, 753-754 Sessile drop shape method, 375-376 coating, 547
Saturation, 507 Setaflash-Closed-Cup Apparatus, 143, 145 thermoplastic marking material, 744-
Saybolt color, solvents, 149 Setaflash test, 686 745
Scanning auger microscopy, 760 Settling Soil, preparation for aerospace and
Scanning electron microscopy, 759, 815- architectural coatings, 701 aircraft coatings cleaning tests,
821 artists' paints, 707 693-694
backscatter electrons, 816 thickeners and rheology modifiers, Solids, 293-294
condenser lens, 819 274-275 as concrete materials, 295-296
cryogenic, 820-821 Shade, 507 content
electron guns, 818-819 Shear flow, thickeners and rheology total, in aerospace and aircraft
environmental, 821 modifiers, 269-270 coatings, 684
image formation, 815-818 Shear loss modulus, 536 by volume, paint, 756
metal coating, 819-820 Shear modulus, relation to tensile by weight, paint, 755-756
objective lens, 819 modulus, 534 density, 301-302
paint film weatherability, 824 Shear storage modulus, 536 paint volume, 303
scan coils, 819 Shear stress, due to gravity, 352 Solid support, gas chromatography, 799-
X-ray microanalysis, 817-818 Shear thickening, 339-341 800
Scattering, 507 Shear thinning, 339 Solubility, 385
Scattering coefficient fluids, drainage equation, 353 cellulose esters, 24
titanium dioxide pigments, 173-174 Sheen, 471 inorganic anti-corrosive pigments, 247
Kubelka-Munk two-constant theory, Sheen Scratch Tester, 561-562 of solvents in water, 154
492 Shore hardness, aerospace and aircraft Solubility parameters, 383-402
Scattering power, Kubelka-Munk two- coatings, 690 applications, 393, 397, 399-401
constant theory, 492 Shore scleroscope, 579 dispersion, calculation, 387, 389-391
Scheppard-Schmitt Scratch Sieving, particle-size measurements, Hansen solubility parameters, 384-385
Dynamometer, 560 317-319 Hildebrand parameters, 384
Schiefer abrasion testing machine, 529- Sikkens Scratch Hardness Tester, 561 hydrogen bonding
530 Silica, 218-219 calculation, 392
Scholzite, X-ray diffraction, 880-881 Silicas, synthetic, as thickeners and temperature effects, 397
Schopper Hardness Tester, 560-561 rheology modifiers, 282-283 nomenclature, 383
Scrape adhesion test, aerospace and Silicates, inorganic anti-corrosive partial, determination, 385-388
aircraft coatings, 688 pigments, 243-244 polar, calculation, 390, 392
Scratch hardness, 555-563 Silicone coatings, 95-98 polymers, 393, 398-399
Bierbaum Microcharacter, 556 addition cure system, 96 solvents, 134
Clemen Scratch Hardness Tester, 556 application methods, 97 supplementary calculations and
Dantuma Scratch Tester, 556-557 applications, 98 procedures, 392-393
du Pont Scratch Testing Machine, 557 catalyzed cross-linking, 411 Solutes, adsorption onto pigments, 313
Erichsen Hardness Tester, 557-558 elastomeric coatings, 96 Solvency, solvents, 132-134
Graham-Linton Hardness Tester, 557- forms, 95-97 Solvent-borne coatings, traffic marking
558 new requirements, 98 materials, 741
Hoffman Scratch Tester, 557-558 oxime cure systems, 96 Solvent/fuel resistance, 663-664
Inspector's Dur-O-Test Pocket Size testing conditions, 97-98 Solvent-reducible coatings, masonry, 727
Hardness Tester, 558-559 unique properties, 95 Solvent reflux process, alkyds, 54-55
Laurie-Baily Hardness Tester, 558-559 Silicone sealants, 736 Solvent rub resistance, 411,542, 664
Parker-Siddle Scratch Tester, 559 Simmons Scratch Tester, 561 Solvents, xvi, 125-154
Pencil Hardness Tester, 559-560 SIS 18 41 77, 551 acidity, 152
Rondeau Scratch Tester, 560-561 SI system, units for rheological variables, acid wash color, 152
Scheppard-Schmitt Scratch 336 active, 131
Dynamometer, 560 Size exclusion chromatography, 837-839 alkalinity, 152
Schopper Hardness Tester, 560-561 amino resins, 62-63 aniline point, 132-133
Sheen Scratch Tester, 561-562 application, 838-839 approved, 4
Sikkens Scratch Hardness Tester, 561 calibration and calculations, 838 aromatics, nonaromatic hydrocarbons
Simmons Scratch Tester, 561 instrumentation, 837-838 in, 152
Steel Wool Scratch Tester, 561-562 Skid resistance, pavement marking tape, balance, 132
Teledyne Taber Shear/Scratch Tester, 745 benzene content, 152
561-562 Skinning, traffic marking materials, 743 classification by chemical type, 125-
Universal Hardness and Adhesion Test Slip resistance, 600-605 131
Instrument, 563 ASTM activity, 600 chlorinated hydrocarbons, 130
Wolff-Wilborn Scratch-Hardness coefficient of friction, 601-602 hydrocarbons, 125-128
Tester, 562-563 determination methods, 603-605 nitrated hydrocarbons, 130
Scuffing methods, 581-582 measurement, 604-605 oxygenated, 127-130
Sealants, 735-740 definitions, 600-601 supercritical carbon dioxide, 131
AAMA standards, 739 lubricants, 603 classification by function, 131-132
Canadian standards, 739 sensor materials, 602-603 coalescing, 393
www.iran-mavad.com

SUBJECT INDEX 921
color, 148-149 Spectrophotometers, 687 versus adhesion and cohesion, 594,

copper strip corrosion, 153 color measurement, 462-463 596
density and specific gravity, 144-148 double beam, 826-827 binder effect, 594
calculations and conversion tables, pearlescent pigments, 231 calculation, 590-591
147-148 techniques, particle-size film formation, 585-586
definitions, 145-146 measurements, 323-324 interdependence of stresses, 587-589
digital density meter, 147 Spectroradiometers, 463 measurement, 589-591
hydrometer methods, 146-147 Specular glass, 470-471 origins, 585-587
pycnometer methods, 147-148 Spin coating, 422 pigmentation effect, 591-595
significance, 144-145 Spinel brown pigments, 214 relative humidity variation, 587
diluent dilution ratio, 133 Spinning riffler, 308-309 solvents effect, 593-596
dilution limit, 133 Spoilage, artists' paints, 707 temperature variation, 586
effect on stress in organic coatings, Spray application, architectural coatings, Tg determination, 586-587
593-596 702 weathering and, 597-598
electrical resistivity, 149-150 Spray outs, 421 Stress memory time constant, 347
emissions, automotive products, 713- Spray rack, accelerated natural Stress relaxation, 347
714 weathering, 639 Stress-strain analysis, description, 543
failure modes associated with, 772- Spreading rate Stress-strain curves
773 contrast ratio at, 493 ductile film, 537
gas chromatography, 803, 805 determination, 492-493 interpretation, 543-544
Heptane Miscibility Test, 154 hiding power, 489-490 paint films, 306
identification, paint, 764-765 hiding power, 482 Strippability, aerospace and aircraft
Karl Fischer Reagent Method, 154 SS-A-118, 676 coatings, 693
Kauri-Butanol Value, 132 SSPC PA2, 435, 437 Strontium chromate, 241
latent, 131 SSPC-VIS1, 435 Strontium yellow, 211
nonvolatile residue, 152 SS-S-200E, 737 Styrene, 43
odor, 149 SS-W-110c, 749 Substrates
o|efins content, 153 Stain chambers, 659 cleaning and pretreatment, 380
organic, resistance, aerospace and Staining, 662-663 composition, effects on film thickness
aircraft coatings, 692 sealants, 737 measurement, 435, 437
oxygenated, 393 Stainless steel flakes dry coatings on, 417-418
purity and composition, 149-151 grade classification, 225 Subtropical climate, 629-630
esters, 151 properties, 224 Sulfur
gas chromatography, 149-151 State implementation plans, 5 detection in plasticizers, 119
ketones, 150-151 by lamp method, 153
State operating permit program, 10
liquid chromatography, 150 in solvents, 153-154
Static coefficient of friction, 600
refractive index, 149 Sulfur dioxide, corrosion-accelerating
Statistics
selection using solubility parameters, effect, 611
in film thickness measurement, 437-
393, 397, 399 Sun, following, accelerated natural
separation from vehicle, 756-757 438
weathering, 639
solubility parameters, 134 inorganic anti-corrosive pigments, 249 Sunchex apparatus, 651
solvency, 132-134 Steel flake, 245
Sunlight
sulfur content, 153-154 Steel Wool Scratch Tester, 561-562 effect on natural weathering, 621-625
supercritical gases, 400-401 Step-shear method, thixotropic recovery, radiant exposure, 622-623
tolerance, amino resins, 62 342-343 seasonal variations, 622-625
viscosity reduction, 133-134 St. Louis gage, particle-size spectral power distribution, 621-623
volatility, 134-144 measurements, 327 electromagnetic spectrum, 644
boiling point/distillation range, 137, Stokes equation, 361 radiation intensity, 632-633
139-140 Stokes E. S. D., 3t0 Sun yellow, 214
evaporation rate, 135-139 Stokes' law, particle-size measurements, Surface, 369-380
flash point, 140-144 320-321 rough, contact angles, 373
vapor pressure, 134-135 Stokes-Smoluchowski-Einstein theory, Surface active agents, 397
water content, 154 338 Surface analysis, X-ray fluorescence
water solubility, 154 Stopped method, 428-429 spectroscopy, 885
(see also Hydrocarbons, solvents) Storage stability Surface area, particle size from, 311-314
Sonic frequency shifts aerospace and aircraft coatings, 685 Surface area to volume ratio, 370
liquid density, 299-301 artists' paints, 706-707 Surface cleaners, automotive products,
solid density, 302 can coatings, 722 711
Sonic sifter, 317-318 traffic marking materials, 743 Surface effects, 370
Soybean oil, 27 Stormer viscometer, 359-360 Surface elasticity, 372
Spatula and hand muller, 509 Straight line drying time recorder, 444 Surface energetics, 369-380
Spatula rub-out method, oil absorption Straight-line reciprocating machines, 531 cleaning and pretreatment of
determination, 253-255 Strain substrates for coating, 380
Specialty paints and coatings, definition, 334-335 coatings application and defects, 378-
bituminous coatings, 16, 20-21 internal, 586 38O
Specifications oscillating, stress response, 345-346 contact angle measurements, 378
considerations, 891 in tension and shear tests, 534 dynamic properties, 373
sources, 891-893 Strain rate thermodynamics, 370-373
Specific gravity, 289-303, 290 definition, 334-335 Surface excess concentration, 370-371
colored organic pigments, 208 effect on flexibility and toughness, 548 Surface finish
definition, 146 Strand Gauge, 721 effects on film thickness measurement,
plasticizers, 117-118 Stress 435,437
solvents, 144-148 definition, 335 masonry, 726
thermoplastic marking materials, 745 internal, 592 Surface interactions, 296
Spectrocolorimeters, 463 in organic coatings, 585-598 Surface tension, 370-371
www.iran-mavad.com

amino resins, 64 coatings and, 841-842 rhamsan gum, 277

measurement, 373-378 combined techniques in problem shear flow, 269-270
dynamic, 376-378 solving, 860-863 synthetic silicas, 282-283
static, 374-376 cure, 412-413 thickening mechanisms, 271-272
Surface thermodynamics, 370-373 dielectric analysis, 842, 855-857 water-soluble, 275
liquid/solid interfaces, 372-373 differential scanning calorimetry, 842- xanthan gum, 277
liquid surfaces, 370-372 845 Thin-layer chromatography, 794-796
Sward hardness, 412 dynamic mechanical analysis, 842, applications, 795-796
Sward Rocker Hardness Test, 573 847-850 Thioindigoid reds, 196
Sward Rocker Hardness Tester, 575-578 experimental techniques, 842 Third party inspection, 777
calculation of number of rocks, 576 industrial applications, 842 "Thixotropic Index" test, 341
compared with K6nig and Persoz reaction kinetics, 845-847 Thixotropic loop, 341-342
hardness values, 578 thermogravimetry, 842, 850-853 Thixotropy
comparison of rockers, 577 thermomechanical analysis, 842, 853- architectural coatings, 700
uses, 578 855 gel coat, 343
Swelling, 385 thermoset cure studies, 857-860 mechanism, 341-342
Syneresis, thickeners and rheology Thermal conductivity test methods, 342-343
modifiers, 274-275 aerospace and aircraft coatings, 693 Thomas-Stormer Viscometer Model ETS-
Synthetic brown oxide, 212 detectors, 797-798 1000, 360
Thermal fatigue, aerospace and aircraft Through-dry state, 441
coatings, 693 Through-dry time, 441
T Thermal gravimetric analysis, 759 Throwpower, automotive products, 714
Thermally stimulated current, 855 Time lapse spectroscopy, 832
Taber Abraser, 530 Thermal mechanical analyzer, 548 Time of flight from light blockage,
aerospace and aircraft coatings, 690 Thermal stability, thermogravimetry, 850 particle-size measurements, 315-
can coatings, 722 Thermodilatometry, 853 316
mar test, 532, 581 Thermodynamic stability, 610 Time-of-wetness, 611-612
Table sampling, particles, 308-309 Thermogravimetry, 842, 850-853 Time-temperature superposition, 859
Tack-free time, sealants, 737 heating rate, 852 Tint, 507
Tag Closed Cup Tester, 142, 144 purge gas, 852 Tinting
Tag Open Cup Flash Point test, 142, 144 sample preparation, 850, 852 hiding power, calculation from, 498-
Tag tester, 686 Thermomechanical analysis, 842, 853- 499
Talc, 218 855 relative hiding power determination,
Tall off, 27 applications, 854-855 untinted white paints, 499
fatty acids, 85 dilatometry, 853 Tinting strength, 507-508
Tape and wrap systems, 732 heating rate, 854 artists' paints, 708
Tape test instrumentation, 853 carbon blacks, 183, 185, 189
adhesion, 517-519 sample preparation, 854 chromatic paints, 508
aerospace and aircraft coatings, 688 Thermoplastic acrylic resins, 40-42 colored organic pigments, 207
can coatings, 722 Thermoplastic pavement markings, white paints, 508
TAPPI Method T649sm, 321 traffic marking materials, 741-742 Titanate green pigments, 214
Technical societies, specification sources, Thermoplastic polymers, 408 Titanium dioxide pigments, 162-176
891-893 Thermoset cure studies, 857-860 characteristics, 164-170
Teledyne Taber Shear/Scratch Tester, Thermoset polymers, 408 color, 169-170
561-562 Thermosetting acrylic resins, 42-46 commodity composition, 166- 168
Temperature Thickeners and rheology modifiers, 268- contaminants, 169
critical, 390 283 crystallites, 164-165
effect on alkali-swellable/solubleemulsions, hazards, 170
flexibility and toughness, 548 277-278 packing, 168-169
natural weathering, 624-626 application properties, 274 particle size, 165-167
variation, stress in organic coatings, associative, 278-280 performance, 170-174
586 mechanisms, 272-273 compatibility, 174
weathering effect, 647 attapulgite clays, 281-282 dispersibility, 171-172
Temperate climate, with pollution, 629 bentonite clays, 282 effects on gloss, 173-174
Tensile adhesion test, aerospace and biopolymers, 277 effects on paint film durability, 172-
aircraft coatings, 688-689 cellulosics, 275-277 174
Tensile creep experiment, 537 classification, 270-271 hiding and opacity, 170-171
Tensile loss modulus, 535 coating consistency, 273-274 product types, 174-177
Tensile modulus, relation to shear in coating manufacturing operations, scanning electron micrographs, 163
modulus, 534 269 scattering coefficient, 173-174
Tensile properties conventional, 275-278 surface, 168
definitions, 536-537 elongational flow, 270 transmission electron micrograph, 162
dynamic (see Dynamic mechanical and definition, 268-269 X-ray diffraction, 872-873
tensile properties) functions, 272-275 (see also White pigments)
Tensile storage modulus, 535 hydrophobe modified Titanium oxide, (see White hiding
Tensile strength alkali-swellable/solubleemulsions, pigment, 500)
pavement marking tape, 745 279-280 Toluene, 126
relation to abrasion resistance, 525 cellulosics, 280 Toluidine red, 192-193
Tensile stress relaxation experiment, 537 nonionic synthetics, 278-279 Tolyl orange, 201
Tensile tests, aerospace and aircraft hydroxypropyl guar, 277 Tooke inspection gage, 429
coatings, 689 inorganic, 281-283 Topcoat, automotive products, 712-713
Terpenes, 127-128 leveling, sag, syneresis, settling, 274- solvent emissions, 713 - 714
Thermal analysis, 841-863 275 Torsion pendulum, cure, 413
classification of material properties, organic, 283 Total light scattering, particle-size
841 organoclays, 282 measurements, 325, 327
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SUBJECT INDEX 923
Total solids, traffic marking materials, TT-P-55B, 726, 729 characteristics, 99

743 TT-P-95C, 727, 729 definition, 99
Total ultraviolet radiometer, 632 TT-P-96D, 726, 729 dry film printing, 105
Touch-up uniformity, architectural TT-P-97D, 729 emulsion polymerization, 100
coatings, 702 TT-P-00620C, 727 FDA status, 100
Toughness, 547-554 TT-P-2756, 692 formulation, 101, 103
aging and weathering effects, 554 TT-S-001657, 737 history, 99
automotive products, 715 TT-S-00227E, 737 inks, 105
cold crack resistance tests, 554 TT-S-00230C, 737 magnetic recording media, 106
cupping tests, 551-552 TT-S-01543A, 737 maintenance and marine finishes, 105-
effect on coating performance, 547- TT-W-572b, 749 106
548 Tubing materials, gas chromatography, manufacture, 99
forming tests, 552-553 799 market, 105-107
humidity effects, 548 Tukon hardness, 564 organosols, 104
impact resistance tests, 553-554 Tung oil, 27 packaging, 105
interpretation, 547 Turpentine, 127 pigmentation, 103-104
Mandrel bend tests, 548-550 Twisting cork hardness tester, 573 plasticizers, 102-104
strain rate effects, 548 plastisols, 104
t-bend tests, 550-551 polymerization, 99
temperature effects, 548 U post-polymerization process, 100
Toxicity powder coatings, 106
amino resins, 66-67 UL-94, 95 primers for plastisols and organosols,
colored organic pigments, 204-206 UL QMJU2, 110 104-105
evaluation, artists' paints, 710 Ultramarine blue, 211 properties, 101
inorganic anti-corrosive pigments, 245 Ultraviolet and visible spectroscopy, PVC latex, 106
pearlescent pigments, 235-236 additive identification, 763-764 solubility, 101-102
polyamides, 87-88 Ultraviolet cured coatings, cans, 719-720 solution characteristics, 102- 103
Trace analysis, paint, 765 Ultraviolet light, 644 solution process, 100
Traffic marking materials, 741-747 Ultraviolet radiation, 449 suspension polymerization, 100
appearance and physical Ultraviolet transmission, automotive trends, 106-107
characteristics, 743-744 products, 713 vinyl chloride copolymer coating
auto-no-track time, 747 Ultraviolet/visible spectroscopy, 865-870 resins, 100-102
epoxy, 741 calibration of instruments, 867 waterborne dispersions, 106
field evaluation, 746-747 electromagnetic radiation, 866 wood finishes, 106
glass beads, 742 instrumentation, 866-869 Vinyltoluene, 43
laboratory testing, 745-746 mercury arc emission spectrum, 868 Violet pigments, inorganic, 210
laboratory testing, 743-746 potential problems, 869-970 Viscoelasticity
liquid coatings, 741 principle of operation, 867 industrial processes and, 348-350
laboratory testing, 743 radiant power, 868 polymers, 572-573
pavement marking tape, 742 spectral interpretation, 867-869 (see also Elastic liquids)
laboratory testing, 745 Unbalanced magnetron sputtering, 110- Viscoelastic models, 346-348
permanent tapes, 742 111 Viscoelastic parameters, 345-346
polyester, 741 Undertone, carbon blacks, 185-186, 188- Viscoelastic properties, measurement,
removable tape, 742 189 548
solvent-borne coatings, 741 Underwriters Laboratories Inc., 892 Viscometers, 683-684
temporary tape, 742 Units, for rheological variables, 336 Viscometry (see Rheology and
thermoplastic material, laboratory Universal color language, 458 viscometry)
testing, 744-745 Universal Hardness and Adhesion Test Viscosity
thermoplastic pavement markings, Instrument, 563 aerospace and aircraft coatings, 683-
741-742 Urea, reactive crosslinking, 409 684
water-borne coatings, 741 Urea resins, 60-61 alkyds, 55
Traffic paint, abrasion resistance tests, Urethane, coal tar, 732 amino resins, 62, 64
532 artists' paints, 708
Transfer efficiency, automotive products, automotive products, 714-715
715 V can coatings, 720
Transmission, light, 448-449 cellulose esters, 24
Transmission electron microscopy, 822- Vacuum plate, 416 changes
824 Van Eyken-Anderson method, hiding artists' paints, 707
electron-optical column, 822-823 power, 489 definition, 335
particle-size measurements, 319-320 Vapor pressure dynamic, 536
types of contrast, 822 osmometry, 836 high-shear, thickeners and rheology
Transportation industry, staining in, 662 solvents, 134-135 modifiers, 274
1,1,1-Trichloroethane, staged phaseout, Varnish, phenolic resins, 83-84 low-shear
11 Vat reds, 194 architectural coatings, 700-701
Tristimulus (filter) colorimeters, 463 Vehicle thickeners and rheology modifiers,
Tristimulus values, 507 failure modes associated with, 772- 274-275
calculation, 453-454 773 medium-shear, thickeners and
from spectral data, 463 identification, paint analysis, 760-761 rheology modifiers, 273-274
TT-C-555B, 728-729 separation from pigment, 756 melt, 839
TT-C-598B, 737 Vickers hardness, versus pencil hardness, plasticizers, 118
TT-F-1098D, 726, 729 565 polymer, 547
TT-P-19, 658 Vinyl chloride copolymer coating resins, reduction, solvents, 133-134
TT-P-19D, 726, 728-729 100-102 relative, 839
TT-P-24D, 727, 729 Vinyl resins, 99-107 shear-dependent, 337-339
TT-P-29, 700 analysis, 100 solution, 839
www.iran-mavad.com

stability, can coatings, 720 controlled condensation testing, 679 Wetting, 372-373
Viscosity cup, conversions, 896-897 cycle testing, 679-680 Wetting-contact theory, 514
Visual system, 450-451 immersion testing, 677-678 White hiding pigments, 499-501
Volatile concentration, aerospace and methods, 677 concentration, 500-501
aircraft coatings, 684 100% relative humidity testing, 678- crystal and particle size, 499-500
Volatile organic compounds 679 dispersion, 500
architectural coatings, 699 specimen preparation, 677 film porosity, 500-501
artists' paints, 710 water fog testing, 678 microvoids, 501
automotive products, 714 Water vapor Whiteness indices, 461-462
can coatings, 720 permeability, masonry, 728 White paints
Clean Air Act, 3-5 transmission rate, aerospace and tinting strength, 508
content determination, 5-8 aircraft coatings, 692 untinted, relative hiding power from
definition, 4 Wavelength, complementary and tinting data, 499
emissions dominant, 455 White pigments, 159-178
from coatings, control, 5 Wavelength dispersive spectrometer, 817 calcium carbonate, 176-177
regulations, 3-12 Waviness, 471 economics of hiding, 161- 162
new source performance standards, 5, measurement, 477, 479 extenders, 176
7 Wax melt characteristics, 850, 852 manufacture, 159-160
regulation information, 11-12 Weak boundary layer theory, 514 market, 159
regulatory definition, 4-5 Wear resistance, aerospace and aircraft research and development, 160
standards coatings, 689-690 substance, 161-162
aerosol spray paints, 8 Weatherability void pigments, 177-178
automobile industry, 8 automotive products, 715 (see also Titanium dioxide pigments;
general application, 8-9 paint film, scanning electron White hiding pigments)
inks, 9 microscopy, 824 Wilhelmy plate, 375, 377-378
masonry treatments, 8 testing, pearlescent pigments, 232,234 Wilson/Tukon Hardness Tester, 571-572
thermogravimetry, 850 Weathering Wire-wound rods, 420-421
Volatility, solvents, 134-144 accelerated, 643-652 WMO instrument house, 634
Volume E. S. D., 311 advantages, 643 Wolf abrasion method, 529
Volume measurements, problems with, aerospace and aircraft coatings, Wolff-Wilborn Scratch-Hardness Tester,
291 691-692 562-563
Voroni tesselation, 614 carbon arc lamp, 648-649 Wollastonite, 220
fluorescent UWcondensation lamp, Wood
649-650 finishes, vinyl resins, 106
W fluorescent UV-salt fog, 650 treated, water repellency, 749
Fresnel reflector, 651-652
WACO Enamel Rater, 721 light, 644-647
Wallace Microhardness Tester H-7, 571- moisture effect, 647 X
572 oxygen effect, 647-648
Washability, architectural coatings, 704- reproducibility, 643 Xanthan gum, 277
705 sealants, 737 Xenon arc lamp, 645-646, 648-649
Water temperature effect, 647 X-ray analysis, 871-887
content in solvents, 154 ultrafast, 652 radiation safety, 871
density, 290 UV light-cyclic immersion, 650-651 (see also X-ray diffraction; X-ray
effect on coatings, 677 xenon arc lamp, 648-649 fluorescence spectroscopy)
residual, plasticizers, 118 amino resins, 65-66 X-ray diffraction, 759, 871-880
Water absorption, water-repellent artificial, masonry, 728 application, 871
coatings, 749 effects on flexibility and toughness, coating failure analysis, 779
Water-based coatings, pearlescent 554 computer-assisted searches, 876-877
pigments, 231 natural, 619-642 d-spacing intensity table, preparation,
Waterborne coating accelerated, 638-640 874
cure, 859 biodeterioration effect, 627-629 goniometer system, 872
masonry, 726-727 exposure angles, 635-638 instrument operation conditions, 874
traffic marking materials, 741 exposure frames, 634-636 limitations, 877-879
Water content, paints, 755 failure modes, 641 manual search procedures, 875-876
Water coverage, metallic pigments, 226- inspection and reporting, 640-642 "matrix flushing" method, 878
227 instruments and sensors, 625 metal pretreatment and other thin
Water erosion, abrasion resistance, 532 mechanical properties, 642 coatings, 880-881
Waterproofing membranes, bituminous moisture effect, 625-628 physical principles, 871-872
coatings, 18, 20 mounting specimens, 638 pigment
Water-repellent coatings, 748-750 nondestructive testing, 641-642 analysis, 879-880
beading, 749 orientation of specimens, 637-638 identification, 762-763
classification, 748 origins of testing, 619-620 procedure for calculating composition,
composition, 748 pollution effect, 627 879
dimensional stability, 749 reporting scales, 641 qualitative analysis, 874-878
paintability, 749 sunlight effect, 621-625 quantitative analysis, 878
physical properties tests, 748-749 temperature effect, 624-626 specimen preparation, 872-874
treated masonry tests, 749-750 (see also Climatology) thin film units, 873-874
treated wood tests, 749 stress development, 597-598 X-ray fluorescence spectroscopy, 759,
water absorption, 749 ultraviolet, coating failure analysis, 779 880-887
weathering, 749 water-repellent coatings, 749 application, 880-88l, 885-887
Water resistance, 666 Weight, 291-293 bulk contaminant detection, 885
aerospace and aircraft coatings, 692 Wells-Brookfield cone and plate comparison to other techniques, 885
automotive products, 715 viscometer, 363 dedicated spectrometers, 882
Water-resistance testing, 677-680 Wet film comb, 425,427 direct comparison method, 884
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SUBJECT INDEX 925
electron beam excited X-ray X-ray scattering, particle-size Z

spectroscopy, 882-883 measurements, 325
empirical methods, 884 Xylenes, mixed, 126 Zabel test, 659
field analysis, 886-887 Zeeman effect, 786
film thickness measurement, 438 Zinc
fundamental parameter methods, 884 Y cathodic protection, 238
on-line units, 882
physical basis, 881-882 Yellowing, artists' paints, 709 coating failure analysis, 778-779
pigment identification, 762 Yellowness indices, 462 in primers, 244
portable units, 882 Yellow pigments Zinc borate, 240-241
procedures, 883 inorganic, 211-212 Zinc chromate, 211
qualitative analysis, 883 (see also Colored organic pigments, Zinc hydroxy phosphite, 243
quality control, 885-886 yellows) Zinc oxide, 244
quantitative analysis, 883-884 Yield behavior, practical aspects, 344 Zinc phosphate, 242-243
scanning, 882 Yield stress Zinc pigment
standard addition method, 884-885 coating layers, 352 grade classification, 224-225
surface analysis, 885 test methods, non-Newtonian behavior,
X-ray microanalysis, scanning electron 344 properties, 224
microscopy, 817-818 Young equation, 372 Zinc potassium chromate, 241
X-ray photoelectron spectroscopy coating Young-Laplace equation, 373 Zinc tetraoxychromate, 241
failure analysis, 768, 778 Young's modulus, 564, 573
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Contents
Preface xi
Introduction xiii
PART 1: REGULATIONS
Chapter 1--Regulation of Volatile Organic Compound

Emissions from Paints and Coatings
by John J. Brezinski
PART 2: NATURALLY OCCURRING MATERIALS
Chapter 2--Bituminous Coatings 15

by Ben J. Carlozzo
Chapter 3mCellulose Esters 23

by L. G. Curtis
Chapter 4~Drying Oils 26

by Joseph V. Koleske
Chapter 5~Driers and Metallic Soaps 30

by Marvin J. Schnall
PART 3: SYNTHETIC MATERIALS
Chapter 6~Acrylic Polymers as Coatings Binders 39

by John M. Friel
Chapter 7--Alkyd and Polyesters 53

by Al Heitkamp and Don Pellowe
Chapter 8--Amino Resins (Reaction Products of Melamine,

Urea, etc. with Formaldehyde and Alcohols) 60
by J. Owen Santer
Chapter 9mCeramic Coatings 68

by Richard A. Eppler
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CONTENTS
Chapter 10mEpoxy Resins in Coatings 74

by Ronald S. Bauer, Edward J. Marx, and Michael
J. Watkins
Chapter 11 ~Phenolics 79
by John S. Fry
Chapter 12~Polyamides 85
by Robert W. Kight
Chapter 13~Polyurethane Coatings 89

Chapter 14~Silicone Coatings 95

by D. J. Petraitis
Chapter 15mVinyl Resins for Coatings 99

by Richard J. Burns
Chapter 16--Miscellaneous Materials and Coatings 108

PART 4: PLASTICIZERS
Chapter 17~Plasticizers 115

by Peter Tan and Leonard G. Krauskopf
PART 5: SOLVENTS
Chapter 18--Solvents 125

by Stephen A. Yuhas, Jr.
PART 6: PIGMENTS
Chapter 19--White Pigments 159

by Juergen H. Braun
Chapter 20mBlack Pigments 179

by Frank R. SpineUi
Chapter 21mColored Organic Pigments 190

by Peter A. Lewis
Chapter 22~Inorganic Colored Pigments 209

by Peter A. Lewis
Chapter 23~Ceramic Pigments 214

by Richard A. Eppler
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CONTENTS vii
Chapter 24mExtender Pigments 2t7

by Henry P. Ralston
Chapter 25--Metallic Pigments 223

by Russell L. Ferguson
Chapter 26--Pearlescent Pigments 229

by Carl J. Rieger
Chapter 27--Inorganic Anti-Corrosive Pigments 238

by M. Jay Austin
Chapter 28mOil Absorption of Pigments 252

PART 7: ADDITIVES
Chapter 29~Bactericides, Fungicides, and Algicides 261

by Vanja M. King
Chapter 30~Thickeners and Rheology Modifiers 268

by Gregory D. Shay
PART 8: PHYSICAL CHARACTERISTICS OF LIQUID PAINTS

AND COATINGS
Chapter 31ADensity and Specific Gravity 289

by Raymond D. Brockhaus
Chapter 32nParticle-Size Measurements 305

by George D. Mills
Chapter 33ARheology and Viscometry 333

by Richard R. Eley
Chapter 34nSurface Energetics 369

by Gordon P. Bierwagen
Chapter 35~Solubility Parameters 383

by Charles M. Hansen
PART 9: FILMS FOR TESTING
Chapter 36--Cure: The Process and Its Measurement 407

by Thomas J. Miranda
Chapter 37--Film Preparation for Coating Tests 415

by Robert D. Athey, Jr.
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viii CONTENTS
Chapter 38--Measurement of Film Thickness 424

by C. M. Wenzler and J. F. Fletcher
Chapter 39--Drying Time 439

by Thomas J. Sliva
PART 10: OPTICAL PROPERTIES
Chapter 40--Color and Light 447

by Fred W. Billmeyer, Jr. and Harry K. Hammond
III
Chapter 41~Gloss 470

by Harry K. Hammond III and Gabriele Kigle-
Boeckler
Chapter 42~Hiding Power 481

by Leonard Schaeffer
Chapter 43--Mass Color and Tinting Strength of Pigments 507

by Julio I. Aviles
PART 11: PHYSICAL AND MECHANICAL PROPERTIES
Chapter 44--Adhesion 513

by Gordon L. Nelson
Chapter 45--Abrasion Resistance 525

by Mark P. Morse
Chapter 4 6 ~ D y n a m i c Mechanical and Tensile Properties 534

by Loren W. Hill
Chapter 47inFlexibility and Toughness 547

by M. P. Morse
Chapter 48mHardness 555

by Paul R. Guevin, Jr.
Chapter 49mStress Phenomena in Organic Coatings 585

by Dan Y. Perera
Chapter 50mSlip Resistance 600

by Paul R. Guevin, Jr.
PART 12: ENVIRONMENTAL RESISTANCE
Chapter 51--Prevention of Metal Corrosion with Protective

Overlays 609
by William H. Smyrl
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CONTENTS
Chapter 52--Natural Weathering 619
by Lon S. Hicks and Michael J. Crewdson
Chapter 53~Accelerated Weathering 643

by Valerie D. Sherbondy
Chapter 54~Biological Deterioration of Paint Films 654

by David L. Campbell
Chapter 55~Chemical Resistance 662

by Alan H. Brandau
Chapter 56~Testing Coatings for Heat Resistance and Flame

Retardance 667
by Wayne Ellis
Chapter 57--Water-Resistance Testing of Coatings 677

by Wayne Ellis
PART 13: SPECIFIC PRODUCT TESTING
Chapter 58--Aerospace and Aircraft Coatings 683

by Charles R. Hegedus, Stephen J. Spadafora,
David F. Pulley, Anthony T. Eng, and Donald J.
Hirst
Chapter 59~Architectural Coatings 696

by Harry E. Ashton
Chapter 60~Artists' Paints 706

by Benjamin Gavett
Chapter 61--Automative Product Tests 711

by Rose A. Ryntz
Chapter 62--Can Coatings 717

by Martin B. Price
Chapter 63--Masonry 725

by Frances Gale and Thomas Sliva
Chapter 64--Pipeline Coatings 731

by Loren B. OdeU and AI Siegmund
Chapter 65--Sealants 735

by Saul Spindel
Chapter 66--Traffic Marking Materials 741

by Larry R. Hacker
Chapter 67--Water-Repellent Coatings 748

by Victoria Scarborough and Thomas J. Sliva
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x CONTENTS
PART 14: ANALYSIS OF PAINTS AND PAINT DEFECTS
Chapter 68--Analysis of Paint 753

by Darlene Brezinski
Chapter 69--The Analysis of Coatings Failures 767

by George D. Mills
PART 15: INSTRUMENTAL ANALYSIS
Chapter 70--Atomic Absorption, Emission, and Inductively

Coupled Plasma Spectroscopy 783
by Dwight G. Weldon
Chapter 71--Chromatography 789

by Rolando C. Domingo
Chapter 72~Electron Microscopy 815

by John G. Sheehan
Chapter 73~Infrared Spectroscopy 826

by Jack H. Hartshorn
Chapter 74--Methods for Polymer Molecular Weight

Measurement 835
by Thomas M. Schmitt
Chapter 75--Coatings Characterization by Thermal Analysis 841

by C. Michael Neag
Chapter 76~UltravioletNisible Spectroscopy 865

by George D. Mills
Chapter 77--X-Ray Analysis 871

by A. Monroe Snider, Jr.
PART 16: SPECIFICATIONS
Chapter 78--Paint and Coatings Specifications and Other

Standards 891
by Wayne Ellis
Appendix 895
Index 899
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Part I: Regulations
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MNL17-EB/Jun. 1995
Regulation of Volatile Organic

Compound Emissions from 1
Paints and Coatings
by J. John Brezinski I
PRIORTOTHE 1960S the coatings industry enjoyed a somewhat TABLE 1--Federal environmental laws administered by the U.S.
predictable regulatory and economic environment. The paint Environmental protection agency.
formulator developing a solvent-based coating selected sol- Law Abbreviation
vents on the basis of evaporation rate, solubility parameter, Clean Air Act, 1970 CAA
density, flammability, and, of course, cost. There was no ap- Amendments of 1977 CAAA-77
parent need to consider the relative photochemical reactivity Amendments of 1990 CAAA-90
of these materials, nor was there any appreciable incentive to Clean Water Act of 1972 CWA
Amendments of 1977
reduce the solvent content of commercially acceptable coat- Safe Drinking Water Act, 1974 SDWA
ings. Toxic Substances Control Act, 1975 TSCA
It was, of course, recognized that objectionable odors were Resource Conservation and Recovery Act, RCRA
released from some paints and coatings. Further, air emis- 1980
sions resulting from the evaporation of solvents during high- Comprehensive Environmental Response CERCLA
Compensation and Liability Act, 1980 (Superfund)
temperature processing of oils and resins caused occasional Superfund Amendments and Reauthorization SARA
complaints from persons living near the coatings plant. The Act, 1986
prevailing view of this period was summarized by Francis Title III, Emergency Planning and Community SARA, Title
Scofield in his article in the 13th edition of the Paint Testing Right-to-Know, 1986 III
Manual entitled "Atmospheric Pollutants" [1].
These "nuisance" types of pollution are a continuing The discussion in this section will focus on the Clean Air
problem but, in general, can be dealt with by dilution and Act and its amendments that, in the author's opinion, have
dispersion of the objectionable materials to bring the had (and will continue to have) the greatest impact on coat-
concentration below a level that can be detected by the
neighboring citizenry. Fortunately, most of the materials ings.
used by the paint industry are not toxic at concentrations
significantly below the range at which they can be de-
tected by the human nose, and sophisticated analytical
procedures are rarely needed to deal with these "nui-
sance" problems. T H E CLEAN AIR ACT AND ITS
Since the 1960s societal concern about health and the envi- AMENDMENTS
ronment has increased appreciably. Actions taken by federal
and state legislative bodies have resulted in a steady ava- California Smog
lanche of new laws and associated regulations that affect
A precipitating factor influencing the basis for selection of
virtually all industry. Among the new federal laws adminis-
solvents for coatings in the 1960s and early 1970s was the
tered by the U.S. Environmental Protection Agency (EPA)
recognition that the emission of solvents from coatings to the
that impact significantly on the coatings industry are those
atmosphere contributed to the growing "smog" problem in
shown in Table 1. They are designed to control the emission
Southern California. The frequency of smog conditions in
of pollutants to air, to water, and to soil.
this area had increased steadily during the 1950s and 1960s
In addition, among the new federal standards administered
as the number of automobiles, trucks, buses, and airplanes
by the Occupational Safety and Health Administration are
increased and as industrial development expanded with the
those that require manufacturers--including those making
accompanying growth of petroleum and chemical processing
paints and coatings--to evaluate the hazards of products
and power plant utilization.
they make and to provide appropriate safety information to
The smog problem was (and is) most acute in the Los
employees and users through the Material Safety Data Sheet
Angeles air basin, an area uniquely situated in a series of
(MSDS) and product labels.
plains that originate in the high mountains to the east. The
9 Hazard Communication Standard (HCS), 1983 basin enjoys predominantly sunny days with cool moist air
9 Occupational Exposure to Hazardous Chemicals in Labo- flowing with a light westerly wind most of the year. These
ratories, 1990 factors cause a nearly permanent temperature inversion
layer, trapping air emissions that combine to produce a per-
11046 College Circle, St. Albans, WV 25177. sistent eye-irritating smog in the basin.
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Copyright9 1995 by ASTMInternational www.astm.org

In a presentation entitled "Solvent Restriction--Problem reactivity in state, federal, and international programs re-
or Opportunity," Dr. John Gordon, then of the University of lated to air quality control.
Missouri-Rolla, discussed the major sources of hydrocarbons
and nitrogen oxides, which together in the presence of UV
radiation react to produce oxidants and ozone, major compo- VOC Definition
nents of smog [2]. The United States Environmental Protection Agency (EPA)
Sunshine was created in 1970 by Congress as part of a plan to consoli-
HC + NOx UV Radiation Smog (03) date several federal environmental activities. Studies directed
by the EPA laboratories in Research Triangle Park, NC of the
Sources of NOx: Flame of almost any kind, volcanoes, inter- photochemical reactivity of materials in a laboratory smog
nal combustion engines, forest fires, cig- chamber revealed that when organic materials and nitrogen
arettes, boilers, space heaters. oxide were irradiated for periods of up to 36 h, even those
Processes that Produce Hydrocarbons solvents considered acceptable under Rule 66 reacted to form
9 Petroleum production, refining, transport peroxides and ozone. Only a few materials showed negligible
9 Internal combustion engines photochemical reactivity, among which were: methane, eth-
9 Natural processes--forests and plants (isoprene and ter- ane, methylene chloride, 1,1,1-trichloroethane, and fluorin-
penes) ated compounds. These studies, which were prompted in part
9 Surface coatings by the passage of the Clean Air Act of 1970, led to the conclu-
A 1962 estimate of the contaminants discharged into the sion that most organic compounds emitted to the atmosphere
Los Angeles air during the summer period revealed that mo- contribute to the formation of ozone. On this basis, EPA
tor vehicles accounted for about 60%, while the use of or- adopted as a regulatory objective the limit of essentially all
ganic solvents (for all purposes) accounted for about 18% of volatile organic compounds emitted to the atmosphere from
the organic gases. About one half of the organic solvent all sources, including paint and coatings applications [3].
emitted was attributed to the coatings industry, chiefly to the
use in paint and coatings. Approximately 66% of the NOx
released was assigned to gasoline (motor vehicle) combus- Regulatory Definition o f VOC
tion, while the combustion of fuels (energy supply) accounted The regulatory definition of volatile organic compounds
for about 26% [1]. (VOC) was revised by EPA in 1992. A part of this definition is
Based on the results of laboratory studies in "smog cham- as follows:
bers," in which a mixture of a solvent and nitrogen oxide was Section 51.100 Definitions 2
exposed for 6 h to light approximately the intensity of noon
Volatile organic compounds (VOC) means any compound
sunlight, the solvents could be classified as "low" or "high" in of carbon, excluding carbon monoxide, carbon dioxide,
photochemical reactivity related to the amount of peroxides carbonic acid, metallic carbides or carbonates, and am-
and ozone produced. These studies formed the basis for the monium carbonate, which participates in atmospheric
well-known Rule 66, an air pollution control regulation photochemical reactions.
passed by the Los Angeles Air Pollution Control District. Rule (1) This includes any such organic compound other than
66 identifies an "approved" solvent as one that contains less the following, which have been determined to have negli-
than 20% by volume of specific chemicals and is further gible photochemical reactivity: methane; ethane; meth-
limited to certain combinations of these chemicals. Thus, ylene chloride (dichloromethane); 1,1,1-trichloroethane
approved solvents can contain no more than designated (methyl chloroform); 1,1,1-trichloro-2,2,2-trifluoro-
amounts of the combinations shown in Table 2. ethane (CFC-113); trichlorofluoromethane (CFC-11);
In effect, Rule 66 promoted the use of specific solvents such dichlorodifluoromethane (CFC-12); chlorodifluoro-
methane (CFC-22); trifluoromethane (FC-23);
as aliphatic and naphthenic hydrocarbons, alcohols, esters, 1,2-dichloro- 1,1,2,2-tetrafluoroethane (CFC-114);
normal ketones, chlorinated hydrocarbons (except trichloro- chloropentafluoroethane (CFC-115); 1,1,1-trifluoro 2,2-
ethylene), and nitroparaffins. Rule 66, superseded in 1976 by dichloroethane (HCFC-123); 1,1,1,2-tetrafluoroethane
Rule 442, Usage of Solvents, by the California South Coast Air (HF-134a); 1,1-dichloro 1-fluoroethane (HCFC-141b); 1-
Quality Management District, was subsequently adopted by chloro 1,1-difluoroethane (HCFC-142b); 2-chloro-
various other state jurisdictions. Renewed interest has devel- 1,1,1,2-tetrafluoroethane (HCFC- 124); pentafluoro-
oped recently in the consideration of solvent photochemical ethane (HFC-125); 1,1,2,2-tetrafluoroethane (HFC-134);
1,1,1-trifluoroethane (HFC- 143a); 1,1-difluoroethane
(HFC-152a); and perfluorocarbon compounds which fall
TABLE 2--Rule 66--Limits of solvent categories in approved into these classes:
mixtures.*
(i) Cyclic, branched, or linear, completely fluorinated
5% 8% 20% alkanes;
Hydrocarbons, alcohols, Aromatic Ethylbenzene, (ii) Cyclic, branched, or linear, completely fluorinated
aldehydes, e s t e r s , hydrocarbons branched ethers with no unsaturations;
ethers or ketones (W/8 C ketones,
having an olefinic or atoms) toluene, or
cycIoolefinic trichloroethane 240 Code of Federal Regulations (CFR) Part 51; Requirements for
unsaturation Preparation, Adoption and Submittal of Implementation Plans; Ap-
proval and Promulgation of Implementation Plans. FederalRegister,
*Calculated as the percent by volumeof the total solvent. Vol. 57, No. 22, 22 Feb. 1992, pp. 3941-3946.
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CHAPTER 1--REGULATION OF VOC EMISSIONS 5
(iii) Cyclic, branched, or linear, completely fluorinated Control Technique Guidelines

tertiary amines with no unsaturations; and
(iv) Sulfur containing perfluorocarbons with no unsat- In 1977, the Agency issued the first of a series of guidance
urations and with sulfur bonds only to carbon and fluo- documents for the states related to various industrial coating
rine. operations or end-use categories. These documents, called
"Control Technique Guidelines (CTG) Series, Control of Vola-
(2) For purposes of determining compliance with emis-
sions limits. VOC will be measured by the test methods in tile Organic Emissions from Stationery Sources," include rec-
the approved State implementation plan (SIP) or 40 CFR ommended VOC emission limits, based on EPA's assessment
part 60, appendix A, as applicable. Where such a method of Reasonably Available Control Technology (RACT): the lim-
also measures compounds with negligible photochemi- its are expressed as pounds of VOC per gallon of coating
cal reactivity, these neglibflity-reactive compounds may (minus water), as applied.
be excluded as VOC if the amount of such compounds is The Clean Air Act Amendments of 1977 directed that states
accurately quantified and such exclusion is approved by had to revise their implementation plans for areas out of
the enforcement authority. compliance with the national ozone standard. The revised
(3) As a precondition to excluding these compounds as SIPs were to include sufficient control of VOC emissions from
VOC or at any time thereafter, the enforcement authority stationery sources, such controls to incorporate the RACT
may require an owner or operator to provide monitoring limits for coatings operations for which a CTG was pub-
or testing methods and results demonstrating, to the lished.
satisfaction of the enforcement authority, the amount of The CTG documents relating to surface coatings opera-
negligibly-reactive compounds in the source's emissions.
tions issued through 1992 are shown in Table 3 with recom-
(4) For purposes of Federal enforcement for a specific mended limits for VOC content.
source, the EPA will use the test methods specified in the
applicable EPA-approved SIP in a permit issued pursu-
ant to a program approved or promulgated under title V NEW SOURCE PERFORMANCE
of the Act, or under 40 CFR part 5 I, subpart I or appendix
S, or under 40 CFR parts 52 or 60. The EPA will not be
STANDARDS
bound by an State determination as to appropriate meth-
ods for testing or monitoring negligibly-reactive com- The control of VOC emissions from new coatings plants
pounds if such determination is not reflected in any of and from significant modifications of existing plants was
the above provisions. addressed by EPA in a series of New Source Performance
Standards (NSPS), the first of which issued in 1980. These
mandatory standards, which apply uniformly to all parts of
The Ozone Standard the country, define the emission sources more narrowly and
The Clean Air Act of 1970 targeted six criteria pollutants for impose a tighter level of emission control than that for related
control: carbon monoxide, lead, nitrogen dioxide, ozone, par- existing sources. The VOC limits defined in the NSPS, ex-
ticulates, and sulfur dioxide. Criteria pollutants are those for pressed as kilograms of VOC per liter of applied solids, are
which criteria were issued by EPA. These documents include based on the best demonstrated technology (BDT) for the
specific coating operation.
national ambient air quality standards (NAAQS)--levels that
The New Source Performance Standards for surface coat-
protect against adverse effects to health and to plants and
ings operations issued through 1992 are shown in Table 4.
materials [4]. Standards for ozone and nitrogen oxides are:
The emission limits in both the CTG and NSPS documents,
Ozone The ozone concentration in the atmosphere can- in the majority of cases, focus on restricting the VOC content
not exceed 0.12 p p m as a daily m a x i m u m one-hour per unit of coating or of coating solids applied in the opera-
average more than once per year. tion, rather than placing a ceiling on individual plant emis-
Nitrogen Dioxide The nitrogen dioxide concentration in sions. The responsibility for establishing emission limits for
the atmosphere cannot exceed 0.053 particular plants, if appropriate, was left to the states [5].
p p m as the annual arithmetic mean con-
centration.
D E T E R M I N A T I O N OF VOC C O N T E N T
CONTROL OF VOC E M I S S I O N S F R O M Federal Reference Method 24

COATINGS
The procedures specified by the federal EPA for testing
paint products for compliance with VOC limits are described
The Clean Air Act addressed air pollution eminating from
in Federal Reference Method 24 [6]. This standard employs
both existing sources and that from future new plant con-
several ASTM test standards, including those shown in Table
struction or significant modification of existing sources.
5.
States with areas that did not comply with the ozone standard Method D 2369 is a key procedure of Federal Method 24.
were given primary responsibility to develop appropriate reg- Since 1980, several important revisions have been made in
ulations for existing sources to meet the time schedule for this standard to make it compatible with revisions in Method
compliance specified by Congress. The Federal EPA was as- 24, including the addition in 1990 of instructions for testing
signed oversight responsibility for the state programs that multicomponent coatings and the deletion of sections dealing
were described in "State Implementation Plans" (SIP). with testing at shorter times. The revised version of Federal
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TABLE 3--VOC content limits in control technique guidelines (CTG) for surface coating operations.
Allowable Limitsb
Lb VOC/Gal Kg VOC/L
Coatings Operation CTG Date" Minus H20 Minus H20
Appliances, large Dec., 1977 2.8 0.34
Auto and light duty trucks May, 1977 Primer, electrodeposit 1.2 0.14
Prime coat 1.9 0.23
Guidecoat (surfacer) 2.8 0.34
Topcoat 2.8 0.34
Final repair 4.8 0.58
Cans May, 1977 Sheet basecoat 2.8 0.34
Interior body spray 4.2 0.51
Side seam 5.5 0.66
End seal compound 3.7 0.44
Fabric May, 1977 Fabric coating 2.8 0.34
Vinyl coating 3.8 0.45
Graphic arts--rotogravure and Dec., 1978 (Consult CTG or state regulations)
flexography
Magnetic tape See Paper coating
Magnet wire Dec., 1977 (Based on the use of an incinerator) 1.7 0.20
Metal coil May, 1977 Prime and topcoat or single coat 2.6 0.31
Metal furniture Dec., 1977 3.0 0.36
Miscellaneous metal parts and June, 1978 Air dry 3.5 0.42
products
Clear coat 4.3 0.52
Extreme performance 3.5 0.42
Powder coatings 0.4 0.05
All others 3.0 0.36
Paper, film and foil May, 1977 2.9 0.35
Plastic parts for business machines None
Polymeric coatings of supporting None; may be
substrates considered
fabric coating
Pressure sensitive tapes and labels See Paper coating
Vinyl and urethane, flexible Fabric: May 1977 Vinyl 3.8 0.45
and/or Graphic
Arts Packaging
Rotogravure,
Dec. 1978
Wood paneling, flat June, 1978 Printed interior panels: 6.0 lb/1000
sq. fl of surface coated
Natural finish plywood: 12.0 lb/
1000 sq. ft of surface coated
Class II finishes 10.0 lb/1000 sq. ft
of surface coated
NOTE:The information presented in this table is not complete. Persons subject to emission control for any of the operations are advisedto consult the state/local
regulations for details.
aCTG documents are available from the National Technical Information Service, 5285 Port Royal Road, Springfield,VA 22161.
bReasonably available control technology (RACT)limits recommended in CTG and, in most cases, adopted in state/local regulations.
Reference M e t h o d 24 is also included in the ASTM Manual on Weight % total volatiles

Determination o f Volatile Organic Compound (VOC) Content less w a t e r less | (Density of coating)
in Paints, Inks, and Related Coating Products, 2nd ed., 1993 e x e m p t solvent ]
VOC =
[7]. (Volume% 1 _ ( Volume% 1
Substantial revisions during 1989-1991 were also m a d e in 100% - \ w at er ] \ e x e m p t solvent]
ASTM D 3960, Practice for D e t e r m i n i n g Volatile Organic or
C o m p o u n d (VOC) Content of Paints and Related Coatings, a voc - (Wo)(Oc)
standard developed in ASTM S u b c o m m i t t e e D01.21 to pro- 100% - Vw - vex
vide a guide for the calculation of VOC and to establish a base (W~ - W~ - W~x)(Dr (1)
for the investigation in ASTM of the precision of VOC co n t en t 100%- (Ww)(Dc/D~)- (W~)(D~/Dr
determination. The definitions a n d symbols used in D 3960 where
are those ad o p t ed by the EPA and included in the Agency
VOC = VOC co n t en t in g/L of coating less w a t e r and ex-
d o c u m e n t "Procedures for Certifying Quantity of Volatile Or- e m p t solvent,
ganic C o m p o u n d s E m i t t e d by Paint, Ink a n d Other Coatings" 141o = weight % of organic volatiles = Wv - Ww - Wex,
that was published in 1984 [8]. Wu = weight % of total volatiles = (100% - weight %
The general expression for calculating VOC c o n t e n t in nonvolatiles), (ASTM D 2369),
gr a m s p er liter of coating less w a t e r and e x e m p t solvent Ww = weight % of w at er (ASTM D 3792 or ASTM D
specified in the EPA Control T e c h n i q u e Guidelines issued 4017),
t h r o u g h 1991 is: 14~x = weight % of e x e m p t solvent (ASTM D 4457),
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CHAPTER 1--REGULATION OF VOC EMISSIONS 7
TABLE 4 - - V O C limits in New Source Performance (NSPS) for surface coatings operations.
Allowable Limitsb
Lb VOC/Gal Kg VOC/L
Coatings Operation NSPS Date~ Applied Solids Applied Solids
Appliances, large Oct.,1982 7.5 0.90
Auto and light duty trucks Dec., 1980 Prime coat
1.3 0.16
Guide coat
11.7 1.40
Top coat
12.2 1.47
Cans (beverage cans only) Aug.,1983 Exterior base
2.4 0.29
Clear base coat
3.8 0.46
Inside spray
7.4 0.89
Fabric (coating) See Polymeric
coating of
supporting
substrate
Graphic a r t s - - r o t o g r a v u r e and Rotogravure only Consult NSPS d o c u m e n t
flexography Nov., 1982
Magnetic tape Oct,, 1988 1.7 0.2
Consult NSPS
Magnet wire None . . . . . .
Metal coil Nov., 1982 w/o emission control device
2.3 0.28
With emission control device
1.2 0.15
Metal furniture Oct., 1982; Apr., 1985 7.5 0.90
Miscellaneous metal parts and None . . . . . .
products
Plastic parts for business machines Jan., 1988 Prime a n d color coat
12.52 1.5
Texture and touch-up
19,2 2.3
Polymeric coatings of supporting Sept., 1989 90% control from process:
substrates Consult NSPS
Pressure sensitive tapes Oct., 1983 1.67 0.20
Vinyl and urethane, flexible June, 1984 8.3 1.0
Wood paneling, flat None . . . . . .
NOTE: The information presented in this table is not complete. Persons subject to emission control for any of the operations are adv/sed to consult the specific
language of the referenced documents and state and local regulations.
~NSPS documents are available from the National Technical Information Service (NTIS), 5285 Port Royal Road, Springfield, VA 22161.
bBest demonstrated technology (BDT) emission limits established as NSPS standards. In the NSPS, the limits are expressed as kilograms of VOC per liter of
applied solids.
Vw = volume % o f w a t e r -- (Ww)(Dc/Dw),
TABLE 5 - - A S T M standards referenced in Federal Reference Vex = volume % of e x e m p t s o l v e n t = (Wex)(Dc/Dex),
Method 24. Dc = density o f c o a t i n g a t 25~ i n g/L ( A S T M D 1475),
ASTM Method Test Method f o r - Dw = density o f w a t e r a t 25~ i n g/L -- 0 . 9 9 7 103, a n d
D,x = density of e x e m p t s o l v e n t a t 25~ i n g/L ( A S T M D
D 2369-81 Volatile Content of Coatings
1475).
D 1475-60 Density of Paint, Varnish, Lacquer, and T o c o n v e r t f r o m g/L t o lb/gal, m u l t i p l y t h e r e s u l t (VOC
Related Products
c o n t e n t ) b y 8.345 10 -3 (lb/gal)/g/L). T o c o n v e r t g/L t o kg/L,
D 3792-79 Water Content of Waterborne Paints by d i v i d e t h e r e s u l t b y 10 a.
Direct Injection into a Gas The general expression for VOC content defined in terms of
Chromatograph the mass of VOC per unit volume of coating solids applied as
D 4017-81 Water in Paints and Paint Materials by Karl s p e c i f i e d i n t h e E P A N e w S o u r c e P e r f o r m a n c e S t a n d a r d s is
Fischer Method
( W , - Ww - We~)Dc
VOCm = (2)
D 4457-85 Analysis of Dichloromethane a n d 1,1,1- v.
Trichloroethane in Paints and Coatings by
Direct Injection into a Gas where
Chromatograph
V O C m = V O C c o n t e n t i n g/L o f c o a t i n g solids, a n d
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V, = Volume % nonvolatile content of the liquid coat- Blends Used in Masonry Water-Repellent Treat-
ing, ASTM D 2697. 3 ments. 4
The EPA would have preferred to limit volatile organic In this standard, a catalyst is added prior to the bake cycle
compound emissions in the Control Technique Guidelines on to simulate the catalytic effect provided by masonry during
the basis of the unit volume of coating solids applied. The actual application of the water-repellent treatment.
adoption in the 1970s of Eq 1, in which VOC content is
defined as mass per unit volume of coating less water and less
Aerosol Spray Paints
exempt solvents, was necessary as no acceptable consensus
procedure was available for determining the volume percent 9 D 5200 Test Method for Determination of Weight Percent
nonvolatile content. In a presentation in Copenhagen in 1990, Volatile Content of Solvent-borne Paints in Aerosol
James C. Berry of U.S. EPA stated: "Though certainly less Cans
than ideal, the major attraction is that the expression permits 9 D 5325 Test Method for the Determination of Weight Per-
the determination of compliance from the analysis of a coat- cent Volatile Content of Water-borne Aerosol Paints
ing sample obtained during a plant inspection. In the sim- These standards were developed for potential use related to
plest case, these units require only one volumetric and one proposed regulations in California to limit the level of volatile
gravimetric measurement" [5]. organic material in aerosol paints.
Studies and discussions in ASTM Subcommittee D01.21
that led to the modification and improvements of ASTM
standards referenced in Federal Method 24 and in ASTM General Application Standards
Practice D 3960 were conducted with the cooperation of EPA 9 D 5201 Practice for Calculating Formulation Physical Con-
personnel of the Office of Air Quality Standards Development stants of Liquid Paints and Coatings
at Research Triangle Park, NC.
The calculation of various physical constants directly from
the paint formulation is a common practice in industry.
OTHER VOC-RELATED METHODS AND ASTM D 5201 describes procedures for the calculation of
STUDIES formulation weight solids, volume solids, solvent content,
and density of liquid paint based on formulation data (not
ASTM development activity on other VOC-related stan- analytical laboratory determinations). The values obtained
dards has expanded significantly since 1980. Many of the may not be acceptable for demonstrating regulatory compli-
standards listed in this section have not been approved by the ance.
Federal EPA for use in demonstration of compliance with 9 D 5286Test Method for Determination of Transfer Effi-
VOC emission control regulations. Use of any of these stan- ciency Under General Production Conditions for
dards to demonstrate compliance should be coordinated with Spray Application of Paints
appropriate regulatory agencies. Among the new standards This standard, a modification of Practice D 5066 developed
developed or in process of development are the following: for use in the automobile industry, describes conditions for
determining transfer efficiency under production conditions
S t a n d a r d s Specific to t h e A u t o m o b i l e I n d u s t r y applicable to spray application of miscellaneous parts.
9 D 5327 Practice for Evaluating and Comparing Transfer Ef-
9 D 5087 Test Method for Determining the Amount of Vola- ficiency under General Laboratory Conditions
tile Organic Compounds (VOC) Released from Sol-
Practice D 5327 provides a useful guide for general re-
vent-Borne Automotive Coatings and Available for
search studies related to transfer efficiency. The general
Removal in a VOC Control Device (Abatement)
approach employed is derived from that developed in Method
9 D 5066 Practice for the Determination of the Transfer Effi-
D 5009 except that D 5327 employs a fixed rather than moving
ciency Under Production Conditions for Spray Ap-
plication of Automotive Paints--Weight Basis spray station.
9 D 5009 Test Method for Evaluating and Comparing Tran- 9 Revision of D 2697, Test Method for Volume Nonvolatile
sfer Efficiency Under Laboratory Conditions Matter in Clear or Pigmented Coatings: Use of the Helium
These standards were developed with the cooperation of Gas Pycnometer (Under Study)
representatives from automotive coating suppliers and the The use of the helium gas pycnometer provides a quick,
Motor Vehicle Manufacturers Association. Method D 5009 reliable approach to the determination of the dry coating
was derived from a study of transfer efficiency conducted for density, a critical parameter in the calculation of volume
the U.S. Environmental Protection Agency [9]. percent nonvolatile content.
9 Direct Measurement of Volatile Organic Material in Water-
Reducible Coatings (Under Study)
Masonry Treatments
Federal EPA funds supported the preliminary investigation
9 D 5095 Test Method for Determination of the Nonvolatile of this novel approach to the "direct" gravimetric determina-
Content in Silanes, Siloxanesl and Silane-Siloxane
4This standard has been accepted by the Federal EPA for use in the
3EPAReference Method 24 does not include an analytical method determination of the VOC of silane- and siloxane-based coatings:
for determining V~, but states that the value be calculated from the Letter, Gary McAllister, EPA, to H. Smith, NJ Dept. of Environmental
coating manufacturer's formulation. Protection, 25 March 1992.
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CHAPTER 1 - - R E G U L A T I O N OF VOC E M I S S I O N S 9
tion of volatile organic content of waterborne coatings [10]. tants; reduction of acid rain; and the protection of ozone in
The method involves collecting, on activated charcoal in the stratosphere.
weighed tubes, the organic effluent evolved on heating a paint Features of the Act that will impact most on the coatings
specimen for 1 h at 110~ while purging the reaction vessel industry include:
with dry nitrogen. Methanol is not captured on the charcoal.
9 D 5403 Test Method for Volatile Content of Radiation Cur-
able Materials Title I m O z o n e Control in the Atmosphere
The test methods in D 5403 determine the weight percent Title I specifically directs EPA to develop control technique
volatile content of paint, coatings, and inks that are designed guidelines and maximum achievable control technology
to be cured by exposure to ultraviolet light or to a beam of (MACT) standards for aerospace coatings and for shipbuild-
accelerated electrons. After radiation cure, the specimens are ing coatings and repair. EPA was also directed to prepare new
baked at 110 + 5~ for 60 min. control technique guidelines for additional coatings uses that
include:
Inks 9 autobody refinishing
9 plastic parts (business machines)
9 D 5328Volatile Organic Compound (VOC40) Content of 9 plastic parts (others)
Non-Heatset Paste Printing Ink Systems at 40~ 9 offset lithography
This standard is patterned, in part, after Method 30 of 9 wood furniture
California's Bay Area Air Pollution Control District in which In addition, EPA plans to promulgate national rules to
the specimen is baked for 1 h at 40~ D 5328 is applicable to control VOC emissions from architectural and industrial
paste printing inks and vehicles that dry primarily by absorp- maintenance coatings and from traffic paints. Solvent emis-
tion, polymerization, or related means without the applica- sion from consumer and commercial products, including
tion of heat. that from aerosols, are currently under study, and regulation
of this broad category of products is planned. In the develop-
ment of these rules, negotiated rulemaking may be employed,
Supplementary Information a process bringing together representatives of EPA, industry,
Further information about the development, significance, the states, and environmentalist groups to negotiate the con-
and limitations of these VOC-related ASTM standards as well tent of a proposed rule.
as about the use of ASTM standards for the demonstration of In CAAA-90, ozone nonattainment areas are placed in five
compliance with VOC emission control regulations is avail- classifications based on the mid-1991 ozone level (Table 6),
able in the ASTM Manual on Determination of Volatile Or- and compliance with the national ozone standard by specific
ganic Compounds in Paints, Inks, and Related Coating years is mandated in the law.
Products [7]. Attachments in the second edition of this man- Increasingly strict provisions, including further reduction
ual include the 1992 revision of Federal Reference Number of VOC emissions, will be imposed on areas, the magnitude to
24 and a publication from EPA's Emission Standards Divi- be related to the severity of the ozone problem. Depending on
sion titled "Procedure for Certifying Quantity of Volatile Or- the area classification, several or all of the following will be
ganic Compounds Emitted by Paint, Ink and Other Coatings" required:
[8]. Included in the latter publication are "VOC Data Sheets" 9 Increased monitoring and more accurate VOC and N O 2
applicable to coatings "as supplied" by the manufacturer and emission inventory
for coatings "as applied" by the user. The form used for "as 9 Revision of state implementation plans to incorporate
supplied" coatings is patterned after a recommendation of RACT limits from previous and future CTGs for all major
the National Paint and Coatings Association. stationery sources
9 New source review and permits for new or modified sta-
tionery sources
9 Reduced emission threshold levels for the definition of
CLEAN AIR ACT A M E N D M E N T S OF 1 9 9 0 major stationery sources, ranging between 10 tons/year for
severe classification areas to I00 for marginal or moderate
The Clean Air Act Amendments of 1990 defined a compre-
areas
hensive long-term approach "to achieve and maintain a
healthy environment while supporting a strong and sus-
tainable economic growth and sound energy policy.''s A TABLE 6--Clean air act amendments--1990 ozone
nonattainment area classifications.
major impetus for these amendments was the continued in-
ability of a number of heavily populated urban areas to meet Years to Achieve
Design Value Compliance,
the requirements of the national ambient air quality stan- Classification (Ozone Level) year
dards for ozone and carbon monoxide.
Marginal 0.121-0.138 3 (1993)
Among the specific issues addressed in the Act are: control Moderate 0.138-0.160 6 (1996)
of ozone in the atmosphere; control of hazardous air pollu- Serious 0.160-0.180 9 (1999)
Severe 0.180-0.280 15 (2005)
Extreme~ 0.280 and above 20 (2010)
5U.S. EPA Office of Air and Radiation, "Implementation Principles
for the Clean Air Amendments of 1990." ~Onlythe Los Angelesarea is in this classification.
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9 Higher VOC emission offset r e q u i r e m e n t s for new or modi- of 1995 sufficient categories a n d subcategories m u s t be listed
fied sources to ensure that 90% of the area sources that emit the 30 most
hazardous air pollutants are subjected to regulation.
Title III--Air Toxics Program

Title V - - S t a t e Operating Permit Program
U n d e r Title III, EPA is directed to evaluate a n d control the
emission of hazardous air pollutants (HAPS). 189 products The state operating p e r m i t p r o g r a m is considered by EPA
are identified in the Act, a n d EPA has the authority to delete as a cornerstone of the CAAA-90 a m e n d m e n t s designed to
or add additional products to this list. I n d u s t r y groups m a y ensure that the ozone n o n a t t a i n m e n t areas meet compliance
petition EPA to delist products. deadlines. This p r o g r a m will impact o n m a n y previously un-
Among the materials included o n the initial HAP list that regulated coatings m a n u f a c t u r e r s a n d users. The final rule
are used in paints a n d coatings are those shown in Table 7. re the operating p e r m i t p r o g r a m was issued in 1992
The control of emissions of hazardous air pollutants is to (57FR32250, 21 July 1992).
be achieved t h r o u g h the p r o m u l g a t i o n of emission standards The operating permit p r o g r a m has been called the "air
for source categories a n d subcategories that emit these prod- pollution equivalent" of the NPDES permit p r o g r a m of the
ucts. The initial list of categories of sources published by EPA Clean Water Act, u n d e r which operating permits are required
(57FR31576, 16 July 1992) included u n d e r Surface Coating of sources that discharge pollutants to water. I n the p r o g r a m
Processes those processes for which a CTG or n a t i o n a l rule u n d e r Title V, all federal a n d state air pollution rules a n d
has b e e n issued or is planned. Also included is the Manufac- regulations will be consolidated u n d e r a single d o c u m e n t
ture of Paints, Coatings and Adhesives. A draft timetable for wherein the states are given authority to m o n i t o r a n d enforce
regulating the categories of sources of hazardous air pollu- the regulations. Sufficient funds will be available to the states
tants was published by EPA in 1992 (57FR44147, 24 Sept. from a m i n i m u m a n n u a l fee of $25 per ton for each regulated
1992). By the end of 1994 emission standards were due for pollutant emitted, the fee to be assessed against all m a j o r
the following surface coating processes: magnetic tapes, sources.
printing/publishing, shipbuilding a n d ship repair, a n d wood Major sources required to have state operating permits in-
furniture. clude those that emit 10 tons or more per year of a single
The Agency was required to p u b l i s h emission limits based regulated hazardous air pollutant or 25 tons per year of a
o n m a x i m u m achievable control technology (MACT) for 40 of c o m b i n a t i o n of hazardous air pollutants. These pollutants
these categories by the end of 1992, with MACT limits to be include those materials for which a n a t i o n a l emission stan-
identified for the r e m a i n i n g categories by 2000. The Act di- dard (NESHAP) has been established. Under Title V of
rects that the health impact a n d economic factors he consid- CAAA-90, a n d the final rule on operating p e r m i t programs,
ered in defining appropriate MACT limits. Further, by the end EPA is to approve (or disapprove) state permit programs
w i t h i n one year of receipt; the m a j o r sources m u s t apply for
TABLE 7--Clean air act amendments--1990 selected hazardous the five-year p e r m i t within one year of the EPA's approval of
air pollutants used in paints and coatings. the state program, a n d all permits m u s t be issued a n d be
ORGANICMATERIALS legally b i n d i n g by the e n d of 1997. U n d e r the rule, states have
Bis (2-ethylhexyl phthalate) the option of exempting all n o n m a j o r sources, with some
Dibutyl phthalate exceptions, from requiring a permit for five years after the
Diethanolamine state p e r m i t p r o g r a m is approved by EPA.
Dimethyl formamide
Dimethyl phthalate The characterization of a m a j o r source in ozone non-
Ethylene glycol a t t a i n m e n t areas is also based o n the a m o u n t of volatile
Formaldehyde organic c o m p o u n d s emitted annually. The threshold a m o u n t
Glycol ethers (ethylene oxide-based) is related to the area classification a n d sources in ozone
Methanol n o n a t t a i n m e n t areas that emit above the designated a m o u n t
1,1,1-trichloroethane (methyl chloroform)~
Methylene chloride~ of VOC shown in Table 8 are identified as m a j o r sources.
Methyl ethyl ketonea These limits vary between 10 tons/year for the "extreme"
Methyl isobutyl ketone~ classification to 100 tons/year for the "marginal or moderate"
2-nitropropane classification.
Styrene
Toluenea For ozone transport regions (e.g., one is established in the
Xylenes~ Northeast), a threshold limit of 50 tons/year of VOC emission
applies.
INORGANICANDOTHER
Ammonia
Antimony compounds TABLE 8--Clean air act amendments--1990 major source
Cadmium compounds~ identification based on VOC emissions: limits for area
Chromium compoundsa classifications.
Cobalt compounds Ozone Nonattainment VOC Emission Limit,
Lead compounds~ Area Classification tons/year
Mercury compounds~
Marginal or moderate 100
~Materials included in the EPA/Industry33/50 Project, a voluntaryindustry Serious 50
initiative to reduce the total release and transfer of 17 targeted chemicals by Severe 25
one third by the end of 1992and by one half by the end of 1995 (using 1988as a Extreme 10
baseline year).
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CHAPTER 1 - - R E G U L A T I O N OF VOC E M I S S I O N S 11
TABLE 9--Code of federal regulations subchapter topics. Title VI--Stratospheric Ozone Protection
Subehapter Subject Parts
The m o s t significant feature of the p r o g r a m to protect
C Air Programs 50-87 ozone in the s t r a t o s p h e r e is the staged p h a s e o u t of 1,1,1-
New Source Performance Standards 60 trichloroethane, a m a t e r i a l widely used in coatings a n d clas-
D Water Programs 104-149
I Solid Waste 240-281 sified as a "VOC-exempt" solvent by the EPA. P r o d u c t i o n (and
J Superfund/Right-to-Know 300- 372 use) will be r e d u c e d in i n c r e m e n t s (from the 1989 a m o u n t )
N Effluent Guidelines and Standards 401-471 b e g i n n i n g in 1993 to a 50% level for the p e r i o d 1996-1999,
R Toxic Substances Control Act 700-799 t h e n to the 20% level for the p e r i o d 2000-2001, after w h i c h
the use of the m a t e r i a l will be prohibited.
TABLE 10--Control technique guidelines and surface coating Title VII--Enforcement

operations reference documents.
EPA is g r a n t e d b r o a d n e w a u t h o r i t y to i m p o s e penalties
EPA Document Reference Coating Operation a n d substantial fines for various actions including: violations
EPA-450/2-77-008 Vol. II Auto and light duty trucks of the State I m p l e m e n t a t i o n Plan; violation of s o m e of the
Cans o p e r a t i n g p e r m i t provisions; a n d false s t a t e m e n t s in records,
Fabric m o n i t o r i n g data, a n d reports. Also i n c l u d e d are provisions
Metal Coil
Paper, film, and foil for field citations b y inspectors.
EPA-450/2-77-032 Vol. III Metal furniture
EPA-450/2-77-033 Vol. IV Magnet wire Scenario for the 1990s
EPA-450/2-77-034 Vol. V Appliances, large CAAA-90 a n d the m y r i a d of n e w federal a n d state regula-
EPA-450/2-78-015 Vol. VI Miscellaneous metal parts and
products tions associated with i m p l e m e n t a t i o n of this c o m p r e h e n s i v e
EPA-450/2-78-032 Vol. VII Wood paneling, flat law that will issue d u r i n g the 1990s will have a m a j o r i m p a c t
EPA-450/2-78-033 Vol. VIII Graphic arts--rotogravure and on the coatings industry. A m o n g the m a n y u n c e r t a i n t i e s are
flexography the n a t u r e a n d level of MACT limits to be defined for essen-
Vinyl and urethane, flexible
tially all coating operations; the level of new o r stricter VOC
TABLE I 1--Regional offices, U.S. Environmental Protection Agency.

Region States Address
Connecticut, Maine, Massachusetts, J. F. Kennedy Federal Bldg.
New Hampshire, Rhode Island, Room 2203,
Vermont Boston, MA 02203
Phone (617) 565-3715
New Jersey, New York, Puerto Rico, 26 Federal Plaza
Virgin Islands New York. NY 10278
Phone (212) 264-2515
Delaware, Maryland, Pennsylvania, Virginia, 841 Chestnut St,
West Virginia, District of Philadelphia, PA 19107
Columbia Phone (800) 438-2474
Alabama, Florida, Georgia, Kentucky, 345 Courtland St. NE
Mississippi, North Carolina, South Atlanta, GA 30365
Carolina, Tennessee Phone (800) 282-0239 in GA
(800) 241-1754 in other Region 4 states
Illinois, Indiana, Michigan, 230 S. Dearborn St.
Minnesota, Ohio, Wisconsin Chicago, IL 60604
Phone (800) 572-2515 in IL
(800) 621-8431 in other Region 5 states
Arkansas, Louisiana, New Mexico, 1445 Ross Ave.
Oklahoma, Texas 12th Floor, Suite 1200
Dallas, TX 75202
Phone (214) 655-2200
Iowa, Kansas, Missouri, Nebraska 726 Minnesota Ave.
Kansas City, KS 66101
Phone (913) 236-2803
Colorado, Montana, North Dakota, 999 18th St.
South Dakota, Utah, Wyoming Suite 500
Denver, CO 80202
Phone (800) 759-4372
American Somoa, Arizona, Nevada, 215 Fremont St.
Hawaii, Guam, California San Francisco, CA 94105
Phone (415) 974-8076
10 Alaska, Idaho, Oregon, Washington 1200 6th Ave.
Seattle, WA 98101
Phone (206) 442-5810
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e m i s s i o n limits for coating operations; a n d the time, U.S. EPA regional offices o r to the specific state regulating
m a n p o w e r , a n d cost a s s o c i a t e d with c o m p l y i n g with the b o d y responsible for air quality control.
m a n y new regulations a s s o c i a t e d with the a m e n d m e n t s . The U.S. E n v i r o n m e n t a l Protection Agency has established
As did the decades of the 1970s a n d 1980s, the 1990s will ten regional offices, each responsible for several states (Table
pose a c o n t i n u i n g challenge to r a w m a t e r i a l suppliers to de- 11).
velop a n d provide e n v i r o n m e n t a l l y acceptable m a t e r i a l s as A m o n g the i n d u s t r y o r g a n i z a t i o n s that provide informa-
well as to p a i n t f o r m u l a t o r s to develop new o r modified tion to their m e m b e r s h i p a b o u t p e n d i n g regulations a n d
coatings with r e d u c e d VOC content. Additionally, i n c r e a s e d g u i d a n c e on c o m p l i a n c e with finalized regulations are Chem-
attention to the i m p r o v e m e n t of coating processes a n d to the ical M a n u f a c t u r e r s Association (CMA), N a t i o n a l Paint a n d
use of a b a t e m e n t e q u i p m e n t for e m i s s i o n control d u r i n g the Coatings Association (NPCA), Dry Colour M a n u f a c t u r e r ' s As-
a p p l i c a t i o n of coatings is expected. sociation (DCMA), a n d Chemical Specialty M a n u f a c t u r e r s
Association (CSMA). Several coatings j o u r n a l s p u b l i s h ex-
cerpts from regulations a n d s u m m a r y reviews.
REGULATION INFORMATION
REFERENCES
Published Sources
F e d e r a l e n v i r o n m e n t a l regulations, including those pro- [1] Scofield, F. in Paint Testing Manual, 13th ed., American Society
m u l g a t e d u n d e r the Clean Air Act, are p u b l i s h e d in the Code for Testing and Materials, Philadelphia, 1972, p. 413.
of Federal Regulations (CFR), a series of b o o k s that are gener- [2] Gordon, J., "Solvent Restriction, Problem or Opportunity," pre-
ally available in m a j o r libraries a n d law libraries. These regu- sentation to the Chicago Coatings Society, 13 Nov. 1978.
[3] EPA Policy Statement, Recommended Policy on Control of Vol-
lations as well as those of related state a n d local codes are
atile Organic Compounds, FederalRegister, 8 July 1977.
also o b t a i n a b l e from the associated r e g u l a t o r y offices. [4] "Glossary for Air Pollution Control of Industrial Coating
Regulations of p a r t i c u l a r interest to the coatings i n d u s t r y Operations," EPA-450/3-83-013R, Environmental Protection
can be found in s u b c h a p t e r s of the Code of Federal Regula- Agency, Washington, DC, December 1983.
tions (Table 9). [5] Berry, J. C., U.S. EPA, "Control of Volatile Organic Compound
The F e d e r a l Control Technique Guidelines for coating op- (VOC) Emissions from Painting Operations in the United
erations are not included in the CFR, b u t are available from States," presentation at the International Symposium on Paint
the National Technical I n f o r m a t i o n Service (NTIS), 5285 and the Environment, Copenhagen, 12-14 Nov. 1990.
Port Royal Road, Springfield, VA 22161. CTG d o c u m e n t s [6] Code of Federal Regulations, Vol. 40, Subchapter C., Part 60,
t h r o u g h 1991 are i n c l u d e d in the EPA p u b l i c a t i o n s listed in Appendix A; Amendments in a Rule published in the Federal
Register, Vol. 57, No. 133, 10 July 1992, pp. 30654-30656.
Table 10.
[7] Manual on Determination of Volatile Organic Compounds in
P r o p o s e d regulations are p u b l i s h e d by the EPA in the Fed- Paints, Inks, and Related Coating Products, ASTM Manual Series,
eral Register. Typically, a p u b l i c (written) c o m m e n t p e r i o d of MNL4, 1989, 2nd ed., 1993.
30 to 90 days on the p r o p o s a l s is allowed, a n d often a public [8] Procedures for Certifying Quantity of Volatile Organic Com-
h e a r i n g is s c h e d u l e d at w h i c h oral c o m m e n t s can be pre- pounds Emitted by Paint, Ink and Other Coatings, EPA-450/3-84-
sented. The c o m m e n t s received are c o n s i d e r e d by the Agency 019, Environmental Protection Agency, Washington, DC, De-
in the d e v e l o p m e n t of a final regulation that is p u b l i s h e d in cember 1984.
the Federal Register together with the r e g u l a t i o n c o m p l i a n c e [9] Development of Proposed Standard Test Method for Spray Paint-
date. ing TransferEfficiency, Vols. I and II, EPA Publication Nos. EPA-
600/2-88-026a and EPA-600/2-88-026b, Environmental Protec-
tion Agency, Research Triangle Park, NC.
Information S o u r c e s [10] Method Development for Measuring the VOC Content of Water-
Based Coatings, EPA Contract No. 68D90055, Work Assign-
Questions relating to the interpretation, applicability, a n d ments No. 28 and 40, Environmental Protection Agency, Re-
c o m p l i a n c e to air quality regulations m a y be a d d r e s s e d to the search Triangle Park, NC.
www.iran-mavad.com

Part 2: Naturally Occurring Materials
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MNL17-EB/Jun. 1995
Bituminous Coatings
by Ben J. Carlozzo 1
INTRODUCTION Most of this material was competing with foreign imports

from the Lake Trinidad region on the Isle of Trinidad off the
General Overview north coast of South America. In the early 20th century,
IN THE UNITED STATES,the terms "bituminous" and "asphal- Mexican asphalt obtained from Mexican crude oil was used
tic" are often used interchangeably. In Europe, bitumen re- extensively in the eastern United States and gained a reputa-
fers to the mixture of heavy hydrocarbons, free of inorganic tion as a high-grade standard paving bitumen.
impurities. Asphalt is often considered the impure form of Today, asphalts are found throughout the world in several
the generic material [1]. For our purposes, the ASTM defini- natural deposits of soft bituminous material or as hard,
tions will be used. glassy, black bitumen associated with certain rock forma-
ASTM Definitions of Terms Relating to Roofing, Water- tions or impregnating various limestone or sandstone-type
proofing, and Bituminous Materials (D 1079-87a) [2] defines formations. Additionally, asphalts are derived from colloi-
bitumen as either "...(1) a class of amorphous black or dark dally dispersed asphalt hydrocarbons in crude petroleum.
colored (solid, semi-solid, or viscous) cementitious sub- This leads to the classification of bitumens into two classes:
stances, natural or manufactured, composed principally of (1) natural asphalts (bitumens) and (2) artificial or oil as-
high molecular weight hydrocarbons, soluble in carbon disul- phalts (petroleum asphalts).
fide, and found in asphalts, tars, pitches and asphaltites; or, The purity of bituminous materials is generally related to
(2) a generic term used to denote any material composed the degree that they are soluble in certain organic solvents.
principally of bitumen." For years, the degree of solubility in carbon disulfide (CS2)
Asphalt is similarly defined as " . . . a dark brown to black has been a typical method for determining the purity of
cementitious material in which the predominating constitu- natural asphalts. ASTM Test Method for Bitumen Content
ents are bitumens which occur in nature or are obtained in (D 4-86) formalizes this procedure with CS2 solubility as the
petroleum processing." While the term has historically im- primary screening test. Most oil asphalts are generally greater
plied the natural deposits (the Trinidad Lake asphalts on the than 99% soluble in CS2.
Island of Trinidad or the Bermudez Lake, Venezuela as- The natural asphalts can be further classified by the geo-
phalts), most asphalt used in the United States today for graphical region of their origin, as well as the extent to which
coatings applications i s from petroleum processing [3]. impurities are present, for example, Trinidad, refined, of ap-
proximately 50 to 57% bitumen; Cuban, refined, of 80 to 90%
purity; Bermudez, refined, of 85 to 92% purity; and various
rock asphalts, i.e., limestone, sandstone, tar sands, etc., with
History and Background of Bitumens varying degrees of bitumen content.
As one of man's oldest engineering materials, the adhesive A separate class of natural bitumens are the asphaltites.
and waterproofing properties of bitumen have been known These are also called the solid bitumens and are asphalts
since the earliest days of civilization. The area between the without impurities (silts, clays, salts, etc.), although their
Tigris and Euphrates rivers in Iraq, long believed to be "the degree of CS2 solubility varies. Examples of these materials
cradle of civilization," contains the earliest deposits of as- are Gilsonite, grahamite, glance pitch, or manjak, as well as
phalt and heavy liquid petroleum. Early historical and bibli- harder materials that show no softening point, such as the
cal accounts tell of the use of asphalt in shipbuilding and pyrobitumens. The most important of these for coatings ap-
foundation mortars. The Egyptians were known to have used plications is Gilsonite.
asphalt in the mummification process; in fact, the part-Per- Artificial bitumens have been classified into three major
sian word for asphalt, "mumiya," is where our word groups [5]:
"mummy" is derived [4]. 1. Oil or petroleum asphalts are soft to hard asphalts of high
The first asphalts produced in the United States were de- solubility in carbon disulfide (more than 99%) and are
rived from California crude oils in the late 19th century. A classed as pure bitumens. They are obtained from the vac-
straight run distillation, often without steam, was able to u u m or steam distillation of crude oils containing high
produce a good-quality material suitable for paving work. asphalt content. The distillation concentrates the colloi-
dally dispersed asphalt into the "still bottoms" or "re-
1Mameco International, Inc., Cleveland, OH. siduum" and is often a solid material.
15
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Copyright9 1995 by ASTM International www.astm.org

Precipitation methods are also used to recover asphalt Specialty Paints and Coatings
from raw lubricating oils. This de-asphalting operation uses Asphalt, coal tar, and other bitumens have been used in
propane or other low-boiling hydrocarbons. The materials several specialty areas in the paint and coatings industry. The
produced are the so-called asphaltic resins, with the hard, predominate use has been in the area of pipe coatings and
high asphaltene asphalts as the precipitate. Variations are automotive under-body coatings, although containment
made by controlling the propane stream. coatings are fast becoming a sizable market.
Oxidized or "blown" asphalts are obtained by blowing air at In pipe coatings, the base bitumen forms an inter-penetrat-
high temperatures through soft or liquid petroleum residues. ing network with a thermosetting resin to form an impervi-
This procedure can take semi-asphaltic materials of low pu- ous barrier to groundwater and the effects of catastrophic
rity and produce considerable amounts of bitumen. The re- rusting. On deep buried pipes or those set in concrete, the
sulting material is harder, with a higher softening point. cost associated with the use of an expensive binder is offset by
the large replacement costs involved. The thermoset resins
2. "Cracked" asphalts are also petroleum derivatives, but are
most frequently used have been the epoxides. The bitumens
obtained from by-products in oil-cracking processes. Resi-
used in these coatings have generally been the coal tars and
dues are distilled to produce asphalt. They are variable in
pitches. This was primarily due to the compatibility of these
composition and may contain a certain amount of
uncracked paraffinic material. These materials represent highly aromatic materials with epoxy resins, as well as the
asphaltic hydrocarbons approximately intermediate in ease of working with a liquid material. The final film hardness
aromaticity between oil asphalts and the completely aro- is derived from the cross-linked epoxy network.
matic, highly condensed bitumens found in coal tars, wa- There has been a growing concern with the toxicity of
ter-gas tars, coal carbonization tars, and their pitches. highly aromatic systems. The result has been that trade sales
and light industrial coatings have moved away from coal tar
3. Coal tar, water-gas tars, and their pitches are derived from or its pitches. Recently, the asphaltites and oil asphalts have
tars. ASTM D 1079 defines tar as " . . . a brown or black been used in these types of coatings. The trend has been to
bituminous material, liquid or semi-solid in consistency, in use softer asphalts. Some form of compatibilizer has also
which the predominating constituents are bitumens ob- been necessary to make these lower aromatic-content sys-
tained.., from the processing of coal, petroleum, oil-shale, tems stable.
wood, or other organic materials." The "free carbon" con- In automotive under-body rustproofing, bituminous coat-
tent, or other benzene insoluble matter, distinguishes coal ings have found extensive use. These materials are modified
tar from the asphaltites and oil asphalts. The latter are with rubbery materials to give flexible coatings with excellent
devoid of free carbon. Coal tars and their products are not adhesion to metal parts. Many years ago, the predominant
included in the category of asphalt. bitumen in use had been coal tar. Today, with the move away
In the early 1960s, approximately 70% of all oil asphalts from highly aromatic products, petroleum asphalts are gen-
were consumed by the road-paving industries with 20% used erally used. To use the harder bitumens such as asphaltites
in roofing. The solid bitumens and asphaltites of natural ori- and petroleum asphalts, plasticizers such as di-octyl phthal-
gin found their greatest consumption in lacquer, paint, and ate or butyl benzyl phthalate are required to soften and
electrical insulation. Today, the paving industry is still the liquify the bitumen. Aromatic processing oils have also been
largest user of these materials, but the scope and area of used for this purpose. Natural and synthetic waxes are added
specialty coatings has broadened considerably. In recent to prevent chipping from road debris.
years, asphalts and other bitumens have become increasingly Given the severe penalties associated with contamination
of groundwater, chemical and moisture-resistant coatings for
important as the cost of other natural and synthetic binders
containment dikes are being used more and more in the
has continued to escalate. Their ability to act as adhesives
chemical process industry. Most state and local regulations
with excellent moisture vapor transmission (MVT) properties
require the use of a containment wall around every storage
continues to result in new and varied uses.
tank that may potentially rupture and contaminate the water
table.
Coatings for this application have included coal tar epoxies
and coal tar resinous systems. Gilsonite-based resinous coat-
Coating Types ings have been widely used and, depending on the chemical
nature of the contained material, petroleum asphalt ure-
The types of asphaltic or bituminous coatings available can thanes and epoxides are available.
be classified, in a large part, by the industry of use. Industries Additional areas where bitumens have shown applicability
considered are: as specialty coatings have included the areas of sealing soil to
1. The paints and coatings industry, where bituminous coat- minimize water penetration (pond liners, seepage control for
ings have been used to protect metal from the effects of levees and dams, and hazardous waste containment) as well
water and oxygen degradation. as sound deadening on sheet metal and binding other bitumi-
2. The roofing industry, where asphalt coatings are used ex- nous materials such as coal or lignite for pelletization.
tensively to weatherproof buildings.
3. The construction industries, where concrete and mortar Roof Coatings
are waterproofed. In roof coatings, bitumens have been important raw mate-
4. The paving industry; where the adhesive properties of as- rials since the turn of the century. Today, many commercial
phalt as binder is put to good use in roads. roofing systems use some form of asphalt or chemically mod-
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CHAPTER 2 - - B I T U M I N O U S COATINGS 17
ified asphalt in their construction. The application of an as- weather-tight seal. After the repairs are complete, a reflective
phalt or polymer-modified hot melt asphaltic material, fol- coating may be applied to act as an ultra-violet (UV) barrier
lowed by the application of a reinforcing membrane, is the and thermal reflector, or additional gravel added. Several
basic construction of a modern built-up-roof (BUR). different types of coatings have been available for each of
In some markets, the current industry trend has been away these purposes.
from the use of hot melt coatings, where a roofing kettle that Asphalt cutbacks and emulsions are the primary coating
heats the materials up to 450~ (232~ to reach their applica- used for restoration. They are applied in heavy applications
tion viscosity is required, and toward cold-applied systems. of 40 to 80 rail thick. This allows the coating to cover minor
Here, the asphalt is usually modified with solvents, fillers, and surface defects that are present on the old roof. Splits and
thixotropes as well as various additives to result in a formula- cracks can be repaired by using these materials with either
tion that can be applied at ambient temperatures with good fiberglass or polyester reinforcements. A final application
flow properties and that which will subsequently dry or cure gives a reasonably water-tight monolithic appearance.
into a weatherproofing membrane. Asphalt emulsions consist of two types. In one, the water is
In these coatings, volatile solvents are varied to control dispersed in the asphalt external phase. In the other, the
cure times. In general, the solvents are either mineral spirits asphalt is dispersed in a water external phase. The first are
or naphthas. While asbestos was long a preferred additive for called water-in-oil (W/O) emulsions. The later are oil-in-wa-
thixotropy and reinforcement, the hazards of working with ter (O/W) emulsions. Roofing emulsions are predominately
and removing old installations with asbestos-containing ma- water-in-oil emulsions. The oil-in-water emulsions are more
terials have driven the products toward asbestos-free roofing widely used in the paving industry and will be discussed in
materials. This has led to the use of cellulose, synthetic, and more detail in that section.
glass fibers as a partial replacement for asbestos. Bentonite The water-in-oil emulsions are produced from finely pow-
and attapulgite clays are then used to obtain the required dered clays, which can act as dispersants for the water. Dis-
thixotropy. Today, there are still a significant number of man- persing agents of this type show some affinity for water or are
ufacturers that continue to use asbestos in their formula- sufficiently hygroscopic to hold water and bring it into dis-
tions. persion in the asphalt. The bentonite clays form extremely
The asphalt portion of these coatings usually consists of colloidal gelatinous mixtures and pastes with water and re-
materials referred to as cutbacks. Various solvents are used to sult in asphalt dispersions of very small particle size, These
cut (solubilize) the asphalt, depending on the cure times smooth buttery emulsions are very stable and can be fibered
required. The solvent predominantly used today is mineral for reinforcement and modified with latex resins to obtain a
spirits, with a flash point (tag closed cup) of 104~ (40~ degree of elasticity. Most commercial products are unmodi-
Faster evaporating versions of these cutbacks have been used fied and yield a final coating possessing all the properties of a
as primers for better substrate adhesion. These materials gel asphalt after evaporation of the water. Several books are
generally use faster aromatic solvents, including toluene, xy- available which offer greater detail in the area of emulsion
lene, and the aromatic naphthas. The asphalt content varies technology [7-9].
from 30 to 70% by weight. Asphalt emulsions can be left untop-coated, but are fre-
The preceding materials, while they can, in the strictest quently coated with reflective topcoats to help control roof
sense, be considered coatings, are actually closer to adhesives top temperatures. For several years, the major type of coat-
in performance; that is, these coatings are applied to hold the ings for this application have been solvent-borne aluminum
reinforcing membranes together. Although the last coat ap- pigmented bituminous coatings. A wide variety of bitumens
plied may be a flood coat of the adhesive coating, the roof is have been used, including asphalt, asphaltite, tar, and pitch.
usually not left this way. Weathering characteristics are sig- Their viscosity has generally been low with moderate levels of
nificantly improved when these roofs are gravel surfaced. volatile solvents present. Most of the solvent-based aluminum
This graveled surface blocks harmful ultraviolet (UV) radi- bitumen paints in use today are asphalt vehicles made from
ation and serves to improve the fire resistance. The most petroleum asphalt cutbacks. The predominate solvent has
common roof gravels are river-washed gravel, crushed stone, been mineral spirits. The pigment used has generally been a
granite, and blast-furnace slag recovered from the iron ore leafing grade of aluminum paste. It is reported that some
reduction process and composed of silicates and alumino- early formulations used cumerone indene resin to improve
silicates of lime [6]. Other materials, also available for this the leafing characteristics and act as an anti-bronzing agent.
purpose, include a variety of small, colored roofing granules, A level of 2 lb (0.91 kg) of aluminum paste per gallon of paint
similar to those used on shingles. is typical in these coatings [IO].
From 400 to 600 lb (181 to 272 kg) of river-washed gravel With the recent increase in environmental legislation and
per 100 ft2 (9.29 m 2) of roof is used, or, if weight considera- an increased awareness of health issues, alternatives to these
tions are important, 50 to 60 lb (22.68 to 27.2 kg) of the solvent-borne coatings are beginning to find their place in the
smaller roofing granules can be used. The bituminous coating market. Specifically, asphalt emulsions of various solids are
is then an adhesive for these gravels. being used in conjunction with new aluminum pigment tech-
Due to weight limitations on existing roofs and costs asso- nology which allows the manufacture of relatively stable wa-
ciated with roof tear-offs and subsequent reroofing, current terborne versions [11,12]. These materials generally consist
philosophy is to maintain the existing roof. When physically of petroleum asphalt emulsions that use organophosphate-
possible, restoration instead of replacement is very cost effec- treated leafing-aluminum pastes. The phosphate passivates
tive. This requires the use of coatings whose purpose is to the aluminum, giving it more stability on storage. The solids
repair damage to the roof and re-establish or maintain the of such coatings vary from 25 to 50% by weight. Additional
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modification similar to other emulsion systems is also used in nature. The anionic and cationic emulsifiers form an emul-
these coatings. sion in which the dispersed phase shows a definite charge.
Newer technologies to stabilize aluminum pigments in wa- These emulsions are said to "break" upon contact with a
ter have recently been introduced. Chemically bound chrome charged aggregate, yielding the exclusion of one phase from
is used to passivate the aluminum [13]. While quite expen- the other. The speed of break can be modified, yielding rapid,
sive, these products are finding use in the automotive indus- medium, or slow setting emulsions. The cationic versions are
try. As their cost decreases, perhaps they will be available for preferred because the coating formed does not re-emulsify.
the waterborne bituminous aluminum market. With anionic emulsifiers, break occurs when emulsions de-
Other technologies exist that are nonbituminous in compo- stabilize due to water loss on drying. One disadvantage of this
sition. These coatings include elastomeric acrylic latexes, sol- is the possibility of re-emulsification in the early stages of
vent and waterborne urethanes, epoxides, and alkyds. These cure. Once the coating has dried, water is no longer a prob-
are usually pigmented with either titanium dioxide (TiO2) or lem.
aluminum pastes to give thermally reflective coatings. These Paving sealers are used to protect new or old asphalt drive-
types of coatings will be discussed elsewhere in this manual. ways or parking lots. The sealers are generally coal tar in
nature due to good resistance to gas and oil. Asphalt sealers
Waterproofing Membranes can also be used, but they must be latex or polymer modified
Bitumen-modified waterproofing membranes are used ex- to improve solvent resistance.
tensively in the construction industry. The most common Other types of bituminous coatings used in the paving
substrate is poured or cast concrete or mortared "cinder industry include slurry seals and micro surfacing, which uses
block." Prestressed concrete in the foundations, walls, and latex or polymer-modified asphalts with fine aggregate filler
roof decks of high-rise buildings is also a suitable candidate as a surface treatment for repair of minor damage to roads.
for these membranes. In the home construction and repair Coal tar is not used in this application because the resulting
industries, cinder block foundations and concrete footers are coating is too slippery. Tack coats consisting of asphalt
commonly waterproofed with bitumen-modified polymeric cutbacks are also used when one layer of asphalt needs to be
coatings. adhered to another.
The bitumen of interest in these markets has predomi-
nately been coal tar pitch and petroleum asphalts. Water-
proofing membranes are generally composed of bitumen in I D E N T I F I C A T I O N OF B I T U M I N O U S
an elastomeric polymer matrix. The aromatic polyurethanes MATERIALS
are frequently used for this purpose.
In coating structural steel and steel reinforcement bars, This section will catalogue several test methods currently
coal tar epoxies have been extensively used. Their composi- available through ASTM for characterization of bituminous
tion and purpose is similar to that of pipe coatings used for paints and coatings. Many of these methods are familiar to
the prevention of underground corrosion. Their composition the coatings chemist as standard paint-related tests found in
can be modified to conform to a particular steel coatings Volumes 6.01 through 6.04 of the Annual Book of ASTM Stan-
application. dards. Several others are under the jurisdiction of Committee
As in other markets, the use of aromatic coal tars is slowly D 8 on Roofing, Waterproofing, and Bituminous Materials.
being replaced by safer soft petroleum asphalts. Environmen- These methods appear in Volume 4.04 of the Annual Book of
tal issues aside, higher tech systems are beginning to be seen. ASTM Standards.
Other types of coatings for rebar in the last five years have
included fused epoxy powder coatings systems and polyethyl-
Tests on Bituminous Materials
ene dip coated systems. While much more expensive than
bitumen-modified systems, their improved performance have The following test methods are used to differentiate one
made them of interest. type of bitumen from another. They also can distinguish mix-
tures of bitumens and their purity. As bitumens are consid-
Coatings for Paving ered pseudo-plastic materials, with no true melt point, soften-
The paving industry is probably the oldest using bitumen ing point and penetration are the two major tests routinely
and its coatings. Asphalt cutbacks have also been known as performed to identify differences within grades of the differ-
"road oils." For years these solvent cut materials were used to ent bitumen classes. Viscosities at elevated temperatures are
seal roads as well as coat aggregates for application to the also very important with several instruments and their meth-
road surface. Today, hot asphalt or cutback is used to prime ods listed.
new paving as well as to repair damaged or worn areas. In earlier editions of this manual, several tests were de-
Today, most road coating uses asphalt emulsions. These scribed that were in common use in 1972. Among the tests
are generally chemically stabilized emulsions. The emulsion described were the solubility of bitumens in carbon disulfide
is prepared beforehand and mixed with aggregate on site and (CSa) to identify the purity of a bitumen sample, since by
is referred to as chip and seal. Hot asphalt is not required in definition only CS2 soluble matter is bitumen. Also listed
this application, making it much easier than the use of hot were tests to determine the presence of asphalt and tar in
mix paving, where the asphalt is heated to melting before suspected mixtures (the Oliensis Spot Test and the character-
application. In paving, oil-in-water emulsions predominate. istics of bituminous samples dispersed in solvent). Today,
The oil-in-water emulsions are formed from the action of a these have been incorporated into the Annual Book of ASTM
chemical emulsifier, either anionic, cationic, or nonionic in Standards and will not be described in detail.
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CHAPTER 2--BITUMINOUS COATINGS 19
On this note, it is important to point out that each industry D 4799-88 Test Method for Accelerated Weathering Test
that uses bitumens has tended to develop their own series of Conditions and Procedures for Bituminous
common pertinent tests over the years. Today most of the Materials (Fluorescent UV and Condensation
pertinent tests have been incorporated as ASTM standards. In Method)
addition to ASTM, other organizations have tried to compile
these tests for their members' use. The Asphalt Institute, an D 4989-90 Test Method for the Apparent Viscosity Flow of
international, nonprofit organization sponsored by members Roofing Bitumens Using the Parallel Plate
of the petroleum asphalt industry, also publishes a handbook Plastometer
that has evolved over the past 50 years as the standard refer-
ence work in the field of asphalt technology and construction, E 96-90 Test Methods for Water Vapor Transmission of
especially in the paving industry [14]. This reference book Materials
cites both ASTM test methods and, where applicable, Ameri-
E 102-81 Test Method for Saybolt Furol Viscosity of
can Association of State Highway and Transportation Offi-
Bituminous Materials at High Temperatures
cials (AASHTO) counterparts to these methods. A large part
of the manual is devoted to practical how-to information
E 108-90 Method for Fire tests of Roof Coverings
about how to use asphalt, as well as comprehensive data on
asphalt technology, and is highly recommended.
Specifications and Test Methods for Asphalt
D 71-84 Test Method for Relative Density of Solid Pitch
and Asphalt
General D 312-89 Specification for Asphalt Used in Roofing
D 4-86 Test Method for Bitumen Content
D 449-89 Specification for Asphalt Used in Dampproofing
D 5-86 Test Method for Penetration of Bituminous and Waterproofing
Materials
D 1328-86 Test Method for Staining Properties of Asphalt
D 36-86 Test Method for Softening Point of Bitumen
(Ring and-Ball apparatus) D 1370-84 Test Method for Contact Compatibility Between
Asphaltic Materials (Oliensis Test)
D 70-82 Test Method for Specific Gravity and Density of
Semi-Solid Bituminous Materials D 1856-79 Test Method for Recovery of Asphalt from
Solution by Abson Method
D 88-81 Test Method For Saybolt Viscosity
D 2042-81 Test Method for Solubility of Asphalt Materials
D 92-90 Test Method For Flash and Fire Points by in Trichloroethylene
Cleveland Open Cup
D 2521-76 Specification for Asphalt Used in Canal, Ditch,
D 95-83 Test Method for Water in Petroleum Products and Pond Lining
and Bituminous Materials by Distillation
D 3461-85 Test Method for Softening Point of Asphalts and
D 140-88 Practice for Sampling Bituminous Materials Pitches (Mettler Cup-and-Ball Method)
D 52%90 Test Method for Accelerated Weathering Test D 4402-87 Test Method for Viscosity Determinations of
Conditions and Procedures for Bituminous Unfilled Asphalts Using the Brookfield
Materials Thermosel Apparatus
D 1079-87 Definitions of Terms Relating to Roofing,

Waterproofing, and Bituminous Materials Specification and Test Methods for Coal Tar, Pitches,
and Highly Cracked Petroleum Products
D 1669-89 Method for Preparation of Test Panels for D 61-75 Test Method for Softening Point of Pitches
Accelerated and Outdoor Weathering of (Cube-in-Water Method)
Bituminous Materials
D 450-78 Specification for Coal Tar Pitch Used in Roofing,
D 1670-90 Test Method for Failure End Point in Dampproofing, and Waterproofing
Accelerated and Outdoor Weathering of
Bituminous Materials D 2318-86 Test Method for Quinoline-Insoluble (QI)
Content of Tar and Pitch
D 4798-88 Test Method for Accelerated Weathering Test
Conditions and Procedures for Bituminous D 2319-76 Test Method for Softening Point of Pitch (Cube-
Materials (Xenon-Arc Method) in-Air Method)
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D 2320-87 Test Method for Density (Specific Gravity) of D 555-89 Guide for Testing Drying Oils
Solid Pitch (Pycnometer Method)
D 562-81 Test Method for Consistency of Paints Using the
D 2415-66 Test Method for Ash in Coal Tar and Pitch Stormer Viscometer
D 2416-84 Test Method for Coking Value of Tar and Pitch D 609-90 Practice for Preparation of Cold-Rolled Steel
(Modified Conradson) Panels for Testing Paint, Varnish, Conversion
Coatings, and Related Coating Products
D 2569-89 Test Method for Distillation of Pitch
D 610o85 Method for Evaluating Degree of Rusting on
D 2764-81 Test Method for Dimethylformamide-Insoluble Painted Steel Surfaces
(DMF-I) Content of Tar and Pitch
D 662-85 Test Method for Evaluating Degree of Erosion of
D 2962-71 Method for Calculating Volume-Temperature Exterior Paints
Correction for Coal-Tar Pitches
D 714-87 Method for Evaluating Degree of Blistering of
D 3104-87 Test Method for Softening Point of Pitches Paints
(Mettler Softening Point Method)
D 1212-85 Test Methods for Measurement of Wet Film
D 4072-81 Test Method for Toluene-Insoluble (TI) Content Thickness of Organic Coatings
of Tar and Pitch
D 1474-85 Test Methods for the Indentation Hardness of
D 4312-89 Test Method for Toluene-Insoluble (TI) Content Organic Coatings
of Tar and Pitch (Short Method)
D 1475-90 Test Method for Density of Paint, Varnish,
D 4616-87 Test Method for Microscopical Analysis by Lacquer, and Related Products
Reflected Light and Determination of Mesophase
in a Pitch D 1540-82 Test Method for Effect of Chemical Agents on
Organic Finishes Used in the Transportation
D 4715-87 Test Method for Coking Value of Tar and Pitch Industry
(Alcan)
D 1542-60 Test Method for Qualitative Detection of Rosin
D 4746-87 Test Method for Determination of Quinoline in Varnishes
Insoluble (QI) Content in Tar and Pitch by
Pressure Filtration D 1640-83 Test Methods for Drying, Curing, or Film
Formation of Organic Coatings at Room
D 4892-89 Test Method for Density of Solid Pitch (Helium Temperature
Pycnometer Method)
D 1644-88 Test Methods for Nonvolatile Content of
D 4893-89 Test Method for Determination of Pitch Varnishes
Volatility
D 1654-79 Method for Evaluation of Painted or Coated
D 5018-89 Test Method for Shear Viscosity of Coal Tar and Specimens Subjected to Corrosive Environments
Petroleum Pitches
D 1849-80 Test Method for Package Stability of Paint
TESTS AND SPECIFICATIONS FOR
COATINGS D 2243-90 Test Method for Freeze-Thaw Resistance of
Water-Borne Paints
General Tests for Coatings
D 2247-87 Practice for Testing Water Resistance of
Several of the test methods familiar to the industrial paints Coatings in 100% Relative Humidity
and coatings chemist can also be used to characterize the
performance and physical properties of bituminous coatings. D 2369-90 Test Methods for Volatile Content of Coatings
The following methods can all be found in Volumes 6.01
through 6.04 of the Annual Book of ASTM Standards. D 2370-82 Test Method for Tensile Properties of Organic
Coatings
Tests and Specifications
B 117-90 Method of Salt Spray (Fog) Testing D 2832-83 Guide for Determining Volatile and Nonvolatile
Content of Paint and Related Coatings
D 522-88 Test Methods for Mandrel Bend Test of Attached
Organic Coatings D 3170-87 Test Method for Chip Resistance of Coatings
www.iran-mavad.com

CHAPTER 2--BITUMINOUS COATINGS 21
D 3359-90 Test Methods for Measuring Adhesion by Tape Paving Sealers

Test D 3320-90 Specification for Emulsified Coal Tar Pitch
(Mineral Colloid Type)
D 3960-90 Practice for Determining Volatile Organic
Compound (VOC) Content of Paints and Related D 3423-84 Practice for Application of Emulsified Coal Tar
Coatings Pitch (Mineral Colloid Type)
G 6-88 Test Method for Abrasion Resistance of Pipeline D 4866-88 Performance Specification for Coal Tar Pitch
Coatings Emulsion Pavement Sealer Mix Formulations
Containing Mineral Aggregates and Optional
Polymeric Admixtures
Solvent-Thinned or Cut-Back Coatings
General Specialty Coatings
D 255-70 Method for Steam Distillation of Bituminous D 41-85 Specification for Asphalt Primer Used in Roofing
Protective Coatings and Waterproofing
D 402-76 Test Method for Distillation of Cut-Back D 43-73 Specification for Creosote Primer Used in
Asphaltic (Bituminous) Products Roofing, Dampproofing and Waterproofing
D 529-90 Test Method for Accelerated Weathering Test D 1187-82 Specification for Asphalt-Base Emulsions for Use
Conditions and Procedures for Bituminous as Protective Coatings for Metal
Materials (Carbon-Arc Method)
D 3105-90 Index of Methods for Testing Elastomeric and Emulsion Coatings

Plastomeric Roofing and Waterproofing General
Materials
D 466-42 Method of Testing Films Deposited from
Bituminous Emulsions
Roof Coatings
D 41-85 Specification for Asphalt Primer Used in Roofing D 529-90 Practice for Accelerated Weathering Test
and Waterproofing Conditions and Procedures for Bituminous
Materials (Carbon-Arc Method)
D 43-73 Specification for Creosote Primer Used in
Roofing, Dampproofing and Waterproofing D 1187-82 Test Method for Asphalt-Base Emulsions for Use
as Protective Coatings for Metal
D 1227-87 Specification for Emulsified Asphalt Used as a
Protective Coating For Built-Up Roofing D 2939-78 Method for Testing Emulsified Bitumens Used as
Protective Coatings
D 2823-90 Specification for Asphalt Roof Coatings
Clay Stabilized Emulsions
D 2824-85 Specification for Aluminum-Pigmented Asphalt
Roof Coatings
Protective Coating For Built-Up Roofing
D 3805-85 Practice for Application of Aluminum-Pigmented
D 2963-78 Test Method for Testing Flow Table Consistency
Asphalt Roof Coating
of Clay-Stabilized Asphalt Emulsions
D 4479-85 Specification for Asphalt Roof Coatings--
D 3320-90 Specification for Emulsified Coal Tar Pitch
Asbestos Free
(Mineral Colloid Type)
D 5076-90 Test Method for Measuring Voids in Roofing and
Anionic Emulsions
Waterproofing Membranes
Waterproofing Membranes Protective Coating For Built-Up Roofing
D 41-85 Specification for Asphalt Primer Used in
Non-Ionic Emulsions
Roofing, Dampproofing and Waterproofing
D 43-73 Specification for Creosote Primer Used in Protective Coating For Built-Up Roofing
Roofing, Dampproofing and Waterproofing
Cationic Emulsions
D 5076-90 Test Method for Measuring Voids in Roofing and D 1227-87 Specification for Emulsified Asphalt Used as a
Waterproofing Membranes Protective Coating For Built-Up Roofing
www.iran-mavad.com

Resin Modified Bituminous Coatings [2] Annual Book of ASTM Standards, Section 4, Volume 4, Roofing,
Waterproofing, and Bituminous Materials, American Society for
Synthetic Resins Testing and Materials, Philadelphia, 1988, p. 100.
D 3468-90 Specification for Liquid-Applied N e o p r e n e a n d [3] Barth, E.J., Asphalt: Science and Technology, Gordon and
Chlorosulfonated Polyethylene used in Roofing Breach Science Publishers, New York, 1962, p. 3.
a n d Waterproofing [4] Martin, O., Bitumen, Teere, Asphalte, Peche Vol. 11, 1951, p. 285.
[5] Barth, E.J., Asphalt: Science and Technology, Gordon and
Breach Science Publishers, New York, 1962, pp. 7-9.
[6] Griffin, C.W., Manual of Built-Up Roof Systems, 2nd ed.,
CONCLUSION McGraw-Hill Book Co., New York, 1982, pp. 141-151.
[7] Barth, E.J., Asphalt: Science and Technology, Gordon and
Breach Science Publishers, New York, 1962, pp. 471-558.
B i t u m i n o u s coatings are still used extensively today. The [8] Bennett, H., Bishop, J.L., and Wulfinghoff, M. F., Practical
waterproofing a n d adhesive properties, coupled with the rela- Emulsions: Materials and Equipment, Vol. 1, Chemical Publish-
tively inexpensive costs for m o s t b i t u m i n o u s materials, con- ing Company, Inc., New York, 1968.
tinue to drive their use in m a n y diverse industrial applica- [9] Bennett, H., Bishop, J.L., and Wulfinghoff, M.F., Practical
tions. The p r e c e d i n g i n f o r m a t i o n will give the r e a d e r an Emulsions: Applications, Vol. 2, Chemical Publishing Company,
u n d e r s t a n d i n g of the c h e m i s t r y a n d uses of b i t u m i n o u s coat- Inc., New York, 1968.
ings in i n d u s t r y a n d a realization that even several t h o u s a n d [10] Edwards, J. D. and Wray, R. I., Aluminum Paint and Powder,
Reinhold Publishing Corp., New York, 1955, pp. 64-69.
years after t h e i r discovery a n d first use the usage of these
[11] Williams, J. E., U.S. Patent No. 4,565,716, 1986.
b i t u m i n o u s r a w m a t e r i a l s as an engineering r a w m a t e r i a l is [12] Besold, R., "Aluminum Flake in Waterborne Coatings: Antago-
still growing. nism or Reality," Proceedings, 18th Annual Higher Solids and
Waterborne Coatings Symposium, New Orleans, LA, 1991.
[13] Chapman, D.P., "Aluminum Pigment Technology for Wa-
terborne and Powder Coatings in the 1990's," Proceedings, 18th
REFERENCES Annual Higher Solids and Waterborne Coatings Symposium,
New Orleans, LA, 1991.
[1] Barth, E.J., Asphalt: Science and Technology, Gordon and [14] The Asphalt Handbook, Bukowski, J. R., Ed., The Asphalt Insti-
Breach Science Publishers, New York, 1962. tute, Manual Series No. 4 (MS-4), 1989.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Cellulose Esters
by L. G. Curtis 1
CELLULOSE ESTERS ARE THE reaction product of combining possible. Hydroxyl content and molecular weight possibili-
organic acids and acid anhydrides with the hydroxyl groups ties expand this range even further.
found on the anhydroglucose repeating units of a cellulose
molecule. The esterification of the cellulose with the acids
and anhydrides occurs quite rapidly and if allowed to proceed
FACTORS A F F E C T I N G P E R F O R M A N C E OF
to completion, forms a triester with each of the an-
CELLULOSE E S T E R S IN COATINGS
hydroglucose units, which contain three hydroxyl groups.
Because the triester is of little practical use, hydrolysis is
Performance properties of cellulose acetate buytrate are
necessary to restore desired levels of hydroxyl content, which
affected by the chemical composition and the viscosity of the
affects various properties of the cellulose ester such as solu-
ester. As butyryl increases, solubility, compatibility, flexibil-
bility and compatibility with other coating polymers.
ity, diluent tolerance, and moisture resistance are increased.
Lower butyryl levels are associated with decreased water
tolerance, grease resistance, hardness, and increased melting
P R O D U C T I O N OF CELLULOSE E S T E R S range. As the hydroxyl content of cellulose acetate butyrate
varies, several characteristics are also affected. Below 1%
For the production of coating-grade cellulose esters, three
hydroxyl, solubility in common coatings type solvents is lim-
organic acids and anhydrides are used, either separately or in
ited but improves as the hydroxyl increases. At levels around
combination with each other. Cellulose acetate is the sim-
5%, solubility in lower molecular weight alcohols occurs. At
plest cellulose ester since only acetic acid and acetic anhy-
higher hydroxyl levels, reactivity increases, providing cross-
dride are used in the esterification reaction. If two different
linking capability with amino and isocyanate resins. How-
organic acids and anhydrides are used simultaneously, the
ever, in noncross-linking systems, higher levels decrease
resultant product is referred to as a mixed ester. Examples of
moisture resistance due to increased hydrophilicity.
mixed cellulose esters are cellulose acetate butyrate and cel-
The viscosity of cellulose esters also influences physical
lulose acetate propionate.
properties of the ester as well as coatings formulated with
In addition to esterification and hydrolysis, several subse-
them. Increasing the viscosity of a particular ester by increas-
quent processing steps are required in the manufacture of
ing the molecular weight slightly lowers its solubility and
cellulose esters including filtration, precipitation, washing,
dewatering, drying, and screening. The final product is a dry, compatibility with other resins, but does not affect hardness
free-flowing powder in most instances, although other physi- and density. Generally, toughness and flexibility are im-
cal forms can be produced. Unlike cellulose nitrate, organic proved with increased molecular weight and viscosity.
esters of cellulose are low in flammability and present no
handling hazards.
APPLICATIONS F O R CELLULOSE E S T E R S
IN COATINGS
T Y P E S OF CELLULOSE E S T E R S
Protective and decorative coatings for various substrates
Several types of cellulose esters are commercially available, can be formulated either as air-dry lacquer systems or as
including cellulose acetate, cellulose acetate propionate, and converting or curing types often referred to as cross-linked
cellulose acetate butyrate. Other esters of lesser commercial enamels. In many such coatings, cellulose esters are included
value are produced, but are not suited for coating applica- as either a modifying resin to impart a specific property to the
tions. Table 1 shows the types of cellulose esters commer- coating or to function as the primary film-forming resin in
cially available. Cellulose acetate butyrate is the most com- the formulation. Both types of coatings can be applied over a
monly used organic cellulose ester for coating applications, variety of substrates ranging from paper products to automo-
and there is an almost infinite number of types that can be biles. Some areas in which cellulose esters are used include
produced because of the acetylbutyryl combinations that are automotive OEM and refinish, wood furniture coatings, lea-
ther coatings, printing inks, plastic coatings, aircraft coat-
~Principal Technical Representative, Eastman Chemical Com- ings, cable lacquers, and various fabric coatings. Cellulose
pany, Building 230, Kingsport, TN 37662. esters are used in coatings to impart such properties as rapid-
23
www.iran-mavad.com

TABLE l - - C o m m e r c i a l cellulose esters (Eastman Chemical Company).

Type Viscosity,~ s Acetyl,b % Propionyl, % Butyryl, % Hydroxyl, % Melting Range, ~
Celhtlose Acetate
CA-394-608 60.00 39.5 . . . . . . 4.0 240-260
CA-398-3 3.00 39.8 . . . . . . 3.5 230-250
CA-398-6 6.00 39.8 . . . . . . 3.5 230-250
CA-398-10 10.00 39.8 . . . . . . . . . 230-250
CA-398-30 30.00 39.8 . . . . . . . . . 230-250
Cellulose Acetate Propionate
CAP-482-0.5 0.50 2.5 45.0 ... 2.6 188-210
CAP-482-20 20.00 2.5 46.0 -.. 1.8 188-210
CAP-504-0.2 0.20 0.6 42.5 --. 5.0 188-210
Cellulose Acetate Butyrate
CAB- 171-158 15.00 29.5 ... 16.0 1.1 230-240
CAB-321-0.1 0.10 18.5 --. 31.2 1.3 165-175
CAB-381-0.1 0.10 13.5 .-- 37.0 1.3 155-165
CAB-381-0.5 0.50 13.5 ... 37.0 1.3 155-165
CAB-381-2 2.00 13.5 ..- 37.0 1.3 175-185
CAB-381-20BP 2.20 14.5 ... 36.0 1.8 175-185
CAB-381-20 20.00 13.5 ... 36.0 1.8 195-205
CAB-381-20BP 16.00 15.5 -.. 36.0 0.8 185-195
CAB-500-5 5.00 4.0 -.. 51.0 1.0 165-175
CAB-531-1 1.90 3.0 ... 50.0 1.7 135-150
CAB-551-0.01 0.01 2.0 ... 52.0 1.8 130-140
CAB-551-0.2 0.20 2.0 .-. 52.0 1.5 127-142
CAB-553-0.4 0.40 2.0 .-- 46.0 4.8 150-160
~ASTMTest Method for Cellulose Acetate Proprionate and Cellulose Acetate Butyrate (Formula A) (D 817) and Test Methods for Viscosity of Cellulose Derivatives
by Ball-Drop Method (D 1343).
bASTM D 817.
d r y i n g , p i g m e n t c o n t r o l , v i s c o s i t y c o n t r o l , film t o u g h n e s s , TABLE 2 - - S o l u t i o n s for viscosity measurement of cellulose

and polishability. acetate, cellulose acetate propionate, and cellulose acetate
butyrate.
Cellulose ester 20~ 20 ~ 20 b 15c 20~ l(F
Acetoned 70 80 . . . . . . . . . . . .
TESTING OF CELLULOSE ACETATE Acetone/water, 96/94 . . . . . . . . . . . . 80 ...
Ethyl alcohoF 8 -.. 8 8.5 ......
C e l l u l o s e a c e t a t e is t e s t e d b y t h e m a n u f a c t u r e r i n a c c o r d - Methyl alcoholf . . . . . . . . . . . . . . . 9
Methylene chlorideg ...... 72 76.5 .-. 81
a n c e w i t h A S T M T e s t M e t h o d s f o r C e l l u l o s e A c e t a t e s (D 871),
w h i c h c o v e r s c o l o r a n d h a z e , c o m b i n e d acetyl, f r e e acidity, Typical Solution Densities, g per mL at 25~
h e a t stability, h y d r o x y l c o n t e n t , i n t r i n s i c v i s c o s i t y , m o i s t u r e 0.85 0.86 1.25 1.23 0.86 1.24
content, sulfur or sulfate content, a n d solution viscosity. aFor cellulose acetate having a max of 40.5% acetyl and for most mixed
C o a t i n g s m a n u f a c t u r e r s u s u a l l y r e s t r i c t t h e i r t e s t i n g t o vis- esters having less than about 40% acetyl and more than about 8% propionyl or
butyryl.
cosity of the ester, solubility a n d a p p e a r a n c e , a n d color a n d bFor cellulose acetate having 40.5 to 42.7% acetyl and for most of the
haze. commercial cellulose acetate propionate and acetate butyrates.
CFor cellulose acetate having 42.7 to 44.8% acetyl and for most of the
commercial cellulose acetate propionate and acetate butyrates; particularly
good for esters containing more than 40% acetyl.
Viscosity aAcetone (99.4 -+ 0.1%) containing 0.3 to 0.5% water and under 0.3% ethyl
alcohol.
V i s c o s i t y m e a s u r e m e n t o f c e l l u l o s e a c e t a t e is c a r r i e d o u t in eEthyl alcohol (95% by volume). Formulas 2B, 3A, or 30 denatured ethyl
a c c o r d a n c e w i t h A S T M T e s t M e t h o d s f o r V i s c o s i t y o f Cellu- alcohol may be used.
fMethyl alcohol (sp gr 20/20~ = 0.785 to 0.795).
l o s e D e r i v a t i v e s b y B a l l - D r o p M e t h o d (D 1343) b a s e d o n t h e gMethylene chloride having a boiling range of 39.2 to 40.0~ and less than
ball d r o p o r f a l l i n g ball p r i n c i p l e . A p r e c i s i o n H o e p p l e r vis- 0.001% acidity calculated as HCL
c o m e t e r is u s e d i n m o s t v i s c o s i t y d e t e r m i n a t i o n s w i t h r e s u l t s
r e p o r t e d in ASTM seconds. F o r m u l a t i o n s for viscosity deter- Color and Haze
m i n a t i o n a r e s h o w n in T a b l e 2.
The same solutions used for ASTM viscosity and solubility
and a p p e a r a n c e testing are normally used for color and haze
Solubility and Appearance m e a s u r e m e n t s . T h e s o l u t i o n is t r a n s f e r r e d t o a s p e c i a l 33-
T h e s o l u b i l i t y a n d a p p e a r a n c e t e s t is p e r f o r m e d t o d e t e r - m m - s q u a r e cell, a n d t h e a n a l y s i s is p e r f o r m e d w i t h a G a r d n e r
m i n e t h e p o s s i b l e p r e s e n c e o f i n s o l u b l e gel p a r t i c l e s , fibers, M o d e l XL-385 c o l o r i m e t e r . L i g h t p a s s e s t h r o u g h t h e s o l u -
flock, o r o t h e r c o n t a m i n a n t s , u s i n g s o l u t i o n s p r e p a r e d for tion, and the p r i m a r y yellowness index and p r i m a r y haze
v i s c o s i t y t e s t i n g . T h e m a t e r i a l t o b e t e s t e d is a d d e d t o 16 oz. values are s i m u l t a n e o u s l y displayed by t h e i n s t r u m e n t . Sec-
(454 g) F r e n c h s q u a r e b o t t l e s a n d v i s u a l l y c o m p a r e d t o a o n d a r y c o l o r , b a s e d o n p l a t i n u m / c o b a l t s t a n d a r d s , a n d sec-
reference standard. o n d a r y haze, b a s e d on scattered light f r o m a m o n o d i s p e r s e
www.iran-mavad.com

CHAPTER 3--CELLULOSE ESTERS 25
polystyrene latex suspension, are calculated. APHA color and tests: acetyl and propionyl or butyryl contents; apparent ace-
ASTM haze are predicted from the secondary values. tyl content; free acidity; ash; color and haze, heat stability,
hydroxyl content; moisture content; sulfur content; and vis-
cosity. Usually color and haze and viscosity are the only tests
T E S T I N G OF CELLULOSE ACETATE run by the coatings manufacturer. The test methods are the
P R O P I O N A T E A N D CELLULOSE ACETATE same as those used in the testing of cellulose acetate.
BUTYRATE
ASTM Test Method for Cellulose Acetate Propionate and

Cellulose Acetate Butyrate (D 817) contains the following
www.iran-mavad.com

MNL17-EB/Jun. 1995
Drying Oils
by Joseph V. K o l e s k e I
D R Y I N G OILS REPRESENT A SMALL PORTION of the huge fats and HOCH2--CH(OH)--CH2OH + 3 RxCOOH
oils industry. 2 In 1987 there were 81 000 metric tons ( - 1 7 8 Glycerol Fatty Acid
million pounds) of drying oils consumed in the United States RxCOOCH2--CH(OOCRx)--CH2OOCRx + 3 H20
[1]. With an expected annual average growth rate of 2.6%, Triglyceride or Drying Oil Water
there should have been 92 000 metric tons consumed in 1992. where R x is anyone of R a, Rb, or R~. This reaction is reversible
Such consumption represents about 3% of the total nonfood and when the oils are heated they can transesterify with Ra,
fats and oils market and about 1% of the combined food and Rb, and Rc capable of changing their positions in an inter- and
nonfood fats and oils national market. The industry is very an intramolecular sense. Drying oils also contain saturated
mature with relatively little growth expected. Within this glycerides of fatty acids, but these are usually present at
industry, whose growth is about the same as the population relatively low levels and they do not participate in drying or
growth of the United States, drying oil consumption, though polymerization phenomenon. Hydrolysis of drying oils re-
relatively very small, has the highest expected growth rate sults in separation into glycerol and the fatty acid.
over the above five-year period. The paint and coating indus- Drying oils can be classified in many ways, but one princi-
try's need for drying oils is in an overall decline along with ple way is to divide them into drying, semidrying, and
other end use markets, such as binders for hardboard, seal- nondrying (an oxymoron term) oils in accordance with their
ants, plasticizers, linoleum, and core oils. Drying oils used in iodine values, which is a measure of unsaturation content.
paints and coatings are being replaced with oil-free, syn- Although such classification has been rather arbitrary,
thetic, petroleum-derived oligomeric and polymeric binders Rheineck and Austin [2] defined the classes as given in Table
carried in a variety of media or in a neat manner. The printing 1.
ink market is the only one expected to have small growth in The main fatty acids found in drying oils and their chemi-
the area of drying oils. cal composition are given in Table 2. The unsaturated-com-
Usually in the fats and oils industry, products solid at room ponent content of selected drying oils was given in Table 3.
temperature are referred to as fats, and products liquid at Stearic (18-carbon) and palmitic (16-carbon) acids are the
room temperature are termed oils. Often times the terms most widely distributed saturated fatty acids found in drying
"fats" and "oils" are used interchangeably within the industry. oils. Except for cottonseed oil, which contains 29% palmitic
Drying oils, except for fish oil, are of vegetable origin. acid, the drying oils listed in Table 3 contain less than about
Chemically, drying oils are water-insoluble, unsaturated 10% of any particular saturated fatty acid residue. The degree
glycerides of long chain fatty acids with the generalized struc- of double bond unsaturation controls the drying rate. The
ture higher the degree of unsaturation or iodine number (see he-
low), the faster the drying or polymerization of the oil. Dou-
CH~--O--OC--Ra
I ble bond position is also important because conjugated
bonds, which is the term used to described two carbon-car-
CH--O--OC--Rb
I bon double bonds separated by one carbon-carbon single
bond, are more susceptible to autooxidation [4].
CH2--O--OC--R c
Physical characteristics of some typical commercial drying
Generalized Triglyceride
oils are given in Table 4. The oils are particularly character-
where R a, Rb, and R~ are the same or different and represent ized by their Iodine Value, which is a measure of the amount
the hydrocarbon chain residues of fatty acids. In simple of unsaturation present, and Saponification Number, which
terms, this means that most oils are mixed triglycerides. The is an indication of fatty-acid chain molecule weight. Selected
triglycerides are produced by the condensation reaction that property requirement ranges or minimum values for various
occurs between a glycerol molecule and three fatty acid mole-
cules: TABLE 1--Classification of drying
oils by iodine value.
ISenior Consultant, Consolidated Research, Inc., 1513 Brentwood Oil Class Iodine Value
Road, Charleston, WV 25314-2307. Drying oil > 140
2Information about this industry is developed by the U.S. Depart-
ment of Commerce. The nature of this market results in information Semidrying 125- 140
Nondrying < 125
that is usually a few years out of date.
26
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C H A P T E R 4 - - D R Y I N G OILS 27
TABLE 2--Main unsaturated fatty acids found in drying oils.

No. No.
Fatty Carbon Double
Acid Atoms Bonds Structural Formula
Linolenic 18 3 HOOC(CH2)7CH=CHCHECH~CHCH2CH=CHCH2CH 3
Linoleic 18 2 HOOC(CH2)7CH~CHCH2CH~CH(CH2)4CH3
Oleic 18 1 HOOC(CH2)7CH~---CH(CH2)TCH3
Eleostearic 18 3 HOOC(CH2)7CH~CHCH~--~-CHCH~---CH(CH2)aCH3
Licanic 18 3 HOOC(CH2)ECH(O)(CH2)4CH--~CHCH--~CHCH--~CH(CH2)3CH3
Ricinoleic 18 1 HOOC(CH2)7CH~---CHCH2CH(OH)(CH2)5CH 3
drying oils a n d the ASTM m e t h o d t h a t contains o t h e r specifi- characteristics. It is often u s e d as an alternative or supple-
cation p r o p e r t i e s are d e l i n e a t e d in Table 5. The ASTM meth- m e n t to tung oil.
ods cited in Table 5 c o n t a i n references to o t h e r ASTM meth- Safflower oil is o b t a i n e d from seed of the p l a n t Carthamus
ods a p p r o p r i a t e for o b t a i n i n g the i n d i c a t e d p r o p e r t i e s a n d tinctorius. This s e m i d r y i n g oil has drying characteristics be-
for o t h e r p e r t i n e n t properties. The following drying oils are t w e e n those of linseed a n d s o y b e a n oils. Because of its low
the m o s t i m p o r t a n t m e m b e r s of this class of coating r a w linolenic acid content, it has low residual u n s a t u r a t i o n after
materials. cure a n d very g o o d anti-yellowing characteristics.
Castor oil is o b t a i n e d from b e a n s of the p l a n t Ricinus S o y b e a n oil is o b t a i n e d from the seeds of the widely g r o w n
communis. The oil differs f r o m the o t h e r oils in t h a t it is p l a n t Soja hispida. Its m a i n use is in the p r e p a r a t i o n of
m a d e u p of a very high p e r c e n t a g e of the hydroxyl-containing alkyds. It has a wide variety of uses o t h e r t h a n as a drying oil.
ricinoleic acid residue. Although the fatty a c i d residues in this I n a n epoxidized form, this oil is widely u s e d as a reactive
oil c o n t a i n on the average only a single d o u b l e b o n d a n d for plasticizer a n d as an acid scavenger. Both epoxidized soy-
this r e a s o n c a s t o r oil is essentially a n o n d r y i n g oil, it can b e b e a n a n d linseed oil have b e e n r e a c t e d with acrylic acid to
converted into a drying oil b y a d e h y d r a t i o n process in w h i c h form p r o d u c t s with residual acrylate functionality a n d m a r k -
its hydroxyl group a n d a n a d j a c e n t h y d r o g e n a t o m are re- edly higher viscosity. These acrylated oils have been used as
c o m p o n e n t s in r a d i a t i o n - c u r e coating systems that are initi-
m o v e d as w a t e r to form a double b o n d conjugate to the previ-
a t e d with free radicals.
ously existing double bond. The resultant p r o d u c t is k n o w n
Although tall oil is classified as a drying oil, it is not a
as d e h y d r a t e d castor oil, w h i c h has g o o d drying characteris-
triglyceride. The p r o d u c t is o b t a i n e d as the m a j o r b y p r o d u c t
tics.
of sulfate or Kraft pulping of pine a n d certain o t h e r soft-
Cottonseed oil is o b t a i n e d from the p l a n t Gossypium
w o o d s such as spruce a n d h e m l o c k that are p u l p e d in Scandi-
malvaceae. Although it is a drying oil, cottonseed oil is s e l d o m navian countries. Crude tall oil is an a p p r o x i m a t e l y 50/40/10
u s e d as a n oil in the p a i n t a n d coating industry. Its m a i n use by weight mixture of fatty acids, r o s i n acids, a n d un-
is as a source of fatty acids that are used in the m a n u f a c t u r e saponifiable c o m p o u n d s such as higher alcohols, waxes a n d
of alkyd resins. o t h e r h y d r o c a r b o n s , a n d sterols.
Linseed oil, w h i c h is o b t a i n e d f r o m seed of the flax p l a n t Tung oil is o b t a i n e d from seeds of the trees Aleurites fordii
Linum usitatissimum, is the m o s t c o m m o n a n d widely used a n d Aleurites montana. This relatively high viscosity a n d re-
oil. It has a high degree of u n s a t u r a t i o n , w h i c h i m p a r t s a fractive index oil is r a p i d drying a n d is used in varnishes a n d
short drying time, due to its large percentages of linolenic a n d alkyds w h e r e w a t e r resistance is of p r i n c i p a l i m p o r t a n c e .
linoleic triglycerides. It is m a r k e t e d in a n u m b e r of modifica- This oil is also k n o w n as w o o d oil, Chinese w o o d oil, chi-
tions including alkali-refined, acid-refined, boiled, blown, n a w o o d oil, a n d m u oil.
a n d p o l y m e r i z e d linseed oil [2]. P o l y m e r i z e d linseed oils of F i s h oils are the only nonvegetable oils in the drying oil
various acid values a n d viscosities are available. class. They are p r i n c i p a l l y o b t a i n e d from m e n h a d e n (Alosa
Oiticica oil is o b t a i n e d f r o m the nuts of the tree Licana m e n h a d e n ) . These oils are s e m i d r y i n g in n a t u r e a n d c o n t a i n
rigida. It has a very high licanic acid content, a n d the three a significant a m o u n t of s a t u r a t e d fatty a c i d residues. I n addi-
c o n j u g a t e d d o u b l e b o n d s of this acid result in r a p i d drying tion to 16 a n d 18-carbon fatty acid residues, fish oils c o n t a i n
TABLE 3--Weight percentage of major unsaturated fatty acid residues in selected drying oils [2,3] (remainder of
oils is essentially all saturated fatty acid residues).
Unsaturated Fatty Acid
Drying Oil Linolenic Linoleic Oleic Eleostearic Licanic Ricinoleic
Cottonseed .-. 40 24 . . . . . . . . .
Castor ... 3 7 . . . . . . 87
Linseed 52 16 22 . . . . . . . . .
Oiticica . . . . . . 6 .-- 78 -..
Safflower 1 75 13 . . . . . . . . .
Soybean 9 51 25 . . . . . . . . .
Sunfloweff 2 75-52 34-14 . . . . . . . . .
Tall Oil Fatty Acids 3 41 46 . . . . . . . . .
Tung 3 4 8 80 . . . . . .
aThere is wide variation in reported values for sunflower oil.
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TABLE 4--Physical characteristics of some typical drying oils [5].

Specific Iodine Refractive
Gravity, Value, Saponification Acid Index,
Oil 25.5/25.5~ Wijs Value Value 25~
Cottonseed 0.919 105 192 1.0 1.465
Dehydrated castor 0.931 135 190 5.0 1.481
Fish 0.925 158 187 4.0 1.485
Linseed 0.926 180 190 3.0 1.478
Oiticica 0.967 150 190 4.0 1.510
Safflower 0.922 145 192 2.0 1.474
Soybean 0.920 135 190 2.5 1.473
Sunflower 0.917 135 192 2.0 1.473
Tall oil .-. 133 196 194.0 -..
Tung 0.915 170 192 0.2 1.517
30 to 40% of a r a c h i d o n i c (20-carbon with four double bonds), ization is initiated by r e a c t i o n of oxygen with an u n s a t u r a t e d
c l u p a n o d o n i c (22-carbon with five double bonds), a n d nisinic fatty acid residue a n d free radical f o r m a t i o n followed by
(24-carbon with five d o u b l e bonds) acid residues. Because of chain p r o p a g a t i o n in w h i c h free radicals react with oxygen to
the presence of acid residues with high degrees of u n s a t u r a - form peroxy radicals w h i c h in t u r n react with o t h e r u n s a t u r a -
tion, fish oils have a strong t e n d e n c y to yellow after cure due tion sites [10]. The p o l y m e r i z a t i o n is t e r m i n a t e d by c o m b i n a -
to residual u n s a t u r a t i o n . Fish oils do r e p r e s e n t a source of tion of various free radicals that exist in the r e a c t i o n mass.
the very long chain fatty acids that are not p r e s e n t in vegeta- Availability of m u l t i p l e d o u b l e b o n d s in s o m e of the mole-
ble oils. Currently, they are not widely used in the coatings' cules results in a crosslinked p o l y m e r i c network.
i n d u s t r y with use often d i c t a t e d b y relative price of linseed Solidification o r p o l y m e r i z a t i o n o f a d r y i n g oil such as
a n d s o y b e a n oils. linseed oil can be t h o u g h t of in the following m a n n e r . W h e n
Although r a w drying oils are used in coating formulations, the drying oil is exposed to air, there is an i n d u c t i o n p e r i o d
the oils are often further p r o c e s s e d before use. S u c h process- d u r i n g w h i c h oxygen is a b s o r b e d a n d it c o n s u m e s antioxi-
ing includes alkali refining, dehydration, d r i e r addition, h e a t d a n t s p r e s e n t in the system. In this step, there is very little
p o l y m e r i z a t i o n that involves heating an oil to selectively ad- a p p a r e n t change in physical or chemical properties. This is
vance m o l e c u l a r weight a n d viscosity, a n d oxidation o r blow- followed by a p e r i o d in which there is a m a r k e d oxygen
ing w h e r e i n air is b u b b l e d into h e a t e d oil a n d oxygen is t a k e n u p t a k e a n d an a p p e a r a n c e of peroxides w h i c h d e c o m p o s e to
up with a resultant m o l e c u l a r weight increase. Drying oils are form free radicals. The free radicals then initate a n a d d i t i o n
also modified b y r e a c t i o n with maleic anhydride, by copoly- p o l y m e r i z a t i o n of the u n s a t u r a t i o n and a crosslinked net-
m e r i z i n g with vinyl m o n o m e r s such as styrene, a n d by w o r k results. During the r e a c t i o n scheme, low m o l e c u l a r
epoxidation. weight cleavage p r o d u c t s including c a r b o n dioxide a n d w a t e r
Reaction with oxygen is the m o s t i m p o r t a n t r e a c t i o n that are formed.
drying oils u n d e r g o in the drying or p o l y m e r i z a t i o n process ASTM D 1640 S t a n d a r d Test Methods for Drying, Curing,
[6, 7]. Oxidation can result in trans i s o m e r formation, cleav- o r F i l m F o r m a t i o n of Organic Coatings at R o o m Tempera-
age of the c a r b o n - c a r b o n chain along with f o r m a t i o n of vola- ture has p r o c e d u r e s r e c o m m e n d e d for d e t e r m i n a t i o n of the
tile byproducts, a n d polymerization. These reactions can be stages a n d rates of film f o r m a t i o n in the drying o r curing of
catalyzed with metallic salts such as cobalt n a p t h e n a t e (see organic coatings that are to be used at r o o m t e m p e r a t u r e .
next chapter) that p r o m o t e free radical f o r m a t i o n by r e a c t i o n I n c l u d e d are m e t h o d s for d e t e r m i n i n g tack-free, dry-to-
with h y d r o p e r o x i d e s a n d o t h e r peroxides that are f o r m e d in touch, dry-hard, dry-through, print-free, a n d dry-to r e c o a t
the oxidation process [8]. F a r m e r a n d coworkers [9] were times. In one instance (Section 7.5.1) a p a r t i c u l a r p r o c e d u r e
first to describe the m e c h a n i s m of a u t o o x i d a t i o n w h e r e i n is specified for drying oils. ASTM S t a n d a r d Test M e t h o d for
they found that four different m o n o h y d r o p e r o x i d e s were Gel Time of Drying Oils (D 1955), deals with d e t e r m i n a t i o n of
f o r m e d w h e n oxygen was r e a c t e d with the methyl ester of the gel t i m e of oiticiica a n d tung oil. This s i m p l e test method,
oleic acid. A different r e a c t i o n p a t h was involved when lin- which" involves heating the oil in a test tube a n d observing the
oleic esters were autooxidized since two m o n o h y d r o - t i m e required for the oil to congeal a r o u n d glass r o d relative
peroxides a n d one cyclic d i p e r o x i d e were formed. Polymer- to a s t a n d a r d of k n o w n behavior, can be used for o t h e r oils
TABLE 5--Selected property requirements for drying oils (indicated ASTM method has other requirements).
Specific Iodine Acid
Gravity, Value, Saponification Value, ASTM
Oil 25/25~ Wijs Value max Method
Castor, raw 0.957-0.961 83-88 176-184 2.0 D 960
Dehydrated castor 0.926-0.937 125-145 188-195 6 D 961
Linseed, raw 0.926-0.931 177 (min) 189.0-195.0 4.0 D 234
Oiticica 0.972 (min) 135 (min) None 8.0 D 601
Safflower 0.922-0.927 140-150 189-195 3.0 D 1392
Soybean, refined 0.917-0.924 126 (min) 189-195 0.3 D 1462
Tung, raw 0.933-0.938 163 I89-195 5.0 D 12
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CHAPTER 4 - - D R Y I N G OILS 29
t h a t have c o n j u g a t e d double b o n d or o t h e r gelling character- [4] Solomon, D.H., The Chemistry of Organic Film Formers,
istics. ASTM S t a n d a r d G u i d e for Testing Drying Oils (D 555) Kreiger, New York, 1977.
is an overall guide to selection a n d use of p r o c e d u r e s for [5] Gallagher, E. C., "Drying Oils," Paint Testing Manual, G.G.
testing drying oils that are c o m m o n l y u s e d in coatings. Sward, Ed., 13th ed., The American Society for Testing and
Materials, Philadelphia, 1972, p. 53.
[6] Harwood, R. J., Chemical Reviews, Vol. 62, 1962, p. 99.
REFERENCES [7] Fox, F. L., Unit Three, "Oils for Organic Coatings," Federation
Series on Coatings Technology, W. R. Fuller, Ed., Federation of
[1] "Fats and Oils Industry Overview," Chemical Economics Hand- Societies for Paint Technology, Philadelphia, 1965.
book, SRI International, Nov. 1990. [8] Russell, G. A., Journal of Chemical Education, Vol. 36, No. 3,
[2] Rheineck, A. E. and Austin, R. O., Film Forming Compositions, 1959, p. 111.
R.R. Myers and J. S. Long, Eds., Marcel Dekker, Inc., New [9] Farmer, E. H. and Sutton, D. A., Journal of the Chemical Society,
York, Vol. 1, No. 2, 1968. 1946, p. 10.
[3] Gunstone, F. D., Chemistry and Biochemistry of Fatty Acids and [10] Cowan, J. C., "Drying Oils," Kirk-Othmer Encyclopedia of Chemi-
Their Glycerides, 2nd Ed., Chapman and Hall, Ltd., 1967. cal Technology, Vol. 8, 3d ed., 1979, pp. 130-150.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Driers and Metallic Soaps

by Marvin J. Schnall I
METALLICSOAPSARE COMPOUNDSof alkaline metals or heavy TABLE l--Coatings applications of metallic soaps.
metals and monobasic carboxylic acids containing from 7 to Applications Metals Acids
22 carbon atoms. The water-insoluble metallic soaps are of
Driers Cobalt, manganese, lead, Tallates, octoates,
particular interest to the coatings industry, although potas- iron, rare earth, naphthenates,
sium and lithium soaps have limited water solubility. cerium, zirconium, neodecanoates,
The applications of metallic soaps in coatings include their zinc, calcium, barium, synthetic acids,
use as driers, catalysts, stabilizers, biocides, bodying agents, bismuth, potassium, linoleates,rosinates
vanadium, aluminum
and flatting agents. An overview of metallic soap applications
is presented in Table I. This chapter concentrates primarily Catalysts Potassium, lithium, Octoates, naphthenates,
on metallic soaps used as driers, although a brief review of cobalt, copper, tin, laurates,
bodying and flatting applications is included. zinc, manganese neodecanoates
Stabilizers Barium, cadmium, tin, Proprietary, sulfates,
zinc, calcium, lead carbonates, stearates
M E T A L L I C S O A P S AS B O D Y I N G A N D
Biocides Copper, tin, zinc, Naphthenates, octoates,
FLATTING AGENTS mercury phenyl acetates,
phenyl oleates,
Aluminum stearates, aluminum octoates, and calcium laurates, butyl oxides
linoleate pulp were at one time widely used as bodying and
Bodying Aluminum, calcium Stearates, octoates,
pigment-suspending agents in solvent-based coatings. Their agents linoleates
advantages include fairly high efficiency and ease of incorpo-
ration. However, they have a number of deficiencies, includ- Flatting agents Zinc, calcium Stearates
ing sensitivity to variations in the formulation and in the
processing of paints, as well as adverse effects on film hard-
The induction period occurs because most drying oils con-
ness and resistance properties. As a result, they have been
replaced to a considerable extent by the bentonite clay and tain natural antioxidants, the effects of which must be over-
organic wax derivatives [2]. come before the drying process can begin. Oxygen is then
Zinc and calcium stearates are used on occasion as flatting absorbed from the air at the unsaturated sites on the oil
additives in clear solvent-based coatings. However, precipi- molecule, and, as the absorption continues, forms peroxides.
tated and fumed silicas are now more commonly used for this These peroxides then decompose to form free radicals which
purpose. Zinc stearate is also used to facilitate sanding of act as catalysts to promote cross-linking of the oil or resin
primers and sealers for wood furniture finishing [2]. molecules at the unsaturated sites, resulting in dried films.
These steps will occur in the absence of driers, but driers
accelerate the process by means of the following mechanisms
T H E O R Y OF O X I D A T I V E D R Y I N G A N D [1,5]:
F U N C T I O N OF D R I E R S [1,5] 1. Removal of natural antioxidants.
2. Acceleration of oxygen absorption.
It is generally accepted that vehicles based on unsaturated 3. Acceleration of peroxide decomposition.
oils, including alkyd resins and oleoresinous varnishes, dry
by oxidation according to the following steps: Naturally occurring antioxidants may be considered as
1. Induction period. negative catalysts for oxidation, whereas driers are positive
2. Oxygen absorption. catalysts, counteracting the effects of the antioxidants.
3. Peroxide formation. The multivalent nature of the drier metal is considered to
4. Peroxide decomposition to free radicals. be a key factor accelerating oxygen absorption in the film.
5. Free radicals promote cross-linking. The drier metal is initially in a divalent state and is converted
to a trivalent state by the presence of oxygen in the film. The
1Coatings consultant, 620 Airport Rd., Suite 304, Chapel Hill, NC metal then releases the oxygen to the film and is converted
27514. back to the divalent form. This action accelerates the process
30
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CHAPTER 5 - - D R I E R S AND METALLIC SOAPS 31
of oxygen absorption, peroxide formation, and peroxide de- Water-dispersible driers may be prepared by adding non-
composition, which is responsible for oxidative film drying. ionic surfactants to naphthenate or synthetic acid driers.
However, proprietary cobalt and manganese drier com-
pounds are available that are purported to be more suitable
DESCRIPTION OF DRIER METALS for water-based coatings.
Trade names of the various commercial drier types avail-
The metals that act as catalysts to promote oxidation and able are listed in Table 2.
which may be used in driers are indicated below:
Cobalt
Manganese t Active Lead
Calcium 1 MISCELLANEOUS DRIERS
Vanadium Zirconium
Zinc Auxiliary Restrictions on solvent emissions have stimulated the de-
Iron velopment of both higher-solids and water-reducible coat-
Rare Earth ings. In the process of formulating these coatings, chemists
Cerium are experiencing difficulty obtaining satisfactory drying
Aluminum properties with the conventional metallic soap driers. Alter-
native drier compounds, including both organics and propri-
Cobalt and manganese, particularly cobalt, are the most etary metallic complexes, are currently being offered [6].
active drier metals. Cobalt promotes surface drying of films, Some typical examples are shown in Table 3. They are usually
while manganese affects both surface and through drying. recommended in combination with conventional metallic
Vanadium has been mentioned in the literature as an active soap driers for improved drying efficiency.
drier but is seldom used in coating formulations. Another class of metallic compounds closely related to
The auxiliary driers are seldom used alone, but rather in driers are loss of dry inhibitors or "feeder" driers. These are
combination with cobalt and/or manganese. Their functions compounds designed to prevent loss of drying efficiency of
are to increase the efficiency of the active drier metals and to paints on aging resulting from the adsorption of driers by
increase film hardness. In the past, lead was the most fre- pigments, particularly carbon black and organic red pig-
quently employed auxiliary drier, but it is presently out of ments. They function by dissolving gradually into the coating
favor due to toxicity. Calcium and zirconium driers are most vehicle so that the metals are available over a period of time
frequently used as lead replacements. Zinc is used primarily rather than immediately. In this manner, they replace the
for improved film hardness and to prevent wrinkling of thick drier metals that have been adsorbed by the pigments,
films. Iron driers are used mainly to improve drying of baking
systems when their dark color can be tolerated. Rare earth
and cerium driers are recommended occasionally for im-
proved through drying and as oxidation catalysts for baking.
Interest in aluminum compounds as auxiliary driers has in- TABLE 2--Commercial drier types [3].
creased recently with the advent of high-solids alkyd resins. Type of Drier Trade Name Supplier
Aluminum compounds are being recommended to improve Synthetic acid Cem-All Mooney Chemical,
film hardness with these resins but may at times adversely division of OMG
affect viscosity stability and promote gelation. NuXtra Huls America
Troymax Troy Corp.
Octoate Hex-Cem Mooney Chemical,
D E S C R I P T I O N OF D R I E R ACIDS division of OMG
Octoate Huls America
To perform their function, driers should be soluble in the
Neodecanoate Ten-Cem Mooney Chemical,
vehicles to which they are added. Solubility is achieved by
division of OMG
reacting the drier metals with organic acids to form metallic
soaps. The most commonly employed acids are as follows: Naphthenate Nap-All Mooney Chemical,
Linoleates division of OMG
Nuodex Huls America
Rosinates Troykyd Troy Corp.
Tallates
Naphthenates Tallates Lin-All Mooney Chemical,
Octoates (2-ethyl hexanoates) division of OMG
Synthetic acids
Water dispersible Hydro-Cem Mooney Chemical,
Neodecanoates division of OMG
Chronologically, the linoleates, rosinates, and tallates were Hydro-Cure Mooney Chemical,
the first types developed, followed by the naphthenates and division of OMG
Nuocure Huls America
the octoates. A more recent development is the synthetic acid Troykyd WD Troy Corp.
type, which is proprietary but closely related to the octoates. Calcicat Ultra adhesives
The synthetic acid and neodecanoate driers can be prepared Aquacat Ultra adhesives
at higher metal concentrations than the other types and are Magnacat Ultra adhesives
gradually replacing the older acids. Zircat Ultra adhesives
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TABLE 3--Alternate drier compounds. T E S T I N G OF D R Y I N G E F F I C I E N C Y

Trade Name Company Composition
The procedures used to determine the stages of film forma-
Activ-8 R.T. Vanderbilt 1,10-phenanthroline
Co. tion during the drying of coatings are described in ASTM Test
Dri-RX Mooney 2,2'-dipyridyl Methods for Drying, Curing, or Film Formation of Organic
Chemicals Inc. Coatings at Room Temperature (D 1640) [4]. With coatings
Drymax Huls America 2,2'-dipyridyl containing metallic driers, it is recommended that the paint
Nutra ADR 10% Huls America proprietary metal
complex samples age overnight following the drier additions before
Nutra LTD 18% Huls America proprietary metal drying tests. The drying conditions, shown in Table 6, are
complex usually specified but are subject to agreement between the
purchaser and the seller.
The methods used to determine the various stages of drying
thereby maintaining satisfactory drying on prolonged stor- may be summarized as follows:
age. Lead compounds, including litharge, were used formerly 1. Set-To-Touch-Time--no transfer of the coating upon
but have been replaced by lead-free compounds based pri- lightly touching the film with the finger.
marily on less soluble forms of cobalt and other drier metals. 2. Dust-Free-Time--(a) cotton fibers dropped on the film can
Commercially available feeder driers are listed in Table 4. be removed by blowing lightly; (b) fine calcium carbonate
All are lead-free metal complexes except for the last item [3]. extender dropped on the film can be completely removed
by blowing gently and wiping with a cloth or brush.
3. Tack-Free-Times--a specified type of paper or aluminum
foil will no longer adhere to the film when applied under
D R I E R L E V E L S IN COATINGS specific conditions.
4. Dry-To-Touch-Time--the film no longer adheres to the fin-
Drier requirements for coatings are usually expressed in ger when pressed firmly and does not rub up when rubbed
terms of percent drier metal based on oxidizable vehicle non- lightly.
volatile content. A typical calculation is as follows [1]: 5. Dry-Hard-Time--a thumb print applied under specified
Assume: conditions is completely removed from the film when pol-
1. In a 1000-g paint formulation, there are 300 g of vehicle ished lightly with a soft cloth.
nonvolatile. 6. Dry-Through-Time--the film is not distorted or detached
2. Cobalt drier used is 12% metal by weight. when the thumb is applied to it in a specified manner and
3. Calcium drier used is 10% metal by weight. rotated through a 90~ angle.
4. Required for optimum drying: 0.05% cobalt plus 0.2% cal- 7. Dry-To-Recoat--a second coat or top coat can be applied
cium (percent metal based on vehicle nonvolatile). without development of lifting or loss of adhesion of the
per 1000 g of paint: first coat.
Cobalt metal required = 0.0005 x 300 g = 0.15 g 8. Print-Free-Time--army duck or cheesecloth applied at a
Calcium metal required = 0.002 x 300 g = 0.6 g pressure of 3.5 or 6.9 KPa no longer marks the film as
determined by photographic standards shown in ASTM
(10% calcium drier required) = (0.6 g calcium metal) = (6 g Test Method for Print Resistance of Lacquers (D 2091) [4].
(0.10 g metal/g drier) In addition to the above subjective tests, a number of me-
drier as supplied)
chanical drying time recorders are available. The instrument
(12% cobalt drier required) = (0.15 g cobalt metal) = (1.25 g referred to most frequently in recent literature is the Byk-
(0.12 g metal/g drier) Gardner Improved Circular Drying Time Recorder [7]. This
drier as supplied) functions by moving a Teflon stylus over the applied film in a
circular path. The pattern left in the film by the stylus after a
The optimum levels of drier metal required will vary de-
complete revolution is observed. Recorders are available
pending on the type of resin system employed and the condi-
which make complete revolutions in 1, 6, 12, or 24-h. With
tions of drying. Typical metal concentrations for a number of
the use of a plastic template, set-to-touch, surface dry, and
common vehicles are indicated in Table 5.
through-dry times may he noted.
Development of film hardness is also an important crite-
rion of drier efficiency. Tests [4] used to measure hardness
TABLE 4--Commercial feeder driers.
include:
Company Trade Name
1. Test Method for Film Hardness by Pencil Test (D 3363)--a
Mooney Chemical, Hex-Cem LFD series of pencils varying in lead hardness from 6B (softest)
division of OMG
Mooney Chemical, through 6H (hardest) are pushed into the film, and the
Hydroxy Ten-Cem
division of OMG Cobalt hardest pencil that will not penetrate the film is noted.
Troy Corporation Troykyd Perma Dry 2. Test Method for Hardness of Organic Coatings by Pendulum
Huls America Nuact Cobalt 254 Damping Tests (D 4366-87)--either a Konig or a Persoz
Huls America Nuact NOPB Pendulum Hardness Tester is employed with the time, in
Huls America Nuact Paste (lead-based)
seconds, noted for the swing amplitude of the pendulum to
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TABLE 5--Typical drier recommendations, percent metal based on vehicle nonvolatile.

2,2'-Dipyridyl,
Cobalt Manganese Zirconium Calcium Zinc 1,10-Phenantbroline 30%
Long oil alkyd-air dry 0.04-0.06 0.1-0.3
0.04-0.06 0.1-0.3
0.04-0.06 0,1-0.2 0.1-0.2
Medium oil alkyd-air 0.04-0.06 0.1-0.3

dry 0.04-0.06 0.1-0.3
0.04-0.06 0.1-0.2 0.1-0.2
Short off alkyd air-dry 0.04-0.06 0.1-0.3

0.04-0.06 0.1-0.3
0.04-0.06 0.1-0.2 0.1-0.2
Chain-stopped alkyd 0.05-0.08 0.2

0.05-0.08 0,1 0.1
Medium oil alkyd-bake 0,0 I-0.03 O.I-0.5

Oil-modified urethane 0.02-0.04 0.1-0.3
0.02-0.04 0.1-0.3
0.02-0.04 0.2
Linseed oil 0.02 0.02 0.1-0.2 0.1-0.2

0,02-0.04 0.1-0.3 0.1-0.15
0.02-0.04 0.1-0.3
Alkyd-oil house paint 0.02-0.03 0.02-0.03 0.2-0.3
0.02-0.03 0.02-0.03 0.2-0.3
0.02-0.04 0.02-0.04 0.1-0.2 0.1-0.2 0.1-0.15
Epoxy Ester 0.03-0.05 0, I-0.2
0.03-0.05 0.1-0.2
Acrylic Modified alkyd 0.04-0.08 0.1 0,1

Oleoresinous varnish 0.02-0.06 0.2
Vinyltoluene alkyd 0.02-0.04 0.1

0.02-0.04 0.1
High solids alkyd 0.04-0.06 0.5-0.9 0.2

0.04-0.06 0.5-0.9 0.2
0.04-0.06 0.2-0.4 0.2-0.4
Water-based alkyds 0.04-0.06 0.1-0.3
(water dispersible 0.04-0.06 0.1-0.3
driers) 0.05-0.1 0.15-0.3 0.15-0.2 0.1-0.3
decrease b y a specified degree w h e n set into oscillation on S P E C I F I C A T I O N S F O R LIQUID P A I N T

the d r i e d film. DRIER
3. Test Methods for Indentation Hardness of Organic Coatings
(D 1474)--either a K n o o p or a Pfund I n d e n t e r is a p p l i e d to Drier specifications as described in ASTM Specification for
a film u n d e r a specified loading, a n d the d e p t h of indenta- Liquid Paint Driers (D 600) involve the following classes:
tion is m e a s u r e d with the a i d of a microscope. The d e p t h is Class A 2-ethyl hexanoic acids in p e t r o l e u m spirits.
converted to either a K n o o p or a Pfund H a r d n e s s N u m b e r Class B N a p h t h e n i c acids in p e t r o l e u m spirits.
using the equations in the standard. Class C N e o d e c a n o i c acids in p e t r o l e u m spirits.
Class D Tall oil fatty acids in p e t r o l e u m spirits.
TABLE 6--Standard drying conditions. Class E Any of the above, plus additives to m a k e the
Condition Typical Value driers w a t e r dispersible.
Class F Other unidentified acids a n d acid blends.
Ambient temperature 23 + 2~
Relative humidity 50 + 5% A c o m p r e h e n s i v e table of liquid p a i n t driers of the above
Film thickness (dry) 12.5 to 45 ~m
Substrate Clean glass classes is given in ASTM D 600 [4]. The typical p r o p e r t i e s of
Lighting No direct sunlight the driers listed a n d r e p r o d u c e d in Table 7 include p e r c e n t
Applicators Doctor blades m e t a l concentration, p e r c e n t nonvolatile content, specific
Coating viscosity Close to normal application
gravity, G a r d n e r Color, a n d G a r d n e r - H o l d t viscosity.
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TABLE 7--Typical requirements of liquid paint driers, a

Metal Typical Specific
Colorb Gardner G-H Viscosity
Concentration, % Nonvolative Gravity, 25/25~ (Test Method (Test Method
Class Metal Min Max Matter, %, Max Min Max D 1544) D 1545)
A Calcium 3.9 4.1 50 0.884 C .-- 3 A
A Calcium 4.9 5.1 60 0.894 0.912 5 C
B Calcium 3.9 4.1 70 0.902 0.937 10 D
B Calcium 4.9 5.1 85 0.932 0.970 11 T
C Calcium 4.9 5.1 46 0.888 ..- 2 A
D Calcium 3.9 4.1 66 0.890 0.918 9 B
E Calcium 3.9 4.1 63 0.905 0.930 8 G
E Calcium 5.9 6.1 76 0.922 0.960 5 N
F Calcium 3.9 4.1 50 0.850 0.884 3 A
F Calcium 4.9 4.1 60 0.900 0.936 4 B
F Calcium 5.9 6.1 74 0.873 0.948 6 N
F Calcium 7.9 8.1 70 0.958 --. 5 B
F Calcium 9.9 10.1 65 1.000 1.030 7-8 K
A Cerium 5.9 6.1 30 0.856 ... 8 A
B Cerium 5.9 6.1 57 0.925 ..- 17 A1
A Cobalt 5.9 6.1 45 0.875 0.900 Blue/purple A
A Cobalt 11.8 12.2 90 1.008 1.060 Blue/purple J
B Cobalt 5.9 6.1 67 0.918 0.970 Blue/purple B
C Cobalt 11.8 12.2 65 0.984 ... Blue A
D Cobalt 5.9 6.1 72 0.912 0.956 Purple C
E Cobalt 4.9 5.1 60 0.926 -.. Red/purple A
E Cobalt 5.9 6.1 71 0.945 0.960 Blue/purple I
F Cobalt 5.9 6.1 70 0.870 0.958 Blue/violet A
F Cobalt 11.8 12.2 80 1.014 1.040 Blue/violet J
A Iron 5.9 6.1 50 0.900 0.930 Dark brown A
B Iron 5.9 6.1 67 0.960 0.990 Dark brown M
F Iron 5.9 6.1 50 0.905 0.930 Brown A
F Iron 8.9 9.1 78 0.950 0.985 Brown A
F Iron 11.8 12.2 75 1.068 ..- Brown A
A Lead 23.8 24.2 65 1.090 1.110 3 A
B Lead 23.8 24.2 67 1.125 1.160 11 B
C Lead 23.8 24.2 61 1.100 ... 2 B
D Lead 23.8 24.2 66 1.100 1.125 10 A2
E Lead 23.8 24.2 71 1.125 1.150 7 A
F Lead 23.8 24.2 67 1.080 1.140 10 A
F Lead 35.8 36.2 81 1.350 1.393 8 H
A Manganese 5.9 6.1 50 0.888 0.920 Red/brown A
B Manganese 5.9 6.1 66 0.930 0.965 17 D
Continued
T E S T I N G OF LIQUID P A I N T D R I E R S 6. Drying power--As d e s c r i b e d in t h e s e c t i o n e n t i t l e d "Test-

ing of D r y i n g Efficiency."
A S T M Test M e t h o d for L i q u i d P a i n t D r i e r s (D 564) [4] out- 7. Viscosity--According to A S T M T e s t M e t h o d for V i s c o s i t y
lines t h e test p r o c e d u r e s e m p l o y e d , i n c l u d i n g b o t h p h y s i c a l o f T r a n s p a r e n t L i q u i d b y B u b b l e T i m e M e t h o d (D 1545).
a n d c h e m i c a l tests. T h e p h y s i c a l tests i n c l u d e : This involves c o m p a r i n g t h e t i m e of travel of b u b b l e s in
t u b e s of t h e s a m p l e v e r s u s G a r d n e r - H o l d t s t a n d a r d tubes.
1. Appearance--observations for clarity a n d c l e a n n e s s in ac- T h e s t a n d a r d s w e r e f o r m e r l y d e s i g n a t e d by l e t t e r b u t are
c o r d a n c e w i t h A S T M Test M e t h o d for Clarity a n d Clean- n o w i n d i c a t e d d i r e c t l y in stokes. A table in D 1545 indi-
ness of P a i n t L i q u i d s (D 2090). cates t h e c o n v e r s i o n f r o m letters to stokes.
2. Color--according to A S T M D 1544, w h i c h e m p l o y s t h e
G a r d n e r n u m e r i c a l c o l o r scale. H o w e v e r , a n u m b e r of C h e m i c a l analysis is u s e d to d e t e r m i n e t h e m e t a l c o n t e n t of
driers, i n c l u d i n g cobalt, m a n g a n e s e , nickel, a n d r a r e earth, l i q u i d p a i n t driers. T h e E D T A m e t h o d is u s e d for m o s t d r i e r
d o n o t fit i n t o this scale a n d are r e p o r t e d descriptively. m e t a l s (Table 8). T h e l i q u i d d r i e r is d i s s o l v e d o r d i g e s t e d in
3. Nonvolatile Content--According to A S T M D 1644, M e t h o d solvents a n d t h e n t r e a t e d w i t h a n excess of s t a n d a r d E D T A
A o r B. M e t h o d A involves h e a t i n g s a m p l e s at 105~ for s o l u t i o n ( d i s o d i u m salt of e t h y l e n e d i a m i n e t e t r a c e t i c a c i d di-
10 m i n , w h i l e M e t h o d B specifies 150~ for 10 m i n . hydrate). T h e excess of E D T A is t h e n t i t r a t e d to a n e n d p o i n t
4. Miscibility with Oil--One v o l u m e of t h e d r i e r s a m p l e is d e t e r m i n e d b y a specified i n d i c a t o r . This m e t h o d is a p p l i c a -
m i x e d w i t h 19 v o l u m e s of r a w l i n s e e d oil. T h e m i x t u r e is ble to single m e t a l d r i e r s only, n o t to d r i e r blends. An E D T A
o b s e r v e d for a n y signs of s e p a r a t i o n o r c l o u d i n g o v e r a m e t h o d is n o t yet a v a i l a b l e for c e r i u m , a n d a n o x i d i m e t r i c
24-h period.
d e t e r m i n a t i o n is specified [ASTM Test M e t h o d for C e r i u m in
5. Stability--The d r i e r s a m p l e is s t o r e d for 7 days at 25~
P a i n t D r i e r s by O x i d i m e t r i c D e t e r m i n a t i o n (D 3970)]. T a b l e 8
- 20~ a n d 50~ a n d e x a m i n e d for i n d i c a t i o n s of clotting,
o u t l i n e s t h e A S T M d e s i g n a t i o n s , i n d i c a t o r s , a n d t i t r a t i n g so-
gelation, o r p r e c i p i t a t i o n .
l u t i o n s for analysis o f d r i e r m e t a l s by E D T A titration.
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TABLE 7--Continued
Metal Typical Specific Colorb Gardner G-H Viscosity

Concentration, % Nonvolative Gravity, 25/25~ (Test Method (Test Method
Class Metal Min Max Matter, %, Max Min Max D 1544) D 1545)
C Manganese 5.9 6.1 50 0,870 .-. 10 A
D Manganese 5.9 6.1 72 0.942 0.972 Brown E
E Manganese 4.9 5.1 42 0.911 ... Brown E
E Manganese 5.9 6.1 69 0.942 0.965 Brown E
F Manganese 5.9 6.1 55 0.870 1.020 18 A
F Manganese 8.9 9.1 80 0.950 1.020 18 H
F Manganese 11.8 12.2 75 1.044 ... 16 C
A Nickel 9.9 10.1 70 1.032 .-. Green A
A Rare earth a 5.9 6.1 30 0.630 0.880 6 E
A Rare earth 11.8 12.2 55 0.977 -.. Yellow/green C
B Rare earth 3.9 4.1 35 0.840 0.855 10 A
C Rare earth 5.9 6.1 35 0.876 ... 8 A5
A Zinc 7.9 8.1 50 0.880 0.906 6 G
A Zinc 17.8 18.2 90 1.068 1.130 7 Z
B Zinc 7.9 8.1 70 0.915 0.960 9 A
B Zinc 9.9 10.1 75 0.980 1.044 8 L
D Zinc 7.9 8.1 70 1.008 ... 11 D
E Zinc 7.9 8.1 42 0.946 ... 2 A
F Zinc 7.9 8.1 60 0.855 0.963 7 C
F Zinc 15.8 16.2 80 1.020 1.100 3 B
A Zirconium 5.9 6.1 30 0.860 0.864 2 A
A Zirconium 11.8 12.2 56 0.960 0.992 4 A
A Zirconium 17.8 18.2 55 1.070 1.074 3 A
A Zirconium 23.8 24.2 77 1.240 -.. 2 J
C Zirconium 5.9 6.1 23 0.864 .-- 2 A5
C Zirconium 11.8 12.2 46 0.976 ... 2 A
E Zirconium 5.9 6.1 31 0.864 ... 4 A
E Zirconmm 11.8 12.2 55 0.975 1.020 4 A
F Zirconmm 5.9 6.1 28 0.855 0.870 2 A5
F Zirconium 11.8 12.2 55 . . . . . . . . . . . .
F Zirconium 17.8 18.2 80 1.090 1.130 4 Z
F Zirconium 23.8 24.2 93 1.240 1.260 6 J
"Source: National Paint and Coatings Association, Chemical Specialties Section, Raw Material Index, April 1978 edition per Gardner Method D 1544.
blf off the scale, as observed by the unaided eye.
~'Only one drier was listed in this category.
aThe metal content represents total rare earth metals calculated as cerium, but the drier contains cerium and lanthanum, as well as minor amounts of other rare
earth metals.
TABLE 8 - - M e t a l analysis by EDTA titration.

ASTM Titrating
Metal Method Solvent Indicator Solution
Cobalt D 2373 Glacial acetic acid PANa Cupric sulfate
Lead D 2374 Glacial acetic acid PAN~ Cupric sulfate
Manganese D 2375 Toluene-ethanol E r i o c h r o m e hlack-T Zinc chloride
Calcium or zinc D 2613 Toluene-ethanol E r i o c h r o m e black-T Zinc chloride
Iron D 3804 Isopropanol E r i o c h r o m e black-T Zinc chloride
Zirc D 3969 HSO-HO Xylenol orange B i s m u t h nitrate
Vanadium D 3988 Isopropanol-HCL Xylenol orange Zinc chloride
Total rare earth D 3989 Isopropanol-HCL Xylenol orange Zinc chloride
a1(2-Pyridylazo)-2-Naphthenol.
REFERENCES [4] Annual Book of ASTM Standards, Books 6.01 a n d 6.03, American
Society for Testing a n d Materials, Philadelphia, 1990.
[1] Hurley, R., "Metal Soaps: Drier Stabilizers a n d Related Com- [5] Godbole, V. A., "Use of Metallic Driers in Organic Coatings,"
pounds," Handbook of Coatings Additives, Chap. 13, Marcel Dek- Paint India, April 1986, pp. 28-25.
ker, Inc., New York, 1987, pp. 485-509. [6] Belletiere, S. J. a n d Mahoney, D. M., "Multi-Metallic Complexes:
[2] Schnall, M., "Thickeners for Solvent-Based Coatings," Handbook The Next Generation of Driers," Journal of Coatings Technology,
of Coatings Additives, Chap. 3, Marcel Dekker, Inc., New York, Vol. 59, No. 752, S e p t e m b e r 1987, pp. 101-108.
1987, pp. 33-34.
[7] Instrument Catalogue, Section 9, "Drying Time," Byk-Gardner,
[3] Raw Materials Index, Chemical Specialties Section, National Paint
& Coatings Association, W a s h i n g t o n , DC, March 1989, pp. 2-11 Inc., Silver Springs, MD, 1990.
a n d pp. 22-27.
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Part 3: Synthetic Materials
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MNL17-EB/Jun. 1995
Acrylic Polymers as Coatings 6

Binders
by John M. Friel I
ACRYLICPOLYMERS, WHICHARE USED as coatings binders, are ranging from a few hundred to a few thousand centipoise. In
comprised chiefly of esters of acrylic and methacrylic acid later years, 100% solid-grade versions became popular since
that are polyrnerized by additional polymerization, usually they reduced the cost and safety concerns associated with
using a free radical mechanism: shipping resins containing high solvent levels. The coatings
manufacturer is then able to dissolve the solid-grade acrylic
H CH 3
in a wide range of solvents, thereby having greater control
I I over the formulation ingredients.
(--CH2--C - - ) - - --(--CH2--C--)--
A wide range of properties can be built into an acrylic
I I coatings binder by careful selection of the type and level of
C ~0 C=0
the acrylic monomers used. Some of the important properties
I t for several acrylic homopolymers are shown in Table 1 [3].
OR OR
Coatings for a wide range of applications can therefore be
An acrylate A methacrylate
custom designed. Some of the principal applications for
Interest in acrylic technology dates back to the 1920s when acrylic solution coatings include automotive finishing, fac-
Dr. Otto Rohm developed a practical process for making ac- tory, and farm implement coatings, general-purpose pig-
rylate esters from ethylene. Shortly afterwards, his associate, mented coatings, aerosol lacquers, and clear coatings for a
Otto Haas, established the first commercial production of multitude of substrates. There are two types of acrylic solu-
methyl and ethyl acrylate in the United States [1]. The first tion polymers: (1) thermoplastic polymers, which harden
commercial use of an acrylic polymer was as an adhesive-like simply by loss of solvent through evaporation; and (2) ther-
interlayer for laminated safety glass. Probably the highest mosetting polymers, which contain functional groups that
profile use of an acrylic began in 1936 with the introduction react with another functional material (i.e., melamine, epoxy,
of thermoplastic, transparent methacrylate sheet. With the isocyanate, etc.) to form a cross-linked network. The advan-
advent of World War II, methacrylate sheet became invalu- tages and disadvantages of each are discussed in detail later
able as a tough, weather-resistant glazing material for mili- in this chapter.
tary aircraft. Since it could be formed easily and had excellent Acrylic emulsion polymers (often referred to as acrylic
optical properties, the transparent plastic was used for air- latexes) have become one of the major binder types in use in
craft canopies, bomber noses, and gun turrets [2]. the coatings industry today. To form an emulsion polymer,
Acrylic technology soon expanded into the coatings indus- the acrylic monomers are emulsified and then polymerized as
try in the form of acrylic solution polymers, followed later by small droplets in a continuous water phase. The droplets are
acrylic emulsions. The acrylics gained widespread market ac- typically stabilized by surfactants, and usually no solvent is
ceptance as coatings binders due to such outstanding proper- present. While acrylic emulsions are generally associated
ties as color stability, transparency, and resistance to weath- with quality architectural coatings, they are also used to for-
ering and aging. The good weathering resistance of acrylic mulate industrial coatings. In fact, the use of acrylic emul-
polymers is primarily due to their resistance to hydrolysis sions in industrial applications is expanding at the expense of
and their lack of absorption of ultraviolet (UV) light, the high-
energy portion of the light spectrum most responsible for TABLE 1--Properties of polymethacrylates and polyacrylates [3].
degradation. PolymerTypes Tensile Strength, psi Elongation, %
Acrylic solution polymers (often referred to as acrylic res-
ins) are generally copolymers of acrylate and methacrylate Polymethacrylate
esters prepared by direct solution polymerization in a solvent Methyl 9000 4
that has a solubility parameter similar to that of the polymer. Ethyl 5000 7
Butyl 1000 230
Typical solvents include aromatics such as toluene and xy-
lene, as well as ketones and esters. Acrylic resins are typically Polyacrylates
supplied at about 30 to 50% solids by weight, with viscosities Methyl 1000 750
Ethyl 33 1800
1Group leader and research fellow, Architectural Coatings Re- Butyl 3 2000
search, Rohm and Haas Co., Research Laboratories, 727 Norristown NOTE:Psi + 14.22 = k g / c m 2.
Road, Spring House, PA 19477. (Reprinted with permissionof Modem Paint and Coatings. Copyright1973).
39
www.iran-mavad.com

solvent-based systems because of the industry's need to con- Tgl and the Tg's of the homopolymers of Monomers
Tg 2 =
trol organic emissions. Over the past 20 years, acrylic emul- 1 and 2 in degrees absolute.
sion manufacturers have made great strides in improving the Since thermoplastic acrylics are not cross-linked to achieve
properties of acrylic emulsions so that they now offer per- a desired level of performance, the concept of Tg and the
formance similar to the solvent-based coatings they are re- ability to manipulate Tg as a means to control properties is
placing. crucial in designing polymers that meet the needs of the
When the first acrylic emulsion designed for use in house coatings market. The marked difference in Tg's, and conse-
paints was introduced in 1953, it had the low-odor, quick- quently polymer characteristics of the acrylics, can phenome-
drying, and easy cleanup features of its water-based competi- nologically be explained by the free-volume theory proposed
tors, styrene-butadiene and poly(vinyl acetate) emulsions; by Fox and Flory [5] and later refined by several others. The
but, in addition, it offered excellent exterior durability that free-volume theory states that the Tg for any given polymer
allowed use in exterior paints. During the past 40 years, it has occurs at that temperature where the fractional free volume
been good exterior durability that enabled acrylic emulsions (i.e., unoccupied space contained within the polymer)
to replace solvent alkyds as the dominant binder in the exte- reaches some universally constant value that remains un-
rior house paint market. changed as temperature decreases below Tg. Above this tem-
perature, the free volume increases, permitting sufficient
molecular motion so polymer flow can begin. In Fig. 1,
Rogers and Mandelkern have plotted specific volume versus
ACRYLIC SOLUTION POLYMERS temperature for a series of methacrylates as a means of estab-
lishing the relationship of Tg to free volume [6]. The arrows
Thermoplastic Resins ( T ) in Fig. 1 indicate the temperature at which there is an
Thermoplastic acrylic resins are acrylic polymers that are inflection in the specific volume curve indicating a sudden
polymerized directly in a suitable solvent and form a film increase in free volume (as temperature increases). This is the
solely by evaporation of the solvent. They do not need to be Tg. From the graph, it can be calculated that, at Tg, free
oxidized or cross-linked to form a hard, resistant finish. They volume accounts for 15% of the total polymer volume [6].
are fast-drying lacquer materials, but they remain perma- Simha and Boyer have independently calculated that at Tg,
nently soluble. free volume accounts for 11% of a polymer's total volume [7].
Acrylic resins are usually supplied in strong solvents such
as toluene, xylene, or methyl ethyl ketone. They are clear, 1.22
colorless solutions and, if left unpigmented, will also dry 1.21 ,, -""
down to clear, colorless films. They are often used in 1.1~
unpigmented form as protective finishes over vacuum metal-
ized plastics and polished metals such as brass. 1.1" ""
Acrylic resins generally make excellent grind media for
dispersing pigments. No external pigment wetting agents are
required to make finely dispersed pigment grinds for high-
gloss lacquers. Also, thermoplastic acrylic polymers are quite 09 ,..,"/", . / ' ~ j
11"111"1~."" ,, "" .,
unreactive and consequently are stable when mixed with pig- m
ments, extenders, and colors. They do not discolor powdered C18 / / " "
metals, such as aluminum.
Acrylics are a uniquely versatile family of polymers since 0 1.05 ...,. ,. .,.// .
an infinite array of properties can be achieved by carefully
- / f/
selecting combinations of the various acrylic monomers. E 1.o3
Each acrylic monomer brings to the polymer its own individ- 1.01 , * / " -
ual performance characteristics based on its molecular struc- '12 ~ ./ .-"
ture. This is particularly true for polymer hardness as deter-
mined by the glass transition temperature (Tg) of the 0 0.97
monomers that make up the homopolymer (only one mono-
0.05
mer) or copolymer (two or more monomers). The Tg of a
polymer is a softening point: it is actually a temperature 0.93
range where the polymer undergoes a second-order transi-
tion. At temperatures below the Tg, the polymer is a glass, but 0.91 C ~ ~ ~ ~ + ~
above the Tg the polymer is a rubbery material. To approxi- 0.89
mate the Tg for a copolymer composition, it is useful to utilize 0.87
the relationship proposed by Fox [4].
0.85
1 _ W 1 W2 0.83 ~ t t t t t t t f t
+ (1) -80 -60 -40 -20 0 20 40 60 80 100 120 140
Temperature, ~
where
FIG. 1 -Specific volume-temperature relations for the poly-(n-
W1 and W2 = the weight ratios of Monomers 1 and 2, re- alkyl methacrylates). (Reprinted with permission from the
spectively, American Chemical Society. Copyright 1957,)
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CHAPTER 6--ACRYLIC POLYMERS AS COATINGS BINDERS 41
On a molecular level, the Tg differences for the acrylic n = K(MW) a (2)

family of polymers can also be easily explained. The acrylates
where
have an alpha-hydrogen atom next to the carbonyl group,
giving them more rotational freedom and hence greater seg- 91 = solution viscosity
mental chain motion than the methacrylates. The methacry- K and a = constants derived experimentally for a specific
lates have a bulky methyl group substituted for the alpha- polymer/solvent combination (for polymethyl
hydrogen atom, which hinders molecular rotation, thereby methacrylate in toluene, K l0 s = 7.1 and a
increasing chain stiffness. The methacrylates are therefore -- 0.73). The type molecular weight used in
higher in Tg, harder, higher in tensile strength, and lower in determining the constants should be specified.
elongation than analogous acrylate polymers. As molecular weight increases, the solution viscosity also
Equally important to Tg and polymer hardness is the length increases, thereby posing handling and application problems
of the ester side chain of the monomer. As the alcohol moiety if the molecular weight becomes too high. For example, high
of the ester side chain becomes larger, the polymer chains are spray solids are desirable for acrylic lacquers because of
pushed further apart, creating additional free volume, e c o n o m y and emissions concerns. The lower the molecular
thereby encouraging greater molecular rotation. Conse- weight of the polymer, the lower the viscosity at a given solids
quently, the polymers b e c o m e increasingly soft (as the ester content, or conversely, the higher the spray solids at spray
side chain becomes larger) until the effects of side-chain crys- viscosity. Consequently, low molecular weight is beneficial to
tallization causes additional hardening effects. Table 2 dem- solids and application concerns, whereas high molecular
onstrates the large range of Tg's that exist for the acrylate and weight is needed for good film properties.
methacrylate family of homopolymers [8]. The obvious answer to the viscosity versus film property
The second most important parameter governing the film dilemma is to reach an o p t i m u m balance by producing an
properties of a thermoplastic acrylic polymer is molecular intermediate molecular weight polymer. For this reason,
weight (MW). Most dry film properties for thermoplastic most thermoplastic acrylic solution polymers have weight-
acrylics improve with increasing molecular weight up to a average molecular weights in the 75 000 to 100 000 range. It is
MW of about 100 000 and then tend to level off. Tensile also helpful to narrow the molecular weight distribution,
strength, elongation, toughness, solvent resistance, and exte- reducing the a m o u n t of low-molecular-weight fractions,
rior durability are all dependent on molecular weight. This which have a deleterious effect on resistance and strength
dependence of strength, elongation, and resistance of the properties, while also minimizing high-molecular-weight
acrylic polymer on molecular weight is primarily due to the portions, which increase viscosity and cause application
greater n u m b e r of chain entanglements (which act almost problems such as cobwebbing of spray-applied acrylic auto-
like cross-links), anchoring the polymer chains at higher mo- motive lacquers.
lecular weight (i.e., longer chain length). Since the application and drying properties of an acrylic
However, the viscosity of a solution polymer is propor- resin are largely controlled by the physical characteristics of
tional to the molecular weight of a polymer according to the the solvent contained in the resin, as well as by the interaction
Mark-Houwink equation [9]. of the polymer and solvent, it is essential to carefully select
TABLE 2--Tg for methacrylate and acrylate homopolymers [8].

Polymer Tg, ~ Polymer Tg, ~
poly(methyl methacrylate) 105 poly(methyl acrylate) 6
poly(ethyl methacrylate) 65 poly(ethyl acrylate) - 24
poly(n-propyl methacrylate) 35 poly(propyl acrylate) -45
poly(isopropyl methacrylate) 81 poly(isopropyl acrylate) - 3
poly(n-butyl methacrylate) 20 poly(n-butyl acrylate) - 55
poly(sec-butyl methacrylate) 60 poly(sec-butyl acrylate) - 20
poly(isobutyl methacrylate) 53 poly(isobutyl acrylate) - 43
poly(t-butyl methacrylate) 107 poly(t-butyl acrylate) 43
poly(n-hexyl methacrylate) - 5 poly(hexyl acrylate)
po]y(2-ethylbutyl methacrylate) 11 (brittle pt) - 57
poly(n-octyl methacrylate) - 20 poly(heptyl acrylate) - 60
poly(2-ethylhexyl methacrylate) - 10 poly(2-heptyl acrylate) - 38
poly(n-decyl methacrylate) - 60 poly(2-ethylhexyl acrylate) - 50
poly(lauryl methacrylate) - 65 poly(2-ethylbutyl acrylate) - 50
poly(tetradecyl methacrylate) - 72 poly(dodecyl acrylate)
poly(hexadecyl methacrylate) (brittle pt) - 30
poly(octadecyl methacrylate) - 100 poly(hexadecyl acrylate) 35
poly(stearyl methacrylate) poly(2-ethoxyethyl acrylate) - 50
poly(cyclohexyl methacrylate) 104 poly(isobornyl acrylate) 94
poly(isobornyl methacrylate) 170(110) poly(cyclohexyl acrylate) 16
poly(phenyl methacrylate) 110
poly(benzyl methacrylate) 54
poly(ethylthioethyl methacrylate) -20
poly(3,3,5-trimethylcyclohexyl-
methacrylate) 79
NOTE:The brittle point measured by a fracture test often approximates Tg.
(Reprinted by permission of John Wiley & Sons, Inc. From Encylopedia of Polymer Science and
Engineering, Vol. l, 2nd ed., New York, Copyright 1985).
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the solvent in which the acrylic is dissolved (see Chapter 18 Up to the mid-1950s, nitrocellulose lacquers were the
entitled "Solvents"). To ensure good solubility of the polymer, major automotive coating in use. Nitrocellulose finishes gave
it is important to match the solubility parameter of the sol- an excellent original appearance but had poor durability,
vent to that of the polymer. The solubility parameter is an particularly gloss retention, and required frequent polishing
estimation of the polarity of a solvent or polymer and is by the car owner for the finish to took good. This problem was
related to the intermolecular energy of the molecule (see eliminated in 1956 when General Motors adopted acrylic lac-
Chapter 35 entitled "Solubility Parameters"). The solubility quers based on poly(methyl methacrylate). The acrylic lac-
parameter concept was defined by Hildebrand [10] and ap- quers gave significantly better durability and allowed for the
plied to coatings by Burrell. Burrell has published the solubil- use of the more modern eye-catching metallic pigments [13].
ity parameters for an extensive list of solvents [11]. The acrylic lacquers generally contain external plasticizers,
For polymers, the solubility parameter can be calculated by such as the phthalates, which contribute to improved chip
knowing the molecular structure of the repeating unit ac- resistance and cold crack resistance. No internal plasticizing
cording to Small's method. Small has published a table of m o n o m e r (i.e., acrylates) is generally contained in automo-
molar attraction constants used to calculate polymer solubil- tive acrylic lacquers, and consequently their Tg is approxi-
ity parameters [12]. mately 105~ with a Tukon hardness of about 22.
Besides being helpful in estimating solubility, the solubility Since they are very hard and fairly high molecular weight
parameter concept is helpful in predicting the resistance of (i.e., 100 000), the thermoplastic solution polymers designed
polymers to solvents or other organics. In general, the more for automotive use are not capable of the excellent molecular
polar acrylic polymers will have the best resistance to hydro- flow that would be expected of softer/lower-molecular-weight
phobic materials, such as gasoline, grease, or oil. More hy- polymers. Consequently, the acrylic lacquers require factory
drophobic acrylics (with low 8 values) will have better buffing and or baking to obtain the kind of m a x i m u m gloss
resistance to polar materials, such as water and alcohol. required for the new car showroom. This disadvantage was
The evaporation rate of the solvent or solvent mixture must shared by the older nitrocellulose lacquers.
Also, because of hardness and high molecular weight, the
also be carefully chosen to accommodate the expected appli-
spray solids percent is tow. Since these lacquers are thermo-
cation method and conditions. For spray application, moder-
plastic, they are permanently subject to softening by strong
ately fast evaporating solvents are needed to avoid running
solvents, such as toluene or acetone, if for some reason they
and sagging of the low-viscosity paint. For roller coating, a
would contact the automotive finish. Conversely, however,
much higher viscosity coating would be used; therefore,
the thermoplastic acrylic lacquers can be easily repaired by
slower evaporating solvents are required to avoid skinning on
an additional coat of paint which "melts" into the original
the roller and to allow for flowout of roller pattern created
coat, leaving no "two-coat" effects or intercoat adhesion prob-
during application of the paint. Since thermoplastic acrylics
lems.
dry by evaporation of solvent alone, extremely slow-drying
solvents, which retard development of properties, should be
avoided. Thermosetting Acrylic Resins
The majority of thermoplastic acrylic solution polymers
Thermosetting acrylic resins are compositionally very simi-
are designed for general-purpose industrial finishing (i.e.,
lar to the thermoplastic-type acrylics, with the exception that
metal furniture and product finishing) and have a Tg of ap-
they contain functional groups, such as carboxyl or hydroxyl,
proximately 50~ This Tg is generally obtained by copoly- that are capable of reacting with another polymeric or mono-
merizing combinations of methyl methacrylate (MMA), butyl meric multifunctional material to produce a three-dimen-
methacrylate (BMA), ethyl acrylate (EA), butyl acrylate (BA), sional network structure. As has already been discussed, the
and ethylhexyl acrylate (EHA). While many other acrylate mechanical properties of thermoplastic acrylic polymers for
and methacrylate monomers exist, as indicated in Table 2, coatings are generally improved by increasing molecular
these few are the primary acrylic monomers that are com- weight, but polymers with overly high molecular weight pro-
mercially available and that are, therefore, the most economi- duce solutions of unworkably high viscosity. An alternate
cally feasible. route to improved film properties is to use a thermosetting
At a Tg of 50~ these acrylic polymers are intermediate in acrylic polymer, converting linear, moderate-molecular-
hardness, having a Tukon hardness of about 11 to 12 [see weight polymer chains to an infinite molecular weight struc-
ASTM Test Methods for Indentation Hardness of Organic ture. This cross-linking reaction takes place after the coating
Coatings (D 1474)]. They are hard enough to dry rapidly to a has been applied to the substrate, often by the application of
tack-free state that allows early handling of the coated prod- heat, hence the term "thermosetting." To be truly cross-
uct and also hard enough to resist marring, print [see ASTM linked, one of the reactive species must have at least two
Test Method for Print Resistance of Lacquers (D 2091)], block reactive sites, while the other species has at least three reac-
[see ASTM Test Method for Blocking Resistance of Architec- tive sites per molecule or chain.
tural Paints (D 4946)], and dirt pickup. Yet, they retain Thermosetting acrylic polymers offer the following advan-
enough flexibility and elongation to have some impact resist- tages over thermoplastic acrylics: (1) improved hardness and
ance [see ASTM Test Method for Resistance of Organic Coat- toughness, (2) better resistance to softening at elevated tem-
ings to the Effects of Rapid Deformation (Impact) (D 2794)], peratures, (3) improved resistance to solvents, stains, and
and some can even be post-fabricated, such as is done with detergents, and (4) lower applied molecular weight, resulting
coil coated stock to produce aluminum gutters, trim pieces, in lower solution viscosity and consequently higher applica-
etc. tion solids.
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Over the years, numerous chemical reactions utilizing vari- epoxy resin required to react with the acrylic to achieve a
ous functional groups have been devised as a means to cross- thoroughly cross-linked system.
link acrylic polymers. However, we will elaborate on some of Styrene or vinyltoluene are often incorporated into the
the more commercially significant thermosetting acrylics, acrylic polymer as "honorary" acrylic monomers because
namely those cross-linked with nitrogen resins, epoxies, and their reaction kinetics with acrylic monomers are fairly good
isocyanates. and because they often improve alkali resistance and are low
in cost. The cross-linking reaction between the carboxyl
Acid-Functional Acrylics Cross-Linked with Epoxy group on the acrylic polymer and the epoxy resin is fairly
Resins sluggish and requires a base catalyst such as dodecyl tri-
Possibly the most resistant acrylic enamels are based on methyl a m m o n i u m chloride, or tri(dimethylaminomethyl)
thermosetting acrylic solution polymers that contain acid phenol. In some instance, melamine-formaldehyde resins are
functionality and are reacted with an epoxy resin. Typically, sufficiently basic to be used as catalyst and have the addi-
the epoxy resin is a condensation product of Bisphenol A and tional advantage of entering into the cross-linking reaction
epichlorohydrin (see Chapter 10 entitled, "Epoxy Resins in [13]. For improved package stability, however, it is preferable
Coatings"). to add the base catalyst to the other components just prior to
use. Even with catalyst, the baking or stoving requirements
H for acid/epoxide systems are fairly high, with 15 to 30 min at
I 150 to 190~ being typical. Of course, the higher the bake
CH2--C--CH2-- temperature, the shorter the bake time required for cure. To
\0 / determine the optimum conditions for a given system, it is
best to cure that system at a variety of baking conditions and
~----~ ~H~ 7
/
then measure properties to determine the temperature and
time required for m a x i m u m performance.
The primary uses for acid-functional acrylics cross-linked
,--, &,--, & with epoxy resin are as appliance enamels and coatings for
interior metal furniture and equipment. Acrylic/epoxy
enamels fill the needs of the appliance industry primarily
because of their excellent alkali/detergent resistance [see
ASTM Practice for Detergent Resistance of Organic Finishes
--O--(z x)--C--(/ \ ) - - O - - C H 2 - - C H - - C H2
\ / I \ / \/ (D 2248-89)], which is critical to the performance of washing
\~/ CH~ \ ~ / O machine coatings. Other properties that are important to the
appliance industry include: hardness, scratch resistance,
The acrylic solution polymer is made acid functional sim- grease resistance, stain resistance, as well as flexibility, im-
ply by incorporating acrylic or methacrylic acid into the pact resistance, and adhesion to metal. Acrylic/epoxy
backbone; when cured under suitable conditions, it reacts enamels, on the whole, offer an excellent balance of these
with the epoxide to form ester linkages between the two important properties. Typical properties for an enamel based
polymers: on an acid-functional acrylic resin cross-linked with a
Bisphenol A based epoxy are shown in Table 3.
E P O X Y - - C H - - C H 2 + ACRYLIC--COOH The disadvantages associated with acrylic/epoxy coatings
\/
are usually concerns brought about by the aromatic nature of
O
the Bisphenol A based epoxy cross-linker. Their most signifi-
EPOXY--CH--CH2 cant limitation is poor resistance to UV light, which restricts
I I their use to interior applications. If used outside, the aro-
OH OCO--ACRYLIC matic Bisphenol A portion of the epoxy would degrade rap-
An alternative reactant to epoxies based on Bisphenol idly, and early chalking would occur. In some of the newer
A/epichlorohydrin is another acrylic polymer wherein epox- high-solids acrylic/epoxies, the epoxy content is very high and
ide sites have been incorporated by polymerizing glycidyl can therefore cause discoloration problems even indoors due
acrylate, glycidyl methacrylate, or allyl glycidyl ether into the to UV light. Where this i~ a problem, an aliphatic epoxy can
acrylic backbone. This approach is limited in use, however, be substituted for at least some of the Bisphenol A based
because both economics and performance favor the Bis- epoxy to reduce sensitivity to UV radiation (see Chapter 10
phenol A type epoxides. Also, in recent years, epoxy manufac- entitled "Epoxy Resins in Coatings").
turers have developed many aliphatic epoxides in an attempt
to mimic the benefits of the workhorse Bisphenol A based Acrylic Polymers Cross-Linked with Amino Resins
products (i.e., resistance properties) without the accompany- Acrylic polymers containing acid or hydroxyl functionality
ing disadvantages (i.e., poor resistance to UV light). can be cross-linked with amino resins such as: urea, mela-
The carboxyl-functional acrylic resins typically have a mo- mine, and benzoguanamine formaldehyde condensates (see
lecular weight in the 10 000 to 50 000 range and a carhoxyl Chapter 8 entitled "Amino Resins") as follows:
content of 5 to 20%. Some higher solids acrylics are lower in
molecular weight with higher acid content. The acid content AMINO RESIN--NHCH2OR + ACRYLIC--COOH >
of the acrylic polymer determines the equivalent weight of AMINO RESIN--NHCH20CO--ACRYLIC + ROH
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T A B L E 3--Application properties for a white enamel based on an c o m b i n a t i o n with a m e t h y l o l a t e d o r b u t y l a t e d m e l a m i n e -

acid functional acrylic resin cross-linked with a Bisphenol A based f o r m a l d e h y d e or b e n z o g u a n a m i n e - f o r m a l d e h y d e conden-
epoxy [14] (baked 30 rain at approximately 180~
sate. U r e a - f o r m a l d e h y d e c o n d e n s a t e s are less d u r a b l e a n d
Tukon hardness 16.2 have been f o u n d to have lower gloss a n d p o o r e r c h e m i c a l
resistance. Hydroxyl functionality is i n c o r p o r a t e d into the
Pencil hardness 2H
acrylic p o l y m e r b y c o p o l y m e r i z i n g m o n o m e r s such as hy-
Solvent resistance, glass droxyethyl acrylate (HEA) o r hydroxyethyl m e t h a c r y l a t e
(HEMA). This type of c o m b i n a t i o n p r o d u c e s cross-linked ac-
Cellosolve acetate, 15 rain 6B
Cellosolve acetate, 60 rain 6B rylic/amino e n a m e l s with o u t s t a n d i n g exterior durability,
Xylol, 15 min 5B g o o d hardness, a n d m a r resistance, as well as excellent resist-
ance to solvent attack. Acrylic/amino t h e r m o s e t t i n g e n a m e l s
Stain resistance, cold-rolled steel were, therefore, very successful in replacing the less d u r a b l e
Mustard, 30 min no stain a l k y d / m e l a m i n e systems in a u t o m o t i v e t o p c o a t applications,
Ink, 30 min trace a n d general industrial finishing. Over the years, the a u t o m o -
tive i n d u s t r y has relied heavily on this type of t h e r m o s e t t i n g
Print resistance, cold-rolled steel acrylic b e c a u s e it offers the o u t s t a n d i n g d u r a b i l i t y of acrylic
82~ 30 min, 2 psi light print lacquers b u t with b e t t e r resistance to solvents a n d elevated
t e m p e r a t u r e s . It also offers significantly higher a p p l i c a t i o n
Detergent resistancea solids. Also, it does not require factory buffing to achieve high
1% detergent, 74~ 200 h Few--6 gloss as do the acrylic lacquer coatings.
A n o t h e r r e a s o n that acrylic/amino resin t e c h n o l o g y be-
Optical properties, CRS (two coats) c a m e so p o p u l a r is b e c a u s e of the versatility of the chemistry,
w h e r e b y p r o p e r t i e s can be readily altered b y varying acrylic
Original 60~ gloss 95.5
Gloss after 16 h at 178~ 95.4 Tg, acrylic m o n o m e r s , acrylic functionality level, a n d cross-
Original color 9.2 linker type a n d level. This is very i m p o r t a n t in general indus-
Color after 16 hr at 178~ 13.0 trial finishing, where coatings often m u s t be c u s t o m t a i l o r e d
to the specific end use. Table 4 briefly d e m o n s t r a t e s the kinds
Microknife adhesion, CRS "H" Value 22.8
of variation in p e r f o r m a n c e w h i c h can be o b t a i n e d by a few
Mandrel Flexibilityb 1/2 in., 1/4 in., 1/8 in. m a n i p u l a t i o n s in c o m p o s i t i o n [17].
An alternate a p p r o a c h to a t h e r m o s e t t i n g acrylic p o l y m e r is
Cold-rolled steel 0-0-0 to p r e p a r e an acrylic p o l y m e r w h i c h contains functionality
Bonderite 1000 0-0-0
a n a l o g o u s to a m e l a m i n e / f o r m a l d e h y d e condensate. Meth-
Reverse impact, inch-lbs (Joule) 31101 or methylol e t h e r groups c a n be a t t a c h e d to an acrylic
backbone, and the resulting p o l y m e r can self-condensate, re-
Cold-rolled steel 22 (2.48)
Bonderite 1000 15 (1.70) sulting in a cross-linked structure without the need for a n
external cross-linking agent. Initially, an acrylic p o l y m e r is
Direct impact, inch-lbs (Joule) m a d e containing a c r y l a m i d e (AM). The p o l y m e r i z a t i o n is
usually a conventional free-radical, solution p o l y m e r i z a t i o n
Cold rolled steel 35 + (3.96 + )
Bonderite 1000 50 + (5.65 +) c a r r i e d out in alcohol or a c o m b i n a t i o n of alcohol and aro-
m a t i c solvent. As in most t h e r m o s e t t i n g acrylic polymers,
~ASTMblister rating. A rating of 10 means no blistering, a rating of 0 means
very large blisters, with intermediate ratings judged by ASTMphoto standards. m e r c a p t a n is usually included to control m o l e c u l a r weight.
~ = no cracks; 9 = delamination. After the p o l y m e r i z a t i o n is complete, the p o l y m e r is t r e a t e d
with f o r m a l d e h y d e to convert it to the methylol amide. An
acid catalyst will b r i n g a b o u t etherification with the alcohol
AMINO R E S I N - - N H C H 2 O R + A C R Y L I C - - O H ) present, usually butanol. The conversion p r o c e e d s as follows
AMINO R E S I N - - N H C H 2 O--ACRYLIC + ROH [18]:
Reactions with a m i n o resins containing an -NH-CH2OH P O L Y M E R - - C O - - N H 2 + HCHO )
group are possible b e c a u s e this group differs from a simple POLYMER--CO--NH--CH2OH
alcohol in that it is far m o r e acidic a n d reactive. Likewise, the
methylol e t h e r (when c a p p e d with alcohol) is m o r e reactive P O L Y M E R - - C O - - N H - - C H a O H + ROH )
t h a n a conventional dialkyl ether. The curing c o n d i t i o n re- P O L Y M E R - - C O - - N H - - C H 2 O R + H20
quired for acid functional acrylics cross-linked with a m i n o
As an alternative process, the AM m o n o m e r can be meth-
resins is a p p r o x i m a t e l y 30 m i n at 150~ while for an analo-
ylolated before being polymerized. The finalized meth-
gous hydroxyl functional acrylic, the r e a c t i o n is m o r e facile,
ylolated a m i d e acrylic p o l y m e r s condense readily w h e n acid
requiring 30 m i n at 125~ with an acid catalyst [15]. Since the
catalyzed at bake conditions of 30 m i n at 150~ The conden-
acid-methylol r e a c t i o n is relatively slow, it allows significant
sation process is a two-stage r e a c t i o n [19]:
self-condensation of the a m i n o resin [16]. This detracts from
the overall toughness a n d resistance properties. 2 POLYMER--CO--NH--CHzOH )
The hydroxyl-functional acrylics are, therefore, favored POLYMER--CO--NH--CH2--O--CH2--
over acid-functional p o l y m e r s a n d are m o s t often used in N H - - C O - - P O L Y M E R + H20
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TABLE 4--Compositions, viscosities, and film properties of HEMA-based copolymers containing a variety of other monomers a [17].
Acrylate Methacrylate Methacrylate Methacrylate
Styrene Styrene Methyl Styrene Ethyl Styrene
Copolymer Composition, % by wt
HEMA 27.5 27.5 27.5 27.5
BA 22.5 . . . . . . . . .
BMA .-. 22.5 22.5 22.5
St 50.0 50.0 . . . . . .
MeSt . . . . . . 50.0 ...
EtSt . . . . . . . . . 50.0
Viscosity in 1/1 xylenefoutanol U-V W+ X+ X+
Solids content, % by wt 47.8 49.4 49.4 48.3
Cross-linking agent, % by wtb 30 30 30 30
Film Properties
Color or yellowness factorb
Initial - 2.4 - 4.6 - 5.2 - 3.0
After 4 h/219~ 6.2 - 0.9 0.6 10.1
Gloss (60~ initial 98 98 94 98
After 4 h/219~ 84 92 84 74
Front impact, in./lb to fail 2 0 0 0
Flexibility, l/s-in, mandrel 0 0 0 0
Knife scratch 7+ 7 7 7
Resistance to:
20% NaOH, 12-day exposure 10 10 10 10
50% HAc, 7-h exposure 10 10 10 10
Butyl acetate, 4-h exposure 6 10 10 3
0.5% Rinso at 74~ blisters 9- 9 9 9
after 4 days of immersion
~Allcopolymers were <1 in Gardner Holdt color. Films baked for 30 rain. at 149~ Ratings: 10 = best or no failure; 0 = complete failure.
bButylatedbenzoguanamine formaldehyde.
(Reprinted with permission of the Journalof Coatings Technology.Copyright 1961.)
further h e a t > ACRYLIC--OH + R--N = C = O >

POLYMER--CO--NH--CH2--NH--CO-- R--NH--COO--ACRYLIC
POLYMER + H20 (a urethane)
If the m e t h y l o l a t e d a m i d e has b e e n etherified b y b u t a n o l The preferred isocyanates are usually aliphatic, such as the
capping, i n s t e a d of w a t e r as a by-product, a mixture of b u t a - a d d u c t of h e x a m e t h y l e n e d i i s o c y a n a t e (HMDI), b e c a u s e of
nol a n d dibutyl ether w o u l d be obtained. These types of self- the p o o r e r color a n d exterior d u r a b i l i t y a s s o c i a t e d with the
condensing acrylic resins will also react with a m i n o resins, a r o m a t i c types of isocyanates. While the a r o m a t i c varieties of
b u t usually there is no justification for so doing (i.e., no isocyanate react faster t h a n the aliphatic types, a wide range
i m p r o v e m e n t s in performance). The strength of the methylol of catalysts are available w h i c h can be used to speed u p the
a m i d e acrylics is that they have no glaring weaknesses a n d cure of aliphatic isocyanates. A few such catalysts include
m a k e very g o o d g e n e r a l - p u r p o s e resins. triethylene diamine, zinc n a p h t h e n a t e , a n d dibutyl tin-di-
l a u r a t e [20].
Acrylic solution p o l y m e r s cross-linked with aliphatic isocy-
Isocyanate-Reactive Acrylics
anates are ideal for a p p l i c a t i o n s w h e r e a durable, high-per-
Acrylic solution p o l y m e r s t h a t are cross-linked with isocya- f o r m a n c e coating is r e q u i r e d b u t where b a k i n g is not feasible
nates (often referred to as acrylic urethanes) are u n i q u e b e c a u s e of the size or t e m p e r a t u r e sensitivity of the object to
a m o n g the various cross-linking systems b e c a u s e they cure be coated. Acrylic u r e t h a n e s are, therefore, invaluable in the
u n d e r a m b i e n t c o n d i t i o n s - - t h e y don't require baking. The t r a n s p o r t a t i o n i n d u s t r y w h e r e high-quality coatings are
isocyanate g r o u p ( - - N = C = O) is extremely reactive a n d will n e e d e d for aircraft, r a i l r o a d cars, trucks, buses, etc. A u t o m o -
cross-link with any type of functionality having a labile hy- bile refinishing, heavy e q u i p m e n t coatings, a n d high-per-
d r o g e n atom. This includes amines, alcohols, ureas, ure- f o r m a n c e m a i n t e n a n c e coatings are also areas w h e r e acrylic
thanes, carboxylic acids, a n d amides. Acrylic p o l y m e r s u r e t h a n e s are a p p r o p r i a t e . The acrylic u r e t h a n e s c o m b i n e
designed to be cross-linked with isocyanate resins generally the i n h e r e n t UV resistance a n d exterior d u r a b i l i t y of acrylics
contain hydroxyl functionality i n c o r p o r a t e d b y p o l y m e r i z i n g with the a m b i e n t cross-linking ability of aliphatic isocyanates
hydroxyethyl acrylate (HEA) o r hydroxyethyl m e t h a c r y l a t e to p r o d u c e hard, tough, chemical-resistant, high-perfor-
(HEMA) into the acrylic backbone. m a n c e coatings. The m a j o r d r a w b a c k of acrylic u r e t h a n e s is
There are six basic types of curing m e c h a n i s m s for ure- that they are a two-package system a n d c a n n o t be m i x e d until
t h a n e coatings [see ASTM T e r m i n o l o g y Relating to Paint, r e a d y for a p p l i c a t i o n b e c a u s e they are so reactive a n d have a
Varnish, Lacquer, a n d Related Products (D 16-75)]. The short "pot life."
two-package polyisocyanate/polyhydroxyl coatings m a k e up Over the years, the hydroxyl-functional acrylics have b e e n
"Type V." Of this class, acrylic u r e t h a n e s b a s e d on weather- i m p r o v i n g in p e r f o r m a n c e , a n d n o w the e m p h a s i s is on
resistant hydroxyl functional acrylics p r e d o m i n a t e . The hy- higher solids content for lower VOCs. To meet m o r e stringent
droxyl functional acrylic reacts with isocyanate resin as fol- VOC regulations, lower-molecular-weight, higher-solids hy-
lows: droxyl functional acrylics have b e e n developed. I n c r e a s i n g
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the solids of the acrylic r e d u c e s solvent levels in the for- TABLE 5--Copolymerization of ethyl acrylate, methyl
m u l a t e d coating. To c o m p e n s a t e for lower m o l e c u l a r weight, methacrylate, and methacrylic acid [23].
one w a y to i m p r o v e p e r f o r m a n c e is to increase hydroxyl Materials:
content, w h i c h in t u r n requires higher levels of isocyanate. 375.0 g Deionized Water
An alternative a p p r o a c h to r e d u c e d solvent o r higher solids 5.1g Surfactant
100.0 g Ethyl acrylate (15 ppm MEHQ)
is to m o d i f y the acrylic u r e t h a n e with a reactive diluent w h i c h 100.0 g Methyl methacrylate (25 ppm MEHQ)
is fluid a n d acts like a solvent b u t t h e n reacts to form p a r t of 4.0 g Glacial methacrylic acid (100 ppm MEHQ)
the cross-linked n e t w o r k [21]. One such diluent is a low- 4.0 mL Ferrous sulfate solution (0.15%)
molecular-weight, difunctional oxazolidine w h i c h is non- 1.0 g Ammonium persulfate in 5 mL of water
0.7 g Sodium formaldehyde sulfoxylate in 5 mL of
reactive with isocyanates until a m b i e n t m o i s t u r e opens the water
ring, releasing b o t h hydroxyl a n d a m i n e functionality [22]. 5 drops t-butyl hydroperoxide (70%)
Procedure:
In a beaker, stir the surfactant with the water until dissolved
R" H H R" and adjust the pH to 9.0 by adding 50% sodium hydroxide
\ / \ /
solution. Transfer this solution into the reaction flask, rinse the
O/C ~N--R--N/C ~O beaker with a small amount of deionized water, add the
monomers and ferrous sulfate, and stir 15 min with flow of
I I I I + 2H20 > nitrogen before adding the initiators. The maximum temperature
H2C CH2 H2C CH2 of 77~ is attained in 12 to 15 min. Stir 15 min after adding the
initiators, then cool to room temperature, adjust to pH 9.5 with
HO HN--R--NH OH 28% aqueous ammonia, and filter; the gums amounted to 0.17%.
I I I I + 2R'CHO The free acid (unneutralized) surfactant can also be used as an
H2C CH 2 H2C CH 2 emulsifier for the above copolymerization. In this case, the period
of purging with nitrogen after charging the monomers should not
This type of functionality has the advantage that it is one exceed 15 min before the addition of initiators to avoid the
formation of polymer emulsion product with excessive viscosity.
p a c k a g e stable with isocyanates as long as m o i s t u r e is ex- Filtration of the finished emulsion gave only 0.05% gums. The
cluded from the paint. Because it has four reactive sites p e r properties of these emulsions were:
molecule, it increases cross-link density for m a x i m u m per-
formance, while it decreases solvent emissions. Surfactant Form Sodium Salt Free Acid
Solids Content, %--Calculated 35.0 36.0
--Found 34.3 35.6
pH at 25~ 5.6 1.8
Viscosity (Brookfield), cP 7.9~ 10.5a
ACRYLIC EMULSION POLYMERS Particle size (light scattering), % 22.8 b 12.3r
Minimum film-forming temperature, ~ 22~ 3tY
An acrylic e m u l s i o n is a t w o - p h a s e system in w h i c h acrylic
~Emulsion adjusted to pH 9.5 before measurement.
p o l y m e r droplets are d i s p e r s e d in an external w a t e r phase, bMeasurement at 2% solids.
usually with the a i d of a n emulsifier (i.e., surfactant). Unlike CMeasurement at 0.4% solids.
s o m e p o l y m e r emulsions, such as alkyds o r epoxides, w h i c h
are emulsified as preexisting resins, acrylic e m u l s i o n s are
m a d e b y a n e m u l s i o n p o l y m e r i z a t i o n process w h e r e i n the Acrylic e m u l s i o n p o l y m e r s (also k n o w n as acrylic latexes)
m o n o m e r droplets are emulsified in w a t e r a n d then p o l y m e r - have long b e e n a m a i n s t a y of the architectural coatings m a r -
ized. A typical acrylic e m u l s i o n p o l y m e r i z a t i o n recipe is ket, p a r t i c u l a r l y in exterior p a i n t s w h e r e their o u t s t a n d i n g
given in Table 5 [23]. d u r a b i l i t y is so i m p o r t a n t . However, in recent years, clean air
The physical c h e m i s t r y of acrylic e m u l s i o n p o l y m e r s is regulations have further s t r e n g t h e n e d the p o s i t i o n of acrylic
emulsions, usually at the expense of solvent alkyds. The use of
m u c h the s a m e as for their solution p o l y m e r analogs, a n d the
acrylic e m u l s i o n s in industrial coatings a p p l i c a t i o n s has also
film p r o p e r t i e s of the e m u l s i o n s can be controlled by m a n i p u -
g r o w n as a result of solvent e m i s s i o n restrictions. At the s a m e
lating p o l y m e r c o m p o s i t i o n a n d m o l e c u l a r weight just as
time, the p r o p e r t i e s of acrylic e m u l s i o n p o l y m e r s in the in-
with acrylic solution polymers. However, the viscosity of an
dustrial coatings m a r k e t has i m p r o v e d so that they n o w offer
e m u l s i o n is unaffected b y p o l y m e r m o l e c u l a r weight since
p e r f o r m a n c e s i m i l a r to their solvent-borne counterparts.
solution principles do not p e r t a i n to e m u l s i o n s (the p o l y m e r
is insoluble in the c o n t i n u o u s w a t e r phase). Therefore, for the
b e s t possible physical properties, the m o l e c u l a r weight of
Acrylic E m u l s i o n s for Architectural Coatings
acrylic emulsions is generally h i g h e r t h a n t h a t of acrylic
solution polymers: 100 000 to 1 000 000 for an e m u l s i o n ver- Architectural coatings are generally c o n s i d e r e d to be coat-
sus 75 000 to 100 000 for a solution polymer. ings i n t e n d e d for on-site a p p l i c a t i o n to residential, c o m m e r -
The particle size of an e m u l s i o n is also very i m p o r t a n t in cial, or institutional buildings; they are also k n o w n as t r a d e
d e t e r m i n i n g p e r f o r m a n c e a n d m u s t be carefully controlled. sales coatings. Over the last 40 years, this m a r k e t has evolved
F o r example, the film-forming ability of a n emulsion, as well from an entirely oil-based m a r k e t to one d o m i n a t e d b y emul-
as its p i g m e n t b i n d i n g capability, is d e p e n d e n t on particle sions. There are three underlying reasons for the takeover of
size, with s m a l l e r particle size being b e t t e r t h a n large particle the architectural coatings m a r k e t b y e m u l s i o n polymers. The
size. Particle size does affect e m u l s i o n viscosity, with large health, safety, a i r quality, a n d o d o r concerns a s s o c i a t e d with
particle size generally being a s s o c i a t e d with low viscosity. the solvents in oil-based p a i n t s have m o v e d p e o p l e t o w a r d s
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water-based latex paints whenever there is not a large penalty pigment volume concentration (PVC) to obtain gloss, the pig-
in performance. Also, latex paints are more tolerant of a wide ment does not contribute significantly to film hardness; it
variety of application conditions and can even be applied over must all come from the polymer.
damp substrates. Thirdly, emulsion polymers, particularly Since these gloss and semigloss latexes are often used over
quality acrylic emulsions, have surpassed oil-based paints for old oil-based enamels, adhesion to aged oil-based paints is
long-term performance and protection in most applications. required. This may be accomplished by copolymerizing adhe-
Although acrylic emulsions generally provide a superior sion promoting functional monomers into the acrylic poly-
level of performance, their cost is somewhat higher than mer backbone. A major breakthrough in latex adhesion
lower-performance emulsions such as vinyl acetates. There- technology came about with the development of ureide func-
fore, in segments of the architectural coatings market where tional acrylic monomers [24]. The adhesion promoter partic-
performance is not critical, such as for interior flat paints, ularly is needed to improve adhesion and blister resistance
acrylic emulsions .are not a dominant binder. However, in when the paint film becomes wet, as it might in a bathroom.
segments where performance and durability are essential, Since the gloss paints are often used in wet areas such as a
such as for exterior flat and gloss paints, acrylic emulsions bathroom, the water resistance of the dry film is also an
control a very large portion of the market both in the United important property. To ensure good water resistance, acrylic
States and abroad. emulsions used in this market often contain hydrophobic
monomers such as styrene.
Interior Coatings Applications Since interior trim paints are so highly visible, overall ap-
The high-volume, interior-flat market is dominated by vinyl pearance properties are critical to the success of the paint job,
acetate copolymers plasticized with a soft acrylate monomer, and features such as flow and levelling, gloss, and film build
usually butyl acrylate at about the 15% weight level. Interior are expected to be similar to oil-based enamels. This level of
flat paints are aimed primarily at broadwall applications. Per- outstanding appearance has been possible in recent years
formance requirements for this market are fairly modest, with the introduction of associative thickeners. The tradi-
with decorative features such as color, sheen level, and hiding tional thickener for latex paints has been hydroxyethyl cellu-
being the more infuential factors determining consumer lose (HEC), which thickens by a flocculation mechanism and
preference. The one resistance property demanded in this usually produces poor flow and gloss. Associative thickeners
m a r k e t is scrub resistance; in this regard, vinyl/acrylics per- loosely bind to the surface of the latex particles through
form satisfactorily. hydrophobic interactions, forming a network structure
There is a small, premium segment of the interior flat which accounts for their thickening action. The degree of
market occupied by all acrylic latexes, and one of the key interaction between the thickener and the latex particle is
features which they offer is improved rheology and applica- largely a result of the surface chemistry of the emulsion parti-
tion characteristics resulting from the better interaction of cles. Smaller particle-size emulsions have greater surface
acrylic latex particles with the new associative thickeners. area and therefore have more interaction with associative
Associative thickeners (also referred to as rheology modifiers) thickeners. More hydrophobic latexes have stronger associa-
dramatically enhance flow, brushability, film build, and spat- tion with the new thickeners. Consequently, small-particle-
ter resistance compared to conventional hydroxyethyl cellu- size, hydrophobic acrylic emulsions have been designed spe-
lose (HEC) thickeners. cifically for use with associative thickeners. These newer
Since interior flat paints contain a high pigment loading to acrylic emulsions optimize thickener interaction and pro-
increase hiding and reduce cost, the acrylic polymers used in duce exceptional flow and gloss. In fact, before these new
this market tend to be fairly soft with good binding capacity. emulsion/thickener systems, truly high-gloss latex paints
Typically, they are copolymers of a hard methacrylate mono- were out of the question. They also improve brushability and
mer such as methyl methacrylate with a soft, commercially film build, while eliminating the problem of roller spatter.
available acrylate m o n o m e r such as ethyl acrylate, butyl acry- Overall, the appearance properties of the newer small parti-
late, or ethylhexyl acrylate. The Tg is generally around 10~ cle-size hydrophobic acrylics, when used in combination
Interior gloss and semigloss paints have much more de- with associative thickeners, rivals that of oil-based enamels.
manding requirements than flat paints since they are used for In an effort to further improve the performance of acrylic
more diverse and challenging substrates such as windows, emulsions, the morphology of emulsion particles has become
cabinets, and doors. Acrylic emulsions play a major role in an additional important variable. In the past few years, new
this market, especially at the high-performance end. They are composite acrylic emulsions have been introduced, particu-
tailored to the specific needs of this market by optimizing the larly into the interior gloss area, which are made up of two or
important variables contributing to performance: composi- more nonhomogeneous phases. They are prepared by a two-
tion, hardness, molecular weight, and particle size. stage polymerization process sometimes referred to as a se-
Acrylic emulsions used in gloss and semigloss paints are quential emulsion polymerization that results in various
copolymers of acrylate and methacrylate monomers and are types of core-shef structures. The goal of this type of poly-
usually harder than emulsions used in flat paints. They gener- merization is to incorporate the best characteristics of the
ally have a Tg in the range of 20 to 50~ The harder polymers different phases.
are necessary to build in block and print resistance, which are The hard acrylic emulsions typically used in interior gloss
needed to keep doors and windows from sticking and to pre- paints provide excellent performance but require consider-
vent marring and film damage associated with softer poly- able amounts of coalescent to achieve film formation (i.e., 10
mers. Since gloss and semigloss paints are formulated at low to 20% by weight on polymer solids). This is undesirable both
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from a cost and an organic emissions perspective. Using a the flocculating mechanism of HEC. Therefore, 100-nm
two-stage polymerization, it is now possible to make hard, emulsions that were designed to have improved chalk adhe-
block-resistant acrylic emulsions that are also flexible and sion sacrificed some of the flow and film build of large parti-
require lower coalescent levels. This type of polymerization cle-size (500-nm) emulsions. In an attempt to combine these
can also be used to achieve a desired surface chemistry while seemingly mutually exclusive properties, particle-size distri-
not disturbing the bulk composition of the latex particle. This butions have been carefully controlled to ensure a tailored
can be useful in optimizing rheology or improving adhesion mixture of small particles that give good adhesion to chalky
characteristics of an acrylic latex. surfaces and large particles that help to improve flow in
formulations thickened with HEC. An additional benefit of
Exterior Coatings Applications these polymers is their high supplied solids, which may be as
By far the most challenging application for any coating is high as 60% by weight compared to 40 to 50% for unimodal
as an exterior paint required to protect a multitude of sub- latexes.
strates in diverse and extreme weather conditions. It is in this Wide particle-size distribution acrylic emulsions do n o t
demanding role that acrylic emulsions have met virtually all significantly address the low film build associated with
requirements and impressed the industry by their outstand- smaller particle-size emulsions when thickened with HEC.
ing durability. One primary reason for their success, as men- Film build is particularly important to an exterior paint be-
tioned earlier for solution acrylics, is their lack of absorption cause the durability of the film is usually proportional to the
of ultraviolet light coupled with their inherent hydrolysis film thickness, i.e., how much paint is applied to the sub-
resistance. Over the years, acrylic emulsions have evolved strate. This was addressed in the 1980s by the Rohm and
from simple polymers troubled by shortcomings, such as Haas Co. with the introduction of a Multilobe | acrylic emul-
poor adhesion or low film build, to sophisticated systems sion, shown in Fig. 2 [26]. This type of polymer has a lobed
incorporating elements designed to address essentially every morphology that is grown out during the polymerization pro-
major challenge experienced by an exterior paint. cess; it does not result from particle aggregation. The lobes of
One of the toughest demands facing exterior flat house this polymer are about 350 nm, but it has an effective hydro-
paints is the need to withstand the freeze-thaw type of expan- dynamic volume of about 1000 nm and is, therefore, very
sion and contraction of dimensionally unstable substrates effective at imparting high film build in paints thickened with
such as pine or other soft woods. To avoid the grain cracking HEC. It also reduces the level of thickener needed to achieve a
that often occurs over this type of substrate, acrylic emul- given viscosity. Since in its commercial form this technology
sions designed for flat house paints are fairly soft, with a Tg in also contains small particles, good adhesion characteristics
the range of 10 to 15~ A coalescing solvent is usually used in are retained while film build is optimized.
the formulation to assist film formation, particularly at lower Other important aspects of weatherability are color reten-
temperatures. When the coalescent leaves, the acrylic paint tion and resistance to chalking. These properties are made
film remains pliable and able to withstand substrate swelling worse by the catalytic degradation effects of TiO 2 on the
and freezing, unlike oil-based house paints which become binder, so that high PVC flat paints are generally poorer than
harder and embrittle on exposure as they continue to cross- low PVC gloss paints. However, the inherent durability of the
link. The primary concern with making the acrylic polymer binder is still a controlling factor, and acrylic polymers have
too soft is that dirt pickup would worsen. Since flat house excellent resistance to sunlight and erosion, which contribute
paints contain a fairly high pigment content (i.e., PVC = 40 to to their very good chalk resistance and color retention.
60%), dirt resistance is enhanced by the pigment loading. Among the common acrylic copolymer compositions in use
Experience over many years indicates that a Tg of 10 to 15~ is commercially, MMA/BA polymers are better than MMA/EA
the optimum range to balance grain-crack resistance with polymers, and higher methacrylate containing binders are
dirt resistance.
For exterior flat house paints, the inclusion of an effective
adhesion promoter in the acrylic backbone is crucial for good
adhesion. The adhesion promoter greatly improves blister
resistance. Furthermore, the improved adhesion enhances
crack resistance over dimensionally unstable wood sub-
strates. Painting over a degraded chalky surface is a common
practice that can be a potential disaster if sufficient adhesion
is not obtained. The chalk acts like a powdery barrier, pre-
venting the emulsion binder from penetrating to the real
substrate and establishing an adhesive bond. Studies have
shown that smaller particle-size acrylic emulsions are much
more effective than larger particle-size emulsions for filtering
down through the chalk and obtaining adequate adhesion.
For this reason, many exterior grade acrylic emulsions have
been designed at a fairly small particle size of about 100 nm
[25].
Small-particle-size, large-surface-area emulsions, when
thickened with HEC, have poorer flow and film build than FIG. 2-Scanning electron micrograph of Multilobe | acrylic
larger particle-size emulsions, which are less aggregated by particles (courtesy of Rohm and Haas Co,).
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better than acrylics containing higher levels of acrylate alkyd paints along with expected advantages in chalk resist-
monomers. Of course, the methacrylate/acrylate levels are ance, color retention, and other decorative qualities. How-
generally determined by the Tg required to achieve the de- ever, to the surprise of some segments of the maintenance
sired balance of crack resistance and dirt pickup. industry, acrylic maintenance emulsions often outperformed
Exterior gloss and semigloss paints are required to with- solvent alkyds for corrosion resistance and overall metal pro-
stand similar tortures as their flat paint counterparts and, in tection. This is partly because the alkyds continue to harden
addition, must provide equally good dirt resistance at much and eventually crack, leaving the substrate exposed and sub-
lower pigment loadings. Acrylic emulsions have been de- ject to the elements. Acrylic emulsions do not continue to
signed that meet all of these challenges and perform very well harden once the paint film is dry, and they remain sufficiently
in environments as diverse as the tropical regions of Asia and pliable to expand and contract with the substrate.
the Philippines to the Scandinavian regions of Europe. Since The one weakness of the acrylic latexes in the area of
the acrylic emulsion engineered for interior gloss/semigloss maintenance coatings was their low Tg, which reflected a
paints are intended to be high-performance systems capable lower hardness than the alkyd paints. This limitation was
of good adhesion even in wet areas, they are often able to be removed by the development of aqueous gloss enamel
used outside as well. Since exterior gloss paints must have binders. These hard latex binders used in interior and exte-
good dirt resistance at low PVC, the acrylic emulsions used in rior gloss paints were fine tuned to maximize corrosion resist-
these paints are harder than those used in flat paints and ance and overall protection. Commercialized in the mid-
generally have a Tg in the area of 20 to 35~ This Tg range can 1980s, this new generation of maintenance vehicles has
provide acceptable dirt resistance while still having good proved very successful in extensive field tests, particularly on
grain-crack resistance. The very hardest acrylic emulsions bridges in the southeastern United States. The small particle
used for interior gloss paints (i.e., above Tg 35~ would not size of these binders fits perfectly with associative thickener
be appropriate outside, at least in areas subject to freezing, technology to give tight water-resistant films, which are an
because they would be more prone to grain crack. improvement over HEC-thickened paints that can have mi-
Since brush marks are much more obvious in a gloss paint croscopic defects as a result of the flocculating mechanism of
than in a flat paint, good flow and levelling is much more HEC [27].
critical for a gloss paint than for a flat paint. Consequently,
older acrylic emulsions intended for semigloss paints (there Acrylic Emulsions for Industrial Coatings
were no high-gloss latex paints until about 1980) are of large
particle size to have the best possible flow with the prevailing Nonreactive Emulsions
thickener of the day, HEC. The flow of these systems could Industrial coatings users, who have traditionally applied
best be described as fair, but overall they have demonstrated solvent-based polymers, have recently been under pressure to
an admirable balance of properties and are still popular to- reduce volatile organic emissions. This is particularly true in
day. However, newer acrylic emulsions intended for exterior California, which has historically been at the forefront of
gloss paint applications, particularly those generally referred clean air legislation. In many instances, these coatings users
to as acrylic enamel vehicles, are small in particle size (i.e., have complied with the stricter environmental legislation by
100 nm) to take advantage of the excellent flow, gloss, and switching over to water-based systems. Acrylic producers
rheology available by using associative thickeners. have responded to the needs of these coatings users by devel-
Over the past ten years, the decorative as well as protective oping more sophisticated emulsions capable of meeting the
capabilities of exterior gloss paints have improved signifi- demanding performance requirements of many different end
cantly to the point where acrylic emulsions are rapidly replac- users. Early emulsions aimed at industrial coatings applica-
ing alkyd enamels as the preferred coating for exterior trim. tions were offshoots of architectural coatings technology and
were often too soft for industrial coatings uses. Also, high
gloss was not possible with these older emulsions. Like the
Acrylic Emulsion Maintenance Coatings
newer gloss enamel emulsions for trade sales use, however,
Maintenance coatings differ substantially from decorative latexes aimed at industrial coatings applications have evolved
coatings since they are used primarily for their protective into hard, resistant binders that match the performance of
features, which prevent substrate deterioration by corrosive their solvent-based counterparts. Without this evolution in
elements. Maintenance coatings are generally used to protect performance, it is unlikely that industrial coatings users
metal surfaces such as bridges, storage tanks, and other in- would switch to latex coatings even with the more severe
dustrial facilities, often in harsh chemical and corrosive envi- emissions regulations.
ronments. The first acrylic latex binders for corrosion- Thermoplastic acrylic emulsions designed for industrial
resistant maintenance coatings were introduced commer- coatings applications generally have to be harder and faster
cially in 1964. They are similar in hardness and composition drying than architectural emulsions and have better corro-
to exterior flat house paint binders with the exception that sion and chemical resistance. The typical Tg range for such
they are formulated with reactive pigments and additives acrylics is about 30 to 70~ The film formation problems
which help prevent rusting. The surfactants and other "salt usually associated with such hard emulsions are somewhat
and pepper" ingredients used in the polymerization of main- alleviated by the controlled application conditions in the fac-
tenance acrylic emulsions are carefully selected so as to not tory, so that low-temperature film formation is generally not
aggravate corrosion. required. For general industrial finishing over metal sub-
These acrylic latex maintenance coatings had the usual strates, industrial acrylic emulsions have borrowed tech-
advantages in application of water-based paints over solvent nology from maintenance finishes and have optimized sur-
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factants, additives, a n d c o m p o s i t i o n s to i m p r o v e r a t h e r t h a n linked, the infinite m o l e c u l a r weight provides for solvent a n d

d e t r a c t from c o r r o s i o n resistance. c h e m i c a l resistance, along with h a r d n e s s a n d toughness. By
N e w e r heterogeneous acrylic e m u l s i o n s c o m p r i s e d of two a d j u s t i n g the level of functionality, the a m o u n t of cross-
o r m o r e phases have recently b e c o m e i m p o r t a n t in the indus- linker, a n d the Tg of the acrylic emulsion, a system c a n be
trial coatings industry. One such type of h e t e r o p o l y m e r , the c u s t o m designed for a specific application.
core-shell polymer, is being used to achieve r a p i d h a r d n e s s F o r m a n y years, the c o n s t r u c t i o n i n d u s t r y has relied on
d e v e l o p m e n t with i m p r o v e d block a n d p r i n t resistance at low hydroxyl functional acrylic e m u l s i o n s r e a c t e d with u r e a o r
VOC. These p r o p e r t i e s allow the m a n u f a c t u r e r to stack, pack, m e l a m i n e to coat p r o d u c t s such as h a r d b o a r d , w o o d panels,
a n d ship coated parts m o r e quickly [28]. Using core-shell shingles, a n d m e t a l coil. In i n t e r i o r applications, such as over
technology, acrylic e m u l s i o n s have been able to rival the w o o d paneling, these e m u l s i o n s offer c o m p a r a b l e cure speed
p e r f o r m a n c e of traditional, high-solvent-content nitrocellu- a n d p e r f o r m a n c e to solvent-based alkyd/urea systems. I n coil
lose lacquers in w o o d coatings a n d furniture finishes. The coating applications, the t h e r m o s e t t i n g acrylics offer high
m a j o r deficiency of acrylic emulsions in these areas is the gloss, excellent durability, g o o d c o r r o s i o n protection, as well
"warmth" of w a t e r - b a s e d coatings c o m p a r e d to solvent-based as g o o d roll coatability. These e m u l s i o n s have b e e n a p p l i e d at
materials. " W a r m t h " is a quality w h i c h refers to the feel a n d line speeds up to 137 m / m i n with g o o d transfer, flow, a n d
a p p e a r a n c e of the coated wood. leveling. Usually these systems are catalyzed with an a c i d
catalyst to achieve the fastest/lowest t e m p e r a t u r e cure. A very
Thermosetting Emulsions g o o d p r o p e r t y b a l a n c e is d e m o n s t r a t e d in Table 6 for a n
Just as is the case with solution acrylics, functional groups aqueous acrylic m e l a m i n e coil coating e n a m e l [29].
can be i n c o r p o r a t e d into the p o l y m e r b a c k b o n e of an acrylic A recent d e v e l o p m e n t in cross-linking acrylic e m u l s i o n
e m u l s i o n so that it can react with a n o t h e r functional m a t e r i a l technology is an epoxy cross-linking, a m b i e n t cure system
after a p p l i c a t i o n to the substrate, f o r m i n g a cross-linked w h i c h has m a n y a p p l i c a t i o n s b u t has been f o u n d to be partic-
polymer. Typically hydroxyl o r hydroxyl/acid functional ularly useful in m a i n t e n a n c e coatings. Besides being a m b i e n t
acrylic emulsions are cross-linked with u r e a o r m e l a m i n e res- curing, a n attractive feature of this system is its excellent
ins. Acid functional acrylic e m u l s i o n s can be cross-linked early p r o p e r t i e s resulting from the high-molecular-weight
with emulsified epoxy resins. The c h e m i s t r y of these systems acrylic emulsion, w h i c h provides a m p l e resistance character-
is identical to the cross-linking c h e m i s t r y discussed earlier istics until the epoxy cross-linking is complete. This n e w
for solvent-based acrylic resins. After the e m u l s i o n is cross- acrylic/epoxy system is c o m p a r e d to an e p o x y / p o l y a m i d e
TABLE 6--Properties for an aqueous acrylic/melamine coil coatings enamel over aluminum
and galvanized steel [29].
Mini-Spangle
Substrate Aluminuma Galvanized Steel~
Primer thickness 0 0.2
Topcoat film thickness 0.9 to 1.0 0.8
Gloss 20~ ~ 65/89 -/80 b
Image clarity Very good Good
Tukon hardness (KHN) 9 9
Pencil hardness
Initial H H
Wet 16 h, 38~ H20 B B
Flexibility--X30 microscope 2-3T 3T
Direct impact, in.-lbs 20 to 25 35
Reverse impact, in.-lbs 15 10
Metal mark resistance Excellent Excellent
Rheology Excellent Excellent
MEK rubs 200 200
Cleveland condensing cabinet, Pass Pass
200 h at 60~
After 1000 h Salt Spray Exposure
X-scribed area
Tape adhesion, % removed 0 0
Lifting None None
Undercutting 1/16 in. 1/16in.
Blistering~ None Mod-Dense, No. 6, No. 8
Exposed edge
Undercutting ... 4/16 in.
Blistering~ ... Mod, No. 2, No. 4
1/8-in. mandrel bend
Blistering~ ... None
White rust ... None
Flat
Blistering~ None None
~Commercial chromate pretreatrnent.
bG1ossdependent on smoothness of substrate.
el-9: Higher numbers indicate srnaller blisters. Blister density is rated as few, moderate, or dense. 10 = no
blisters.
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TABLE 7--Resistance characteristics of acrylic/epoxy water-borne coatings versus

conventional controls [30].
3 Weeks, Air Dry
Acrylic/Epoxy Epoxy/
Formulation Polyamide Alkyd
Solvent Resistance
MEK rubs to remove >300 >300 120
Lifted
Spot tests, 15 rain.
MEK Mod. soft Mod. soft Lifted
Toluene Mod. soft Mod. soft Lt. soft
Butyl acetate Lt. soft Lt. soft Lt, soft
Gasoline Lt. soft Lt. soft Lt. soft
Butyl cetlosolve Lt. soft Mod. soft Mod. soft
Stain Resistance
Spot tests, 24 h
Mustard OK Lt. stain Med. stain
Coffee OK OK OK
Red ink OK Lt. stain Hvy. stain
Cola OK OK OK
Grape juice OK OK OK
Acid/Base Resistance
24-h immersion, on concrete
HCI No effect No effect No effect
NaOH No effect No effect Dissolved
Accelerated Exposure, 300 h of QUV Exposure
Gloss retention, percent 63 4 4
Fade resistance (green coatings) Good Very poor Poor
800 h of Fade-O-Meter exposure
Gloss retention, % 49 2 10
NOTE:Lt. = light; Mod. = moderate; Med. = medium; Hvy. = heavy.
(Reprinted with permission of the American Paint and Coatings Journal. Copyright 1992.)
coating and an alkyd coating in Table 7 [30]. The strong [9] Rodriguez, F., Principles of Polymer Systems, McGraw-Hill Book
points of the acrylic emulsion/epoxy system are its stain, Co., New York, 1970, p. 154.
solvent, and c h e m i c a l resistance, along with o ut st an d i n g [10] Hildebrand and Scott, The Solubility of Non-Electrolytes, 3rd ed.,
weathering. No less a key feature is its very good co r r o si o n Rheinhold Publishing Corp., New York, 1949, pp. 129, 301.
p e r f o r m a n c e [31]. [11] Burrell, H., Official Digest, Vol. 27, No. 369, 1955, p. 726.
[12] Small, P. A., Journal of Applied Chemistry, Vol. 3, 1953, p. 71.
[13] Solomon, D. H., The Chemistry of Organic Film Formers, Robert
E. Krieger Publishing Co., Huntington, NY, 1977, p. 273.
[14] "Acryloid Thermosetting Acrylic Resins," revised October 1966,
REFERENCES
Rohm and Haas Company promotional literature C-170, Spring
House, PA.
[1] Chemicals for Industry, Rohm and Haas Company 1909-1959,
[15] Solomon, D. H., The Chemistry of Organic Film Formers, Robert
The Lakeside Press, R. R. Donnely & Sons Co., Chicago, IL,
E. Krieger Publishing Co., Huntington, NY, 1977, pp. 277-281.
1959, p. 20.
[2] Chemicals for Industry, Rohm and Haas Company 1909-1959, [16] Saxon, R. and Lestienne, F. C., Journal of Applied Polymer Sci-
The Lakeside Press, R. R. Donnely & Sons Co., Chicago, IL, ence, Vol. 8, 1964, p. 475.
1959, p. 21. [17] Petropoulos, J. C., Frazier, C., and Cadwell, L. E., "Acrylic
[3] Brendley, W. H. Jr., "Fundamentals of Acrylic Polymers," Paint Coatings Cross-linked with Amino Resins, Symposium on Ther-
and Varnish Production, July 1973. mosetting Acrylic Resins," Official Digest, Vol. 33, 1961, p. 729.
[4] Fox, T. G., Bulletin of the American Physics Society, Vol. 1, 1956, [18] Solomon, D. H., The Chemistry of Organic Film Formers, Robert
p. 123. E. Krieger Publishing Co., Huntington, NY, 1977, p. 283.
[5] Fox, T. G., Jr. and Flory, P. J., Journal of Applied Physics, Vol. 21, [19] Christenson, R. M. and Hart, D. P., Official Digest of the Federa-
1950, p. 581. tion of Societies for Paint Technology, Vol. 33, p. 696.
[6] Rogers, S. and Mandelkern, L., Journal of Physical Chemistry, [20] North, A. G., Journal of Paint Technology, Vol. 43, No. 557, 1971,
Vol. 61, 1957, p. 985. p. 47.
[7] Simha, R. and Boyer, R. F., Journal of Chemical Physics, Vol. 37, [21] Watson, D. M. and Schall, D. C., American Paint and Coatings
No. 5, t 962, p. 1003. Journal, 19 Aug. t991, p. 58.
[8] Kine, B. B. and Novak, R. W., "Acrylic and Methacrylic Ester [22] Private communication, D. C. Schall, Rohm and Haas Co.,
Polymers," Encyclopedia of Polymer Science and Engineering, Spring House, PA, 1991.
2nd ed., H. F. Mark, N. M. Bikales, C. G. Overberger, G. Menges, [23] "Emulsion Polymerization of Acrylic Monomers," Product Bul-
and J. I. Krosckwitz, Eds,, Vol. I, John Wiley and Sons, New letin CM-104 A/cf, Rohm and Haas Co., Spring House, PA.
York, 1985, pp, 257-258. [24] Hankins and Melamed, U.S. Patent 2,881,171, 1959.
www.iran-mavad.com

[25] Harren, R. E., Organic Coatings: Their Origin and Development, [29] Rohm and Haas Co. promotional literature, "82C2," October
R. B. Seymour and H. F. Mark, Eds., Elsevier Science Publishing 1980, p. 2.
Co., Inc., New York, 1990, p. 297. [30] Mercurio, A., American Paint & Coatings Journal, 20 Jan. 1992,
[26] Rohm and Haas Company photograph. p. 43.
[27] Harren, R. E., Organic Coatings: Their Origin and Development, [31] Klepser, R. J., "Water-based Maintenance Coatings Systems,"
R. B. Seymour and H. F. Mark, Eds., Elsevier Science Publishing Maintaining Structures with Coatings, Proceedings of SSPC 91,
Co., Inc., New York, 1990, p. 309. Steel Structures Painting Council, Pittsburgh, PA, 1991, pp. 96-
[28] Roman, N., Modern Paint and Coatings, November 1991, p. 38. 97.
www.iran-mavad.com

MNL17-EB/Jun. 1995
7
Alkyd and Polyesters
by Al Heitkamp ~and Don Pellowe 2
ALKYD RESINS, COMMONLYKNOWN AS "ALKYDS,"are synthetic oxidative polymerization and cross-linking that took place
polymeric materials that have been used in the coating in- through coreaction of oxygen and the carbon-carbon bond
dustry since the 1930s. Today they continue to be the unsaturation part of the fatty acids. The use of vegetable oils
"workhorse" polymers for the paint, coating, and printing ink and fatty acids as coreactants with the early developed poly-
industries. Alkyd and chemically modified alkyd polymers esters was the technological breakthrough that led to alkyd
find use in most types of liquid organic coatings for architec- resins being the predominate binder for organic coatings.
tural, air-dry, and baked industrial and maintenance coat- Other developments contributed to the general interest in the
ings. Alkyds are a special class of polyesters that often have products such as new techniques for the production of
vegetable oil or fatty acids coreacted into the polyester, and phthalic anhydride, synthetic glycerin, and other new, novel
these compounds provide the distinctive air-cure feature of polyhydric alcohols.
many of these compounds. Typically, an alkyd could be based on glycerin as the polyol,
Three major classifications of alkyds are those designed for phthalic anhydride as the polybasic acid, and soya or linseed
conventional solids, higher solids, and water-borne coatings. oil as the vegetable oil. These compounds are coreacted and
Because there are a large variety of commercially available then reduced with aliphatic or aromatic petroleum-based hy-
intermediates and chemical modifiers--i.e., m o n o m e r s - - f o r drocarbon solvents. Monofunctional fatty acids such as tall
the preparation of alkyds, they continue to be the most versa- oil fatty acids or special blended fatty acids are commonly
tile type of polymers for coatings and printing inks. found in alkyds as alternatives to vegetable oils.
Most alkyds are film-forming polymers with a relatively
low glass transition temperature (Tg), i.e., below 0~ They are
easily pigmented and readily accept additives to form coat- ALKYD SYNTHESIS, PROCESSING AND
ings with a wide range of appearance, performance, and ap-
MANUFACTURE
plication characteristics. Alkyds are extensively used on
wood, metal, plastic, composite, and other substrates such as Three major categories of chemical intermediates are uti-
primers, topcoats, maintenance paints, undercoatings, exte- lized in the manufacture of alkyd resins:
rior trim paints, wall paints, and similar end uses.
Polyesters for coatings are based on a coreaction of 9 Polybasic organic acid/anhydride--example, phthalic an-
polyhydric alcohols and polybasic acids. Such polyesters may hydride
be prepared from one or more polyhydric alcohols and poly- 9 Polyhydric alcohol--example, glycerin
basic acids to meet particular coating performance require- 9 Monobasic fatty acid or triglyceride--example, soya fatty
ments. acids or soya oil
The stoichiometric proportions and the equivalent weight of
these monomers lead to the desired physical properties and
HISTORY molecular weight distribution of the resulting alkyd. The sol-
vent selection and quantities used influence the viscosity,
Although condensation products of dihydric alcohols and nonvolatile content, and the solvent evaporation rate from
dicarboxylic acids were known at the start of the 20th Cen- coating films.
tury, alkyds modified with drying oils were developed in the Alkyd processing is mainly a condensation reaction be-
late 1920s by Kienle et al. [1-5]. The early condensation tween hydroxyl and carboxyl groups of the chemical interme-
products were not soluble in common solvents and did not air diates. The main by-product of the reaction is water, and it
dry until monofunctional acid or fatty acids were incorpo- must be removed during the polymerization process or it will
rated into the polymeric material. Kienle coined the term transesterify back into the alkyd and change characteristics.
"alkyd" from the alcohols ("al") and acids ("cid") used in their Other chemical reactions are possible during preparation,
preparation. The early spelling of"alcid" was later changed to and these include dimerization of fatty acids or vegetable oils
the current form, "alkyd." Air-dry films were the result of depending on their unsaturation and the alkyd processing
temperature. Vegetable oils (triglycerides) are used for eco-
iMcWhorter Technologies, 1028 South Third Street, Minneapolis, nomical alkyd manufacture, whereas fatty acid blends are
55415. used in high-performance alkyds--particularly in higher sol-
2Retired, formerly employed by Frost Paint. ids and water-borne types.
53
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An alkyd resin can be modified with a number of intermedi- dry nitrogen or carbon dioxide, is introduced to "blanket" the
ates. Some of the more common types are: vapor space above at the top of the reaction vessel. The
reaction mixture is heated from 350 to 500~ (175 to 260~
9 Acrylates The main polymerization occurring is by condensation to
9 Benzoic acid form ester groups. Water of condensation exits from the top
9 Epoxides opening of the reactor. Vigorous mixing and agitation are
9 Isocyanates required throughout the process to insure uniformity of the
9 Paramethyl styrene final resin (Fig. 1). The product provided by this process
9 Phenolics depends greatly on the procedure conditions followed in tem-
9 Polyamides perature and timely removal of water-of-reaction by-product.
9 Rosin
9 Silicone
9 Styrene Solvent Reflux P r o c e s s
9 Vinyl toluene
In the solvent reflux process, an azeotropic solvent such as
xylene is commonly used in the reaction. The purpose of the
More than one of the above compounds are often used to
azeotropic solvent is to aid in removal of water formed during
impart particular characteristics when an alkyd is modified.
the condensation reaction. The reflux solvent and water vola-
There are two major methods of preparing or processing
tilize together and liquefy in a condenser placed above the
alkyds for both laboratory and production scale. These meth-
reaction vessel. A separator or Dean-Stark trap below the
ods are the fusion and solvent reflux processes.
condenser collects this liquid mixture, and the azeotrope sol-
vent is returned to the reaction vessel (Fig. 2). The choice of
Fusion P r o c e s s azeotrope solvent affects the temperatures maintained dur-
ing the reaction.
In this method of manufacture, the alkyd intermediates are In both fusion and solvent reflux processes, acid number
charged into the reaction vessel. Then an inert gas, such as and viscosity are measured until the final desired values are
MOTOR g~ i'~ ~'.:"~;'J
THERMOMETER
GLASS BEARING
MM O.D. TUBING
C
NIUM FOIL
RS ALL CORKS
I-1 r- IVll ~ I-" r-II:: I - t l L , ~ L 13 L A ~ - L ; U L

HEATING MANTLE
FIG. 1-Apparatus for fusion cooking of alkyds. (Diagram courtesy of ICI Hercules
Alkyd Reports.)
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CHAPTER 7 - - A L K Y D AND P O L Y E S T E R S 55
ALLEQUIPMENTHAS29/42JOINTS
,EDRICH'S
NDENSER
MOTOR
TRUBORESTIRRER4 SOLVENT
THERMOMETER II LAYER
L E T ~ WATEF SEPARATORY
CO2IN TRAP
,. SAMPLE
HEMISPHERICALGLAS-COL
HEATINGMANTLE
FIG. 2-Laboratory apparatus for solvent cooking of alkyds. (Diagram courtesy of ICI
Hercules Alkyd Reports.)
reached. Then the alkyd is thinned with the desired type and Viscosity
amount of organic solvent. Only a small amount, usually less
The viscosity of alkyds covers a wide range and must be
than 3% by typically 1% of the total weight, of the reflux or
compared to the nonvolatile content and type organic solvent
azeotrope solvent remains in the alkyd. The solvent reflux
used, ASTM D 1545: Test Method for Viscosity of Transpar-
process advantages are less emission of by-products to the
ent Liquids by Bubble Time Method [6]. The bubble tubes
atmosphere and faster processing time. Also, a greater variety
and measured times in seconds are easy to run with proper
of alkyds can be made by this process. The final alkyd solu- testing equipment and a constant temperature set at 25~
tion properties are measured at 25~ Typical tests include Viscosity is important in reflecting alkyd molecular weight
color, acid number, hydroxyl number, hardness, viscosity, and the final coating application properties, thickness, and
and percent nonvolatiles. minimizing batch-to-batch variation of each specific alkyd.
Relatively high-molecular-weight alkyds need to be reduced
RAW MATERIALS (INTERMEDIATES) FOR to application viscosity with a greater amount of solvent or
ALKYD RESINS solvent mixture or with solvents that have a particular sol-
vency for the specific alkyd.
Typical polybasic acids, polyhydric alcohols, and mono-
basic fatty acids or oils are given in Tables 1, 2, and 3. The
numerous possible raw materials available and economic NONVOLATILE CONTENT
considerations of these lead to versatility of alkyds and to a
wide range of commercially available products. The nonvolatile content of alkyd solutions is determined
with ASTM D 1259: Test Method for Nonvolatile Content of
PHYSICAL PROPERTIES Resin Solutions. Alkyd specifications are designed to show a 1
or 2% variation from an agreed on nonvolatile by weight
The most common physical properties used to identify requirement. This method is sometimes varied to a higher
characteristics of alkyd resins are determined by ASTM oven temperature of 150~ and a shorter dwell time in resin
methods. processing use.
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TABLE 1--Acids and anhydrides used in alkyd manufacture. TABLE 3--Vegetable oils used in alkyd manufacture.
POLYFUNCTIONAL VEGETABLEOILS
Adipic acid Castor oil
Azelaic acid aCoconut oil
Chlorendic anhydride Corn oil
Fumaric acid Cottonseed oil
~Isophthalic acid Dehydrated castor oil
~Maleic anhydride ~Linseed oil
aphthalic anhydride Safflower oil
Succinic acid aSoybean oil
Sebacic acid Tung oil
Citric acid Walnut oil
aTrimelletic anhydride Sunflower oil
MONOFUNCTIONAL Menhadden oilb
Abiatic acid Palm oil
~Benzoic acid
Caproic acid aMostcommonlyused in commercialalkyds.
bAnonvegetableoil derived from fish.
Caprylic acid
Capric acid
Castor oil acids
Coconut oil acids Density
Cottonseed fatty acids
Lauric fatty acids The density or specific gravity of alkyds is also referred to
Linoleic acid as the weight per gallon or density and can be determined by
Linolenic acid following ASTM D 1475: Test Method for Density of Paint,
Oleic acid Varnish, Lacquer, and Related Products [9].
Tallow acids
aTall oil fatty acids
Tertiary-butyl benzoic acid
Special blended fatty acids Flash Point
aMost commonlyused in commercialalkyds.
The flash point of alkyds is mainly of importance as it
pertains to shipping the products and formulated paints, i.e.,
Alkyd resin solutions vary from 30% nonvolatile (flat wall, to bill of lading and other regulations. ASTM D 3278: Test
medium-oil alkyds) to 100% nonvolatile content by weight Methods for Flash Point of Liquids by Setaflash-Closed-Cup
(very long oil alkyds for exterior paints, stains, latex modi- Apparatus [10] is the most common test that will provide
fiers, and similar products). conformance with Department of Transportation regula-
tions. However, other ASTM methods are utilized. The
method utilized depends on flash cup availability and other
specified requirements.
Color Neat alkyds have low vapor pressure. Therefore, the flash
point of an alkyd solution reflects the flash point of the
The color of alkyd solutions is determined by comparison
solvent used to dissolve the alkyd. It is recommended that
with a range of color standards referred to as the Gardner-
flash points on alkyd solutions actually be measured by labo-
Holdt color standards, ASTM D 1544: Test Method for Color
ratory determination. The flash point of an alkyd solution is
of Transparent Liquids (Gardner-Holdt Scale) [8]. The color
different from that of the actual solvent or solvents incorpo-
or degree of yellowness of the alkyd solution may or may not
rated into the solution.
have an effect on the color of the final coating films.
TABLE 2--Polyhydric alcohols used in alkyd manufacture. Drying Properties

POLYHYDRICALCOHOLS The drying properties of alkyds are of importance when
aGlycerin
aEthylene glycol describing the product. Metallic driers are based on cobalt,
Propylene glycol manganese, iron, lead, calcium, and rare earths reacted with
Trimethylol propane synthetic organic acids, such as vegetable fatty acids, to form
aNeopentyl glycol soaps. When these driers are added to the alkyd-based coat-
Hexylene glycol
Pentanediol ing, they act as catalysts and accelerate the rate of air drying
1,3-Butylene glycol and cross-linking. Driers are formulated in combinations or
Diethylene glycol blends to maximize desired dry film surface and interior
Triethylene glycol characteristics. In recent years, synthetic acid-based metallic
~Pentaerythritol
Methyl glucoside driers have gained popularity for two main reasons: (1)
Dipentaerythritol higher metal concentration in the drier, and (2) greater uni-
Sorbitol formity of drier performance. Methods associated with deter-
aTrimethylpentanediol mining drying are given in ASTM D 1640: Test Methods for
Trimethylol ethane
Drying, Curing, or Film Formation of Organic Coatings at
~Mostcommonlyused in commercialalkyds. Room Temperature [11].
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CHAPTER 7 - - A L K Y D AND P O L Y E S T E R S 57
Acid Value H I G H E R S O L I D S ALKYD R E S I N S

The free organic acid groups present in the nonvolatile
Higher solids alkyds have been developed to reduce organic
portion of an alkyd resin is an important property for pig-
solvent emissions in those applications under regulatory re-
ment wetting and performance properties of organic coat-
strictive requirements. This is accomplished by the develop-
ings. The acid value of alkyds is typically determined with
ment of polymers with lower viscosities than so-called con-
ASTM D 1639: Test Method for Acid Value of Organic Coat-
ventional alkyds. The design and processing of higher solids
ing Materials [12]. Reasonably accurate and consistent re-
alkyds result in a lower average molecular weight than con-
sults can be obtained with this test procedure.
ventional alkyds. A narrower molecular weight range of the
resin species is necessary to meet air-dry, nonvolatility, and
performance properties of the coatings. Another important
Hydroxyl Value factor is solvent selection. Organic solvents with greater vis-
The hydroxyl value or number is a measurement of the free cosity reduction of the base or neat alkyd are needed to lower
hydroxyl groups remaining in the alkyd that have not been coating hydrocarbon atmospheric emissions. The release of
reacted with carboxyl groups during the condensation stage these solvents during coating film formation is an important
of the alkyd resin preparation process. Hydroxyl value deter- consideration.
minations are more difficult to perform than acid number The higher solids alkyd resins are available in all classes of
determinations. There are several reasons for this. First, the "conventional alkyds" such as those shown in Table 6.
hydroxyl group can be sterically hindered or less available Higher solids alkyds can replace their conventional solids
within the polymer and thus difficult to reach with the reac- counterparts in many coating applications, thus affording
tants. Second, hydroxyl groups on primary carbon atoms are decreased atmospheric emissions. Such products are used in
more reactive than those on secondary carbon atoms, and air-dry architectural enamels and both air-dry and baking
these are more reactive than those located on a tertiary car- industrial primers and topcoats.
bon atom. Tertiary-positioned hydroxyl groups are the most
difficult to esterify in this determination. Manufacturers can W A T E R - B O R N E ALKYD R E S I N S
often specify methods that can be used for secondary hy-
droxyl groups. Water-borne alkyds obtain their water reducibility by the
Hydroxyl numbers are important in determining equiva- use of coupling solvents and amine-neutralized carboxyl
lent weight, which in turn is important to determining the groups on the polymer. Typical coupling solvents are ethyl-
amount of urea formaldehyde, melamine formaldehyde, or ene glycol monobutyether, propylene glycol monoethylether,
urethane prepolymer to react with the alkyd. In the case of propylene glycol monopropylether, and four-carbon alcohols
oil-modified urethanes, also called uralkyds, the hydroxyl such as s-butyl alcohol. Water-borne alkyds are available in
groups coreact with free isocyanate functionality. Although most classes of "conventional alkyds" such as those shown in
theoretical equivalency based on hydroxyl numbers is a good Table 7.
guideline to establishing performance characteristics, a lad-
der of co-reactant ratios is important to optimizing particular
performance characteristics. SATURATED P O L Y E S T E R S
Saturated polyesters are also called oil-free alkyds. The oil

or fatty acid modification is zero percent, and this factor
ALKYD R E S I N CLASSIFICATION results in a polymer that cannot be air dried to a cross-linked
coating. Rather, these polymers are formulated with a curing
Unmodified alkyds are classified into four types that de- agent or cross-linker and baked. The curing agent can be a
pend on oil content--very long-oil, long-oil, medium, and urea-formaldehyde or a melamine formaldehyde resin, both
short-oil alkyds. Properties such as speed of drying, ease of of which require baking. Polyurethane prepolymers can be
brushing, film flexibility, chemical resistance, and exterior coreacted with polyester resins for air-dry or low-bake coat-
gloss retention are all dependent on the oil content. These ings in two-component systems. In such systems, the satu-
properties are summarized in Table 4. rated polyester provides the hydroxyl groups for cure with
A summary of alkyd resins comparing types of oil/fatty free isocyanate groups on the polyurethane prepolymer.
acids, nonvolatile, solvent, and typical application is given in The physical properties of these coatings are outstanding
Table 5. due to the absence of fatty acids, and they afford coatings
with excellent color retention, flexibility, exterior durability,
and hardness.
TABLE 4--Alkyd resin properties related to oil length, The type of resins can be adapted to provide higher solids
Very Long oil LongOil Medium Short Oil saturated polyesters by redesigning the polymer and using
Oil content Highest ( ) Lowest organic solvents with appropriate solvency rather than the
Speed of drying Slowest < ) Fastest customary blends of aromatic hydrocarbons with ketones,
Ease of brushing Best < ) Worst alcohols, and glycolethers.
Film flexibility Highest < > Lowest Water-borne polyesters are available through design of
Chemical resistance Worst < ) Best polymers having acid numbers in the range of 40 to 60. When
Exterior gloss retention Worst ( ) Best
these products are neutralized with an amine, they become
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TABLE 5--Description of unmodified alkyd resins.

Oil or Typical
Type Alkyd Fatty A c i d Nonvolatiles Solvent Applications
Very long Linseed 85-100% Aliphatic hydrocarbon Exterior latex
Soya modifier
Tall oil House paint modifier
Oil-based stain and
ink vehicles and
modifiers
Long Linseed 60-70% Aliphatic hydrocarbon Architectural coatings

Safflower Maintenance coatings
Soya One-coat enamels
Sunflower Exterior enamels
Tall oil acids Primers
Topcoats
Medium Linseed 45-50% Aliphatic hydrocarbon Farm implements

Safflower Aromatic hydrocarbon Railway equipment
Soya Maintenance
Sunflower
Tall oil acids
Blends
Short Castor 50% Aromatic hydrocarbon Industrial coatings

Dehydrated or Rule 66-type
castor solvent blenda
Coconut
Linseed
Soya
Tall oil acids
Blends
~AtypicalRule 66 type solventis isobutanol,VM&Pnaphtha, and xyleneat 8% maximumvolumesolids.Rule
66 is a 1966regulationfrom California'sSouth CoastDistrictthat restricted the amount of aromatichydrocarbon
solventin a coatingformulation.In the 1960s,research indicatedthat these types of solventscontributedgreatly
to atmospheric ozone formation. Rule 66 legislationwas adopted by many other local and state regulators.
soluble in blends of water a n d cosolvents a n d yield systems SILICONE-MODIFIED POLYESTERS

with low-volatile organic c o m p o u n d content. F o r m u l a t i o n of
a coating from these products involves the use of water-borne Conventional Types
or water-tolerant ureas a n d melamines. The cured films offer Silicone modification of polyesters is accomplished by use
excellent hardness, gloss, a n d flexibility. of a silicone intermediate incorporated t h r o u g h reaction at a
30 a n d 50% level. The silicone intermediates are of either
hydroxy or methoxy functionality, a n d w h e n they are reacted
TABLE 6--Higher solids alkyd resin types and end uses. with the polyester, water or m e t h a n o l is eliminated. This
Type Typical End Use modification improves the weatherability and/or heat resist-
Long oil Architectural enamels ance of the alkyd a n d resulting organic coating. The silicone-
Medium oil Transportation enamels modified polyesters are available in both self-curing a n d bak-
Short oil General industrial air-dry ing ( m e l a m i n e formaldehyde resin cross-linked) types. They
and bake enamels are used as coil coatings for prefabricated building panels,
Benzoic acid terminated Implement enamels
Phenolic modified Primers prefabricated architectural products, metal advertising sign
Silicone modified Maintenance topcoats stock, a n d other applications requiring excellent exterior du-
Copolymer Aerosol enamels rability and/or good heat resistance.
TABLE 7--Waterborne alkyd resin types and end uses. Higher Solids Types
Type Typical End Use Higher solids silicone-modified polyesters are m a d e by
Long oil Stains and enamels (limited lowering the polyester base molecular weight and/or u s i n g
package stability) oxygenated solvents such as ketone and ester types as re-
Medium oil General industrial air-dry enamels placements for aromatic hydrocarbons. This s u b s t i t u t i o n
Short oil General industrial baking
enamels, automotive under the yields increased solvency, lower viscosities, lower solvent
hood parts a m o u n t s , a n d higher nonvolatile c o n t e n t for the polyester
Benzoic acid terminated Implement enamels solution. The end uses are similar to c o n v e n t i o n a l solvent-
Phenolic modified Primers b o r n e silicone polyesters. However, the higher solids, sili-
Silicone modified Maintenance topcoats
cone-modified polyester resins do n o t have the self-cross-link-
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CHAPTER 7--ALKYD AND POLYESTERS 59
ing option available for conventional types a n d are always [12] ASTM D 1639: Test Method for Acid Value of Organic Coating
c o m b i n e d with a cross-linking agent. Materials," Annual Book of ASTM Standards, Section 6, Vol.
6.01, 1992, pp. 192-193.
REFERENCES
[1] Kienle, R. H. and Ferguson, C. S., Industrial and Engineering BIBLIOGRAPHY

Chemistry, Vol. 21, 1929, p. 349.
[2] Kienle, R. H. and Hovey, A. G., Journal of the American Chemi- Blegen, J. R. and Fuller, W. P., Alkyd Resins, Unit 5 of the Federation
cal Society, Vol. 51, 1929, p. 509. Series of Coatings Technology, Philadelphia, PA, 1967.
[3] Kienle, R. H. and Hovey, A. G., Journal of the American Chemi- Holmberg, K., High Solids Alkyd Resins, Marcel Dekker, Inc., New
cal Society, Vol. 52, 1930, p. 3636. York, 1987.
[4] Kienle, R. H., Industrial and Engineering Chemistry, Vol. 22, Oldring, P., Resins for Surface Coatings, SITA Technology, London,
1930, p. 590. 1987.
[5] Kienle, R. H., U.S. Patent 1,893,873, 10 Jan. 1933. Keane, J., et al., Systems and Specifications, Vol. 2, 4th ed., Steel
[6] ASTM D 1545: Test Method for Viscosity of Transparent Liquids Structures Painting Council, Pittsburgh, PA, 1985.
by Bubble Time Method, Annual Book of ASTM Standards, Sec- Kask, T. and Lesek, F., Processes and Equipment for Alkyd and Unsat-
tion 6, Vol. 06.03, 1992, pp. 214-215. urated Polyester Resin Manufacture, Progress in Organic Coatings,
[7] ASTM D 1259: Test Methods for Nonvolatile Content of Resin Vol. 19, Elsevier Science Publishing Co., New York, 1991, pp.
Solutions," Annual Book of ASTM Standards, Section 6, Vol. 283-331.
06.03, 1992, pp. 212-214. Patton, T. C., Alkyd Resin Technology: Fo~7,nulating Techniques and
[8] ASTM D 1544: Test Method for Color of Transparent Liquids Allied Calculations, Interscience Publishers, Division of John Wiley
(Gardner-Holdt Scale)," Annual Book of ASTM Standards, Sec-, & Sons, New York-London, 1962.
tion 6, Vol. 06.02, 1992, pp. 267-268. Payne, H., Organic Coating Technology, Vol. 1, Chapter 7, John Wiley
[9] ASTM D 1475: Test Method for Density of Paint, Varnish, Lac- and Sons, New York-London, 1965.
quer, and Related Products," Annual Book of ASTM Standards, Singer, E., "Fundamentals of Paint, Varnish, and Lacquer Technol-
Section 6, Vol. 06.01, 1992, pp. 178-180. ogy," Chapter IV, American Paint Journal, 1957.
[10] ASTM D 3278: Test Methods for Flash Point of Liquids by "The Technology of Alkyd Resins," Barrett Division of Allied Chemi-
Setaflash-Closed-Cup Apparatus," Annual Book of ASTM Stan- cal, Toledo, OH, 1958.
dards, Section 6, Vol. 6.03, 1992, pp. 406-412. Von Fischer, W., Paint and Varnish Technology, Chapter IX, Reinhold
[11] ASTM D 1640: Test Methods for Drying, Curing, or Film Forma- Publishing Corporation, New York, 1948.
tion of Organic Coatings at Room Temperature," Annual Book of Zacharias, K., "Raw Materials Index, Resin Section," National Paint
ASTM Standards, Section 6, Vol. 6.01, 1992, pp. 194-197. and Coatings Association, Washington, DC, 1988.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Amino Resins (Reaction

Products of Melamine, Urea,
etc. with Formaldehyde and
Alcohols)
by J. O w e n Santer 1
INTRODUCTION
Definition and Description /

C=O
AMINO, OR AMINOPLAST,RESINS for coatings are the p r o d u c t s of
the r e a c t i o n of either urea (Fig. 1) o r m e l a m i n e (Fig. 2) with FIG. 1-Urea.
f o r m a l d e h y d e a n d an alcohol. Besides u r e a a n d melamine,
o t h e r c o m p o u n d s with s i m i l a r f u n c t i o n a l i t y - - s u c h as
b e n z o g u a n a m i n e , glycoluril, e t c . - - a r e also used in specific
a p p l i c a t i o n s where certain p r o p e r t y advantages are required.
However, use of these m a t e r i a l s is quite limited, a n d sales of
a m i n o resins are d o m i n a t e d b y those b a s e d on u r e a a n d mela-
mine, with U.S. c o n s u m p t i o n of a b o u t 100 million lb (45
106 kg) p e r year.
As p r e p a r e d , a m i n o resins are usually water-white, viscous NH 2
m a t e r i a l s which m a y c o n t a i n a d d e d solvent to reduce viscos- FIG. 2-Melamine.
ity for ease of handling. W h e r e a solvent is used, it is m o s t
often an alcohol such as n-butanol, iso-butanol, o r iso-propa-
ways m a d e with m e t h a n o l or c o m b i n a t i o n s of m e t h a n o l a n d
nol, all of w h i c h are excellent solvents for a m i n o resins.
butanol, a l t h o u g h a small n u m b e r of high-solids resins are
Mixed solvents, such as n- o r iso-butanol with xylene are also
available which are m a d e exclusively with butanol.
used, especially for the h i g h e r - m o l e c u l a r - w e i g h t resins m a d e
with b u t a n o l as a co-reactant. S o m e a m i n o resins are w a t e r
soluble or w a t e r reducible with co-solvent.
Amino resins for coatings are g r o u p e d s o m e w h a t a r b i t r a r -
Where Used
ily into two classes: (1) high solids resins, i.e., resin solutions Amino resins are used in coatings to cross-link the p r i m a r y
at ---80% solids (weight/weight), including resins which con- film-former, usually a n acrylic, polyester, o r alkyd resin
tain no solvent, a n d (2) conventional resins, i.e., resin solu- carrying p r i m a r y o r s e c o n d a r y hydroxyl groups. The cross-
tions at < 8 0 % solids (weight/weight). linking r e a c t i o n ("cure") is p r i n c i p a l l y one of trans-etherifica-
tion between hydroxyl groups on the p r i m a r y film-former
a n d alkoxymethyl groups on the a m i n o resin. In a d d i t i o n to
History the trans-etherification reaction, the a m i n o resin a l m o s t al-
Historically, the first a m i n o resins used in coatings were ways u n d e r g o e s self-condensation reactions.
the r e a c t i o n p r o d u c t s of u r e a o r m e l a m i n e with formalde- The m a j o r b y - p r o d u c t s of the cure r e a c t i o n include m e t h a -
hyde a n d b u t a n o l (either n- or iso-). They were substantially nol a n d / o r butanol, formaldehyde, a n d water. Cure t e m p e r a -
p o l y m e r i c a n d were f o r m u l a t e d at a b o u t 50 to 60% solids in tures are in the range of 180 to 400~ (82 to 204~ for t i m e s
butanol/xylene mixtures. They have been c o m m e r c i a l l y avail- w h i c h vary from 20 to 30 m i n at the lower end of the t e m p e r a -
able for a b o u t 60 years. Parenthetically, it should be noted ture range to p e r h a p s only 30 s at the u p p e r end. An a c i d
that resins m a d e by reacting u r e a o r m e l a m i n e with formal- catalyst m a y be used to accelerate cure, d e p e n d i n g on the
d e h y d e w i t h o u t subsequent r e a c t i o n with an alcohol have cure t e m p e r a t u r e a n d the p a r t i c u l a r a m i n o used. Claims have
b e e n available for 70 years o r more. These resins are used as been m a d e for a m i n o resin f o r m u l a t i o n s w h i c h cure at r o o m
m o l d i n g p o w d e r s a n d adhesives a n d are generally unsuitable t e m p e r a t u r e , but as far as is known, no such f o r m u l a t i o n s are
for coatings applications. presently c o m m e r c i a l l y available.
High-solids coating resins, usually m a d e with higher ratios Urea resins are less expensive t h a n m e l a m i n e resins, w h i c h
of r e a c t e d f o r m a l d e h y d e t h a n the older, conventional resins, is u n d e r s t a n d a b l e given that m e l a m i n e is m a d e f r o m urea.
have been available for a b o u t 35 years. They are a l m o s t al- Urea resins are also faster curing t h a n m e l a m i n e resins, b u t
are m o i s t u r e sensitive a n d therefore not suitable for use out-
1Principal technologist, Monsanto Chemical Co., 730 Worcester doors. They are used widely for w o o d finishing, e.g., furni-
Street, Springfield, MA 01151. ture, kitchen cabinets, a n d in paper, film, a n d foil applica-
60
9
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Copyright 1995 by ASTM lntcrnational www.astm.org

CHAPTER 8 - - A M I N O R E S I N S 61
tions. Wood and paper applications capitalize on the >NCH2N< (methylene) or >NCH2OCH2N< (methylene
relatively rapid cure of the urea resin since lower tempera- ether) bridge. The reactions leading to self-condensation may
tures must be used to avoid damage to the substrate. In some be written as follows:
wood applications, cure temperature is at or near ambient.
>NCH2OR + HN< ~ >NCH2N< + ROH (5)
Melamine resins, on the other hand, find much b r o a d e r
R = H, alkyl
application since they are not nearly as water sensitive as the
ureas. Perhaps the largest single use for melamine resins is in >NCH2OH + HOCH2N< ~ >NCH2OCH2N< + H20 (6)
automotive OEM (original equipment manufacture), where
The bridging groups in amino resins manufactured for
the finished paint must stand up to extremes of temperature,
coatings applications are predominantly methylene ether
humidity, and the degradative effects of sunlight, etc, Mela-
bridges. When formulated and cured, additional bridges of
mine resins are used also in coil coatings, metal containers,
both types may be formed; how many of each will depend on
etc. (see E n d U s e s o f A m i n o R e s i n s ) .
factors such as the composition of the amino resin, cure
temperature, and catalyst level.
It can be seen, then, that a variety of amino resins may be
SYNTHESIS OF AMINO RESINS prepared, with properties which depend on such factors as
the choice of starting material, i.e., urea, melamine, etc., the
Reactions of Synthesis combining ratios of the various reactants, the choice of alco-
The synthesis of amino resins for coatings is a two-step hol (or alcohols, if more than one is used), and the degree of
process. In the first step, the parent compound is reacted with polymerization of the resin. The principal manufacturers of
formaldehyde (methylolation reaction); in the second, the amino resins for coatings typically offer a product line of 25
methylolated intermediate is reacted with an alcohol (etheri- or more resins. A generalized composition of a typical mela-
fication reaction). Equations 1 through 4 exemplify the pro- mine resin is shown in Fig. 3.
cess, with urea as the parent compound. Reactions with mel-
amine are analogous. Structure/Property Variations
H2NCONH2 + CH2O ) H2NCONHCH2OH (1) The difference between conventional solids and high-solids
monomethylolurea a m i n o resins represents not so much a difference in solids
HaNCONHCH20H + CH20 ) content as it does a distinction between resin structures. The
HOCH2NHCONHCH20H (2) conventional solids (<80%) resins are made from melamine
dimethylolurea or urea reacted with relatively low levels of formaldehyde,
typically 1.5 to 2.0 tool for urea resins and 2.5 to 3.5 tool for
HOCH2NHCONHCH20H + ROH ) melamine resins, and etherified with either n- or iso-butanol.
HOCH2NHCONHCH2OR + H20 (3) Because of these low reaction ratios, considerable self-con-
HOCH2NHCONHCH20R + ROH ) densation takes place during the synthesis, leading in the case
ROCH2NHCONHCH2OR + H20 (4) of melamine resins to products with degrees of polymeriza-
bis(alkoxymethyl)urea tion (DP) ->3 and perhaps somewhat higher for the ureas.
Because of the relatively high polymer content, these resins
Reactions shown in Eqs 1 and 2 proceed quite rapidly when are viscous and must be reduced with solvent to less than 80%
catalyzed by either acid or base. Reactions shown in Eqs 3 to obtain a manageable viscosity.
a n d 4 take place only under acid conditions, with the rate of Another, possibly the major, contributor to high viscosity is
reaction strongly pH dependent; the lower the pH, the faster the residual imino (>NH) and methylo] (>NCH2OH) groups
the reaction. All four reactions are equilibrium reactions. on the amino resin, which can form strong hydrogen bonds
Hence, the extent of the reaction is dependent on the charge with unshared electrons on nitrogen and oxygen.
ratios of the various reactants and on whether or n o t the The high-solids amino resins have much higher levels of
reactions are driven by removal of by-products in order to combined formaldehyde than the conventional solids resins.
shift the equilibrium. Typical values for combined formaldehyde are in the range
The reactions of melamine are similar to those of urea with 2.0 to 2.7 for urea resins and 3.5 to 6.0 for melamine resins.
one exception. With urea, two of the four available hydrogens The etherifying alcohol is most often methanol, although res-
are readily reacted with formaldehyde (Eqs 1 and 2), while
the remaining two hydrogens react more slowly and require
an excess of formaldehyde to force the reaction. With mela- ROCH2\ /CH2OH
mine, on the other hand, all six hydrogen atoms may be
reacted with relative ease to give hexa(methylol)melamine. ROCH2./N"'~NI~N'H
The kinetics of the methylolation reactions of urea and
melamine have been studied extensively [1-7], but there is
nothing in the literature on the kinetics of the etherification
N. N
reaction. Although both of these reactions are superficially
straightforward, a number of other reactions may take place
N
which complicate the kinetics. These reactions are all self- ROCH2/ "CH 2 0 ' ' 9
condensation reactions in which two or more molecules of FIG, 3-Representative structure of a mela-
the parent species are joined together through either a mine resin,
www.iran-mavad.com

ins made with both methanol and butanol or even butanol polar, i.e., carries appreciable > N H and >NCH2OH groups,
alone are also widely used. These resins are less polymeric, and (2) the solvent is not low boiling. Apparently, the increase
with DP <3, and usually more fully etherified and so less in viscosity as solvent evaporates slows the diffusion rate and
polar than the conventional resins. In some cases, these res- effectively prevents complete removal of solvent within the
ins are sufficiently low in viscosity that no solvent is needed. time frame of the test. There may also be a hydrogen-bonding
Where solvent is required, it is usually either isopropanol or effect between solvent and resin which contributes to the
butanol (n- or iso-). Resins are also made which can be retention of solvent.
reduced with water. Other test methods involve much higher temperatures,
where resin condensation/degradation does occur. One stan-
dard method is the ASTM Test Methods for Volatile Content
Analysis/Analytical Methods of Coatings (ASTM D 2369), where a small resin sample (0.3
Structural analysis of amino resins has been reviewed by to 0.5 g) is diluted with xylene and placed in a 110~ oven for
Christensen [8 ]. Methods discussed include 1H NMR and 13C 1 h. There are a number of other, similar tests.
NMR for determining levels of combined formaldehyde and
alcohol, analysis of alkoxy groups by Zeisel cleavage, and by Viscosity Measurement
trans-etherification followed by gas chromatography. Chris- Amino resin viscosities are most commonly measured by
tensen [8] and Kambanis and Rybicky [9] also describe non- the Gardner bubble viscometer method. This method is simi-
destructive methods for removing solvent from amino resin lar to the Test Method for Viscosity of Transparent Liquids by
solutions in order to determine nonvolatile content. Bubble Time Method (ASTM D 1545). A tube containing the
Classically, amino resins for coatings have been character- resin under test is placed in a rack containing reference tubes
ized by three test procedures. These procedures, which tell of known viscosity. The tubes are equilibrated to 25~ in a
the coating formulator most of what he needs to know with constant temperature bath. The rack is quickly inverted, and
regard to formulation and cure conditions, are measurement the rate of rise of an air bubble in the sample tube is com-
of (1) solids content, (2) viscosity, and (3) solvent tolerance. pared against similar bubbles in the reference tubes. The
These are discussed below. reference tubes are letter graded A through Z and Z1 through
Z6.
Solids Content
The most common methods used to determine solids con- Solvent Tolerance
tent are gravimetric. Solvent is allowed to evaporate from a There are a number of different solvent tolerance tests. All
weighed sample under carefully controlled conditions of time involve titrating a weighed sample of the amino resin with a
and temperature. The sample is then reweighed. The loss in standard reagent (solvent). The object of the test is to mea-
weight gives a measure of solvent content, and the solids sure how much of the reagent the amino resin can accept
content is obtained by difference. One difficulty with this test before the solution turns cloudy/milky. Results are typically
is the tendency of amino resins to deformylate and/or self- reported in milliliters of reagent per gram of sample. Typical
condense when heated, with evolution of formaldehyde, alco- reagents used include xylene, iso-octane, and the iso-octane/
hol, and water. To the extent that this occurs, the measured decahydronaphthalene/toluene mixture described in ASTM
solids content will be lower than the "true" value. Frequently, Test Method for Solvent Tolerance of Amine Resins (D 1198).
however, the paint formulator is interested in the "contrib- While the immediate objective of the solvent tolerance test
uted solids," i.e., what fraction of the amino resin solution is to determine the amount of reagent which the amino resin
remains in the cured film. In that case, a solids test method can accept before solution clouding occurs, the real purpose
which approximates the time and temperature of cure might of the test is to gain insight into the structure and composi-
be more appropriate. tion of the resin and hence have a better understanding of
For these reasons, solids test methods fall into two groups: how it will perform in a given coating application. In general,
(1) methods which reflect the solids content in the absence of amino resins of high molecular weight, or having high levels
self-condensation, etc., and (2) other methods, which reflect of polar functional groups, i.e., >NH, >NCH2OH, will have
varying degrees of self-condensation in addition to loss of limited compatibility with the typical hydrocarbons used and
formaldehyde and solvent(s). hence will give low tolerance test results. Experience shows
The most common of the first methods is the so-called foil that a low tolerance value means a faster curing resin and vice
solids test, which is used almost universally for high-solids versa, especially in the absence of acid catalyst. However,
amino resins. Essentially, a 1-g sample of resin solution is although the tolerance test represents a quick and easy way to
weighed onto a piece of preweighed aluminum foil. The foil is measure potential cure response, it does not uniquely define
folded over on itself and the sample compressed between the the resin structure. Thus, a low tolerance reading can be
two foil surfaces to provide a thin film about 3 to 4 in. (7 to 10 caused by either high polarity or high molecular weight or
cm) in diameter. The foil is then opened up to give a thin film both.
on each foil surface. The foil is placed in a 45~ oven for 45
min, at the end of which time it is removed, reweighed, and Size Exclusion and High-Performance Liquid
the solids content calculated. These conditions are known to Chromatography
be sufficiently mild that no resin condensation occurs; nor To obtain more detailed knowledge of resin structure,
does the resin lose formaldehyde via demethylolation. Sur- amino chemists now rely very heavily on gel permeation or
prisingly, the foil solids test may on occasion overestimate size exclusion chromatography (SEC) and on high-perform-
the solids content, particularly when (1) the resin is relatively ance liquid chromatography (HPLC). The size exclusion
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CHAPTER 8--AMINO RESINS 63
chromatograph provides an excellent measure of number acted. For example, see hexa(methoxymethyl)melamine
and weight-average molecular weight and molecular weight (HMMM) (Fig. 6), which has exactly 6 mol each of combined
distribution (polydispersity), while HPLC, which fractionates formaldehyde and methanol per mole of melamine. Unlike
the resin components primarily by functional groups, pro- HMMM, most resins are, of course, mixtures of products
vides information on resin composition. The more polar spe- which are best described by an average composition. One of
cies are eluted first, followed by the less polar fractions. Thus, the most widely sold commercial high-solids methylated mel-
taken together, SEC and HPLC provide detailed information amine resins has an average combining ratio melamine/form-
on molecular weight and functionality which cannot be di- aldehyde/methanol of about 1/5.6/5.1. Because methanol re-
rectly obtained or inferred from any of the various solvent acts with an already-reacted formaldehyde molecule, a resin
tolerance tests. Size exclusion and liquid chromatograms for can never have combined methanol greater than the com-
a representative commercial high-solids methylated mela- bined formaldehyde. The excess formaldehyde, 0.5 tool in
mine resin are shown in Figs. 4 and 5. the commercial example, represents formaldehyde which
has not reacted with methanol and which must therefore
Combining Ratios be present as methylol (>NCH2OH), bridging groups
Amino resins may also be characterized by measurement (>NCHzOCH2N<), and acetals (>NCH2OCH2OCH3). Acetals
of the amounts of formaldehyde and alcohol which have re- are formed when an excess of formaldehyde is used in the
400 -
mV Monomer
350 -
300 -
I
250"~
200 - Dimer
150 ~
100-
50 -
20 25 30 35 40 45
Minutes
FIG. 4-Size exclusion chromatogram of a typical high-solids methylated mela-
mine resin.
600"-
mV
500- Hexamethoxy
400 - Penta-
methoxy
350-
200 -
Tetra-
I A I
100-
0 -
20 25 30 35 40 45 50
Minutes
FIG. 5-High-performance liquid chromatogram of a typical high-solids methylated
melamine resin.
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in Analysis/Analytical Methods. The problem is particularly

(C H 30C H2)2N...h/N__,h/N(CH 20C H 3)2 acute with resins having high methylol functionality.
II I
N.~N
Viscosity
The viscosity of an amino resin is a function of (1) polymer
N(CH2OCH3)2 content (degree of polymerization) and (2) the nature of its
FIG. 6-Hexa(methoxymethyl)melamine. functional groups. The latter may be a more important con-
tributor to viscosity than the former.
Amino resins are not generally very polymeric, especially in
synthesis. They are therefore present in many high-solids
comparison with other coating resins, e.g., polyesters, alkyds,
amino resins.
and acrylics. Typically, average degrees of polymerization are
Determination of combining ratios may be done most eas-
in the range of I to 5. High-molecular-weight "tails" increase
ily by either IH or 13C NMR techniques [8]. Older methods
viscosity significantly.
involve complete hydrolysis of the resin to the starting mate-
Because of strong hydrogen bonding, resins carrying sig-
rials, followed by wet-chemical analysis for formaldehyde
nificant amounts of >NH and >NCH2OH functionality are
and gas chromatographic determination of alcohol (metha-
quite viscous, even though they may not be highly polymer-
nol or butanol).
ized. There is a marked drop in viscosity when amino resins
Free Formaldehyde are diluted with solvent, largely due to breaking of hydrogen
bonds. Good solvents (e.g., alcohols) are more effective at
Amino resins always contain some unreacted formalde- reducing viscosity than poor ones [11 ]. Methanol is probably
hyde, usually referred to in product specifications as "free" the best, although it is not widely used because of its low
formaldehyde. Free formaldehyde may be analyzed quantita- boiling point. Isopropanol is almost as effective, and because
tively by a number of methods. One of the most commonly it is somewhat higher boiling, represents a good compromise.
used is the sodium sutfite method [10]. Formaldehyde reacts
rapidly and completely with aqueous sodium sulfite to form a
bisulfite addition complex. Sodium hydroxide is liberated Surface Tension
quantitatively on a mole-for-mole basis
The surface tension of amino resins is quite strongly re-
CH20 + Na2SO3 + HaO ~NaOH + CHa(OH)NaSO3 (7) lated to the nature of the etherifying alcohol and is much less
The NaOH is either titrated directly with a standard HC1 affected by the level of combined formaldehyde and alcohol.
In the author's laboratory, surface tension measurements on
solution, or neutralized with a known excess of standard HC1,
which is then back-titrated with NaOH. Care must be taken to high-solids, solvent-free resins using a DeNouy tensiometer
ensure that reacted formaldehyde, particularly methylol have given values ranging from about 45 dynes/cm for meth-
groups, is not analyzed as free formaldehyde. This can occur ylated resins to about 28 dynes/cm for butylated resins. Mixed
methyl/butyl resins give intermediate values, depending on
because of the following reaction, which can be minimized by
performing the titration as rapidly as possible at cool temper- the methyl and butyl content. The reduction in surface ten-
atures, e.g., room temperature or lower. sion vghen butanol is the etherifying alcohol may be one rea-
son that high-solids butyl and methyl/butyl resins provide
>NCH2OH ) >NH + CHaO (8) improved flow and leveling in high-solids formulations com-
pared to their fully methylated counterparts.
PHYSICAL PROPERTIES
REACTIONS OF AMINOS IN COATINGS
General
Amino resins are typically viscous liquids, with an amine-
Cure Reactions
like odor. Depending on composition, they may also smell of Amino resins in coating formulations cure by reactions
formaldehyde and/or solvent. They are readily soluble in alco- which are chemically and mechanistically similar to those
hols, ketones, hydroxy-functional glycol ethers, esters, etc., which take place during synthesis of the resin. The principal
but have limited solubility in hydrocarbons. Some resins, reaction of cure is one of trans-etherification, wherein a hy-
especially methylol-rich resins with low levels of both com- droxyl group on the primary film-former (acrylic, polyester,
bined formaldehyde and combined methanol, are water solu- or alkyd) reacts with an alkoxymethyl group on the amino
ble. Many more are water reducible in the presence of other resin
solvents, e.g., alcohols and glycol ethers.
Because of their resinous nature, aminos have neither a >NCH2OR + HO--A ~ >NCH20--A + ROH (9)
well-defined freezing point nor boiling point. Uncured resins where
typically have glass transition temperatures around -40~
R = alkyl, and
When heated, they undergo decomposition, with release of
A = primary film-former.
formaldehyde and alcohol, at temperatures above about
140~ This tendency to decompose causes difficulties in de- Additionally, direct etherification may take place, the end
termining the solids content of resin solutions, as described result being the same
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>NCH2OH + HO--A ) >NCH20--A + H20 (10) enced by heat. The trans-etherification reaction takes place
very rapidly under strong acid catalysis, even at low tempera-
where
tures. This is especially true for aminos with a high level of
A = primary film-former. alkoyxmethyl substitution, i.e., a very low NH content, which
tends to inhibit catalysis. Thus, most formulations involving
These two reactions both result in chemical bond forma-
resins with high alkoxymethyl ether content and designed for
tion between the amino and the primary film-former (co-
low-temperature cure (250~ or lower) will call for a sulfonic
condensation). Two other reactions may also take place, both
acid catalyst, either blocked or free.
of which involve reaction of the amino resin with itself (self-
condensation). These are Although the individual reactions of cure are reasonably
well understood and have been described in numerous pa-
>NH + ROCHzN< ) >NCH2N< + ROH (11) pers [13-18], there is still much to be learned about the overall
where behavior of amino resins during cure, in particular the rela-
tive contributions of each of the various reactions. One of the
R = H, alkyl. difficulties is, of course, that the coating becomes intractable
>NCH2OH + HOCH2N< ) >NCH2OCHzN< + H20 (12) as cure progresses. Hence, a majority of studies involve analy-
sis of the by-products of cure [13,17,30]. Other methods, such
Besides the co-condensation and self-condensation reac- as dynamic mechanical analysis [19], nuclear magnetic reso-
tions, hydrolysis and deformylation reactions may also occur nance [20,21], FTIR [17], ESCA, etc. investigate the structure
>NCH2OR + H20 ) >NCHzOH + ROH (13) of the cured film.
These techniques are useful not only for analyzing the
>NCH2OCH2OR + H20 ) >NCH20H + CH20 + ROH (14) freshly cured coating, but also as a means of following the
>NCHzOH ~ >NH + CH20 (15) coating through its lifetime, either natural or accelerated.
The relative contributions to cure of the co-condensation and

self-condensation reactions will depend on a variety of fac- Degradation and Weathering
tors. These include:
Amino-based cross-linked coatings exposed to the atmo-
1. The functionality of the amino resin, i.e., the relative pro-
sphere are subject to both hydrolysis and UV-degradation.
portions of >NCH2OR, >NCH2OH, and >NH groups pres-
The mechanisms by which melamine resins hydrolyze have
ent initially, as well as those generated during formulation
and/or cure. been described in detail by Berge [22-24], who was the frst to
distinguish between mono- and di-substituted nitrogen with
2. The functionality (hydroxyl number) of the primary film-
former (coreactant). respect to their behavior towards acid or base hydrolysis.
3. The amino/coreactant ratio. Thus, in an alkaline medium, hydrolysis of an alkoxymethyl
4. The level and type of catalyst (weak acid/strong acid). group on a singly substituted nitrogen is initiated by removal
5. Cure time and temperature. by the base of the proton attached to nitrogen
A coreactant resin with a low hydroxyl number is best if --NHCH2OR + B ) --I~ICH2OR + BH (16)
formulated with a "polar" amino (i.e., one rich in >NH and/or
--NCH2OR ) - - N = CH2 + OR- (17)
>NCH2OH) since these groups help build molecular weight
during cure via self-condensation, particularly if little or no - - N = CH2 + H20 ) --NHCH2OH (18)
catalyst is present. Conversely, a high hydroxyl resin is best if
OR- + BH + ) ROH + B (19)
matched with an alkoxymethyl-rich amino and cured with a
strong acid catalyst. Where high cure temperatures are em- This mechanism is clearly not applicable to di-substituted
ployed (e.g., can or coil coating operations), the choice of nitrogen (N(CH2OR)2), and these groups are in fact extremely
amino resin is less obvious, and, in practice, both polar and resistant to alkaline hydrolysis.
nonpolar aminos are used. On the other hand, acid hydrolysis takes place readily for
Acid catalysts are usually used as an aid in curing amino- both mono- and di-substituted nitrogen. Berge proposed two
based formulations. These catalysts include very strong mechanisms (a) specific acid catalysis
acids such as p-toluenesulfonic acid (PTSA), dodecyl-
>NCH2--OR + H + :, >NCH2OHR + (20)
benzenesulfonic acid (DDBSA), dinonylnaphthalenedi-
sulfonic acid (DNNDSA), etc., and weaker acids such as phe- >NCH2OHR + ) >NCH~- + ROH (21)
nyl acid phosphate (PAP), butyl acid phosphate (BAP), etc.
> N C H f + H20 ) >NCH2OH + H + (22)
Amine blocking agents are sometimes used to help minimize
resin advancement prior to cure. Some coatings, particularly and (b) general acid catalysis
those designed for high-bake temperatures, need no catalyst,
>NHCHzOR + HA ) >NCH2OHR + + A- (23)
relying instead on the combination of high temperature and
perhaps carboxylic acid functionality on the primary film- >NHCH2OHR + + A- ) >N = CH 2 + ROH + HA (24)
former to bring about cure [12]. While all of the various
- - N = CH 2 + H20 ) --NHCHEOH (25)
reactions which take place during cure are accelerated by
either acid or heat, it is fair to say that reactions of Berge's work with melamine resins is undoubtedly relevant
transetherification are most influenced by catalyst level and to acid hydrolysis of paint films, which has been studied by a
type, while reactions of self-condensation are most influ- number of workers.
www.iran-mavad.com

English et al. [25,26] found that coatings prepared from in exterior applications, despite some of the recent difficulties
highly alkylated melamines underwent extensive hydrolysis described earlier in connection with water spotting and acid
of residual methoxy groups during two years exposure in etch of automobiles. Besides automobiles, they are used in
Florida, but there was no evidence of hydrolysis of bonds appliance formulations (both coil appliance and conven-
between melamine and the primary film-former. Bauer [27- tional post-sprayed), general metal applications, container
28] used IR to analyze acrylic-melamine coatings exposed to coatings (beer and beverage cans), etc.
both UV and moisture and found evidence of hydrolysis of In choosing an amino resin for a particular application,
both residual methoxy groups and acrylic-melamine bonds, consideration must be given not only to interior versus exte-
with the rate of hydrolysis being faster in the presence of UV rior use, but also to possible restrictions on cure conditions
light. The rate of hydrolysis was slowed considerably when a and compatibility of the amino resin with its co-reactant
hindered amine light stabilizer was used. resin, both when formulated and as the paint film is formed
In recent years, degradation of melamine-containing auto- during solvent flash-off and cure, etc. Compatibility of the
motive coatings has been particularly severe because of etch- amino is especially important in water-borne coatings, which
ing and spotting due to "acid rain." The problem is com- are becoming more widely used. Another factor is the stabil-
pounded because modern high-solids automotive coatings ity of the amino towards advancement (molecular weight
use very high levels of melamine resins (35 to 45% of total buildup) during storage of the formulated paint.
binder weight), giving rise to correspondingly high levels of Benzoguanamine-based (Fig. 7) amino resins are used
acrylic-melamine bonds and residual alkoxymethyl groups in where film flexibility and hardness are required, as in some
the cured film, all of which are susceptible to hydrolysis appliance applications (e.g., refrigerator doors made from
under acid conditions. Suppliers of high-solids coatings for coil stock, etc.). They also have good corrosion and humidity
automobiles are presently evaluating and using alternative and detergent resistance. Their use is limited by cost and poor
cross-linkers, such as isocyanates and epoxies, which are exterior durability due to the pendant phenyl group on the
more stable under acid rain conditions and which can serve benzoguanamine molecule.
as either a partial or complete replacement for melamines. An Glycoluril (Fig. 8) resins have been available for about a
interesting aspect of the acid etch problem is that the damage dozen years. They may require a higher cure temperature or a
always occurs to relatively new coatings. If a newly painted higher catalyst level than melamine-based resins, but show
automobile is protected from the acid environment for the excellent corrosion and humidity resistance and release
first six to twelve weeks, damage thereafter is much less lower amounts of formaldehyde during cure [29].
severe. An obvious conclusion is that the paint is undergoing
additional cure (probably melamine self-condensation) as it
ages.
Automotive paint manufacturers are also actively pursuing ENVIRONMENTAL/TOXICITY
waterborne systems, which use higher molecular weight, less
functional coreactant resins, and lower levels of melamine The past 20 years have seen increased emphasis on the
cross-linker and which are therefore less severely degraded quality of the environment both in the workplace and beyond.
by acid rain. At the present time, however, these waterborne In the coatings industry, this has meant strict controls on
systems are only used in the base coat, where acid attack is in exposure of workers to hazardous ingredients in the coating
any case minimized by the protective clear top coat. It is the formulation when applied, as well as on the nature and
top coat, with its high melamine content, which is the princi-
.2.yN.yN.2
pal site for acid attack. But it is also the high level of mela-
mine resin which provides the excellent gloss and "distinct-
ness of image" (DOI), characteristic of basecoat/clearcoat
technology. The melamine resin also minimizes the amount
of solvent required because of its low viscosity at high-for-
mulated solids, behaving in some ways as a reactive diluent
and plasticizer.
E n d Uses o f A m i n o R e s i n s
Amino-based surface coatings protect and decorate the
substrate to which they are applied. Their technology and use
has developed over many years. As already mentioned, resins FIG. 7-Benzoguanamine.
based on urea and melamine dominate the field. Urea resins
are traditionally used in clear coatings for wood, e.g., furni-
ture, kitchen cabinets, in paper, film, and foil applications, H H
and in some appliance and general industrial coatings. They
are also used to some extent in automotive primers. They
cannot be used in automotive topcoats because of their sensi-
tivity to hydrolysis. "N~ ~'N ~
Melamine resins are much more widely used. They give H H
better chemical resistance, as well as resistance to weathering FIG. 8-Glycoluril.
www.iran-mavad.com

a m o u n t s of volatile organics (the so-called VOCs) released to [2] Gordon, M., Halliwell, A., and Wilson, T., Journal of Applied
the e n v i r o n m e n t w h e n the f o r m u l a t i o n is cured. Polymer Science, Vol. 10, 1966, p. 1153.
Amino resin suppliers have r e s p o n d e d to these environ- [3] Gordon, M., et al., "The Chemistry of Polymerization Processes,"
m e n t a l challenges in a n u m b e r of ways. Chief a m o n g these SCI Monograph No. 20, Society of Chemical Industry, London,
has been a progressive shift t o w a r d s higher-solids, lower- 1966, p. 187ff.
molecular-weight aminos, w h i c h are n o w the resins of choice [4] Aldersley, J. W. et al., Polymer, Vol. 9, 1968, p. 345.
[5] Okano, M. and Ogata, Y., Journal of the American Chemical
of coatings formulators. M a n y a m i n o resins are supplied at
Society, Vol. 74, 1952, p. 5728.
100% nonvolatiles, especially for the a u t o m o t i v e industry.
[6] Braun, D. and Legradic, V., Angewaudte Makromolekular
W h e r e solvents are needed, those presenting the least h a z a r d Chemie, Vol. 35, 1974, p. 101.
to w o r k e r a n d e n v i r o n m e n t are selected. F o r their part, p a i n t [7] Tomita, B., Journal of Polymer Science, Vol. 15, 1977, p. 2347.
p r o d u c e r s have i n c r e a s e d the functionality of the c o r e a c t a n t [8] Christensen, G., "Analysis of Functional Groups in Amino Res-
resin while lowering its m o l e c u l a r weight to m i n i m i z e solvent ins," Progress in Organic Coatings, Vol. 8, 1980, pp. 211-239.
use with the object of b u i l d i n g m o l e c u l a r weight to the maxi- [9] Kambanis, S. M. and Rybicki, J., Journal of Coatings Technology,
m u m possible extent d u r i n g cure. This has m e a n t using Vol. 52, No. 667, 1980, p. 61.
h i g h e r levels of a m i n o resin, as m u c h as 40 to 50% of total [10] Walker, J. F., Formaldehyde, 3rd ed., Robert E. Krieger Publish-
b i n d e r weight in s o m e cases. ing Co., Huntington, NY, 1975, p. 486.
Perhaps the m o s t i n t r a c t a b l e e n v i r o n m e n t a l p r o b l e m with [11] Hill, L. W. and Wicks, Z., Progress in Organic Coatings, Vol. 10,
a m i n o resins is the use of f o r m a l d e h y d e in t h e i r m a n u f a c t u r e . 1982, p. 55.
F o r m a l d e h y d e is r e c o g n i z e d b y the I n t e r n a t i o n a l Agency for [12] Yamamoto, T., Nakamichi, T., and Ohe, O., Journal of Coatings
R e s e a r c h on Cancer (IARC) as a carcinogen. The A m e r i c a n Technology, Vol. 60, No. 762, 1988, p. 51.
Conference of G o v e r n m e n t a l I n d u s t r i a l Hygienists (ACGIH) [13] Blank, W., Journal of Coatings Technology, Vol. 51, No. 656,
lists f o r m a l d e h y d e as an "A2" substance, i.e., one suspected of 1979, p. 61.
[14] Blank, W., Journal of Coatings Technology, Vol. 54, No. 687,
carcinogenic potential for m a n , a n d the O c c u p a t i o n a l Safety
1982, p. 26.
a n d Health A d m i n i s t r a t i o n (OSHA) has set w o r k p l a c e expo-
[15] Santer, J. O. and Anderson, G. J., Journal of Coatings Technology,
sure limits of 0.75 p p m (8-h t i m e w e i g h t e d average) a n d 2 Vol. 52, No. 667, 1980, p. 33.
p p m (15-min s h o r t - t e r m exposure limit). [16] Santer, J. O., Progress in Organic Coatings, Vol. 12, 1984, p. 309.
The f o r m a l d e h y d e content of a m i n o resins is p r e d o m i - [17] Lazzara, M. G., Journal of Coatings Technology, Vol. 56, No. 710,
n a n t l y "combined," i.e., chemically reacted, a n d r e p r e s e n t s 1984, p. 19.
a b o u t 30 to 50% by weight of the resin. A small a m o u n t , [18] Nakamichi, T., Progress in Organic Coatings, Vol. 14, 1986, p. 23.
ranging from a b o u t 0.1 to a b o u t 3% is present free, o r un- [19] Hill, L. W. and Kozlowski, K., Journal of Coatings Technology,
r e a c t e d (see the section entitled A n a l y s i s / A n a l y t i c a l Meth- Vol. 59, No. 751, 1987, p. 63.
ods). Amino resin suppliers have m a d e c o n s i d e r a b l e progress [20] Bauer, D. R., Progress in Organic Coatings, Vol. 14, 1986, p. 45.
over the p a s t several years in lowering the level of free formal- [21] Bauer, D. R., Progress in Organic Coatings, Vol. 14, 1986, p. 193.
d e h y d e in their products, w h i c h is i m p o r t a n t b e c a u s e of [22] Berge, A., Kvaeven, B., and Ugelstad, J., European Polymer Jour-
OSHA labelling requirements. nal, Vol. 6, 1970, p. 981.
In an ideal situation, all of the c o m b i n e d f o r m a l d e h y d e [23] Berge, A., Advances in Organic Coatings Science and Technology,
w o u l d r e m a i n in the coating after cure as p a r t of the p o l y m e r Vol. 1, 1979, p. 23.
network, In practice, however, some of the c o m b i n e d formal- [24] Berge, A., Gudmundsen, S., and Ugelstad, J., European Polymer
Journal, Vol. 5, 1969, p. 171.
dehyde a n d all of the free f o r m a l d e h y d e is released d u r i n g
[25] English, A. D., Chase, D. B., and Spinelli, H. J., MacromoIecules,
cure a n d m a y r e a c h the environment, d e p e n d i n g on the me-
Vol. 16, 1983, p. 1422.
chanics of the coating a n d curing operation. It is the p a r t i a l [26] English, A. D. and Spinelli, H. J., Journal of Coatings Technology,
release of c o m b i n e d f o r m a l d e h y d e d u r i n g cure w h i c h is of Vol. 56, No. 711, 1984, p. 43.
m o s t concern, since the a m o u n t released c a n easily be several [27] Bauer, D. R., Journal of Applied Polymer Science, Vol. 27, 1982, p.
times t h a t of the free formaldehyde. I n c i n e r a t i o n of off gases, 3651.
w h e r e possible, is the best solution. [28] Bauer, D. R. and Briggs, L. M., "Characterization of Highly
Crosslinked Polymers," American Chemical Society Symposium
Series No. 243, Washington, DC, 1984.
REFERENCES [29] Parekh, G. G., Journal of Coatings Technology, Vol. 51, No. 658,
1979, p. 101.
[1] DeJong, J. I. and DeJonge, J., Recueil de Travail Chimie Pay-Bas, [30] McGuire, J. M. and Nahm, S. H., Journal of High-Resolution
Vol. 71, 1952, p. 643. Chromatography, Vol. 14, 1991, p. 241.
www.iran-mavad.com

MNLI7-EB/Jun. 1995
Ceramic Coatings
by Richard A. Eppler ~
CERAMIC COATINGS ARE AN ALTERNATIVE t o organic paints for GLAZES

surface coating applications. When painting with a suitable
material will meet all service requirements, it is almost al- A ceramic glaze is a vitreous coating applied to a ceramic
ways less expensive to paint. However, organic paints have substrate, usually a whiteware. Glazes are applied to their
limitations in several areas where ceramic coatings are a substrates by one of several powder-processing techniques:
more suitable selection. dipping, spraying, and waterfall. The raw materials are both
crystalline oxides and frits. In these wet processes the raw
Vitreous (glassy) ceramic coatings are chosen for applica-
materials are dispersed in an aqueous slip for application.
tion over a substrate for one or more of several reasons [1].
After application, the coatings must be dried and fired at high
These coatings may be applied to a substrate surface in pref- temperatures (up to 1300~ typically 1000 to 1100~ to fuse
erence to an organic paint to render the surface chemically them onto the substrate.
more inert, impervious to liquids and gases, more readily
cleanable, and more resistant to service temperature, abra-
sion, and scratching. Applications for Glazes
The chemical durability of ceramic coatings in service sub- Ceramic glazes find their way into a wide range of applica-
stantially exceeds that of organic paints [2]. Vitreous coatings tions ranging from coffee mugs to automotive spark plugs.
are formulated to be resistant to a variety of reagents, from The major markets for ceramic coatings have different re-
acids to hot water to alkalies, as well as to essentially all quirements, but one common theme is chemical durability
organic media. The only important exception is hydrofluoric and cleanability.
acid, which readily attacks all silicate glasses. This outstand- The major products that normally use glazes are distrib-
ing durability, combined with a very smooth surface, renders uted as follows:
many ceramic coatings suitable for applications requiring the 43.9% Sanitaryware
highest standards of cleanability such as ware that comes in 32.9% Wall and floor tile
contact with food and drink. These coatings are also suitable 10.9% Tableware
for applications requiring true hermeticity, usually to protect 9.5% Artware
2.8% Electrical porcelain and electronics
sensitive electronic equipment. No organic resins are truly
hermetic. The total market for these products in the United States
was reported to be $3459 billion for 1989 [3], of which the
Even the most thermally stable organic resins depolymer-
glaze typically consumed 10 to 15% of the total manufactur-
ize at temperatures on the order of 300~ Hence, organic
ing cost. Hence, the value of the protective, functional, and
paints are not suitable for applications requiring thermal
decorative properties provided by the coating usually far
stability above 300~ For example, stove side panels are outweighs the cost.
painted, but stove tops are porcelain enameled. A similar
argument can be made for abrasion resistance. Organic res-
ins are soft (Moh 2 to 3). By contrast, vitreous coatings are Leadless Glazes
harder (Moh 5 to 6), and some plasma coatings are much Glazes are essentially mixtures of silica with other oxides
harder. For example, alumina coatings, plasma sprayed, have added to permit the glaze to form at a readily achievable
Moh = 9. temperature. In a leadless glaze, the alkali and alkaline earth
Vitreous coatings are thin layers of glass fused onto the oxides, together with magnesia (MgO), zinc oxide (ZnO), and
surface of the substrate. When the substrate is a ceramic, the boron oxide (B203), are used to provide the fluxing action.
coating is called a glaze. When the substrate is a metal, the Table 1 gives the formulas of a few typical ceramic glazes.
coating is called a porcelain enamel. When the substrate is a Glaze 1 is a feldspathic glaze suitable for use on soft paste
porcelains or hard stoneware [4]. This glaze is typical of that
glass, the coating is called a glass enamel.
used on medieval Chinese porcelains.
Glaze 2 is a sanitary-ware glaze [5]. It is derived from the
1Consuhant, Eppler Associates, 400 Cedar Lane, Cheshire, CT soft paste porcelain glaze by the addition of ZnO in large
06410.
quantity. Increasing the melting rate by increasing the per-
68
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CHAPTER 9--CERAMIC COATINGS 69
TABLE 1--Typical ceramic glazes in weight percent.

Glaze Na20 KzO CaO MgO ZnO SrO BaO PbO B203 A1203 SiO2 ZrO2
1 2.24 3.24 9.71 0.44 0.00 0.00 0.00 0.00 0.00 14.44 69.90 0.00
2 2.05 3.12 11.15 0.00 5.39 0.00 0.00 0.00 0.00 18.58 59.71 0.00
3 6.54 1.47 7.67 0.16 10.18 0.00 0.00 0.00 1.36 10.36 62.25 0.00
4 1.81 2.71 9.16 0.62 10.94 3.07 2.50 0.00 5.47 7.37 55.79 0,57
5 3.06 1.72 7.65 0.00 0.00 0.00 0.00 16.08 6.04 9.57 55.88 0,00
6 2,46 0.00 3.09 0,00 0.00 0.00 0.00 35.30 8.93 7.04 42.45 0,72
7 0.00 0.00 0.00 0.00 0.00 0~00 0,00 88.14 0.00 0.00 11.86 0,00
8 0.85 1.91 10.08 0.00 0,00 0.00 0,00 28.87 4.20 9.17 35,99 8.92
cent of fluxes yields a fast-fire, wall-tile glaze such as Glaze 3 TABLE 2--Test methods for ceramic glazes [12].
[6]. To produce a glaze for dinnerware, the coefficient of Number Title
t h e r m a l expansion m u s t be reduced to m a t c h that of the
C 1027 Test Method for Determining Visible Abrasion
ware. Glaze 4 is a n example of a glaze for vitreous hotel c h i n a Resistance of Glazed Ceramic Tile
[7]. C 650 Test Method for Resistance of Ceramic Tile to
Chemical Substance
C 609 Test Method for Measurement of Small Color
Lead-Containing Glazes Differences Between Ceramic Wall or Floor Tile
C 554 Test Method for Crazing Resistance of Fired Glazed
Litharge (PbO) is used in glazes for several reasons [8], the Ceramic Whitewares by a Thermal Shock Method
most i m p o r t a n t of which is the strong fluxing action of PbO, C 424 Test Method for Crazing Resistance of Fired Glazed
Whitewares by Autoclave Treatment
which allows the f o r m u l a t i o n of glazes that m a t u r e at tem- C 556 Test Method for Resistance of Overglaze Decorations to
peratures lower t h a n their leadless counterparts, leading to Attack by Detergents
greater flexibility in the f o r m u l a t i o n of the glaze to o b t a i n C 539 Test Method for Linear Thermal Expansion of
desired properties, .Glazes for electronic substrates, artware, Porcelain Enamel and Glaze Frits and Ceramic
a n d some dinnerware, a n d tiles c o n t a i n lead oxide. However, Whiteware Materials by the Interferometric Method
C 372 Test Method for Linear Thermal Expansion of
PbO is highly toxic. Therefore, use of lead-containing glazes Porcelain Enamel and Glaze Frits and Fired Ceramic
requires special care in processing a n d in testing the ware Whiteware Products by the Dilatometer Method
produced. C 584 Test Method for 60-deg Specular Gloss of Glazed
Glaze 5 i n Table 1 is a n example of a lead-containing din- Ceramic Whitewares and Related Products
C 1034 Test Method for Lead and Cadmium Extracted from
nerware glaze [9]. Glaze 6 is a n example of a clear glaze Glazed Ceramic Cookware
suitable for use o n artware a n d hobbyware bodies [10]. Glaze C 738 Test Method for Lead and Cadmium Extracted from
7 is an example of a coating used on integrated circuit pack- Glazed Ceramic Surfaces
ages to seal t h e m [11]. C 895 Test Method for Lead and Cadmium Extracted from
Glazed Ceramic Tile
Satin and Matte Glazes

a n d Glaze Frits a n d Fired Ceramic Whiteware Products by
Satin a n d matte effects are due to dispersed oxide crystals the Dilatometer Method.
of appropriate refractive index in the glaze [5]. Calcium alu- Several other ASTM methods are concerned with chemical
minosilicate a n d zinc silicate crystals are c o m m o n l y used.
durability. These include: C 6 5 0 - - T e s t Method for Resist-
The crystals m u s t be very small a n d evenly dispersed if the
ance of Ceramic Tile to Chemical Substances; a n d C 5 5 6 - -
glaze is to have a smooth, velvet appearance. Glaze 8 in Table Test Method for Resistance of Overglaze Decorations to At-
1 is a n example of a matte glaze.
tack by Detergents. Of particular c o n c e r n are ASTM methods
used to control release of lead and c a d m i u m from glazed
Testing o f Glazes surfaces, These include: C 1034--Test Method for Lead a n d
C a d m i u m Extracted from Glazed Ceramic Cookware;
ASTM Committee C-21 on Ceramic Whitewares a n d Re- C 7 3 8 - - T e s t Method for Lead a n d C a d m i u m Extracted from
lated Products has developed several test methods to evaluate Glazed Ceramic Surfaces; a n d C 8 9 5 - - T e s t Method for Lead
the physical properties of ceramic glazes. These are listed in a n d C a d m i u m Extracted from Glazed Ceramic Tile; as well as
Table 2 [12]. These tests form the basis for most quality C 1035--Specification for Lead and C a d m i u m Extracted
control testing programs. from Glazed Ceramic Cookware.
There are several m e t h o d s concerned with the fit of the
glaze to the substrate. These include: C 5 5 4 - - T e s t Method for
Crazing Resistance of Fired Glazed Ceramic Whitewares by a
Thermal Shock Method; C 4 2 4 - - T e s t Method for Crazing PORCELAIN ENAMELS
Resistance of Fired Glazed Whitewares by Autoclave Treat-
ment; C 5 3 9 - - T e s t Method for Linear T h e r m a l E x p a n s i o n of Porcelain e n a m e l coatings are ceramic coatings designed
Porcelain E n a m e l a n d Glaze Frits a n d Ceramic Whiteware for application to metals. Conventional porcelain e n a m e l
Materials by the Interferometric Method; and C 3 7 2 - - T e s t coatings are prepared in a n aqueous system a n d applied to
Method for Linear T h e r m a l Expansion of Porcelain E n a m e l the substrate by spray, dip, or flow coating. The coating is
www.iran-mavad.com

dried before firing. Newer technology involves dry applica- Cover Coat E n a m e l s
tion of powdered porcelain e n a m e l by electrostatic spray.
Cover coat porcelain enamels are formulated to provide
The total market for porcelain-enameled products was re-
specific color a n d appearance characteristics, a b r a s i o n resist-
ported to be $5486 billion i n 1989 [13]. About 86% of the
ance, surface hardness, a n d resistance to corrosion, heat, a n d
products are appliances, such as ranges, water heaters, h o m e
t h e r m a l shock. They c a n be clear, semiopaque, or opaque.
laundry, a n d dishwashers. About 6% are cast-iron sanitary
Opaque enamels such as E n a m e l 5 are used for white a n d
ware, a n d 8% are architectural, cookware, a n d miscellaneous
pastel coatings [18]. They c o n t a i n high c o n c e n t r a t i o n s of
items.
titania (TiO2) to provide the opacification. S e m i o p a q u e
A porcelain e n a m e l m u s t be formulated such that it will
enamels like E n a m e l 6 are used for most m e d i u m - s t r e n g t h
b o n d to the metal substrate. For proper adherance of the
colors. Clear enamels like E n a m e l 7 are used to produce
e n a m e l to the metal, it is necessary to develop a c o n t i n u o u s
strong, bright colors. They are similar to g r o u n d coat formu-
electronic structure across the interface [14]. This structure is
lations without the adherance oxides.
developed by saturating the e n a m e l coating a n d the substrate
metal with a n oxide of the metal [15], which for iron a n d steel
substrates is ferrous oxide (FeO).
Testing o f Porcelain E n a m e l s
Certain t r a n s i t i o n metal oxides, such as cobalt oxide (COO),
nickel oxide (NiO), a n d cupric oxide (CuO), can be added to Test m e t h o d s for porcelain e n a m e l coatings are u n d e r the
a n e n a m e l f o r m u l a t i o n to improve the adherence between the jurisdiction of ASTM Committee B-8 o n Metallic a n d Inor-
metal a n d the substrate. G r o u n d coat enamels c o n t a i n ganic Coatings. The methods are listed in Table 4. Again, they
adherance oxides, while cover coat enamels do not. form the basis for most quality control test programs.
Several of these test methods are c o n c e r n e d with the chem-
ical durability of porcelain enamels. They include: C 2 8 2 - -
G r o u n d Coat E n a m e l s Test Method for Acid Resistance of Porcelain E n a m e l s (Citric
A general-purpose g r o u n d coat e n a m e l like E n a m e l 1 in Acid Spot Test); C 6 1 4 - - T e s t Method for Alkali Resistance of
Table 3 is a n alkali borosilicate c o n t a i n i n g small a m o u n t s of Porcelain Enamels; C 7 5 6 - - T e s t Method for Cleanability of
adherance oxides to promote the b o n d i n g process. E n a m e l 2 Surface Finishes; C 5 3 8 - - T e s t Method for Color Retention of
is a h o m e l a u n d r y enamel that has been formulated for out- Red, Orange, a n d Yellow Porcelain Enamels; C 8 7 2 - - T e s t
standing alkali resistance t h r o u g h the addition of large q u a n - Method for Lead a n d C a d m i u m Release from Porcelain
tities of zirconia (ZrO2) [16]. Hot water t a n k coatings like E n a m e l Surfaces; a n d C 2 8 3 - - T e s t Method for Resistance of
E n a m e l 3 have very stringent thermal- a n d corrosion-resist- Porcelain E n a m e l e d Utensils to Boiling Acid. A related issue
ance requirements. is the possibility of defects providing a pathway from the
E n a m e l 4 is a c o n t i n u o u s clean coating. This is a porous surface to the substrate, usually called c o n t i n u i t y of coating.
coating which provides a m e a n s of volatilizing a n d removing Methods in this area include: C 5 3 6 - - T e s t Method for Conti-
food soils from the i n t e r n a l surfaces of ovens during n o r m a l nuity of Coatings in Glassed Steel E q u i p m e n t by Electrical
operation [17]. Testing; C 7 4 3 - - T e s t Method for Continuity of Porcelain
TABLE 3--Typical porcelain enamels in weight percent.

Oxide Enamel1 Enamel2 Enamel3 Enamel4 Enamel5 Enamel6 Enamel7
Li20 0.88 0.81 1.33 0.52 0.89 1.10 1.76
Na20 13.15 12.60 13.92 7.30 9.41 8.58 12.23
K20 2.30 1.56 0.00 1.47 6.13 9.15 3.83
CaO 6.18 2.80 2.04 0.65 0.00 0.00 0.00
MgO 0.00 0.18 0.00 0.00 0.00 0.00 0.00
ZnO 0.00 0.26 1.27 0.00 0.00 1.04 0.00
BaO 7.27 0.73 0.56 0.00 0.00 0.00 0.00
CoO 0.47 0.36 0.47 0.03 0.00 0.00 0.00
NiO 0.29 0.31 0.00 0.03 0.00 0.00 0.00
CuO 0.20 0.00 0.00 13.99 0.00 0.00 0.00
B203 15.37 15.99 7.60 1.18 16.13 16.53 7.11

A]203 6.35 11.50 2.02 41.38 2.25 1.34 2.72
Cr20 s 0.00 0.00 0.00 1.24 0.00 0.00 0.00
Sb203 0.00 0.00 0.00 0.30 0.00 0.00 0.00
SiO2 44.01 41.55 56.05 24.20 40.97 46.74 59.07

ZrO2 0.00 6.36 11.66 7.24 0.00 0.00 7.86
TiO2 0.00 2.55 0.00 0.03 20.97 13.25 3.58
MnO2 0.20 0.66 1.81 0.03 0.00 0.00 0.00
P205 0.70 0.45 0.00 0.00 1.30 0.00 0.00
Nb205 0.00 0.00 0.00 0.00 0.06 0.00 0.00
WOs 0.00 0.00 0.00 0.00 0.05 0.00 0.00
MoOs 0.00 0.00 0.00 0.00 0.00 0.00 0.47
F 2.71 2.31 2.19 0.72 3.17 3.93 2.35
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CHAPTER 9 - - C E R A M I C COATINGS 71
E n a m e l Coatings; a n d C 5 3 7 - - T e s t M e t h o d for Reliability of TABLE 5--Test methods for glass enamels [12].
Glass Coatings on Glassed Steel R e a c t i o n E q u i p m e n t by H i g h ASTM
Voltage. Method Subject
C 724 Test Methods for Acid Resistance of Ceramic
Decorations on Architectural-Type Glass
C 735 Test Method for Acid Resistance of Ceramic
Decorations on Returnable Beer and Beverage Glass
GLASS ENAMELS Containers
C 675 Test Methods for Alkali Resistance of Ceramic
Glass e n a m e l s are vitreous coatings a p p l i e d on glass. They Decorations on Returnable Beverage Glass
Containers
provide a m e a n s of decoration, not an i m p r o v e m e n t in c h e m - C 676
Test Method for Detergent Resistance of Ceramic
ical d u r a b i l i t y or in cleanability. These coatings m u s t be ma- Decorations on Glass Tableware
t u r e d at t e m p e r a t u r e s b e l o w the d e f o r m a t i o n p o i n t of glass C 824 Practice for Specimen Preparation for Determination of
(1000 to 1200~ o r 538 to 649~ Hence, they require large Linear Thermal Expansion of Vitreous Glass
quantities of fluxing elements so t h a t c h e m i c a l d u r a b i l i t y is Enamels and Glass Color Frits by the Dilatometer
Method
difficult to achieve. C 927 Test Method for Lead and Cadmium Extracted from
Glass e n a m e l s are p r o d u c e d in ready-to-use form (paste, the Lip and Rim Area of Glass Tumblers Externally
t h e r m o p l a s t i c s , s p r a y m e d i u m s , ultraviolet curable me- Decorated with Ceramic Glass Enamels
d i u m s ) b y a few select m a n u f a c t u r e r s . They r e p r e s e n t a spe- C 978 Test Method for Photoelastic Determination of
Residual Stress in a Transparent Glass Matrix Using
cialty p r o d u c t that is m o r e a k i n to organic p a i n t s t h a n to a Polarizing Microscope and Optical Retardation
o t h e r c e r a m i c coatings. The m a r k e t s for this specialty prod- Compensation Procedures
uct are c a t e g o r i z e d as tableware, glass containers, architec- C 777 Test Method for Sulfide Resistance of Ceramic
tural, lighting, a n d automotive. As s u p p l i e d to the user, glass Decorations on Glass
e n a m e l s are m e c h a n i c a l mixtures of pigments, fluxes, a n d
organic s u s p e n d i n g media. The r e q u i r e m e n t for low ma-
turing t e m p e r a t u r e s necessitates the use of very high lead Testing of Glass Enamels
oxide c o n t a i n i n g borosilicates for the flux. Leadless fluxes are Test m e t h o d s for glass e n a m e l s are u n d e r the j u r i s d i c t i o n
u n d e r development, b u t have n o t yet achieved c o m m e r c i a l l y of S u b c o m m i t t e e 14.10 on Glass D e c o r a t i o n of ASTM Com-
acceptable properties. The organic s u s p e n d i n g m e d i a are mittee C-14 on Glass a n d Glass Products. These m e t h o d s [12]
similar to m a t e r i a l s u s e d to m a k e organic paints. are listed in Table 5.
Most of these m e t h o d s are c o n c e r n e d with the c h e m i c a l
TABLE 4--Test methods for porcelain enamels [19]. d u r a b i l i t y of glass decorations. They include: C 7 2 4 - - T e s t
Number Title Methods for Acid Resistance of Ceramic Decorations on Ar-
chitectural-Type Glass; C 7 3 5 - - T e s t M e t h o d for Acid Resist-
C 448 Test Methods for Abrasion Resistance of Porcelain ance of Ceramic Decorations on R e t u r n a b l e Beer a n d Bever-
Enamels
C 282 Test Method for Acid Resistance of Porcelain Enamels age Glass Containers; C 6 7 5 - - T e s t M e t h o d s for Alkali
(Citric Acid Spot Test) Resistance of Ceramic Decorations on R e t u r n a b l e Beverage
C 614 Test Method for Alkali Resistance of Porcelain Enamels Glass Containers; C 6 7 6 - - T e s t M e t h o d for Detergent Resist-
C 756 Test Method for Cleanability of Surface Finishes ance of Ceramic Decorations on Glass Tableware; a n d
C 538 Test Method for Color Retention of Red, Orange, and
Yellow Porcelain Enamels C 9 2 7 - - T e s t M e t h o d for L e a d a n d C a d m i u m E x t r a c t e d f r o m
C 839 Test Method for Compressive Stress of Porcelain the Lip a n d R i m Area of Glass T u m b l e r s Externally Deco-
Enamels by Loaded-Beam Method r a t e d with C e r a m i c Glass Enamels.
C 536 Test Method for Continuity of Coatings in Glassed
Steel Equipment by Electrical Testing
C 743 Test Method for Continuity of Porcelain Enamel
Coatings REFRACTORY COATINGS
C 374 Test Methods for Fusion Flow of Porcelain Enamel
Frits (Flow-Button Methods)
C 346 F l a m e s p r a y techniques can be used to a p p l y c e r a m i c coat-
Test Method for 45-degree Specular Gloss of Ceramic
Materials ings in the m o l t e n state to heat-sensitive o r massive sub-
C 872 Test Method for Lead and Cadmium Release from strates that c a n n o t themselves be h e a t e d to high tem-
Porcelain Enamel Surfaces peratures. Most c e r a m i c coating m a t e r i a l s u s e d currently c a n
C 539 Test Method for Linear Thermal Expansion of be a p p l i e d b y flame spraying [20]. Silicates, silicides, car-
Porcelain Enamel and Glaze Frits and Ceramic
Whiteware Materials by the Interferometric Method bides, oxides, a n d nitrides have all been d e p o s i t e d by this
C 537 Test Method for Reliability of Glass Coatings on process.
Glassed Steel Reaction Equipment by High Voltage I n these processes, the coating m a t e r i a l is m e l t e d a n d p r o -
C 283 Test Method for Resistance of Porcelain Enameled jected as h e a t e d particles onto the suhstrate, w h e r e it instan-
Utensils to Boiling Acid
C 285 t a n e o u s l y solidifies as a coating. Three m e t h o d s of h e a t i n g
Test Method for Sieve Analysis of Wet-Milled and Dry-
Milled Porcelain Enamel a n d propelling the particles in a plastic c o n d i t i o n to the
C 703 Test Methods for Spalling Resistance of Porcelain- s u b s t r a t e surface include: (1) c o m b u s t i o n flame spraying, (2)
Enameled Aluminum p l a s m a arc flame spraying, a n d (3) d e t o n a t i o n gun spraying.
C 385 Test Method for Thermal Shock Resistance of C o m b u s t i o n flame spraying is used for c o a t i n g m a t e r i a l s t h a t
Porcelain-Enameled Utensils
melt readily. P l a s m a arc flame spraying is used for very re-
www.iran-mavad.com

fractory materials such as metal carbides. Detonation gun this system, the slip is broken into droplets either by air
spraying is used for hard, wear-resistant materials such as atomization or by centrifugal force from a sharp-edged rota-
tungsten carbide. ting surface. The drops acquire a high negative charge and
Flame spray coatings generally lack smoothness and are are dispersed as a fine mist. They are driven forward to the
usually porous. They are, therefore, limited to applications grounded substrate following the lines of force. Hence, coat-
such as thermal barrier coatings, where porosity is a virtue, ing material can reach the underside of the ware, and full-
and wear-resistant coatings, where the materials cannot be edge coverage is achieved.
applied readily by any other technique. There are other techniques for specific applications. Tile
require only one face to be glazed, but with a very smooth
coating. This suggests the waterfall, or curtain technique
Testing of Refractory Coatings [21], where a continuous feed of tiles is carded under a
There is only one test method for flame spray coatings in curtain of fluid slip. Painting and brushing are seldom used
the ASTM standards: C 633--Test Method for Adhesion or except for special effects and for applying glaze to inacces-
Cohesive Strength of Flame-Sprayed Coatings [19]. sible areas.
For substrates which require precisely positioned areas of
coating, the silk screen process can be used [20]. Finely pow-
COATING APPLICATION dered dry coating material is dispersed as a smooth paste.
Using a squeegee, this paste is pressed through the open areas
Ceramic coatings are applied to their substrates by one of of a fine mesh screen stretched on a frame. For coating a total
several powder-processing techniques. In wet processes the piece, costs are excessive.
raw materials are dispersed in a slip. Slip preparation in- There are a few techniques of application that do not re-
volves mixing the ingredients, particle-size reduction, disper- quire the preparation of a slip. They include flame spraying,
sion in water, and the addition of minor amounts of additives dry powder cast iron enameling, and electrostatic dry powder
to modify the rheological properties of the slip [21-22]. These enameling.
processes are carried out together in a ball mill comprising a Flame spraying can be used to apply ceramic coatings in
rotating cylinder partly filled with freely moving, impact- the molten state to heat-sensitive or massive substrates.
resistant shapes. Flame spray coatings generally lack smoothness and are usu-
The application process for a ceramic coating must be ally porous. Equipment and material costs are generally high.
straightforward and foolproof, reproducible, economical, In dry powder cast-iron enameling, a casting is heated in a
and flexible [21]. Selection of the application technique is one furnace to red heat. It is then withdrawn from the furnace
of the most important decisions the coatings engineer makes. and, while still hot, dusted with dry powdered frit by means
Criteria for this selection are type of ware, shape and size of of a vibrating sieve placed over the surfaces to be coated. The
ware, throughput required, energy and labor costs, and space powdered frit melts and adheres as it falls on the hot surface.
available. All of these factors affect the quality and the cost of This process is also extremely operator sensitive.
a coating process, so that the best solution must be deter- The most important dry application method, and the one
mined on an individual basis. most recently introduced, is dry powder electrostatic applica-
Dipping is a simple, efficient, rapid technique requiring no tion of all-fritted coatings to conductive substrates. This tech-
capital equipment. The ware is immersed in the coating slip, nique involves charging individual coating particles at a high
moved around in a controlled way, removed from the slip, voltage and then spraying them towards the substrate sur-
shaken to remove excess slip, and set down to drain and dry. face. Charging of particles is accomplished by encapsulating
Any bare spots are touched up with a finger wet with coating the coating material with an organic silane. It is then sus-
material. Its limitations are extreme sensitivity to operator pended in clean compressed air in a fluidized bed container
skill and difficulty in automating volume production. [27]. The fluidized powder is siphoned and propelled through
Spraying is a process whereby a coating slip is broken powder feed tubes to special electrostatic powder guns for
down into a cloud of fine particles that are transferred to the low-pressure application. The powder carries a potential of
substrate by either pneumatic, mechanical, or electrical up to 100 kV, which causes it to seek out and attach itself to
forces. The method requires a gun, a container or feed mech- the grounded workpiece. Capital costs of this process are
anism, an impelling agency, and a properly designed hood or substantial, but operating costs are reduced through elimina-
booth maintained under negative pressure [23]. Spraying tion of slurry preparation and drying of the ware.
lends itself to high-volume automated systems [24]. The arti-
cles are continuously fed under a battery of angled spray
guns. Coating reclaim is an essential part of automated sys-
tems. REFERENCES
Slip can also be applied mechanically with a rotating atom-
[1] Eppler, R. A., "Glazes and Enamels," Chap. 4, Glass Science and
izer. Slip is passed onto a set of closely spaced rotating disks
Technology, Vol. 1, Academic Press, New York, 1983, pp.
which throw the coating into a fan of droplets. Costs are
301-337.
similar to spraying. The primary use of this technique is in [2] Eppler, R. A., "Corrosion of Glazes and Enamels," Chap. 12,
producing textured coatings on tile. Corrosion of Glass, Ceramics, and Ceramic Superconductors,
If the substrate is conductive (that is, a metal), the surface D. E. Clark and B. K. Zoitos, Eds., Noyes Publications, Park
quality and uniformity of a ceramic coating can be improved Ridge, NJ, 1992.
by using the electrostatic spray coating technique [25,26]. In [3] Ceramic Industries, August 1990, p. 36.
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CHAPTER 9--CERAMIC COATINGS 73
[4] Tichane, R., "Ching-te-Chen; Views of a Porcelain City," N.Y. Enamel Resistance and Experimental Results Obtained," Ameri-
State Institute for Glaze Research, Painted Post, NY, 1983. can Ceramic Society Bulletin, Vol. 56, No. 12, 1977, pp. 1064-
[5] Singer, F. and German, W. L., "Ceramic Glazes," Borax Consoli- 1067.
dated, 1964. [17] Monteith, P. G., Linhart, O. C., and Slaga, J. S., "Performance
[6] Orth, W. H., "Effect of Firing Rate on Physical Properties of Tests for Properties of Low Temperature Thermal Cleaning
Wall Tile," American Ceramic Society Bulletin, Vol. 46, No. 9, Oven Coatings," Proceedings, PEI Technical Forum, Vol. 32,
1967, pp. 841-844. 1970, pp. 73-79.
[7] O'Conor, E. F., Gill, L. D., and Eppler, R. A., "Recent Develop- [18] Shannon, R. D. and Friedberg, A. L., "Titania-Opacified Porce-
ments in Leadless Glazes," Ceramic Engineering Society Proceed- lain Enamels," Illinois University Engineering Experimental Sta-
ing& Vol. 5, Nos. 11-17, 1984, pp. 923-932. tion Bulletin, Vol. 456, 1960.
[8] Eppler, R. A., "Formulation and Processing of Ceramic Glazes [19] ASTM Annual Book of Standards, Part 2.05: Metallic and Inor-
for Low Lead Release," Chap. 10, Proceedings, International ganic Coatings.
Conference of Ceramic Foodware Safety, J. F. Smith and M. H. [20] Taylor, T.A., Bergeron, C.G., and Eppler, R.A., "Ceramic
McLaren, Eds., Lead Industries Association, New York, 1976,
Coating," Metals Handbook, 9th ed., Vol. V, ASM International,
pp. 74-96.
Metals Park, OH, 1982, pp. 532-547.
[9] Marquis, J. E., "Lead in Glazes--Benefits and Safety Precau-
[21] Taylor, J. R. and Bull, A. C., Ceramics Glaze Technology, Perga-
tions,"American Ceramic Society Bulletin, Vol. 50, No. 11, 1971,
mon Press, Oxford, England, 1986.
pp. 921-923.
[10] Eppler, R. A., "Formulation of Glazes for Low Pb Release," [22] Reed, J. S., Introduction to the Principles of Ceramic Processing,
American Ceramic Society Bulletin, Vol. 54, No. 5, 1975, pp. John Wiley & Sons, New York, 1988.
496-499. [23] Bloor, W. A. and Eardley, R. E., "Environmental Conditions in
[11] Tummala, R. R. and Shaw, R. R., "Glasses in Microelectronics Sanitary Whiteware Shops, II. Glaze Spraying Shops," Transac-
in the Information-ProcessingIndustry," "Commercial Glasses," tions, Journal of the British Ceramic Society, Vol. 77, No. 2, 1978,
Advances in Ceramics, Vol. 18, American Ceramic Society, Co- pp. 65-69.
lumbus, OH, 1986, pp. 87-102. [24] Whitmore, M., "Spraying of Earthenware Flatware," Transac-
[12] ASTM Annual Book of Standards, Part 15.02: Glass, Ceramic tions, Journal of the British Ceramic Society, Vol. 73, No. 4, 1974,
Whitewares. pp. 125-129.
[13] Ceramic Industries, August 1990, p. 49. [25] Hebberlein, K., "Electrostatic Glazing of Tableware," Berichte
[14] Pask, J. A., "Chemical Reaction and Adherance at Glass-Metal der Deutschen Keramischen Gesellschaft, Vol, 53, No. 2, 1976, pp.
Interfaces," Proceedings, PEI Technical Forum, Vol. 22, 1971, pp. 51-55.
1-16. [26] Lambert, M., "Industrial Application of Electrostatic Enam-
[15] King, B. W., Tripp, H. P., and Duckworth, W. H., "Nature of elling to Parts in Sheet Steel and Cooking Equipment," Vitreous
Adherance of Porcelain Enamels to Metals," Journal of the Amer- Enameller, Vol. 24, No. 4, 1973, pp. 107-109.
ican Ceramic Society, Vol. 42, No. 1t, 1959, pp. 504-525. [27J ASM Committee on Porcelain Enameling, "Porcelain Enamel-
[16] Eppler, R. A., Hyde, R. L., and Smalley, H. F., "Resistance of ing," Metals Handbook, 9th ed., Vol. 5, ASM International,
Porcelain Enamels to Attack by Aqueous Media: I--Tests for Metals Park, OH, 1982.
www.iran-mavad.com

MNL17-EB/Jun. 1995
10
Epoxy Resins in Coatings
by Ronald S. Bauer, 1 E d w a r d J. Marx, 2 and Michael J. Watkins 2
EPoxy RESINSHAVEBECOMEtechnologically important materi- tain one or more epoxy (oxirane) groups per molecule. The
als that find extensive application in high-performance coat- epoxy resins most widely used by far in coatings are the
ings, adhesives, and reinforced plastics. Almost since their bisphenol A based epoxy resins, the generalized structure of
commercial introduction in 1950, epoxy resin systems have which is given in Fig. 1. In commercial products, the n value
been used in protective coatings. Historically, protective ranges from 0 to about 25, although higher-molecular-weight
coatings were the largest single end use for epoxy resins. thermoplastic resins having n values of 200 or more are avail-
Although in recent years the noncoating applications of ep- able. As n increases, the epoxy equivalent weight (EEW) in-
oxy resin have been growing, coatings still represent about creases, as does the number of hydroxyl groups. Thus epoxy
half of the annual epoxy resin usage. resins with low n values are normally cured by reaction of the
Epoxy resin coatings offer a unique combination of adhe- epoxy group, whereas those resins with higher n values are
sion, chemical resistance, and physical properties that pro- cured by reaction of the hydroxyl functionality.
vide outstanding protection against severe corrosive environ- Resins having n values less than 1 are viscous liquids; they
ments. They are used extensively in coatings for refineries, are used mainly in ambient-temperature cure coatings, elec-
chemical plants, and marine equipment such as offshore trical castings, flooring, electrical laminates, and fiber-rein-
drilling platforms and merchant ships. Other important ap- forced composites. These applications require liquid resins
plications where epoxy resin coatings are used almost exclu- having good flow and are cured through the epoxy ring. The
sively because of the corrosion protection they afford include higher n value resins, particularly those above 3000 molecu-
automotive, aircraft, and appliance primers as well as to lar weight, are normally used in solution and find their great-
protect both the inside and outside of pipe. Epoxy resins are est application in heat-cured coatings. In these resins the
the predominant thermosetting resin used for the interior concentration of epoxy groups is low, and so they are cured
linings of beer and beverage cans, cans for hard-to-contain with materials that react with the hydroxyl groups along the
food products such as sauerkraut, tomato juice, and meat backbone. Table 1 displays a range of typical epoxy resins
products, and for chemical-resistant linings of pails and that are commercially available along with their properties
drums. These coatings are used not only to protect the metal and applications.
of the container from corrosion, but also to protect the flavor
of the contents, which can be affected by direct contact with
metal. CURING AGENTS
The principal components of any epoxy resin coating sys-
tem are the epoxy resin and the curing agent or hardener. Epoxy resins are reactive intermediates composed of mix-
Epoxy resins are reactive intermediates that can be liquid or tures of oligomeric materials containing one or more epoxy
solid, and they are converted into the final coating by reaction groups per molecule. To convert epoxy resins into useful
with curing agents (hardeners). Curing agents function by products, they must be cross-linked or "cured" into a three-
reacting with specific groups in the epoxy resin molecule to dimensional polymer network. Cross-linking agents, or
give a three-dimensional, infusible polymer network. Al- curing agents as they are generally called, function by reac-
though the resin and curing agent are common to all epoxy tion with or cause the reaction of epoxide or hydroxyl groups
coatings, other materials are incorporated to achieve the in the epoxy resin. The number of curing agents that have
desired rheological characteristics, cure speed, and film per- been developed over the years for epoxy resins is overwhelm-
formance. ing. Selection of the curing agent is as important as that of the
base resin; it is dependent on the performance requirements
of the film and the constraints dictated by the specific method
RESIN TYPES of application.
The most important types of curing agents used in epoxy
Generically, epoxy resins can be characterized as a group resin coatings are the amine-functional materials for ambi-
of commercially available oligomeric materials which con- ent-cure coatings and the amino- and phenoplast resins for
heat-cured systems. The principal amine-functional curing
1Research adviser and 2senior research chemist, Shell Develop- agents used in ambient-cure coatings are aliphatic amine ad-
ment Co., Westhollow Research Center, P.O. Box 1380, Houston, TX ducts of epoxy resins, polyamides, and ketimines. Amine-
77521-1380. functional materials cure epoxy resins by polyaddition
74
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CHAPTER IO--EPOXY RESINS IN COATINGS 75
o F --I
CH2- CHCH2 - ' ~ O ~ CH2CHCH2Jn -- O- CH2CH-CH 2
CH3
n is typically 0 to 1 for liquid resins with solid resins

having n values as high as 15 or more
FIG. I-Idealized structure of a bisphenol epoxy resin.
TABLE 1--Typical properties of bisphenol-based epoxy resins.

Approximate
Average Average Average Viscosity, Softenin~
Molecular Wt EEW~ Value of n P, 25~ Point, ~ v Applications
350 182 ... 80 ..- Solventless and solvent-borne ambient cure
coatings, electrical encapsulation, flooring, and
filament winding
380 188 0.2 140 ...
600 310 1 Semisolid 40 Solvent-borne, ambient cure coatings
900 475 2 Solid 70
1400 900 4 Solid 100 Powder coatings
2900 1850 10 Solid 130 Heat cure, solvent-borne coatings for cans, drums,
primers, etc.
3750 3050 13 Solid 150
aEEW = epoxideequivalent weight, i.e., grams of resins needed to provide 1 M equivalent of epoxide. Alsoreferred to as WPE (weight per epoxide) and EMM
(epoxy molar mass). All three terms are interchangeable.
bSoftening point by Durran's mercury method [ASTMSpecification for Epoxy Resins (D 1763)].
t h r o u g h reaction of the amine with the epoxy groups. Amino- package" type ambient cure epoxy coatings, air dry epoxy
and phenoplast cross-linking resins are generally etherified esters, prepared by esterifying epoxy resins with unsaturated
urea-formaldehyde, melamine-formaldehyde, and phenol- fatty acids, dry by the same m e c h a n i s m as alkyd resins.
formaldehyde condensates. The amino- and phenoplast res- Historically ambient-cure coatings have been applied out of
ins cure by condensation with the backbone hydroxyls of the solvent, typically at about 40% weight solids. However, with
epoxy resin with elimination of water or an alcohol. the regulation of emissions of volatile organics, the trend has
Aliphatic amines such as ethylene diamine (EDA), diethyl- been toward coatings with lower volatile organic content,
ene triamine (DETA), and triethylene tetramine (TETA) have 100% solids, and waterborne systems.
always been popular curing agents for epoxy resins because Heat-cure coatings are used in industrial finishes, auto-
of their ability to readily cure at r o o m temperature. However, motive primers, appliance primers, pipe coatings, and coat-
aliphatic amines present certain handling hazards because of ings for beer and beverage cans, as well as cured coatings for
their high basicity and relatively high vapor pressure. Epoxy/ pails and drums. Conventional solvent-borne and waterborne
amine adducts, amine-terminated polyamides, ketimines, heat-cured coatings are based on the higher-molecular-
and other modified polyamines are less hazardous derivatives weight epoxy resins, and they are generally cured t h r o u g h
of aliphatic amines and often provide performance and han- reaction of the hydroxyl groups. Powder coatings, however,
dling advantages. are generally manufactured from intermediate molecular
weight solid resins and are cured t h r o u g h the epoxy group.
The usual curing agents for heat-cured epoxy resin coatings
EPOXY RESIN COATINGS are amino- and phenoplast resins, as well as dicyandiamide
and polycarboxlic acids, which are used in powder coatings.
There are a n u m b e r of possible ways to classify epoxy resin
coatings. Since curing agent types have been divided into
ambient-cure and heat-cure, for convenience the types of TWO-PACKAGE, AMBIENT-CURE
epoxy coatings can also be classified similarly. The bulk of the COATINGS
ambient-cure or "air-dry" coatings are cured with polyamines
or modified polyamines and generally find application as By far the largest volume of ambient-cure epoxy resin coat-
maintenance and marine or architectural coatings. Ambient- ings are the "two-package" type, which are typically manufac-
cure coatings are based on low-molecular-weight epoxy res- tured from liquid or low-molecular-weight solid epoxy resins
ins having high epoxy group content and are generally cured cured with a polyamine, amine adduct, or polyamide. A two-
through reaction of the epoxy group. In addition to the "two- package coating, as the n a m e implies, is a two-part system:
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the epoxy component and the curing agent, which are pack- agents can be considered blocked polyamines, which in the
aged separately and often in volume ratios of 2 to 1 or 4 to 1 of presence of water hydrolyze to produce a ketone and a poly-
epoxy component to curing agent. Two-package epoxy coat- amine. These ketimines react at a practical rate of cure under
ings are mixed just prior to application and are characterized ambient conditions. Atmospheric moisture, which is ab-
by a limited working life or pot life after the resin and curing sorbed during and following application of the coating,
agent components are mixed. Commercial systems will have serves as the source of water required to activate the curing
pot lives of a few hours to a couple of days, with typical agent. Ketimine curing agents are similar in behavior to the
working times of about 8 to 12 h. aliphatic amine polyamines and amine adducts in rate of cure
Two-package epoxy resin coatings include a broad range of and performance of cured films, but they provide much
products and properties. Specific film properties depend on longer pot lives.
selection among many epoxy resins, curing agents, pigments, Typical applications of two-package coatings of the above
and modifiers, as well as the ratios of these materials. Resins type are in heavy-duty maintenance and marine coatings,
differ primarily in molecular weight. As the molecular weight tank linings, aircraft primers, internal pipe coatings, for gas
of the resin increases, the flexibility, flexibility retention, film- transmission lines, coatings for plastic products, and high-
leveling properties, and pot life of the coating increase. How- performance architectural coatings.
ever, cross-link density decreases with increasing molecular
weight, resulting in reduced solvent and chemical resistance
as well as nonvolatile content of the paint at application EPOXY RESIN ESTER, AMBIENT CURE
viscosity. COATINGS
Although aliphatic polyamines are less expensive and have
been used extensively as curing agents, polyamine adducts, Epoxy resin esters are prepared by esterifying the resin
amine-terminated polyamides, and ketimines are generally with vegetable oil fatty acids. Epoxy esters are usually pre-
preferred. Among the advantages provided by aliphatic pared from solid epoxy resins having EEWs in the range of
amine adducts are: 900. As in conventional alkyd technology, these coatings are
9 Milder odor. made by esterifying the resin with fatty acid at temperatures
9 Lower volatility. of 400 to 450~ (204 to 232~ Initially, the fatty acid reacts
9 Less tendency to produce blush when coatings are applied with the epoxy ring at lower temperatures, forming hydroxyl
under conditions of high humidity. esters. Subsequently, these hydroxyl groups and those al-
9 Greater suitability for application at low temperature. ready present in the resin are esterified at higher tempera-
9 Less tendency to corrode metal containers. tures with the aid of esterification catalysts and with azeo-
Two general types of polyamine adducts are available, i.e., tropic removal of water. Typically, between 30 and 90%
those based on a low-molecular-weight liquid epoxy resin and esterification is chosen, depending on the oil length desired.
those based on a high-molecular-weight solid epoxy resin. Like alkyd resins, epoxy resin esters may be made in long,
The performance properties of amine-cured coatings are not medium, and short oil lengths. The oil length refers to the
significantly different from those of aliphatic polyamine degree of esterification of the epoxy resin with the fatty acid:
cured systems. Like polyamines, amine adducts offer maxi- long indicates 70 to 90% esterification, medium indicates 50
m u m resistance to solvents, acids, and other highly corrosive to 70% esterification, and short indicates 30 to 50% esterifica-
chemicals. Initial flexibility and impact resistance are excel- tion. By proper selection of acids and adjustment of reaction
lent, and retention of these properties is adequate for most ratios, long, medium, or short oil esters may be prepared with
uses over rigid or semi-rigid substrates. drying, semidrying, or nondrying characteristics. The terms
More pounds of polyamide curing agents are consumed "drying" or "air dry"are used instead of ambient-cure since
annually in the United States than any other type of epoxy cross-linking of epoxy resin esters does not involve a curing
resin curing agent. Polyamides are obtained from the con- agent. Air-dry epoxy resin ester coatings are "one-package" or
densation of dimerized and/or trimerized fatty acids with ali- one-component systems, since they cross-link or cure only on
phatic polyamines such as diethylene triamine and triethyl- exposure to air.
ene tetramine to give an amine-terminated polyamide. Air-dry epoxy ester coatings are used in maintenance and
Polyamide cured epoxy coatings develop superior adhesion marine coatings, especially where mildly corrosive condi-
to moist and poorly prepared surfaces, and they provide a tions are encountered. They do not, however, possess the
high degree of corrosion resistance. Like epoxy resins, poly- outstanding chemical resistance of amine-cured epoxy coat-
amides are also mixtures of oligomers. Thus, a range of poly- ings, but they are superior to alkyd paints. In addition, their
amides which vary in viscosity, amine equivalent weight, and toughness and durability make them well suited for long-
reactivity is available. Polyamide cured coatings exhibit wearing floor finishes.
somewhat better retention of flexibility and impact resistance
on aging than polyamine adducts. Although resistance to sol-
vents and acids is not quite as good as with other types of HEAT-CURED SOLVENT-BORNE EPOXY
amine curing agents, polyamides are adequate for most R E S I N COATINGS
applications where amine cure epoxy coatings are used.
Ketones add reversibly to primary amines with the loss of Conventional solvent-borne heat-cured or "baked" epoxy
water to give ketimines. The ketimines obtained from the resin coatings are based on high-molecular-weight epoxy res-
typical polyamine curing agents have rather low volatility ins, that is, resins with EEWs around 1750 or greater. The
compared to the precursor polyamine. Ketimine curing concentration of epoxy groups is low in these resins, and
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CHAPTER I O - - E P O X Y R E S I N S IN COATINGS 77
cross-linking occurs principally through the hydroxyl func- exceptional corrosion protection and because they are depos-
tionality. Thermosetting resins such as urea-formaldehyde, ited uniformly to all areas of the automobile, even in areas
melamine-formaldehyde, and phenol-formaldehyde resins which would be inaccessible to other coating application
are used as cross-linkers for the coatings of this type. This methods such as spray. Because of their major importance,
cross-linking requires heat, and usually a strong acid catalyst the remainder of this discussion will deal with CED automo-
is used to accelerate the cure. Thus, these systems are sup- tive primers.
plied as "one-component" systems, i.e., the resin, curing The preparation of CED coatings generally begins by react-
agent, and accelerator are packaged together. ing a bisphenol A based liquid epoxy with bisphenol A to give
Aminoplast (urea-formaldehyde or melamine-formalde- an epoxy resin with an epoxy equivalent weight in the range
hyde) cross-linking resins are used because of their good
of 500 to 1000. This epoxy resin is then reacted with a flexi-
color and relatively low cure temperature. They are typically
bilizing diol. This diol can be an aliphatic diol or a polyether
used in linings for beer and beverage containers and as clear
diol. The principal requirement is that the diol contain pri-
coatings for brass and jewelry. Pigmented aminoplast cured
coatings are used as coatings for industrial equipment, appli- mary hydroxyl functionality. These primary hydroxyls are re-
ances, and hospital and laboratory furniture. Phenoplast acted with the epoxy groups in the presence of a suitable
(phenol-formaldehyde) cured coatings are more chemically catalyst (e.g., a tertiary amine) to form ether linkages be-
resistant, and they find application in beer and beverage tween the epoxy and the flexibilizing diol. At this point, the
containers (particularly in Europe), drum and pail linings, resin will have an epoxy equivalent weight in the range of
internal coatings for pipe, wire coatings, and appliance 1000 to 1500. The remaining epoxy functionality is then re-
primers. Phenoplast resins, generally giving coatings of acted with amines. Generally, secondary amines are chosen
poorer color than arninoplast resins, are used only when max- to minimize further chain extension. One favored method to
i m u m resistance to solvents and other chemicals is required. accomplish this is to use a diketimine of diethylene triamine.
During coating preparation, the ketimine groups decompose
to give primary amines. These primary amines are fairly ba-
HEAT-CURED WATERBORNE EPOXY sic, resulting in stable dispersions at a relatively high bath pH
COATINGS (pH > 6). At this point, the CED resin preparation is com-
plete. In practice, specialized CED resins are used to make
The earliest epoxy resin coatings for beer and beverage the pigment grind pastes. These are developed to efficiently
containers were solvent-borne amino- or phenoplast cured make stable pigment dispersions, which retain good stability
systems, the particular systems used being dependent on the in the CED coating bath.
application. Although application technology has changed Curing agents used are generally blocked isocyanates.
over the years and is now dominated by waterborne systems, These are chosen to be stable and unreactive in the coatings
the coatings are still basically amino- or phenoplast cured bath, but to unblock and cure the coating at baking tempera-
systems. These coating systems are based on high-molecular-
ture. An example of such a curing agent would be the reaction
weight epoxy resins onto which are grafted terpolymers of,
product of 3 mol of toluene diisocyanate with 1 tool of tri-
for example, styrene/methacrylic acid/ethyl acrylate. These
methylolpropane. This is then reacted with 3 mol of a suitable
epoxy/acrylic graft polymers are neutralized with base, such
as dimethylethanolamine, to give a resin easily dispersible in blocking agent, such as 2-ethyl-1-hexanol. Catalysts such as
water. The dispersed resin can then be cured with an ami- tin or lead salts are generally used to facilitate unblocking
noplast resin to give coatings with properties that make them and coating cure. The coating is prepared by blending the
suitable for beer and beverage containers. resin with pigment paste, curing agent, catalysts, additives,
and solvents. A low-molecular-weight organic acid, such as
lactic or acetic acid, is then added to the mixture to make
ELECTRODEPOSITION COATINGS a m m o n i u m salts with the amine groups in the resin. This
mixture is then dispersed in water to make the CED coating.
Epoxy resin electrodeposition coatings are also waterborne Solvents may be required in the preparation of the CED resin
coatings formulated from either anionic or cationic epoxy or other components. In order to reduce the volatile organic
resin polymers. The part to be coated is dipped into the compound content of the finished coating, it is usually sub-
electrodeposition bath, and an appropriate electrical charge jected to a vacuum stripping step which can reduce VOC to
is applied, causing the coating to deposit onto the part. The less than 0.7 lb/gal. When the automobile is dipped into the
part is then removed from the bath, rinsed, and baked to cure CED bath, a negative charge is applied to it (making it the
the coating. In the United States, epoxy-based electrodeposi-
cathode) relative to counter electrodes in the bath. Electroly-
tion coatings account for over 92% of all electrodeposition
sis of water occurs, forming hydroxide ions in the immediate
coatings. Epoxy-based cathodic electrodeposition (CED) au-
tomotive primers dominate this application, accounting for vicinity of the automobile surface. These hydroxide ions react
over 82% of all electrodeposition coatings. Over 40 million with the a m m o n i u m ion groups in the resin near the surface,
pounds of epoxy resin are used in the United States in CED regenerating the neutral amine groups and causing the coat-
automotive primers, making this one of the largest single end ing to be deposited onto the surface. In this way, a uniform
uses for epoxy resins in coatings. Virtually every automobile film is applied to the entire conductive surface of the automo-
made in the United States, Europe, and Japan is primed with bile. The automobile is then removed from the bath, rinsed,
a CED primer. CED primers are used because they afford and baked.
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E P O X Y R E S I N P O W D E R COATINGS greater than about 650 are nonsintering and extremely

friable. They have relatively low melt viscosity and high reac-
Powder coatings are produced by melt blending homoge- tivity via the terminal oxirane functionality. The addition
nous dispersions of nonvolatile solid resins, curing agents, reaction with amines, phenolics, or carboxylic acid func-
pigments, fillers, and various additives. The dispersion is tional curatives allows a wide range of formulations. The
solidified by cooling, ground into a finely divided powder primary limitations for bisphenol-A based epoxy resins in
form, and classified for subsequent use. The resultant powder powder coatings are yellowing and loss of gloss that occur
is normally electrostatically deposited onto grounded sub- when these coatings are exposed to exterior weathering con-
strates and, through the application of heat, converted into ditions.
very high performance thermoset films. The process of apply- Powder coatings are broadly divided into either "func-
ing coating powders allows nearly 100% powder utilization tional" or "decorative" uses. Functional coatings are normally
and evolves almost no volatile organic compounds. applied at film thicknesses greater than about 3 mi] and are
The 1970's volatiles regulations and energy concerns raised expected to withstand some rather severe service. Examples
interest in powder coating technology. The real sustaining of functional uses are coatings for exterior and interior pipe,
driving forces for growth, however, have been improvements rebar, and various electrical devices. Although decorative
in powder coating raw materials, formulations, manufactur- powder coatings are functional, these are normally used at a
ing technology, and application equipment. The advantages film thickness of 3 mil or less and are not expected to perform
for the use of powder coatings can best be summed up in the significantly better than baked films derived from "wet" coat-
"Four E's," used by The Powder Coating Institute: (1) excel- ings. Some examples of decorative uses are coatings for appli-
lence of finish, (2) economy in use, (3) energy efficiency, and ances, furniture, and underhood automotive parts.
(4) environmental acceptability. The Clean Air Act, as
amended in 1990, has contributed to even greater interest in
the use of powder coatings to meet more stringent volatile
organic requirements. Powder coatings is the fastest growing
REFERENCES
area of coatings technology. Growth rate for powder coatings
[1] Lee, H. and Neville, K., Handbook of Epoxy Resins, McGraw-Hill
in the 1990 to 1995 time frame is projected to be at 10 to 12% Book Co., New York, 1967.
versus a conventional "wet" coatings rate of about 2%. [2] May, C. and Tanaka, Y., Epoxy Resins Chemistry and Technology,
The unique characteristics of solid epoxy resins account for Marcel Dekker, Inc., New York, 1973.
their choice by formulators for use in powder coatings appli- [3] Bauer, R. S., Epoxy Resin Chemistry, ACS Symposium Series 114,
cations. Bisphenol-A based epoxides with equivalent weights American Chemical Society, Washington, DC, 1979.
www.iran-mavad.com

MNL17-EB/Jun. 1995
ii
11
Phenolics
by John S. Fry 1
DEEINmON: a polymeric, resinous reaction product of a phenol CHEMISTRY

with an aldehyde. Said products may be used alone or in formu-
lations with other polymers to produce useful coatings. The reaction of phenol with aldehydes to produce resinous
products was difficult to understand in the early years be-
cause many of said products were insoluble or infusible. After
studying the variables, Baekeland at least defined the condi-
HISTORY tions to produce three stages of products: "A" stage--soluble
and fusible; "B" stage--insoluble, but swellable and
Phenolic resins, initially commercialized in 1909, were the softenable; and "C" stage--cured to an insoluble and heat-
first completely synthetic materials for the burgeoning plas- resistant material. With the advent of modern analytical
tics business. The expansion of several new technologies of tools, the chemistry of the reactions has been more fully
the time, namely the electrical, communications, and auto- defined by various workers [2,3]. A brief description follows.
motive industries, all required and depended on new materi-
als that had better electrical insulating properties, higher
heat resistance, and improved resistance to chemicals, acids, RAW M A T E R I A L S
oils, and moisture. The heat-reactive resins, developed by Dr.
Leo H. Baekeland [1], were formulated into blends that were The commercially important phenols used in coatings res-
convenient for mass production compression moldings and ins are shown in Fig. 1. While phenol is the most common,
satisfied the above-mentioned requirements. Improved and the substituted phenols are also used to vary the solubility
new items such as coil supports, commutators, distributor and reactivity properties of resins. The cresols, butyl phenol
heads, telephone sets, vacuum tube bases, radio parts, and and bisphenol-A, are widely employed while the others have
electrical switches all blossomed onto the market within a limited or specialty uses.
few years. Phenol has three aldehyde reactive ring positions; the 2 and
6 carbon atoms (ortho) and the 4 position (para). Phenols
with substituents in the above positions have lower func-
tionalities and are frequently used to modify resin properties.
FIRST PHENOLIC COATINGS The aldehyde co-reactant of choice for the phenols is form-
aldehyde, the most reactive of those commercially available.
Concurrent with the above developments, the nonheat-re-
Formaldehyde, a gas, is conveniently handled as an aqueous
active phenolics or "novolak" resins were prepared as a
solution (formalin) or as a solid polymeric form known as
hoped-for substitute for shellac. These resins were not as
paraform. Formaldehyde in aqueous solutions exists as hy-
resilient as shellac and, when used alone, were not successful
drated glycols or low-molecular-weight glycol ethers.
in coatings. However, combined with the formaldehyde do-
nor, hexamethylene tetramine, the novolaks could be com- CH20 + H20 ) HOCH2OH- HOCH20[CH20]H
pounded into another set of thermosetting molding materials Both of the above forms of formaldehyde depolymerize on
which found early use in phonograph records. heating to supply reactive formaldehyde for the phenolic re-
While the above-mentioned novolaks had to wait for suc- actions. The type of reaction products and resins formed de-
cess in coatings, the alcohol solutions of the heat-reactive pends on the catalysts and conditions used.
resins were found, by 1911, to form excellent films when
baked and cross-linked. These coatings, still in wide use to-
day, are hard and glass-like and have excellent resistance to B A S E CATALYST
chemicals, acids, water, and solvents. Early applications in-
cluded protective coatings for brass beds as well as other Strong base catalysts (pH above 8) produce initial reaction
hardware items. These solution resins also initiated the man- products such as the methylol phenols shown in Fig. 2a.
ufacture of laminates, which engendered radio circuit boards Phenol can produce five different methylol-related species,
and, later, printed circuit boards. while the substituted phenols, with lower functionality, pro-
duce fewer methylol derivatives. Further reaction causes the
~Consuhant, 14 Westbrook Ave., S. Somerville, NJ 08876. methylol groups to condense with other ring positions (meth-
79
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~ ~H3~CH3~
OH OH OH OH
OH
CH3
CH3 CH3
Phenol Orthocresol Metacresol Paracresol
Xylenols
OH OH OH OH OH
0 ()
CH3-C-CH3 CH3-C-CH3 CH3-C-CH3
0
I I I
cn3 CH 2 CH2
I I
CH 3 CH3=C-CH 3
I
CH3
OH
2,2 Bis (4- p-Phenyl p-tert-Butyl p-tert p-tert-Octyl
Hydroxylphenyl) Phenol Phenol Amylphenol Phenol
Propane
(Bisphenol-A)
FIG. 1-Phenols used to make phenolic resins.
ylene link) or to etherify with other alcohol groups (meth- the 4 to 7 range. Under such conditions, the formaldehyde
ylene ether links) (Fig. 2b). Additional reaction raises the addition to the phenolic ring is highly directed to ortho sub-
molecular weight to branched, heat-reactive resin products stitution. With excess formaldehyde, hemi-formals and ortho
which are dehydrated, dissolved in solvents, or isolated as methylol groups are formed. Using lower formaldehyde levels
grindable solids for later formulation. leads to the formation of nonheat-reactive ortho-ortho
novolaks. With the highly reactive para ring position still
open, these resins have been employed in relatively rapid
ACID CATALYST crosslinking formulations.
At a pH of 0.5 to 1.5, the acid-catalyzed phenol-formalde-

hyde reaction proceeds through an unstable addition inter-
mediate to condensed, methylene-linked phenolic rings (Fig.
3). When phenol is used, highly branched "novolaks" are TESTING OF PHENOLIC RESIN PRODUCTS
obtained. However, when substituted phenols are used, the
functionality of the system is reduced to two and mostly Typical quality control tests for phenolic resin products
linear resins are formed. may include the following.
1. Gel time [ASTM Test Method for Determining Stroke
Cure Time of Thermosetting Phenol-Formaldehyde Resins
INTERMEDIATE pH CATALYSIS (D 4640-86)] (heat-reactive resins).
2. Volatile content [ASTM Test Method for Volatile Content
When salts of zinc, magnesium, or aluminum are used as in Phenolic Resins (D 4639-86)].
catalysts, the pH of the phenol-formaldehyde reaction falls in 3. Viscosity (solution).
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CHAPTER ll--PHENOLICS 81
OH OH OH
+ CH20 Base
~ ~ C
' H2OH
+
r CH2OH
OH OH
+
< ~ H2OH HOCH2~ H2OH
,'H2OH
OH
HOCH2~ CH2OH
CH2OH
FIG. 2a-Base-catalyzed initial reaction products.
OH OH OH
~ H2OH Base y ~
CH2
~ CH2OH+H20
METHYLENELINK
Or
OH OH
0 0 + H20
METHYLENE ETHER
FIG. 2b-Methylol phenol reaction products.
www.iran-mavad.com

OH
CH20
H+
~- HO
Acid
~ CH 2 ~ O H
Q
CH2
FIG. 3-Acid-catalyzed reaction products.
4. pH [ASTM Test Method for Measuring Apparent pH or result, these products find applications in oil industry drill
Water Insoluble Phenol-Formaldehyde Resins (D 4613- pipe, production pipe, as drum and pail linings, tank linings,
86)]. printing plate backing, printed circuit masks, and as corro-
5. Color (Gardner). sion-resistant hardware coatings. Tests performed on such
6. Specific gravity. coatings may include:
Other tests to characterize resins may be used: 1. Electrical properties.
I. Molecular weight distribution and free phenols--gel per- 2. Physical and mechanical.
meation chromatography. 3. Environmental resistance.
2. Structure analysis--NMR, I.R. 4. Applications.
3. Thermal analysis (curing curves).
4. Free formaldehyde-hydroxyl amine method.
P h e n o l i c s as Crosslinking Agents for Other
Polymers
Coatings based on heat-reactive phenolics alone are not
H E A T REACTIVE R E S I N S IN COATINGS
very flexible. To obtain better toughness and flexibility for
applications such as can coatings or coil coatings, the pheno-
Alcohol-Soluble Resins
lic resins are combined with a linear resin, such as an epoxy
The thermosetting, alcohol-soluble resins are based on resin, in ratios of about 15/85 to 50/50 phenolic/epoxy. Upon
muhifunctional monomers such as phenol, cresols, xylenols, baking, the phenolic resin's methylol groups react with the
and bisphenol-A. These resins are also soluble in ketones, secondary hydroxyls of the epoxy resin backbone to cross-
esters, and glycol ethers, but insoluble in aromatic and ali- link the system (Fig. 4). Depending on the ratio used, some of
phatic hydrocarbons. They are compatible with amino resins, the phenolic resin may self condense, but to a lesser extent
epoxies, polyamides, and poly(vinyl butyral) and are, in many than the pictured cross-linking reaction. In the case of can
cases, formulated with said resins as crosslinking agents. The coatings, thin films (0.2 mil) are applied to tin plate or tin-free
resins are commercially available as solvent solutions, solids, steel and typically baked for 10 to 12 rain at 200~ The coated
or waterborne systems. Low-molecular-weight resins with a metal is then formed into can bodies and lids, and foods are
high methylol content form water solutions, while higher mo- then packaged. The linings have to withstand a steam steril-
lecular weight resins may be used in dispersion form [4,5]. ization cycle of about 90 min at 250~ (121~ while protect-
Once formulated into vehicles, the resins may be applied by ing the metal and the food. For beer and beverage cans,
spray, dip, brush, or roller coating methods. The films are phenolics based on bisphenol-A may be used to minimize
then baked at typical temperatures of 135 to 250~ for times critical taste effects. Similar formulations have been used for
varying from several minutes to several hours. When used wire coatings or coil coating primers. Phenolic/epoxy systems
alone, phenolic resins crosslink with the release of water to are also more resistant to alkalies than phenolics alone and
form 0.2 to 1.0-mil films. Since volatiles are released during are used for linings when basic substances are packaged.
cure, bubbles may develop in thicker films. Multiple coats
may be applied as long as the intermediate coats are given a
Heat-Reactive Aromatic Soluble Resins
short bake.
Baked phenolic coatings are hard and glass-like with excel- Heat-reactive resins or copolymers based mainly on substi-
lent resistance to organic solvents, boiling water, acids, and tuted phenols such as p-tertiary butyl phenol or those with
acidic or neutral inorganic salts. They are not resistant to higher alkyl groups form resins which are soluble in aromatic
alkalies unless combined with epoxides as will be discussed solvents and even tolerate some aliphatic diluents. These res-
later. These phenolic coatings have excellent electrical resist- ins are blended with blown oils or alkyd resins to form electri-
ance and also resist dry heat to 370~ for short periods. As a cal coil and armature impregnation varnishes. Such var-
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CHAPTER l l - - P H E N O L I C S 83
CH3
OH
CI-I3
CH2
I
EPOXY
A1 PHENOLIC
CH 3
OCH2-CH-CH2
I
CH3 0
+H20 I
I
CH2
OH
FIG. 4-Crosslink formation.
nishes may be used in both new and reconditioned electrical droxyl group to form ether-type crosslinks which are resist-
equipment. ant to chemicals, moisture, and heat (Fig. 5). Since this reac-
tion does not produce by-products, thick films may be
Nonheat-Reactive Resins--Unsubstituted obtained via powder coatings or high solids solution coat-
ings. Such coatings find application as pipe coatings, rein-
The acid-catalyzed reaction of formaldehyde with an ex- forcement bar, and electronic encapsulation coatings.
cess of phenol and/or cresols produces the nonheat-reactive,
novolak-type resins. These resins do not form useful films by
Varnish Resins
themselves, but when formulated with polyfunctional epoxy
resins they act as co-reactants (hardeners) to produce ther- Substituted phenols containing the ten-butyl group or
moset systems. In this case, the chemistry involves the base- higher alkyl groups are reacted with formaldehyde under
catalyzed reaction of an epoxy group with the phenolic by- acidic conditions to produce "oil soluble" novolak resins.
B
O.CH2_CH_CH2 +
\o/
FIG. 5-Epoxy phenolic reaction.
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Additionally, substituted phenols may be co-reacted with tall and aluminum-pigmented topcoats have been successfully
oil resin and formaldehyde to form modified resins, which used for maintenance painting of major steel structures such
are also "oil soluble." While they are again nonfilm formers, as bridges and airport light towers [7].
combined with drying oils or alkyds, the above resins pro- While phenolic resin technology represents a mature field,
duce useful air-dry or baking formulations. Varnishes based the product class is hardly pass6. Newer resins, formulations
on natural oil-soluble resins and drying oils were known long for waterborne, high solids and powder coatings, and the
before phenolic resins, but the advent of the synthetic pheno- continued high performance in container and pipe coatings
lic resins led to more consistent production quality. Var- all indicate a promising future for this class of materials.
nishes were originally prepared via a "cook" method where
the phenolic resin was dissolved in the oils at 230 to 310~
while the oil then polymerized to a specified viscosity. After REFERENCES
adding solvents, the varnish was cooled and then finished
with additives such as driers, UV absorbers, and anti-skin- [1] Baekeland, L. H., Industrial Engineering Chemistry, Vol. 1, No. 3,
ning agents. In the 1950s, novel phenolic resins of higher 1909.
molecular weight allowed the cold blend preparation of var- [2] Megson, N. J. L., Phenolic Resin Chemistry, Academic, New York,
nish vehicles [6]. In this process, the resin is dissolved in the 1958.
solvents and the oils and additives are added at mild tempera- [3] Martin, R.W., The Chemistry of Phenolic Resins, Wiley, New
tures. Such vehicles are still used as baked can coatings, air York, 1956.
[4] Harding, J., U.S. Patent 3,823,103, 1974 (to Union Carbide Corpo-
drying clear wood coatings, porch and deck enamels, mainte-
ration).
nance paints, and as alkyd reinforcements. [5] Fry, J. S., U.S. Patent 4,124,554, 1978 (to Union Carbide Corpora-
In the 1980s, high solids coatings were mandated by vari- tion).
ous federal and state regulations. Newer phenolic varnish res- [6] Richardson, S. H., Paint and Varnish Production, August 1955.
ins were introduced that allowed vehicle solids of 70 to 80% [7] Yee, A. and Fry, J. S., American Paint and Coatings Journal, 23
to be achieved. Applied with airless spray, air drying primers June 1986, p. 41.
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MNL17-EB/Jun. 1995
Polyamides
by Robert W. Kight 1
POLYAMIDES ARE POLYCONDENSATIONproducts of dimerized Monocyclic COOH

fatty acids and polyamines. Reactive polyamides are oligo-
mers designed primarily for use in the manufacture of two- (I ~H2)8
component polyamide/epoxy coatings and adhesives. The
two-component coatings are generally labeled Part A and
Part B, with the polyamide usually (though not always) con-
tained in Part B. The polyamide may function as the curing
<~ (CH2)s--COOH
CH~CH--(CH2)4--CH 3
agent, coreactant, or hardener for epoxy resin. Polyamides (CH2)4

should not be considered as catalysts although they may I
initiate the reaction; the polyamide reacts with the epoxy CH3
resin and becomes part of the polymer. The majority of poly- Polycyclic COOH
amides used in coatings are viscous liquids that are usually I
supplied by the coatings manufacturer as a solution in or-
ganic solvents. The solution may be a clear amber liquid or
may contain pigments in colored systems.
ACIDS
~
CH3--(CH2)4~~.~
(CH2)7--COOH
The dibasic fatty acids of commercial importance used to (Ctt2)4

manufacture polyamide curing agents are prepared by di- I
CH3
merizing unsaturated C18 fatty acids from linseed, soya, or tall
oils. Linseed and soya fatty acids are extracted from flax and AMINES
soybeans, respectively. Crude tall oil (CTO) is a by-product
from the Kraft process for papermaking and is a mixture of The dimer acids are reacted with various polyamines to
fatty acids and rosin acids, from which the fatty acids are form polyamides and a variety of other useful products.
separated by distillation. The tall oil fatty acids are a mixture The polyamines commonly used in industry are polyethyl-
of Cla isomers with a variable number of double bonds. Some ene polyamines of various chain lengths that are linear,
of the isomers combine via Diels-Alder addition and other branched, or cyclic. The linear polyethylene polyamines are
mechanisms to form C36 dibasic acids or dimer acids. The characterized as secondary amine groups separated by ethyl-
dimer acids produced may be acyclic, monocyclic, or ene chains, terminated on either end by primary amine
polycyclic in structure, depending on the location and num- groups. Diethylenetriamine is an example of a simple linear
ber of double bonds in the feedstock. Many isomers are polyethylene polyamine.
present in commercial dimer acids, most of which are HzN--CH2--CH2--NH--CH2--CH2--NH2
difunctional carboxylic acids [I]. Examples of three possible
isomer types follow. The cyclic and branched polyamine isomers contain terti-
ary amine groups in addition to the primary and secondary
Acyclic CH 3 amine groups. Aminoethylpiperazine is an example of a cy-
clic polyamine.
CH3[ (~ H2)7 /CH2--C~H2
(~H2)8 ~H H2N--CH2--CH2--N NH
\ /
CH C CH2--CH 2
I I The reaction between dimerized fatty acids and poly-
(~H2)7 (~H2)7 amines yield amide oligomers with amine group termination.
These amide oligomers are used as coreactants with epoxy
COOH COOH
resins in high-performance coatings, as well as components
'Technical Service Representative, Union Camp Corporation, P.O. of a variety of other useful commercial compositions includ-
Box 2668, Savannah, GA 31402. ing two-component adhesives.
85
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EARLY H I S T O R Y and for the imidazoline
Polyamides were commercialized in the late 1950s for use H2N--CH2--CH2--NI ~-C34
with epoxy resins in the manufacture of two-component ad- C~2/N
hesives and high-performance coatings. The early commer-
CH2
cial epoxy/amine coatings contained aliphatic amines, pri-
--C N - - C H 2 - - C H 2 - - N H2
marily diethylenetriamine, which had several negative fea-
II r
tures, such as requiring critical mix ratios and toxicity. The N CH 2
\/
introduction of polyamides allowed the coatings manufac-
CH2
turer to produce high-performance coatings characterized by
convenient mix ratios, such as 1:1 or 2:1, with very low Commercial products range from about 35% to more than
toxicity. 80% imidazoline to allow the coatings formulators latitude in
Epoxy/polyamide coatings find utility in a wide variety of customizing the properties of their products.
applications, Such as industrial maintenance coatings, ma- Other properties of the polyamide that are important to the
chinery and equipment enamels, and marine applications. coatings formulator are the amine value, which is related to
The presence of the long fatty chains gives coatings with active hydrogen equivalent weight, and the viscosity level of
much better flexibility as well as better wetting and adhesion the polyamide in solvents. Amine values range from about
than was obtained with the earlier aliphatic amine cured 100 to about 400, with active hydrogen equivalent weights of
systems. about 550 to 140, respectively. The active hydrogen equiva-
The epoxy/polyamide coatings are not, however, without lent weight is used to calculate the amount of polyamide
some disadvantages. The advantage of having a long usable required to react with a given amount of an epoxy resin of
pot life comes with a much slower cure rate; thus epoxy/ known epoxide equivalent weight. The ratio of these values,
polyamide coatings generally take 8 to 10 h to reach an early known as the stoichiometric mix ratio, is most often only a
cure and three to four days for a full cure. Another disadvan- starting point for the formulator. By varying the mix ratio of
tage is that epoxy/polyamide coatings are prone to severe the polyamide to the epoxy resin, certain properties of the
chalking during exterior weathering. cured coating are enhanced (and others are sacrificed) to
obtain specific application properties.
S Y N T H E S I S OF P O L Y A M I D E S
Polyamides are polycondensation products of difunctional

fatty acids and polyfunctional amines. In a typical commer-
CHEMICAL PROPERTIES
cial example, 1 mol of dimer acid is reacted with 2 mol of
The total amine value of the polyamide is determined by
diethylenetriamine. During this condensation reaction, 2 mol
potentiometric titration using ASTM Test Method D 2073:
of water are evolved. As the reaction proceeds, an interesting
Test Methods for Total, Primary, Secondary, and Tertiary
side reaction occurs: an additional mol or so of water evolves
Amine Values of Fatty Amines, Amidoamines, and Diamines
from a secondary reaction. One of the primary amine groups
by Referee Potentiometric Method. Note, however, that the
reacts with the dimer acid to form an amide linkage, which is
methods specified therein for primary, secondary, and terti-
a nitrogen bonded carbonyl. In addition, the ethylene chain
ary amine values are not applicable to polyamides. The total
next to the amide function and the secondary amine nitrogen
amine value is commonly listed in the specification proper-
are incorporated into a five-membered ring, known as an
ties of commercial polyamides and is defined as the number
imidazoline ring. This condensation reaction, which also
of milligrams of potassium hydroxide equivalent to the basic-
evolves water, eliminates an active hydrogen to yield a terti- ity in 1 g of sample.
ary amine group. The degree of cyclization obtained is con- The acid value, generally less than 5, that is also specified in
trolled to yield a product with specific useful properties, such commercial polyamides is defined as the number of milli-
as improved solubility and compatibility and longer pot life. grams of potassium hydroxide required to neutralize 1 g of
Similar reactions occur at the other carboxylic acid group of sample. The acid value may be determined using ASTM Test
the dimer [2]. If 50% of the diethylenetriamine present in the Method D 2076: Test Methods for Acid Value and Amine
polyamide is cyclized to imidazoline, a total of 3 tool of water Value of Fatty Quaternary Ammonium Chlorides. The proce-
of reaction is evolved. These products are shown in the fol- dure specified for determining the amine value in Method
lowing structures: D 2076 is not applicable to polyamides.
For the polyamide The imidazoline content is not specified in commercial
polyamides except in special cases where the level is deemed
O critical. The level of imidazoline is usually controlled by the
II polyamide manufacturer to provide products with specific
H2N--CH2--CH2-- N, - C H 2 - C H 2 - N - C - C2A
compatibility and/or solubility. Imidazoline level can best be
H H measured by scanning the polyamide with an infrared spec-
trophotometer and comparing the absorption at 6.25/zm to
O the absorption at 6.05/~m. The imidazoline ring absorbs at
- - C - - N - - C H 2 - - C H 2 - - N - - C H 2 - - C H 2 - - N H2 6.25 /zm, and the nitrogen-bonded carbonyl, or amide, ab-
I I sorbs at 6.05/~m. The result is reported as either a ratio of
H H imidazoline:amide (I/A) or as a percentage. In the example
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CHAPTER 1 2 - - C H E M I C A L DESCRIPTIONS 87
reaction described previously, the imidazoline ratio would be The reaction of the oxirane ring and active hydrogen,
1.0 and the percentage would be 50%. which also occurs at the secondary amine sites in the polyam-
ide, is one mechanism for the cross-linking that occurs. A
secondary reaction occurs between pendant hydroxyl groups
PHYSICAL PROPERTIES in the epoxy resin molecule and other oxirane rings present,
which is another mechanism for the cross-linking reaction
Polyamides are supplied commercially in solution or as [3]. Because of this latter reaction it is desirable to mix the
100% reactive liquids depending on the handling and storage polyamide and epoxy in less than a stoichiometric ratio to
requirements of the coatings manufacturer. For ease of han- provide coatings with m a x i m u m cross-link density. Such
dling, they may be supplied in various solvents. Most polyam- coatings will be characterized by excellent impact and chemi-
ides suitable for coatings applications are quite viscous, and cal resistance but will tend to be less flexible. To provide more
these polyamides are soluble in a variety of organic solvents flexible coatings with greater elongation, the use of close to or
including alcohols, glycol ethers, ketones, and aromatic hy- greater than the stoichiometric ratio is recommended.
drocarbons. Thus the coatings manufacturer has consider- Polyamide/epoxy coatings contain organic solvents, which
able latitude in selecting specific solvents for optimum appli- when applied appear to dry because of solvent evaporation.
cations properties. This early dry time is not, however, an indication of cure.
The percent nonvolatile content of polyamide solutions Cure results from a chemcial reaction between the polyamide
may be determined in accordance with ASTM Test Method and epoxy resins that generally requires about 8 to 10 h
D 1259: Test Method for Nonvolatile Content of Resin Solu- before the film will resist mechanical deformation. Chemical
tions. Commercial polyamides are generally supplied in a resistance of the coating is not achieved before three to four
single organic solvent at between 60 and 80% solids, which days, and ultimate cure is achieved after about three weeks.
provides a handleable viscosity. The coatings formulator fur- Polyamide/epoxy coatings may be applied by any conven-
ther dilutes the polyamide solution with more of the same tional commercial applicator, including spray, brush, or
solvent, or with a solvent blend, to form one component of roller. The coatings formulator may design the solvent system
the two-component system. for a particular type of applicator. Polyamide/epoxy coatings
The polyamide component may be clear or may contain may be applied to wood, concrete, or steel. For optimum
pigments in colored coatings formulations. The color of the adhesion to the substrate, the surface to be coated should be
polyamide or polyamide solution is determined in accord- thoroughly cleaned and degreased. Polyamide/epoxy coat-
ance with ASTM Test Method D 1544: Test Method for Color ings are not normally applied to wood: when so used, the
of Transparent Liquids (Gardner Color Scale). wood surfaces should be first cleaned thoroughly and any old
The viscosity of the polyamide may be measured at ele- loosely adhering paint removed. Concrete surfaces may be
vated temperature in accordance with ASTM Test Method chemically acid etched or mechanically brushed. Steel sur-
D 2196: Test Method for Rheological Properties of Non-New- faces should be sandblasted, if possible, or at a minimum
tonian Materials by Rotational (Brookfield) Viscometer. The should be wire brushed and chemically cleaned [4,5].
viscosity of commercial polyamides is typically specified at 75
or 150~ The viscosity of polyamide solutions that may also
be measured by this method is generally specified at 25 or ENVIRONMENTAL/TOXICITY
40~ The viscosity of polyamide solutions may also be mea- CONSIDERATIONS
sured in accordance with ASTM Test Method D 1545: Test
Method for Viscosity of Transparent Liquids by Bubble Time In response to environmental concerns over the emission
Method. A modification of this Method is usually used in of organic compounds into the atmosphere, many coatings
which the polyamide solution is placed in a sample tube, the manufacturers have begun to produce high solids coatings
viscosity is compared to Gardner-Holdt Letter standard that contain much lower levels of volatile organic compounds
tubes, and the observation is reported as the alphabetic letter (VOCs). These products do not contain polyamides; instead,
of the tube most closely matching the sample. A plus ( + ) or a amidoamines are used, products formulated from m o n o m e r
minus ( - ) is then used to indicate that the viscosity is greater fatty acid rather than dimer acid [6]. A significant volume of
or less than the designated letter. polyamide/epoxy coatings continues to be used.
Though polyamides are less toxic than aliphatic amines
and amine adducts, direct contact exposure with the skin,
eyes, and the respiratory system must be avoided. Polyamide
R E A C T I O N OF P O L Y A M I D E S IN C O A T I N G S
solutions must also be handled with care to avoid exposure to
ignition sources as they contain flammable or combustible
Polyamides react with epoxy resins in several stages to
solvents and the vapor level from polyamide solutions must
form a complex insoluble cross-linked matrix. The initial re-
be monitored in the workplace to avoid overexposure to the
action is between the terminal primary amine groups of the
organic solvents present.
polyamide and the oxirane ring of the epoxy resin. The active
Polyamide manufacturers supply material safety data
hydrogen opens the ring and the oligomers join end to end.
sheets (MSDS), which should be consulted for hazard infor-
This initial reaction can be represented by the following
mation and guidance on the safe use of the products. The
simplified structure.
MSDS also contains information regarding procedures to fol-
O OH low if a spill occurs, as well as guidelines for hazardous waste
/\ I ~ J disposal. Those polyamide solutions that are classified as
H2C--CH-- + H--N-- ~--N--CH2--CH-- hazardous waste due to the presence of organic solvents must
www.iran-mavad.com

be incinerated. Liquid (100%) p o l y a m i d e s are not generally REFERENCES

classified as h a z a r d o u s waste t h o u g h their disposal m a y be
r e g u l a t e d as an oil b e c a u s e of their liquid nature; these p r o d - [1] McMahon, D. and Crowell, E., "Characterization of Products
from Clay Catalyzed Polymerization of Tall Oil Fatty Acids,"
ucts m u s t be either i n c i n e r a t e d o r a b s o r b e d b y a suitable
Journal of the American Oil Chemists Society, Vol. 51, 1974, p. 522.
solid a b s o r b e n t m e d i u m , such as a g r o u n d clay a b s o r b e n t [2] Lee, H. and Neville, K., "Amides and Miscellaneous Nitrogen
product, a n d p l a c e d in a s a n i t a r y landfill. Compounds as Epoxy-Resin Curing Agents," Handbook of Epoxy
T h o u g h p o l y a m i d e s are reactive in the presence of epoxy Resins, McGraw-Hill, New York, 1967, Chapter 10, pp. 2-12.
resin, they are quite stable c o m p o u n d s w h e n kept in a cool, [3] "Epoxy Resins," Encyclopedia of PolymerScience and Engineering,
2nd ed., John Wiley & Sons, New York, 1988, Vol. 6, pp. 348-354.
d r y environment, a n d they m a y r e m a i n u n c h a n g e d for a y e a r
[4] "Polyamides from Fatty Acids," Encyclopedia of Polymer Science
o r more. P o l y a m i d e s m a y b e stored in d r u m s o r tanks con- and Engineering, 2nd ed., John Wiley & Sons, New York, 1988,
s t r u c t e d of stainless steel or a l u m i n u m . C a r b o n steel tanks Vol. 11, pp. 476-489.
s h o u l d be avoided b e c a u s e of d a r k e n i n g of the p r o d u c t from [5] Allen, R., "Epoxy Resins in Coatings," Federation Series of Coat-
iron c o n t a m i n a t i o n . ings Technology, 1972, Unit 20.
[6] Bozzi, E., "Epoxy Resins in High Solids Coatings," The Epoxy
Resin Formulators Training Manual, James Kaszyk, Ed., The So-
ciety of the Plastics Industry, Inc., New York, 1984, Chapter XIII,
pp. 149-162.
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MNL17-EB/Jun. 1995
13
Polyurethane Coatings
by Joseph V. Koleske 1
INTRODUC~ON Excess isocyanate groups capable of reacting at the time of

application may be contained in the reaction products. ASTM
THERMOPLASTIC POLYURETHANES WERE FIRST developed by has classified such polyurethanes into six general types
Otto Bayer [1,2] in the Leverkusen laboratories of I. G. Far- [ASTM Terminology Relating to Paint, Varnish, Lacquer, and
benindustrie AG in 1937 [3,4] as they searched for a product Related Products (D 16)] [8]:
that would be competitive with the polyamides, now known Type I. "One-package prereacted" polyurethane coat-
as nylons, that had been introducedby duPont. Shortly there- ings are characterized by the absence of any significant
after, Schollenberger and coworkers [5] used formula modifi- quantity of free isocyanate groups. They are usually the
cation to prepare elastomeric polyurethane products from reaction product of a multifunctional isocyanate and a
Bayer's products that were like nylon or other engineering polyhydric ester of vegetable oil acids and are hardened
plastics in physical characteristics. with the aid of metallic dryers such as cobalt napthenate,
Polyurethanes are widely used in coatings, flexible and manganese neodecanoate, and similar compounds. For
rigid foams, elastomers, and composites. In an overall sense, example, linseed oil and glycerol may be first reacted and
then modified with a diisocyanate that reacts with a part
the polyurethane business is huge and is concerned with rigid or all of the available hydroxyl groups. If any residual
foams, flexible foams prepared in both slab and molded isocyanate is present, it is removed by addition of a
forms, elastomers, including reaction-injection-molded prod- monofunctional alcohol. Catalysts such as dibutyltin ox-
ucts, and coatings. Excluding coatings, the 1988 U.S. con- ide and dibutyltin dilaurate are used to promote ure-
sumption of polyurethanes was about 2750 million lb (1.25 thane-linkage formation. The coatings are also called
million metric tons) with the forecast for 1993 about 3150 uralkyds, urethane-modified alkyds, urethane alkyds,
million lb (1.43 million metric tons) [6]. In 1991, the national and oil-modified urethanes. Cure is achieved by the oxi-
market for polyurethane coatings was about 209 million lb dative crosslinking of unsaturated fatty acid molecules.
(95 000 metric tons) [7]. Although the market for polyure- They are often used as automobile refinish coatings and
thane coatings is large and growing, it is readily apparent that wood and floor finishes because they provide improved
scuff, water, and stain resistance over those of conven-
it represents only about 5 to 10% of the total domestic poly- tional alkyds.
urethane market. In 1991 consumption of polyurethanes for
coatings in Western Europe and Japan was 301 and 100 Type II. "One-package, moisture cured" polyurethane
coatings are isocyanate-terminated, polyester or poly-
million lb (137 000 and 46 000 metric tons), respectively [7].
ether prepolymers that are capable of reacting with ad-
Reasons for the use of polyurethane coatings include: high- ventitious moisture to form mainly urea linkages be-
performance characteristics such as flexibility, toughness, tween the molecules and the final coating is a
strength, and abrasion resistance; chemical resistance such polyurethane/polyurea coating. For the most part, these
as water, detergent, many industrial chemicals, and stain polyurethanes are used as clear coatings. They are often
resistance; good light stability when aliphatic isocyanates are used as sealers for concrete and wood, floor finishes, and
used; and low temperature-cure characteristics. The latter deck finishes.
factor is a major reason for use of polyurethanes on plastic Type III. "One-package, heat cured" polyurethanes
substrates. cure or crosslink by thermal release of blocking agents
which results in regeneration of active isocyanate groups
that will subsequently react with active hydrogen groups
DEFINITIONS contained in the formulation. The coatings are often
used in coil coatings and electrical wire coatings.
ASTM [8] defines polyurethane coatings as vehicles contain- Type IV. "Two-package catalyzed" polyurethanes are
ing a minimum of 10% by weight on a nonvolatile vehicle made up of one package that contains a prepolymer
basis of a multifunctional isocyanate monomer reacted in having free isocyanate groups and a second package that
such a manner as to yield polymeric systems with urethane is a catalyst, initiator, accelerator, and/or crosslinking
agent. Catalysts are compounds such as metal nap-
linkages, active isocyanate groups, or multifunctional isocya- thenates or tertiary amines. Initiators or crosslinking
hate monomers in any ratio, proportion, or combination. agents are glycols or other monomeric, multihydroxyl- or
amine-functional compounds. Pot life is limited after the
JSenior consultant, Consolidated Research, Inc., 1513 Brentwood two packages are combined. These coatings are not
Road, Charleston, WV 25314-2307. widely used.
89
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Type V. "Two-package polyol" polyurethanes coatings Raw Materials

have one package that contains an isocyanate-termi-
nated prepolymer or a multifunctional isocyanate and a Isocyanates
second package that is made up of a polymer that con- Two types of isocyanates are used in coatings--aliphatic
tains active hydrogen groups. These relatively low molec- and aromatic. Polyurethanes prepared from either type isocy-
ular weight polymers are usually polyesters, polyethers, anate have excellent chemical and physical properties. Aro-
or acrylics. The second package may or may not contain
a catalyst. After mixing the two packages, the systems matic isocyanates are used in products where weathering
have limited pot life. These coatings, which are high- resistance, particularly sunlight or ultraviolet light resist-
solids in nature, are used in high performance areas such ance, is not important because of discoloration, which almost
as automobile refinishes, original automotive equipment always manifests itself as yellowing. Yellowing in itself is a
clear coats over pigmented decorative coatings, aircraft loss of an aesthetic property, but its cause and result do not
coatings, truck and bus coatings, and industrial-struc- deleteriously affect mechanical properties. Ultraviolet light
ture maintenance coatings. attacks the labile hydrogen atoms on the aromatic ring struc-
Type VI. "One-package nonreactive lacquer" is a sys- ture. Aliphatic isocyanates are less reactive and more costly
tem that basically is a solution of a high molecular than aromatic isocyanates and, while these factors can be
weight polyurethane (weight-average molecular weight cost considerations, aliphatic isocyanates are widely used for
from about 40,000 to 100,000). They are characterized by both interior and exterior applications.
the absence of any significant quantity of free isocyanate The two main aliphatic isocyanates currently used are 4,4'-
groups, and they are converted into a solid film by solvent
diphenylmethane diisocyanate (MDI) and toluene diisocya-
evaporation. The lacquers are low solids, about 10-15%
by weight, in nature because of the high molecular nate (TDI), which is a mixture of the 2,4- and 2,6-isomers.
weight involved and concomitant high viscosity of such Moisture-cure urethanes and urethane alkyds usually employ
molecules in solution. These films have very high gloss TDI, though MDI has some use due to its low vapor pressure.
and are used in the textile industry to achieve the "wet Xytylene diisocyanate (XDI) is used to some extent, but
look" that was popular in the late 1970s. They are used mainly in Japan. Recently tetramethylxylylene diisocyanate
today for the popular cast or transfer-process fabric coat- (TMXDI) and isopropenyl dimethyholuene diisocyanate
i~ngs as well as other fabric coatings. (TMI) have been introduced by American Cyanamid. Naph-
Three other types of polyurethanes not included in the thalene diisocyanate has also been used.
ASTM classifications are polyurethane and polyester- and Aliphatic isocyanates are more costly, and they are used for
polyacrylic-urethane powder coatings, ultraviolet light-cur- urethane coatings that require excellent sunlight resistance
able urethanes, and waterborne urethanes [7]. The first two and no discoloration. These coatings are used on plastics,
types have been considered as energy-activated materials and automobiles, signs, and similar outdoor end-use products.
thus related to the ASTM Type III coatings. The main aliphatic isocyanates are hydrogenated MDI
(4,4'dicyclohexylmethane diisocyanate, HMDI, or H12MDI),
hexamethylene diisocyanate (HDI), particularly in a biuret or
trimer form for improved vapor pressure, mixtures of 2,2,4-
and 2,4-4-trimethyl hexamethylene diisocyanate (TMHDI),
CHEMISTRY 1,4-cyclohexane diisocyanate (CHDI), and isophorone diiso-
cyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl iso-
As with many phases of chemistry, one can consider the cyanate or IPDI) [9]. IPDI and HI2MDI are the isocyanates
chemistry of urethane coatings in a simple or a complex most widely used in coating preparation.
Type III polyurethane coatings, including powder coatings,
manner. Simplistically, urethane coatings contain urethane
employ blocked isocyanates that provide room-temperature
linkages, - - N H C O - - , that are formed through a rearrange-
stable, one-package systems that are activated at elevated
ment reaction when an hydroxyl group reacts with an isocya-
temperatures. At elevated temperatures, the molecules disso-
nate group and that can be represented with monofunctional
ciate and the blocking group leaves, freeing the isocyanate
materials as follows
functionality that then readily reacts due to its nature and the
ROH + R'NCO ~RO--C--NR' kinetic effect of elevated temperature with available active
II I hydrogen groups. Blocking groups are proton donors such as
O H E-caprolactam, malonic, and acetoacetic esters as well as
other enolizable esters, ketoximes, phenol, etc. For example,
In actual practice, functionalities of two or greater are usually trimethylolpropane (TMP) can be reacted with TDI and then
involved. In addition, there are many ramifications of this blocked by reacting the free isocyanate groups with phenol:
reaction that will lead to the polyurethane products currently
in use. It is interesting to note that urethane formation takes C2HsC(CH2OH)3 + C6Ha(CHa)(NCO)2
place through a rearrangement reaction and that no by-prod- TMP TDI
ucts are formed. The following information is meant to give C2HsC(CH2OCONH--C6H3(CH~)--NCO)3
ISOCYANATE-TERMINATED ADDUCT
the reader a brief excursion into the raw materials and some
of the reactions that are important to polyurethane chemis- C2HsC(CH2OCONH--C6Ha(CH3)--NCO) 3 + 3 C6Hs--OH
try. Other linking groups that may be found in polyurethane ISOCYANATE-TERMINATED ADDUCT PHENOL
coatings are allophanate, urea, biuret, and isocyanurate C2HsC(CH2OCONH--C6Ha(CH3)--NHOCOC6Hs)3
groups. These linkages will be discussed later. PHENOL-BLOCKED TRIISOCYANATE
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CHAPTER 13--POLYURETHANE COATINGS 91
Technology such as this is used in polyurethane powder coat- Polyfunctional amines, which form urea linkages with iso-
ings. cyanates, are also used as chain extenders. Low-molecular-
weight compounds such as ethylenediamine are used as
Active Hydrogen Sources chain extenders to make polymers for Type VI lacquers.
Isocyanates readily react with active hydrogen sources Amine-terminated oligomers based on the alkylene oxides are
such as hydroxyl groups and amines. Hydroxyl groups are available [14-16].
usually supplied by polyfunctional compounds such as gly-
cols, triols, tetraols, polyester polyols, polyether polyols, Catalysts
acrylic polyols, and polylactone polyols. Polyether polyols are
Catalysts are often used to promote the reaction between
usually poly(propylene oxide) polyols that may or may not be
isocyanates and hydroxyl-containing compounds. Only small
copolymerized with ethylene oxide in a random manner or in
amounts, on the order of 10 to 100 parts per million, of
an end-capping manner to provide primary hydroxyl end
catalyst are needed to cause marked increases in reaction
groups. These polyols, which are described in detail else-
rate. Popular catalysts include dibutyltin dilaurate, stan-
where in the manual, are usually di- or trihydroxyl functional
nous octoate, and zinc octoate. Diaza(2.2.2)bicyclooctane
compounds, though higher functionalities are used in special
(DABCO), dibutyltin diacetate, bismuth stearate, and zirco-
cases, that have number-average molecular weights of from
nium octoate have been used.
about 200 to 3000. Polyols function as soft segments and
impart flexibility to polyurethanes [10]. As would be ex-
pected, primary hydroxyl groups react much more rapidly
than secondary hydroxyl groups, and tertiary hydroxyl Reactions
groups react slower than either other type. For example, pri-
As indicated above, hydroxyl groups react with isocyanates
mary hydroxyl groups reacted about 3.5 faster with phenyl
to form polyurethanes. Multifunctional reactants are used to
isocyanate than secondary hydroxyl groups and about 200
times faster than tertiary hydroxyl groups [11]. It was also link molecules as in Type I urethane alkyd [17] to cause mo-
found that n-butanol reacted five times faster with the isocya- lecular chain length increase in either a prereaction to form
nate group in the para- or 4-position group than with the the final polyurethane that could be used in a Type VI lacquer
isocyanate next to the methyl group in 2,4-toluene diisocya- coating or to form prepolymers that are later reacted in two-
nate. This demonstrated that neighboring groups can signifi- package coatings as would be used in Type IV and Type V
cantly affect isocyanate reactivity. coatings. In other instances, multifunctional (usually di-
Low-molecular-weight or monomeric compounds are used functional) isocyanates are used to end cap diols, triols, and
as chain extenders when preparing polyurethanes [12], and tetraols with isocyanate functionality as is needed for Type II,
these chain extenders in combination with the isocyanates IV, and V coatings. Both hydroxyl-functional and isocyanate
are termed "hard segments" that function as pseudocross- functional prepolymers are used. For example:
links [13]. In high-molecular-weight polyurethanes, such as HO--R--OH + 20CN--R'--NCO
those used for Type VI products, these chain extenders repre- DIOL DIISOCYANATE
sent only a few percent of the total polymer molecular weight OCN--R'NHCOO--R--OOCNHR'--NCO
yet play a significant role in final physical properties. Glycols ISOCYANATE-TERMINATED PREPOLYMER
and low-molecular-weight triols require relatively large
amounts of isocyanates, usually the most costly ingredient, 2 HO--R--OH + OCN--R'--NCO
and impart hardness and rigidity to the final coating. These DIOL DIISOCYANATE
compounds are also used as initiators for preparation of the HO--R--OOCNH--R'NHCOO--R--OH
various polyols with glycerol often used for poly(propylene HYDROXYL-TERMINATED PREPOLYMER
oxide) polyols and with glycols and triols such as 1,4-butane- Other prepolymers can be prepared by reacting, for example,
diol, diethylene glycol, trimethylolpropane, and the like, of- an hydroxyl-terminated prepolymer with two molecules of
ten used for polylactone polyols. Polyesters other than poly- diisocyanate to produce an isocyanate-terminated prepoly-
lactones are prepared from difunctional carboxylic acids, mer that contains urethane linkages in the central portion of
particularly adipic acid, and glycols, particularly ethylene the prepolymer. It should be apparent that this method of
glycol, diethylene glycol, butanediols, and 1,6-hexanediol. An chain extension cannot be carried too far since viscosity will
excess of glycol is used to ensure that most end groups in the increase very rapidly as chain extension takes place, which is
polyester are hydroxyl groups. Acrylic polyols are prepared not a desirable result if materials for high-solids or other
from hydroxy functional compounds, particularly 2-hydroxyl energy-conserving formulations are produced.
ethyl and 2-hydroxypropyl acrylate and methacrylate, other Moisture-cure polyurethanes are molecules with free isocy-
acrylates and methacrylates, and other ethylenically unsatu- anate end groups. Sufficient quantities of isocyanate are re-
rated, copolymerizable monomers. Examples of such mono- acted with polyols such that there are more equivalents of
mers are ethyl acrylate, butyl acrylate, styrene, vinyl esters, isocyanate groups compared to hydroxyl groups. For exam-
etc. Epoxide, silicone, vinyl, phenolic, and oligomers that
ple, a trifunctional oligomer or polyol can be reacted with an
contain hydroxyl groups are also reacted with isocyanates to
isocyanate under moisture-free conditions and then pack-
form urethane linkages and accompany property enhance-
aged under moisture-free conditions.
ment in specialty finishes. The epoxide, vinyl, and phenolic-
based materials have good chemical resistance, and the sili- OLIGOMER(OH) 3 + 3 R'(NCO) 2
cone-based materials have good thermal resistance. OLIGOMER(O--CONHR'NCO)3
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Exact ratios of hydroxyl to isocyanate are seldom used, and creases which often are undesirable in various polyurethane
final free isocyanate content usually ranges between about 3 formulations.
and 16% [7]. Moisture-free conditions are achieved by blan-
keting the system during preparation and storage with dry
O
nitrogen. Since these products are almost always prepared in
II
solution, the solvent used for the reaction and for any dilution
to final product must be carefully dried to exclude moisture.
2 --R'NCO --R'N NR'--
Solvent drying can be done with molecular sieves. When \/
applied to a substrate and contacted with ambient moisture, C
these products cure by reaction with water to form an unsta- O
ble carbamic acid intermediate that dissociates into an amine
and carbon dioxide. The amine in turn rapidly reacts with URETIDINE DIONE
isocyanate to form a urea linking group. This can be de-
scribed by the following reaction scheme:
--R'NCO + H20 ~ [--R'NHCOOH] > --R'NH2 + CO2 T O

CARBAMICACID, AN II
UNSTABLE INTERMEDIATE /%
3 --R'NCO --R'N NR'--
--R'NCO + --R'NH2 ~ --R'NHCONHR'-- I I
UREA LINKAGE O~-~C C~-~O
\/
--R'NCO + --R'NHCONHR'-- ~ --R'NHCON(CONHR--)R'-- N
BIURET LINKAGE I
R--
The first reactions leading to urea linkages predominate. ISOCYANURATE
These systems cure relatively slowly, which allows time for
the evolved carbon dioxide to leave before it is undesirably
entrapped in the solidifying film. Biuret linkages are formed
in thermally accelerated systems, particularly at IO0~ or Thermoplastic Polyurethanes
higher, and they contribute to cross-linking (note that biurets
can be equivalent to trifunctional isocyanates). Even though Thermoplastic polyurethanes are used in Type VI lacquers
these cured films, strictly speaking, are urethane/urea poly- and in many industrial end uses that require solid products.
mers, they are usually referred to as polyurethanes. Their chemistry is similar to that of prepolymers except
Isocyanates will also react with urethanes to produce al- short-chain extenders are used to connect the prepolymer
lophanate linkages. molecules and build them into long polymeric materials. In a
structural sense, they may be described as linear block co-
--R'NCO + --R'NHCOOR'-- ~ --R'N(CONHR'--)COOR'-- polymers of the ABn type. One of the blocks is a relatively
AN ALLOPHANATELINKAGE long, number-average molecular weight of about 300 to 3000,
polyether or polyester that forms the soft or flexible segment.
Isocyanates are less reactive with urethanes than with ureas, The other block is formed by the reaction of a diisocyanate
and temperatures of about 120 to 140~ are required to give a and a low-molecular-weight diol chain extender. The polar
significant reaction rate for the formation of allophanate link- nature of the urethane linkages in the hard segment results in
ages. Allophanate formation results in branching in the poly- hard segment aggregation and domain segregation from the
meric network. soft segment. The hard segments act as pseudo cross-links,
Carboxylic acids will react with isocyanates to form unsta- and as a result tough, strong, elastomeric macromolecules
ble mixed anhydrides that decompose into an amide and are formed.
carbon dioxide. In a mole sense, these polymers can be viewed as polyol/
R'NCO + RCOOH > R'NHCOOCOR2 > R'NHCOR + CO2 T diisocyanate/short-chain extender polymers that are formed
MIXEDANHYDRIDE AMIDE in an equivalents ratio of 1/X/(X - 1). The n u m b e r X c a n vary
from 1 or less to as much as 20 or more, though more
This reaction is important to keep in mind when polyesters typically in coatings X has a value of one or less to about 3 or 4
prepared from glycols and dicarboxylic acids are used or [10,13]. Because of solubility characteristics, a ratio of about
when acid numbers are unexpectedly high in polyether, poly- 1/2/1 is often used. A small excess of hydroxyl groups is used
lactone, or other polyols. The end product of this reaction to keep final free isocyanate content and storage reactivity at
results in stoppage of chain growth and a lower than expected a nil level. When the wide range of values of X, the types of
molecular weight. In most cases this is undesirable. Amides isocyanates, the types and functionalities of polyols, and the
will react with isocyanates to form acyl ureas. range of polyol molecular weight available is considered, it is
Isocyanates will dimerize (aromatic) to form uretidine di- readily apparent that a myriad of polyurethanes can be pre-
ones and trirnerize (aromatic and aliphatic) to form isocya- pared and that a broad range of mechanical and chemical
nurates. These reactions decrease the expected equivalent properties can be achieved. The chemistry is basically isocya-
weight of isocyanates, a cost factor, and will lead to branch- nates reacting with hydroxyl groups to form urethane link-
ing, cross-linking, and unexpected molecular weight in- ages.
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CHAPTER 1 3 - - P O L Y U R E T H A N E COATINGS 93
Radiation-Curable Urethanes [18-20] boxylic acid-containing diol such as dimethylolpropionic

acid (2,2-bis(hydroxymethyt) propionic acid), dihydroxyben-
Acrylate-terminated polyurethanes are used in a number of zoic acid, sulfonic acids as 2-hydroxymethyl-3-hydroxy-
ultraviolet light and electron beam curable formulations. The propanesulfonic acid, and similar compounds. For example:
products are termed "urethane acrylates" or "acrylated ure-
thanes." They are prepared by first forming an isocyanate- 2 0 C N - - R ' - - N C O + CH3--C(CH2OH)2--COOH .
terminated prepolymer from a polyol and then end capping CH3
the prepolymer with an hydroxy acrylate such as 2-hydroxy- !
ethyl acrylate. The reactions leading to urethane acrylates are OCN--R'--NHCOOCH2~CHzOOCHN--R'--NCO
almost always carried out in an inert solvent.
COOH
20CN--R'--NCO + HO--POLYOL--OH >
[ + (n + 1 ) H O - - P O L Y O L - - O H
OCN--W--NHCO--O--POLYOL--O--OCNH--R'--NCO
ISOCYANATE-TERMINATEDPREPOLYMER CH3
I
OCN--R'--NHCO--O--POLYOL--O--OCNH--R'--NCO+ HO--(POLYOL--OOCHN--R'--NHCOOCH2CCH2OOCHN--
CH2~-CHCOOCH2CH2--OH /
COOH
2-HYDROXYETHYL ACRYLATy
R'--NHCOO),--POLYOL--OH
CH2~CHCOOCH2CH2--O--OCNH--R'--NHCO--O--POLYOL-- WATER DISPERSIBLE POLYURETHANE
O--OCNH--R'--NHCO--OCH2CH2OOCHC=CH2
Water-borne polyurethane laminating adhesives that are
A URETHANE ACRYLATE completely free of volatile organic compounds are expected
to be the next developments in this area [25]. These adhesives
The reactions as depicted above have been idealized. In all are expected to be for the low-to-medium demand product
commercial and most laboratory preparations there is a sig- area such as for snack food and similar packaged products.
nificant amount of reaction between the ingredients so that
chain extension occurs and molecular weight increases. This
causes the final product to have a markedly higher-than-
expected viscosity. Oligomeric compounds such as these are
Powder Coatings
formulated with triacrylates such as trimethylolpropane
triacrylate to provide cross-linking, monomeric acrylates, Polyurethane powder coatings are usually urethane-modi-
N-vinyl pyrrolidone, or other compounds for viscosity reduc- fled polyesters and polyacrylics that cure at high tempera-
tion to provide low-viscosity, essentially 100% solids systems tures. High temperatures are needed for the powdered poly-
that will cure when exposed to actinic radiation. In formula- mer to flow and level to the extent needed for a particular end
tions, the urethane acrylate is considered as the main ingredi- use. The key to successful powder coatings is related to a
ent contributing to mechanical properties of the cured film. balance between molecular weight and related viscosity and a
When the actinic radiation source is ultraviolet light, a cross-linking mechanism that is stable under storage condi-
photoinitiator (for example, 2,2-diethoxyacetophenone or tions and not effected to any significant degree until flow and
benzophenone in combination with an amine synergist, etc.) leveling takes place at the cure temperature. Another require-
is added as a free radical source. Electron beam curable ment is that the glass transition temperature should be suffi-
formulations do not require a photoinitiator. ciently high that the powder does not block during storage.
Radiation-cured polyurethanes are often used on plastic The main end use for powdered polyurethanes is in the major
substrates that require only low or moderate curing tempera- appliance market--refrigerators, dryer drums, range cabi-
tures such as clear overprint lacquers on vinyl decals, elec- nets, etc.--coatings.
tronic circuit boards, "no wax" vinyl flooring, and tile. Al-
though radiation-cured colored and pigmented inks and
coatings are used in the marketplace, the skill needed in
preparing such products, because of difficulty with light pen-
etration or absorption, is readily apparent.
MARKETS
Water-Borne Polyurethanes Polyurethanes of the various types are used in a number of
Water-borne polyurethanes are prepared in bulk or in a market areas and end uses. Many of these were mentioned
solvent by first preparing an ionomer prepolymer that is above. Two features of polyurethane coatings that have been
neutralized and then chain extended to a desired molecular often looked on as disadvantages are high cost and special
weight. The polymer then is dispersed into water. Both handing of the potentially hazardous isocyanates that are
cationic [21,22] and anionic [23,24] systems are known. used in manufacture or as curing agents. However, the vari-
Cationic systems employ an amine-containing diol such ous industry segments have been able to develop safe han-
as diethanolamine, methyl diethanolamine, N,N-bis(hy- dling and use methods that overcome one of the objections.
droxyethyl)-a-aminopyridine, lysine, N-hydroxyethylpiperi- The very- high performance characteristics of polyurethanes,
dine, and similar compounds. Anionic systems use a car- their ability to cure at lower baking temperatures, and the
www.iran-mavad.com

T A B L E 1--Polyurethane end uses. REFERENCES

HOME FURNISHINGS PLASTIC SUBSTRATES
Drum dryers Fascia [I] Bayer, 0., Modern Plastics, Vol. 24, 1947, p. 149.
Furniture Electronic parts and [2] Wright, P. and Cumming, A. P. C., Solid Polyurethane Elasto-
"No wax" flooring and tile equipment mers, Elsevier Publishing Company, Amsterdam, 1969.
Range cabinets Optical fibers
Printed circuit boards [3] Bayer, O., Rinke, H., Siefken, W., Orthner, L., and Schild, H.,
Refrigerators
Wood floors Sheet molding compound German Patent 728,981 (1942).
[4] Bayer, O., Angewandt Chemie, Vol. A59, 1947, p. 275.
INDUSTRIAL MAINTENANCE RECREATIONAL PRODUCTS [5] Schollenberger, C.S., Scott, H., and Moore, G.R., Rubber
Bridges Golf balls World, Vol. 137, No. 4, 1948, p. 549.
Industrial buildings Golf clubs
Gym floors [6] Smith, R. M., "Polyurethanes," Supplement C, Report No. 10C,
Marine coatings
Plant equipment Toys SRI International, Menlo Park, CA, May 1991.
Public utility works [7] Linak, E., Kalt, F., and Takei, N., "Urethane Surface Coatings,"
Roof coatings TEXTILES Chemical Economics Handbook, SRI International, Menlo Park,
Windows Apparel CA, August 1992, p. 592.8000.
Leather
Tarpaulins [8] ASTM D 16: Terminology Relating to Paint, Varnish, Lacquer,
MISCELLANEOUS
Aerospace coatings Upholstery and Related Products, Vol. 06.01, ASTM Book of Standards,
Luggage 1992.
Magnetic tape coatings TRANSPORTATION [9] "Chemical Products for Resins, Coatings, Sealants, Adhesives,
Mast and spar finishes Aircraft and Elastomers," Hill America Inc., Piscataway, NJ, 1992.
Medical equipment Automotive OEM
Automotive refinish [10] Seefried, C. G., Jr., Koleske, J. V., and Critchfield, F. E., "Ther-
Safety glass
Shoes Golf carts moplastic Urethane Elastomers. I. Effects of Soft Segment Vari-
Vinyl decal overprints Motorcycles ations," Journal of Applied Polymer Science, Vol. 19, 1975, p.
Wire coatings Railroad cars 2493.
Trucks and buses [11] Bailey, F. E. and Koleske, J. V., Alkylene Oxides and Their Poly-
Vans
mers, Marcel Dekker, Inc., New York, 1991, p. 218.
i m p r o v e d total coating solids, i.e., d e c r e a s e d volatile o r g a n i c [12] Critchfield, F. E., Koleske, J. V., Magnus, G., and Dodd, J. L.,
c o m p o u n d content, that can be o b t a i n e d are factors that "Effect of Short Chain Diol on Properties of Polycaprolactone
offset their high cost. F o r example, p o l y u r e t h a n e s are replac= Based Polyurethanes," Journal ofElastoplastics, Vol. 4, January
ing poly(vinyl chloride) plastisols as u n d e r c o a t i n g s a n d seal- 1972, p. 22.
ants in the a u t o m o t i v e a n d o t h e r t r a n s p o r t a t i o n coating m a r - [13] Seefried, C. G., Jr., Koleske, J. V., and Critchfield, F. E., "Ther-
ket. Lower coating thickness a n d equivalent o r i m p r o v e d moplastic Urethane Elastomers. II. Effects of Hard Segment
p e r f o r m a n c e m a k e the a p p l i e d cost of the p o l y u r e t h a n e c o m - Variations," Journal of Applied Polymer Science, Vol. 19, 1975, p.
2503.
petitive with the plastisol. The textile a r e a is a m o d e r a t e
[14] Lee, J. M. and Winfrey, J. C., U.S. Patent No. 3,236,895 (1966).
g r o w t h a r e a for t h e r m o p l a s t i c p o l y u r e t h a n e lacquers with
[15] Yeakey, E. L., U.S. Patent No. 3,654,370 (1972).
the excellent c o m b i n a t i o n of p r o p e r t i e s as the m a i n driving
[16] Bishop, T. E., Coady, C.J., Zimmerman, J. M., Noren, G. K.,
force for use. These include g o o d elasticity at low t e m p e r a -
and Fisher, C. E., European Patent Publication 209,641 (1987).
tures, a b r a s i o n resistance, solvent a n d w a t e r resistance, d r y [17] Christenson, R. M. and Erikson, J. A., U.S. Patent 4,222,911
cleanability, m a c h i n e washability, a n d a n ability to be pre-
(1980).
p a r e d in a b r o a d variety of tensile/elongation properties. I n [18] Salim, M. S., Polymer, Paint, Colour Journal, Vol. 177, No.
addition, the high p e r f o r m a n c e can be achieved with very 4203,762 (1987).
thin coatings t h a t do not m a r k e d l y increase fabric weight o r [19] Martin, B., Radiation Curing, Vol. 13, No. 4, August 1986, p. 8.
change styling factors such as drape. To decrease volatile [20] Hodakowski, L.E. and Carder, C.H., U.S. Patent 4,131,602
organic content, new low-viscosity, aliphatic isocyanates [26] (1978).
a n d p o l y u r e t h a n e polyols [27] are being developed. Although [21] Scriven, R. L. and Chang, W. H., U.S. Patent 4,046,729 (1977).
it is n o t a c o m p l e t e listing, Table 1 is a s u m m a r y of m a n y end [22] Scriven, R. L. and Chang, W. H., U.S. Patent 4,066,591 (1978).
uses for p o l y u r e t h a n e coatings. [23] Scriven, R. L. and Chang, W. H., U.S. Patent 4,098,743 (1978).
I n the five-year p e r i o d b e t w e e n 1991 a n d 1996, it is esti- [24] Milligan, C., U.S. Patent 3,412,054 (1968).
m a t e d t h a t the U.S. p o l y u r e t h a n e coating m a r k e t will g r o w at [25] Long, D. and Barush, J., "VOC-Free Adhesive Use Grows Due to
a c o m p o u n d e d a n n u a l rate of 5% o r f r o m 209 million lb to Increased Performance," Adhesive Age, Vol. 36, No. 10, Septem-
265 million lb (95 000 to 123 400 metric tons) [7]. It is ex- ber 1993, p. 42.
p e c t e d that the two-package (ASTM Type IV a n d V) systems [26] Wojcik, R. T., "Super-Low-ViscosityAliphatic Isocyanate Cross-
will have a l m o s t d o u b l e the c o m p o u n d e d a n n u a l g r o w t h rate linkers for Polyurethane Coatings," Modern Paint and Coatings,
of the overall u r e t h a n e coating market, i.e., a b o u t 10%, with Vol. 83, No. 7, July 1993, p. 39.
c o n s u m p t i o n rising from 84 million lb in 1991 to 133 million [27] Gardon, J. L., "Polyurethane Polyols: Ester-Bond Free Resins
lb in 1996 (38 200 to 60 500 m e t r i c tons). W a t e r b o r n e a n d for High Solids Coatings," Journal of Coatings Technology, Vol.
p o w d e r e d p o l y u r e t h a n e s are also i m p o r t a n t growth areas. 65, No. 819, April 1993, p. 25.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Silicone Coatings
by D. J. Petraitis ~
UNIQUE PROPERTIES OF SILICONES THAT implants such as heart pacemakers. They have also been used
M A K E T H E M U S E F U L AS C O A T I N G S to coat temporary implants such as catheters and surgical
drains. Also, thin silicone elastomer coatings are used to
Silicone based coatings are among the most useful materi- provide soft tissue replacements by forming an envelope to
als for a wide variety of applications. Because the basic bond encapsulate gels and/or normal saline solutions. Recent ap-
energies of Si--C and Si--O bonds are so high, the chemical plications for biocompatible silicone coatings include drug
processes usually associated with aging of coated surfaces are delivery devices for both transdermal and long-term im-
often much slower and in many situations virtually elimi- plantable, controlled-release drug delivery.
nated for silicone coatings. Also, because the Si--O and A final characteristic which makes silicone coatings useful
Si--C bonds are not present in the natural organic world, is their inherently low or nonflammability. Typically, silicone
biocompatibility and resistance to degradation via biochemi- elastomer coatings have been rated SE-I when tested via
cal and biophysical processes are also significantly reduced. Underwriters' Laboratories Flame Test (UL-94). This prop-
In a similar manner, some silicone resinous coatings and erty makes silicone coatings ideal for conformal coating of
fluorosilicone based coatings, in particular, have excellent various electrical circuits and devices. In the event of cata-
solvent resistance. strophic thermal degradation, the silicone coatings can and
Silicone coatings based on trifluoropropyl methyl poly- do provide an SiO2 ash coating which may permit the emer-
siloxanes have resistance to swelling from such agents as gency operation of the electrical device on a short-term tem-
gasoline, jet fuel, solvents, and various other reagents. Highly porary basis.
branched resinous silicone coatings chemically begin to ap-
proach the properties of silica surfaces as the organic pen-
dant content is reduced. As the organic pendant groups are F O R M S OF S I L I C O N E C O A T I N G S
reduced, the SiO4/2 content increases and the chemical resist-
ance increases. Such resinous coatings can provide physical Silicone coatings are available in various forms ranging
scratch resistance as well as chemical resistance. Silicone from a hard, rigid resin to a compliant elastomer to a soft,
elastomeric coatings, however, do not provide good resist- almost gel-like character. The rigid resins are typically sup-
ance to strong acids and/or bases. Strong acids or bases, in plied in a solvent solution and are mixed with curing agents
particular at elevated temperatures, can cause depolymeriza- prior to application. Among the most common curing agents
tion of the siloxane backbone, resulting in failure, or in the are lead and zinc octoate, which require approximately 1 h at
case of silicone elastomeric coatings, dissolution of the coat- 250~ to attain complete cure. The cross-linking mechanism
ing itself. involves the condensation of silanol groups
In a similar manner, silicone coatings are resistant to virtu-
~-~SiOH + H O S i ~ ~ ~ S i O S i F + H20
ally all frequencies of the electromagnetic spectrum. For
complaint coatings, silicones are unsurpassed in resistance to Specific coating applications include jet engine components,
hard radiation, such as that from a cobalt-60 source for doses furnace parts, incinerators, high-temperature appliances,
in excess of 20 Mrd, as well as the ultraviolet and infrared and missile coatings. In addition, specific silicone resins have
frequencies. When combined with their hydrophobicity and been designed to mix with organic coatings and paints, pro-
oxygen and ozone resistant properties, silicones provide ex- viding higher performance under moderate heat environ-
cellent weatherability characteristics, and when these prop- ments.
erties are combined with the resistance to atomic oxygen in By varying the R group:Si ratio, the hardness of the final
low earth orbit, silicone coatings provide protection for or- coatings can be varied. As the R: Si ratio is decreased, the
ganic substrates in varied spacecraft applications. cross-link density of the resin effectively increases. Similarly,
Another family of applications which combine the chemi- variation of the R group itself can result in somewhat differ-
cal and biochemical characteristics of silicones are those ent flexibility and other properties. Properly designed and
which are used to provide coatings for medical devices. Sili- condensed resins can be fornmlated to provide hard silica-
cone coatings are used to encapsulate and seal permanent like abrasion-resistant coatings. Such coatings often involve
the condensation of alkoxy groups with silanol groups as well
1Vice president, Operations, NuSil Technology, 1040 Cindy Lane, as condensation between silanol groups alone. Technology to
Carpinteria, CA 93013. minimize shrink and maximize adhesion during the cure
95
www.iran-mavad.com

needs to be incorporated to prevent cracking and subsequent which are often used as plasticizers in plastics and also as
flaking of the coating from the substrate. Aminofunctional catalysts for other silicone coatings.
alkoxy silanes are often incorporated into the formulation to There are other silicone elastomeric cure systems, and one
simultaneously optimize cure rate and adhesion. of the most significant applications is to coat fiberglass blan-
Silicone elastomeric coatings incorporate the use of poly- kets for fire resistance. Spark protection welding blankets are
meric siloxanes with appropriate cross-linkers to provide a common application for peroxide-cured silicone coatings.
compliant, flexible coatings. Among the cure mechanisms Since peroxide-cured silicones require higher temperature
which result in elastomers are the following cures, their usefulness is constrained by the substrate upper
temperature limits. Also, selectivity of the specific peroxide is
1. ~ S i O H + HSi-~- sn ~ ~SiOSiw~ + H2
critical to prevent poor cures due to the oxygen inhibition;
2. ~ S i O H + CH3COOSi~ ~ ~ S i O S i ~ + CH3COOH
3. ~--~SiOH + ROSin--- sn ~ ~ O S i - ~ + ROH characteristic of many peroxides.
Another novel silicone elastomer coating which has been
4. ~SiCH~---CH2 + HSi I~ Pt ~ ~SiCH2CH2Si~
Sn developed is a combination cure involving the ultraviolet
5. ~ S i O H + R2NOSi~-s--~2 ~ S i O S i ~ + R2NOH
photoinitiation via free radical formation to provide cross-
These elastomeric coatings can range from extremely tough, linking. This ultraviolet mechanism is often combined with a
high-strength elastomers to soft gel-like coatings. Typically, standard cure mechanism to provide a combination cure.
the elastomer could have properties within the following This system provides quick surface cure followed by the
ranges: slower room temperature cure of unexposed, shadowed areas
Durometer: Type 00 = 10 to ultimately provide a fully cured conformal coating. Pro-
Type A = 70 cesses using the combination cure can be used to minimize
Tensile Strength: 0.34 to 13.8 MPa the time and space required to hold the coated parts until
Elongation: 50 to 1500% cure is completed before downstream assemblies can take
Tear Strength: 0.88 to 43.8 kN/m place.
Other cure systems have been developed for silicone elasto-
The properties and the cure systems which are chosen for
mers, but they find limited use as coating materials and were
these elastomeric coatings depend, to a large extent, on the
generally developed for specific applications such as building
end use and the method of application. For instance, the
sealants or glazing compounds.
SiOH + HSi (No. 1) mechanism is often used to provide
The most common form for silicone coatings is a disper-
release coatings for backing paper for pressure sensitive ad-
sion of the silicone in solvent. If the coating is based on a
hesives. The actual coating itself has poor strength but attains
tough elastomeric silicone, the uncured elastomer base is
its properties by simply impregnating the substrate.
most commonly described as a dispersion because it contains
The acetoxy cure system (No. 2) is used where one-part insoluble components such as high surface area fumed silica
convenience is desired, where relatively slow cure is accept- for reinforcement and often other solid components such as
able, and where acetic acid given off during the cure is not a titanium dioxide pigments for coloration or reflectivity prop-
problem. erties. The carrier solvent for these dispersions may include
The oxime (No. 5) cure system provides many of the prop- chlorinated hydrocarbons, fluorochlorohydrocarbons, and
erties of the acetoxy cure system, but results in an oxime both aromatic and aliphatic hydrocarbons. The dispersions
leaving group instead of an acetic acid leaving group. Among also often include blends of solvents to provide the proper
the applications for the oxime cure systems are coatings for combinations of flow, evaporation, and application ease.
electronic components and protection for organic compos- Among the most common solvents for silicone dispersions
ites to prevent atomic oxygen degradation, and coating of are 1,1,1-trichloroethane, VM&P naphthas, and xylene. Low-
quartz blankets to provide adequate emissivity and reflectiv- molecular-weight alcohols such as ethanol and isopropanol
ity characteristics for certain thermal protection surfaces on and ketones such as acetone are not suitable because sili-
the space shuttle. The alkoxy 2-part (No. 3) cure system, when cones are generally incompatible with these lower-molecu-
combined with certain thermal enhancing fillers such as iron lar-weight oxygen-containing solvents. Fluorosilicones re-
oxide, glass microballoons, and various fibers, is often used to quire the use of such solvents as methyl ethyl ketone and
provide ablative and thermally insulating coatings. Various methyl isobutyl ketone for adequate dispersing. Fluo-
products incorporating the alkoxy two-part cure system are rosilicone-dimethyl copolymer-based silicones can be dis-
used to protect surfaces and components exposed to plume persed adequately in 1,1,1-trichloroethane for thin layer ap-
radiation from various rocket motors and jet engines. plication.
The addition cure system (No. 4) has characteristics which True solutions can also be made if the silicone contains no
permit rapid heat-accelerated cure, tough physical proper- insoluble components. For example, true solutions can be
ties, virtually nil shrinkage, and, due to the platinum catalyst, made for unfilled silicones or for silicones that are resin
the best overall flame resistance. Applications include solar reinforced. These coatings have limited use, however, be-
cell protection, particularly for satellites, and burn-through cause the final cured elastomeric coating lacks the overall
protection for the liners of solid rocket motors. The only toughness of the filled materials.
negative characteristic of the addition cure system is its sus- Recent developments have resulted in silicone coatings
ceptibility to inhibition. Because the system contains parts- which have not involved the use of solvents. Because of envi-
per-million levels of platinum catalyst, it can be readily ronmental concerns, the use of solvent carriers for disper-
"poisoned." Among the most common inhibitors are sulfur- sions and solutions has become less desirable. In particular,
containing organic rubbers and organo-tin compounds fluorochlorocarbons and chlorinated hydrocarbons, despite
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CHAPTER 1 4 - - S I L I C O N E COATINGS 97
their low toxicity and nonflammability, are being phased out therefore solvent is merely evaporated at ambient pressures.
because of Montreal Protocol Agreements. Similarly, hydro- The solvent evaporation can also be enhanced by air circula-
carbon solvents are undesirable because of their flammabil- tion and by acceleration with heat. However, the application
ity, toxicity, and environmental effects. Silicone-based con- of heat should be limited or applied in a stepwise manner to
formal coatings have been developed without solvent prevent solvent entrapment below the surface resulting in
carriers. However, thin layer applications are difficult unless solvent bubble formation. Also, for one-part silicone coatings
the viscosity is low enough to permit proper coating. Unfortu- which are cured via moisture activation, it is ineffective to use
nately, the technology for high-strength, low-viscosity, 100% heat acceleration because humidity is obviously reduced in a
solids, silicone coating does not exist. The current products, normal air circulating oven. If accelerated cure is required for
therefore, when cured, are very low strength and do not one-part coatings, a steam autoclave may be used, but only
provide coatings that are resistant to handling. Research is after all of the carrier solvent is removed.
ongoing to develop water-based dispersions, but to date, the
demonstrated physical properties, although higher than the
100% solids coatings, are significantly less than the current TESTING CONDITIONS
solvent-based silicone coatings.
The test requirements for silicone coatings include MIL-I-
46058C for qualifying silicone coatings as insulating com-
Methods of Applications pounds for electrical coating applications of printed circuit
The methods of applications for silicone coatings depend board assemblies. MIL-I-46058C includes the following tests:
on the device being coated and the specific type of silicone Curing Time and Temperature
being used. Dipping, spraying, and painting are the most Appearance
common types of application. The thinnest coatings result Coating Thickness
from spraying of two solvent dispersion utilizing standard Fungus Resistance
aerosol spray guns. Needless to say, experience involving Insulation Resistance
aerosol spraying is critical for acceptable coatings. Among Dielectric Withstanding Voltage
the variables to consider are the following: viscosity, solvent, Leakage Current Testing
percent solids, pot life, and cure system choices. Q Resonance
The most securely sealed surface layer is accomplished by Q Resonance after Immersion
dip coating. Again, variables including solvent, bath life, and Thermal Shock
cure systems must be optimized. Additionally, the evapora- Flexibility
tion of solvent during the dip processing needs to be compen- Thermal Humidity Aging
sated for by periodically or continuously adding make-up sol- Flammability
vent to maintain optimal bath viscosity. If a one-part Materials which are used in applications for spacecraft are
humidity-actuated cure system is used, consideration must tested via ASTM Test Method for Total Mass Loss and Col-
be given to provide a dry blanket over the bath to prevent a lected Volatile Condensable Materials from Outgassing in a
partially cross-linked elastomeric skin from forming. Dry ar- Vacuum Environment (E 595). This test is used to determine
gon is often utilized to prevent moisture in the air from the amount of collected volatile condensable material and
reacting with the silicone base coating. Another consider- total mass loss that eludes from a material when exposed to
ation for the dip coatings is the possibility of air bubble 125~ for 24 h at vacuum less than 5 10 .2 torr. Basically,
inclusion. Again, several variables need to be considered. the maximum CVCM value for coatings intended for space
Low viscosity, controlled immersion and withdrawal rates, applications is 0.1% and the m a x i m u m TML is 1.0%. The
and vibration of the bath and/or object to be coated can be coatings intended for satellite applications require these high
used to minimize bubble entrapment. Similarly, the use of levels of purity to prevent the contamination of solar cells,
two distinct solvents with different rates of evaporation are optical surfaces, and other sensitive instrumentation. For
often used to ensure uniform coating with minimal drip re- most silicone materials, extended devolatilization is required
gions and minimal bubble formation. for the polymeric components prior to compounding into the
Painting or brush coating substrates is yet another method finished product.
to apply a uniform silicone coating. Painting, however, is For silicone elastomeric coatings, the physical properties
usually not applicable for either large areas or mass produc- of the cured elastomer are critical parameters. The tensile
tion coatings. For painting application, virtually all of the strength, elongation, and modulus are defined in ASTM Test
variables discussed in the above dipping and spraying also Methods for Rubber Properties in Tension (D 412). Durom-
apply. eter and tear strength measurements are defined in ASTM
Regardless of the methods of application, the cure parame- Test Method for Rubber Property--Durometer Hardness
ters demand significant considerations. Vacuum exposure (D 2240) and ASTM Test Method for Tear Strength of a
may be used to remove air bubbles and to ensure flow under Convential Vulcanized Rubber and Thermoplastic Elastomer
surface irregularities or impregnation of porous substrates. (D 624) respectively. The viscosity, nonvolatile content, and
Vacuum treatment may also be used to enhance removal of specific gravity tests are defined in ASTM Test Method for
the solvents, but care should be taken to prevent evaporation Viscosity of Adhesives (D 1084), ASTM Test Method for
of the reactive volatile components which would prevent cure Weight Loss of Plasticizers on Heating (D 2288), and ASTM
even after removal from the vacuum. Of course, most com- Test Method for Specific Gravity (Relative Density) and Den-
monly, the vacuum removal of solvent is unwarranted and sity of Plastics by Displacement (D 792), respectively.
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Other tests have been developed for silicone coatings to ings. Similarly, silicone elastomeric coatings are produced by
meet the requirements of specific applications. Included the addition of iron oxide, glass or ceramic microballoons,
among these are the "blocking" test to determine the propen- and graphite fibers, which provide ablation protection.
sity of silicone coatings to cause "sticking" to contacted sur- Launch vehicles, launch equipment, and thrust reversers are
faces after application and cure. This test involves contact often coated with specially formulated silicone ablative coat-
between the silicone-coated surface and the surface to be ings. The incorporation of phenyl siloxanes into the basic
tested by subjecting the interface to an applied pressure for a silicone polymeric species provides increased ablative prop~
fixed time followed by measurement of the force needed to erties, and various copolymers--including silicone-boranes
reseparate the surfaces. A variety of tests have been developed and silphenylenes--have and are being evaluated to provide
to measure the adhesive force of the coating on the substrate. protection from impingement of high-energy lasers.
Again, a number of tests which are oriented toward the spe- As discussed previously, the biocompatibility of silicones
cific application have been developed and revised. makes them ideal for medical applications. Coating perma-
nent implants as well as temporary implants with silicones
provides improved safety and efficacy. Foley catheters coated
SPECIFIC APPLICATIONS FOR SILICONE with silicone elastomers result in less patient discomfort and
COATINGS reduced infection rates. For similar reasons, temporary pres-
sure-sensitive silicone adhesive coatings are used to provide
Among the varied applications for silicone coatings is the adhesion directly to the skin. Combinations of silicone coat-
conformal coating of electronic circuit boards. Because of ings are being investigated for use in various drug delivery
their previously described stability properties, silicones make devices. Specifically layered coatings of silicones impreg-
ideal conformal coatings. Silicone coatings typically have nated with drugs can be used for transdermal drug delivery.
stiffening points of -65~ and can be formulated with When combined with a silicone pressure sensitive adhesive, a
stiffening points as low as - 115~ This makes them ideal for complete system of controlled drug delivery devices can be
extreme environment electronic device protection. fabricated.
Silicone coatings are used almost exclusively to provide
protection from atomic oxygen degradation in low earth orbit
(approximately 100 to 500 miles high). Atomic oxygen degra- NEW REQUIREMENTS FOR SILICONE
dation is significant enough to rapidly erode and degrade COATINGS
organic substrates including epoxies, urethanes, and polyes-
ter-based thermosets. Coating protection permits the use of Research and development efforts continue to provide sili-
composite materials in space applications where the advan- cone coatings with even more stringent requirements and
tages of high strength and low weight associated with com- specifications. Electrical coatings with semiconducting prop-
posite materials would be unusable due to their atomic oxy- erties for electronic applications and elastomeric coatings
gen degradation. with volume resistivities in the 10-4 to 10-5 ohm-centimetre
The high-temperature stability and excellent dielectric range are being investigated. Silicone coatings with variable
properties of silicone resins make them ideal impregnant electric properties are also being researched.
coatings for high-energy capacitors used in jet engine ig- Similarly, silicone coatings which provide specific biologi-
nitions. The inherent stability of silicone coatings when com- cal properties are also being developed. Specifically, hydro-
bined with specific fillers including zinc oxide, titanium diox- philic silicone coatings are being developed for reduced
ide, and zinc orthotitanate are often used to provide specific thrombogenicity, and microporous coatings are under devel-
emissivity and reflectance required for thermal control coat- opment for controlled tissue in-growth response.
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MNL17-EB/Jun. 1995
15
Vinyl Resins for Coatings
by Richard J. Burns 1
VINYL RESINS FOR COATINGS History
Definition About 1912 Ostromislenski pioneered the industrial inves-

tigation of vinyl polymers and made and fractionated
THE VINYL RESINS USED IN s o l v e n t - b a s e d c o a t i n g s , i n k s , a n d poly(vinyl chloride). E. W. Reid invented the copolymers of
adhesives are low-to-medium molecular weight co- and vinyl chloride and vinyl acetate in 1928. In 1933, Davidson
tercopolymers of vinyl chloride, vinyl acetate, or other mono- and McClure described applications of vinyl resins including
mers to improve solubility. Functional monomers contribute their use as swimming pool coatings [1].
specific properties; thus, carboxylic acid-containing mono- Commercial production of poly(vinyl chloride-vinyl ace-
mers provide adhesion, while hydroxyl-containing mono- tate) resins was begun in 1936. Carboxyl-modified copoly-
mers contribute to reactivity, compatibility with other resins mers were introduced in 1939 and hydroxyl-modified resins
and polymers, or adhesion to specific surfaces. These modi- in 1945. The first commercial use of these vinyl resins was in
fied vinyl resins are most often used as thermoplastic, sol- 1936 as a coating for the inside of beer cans.
vent-soluble lacquers, though by formulating with appropri- Organosol and plastisol coatings technology that permitted
ate modifiers, air-dry or baking finishes can be produced the use of very-high-molecular-weight resins were developed
having thermoset-like properties. about 1943 [2,3].
Special techniques have been developed that enable the use
of high-molecular-weight vinyl chloride homopolymers as
dispersions in organic media called plastisols or organosols
that require a heat fusion step to form films or coatings. Vinyl
Polymerization
chloride homopolymers and copolymers are also com- Vinyl chloride monomer is a gas at standard conditions
pounded for use as powder coatings for application by either with a boiling point of - 13.9~ Polymerization is carried out
electrostatic spray or fluidized bed techniques. Water-based in autoclaves under moderate to high pressure. The reaction
vinyl chloride polymers and copolymers include high-molec- is typically initiated by free radical generating compounds
ular-weight polymer latexes that require heat to fuse, and also such as peroxides. The polymerization is exothermic, and
aqueous dispersions of low-molecular-weight polymers that reaction temperature regulation is necessary to control the
utilize coalescents to form films at room temperature. growth (molecular weight) of the polymer. The use of high
pressure and low temperature generally favors the formation
of high-molecular-weight resins, and chain transfer agents
are commonly used to control molecular growth. The num-
General ber average molecular weight (M,) of commercially available
solvent-soluble vinyl chloride homopolymers and copoly-
Important characteristic features of vinyl resins/coatings mers ranges from a low of a few thousand to about 45 000.
are: (1) relatively high glass transition temperature; (2) excel- The M, of vinyl resins used for plastisol and organosol coat-
lent resistance to water, alcohols, aliphatic hydrocarbons, ings ranges between about 60 to 110 000 [4].
vegetable oils, dilute acids, and alkali; and (3) inertness in
contact with foods (FDA-listed resins only).
Vinyl resin films can be degraded by exposure to high
temperatures or by long-term exposure to ultraviolet light, Manufacture
with a resultant change in color from clear to amber, red, and Vinyl resins for coatings are made by several processes.
eventually black. Suitable heat stabilizers are employed that Polymerization by solution and suspension processes is used
allow the processing of vinyl coatings at high temperature, to make the solvent-sofuble resins, while emulsion or disper-
while proper pigmentation helps to protect vinyl coatings sion polymerization is used to make the much higher molecu-
from attack by UV light. Some stabilizer systems can provide lar weight polymers for plastisols and organosols. Some sol-
limited protection to clear vinyl films. vent-soluble grades are also made by the emulsion process.
Post-polymerization processes are applied to some resins to
~Union Carbide Corporation, B o u n d Brook, NJ 08805. achieve special properties.
99
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Copyright91995 by ASTM International www.astm.org

Solution Process Vinyl Chloride Copolymer Coating Resins

Polymerization is carried out in a solvent in a batch or Four types of solvent-soluble coating resins offered by
continuous process. The viscosity of the reaction medium Union Carbide are shown in Table 1. These polymers are
increases as m o n o m e r is converted to polymer, and the extent produced by the solution polymerization process.
of polymerization can be monitored and controlled via vis- 1. Vinyl chloride-vinyl acetate copolymers.
cometry. When the appropriate viscosity is attained, the auto- 2. Carboxyl-modified vinyl chloride-vinyl acetate copoly-
clave varnish is stripped of unreacted vinyl chloride monomers.
mer, and the polymer is precipitated by the addition of water 3. Hydroxyl-modified copolymers of two types:
or water/alcohol mixtures; the slurry is centrifuged to remove a. Hydroxyalkyl acrylate modified directly polymerized.
most of the liquid, then the resin is dried in fluid-bed dryers. b. Vinyl-alcohol-modified polymer derived from poly(vinyl
The particle size of the dried resins produced by this process chloride-vinyl acetate) in a post-polymerization process.
ranges from about 75 to about 200 ~m, and the particle shape 4. Epoxy-modified vinyl chloride copolymers.
is irregular.
Other suppliers of solvent-soluble vinyl resins and their
product lines are listed in Tables 2 through 5 for Denka
Kagaku, BASF, Wacker Chemie, and Nissan.
Suspension Polymerization
Suspension polymerization is generally carried out in a FDA Status
water medium. High-molecular-weight water-soluble colloi- Vinyl copolymer resins are listed by chemical identity in
dal polymers are used in small amounts to stabilize the drop- several U.S. Food and Drug Administration regulations such
lets of suspended monomer(s) to control particle size. The as 21CFR 175.300, 176.170, 176.180, and 177.1210 as compo-
stabilizer used remains with the resin during and after poly- nents of coatings on metal and paper substrates for use as
merization and resin recovery. Normally the preparation of food contact surfaces of articles used in processing, manufac-
solutions of suspension resins requires that mild heating be turing packing, producing, heating, packaging, holding, or
employed to achieve m a x i m u m clarity of solutions at mini- transporting food, or as components of closures with sealing
m u m viscosity. Particles of suspension vinyl resins are char- gaskets for food containers. Vinyl chloride-acetate copoly-
acterized as spherical with a size between 100 to 300/~m. mers, hydroxyl-modified vinyl chloride-acetate copolymer,
and several other vinyl chloride copolymers made with
monomers having acid or ester functionality are described.
Emulsion Polymerization
Vinyl Resins--Analysis
Like the suspension process, emulsion polymerization is
also carried out in water, but in place of water-soluble poly- There are many references to chemical methods for identi-
mers, surfactants are normally used to stabilize the smaller fying and characterizing vinyl resins [5,6]. However, the in-
m o n o m e r droplets during polymerization. A special form of frared spectra of vinyl resins are very useful for qualitative
emulsion polymerization called dispersion polymerization and quantitative purposes. Spectra of neat vinyl resins can be
uses an oil-soluble rather than water-soluble initiator and found in sources such as atlases, encyclopedia of plastics, or
produces resin of particles size ranging from about 0.2 to 2 specific papers dealing with the subject [7-9].
/~m. These high-molecular-weight powdered products are Also, several ASTM documents deal with the identification
used in plastisol and organosol coatings. and characterization of vinyl resins used in coatings materi-
als. ASTM Guide for Testing Poly(Vinyl Chloride) Resins
(D 4368-89) describes methods for homo- and copolymer vi-
nyl resins to determine important characteristics such as
Post-Polymerization Process total chlorine content for composition, dilute solution vis-
cometry to assess polymer molecular weight, high and low
Some vinyl-alcohol modified resins are prepared in a two- shear viscosity measurements to characterize vinyl disper-
step process. The first step consists of the preparation of a sion resins for plastisols and organosols [10].
poly(vinyl chloride-acetate) copolymer by either a solution or ASTM Test Method for Infrared Identification of Vehicle
suspension process. Next, the copolymer resin is dissolved in Solids from Solvent-Reducible Paints (D 2621-87) covers the
a suitable solvent and a catalyst is added to partially hydro- qualitative characterization of separated paint vehicle solids
lyze the pendant acetoxy groups to yield a vinyl alcohol moi- by infrared spectroscopy. A spectrum for an ortho-phthalic
ety. The modified resin is then precipitated from solution and alkyd, vinyl chloride-acetate modified vehicle is presented
dried as described for the solution process. The resin thus [11].
formed has only secondary hydroxyl groups, which accounts ASTM D 2124-70 (Reapproved 1988), Test Method for
for its unique solubility/compatibility properties. Analysis of Components in Poly(Vinyl Chloride) Compounds
These vinyl-alcohol-containing resins differ from those Using an Infrared Spectrophotometric Technique, presents
prepared directly using other hydroxy-containing monomers methods whereby vinyl compounds can be separated into
in their compatibility with alkyds and in the rate of reactivity components including resins, plasticizers, stabilizers, and
with coreactants such as isocyanate or amino-formaldehyde fillers. Each component can then be analyzed by infrared
cross-linkers. technique [12].
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CHAPTER 1 5 - - V I N Y L R E S I N S FOR COATINGS 101
TABLE 1--Typical properties of UCAR | solution vinyl resins.

Polymer Composition,
wt% Reactive Inherent Glass Solution
UCAR| Functionality Viscosity, Transition Average Viscosity ~'
Solution Po/y(vinyl Poly(vinyl ASTM Temperature Molecular at 25~
Vinyl chloride) acetate) Other Type Wt% D 1243 (Tg), ~ Wt, M.* cP
VYNS-3 90 10 . . . . . . . . . 0.74 79 44 000 1300 i
VYHH 86 14 . . . . . . . . . 0.50 72 27 000 600
VYHD 86 14 . . . . . . . . . 0.40 72 22 000 200
VMCH 86 13 1a Acid 1.0 0,50 74 27 000 650

VMCC 83 16 1a Acid 1.0 0.38 72 19 000 100
VMCA 81 17 2a Acid 2.0 0.32 70 15 000 55
VERR-40 82 9 9 b'c Epoxy 1.8g~ --- 67 15 000 --.
VAGH 90 4 6d Hydroxyl 2.3 0.53 79 27 000 1000

VAGD 90 4 6d Hydroxyl 2.3 0.44 77 22 000 400
VAGF 81 4 15e Hydroxyl 1.~ ~ 0.56 70 33 000 930

VAGC 81 4 15e Hydroxyl 1.9 0.44 65 24 000 275
VROH 81 4 152 Hydroxyl 2,0 0.30 65 15 000 70
VYES-4 67 11 22 e Hydroxyl 3.0 0.15 54 5 5O0 2O

*Referenced to polystyrene standard.
~Maleic acid.
VEpoxy-containing monomer.
CSolution--40% resin in MEK/toluene 3 2.
aPoly(vinylalcohol).
~Hydroxy alkyl acrylate.
/Oxirane oxygen.
gOn solids.
h30%resin in MEK.
J20% resin in MEK.
TABLE 2 w S o l u t i o n vinyls from Denki Kagaku.

Composition, wt%
Vinyl Vinyl Carboxylic Acrylic Inherent
Grade Chloride Acetate Acid Ester Viscosity
1000A 86 14 . . . . . . 0.5
1000AS 86 14 . . . . . . 0.4
IO00C 86 13 1 --- 0.5
1000CS 86 13 1 -.. 0.4
1000GKT 91 3 ..- 6 0.5
TABLE 3 - - S u s p e n s i o n vinyls for solution coatings--BASF. s t r o n g a d h e s i o n is d e s i r e d , t h e r e a r e s p e c i a l c o a t i n g s s u c h as

Composition, wt% s t r i p p a b l e o r p e e l a b l e c o a t i n g s w h e r e a d h e s i o n is n o t w a n t e d .
Vinyl Vinyl Isobutyl Approximate Solution T a b l e 6 lists t h e r e l a t i v e a d h e s i o n o f s e v e r a l v i n y l r e s i n s t o
Grade Chloride Ether Viscosity," MPa.s various polymers and substrates.
The resin selection may be made on the need for reactive
MP-25 75 25 35
MP-35 75 25 35 functionality to produce cross-linked coatings that change
MP-45 75 25 45 the nature of the coating from thermoplastic to thermoset-
MP-60 75 25 60 like properties that are characterized by improved solvent or
a20% resin solutions in toluene. stain resistance.
Formulation of Solution Coatings Solubility

A typical vinyl coating usually consists of resin, solvent(s),
Variation in the ratio of vinyl chloride to vinyl ester and the
plasticizer, pigments (required for exterior exposure), and d e g r e e o f p o l y m e r i z a t i o n p r o d u c e a w i d e r a n g e o f v i n y l poly-
o p t i o n a l i n g r e d i e n t s s u c h as s t a b i l i z e r s , m o d i f y i n g r e s i n ( s ) , mers with different solubility characteristics. Highest solubil-
and cross-linker(s). ity is f a v o r e d b y l o w v i n y l c h l o r i d e c o n t e n t a n d l o w m o l e c u l a r
T h e r e s i n is n o r m a l l y s e l e c t e d o n t h e b a s i s of its a b i l i t y t o w e i g h t . T h i s r e l a t i o n s h i p i n t e r m s of v i s c o s i t y o f r e s i n s o l u -
p r o v i d e a d h e s i o n to t h e s u h s t r a t e , W h i l e , i n m o s t cases, t i o n s is c o m p a r e d i n T a b l e 1.
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TABLE 4--Suspension vinyls for solution coatings--Wacker Chemie.

Composition,wt%
Vinyl Vinyl Acrylic Inherent
Grade Chloride Acetate Acid Ester Viscosity
E 15/45 85 15 9.. 0.5
H 15/45 85 15 9.. 0.5
H 15/50 85 15 9.. 0.6
H 40/43 60 40 9.. 0.46

H 40/50 60 40 9.. 0.6
H 40/55 60 40 ... 0.7
H 40/60 60 40 ... 9-. 0.88

E 15/45M 84 15 1 9.. 0.5
H 15/45M 82 17 1 9.. 0.56
E 15/40A 85 ..- 15 0.4

E 20/55A 80 ... 20 0.68
E 22/48A 78 7 15 0.56
TABLE 5--Suspension vinyls for solution coatings--Nissan. aromatic h y d r o c a r b o n s a n d m a k i n g up the difference with
Composition,wt% esters a n d aliphatic h y d r o c a r b o n s [13]. Though it was neces-
Vinyl Vinyl Vinyl sary to use more oxygenated solvents, the p e r f o r m a n c e of
Grade Chloride Acetate Alcohol Acid c o m p l i a n t coatings stayed the same. Typical solvent blends
used for spray application a n d the reformulated c o m p l i a n t
MPR-TA 91 3 6 ...
MPR-TS 87 13 . . . . . . systems are shown i n Table 7.
MPR-TM 86 13 ... 1
S o l u t i o n Characteristics
Vinyl solution resins are dissolved by ketones, esters, cer- F r o m the time a vinyl resin is dissolved, the viscosity of
tain chlorinated solvents, a n d some nitroparaffins. As a class, solutions increases with time until a n e q u i l i b r i u m is reached
ketones are the best solvents i n terms of the ability to dissolve after which the viscosity r e m a i n s constant. This behavior is
higher solids at lower solution viscosity. Hydrocarbons are believed due to the f o r m a t i o n of regions of microcrystallinity
chiefly used as diluents primarily to lower cost. Aromatic a n d between polymer molecules in solution. The extent of the
aliphatic h y d r o c a r b o n s c a n be usd as diluents. Aromatic hy- viscosity increase is d e p e n d e n t on: (a) resin molecular
drocarbons, chiefly toluene a n d xylene a n d higher boiling weight; (b) solids c o n t e n t of the solution; (c) a n d the strength
fractions such as Aromatic 100 or 150, are preferred as they of the solvent blend. The viscosity increase m a y be small or so
can be used at high levels, in the range of 50 to 65% of the large that the solution sets to a gel. Properly formulated vinyl
solvent b l e n d depending on the resin composition, molecular resin solutions usually reach a n e q u i l i b r i u m viscosity i n
weight, a n d desired solids. The Aromatic 100 a n d 150 are a b o u t 3 to 5 weeks. Guidelines for the p r e p a r a t i o n of viscosity
usually used only in baking finishes. stable solutions for resins of varying molecular weight are
Aliphatic h y d r o c a r b o n s can be used in limited a m o u n t s , up s h o w n in Table 8.
to a b o u t 30% of the solvent blend. Higher levels can lead to Vinyl chloride copolymer solutions also exhibit what is
viscosity instability, a n d only low boiling aliphatic hydrocar- k n o w n as the m e m o r y effect. W h e n a vinyl resin solution is
bons, those with boiling points up to 117~ are suitable. The heated to a b o u t 60~ the effect of microcrystallinity is elimi-
use of higher boiling aliphatic h y d r o c a r b o n s can cause pre- nated. If the solution is then cooled to its original tempera-
cipitation of the resin d u r i n g drying. ture, the viscosity will n o t immediately r e t u r n to its original
Alcohols are strong precipitants for vinyls a n d are n o t value because of the time lag needed for the effect of the
generally used in unmodified vinyl lacquers. However, in microcrystallinity to redevelop. With time, the viscosity of the
some cases vinyls, usually hydroxyl-modified vinyls, are read- solution will r e t u r n to the same value as that of a solution that
ily formulated with other resins that are carried in alcohol. was not heated. The converse relationship hold w h e n vinyl
With these, up to 15 to 20% alcohol m a y be used in the solvent solutions are cooled. A graphical p r e s e n t a t i o n of the m e m o r y
blend. Careful attention m u s t be paid in vinyl coating formu- effect is presented in Fig. 1.
lations that c o n t a i n alcohols to be sure that problems do n o t
develop d u r i n g application a n d drying of the coatings. Glycol
ethers a n d glycol ether esters are sometimes used in vinyl Plasticizers
coatings to improve flowout of baked coatings. Plasticizers are often used with vinyl resin coatings to im-
I n response to regulations restricting the type a n d a m o u n t prove flexibility, formability, a n d impact resistance of the
of solvents used in coatings, such as Los Angeles Rule 66 a n d coating. M o n o m e r i c as well as polymeric plasticizers or com-
later versions, vinyl coatings were reformulated as c o m p l i a n t patible polymers with low glass t r a n s i t i o n t e m p e r a t u r e (Tg)
systems by reducing the a m o u n t of b r a n c h e d ketones a n d m a y be used to plasticize a vinyl coating.
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TABLE 6RAdhesion of vinyl resins.

Product Type
Hydroxy
Carboxy Modified WB
Copolymer Modified VAGH Vinyl
Substrate VYHH VMCH VAGF AW-875
Steel 0 10 5 0
Galvanized 0 10 5 0
Paper (glassine) 10 10 10 10
Aluminum foil 0 10 7 10
Polyethylene, treated 0 0 0 0
Polypropylene, treated 0 0 0 0
Polysulfone 7 10 10 10
Acrylic 10 10 10 10
PVC plastic I0 10 10 10
ABS plastic 10 I0 10 10
Polycarbonate 10 10 10 10
Polyphenylene oxide 4 I0 0 0
Polyethylene terephtalate 0 0 5 0
Impact polystryene 0 0 0 0
Inked surface 0 5 8-10 5
Rating: 10 = Pass Scotch Tape Test, no loss of adhesion.
5 = Some loss of adhesion, not recommended.
0 = No adhesion.
TABLE 7--Typical solvent mix for spray-applied coatings, Memory Effect

composition, wt%.
180
Compliant with Rule
66/EPA
Non-Regulated Rule 66 Compliant 33/50 Initiative ~
MIBK 50 MEK 14 MEK 7
Toluene or Xylene _ 50
_ Butyl acetate 46 Acetone 3 .g
100% Cyclohexanone 9 MIAK 15
Toluene 12 Butyl acetate 40
Xylene 7 Cyclohexanone 9
VM&P naphtha 1___22Toluene
100 VM&P naphtha 20
6 g
Cooled
~50% reduction of MEK and toluene, which are EPA 33/50 listed solvents.
Ambient
Heated
TABLE 8--Guidelines for viscosity stable solution.
Resin Molecular Maximum Typical Solvent
Weight 10- 3 Resin Solids Blend, wt%
I / I I I
44 VYNS-3 15 MEK/toluene, 67/33 0 1 2 3 4 5

27-34 VAGF, VAGH, 25 MIBK/toluene, 50/50 Weeks
VMCH, VYHH FIG. 1 - M e m o r y effect,
19-22 VAGC, VAGD, 28 MIBK/toluene, 50/50
VMCC, VYHD
15 VERR, VMCA, 33 MIBK/toluene, 33/67 Pigmentation
VROH
5.5 VYES-4 60 MEK/toluene, 10/90 Vinyl coatings are p i g m e n t e d (1) to achieve the desired
color, a n d (2) to prevent degradation of the vinyl resin from
the effect of ultraviolet light for coatings that are i n t e n d e d for
Phthalate, phosphate, a n d glycol ester plasticizers are typi- use outdoors [14]. Most organic a n d inorganic pigments can
cally used. Plasticizers are selected to meet the r e q u i r e m e n t s be used. However, basic pigments m u s t be avoided with
of the coating that m a y include low-temperature flexibility, carboxyl-modified resins, as these pigments can react to form
resistance to extraction by solvents, resistance to migration, irreversible gel.
to humidity, etc. Blends of plasticizers m a y be required to P r i m e or color pigments which absorb UV r a d i a t i o n m u s t
meet specific requirements. Table 9 presents a listing of plas- be used at a level sufficient to protect the vinyl resin. Extender
ticizers that are c o m m o n l y used with vinyl resins. Care m u s t pigments or fillers do n o t absorb UV r a d i a t i o n a n d can only
be exercised in choosing the level of plasticizer as excessive he used in c o m b i n a t i o n with a UV absorbing pigment. For
a m o u n t s tend to make the film soft a n d p r o n e to dirt reten- t i t a n i u m dioxide (TiO2) pigments, a m i n i m u m level of a b o u t
tion. Ordinarily, a level of 25 p h r (parts per h u n d r e d parts 75 p h r is needed to provide resistance to UV light. Other
resin) of plasticizer is considered a b o u t m a x i m u m for use inorganic pigments can be used to replace TiO2 by substitut-
with coating resins. ing o n a n equal volume basis. Organic p i g m e n t s that are
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TABLE 9--Typical plasticizers compatible with solution vinyls.

Phthalates Linear Dibasic Acid Esters
Butyl benzyl phthalzate (BBP) Di-n-butyl sebacate (DBS)
Di-2-ethylhexyl phthalate (DOP) Di-2-ethylhexyl adipate (DOA)
Diisooctyl phthalate (DIOP) Diisononyl adipate (DINA)
Diisononyl phthalate (DINP) Di-2-ethylhexyl azelate (DOZ)
Diisodecyl phthalate (DIDP)
Phosphates
Citrates
Tri-2-ethylhexyl phosphate (TOP)
Acetyl trim-butyl citrate Isodecyl diphenyl phosphate
Epoxies Polymerics
Epoxidized soybean oil (ESO) Adipic acid polyesters
2-Ethylhexyl epoxytallate Azelaic acid polyesters
manufactured to smaller particle size are used at a lower Careful consideration must be given to the selection of the
concentration, and blends of inorganic and organic pigments solvent/diluent mix for organosols to attain the highest solids
are often used to achieve the desired color. Excessive high coupled with good viscosity stability. Commercial organosols
loading of pigments can lead to early chalking. of 50 to 55% nonvolatile by weight are typical.
Plastisols and organosols require a high baking tempera-
Organosols and Plastisols ture of about 350~ (177~ to fuse the films. At elevated
A plastisol is a dispersion of discreet particles of high- temperature, the plasticizer or plasticizer diluent mix exerts a
molecular-weight vinyl homopolymer resin in plasticizer, strong solvating or swelling effect on the dispersed PVC resin
with a low level of heat stabilizers sufficient to prevent degra- particles. At fusion, the resin no longer exists as discreet
dation during baking (fusing). Plastisols normally require a particles, but rather as a continuous, homogeneous film.
minimum amount of about 55 to 60 parts plasticizer per Films of plastisols or organosols need only to reach fusion
hundred parts of resin to form a fluid mix. The viscosity of the temperature and do not have to be held at the fusion tempera-
dispersion is dependent on packing effects, the volume of ture for a long time period. Undercuring or baking at temper-
dispersed resin relative to the volume of liquid plasticizer, the atures lower than that required for fusion will yield films
size and shape of the suspended particles, solvating or swell- deficient in tensile strength, elongation, abrasion resistance,
ing effect of the plasticizer on the resin particles, and the and all other properties.
viscosity of the liquid plasticizer. The relatively high levels of Plastisols and organosols also require the use of heat stabi-
plasticizer needed to produce a flowable liquid mix results in lizers to protect the vinyl resin against degradation during the
the formation of fused films too soft for use as coatings. fusion bake. Heat stabilizers are usually combinations of
Plastisol coatings are usually formulated with the addition of metal salts of organic acids in combination with epoxidized
coarser particle-size PVC resins called extenders from sus- oils or liquid epoxy resins. Special attention must be given to
pension or bulk (mass) polymerization that allow the use of the selection of heat stabilizers for organosols modified with
less plasticizer and thus harder films. Additionally, small solvent-soluble resin, especially when carboxyl-modified
amounts of thinner, usually aliphatic hydrocarbon, are used polymers are used. In such cases, the metallic salts must be
(up to about 10 wt%) to reduce viscosity and provide better avoided as these will usually cause gellation; typically, mer-
flow and leveling of the plastisol coating. Plastisol coatings do capto tin or tin ester compounds are used in combination
not adhere well to most substrates and most often require the with an epoxy stabilizer.
use of a suitable primer. The type of pigment and level of pigment used in pig-
An organosol differs from a plastisol in that much lower mented organosols follow the guidelines given for solution
levels of plasticizer are used. A combination of weak solvents vinyl resins.
called dispersants in combination with hydrocarbon solvents It is, however, more difficult to prepare pigmented
called diluents are used to provide sufficient fluid to make a plastisols because there is generally little solvent used to
fluid dispersion. Because lower levels of plasticizer are used, control viscosity. Low oil absorption pigments must be used
films with much greater hardness can be obtained. to avoid excessively high viscosity.
Commercial organosols are usually modified with a sol-
vent-soluble resin to prevent mud cracking or film splitting
during the bake to fuse the film. The modifier resin may Primers for Plastisols and Organosols
contain carboxyl groups to make self-adherent coatings, or it
may be a hydroxyl containing resin to provide functionality to Plastisol coatings need a primer to develop good adhesion
react with cross-linkers such as amino or phenol/formalde- to metal substrates. An organosol coating may also require a
hyde resins to achieve a degree of thermoset properties. primer if it is not modified with an adhesion-promoting mod-
Though vinyl copolymers are usually the modifier of choice ifier. Suitable primers can be formulated from carboxyl-mod-
for organosols, other polymers such as acrylic polymers may ified vinyl resins and may require the use of thermoset resins
be used. such as amino-formaldehyde or phenolic resins to provide
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CHAPTER 15--VINYL RESINS FOR COATINGS 105
resistance to excessive softening from highly plasticized rine, soups, and so on. Decorative foil for floral wrappings,
plastisol or organosol coatings. decorative labels, and coatings for aluminum foil for the
vapor barrier insulation for construction applications are
also coated with vinyl resin coatings.
MAJOR MARKET AREAS FOR VINYL
COATINGS Inks
R i g i d Packaging The major markets for vinyl inks are on vinyl surface prod-
ucts such as floor and wall coverings, swimming pool liners,
Liners for Interior Surface Coatings, Cans, Can Ends, vinyl upholstery, and garment fabrics. Ink formulation is
Closure~Caps and Crowns quite similar to that used with coatings except solvent choices
The first commercial use for vinyl coatings was as the are somewhat narrowed and higher pigment loadings are
topcoat lacquer for the inside of beer cans. As beverage cans needed to achieve hiding in the thin films typical of inks.
evolved from three- to two-piece construction, the vinyl coat- Vinyl inks are often reverse printed on a clear vinyl film,
ing also changed from lacquer to hydroxy vinyl/amino-form- and the printed film is then laminated to substrates such as
aldehyde thermosets to meet the need for higher corrosion wood or metal to make articles having simulated wood finish.
resistance. Thermoset coatings of epoxy-modified vinyl resin Vinyl inks are printed by gravure or screen process because
with carboxyl-modified vinyl resin are used to coat on coil these presses are compatible with the strong solvents needed
stock. The coated coil stock is then formed into the stay-on for vinyls; flexographic printing is not suitable for vinyls be-
tab can ends, an application that requires excellent mechani- cause the plates are susceptible to solvent attack. Inks for
cal properties to withstand the forming steps without crack- highly plasticized vinyl surfaces are usually formulated with
ing. ester solvents to avoid excessive softening of calendered films
Organosol coatings containing a solution resin component, and puckering of the films.
usually carboxyl-type for adhesion, have also been used on
precoated stock for can ends. Vinyl organosols are further
modified with amino-formaldehyde or phenolic resins to up- Dry Film Printing (Hot Stamp Transfer)
grade chemical resistance and permit the use of such coat- In this application, vinyl inks are printed on a carrier sheet
ings for packaging food that will be autoclaved to sterilize the such as polyethylene terephthalate, polyethylene, polypropyl-
contents [15]. ene, or other suitable surfaces to which the ink will not
Vinyl lacquer and vinyl thermoset coatings are used as size adhere strongly. The inks are applied and dried usually in
coats for metals that are formed in caps and closures for jars web form. When ready for use, the printed carrier film is
or as crowns for beverage bottles. These systems serve as the placed with the inked side on the surface to be decorated. A
primer coat for gasketing compounds made with plastisol or heated die presses the composite to make intimate contact
vinyl resin dry blends. with the surface, so that when the die is removed, the ink is
firmly bonded to the substrate and the carrier is peeled away
cleanly.
Flexible Packaging
Solvent-soluble carboxyl-modified vinyl chloride copoly-
Maintenance and Marine Finishes
mers have good adhesion to most materials used in flexible or
semi-rigid packaging including aluminum foil, paper and Heavy duty marine finishes were developed in the mid-
plastic films such as polyethylene terephthalate, polycarbo- 1940s. These systems consisted of a poly(vinyl butyral) wash
nate, PVC, and cellophane. This type of resin is used for its primer, vinyl-red lead anticorrosive intermediate coatings
adhesion characteristic, ease of heat sealing, and resistance [based on poly(vinyl alcohol)-modified resin needed for adhe-
to attack by the packaged product. The vinyl resin may be sion to wash primer], and vinyl copolymer/wood rosin/
used alone or modified with plasticizers or other resins and cuprous oxide anti-foul top coats. This system has become
polymers to formulate heat-sealable coatings for applications the subject of numerous specifications; many U.S. Govern-
requiring varying degrees of force needed to open the con- ment agencies and agencies of other governments have writ-
tainer. This could range from applications such as blister ten specifications with this coating system specified for use
packaging where the bond needs to be strong enough to cause below the waterline of ships.
substrate failure when the package is opened, to items such Because of their good water resistance, good weathering
as jellies or cream containers found in restaurants where a qualities, flexibility, fast dry and ease of application, and
tight but readily peelable bond is required. repair, vinyls quickly became established as maintenance fin-
Vinyl coatings are also used to coat collapsible metal tubes ishes. This area includes coatings for locks, dams, appurte-
for packaging materials such as pharmaceutical prepara- nant structures for waterways, interior linings for potable
tions, toothpastes, and the like where the need is for a very water tanks, steel structures such as bridges, electrical
flexible coating that will not crack nor be attacked by the towers, equipment in chemical plants, and the like. Many
contents of the package even though high stresses from col- specifications have been written that require the use of vinyls
lapsing and rolling up the tube are encountered. as maintenance paints [16,17].
Other applications include decorative coatings for the alu- The early vinyl maintenance and marine finishes were ap-
minum foil paper laminates for cigarette packaging, food plied by air atomizing spray guns at low solids. Several coats
wrappers for fast food restaurant items, for butter, marga- were needed to attain coverage sufficient for good corrosion
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protection. High-build airless spray-applied vinyl coatings PVC Latex

were developed in the 1970s to fill the need for coatings
Emulsion polymerized vinyl chloride homopolymers and
systems that could be applied in fewer coats at less expense
copolymers are used in the latex form not so much to make
[18].
finished coatings but rather as material coated on a base or
support to provide the substrate for items such as wall cov-
Wood Finishes erings, backing for carpeting, and the like. In a sense, such
use could be considered analogous to a waterborne version of
Reactive heavy duty vinyl finishes for wood have been de-
an organosol coating. The vinyl chloride homopolymers need
veloped consisting of a hydroxyl-modified vinyl resin cross-
to be modified with a substantial loading of plasticizer, and
linked with amino/formaldehyde resins. Alkyd resins were
some grades are sold as preplasticized latexes. These water-
often added to improve film build. Such finishes became
based materials require a high temperature bake to fuse the
established as the standard for kitchen cabinets because of
resin plasticizer mix into a continuous film.
their retention of excellent adhesion and water resistance,
By varying the type and amount of comonomer used to
particularly when the coated wood becomes wet from high
make emulsion polymerized copolymer latexes, lower Tg
humidity or water splashing. These finishes also have excel-
products are available that can use lower temperature bakes
lent resistance to a variety of household chemicals, solvents,
to form films.
and stains and have been used as fine furniture finishes [19].
Magnetic Recording Media Waterborne Vinyl Dispersions

Waterborne vinyl dispersions made from solution-poly-
Vinyls, especially hydroxy-modified vinyls, have been used
merized vinyl copolymers became available in the 1980s.
as binders for magnetic iron oxide tapes since the beginning
These waterborne vinyl dispersions are of medium molecular
of the development of tape recording. The vinyl resins are
weight and have high Tg, about 80~ Coalescents are needed
used because of their good adhesion, abrasion resistance, and
with these products to form a film. Some dispersions are
good pigment wetting properties. The early binder formula-
available with a glycol ether coalescent already present in the
tions used alkyd resin as plasticizers, then polyesters; cur-
product, and a co-solvent free variety is also available. With
rently, polyurethane resins are used as the plasticizer as the
the latter, the formulator can choose whichever coalescent,
technology of tapes advanced and placed more stringent re-
glycol-ether, glycol-ether ester, plasticizer, or blend of co-
quirements on the performance of magnetic tape for audio
alescents that best meets performance requirements. A line of
and video [20].
waterborne vinyl dispersions is shown in Table 10.
Waterborne vinyl dispersions are used in many ink, coat-
Powder Coatings ing, and heat-sealable coating applications where solvent-
based vinyl coatings had been used.
Vinyl powder coatings are formulated with vinyl chloride
homopolymers and copolymers for application by fluidized
bed, powder spray, or electrostatic powder spray. Powder Trends i n V i n y l Coatings
coatings are prepared by dry compounding resins, plasti-
cizer, pigments, and additives in ribbon blenders followed by To meet the VOC requirements that are either in place or
attrition or dispersion to powder in mixers such as the proposed for the future, developments in vinyl coatings have
Henschel mixer. Some powder coatings are prepared by a centered on high solids and waterborne systems.
melt mix technique followed by cryogenic grinding. This lat- For high solids vinyl coatings, substantially increased resin
ter technique produces powders of smaller particle size [21]. solubility was achieved by reduction in the polymer molecu-
Powder coatings prepared by dry compounding are usually lar weight, so that viscosity stable solutions could be pre-
applied by fluidized bed or by spray techniques. The metal pared at two to three times the level of solids content that was
parts are heated for fluid bed application so that the powder possible with earlier vinyl resins. However, at the low molec-
will adhere to the part and begin to flow to form a film. A bake ular weights needed for high solubility, the performance of
after the powder application is needed to complete the film- coatings made from such resins was greatly reduced in terms
forming process by fusion or melting. of chemical resistance and physical properties. As a result,
Cryogenically ground powder coatings are applied by elec- high solids vinyl resins are modified to contain hydroxyl func-
trostatic powder spray. With the electrostatic method, it is tionality to allow for reaction with added coreactant materi-
not necessary to preheat the parts, but a bake is necessary als to build molecular weight. Though the high solids resins
after application to fuse the powder to a film. The finer parti- may be used alone for less demanding applications, they are
cle size allows the deposition of smoother and thinner films
than is attainable from fluidized bed or powder spray pro- TABLE 10--A line of waterborne vinyl resins dispersions.
cess. However, the high costs of cryogenic grinding made
Composition, wt%
these materials substantially more expensive than dry grind-
ing and as a consequence, the cryogenic ground powders Grade Solids Water~ Cosolventb pH
account for only a small share of the PVC powder-coating AW-850 38 50 12 7.0
market. AW-875 39 61 ..- 7.0
PVC powder coatings are used to coat products such as aContains less than 2% amines.
pipe, fencing, and metal furniture. bEthylene glycolmonobutylether.
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b e s t used either as a reactive system, with a m i n o - f o r m a l d e - [9] An Infrared Spectroscopy Atlas for the Coatings Industry, 4th ed.,
h y d e o r isocyanate cross-linker, o r as modifiers for alkyds, Vols. I and II, D. R. Brezinski, Ed., Federation of Societies for
polyester-isocyanate, o r e p o x y - a m i n e coatings to i m p r o v e Coating Technology, Philadelphia, 1991.
initial drying o r set-to-touch rate, or to improve r e c o a t a b i l i t y [10]ASTM Guide for Testing Poly(Vinyl Chloride) Resins
[21]. (D 4368-89), ASTM Book of Standards, Vol. 06.03, American
The waterborne vinyl dispersions previously described rep- Society for Testing and Materials, Philadelphia, 1993.
[11] ASTM Test Method for Infrared Identification of Vehicle Solids
resent an alternative to high solids vinyls as a way to for-
from Solvent-Reducible Paints (D 2621-87), ASTM Book of Stan-
mulate low VOC coatings. The waterborne vinyls are compat-
dards, Vol. 06.01, American Society for Testing and Materials,
ible with a wide variety of other waterborne resins with low Philadelphia, 1993.
VOC content such as acrylics, alkyds, urethanes, and amino- [12] ASTM Test Method for Analysis of Components in Poly(Vinyl
formaldehyde cross-linkers. Chloride) Compounds Using an Infrared Spectrophotometric
Technique [D 2124-70 (1988)], ASTM Book of Standards, Vol.
08.01, American Society for Testing and Materials, Philadel-
phia, 1993.
REFERENCES
[13] Burns, R. J. and McKenna, L. A., Paint and Varnish Production,
February 1972.
[1] Industrial and Engineering Chemistry, Vol. 25, No. 6, June 1933.
[14] Hardman, D. E. and Brezinski, J. J., "Pigmented Vinyl Copoly-
[2] Myers, R. and Long, J. S., Eds., Treatise on Coatings, Film Form-
ing Compositions, Vol. 1, Part II, Dekker, New York, 1968. mer Coatings: A Discussion of Factors Influencing Exterior
[3] Powell, G. M., Federation Series on Coatings Technology, Unit 19, Durability," Official Digest, Vol. 36, No. 476, 1964, pp. 963-984.
Federation of Societies for Paint Technology, Philadelphia, [15] Good, R. H., ACS Symposium Series 365, American Chemical
April 1972. Society, Washington, DC, 1988, pp. 203-216.
[4] Breziuski, J.J., Koleske, J.V., and Potter, G.H., "Hydrody- [16] Corps of Engineers CW-099040, U.S. Department of the Army,
namic Properties of Vinyl Chloride-Vinyl Acetate Copolymers in August 1981.
Dilute and Concentrated Solutions," Proceedings of X1 Congress [17] Steel Structures Painting Council, Pittsburgh, PA, Paint No.
FATIPEC, Florence, Italy, 1972. SSPC-9.
[5] Paint Testing Manual, ASTM STP 500, 13th ed., G. G. Sward, Ed., [18] Martell, R. J. and Yee, A., Journal of Protective Coatings and
ASTM, Philadelphia, 1972. Linings, Vol. 5, No. 9, September 1988.
[6] Crompton, T. R., Analysis of Plastics, Pergamon Press, New [19] Mayer, W. P., Journal of the Oil and Colour Chemists Associa-
York, 1984. tion, Vol. 73, No. 4, April 1990.
[7] Infrared Spectra Atlas of Monomers and Polymers, Sadtler Re- [20] Kreiselmaier, K.W., "Pigmentation of Magnetic Tapes," Pig-
search Labs, Philadelphia, 1980. ment Handbook, Vol. Ill: Applications and Markets, T. C. Patton,
[8] Burley, R. A. and Bennett, W. J., "Spectroscopic Analysis Ed., John Wiley & Sons, New York, 1973.
of Poly(Vinyl Chloride) Compounds," Applied Spectroscopy, [21] Ginsberg, T., "Vinyl-Modified Epoxy Coatings," Modern Paint
APSPA, Vol. 14, 1960, p. 32. and Coatings, November 1988.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Miscellaneous Materials and 16

Coatings
by Joseph V. Koleske 1
THIS CHAPTER IS CONCERNED WITH A VARIETY of products that HO--[CH(CH3)--CH2~L - O - R - O - [ C H 2 - C H ( C H 3 ) ] b - O H

are not discussed elsewhere in the manual. Some topics are Poly(propylene oxide) Polyol
mentioned only briefly to indicate that the area has not been
H--[O(CH2)40--CO(CH2)4CO].--O(CH2)40--
forgotten and that the topic is not within the scope of the
[CO(CH2)4CO--O(CH2)40]v--H
manual.
Poly(1,4-butanediol adipate) Polyester Polyol
H--[O(CH2)5CO]s--O--R'--O--[CO(CH2)sO]t--H
POLYOLS
Poly+caprolactone Polyol
Polyols, or polyalcohols as they are sometimes known, are trifunctional hydroxyl compounds though the adipates are
compounds containing one or more, but usually two or more, almost always difunctional in nature. Higher functional
free hydroxyl groups. Most definitions, and particularly those polyols are known and available, but their usage is less com-
over ten years old, list typical polyols as compounds such as mon than that of the di- and trifunctional products. In the
ethylene glycol, propylene glycol, neopentyl glycol, glycerol above structural formulas, R and R' may be the same or
or glycerin, trimethylolpropane, pentaerythritol, and sorbitol different and - - O - - R - - O - - and - - O - - R ' - - O - - are the resi-
that were used in the preparation of alkyds and polyesters. dues of the polyhydric alcohol initiators.
Today the word "polyols" is far more encompassing and more Difunctional and trifunctional PPOs are usually initiated
often than not refers to alkylene oxide [1 ] and E-caprolactone with 1,2-propylene glycol and glycerol, respectively. The adi-
[2] adducts of the above-mentioned and other monohydric or pate polyols are usually prepared with an excess of diol, so
polyhydric alcohols, low-molecular-weight polyesters pre- most end groups are hydroxylic rather than carboxylic in
pared from the above mentioned as well as other polyhy- nature. Since these polyols are prepared by a condensation
droxyl compounds and dicarboxylic acids (particularly adipic reaction, there is no need for an initiator. Caprolactone
acid) [3-5], polytetrahydrofurans prepared by a cationic polyols are initiated with a variety of diols and triols such as
ring-opening polymerization of tetrahydrofuran [6, 7], and diethylene glycol, ethylene glycol, 1,4-butanediol, trimethylol
low-molecular-weight polycarbonates [8-10]. There are propane, glycerol, etc. The above structure for PPO indicates
other compounds that meet the above definition, but they are that the hydroxyl groups are both secondary, which is the
not usually termed polyols. Compounds such as these are usual case. However, from time to time a primary hydroxyl
certain vinyl chloride copolymers, hydroxyl-containing glyc- group will be found due to an unexpected opening of the
idyl ether compounds, vinyl alcohol copolymers, and so on. propagating 1,2-epoxide. The subscripts a, b, u, v, s, and t in
This chapter will not be concerned with these latter com- the above structural formulas can be the same or different,
pounds since they are dealt with elsewhere in the manual. and they can take on a wide variety of values with the number
Polyols are important compounds used in the manufacture average molecular weight ranging from about 150 to 3000 for
of alkyds and polyurethane coatings, of intermediates used in polyols usually used in coatings. Details about preparation of
radiation curable formulations, as copolymerizable ingredi- urethane coatings based on polycaprolactone polyols for ri-
ents in high solids and cationic photocure systems, as well as gid substrates [11] and flexible substrates [12] are available.
in a number of other end uses including elastomeric fibers, A variety of other specialty polyols also exist such as
dentistry, artifact preservation, and pharmaceutical prepara- poly(butylene oxide) and polybutadiene polyols, which are
tions. The two main classes of polyols used in coatings are the useful when very high levels of barrier hydrophobicity are
polyether polyols, which are typified by the poly(propylene needed [13]. Poly(tetramethylene oxide) polyols also have
oxide) polyols (PPO), and the polyester polyols, which in- good hydrophobic character. New polyols are also being de-
clude both poly(glycol adipates) (PEA) and poly+capro- veloped, including polyols based on lactose that have flame-
lactone polyols (PCP). Both classes of polyols are available as retardant characteristics as well as polyols with different end
difunctional and capping, etc. [14]. Although new polyols such as these are
often designed, for use in the manufacture of polyurethane
~Senior consultant, Consolidated Research, Inc., 1513 Brentwood foams and elastomers, they can be and are used in coating
Road, Charleston, WV 25314-2307. formulations.
108
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CHAPTER 1 6 - - M I S C E L L A N E O U S 109
End capping polyols can provide adducts with different Polyurethane Raw Materials: Determination of Gardner and
properties. For example, poly(propylene oxide) polyols which APHA Color of Polyols (D 4890).
contain terminal secondary hydroxyl groups can be end cap-
ped with ethylene oxide to provide polyols with more reactive
primary hydroxyl groups [1, 7]. Ways to apply nuclear mag- CYCLOALIPHATIC E P O X l D E S
netic resonance to measure the ethylene oxide content of
these and other propylene oxide/ethylene oxide copolymers is Although the topic of epoxides in coatings is the subject of a
detailed in ASTM Test Methods of Polyurethane Raw Materi- separate chapter in this manual, that chapter deals with glyc-
als: Determination of the Polymerized Ethylene Oxide Con- idyl or 1,2-epoxides that are not attached to a ring structure.
tent of Polyether Polyols (D 4875). Also described in the liter- Such epoxides are the largest volume products of all epoxides
ature [1, 7] are polyols modified to have amine, allyl, carboxyl, used, and the main products in this class are the diglycidyl
cyano, and vinyl ether end groups. Glycols that are solid ethers of bisphenol A. However, there is a special class of
and/or that have subliming characteristics, as 2,2'-dimethyl- epoxides, termed "cycloaliphatic epoxides," that are used in
3-hydroxypropyl 2,2'dimethyl-3-hydroxypropionate, can be specialty coatings and in cationic radiation-cure coatings.
modified with a few ethylene or propylene oxide groups to These epoxides are characterized by a saturated ring struc-
yield new polyols that are liquid, have low viscosity, and do ture that imparts a high degree of weatherability and excel-
not sublime with even a few molecules of ethylene oxide lent electrical properties such as dielectric constant, dissipa-
having nil or very little effect on moisture resistance [15]. tion factor, dielectric breakdown voltage, etc., to coatings and
Polyols can be end capped with an anhydride to form adducts other products made from them. The good weatherability of
that have free carboxylic acid functionality or a mixture of it the cycloaliphatic epoxides is apparent from the fact that they
and hydroxyl functionality as has been done with the poly-~- have been used for decades to make the large electrical insu-
caprolactone polyols [I 6] or the alkylene oxide capped glycols lators used in substations [20]. These compounds react well
[17]. In other instances, poly(propylene oxide) polyols have with carboxylic acids, as evidenced by their time-honored use
had carboxyl groups grafted to their backbone with acrylic or as acid scavengers, and this reactivity often forms the basis
methacrylic acid. These grafted polyols retain their original for their use in coating formulations.
hydroxyl end groups and are used in coating formulations The main commercial cycloaliphatic epoxide is 3,4-ep-
[18]. oxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate that
Polyols can be incorporated into alkyds, made into mois- has the structure
ture-curing urethanes, can be cross linked with aminoplasts,
H H H H
and can be cross linked with cycloaliphatic epoxides when \/ k/ H
terminated with carboxylic acid end groups. In using the O
/c\ II /c\ /
polyols, the hydroxyl number [19] is their most important
physical characteristic to be measured and used. Five wet
chemical methods and two nuclear magnetic resonance
methods for determining the hydroxyl number are given in
H/ \/c\ / \/c\ / \ H
ASTM Method for Testing Polyurethane Polyol Raw Materi-
als: Determination of Hydroxyl Numbers of Polyols (D 4274) H H H H
and in ASTM Method for Testing Polyurethane Raw Materi- This epoxide is well known by the familiar name designation
als: Determination of Primary Hydroxyl Contents of Poly- ERL-4221. Table 1 contains the properties of this epoxide and
ether Polyols (D 4273), respectively. The equivalent weight or other cycloaliphatic epoxides that are commonly known in
combining weight of a polyol is determined from the hy- the industry. Epoxide equivalent weight can be determined
droxyl number by the following relationship with ASTM Test Methods for Epoxy Content of Epoxy Resins
Equivalent Weight = 56 100/Hydroxyl Number (D 1652). Manufacturers can also be helpful in supplying
information about methods of analysis for specific products.
when potassium hydroxide is used as the titrating agent. Of Usually these epoxides are reacted with polyols that function
course, if functionality is known, polyol molecular weight can as flexibilizing agents for the highly cross-linked polymeric
be calculated by multiplying the equivalent weight by the network that results. These epoxides polymerize by nucleo-
functionality. Manufacturers provide information about hy- philic attack on the epoxide ring to form an ether linkage and
droxyl number and usually about methods for analytically a hydroxyl group on the ring. The hydroxyl group that is
determining it. formed on the ring is quite acidic in character andwill readily
Another important reactivity parameter is the acid number open other cycloaliphatic epoxide groups.
described in ASTM Test Method for Polyurethane Raw Mate- In the coatings industry, cycloaliphatic epoxides are used
rials: Determination of Acid and Alkalinity Numbers of as a major formulating ingredient in cationic, photocurable
Polyols (D 4662). Acidity and alkalinity in polyols can affect formulations [22]. Usually they are formulated with polyols,
reactivity, shelf life, color, and hydrolytic stability of coatings onium-salt photoinitiators, and other ingredients. The onium
prepared from polyols. Polyethers and poly-ecaprolactone salts photolyze in the presence of ultraviolet light to form
polyols usually have very low acid numbers. However, due to strong protic acids that cause rapid polymerization of the
the nature of the condensation reaction coupled with transes- epoxides as well as their copolymerization with active hydro-
terification used to produce polyester polyols, these polyols gen compounds such as polyols. The presence of alkalinity
have relatively high acid numbers. Color, which has obvious including even very weak bases can result in neutralization of
implications, can be determined with ASTM Test Method for the protic acids formed by photolysis. Since the protic acids
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TABLE l--Commercial cycloaliphatic epoxides and their physical properties [20,21].

Specific Color, 1933 Epoxide
Viscosity, cP Gravity, Gardner Equivalent Boiling Point, ~ Vapor Pressure Solidification or
Chemical Name at 25~ 25/25~ (max) Weight (mm Hg) at 20~ m m Hg Glass Point, ~
3,4-Epoxycyclohexylmethyl3,4- 3"50-450 1.175 1 131-143 354 (760) <0.1 -20
epoxycyclohexane carboxylate
Bis(3,4-epoxycyclohexylmethyl)adipate 550-750 1.15 1 190-210 258 (10) <0.1 9
2-(3,4-Epoxycyclohexyl-5,5-spiro-3,4- 7000-17 000 1.18 2 133-154 >250 (760) <0.01 <0
epoxy)cyclohexane-m-dioxane at 38~
1-Vinyl-epoxy-3,4-epoxycyclohexane <15 1.18-1.10 1 70-74 227 (760) 0.1 -55
function as initiators, their neutralization will cause a TABLE 2--A partial listing of polymeric films available for
marked decrease in polymerization rate. It may even result in coating or other uses [27].
nil reactivity. Coatings such as these are used as conformal Available as
coatings [23-25] in the electronics industry because of their Type Polymer Conventional Film shrink Film
excellent electrical (MIL-I-46058C approved, QPL Type ER) Cellophane Yes No
flammability (UL QMJU2 at a 2-mil thickness) and water Cellulose acetate Yes No
permeability properties, as exterior can and other packaging Cellulose acetate-butyrate Yes No
coatings, overprint varnishes, printing inks for paper and Cellulose triacetate Yes No
metal, etc. Ethylene/vinyl acetate Yes
copolymer
Cycloaliphatic epoxides have been reacted with the free Fluorocarbon Yes No
carboxylic acid groups on anhydride adducts of polyols [26]. Ionomer Yes No
Such coatings are characterized by pot lives of less than 8 h, Nylon Yes Yes
high solids, and low-temperature curing capabilities with Polycarbonate Yes No
Polyester Yes Yes
very high gloss and depth of image, high hardness, excellent Polyethylene Yes Yes
solvent resistance, adhesion, and toughness. In other in- Polyethylene linear low density Yes No
stances, the epoxides have been reacted with polyols in the Polypropylene, nonoriented Yes No
presence of triflic acid salts (as diethylammonium triflate, 3M Polypropylene, oriented Yes Yes
Polyurethane Yes No
Co.). In this case, shelf lives of more than eight months have Poly(vinyl alcohol) Yes No
been obtained and the formulated systems have high solids Poly(vinyl chloride) Yes Yes
coupled with low viscosity and low temperature-cure charac- Polyvinylidine chloride Yes Yes
teristics. Cured coatings have an excellent balance of proper-
ties similar to those described above.
ode sputtering, and ion plating of aluminum, copper, chro-
mium, gold, silver, and silicon monoxide [32]. Many special
COATING FILMS effects can be produced including multilayers for cost and
protection, iridescent effects by using compounds with high
Films of many different polymers are available in different (CeO2, ZnS) and low (MgF2, SiO) refractive index, dyeing--
forms for use as functional and decorative coatings, adhesive particularly of aluminum to achieve a gold color and other
backings, and other uses. Some of these materials [27,28] are colors, and glass coatings on plastic optical parts. Coatings
listed in Table 2. A directory of film manufacturers that lists formed by such vacuum deposition processes are most often
the manufacturer product name or number and a short de- applied to plastic substrates with end uses for the coated
scription of the product is available [29]. Full description of parts including automotive parts, plastic and paper webs for
these films and their uses is beyond the intent and scope of decorative and functional packaging of cosmetics, drugs,
this manual. clothing, foods, etc., household fixtures, data storage sys-
tems, optical components, semiconductor devices, and glass
for automotive and architectural applications. As indicated
METALLIC COATINGS [28,30,31] above, the packaging industry has a very large use for thin
metallic films on paper and plastic substrates.
Metallic films are used in a variety of ways. Some metallic A new plasma technique [33] known as unbalanced magne-
coatings are described elsewhere in this manual. The previ- tron sputtering (UBM) has advantages over conventional bal-
ously described coatings are formulations wherein powdered anced magnetron sputtering (CBM), which is usually used to
or flaked metals are combined with a binder. However, solid metalize silicon wafers and architectural glass. In such tech-
metallic films are used as coatings in other ways familiar to niques, an argon plasma is used to remove atoms from a
us. Such films are both functional and decorative in nature. negatively charged target, and magnets are then placed at the
Metals can be applied to plastics and glass by a variety of outer edges of the target, which is made the cathode. Each of
processes including the physical vapor deposition processes the magnets produces a field of the same strength, and be-
known as vacuum metallizing by thermal evaporation, cath- cause of this the system is termed "balanced." This conven-
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CHAPTER 16--MISCELLANEOUS 111
tional system works well when the substrate is silicon and the Phenoxy
coating is thin. However, in certain end uses, thick, dense
Polyhydroxyethers which are commonly known as phe-
coatings with excellent adhesion are required, and it is herein noxy polymers or merely phenoxy, are high-molecular-
that UBM has significant advantages for applying coatings of weight, high-performance thermoplastic materials that are
hard, wear-resistant alloys such as TiN, NbN, TiC, CrN, similar in character to the diglycidyl ethers of bisphenol A
TiNbN, and the like to metal-cutting saw blades and other that are described in Fig. 1 of the manual chapter entitled
tools, cams, and gears. "Epoxy Resins in Coatings." However, there are significant
Metallic and ceramic coatings are also applied to metals by differences that make the phenoxy polymers separate and
a thermal spray technique in which a metallic or ceramic unique polymers [37-39]. These polymers have the structure
wire, rod, or powder is melted and driven through air or a
--[O--C6H4--C(CH3)2--C6H4--O--CH(OH)--CH2]n -
vacuum at high velocities [34,35]. The molten material,
which can range from soft, abradable nickel-graphite to hard where n is about 100, indicating a molecular weight of about
ceramic zirconia, is deposited on a surface of base metal to 30 000 compared with a molecular weight of about 300 to
which it bonds through chemical and mechanical processes. 10 000 for the diglycidyl ethers of bisphenol A. In addition,
Thermally sprayed coatings are used as abrasion, corrosion, phenoxy polymers do not have active epoxide end groups and
and heat barriers for expensive machined components, cast- are thermally stable materials with no limit on shelf life, are
ings, and other parts used in hostile chemical, mechanical, tough and ductile, and can form useful, resistant films by
solvent evaporation without cross-linking. The hydroxyl
and thermal environments encountered in automotive,
functionality associated with phenoxy polymers provides a
spacecraft including aerospace and aircraft, and industrial
site for cross-linking with isocyanates, epoxides, or ami-
applications. The special protection provided by these coat-
noplasts. Films from these polymers are considered to have
ings is needed to improve reliability and durability. excellent physical and chemical resistance properties when
Other metal deposition processes for protective, cost sav- the polymer is in a thermoplastic form, but if improved resist-
ings and/or decorative coating metal, glass, and plastics in- ance to certain solvents is needed, the polymers may be cross-
clude electrodeposition by electroplafing (Cu, Ni, Cr) and linked. The high molecular weight of these polymers results
electroless plating (Cu) and galvanizing (Zn). Other than this in relatively low solids (-20%) coating systems, and this
brief introduction, the metallic coatings mentioned in this might be a restriction to their use in today's climate for high
short chapter are beyond the scope and intent of the manual solids. The excellent properties of these polymers has led
and will not be treated further. researchers into investigations of ways for advancing
molecular weight of the diglycidyl ethers of bisphenol A dur-
ing the curing stages [40].
SPECIALTY ORGANIC COATINGS
Polysulfides Parylene Coatings [41,42]
Parylene coatings are applied by exposing a substrate to a
Liquid polysulfide coatings [36] have excellent barrier
gaseous atmosphere of p-xylylene. The gaseous m o n o m e r is
properties due to low permeability, good chemical and
stable, but when it is condensed on a substrate it spontane-
weather resistance, adhesion, low shrinkage, and low-tem- ously polymerizes to form high-molecular-weight, linear,
perature flexibility coupled with good stress relaxation char- poly(p-xylylene), which is commonly known as parylene [43].
acteristics. These coatings are based on polysulfide polymers The resultant coating of crystalline polymer provides a
prepared pinhole-free coating with an outstandingly uniform thickness
HS--(C2HaO--Ctf2OC2Ha--S--S)xC2H4OCH2OC2H4SH and conformality even over pointed objects such as a needle.
The polymer has excellent electrical properties, including
from bis(2-chloroethyl)formal, 1,2,3-trichloropropane and high dielectric breakdown voltage, low dielectric constant
sodium polysulfide. The polymers are available in a molecu- and dissipation factor, and high-volume resistixdty due to low
lar weight range of 1000 to 8000. The thiol or mercaptan end moisture absorption and freedom from ionic impurities.
groups of this polymer provide sites for curing in an oxidative Parylene is used for coating printed wiring assemblies, semi-
manner with manganese dioxide, dicumene hydroperoxide conductors, capacitors, electrets, contamination and corro-
and organic peroxides in general, p-quinonedioxime, by reac- sion control, medical and surgical devices, as well as similar
tion with glycidyl epoxides in the presence of tertiary amines, end uses that require an inert coating that can be uniformly
or by reaction with multifunctional isocyanates. The poly- applied in a very thin film.
mers are used as rubbery coatings and sealants in buildings
and civil engineering projects requiring excellent ultraviolet
light resistance and other general weatherability properties. REFERENCES
Polysulfide coatings have been commercially used for over 50
[I] Bailey, Jr., F. E. and Koleske, J. V., Alkylene Oxides and Their
years. The most recent use of the polymers is to provide Polymers, Marcel Dekker, Inc., New York, 1991.
chemically resistant barrier coatings on chemical-contain- [2] Hostettler, F. and Young, D. M., U.S. Patent 3,169,945 (1965).
ment storage-tank dikes that protect the environment from [3] Dombrow, B. A., "Esterification Process," U.S. Patent 3,162,616
chemicals that could cause serious pollution problems. (1964).
www.iran-mavad.com

1 12 PAINT AND COATING TESTING MANUAL
[4] Le Bras, L. R. et al., "Oxides of Tin as Catalysts in the Prepara- [23] "ENVIBAR UV1244 and UV1244T EnvironmentalBarrier Coat-
tion of Polyesters," U.S. Patent 3,157,618 (1964). ings," Specialty Coating Systems, Inc., Indianapolis, 1988.
[5] Voss, H., "Process for Making Polyester Polyols Having a Low [24] Koleske, J. V., "Conformal Coatings Cured with Actinic Radi-
Acid Number," U.S. Patent 3,907,863 (1975). ation," U.S. Patent 5,043,221 (1991).
[6] Dreyfuss, P. and Dreyfuss, M. P., Advances in Polymer Science, [25] Koleske, J. V., "Conformal Coatings Cured with Actinic Radi-
Vol. 4, 1967, p. 528. ation," U.S. Patent 5,155,143 (1992).
[7] Bailey, F. E. and Koleske, J. V., "Polyoxyalkylenes," Ullmann's [26] Smith, O. W. and Koleske, J. V., U.S. Patent 4,086,293 (1978).
Encyclopedia of Industrial Chemistry, Vol. A21, VCH Publishers, [27] Anon., "Materials Listing," Packaging, Vol. 34, No. 3, February
Inc. Weinheim, Germany, 1992, pp. 579-589. 1989, pp. 110-111.
[8] Hostettler, F. and Cox, E. F., U.S. Patent 3,301,824 (1967). [28] Packaging Encyclopedia, Cahners Publishing Co., Newton, MA,
[9] Harris, R. F., Joseph, M. D., Davidson, C., Deporter, C. D., and 1989.
Dais, V.A., "Polyurethane Eastomers Based on Molecular [29] Satas, D., "Directory of Films Manufacturers," 2d ed., Satas &
Weight Advanced Poly(ethylene ether carbonate) Diols. I. Com- Associates, Warwick, RI, 1990.
parison to Commercial Diols," Journal of Applied Polymer Sci- [30] Winterhalter, H., "Vakuum-Bedampfen yon Kunststoff-Form-
ence, Vol. 41, 1990, pp. 487-507. teilen," Veredeln von Kunstoffe-Oberfldchen, K. Stoeckhert, Ed.,
[10] Takata, T., Igarashi, M., and Endo, T., "Synthesis and Cationic Hanser Verlag, Miinchen, 1974, pp. 75-106.
Ring-Opening Polymerization of a Cyclic Carbonate, 5-Meth- [31] Hartwig, E., "High Vacuum Roll Coating," Web Processing and
ylene-l,3-dioxan-2-one," Journal of Polymer Science: Part A: Converting Technology and Equipment, D. Satas, Ed., Van Nos-
Polymer Chemistry, Vol. 29, 1991, pp. 781-784. trand Reinhold, NY, 1984, pp. 182-212.
[11] Comstock, L. R., Milligan, C. L., and Monter, R. P., "Urethane [32] Bnschbeck, W. and Butrymowicz, D., "Vacuum Metallizing,
Coatings Derived from Caprolactone Polyols, I. Rigid Substrate Sputtering, and other Plasma Processes," Leybold AG, Hanau,
Coatings," Journal of Paint Technology, Vol. 44, No. 573, 1972, Germany, presented at The Center for Professional Advance-
pp. 63-70. ment in Finishing and Decorating Plastic Surfaces, October
[12] Comstock, L. R., Gerkin, R. M., Milligan, C. L., and Monter, 1991, pp. 1-47.
R. P., "Urethane Coatings Derived from Caprolactone Polyols, [33] Comello, V., "New Coatings are a Cinch with New PVD Method,"
II. Flexible Substrate Coatings," Journal of Paint Technology, R & D Magazine, Vol. 34, No. 1, 1992, p. 59.
Vol. 44, No. 574, 1972, pp. 75-83. [34] Fowler, D. B., "Metallographic Evaluation of Thermally
[13] Basque, D. E. and Rajangam, G. D., "Specialty Polyols Achieve Sprayed Coatings," ASTM Standardization News, Vol. 19, No. 5,
Improved Performance Traits," Adhesives Age, Vol. 34, No. 8,
May 1991, p. 54.
July 1991, pp. 17-18.
[35] Diaz, D. J. and Blann, G.A., "Thermally Sprayed Coatings,"
[14] Monks, R., "New Additives and Polyols Surface at Urethane ASTM Standardization News, Vol. 19, No. 5, May 1991, p. 48.
Conference," Plastics Technology, Vol. 33, No. 6, June 1992, pp.
[36] Flanders, S. K., Modern Paint and Coatings, Vol. 79, No. 6, June
47-51.
1989, p. 62.
[15] Koleske, J. V. and Knopf, R. J., U.S. Patent 4,163,114 (1979).
[37] Reinking, N. H., Barnabeo, A. E., and Hale, W.F., "Polyhy-
[16] Smith, O. W. and Koleske, J. V., U.S. Patent 4,096,125 (1978).
[17] Smith, O.W., Koleske, J.V., and Knopf, R.J., U.S. Patent droxyethers. I.," Journal of Applied Polymer Science, Vol. 7, 1963,
4,171,423 (1979). p. 2135.
[18] Barksby, N. and Gerkin, R. M., "Acid-Grafted Polyethers: Their [38] Reinking, N.H., Barnabeo, A.E., and Hale, W.F., "Polyhy-
Use in Low-VOC Coatings," Modern Paint and Coatings, Vol. 80, droxyethers. I.," Journal of Applied Polymer Science, Vol. 7, 1963,
No. 6, June 1990, pp. 34-43. p. 2145.
[19] Wellons, S. L., Carey, M. A., and Elder, D. K., "Determination of [39] "PAPHEN | Phenoxy Resins," Phenoxy Associaties, 454 S. An-
Hydroxyl Content of Polyurethane Polyols and Other Alcohols," derson Rd., Rock Hill, SC, Brochure, 1993.
Analytical Chemistry, Vol. 52, 1980, p. 1374. [40] Whiteside, R. C., Sheih, P. S., and Massingill, J. L., "High Per-
[20] "Cycloaliphatic Epoxides for Electrical and Electronic Applica- formance Epoxy Resins for Container Coating Applications
tions," Brochure F-50010, Union Carbide Corporation, Dan- Based on in-situ Advancement Technology," Journal of Coatings
burg, CT, August 1984, pp. 1-19. Technology, Vol. 62, No. 788, 1990, p. 61.
[21] Union Carbide Corporation, "Cycloaliphatic Epoxide Systems," [41] Gorham, W. F. and Niegisch, W. D. in Encyclopedia of Polymer
Brochure F-42953B, March 1978, pp. 1-18, and "ERL-4206: Science and Technology, Vol. 15, John Wiley and Sons, New
Low Viscosity Reactive Diluent," Brochure F-50033, May 1985, York, 1971, pp. 98-124.
pp. 1-12. [42] Lee, S. M., Kirk-Othmer Encyclopedia of Chemical Technology,
[22] Koleske, J. V., "Cationic Radiation Curing," Federation Series Vol. 24, 3d ed., John Wiley and Sons, New York, 1983, pp.
on Coatings Technology, June 1991, Federation of Societies for 744-771.
Coatings Technology, Blue Bell, PA, pp. 1-27. [43] Gotham, W. F., U.S. Patent 3,342,754 (1967).
www.iran-mavad.com

Part 4: Plasticizers
www.iran-mavad.com

MNL17-EB/Jun. 1995
17
Plasticizers
by Peter Tan 1 and Leonard G. Krauskopf 2
PAINTANDCOATINGFORMULATIONSoften incorporate high boil- and 1.35 at 20/20~ viscosities between 50 to 450 cSt, vapor
ing fluids as plasticizers where rigid or brittle resins fail to pressure of less than 3.0 m m of mercury at 200~ and flash
meet toughness and flexibility requirements. The primary points greater than 120~ (248~ They are generally stable
function of the plasticizer is to impart flexibility to the resin, and innocuous and should not be considered a significant
thus minimizing film cracking. Depending on resin and other threat to humans or the environment [5-6].
ingredients used in the system, plasticizer choice may affect Plasticizer extenders are commonly used in extruded or
compatibility, toughness, flammability, smoke generation, molded flexible plastic shapes. Extenders are low-cost or-
heat and light stability, and other aging or permanence-re- ganic oils that may be subdivided as groups of aliphatic,
lated performances. Plasticizers are primarily employed in aromatic, or chlorinated hydrocarbons. They are seldom
heavy gage coatings and/or when improved toughness is reused in coatings due to their relatively high volatility and
quired for industrial, automotive, and appliance applica- limited compatibility in polar resins.
tions. This chapter lists the basic properties of plasticizers and
Plasticizers function by reducing the glass transition tem- methods for their determination. Methods for the isolation,
perature of the resin to a point below its application tempera- identification, and quantitative determinations of these plas-
ture. The chemical mechanism of plasticization involves a ticizers are also included.
strong polar association of polymer-plasticizer molecules,
but not a chemical reaction between them. Plasticizers fun-
damentally reduce Van Der Waals forces between polymer- PHYSICAL A N D CHEMICAL P R O P E R T I E S
polymer molecules in the amorphous regions and do not
penetrate crystallites [1-3]. The plasticized morphological Acidity
phase is then of a different nature than that of the neat
polymer and has unique mechanical properties. Plasticizer acidity may be due to improper processing, deg-
radation during storage, contamination, presence of by-prod-
The absence of a chemical bond between the plasticizer
ucts, or residual catalyst. ASTM Test Method for Acidity in
and the polymer impairs permanence; plasticizer molecules
Volatile Solvents and Chemical Intermediates Used in Paint,
are free to leave the polymeric coating by means of extraction
Varnish, Lacquer, and Related Products (D 1613) may be
and volatility. Plasticizer loss, however, is minimal in most
used for determination of acidity. Either ethyl or isopropyl
applications except for very low molecular weight plasticizers
alcohol may be used as diluent for the plasticizer, which is
and/or exposure to very severe thermal conditions. Thus,
titrated with aqueous sodium hydroxide or potassium hy-
plasticized coatings products have high durability and long
droxide to the phenolphthalein end point. Results may be
service life in most applications. Plasticizers are liquids of
expressed in weight percent, as weight equivalents of acetic
molecular weight greater than that of solvents--to limit vola-
acid, acid number (milligrams potassium hydroxide con-
t i l i t y - b u t are not solids, such as alloying polymers, etc. It
sumed per gram of sample), or if the plasticizer is an ester, as
should be noted that cross-linked resinous coatings signifi-
weight percent of the parent acid of the ester (see section
cantly reduce plasticizer loss due to diffusibility and volatil-
entitled "Ester Value").
ity. Several thousand high boiling fluids are potential plasti-
cizers for coatings applications. The choice of plasticizer is
dependent on compatibility with the resin in use, cost, and Color
other desired attributes.
The majority of plasticizers are colorless. As a class, esters
Plasticizers may be classified by both chemical structure
are very stable chemical reagents. However, exposure to ab-
and performance characteristics, as shown in Table 1 [4].
normal conditions such as high thermal or ultra-violet en-
Typical plasticizers are liquid esters of molecular weight be-
ergy, moisture, or chemically active surfaces may induce de-
tween about 200 to 800, with specific gravities between 0.75
velopment of color bodies and/or chemical decomposition of
the plasticizers. Higher molecular weight phthalates, poly-
tManager, Marketing Technical Services, Exxon Chemical Asia meric plasticizers, and chlorinated paraffins may range in
PTE LTD, Intermediates Technology Center, Block 14 (Maxwell) No.
02-03, Science Park Drive, Singapore 0511. color from light to bright yellow. ASTM Test Method for
2Research associate, Exxon Chemical Company, Intermediates Color of Clear Liquids (Platinum-Cobalt Scale) (D 1209) is
Technology, P.O. Box 241, Baton Rouge, LA 70821. the standard color measurement method for plasticizers.
115
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TABLE 1--Plasticizer family/performance grid.

General Strong Low Low Low Flame
Family Purpose Solvating Volatility Temperature Diffusibility Resistant Stabilizer
Phthalates X ,/ ,/ ~/ ~/ ...
Trimellitates . . . . . . X ,/ ,/ ...
Aliphatic dibasic . . . . . . . . . X . . . . . .
esters
Phosphates ... ,/ ... ,/ ... X
Epoxides . . . . . . ,/ ,/ . . . . . . X
Polyesters . . . . . . ~/ ..- X -..
Extenders X . . . . . . ~/ . . . . . .
NOTE: X = Primary performance function.
Source: Society of Plastics Engineers, Regional Technical Conference (SPE, RETEC) Vinyl I; 1992; reprinted with permission.
APHA is a scale that is likewise used for liquids of low color. 3. Dark tarnish (3a,b) magenta, multicolored.
The standards are based on platinum solutions without co- 4. Corrosion (4a,b,c) transparent black, jet black.
balt and are described in ASTM Standard Method of Testing The historical application of copper corrosion testing to
Urethane F o a m Polyol Raw Materials (D 2849). plasticizers was an attempt to measure effects contributed by
ASTM Test Method for Color of Transparent Liquids residual sulfur c o m p o u n d s due to sulfur-based catalysts,
(D 1544) employs the Gardner Color Scale for amber a n d which m a y hydrolyze to acidic pH in the presence of mois-
dark-colored plasticizers which cannot be read on the plati- ture. Current commercial grade plasticizers do not typically
num-cobalt (Pt-Co) or APHA scales. Gardner standards are contribute to copper corrosion. Commercial grade alkyl sul-
colored disks held in a "Hellige" gage. Gardner values of ' T ' fonate esters of phenol [7] are plasticizers in which the sulfur
and "2" are approximately equivalent to 250 and 400, respec- is organically "combined" and not readily susceptible to hy-
tively, on the APHA scale. The Gardner scale goes up to "18" drolyses.
for use with increasingly darker amber and brownish color
liquids.
The platinum-cobalt scale is also known as the Hazen scale, Distillation Range
but readers should be aware of potential confusion with The Most plasticizers have high boiling points or boiling
American Public Health Association (APHA); APHA adopted ranges. This property can be used as a measure of its degree
a version of this scale in which a Hazen color of one is the of permanence or resistance to loss through volatilization.
same as APHA 100. To avoid confusion, it is r e c o m m e n d e d Presence of lighter components can also be detected. The
that only the Pt-Co scale be used when referring to Procedure measurement of vapor pressure is a costly and time-con-
D 1209. suming procedure. Thus, commercial liquids of high molecu-
The APHA color scale in ASTM D 2849 reflects a slightly lar w e i g h t - - l o w vapor pressures--are typically characterized
greenish hue for APHA versus the Pt-Co scale, which is by boiling ranges in which one determines initial, mid, and
slightly yellowish. The scale readings are similar in the 25 to final (or drypoint) boiling point temperatures. For fluids with
50 range, but in the vicinity of 100 Pt-Co, the APHA scale (Pt dry point > 140~ ASTM Test Method for Distillation of Pe-
only) reads 10 to 20 units lighter (lower). Both the Pt-Co and troleum Products (D 86) is used. Fluids with dry point
APHA scales cover a range from "3" up to "500," but are < 140~ are measured using ASTM Test Method for Distilla-
r e c o m m e n d e d for use for liquids having colors -<250 units. tion Range of Volatile Organic Liquids (D 1078). For very
An instrumental method (Hunter Colorimeter) that is five high boiling fluids or where decomposition m a y occur, distil-
to seven times more precise m a y also be used for color mea- lation m a y be done under v a c u u m regulated at 5 m m Hg. The
surement, replacing the subjective comparisons of the above initial and final boiling points or the mid boiling point are
methods using Nessler tubes; while c o m m o n l y used in com- typically reported.
mercial practice, the Hunter Colorimeter is not yet defined as Gas chromatographic (GC) techniques are c o m m o n l y ap-
an ASTM method. plied as a fundamental measure of plasticizer chemical purity
and isomer distribution. Direct relationships between GC
Copper Corrosion traces and boiling ranges have not yet been established for
ASTM Test Method for Detection of Copper Corrosion plasticizers.
from Petroleum Products by the Copper Strip Tarnish Test Both distillation range and GC analyses are means to relate
(D 130), and ASTM Test Method for Copper Corrosion of vaporization characteristics of plasticizers to practical needs.
Industrial Aromatic Hydrocarbons (D 849), which is nor- The fundamental characteristic of vapor pressure m a y be
mally applied to hydrocarbon solvents, m a y be used to evalu- measured by ASTM Test Method for Vapor Pressure-Temper-
ate the copper corrosive tendencies if suspected to be sourced ature Relationship and Initial Decomposition Temperature
in plasticizer. The appearance of a copper strip, which has of Liquids by Isoteniscope (D 2879). The log of plasticizer
been immersed in the test fluid, under standard conditions, is vapor pressure varies linearly with the reciprocal absolute
c o m p a r e d with twelve special standard strips classified as temperature (degrees Kelvin) according to the Clausius-
Clapeyron equation [8]
follow:
1. Slight tarnish (la,b) light orange, dark orange.
2. Moderate tarnish (2a,b,c,d,e) claret red, brassy, or gold. In - R ~22 - ~
1) (1)
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CHAPTER 17--PLASTICIZERS 117
where ods for Flash Point of Liquids by Setaflash Closed Cup Appa-
P1 and P2 = vapor pressure, g.cm2.s -2, ratus (D 3278).
T1 and T2 = respective temperatures, K, Flash point values are reported for commercially sig-
AH = molar heat of vaporization, cal.g- 1, and nificant monomeric plasticizers in E. J. Wickson's Handbook
R = gas constant, 1.99 cal ~ on PVC Formulating [7]. While not a very good analytical tool,
Vapor pressure values are useful to estimate normal boiling flash points will reflect presence of nonparent, low-flash-
points at 760 m m mercury and solubility parameters [1]. point contaminants.
Sears and Darby have reported that the vapor pressure of
binary plasticizer blends may be expected to fall between the P o u r Point
values of the neat plasticizers, but cannot be predicted from a
knowledge of the blend ratio and the neat vapor pressures. Due to the high molecular weight and isomeric mixtures of
plasticizers, few have distinct freezing points. The pour point
can be useful information for handling plasticizers during
Ester Value cold seasons. Method of measurement is described in ASTM
Esters are the largest group of materials that are commer- Test Methods for Pour Point of Petroleum Oils (D 97). Plasti-
cially useful as plasticizers. This is a result of reasonable costs cizer pour point temperatures may also be estimated from
and broad utility in a wide range of polymers having moder- viscosity/temperature plots as the temperature at which kine-
ate to high polarity characteristics. Ester value can be used to matic viscosity is 50 000 cSt. Most plasticizers have pour
estimate the purity or ester content of the plasticizer. ASTM points of less than - 30~ [7]; no known relationship exists
between pour point and plasticizer performance properties in
Test Method for Ester Value of Lacquer Solvents and Thin-
ners (D 1617) or ASTM Methods of Sampling and Testing polymers under low-temperature conditions.
Plasticizers Used in Plastics (D 1045) may be used for this
determination. The methods involve saponification of the Refractive I n d e x
ester in a known excess amount of KOH. The excess amount
of KOH is then determined by titration with standard sulfuric The refractive index of a plasticizer is measured using
acid. The amount o f / ( O H consumed in the saponification ASTM Test Method for Refractive Index and Refractive Dis-
process is a measure of the ester content of the plasticizer. persion of Hydrocarbon Liquids (D 1218). Refractive index is
A gas chromatography method, ASTM Test Method for often thought of as a means of identifying the plasticizer. This
Purity of Monomeric Plasticizers by Gas Chromatography is an erroneous assumption. It may be used, however, to
(D 3465), may also be used to determine the purity of mono- differentiate between classes of plasticizers, as, for example,
merle plasticizers. The GC method does not provide "ester between phthalates and adipates [10]. When used with other
values." It is useful to characterize major isomers present physical measurements, refractive index may be used as a
versus known standards and to ascertain trace quantities of supplemental test. Refractive index can also be used to check
nonparent organic compounds. GC instrumentation is costly for product contamination, but it is only useful to distinctify
and requires comparison of output traces against a library of commercial materials having very widely different refractive
known materials that have been characterized under a spe- indices.
cific set of conditions using specific GC instruments and col-
umns. R e s i d u a l Odor
Residual odor may be contributed by reaction by-products
Flash P o i n t from manufacturing or by residual raw ingredients which are
Most plasticizers are high flash materials. Either ASTM often more volatile and odorous than the plasticizer. When
Test Method for Flash and Fire Points by Cleveland Open Cup ASTM Test Method for Odor of Volatile Solvents and Diluents
(D 92) or ASTM Test Method for Flash Point by Pensky- (D 1296) is used, tests at elevated temperatures (about 150~
Martens Closed Tester (D 93) may be used. Preference should can be considered to improve detection. Since odor is a
be for the dosed cup method; this yields a more conservative subjective characteristic, generalizations for plasticizers are
number and is consistent with Department of Transportation limited to terms such as "mild and characteristic."
(DOT) regulations in the United States. DOT has revised the
definitions and classifications of hazardous materials, effec- Sampling
tive 1 Oct. 1993, as follows:
To obtain representative samples of plasticizers for evalu-
Flash Point ation, ASTM Methods for Sampling and Testing Plasticizers
Not Regulated >_93~ (200~ Used in Plastics (D 1045) may be followed. ASTM Recom-
Combustible 61 to 92.5~ (142 to 199~ mended Practice for Sampling of Industrial Chemicals
Flammable <_60.5~ (141~ (E 300) can also be used.
The "flash point" is defined as the minimum temperature at

Density a n d Specific Gravity
which a liquid gives off vapor within a test vessel in sufficient
concentration to form an ignitable mixture with air near the Density is an important characteristic for design engineer-
surface of the liquid as determined by ASTM Test Method for ing of plasticizer storage and building facilities. Specific grav-
Flash Point by Tag Closed Tester (D 56) or ASTM Test Meth- ity is the density of the given reagent relative to that of water
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at the specified temperature; it is generally used in the charac- in isomeric structure ranging from normal (unbranched) to
terization of plasticizers or as a means to detect gross con- very specific and/or randomly branched structures. Two alco-
tamination. Specific gravity at 20/20~ is measured with hols have found wide usage in synthesis of commercial plasti-
ASTM Test Methods for Specific Gravity of Liquid Industrial cizers--2-ethylhexanol and isononanol--a mixture of ran-
Chemicals (D 891) and is commonly employed in industry. domly branched (primarily methyl branched) nonyl isomers.
Commercial plasticizers typically fall within the range of 0.92 Table 2 is a summary of typical properties of plasticizers
to 1.50 sp gr at 20/20~ ASTM Test Method for Density and derived from these two alcohols with the major parent
Relative Density of Liquids by Digital Density Meter (D 4052) acids--phthalic, trimellitic, and adipic [11].
is the recommended procedure to measure specific gravity of
fluids that lie between 0.68 and 0.97; this method is applica-
ble to hydrocarbons that are commonly used as plasticizer METHODS OF IDENTIFICATION
extenders.
A plasticizer may initially be characterized by its functional
Viscosity groups. While absolute identification is complicated without
sophisticated chemical or instrumental methods, it is possi-
Viscosity measures the fluid's resistance to flow; the thicker ble to identify the type of plasticizer by functional groups or
the fluid, the higher its viscosity and the greater its resistance presence of elements associated only with the plasticizer by
to flow under gravity. In ASTM Test Method for Kinematic the use of infrared analyses or wet chemistry. Most plasticiz-
Viscosity of Transparent and Opaque Liquids (and the Calcu- ers are a member of one of the following families:
lation of Dynamic Viscosity) (D 445), time is measured in Plasticizer Type~Functional Group
seconds for a fixed volume of the fluid to flow under gravity Adipates
through the capillary of a calibrated viscometer at constant Chlorinated compounds
temperature. The kinematic viscosity of a plasticizer varies as Epoxides (oxirane)
a log log function versus the log of absolute temperature Phosphates
according to the following equation Phthalates
log log ~ ---A - B log T (2) Polyesters
Trimellitates
where
= kinematic viscosity, centistokes,
T = temperature, degrees Kelvin, and Isolation of Plasticizers
A and B = constants. Plasticizers may be separated from a lacquer or dried film
This reflects the tremendous influence of temperature on by solvent extraction if it is to be analyzed. The lacquer is first
viscosity and allows one to interpolate viscosity values at dried to remove all solvents present. The dried solid is then
specified temperatures. The kinematic viscosity (centistokes) solvent extracted (in an appropriate apparatus) with hot ethyl
can be converted to its dynamic viscosity (centipoise) by ether or another appropriate solvent that will extract the
multiplying by the true density of the fluid at the specified plasticizers while leaving most of the resins behind. The ex-
temperature: dynamic viscosity, cP = kinematic viscosity, tractant is concentrated, and a small amount of methyl or
cSt, times density. ethyl alcohol is added. This will cause some of the dissolved
resin to precipitate out. Next, filter and concentrate the ex-
tractant. ASTM Test Method for Acetone Extraction of Phe-
Water
nolic Molded or Laminated Products (D 494) may be applied.
Residual water from manufacturing processes and mois-
ture absorbed from the atmosphere can affect the quality and
Instrumental Methods
clarity of coatings. Water content can be measured using
ASTM Test Method for Water in Volatile Solvents (Fischer Modern instrumental analytical methods are able to
Reagent Titration Method) (D 1364). Plasticizers are hydro- separate, identify, and quantify components in composite
phobic liquids and typically have a limited capacity to take up mixtures. Rapidly falling costs of such instruments have en-
water and/or be dissolved into water. Higher-molecular- abled instrumental methods to be more widely available.
weight phthalates are practically insoluble in water with solu- These include gas chromatography (GC), high-performance
bilities in the 0.1 to 1.2 mg/L (ppm) range with even less liquid chromatography (HPLC), infrared spectroscopy
solubility in salt water [6]. (FTIR), and other emerging analytical instruments like su-
percritical fluid chromatography (SFC), GC/FTIR, and
GC/MS (mass spectrometry).
Typical Properties
As shown in Table 1, commercial plasticizers fall into about
Infrared Spectrophotometry
seven chemical family groups (eight if we were to add a
"miscellaneous" grouping). The major plasticizer types in use An infrared scan of the isolated plasticizer is by far the best
are phthalates, trimellitates, and aliphatic dibasic esters such way to identify the functional groups in the molecule. Mix-
as adipates. The families of esters are formed by reacting the tures of plasticizers can present problems due to masking
parent acid with monomeric alcohols ranging from C4H9OH effects. If one or more of the component plasticizers is known
(butanol) to C13H27OH (tridecanol); the alcohol may also vary and its IR scan available, subtracting it from the IR scan of
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CHAPTER 17--PLASTICIZERS 119
TABLE 2--Typical physical properties of plasticizer esters made with isononyl and 2-ethylhexyl alcohols.
Phthalate Trimellitate Adipate
DOP DINP TOTM TINTM DOA DINA
Alkyl 2EH INA 2EH INA 2EH INA
Molecular weight 390 424 546 596 370 404
Specific gravity at 20/20~ (68~ 0.986 0.973 0.992 0.979 0.927 0.924
Refractive Index n2D~ 1.484 1.486 1.482 1.484 1.445 1.449
Viscosity, cSt at 20~ 83 102 312 430 16 26
Pour point, ~ - 47 - 48 - 46 - 40 < - 60 - 59
Vapor pressure, mm Hg at 200~ 1.2 0.5 0.08 0.03 2.5 1.5
Mid boiling point, ~ at 5 turn Hg 230 245 300 331 215 233
Flash point, ~ 204 213 221 241 193 199
Color, Pt-Co <25 <25 < 100 < 100 <25 <25
Source: Edenbaum, J., Plastics Additives and Modifiers Handbook, Van Nostrand Reinhold, New York, 1992, p. 362. Reprinted with
permission.
NOTE:DOP di(2-ethylhexyl) phthalate
DINP di (isononyl) phthalate
TOTM tris(2-ethylhexyl) trirnellitate
TINTM tris(isononyl) trimellitate
DOA di(2-ethylhexyl) adipate
DINA di(isononyl) adipate
the mixture m a y aid in identification of the o t h e r c o m p o n e n t . Sulfur

Other c h r o m a t o g r a p h i c techniques could be used to s e p a r a t e
Add two to three d r o p s of 10% solution of lead acetate to
the c o m p o n e n t s before scanning.
2 m L of a 10% solution of s o d i u m hydroxide. Add this mix-
ture to 5 m L of the filtrate, A b l a c k p r e c i p i t a t e of l e a d
Liquid Chromatography sulphide indicates the presence of sulphur, Positive identifi-
cation suggests that the s a m p l e is either a s u l p h o n a m i d e o r
C o l u m n c h r o m a t o g r a p h y involves d i s t r i b u t i o n of sub-
sulphate.
stances b e t w e e n liquid (mobile phase) a n d substrate (solid
phase). C o l u m n a n d thin layer c h r o m a t o g r a p h y can be used.
I n s t r u m e n t a l m e t h o d s using h i g h - p e r f o r m a n c e liquid chro- Nitrogen
m a t o g r a p h y (HPLC) with ultraviolet detection can be used
for separation, identification, a n d quantification of plasticiz- Bring 2 mL of the filtrate to boil in a test tube. Add five
ers w h i c h possess a suitable c h r o m o p h o r e . d r o p s of a 10% solution of N a O H a n d five d r o p s of 10%
ferrous sulphate solution. W h e n cold, add, dropwise, a 10%
solution of h y d r o c h l o r i c acid until the solution is acidic a n d
Gas Chromatography the precipitate of ferrous h y d r o x i d e has dissolved. Avoid us-
By c o m p a r i n g relative r e t e n t i o n t i m e s a n d p e a k s h a p e s ing a n excessive a m o u n t of acid. A blue or green color o r blue
with k n o w n samples, a plasticizer o r mixture can often be precipitate indicates p r e s e n c e of nitrogen. A positive test sug-
identified a n d quantified. W h e n coupled with IR (i.e., gests that the plasticizer could be an amide.
GC/FTIR), the IR s p e c t r u m of each c h r o m a t o g r a p h i c p e a k
can assist in the identification of functional groups a n d hence Chlorine
plasticizer identity.
Acidify 5 m L of the filtrate with several d r o p s of dilute
sulfuric acid a n d b r i n g it to boil. Cool a n d acidify with nitric
Qualitative Methods acid. Add several d r o p s of a 10% silver nitrate solution. A
F o r the detection of nitrogen, chlorine, sulphur, o r phos- white precipitate indicates the presence of a c h l o r i n a t e d com-
phorus, the s a m p l e needs to be fused with metallic sodium. pound.
This p r e p a r a t i o n should be c a r r i e d out in a fume h o o d and
caution observed w h e n h a n d l i n g metallic sodium. A small
Phosphorus
a m o u n t (about 3 m m 3) of metallic s o d i u m is p l a c e d in a d r y
6-in. (15.24-cm) test tube. The test t u b e should be held verti- Boil 5 m L of the filtrate with 3 m L of c o n c e n t r a t e d nitric
cally by c l a m p i n g it at the o p e n end. The test t u b e is t h e n acid for I rain. Cool and a d d twice the v o l u m e of 10% a m m o -
h e a t e d until a cloud of s o d i u m v a p o r begins to form. Remove n i u m m o l y b d a t e solution. H e a t to a b o u t 60~ a n d set aside to
the flame immediately. Add two to three d r o p s of the plasti- cool. A yellow precipitate indicates the presence of p h o s p h o -
cizer s a m p l e directly to the s o d i u m vapor. W h e n the test tube rus. P h o s p h a t e plasticizers will result in a positive test.
is cold, b r e a k off the end with the s o d i u m in a m o r t a r . Add
several milliliters of alcohol to d e s t r o y u n r e a c t e d sodium.
Add a b o u t 20 rnL of distilled o r deionized water, g r i n d u p the
Phthalates
sample, transfer to a beaker, b r i n g to boil, and filter. The Add a b o u t 0.05 g of resorcinol and 0.05 g of p h e n o l to sepa-
filtrate is t h e n used for the c h e m i c a l detection of the ele- rate 6-in. (15.24-cm) test tubes. Add to each test t u b e two to
ments. three drops of the isolated plasticizer a n d a d r o p of concen-
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trated sulfuric acid. Heat the contents in an oil bath at 160~ compatible it will be with the given polymer. Many materials
for several minutes. Cool and add 2 mL of distilled water and have been characterized in this fashion. Exxon Chemical
2 mL of 10% sodium hydroxide solution and stir. The pres- Company has developed a computerized capability to define
ence of phthalate is indicated by a pronounced green fluores- the location of various solvents and plasticizers relative to
cence in the tube with resorcinol, and the tube with phenol that of various polymers; it is called the CO-ACT| program
will be red. and contains information on more than 1200 resins, solvents,
and plasticizers [15].
Compatibility data for different plasticizer resin systems
PERFORMANCE PROPERTIES are available in various publications [1,16-17]. The plasticiz-
ers are usually presented as compatible, incompatible, or
Compatibility partially compatible with the resins. These data are often not
useful due to incomplete description of the resin or a lack of
Compatibility is the ability of two or more substances to standard approach in the test and reporting of observations.
mix together without objectionable separation [12]. In the Where Hansen parameters are available for the plasticizers
case of plasticizers, it is primarily a measure of the solvency and resins, comparison of three-dimensional Hansen solubil-
or strength of positive interactions between the plasticizer ity parameters provide a better measure of compatibility as
and the polymer which attract them together. described earlier. Table 3 lists generalized examples of plasti-
Solvency is the extent (or amount) of interaction of plasticizers and their compatibility with various coating resins.
cizer or solvent molecules at the surface of a polymer particle;
a solid solution results when the polymer and plasticizer--
and possibly additional reagents--become molecularly ho-
Permanence
mogeneous. The degree to which a homogeneous solution, or "Reactive" plasticizers are specialty types designed to self-
miscibility, is stable is a function of the plasticizer/polymer polymerize or graft onto the polymeric resin during the
interactions when in the presence of other reagents employed curing process. But, in most cases, plasticizers do not chemi-
in the coating formulation; it must be recognized that the cally react with the polymer. They function by an overall
presence of these additional reagents can compete with the solvating action that is less strong than that of a good solvent,
polymer/plasticizer interactions. The rule of thumb "like dis- but stronger than that of incompatible reagents such as lubri-
solves like" applies, but more specific knowledge is required cants. This interaction imparts a slight effect on plasticizer
to avoid results that appear to be anomalous. "permanence," or more properly "transience." One of two fac-
Dried polymeric coatings may be considered as solid solu- tors are generally the controlling influence over loss of plasti-
tions; the limits of miscibility are impacted by all of the cizer:
reagents that become components of the coating--those in- 9 Rate of diffusion of plasticizer from the resin bulk to the
tentionally added, as well as inadvertent contaminates and/or surface.
degradation products formed in the coating process. When 9 Rate of loss of plasticizer from the surface.
plasticizers are employed, they have a major effect on com- The slowest rate of the two is the controlling factor under
patibility, primarily due to the level, or concentration, used in any specific set of conditions. Volatility and extraction by
the polymer. If we accept the definition of a solution as a aqueous reagents are generally surface-controlled losses,
homogeneous mixture of two or more types of molecules, while rate of diffusion controls loss under oil immersion and
then "solvency" is a measure of a given solvent or plasticizer similar tests. The subject is very complex [1-2], but one may
to homogenize and interact with a given polymer. Quantifica- consider plasticizer vapor pressure as a key predictor of vola-
tion of this "interaction" has been elusive; scales which have tile loss, while diffusion-controlled losses are improved with
been devised are capable of measuring only gross differences. plasticizers of higher molecular weight and branchiness in
Observations of phase separation of plasticizer/polymer have the chemical structure.
been more finite than that predicted in many cases, while on Resistance to washing is typically characterized as a func-
the other hand, observations of symptoms (compatibility) are tion of thermal and/or humidity cycling exposures. This is a
incapable of separating "solvency" from other interfering measure of the aging resistance of the plasticized polymeric
mechanisms that are concurrent, such as diffusibility. coating.
Hansen publications [13-14] define the total solubility pa-
rameters of polymers, solvents, and other reagents as a func-
tion of three component parameters: Low-Temperature Properties
)kT = (~t~ + ~tp2 -{- }~)1/2, ( c a l / c m 3 ) l / 2 (3) Some applications require flexibility and impact resistance
at low temperatures. This property may be significantly im-
where proved at increased plasticizer levels, as well as being a func-
hr = total solubility parameter, tion of the plasticizer type [1 ]. For example, at approximately
hd = dispersion parameter, 50 PHR, plasticizer in poly(vinyl chloride) phthalates of lin-
hp = polarity parameter, and ear alcohols impart about - 10~ improvement in low-tem-
hh = hydrogen bonding parameter. perature brittleness over branched, DOP-type, phthalate
The location of polymers and other non-ionic reagents may plasticizer. Dialkyl adipates, however, impart about -25~
be defined on this three-dimensional grid. Hansen states that improvement over the brittleness value of DOP-plasticized
it may be assumed that the closer a plasticizer lies to the PVC as measured by ASTM Test Method for Brittleness Tem-
center of the polymer solubility space of a polymer, the more perature of Plastics and Elastomers by Impact (D 746).
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CHAPTER 17---PLASTICIZERS 121
TABLE 3--Plasticizers and their compatibility with coating resins.

Plasticizer CA CAB CN EC PMMA PS VAc VB PVC VC/VAc
Phthalates
DOP I C C C C C I P C C
DIOP I C C C C C C P C C
DINP P C C C C C C P C C
DIDP P C C C P C P P C C
Trimellitates
TOTM P C C C P C P P C C
TINTM P C C C P C P P C C
Phosphates
TCP C C C C P C C C C C
TOP P P C C I C I C C C
Acyclic esters
DOA P C C C P C P P C C
DINA P C C C P C P P C C
DOZ P C C C P C P P C C
DOS P C C C P C P P C C
Epoxidized
S o y b e a n oil I P C C I I I I C C
(2EH) tallate I C C C I I I C C C
Polyesters
Adipic/Diol P C C C P C P P C C
Phthalic/Diol P C C C P C P P C C
C = Compatible; P = Partially compatible; I = Incompatible.
RESINS
CA = Cellulose Acetate
CAB = Cellulose Acetate/Butyrate
CN = Cellulose Nitrate
EC = Ethyl Cellulose
PMMA = Methyl Methacrylate
PS = Polystyrene
VAc = Vinyl Acetate
VB = Vinyl Butyral; 19 wt% Vinyl Alcohol
PVC = Vinyl Chloride
VC/VAc = Vinyl Chloride/Vinyl Acetate Copolymer: 90/10
PLASTICIZERS
Phthalates
DOP = di(2-ethylhexyl)
DIOP = di(isooctyl)
DINP = di(isononyl)
DIDP = di(isodecyl)
Trimellitates
TOTM = tris(2-ethylhexyl)
TINTM = tfis(isononyl)
Acyclic Esters
DOA = di(2-ethylhexyl) adipate
DINA = di(isononyl) adipate
DOZ = di(2-ethylhexyl) azelate
DOS = di(2-ethylhexyl) sebacate
NOTE: Compatibility of plasticizers in specific polymers is a function of relative concentration (PHR), as well
as the presence of other formulating reagents and residuals present in polymers. The above ratings are
based on plasticizer levels typically used in coatings applications (<40 PHR).
Commercial coatings require the optimum choice of plasti- REFERENCES

cizer type and concentration to meet required costs, hardness
or modulus, permanence, and low-temperature properties. [1] Sears, J. K. a n d Darby, J. R., The Technology of Plasticizers, J o h n
Wiley a n d S o n s , N e w York, 1982.
[2] K r a u s k o p f , L. G., N a s s , L. I., a n d Heiberger, C. A., Eds., "Plasti-
cizers," Encyclopedia of PVC, 2 n d ed., Vol. 2, M a r c e l Dekker,
Inc., N e w York, 1988.
[3] Gould, R. F. Ed., Plasticization and Plasticizer Processes, A m e r i -
Acknowledgments c a n C h e m i c a l Society, W a s h i n g t o n , DC, 1965.
The authors would like to acknowledge the contributions, [4] K r a u s k o p f , L. G., "Plasticizer S t r u c t u r e / P e r f o r m a n c e R e l a t i o n -
ships," Society of Plastics E n g i n e e r s , Brookfield, CT, Vinyl I
consultation, and review given by their co-workers Arthur D.
RETEC, 30 Sept.-1 Oct. 1992.
Earlywine and Thomas M. Larson.
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[5] Cadogen, D. F., "Plasticizers. A Consideration of Their Impact [12] Whittington, L. R., Whittington's Dictionary of Plastics, Tech-
on Health and The Environment," Journal of Vinyl Technology, nomics, Westport, CT, 1978, p. 66.
Vol. 13, No. 2, 1991, pp. 104-108. [13] Hansen, C- M., "The Three Dimensional Solubility Parameter
[6] Group, E. F., Jr., "Environmental Fate and Aquatic Toxicology and Solvent Diffusion Coefficient, Their Importance in Surface
Studies on Phthalate Esters," Environmental Health Perspec- Coating Formulation," Copenhagen Danish Technical Press,
tives, Vol. 65, 1986, pp. 337-340. 1967, p. 41.
[7] Wickson, E. J., Ed., Handbook of PVC Formulating, John Wiley [14] Hansen, C. M. and Beerbower, A., "Solubility Parameters," En-
& Sons, New York, 1993. cyclopedia of Chemical Technology, Supplement Volume, 2nd
[8] Lange, Handbook of Chemistry, 10th ed., McGraw-Hill, New
Ed., 1971.
York, 1961, p. 1717.
[9] Federal Register, Vol. 55, No. 246, Rules and Regulations, CFR
[15] Dante, M. F., Bittar, A. D., and Caillault, J. J., "Program Calcu-
173.120, 21 Dec. 1990. lates Solvent Properties and Solubility Parameters," Modem
[10] Keller, K. and Krauskopf, L. G., Technical Report 91PPIT L272, Paint and Coatings, September 1989.
"Refractive Indices of Commercial Plasticizers and Other Petro- [16] Riley, H. E., "Plasticizers," Paint Testing Manual, American So-
chemicals," Exxon Chemical Co., Baton Rouge, LA, 1991. ciety for Testing and Materials, 1972.
[11] Edenbaum, J., Plastics Additives and Modifiers Handbook, Van [17] Modem Plastics Encyclopedia, McGraw-Hill, Inc., New York
Nostrand Reinhold, New York, 1992, p. 362. City, published annually.
www.iran-mavad.com

Part 5: Solvents
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MNL17-EB/Jun. 1995
18
Solvents
by Stephen A. Yuhas, Jr.
SOLVENTSARE SUBSTANCES,usually liquids, which are capable I. Hydrocarbon solvents--organic compounds comprised of
of dissolving other substances to bring them into liquid form. molecules consisting only of hydrogen and carbon atoms.
In paints and coatings, solvents dissolve the solid or semi- 2. Oxygenated solvents--organic compounds comprised of
solid film-forming resins and reduce viscosity so that the molecules consisting of hydrogen, carbon, and oxygen at-
paint can be applied as a uniform, thin film to a surface. oms.
Although solvents are transient components of a paint, they 3. Other solvents--organic compounds consisting of hydro-
significantly affect not only the application characteristics of gen, carbon, and atoms other than oxygen, such as chlo-
a paint, but also the appearance, physical properties, and rine or nitrogen, or inorganic compounds such as water or
durability of the coating. supercritical carbon dioxide.
The two most important performance requirements that
must be considered in selecting the proper solvent for any Hydrocarbon Solvents
end use are solvency and evaporation rate. These key proper-
ties control initial paint viscosity during application, coating The vast majority of hydrocarbon solvents are derived from
viscosity at various stages of drying, and final coating appear- petroleum, although a few are of vegetable origin. Therefore,
ance. Solvents must evaporate relatively quickly during ini- hydrocarbon solvents may be regarded as being "natural
tial drying to prevent excessive flow and sag, but must evapo- products." Most are physically separated from petroleum by
rate more slowly in the later stage to provide good leveling distillation and other refining processes. As a result, hydro-
and adhesion. carbon solvents tend to be mixtures of organic compounds
Solvency and evaporation rate are often measured indi- (rather than pure chemicals), and they may vary in composi-
rectly since direct measurements are not always feasible or tion depending on feedstock source.
convenient. In addition, there are numerous other solvent Solvency of hydrocarbons is relatively weak compared with
properties that must be considered for specific applications. oxygenated and other solvents. Being of natural origin, they
These are often listed as requirements in the solvent specifi- are good solvents for natural resins and natural-modified res-
cations and include measures of purity, uniformity, safety, ins such as drying oils, varnishes, alkyds, asphalt, rosin, and
and compliance with air pollution regulations. petroleum resins. However, they are generally poor solvents
There are many different solvents used by the coatings for synthetic resins such as vinyls, epoxies, urethanes,
industry. To facilitate their review and comparision, it is con- acrylics, and nitrocellulose. Hydrocarbon solvents are usually
venient to classify them chemically into three general catego- used as low-cost diluents in solvent blends. Other distinguish-
ries: hydrocarbons, oxygenated, and others. Each category ing characteristics of hydrocarbon solvents are low specific
will be discussed separately in the sections that follow. gravity and complete water immiscibility.
Solvents may also be classified according to the function Hydrocarbon solvents may be further subclassified into
they perform: active, latent, and diluent. An active solvent is a four subcategories: aliphatics, aromatics, naphthenes, and
true solvent for the film-forming resin and has the major role terpenes.
in dissolving it. A latent solvent alone will not dissolve the
resin, but behaves as an active solvent or has a synergistic Aliphatic Hydrocarbons
effect when used in combination with an active solvent. A Most aliphatic hydrocarbon solvents are manufactured by
diluent usually has no solvency for the resin, but is tolerated distilling the appropriate boiling range fractions from crude
by it in blends. Diluents are added to reduce cost and vehicle oil and subsequently treating them to improve odor and color
viscosity through dilution. stability. These saturated organic molecules are generally
mixtures of straight chain or normal-paraffins and branched
chain or iso-paraffins, with perhaps some cycloparaffins [1].
CLASSIFICATION B Y CHEMICAL T Y P E Unique, distinguishing characteristics of commodity ali-
phatic hydrocarbons are: very weak solvency, low odor, spe-
Solvents can be broadly classified by chemical type into cific gravity, and cost. Although they are active solvents for
three categories: some varnishes and alkyds, they are used primarily as low-
cost diluents in solvent blends. Weak solvency is not neces-
1Chemical engineer, technical consultant, Solventures, Inc., 56 sarily a disadvantage of aliphatic hydrocarbons. They are pre-
Wick Drive, Fords, NJ 08863. ferred as carrier solvents in vinyl organosols and as reaction
125
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diluents in certain polymer syntheses because of their low phatic n a p h t h a distillate from crude oil is processed t h r o u g h
tendency to dissolve or swell polymers. a catalytic reformer to rearrange the molecules into cyclic
Examples of some typical aliphatic solvents used by the and polycyclic compounds, which are further dehydro-
coatings industry are shown in Table 1 together with their genated to aromatics. Various aromatic solvents are then
ASTM specification references. Others are commercially separated by distillation [1].
available as aliphatic naphthas having producer-defined dis- There are only four aromatic solvents c o m m o n l y used by
tillation ranges. The fastest-evaporating solvents--hexane, the coatings industry: toluene, mixed xylenes, and two high-
heptane, and lacquer d i l u e n t - - a r e often used as the diluent flash aromatic naphthas. Evaporation rates of these four
c o m p o n e n t of fast-drying lacquers, where one of their impor- major aromatic solvents range from fast to very slow. ASTM
tant functions is to reduce cost. specification references and key properties are summarized
Mineral spirits is the most c o m m o n l y used aliphatic sol- in Table 2. Distinguishing characteristics of aromatic sol-
vent. (Outside the United States, mineral spirits is often vents, relative to h y d r o c a r b o n solvents, are stronger solvency
called white spirits.) It is the c o m m o n "paint thinner" sold in and odor, high specific gravity, and higher cost.
retail stores and is used in architectural paints, varnishes, Toluene is a pure chemical, methylbenzene. It is a fast-
and stains. It has the right combination of moderate solvency evaporating solvent used as an active solvent for certain res-
and moderately slow evaporation rate to impart proper ins, as a lacquer diluent, in spray paints, aerosols, and in a
brushability, leveling, and wet edge. variety of industrial coatings.
Mineral spirits is a distillation fraction boiling between Mixed xylenes are used as paint solvents and in thinners.
300~ (149~ and 400~ (204~ with a m i n i m u m flash point Xylene is a mixture of three isomers: ortho-, meta-, and
of 100~ (38~ Four types are defined in ASTM D 235, Speci- paraxylene, plus ethylbenzene. Solvent xylene from different
fication for Mineral Spirits (Petroleum Spirits) (Hydrocarbon producers m a y vary in composition, resulting in slight differ-
Drycleaning Solvent). "Low dry point" mineral spirits, re- ences in properties and performance [2]. Xylene has a moder-
ferred to as Stoddard solvent, has a faster evaporation rate ate evaporation rate and is used primarily in industrial coat-
and is used as a dry-cleaning solvent. ings.
VM&P naphthas have about the same solvency as mineral The individual components of mixed xylene solvent are
spirits, but have a m u c h faster evaporation rate. They are also isolated and marketed separately as chemical intermedi-
distillation fractions having boiling ranges between 250~ ates which are used by the coatings and chemical industries.
(121~ and 300~ (149~ ASTM D 3735, Specification for
Phthalic anhydride, used in the manufacture of alkyd resins,
VM&P naphthas, defines three types. They are used primarily
is produced from orthoxylene. Terephthalic acid, also used in
in spray-applied, industrial finishes.
the manufacture of resins, is produced from paraxylene. Sty-
Several hydrocarbon solvent producers also manufacture
rene is produced from ethylbenzene.
and market complete lines of pure, isoparaffinic solvents,
Two high-flash aromatic naphthas r o u n d out the aromatics
which are synthetically produced from pure petroleum com-
most c o m m o n l y used by the coatings industry.
ponents. Unique characteristics of the isoparaffins are that
they have very weak solvency and are virtually odorless. Ex- Type/--Aromatic 100 has a flash point not less than 100~
amples are odorless mineral spirits and odorless VM&P (38~
naphtha. Type H - - A r o m a t i c 150 has a flash point not less than 150~
(60~
Aromatic Hydrocarbons Aromatic 100 consists mainly of C9 aromatics, while Aro-
Aromatic hydrocarbons, which are cyclic, unsaturated matic 150 is a mixture of predominantly C~0 aromatics. Both
compounds, are also made from petroleum. However, their are slow evaporating and are used in baked industrial coat-
manufacture requires additional processing steps. An ali- ings.
TABLE 1--Typical properties of selected aliphatic hydrocarbon solvents.

Specific Evaporation Flash Kauri- Aniline
ASTM Gravity, Distillation Rate, Point, Butanol Point,
Solvent Specification 60/60~ Range, ~ n-BuAc = 100 TCC, ~ (~ Value ~ (~
Hexanes D 1836 0.68 64-70 1500 <0 ( < - 18) 32 150 (66)
Heptane ..- 0.73 94-99 600 18 ( - 8 ) 36 129 (54)
Lacquer diluent ... 0.75 93-115 400 20 ( - 7) 40 120 (49)
VM&P naphthas D 3735
Type I "Regular" 0.75 12ff-150 200 41 (5) 38 117 (47)
Type II "High Flash" 0.76 140-175 150 81 (27) 40 110 (43)
Type III "Odorless''a 0.72 120-150 210 41 (5) 29 165 (74)
Mineral spirits D 235
Type I "Regular" 0.79 150-210 10 108 (42) 37 130 (54)
Type II "High Flash" 0.79 177-210 8 142 (61) 36 135 (57)
Type III "Odorless"a 0.76 150-210 10 104 (40) 27 184 (84)
Type IV "Low Dry Point," 0.77 150-185 15 104 (40) 38 123 (51)
"Stoddard Solvent"
Deodorized kerosene ... 0.81 177-265 2 142 (61) 30 160 (71)
~Isoparaffinic hydrocarbon.
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CHAPTER 18--SOLVENTS 127
TABLE 2uTypical properties of selected aromatic hydrocarbon solvents.

Mixed
Specific Evaporation Flash Kauri- Aniline
ASTM Gravity, Distillation Rate, Point, Butanol Point,
Solvent Specification 60/60~ Range, ~ n-BuAc = 100 TCC,~ (~ Value ~ (~
Toluene D 841 0.872 110-111 180 45 (7) 105 48 (9)
Mixed xylenes D 843 0.871 137-142 70 83 (28) 98 51 (10)
ortho-xylene D 4076 0.885 143-145 65 90 (32) 106 51 (10)
meta-xylene .-. 0.869 139-140 70 81 (27) 97 51 (10)
para-xylene D 5136 0.866 138-139 70 81 (27) 93 52 (11)
Ethylbenzene D 3193 0.872 136-137 74 70 (21) 95 52 (11)
High flash aromatic naphthas D 3734
Type I "Aromatic 100" 0.874 150-175 20 108 (42) 91 56 (13)
Type II "Aromatic 150" 0.895 180-215 5 150 (66) 95 60 (15)
Naphthenic Hydrocarbons contains mostly a-pinene with lesser quantities of/3-pinene

Most of the aliphatic hydrocarbon solvents contain minor and small amounts of other terpene hydrocarbons.
amounts of naphthenes, i.e., cycloparaffins, cyclic aliphatics. Steam-distilled wood turpentine is obtained from oleoresin
Properties of naphthenes, with respect to solvency, odor, and within the wood of pine stumps or cuttings, either by direct
specific gravity, are intermediate between aliphatics and aro- steaming of the mechanically disintegrated wood or after sol-
matics. vent extraction of the oleoresin from the wood. It consists
Purely naphthenic hydrocarbon solvents currently have primarily of a-pinene, with small quantities of dipentene and
very limited commercial availability. Cyclohexane, a pure other terpenes.
naphthenic hydrocarbon, finds applications not as a solvent Sulfate wood turpentine is recovered during the conversion
but as a chemical intermediate in the manufacture of nylon of wood to pulp by the sulfate (Kraft) paper-making process.
fiber and engineering resins, plasticizers, polyurethane, poly- It is a mixture of ~- and /3-pinene, with small amounts of
ester, and epoxy resins. Properties are summarized in other terpene hydrocarbons.
Table 3. Destructively distilled wood turpentine is obtained by frac-
tionation of certain oils recovered from the destructive distil-
Terpenes lation of pine wood. It is a complex mixture of a wide variety
Terpene solvents are obtained from pine trees and to a of aromatic hydrocarbons with only moderate quantities of
terpenes being present.
much lesser extent as a by-product of the citrus industry.
Standard methods of sampling and testing turpentine are
They are the oldest solvents used in coatings, predating an-
described in ASTM D 233, Methods of Sampling and Testing
cient Egyptian civilization [1,3]. The main solvents in this
Turpentine.
group are turpentine, dipentene, and pine oil. Chemically,
they are mixtures of Cw unsaturated hydrocarbon com-
Dipentene is obtained by fractional distillation from crude
oils recovered in the several commercial methods of process-
pounds. A good review of terpenes may be found in ASTM
ing pine wood during the production of turpentine. It has
D 804, "Standard Definitions of Terms Relating to Naval
somewhat stronger solvency and slower evaporation rate
Stores and Related Products."
than turpentine. Standard test methods for sampling and
Terpene solvents have volatiles similar to mineral spirits.
testing dipentene are described in ASTM D 801, Methods of
However, they have only minor commercial significance to-
Sampling and Testing Dipentene.
day because they are more expensive than hydrocarbon sol-
Pine oil is a unique material separated during the four
vents. Although their solvency is greater than that of aliphatic
commercial turpentine production methods. Unlike the other
hydrocarbons, they have a much narrower range of solvency
hydrocarbon solvents, pine oil consists mainly of terpene al-
and evaporation rate and a stronger odor. Furthermore, be-
cohols, with a variety of small quantities of other oxygenated
cause of their unsaturated structure, they are restricted in
terp~nes. Pine oil has strong solvent power due to the oxygen
some areas by air pollution regulations.
funciionality. However, its evaporation rate is very slow. Pine
There are four kinds of turpentine, as specified in ASTM
oil is generally used in additive quantities, i.e., 5 wt% of the
D 13, Specification for Spirits of Turpentine, depending on
total solvent, to provide good coating flow out and wetting
the source and method of production [1,4].
properties. Standard methods for sampling and testing pine
Gum turpentine or gum spirits is produced by distilling the oil are described in ASTM D 802.
crude gum or oleoresin collected from living pine trees. It
d-Limonene is a relatively new commercial terpene hydro-
carbon solvent recovered and purified from by-products of
TABLE 3--Typical properties of cyclohexane. the citrus industry.
Typical properties of some selected terpene solvents are
ASTM specification D 3055
Specific gravity, 60/60~ summarized in Table 4 [5,6].
0.782
Distillation range, ~ 174-178
Evaporation rate, n-butyl acetate = 100 1000 (estimated)
Flash point, ~ (~ - 4 (-20)
Oxygenated Solvents
Kauri-butanol value 52 Oxygenated solvents contain oxygen functionality in the
Aniline point, ~ (~ 93 (34)
molecules. Unlike hydrocarbon solvents, oxygenated solvents
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TABLE 4--Typical properties of selected terpene solvents.

Wood
Turpentine Dipentene Pine Oil
ASTM specification D 13 . . . . . .
ASTM test method D 233 D 801 D 802
Specific gravity, 60/60~ 0.865 0.853 0.923
Distillation range, ~ 150-170 170-190 200-225
Evaporation rate, n-butyl 40 18 5
acetate = 100
Flash point, TCC, ~ (~ 95 (35) 120 (49) 130 (54)
Kauri-butanol value 56 62 >500
Aniline point, ~ (~ 70 (21) 32 (0) <-4 (<-20)
are synthetically p r o d u c e d . Therefore, they are s o m e w h a t rate. They are extensively u s e d as active solvents in synthetic
h i g h e r in cost. Most are pure, s i n g l e - c o m p o n e n t c h e m i c a l resin lacquers a n d paints. The very slow e v a p o r a t i o n rate of
products, c o m p a r e d with h y d r o c a r b o n solvents which t e n d to i s o p h o r o n e m a k e s it useful in b a k e d industrial coatings.
be complex mixtures. Consequently, oxygenated solvents
have very n a r r o w distillation ranges, s o m e as n a r r o w as 1~ Esters
Relative to the h y d r o c a r b o n s , oxygenated solvents have Esters used as solvents are alkyl acetates a n d p r o p i o n a t e s
m u c h stronger solvency a n d are used as active solvents for a n d glycol e t h e r acetates. Several o t h e r types of ester solvents
most synthetic resins. Their strong solvency, together with are also c o m m e r c i a l l y available as specialty products. The
the wide r a n g e of volatilites available, m a k e s t h e m a n ex- alkyl esters cover a wide range of volatilities, m a i n l y methyl
t r e m e l y i m p o r t a n t g r o u p of solvents for the coatings industry. t h r o u g h hexyl esters. Glycol e t h e r acetates are slow-evaporat-
Other distinguishing characteristics include h i g h e r specific ing, a n d they are used as r e t a r d e r solvents in solvent-based
gravity a n d p a r t i a l to c o m p l e t e w a t e r solubility. coatings a n d as coalescents in latex paints.
There are four p r i n c i p a l types of oxygenated solvents Esters have strong solvency, a l t h o u g h generally slightly
widely used in coatings: ketones, esters, glycol ethers (ether w e a k e r t h a n ketones of s i m i l a r volatility. They are character-
alcohols), a n d alcohols. T h r o u g h blending, a l m o s t a n y de- ized by their pleasant, sweet, fruity odors. All esters have
sired c o m b i n a t i o n of p e r f o r m a n c e p r o p e r t i e s can be ob- n a r r o w distillation ranges since they are relatively p u r e com-
tained. pounds.
Typical p r o p e r t i e s of the m o s t c o m m o n ester solvents are
Ketones s u m m a r i z e d in Table 6. As with ketones, their solvencies fol-
Ketones are c h a r a c t e r i z e d chemically by a c a r b o n y l g r o u p low a general pattern, d i m i n i s h i n g with increasing m o l e c u l a r
b o n d e d to two c a r b o n a t o m s or alkyl groups in the molecule. weight a n d with increasing b r a n c h i n g of the molecule. Evap-
This versatile class of solvents has powerful solvency and a o r a t i o n rate also decreases with increasing m o l e c u l a r weight,
wide range of e v a p o r a t i o n rates, from very fast-evaporating b u t increases with i n c r e a s e d branching, n-Butyl acetate, one
acetone to slow-evaporating isophorone. Ketones are further of the most i m p o r t a n t ester solvents, has a m e d i u m evapora-
c h a r a c t e r i z e d by their strong, s h a r p odors. They have n a r r o w tion rate. It is used as a reference for expressing e v a p o r a t i o n
distillation ranges b e c a u s e of t h e i r high purity. Acetone is rates of o t h e r solvents.
c o m p l e t e l y w a t e r miscible, while o t h e r ketones have varying
degrees of w a t e r solubility. Properties of selected ketones, Glycol Ethers
with their ASTM specification references, are s u m m a r i z e d in Glycol ethers are e t h e r alcohols, having b o t h ether a n d
Table 5. (Diacetone alcohol is included in this category since alcohol functionality. The ethylene glycol ethers, derived
this ketone alcohol functions m o r e as a ketone t h a n a n alco- from ethylene oxide a n d alcohols, have been widely used in
hol.) coatings. However, b e c a u s e of health h a z a r d c o n c e r n s associ-
Acetone is very fast-evaporating. It is often used in aerosols ated with certain ethylene glycol ethers, they are being re-
a n d sprayed coatings, p a r t i c u l a r l y in nitrocellulose a n d p l a c e d in m a n y a p p l i c a t i o n s b y p r o p y l e n e glycol ethers w h i c h
acrylic lacquers, to effectively reduce viscosity for s p r a y ap- are derived from p r o p y l e n e oxide.
plication a n d then quickly flash off d u r i n g the spraying pro- Glycol ethers have a truly unique c o m b i n a t i o n of p r o p e r -
cess. Methyl ethyl ketone (MEK) has a fast e v a p o r a t i o n rate ties: strong solvency, slow e v a p o r a t i o n rate, c o m p l e t e w a t e r
a n d methyl isobutyl ketone (MIBK) a m o d e r a t e e v a p o r a t i o n miscibility, high flash point, a n d m i l d odor. They are often
TABLE 5--Typical properties of selected ketone solvents.

Purity Specific Evaporation Flash Toluene
ASTM Test, Gravity, Boiling Rate, Point, Dilution
Solvent Specification ASTM 20/20~ Point, ~ n-BuAc = 100 TCC,~ (~ Ratio
Acetone D 329 D 1363 0.792 56 1160 0 (-18) 4.5
Methyl ethyl ketone D 740 D 2804 0.806 80 570 20 ( - 7) 4.3
Methyl isobutyl ketone D 1153 D 3329 0.802 116 165 60 (16) 3.6
Methyl isoamyl ketone D 2917 D 3893 0.814 145 50 96 (36) 4.1
Methyl n-amyl ketone D 4360 D 3893 0.817 151 40 102 (39) 3.9
Diacetone alcohol D 2627 ... 0.940 170 12 120 (49) 3.0
Isophorone D 2916 D 2192 0.922 215 3 180 (82) 6.2
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TABLE 6--Typical properties of selected ester solvents.

Solvent Specification ASTM 20/20~ Point, ~ n-BuAc = 100 TCC, ~ (~ Ratio
Methyl acetate . . . . . . 0.904 55 1180 0 ( - 18) 2.9
Ethyl acetate D 4614~ D 3545 0.901 77 410 24 ( - 4 ) 3.1
Isopropyl acetate D 3131 D 3545 0.873 88 360 35 ( + 2) 3.0
n-propyl acetate D 3130 D 3545 0.889 101 230 55 (13) 3.2
Isobutyl acetate D 1718 D 3545 0.871 115 145 62 (17) 2.7
n-butyl acetate D 4615~ D 3545 0.883 126 100 81 (27) 2.8
n-amyl acetate D 3540 D 1617 0.876 140 40 101 (38) 2.3
Methyl amyl acetate D 2634 D 1617 0.858 148 20 96 (36) 1.7
n-hexyl acetate D 5137 D 1617 0.874 165 17 134 (57) 1.8
n-butyl propionate . . . . . . 0.876 145 45 100 (38) 2.1
n-pentyl propionate . . . . . . 0.872 168 18 135 (57) 1.8
2-ethoxyethyl acetate b D 3728 D 3545 0.974 156 20 126 (52) 2.5
PM acetatec D 4835 D 4773 0.969 146 34 114 (46) 2.6
~Four grades.
bEthyleneglycol monoethylether acetate.
cPropylene glycolmonomethylether acetate.
used i n small percentages in lacquers a n d lacquer t h i n n e r s as resins, a n d certain alkyds. They are also useful coupling sol-
retarder solvents to m a i n t a i n coating flow a n d leveling after vents, with glycol ethers, to solubilize water-reducible resins.
most of the other solvents have evaporated. I n these applica- I n addition to their use as solvents, latent solvents, a n d cou-
tions, their water miscibility is beneficial in reducing mois- pling solvents, alcohols are used as chemical raw materials
ture blush. Glycol ethers are also widely used as coupling for the m a n u f a c t u r e of other solvents (e.g., ketones a n d es-
solvents i n water-based coatings to solubilize the water-re- ters), m o n o m e r s , a n d synthetic polymers.
ducible polymers. Methanol is the fastest evaporating alcohol. It is the only
Chemical terminology for the glycol ethers is cumbersome. alcohol which has some solvency for nitrocellulose. Metha-
For example, 2-ethoxyethanol is also referred to as ethylene nol, historically k n o w n as wood alcohol, is n o w rarely used as
glycol monoethyl ether. Therefore, they are often identified a solvent because of its relative toxicity.
by their c o m m e r c i a l b r a n d names. Typical properties of se- Pure ethyl alcohol (ethanol) is restricted in use by law to
lected glycol ethers are s u m m a r i z e d in Table 7. beverages a n d to scientific a n d analytical purposes. It c a n n o t
be used without a federal g o v e r n m e n t permit. Commercial
Alcohols ethyl alcohol, for solvent a n d chemical i n t e r m e d i a t e use, is
Mcohols are chemically characterized as organic com- d e n a t u r e d with any of a large n u m b e r of government-ap-
p o u n d s having a single hydroxyl group. This structure improved substances to make it unfit for use in beverages. There
parts some degree of water solubility to alcohols, complete are close to 100 approved d e n a t u r e d f o r m u l a t i o n s available
for the lower members, methanol, ethanol, a n d propanol, a n d in both 95 vol% (190 proof) a n d a n h y d r o u s (200 proof)
partial for the higher m e m b e r s of the family. Alcohols are grades. Because of the large multiplicity of grades, ASTM
further characterized physically as having mild, pleasant specifications have not been established for ethyl alcohol.
odors. Typical properties of selected alcohols are s u m m a - Isopropyl alcohol can replace ethyl alcohol in most coating
rized in Table 8. solvent applications.
By themselves, alcohols are very poor solvents or n o n - Butyl alcohols (butanols) differ in volatility a n d solvency
solvents for most polymers. There are few exceptions; ethanol a m o n g the four isomers, which are: normal, secondary, iso-,
is a solvent for shellac, poly(vinyl acetate), poly(vinyl bu- a n d tertiary. All have moderate volatility. B r a n c h i n g in-
tyrate), some phenolics, a n d n a t u r a l resins. Alcohols find ap- creases volatility a n d decreases solvency, n - B u t a n o l is by far
plications as latent solvents or co-solvents for nitrocellulose the most widely used isomer, t-Butanol is a solid at r o o m
lacquers, m e l a m i n e - f o r m a l d e h y d e a n d urea formaldehyde temperature.
TABLE 7--Typical properties of selected glycol ether solvents.

Solvent Specification ASTM 20/20~ Point, ~ n-BuAc = 100 TCC, ~ (~ Ratio
2-Methoxyethanol~ D 3128 ... 0.966 125 56 103 (39) 4.0
2-Ethoxyethanolb D 331 --. 0.931 136 35 108 (42) 4.9
2-ButoxyethanoF D 330 ... 0.902 171 6 150 (66) 3.5
Propylene glycol D 4837 D 4773 0.923 121 71 94 (34) 5.2
monomethyl ether
Dipropylene glycol D 4836 D 4773 0.956 188 3 167 (75) 4.2
monomethyl ether
aEthylene glycol monornethylether.
bEthyleneglycol monoethylether.
CEthyleneglycolmonobutylether.
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TABLE 8--Typical properties of selected alcohol solvents.

Solubility, 20~
Purity Specific Evaporation Flash wt%
ASTM Test, Gravity, Boiling Rate, Point,
Solvent Specification ASTM 20/20~ Point, ~ n-BuAc= 100 TCC, ~ (~ In Water Water In
Methanol D 1152 E 346 0.793 64 600 52 (11) Complete Complete
Ethanol (anhydrous) . . . . . . 0.790 78 260 55 (13) Complete Complete
Isopropanol D 770 ...a 0.786 82 230 54 (12) Complete Complete
n-Propanol D 3622 ...4 0.804 97 100 74 (23) Complete Complete
sec-butanol D 1007 ...a 0.808 99 120 74 (23) 20.0 36.3
Isobutanol D 1719 ...a 0.803 107 70 85 (29) 9.5 14.3
n-butanol D 304 ...4 0.811 117 50 97 (36) 7.9 20.8
n-amyl alcohol D 319 ..-~ 0.813 130 30 91 (33) 1.7 9.2
Methyl isobutyl D 2635 ...~ 0.808 131 30 103 (39) 1.6 6.3
carbinol
2-ethyl hexanol D 1969 D 5008 0.834 182 <1 164 (73) 0.1 2.6
~Purityand identity of these pure compounds are determined by a combination of tests of specificgravity (ASTMD 268 or D 4052), boiling point, and distillation
range (ASTMD 1078).
The higher-boiling alcohols are used in relatively small 1,1,1-trichloroethane ( m e t h y l c h l o r o f o r m ) has f o u n d sol-
a m o u n t s in solvent blends, a n d they find a p p l i c a t i o n s m a i n l y vent a p p l i c a t i o n s in coating f o r m u l a t i o n s b e c a u s e it is con-
in b a k e d industrial coatings. sidered to be n o n - p h o t o c h e m i c a l l y reactive by m a n y regula-
tory agencies, a n d therefore it does not have to be i n c l u d e d in
m e a s u r i n g volatile organic c o m p o u n d (VOC) content [1].
Other Oxygenated Solvents
Trichloroethylene is widely used for metal cleaning in va-
Specialty oxygenated solvents include f u r a n solvents a n d p o r degreasing operations. (See ASTM D 3698, Practice for
o r g a n i c carbonates. Currently, they are not specified b y
Solvent V a p o r Degreasing Operations.)
ASTM standards. I n f o r m a t i o n a b o u t t h e m m a y be o b t a i n e d
Use of c h l o r i n a t e d solvents is declining due to (a) global
f r o m their suppliers.
c o n c e r n s a b o u t t h e i r d a m a g i n g effects on the earth's protec-
F u r a n solvents of c o m m e r c i a l interest include furfuryl al-
cohol, t e t r a h y d r o f u r a n (THF), a n d t e t r a h y d r o f u r f u r y l alco- tive o z o n e layer a n d (b) c o n c e r n s a b o u t the toxicity a n d
hol. These solvents have a cyclic e t h e r structure a n d are char- carcinogenicity of m a n y c h l o r i n a t e d solvents.
acterized by exceptionally strong solvency for s o m e synthetic
resins, especially vinyls.
Ethylene a n d p r o p y l e n e c a r b o n a t e s are cyclic organic es- Nitrated Hydrocarbons
ters w h i c h are good solvents for m a n y organic a n d i n o r g a n i c
materials. The f o r m e r is a solid at r o o m t e m p e r a t u r e . Charac- N i t r o g e n - c o n t a i n i n g h y d r o c a r b o n solvents include nitro-
teristics of these c a r b o n a t e s include high flash point, very paraffins a n d N-methyl-2-pyrrolidone (NMP). These are not
slow e v a p o r a t i o n rate, high specific gravity, a n d very low currently specified b y ASTM s t a n d a r d s .
odor. There are four nitroparaffinic solvents c o m m e r c i a l l y avail-
able: n i t r o m e t h a n e , nitroethane, 1-nitropropane, a n d 2-ni-
Other Solvents t r o p r o p a n e (2NP). Of these, 2NP is of m o s t interest to the
Chlorinated Hydrocarbons coatings industry. It has an e v a p o r a t i o n rate s i m i l a r to t h a t of
n-butyl acetate, a n d it is r e p o r t e d to have fast solvent release
Chlorinated solvents obviously c o n t a i n chlorine a t o m s in
f r o m coating films.
the molecules. This gives t h e m u n i q u e features of non-flam-
mability, i.e., no flash point, a n d very high specific gravity. NMP is a specialty solvent having strong solvency, high
Several c h l o r i n a t e d solvents specified by ASTM s t a n d a r d s are flash point, c o m p l e t e w a t e r solubility, a n d high specific grav-
s u m m a r i z e d in Table 9. ity. It is r e p o r t e d to be b i o d e g r a d a b l e a n d have a low o r d e r of
Methylene chloride has long b e e n the active ingredient in toxicity. Applications include p a i n t strippers, w a t e r - b a s e d
m o s t p a i n t removers. It has strong solvency to soften a n d coatings, printing inks, a n d r e a c t i o n solvent for high-temper-
swell c u r e d p a i n t films a n d a very fast e v a p o r a t i o n rate. a t u r e resins.
TABLE 9--Typical properties of selected chlorinated hydrocarbon solvents.

Specific Evaporation
ASTM Gravity, Boiling Rate,
Solvent Specification Grade or Application 20/20~ Point, ~ n-BuAc= 100
Methylene chloride D 3506 Pentachlorophenol solutions 1.366 39 1450
D 4079 Vapor degreasing
D 4701 Technical grade
1,1,l-trichloroethane D 4126 General solvent; vapor degreasing 1.327 72 600
Trichloroethylene D 4080 Vapor degrcasing 1.465 86 450
Perchloroethylene D 4081 Dryclea-ning 1.625 121 210
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Supercritical Carbon Dioxide [7] The UNICARB~g~ process has been developed to utilize
It has long been known that certain gases under su- supercritical carbon dioxide in airless sprayed coating opera-
percritical temperature and pressure conditions can behave tions. It has numerous advantages in this application. The
as solvents. They have become useful in a variety of industrial temperatures and pressures necessary to use supercritical
and analytical separation processes, such as extraction, poly- carbon dioxide are well within the capabilities of present hot,
mer fractionation, chromatography, and catalyst regenera- airless spray systems.
tion, and as a reaction medium. Carbon dioxide has low toxicity, is non-flammable, inert,
Supercritical fluids have properties intermediate to those inexpensive, and readily available. Supercritical carbon diox-
of normal liquids and gases. The supercritical fluid region on ide has high solubility in most coating formulations, and it is
a phase diagram corresponds to temperatures and pressures a good viscosity reducer for polymer solutions. In the actual
near or above the critical point of the fluid where the proper- spraying process, it behaves as a highly volatile solvent, pro-
ties of the liquid and gas are similar or identical, so that in ducing vigorous atomization that can remedy many of the
effect only one fluid phase, which is simultaneously liquid- defects of airless spraying, thereby achieving high quality
like and gas-like, exists (Fig. 1). coatings.
Supercritical carbon dioxide has many useful attributes
which make it attractive as a diluent for spray-applied coat-
ings. Carbon dioxide is environmentally compatible because CLASSIFICATION BY FUNCTION
it is not regarded as a volatile organic compound (VOC). It
acts as a hydrocarbon diluent and replaces organic solvents Solvents can be classified according to the function they
to the extent of 10 to 30 vol% of a formulation. Low VOC perform in an end-use application: active solvents, latent sol-
coatings can be formulated with existing high-performance vents, and diluents.
polymer systems, and 70 to 80% reductions in VOC are
achievable. Using carbon dioxide as a coating solvent effects
a net reduction in the amount of "green house" carbon diox- Active Solvents
ide that is otherwise produced as a result of coating opera- Active solvents are sometimes called "true solvents." They
tions. are the ones that really do the work to dissolve resins and
other film formers. Active solvents are usually the more ex-
pensive ones with strong solvent power: ketones, esters, and
5000 _ /
glycol ethers. They are essential for dissolving film-forming
resins and for effectively reducing viscosities of paints, var-
nishes, and lacquers for application.
Relative solvency of active solvents, particularly for lac-
quers, may be determined by ASTM method D 1720, Dilution
1000 L,OUID .,,.,,e Ratio of Active Solvents in Cellulose Nitrate Solution, and
expressed in terms of toluene dilution ratio. Stronger solvents
_- REGION/ CRITICAL will tolerate more hydrocarbon diluent and still keep resins in
O _ / POINT solution. High toluene dilution ratio values indicate strong
/ solvency. Typical values for selected active solvents may be
- SOLID / VAPOR compared in Tables 5 through 7.
-- REGION / REGION
100 / Latent Solvents
By themselves, latent solvents are either poor solvents or
nonsolvents for most coating resins. However, they possess a
RIPLE hidden or latent solvency which manifests itself when they
Z L / POINT are used in combination with active solvents. Latent solvents
then behave as if they were strong active solvents. This syner-
gism is used to advantage in formulating nitrocellulose lac-
quers in particular. Latent solvents are often alcohols, and
they are intermediate in cost.
==
Diluents
Diluents are generally nonsolvents if used alone with syn-
thetic resins. Their function is to participate in solvent blends
1 to provide viscosity reduction through dilution of lacquers
and paints and to reduce the cost of thinners and coating
-160 -120 -80 -40 0 40 80 120
TEMPERATURE IN ~'F 2Union Carbide Chemicals and Plastics Co. Inc., 39 Old Ridgebury
FIG. 1-Phase diagram for carbon dioxide [7]. Road, Danbury, CT 06817-0001.
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solvent blends. Diluents are uslaally low-cost hydrocarbon rectly compared by measuring the viscosities of solutions at
solvents. different resin concentrations and plotting viscosity versus
There is usually a limit to how much diluent will be toler- resin concentration.
ated by coating resins in a solvent blend. If the limit is
exceeded, the resins will start to gel or precipitate from solu- Kauri-Butanol Value
tion. Aromatic hydrocarbon solvents are usually tolerated in Kauri-butanol value (KBV) is one measure of the solvent
greater amounts than are aliphatic hydrocarbons. power of hydrocarbon solvents. High KBV indicates rela-
ASTM Method D 1720 may be used to determine the relatively strong solvency and often relatively high aromatics
tive tolerances for hydrocarbon diluent when n-butyl acetate content as well. Typical KBVs may be compared in Tables 1
is used as the reference active solvent. In the test, the maxi- through 4.
mum ratio of hydrocarbon diluent to n-butyl acetate that will KBV is a continuous scale and is sometimes used as an
be tolerated by a solution of 8 g of nitrocellulose in a total of indicator of aromatics content; low aromatic (aliphatic) hy-
100 mL of solvent and diluent is determined. This provides a drocarbons have low KBVs and weak solvency, while highly
measure of the suitability of the diluent for lacquer solvent aromatic hydrocarbons have high KBVs and relatively strong
formulations. For example, the toluene dilution ratio of n- solvency. For example, odorless mineral spirits at the low end
butyl acetate is 2.8, while the VM&P naphtha dilution ratio is of the scale has a KBV of about 27, regular mineral spirits
only 1.2, indicating a much greater tolerance for toluene than about 37, and aromatic hydrocarbons close to 100.
for VM&P naphtha. KBV is defined in ASTM Method D 1133, Kauri-Butanol
Value of Hydrocarbon Solvents, as the volume in milliliters of
the solvent at 25~ required to produce a defined degree of
Solvent Balance turbidity when titrated into a specified quantity of a standard
In formulating coating solvents and thinners, careful atten- clear solution of kauri resin in n-butyl alcohol. Kauri resin, a
tion must be paid to the proper balance of solvency and natural product, now archaic, was once used as a coating
evaporation rate. Generally, expensive active solvents are resin. However, standard test solutions are available from
kept to a minimum amount sufficient to provide adequate chemical supply companies. The kauri resin solution is stan-
solvency and viscosity reduction. Diluent content is usually dardized against toluene, which has an assigned value of 105,
maximized to keep cost low. and a mixture of 75% n-heptane and 25% toluene on a volume
Evaporation rate of each component must be considered in basis, which has an assigned value of 40.
selecting appropriate active solvents and diluents depending The procedure is to accurately weigh 20 g of standardized
on the method of coating application. As the applied coatings kauri-butanol solution into an Erlenmeyer flask and bring the
dry, the balance of active solvents and diluents remaining in flask and its contents to 25~ in a water bath. It is then titrated
the wet coating must be such that solvency for the coating with the solvent being tested to a turbidity end point that
resin remains sufficiently strong throughout the drying pro- occurs when the sharp outlines of 10-point print on a sheet
cess. Otherwise, resin blush, i.e., precipitation or separation placed under the flask are obscured or blurred but are not
of the resin, can occur resulting in loss of gloss, incompatibil- illegible. Turbidity at the end point is caused by precipitation
ity, haze, or other serious coating defects. of the kauri resin at incipient incompatibility.
This test is not applicable to oxygenated solvents.
Aniline Point
KEY PERFORMANCE REQUIREMENTS
Aniline point (or mixed aniline point) is another measure of
solvency of hydrocarbon solvents. In addition, it is often used
Solvency to provide an estimate of the aromatics content of hydrocar-
Solvency is the foremost performance requirement of a bon mixtures. Aromatic hydrocarbons (strong solvents) ex-
solvent. From a practical perspective, the term "solvency" to a hibit the lowest aniline points and aliphatics (weak solvents)
coatings formulator refers to the ability of a solvent to (a) the highest. Naphthenes have values between those for aro-
dissolve resins, (b) hold those resins in solution in the pres- matics and aliphatics. In homologous series, the aniline point
ence of diluents, and (c) efficiently reduce viscosity of resin increases with increasing molecular weight, i.e., decreasing
solutions, lacquers, and paints. In general, relative solvency is solvency.
measured indirectly by determining compatibility of speci- Aniline point is defined in ASTM Method D 611, Aniline
fied resins or a chemical reagent with the solvent under test. Point and Mixed Aniline Point of Petroleum Products and
Three test methods are most often used for measuring and Hydrocarbon Solvents, as the minimum equilibrium solution
expressing relative solvent strength: kauri-butanol value, ani- temperature for equal volumes of aniline and solvent. The
line point, and diluent dilution ratio. The first two test meth- reagent for this test is aniline, a clear liquid at room tempera-
ods are used exclusively for hydrocarbon solvents and the ture. The procedure requires that equal volumes of aniline
latter test for only oxygenated solvents. Although these meth- and hydrocarbon solvent are placed in a jacketed tube and
ods are somewhat archaic, the values obtained have been mechanically mixed. The basic apparatus is shown in Fig. 2,
found to be useful in estimating general solvency for many although ASTM D 611 also describes alternative variations in
coating resins. the manual apparatus and an automatic apparatus as well.
Another method, a viscosity reduction test, provides a Hydrocarbon solvents containing less than 50% aromatics
means of direct measurement of solvent power when a spe- will generally form an incompatible, turbid mixture at room
cific resin under consideration is employed. Solvents are di- temperature [8]. Therefore, the stirred mixture is heated at a
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CHAPTER 1 8 - - S O L V E N T S 133
added to a unit volume of solvent to cause the first persistent

heterogeneity (precipitation) in the solution at a concentra-
tion of 8 g of cellulose nitrate per 100 mL of combined sol-
~ .~ANILINEPOINT vent plus diluent at 25~
The procedure is to dissolve carefully dried nitrocellulose
IL -11tl in the oxygenated (active) solvent, and with stirring, add hy-
drocarbon diluent by titration. The end point occurs at the
first persistent appearance of resin precipitation or gelation.
Additional active solvent is then added to redissolve the resin,
and titration is continued to a second end point. The data are
plotted to determine the ratio of diluent to active solvent at
exactly 8 g of cellulose nitrate per 100 mL of total solvent.
Most often, toluene is used as the diluent in the test, and the
result is expressed as the "toluene dilution ratio." However,
other hydrocarbons, e.g., VM&P naphtha, may also be used,
thereby producing different (lower) values expressed as
"naphtha dilution ratios." Although cellulose nitrate is used
as the "reagent" in this test, and the results are most meaning-
FIG. 2-Aniline point apparatus. ful for formulating nitrocellulose lacquers, it has been found
from experience that the solvency ranking of oxygenated sol-
vents according to their diluent dilution ratios applies to
controlled rate until the two phases become miscible and other coating resins as well.
dear. The stirred mixture is then allowed to cool at a con- As described in the Section entitled "Diluents," ASTM
trolled rate until it suddenly becomes cloudy throughout. The D 1720 may also be applied to compare and measure the
temperature at this end point is recorded as the aniline point suitability of specific diluents for use in lacquer solvent and
of the solvent. thinner formulations by using n-butyl acetate as the reference
Hydrocarbon solvents containing more than 50% aromat- active solvent in the test.
ics will generally form dear, miscible solutions with aniline
at room temperature [8]. When this occurs, the stirred mix-
ture must be cooled below room temperature at a controlled Dilution Limit
rate until the cloudy transition point suddenly appears. The Some resins are soluble at high concentrations in a solvent
temperature at this cloud point is the aniline point. but become incompatible and precipitate when diluted below
With hydrocarbons having high aromatics content, the ani- a critical concentration, which is termed the dilution limit.
line point may be far below room temperature and below the Sometimes, this concentration is within the range of practi-
temperature at which aniline will crystallize from the aniline- cal formulations. Therefore, it is important to know whether
sample mixture. To treat this circumstance, it becomes nec- a dilution limit exists for a particular resin. To determine the
essary to perform a "mixed aniline point" test. Instead of dilution limit, a known weight of resin is dissolved in the
using equal volumes of aniline and sample, a mixture con- solvent. Solvent is then added until precipitation, the first
taining two volumes of aniline, one volume of sample, and persistent cloudiness, appears. Dilution limit is expressed as
one volume of n-heptane of specified purity is made. The test the percent by weight of resin at the end point [8].
is then performed as described above, and the result is re-
ported as the "mixed aniline point." Again, low values indi- Viscosity Reduction
cate strong solvency (the opposite of kauri-butanol values).
Unlike the continuous KBV scale, a disadvantage of the The relative solvency of different solvents for a given resin
aniline point and mixed aniline point is that the two scales may be compared with each other or with a reference solvent
are not continuous. Therefore, it is difficult to directly com- by measuring the viscosities of different concentrations of the
pare high- and low-aromatic content solvents [8]. given resin in each of the solvents. The viscosities are then
This test is not applicable to oxygenated solvents. plotted as a function of resin concentration. An example is
shown in Fig. 3 [I].
Diluent Dilution Ratio Viscosities of resin solutions can be measured precisely by
The diluent dilution ratio test measures the solvency of ASTM Method D 445, Kinematic Viscosity of Transparent
oxygenated (active) solvents by determining their ability to and Opaque Liquids, or by ASTM Method D 1725, Viscosity
hold in solution a difficult-to-dissolve resin, nitrocellulose, in of Resin Solutions. A simpler, more wideJy used, but less
the presence of hydrocarbon diluent. The test measures the precise method for determining resin solution viscosities is
maximum ratio of hydrocarbon diluent to oxygenated solvent ASTM Method D 1545, Viscosity of Transparent Liquids by
that can be tolerated by the nitrocellulose solution. Strong Bubble Time Method (Gardner-Holdt Viscosity).
oxygenated solvents provide a high tolerance for diluent and At high resin concentrations, solution viscosity will depend
have high diluent dilution ratios. Typical values may be com- on solvency of the solvent and solubility of the resin. How-
pared in Tables 5 through 7. ever, at low resin concentrations, the solution viscosity be-
ASTM Method D 1720 defines diluent dilution ratio as the comes more influenced by viscosity of the pure (neat) solvent.
maximum number of unit volumes of a diluent that can be Viscosities of selected solvents are listed in Table 10 [17].
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5OO TABLE lO--Viscosities of typical commercial solvents.

Viscosity,
Solvent Cp at 25~
Hydrocarbons
VM&P naphtha 0.68
100
Mineral spirits 1.10
Toluene 0.62
Xylene 0.67
50 High-flash aromatic naphtha 1.08
Ketones
Acetone 0.31
Methyl ethyl ketone 0.41
Z Methyl isobutyl ketone 0.56
Methyl isoamyl ketone 0.73
Methyl amyl ketone 0.77
Isophorone 2.3
j, Esters
Ethyl acetate 0.45
Isopropyl acetate 0.52
Isobutyl acetate 0.68
n-butyl acetate 0.68
n-amyl acetate 0.83
Propylene glycol monomethyl ether acetate 1.1
Ethylene glycol monoethyl ether acetate 1.2
Ethylene glycol monobutyl ether acetate 1.7
0.5
Alcohols
Ethanol 1.1
0.2 1 I I I I I I n-propanol 2.0
0 10 20 30 40 50 60 i-propanol 2.4
n-butanol 2.6
Resin Concentration, vol % s-butanol 2.9
FIG. 3-Effect of solvent type on solution viscosity (medium n-amyl alcohol 3.7
oil alkyd in four hydrocarbon types) [1].
Glycol Ethers
Propylene glycol monomethyl ether 1.7
Solubility Parameters Ethylene glycol monoethyl ether 1.9
Ethylene glycol monobutyl ether 2.9
Great strides have been made in developing theoretical
models to describe solvency and to predict the capacity of a
pure solvent or solvent blend to dissolve a given resin. The discussion of solubility parameters can be found in Chapter
concept of solubility parameters was first proposed by 35.
Hildebrand [9,10], and it was applied to practical applica- A very comprehensive source of solubility parameter infor-
tions in the coatings industry by Burrell [11]. Further refine- mation and data is the "CRC Handbook of Solubility Parame-
ments and enhancements to the solvency model made by ters and Other Cohesive Parameters" by A. F. M. Barton
Burrell [12], Crowley [13], Hansen [14,15], and others have (CRC Press, 1983). A simpler, two-dimensional approach to
resulted in the evolution of a model that is workable, reason- solubility parameters, employing only the dispersion and hy-
ably accurate in its predictions, and useful as a formulating drogen bonding parameters, is described in ASTM Method
tool. D 3132, Test for Solubility Range of Resins and Polymers.
The three-dimensional solubility parameter is the most Most major solvent suppliers have developed computer pro-
widely used method for predicting miscibility/solvency be- grams, based on the solubility parameter concept, to aid in
formulating solvent blends to optimize solvency, obtain de-
tween solvents and polymers. In this method, each polymer
sired performance requirements, and minimize cost.
and each solvent is characterized by three solubility parame-
ters: 8d representing dispersion forces, 8p representing polar
forces, and 8h representing hydrogen bonding forces. There- Volatility
fore, polymers and solvents can be represented by points in a Volatility of a solvent describes its inherent tendency to
three-dimensional plot using the three solubility parameters. transform from a liquid to a vapor. The fundamental control-
Each polymer point may constitute the center of a sphere, ling property is vapor pressure. Volatility is manifested by
the so-called "sphere of solubility," of radius R, known as the such properties as evaporation rate, boiling point, and flash
radius of interaction. Solvents whose points lie at a distance point.
less than R from the center of the polymer's sphere, i.e.,
within the sphere, should dissolve the polymer. Conversely, Vapor Pressure
solvents whose point coordinates lie outside of the sphere are All liquids have a tendency to vaporize and become gases,
not expected to dissolve the polymer [16]. A more thorough depending upon their relative vapor pressures. A solvent's
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liquid vapor pressure is the pressure exerted by molecules at TABLE 1l--Vapor pressures of typical commercial solvents.
the liquid surface in their attempt to escape the liquid phase Vapor Pressure
and penetrate their gaseous environment. In a physical sense, Solvent at 20~ mm Hg
vapor pressure is the force exerted on the walls of a dosed Hydrocarbons
container by the vaporized portion of the liquid. Conversely, VM&P naphtha 5.2
it is the force which must be exerted on the liquid to prevent it Mineral spirits 3.4
from vaporizing further. For a given liquid solvent, vapor Toluene 38
Xylene 9.5
pressure is a function purely of temperature. The more vola- High-flash aromatic naphtha <1
tile a solvent, the higher the liquid vapor pressure at a speci-
fied temperature and the faster the vaporization, i.e., evapo- Ketones
ration rate. A knowledge of the vapor pressure/temperature Acetone 185
relationship is important in the safe design of solvent storage Methyl ethyl ketone 85
Methyl isobutyl ketone 16
and distribution equipment to minimize solvent losses by Methyl isoamyl ketone 4.0
vaporization. Methyl amyl ketone 1.0
Relative vapor pressures of pure solvents and blends are Isophorone 0.3
measured at 100~ (38~ by ASTM Method D 323, Reid Va-
Esters
por Pressure (RVP). The RVP apparatus consists of a double-
Ethyl acetate 76
chamber bomb fitted with a pressure gage. The lower cham- Isopropyl acetate 48
ber, which has one quarter the capacity of the upper cham- Isobutyl acetate 12.5
ber, is filled with the liquid solvent sample. The sample and n-butyl acetate 7.8
its chamber are chilled to 0~ (32~ to reduce premature n-amyl acetate 4.0
evaporation, the bomb is sealed, and it is immersed in a 100~ Propylene glycol monomethyl ether acetate 3.7
Ethylene glycol monoethyl ether acetate 1.7
(38~ water bath. To assure full opportunity for vaporiza- Ethylene glycol monobutyl ether acetate 0.29
tion, the bomb is removed from the bath periodically for a
brief vigorous shaking. When an equilibrium temperature is Alcohols
reached and when the bomb pressure gage (which initially Ethanol 44
registered zero) has stabilized at maximum value, the pres- i-propanol 31
n-propanol 15
sure is recorded. After applying appropriate correction fac- s-butanol 12
tors, the pressure is reported as Reid vapor pressure at 100~ n-butanol 4.4
(38~ n-amyl alcohol 2.0
Alternatively, vapor pressure of a solvent can be measured
Glycol Ethers
over a wide range of temperatures by ASTM Method D 2879, Propylene glycol monomethyl ether 11
Vapor Pressure by Isoteniscope. This procedure utilizes a Ethylene glycol monoethyl ether 4.1
differential manometer, one leg of which is exposed to satu- Ethylene glycol monobutyl ether 0.9
rated vapor while the other is evacuated. Measurements are
reported in absolute units. Absolute vapor pressures of se-
lected solvents at 20~ are listed in Table 11 [6,17]. Evaporation rates of solvents are always expressed on a
relative basis. They are not absolute values in practical situa-
Evaporation Rate tions because evaporation rates are dependent upon numer-
ous environmental factors including temperature, airflow,
Evaporation rate of a solvent is second only to solvency in humidity, exposed surface area, and the presence of resin and
its importance to the coatings industry. Although solvents are pigment. Humidity has no effect on the evaporation of hydro-
transient ingredients of a coating, they perform vital func- carbon solvents, but it can significantly retard evaporation of
tions but must ultimately leave the coating film by evapora- oxygenated solvents which are completely or partially water
tion. During application of a coating, solvents play a role in miscible.
controlling flow characteristics as the film forms. If solvent It is common practice to express evaporation rates relative
evaporation is too fast, the coating film will not level and flow to n-butyl acetate, a widely used, medium-evaporating sol-
out to form a smooth surface, the result being a rough, "or- vent as a reference. Evaporation rate of n-butyl acetate is
ange peel" effect in spray-applied coatings, or brush marks if arbitrarily assigned a value of 100 (or sometimes 1.0 depend-
brush applied. Conversely, if solvent evaporation is too slow, ing on the scale used). Solvents evaporating faster than n-
the coating may run and sag on vertical surfaces, or solvents butyl acetate have higher values for evaporation rate; those
may become trapped in the film as it cures, thus impairing solvents evaporating slower have lower numerical values. Use
performance properties of the coating. of a reference standard compensates for differences in test
Proper solvent balance, the ratio of active solvent to dilu- procedure or environmental factors.
ent, is also important. If this balance becomes upset as a Numerous techniques have been used for measuring rela-
result of composition changes during evaporation, resin pre- tive evaporation rates, some of them gravimetric, some volu-
cipitation can occur, thereby causing a loss of film integrity. metric. The ones currendy most widely used are based on the
Therefore, solvent evaporation rate is a key factor in the gravimetric procedure and instrumentation (or some varia-
formulation of coatings. Relative evaporation rates of se- tion thereof) described in ASTM D 3539, Test Method for
lected solvents of various types may be compared in Fig. 4 Evaporation Rates of Volatile Liquids by Shell Thin-Film
and in Tables 1 through 9. Evaporometer. In this method, a measured volume of liquid
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136 P A I N T A N D C O A T I N G T E S T I N G M A N U A L
Aliphatic Aromatic Glycol

I~o_
HC HC Ketones Acetates Ethers Alcohols Others
~-H-exane~ACetone_R~l~ Methylene
8O~ . Chloride
Cyclohexane~j
7 ~ ' i ~
60~_! ~H e, .p't a n ]e i ' : ~i [ i II! ~; : I ''"
:K' ' ~ ' 1,1,1-Tri-
50~
Benzene i~h~0roethane
40~_ Lacquer~ i ITrichloro-
~ E t h y l i [I I : '
~Diluent .... ] , ! 1 - ~ 1 : I .I,, :t : Il eetl
thyle?e
Isopropyl= ~: ;
3D~ ~ , ~
:ij,:ii'i,!ii:i ~J:l,l;!: I
iiiii!: ;Iii:i}I ;~iI]~Ii I : :

, t
Lj [9
:VM&P ~ , ~ n-Prop: i -Isopropyl: Perchloro-

20~_ Napht~ " : 9i ; i i 1 .;:,
... e t ih~yi ll~einu ei a
Toluene 1 I i ! I I ! I ' i ,
r
i,, 'li~ i
Isobutyl
Illli li
i,'~/;,, ~lil ~lil
ill. i i l l ~ l
_ ~ 2-Nitro--
n - P r o p y l _ ~
9C}
' , !i i; ' .. . s e c. - Bc u-t yBl ~ u t y l ~ ~
.80_
'~ . .. ;~ ~_ ~Methoxy- I E E E ~
7o_ ~ ~ Xylene= propanol Isobutyl-
~o
'~ ~, ~ ~Metho _
50_ '~-----:
' =ethanol :: n-Butyl
0 ii
4o_ ~ - ~ ~ ~= W a t e r
_~ ~ ~ ~ Turpentine
O~ ~ propyl n o l ~-
30_ ~ ~ ~ __ ~ a ~ A m y l ~ ~
. . . .
iii
~ Ethoxyethyli ~
20_ ~ "Aromatic- --Methyl Amyl~- - ~ - - - ~
~m i_ _ . ~~ lOO . . . lt!!i~,~
. ~:y'il':'~'
" ' ,[!:
. ., . .. ., , ~" ' ! I' pentene
n.- [ I i I ' ! I ~ . . . .
:: I :1
I
. . .: . I
:
;: ; :; ; :
:
i' DiacetonelJiii : : : , :,,,, , i . . . . . . : ; : : : 4 ;
, : :' i J ii i .... Alcohol I i I ; I,,, :, ~ : .......

Mineral I , ,, ,,,, , ~: :
]o_.
9
7_.
Spirits
- ,!~
,,
l
,
; ! i
--L~--
I ;
J ~ ' -i-+-~-;
~, 9
ill iil
~
= , ~!;
I',,
- propanol~
....
, ===
~
ii;:,
6_ l,aliiii ..... !II ii',, ! ! ,, ', ~ ~

' , ' ' I ! 1', , I i . ~, , I i [ , , i ! i ! I I! ~ethanol~--
' ' '~Aromatic I , , ,','~~ ',,, ....
5_ 150 =__ .
' I
! 1, ~,-
~-. IsophoroneJ, i : i ,I I ! ii Ii I
I] : i! I I
B u t o x y e t h y I - ~ -~
i!!il:J li' ~ ,u,,, ,, I
; : ~ i ~ ~ i ; i i L I ; ili ; i I i i i ! i i '. i ~ ! '. I ~ i
Deodorized i I I i i i ! .,. t I I : : i 11 ~ , ; , ',
2-'t K e r o s,esneen e ' DE(IMEi ' ~ '
I ~ , l l l i i I t li,i~! ,i,,,lili~,!!! :~lil!
I :: ! I i.!1 ,~ ill
,J!;,llltil I
:,,, Ill
i I jR l !1 '~
i I:l i i [ '
, :i ! i .". . . i t! ,it DEGEE d
L, I! i
Aliphatic Aromatic ; Ketones Acetates Glycol Alcohols Others
HC HC Ethers
FIG. 4 - R e l a t i v e s o l v e n t e v a p o r a t i o n r a t e s .
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solvent is spread on a known area of filter paper that is sus- suppliers have developed computer programs to model and
pended from a sensitive balance in a controlled environment predict evaporation rates of solvent blends [25-29].
cabinet. Weight loss of the filter paper/solvent liquid is mea- The information presented so far has dealt with the evapo-
sured as a function of time as the solvent evaporates. ration of neat (pure) solvents. The presence of resin solute,
Early models of the apparatus use a Jolly spring as the e.g., in a lacquer or paint, retards solvent evaporation as
gravimetric measuring device and require manual measure- illustrated in Fig. 8. In addition, some solvents are preferen-
ment of weight and time (Fig. 5). More recent models employ tially retained more than others by certain polymers due to
an electrobalance and automatically record weight loss ver- solvent/polymer interactions arising from factors such as po-
sus time (Fig. 6). The Shell Thin-Film Evaporometer and the larity and hydrogen bonding.
As solvent evaporation from a coating film progresses, it
Chevron Research Evapograph operate under similar princi-
slows down markedly. The evaporation rate-limiting factor
ples.
changes from neat solvent volatility to diffusion through the
The basic procedure with both the manual and automatic
coating film. Diffusion-limited evaporation is much slower
instruments is similar. The evaporation chamber and sample
U9].
are conditioned to 25~ (77~ Airflow rate (21 L/rain) and Actual evaporation of solvents from polymer films must be
relative humidity (less than 5%) in the chamber are set. A determined empirically. Although there are no standard test
filter paper, 90 m m in diameter, is horizontally suspended in methods for doing so, various experimental procedures are
the evaporation chamber from the weight-sensing device. reported in the literature [8]. Murdock and Wirkus [20], as
The solvent sample (0.7 mL) is added from a hypodermic well as Hays [21], tagged solvents with carbon-14 and mea-
syringe and distributed over the entire area of the filter paper sured residual radioactivity after the bulk of the solvent had
within a period of 10 s. Data are reported as time in seconds evaporated. More recently, gas chromatography has been
for 10% solvent weight increments through the evaporation used effectively. Sletmoe modified a Shell thin-film evap-
cycle, and they are plotted as percent solvent evaporated orometer to permit sampling and subsequent analysis of
versus elapsed time (for example, see Fig. 7) [8,18]). evaporating vapor [22]. Lesnini evaporated the solvent from a
The procedure is repeated using n-butyl acetate as the ref- series of solution aliquots and used a gas chromatograph to
erence standard. Elapsed time for 90% evaporation of speci- determine the type and amount of solvent remaining [23]. He
men and standard are determined. Evaporation rate of the dissolved the resin solution in a carrier solvent to ensure that
solvent specimen is calculated as the ratio of 90% evapora- a representative sample of the retained solvent was recovered
tion time for n-butyl acetate standard divided by the 90% for analysis.
evaporation time for the solvent specimen and normalized so A similar empirical procedure was used by a major solvent
that the evaporation rate of n-butyl acetate is 100 (or 1.0). The supplier to develop a database and appropriate algorithms
90% evaporation time is generally used since some curvature for a solvency/evaporation rate computer program [24,25].
of the plot usually occurs above that data point. Evaporation The program models solvency and evaporation rates of sol-
vent blends from coating films, taking into account specific
plots for pure solvents are nearly straight lines. Solvent mix-
resin/solvent interactions. It calculates evaporation data for
tures or blends produce curved plots, the curvature becoming
solvent blends evaporating from coating films and the com-
more extreme as differences in the evaporation rates of indi-
positions and solvency interaction radii of the solvent blends
vidual blend components become greater. Several solvent
remaining in the film at any time.
AIB ,=,, ~-~ Boiling Point~Distillation Range

Vapor pressure of a solvent increases as its temperature
increases, as illustrated in the generalized graph in Fig. 9. If a
solvent is heated to a high enough temperature, its vapor
ROT( pressure will eventually rise to a value equal to 1 atm (e.g.,
760 mm mercury pressure at sea level). At that point, the
ORT solvent will vaporize not only from the surface of the liquid,
but vapor bubbles will form within the body of the liquid.
This phenomenon is called "boiling," and the corresponding
temperature at which it initially occurs is the "boiling point"
[30]. When a solvent consists of a mixture of chemical com-
ponents, as is the case with most hydrocarbon solvents, boil-
ing occurs over a range of temperatures referred to as the
"boiling range" or "distillation range." Single-component,
pure solvents have single, unique boiling points or very nar-
BRACKET row distillation ranges.
AIR
Distillation temperature or range is an important physical
property which is listed in all solvent specifications. It is
useful as an identification test (in combination with other
tests, such as specific gravity), but will not differentiate be-
tween solvents of similar boiling point or range. Distillation
FIG. 5 - T h i n 4 i l m evaporometer, range also gives an indication of solvent purity. This is partic-
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FIG. 6-Automatic thin-film evaporometer.
100 - -
8O m
40
20
0P" I I I I I I I
0 10 2o 30 40 50 60 70 8o
Time. Minutes
FIG. 7-Evaporation rates of typical solvents (Chevron Research Evapograph at 80~
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Q
I~F at --
/ I Xylene
" Xylene from
9e . . . 9 9
,.c
60
.-
O
60
~ 20
o
0
0 40 80 120 160 200 240 260 300
Evaporation Time, Minutes
FIG. 8-Evaporation rate of xylenemNeat, and from a 40% solution of medium oil alkyd
(Chevron Research Evapograph at 80~
i ATM.
SOLVENT
VAPOR
PRESSURE
maHg
xlO0
TEMPERATURE Boiling
Point
FIG. 9-Solventvaporp~ssu~ versus ~mperatum (idealized represent~ion)[30].
ularly true for oxygenated solvents, w h i c h are relatively p u r e tion a b o u t e v a p o r a t i o n rate. Evaporation/distillation t e m p e r -
c o m p o u n d s . The m o r e n a r r o w the distillation range, the ature c o m p a r i s o n s should not be m a d e b e t w e e n d i s s i m i l a r
m o r e p u r e is the solvent. Therefore, it is a useful test for types of solvents since such p r e d i c t i o n s w o u l d be erroneous.
detecting the presence of i m p u r i t i e s o r c o n t a m i n a n t s . However, for s i m i l a r types of solvents, a n d for h y d r o c a r b o n
I n addition, distillation t e m p e r a t u r e m a y be used to ap- solvents in particular, distillation d a t a c a n be u s e d effectively
p r o x i m a t e the relative e v a p o r a t i o n p r o p e r t i e s of one solvent as a first a p p r o x i m a t i o n o r gross m e a s u r e of relative evapora-
versus another, a l t h o u g h it does not provide precise information rate. F o r h y d r o c a r b o n solvents, the 50% distillation
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point (i.e., the temperature at which 50% of the solvent has 800
distilled) has been found to have a good correlation with 64)0
evaporation rate [8]. 400
The McArdle-Robertson evaporation index is based on the 300
50% distillation temperature [31]. It is intended primarily to
apply to straight-run paraffinic naphthas having distillation
ranges of not more than 40~ and to compare their relative I00
evaporation times, as illustrated in Fig. 10. 80
There are three ASTM distillation test methods which are 60
used for different kinds of solvents: 40
C 30
1. ASTM D 86, Distillation of Petroleum Products, is in-
tended to be used for wide-boiling hydrocarbon solvents 20
such as VM&P naphthas and mineral spirits.
2. ASTM D 850, Distillation of Industrial Aromatic Hydrocar- lO
8
bons and Related Materials, is intended for narrow-boiling
6
aromatic solvents such as toluene, ethylbenzene, and xy-
lenes. 4
3
3. ASTM D 1078, Distillation Range of Volatile Organic Liq-
uids, is intended for narrow-boiling solvents, oxygenated 2
solvents in particular, and also for certain hydrocarbon
solvents, chlorinated solvents, and others. 1
60 80 100 120 140 160 180 200
The same solvent sample, tested by each of the three ASTM 50% Distillation Point, C
methods, may produce different distillation data due to varia- FIG. lO-McArdle-Robertson index for estimating
tions in the equipment and procedures. It is important, there- evaporation rate from distillation temperatures
fore, when presenting distillation data or solvent specifica- (courtesy of Industrial Chemistry).
tions, to indicate the test method used.
The basic test procedure described in all three test methods point is taken as the thermometer reading 5 min after the
is similar, although there are differences as noted in Table 12. 95% distillation point.
The sample is heated in a glass distillation flask until it boils. 4. Decomposition Point--The temperature reading that coin-
Solvent vapors are cooled and condensed by passing them cides with the first indication of decomposition of the liq-
through a jacketed, water-cooled tube. Condensate is col- uid in the flask. Decomposition, if it occurs, is evidenced by
lected in a calibrated receiver. Distillation temperatures are smoke and fumes in the flask; the temperature ceases to
registered on a thermometer immersed in the vapor in the rise and begins to fall.
neck of the distillation flask. Distillation temperatures are Two common sources of error or bias in distillation data
usually recorded at the initial boiling point, and when 5, 10, are (a) improper placement of the thermometer in the distil-
and each additional 10% up to 90%, and 95% of the sample lation flask, and (b) failure to make appropriate corrections
have distilled over, and at the dry point. Typical distillation for barometric pressure. The thermometer must be posi-
temperatures of selected commercial solvents are listed in tioned exactly as shown in Fig. 13. Higher placement will
Tables 1 through 9. result in consistently lower temperature readings; lower
The basic assembly of the manual distillation apparatus is placement may give higher readings.
illustrated in Fig. 11. Automatic distillation equipment (Fig. Distillation temperature readings must be corrected for
12) employing the same basic principles is available. The au- deviations from standard sea-level barometric pressure. Oth-
tomatic equipment uses a thermocouple for temperature erwise, tests run at high altitude or low barometric pressure
measurement and an automatic moving photocell sensing will result in inaccurate, low distillation temperatures, while
device to measure liquid level in the receiver. A recorder high barometric pressure will cause high distillation temper-
charts the volume of distillate recovered versus temperature. atures. Correction factors appropriate for specific solvents
There are specific terms to describe key temperatures in all are listed in the ASTM test methods.
ASTM distillations:
1. Initial boiling point--The temperature indicated by the Flash Point
distillation thermometer at the instant that the first drop of Flash point is another manifestation of volatility. The flash
condensate falls from the condenser tube into the receiver. point of a liquid is defined as the lowest temperature at which
2. Dry point--The temperature indicated at the instant that the liquid gives off enough vapor to form an ignitable mixture
the last drop of liquid evaporates from the lowest point in with air to produce a flame when a source of ignition is
the distillation flask. brought close to the surface of the liquid under specified
3. End point, final boiling point, or maximum temperature-- conditions of test at standard barometric pressure (760
The maximum thermometer reading obtained during the mmHg, 101.3 kPa). Appropriate corrections must be made
test. This usually occurs after the evaporation of all liquid for barometric pressure deviations from standard pressure
from the bottom of the distillation flask. If there are "heav- since flash point is dependent on vapor concentration, which
ies" in the sample, and there is no clean dry point, the end is governed by vapor pressure.
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TABLE 12--Comparison of ASTM distillation test methods for solvents.

ASTM D 1078,
ASTM D 86, ASTM D 8 5 0 , Narrow-Boiling
Wide-Boiling Narrow-Boiling Oxygenated
Sample Type Hydrocarbons Aromatics (and others)
Sample size, mL 100 100 100
Distillation flask size, mL 125 200 200
Number of specified thermometers 2 8 14
Insulating shield hole size, mm 50 25-50 a 38
Condenser temperature, ~ 0-6~ 10-20 0-5~
Rate of heat up to IBP, time, min 5-15 a 5-10 5-154
Rate of distillation, mL/min 4-5 5-7 4-5
95% point to EP, time, min 5 .-- 5
~Varies depending on boiling point and range of sample.
.--Thermometer
Distillation.
Flask Condenser~
' ~ll, Ll~llqti~llll Jill I, J, iliilll~iflliJ lilloql Ililllll~
Insulation ~ rd// IIII
~/Graduated
Shleld-.....~. Cylinder
Burner ~
FIG. 11-Apparatus assembly for distillation test.
S i m i l a r to the v a p o r p r e s s u r e / t e m p e r a t u r e relationship, solvent. Just as "flash point" represents the lower t e m p e r a t u r e

solvent v a p o r pressure concentration in air is also a function limit for ignition, there is also an u p p e r limit b e y o n d w h i c h
of t e m p e r a t u r e , as shown in the generalized illustration in the vapor/air m i x t u r e is too rich to ignite a n d burn. The v a p o r
Fig. 14 [30]. At low t e m p e r a t u r e s , there is insufficient v a p o r c o n c e n t r a t i o n at the u p p e r t e m p e r a t u r e limit is called the
c o n c e n t r a t i o n (fuel) available to ignite a n d p r o d u c e a flame. " u p p e r f l a m m a b l e limit" or "upper explosive limit" (UEL). It
In this t e m p e r a t u r e region b e l o w the flash p o i n t t e m p e r a t u r e , must be emphasized that these phenomena apply only to equi-
the solvent v a p o r c a n n o t be ignited by a s p a r k o r flame. librium, closed systems. F o r h y d r o c a r b o n solvents, the LEL is
As the t e m p e r a t u r e of the solvent is gradually increased, usually a b o u t 1 vol% solvent v a p o r in air, a n d the UEL is
there is an a c c o m p a n y i n g increase in v a p o r c o n c e n t r a t i o n a b o u t 7 vol%, b u t for oxygenated solvents, these values can
above the surface of the liquid. At a certain t e m p e r a t u r e , vary over a wide range.
there will be sufficient v a p o r (fuel) to form a f l a m m a b l e (or Flash p o i n t is one i n d i c a t o r of the relative f l a m m a b i l i t y
explosive) mixture, a n d a fire will o c c u r if a s p a r k o r flame is h a z a r d of solvents a n d solvent-containing products. The U.S.
introduced. The t e m p e r a t u r e of the liquid at this p o i n t is D e p a r t m e n t of T r a n s p o r t a t i o n (DOT) a n d the U.S. Depart-
called the "flash point," a n d the c o n c e n t r a t i o n of v a p o r at this m e n t of L a b o r (OSHA) designate "flammable liquids" as
t e m p e r a t u r e is called the "lower f l a m m a b l e limit" o r "lower those having flash points b e l o w 100~ (38~ These require
explosive limit" (LEL). Typical flash points of selected com- special p a c k a g i n g a n d handling. I n t e r n a t i o n a l cargo regula-
m e r c i a l solvents are listed in Tables 1 t h r o u g h 8. tions specify a 140~ (60~ flash p o i n t as the u p p e r limit for
At t e m p e r a t u r e s above the flash point, a f l a m m a b l e mixture "flammable liquids." In a d d i t i o n to being used to classify
of solvent v a p o r and air is p r e s e n t above the surface of the m a t e r i a l s in g o v e r n m e n t regulations, flash p o i n t limits are
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lowest flash point largely determines the flash point of the

mixture when that component is present in substantial pro-
portion, e.g., 5% or more. Mutually miscible mixtures of
flammable/nonflammable liquids exhibit a direct, though of-
ten complex, relationship between flash point and the con-
centration of the flammable component, e.g., alcohols and
water.
Chlorinated solvents, most of which are nonflammable,
will have various effects in mixtures with flammable solvents.
Some will suppress (i.e., raise or prevent) the flash point of
flammable liquids because of the high vapor pressure of the
nonflammable chlorinated solvent. However, some mixtures
of chlorinated solvents and flammable liquids will lower the
flash point below that of the flammable liquid, e.g., mineral
spirits and methylene chloride [32].
It is good practice to actually measure the flash point of
solvent blends because of the uncertainty of making predic-
tions. There are several test methods commonly used.
Tag Open Cup--ASTM Method D 1310, Flash Point and
Fire Points of Liquids by Tag Open-Cup Apparatus, may be
used for determining the open cup flash points of liquids
having flash points between zero and 325~ ( - 18 and 165~
The sample is cooled to at least 20~ (ll~ below the ex-
pected flash point, and it is placed in an uncovered cup
jacketed by a heat transfer fluid. The sample cup is filled to a
depth of approximately ~/8 in. below the edge, and it is heated
at a slow, constant rate. Temperature is measured by a ther-
mometer immersed in the sample. A small test flame is
passed at a uniform rate across the surface of the cup at 2~
(I~ intervals of temperature rise until a flash of flame is
observed. The sample temperature corresponding to the flash
of flame is the "flash point" (Fig. 15).
"Fire point" can be determined with the same apparatus by
continuing the test. Fire point is defined as the lowest temper-
FIG. 12-Automatic distillation apparatus. ature at which sustained burning of the sample takes place
for at least 5 s.
often listed as one of the requirements in solvent specifica- Although the Tag Open Cup Flash Point test may appear to
tions, for hydrocarbon solvents in particular. Flash point may represent real life situations of open containers or accidental
also be used to indicate the presence of impurities or contam- solvent spills, the test results could be misleading, especially
inants in a given liquid, such as the presence of residual for solvent blends. As the sample is slowly heated, the lightest,
most volatile component in the blend may escape without
solvents in solvent-refined drying oils.
being ignited. Therefore, closed cup test methods are now
Flash point is roughly inversely proportional to volatility.
preferred by most regulatory agencies.
The most volatile solvents tend to have the lowest flash
Tag Closed Cup--ASTM Method D 56, Flash Point by Tag
points, which are indicative of the greatest fire hazard. With Closed Cup Tester, uses an apparatus which confines solvent
mixtures of miscible solvents, the component having the vapors in a closed cup (Fig. 16). It is intended for testing
liquids (a) which contain no suspended solids, (b) which do
not form a surface film under test conditions, (c) with viscosi-
ties below 9.5 cSt at 77~ (25~ or below 5.5 cSt at 104~
(40~ and (d) flash points below 200~ (93~
The 50-mL sample, cup, and heat transfer fluid in the cup
jacket are cooled to 20~ (11~ below the expected flash
point. With the cup lid closed, the sample is heated at a
specified slow, constant rate, as measured by a thermometer
immersed in the sample. A small test flame of specified size is
momentarily directed into the cup through an opening in the
lid that is simultaneously opened at regular intervals of tem-
perature rise; after each I~ (0.5~ for samples with flash
points below 140~ (60~ or 2~ (1~ for samples with flash
points above 140~ The flash point is taken as the lowest
temperature at which application of the test flame causes the
FIG. 13-Position of thermometer in distillation flask. vapor in the cup to ignite.
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I/EL ~ ''! .... '~ :"1%4,,! "~ ii ~' : +v~!+i- i . . . . . ~'

6
SOLVENT :~ ~4 , ~ ,~- ' , ~ ~,~' ~ 4 ~ c ~ - ~ d : N + N 4 ~ ' , ~ , ' , : r : : ,, I : ~i
9 " - ~ x ' . x ' , x ' , ' ~ ~ ~ 2 ' ~_ ?-l!![!ii!!
~ ii j pili,~j j~i~,~j],~jl]~kllj,ll] I~kI I'~kl I'll] I [~11[11!1;I ; :L

I~ ~I~ ~0 F][.R~ q~ I~k I~lI/ll%lll~l';r%'lil'~ll~ll~llll~lll%kiil%k1311L~l~l!lHllLlllllllllllll//lll
9 /,~ --- -- ~ I~ l~i ~ ~ l~ "I~ ~ ' II|il,llliLHLi[lIllll[/i!illll;HI
V I I I I I I 116 1~1Pll l'MIrll4i ,~ki~l~kl

~ N ~ i~ ~ 1"%1 IN ] I'N!t ] IIll Jill
IIN ~ "1%1 ] T~ b'~LllT% I T%L I "l~ I ~kl $ f~l 82 I I i I I | I I il lll[lliIIl|
| t ~ ~ I ) ] I 1l ) 1J~ NJ~LLL~LLI~IL[I%III~kiI*~kl N-I N I N ] f ~ ~Pf~d IlIH]l!l~!J ] I ~ I I ~ i ILI I I l ] | l l l l |

| I ] I 1 ] J I I J I ) IN P'N J'NI~tT'NIININ 134 P%l I'N!l"klll~ii[ll]llllll I [ I [ I I [ I I[I Ilil[[l]|
I I I I [ [ i I [ I I I HI r,,ki I'id I'NII~[PI~[~LIII~,[ C"k[ lNd P'td PNII~Ill itlilIlllHi I I I I i I i I 11111 ]li i II|
11 i I I I I1 i I I [ [ [Ir%ll"tl'r"LIl~'~lllR~'LilT'tllr'~l C'I, ININ I l'lLl'i'JlllllllltllllN[ I ]llllllllll/[lllIll
1 1.5 ~ 2 2.5 3 4 " 5 6 7 8 9 I(]
Flash
Point TEMPERATURE
FIG. 14-Solvent vapor concentration versus temperature (idealized representa-
tion) [30].
Pensky-Martens--ASTM Method D 93, Flash Point by The Setaflash apparatus has certain advantages over other
Pensky-Martens Closed-Cup Tester, is intended to be used for flash point measuring devices. It requires only a 2 to 4-mL
viscous liquids, suspensions of solids, and liquids that tend to sample instead of 50 to 70 mL. In the flash point verification
form a surface film under test conditions. It differs from the mode of operation, test time is only I or 2 rain (Fig. 19).
Tag Closed Cup Test in that (a) it employs an air bath device To perform a "flash/no flash" test, 2 mL of sample is intro-
instead of a liquid jacket around the test cup, and (b) the duced by means of a syringe through a leakproof entry port
sample is mechaflically stirred during the test (Figs. 17 and into the tightly closed Setaflash tester or, with very viscous
18). This test method is particularly suited for samples such materials, directly into the cup that has been brought to the
as resin solutions, paints, varnishes, lacquers, printing inks, required test temperature. As a "flash/no flash" test, the expec-
and certain adhesives. Materials with flash points as high as ted flash point temperature may be a specification or other
285~ (140~ can be tested. operating requirement. After 1 rain, a test flame is applied
The sample and tester are first brought to a temperature of inside the cup and note is taken whether or not the specimen
60~ (15~ or 20~ (11~ lower than the expected flash point,
flashes. A fresh specimen must be used if a repeat test is
whichever is lower. The sample is then heated at a slow,
necessary.
constant rate with continual stirring to provide uniform tem-
For a finite flash point measurement, the temperature is
perature throughout and to prevent formation of a surface
sequentially increased through the anticipated range, the test
film which would otherwise retard solvent vaporization. A
flame being applied at 9~ (5~ intervals until a flash is
small test flame is momentarily directed into the cup through
observed. A true determination is then made using a fresh
a shuttered opening in the lid at regular temperature intervals
with simultaneous interruption of stirring. The flash point is specimen, starting the test at the temperature of the last
the lowest temperature at which application of the test flame interval before the flash point of the material and making
causes vapor in the cup to ignite. tests at increasing I~ (0.5~ intervals.
Setaflash--ASTM Method D 3278, Flash Point of Liquids Equilibrium Flash Point--The Tag Closed Cup and Pensky-
by Setaflash-Closed-Cup Apparatus, describes procedures for Martens flash point test methods depend on a definite rate of
(a) determining whether a material does or does not flash at a temperature increase to control the precision of the test
specified temperature, or (b) determining the lowest finite method. However, the rate of heating may not in all cases give
temperature at which a material does flash. The test methods the accuracy expected because of the low thermal conductiv-
are applicable to paints, enamels, lacquers, varnishes, and ity of some liquids such as paints, resin solutions, and related
related products having a flash point between 32 and 230~ (0 viscous materials. To reduce this effect, ASTM Method
and 110~ and viscosity lower than 150 St at 77~ (25~ D 3941, Flash Point by the Equilibrium Method with a
These test methods are similar to international standards ISO Closed-Cup Apparatus, uses a slow rate of heating to provide
3679 and ISO 3680. a uniform temperature throughout the specimen.
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03
r
j t,
FIG. 16-Tag closed-cup flash point tester.
FIG. 15-Tag open-cup flash point tester. S t a n d a r d closed cups are used, i.e., Tag, Pensky-Martens,
or Setaflash, a n d this test is r u n such that the air/vapor space
above the s p e c i m e n attains a s a t u r a t i o n c o n c e n t r a t i o n of
The s p e c i m e n is heated in a closed cup of s t a n d a r d design v a p o r before the test flame is applied. The s p e c i m e n is held at
in a suitable w a t e r b a t h at a rate of 1.O~ (0.5~ in not less the specified t e m p e r a t u r e for at least a 10-min p e r i o d before
t h a n 1.5 rain so that the difference in t e m p e r a t u r e b e t w e e n the test flame is applied. This test m e t h o d does not provide
the s p e c i m e n in the cup a n d the b a t h never exceeds 3.5~ for the d e t e r m i n a t i o n of the actual flash point, b u t only
(2.0~ Flash d e t e r m i n a t i o n s are m a d e at intervals of n o t less w h e t h e r a s p e c i m e n does or does not flash at a specified
t h a n 1.5 rain. Since the s p e c i m e n is heated at a r e d u c e d rate, temperature.
a longer t i m e interval b e t w e e n each d e t e r m i n a t i o n is neces-
sary to re-establish the s a t u r a t i o n c o n c e n t r a t i o n of v a p o r in
the air space above the s p e c i m e n after each flash test.
Equilibrium Flash~No Flash--ASTM M e t h o d D 3934, Flash/ PHYSICAL PROPERTIES
No F l a s h T e s t - - E q u i l i b r i u m M e t h o d by Closed-Cup A p p a r a -
Density and Specific Gravity
tus, does not d e t e r m i n e a finite flash point, b u t it verifies
w h e t h e r o r n o t flashing occurs at a single specified t e m p e r a - Significance
ture, w h i c h m a y be a p r o d u c t specification or agency require- Specific gravity is an i n h e r e n t p r o p e r t y w h i c h is listed as a
ment. The d e t e r m i n a t i o n is m a d e m o r e a c c u r a t e b y ensuring r e q u i r e m e n t in all solvent specifications a n d is often used to
that the flash test is carried out only w h e n the m a t e r i a l u n d e r set specifications. It is a good, simple, qualitative test w h e n
test a n d the air/vapor mixture above it are in a p p r o x i m a t e used with o t h e r tests to establish or confirm the identity of a
e q u i l i b r i u m at the specified t e m p e r a t u r e . solvent. I n addition, it is useful for quality control, to provide
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or tank trucks to calculate costs and freight rates, and for

PILOT~ ~ . ~ i/ / - ~ SHUTTER inventory measurement and control.
It is customary to buy and sell hydrocarbon solvents on a
volumetric basis (e.g., gallons, litres), converting measured
FRONT values to volume at a standard temperature of 60~ (15.56~
International transactions, however, are made on a gravimet-
ric basis (e.g., metric tons) calculated at a standard 60~
HANDLE(OPTIONAL) temperature.
(MUSTNOTTIPEMPTYCI For oxygenated and other solvents, commercial transac-
tions are customarily made on a gravimetric basis (e.g.,
ST,RRER DR,VE FLEX,BLE pounds, kilograms, tons) converting measured values to
SHAFT {PULLEYDR,VEOPTIONAL)~-~
FLAMEEXPOSUREDEVICE ,~/~/ I'l X'SHUTTEROPERATINGKNOB weight at a standard temperature of 20~ (68~ However,
LID. ~ ,~. ~ t ~ T H E R M O M ETER there is a trend toward changing the standard temperature to
25~ (77~
DISTANCEPIECE Finally, a knowledge of specific gravities of solvents and
other paint components is important for the formulation of
paints, varnishes, and lacquers. It is often necessary to make
conversions between weight and volume bases and to calcu-
r PLATE~/ ~ It late parameters such as pounds per gallon or kilograms per
STOVE{ / r"T3 I,
I AIRBATH. . ~ litre.
/"j::[ Typical specific gravities of selected commercial solvents

are listed in Tables 1 through 9.
1 Definitions
TYPE(FLAMETYPESHOWN) ~ [
The terminology relating to density and specific gravity is
L_ _.J often confusing: density and apparent density, specific grav-
FIG. 17-Pensky-Martens closed-cup flash point tester. ity and apparent specific gravity, mass and apparent mass
versus weight. Definitions for these terms as they are applied
10~ ~ in ASTM standards are contained in ASTM E 12, Definitions
of Terms Relating to Density and Specific Gravity of Solids,
FLAME E X P O S U R E -- m---THERMOMETER Liquids, and Gases. Key definitions pertaining to liquid sol-
DEV,CE& I. III vents are as follows.
%@f I/J[T
d e n s i t y - - t h e mass of a unit volume of a material at a
specified temperature. The units shall be stated, such as
grams per millilitre, grams per cubic centimetre, pounds
I,t HERMOMETER per cubic foot, or other. The form of expression shall be
I .\ 13 l b: I ~ r i m ADAPTOR
"density at x"
where x is the temperature of the material.
9 f
density, a p p a r e n t - - t h e weight in air of a unit volume of

a material at a specified temperature. The units shall be
stated. The form of expression shall be
"apparent density at x"
where x is the temperature of the material.
TESTCUP " - - i , ' ~ ~
/,,, l specific gravity--the ratio of the mass of a unit volume
of a material at a stated temperature to the mass of the
same volume of gas-free distilled water at a stated tem-
k 0 IN CONTACTWITHTHE perature. The form of the expression shall be
INNER FACEOF COVER "specific gravity x/y~ "
;--" M .I THROUGHOUTITS
CIRCUMFERENCE where x is the temperature of the material and y is the
temperature of the water. The term "relative density"
FIG. 18-Pensky-Martens flash point test cup and cover as-
sembly.
with the same meaning as specific gravity is becoming
more widely used than "specific gravity."
specific gravity, a p p a r e n t - - t h e ratio of the weight in air
a check on product uniformity, and to detect gross contami-
of a unit volume of a material at a stated temperature to
nation. the weight in air of equal density of an equal volume of
Accurate specific gravity values are essential for the calcu- gas-free distilled water at a stated temperature. The form
lation of the volume occupied by a product whose weight is of expression shall be
known or of the weight of a product when the volume is "apparent specific gravity x/y~
known. This information is necessary for accurately sur- where x is the temperature of the material and y is the
veying large shipments by vessels, barges, railroad tank cars, temperature of the water.
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FIG. 19-Setaflash tester.
API g r a v i t y - - a special function of relative density (spe- vacuo" by the application of an air buoyancy correction, and
cific gravity) 60/60~ (15.56/15.56~ represented by: it is then considered synonymous with mass.
141.5 All of the definitions listed above are based on either "mass"
API gravity, degrees - 131.5 or "weight in air," with the distinction being that air
sp gr 60/60~
buoyancy corrections have been applied in the former case
No statement of reference temperature is required, since
60~ is included in the definition. API gravity applies and not in the latter. Density and specific gravity are based on
specifically to crude petroleum and to petroleum prod- mass and should be similarly constant. Apparent density and
ucts such as hydrocarbon solvents. Gravities are deter- apparent specific gravity are based on weight in air, and
mined at 60~ (15.56~ or are converted to values at 60~ therefore they are subject to change with atmospheric condi-
by means of standard tables. These tables are not applications, locality, and altitude. These changes may be negligible,
ble to nonhydrocarbons nor to essentially pure hydrocar- depending on the accuracy required for the particular appli-
bons such as the aromatics. cation.
A brief discussion of these definitions may be useful. In
scientific terminology, mass is a measure of the quantity of Hydrometer Methods
material in a body, and it is constant regardless of geographi- Hydrometer methods are the quickest, simplest means for
cal location, altitude, or atmospheric conditions as long as no measuring density, specific gravity (relative density), and API
material is added or taken away. Weight is the force with gravity, especially in the field. These methods are based on
which a body is attracted to the earth, and it varies from place the principle that the specific gravity of a liquid varies directly
tO place with the acceleration of gravity. with the depth of immersion of a body floating in it. The
When an equal-arm balance is used to compare an object floating body, called a hydrometer, is graduated in units of
with standards of mass ("weights"), the effects of variations in density, specific gravity, or API gravity units. Hydrometers
the acceleration of gravity are self-eliminating and need not are useful when accuracy to three decimal places is adequate.
be taken into account, but the apparent mass of the object is The sample is brought to the prescribed temperature, and it
slightly different from the true mass because of the buoyant is transferred to a clear glass or plastic cylinder which is at
effects of the surrounding air. Mass can then be computed approximately the same temperature. The appropriate hy-
from apparent mass by applying a correction for air drometer, having the scale of interest, is lowered into the
buoyancy. When a spring balance is used, an additional cor- sample and is allowed to float freely and settle. After tempera-
rection accounting for the local value of the acceleration of ture equilibrium has been reached, the hydrometer scale is
gravity is required for the computation of mass. read. Note is made of the hydrometer scale graduation near-
For many commercial and industrial processes the scien- est to the apparent intersection of the horizontal plane sur-
tific distinction between mass, apparent mass, and weight is face of the liquid (Fig. 20). Temperature of the sample is read
of no practical consequence and is therefore ignored. The from a separate thermometer or from a thermometer inte-
term "weight" in general practice has been accepted as being grated into the design of the hydrometer.
the value secured when an object is weighed in air. This Detailed descriptions of test methods for the proper use of
"weight" or "weight in air" is often converted to "weight in hydrometers can be found in ASTM Method D 891 (Method
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HORIZONTALPLANE
SEE DETAIL j,,, SURFACEOF LIQUID
- BOTTOMOF
LIQUID- MENISCUS
Tubing
Line Cut
Lmond Pencil
READSCALE ~ ' i O.D.
DETAIL
FIG. 20-Hydrometer and Meniscus detail.
A), Specific Gravity, Apparent, of Liquid Industrial Chemi-

cals; ASTM Method D 287, API Gravity of Crude Petroleum
and Petroleum Products (Hydrometer Method); and ASTM
Method D 1298, Density, Relative Density (Specific Gravity),
or API Gravity of Crude Petroleum and Liquid Petroleum
Products by Hydrometer Method. FIG. 21-Bingham-type pycnometer.
For hydrocarbon solvent naphthas, values can be measured
on a hydrometer at convenient temperatures, the readings of
density may then be reduced to 15~ and readings of relative held by the pycnometer when equilibrated to volume at the
density (specific gravity) and API gravity at 60~ are obtained bath temperature to be used for the determination. The liquid
by means of international standard tables. By means of these sample is introduced into the tared, clean, dry pycnometer,
tables, values determined in any one of the three systems of equilibrated to the desired temperature, and weighed. The
measurement are convertible to equivalent values in either of relative density (specific gravity) or density is then calculated
the other two systems so that measurements may be made in from this weight and the previously determined weight of
the units of local convenience. water required to fill the pycnometer at the same tempera-
ture, both weights being corrected for the buoyancy of air.
Pycnometer Methods Lipkin BicapillaryPycnometer--TheLipkin bicapillary pyc-
Pycnometer methods for measuring specific gravity are nometer is another type that is capable of high accuracy and
more accurate and precise than hydrometer methods. They precision when density or specific gravity needs to be deter-
are used when accuracy to four or more decimal places is mined to five decimal places [33]. Its use is described in
required. ASTM Method D 891 (Method B), Specific Gravity, ASTM Method D 941, Density and Relative Density (Specific
Apparent, of Liquid Industrial Chemicals, describes the gen- Gravity) of Liquids by Lipkin Bicapillary Pycnometer.
eral test method for using a pycnometer. The liquid sample is drawn into the pycnometer and
A pycnometer is a tared vessel which is filled with water weighed. It is then equilibrated at the test temperature, and
and weighed. It is then filled with the sample and weighed. the positions of the liquid levels in the capillaries are ob-
Water, sample, and pycnometer are at a specified tempera- served (Fig. 22). The density or relative density of the sample
ture. The ratio of the weight of sample to weight of water in is then calculated from its weight, a calibration factor propor-
air is the apparent specific gravity. tional to an equal volume of water, and a term that corrects
Bingham Pycnometer--A Bingham-type pycnometer may for the buoyancy of air.
be used when density or specific gravity needs to be deter-
mined to five decimal places (Fig. 2 I). Its use is described in Digital Density Meter
ASTM Method D 1217, Density and Relative Density (Specific A rapid, direct-reading, instrumental method for measur-
Gravity) of Liquids by Bingham Pycnometer. ing density or specific gravity is by means of a digital density
The pycnometer is first carefully calibrated by determining meter. Its use is described in ASTM Method D 4052, Density
the weight of freshly boiled and cooled distilled water (dis- and Relative Density of Liquids by Digital Density Meter. A
tilled from alkaline permanganate through a tin condenser) small amount of sample (several millilitres) is introduced
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Density, g/mL at 20~

20_+.2 ~.J~-29~ ' ~illary Relative density, 20~176
0.9 to 1.1, Uniform Relative density, 60~176 (15.56~176
: 01 Percent Commercial density, pounds (in air)/U.S, gal. at 60~
50 to 55 ~ oughout Scale Length Commercial density, pounds (in air)/U.K, gal. at 60~
.,-'8- ). - - 6.0 Max. Tables of factors versus temperature are presented for ben-
zene, toluene, mixed xylenes, o-,m-,p-xylene, and cyclohex-
L 9
~6-
Juations anr
rt Lines at Each I mm ASTM Method D 2935, Apparent Density of Industrial Aro-

L4" ]er Lines at Each 5 mm matic Hydrocarbons, describes the measurement of apparent
h,. ,
ibered as Shown density in pounds (in air) per U.S. gallon at convenient tem-
r--2
: ~
perature using a hydrometer and reporting values at any
~" specified temperature. This method contains tables of
"pounds in air per U.S. gallon" versus temperature. It applies
~o ) only to the following solvents: benzene, toluene, mixed xy-
_+0.5 mL Capacity, lenes, o-,m-,p-xylenes, ethylbenzene, and cyclohexane.
P. - - Approx. 20
ASTM Method E 201, Calculation of Volume and Weight of
Industrial Chemical Liquids, presents tables for use in calcu-
lating the volume and weight of the following solvents: ace-
tone, ethyl acetate (85 to 88 wt%), ethylene dichloride, ethyl-
Material-- Weight ene glycol monomethyl ether, isobutyl alcohol, isopropyl
Pyrex Glass 30G Max. alcohol (anhydrous), isopropyl alcohol (91 vol%), methyl
ethyl ketone, methyl isobutyl ketone, and perchloroethylene.
All Dimensions in Millimetres A method is given for calculating the volume at 60~ from a
volume observed at another convenient temperature. (Tables
FIG. 22-Lipkin-type pycnometer. at 20~ can be calculated from the data and information
provided.)
into a vibrating quartz tube in the instrument at a preset Also, a method is given for determining the weight in
temperature. Operation of the instrument is based on the pounds per U.S. gallon (in air) at 60~ from an observed
principle that the oscillation of the quartz tube is damped as a specific gravity and to compute therefrom the weight in
function of the density of the sample within it. The instru- pounds of a given volume of the liquid in U.S. gallons at 60~
ment provides a digital readout of either density or specific
gravity. Color
Calculations a n d Conversion Tables Most solvents are "water-white" or clear and essentially
colorless. Color is an important specification requirement. If
ASTM Standard D 1250, Petroleum Measurement Tables, is a solvent has color greater than the specification limit, it may
a description of the tables which comprise Chapter 11, Sec- be an indication of (a) inadequate processing, (b) contamina-
tion 1, of the API Manual of Petroleum Measurement Stan- tion that might have occurred during storage and distribu-
dards and which are distributed in three base systems of meation, e.g., pickup of rust from tanks or pipes or color extracted
surement: ~ ~ 60~ relative density, ~ 60~ and from improper tank linings or loading hoses, or (c) oxidative
kilograms per cubic meter, ~ 15~ These tables apply to degradation as a result of aging.
crude petroleum and to all normally liquid petroleum prod- The property of color of a solvent varies in importance with
ucts derived therefrom, which includes hydrocarbon solvent the application for which the solvent is intended, the amount
naphthas. They do not apply to oxygenated and other solvents of color that can be tolerated being dependent on the color
nor to pure hydrocarbon solvents such as the aromatics. characteristics of the material in which it is used. For exam-
ASTM Method D 1555, Calculation of'Volume and Weight ple, solvent color may undesirably contribute color to white
of Industrial Aromatic Hydrocarbons, contains tables for use paints or to fabrics if it is used for dry cleaning. Solvents that
in calculating the weights and volumes of the following are off-specification in color are often found to be off-specifi-
solvents: benzene, toluene, mixed xylenes, o-,m-,p-xylene, cation in other properties as well.
cumene, ethylbenzene, high-flash aromatic naphthas, and There are two visual test methods used for measuring the
cyclohexane. A method is given for calculating the volume at color of solvents; Platinum-Cobalt Color and Saybolt Color.
60~ from an observed volume at any convenient tempera- Table 13 compares the approximate color values of the two
ture. scales.
ASTM Method D 3505, Density or Relative Density of Pure Platinum-Cobalt Color

Liquid Chemicals, describes the measurement of density or ASTM Method D 1209, Color of Clear Liquids (Platinum-
relative density using a Lipkin bicapillary pycnometer, and it Cobalt Scale), describes a procedure for the visual measure-
provides methods for reporting results in the following units. ment of the color of nearly colorless liquids. It is used for all
Density, g/cm 3 at 20~ oxygenated solvents, most other solvents, and is gradually
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CHAPTER 1 8 - - S O L V E N T S 149
TABLE 13--Approximate comparison of platinum-cobalt and solvents. This system of color measurement is not commonly
Sayboh color scales. employed outside of the petroleum industry.
Platinum-Cobalt Color, Saybolt Color, In this method, a column of sample is viewed vertically,
ASTMO 1209 ASTMD 156 and its color is compared with that of a reference glass disk in
Lightest 0 + 30 the Saybolt chromometer. The height of the column of liquid
10 +28 is adjusted until the observed color intensity is equal to that
20 +26 of the colored glass disk. The depth of the liquid column is a
30 +23
40 +21 measure of the Saybolt color, which is read directly from a
50 +19 scale on the instrument. The scale runs from + 30 for color-
70 + 15 less liquids to - 3 0 for dark liquids.
100 + 10
150 +3
180 0 Odor
200 - 3
250 -8 Odor is an inherent, characteristic property of most sol-
Dark amber 300 - 23 vents. Evaluation of the characteristic odor by a trained per-
son is a quick and simple means of identifying a solvent
(when combined with other tests) as well as for determining
being used also for hydrocarbon solvents, where Saybolt its suitability for an application from an odor point of view.
Color still predominates. Residual odor can be used to detect the presence of low-
For a number of years the term "water-white" was consid- volatility materials that may be associated with manufacture,
ered sufficient as a measurement of solvent color. Several product degradation, or contamination during distribution.
expressions for defining "water-white" gradually appeared, ASTM Method D 1296, Odor of Volatile Solvents and Dilu-
and it became evident that a more precise color standard was ents, describes procedures for testing both the characteristic
needed. This was accomplished in 1952 with the adoption of and residual odors of solvents. It involves dipping strips of
ASTM Test Method D 1209 using the platinum-cobalt (Pt-Co) filter paper into the sample and into a reference standard. To
scale. judge characteristic odor, an immediate comparison is made
This test method is similar to the description given in between the odor of the sample and reference standard on the
"Standard Methods for the Examination of Water and Waste filter paper. Residual odor is judged by permitting the papers
Water" [34] and is sometimes referred to as "APHA Color." to dry in air at room temperature and examining them at
The properties of these platinum-cobalt color standards were suitable time intervals for differences in odor.
originally described by A. Hazen in 1892 in a paper entitled,
"New Color Standard for Natural Waters" [35]. He assigned
Electrical Resistivity
the number 5 (parts per ten thousand) to his platinum-cobalt
stock solution. Control of electrical resistivity is critical to the application
Subsequently the American Public Health Association of electrostatically sprayed coatings. It impacts the transfer
(APHA) in their first edition (l 905) of "Standard Methods for efficiency (efficiency of paint application), coating appear-
the Examination of Water" used exactly the same concentra- ance, and economics. Electrical resistivity of the paint must
tion of reagents as did Hazen, and they assigned the color be properly adjusted to obtain optimum atomization charac-
designation 500 (parts per million) to the same stock solu- teristics and deposition. The adjustment is mainly accom-
tion. (The parts per million nomenclature is not used since plished through appropriate selection of solvents [36]. Non-
color is not referred directly to a weight relationship.) polar solvents, such as hydrocarbon solvents, have high elec-
The terms "Hazen Color" and "APHA Color" should not be trical resistivity (low conductivity). Polar solvents such as
used for solvents because they refer primarily to water. The ketones, alcohols, glycol ethers, and esters generally have low
recommended nomenclature for referring to the color of or- electrical resistivity (high conductivity), although some (e.g.,
ganic liquids is "Platinum-Cobalt Color, Test Method higher molecular weight esters) have high resistivity. Typical
D 1209." values for commercial solvents are shown in Table 14.
The method involves comparing visually the color of the An ASTM method, Electrical Resistivity of Liquid Paint
solvent sample with colors of standard dilutions of the Pt-Co and Related Materials is currently under development. It de-
stock reference solution in Nessler tubes. The tubes are scribes the use of two different test meters and probes,
viewed vertically. The color standards are aqueous solutions Ransburg and BYK-Gardner. Electrical resistivity values are
of mixtures of cobalt chloride, potassium chloroplatinate, often expressed in terms of "Ransburg megohms," which are
and hydrochloric acid. The scale runs from zero for pure read from the meter scale. Multiplication of these values by
water to 500 for the stock solution of 1.000 g of cobalt chlo- an appropriate cell constant, which is typically about 132,
ride, 1.245 g of potassium chloroplatinate, and 100 mL of converts Ransburg megohms to specific resistivity in meg-
hydrochloric acid made up to 1 L of solution. Most solvents
ohm-era units.
have color values of less than 5 on the Pt-Co scale.
Refractive Index
Saybolt Color Refractive index is defined as the ratio of the speed of light
ASTM Method D 156, Saybolt Color of Petroleum Prod- through a vacuum to the speed of light through the sample.
ucts, is used most often to measure the color of hydrocarbon Although this property may have no fundamental signifi-
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TABLE 14--Electrical resistance of typical commercial solvents. In this analytical technique, a m i n u t e a m o u n t of solvent
Ransburg Megohms s a m p l e (microlitres) is injected b y m e a n s of a h y p o d e r m i c
syringe into a h e a t e d injection p o r t in the i n s t r u m e n t , w h e r e
Hydrocarbon solvents >20
Ketones <1 it is instantly vaporized. The solvent vapors are carried into a
Alcohols <1 GC c o l u m n b y m e a n s of an inert c a r r i e r gas: helium, hydro-
Glycol ethers <1 gen, o r nitrogen. The c a r r i e r gas is the eluent w h i c h trans-
Esters p o r t s the solvent c o m p o n e n t s in v a p o r form t h r o u g h the GC
Ethyl acetate 6
column, w h i c h is m a i n t a i n e d at a certain c o n s t a n t or pro-
n-butyl acetate 16
Hexyl acetate >20 grammed temperature.
Ethoxyethyl acetate 3 The GC c o l u m n consists of a long, coiled tube, typically 1/8-
Methoxypropyl acetate 3 to 1/4-in. inside d i a m e t e r a n d m a d e of stainless steel, copper,
or glass. The t u b e is p a c k e d with a p o w d e r e d , p o r o u s sub-
strate o r support, w h i c h is coated with an absorbent, station-
cance to the practical solvent user a n d is generally not a ary liquid phase. Alternatively, a n d in m o r e c o m m o n use
specification requirement, the test is useful b e c a u s e m e a s u r e - today, the GC c o l u m n consists of a long, coiled capillary tube
m e n t s can be m a d e quickly a n d precisely. As with specific IA6-in. or less in diameter, w h i c h does not c o n t a i n the pow-
gravity, refractive index is characteristic (although not d e r e d packing support. Instead, the interior walls of the capri-
uniquely so) of different solvents, a n d it is very sensitive to lary tube are coated with the liquid s t a t i o n a r y phase.
differences in c o m p o s i t i o n of solvent blends. Therefore, it is The s t a t i o n a r y liquid p h a s e has the ability to preferentially
useful for distinguishing b e t w e e n a r o m a t i c a n d s a t u r a t e d hy- a d s o r b certain c o m p o n e n t s of the v a p o r i z e d solvent sample.
d r o c a r b o n solvents a n d for checking p u r i t y a n d u n i f o r m i t y of It is selected on the basis of the analysis to be p e r f o r m e d . The
batches. s t a t i o n a r y p h a s e can in s o m e cases b e a n o n p o l a r liquid, for
ASTM M e t h o d D 1218, Refractive Index a n d Refractive instance a h y d r o c a r b o n oil, b u t in o t h e r cases a better separa-
Dispersion of H y d r o c a r b o n Liquids, is designed to m e a s u r e tion of solvent c o m p o n e n t s can be o b t a i n e d b y e m p l o y i n g a
these p r o p e r t i e s with high precision. F o r r o u t i n e e x a m i n a - highly p o l a r liquid.
tion o r quality control, s i m p l e r i n s t r u m e n t s with less accu- Actual s e p a r a t i o n of solvent c o m p o n e n t s is achieved b y a
r a c y are satisfactory. c o n t i n u o u s l y alternating process of a d s o r p t i o n a n d vaporiza-
tion as the solvent vapors pass t h r o u g h the GC column. Dif-
ferences in a d s o r p t i o n characteristics a n d volatilities cause
the individual s a m p l e c o m p o n e n t s to pass t h r o u g h the col-
PURITY AND COMPOSITION
u m n at different rates. The c o m p o n e n t s are eluted from the
c o l u m n as individual b a n d s s e p a r a t e d by zones of inert car-
Gas Chromatography
rier gas.
Gas c h r o m a t o g r a p h y (GC), also referred to as gas-liquid At the end of the GC column, the c a r r i e r gas a n d s a m p l e
c h r o m a t o g r a p h y (GLC), is c o m m o n l y used for the analysis of c o m p o n e n t s flow t h r o u g h a sensitive detector, w h i c h is capa-
p u r i t y a n d c o m p o s i t i o n of solvents. GC is a powerful analyti- ble of indicating the presence of the c o m p o n e n t s qualitatively
cal tool, very sensitive, r a p i d a n d simple in execution. It is a n d quantitatively. The d e t e c t o r m a y be a t h e r m a l conductiv-
capable of furnishing a c c u r a t e qualitative a n d quantitative ity cell, a flame i o n i z a t i o n detector, or an electron c a p t u r e
i n f o r m a t i o n from extremely small a m o u n t s of s a m p l e [37]. detector. There are also o t h e r less c o m m o n types of detectors.
TABLE 15--ASTM gas chromatography methods for analyzing purity and composition of
solvents.
Compound Method Compound Method
Benzene D 4492 Mineral spirits D 3257
(aromatics content)
n-butyl acetate D 3545 /-octane D 2268
/-butyl acetate D 3545 n-propyl acetate D 3545
Cyclohexane D 3054 i-propyl acetate D 3545
Dipropylene glycol D 4773 i-propyl benzene D 3760
monomethyl ether
Ethanol (SD-3A) E 1100 Propylene glycol E 202
2-ethoxyethyl acetate D 3545 Propylene glycol D 4773
monomethyl ether
Ethyl acetate D 3545 Propylene glycol D 4773
monomethyl ether
acetate
Ethylene glycol E 202 1,1,1-trichloroethane D 3742
n-heptane D 2268 Trichlorotrifluoroethane D 3447
Methanol E 346 Turpentine D 3009
Methyl amyl ketone D 3893 Xylenes (mixed) D 2306
Methyl ethyl ketone D 2804 o-xylene D 3797
Methyl isoamyl ketone D 3893 p-xylene D 3798
Methyl isobutyl ketone D 3329
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Any material other than the carrier gas going through the
detector will cause a peak to be plotted on a recorder chart.
The time required for a component to flow through the nA nA1
column, under a given set of operating conditions, when
compared to the time for known compounds, helps to
2
identify the component. The amount of that component is
proportional to the area under the recorder chart peak. Mod-
ern gas chromatographs often have a digital integrator which
prints out the elution time and the area under the peak.
Temperature, column length and size, type and amount of
stationary liquid phase, carrier gas pressure and flow rate,
and sample size are some of the variables that can be changed
to effect desired separations.
Versatility of gas chromatography in solvent analysis is
(9
very great. Good ASTM references on gas chromatography .>_ ns
include "ASTM Standards on Chromatography," second edi-
tion; ASTM Practice E 260, packed Column Gas Chromatog- e-
raphy; and ASTM Practice E 355, Gas Chromatography n"
Terms and Relationships. Specific ASTM GC methods for
analyzing the purity and composition of solvents are listed in
Table 15. ne
t,,_ ~mL~
Liquid Chromatography VI VII VIII VrV
There are two ASTM methods which utilize a liquid chro-
End
matography procedure for measuring the volume percent- Saturates ~,~ Aromatic
Portion
ages of aromatics, olefins, and saturated aliphatics (paraffins Portion Podion (Aromatios
and naphthenes) which comprise a hydrocarbon solvent and
| Ak~oho0
naphtha. Both methods involve the physical separation of
these hydrocarbon types by passing the hydrocarbon sample
through a tube packed with silica gel. The technique is based
Volume of Percolate
on the principle that polar compounds are adsorbed more I
strongly by silica gel than are nonpolar saturated com- FIG. 23-Typical adsorptogram by ASTM Method D 936.
pounds.
A hydrocarbon solvent sample is passed through a glass
suring the length of each zone in a long, narrow extension of
column packed with silica gel. Then, alcohol, which is more
the silica gel column.
strongly adsorbed than any hydrocarbon, follows the sample
through the column, desorbing and forcing the hydrocarbons
out. Saturated compounds are eluted first, unsaturated com- Purity o f Ketones
pounds next, and then aromatics.
In ASTM Method D 936, Aromatic Hydrocarbons in Olefin- ASTM Method D 2192, Purity of Aldehydes and Ketones, is
Free Gasolines by Silica Gel Adsorption, small samples of the an alternative to gas chromatography for measurement of the
emerging sample are periodically collected. The refractive purity of ketone solvents. This is a wet chemical procedure
index of each fraction is measured. From this information, and is applicable for testing ketones having greater than 98%
the relative percentages of aliphatics and aromatics can be purity.
determined, as illustrated in Fig. 23. Precision is good, but the The test is based on the reaction of ketones with hydroxyl-
procedure is slow. amine to form an oxime. Hydroxylamine hydrochloride is
ASTM Method D 1319, Hydrocarbon Types in Liquid Pe- first converted in part to free hydroxylamine by reaction with
troleum Products by Fluorescent Indicator Adsorption (FIA), a known amount of aqueous triethanolamine.
is a refinement of the silica gel adsorption procedure. A mix-
H2NOH.HCI + (HOCH2CH2)3N ) H2NOH +
ture of fluorescent dyes is added to the hydrocarbon solvent
(HOCH2CH2)3N.HC1
sample before it is put into the silica gel column. When all of
the sample has been adsorbed on the silica gel, alcohol is The free hydroxylamine then reacts with the ketone to form
added under pressure to desorb and force the sample down an oxime.
the column. The fluorescent dyes are also selectively sepa-
R1R2C = 0 + H2NOH > R1R2C = NOH + H20
rated with the sample fractions, and they make the bound-
aries of the aromatics, olefins, and saturates clearly visible where R 1 and R2 are alkyl groups.
under ultraviolet light. The zone of aromatics fluoresces vio- The amount of hydroxylamine consumed, which is deter-
let, and the zone of olefins fluoresces a chartreuse color. The mined by titration of the excess base with standard sulfuric
zone of paraffins plus naphthenes remains colorless. Volume acid, using bromophenol blue indicator, is a measure of the
percentage of each hydrocarbon type is determined by mea- ketone originally present. Water, alcohols, saturated esters,
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and hydrocarbons do not react with the reagent, but large The test is performed by agitating a sample with sulfuric
amounts of inert organic solvents are undesirable because of acid under prescribed conditions. The color of the acid layer
the possible effect on the indicator. is compared with colors of aqueous reference solutions con-
taining various concentrations of cobalt chloride, ferric chlo-
ride, potassium chromate, and potassium dichromate. The
Purity of Esters color scale ranges from zero for distilled water to 14 for the
ASTM Method D 1617, Ester Value of Solvents and Thin- darkest reference color standard. The color developed in the
ners, is an alternative to gas chromatography for the mea- acid layer gives an indication of impurities in the aromatic
surement of purity of ester solvents. It may also be used for hydrocarbon which if sulfonated would cause the material to
determining the ester content of lacquer thinners. be discolored.
This is a wet chemical test and involves the reaction of the
solvent sample with a measured excess of aqueous potassium
hydroxide, using isopropanol as a mutual solvent if necessary Alkalinity
R~COOR 2 + KOH > [RICOO]-K + + R2OH ASTM Method D 1614, Alkalinity in Acetone, specifically
where R 1 and R 2 are alkyl groups. The amount of potassium covers the determination in acetone of alkalinity calculated
hydroxide consumed, which is determined by titrating the as ammonia (NH3). The sample is added to an equal volume
excess with standard mineral acid, is a measure of the of water previously neutralized to the methyl red indicator
amount of ester originally present. end point. If alkalinity is detected, it is titrated with 0.05 N
This test method has its greatest application where the sulfuric acid and is reported as weight percent ammonia.
solvent or thinner is not a pure ester. The type of ester present
must be known to perform the calculations. The test may also
be used for assessing compliance with ester specifications. Benzene Content
Benzene is classed as a toxic and carcinogenic compound.
A knowledge of the concentration of benzene may be an aid in
IMPURITIES evaluating the possible health hazards to persons handling
and using solvents, but the ASTM test methods are not in-
Acidity tended to evaluate such hazards. In addition, benzene con-
Solvents may have residual acidity from manufacturing tent is an important specification requirement for aromatic
processes, or acidity may be present as a result of contamina- hydrocarbons used as chemical intermediates.
tion or decomposition during storage or distribution. Acidity ASTM Method D 4367, Benzene in Hydrocarbon Solvents
is undesirable since it may cause corrosion of storage tanks by Gas Chromatography, may be used to determine benzene
and lines. Also, it may cause reactions with basic pigments content of hydrocarbon solvents at levels from 0.01 to I vol%.
resulting in color changes. An internal standard, methyl ethyl ketone (MEK), is added to
ASTM Method D 847, Acidity of Benzene, Toluene, Xy- the solvent sample, which is then introduced into a gas chro-
lenes, Solvent Naphthas, and Similar Industrial Aromatic Hy- matograph equipped with two columns connected in series.
drocarbons, expresses acidity in terms of milligrams of so- The specimen passes first through a column packed with a
dium hydroxide consumed when 100 mL of sample are nonpolar stationary liquid phase, methyl silicone, which sep-
titrated using phenolphthalein indicator. If two drops or less arates components by boiling point. After octane has eluted,
of standard 0.1 N sodium hydroxide solution produce a per- the flow through the nonpolar column is reversed, flushing
sistent pink end point, the sample is reported to contain no out components higher boiling than octane. The octane and
free acid. lighter components then pass through a column with a highly
ASTM Method D 1613, Acidity in Volatile Solvents and polar phase, 1,2,3-tris(2-cyanoethoxy)propane, which sepa-
Chemical Intermediates Used in Paint, Varnish, Lacquer, and rates the aromatic and nonaromatic compounds. The eluted
Related Products, expresses total acidity in terms of weight components are detected by a conventional detector and are
percent acetic acid or as milligrams of sodium hydroxide recorded on a strip chart. Peak areas are measured, and the
required to neutralize one gram of sample. The test is per- concentration of benzene is calculated by reference to the
formed by mixing 50 mL of sample with an equal volume of internal standard.
water (or with an equal volume of alcohol if the sample is not ASTM Method D 4534, Benzene Content of Cyclic Products
water soluble) and titrating with aqueous 0.05 N sodium hy- by Gas Chromatography, applies to cyclohexane, toluene,
droxide solution to the phenolphthalein end point. individual C8 aromatics, cumene, and styrene. Benzene may
be determined over a range from 5 to 300 mg/kg (5 to
300 ppm). The test is performed with a gas chromatograph
Acid Wash Color
equipped with a flame ionization or other detector and a
ASTM Method D 848, Acid Wash Color of Industrial Aro- column containing a polar stationary liquid phase such as
matic Hydrocarbons, is a test used for benzene, toluene, tetracyanoethylated pentaerythritol. A reproducible volume
xylenes, refined solvent naphthas, and similar aromatic hy- of sample is injected. Quantitative results are obtained from
drocarbons. Acid wash color is a measure of chemical reactiv- the measured area of the recorded benzene peak by using a
ity of trace impurities rather than a measure of the color of factor obtained from the analysis of a blend of known ben-
the sample itself. zene content.
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Nonaromatic Hydrocarbons in Aromatics sulfuric acid, and mercuric chloride. The dissolved sample is
then titrated at 0 to 5~ with a bromide-bromate solution.
ASTM Method D 2360, Trace Impurities in Monocyclic Ar-
(The titration is run at low temperature since addition of
omatic Hydrocarbons by Gas Chromatography, covers the
bromine to olefinic molecules proceeds rapidly and com-
determination of total nonaromatic hydrocarbons and trace
pletely at temperatures down to or below 0~ while compet-
monocyclic aromatic hydrocarbons at levels of 0.0005 to 1
ing reactions with aromatics and compounds of sulfur, nitro-
percent by weight in high-purity benzene, toluene, and mixed
gen, or oxygen, if present, are minimized.) End point of the
xylenes by gas chromatography. This inspection is of particu-
titration is indicated by a dead-stop electrometric titration
lar importance when these high-purity aromatics are used as
apparatus. Bromine number is calculated from the weight of
chemical intermediates.
sample and from the volume of bromide-bromate reagent
This test method is performed using an internal standard,
titrated. Values are generally in the range of 1 to 100.
n-butylbenzene, added to the specimen which is then intro-
Hydrocarbon solvents usually have a bromine number of
duced into a gas chromatographic column. The sample
less than one. Therefore, for greater accuracy, precision, and
passes through the column, which contains a polyethylene
discrimination, it is more appropriate to use ASTM Method
glycol stationary liquid phase, and it is separated into nonaro-
D 1492, Bromine Index of Aromatic Hydrocarbons by Cou-
matic and aromatic components. The components are de-
lometric Titration, or ASTM Method D 2710, Bromine Index
tected by a flame ionization detector as they elute from the
of Petroleum Hydrocarbons by Electrometric Titration. Bro-
column and appear as peaks on the chromatogram. Peak
mine index is defined as the number of milligrams of bromine
areas are measured, and the concentration of the composite
consumed by 100 grams of sample (as compared with bro-
nonaromatics and each trace aromatic component is calcu-
mine number which is expressed as grams of bromine con-
lated with reference to the internal standard.
sumed by I00 grams of sample). Although the test procedures
differ, bromine index is the more sensitive test and may be
Nonvolatile Residue assumed to be numerically equal to 1000 times the bromine
number.
ASTM Method D 1353, Nonvolatile Matter in Volatile Sol- In the coulometric titration method, the specimen is added
vents for Use in Paint, Varnish, Lacquer, and Related Prod- to an electrolyte solution consisting of glacial acetic acid,
ucts, describes the analytical measurement of residual matter methanol, potassium bromide, and mercuric acetate, and it is
in solvents that are intended to be 100% volatile at 105 +_ 5~ titrated with electrolytically generated bromine at room tem-
Volatile solvents are used in the manufacture and application perature. End point is determined by a dead-stop method
of paint, varnish, lacquer, and other related products, and the when excess bromine is detected. The time of titration and
presence of any residue may affect the product quality or generation current are proportional to the bromine generated
efficiency of the process. and consumed by the sample.
Nonvolatile residues may consist of oil contamination, dis-
solved solids, rust, sand, or dirt. Trace oil contamination,
which could cause cleaning solvents to leave an objectionable Sulfur Content
deposit of oily residue, often will not be detected by any other Crude petroleum usually contains traces of sulfur com-
specification test. pounds, the greater proportion of which are generally re-
This test is performed by evaporating to dryness 100 mL of moved during refining since they might otherwise cause ob-
solvent in a carefully cleaned, dried, and tared evaporating jectionable corrosive tendencies and foul odors in refined
dish of platinum, aluminum, ceramic, or glass, first on a products such as hydrocarbon solvents. There are several test
steam bath and then in an oven at 105 _ 5~ Weight of any methods which directly measure sulfur content or which in-
residue remaining in the dish is determined, and the result is dicate their presence indirectly.
reported as milligrams of nonvolatile residue per 100 mL.
Copper Strip Corrosion
ASTM Method D 130, Detection of Copper Corrosion from
Olefins Content
Petroleum Products by the Copper Strip Tarnish Test, indi-
Olefins are undesirable impurities in hydrocarbon solvents. cates the presence of corrosive compounds (such as sulfur
They are unsaturated, reactive compounds that tend to oxi- compounds) in hydrocarbon solvents and other petroleum
dize, causing solvent discoloration and objectionable non- products by their effect on a highly polished test strip of
characteristic odor. The level of olefins present can be deter- copper. The polished copper strip is immersed in the solvent
mined by reacting them with bromine. The amount of sample in a test tube and heated for 3 h at I00~ At the end of
bromine that will react is a measure of the olefin content. this period, the copper strip is removed, washed, and com-
ASTM Method D 1159, Bromine Number of Petroleum pared with ASTM Copper Strip Corrosion Standards. Rating
Distillates and Commercial Aliphatic Olefins by Electro- classifications range from "1a--slight tarnish," light orange,
metric Titration, is used for testing materials which have almost the same as the freshly polished strip, to "4c--
fairly high olefin contents. Bromine number is defined as the corrosion," jet black.
number of grams of bromine that will react with 100 g of ASTM Method D 849, Copper Corrosion of Industrial Aro-
sample. matic Hydrocarbons, is similar to ASTM D 130 but applies
The test is performed by first dissolving the hydrocarbon specifically to aromatic hydrocarbons. The sample and pol-
sample in a titration solvent composed of specified propor- ished copper strip are placed in a flask fitted with a condenser
tions of glacial acetic acid, carbon tetrachloride, methanol, and are placed in a boring water bath for 30 min. At the end
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of this period, the copper strip is removed and compared with The triiodide thus consumed is coulometrically replaced.
the ASTM Copper Strip Corrosion Standards. Aromatic sol-
31- ~13 + 2e-
vents are reported to pass the test if the copper strip ratings
are "la" or "lb," indicating only "slight tarnish"; all other These microequivalents of triiodide generated are equal to
ratings are considered failures. the microequivalents of sulfur dioxide entering the titration
cell. The sample result is compared with that of known cali-
Doctor Test bration standards, and appropriate calculations are made to
The Doctor Test is a very sensitive qualitative test for de- report the sulfur concentration.
tecting hydrogen sulfide and mercaptan sulfur in hydrocar-
bon solvent naphthas. It is described in section 6.1.10 of
Water Content
ASTM Specification D 235 for Mineral Spirits.
The test is performed by vigorously shaking together in a Dissolved water can have adverse effects on solvent end-use
test tube the solvent being tested and an aqueous sodium applications. For example, it can reduce solvency. Water can
plumbite solution. A small amount of pure, dry flowers of cause reactions with isocyanates during polyurethane prepa-
sulfur is added so that practically all of it floats on the inter- ration and with moisture-cure polyurethane paints and var-
face between the solvent and the sodium plumbite solution nishes causing polymerization and gelation during storage.
after shaking. If the solvent is discolored or if the yellow color Metallic pigments can react with water to generate hydrogen
of the sulfur film is noticeably masked or discolored and gas, which can expand and burst paint cans. Dissolved water
blackened, the test is considered positive and the solvent is can act as a catalyst poison when a solvent is used as a
reported as "sour." If the solvent remains unchanged in color reaction diluent for polyolefin polymerization.
and the sulfur film is bright yellow or only slightly discolored
with gray or flecked with black, the test is considered negative Karl Fischer Reagent Method
and the solvent is reported as "sweet." ASTM Method D 1364, Water in Volatile Solvents (Fischer
Reagent Titration Method), is a quantitative test. It is based
Sulfur by Lamp Method on reactions involving the reduction of iodine by sulfur diox-
ASTM Method D 1266, Sulfur in Petroleum Products ide in the presence of water. These reactions can be used
(Lamp Method), is used for quantitatively measuring total quantitatively when pyridine and an alcohol are present to
sulfur content of solvents. The sample is burned in a wick react with the sulfur trioxide and hydroiodic acid produced in
lamp in an artificial atmosphere of 70% carbon dioxide and the reagent.
30% oxygen to prevent formation of nitrogen oxides. A solu-
tion of hydrogen peroxide is used to absorb the oxides of H20 + 12 + SO 2 + 3CsH5N ~ 2C5H5N.HI + C5H5N.SO 3
sulfur which are formed during combustion and to oxidize CsHsN-SO3 + ROH ~ CsHsN-HSO4R
them to sulfuric acid. After flushing with air to remove dis-
To determine water content, Fischer reagent (a solution of
solved carbon dioxide, the absorbent is titrated with a stan-
iodine, pyridine, and sulfur dioxide in the molar ratio of
dard solution of sodium hydroxide. Sulfur is calculated as
1 : 10:3) dissolved in anhydrous 2-methoxyethanol is added to
percent by weight from the weight of sample burned and the
a solution of the sample in anhydrous pyridine-ethylene gly-
volume of sodium hydroxide reagent required to titrate the
col (1:4) until all water present has been consumed. This is
acid in the absorbent. Alternatively, the sample may be
evidenced colorimetrically by the persistence of an orange-
burned in air, in which case the sulfur as sulfate in the
red end-point color or electrometrically by an indication on a
absorbent is reacted with barium chloride to precipitate bar-
galvanometer or similar current-indicating device which
ium sulfate, and the sulfur content is determined gravimetri-
records the depolarization of a pair of noble-metal elec-
cally.
trodes. The reagent is standardized by titration of measured
Trace Sulfur by Coulometry amounts of water.
Alternatively, automatic instruments are commercially
ASTM Method D 3961, Trace Quantities of Sulfur in Liquid
available which operate on a coulometric principle according
Aromatic Hydrocarbons by Oxidative Microcoulometry, is a
to ASTM Method E 1064, Water Content of Liquid Organic
highly sensitive quantitative test for the determination of sul-
Chemicals by Coulometric Karl Fischer Titration. A mea-
fur content in the range of from 0.5 to 100 mg/kg (0.5 to
sured quantity of sample is introduced into a titration cell
100 ppm). The test may be extended to higher sulfur concen-
containing reagent which undergoes the Karl Fischer reac-
trations by appropriate sample dilution. Although the test
tions. Iodine is coulometrically regenerated, the amount of
method applies specifically to aromatic hydrocarbons, it may
current required being proportional to the water content of
also be used for other solvents.
the sample.
The test is performed by injecting a measured liquid sam-
ple into a quartz combustion tube in an electric furnace Heptane Miscibility Test
maintained at about 800~ and having a flowing stream of gas
Oxygenated solvents are capable of dissolving sizable
consisting of about 80% oxygen and 20% inert gas. Oxidative
amounts of water. They can he checked qualitatively for
pyrolysis converts the sulfur to sulfur dioxide which then
water content by ASTM D 1476, Heptane Miscibility of Lac-
flows into a titration cell where it reacts with triiodide ion
quer Solvents. Heptane is water immiscible and has a very
present in the electrolyte.
low tolerance for water in solvent blends. The test is per-
13 + 5 0 2 q- H20 , SO 3 -1- 31- + 2H + formed by mixing the solvent sample under test with heptane
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in a 1 : 19 p r o p o r t i o n a n d agitating. A clear solution indicates [14] Hansen, C. M., "The Three Dimensional Solubility Parameter--
miscibility a n d low w a t e r c o n t e n t (less t h a n a b o u t 0.5 wt%) in Key to Paint Component Affinities,"Journal of Paint Technology,
the solvent sample. A t u r b i d solution indicates i m m i s c i b i l i t y Vol. 39, No. 505, 1967.
a n d the presence of high w a t e r content in the solvent sample. [15] Hansen, C. M., "The Universality of the Solubility Parameter,"
Industrial Engineering Chemistry Product Research & Develop-
ment, Vol. 8, 1969, p. 2.
[16] Huyskens, P. L. and Haulait-Pirson, M. C., "Dissolving Power of
Water Solubility Solvents and Solvent Blends for Polymers," Journal of Coatings
Certain oxygenated solvents are completely miscible, e.g., Technology, Vol. 57, No. 724, 1985.
m e t h a n o l , isopropanol, acetone. This p r o p e r t y can provide a [17] "Properties of Solvents," brochure, Shell Chemical Co., Hous-
ton, 1990.
qualitative m e a n s for i n d i c a t i n g the presence or absence of
[18] "Evaporation Rates of Solvents as Determined Using the Shell
water-insoluble c o n t a m i n a n t s , such as oils, paraffins, olefins,
Automatic Thin Film Evaporometer," Technical Bulletin
aromatics, high m o l e c u l a r weight alcohols, ketones, etc. Wa- IC:69-39, Shell Chemical Co., Houston, 1969.
ter-insoluble m a t e r i a l s in the solvents m a y interfere with [19] Ellis, W. H., "Comparative Solvent Evaporative Mechanisms for
m a n y of their end-uses. Conventional and High Solids Coatings," Journal of Coatings
ASTM M e t h o d D 1722, W a t e r Miscibility of W a t e r - S o l u b l e Technology, Vol. 55, No. 696, January 1983, p. 63.
Solvents, covers the d e t e r m i n a t i o n of the miscibility of water- [20] Murdock, R. E. and Wirkus, W. J., "A Method for Measuring
soluble solvents with water. The s a m p l e is diluted to 10 vol- Solvent Release Using Radiotracers," Official Digest, Federation
u m e s of w a t e r in a glass g r a d u a t e d cylinder. The resulting of Societies for Coatings Technology, Vol. 35, 1963.
mixture is viewed t h r o u g h the length of the c o l u m n of liquid [21] Hays, D. R., "Factors Affecting Solvent Retention: Carbon-14
Tagged Solvents in Poly(Methyl Methacrylate) Films," Official
t o w a r d a d a r k b a c k g r o u n d while being transversely illumi-
Digest, Federation of Societies for Coatings Technology, Vol. 36,
nated. The s a m p l e is r e p o r t e d to pass the test if there is no 1964.
evidence of cloudiness o r t u r b i d i t y initially a n d after 30 rain. [22] Sletmoe, G. M., "The Calculation of Mixed Hydrocarbon-Oxy-
genated Solvent Evaporation," Journal of Paint Technology, Vol.
42, 1970.
[23] Lesnini, D. G., "Concentrations of Evaporating Mixtures," pre-
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[12] Burrell, H., "The Challenge of the Solubility Parameter Con- Chemical Journal, Vol. 14, 1892, p. 300.
cept," Journal of Paint Technology, Vol. 40, 1968, p. 197. [36] Olson, C., "Improving Resistivity Control in Coatings for Opti-
[13] Crowley, J. D., Teague, G. S., and Lowe, J. W., "A Three Dimen- mal Electrostatic Spraying Systems," American Paint and Coat-
sional Approach to Solubility: Part I," Journal of Paint Technol- ings Journal, 4 Feb. 1991, p. 70.
ogy, Vol. 38, No. 496, 1966, p. 269, and "Part II," same journal, [37] Keulemans, A. I. M., "Gas Chromatography," 2nd ed., Reinholdl
Vol. 39, 1967, p. 504. New York, 1959.
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Part 6: Pigments
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MNLI7-EB/Jun. 1995
White Pigments
by Juergen H. Braun 1
INTRODUCTION developed countries making the product at somewhat lower

quality for regional consumption.
ALMOSTEVERYTHINGMAN-MADEthat is white or light in color In the United States and other developed countries, one
contains white pigment in its surface: houses inside and out- half of the TiO2 pigment is used in coatings, one quarter in
side, industrial articles, plastics, glazes, rubber, printed sur- paper, and 15% in plastics. All other end uses, pigmentary
faces, many paper products, and even some foods. Only pa- (inks, floor coverings, elastomers, roofing granules, fibers,
pers and textiles can be white without pigment. fabrics, sealants, foods, etc.) and nonpigmentary (ceramics,
Virtually all this whiteness and lightness is supplied by welding rods, etc.), account for the remaining 10%. In less
titanium dioxide (TiO2) pigments. Void pigments make a mi- developed countries, most of the TiO2 pigments go into paints
nor contribution. The classic white pigments--lithopone, and plastics.
zinc sulfide, and the white leads--have essentially disap-
peared from commerce because TiO 2 pigments perform
much better, are much cheaper, and are nontoxic. Zinc oxide
Manufacture
is still added to some paints as a mildewstat, but not as a
white pigment. TiO2 particles, the active ingredient of pigment, are made
TiO2 pigments are manufactured by a major, globally dis- by two processes:
tributed industry. Its products are sold for many applications; 1. The old sulfate route dissolves the ore in sulfuric acid,
however, more than half of all white pigment goes into paints. purifies the aqueous solution of titanyl sulfate, precipitates
In many coatings, white pigment is the single most expensive a hydrous titania gel, and calcines the gel to crystallize it
ingredient. To select the right pigment grade and use it well is into aggregates of pigment particles, which, in turn, must
an important challenge to the paint manufacturer. be ground.
This chapter will familiarize coating manufacturers with 2. The newer, "greener" chloride route chlorinates the ore
white pigments and help them understand their options for and purifies the TIC14 intermediate by distillation and
selection, utilization, and testing. Toward this objective, I will chemical treatments. TIC14 is then flame oxidized to pig-
first outline the commerce and manufacture of white pigmentary TiO2 particles and chlorine. The chlorine is recy-
ments and then discuss their function, the substances that cled.
serve this function, and the commodities available. I will Sulfate processes are low-tech, labor-intensive operations
distinguish between product characteristics that describe the in batch mode. Chloride processes are high-tech, automated,
pigment itself and product performance, which are proper-
continuous operations. Sulfate and chloride products do not
ties of paint films, that is, systems composed of pigment and
differ much in performance except that chloride TiO2 is purer
binder.
and thus brighter.
Waste disposal is a significant factor and constraint. The
sulfate process generates vast quantities of dilute sulfuric
Commerce
acid and iron(II)sulfate from its ilmenite (FeTiO3) ingredi-
The white pigment market is served almost exclusively by ent. 2 The chloride process makes iron(III)chloride by-prod-
titanium dioxide pigments. Globally, six billion pounds are uct in much lesser quantities that are dependent on ore com-
produced annually at a value of six billion dollars. The value position: rutile (TiO2), anatase (TiO2), leucoxene (TiO2/
of TiO2 pigments exceeds by far the combined value of all FeTiO3), and ilmenite (FeTiO3).
color pigments. After the primary pigment particles are made by either
Five manufacturers share two thirds of the world market. process, their surfaces are treated to adapt the pigment to a
Most of these producers operate several large plants located variety of end uses. These treatments are carried out in aque-
in industrialized countries. The largest of these plants makes ous suspension followed by drying, grinding, and dry treat-
about two million pounds of pigment a day. Their products ment operations. Pigments are also converted into slurry
are of similar quality. A few small plants operate in the lesser grades.
IConsultant, 614 Loveville Road, Building E, Apartment l-H, 2The iron-free minerals, rutile and anatase, do not dissolve in
Hockessin, DE 19707-1616. sulfuric acid and cannot be used as such in sulfate processes.
159
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By either process, manufacture involves five steps: Hiding also can be achieved by the absorption of light that
1. Digestion of the ore. is involved in colored and black surfaces and pigments. Opti-
2. Purification of the intermediate. cal absorption is decisively more efficient than optical scat-
3. Crystallization of pigment particles. tering. Thus, less color or black than white pigment is re-
4. Treatment of the pigment surface. quired for hiding. Dark and black paint films can therefore be
5. A variety of finishing operations. thinner than their white and light counterpartsP
Table 1 relates appearance characteristics of surfaces to the
optical p h e n o m e n a that cause them. If all light is absorbed by
Research and Development a surface, none scattered, the surface is perceived as black. If
all light is scattered, none absorbed, the surface is seen as
For 50 years, the TiO2 industry has been large, competitive, white. If a portion of the light is scattered and another por-
and profitable enough to dedicate sizable science and engi- tion absorbed, the surface is gray. If the absorption and scat-
neering resources to product improvement. These efforts tering is wavelength dependent, for example, if red light is
have been remarkably successful. Today's Ti02 pigments are absorbed and green light is scattered, the surface is colored
complex structures composed of an optically active core with by the scattered green portion of the light. Even though
shells that adapt the pigment to specific end uses. Each feature c o m m o n usage refers to objects as colored, i.e., red cars,
is carefully designed into each pigment grade, optimizing it green mountains, almost always only their surfaces matter. 6
for its specific application. Their optical performance ap- The return of light from a surface is caused by reflection at
proaches the light-scattering effectiveness calculated from the surface and scattering from beneath with pigment
concepts of theoretical physics.
causing the scattering. The optical action itself occurs at or in
Experts in pigment technology, with the help of specialists pigment particles, not on but within the surface. Light re-
in optics, surface chemistry, fine-particle technology, and flected at the surface does not usually change its color. 7
chemistry have resolved m a n y of the compromises between Light scattered and returned from inside the coatings
often conflicting requirements. End users can contribute to makes a surface look white or, if color pigments are involved,
progress by suggesting new opportunities. Solving pigment gives color to the surface. It is the white pigment in the
problems does, however, require expertise in pigment tech-
coatings that does most of the light scattering.
nology.
Light scattering can be explained quantitatively from opti-
cal theories. Geometric optics give a graphic but superficial
picture that accounts well for effects of refractive indices of
THE FUNCTION OF PIGMENTS potential pigments but unreliably for effects of pigment parti-
cle size. Wave optics and electromagnetic theory provide a
Most coatings have two functions, aesthetic and protective. more accurate but quite abstract model, accounting for parti-
More often than not, manufactured surfaces are visually un- cle size but not for effects of particle shape, orientation, and
attractive and therefore coated for aesthetic appeal. The coat- crowding.
ing hides the substrate's discolors and contrasts and provides The o p t i m u m particle size at which a population of white
a visually pleasing appearance or identification. Pigments 3 pigment particles scatters a m a x i m u m a m o u n t of light is
are not directly involved in the protective function of coat- about 8 0.2/~m for green and white light. Blue light is scat-
ings. tered more efficiently by smaller particles, red light by larger
Pigments supply the hiding and color of a coating. They are ones. For pigments of high refractive indices, the theoretical
incorporated in surfaces to make t h e m look bright or dark, curve of optical effectiveness versus particle size has a sharp
colorful or drab, white or black, either m o r e appealing or peak (Fig. 1). For pigments of lower refractive indices, the
more appropriate to whatever the intended service. Toward peak broadens but the optimal size near 0.2/~m does not
that end, pigments must hide the unattractiveness of a sub- change much.
strate. Thus, pigments serve the h u m a n eye. They interact The pronounced wavelength dependence of o p t i m u m scat-
with visible light and cause surfaces to be seen in colors4: tering causes a subtle color effect by white pigments in col-
chromatic colors like red, blue, and green or achromatic ored coatings. Their color shifts toward red if the white pig-
colors like black, gray, and white. ment is larger than optimal. Color shifts toward blue if the
To understand this primary aesthetic function of pigments, white pigment is smaller. This "undertone" is visible in col-
let us consider the interactions of visible light with matter at
or near surfaces. Involved are two mechanisms of optics: light SThe transparency of white clothes, in particular wet, white
scattering and light absorption. clothes, illustrates the relative hiding effectiveness of white and
color.
White or bright hiding is achieved by light scattering, an 6This comes about because visible light and thus human vision
optical mechanism by which a ray of light is scattered as it penetrates pure gasses to a depth of about 10 m, pure liquids to
hits an interface. White pigments are substances selected to about 10 +2 m, dielectric solids to about 10 -3 m, and metals to about
scatter light very well. 10-9 m, a range of 15 orders of magnitude.
7Exceptions are the colored metals--gold, copper, and their al-
l o y s - a n d extremely strong colorants, for example, copper phtha-
3Anticorrosive "pigments" do not meet Webster's definition of a locyanine and hematite.
pigment as "a substance that imparts black or white or color to other 8The uncertainty is not in the optical calculation hut reflects diffi-
materials." culties in defining the size of particles other then spheres. What, for
4In most technical contexts of color and colorants, white, gray, and example, is larger, a large snake or a small monkey? It depends on the
black are considered colors. perspective of the observer.
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CHAPTER 1 9 - - W H I T E PIGMENTS 161
TABLE 1--Optics and appearance. pigment. Economics discriminate severely against pigments
If the Pigment in the Coating Then the Coating of low optical effectiveness.
Absorbs Scatters Returns And The economics of hiding are illustrated by Fig. 2, a plot of
Light Light Light Looks the cost of hiding as a function of pigment volume concentra-
All None None Black tion for the case of a typical white paint applied to hide color
None All All White contrasts of a substrate. The film is composed of a Tie2 pig-
Some Some Some Gray ment at $1 per pound and a density of 4 g/mL dispersed in a
Some,in specificwavebands Colored resin at $1 per pound and a density of 1 g/mL. Hiding cost has
a distinct minimum. At too low a pigment volume concentra-
tion, the film must be thick to hide. The cost of hiding in-
ored coatings and in white coatings at incomplete hiding. In creases because additional resin is required to deliver the film
gray coatings the effect can be quite obvious and at times thickness. At too high a pigment volume concentration, the
objectionable. white pigment is used inefficiently, also increasing cost,
Pigments can act by themselves but are usually used in albeit at a lower rate.
combinations: white pigment with a small amount of color or
black pigment, white pigment with one or more color pig-
ments, combinations of color pigments, color pigments with
some black pigment, etc. Some types of pigment particles T H E S U B S T A N C E OF W H I T E P I G M E N T
scatter light, others absorb it. White pigments deliver white
appearance by scattering all light (see Table 1). Black pig- White pigments translate light scattering into hiding
ments absorb all light. Color pigments create color by absorp- power, brightness, and opacity of thin films. The films, in
tion of light of specific wave bands. Sometimes, though, the turn, hide the color and contrasts of the substrate.
wavelength-specific absorption by color pigments is aug- To serve as an effective white pigment, a substance must
mented by wavelength-specific scattering. meet requirements that limit the selection to less than one
Pigments, because they are particulates, can affect surface dozen from among the thousands upon thousands of natural
texture and texture-related appearance characteristics: gloss and man-made chemicals. A potential white pigment must:
and sheen.
9 have an extremely high refractive index
Pigments do the optical, that is, the aesthetic work; they
provide the color and the hiding. Binder keeps the pigment In addition the substance must be:
on the substrate and does the mechanical and the chemical 9 stable
work that protects the substrate from the environment. The 9 almost colorless
less effective the pigment in its optical function, the thicker 9 suitable for manufacture in optimized, colloidal particle
the coating must be to hide and provide the desired color. size
Thick coatings, however, cost more than thin ones. Since the 9 a solid
cost of binder increases proportionally to film thickness, film 9 insoluble in water and organic solvents
costs are inversely proportional to the effectiveness of the 9 safe in manufacture, end use, and as a waste
0
0 .2 .4 .6 .8 1.0
Diameter, pm
Calculations: W. D. Ross, Du Pont Company
FIG. 1-Scattering by spheres of rutile in resin. From Braun, J. H., Introduction to
Pigments, monograph in the Federation Series on Coatings Technology, Federation
of Societies for Coatings Technology (United States), 1993.
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The Cost of Hiding* thicker, increasing binder cost. In coatings above the critical
Schematic pigment volume concentration, extenders create a network of
interconnected voids. These pores enhance the hiding effec-
tiveness of the pigments. This indirect hiding contribution of
voids is cheap to achieve in a paint but comes at the expense
of mechanical and chemical film qualities. Pores (1) concen-
trate mechanical stresses to where they initiate fracture and
(2) conduct aggressive chemicals from the surface into the
depth of the paint film. The hiding improvements and the
quality detriments of coatings above their critical pigment
volume concentration can be quite large.
TiO 2 PIGMENTS
5 I I I I
0 10 20 30 40
Titanium dioxide has obsoleted all other white pigments
Pigment Volume Concentration, %
because TiO 2 is cheaper to use and much safer than other
Contrast Ratio: .98 [ TiO, : 1 $/lb 4 g/ml pigments. TiO2 pigments are the most effective scatterers of
SX: 12.0 [ Resin: 1 $/Ib 1 g/ml visible light. They hide better and provide more lightness.
FIG. 2-The cost of hiding. From Braun, J. H., Introduction to They are more stable and less toxic.
Pigments, monograph in the Federation Series on Coatings Figures 3 and 4 show what TiO 2 pigments "look" like. Fig-
Technology, Federation of Societies for Coatings Technology ure 3 is a transmission electron micrograph of an uncoated
(United States), 1993. TiO 2pigment grade dispersed in a dispersant by conventional
techniques of grid preparation. Single crystals, twins, aggre-
gates, and small agglomerates are visible. Weakly bonded
Of these, the requirement of an extremely high refractive
agglomerates, though, are not distinguishable from strongly
index, larger than 2.0, is essential and is most restrictive.
bonded aggregates because micrographs do not show
Most materials with high refractive indices are hydrolytically strength of bonding. Figure 4 shows a set of electron scanning
unstable. A combined requirement for extreme refractive in- micrographs of dry pigment in bulk and as an individual floc.
dex plus stability eliminates all but a few substances. Visible are masses and individual crystallites, single and
High density is a disadvantage for a pigment. Pigments twinned. At highest magnification, scanning electron micros-
function by volume yet are sold by weight. Thus, a high-
density pigment contains fewer particles per pound to do its
optical work than a low-density pigment.
Because of its optical performance, safety, and cost, tita-
nium dioxide has become the only white pigment of commer-
cial significance. In the foreseeable future, it is quite unlikely
that a better white pigment will be found to replace TiO2
because its performance advantage results from a combina-
tion of a uniquely high refractive index with other essential
characteristics.
TiO2 has the highest refractive index of all ordinary, color-
less, and stable substances, significantly higher even than dia-
mond. Refractive indices of most compounds such as TiO 2
have been measured and can even be calculated from pure
theory. No colorless substance, neither real nor hypothetical,
has been found 9 that has a higher refractive index than ZiO 2.
Before the commercialization of titanium dioxide, litho-
pone (BaSO4/ZnS), zinc oxide, zinc sulfide, and white lead
[lead(II)hydroxy carbonate] served as white pigments. All
have lower refractive indices, scatter less effectively, and are
much less cost effective.
Not only particulates but also air voids in coatings scatter
light as if they were particles. But air voids are far less effec-
tive than TiO2. Voids thus contribute to hiding but at direct or
indirect costs. In coatings below their critical pigment vol-
ume concentration, voids scatter light and hide as such. But
because they do not hide as well as TiO 2, films must be
9Extreme pressure phases ofTiO2could be expected to have higher FIG. 3-Transmission electron micrograph of TiOa pig-
densities combined with higher refractive indices, ment.
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FIG. 4-Scanning electron micrographs of TiO= pigment.
copy shows crystals significantly more rounded than they replaced by rutile because, in organic media, rutile has an
actually are. 18% scattering advantage over anatase.
TiO2 pigments are made in two crystal phases, rutile and For the sake of clarity I will distinguish between character-
anatase, that differ in lattice structures, refractive indices, istics and performance of a pigment. Composition, for exam-
and densities. Anatase was the first commercial titanium di- ple, is a characteristic of a pigment that is essentially inde-
oxide pigment but, for the coatings industry, has now been pendent of its environment. By contrast, hiding power
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describes the performance of a system, a pigment within a istics, however, dictate equally specific performance attrib-
paint film. Hiding is a film characteristic that depends on utes. These crucial relationships are described.
pigment volume concentration and a host of formulation and Refractive index and density are paramount to optical
application parameters of the paint in which the pigment was function, but they are not subject to manipulation. Crystal
evaluated. phase impacts weathering and light-scattering performance.
Characteristics are properties of the commodity: composi- Particle size controls light scattering and has effects on color.
tion, density, particle size, etc. They can be measured on the Surface characteristics are designed into the product through
commodity, either dry powder or slurry. Granted, some prod- chemical treatments reflected by commodity composition.
uct characteristics are affected by the ambiance in which they The treatments improve dispersibility, durability, and gloss
are measured but only in secondary ways. Particle size is an performance. High purity of the pigment makes for bright-
example of a characteristic affected by method of measure- ness.
ment.
At the state of the art it does not appear possible to estab- TiO 2 Crystallites
lish rigid links between pigment characteristics and perform- The active ingredients of a TiO2 pigment commodity are its
ance. Thus, the pigment commodity cannot be defined TiO2 crystallites. Other components of the commodity affect
exclusively in terms of its characteristics. Certain characteris- the commodity density but do not affect the crystallite den-
tics can be measured reliably. Their results bear on but do not sity nor the refractive index of the pigment. Neither the re-
guarantee performance. Clearly, complete specifications for fractive index nor the density of any chemical can be manipu-
pigments must include both product characteristics as well as lated independently by conventional technology. 11
product performance measures. Two crystal phases of titanium dioxide serve as pigments:
A few generalizations of the connection between pigment rutile and anatase. They differ in refractive indices, densities,
characteristics and product performance are appropriate: and weathering performance because rutile and anatase dif-
9 High gloss pigments: (l) pack densely as indicated by mea- fer by the arrangement of the titanium and oxygen ions
sures of oil absorption, liquid demand, and interstitial within the crystals (Fig. 5). Rutile crystals are elongated, are
space; (2) contain few agglomerates larger than about 0.5 denser, and have higher refractive indices) 2 Because of their
p.ml~ and (3) have hydrous oxides contents that are low and higher refractive indices, rutile pigments scatter light more
TiO2 contents that are correspondingly high [1]. effectively than anatase products. They are also much less
9 Pigments intended for high-pigment volume concentration prone to chalk.
paints contain up to 20 wt% hydrous oxides because fluffy Rutile absorbs slightly more violet light than anatase and is
oxides act as very efficient extenders. TiO2 contents are slightly more yellow in bulk. However, little, if any, of this
correspondingly low. yellowness extends into pigment applications.
9 Satisfactory outdoor durability precludes the presence of TiO 2 is a UV-energized oxidation catalyst of organic poly-
more than about 1 wt% anatase phase with the rutile [2]. mer. Anatase surface is about ten times more reactive than
9 Product fractions smaller than about 0.1 /zm and larger rutile surface. It takes only 10% anatase in rutile to reduce to
than about 0.4/~m constitute losses to optical performance one half the life expectancy of a paint film. Thus, for all
because particles that are too large or too small scatter light exterior applications, the phase purity of rutile pigments is
inefficiently. quite important.
9 Impurity metal ions within the rutile crystals can degrade During paint manufacture or usage, titanium dioxide can-
brightness dependent on the nature of the metal ion. Cer- not undergo transitions of crystal phase, that is, it cannot
tain ions degrade color in concentrations as low as 0.000 01 change its lattice structure. This contrasts to most organic
wt%. Effects of ion contaminants on characteristics other pigments, many of which phase convert readily, usually with
than brightness are generally insignificant. Hydrous oxide dramatic loss of optical performance. For example, an
coatings can tolerate a much higher concentration of impu- unstabilized a-copper phthalocyanine pigment, upon expo-
rity metal ions in the coating without much effect. sure to an aromatic solvent, grows into long needles of
9 Hydrous oxide coatings on pigment have ion-exchange /3-copper phthalocyanine, losing most of its color strength in
characteristics. Their exchangeable ion content affects pig- the process.
ment performance in applications that are sensitive to pH
Phase Analysis One percent or more of anatase in rutile
(acid-catalyzed coatings) or the presence of electrolyte
pigment is considered undesirable because it increases the
(electrocoatings).
catalytic reactivity of the pigment. Fortunately, the phase
9 Pigment surface area affects oil absorption.
analysis of TiO z pigment is cheap, convenient, and reliable.
Some of these effects a r e sufficiently well quantified for Phase purity of pigment is usually measured by X-ray dif-
translation into specifications. fraction, for example, ASTM Test Method for the Ratio of
Anatase to Rutile by X-ray Diffraction (D 3720-90). Conven-
Pigment Characteristics tional diffractometers can detect 1% of pigmentary anatase in
TiO2 pigment has to meet stringent specifications of crystal 99% rutile by using peak intensity ratios or instrument
phase, particle size, surface characteristics, and purity. As
with all chemicals, every product characteristic has some lIDensity and refractive indices of inorganic oxides can be in-
effect on every performance quality. Some specific character- creased together, but only at extreme pressures and astronomic cost.
12Actually,TiO2crystals have two principal refractive indices each.
These two refractive indices do not differ much. They enter all
WParticle size measured as Stoke's settling diameters by sedimen- relevant considerations of pigment as an appropriately weighted av-
tation methods. erage.
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CHAPTER 19--WHITE PIGMENTS 165
D ensity, Refractive
Typical Crystals Crystal Structures g/ml Index*
Rutile 4.3 2.7
~~ 9Ttianuim
0 Oxygen
Anatase 3.8 2.5
* Weighted Average of E and to Refractive Indices
FIG. 5-Titanium dioxide crystals. From Braun, J. H., Introduction to Pigments, monograph in the Federation
Series on Coatings Technology, Federation of Societies for Coatings Technology (United States), 1993.
counts. With careful attention to instrument alignment and grain boundaries and are thus strongly bonded. Agglomer-
sample preparation, a bit less anatase can be detected. Other, ates are associations of crystallites and aggregates bonded by
more complex techniques are more sensitive. However, why relatively weak forces. Flocs are weakly bonded associations
bother since less than 1 wt% anatase does not contribute of crystallites, aggregates, and agglomerates formed sponta-
m u c h to the catalytic activity of the pigment. neously in a liquid or even in air.
The hydrous and anhydrous oxides contributed by pigment The shear forces of paint application can disperse flocs.
treatment are not detectable by X-ray diffraction because However, they are likely to reassociate. Paint grinding breaks
they are either truly a m o r p h o u s or subcrystalline, that is, too most agglomerates if (1) the mill base is formulated to proper
small and/or too disorganized. Their diffraction lines are viscosity and (2) the mill is operated well. Aggregates can be
diffuse and drowned in the TiOz signal. broken only by high-intensity mills. Crystallites cannot ordi-
narily be broken. Aggregates and crystals, once broken, do
not reassemble because aggregate bonding and crystal
Pigment Particle Size growth require thermal activation to m a n y hundred degrees
TiO 2 pigment particles are submicroscopic, so small that centigrade. TiO2 pigments do not degrade in conventional
one pigment particle is to the size of a m a n as the size of a paint and plastics processing.
m a n is to the size of the earth. Thus, intuitive judgments The inclusion of casual contact in the definition of "parti-
based on macroscopic experiences are often misleading. cle" is important because it links size to concentration. At low
The particle size of pigment grades is tailored to the re- pigment concentration, the frequency of particle overlap in a
quired optical performance. Pigment size depends critically beam of light is low and the casual contact contribution to
on definition of "particle." For paint optics, the particle is the effective size is small. At high concentration, casual contacts
object a light beam meets in the paint film. Its size is a are a b u n d a n t and contribute significantly to the particle size
composite of primary particles, aggregates, agglomerates, as seen by a light beam penetrating a paint film.
flocs, and even of casual contact of any of these assemblies. Optimal scattering performance calls for optimal particle
Primary particles are individual single crystals and crystallo- size. Particles that are too small in the extreme, molecular
graphic twinsJ 3 They average from 0.1 to 0.3/~m in median dispersions, scatter almost no light; particles too large, mac-
diameter by weight with a geometric standard deviation of roscopic crystals, are transparent. The particle size at which a
about 1.4. TMAggregates are associations of crystallites sharing population of TiOz particles scatters a m a x i m u m a m o u n t of
light is about 0.2/zm for green ~5and white light. Blue light is
scattered more effectively by particles closer to about 0.16
13Twoor more single crystals intergrown according to some deduc-
ible law of symmetry.
14Geometric standard deviation = l/z (Ds4/Ds0 + Ds0/Dl6),with D = 15For whiteness and brightness, green light matters most because
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/~m, red light by particles of about 0.23 t~m. This optically 36

effective particle size is likely to differ from the size measured ,-~ 32
by analysis.
28
Particle-size distributions of commercial TiO2 pigments
are narrower than those of many so-called monodisperse 24
particulates (Fig. 6). Population statistics approach "log-nor- 20
mal" character, that is, a logarithmic transform converts the
size distribution curve to "normal" (Gaussian) probabilities.
Appropriately ground, pigment dispersions contain less than r 12
5 wt% of particles smaller than 0.10 and larger than 1.0/~m. 8
The mean particle size of pigment grades is tailored to the
required light scattering performance. Pigment grades com- 9-~
9
4
posed of small particles are made for applications at low- 0

pigment volume concentration. 0 .1 .2 .3 .4 ,5
The pronounced wavelength dependence of optimum scat- Particle D i a m e t e r , p m

tering causes a subtle color effect caused by white pigments FIG. 6-Particle size distribution of TiO2 pigment. From
in colored coatings. Their color shifts toward red if the white Braun, J. H., Introduction to Pigments, monograph in the Fed-
pigment is larger than optimal or toward blue if the white eration Series on Coatings Technology, Federation of Societies
pigment is smaller. This "undertone" is visible only in gray for Coatings Technology (United States), 1993.
and colored coatings and in white at incomplete hiding. In
gray coatings the effect can be quite obvious, sometimes 9 Sampling statistics is a frequent problem considering small
objectionable, sometimes desirable. Small size TiO2 grades quantities or low concentrations of pigment in samples.
with blue undertone are used to make colors look "cleaner," 9 In microscopy, transmission images bear little resemblance
i.e., less yellowishJ 6 to ordinary visual perceptions based on observation of sur-
Large particles in a paint film are detrimental to gloss. faces. Scanning micrographs, by contrast, correspond to
Thus, the coarse tail of the size distribution of TiOz pigments h u m a n vision. Differences become apparent when compar-
impacts gloss performance [1]. Figure 7 shows what particle ing Figs. 3 and 4.
size range impacts which performance characteristic. 9 In light-scattering methods, the extreme refractive index of
Paint grind gages reveal the presence of minute quantities TiO2 affects computational interpretation.
of grit, clumps composed of tens of thousands of primary 9 No certified standards are available pertaining to the size
particles. Grind gages do not respond to pigmentary particle range of pigments.
sizes. For TiO2 pigments, the presence of grit has no detect-
Numerous methods have been used for the size analysis of
able optical effects.
pigments: Andreasan pipette, disk centrifuges, transmission
Particle size control is one of the manufacturing secrets of
electron microscopy, light-scattering measurements, field
the TiO2 industry. Additives and process conditions during
flow fractionation, etc. They are too complex and far too
crystallization and grinding operations are crucial to particle
costly for routine analysis.
size and product performance in both chloride and sulfate
Lately two methods have advanced TiOz technology be-
processes.
cause reproducible results can be obtained routinely: X-ray
Particle Size Analysis--Up front a warning: Particle-size sedimentation and the X-ray disk centrifuge. Both are usually
analysis and the interpretation of analytical data calls for spe- combined with ultrasonic dispersion.
cialized expertise. Potential pitfalls are so numerous that seri- X-ray sedimentation measures the Stokes' diameters of
ous misinterpretation is the rule rather than the exception, particles settling in water by gravity. Settling causes density
particularly in the interpretation of electron micrographs. differences in the suspension that are detected by absorption
Problems arise in several ways. Two definitions of "parti- of X-rays. Brownian motion interferes with settling and dis-
cle," be it clump, agglomerate, aggregate, or crystallite, are torts the small end of the size distribution curve of the parti-
vitally important: (1) the particle of the analysis and (2) the cle population. The X-ray disk centrifuge substitutes centrifu-
particle that matters within the intended application. The gal force for gravity, thus avoiding misrepresentation of small
analytical particle is almost never the same as the particle in a particle fractions.
paint film that interacts with light:
9 Dispersion is a true grinding operation that reduces particle Commodity Composition
size. In spite of this, grinding must be an integral part of the The TiO~ in the pigment is its optically active ingredient.
analytical procedure. Otherwise, the softest and largest Other components adapt it to its end use. The commercial
clumps become valid members of population statistics. products have compositions that fall into one of three catego-
9 In sample preparation, dispersive work expended upon ries: (1) uncoated pigments, (2) coated pigments, and (3)
minute samples can add up to enormous energy concentra- slurries.
tions that can break crystallites that cannot be broken en Uncoated pigments contain 98% or more titanium dioxide;
masse. some contain up to about 1% aluminum oxide (anhydrous),
and other products contain less than about 0.5% aluminum
~6Becausedirt is colored by iron and thus reddish gray, a reddish or oxide with some other inorganic, anhydrous oxides. Organic
yellowish cast is perceived as "dirty." additives and their decomposition products may be present
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. ~ Optical Range
Tinting Strength
Hiding Power Paint Film Performance Range - ~
Undertone
Particle loss Dispersion
Frequency Film Fineness
by Weight
0.1 0:5 . . . . 1:0 510 . . . . 1(;.0
Diameter,
FIG. 7-TiO 2 aggregate size distribution. From Braun, J. H. and Fields, D. P., "Gloss of Paint Films, I1,"
Journal of Coatings Technology, Vol. 66, No. 828, 1994, p. 93.
in concentrations of fractional weight percents. Uncoated zirconium, boron, zinc, cerium, and tin, usually in concentra-
pigments are used in plastics and paper. In coatings, wet- tions of less than 1%.
treated pigments are preferred because they are easier to Rutile pigments are made suitable for extreme exposure by
disperse into liquids of low or moderate viscosity. encapsulating individual particles in glassy silica sheaths. Sil-
Minor constituents, either carded over from the ore or ica surface treatments on TiO2 pigments were once consid-
added in the manufacturing process, can be important in ered detrimental to gloss performance. Silica on pigment,
determining pigmentary properties because they can control however, comes in two distinct modifications, either "fluffy"
crystallite size. Sulfate pigments retain up to 0.3% niobium or "dense." Fluffy silica does indeed reduce gloss and is pre-
pentoxide and 0.3% phosphorus pentoxide from the ore. They cipitated onto pigments intended for dry hiding paints to
also contain up to 0.2% alumina, added to compensate for the increase oil absorption. Dense silica is used to encapsulate
presence of niobium. Compensation minimizes discoloration the TiO2 particle in a distinct shell to make the pigment
by the semiconductor imbalance that pentavalent and triva- durable in severe exposure.
lent cations can cause in the rutile lattice. Special high oil absorption products are made for paints
Chloride process pigments contain practically no un- formulated for dry flat hiding, that is, above the critical pig-
wanted impurities because the titanium tetrachloride inter- ment volume concentration. They contain fluffy coatings, 5 to
mediate can be purified effectively. They contain about 1% 15% hydrous silica and 2 to 6% hydrous alumina, for better
pyrogenic alumina added for better process control and for spacing and improved optical efficiency in vehicle-starved
photochemical stability improvement. formulations. The fluffy silica increases oil absorption and
Trace constituents are generally unimportant except for water demand by the pigment. Gloss is reduced.
transition metals such as iron, chromium, vanadium, etc., Slurry products for coatings applications are usually based
which degrade color by semiconductor mechanisms. on coated pigments. In addition to the coated product, they
Besides inorganic constituents, most uncoated and many contain organic dispersants and stabilizers. Predispersed pig-
coated pigments contain up to 0.5% of an organic grinding ments, sold as aqueous slurries, contain from 60 to almost
aid to improve flow in the fluid energy mill to achieve a more 80% titanium dioxide by weight. They are stabilized with low
uniform grind. The grinding aids are usually polyhydroxyl concentrations of organic chemicals.
compounds (for example, trimethylol propane, triethanola- Odorless amines are added for pH control. Together with
mine, etc.) that can undergo some pyrolytic degradation in preservatives, about 1% of organic material is present. Pig-
the mill. ment loading in slurry is limited by the concentration at
For use in coatings, i.e., to be dispersible by the conven- which the slurry becomes too thick to be pumped. Slurries of
tional paint-making equipment, TiO2 pigments are "coated." lightly treated grades are available at higher solids contents
In aqueous suspension, hydrous aluminum oxides are precip- than slurries of heavily treated, dry flat grades. The slurries
itated onto the surfaces of pigment particles. Interior grades can be shear thickening. Effects can be severe.
contain a coating of up to 5% hydrous alumina for ease of The pigment industry describes its products and the hy-
dispersion. Durable grades have another coating that usually drous oxides they contain in terms of their analytical equiva-
consists of about 2% silica and sometimes also oxides of lents, alumina (A1203), silica (SiO2), and water (H20) or tools-
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ture content. Such description does not imply structure or nents are either impurities present in the ore and not re-
chemical characteristis of the components but reflects analyt- moved in the purification process or additives designed to
ical results. The actual components of pigment coatings are control crystal structure and growth and to regulate agglom-
hydrous oxides: boehmite (7-AIOOH), diaspor (a-AIOOH), eration. This fortuitous surface is not necessarily suitable for
hydrargillite ['y-AI(OH)3], etc. a given end-use application; thus, crystallite surfaces are
Product descriptions in terms of analytical results are pre- modified by treatments.
ferred because they can be verified. By contrast, the precise The surfaces of TiO 2 pigments are wetted readily. They are
structural analysis of colloidal coatings on pigment surfaces usually hydrophilic and disperse spontaneously into water.
is always difficult and often beyond the capability of even the The energy of wetting is high, aiding dispersion into organic
most sophisticated analytical techniques. Results are usually liquids. The ease of wetting of TiO 2 pigments contrasts with
ambiguous. But because coatings are precipitated from aque- wetting problems of organic color pigments, most of which
ous solution, the alumina coatings on coated TiO2 pigments are hydrophobic and have a low negative free energy of
contain structural water, i.e., they are hydrous. wetting. Water does not wet them without the help of surfac-
Wet treatments have profound effects on dispersibility and tants. Suitable organic solvents may wet organic pigments
durability. In dry hiding paints, they affect hiding through oil but often only sluggishly.
absorption and spacing. Brightness is not usually affected. Since unmodified pigments tend to cake and flow poorly,
Process details of wet treatment are guarded secrets of the they are treated with up to 0.5% of a grinding aid, usually
TiO2 industry. The patent literature provides little guidance organic polyhydroxyl compounds, to improve dry flow. These
because the most and least effective processes can be de- organic materials remain on the pigment surface. Silicone
scribed by equally factual performance claims. treatment can be used to make dry pigment flow like sand,
but the pigment becomes hydrophobic and unsuitable for
Elemental Analysis--Chemical analysis of pigments pre- most coatings applications.
sents no particular problems. The quality of the data meets
the requirements of pigment and coatings technologies. For Surface Analyses--Surface analysis of pigments involves
routine analyses, conventional, wet analytical methods, for three interrelated subjects: surface area, surface composi-
example, ASTM Test Methods for Chemical Analysis of White tion, and surface chemistry. For data interpretation, sample
Titanium Pigments (D 1394-76), have been replaced by in- density data are also required. Methods and results tend to be
strumental techniques for cost savings, not data quality. Alu- more interesting to the scientist than the practitioner.
m i n u m and silicon contents are usually determined by X-ray Instrumental surface area determinations are now routine.
fluorescence techniques. Water content is analyzed as weight Nitrogen adsorption is used widely. Reliability of results is
loss of volatiles by thermogravimetric analysis (TGA). satisfactory. Data are affected by the composite character of
pigments and its response to sample preparation.
Pigment Surface The modern methods of surface analysis, Microprobe,
Because pigment particles are so very small, their surfaces ESCA, etc., have been used to study pigment surfaces and
are enormously large. One pound of untreated TiOz has a have yielded interesting results and valuable insights. Costs
surface of about one acre. Thus, surface characteristics have and technical complexity preclude their widespread and rou-
a profound impact on a pigment's interactions with all the tine uses.
other components of paints. Furthermore, pigment surfaces Surface adsorption by pigments has been explored exten-
are complex composites reflecting the nature of the commod- sively by surface calorimetry and in terms of adsorption iso-
ity. therms, etc. Ambiguities introduced by the composite
The rutile component of most TiO2 pigments contributes 0 character of the surfaces have their impacts.
to 10 m2/g of surface area. Inorganic treatments with hydrous The density of a pigment can be measured precisely and
aluminas and silicas can more than double the total surface quickly by a helium densitometer. However, for fine powders
area of a pigment. Most pigment surfaces are composites of of known composition, calculated densities are often more
Ti--O, Ti--OH, A1--O, and A1--OH groups. Many pigment reliable than measured values. Density calculation requires
surfaces include Si--O and Si--OH units. Silica-encapsu- knowledge of the pigment composition and the density data
lated grades have few if any Ti--O and T i - - O H surfaces. for the pure component oxides. It is decisively important to
The surface areas themselves are not homogeneous. Usu- include in the calculation the total water content: absorbed
ally they are composites to which TiO2 contributes 0 to 10 moisture plus the structural water of the hydrous oxides.
m2/g TiO2 and 5 to 10 m2/g pigment, hydrous aluminas with
about 200 m2/g A12Oa.xH20 and 2 to 8 m2/g pigment, silicic Pigment Packing
acid with about 150 m2/g SiO2.xH20 and 0 to 10 m2/g pigment, The packing density of pigment particles affects paint film
silica glass 5 to 10 m2/g SiO2 and 5 to 10 m2/g pigment, etc. performance. This density is an inverse measure of intersti-
The chemical and physical characteristics of the surface are tial volume, a reflection of the way pigment particles aggre-
specific to the component. Granted, the components share gate and agglomerate into either stringy assemblies that hay-
important similarities. They are all hydrophilic oxides with stack loosely or compact clumps that pack densely.
high-energy surfaces. Effects of packing density on performance are profound.
Even the surfaces of titanium dioxide crystallites them- Packing characteristics determine the critical pigment vol-
selves are not just composed of titanium and oxygen ions. In ume concentration of a pigment. Through the critical pig-
the sulfate process, while the ruffle crystallites grow, insolu- ment volume concentration, pigment packing affects virtu-
ble components accumulate on their surfaces. Those compo- ally all characteristics of paint films [3]. Fluffy pigments have
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a low critical pigment volume concentration; particulates Contaminants

that pack densely have high critical pigment volume concen- Extraneous metal ions within rutile crystallites can de-
trations. In effect, the critical pigment volume concentration grade the brightness of pigment. Nickel and chromium can
itself is a measure of the interstitial volume of wetted pigment be detrimental in concentrations as low as a few parts per
particles. Adsorption layers are also involved, but in most million. Involved are semiconductor mechanisms. Substitu-
instances their contribution is minor. tion of extraneous ions for Ti4 in the TiO2 lattices discolors
Practitioners of coatings technology have long been aware the crystals usually towards gray or yellow,
of the importance of packing. They used oil absorption of a Impurities and co-products introduced by the treatment
pigment as one of its most important descriptors. Oil absorp- chemicals are far less detrimental to brightness. Co-products
tion is still used today because it reveals so much about the can, however, affect specialized performance requirements.
pigment even though linseed oil has lost its importance as a Certain ions can, for example, inhibit cure of acid or base-
binder. catalyzed coatings or cause film defects in electrocoatings.
Oil absorption is primarily a measure of wet packing com- Purity and brightness of TiO2 crystallites are process re-
plicated by the involvement of adsorption layers, dispersion lated. TiO2 crystallites made by the chloride process are purer
work, and flocculation. The measure predates the insights of and brighter than sulfate products.
Asbeck/Van Loo into structure and performance of paint The co-product content of a pigment commodity is usually
films. 17 Thus, the connection between oil absorption--the not a matter of poor operating practice but set by complex
practical measure--and the scientific concept--critical pig- compromises between conflicting performance require-
ment volume concentrations--is unnecessarily convoluted. ments.
Oil absorption of different pigments cannot be compared Trace Analyses--Trace impurities in pigments are analyzed
because the measure is based on weights, not volumes. Criti- by conventional emission spectroscopic and X-ray fluores-
cal pigment volume concentration, by contrast, is based on cence methods. Results are considered reliable though not
volumes and lends itself readily to comparisons of particu- particularly precise.
lates that differ in densities.
At its best, when oil absorptions of similar pigments of Color
identical densities are measured by an experienced individual Titanium dioxide is a virtually colorless dielectric with
who uses a standardized procedure to his personal end point, some semiconductor characteristics due to small amounts of
oil absorption values become a reasonably precise measure of contaminants. Ruffle absorbs in the violet end of the visible
the packing of pigment particles in oil. spectrum. Figure 8 shows schematically the reflectances of
For wetted particles, pigment packing is not affected much
by the nature of the liquid, water, oil, or solvent provided the Titanium Dioxide / Carbon Black
particles are not flocculated. In practice, surfactants must be
added or be present as a natural component of the system as
it is in raw linseed oil. "Liquid absorption" values agree pretty lOO
well with each other if they are based on relative volumes of a White
90-
pigment in a variety of liquids.
Incidentally, oil absorption values correlate inversely with
the bulk density of a given pigment. The fluffier the pigment
packs in air, the more loosely it packs in liquids.
70
Packing Measures--In spite of its many shortcomings, oil
absorption is the only measure of packing that is widely 60
accepted. The test is a titration of raw linseed oil into dry
50
pigment powder to an end point at which the mass cakes.
Two procedures are in common use: ASTM Test Method for
40
Oil Absorption of Pigments by Spatula Rub-out (D 281-84),
and ASTM Test Method for Oil Absortion of Pigments by 30
Gardner-Coleman Method (D 1483-84).
Precision of oil absorption data is poor unless all measure- Dark Gray
20
ments in the data set are made by one experienced individual.
For tests by different laboratories, the spatula method has a 10-
coefficient of variation of 12%, with 5.3% for the Gardner- Black
Coleman method. Data obtained by two analysts tend to I I
0.4 .5 .6 .7
differ because the end point of the titration is more difficult to
define than to reproduce. Wavelength, gm
FIG. 8-Reflectances of white, gray,and black
17Asbeckand Van Loo recognized that the characteristics of paint paints. From Braun, J. H., Introduction to Pig-
films involve volume rather than weight considerations, no small ments, monograph in the Federation Series on
matter when densities of paint film components can range from 0.9 Coatings Technology, Federation of Societies
to 6 g/mE for Coatings Technology (United States), 1993.
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100
Relative I ....
Hiding .0~ ~
Power,%
8r
60
Non Porous Porous
Films Films
4C
2C
Pigment
Volume
Concentration, %
, I , I , I >
10 20 30 40 50
CPVC
FIG. 9-Hiding power of paint films. From Braun, J. H., Introduction to Pigments, monograph in the
Federation Series on Coatings Technology, Federation of Societies for Coatings Technology (United States),
1993.
white, gray, and black paints pigmented with only TiOz, with blue light more efficiently. As a result, pigment of a smaller
TiO z and carbon black, and with only carbon black, respec- average particle size will shade bluer both tinted coatings and
tively. Absorption of far violet light imparts a slight yellow white coatings at incomplete hiding. Pigment of larger aver-
hue to large crystals. The anatase absorption edge is at a age particle size will shade redder in the same systems. Most
shorter wavelength than rutile, shifted almost completely TiO2 grades for coatings applications are neutral in this parti-
into UV wave lengths. Thus, anatase crystals are slightly less cle-size-related undertone. Products intended for very low
yellow. All this does not matter m u c h in coatings. For high- end-use concentrations are often bluish. Red undertone pig-
purity pigment, dry powder color does not correlate with end ments are not in demand.
use color because most polymers contribute far more yel- Color Measurement--Color measurements of pigment are
lowness than the pigment. performed on dry pressed pellets. Modern spectrophotome-
Pigment brightness matters less in most coatings applica- ters provide data with more than sufficient precision for most
tions than one might presume. Most coatings, even white purposes of pigment quality control. Most of these instru-
ones, are toned, that is, their brightness is reduced intention- ments can report their results in any of several color coordi-
ally by addition of carbon black or color pigments. Purity, nates. The L*a*b .21 system seems particularly well suited to
thus brightness, is important only for white coatings that are describe variations on the theme of white.
usually not toned: coatings for light fixtures, m a n y coil coat-
ings, most inks, and ink-similar paints. Hazards
Chloride process pigments are intrinsically brighter and TiO 2 pigment is a benign chemical. Its hazards, and the
whiter than their sulfate counterparts. Typically, chloride relative lack thereof, are detailed in Material Safety Data
process pigments average 99.5% L .18 lightness, 19 and 98.5% Sheets that must a c c o m p a n y any U.S. shipment. TiO z pre-
sulfate pigments, z~ The difference between chloride and sul- sents no p r o n o u n c e d health hazards; it is neither corrosive
fate pigments, an L* lightness difference of 1%, is about ten nor acutely toxic and does not appear to be a significant
times larger than the least visible difference. carcinogen nor embryo toxin in the workplace. As a dry pow-
TiOz particle size has a significant effect on the color of der, TiO 2 can become a nuisance dust that may require con-
tinted coatings and thin white films. Smaller particles scatter trol.
TiOz pigment cannot burn nor explode, neither as a dry
taCIELAB (Commision International de l'Eclairage, 1978) metric powder nor as aqueous slurry. Neither the dry pigment nor
of lightness. the slurry is corrosive nor reactive. The hazards of pigment
~gBrightness/lightness of a dry pressed pigment pellet.
2~ very first approximation, a TiO2 pigment with an L* lightness
of 98.5% contains a three times higher concentration of colorant 2tCIELAB (Commision International de l'Eclairage, 1978) metric
impurities than a pigment of 99.5% brightness: 1.5%/0.5% = 3. of color.
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2.25 o_O~.o
~ 2.00
~-~ ,-, 1.75
[a \
1.(X)
O.75 I I I I I
0 5 10 15 20 25 30 35
Pigment Volume Concentration, %
FIG. 10-Scattering coefficient of TiO2 [4]. From Bruehlman, R. J., Thomas, L. W., and Gonick, E., "Effect of Particle Size and
Pigment Volume Concentration on Hiding Power of Titanium Dioxide," Official Digest, Vol. 33, No. 433, 1961, p. 252.
dispersions in organic liquids reflect the characteristics of the dry hiding, that is, light scattering at air/pigment interfaces,
liquids. causes hiding to increase again.
Crowding of pigment particles diminishes light scattering
substantially [4] (Fig. 10). Effects become apparent at pig-
Pigment Performance ment volume concentrations above about 8 vol%. More than
The TiO2 industry sells light scattering for the price of TiO 2 half of a pigment's scattering effectiveness can be lost be-
because there is no better and cheaper way to achieve effec- tween 8 vol% and the critical pigment volume concentration.
tive hiding by thin films that are white or light in color. Thus, A simple optical model explains the effects [5]. Improvements
optical effectiveness is the primary performance characteris- in pigment effectiveness achieved through control of crowd-
tic of the pigment. However, TiO 2 pigment is well optimized ing are likely to be fairly insignificant [6].
and functions near its theoretical potential. Between prod- The optics within paint films are quantified by the Kubelka-
ucts developed for similar end use, light scattering differ- Munk theory that combines for thin films the effects of light
ences are too small to matter or be measured. Thus, secon- scattering (usually by white pigment) and light absorption
dary performance characteristics can be commercially (usually by color pigment). The model serves exceedingly well
decisive. in spite of some theoretical limitations. Kubelka-Munk equa-
tions provide a basis or an explanation for most performance
Hiding and Opacity measurements: hiding, opacity, and tinting strength.
Pigment sells by weight but scatters light, that is, functions,
by its volume. The particle size of TiO2 for white pigment Measurements of Light Scattering--Until recently, pigments
applications was optimized for the scattering of visible light, and paint films were evaluated by visual comparisons, for
first experimentally, later confirmed by theory. Commercial example, ASTM Test Method for Relative Tinting Strength of
grades perform near theoretical potential. A rutile particle of White Pigments by Visual Observation (D 332-87). The eye
about 0.2 /xm diameter is optimal for green light, the wave was more sensitive than available instruments, and the math-
lengths of greatest sensitivity of the h u m a n eye. ematics of Kubelka-Munk was too complex for routine calcu-
Figure 1 illustrates the relationship between scattering lations.
power and particle diameter. The Mie theory can specify the Two developments make quantitative evaluation of pig-
optimal diameter for the scattering of an electromagnetic ments now appropriate: (1) optical instruments have become
wave by a dielectric particle with great precision, but the more sensitive and more reliable than the eye, and (2) the
result is limited to single spheres. This complex and abstract least of computers can calculate results on the spot.
theory must be translated (1) from a sphere into a real parti- Light scattering and light absorption of paint films can be
cle of elongated, angular shape, (2) from a single, isolated quantified independently using light reflectance or transmis-
particle to assemblies of massive numbers, and (3) from sion measurements of thin n films drawn over black and white
mono-size particles to particle-size distributions. The task is substrates. In addition, film thickness or film weight and
formidable, yet significant progress has already been made. composition must be measured. ASTM Test Method for Hid-
Figure 9 illustrates the effects of pigment concentration on ing Power of Paints by Reflectometer (D 2805-88), describes
hiding a paint film. At first, hiding increases in direct propor- such a test.
tion to concentration. Then, the crowding of pigment parti-
cles causes the increase to diminish, to reach a maximum,
22Thin enough to show obvious contrast between regions drawn
and to decrease toward the critical pigment volume concen- over black and white backgrounds but thick enough to look uniform
tration. Beyond the critical pigment volume concentration, rather than mottled.
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Relatively cheap and very reliable spectrophotometers can 4. The distribution of particles has to be stabilized against
measure reflectances in any specific and narrow wave band. reversible flocculation.
By measurements, wave band by wave band across the spec- Nonaqueous systems flocculate by Brownian motion
trum of visible light, applicability of hiding power measure- and are stabilized against flocculation by surfactants
ments is extended from black and white to color. Paints of that provide steric hindrance. Aqueous dispersions floc-
different hues can be compared and results expressed sepa- culate by: (1) electrostatic attraction and by (2)
rately for performances of white and color pigments. Com- Brownian collisions. They are charge stabilized by ionic
puter programs are available for data evaluation. dispersants.
Tinting strength tests, ASTM Test Method of Relative Tint- Rheology matters decisively. Grinding in a shear-thicken-
ing Strength of White Pigments by Reflectance Measurement ing rheology regime, dilatent grinding, is highly effective. By
(D 2745-89), measure the relative light scattering of a white contrast, shear-thinning rheology of the grind charge absorbs
pigment by overwhelming the slight intrinsic absorptions of energy into reversible bonding, wasting much of it as heat.
binder and pigment with a massive absorption by a standard- High viscosity helps the energy transfer from mill to particu-
ized addition of colorant. Measured are thick films of infinite late. Thus, other parameters equal, grinding "viscous" is more
hiding. 23 The same test serves for the evaluation of color effective than grinding "thin," and grinding "well cooled" is
pigment. Here, the slight intrinsic scattering of the color more effective than grinding "hot."
pigment is drowned by the massive scattering from standard- Flocculation degrades optical performance. White pig-
ized addition of a white pigment. ments can lose only a moderate fraction of hiding, rarely as
Absorption of light within the paint film increases the hid- much as 30%. By contrast, color pigments can lose most of
ing power of the film. The effect is quite pronounced. It can be their color.
caused by pigment or binder. When caused by a TiO2 pigment Excessive or inappropriate grinding does not degrade TiO2.
of low brightness, this low-purity product can get undeserved Nor does optical performance improve with grinding because
credit for a hiding power advantage over purer products.
most of the pigment is dispersed very early in the grind cycle.
Also, off-color extenders and colored polymers can boost hid-
A few parts per million of undispersed grit, however, can
ing power incidentally or deliberately. This hiding improve-
degrade film fineness from "excellent" to "inadequate."
ment comes at the expense of brightness.
Measurement of Dispersibility--This author knows of no
Dispersibility reliable and useful measurement of dispersibility. Granted, it
To make a paint, dry powder has to be distributed in liquid is possible to use standardized procedures to establish a rank-
composed of binder and solvent. The process is called disper- ing of pigment samples against specific performance require-
sion or paint grinding. ments. Such a ranking cannot be quantified and does not
The ease with which a powder can be dispersed in a liquid translate from one application to the other.
depends primarily on its particle size. As pigments go, TiO2 at In one such scheme, a paint is made by a minutely stan-
0.2 /~m size is large and easy to disperse, almost as easy as dardized, low-shear dispersion procedure. The paint is then
extenders, much easier than most color pigments. For all but tested for grit by one of several conventional fineness gages.
glossy coatings, TiO 2 can be stirred into liquids with high- The "residual grit" aspect of dispersion is usually evaluated
speed agitators. High-gloss finishes require more powerful by fineness-of-dispersion gages, for example, ASTM Fineness
equipment: media, roll, or ball mills. of Dispersion of Pigment-Vehicle Systems (Method D 1270).
Dispersing involves four distinct stages during which most The gages are shallow, tapered channels precision machined
of the energy of grinding converts to heat: into steel blocks. A paint sample is scraped into the channel.
1. Liquid replaces air-solid interfaces with liquid-solid inter- The surface of the paint wedge is then examined to see at
faces. what depth the diameters of largest agglomerates exceed the
The ease of wetting depends on (a) energy characteris- depth of the channel. This point is visible as a transition from
tics of the surface of the solid and (b) the chemical smooth to streaked paint surface.
affinity between solid and liquid. TiO2's high-energy sur-
face wets well. By contrast, the low-energy surfaces of
Pigment Effects on Paint Film Durability
organic color pigments wet only with difficulty.
2. Bonds between particles are broken. Durability is the continuance of decorative and protective
TiO2 crystals are not broken in ordinary mills. Bonds performance of paint films and their components under the
between crystals range in strength from strong within influence of weathering. Lack of weathering resistance mani-
aggregates to weak within agglomerates. Weak aggre- fests itself as: (1) oxidation of polymer ultimately to carbon
gates can be broken in the high-energy mills of pigment dioxide and water; (2) discoloration and fading of color pig-
and plastics technologies, not, though, by equipment ments; and (3) chalking of the TiO2 with concomitant erosion
common in coating technology. Agglomerates break in and gloss loss. Instability of substrates introduces additional
high-speed dispersers. degradation effects.
3. Particles are distributed throughout the liquid. For paint films with TiO2, concerns involve the weathering
The more viscous the liquid, the more power is required resistance of the films themselves. Exposure to sunlight,
to mix and distribute and the more effective the grind. moisture, and oxygen changes the appearance of paint films.
Some films chalk and eventually erode to their substrates;
2SThick enough so that a further increase in thickness does not others discolor and fade well before chalking becomes a
affect reflectance. problem.
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Degradation of coatings occurs because paint films are of a super-durable pigment. Their silica sheaths are barely
slowly oxidized by air. Sunlight triggers the degradation reac- visible on the transmission electron micrograph. The silica
tions. In the dark, paint films can last for centuries, even sheaths, themselves, after the TiO 2 was dissolved out, are
millennia. In light, durability depends on binders, pigments, shown in the transmission electron micrographs of Fig. 12.
and the conditions of exposure. High humidity, particularly Even the holes are visible through which the rutile cores were
condensation, aggravates degradation. dissolved.
Only the ultraviolet (UV) portion of sunlight causes degra- Intermediate levels of weathering resistance are attained
dation directly because it has an energy content sufficient to by partial encapsulation of the rutile in silica and/or alumina
break chemical bonds. The degradation of UV-A and UV-B with or without zirconia and by bulky coatings of hydrous
light 24 is irreversible for polymers and for all organic and aluminum and silicon oxides on rutile.
some inorganic pigments. A few inorganic pigments are ther- Alternate approaches to chalking control are less effective
modynamically stable. Titanium dioxide is stable, but its or cause performance problems in coating applications. They
catalytic characteristics are activated by UV above 3.08 eV. In involve attempts to: (1) recombine holes and electrons at the
effect, the band gap of TiO225 is within the energy levels TiO2 surface by semiconductor mechanisms whereby the
present in sunlight. All white pigments share some of this products are slightly yellow; and (2) prevent the hydroxyl-
attribute. Extenders are stable and inert. Their band gaps are ation of the TiO2 surface, i.e., interfere with one step of the
too large to be activated by the UV components of sunlight. chalking sequence, causing products to be gritty.
Titanium dioxide affects the durability of paint films in two
Durability Testing--Durability of coatings can neither be
distinct and opposing ways: (1) As a strong UV absorber, TiO 2
measured nor be predicted quantitatively. The best state-of-
protects the paint film, and (2) as an UV-activated oxidation
the-art technology can do is rank coatings. Cost per sample
catalyst, TiO2 degrades binders [7].
are exorbitant, precision is poor, and the time lag is prohibi-
Three characteristics of TiO 2 are functionally disparate but
tive for many purposes. Years of outdoor or months of accel-
are manifestations of a single fundamental characteristic of
erated exposure are required for the pigment and binder
dielectric matter: (1) its unique refractive index, which makes
combinations for which durability is important, that is, for
TiO2 the best white pigment; (2) its extreme UV absorptivity;
durable pigment in durable binder.
and (3) UV catalytic activity of the TiO2 surface.
Testing is done by simulation of a "real" world. Paints are
Light of more than 3.08 eV, water, and oxygen are all
made from experimental pigment and usually several pig-
essential for the TiO2-catalyzed degradation of binder. Their
ment standards. Panels are painted. They are exposed where
reactions combine into a cycle that generates two free radi-
weathering is severe but is not necessarily representative of
cals from each active UV photon [8].
the intended application. Certain appearance characteristics
TiO 2
H20 + 02 + hv(uv) ) .OH + .HO2 are measured regularly and often: chalk, color, gloss, etc.
Finally, data are reduced, correlated, and compared. Repro-
The hydroxyl and peroxyl free radicals are highly reactive
agents that oxidize and thus degrade essentially any organic
polymer
2-HO + 2.HO 2 + CH4 ~ CO2 + 4 H20
The chain of chalking events is cyclic with respect to TiO 2
and can be disrupted by exclusion of either UV, water, or
oxygen.
Durability Control--The TiO 2 industry inhibits the catalytic
activity of the TiO2 surface and improves the weathering
resistance of its products by encapsulation in amorphous
silica. The shell is a true silica glass precipitated from aque-
ous solution by technology invented by DuPont in the 1960s
[9]. Encapsulation of TiO2 made it practical to paint cars in
white and bright colors. Meanwhile, binders were improved
to that less effective deactivation of the TiO2's catalytic activ-
ity suffices for satisfactory performance of automotive fin-
ishes in temperate climates.
The SiO2 glass prevents contact between the catalytic sur-
face of rutile and the organic vehicle and provides a surface
for recombination of free radicals. Figure 11 shows particles
24UV-Ais the UV wave length region near to visible light, UV-B is

the medium UVregion, and UV-Cis the far (shortest wave length) UV
light. Sunlight contains little UV-B and essentially no UV-C.
2SThe band gap is the "forbidden" energy gap between the valence
band and the conduction band of a semiconductor. In the language
of physics: "UV light induces semiconductor characteristics in TiO2";
in the language of chemistry: "UV light reduces colorless TiO2 to
black Ti203." FIG. 11-Encapsulated Ti02 pigment.
www.iran-mavad.com

Since the volume concentration of white pigments in paint

films must be much higher for hiding than the concentration
of color pigments and black, the burden of improvement falls
on TiO 2 producers. They have increased gloss performance of
grades that serve the automotive and industrial markets.
Gloss matters are complicated because a fundamental dif-
ference exists between the measured gloss that guides coat-
ings formulation and the perceived gloss that sells cars [1].
These two operational definitions of gloss, one based on in-
strumental measurement of an intensity of image and the
other on the h u m a n perception of a distinctness of image,
differ profoundly in substance. However, they correlate well
enough to guide quality control and pigment development by
incremental improvement. The fundamental difference be-
tween measured and perceived gloss can, however, misdirect
the strategy of product development, for example, a focus on
increasing the refractive index.
A mechanism by which pigment causes the surface
roughness that degrades gloss explains [1] that pigments di-
minish gloss by an interplay between the surface tension of
the wet film with the compressive strength of a particulate
bed and a gel structure that develops within the film while it
cures. While the film is fluid, surface tension maintains the
surface at a molecular smoothness that results in "perfect"
intensity-of-image gloss. As the film dries, the structure
within the wet film strengthens until it overcomes the surface
tension that maintains gloss. Shrinkage of the partially cured
film continues, but now shrinkage becomes uneven on a mi-
croscopic scale because only the binder/solvent combination,
not the pigment, shrinks. Thus, micro-roughness develops
FIG. 12-Silica shells from encapsulated pigment. and diminished gloss.
Gloss Measurement--Gloss measurement has long been
ducibility is barely sufficient to tell an interior grade pigment routine: ASTM Test Method for Specular Gloss (D 523).
from a durable grade without testing replicates. Experimen- Many conventional gloss meters are on the market. Most
tal durability differences within grades are not generally de- perform well for coatings pigmented with white and color
tectable [10]. pigments. 27 They come with measuring heads for three spec-
Results from one binder system cannot be extrapolated ular angles, generally 20, 60, and 85 ~. High-gloss surfaces are
quantitatively to binders involving different polymer chemis- best measured at low (20 ~) specular angle, medium glosses at
try, nor can a single acceleration factor predict outdoor per- medium angle, and matte surfaces at grazing angle (85~ The
formance from accelerated exposures [11]. selection of the proper specular angle improves instrumental
Pigment manufacturers supplement their exposure testing precision.
by science-based analyses of the catalytic activity of the pig- The conventional gloss meters measure the intensity of
ment. light reflected by a surface, the intensity-of-image component
of gloss. The human eye, by contrast, perceives the distinct-
Pigment Effects on Gloss ness-of-image component of gloss. Thus, haze and so-called
Powders do not have a gloss; only surfaces can be glossy. distinctness-of-image 28 data are used to supplement the con-
Within surfaces, particulates affect gloss, for example, pig- ventional gloss measurements.
ments in paint films. They are detrimental, particularly to the
dimension of gloss perceived by the h u m a n eye. Compatibility
Naturally glossy surfaces occur on liquids and amorphous Usually, TiO 2 is used in combination with other pigments.
solids. 26 Particulates in paint film, pigments, extenders, and Interactions between pigments can occur and are detrimental
some additives reduce gloss because they roughen the film to performance. Often, hiding is decreased, color strength is
surface. The more particulate is in the film, the lower its lost, and chroma is reduced; occasionally, the hue shifts
gloss. Clear paint films are glossy if they are thick enough. slightly.
Thin films can telegraph the roughness of the substrate to the Most interaction problems involve surface chemistry. The
surface of the paint film, reducing its gloss. immediate cause of the problem is flocculation. Either the
26Single crystals are an exception, but their surfaces are small. 27For coatings that contain flake pigments, the interpretation of
Glass is an amorphous solid. Polished surfaces are not "natural." angle-dependent reflectance measurements is complicated.
Incidentally, only liquids, amorphous solids, and single crystals can 28The distinctness-of-image instrument is really an intensity-of-
be transparent. image meter sensitized towards distinctness of image.
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white or one o[ the color pigments has flocculated. Almost for satisfactory performance including high gloss at ex-
inevitably, the color pigment is at fault. ceptionally severe conditions, for example, at the hori-
Most color pigments enter the market as toners, lakes, or zontal position in the humid subtropics.
dispersions, that is, complex composites that can contain Durability must be manufactured into the pigment sur-
more surfactants and modifiers than colorant. These addi- face.
tives are chemically reactive and can interact detrimentally 9 Gloss: Conventional--Flashy
with the surfactants or additives of the paint formula. Dry
Conventional pigments satisfy the gloss requirements of
TiO 2 pigments, 29 by contrast, contain no surfactants and are most architectural and trade-sales applications and of
inert and chemically less complex with far fewer possibilities many industrial coatings. High-gloss pigments are aimed
of adverse interactions. at automotive and some flashy industrial finishes.
Chemical interactions between pigments are problems of
the past caused by reactive pigments. White lead, for exam- High-gloss application call for pigments of small agglom-
ple, was incompatible with Ti02 because UV exposure could erate size and low oil absorption.
cause gross, though temporary, discoloration. Few modern 9 Dispersibility: Conventional--Low Shear
pigments are susceptible to these problems. Conventional pigments are designed to be dispersed by
Problems between Ti02 pigment and resins or additives do, equipment developing moderate to high shear3~ media
however, occur occasionally because many paint films con- mills, ball mills, roller mills, and high-speed dissolvers at
tain much higher concentrations of TiO 2 than of additives or low rates of throughput. Special pigments are available
of color pigments. Components of Ti02 pigment can thus for low-shear, high-rate dispersion by high-speed dis-
have significant leverage even if present in relatively small solvers and for stir-in with screening.
concentrations on the pigment. Problems are usually quite Dispersibility is promoted by surface treatments at some
specific to the paint formula. Several such problems have detriment to gloss.
been recognized and are resolved through specialized Ti02 Unlike many color pigments, TiO 2 pigments are dispersi-
grades made, for example, for electrocoating primers and for ble enough not to require predispersion.
acid-catalyzed paints. 9 Undertone: Neutral--Blue
In coatings applications, the undertone of the pigment,
Product Types blue, neutral, or red, is rarely an issue. Thus, most coat-
ing grades have a neutral undertone. Blue undertone pig-
ASTM D 476-84 distinguishes four types of TiO2 pigments ments are preferred in applications at very low pigment
(Table 2): one anatase type and three ruffles: interior, exte- volume concentration. Red undertone pigments do not
rior, and pigment for paints formulated above the critical appear to be in demand.
pigment volume concentration. The standard was formulated Undertone is affected by pigment volume concentration
in 1939 with two classes of pigments. In the years since, the and controlled by the size of the primary TiO 2 particle,
design of pigments has progressed to where the coatings small for blue, intermediate for neutral, and large for red.
industry can now select the most suitable pigment grade for a
specific application from far more than two or four TiO2 There are also specific coatings applications addressed by
types, Granted, a single TiO 2 grade could serve diverse needs special product designs.
but would do so only moderately well. Optimal performance 9 Grades intended for coatings below the critical pigment vol-
in any application demands specialized pigment grades that ume concentration.
satisfy specific requirements of optics, surface chemistry, and Most TiO2 pigments, conventional interior and exterior
dispersion technology. Some of these requirements can be grades, conventional and high-gloss products, conven-
met only through compromise. tional and low-shear dispersible pigments, the neutral
The diversity of products can be described in terms of four and blue undertone pigments, are all suitable for applica-
specific performance dimensions: durability, gloss, dis- tions below the critical pigment volume concentration.
persibility, and undertone. Then there are products aimed at 9 Grades intended for applications above the critical pigment
specific applications: enamel paints, dry hiding paints, pig- volume concentration.
ment slurries, acid-catalyzed coatings, electrocoated primers, Heavily treated, low-gloss products perform better in
etc. Finally, pigment grades are designed for the specific dry-hiding paints than grades made for high and moder-
requirements of whole industries: coatings, plastics, paper, ate gloss. In effect, the pigment contains its own, excep-
and ink. tionally effective extender.
These are the products designed to specific performance 9 Slurries intended for waterborne paints.
dimensions in coatings:
Aqueous slurries are suited only for waterborne applica-
9 Durability: Interior--Exterior--Severe Exposure tions. The costs of dispersion operations are borne by
Interior grades are unfit for exterior applications except pigment manufacturers. For medium- and large-scale op-
when used underneath top coatings that absorb all light erations, savings from the elimination of a process step
of wavelengths below 400 nm. All-purpose pigments are outweigh the costs of slurry-handling facilities.
exterior durable in appropriately durable vehicles at 9 Other specialized grades are made as opportunities are recog-
moderate severity of exposure and for moderate appear- nized and solutions developed.
ance requirements. Severe exposure grades are intended
3~ shear within coatings technology. The plastics industry
29Slurry grades do contain some organic surfactant, uses several more powerful mills.
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TABLE 2--Excerpt from ASTM Standard D 476-84: Specification for titanium dioxide pigments.
Type I Type II Type III Type IV
Anatase Ruffle Ruffle
Free chalking Medium chalk resistant Highly chalk resistant
Typical White exterior house Low-medium PVC Medium-high PVC Exterior coatings requiring
Application paints; interior use enamels and enamels; alkyd excellentdurability and
lacquers and emulsion gloss retention
flat wall paints
TiO2, min, % 94 92 80 80
Finally, industries other than coatings are targeted by spe- 5. Identical performance objectives can be achieved by differ-
cific products: ent product designs.
9 Plastics Nevertheless, I have attempted classification of state-of-
Plastics are pigmented by products most of which are the-art products in terms of six performance parameters and
optimized for performance at PVCs of less than 1 vol%. intended applications: concentration, gloss level, exposure,
Durability and dry-flow characteristics can be important optics, slurry, and dispersion. Permutations of these require-
to the plastics industry. High-gloss and low-shear dis- ments make for 72 potential product niches for coatings ap-
persibility are usually not required. plications alone. Fourteen of the niches are occupied by com-
9 Paper mercial products. They are shown in Table 3. All major
The wet-end stage of paper making uses aqueous slurries. manufacturers sell at least several of these products as spe-
Slurry handling and optics are important; low-shear dis- cific grades or by equivalent sub-classifications within grades.
persibility, high gloss, and durability are not important. About two thirds of the potential product niches appear to
9 Ink serve no practical purpose. For example, aqueous pigment
slurries are not suited for solvent-based paints, and high-PVC
Inks require pigments that are high in gloss. Compatibil-
paint films are not made to have flashy gloss.
ity with a wide range of solvents and vehicles is often
Obviously, the multiplicity of grades creates costs and in-
important.
centives for the development of universal grades. Lately some
9 Miscellaneous end uses
of these attempts have been partially successful, and a few
Pigmentary applications (floor coverings, elastomers, "universal" products have appeared on the market.
roofing granules, fibers, fabrics, sealants, food additives, Conspicuously absent from this table are anatase pig-
etc.) and nonpigmentary applications where pigment is ments. They and the extended TiOz grades that used to domi-
used for its TiO2 content (ceramics, welding rods, etc.) or nate TiOz markets are no longer used in coatings.
as a low-cost, mono-disperse particulate (for example, as
catalyst support).
Also, the same products can be packaged in different ways, OTHER WHITE PIGMENTS
bag, semi-bulk, or bulk, or analyzed for special purposes, for
example, food additive purity. Each such product may enter In coatings, only void hiding competes with TiO 2. The
commerce under its own grade designation. classic white pigments--lithopone, zinc sulfide, zinc oxide,
The wrong grade of TiO 2 pigment for any specific applica- and white lead--are far less cost effective. White lead is also
tion will still be inert, white, and will hide well. But, the too toxic. Pigmentary zinc oxide is still being used in paint,
inappropriate pigment will fall short of expectations on sec- not as a white pigment but as a mildewstat.
ondary performance characteristics such as durability, gloss, Extenders--colorless g r o u n d minerals and precipitated
or rheology. This is in marked contrast to most color pig- particulates--are sometimes described as pigments 31 and are
ments where a grade inappropriate to an application is likely advocated as supplements for true white pigments. Extenders
to fail grossly. are formulated into coatings to reduce costs by replacing
Matters of pigment classification are complicated by inter- expensive polymer with cheaper mineral. Below the critical
actions among requirements: pigment volume concentration, that is, in films with excess
1. Certain requirements are mutually exclusive. For example, polymer, extenders do not scatter light because their refrac-
aqueous pigment slurries are obviously suitable only for tive indices are too low. In films with excess particulates
waterborne applications. (films above their critical pigment volume concentration),
2. Some industry requirements overlap. Paper coatings re- extenders hide indirectly by creating pores. Only in very po-
semble dry hiding paints and are served by similar prod- rous films do extenders scatter light at the particulate/air
ucts. interface.
3. Optimal performance in one dimension can come at the In colonial times, calcium carbonate (CaCO3) was used as a
expense of performance in another dimension. Flashy white pigment. The pigment was made in situ by the reaction
gloss can be attained only at the expense of pigment char- of atmospheric carbon dioxide with "whitewash," a brushed-
acteristics that promote stir-in dispersibility. on slurry of calcium hydroxide. The pigment was held to-
4. Premium performance can require additional process gether by minimal amounts of binder. Light was scattered at
steps, increasing the cost of manufacture. Pigments for
severe exposure and grades for flashy finishes are sold at a 31They do not "... impart black or white or a color to other
premium because they are more expensive to make. materials," thus do not meet Webster's definition of a pigment.
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TABLE 3--Commercial TiO2 pigment grades.

Product Intended Intended Intended Pigment Intended
Type PVCa Gloss Exposure Delivery Dispersion
1 Lowb Flashy: Indoors Dry High Sheard
2 Lowb Flashy: Indoors Slurry: Dispersed
3 Lowb Flashy: Outdoors Dry High Sheard
4 Lowb Flashy: Outdoors Slurry~ Dispersed
5 Love~ Flashy: Extremef Dry High Sheara
6 Love~ Flashy: Extremef Slurry~ Dispersed
7 Lowb Discreet a Extremer Dry Low S. h'i'i
8 Lowb Discreetg Extremef Slurry: Dispersed
9 Lowb Discreete Extremer Dry Low S. h'i'i
10 Lowb Discreete Extremef Slurry: Dispersed
11 Lowb Discreeff Extremef Dry Low S. h'i'/
12 Lowb Discreet g Extremef Slurry* Dispersed
13 Highk Discreet g Indoorsl Dry Low S. h ' '
14 Highk Discreetg Indoorst Slurry~ Dispersed
~Pigmentvolume concentration,pigments plus extenders, in the paint film.
bAlwaysbelow the critical pigment volumeconcentration.
CApplicationsfor which gloss is maximizedat direct or indirect expense.
aMedia mills and the like at moderate or low throughput, optimizedmill base.
CAqueousslurries.
fIncludinghorizontal exposure to tropical and subtropicallevels of UV radiation.
gGloss levels from flat through semiglossto high gloss but excludingextremelyhigh gloss.
hHigh shear dispersionis generallynot required for less than extreme levels of gloss.
/High-speed dispersers and the like.
iThe film qualities of low-shear dispersionare generallynot satisfactory for flashy finishes.
kAbovethe critical particulate volumeconcentration.
lCoatings above the critical pigment volumeconcentration are usually not suited for outdoors.
the CaCO3/air interface. Because the service life of the coating Another, less successful product, P i t t m e n t | generated pig-
was m i n i m a l , whitewashing ceased w h e n wages increased ment-sized air voids in p a i n t films by evaporation of droplets
with industrialization. of a n organic solvent emulsified in the paint.
If the voids are of sub-pigmentary size, small enough to
Void Pigments lose their individual optical identity, they do not scatter m u c h
Air-filled voids in a p a i n t film can either act as if they were light b u t collectively decrease the refractive index of the ma-
p i g m e n t particles or e n h a n c e the effectiveness of a true pig- trix. A composite refractive index of polymer a n d air takes the
ment. Both m e c h a n i s m s have b e e n i m p l e m e n t e d in coatings. place of the index of polymer alone. This decrease of matrix
Pigmentary a n d sub-pigmentary voids contribute to hiding
of all dry hiding paints films, that is, films starved of binder.
Somewhere above the critical p i g m e n t volume c o n c e n t r a t i o n
voids join into a n i n t e r c o n n e c t e d network of pores. The pores
become stress concentrators that degrade the m e c h a n i c a l
qualities of the paint film. The network conducts chemical
c o n t a m i n a n t s into the p a i n t film a n d to the substrate, dimin-
ishing the chemical a n d protective qualities of the film.
It is t h r o u g h the creation of pores that extenders contribute
to light scattering. This scattering comes at the expense of
film qualities. Problems can be avoided if the voids are sealed
a n d spherical.
Voids of p i g m e n t a r y size scatter light like particles, a b o u t
as effectively as p i g m e n t a r y zinc sulfide b u t not nearly as well
as TiO2 pigment. Unlike i n t e r c o n n e c t e d pores that degrade
p a i n t films, sealed spherical voids are not, per se, detrimental
to mechanical a n d chemical film qualities.
One commerical product, Rhopaque | (Fig. 13), generates
sealed, spherical air voids i n paint films from plastic beads
that have one concentric void. The beads are added to the
paint as a n aqueous dispersion of water-filled resin balloons
that lose their water as the film dries. These voids are protec-
ted by the thickness of their own plastic shells from the
crowding that diminishes the scattering effectiveness of con-
ventional white pigment. Their direct light-scattering effec- FIG. 13-Rhopaque| From Braun, J. H., Introduction to Pig-
tiveness is only 12% of scattering by the same volume of ments, monograph in the Federation Series on Coatings Tech-
rutile. I m m u n i t y to crowding increases the effective light nology, Federation of Societies for Coatings Technology
scattering of voids. (United States), 1993.
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!78 PAINT AND COATING TESTING MANUAL
[2] Braun, J. H., "TiO2's Contribution to the Durability and Degra-

dation of Paint Films: II. Prediction of Catalytic Activity," Jour-
nal of Coatings Technology, Vol. 62, No. 785, 1990, p. 37.
[3] Asbeck, W. K. and Van Loo, M., "Critical Pigment Volume Rela-
tionship," Industrial and Engineering Chemistry, Vol. 41, 1949, p.
1470.
[4] Bruehlman, R. J., Thomas, L. W., and Gonick, E., "Effect of
Particle Size and Pigment Volume Concentration on Hiding
Power of Titanium Dioxide," Official Digest, Vol. 33, No. 433,
1961, p. 252.
[5] Fitzwater, S. and Hook, J. W., "Dependent Scattering Theory: A
New Approach to Predicting Scattering in Paints," Journal of
Coatings Technology, Vol. 57, 1985, p. 39.
[6] Braun, J. H., "Crowding and Spacing of Titanium Dioxide Pig-
ments," Journal of Coatings Technology, Vol. 60, No. 758, 1988,
p. 67.
[7] K~impf, G., Papenroth, W., and Holm, R., "Degradation Pro-
cesses in TiO2-Pigmented Paint Films on Exposure to Weather-
ing," Journal of Paint Technology, Vol. 46, 1974, p. 56.
[8] V61tz, H., K~mpf, G., Fitzky, H. G., and Kl~iren, A., "Experi-
mentelle Techniken zur Erfassung des inneren Abbaus und der
Schutzwirking durch TiO2-Pigmente in Anstrichen bei Be-
witterung," Farbe+Lack, Vol. 82, 1976, p. 805.
[9] Werner, A. J., "Titanium Dioxide Pigment Coated with Silica
and Alumina," U.S. Patent 3,437,502 (1969).
[lo] Braun, J. H., "Titanium Dioxide's Contribution to the Durability
of Paint Films," Progress in Organic Coatings, Vol. 15, 1987, p.
249.
[11] Simms, J. A., "The Acceleration Shift Factor and its Use in Eval-
uating Weathering Data," Journal of Coatings Technology, Vol.
59, 1987, p. 45.
FIG. 14-Vesiculated beads. From Braun, J.H., Intro-
duction to Pigments, monograph in the Federation Series on
Coatings Technology, Federation of Societies for Coatings BIBLIOGRAPHY
Technology (United States), 1993.
Published scientific a n d technical i n f o r m a t i o n on p r o d u c t s
refractive index has a p o t e n t effect on the scattering of a n y of this highly competitive i n d u s t r y is sparse. The i n f o r m a t i o n
true p i g m e n t p r e s e n t in the p a i n t film. p r e s e n t e d here is b a s e d largely on insights developed d u r i n g a
A p r o d u c t c o m p o s e d of vesiculated a n d p i g m e n t e d p o l y m e r c a r e e r in p i g m e n t technology, s u p p l e m e n t e d b y these texts:
b e a d s m a k e s use of this effect. The product, Spindrift | (Fig.
14), is suitable only for low-sheen paints b e c a u s e the b e a d s Braun, J. H., White Pigments, monograph in the Federation Series on
act as a flatting agent. They have to be larger t h a n TiO2 Coatings Technology, Federation of Societies for Coatings Tech-
particles b e c a u s e each b e a d has to a c c o m m o d a t e several pig- nology (United States), in preparation.
m e n t particles plus voids a n d s o m e binder. Braun, J. H., Introduction to Pigments, monograph in the Federation
A third a p p r o a c h to void hiding, the use of stretched foam, Series on Coatings Technology, Federation of Societies for Coat-
is very efficient. Hiding can be achieved w i t h o u t any p i g m e n t ings Technology (United States), 1993.
with less p o l y m e r on the s u b s t r a t e t h a n by any conventional Braun, J. H., Baidins, A., and Marganski, R. E., "TiO 2 Pigment Tech-
paint. But f o a m coatings are p r e s s u r e sensitive. They are too nology--A Review," Progress in Organic Coatings, Vol. 20, No. 2,
sensitive for p a i n t a p p l i c a t i o n s b u t are suitable for opacifica- 1992, pp. 105-138.
tion of textiles, c u r t a i n fabrics in particular. Hunter, R. S. and Harold, R. W., The Measurement of Appearance,
2nd ed., John Wiley & Sons, New York, 1987.
Acknowledgments Judd, D. B. and Wyszecki, G., Color in Business, Science and Industry,
I a m i n d e b t e d to m y f o r m e r colleagues for advice, counsel, 3rd ed., John Wiley & Sons, New York, 1975.
a n d the insights I developed d u r i n g m y c a r e e r in DuPont's Patton, T. C., Pigment Handbook, Vols. I, II, III, John Wiley & Sons,
white a n d color p i g m e n t s businesses. Special thanks go to A. New York, 1973.
Baidins a n d R. E. Marganski, m y co-authors in a literature Patton, T. C., Paint Flow and Pigment Dispersion, 2nd ed., John Wiley
review of Ti02 technology, a n d to D. A. H o h z e n and R. C. and Sons, New York, 1979.
Crafl-Tulloch, w h o helped review a n d revise the manuscript. Steig, F. B., Jr., "Opaque White Pigments in Coatings," ACS Sympo-
sium Series 285, Applied Polymer Science, 2nd ed., R. W. Tess and
REFERENCES G. W. Poehlein, Eds., American Chemical Society, Washington,
DC, 1985.
[1] Braun, J. H. and Fields, D. P., "Gloss of Paint Films, I and II," Thiers, E., Will, R., Leder, A., and Shimosato, J., "Titanium Dioxide
JournalofCoatings Technology, Vol. 63, No. 799, 1991, p. 43, and Pigments," CEH Marketing Research Report, SRI International,
Vol. 66, No. 828, 1994, p. 93. Menlo Park, CA, 1991.
www.iran-mavad.com

MNL17-EB/Jun. 1995
i
Black Pigments
by Frank R. Spinelli 1
BLACKPIGMENTSFALLINTOthree classes [1 ] (Table 1). The first fastness and chemical resistance, they are used in the paint
two classes derive their color characteristics from the ele- industry chiefly in metal-protective primers. It should be
ment carbon, the third class from ferrous oxide, Fe304. Class noted that black iron oxide, Fe304, will oxidize at high tem-
1 blacks are carbon blacks, which are composed of 90% or peratures to red or brown ferric oxide, Fe203. Iron oxide
more of elemental carbon. Class 2 blacks may be referred to blacks have very poor color and strength properties com-
as "carbonaceous pigments," which range from 8 to 88% ele- pared to carbon blacks.
mental carbon.
CARBON BLACKS (CLASS 1)

CARBONACEOUS PIGMENTS (CLASS 2)
Carbon black is the most important black pigment for
This class of blacks, perhaps the least important for paints paints and coatings. This unique, strictly manmade material
and coatings, is composed of two main types: offers great versatility in end use performance. Through vari-
ation in key properties, by careful control of manufacturing
Mineral Blacks conditions, a broad range of grades is commercially avail-
able. To provide a better understanding of carbon black as a
Mineral blacks are finely ground derivatives of coal and pigment in paints and coatings, the effects of carbon black
shale and are mixtures of carbon, aluminum silicates, silica, property variations on its optical functioning in dispersed
and iron oxides. They can be characterized as having poor
media are herein defined. This involves some discussion of
jetness, very low tinting strength, low oil absorption, very
how carbon black is formed as well as identification of its key
brown undertone, and poor dispersibility. Consequently, they
parameters. Following is an elucidation of the mechanisms of
are rarely used in the paint industry.
carbon black optical function and how they are influenced by
variations in each of the key parameters. Based on this
Bone Blacks knowledge, certain guidelines for selection of a grade of
carbon black are enumerated. As a corollary, the subjects of
Bone blacks are made by destructive distillation of solvent-
achieving optimal quality dispersion and its importance to
extracted cattle and sheep bones and contain only from 8 to
end use performance are addressed. Finally, techniques of
17% carbon with the remainder mostly calcium phosphate.
measurement of carbon black coating's optical performance
During the "calcination" (8 h at 800~ the organic matter is
properties are outlined with reference to the appropriate
decomposed and the resulting carbon forms a thin, porous
ASTM tests where applicable.
film on the surface of the mineral network, creating a large
carbon surface area per unit of weight. Consequently, they
have high color and great adsorptive ability, but very weak Carbon Black Optical Function
tinting strength. Oil absorption is quite low, and aqueous
dispersibility is excellent. Bone blacks are used only in spe- General Nature of Carbon Black
cialty finishes where high color with low oil absorption is 1. Principles of Formation--The formation of carbon black
essential. requires the application of thermal energy to a hydrocarbon,
usually by incomplete combustion (limited oxygen supply),
which results in the rupture of C - - H bonds [2]. This first
IRON OXIDE BLACKS (CLASS 3) stage is often called "cracking" (Fig. 1A). The reaction prod-
ucts are aromatic radicals and dicarbon radicals, highly reac-
Naturally occurring as the mineral magnetite, these blacks tive species, which combine to form hexagonal lattices in a
are synthesized by reacting ferrous sulfate, FeSO4, with alkali planar configuration. Several "layer planes" then tend to stack
and then oxidizing to ferrous oxide, Fe304 (black magnetic to form crystallites (Fig. 1B). These crystallites tend to form
oxide). Having the highest density as well as excellent light spherical prime particles that continue to grow, forming pri-
mary aggregates, the characteristic units of carbon black (Fig.
~Technical consultant for Cabot Corporation, Special Blacks Divi- 2). Both prime particle and primary aggregate distributions
sion, 157 Concord Rd., Billerica, MA 01821. are typically broad since a great number of layer planes and
179
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TABLE 1--Classification of black pigments.

Type Source Specification Color Index and Name
Class 1: Carbon Blacks
(a) Furnace Oil ...
(b) Channel Gas D 561 77226; pigment black 7
(c) Lamp Oil D 209 77226; pigment black 7
(d) Thermal Oil and gas ...
(e) Acetylene Gas ...
Class 2: Carbonaceous Pigments
(a) Mineral Coal
(b) Bone Bones D 210 77267; pigment black 9
Class 3: Iron Oxides
(a) Synthetic Copper D 769 77499; pigment black 6
(b) Natural Ore ... 77499; pigment black 6
NOTE: From ASTM Paint Testing Manual, Black Pigments 2.8.4; 13th ed., 1972.
(AROMATIC (DICARBON
RADICAL) RADICAL)
c ~ C H 3 6 *~,'~* *
CH4 + CRACKI~* ' ~. / ~ f9' * "4" C2 "~" H 2
A
T ~
INTERACTIO~NOF
REACTIVE SPECIES
(HEXAGONALLATTICE
LAYERPLANE) B
(NUCLEATIONOR
CRYSTALLITEFORMATION)
FIG. 1-Formation of carbon black. Asterisks indicate active sites.
crystallites are going t h r o u g h the described processes, b u t 2. Types~Processes [ 3 ] - - T h e r e are five types of industrial
not in phase. Those particles a n d aggregates which b e g a n carbons which fall in the general category of c a r b o n black.
f o r m a t i o n sooner w o u l d have longer growth times a n d w o u l d I n c l u d e d are l a m p b l a c k , channel black, furnace black, ther-
be larger. By choice of h y d r o c a r b o n feedstock a n d careful mal black, and acetylene black. E a c h of these is m a d e b y a
control of r e a c t i o n conditions, the key p r o p e r t i e s of p r i m e different process and, consequently, has some unique p r o p e r -
particle size, p r i m a r y aggregate size, porosity, structure, a n d ties (Table 2).
surface c h e m i s t r y are varied to create the s p e c t r u m of com- L a m p b l a c k Process. Oils or resins are b u r n e d in shallow
mercial c a r b o n blacks. p a n s in a n enclosure with restricted air supply, a n d the smoke
www.iran-mavad.com

CHAPTER 20--BLACK PIGMENTS 181
This process can produce carbon blacks of particle sizes rang-

ing from about 30 to less than 10 nrn. The resultant blacks
CRYSTALLITE ~ , , g P - - PRIME PARTICLE
have typically higher volatile contents (chemisorbed oxygen
complexes on the surface) because of the presence of oxygen
during formation. Though channel blacks have virtually dis-
appeared from industry, a variant called roller process
blacks, made from feedstocks other than natural gas, are still
produced in limited quantities in Germany.
Furnace Process Blacks. These are made by partial com-
bustion of a hydrocarbon in a closed reactor (or furnace)
under well-defined conditions. The precursors of m o d e r n oil
furnace blacks were the gas furnace blacks, which are no
longer produced.
Oil Furnace Process. A hot flame is first created by burning
/
PRIMARYAGGREGATE gas with air inside a closed furnace, and then a liquid hydro-
FIG. 2-Growth to particles and aggregates. carbon is atomized into the hot flame zone. Furnace designs
and reactor configurations vary considerably, but the princi-
ple is the same (Figs. 5a and 5b). The feedstock is usually a
is passed through settling chambers prior to venting (Fig. 3). medium-molecular-weight aromatic oil that must be heated
Carbon black deposited on the cool walls of the chambers is to 200 to 250~ to have sufficient fluidity. Yields are high (30
subsequently scraped off by motor-driven ploughs. The prin- to 60%), air pollution is virtually nil, and it offers superior
cipal feedstocks are coal tars or petroleum residual oils. process control capability. Blacks ranging in prime particle
Lampblack's major usage in the coatings industry is as a size from 100 down to about 10 nm, with variations in struc-
tinting pigment. It exhibits excellent antiflocculation proper- ture level (degree of aggregation of prime particles), can be
ties and an extremely blue undertone. Though lampblacks produced by varying furnace conditions, feedstock proper-
have been replaced by furnace blacks to some extent on a ties, residence times (time in hot zone), and quench distances
tinting strength basis, substantial quantities are still pro- (how far downstream the cooling sprays are introduced into
duced for special applications. the furnace).
Channel Process. Until about 1975, this process was the Oil Furnace Carbon Blacks. These essentially satisfy all re-
leading source of carbon blacks for the coatings industry. Its quirements of industrial blacks and account for 95% of all the
demise was brought about by two principal factors: (1) the carbon black produced today.
escalating cost of natural gas and (2) the increasing Thermal Cracking or Thermal Decomposition--A final cate-
stringency of air pollution regulations. gory of carbon black processes uses thermal cracking or ther-
The process (Fig. 4) involves partial burning of natural gas mal decomposition of a gaseous hydrocarbon in the absence
with insufficient air. Small fan-shaped flames from gas of flame. This includes thermal blacks and acetylene blacks,
burner tips (2000 or more) are housed in sheet metal build- which are not used in the coatings industry.
ings or "hot houses" and are arranged so that they impinge on
channel irons suspended above hoppers. Using scrapers and M e c h a n i s m s o f Interaction with Light [4]
a reciprocating action of the channel irons, the deposited Since coatings vehicles are usually transparent resin solu-
carbon is collected in the hoppers and passed through the tions, the function of a pigment in rendering the coating
collection system. Yields are characteristically very low, opaque and imparting a desired color is to intercept and
reaching a m a x i m u m of about 5% with the coarser grades. modify incident visible light. Carbon black accomplishes this
TABLE 2--Typical analyses of carbon black grades from five different processes.
Type: Furnace Thermal Channel

Symbol: HAF MT FT EPC Lampblack
Property ASTMNo.: N-330 N-990 N-880 Acetylene $300 Lb
Average particle 28 500 180 40 28 65
diameter, nm
Surface area (BET), m2/g 75 47 13 65 115 22
DBPA, mL/100 g 103 36 33 250 100 130
Tinting strength, % SRF 210 35 65 108 180 90
Benzene extract, % 0.06 0.3 0.8 0.1 0.00 0.2
pH 7.5 8.5 9.0 4.8 3.8 3.0
Volatile material, % 1.0 0.5 0.5 0.3 5 1.5
Ash, % 0.4 0.3 0.1 0.0 0.02 0.02
Composition, %
C 97.9 99.3 99.2 99.7 95.6 98
H 0.4 0.3 0.5 0.1 0.6 0.2
S 0.6 0.01 0.01 0.02 0.20 0.8
O 0.7 0.1 0.3 0.2 3.5 0.8
NOTE:From Encyclopediaof ChemicalTechnology,Vol. 4, 3rd ed.
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translates to about 2 to 3% carbon black by weight in most

vehicle systems. Loadings of carbon black above the opacity
loading level will not further enhance the color (blackness).
2. Light Scattering [5]--Another factor that contributes to
carbon black's appearance is its relatively weak light-scatter-
ing ability. When dispersed in a vehicle, individual aggregates
of carbon black are much too fine to be efficient scatterers [6].
Nevertheless, light scattering plays a significant part in the
details of carbon black optical performance.
Carbon Black Parameters Affecting the Optical

Function
General Principles
When dispersed in a transparent vehicle, the primary ag-
gregates of carbon black are the optically functional units.
Thus, the optical function is affected by variations in the two
key carbon black parameters which determine aggregate size:
prime particle size and structure.
As primary aggregates decrease in size, the specific surface
area increases and incident light must penetrate more car-
bon, which results in increasing light absorption. Both ab-
sorption and scattering efficiencies (per unit weight of carbon
FIG. 3-Old plant for lampblack manufacture. black) increase with decreasing aggregate size (Fig. 7) down
to a size equal to about one third the wavelength of the
incident light, D (about 180 nm for "white light"). Further
by means of two mechanisms: light absorption and light scat- decreases in aggregate size show a leveling off of absorption
tering. efficiency and a decrease in scattering efficiency.
1. Light Absorption--By nature of its quasigraphitic micro- The size of the prime particle determines the size of the
structure, carbon black strongly absorbs visible light across primary aggregate at a fixed level of aggregation. The level of
the spectrum. In dispersed media, because of its relatively aggregation is known in the carbon black industry as struc-
fine particle size and high surface area, it is an extremely ture. It is a parameter that not only indicates the average
efficient light absorber and thus appears black. To achieve number of prime particles composing a primary aggregate,
opacity, it is necessary to have a sufficient number of carbon but also the degree of anisometry, branching and chaining or
black aggregates distributed throughout the resin matrix to shape irregularity (Fig. 8). The higher the structure, the
intercept virtually all of the incident light (Fig. 6). This condi- greater the void space within and around a primary aggre-
tion is often referred to as the opacity loading level and gate. In fact, the extent to which a carbon black absorbs oil or
8" ='
! Steel channel I
'I'" Tip<-" il'~/Carbon black/~
]distance ~ deposit // Cyclone
9 ~_.i~/'Flame if' ~ ~collector i Er~
Lava burner tip --'O,~l 1/4 burner# \ / J i
Enlarged view pipe // Black / ,~Bulkstora""

:' %e
of burner and Returnj/ :lent j. / . >~ )elletizedI
burnerchannel.,Hot__ air //,, tir y(, .~ ~
Blower
.,,/l"t'~houses~,/l"~"~. Bolter I Agitator | Pelletizing ~ 1-1
t"" ~ ,/ Burner I~ "~
I I I f~channels II ~ Lv. tank...-J ~/"
".~.~,::-'.'~-.:,'7-1.,equipmentBelt ]',~' S,tandardi
,I I.!.,1
-'-- , Air ....... II i
L o"0.
--=I'I'' k~ L conveyor, hopperl
Screw conveyor discharge black

FIG. 4-Channel process for carbon black manufacture.
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dibutylphthalate (DBP), which fills the void spaces, is a com- equal to one third the wavelength of incident light, the ab-
m o n industry measure of its structure. sorption efficiency, and consequently tinting strength, levels
off and becomes independent of further decreases in size.
Jetness This phenomenon can be seen in Fig. 9 as well.
The industry term for degree of "blackness" is "jetness,"
which increases with decreasing aggregate size for two rea- Opacity
sons: (1) increasing light absorption efficiency and (2) de-
The extent to which a coating will cover or "hide" a sub-
creasing light-scattering efficiency. As primary aggregates be-
strate is a function of the nature of the pigment and its
come smaller, incident light must penetrate more carbon,
loading level. As mentioned earlier, the opacity loading level
resulting in more light absorption per unit weight of black.
of carbon black in a coating system is usually 3% by weight or
Also, despite the individual variations of absorption and scat-
less for normal paint film thicknesses (around 1.0 mil). With
tering efficiencies per unit weight shown in Fig. 7, the ratio
much thinner films, higher loadings would be required to
[4] of absorption efficiency to scattering efficiency, A/S, es-
sentially increases continuously with decreasing aggregate achieve opacity. In other words, there must be a sufficient
size. Thus, both mechanisms, absorption and scattering, are number of primary aggregates dispersed throughout the film
synergistic with respect to jetness, and the degree ofjetness is to prevent any significant amount of incident light from pass-
controlled by the A/S ratio. The smaller the aggregate, the ing through.
higher the A/S ratio and the jetter the black. Carbon black creates opacity through the two mechanisms
Structure can also be a measure of aggregate size for a cited earlier, absorption and scattering of visible light. In fact,
given prime particle since it reflects the number of prime opacity of carbon black can be considered as being directly
particles composing a primary aggregate. In this sense it is proportional to the sum of_the absorption coefficient and the
also an indicator of scattering efficiency. Low-structure scattering coefficient, (A + S). This means simply that light
blacks have smaller primary aggregates, exhibit less scatter- that is either absorbed or scattered is not transmitted through
ing, and have higher A/S ratios. High-structure blacks have the film. From this relationship, it is also possible to predict
larger primary aggregates, exhibit more scattering, and have that optimum opacity, as a fixed loading, would be rendered
lower A/S ratios. Given two carbon blacks of comparable by blacks having an aggregate size close to one third the
prime particle size, the black of lower structure (smaller, wavelength of incident light (in short, blacks in the regular to
more compact primary aggregates) will show the higher medium color categories for white light of 180 nm, as per Fig.
jetness because of a higher A/S ratio. 7).
One convenient way to express the opacity of films is to use
Tinting Strength the parameter called optical density. This is a function of the
Carbon black's primary tinting application is to make gray percent of incident light transmitted as follows:
colors by blending with a white pigment. Addition of a fixed
Optical Density = - LOG10T~
amount of a number of different carbon blacks to a titanium
dioxide, TiOz, dispersion, for example, will result in various where
depths of gray color. The darkest gray will represent the car- Tx = Transmitted light/incident light, and
bon black highest in tinting strength. Since even a dark gray h = Wavelength of incident light.
surface reflects a great amount of light relative to a black
An optical density of 1.0 would indicate a transmission of
surface, the increment of light scattered by the carbon black
1% (0.01), 2.0 would indicate a transmission of 0.1% (0.001),
is insignificant. For this reason, the controlling mechanism in
etc. Since T will vary somewhat with wavelength, it is neces-
tinting strength is light absorption [7]. Finer primary aggre-
sary to use the subnotation to denote the wavelength of the
gate size, which favors increased absorption, will enhance
tinting strength (Fig. 9). As the primary aggregate size is de- incident light. Further, there is a logarithmic relationship
with film thickness (expressed as weight of coating per unit
termined both by prime particle size and structure, higher
area) for a fixed carbon black loading, i.e.
tinting strength is favored by fine-particle-size, lower struc-
ture blacks. However, as shown in Fig. 7, at an aggregate size Optical Density -- - In (grams/m 2)
Water Quench
"'X AA, A/ ...... (

PRODUCTS
CARBON BLACK
gasair,,~.,.. 2100 - 3 0 0 0 ~ F -,, 400 ~ F /
CO 2
feedstock ~/~___.w~,"
\
Yield: 30 - 6 0 %
CO
H~
N2
H20
FIG. 5a-Oil furnace reactor.
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O0
c3
Air Conveyor Collector ('~ ~----Elevator Discharge Tubing

BucketElevatorIr
QuaternaryCyclone .. ', ~ 1 1 ~ X ~ I,~X~ MagneticSeparator
TertiaryCyclone UnitExhausterf .
SecondaryCyclonp\ ~ // S t a C K ~ J l / I~lC ~__VibratingScreens
PrimaryCyclone / \ ~ ~i,----. Bag Filter'~ ,t:' ~~__~.~l~lv,e'r~~o, ,~~1. _ _ ~ l[tJ"l~ ~Air Fan.~'.Belt Conveyor
/ -~ ~ l J ,Exhauster, II ~: ~
.LI II ~ ~ ~ _ w~-~=,,~;IrF~terBags- "~r]L /11 ~: Bag Berquist
III "Packing Tank/
RiserPipe""~II
L~.~IIltt~I~!~'~-~~]~. _ , AgitatorTank '" LL[I Tank ~ y
Refectory ' '~ SliderBelt ~ P e l ~ : i u Z ~ g } ~ II

Burner ~, r ~ " ~ m -~i~l'~-"-~--- ~ "-d ~ .~' ~ ! Conveyor ~k ~1'1 ~'~
" 3 ? " ~ ~ 2%. I ScrewConveyor Rotary VacuumFilter /
Carbon Black Furnaces Air Fan Air Conveyor Slurry Bag Filter Feeder CoveredHopperCar
System Recovery Compartments
System www.iran-mavad.com

FIG. 5b-Oil plant.
furnace
Light
Absorption ////
/////l Lig
HT
~ Scattering
Low
" ~"
"
41.
" *t.
ll~t:;
"
* "0
i .5 ,
"l
-UlBi
~
9 #, : . , : 1
Q"
~ J
-
|
.... ,is ir
o o " ,l/~ o o l9 9 I t'~& 9 I
" "-I ~ " " J: " - -~- I
I ''.o " ..o- . . . . I ~-,.~
I o 9 9 ~ P a i n t Film Qo9
MEDIUM
FIG. 6-OPTICAL FUNCTION OF CARBON "1

BLACK. This diagram is an oversimplification of
how carbon black functions in that primary ag-
gregates are depicted as spherical and of
roughly the same size. In reality, the aggregates
are irregular in shape and occur as a distribution
of sizes, which complicates the optical function-
ing considerably. However, the fundamental
processes as shown still represent the theoreti- HIGH
cal basis for more complete treatments of the
subject.
Undertone
In the carbon black industry, blacks are visually character- FIG. 8-Structure comparison.
ized as having a blue or brown undertone or some gradation
in between when dispersed in a coating system. In a black
coating it is called mass tone and in a gray it is called tint
tone. The phenomenon of undertone results from the fact
that both scattering and absorption efficiencies of carbon
black vary with wavelength [8]. Preferential absorption of
blue light tends to make the unabsorbed light reaching the
observer favor the red end of the spectrum (browner tone).
The degree of preferential absorption/scattering of the blue 300 ' '1''1 I " ' I '
end of the spectrum increases with decreasing aggregate size.
Thus, in a gray finish, where the absorption mechanism is in
20O
Absorption ~-3
I
I S- ~ ~% g 100
so
b.
Scattering * D
V zo , ,J, , I I , , I'~
High Color Medium Color RegularColor Low Color 50 75 100 200 500 750
Blacks Blacks Blacks Blacks
Da(nm)
AGGREGATE SIZE
FIG. 7-CARBON BLACK OPTICS. *D M3 = An aggregate Particle Size
size equal to one third the wavelength of the incident light. FIG. 9-Tinting strength of a range of carbon blacks.
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control, the finer the aggregates the browner the tint tone. In bility to vehicle penetration or greater ease of dispersion.
mass tone we have the more complex situation where both While lower structure blacks are more difficult to disperse
preferential scattering and preferential absorption, each with ultimately, they contain less occluded air (lower density) to
a separate wavelength dependency, contribute to undertone. be displaced so that they incorporate or "wet-out" more read-
ily.
Gloss Surface chemistry can be a factor in dispersion both as
The term gloss is generally taken to mean the specular volatile content or simply as adsorbed moisture. Higher vola-
reflectance of a surface measured at some specific angle (for tile content, acting as a built-in dispersing agent, tends to
example, 60~ As with any pigment added to a transparent favor easier dispersion. Adsorbed moisture, present in all
vehicle, the gloss of the dried film will be influenced by the carbon blacks in proportion to surface area and ambient
loading and the properties of the carbon black. Starting with conditions in limited amounts, has proven to be beneficial to
an unpigmented coating having optimal gloss in the dried dispersion in liquid systems.
film and adding a given carbon black incrementally (assum- Density and physical form of carbon black also influence
ing excellent dispersions), a point will be reached where gloss dispersibility. Carbon black as produced is extremely "fluffy"
begins to deteriorate until eventually the finish becomes flat. and must be substantially densified (removal of occluded air
Since it is the resins in the dry film which create the smooth by agitation), usually to over 10 lb/ft 3 for handling purposes.
surface for reflection, the addition of particulate substances When the densification is done by rotary agitation in drums,
such as pigments or fillers in significant concentrations can either wet or dry, the result is spherical pellets, which offer
only interfere with the "smoothness" of the surface. ease of handling and reduced dusting. Densification packs
The properties of carbon black that affect the gloss of a agglomerates more closely, increasing interaggregate attrac-
coating are: aggregate size, structure, and surface chemistry. tion and making dispersion more difficult. Pelletization adds
Other factors being constant, the finer the aggregate size the the dimension of pellet hardness which must be overcome
less the effect on surface texture. The finer aggregate blacks prior to actual dispersion. However, pelleted blacks "wet-out"
tend to give coatings with higher gloss when properly dis- very quickly and are thereby suitable for certain types of
persed. equipment (Table 3).
Higher structure, which means more void space and there- Optimal dispersion of carbon black can be defined as that
fore higher oil absorption, tends to work against gloss. This is condition in which all agglomerates are broken down into
because more vehicle is "tied up" for a given loading of black
their constituent primary aggregates; each aggregate is sepa-
in comparing a higher structure with a low structure black.
rated from the others, and the surface of each is completely
Once again we must emphasize the importance of quality of
covered by resin. Primary aggregates are the characteristic
dispersion. Since higher structure blacks are somewhat eas-
units of carbon black and are not broken down under normal
ier to disperse, the effect of structure can only be properly
dispersion conditions. The steps involved in the dispersion
observed in cases where optimal dispersion has been
process are:
achieved.
Surface chemistry generally refers to the amount of volatile 1. Incorporation (Wetting)--This step involves the displace-
content or chemisorbed oxygen complexes on the surface ment of occluded air and covering the surface of agglomer-
(that is, hydroxy|ic, carboxylic, quinonic, or lactonic groups). ates with vehicle, yielding a workable dispersion mix.
Carbon blacks often are chemically oxidized after formation Sometimes this is referred to in the coatings industry as pre-
(aftertreatment) to increase volatile content. While this is mixing.
usually done to improve rheological properties (for example, 2. Pellet Breakdown--When pelleted black is used, Step 1,
flow, viscosity), it normally creates improved gloss as well. Incorporation, is easier since initial mixing causes little, if
The volatile content acts as a built-in dispersing agent, ser- any, pellet fracture. Thus, at the worst, larger pellet fragments
ving to reduce the amount of vehicle needed to completely need to be "wetted" by vehicle. Pellet breakdown must then be
wet the surface of the black.
accomplished by the application of additional energy (for ex-
ample, longer mixing) after Step 1.
The Effect of Dispersion Quality 3. De-Agglomeration--This is the principal step in achiev-
ing optimal dispersion and the one that consumes most of the
General Principles
applied energy. Interaggregate attractive forces must be over-
The influence of the key carbon black parameters on dis- come to break down agglomerates into their constituent pri-
persibility must first be defined [9]. As the primary aggregates mary aggregates.
of carbon black become finer, dispersion becomes more diffi-
cult for two reasons: (1) higher energy needed to "wet" the
higher surface areas and (2) greater attractive forces between TABLE 3--Preferred form of carbon black.
aggregates because more particles per unit weight of carbon Preferred Form
black means smaller interaggregate distances. Equipment Fluffy Pellets
Structure plays a key role as well. Low structure blacks
Two-roll mill X
allow closer "packing" (higher density), which results in Three-roll mill X
smaller interaggregate distances and stronger attractive Steel ball mill X
forces or more difficulty in dispersion, ttigher structure Attritor X
means more void space (lower density), which reduces Disk disperser X
interaggregate attractive forces and provides greater accessi- Sand/shot mill X X
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4. Stabilization--At this stage, in order to stabilize the that is, using color and/or gloss development, which are ex-
deagglomerated aggregates, each of the aggregates must ad- tremely sensitive to small variations in degree of mi-
sorb sufficient vehicle to completely deactivate its surface. crodispersion.
This process can often be facilitated by the use of dispersing
agents.
Selecting a Grade o f Carbon Black for Coloring
To function efficiently in an optical sense, carbon black
must be optimally dispersed. The primary aggregates which Black Coatings
characterize carbon black must be separated from one an- For coloring purposes, a grade of carbon black should be
other and distributed fairly uniformly throughout the vehicle selected that is as low as possible in surface area, but consis-
matrix to be most efficient at intercepting incident light. tent with end use color specifications. This enables the for-
Choosing a grade with high surface area for high color appli- mulator to take advantage of the greater ease of dispersion
cations, for example, must be combined with designing an and lower cost associated with the lower surface area. The
effective dispersion system to ensure full color development. desired structure level would be high enough to give accept-
Mill base formulations, grade selection, physical form of car- able dispersibility, but not so high as to adversely affect gloss
bon black (fluffy or pellets), and premixing as needed all play or rheology. In some cases the use of aftertreated grades will
a part in ensuring quality dispersion. Perhaps the most im- give an edge in dispersion and gloss as well as protect the
portant factors in mill base formulation are: (1) providing rheology at higher loadings. Normally, at opacity level load-
sufficient vehicle solids to accommodate the carbon black ings, rheology is only a problem when more concentrated
surface (Table 4) and (2) adjusting viscosity to a level suitable
mill bases are used.
for the chosen dispersion equipment. Implicit in the selection of a grade of carbon black is the
Dispersion Mechanisms choice of the fluffy or pelleted form. The choice is usually
made on the basis of dispersion equipment available or on
Available liquid system dispersion equipment utilizes ei-
ease of incorporation or both. Listings of preferred forms for
ther or both of the two main dispersion mechanisms: (1)
best results with each of the major pieces of equipment are
shearing force and (2) collision of agglomerates with each helpful (Table 3). Regarding ease of incorporation, if, for
other and with dispersion media particles. These mecha-
example, a steel ball mill which is a very effective disperser is
nisms describe the manner in which energy is applied to to be used, the edge in dispersion provided by the fluffy form
carbon black agglomerates during the dispersion process. is not really needed, so it is wise to consider the pelleted form
For example, disk disperses and three roll mills use shearing
which will "wet in" quickly and which creates less dust on
force while ball mills, sand mills, and attritors rely on colli-
handling.
sions. Candidate grades must be dispersed in the specific formu-
Dispersion Quality Testing lation in which they are intended to be used. Keeping in mind
the sensitivity of color and gloss development to dispersion
It is possible to stabilize carbon black dispersions at vari- quality, it is useful to evaluate jetness and gloss both at the
ous levels of deagglomeration. The term macrodispersion is
end of the prescribed grind cycle and again after an extended
applied to very moderate levels of deagglomeration at which
cycle. This technique not only identifies which of the candi-
only the larger agglomerates are fractured. Microdispersion,
dates will provide the color and gloss levels needed, but also
on the other hand, refers to levels of deagglomeration ap- indicates whether or not full color value from a given grade
proaching the ideal of single primary aggregates.
will be achieved under the prescribed dispersion conditions.
The most accurate way to measure dispersion quality is The factors of carbon black cost and dispersibility must be
microscopically. Using X100 optical micrographs, it is possi-
weighed against desired color and gloss levels in making a
ble to set up a classification system. However, it is costly and
final decision. Some commonly used oil furnace grades for
time consuming and somewhat impractical for production
the coatings industry are listed in Table 5.
control. More commonly used in the coating industry is the
grind gage (Hegman gage, paint club gage, etc.). These de- Black Tinted Coatings
vices do not measure microdispersion. Since it is mi- While selecting a black for tinting purposes involves the
crodispersion that largely determines color performance, it is
principles mentioned earlier under General Natures of Carbon
possible to have two identical mill bases, both "off-scale" on a Black on mass tone color, some key points need emphasis.
grind gage, one of which is significantly poorer in dispersion
The selection depends upon required tinting strength (see
quality. The better dispersed system would be blacker (jetter)
Table 5), tint tone, and relative ease of dispersion.
and glossier. This leads to the most practical indirect method,
Tint tone (see under Carbon Black P a r a m e t e r s Affecting
the Optical Function the section on Undertone) refers to the
TABLE 4--Suggested vehicle solids to carbon black ratios for mill color undertone in tinting. If very blue undertone is needed,
base compositions. grades such as LCF 2 and LCF 3 are suggested. Sometimes it
Suggested Ratio, is necessary to sacrifice some tinting strength by going to
Nitrogen Surface Vehicle Solids/Carbon grades with larger aggregate size in order to maximize blue
Type Area, m2/g Black tint tone (for example, going from LCF 1 to LCF 2). High-tint-
High color 230-560 3.5/1 to 4.5/1 strength blacks tend to give browner undertone, which is
Medium color 200-220 2.5/1 to 3.0/1 desirable in some applications.
Regular color 45-140 1.5/1 to 2.0/1 Finally, where dispersion stability (that is, flocculation re-
Low color 25-40 1.0/1 sistance) is critical, aftertreated blacks can be helpful. MFF
www.iran-mavad.com

TABLE 5--Oil furnace black color grades for coatings.

DBP
Absorption, Tinting Volatile Density,
Surface Particle cc/100 g lb/ft3
Jetness Area (BET), Size, Strength, Content,
Grade Index~ m2/g nm Fluffy Pellets % % Fluffy Pellets
ASTM Test N/A D 3037 N/A D 2414 D 3265 D 1620 D 1513

High HCF 3 60 560 13 90 80 100 9.0 17 27
color HCF 2 64 560 13 100 90 100 9.5 16 25
HCF i 69 340 16 105 100 116 9.5 11 24
Medium MCF 4 70 230 15 70 64 120 2.0 14 29

color MCF 3 74 220 16 112 105 122 1.5 8 21
MCF 2 73 210 17 74 68 120 1.5 15 28
MCF 1 78 200 18 122 117 118 1.5 9 19
Flow Long flow, LFF 83 138 24 60 55 112 5.0 15 32

grades Medium flow, MFF 84 96 25 72 69 112 3.5 14 30
Regular RCF 4 83 112 24 65 60 116 1.0 15 31

color RCF 3 84 94 25 70 65 110 1.0 19 28
RCF 2 87 80 27 85 72 104 1.0 13 29
RCF 1 90 85 27 100 .-. 92 1.0 12 ...
Low color LCF 4 93 43 37 95 ... 80 1.0 11 ...

grades LCF 3 95 42 41 ... 121 62 1.0 ..- 22
LCF 2 96 35 50 ... 90 60 1.0 -.. 27
LCF 1 99 25 75 72 64 58 0.5 18 33
aBased on Nigrometer scale values so lower numbers indicate higher jetness.
NOTE: Above data typical of commercial grades representative of the indicated categories [11].
( m e d i u m flow furnace) black, for example, exhibits excellent 10,000 I - I I 1 I I I --

stability and high tinting strength and is often used for tinting 6,000
9 Oil-type rubber blacks
in p o o r e r wetting vehicles. 6,000 I - O Gas4ype rubber blacks /s
5'000 I - O Oil-type color blacks /
4,000 I - + Gas-type color blacks
Measuring Appearance Properties of Carbon

Black Coatings
A black coating p i g m e n t e d with c a r b o n black at the opacity
2,000[
0,< 3,000 r
level (less than 3% by weight) will probably reflect only ab o u t

1% of the light incident u p o n it. This presents s o m e u n i q u e
p r o b l e m s in trying to m a k e absolute i n s t r u m e n t a l m e a s u r e -
me nt s since the sensitivity of available i n s t r u m e n t s is simply
not adequate. F o r this reason, it has been traditional in the
c a r b o n black industry and even a m o n g end users to d e p e n d 300 o ~r~
u p o n visual j u d g e m e n t s of a p p e a r a n c e properties in m a n y +4-
cases. While no one challenges the incredible sensitivity and
versatility of the h u m a n eye, it has the d r a w b a c k of not being
able to quantify its observations. Nevertheless, using special
100| I I I I I
techniques, it is possible to obtain quantitative measure- 50 60 70 80 90 100 110 120
me nt s on all a p p e a r a n c e properties as outlined below. Nigromater value
FIG. 1 0 - N i g r o m e t e r values versus particle size for a range of
Jetness carbon blacks.
Jetness or blackness is a function of B E T surface area, i.e.,
inversely p r o p o r t i o n a l to aggregate size (Fig. 10). Tradition- nates [10] to quantitatively m e a s u r e jetness an d mass tone as
ally, the industry assigned n i g r o m e t e r "scale" values, w h i ch well.
are a direct function of the a m o u n t of light reflected by
dispersed samples (coatings, plastics, etc.). S m a ll e r "scale"
values indicated jetter carbon blacks. However, the m o d e r n Undertone
a p p r o a c h is to m e a s u r e the spectral reflectance of a black The mass tone is m e a s u r e d as described above in the sec-
dispersion, w h i c h is m a d e possible by the e n h a n c e d sensitiv- tion on jetness. This is an i m p o r t a n t tool b ec a us e visual
ity of cu rr en t instrumentation. The spectral reflectance ratings of jetness are usually influenced by u n d e r t o n e varia-
curves can then be converted to H u n t e r L, a, b; or CIE coordi- tions a m o n g blacks being rated.
www.iran-mavad.com

Tint tone, on the o t h e r hand, can n o r m a l l y be m e a s u r e d Dispersion quality and its i m p o r t a n c e in realizing the full
directly via absolute reflectance (versus a white s t a n d a r d ) optical potential of a given grade has also been addressed.
using a s p e c t r o p h o t o m e t e r o r a colorimeter. However, com- Therefore, in the grade selection process, the physical f o r m of
m o n practice is to m e a s u r e against a gray s t a n d a r d (ASTM c a r b o n black as well as key p a r a m e t e r s m u s t be c o n s i d e r e d in
D 3265: Test M e t h o d for C a r b o n Black-Tint Strength). light of the chosen d i s p e r s i o n technique.
Tinting Strength
As illustrated in Fig. 9, tinting strength increases with de-
creasing particle size. The differential m e a s u r e m e n t tech- REFERENCES
nique, d e s c r i b e d above, is u s e d to assign tinting strength
values. The procedure, ASTM Test D 387-86, Test M e t h o d for [1] Spengeman, W.F., ASTM Paint Testing Manual, Black Pig-
Color a n d Strength of Color Pigments with a Mechanical ments, 2.8.4, 13th ed., 1972.
Muller, involves dispersing c a r b o n b l a c k together with a [2] Boonstra, B. B., "A, B . . . . Z of Carbon Black," an internal publi-
white p i g m e n t in a wetting oil or other suitable vehicle. The cation of Cabot Corporation.
refectance of this d i s p e r s i o n versus a s t a n d a r d gray tile or [3] Dannenberg, E. M., "Carbon Black," Encyclopedia of Chemical
gray vitreous e n a m e l is t h e n a m e a s u r e of its tinting strength.
Technology, Vol. 4, 3rd ed., Wiley-Interscience, New York, 1978,
pp. 631-666.
While it was c u s t o m a r y in the c a r b o n b l a c k i n d u s t r y for m a n y
[4] Donoian, H. C. and Medalia, A. I., Journal of Paint Technology,
years to r e p o r t tinting strength as a p e r c e n t of a reference Vol. 39, 1967, p. 716.
black (for example, IRB No. 4), some suppliers are n o w using [5] Mie, G., Annalen der Physik, Vol. 25, No. 4, 1908, p. 377.
an i n d e p e n d e n t tinting strength index, allowing strength [6] Kubelka, P. and Munk, F., Zeitschrift f~r Technische Physik, Vol.
c o m p a r i s o n s only within their own p r o d u c t lines. 12, 1931, p. 593.
[7] Medalia, A. I. and Richards, L. W., "Tinting Strength of Carbon
Gloss Black," Journal of Colloid and Interface Science, Vol. 40, 1972, p.
Clearly, this p r o p e r t y a n d the m a n n e r in w h i c h it is mea- 233.
sured is not u n i q u e for c a r b o n black coatings. W h e t h e r the [8] Donnet, J. B. and Voet, A., Carbon Black, Marcel Dekker, New
York, 1976.
p i g m e n t a t i o n is black o r any o t h e r color, the test (for exam-
[9] Cabot Corporation, Special Blacks Division, Technical Report
ple, for 60 ~ gloss) is the same.
S131, 1989.
U0] Judd, D. B. and Wyszecki, G., Color in Business, Science, and
Industry, 3rd ed., Wiley, New York, 1975.
SUMMARY {11] Cabot Corporation, Special Blacks Division, Technical Report
S136, 1988.
Individual key c a r b o n black p a r a m e t e r s have b e e n viewed NOTE: References 2, 9, a n d 11 are Cabot C o r p o r a t i o n inter-
from the s t a n d p o i n t of their influence on the optical function. nal publications copies of which are available from:
It is i m p o r t a n t to emphasize, however, that these p a r a m e t e r s Cabot C o r p o r a t i o n
do not o p e r a t e separately. The effect on optical functioning, Special Blacks Division
a n d therefore on p i g m e n t a r y properties, is a c o m b i n e d one. 157 Concord R o a d
E a c h p a r a m e t e r w h e n varied influences the o t h e r p a r a m e - Billerica, MA 01821
ters, w h i c h are also varying. Thus the situation is d y n a m i c Phone: 800-462-2313, Fax: (508) 670-7035
a n d complex. TLX: 947119
www.iran-mavad.com

MNL17-EB/Jun. 1995
iiii
21
Colored Organic Pigments
by Peter A. L e w i s I
D E F I N I T I O N OF A P I G M E N T ganic compound. As such, Barium Lithol red (PR 49:1) and

the PTMA-based Rhodamine (PV 1) are considered toners. In
Before entering into any discussion relating to pigments, it the coatings industry, the term "toner" may be used to refer to
is first necessary to clearly define what is meant by a pigment a secondary color that is added to alter the hue of the paint.
as opposed to a dyestuff. In many earlier texts on color, the The term "lake" now has an accepted definition as that used
terms "pigment" and "dyestuff" are used almost interchange- in America.
ably. A most confusing European term, the use of which should
A definition of a pigment has been proposed by the Dry be discouraged, is "pigment dyestuff," technically an
Color Manufacturers Association (DCMA) 2 in response to a oxymoron. This term is meant to refer to insoluble organic
request from the Toxic Substances Interagency Testing Com- pigments devoid of salt-forming .groups, for example,
mittee. This definition was developed specifically to enable Benzimidalone Orange (PO 36).
differentiation between a dyestuff and a pigment with the
intention of forever ending the confusion surrounding these
two terms. As such it is worthwhile reproducing this defini-
tion in its entirety:
"Pigments are colored, black, white or fluorescent partic- INTERNATIONAL NOMENCLATURE--THE
ulate organic and inorganic solids which usually are C.I. S Y S T E M
insoluble in, and essentially physically and chemically
unaffected by, the vehicle or substrate in which they are In any m o d e m publication discussing pigments of any de-
incorporated. They alter appearance by selective absorp- scription, it is likely that the author will make use of the
tion and/or by scattering of light. coding system as published as a joint undertaking by the
Pigments are usually dispersed in vehicles or substrates
Society of Dyers and Colourists (SDC) in the United Kingdom
for application, as for instance in inks, paints, plastics or
other polymeric materials. Pigments retain a crystal or and the Association of Textile Chemists and Colorists
particulate structure throughout the coloration process. (AATCC) in the United States.
As a result of the physical and chemical characteristics of This system is known as the "Colour Index," [1 ] and as such
pigments, pigments and dyes differ in their application; is a recognized trademark, hence the retention of the "u" in
when a dye is applied, it penetrates the substrate in a "colour" whenever reference is made to a "Colour Index"
soluble form after which it may or may not become name or number.
insoluble. When a pigment is used to color or opacify a
The Colour Index (C.I.) identifies each pigment by giving
substrate, the finely divided insoluble solid remains
throughout the coloration process." the compound a unique "Colour Index Name" and a "Colour
Index Number." This description is proving to be most valu-
Additionally, the terms "lake" and "toner" are encountered able to persons within the coatings industry responsible for
when dealing with pigments. American terminology, as ap- assembling data on the composition of a coatings formula-
plied to pigments, defines a toner as an organic pigment that tion for documents such as Material Safety Data Sheets or
is free of inorganic extender pigments or carriers; as such, the hazard data sheets. As such the identification of a pigment by
pigment is unadulterated and exhibits maximum tinting ca- mention of its C.I. name and number unequivocally identifies
pacity for the pigment type. A lake, conversely, is an organic the chemical composition of the pigment in a manner accept-
colorant that has been combined with an inorganic substrate able to most government bodies. For example, DNA Orange
or extender such as barium sulfate (Blanc Fixe) or alumina. has the Colour Index name of Pigment Orange 5 (PO 5) and
In European terminology toners are considered to be water- the Colour Index number of 12075.
soluble acid or basic dyestuffs that are converted to insoluble The Colour Index Name for a pigment is abbreviated as:
pigmentary forms by appropriate precipitation with an inor-
PB-- Pigment Blue PBk-- Pigment Black
PBr-- Pigment Brown PG-- Pigment Green
1Coatings industry manager, Sun Chemical Corp., Colors Group,
Cincinnati, OH 45232. PM-- Pigment Metal PO-- Pigment Orange
2Dry Colors Manufacturers Association, North 19th St., Arlington, PV-- Pigment Violet PR-- Pigment Red
VA 22209. PW-- Pigment White PY-- Pigment Yellow
190
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CHAPTER 21--COLORED ORGANIC PIGMENTS 191
CLASSIFICATION OF P I G M E N T S BY diazotization and coupling. Diazotization involves reacting

CHEMISTRY the primary amine portion of the molecule with nitrous acid
to yield a "diazonium salt," which is then immediately "cou-
Pigments used in paints and coatings may be broadly di- pled" to the other half of the molecule to yield the colored
vided into opaque or hiding whites and colored toners. All the pigment.
opaque whites are inorganic compounds and as such fall Figure 1 illustrates the structure of a series of metallized
outside the contents of this chapter. For the sake of clarity it azo reds that are of considerable commercial importance and
should be noted that such compounds include the following: that find some, albeit limited, use within the coatings indus-
Lithopone (co-precipitate of barium sulfate and zinc try. Each of these structures features a molecule based on the
sulfide) coupling of a naphthalene ring structure to a benzenoid
Zinc oxide structure. A brief description of the more common metallized
White lead (basic lead carbonate) azo reds is as follows:
Antimony oxide Lithol Reds--Barium Lithol PR 49: 1, C.I. No. 15630: 1;
Titanium white (mixture of titanium dioxide and blanc Calcium Lithol PR 49:2, C.I. No. 15630:2.
fixe) Discovered in 1899, this pigment's major use is in the print-
Titanium dioxide (rutile form) ing ink industry and finds only limited application within the
The colored pigments as covered in this section are all coatings industry at masstone levels, that is, at a level where
organic in nature and as such contain a characteristic group- the tinting strength of the pigment is not diluted with a white
ing or arrangement of atoms known as a "chromophore," tint base, for such reds as those used on tool boxes, fire
which imparts color to the molecule. In addition, the mole- extinguishers, and the cheaper lawn mowers where the
cule is likely to feature a number of modifying groups called fastness properties of the pigment are acceptable.
"auxochromes" that alter the primary hue of the pigment in a The pigments are bright reds with high tint strengths and
more subtle way such as shifting a red to a more yellow shade good dispersion characteristics; the barium salt is lighter and
or a blue to a more red shade while still maintaining the
primary hue of red or blue rather than pushing the hue over HO COO-
to an orange or a violet.
Perhaps the most important of the chromophores is the azo H3~SO N=N~ LITHOL
chromophore ( - - N = N - - ) . The naphthol reds, monoarylide
PR 57 AddCI RUBINE
and diarylide yellows, benzimidazolones, pyrazolones, and
C 3
azo condensation pigments are all examples of organic pig-
ments that feature the azo chromophore. Of equal impor- 140 COO-
tance is the phthalocyanine structure based upon the com-
pound tetrabenzotetra-azaporphin; halogenation of this C~.~__ N=N~ RED2B
compound results in a major shift in hue from a blue to a
PR 48 CH3~CI Exchange
CH3 SO3- ~ Positions
green. Pigments are also derived from heterocyclic structures
such as translinear quinacridone and carbazole dioxazine
violet. Finally there are pigments that result from the vat HO CO0-
dyestuffs and miscellaneous metal complexes.
PR 52
C ~ N=N~ CHa--,C2H
BON RsEMethyl
D ene(--CH~--) Addition
CLASSIFICATION OF P I G M E N T S BY COLOR Ct SO3-
Reds HO COO-
Metallized Azo Reds C2HS ~'~
Many reds used within the coatings industry contain the PR 200 I ~ S O N=N- - ( ~ -Co0- Subtract-COOH
azo chromophore (--N~---N--) and as such are termed "azo C a-
reds."
A further subdivision is possible into acid, monoazo metal-
HO
lized pigments such as Manganese Red 2B (PR 48:4) and
nonmetallized azo reds such as Toluidine Red (PR 3). Typi- C2Hs NN
cally, each of the metallized type contains an anionic group- CLARIONRED
PO46 C~Hs--~CH3 SubtractCH2
ing such as sulfonic (--SO3H) or carboxylic acid (--COOH),
which will ionize and react with a metal cation such as cal-
cium, manganese, or barium to form an insoluble metallized
azo pigment. HO
Conversely nonmetallized azo reds do not contain an an- CH~ NN
ionic group in their structure and therefore cannot complex
PR 53 CI~SO_= ~ REDLAKEC
with a metal cation.
All azo reds contain one or more azo groups by definition
and are all produced by a similar reaction sequence involving FIG. 1-Structure of metallized azo reds.
www.iran-mavad.com

yeUower in shade than the calcium salt, which may best be Characterized by outstanding cleanliness, brightness, and
described as a medium red. Neither pigment can be recom- color purity, the manganese salt offers a very blue shade with
mended for outdoor exposure work since their exterior dura- improved lightfastness as compared to the calcium salt. As
bility is inadequate for such situations. Additionally, they such, the manganese salt is suitable for outdoor applications
cannot be used in applications requiring pigments of high and, as with the Manganese Red 2B, can be used in blends
acid or alkali fastness since the Lithol Reds will hydrolyze with Molybdate Orange (PR 104) to give bright, economical
under such conditions to give weaker, yellower shade prod- reds.
ucts. BON Maroon--PR 63: 1, C.I. No. 15880: 1.
Permanent Red 2 B - - B a r i u m Red 2B, PR 48:1, C.I. No. Illustrated in Fig. 2, BON Maroon was first synthesized in
15865 : 1; Calcium Red 2B, PR 48 : 2, C.I. No. 15865 : 2; Manga- 1906 by Ernst Gulbransson of Farbwerken Meister, Lucius
nese Red 2B, PR 48:4, C.I. No. 15865:4. and Bruning. The manganese salt is the only one that finds
Discovered in the 1920s, the Red 2B pigments are azo reds commercial significance rather than the calcium or barium
prepared from coupling diazotized 1-amino-3-chloro-4- variation. Its lightfastness is such that the pigment can be
methyl benzene sulfonic acid (2B acid) onto 3-hydroxy-2- used at masstone levels for implement and bicycle finishes.
naphthoic acid (BON). Over 40 years ago, when specifications were not as demand-
A major outlet for the barium and calcium pigments is in ing, BON Maroon actually found application in automotive
baked industrial enamels, which do not require any apprecia- finishes.
ble outdoor fastness properties. Use in alkaline systems is
again severely restricted due to the tendency of these metal
Non-MetaUized Azo Reds
salts to hydrolyze in highly alkaline environments. The bar-
ium salt is characterized by a clean, yellow hue as compared As implied by their classification, the nonmetallized azo
to the bluer calcium salt. The barium salt has a poorer light- reds do not contain a precipitating metal cation and as such
fastness and weaker tinting strength but a slightly better bake offer increased stability to hydrolysis in highly acidic or alka-
stability as compared to the calcium salt. line environments as compared to the metallized azo reds
The term "lightfastness," used throughout this section, re- previously covered.
fers to the pigments ability to withstand exposure to light, Toluidine Red--PR 3, C.I. No. 12120.
both direct and indirect, natural and artificial, without suffer- This pigment, shown in Fig. 3, first synthesized in 1905, is
ing any visible change in appearance. The most damaging chemically the reaction product from coupling the diazo-
component of light appears to lie in the ultraviolet region of nium salt of 2-nitro-4-toluidine (MNPT) onto 2-naphthol
the spectrum and, as such, a rapid evaluation of a pigment's (beta naphthol).
likely reaction to long-term exposure to light can be assessed Various shades of Toluidine Red are available commer-
using exposure equipment that maximizes exposure to UV cially described as "extra light, light, medium, dark and extra
light. Many high-performance pigments are exposed under dark" as are grades offering "haze resistance" and being "easy
application conditions in specially maintained areas in Flor- dispersing" (ED).
ida to more fully evaluate their fastness to outdoor exposure Almost the entire U.S. production of Toluidine Red, an
and weatherability. amount in excess of 0.75 million kilos, is consumed by the
The Manganese Red 2B has sufficiently improved lightfast- coatings industry. The pigment provides a bright, economical
ness to allow its use in implement finishes and aerosol spray red of acceptable lightfastness when used in full shade cou-
cans for touch-up paints. This salt is bluer, dirtier, and less pled with a high degree of color intensity and good hiding
intense as compared to the calcium salt. Extension of the power. However, the pigment is not fast to white overstriping
Manganese pigment with any pigment such as titanium diox- since it will bleed through, turning the white to pink, and
ide or Molybdate Orange (PR 104) to an amount greater than
15% is not recommended since its fastness properties will
suffer. so;- H~___/COO-
E ~
Lithol Rubine Red--Calcium Lithol Rubine, PR 57:1, C.I.
No. 15850: 1. N=N Ca 2"
Made by coupling 3-hydroxy-2-naphthoic acid (BON) onto
diazotized 2-amino-5-methyl benzene sulfonic acid (4B acid),
this blue shade red was discovered in 1903 and has found
widespread use in the printing ink industry ever since as the 2-naphthylamine-l-sulfonic acid ,3-hydroxy-2-naphthoic acid (BON)
process "magenta" of the four color printing process. FIG. 2-Structure of BON Maroon, PR 63:1.
A dean, blue shade red with high tint strength, its major
application in the coatings industry is for interior applica-
tions calling for an inexpensive red with both good solvent HO
and heat resistance. Again the pigment must be used at near NO2 N=N
masstone levels to maximize its fastness properties.
BON Reds--Calcium BON Red, PR 52: 1, C.I. No. 15860: 1;
Manganese BON Red, PR 52:2, C.I. No. 15860:2.
Manufactured by coupling diazotized 1-amino-4-chloro-3- CH MNPT
methyl benzene sulfonic acid onto 3-hydroxy-2-naphthoic Beta Naphthol
acid (BON), these reds first were commercialized in 1910. FIG. 3-Structure of Toluidine Red, PR 3.
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shows a marked tendency to bleed in high Kauri-Butanol HO

(KB) solvents.
Toluidine Red is used at masstone levels, that is, in full NO~
shade without the addition of opaque extenders such as tita- N =N ~ ParaRed(PR 1)
nium dioxide or zinc oxide, in such coatings as farm imple-
ments, lawn and garden equipment, and bulletin paints kL.__/
where a bright, economical red of moderate lightfastness is
required to fill the user specification. Because of the pig- p-nitroaniline )beta naphthol
ment's poor durability in tint shades, that is as a reduction
with white, it is rarely used at reduced levels.
Para Reds--Para Red, PR 1, C.I. No. 12070; Chlorinated HO
Para Red, PR 4, C.I. No. 12085; Parachlor Red, PR 6, C.I. No.
12090.
NO2- ~ N c I ----N ParachlorRed(PR4)
Shown in Fig. 4, each of these three pigments is based on
the coupling of a primary amine to beta naphthol. The posi-
tion of the -chloro or -nitro auxochromes on the molecule
controls the shade of the pigment. In fact Chlorinated Para o-chloro-p-nitroanUine ,beta naphthol
Red differs from Parachlor Red only in the position of the
-nitro and -chloro groups on the benzene ring. As such these
pigments are isomers. HO
Use of these pigments in the coatings industry has declined
rapidly due to the ever increasing and exacting demands
placed upon colored finishes by the industry. All of these
CI ~N----N~ ChlorinatedParaRed(PR6)
pigments will bleed in solvents typically used in the coatings
industry and as such cannot be used in any finish that re-
NO2
quires overstriping.
As a class of insoluble azo reds, they are characterized by p-chloro-o-nitroaniline > beta naphthol
intense shades of red through to a scarlet. Their good alkali FIG. 4-Structure of the para reds.
resistance, lightfastness, and durability when considered as a
function of their cost recommends them for use in latex
paints and outdoor signs. At temperatures above 250~ overstriping fastness have limited its more widespread use.
(121~ the pigments will sublime. Lightfastness of tints is Lightfastness at both tint and full shade is rated good.
significantly inferior to that of the pigments at full shade. Pigment Orange 38, C.I. No. 12367. A very yellow shade,
Naphthol Reds--Naphthol Reds are chemically defined as bright red with good solvent fastness. Can be used in baking
monoazos of 2-hydroxy naphthoic acid N-arylamides without enamels at high concentrations without showing any ten-
anionic salt forming groups. Their individual properties are dency to bloom.
dependent upon the specific composition of the pigment in Pigment Red 5, C.I. No. 12490. Showing only marginal
addition to the conditioning steps used in their manufacture. fastness to heat and solvents this pigment, nevertheless, finds
As a class they are a group of pigments that exhibit good application in implement coatings. The opaque grade of this
tinctorial properties combined with moderate fastness to pigment can be combined with iron oxide to give an economi-
heat, light, and solvents. The Naphthols are extremely acid, cal red with high hiding.
alkali, and soap resistant pigments, properties which lead to Pigment Red 146, C.I. No. 12485. A very blue shade red that
their use in masonry paints and latex emulsions. finds its major use in interior architectural applications. Its
Naphthol Reds may be described as "medium perform- poor exterior durability makes the pigment unsuitable for
ance" reds since they exhibit properties that fall somewhere outdoor finishes.
between the Toluidine Reds and Quinacridones, with a cost Pigment Red 170, C.I. No. 12475. Increasingly important as
that corresponds accordingly. Those Naphthol Reds of com- a medium performance, moderately priced red, this pigment
mercial significance may be briefly covered as: is available as both a transparent and an opacified grade.
Manufacturing techniques are used to produce the pigment
Pigment Red 7, C.I. No. 12420. Used in architectural paints in two crystal phases, each exhibiting a unique hue. The
and some baking enamels. Offering acceptable lightfastness, opaque grade finds use in farm tractor and implement fin-
even in tints, this pigment suffers from poor durability in ishes. Its use with iron oxides allows a practical approach to
exterior applications. formulating reds with acceptable lightfastness, hiding, and
Pigment Red 22, C.I. No. 12315. A light, yellow shade Naph- economics.
thol used in air drying alkyds and aqueous systems that can Pigment Red 187, C.I. No. 12486. A transparent pigment
be satisfied with this pigments marginal lightfastness. with excellent heat fastness, moderate durability, and good
Pigment Red 112, C.I. No. 12370. A newer Naphthol Red bleed resistance. Its uses extend to bicycle coatings, coil, and,
that possesses a very clean, yellow hue and that finds use in powder coatings.
both industrial and architectural coatings. The tendency of Pigment Red 188, C.I. No. 12467. A yellow, clean shade red
the pigment to bloom at high concentrations and its poor with acceptable durability at all depths of shade. It is fast to
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194 P A I N T AND COATING T E S T I N G M A N U A L
5
4
3
6
N~
N[ 0
H
Cj
II
0
H
I 2'
5'
4'
Colour Index Substituents

Colour Index Name Number 2 4 5 2' 4' 5'
PR 2 ...................... 12310 CI H CI H H H
PR 7 . . . . . . . . . . . . . . . . . . . . . . 12420 CH3 CI H CH3 CI H
PR 9 ...................... 12460 CI H CI OCH 3 H H
PR 10 . . . . . . . . . . . . . . . . . . . . . 12440 CI H CI H CH3 H
PR 14 . . . . . . . . . . . . . . . . . . . . . 12380 NOr CI H CH 3 H H
PR 17 . . . . . . . . . . . . . . . . . . . . . 12390 CH3 H NO2 CH3 H H
PR 22 . . . . . . . . . . . . . . . . . . . . . 12315 CHa H NOa H H H
PR 23 . . . . . . . . . . . . . . . . . . . . . 12355 OCH3 H NO2 H H NO2
PR 112 . . . . . . . . . . . . . . . . . . . . 12370 CI CI CI CHa H H
FIG. 5-Generic structure and key to the naphthol reds.
overstriping at temperatures below 160~ and therefore finds O H

II I
use in the higher quality industrial finishes. Figure 5 illus-
trates the generic structure of the naphthol molecule and
gives the chemistry of several of the types discussed above.
I II
High-Performance Reds H O hydrogen
: : < bond
These types of pigments may be broadly defined as prod- O t:'1 formation
ucts that will meet the exacting demands of the automotive [I I
industry with respect particularly to the outdoor exposure
requirements demanded by exposure in Florida and Arizona
for as little as two and as long as five years.
The high-performance reds considered fall into four basic I II
H O
classes: quinacridone reds and violets, vat dyestuff based reds
FIG. 6 - T r a n s linear quinacridone showing proposed
such as perylenes, benzimidazolone reds, and disazo conden-
hydrogen bonding mechanism.
sation reds.
Quinacridone Reds--These are heterocyclic in nature since
their structure comprises a fused ring in which the ring atoms in the dyeing of cotton. Only their high cost limits the more
are dissimilar, being a combination of carbon and nitrogen widespread use of these pigments throughout the coatings
rather than only carbon as we have seen in the previous industry.
pigments discussed, as shown in Fig. 6. Addition of differing Anthraquinone Red, PR 177, C.I. No. 65300. A medium
auxochromic groups such as methyl (--CH3) and chlorine shade red with excellent all round fastness properties. Again
(--C1) gives Pigment Red 122 and Pigment Red 202, respec- finds major use in the automotive industry for the production
tively, both described as magentas. of clean, bright red coatings.
The theory behind the superior durability of pigments with
Brominated Pyranthrone Red, PR 216, C.I. No. 59710. A
the quinacridone structure is that considerable hydrogen
yellow shade red that also can be classed as an automotive
bonding occurs between molecules through the carbonyl
grade pigment because of its excellent fastness properties.
(wC~-~O) and imino (~--~N--H) ring atoms.
Neither light nor dark shades will suffer on prolonged expo-
As a group of pigments the quinacridones find their pri-
mary uses in automotive, industrial, and exterior finishes. A
minor use is in the preparation of quality furniture stains and TABLE 1--Types of quinacridone.
finishes. The pigments combine excellent tinctorial proper- Colour Index Name Hue Comments
ties with outstanding durability, solvent fastness, lightfast- PO 49 Gold Quinacridone quinone
ness, heat fastness, and chemical resistance. Table 1 lists PR 122 Magenta 2,9-dimethyl
those shades currently commercially available. PR 192 Red-yellow Mono methyl
Vat Reds--Vat Red pigments based upon anthraquinone PR 202 Magenta 2,9-dichloro
PR 206 Maroon Solid solution
include such structures as Anthraquinone Red (PR 177), PR 207 Scarlet 4,11-dichloro
Perinone Red (PR 194), Brominated Pyranthrone Red (PR PR 209 Red-yellow 3,10-dichloro
216), and Pyranthrone Red (PR 226) as shown in Fig. 7. PV 19 Violet-blue Beta crystal
The term "vat pigments" originates from the fact that this PV 19 Red-yellow Gamma crystal
PV 42 Maroon Solid solution
class of pigments is related to the vat dyestuffs used originally
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0 NH2
II
R _ _ N / C ~ C"" N__ R
IJ IL
0
R = -06H3002H5 PR 123 Vermillion

II R = -CBH3(CH3)2 PR 149 Scarlet
NH2 O R = -CH3 PR 179 Maroon
R = -CsHsOCH3 PR 190 Red
Anthraquinone Red (PR 177) R=-H PBr 26 Bordeaux
R = -C6HsCI PR 189 YellowShade Red
R = ~ !,~ N=N ~ ~> PR 178 Red

O O
FIG. 8-Structure of typical perylene.
N~C~___~C%N
Perinone Red (PR 194)
FIG. 9 - S t r u c t u r e of Pigment Red 224.

O
N,N'-substituted perylene-3,4,9,10-tetracarboxylic di-imide.

An exception of note is Pigment Red 224, Fig. 9, which is
derived from the perylene tetracarboxylic dianhydride.
Br3
Benzirnidazolone Based Reds--This subdivision of reds in-
cludes such pigments as Pigment Reds 171, 175, 176, 185,
and 208. Benzimidazolone-based reds are azo reds that con-
CI II tain the benzimidazolone structure as part of their makeup.
O
The reds all possess the generic structure based upon a cen-
Brominated Pyranthrone Red (PR 216) tral naphthol molecule as illustrated in Fig. 10. Such struc-
tures exhibit a significantly high molecular weight that
greatly influences the pigments fastness properties.
D Benzimidazolone reds are used primarily in the coloring of
O
LI plastics because of their outstanding heat stability, although
some uses are found within the coatings marketplace. They
show excellent fastness to light at all depths of shade, good
weatherability, and excellent fastness to overspraying at ele-
Br2
vated temperatures. They all find use in coil coatings, powder
coatings, camouflage paints, automotive refinish, and farm
IL
O
Pyranthrone Red (PR 226)

FIG. 7-Structure of typical vat reds.
~
sure in Florida. Transparency is generally not adequate for OH 0 ~ . / . . , . ~ N/
Y
|
this pigment to be used in metallic or mica finishes. H
Perylene Reds--These pigments provide pure, transparent
shades and novel styling effects when used in metallic alumi- Co|our
n u m and mica finishes. The perylenes offer improved flow Index
Name X Y
characteristics when used in high-solids formulations. Pery-
lenes may also be described as vat pigments and in fact are PR 171 OCH3 NO2
PR 175 COOCH3 H
the only class of Vat pigments that were developed specifi- PR 176 O C H ~ CONHCsHs
cally for the pigment marketplace rather than as dyestuffs. PR 185 OCH3 S02NHCH3
Almost all of the perylenes have a structure as shown by the PR 208 C00C4H9 H
generic formula given as Fig. 8, that is, they are based upon FIG. lO-Structure of the benzimidazolone reds.
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implements where cheaper, less stable pigments would be volume used followed by Pigment Red 198. Pigment Red 88 is
inadequate. widely used in automotive finishes, but the bleed resistance of
Pigment Red 175 is a highly transparent red with good Pigment Red 198 limits its use. The commercially availability
lightfastness that finds application in automotive base coat/ of these pigments has suffered in recent years with many
clear coat systems since it is not sufficiently durable for top products having been withdrawn from the marketplace by
coat systems. Pigment Red 171 is also a transparent pigment the almost exclusive supplier, Bayer.
but with a maroon shade that finds use in industrial systems.
Pigment Reds 176, 185, and 208 find considerable use in Novel High-Performance Reds
quality printing ink applications but currently no use in the In recent years several novel organic reds have been com-
coatings industry. mercialized and targeted directly at the requirements of the
Disazo Condensation Reds--These types of pigments have coatings marketplace.
been available commercially in Europe since 1957 and in the Pigment Red 257, Fig. 15, is a nickel complex with a red-
United States since 1960. Their outstanding fastness proper- violet masstone and a magenta undertone that exhibits
ties have resulted in their use in high-quality industrial fin- fastness properties similar to that of quinacridone. Pigment
ishes. Red 257 is particularly useful in the formulation of high-
Figure 11 illustrates three typical structures of the disazo quality industrial and automotive coatings. The pigment also
condensation reds. The figure merely serves to show the size exhibits excellent rheological properties in highly pigmented
and variation of the structures of pigments within this class; systems.
no Colour Index names are available at present.
c cF3
Pigment Red 242, Fig. 12, is a bright yellow shade disazo
condensation pigment with excellent fastness properties that
is finding increased use in high-quality industrial finishes and
as a lead replacement pigment for those high-quality coatings
that now must be formulated lead free. N N
Pigment Red 214, Fig. 13, is another example of a disazo // \\
N N
condensation red with properties similar to Pigment Red 242.
Thioindigoid Reds--The thioindigoid chromophore serves
as a nucleus for a wide range of red to violet pigments includ-
ing such as Pigment Reds 86, 87, 88, 181, and 198, Fig. 14. NH ' - - ( ~ _ ~ N H ~
These pigments are all noted for their brightness of shade and
generally good fastness properties, resulting in their use in CI
the coatings industry with Pigment Red 88 being the largest FIG. 12-Structure of Pigment Red 242.
AN co-NHR NHC NNA CI~. CI C I ~ CI
N N
// \\
N N
A R
CI
Pigment
Red 144 CI
M.Wt. 828.5 FIG. 13-Structure of Pigment Red 214.
CI
A O D
CI
Red
M.Wt. 863
D 0 A
CI CI
c,.@
A B C D
CHa --CHa -H -Br -H PR 86
-H -H -H -CI PR 87
-CI -H -H -CI PR 88
-CH3 -H -CI -H PR 181
-CI -H -H -CH3 PR 198
Red -H -CI -H -CH3 PV 36
M.Wt. 803 -CHa -CI -H -CH3 PV 38
FIG. 11-Structure of the disazo condensation reds. FIG. 14-Structure and key thioindigoid reds.
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CI
CI~ CI
_ /~ H
Ni ."
/ \ N'--H
I/I--O N~..]// FIG. 17-Generic structure of pyrrolo-pyrrole.
N= Ci
CI
CI
FiG. 15-Structure of Pigment Red 257. ~I=C~C--,N,
N II
I; ,[ )N--e,,--N( IL "I
O "~/~ c i c ~-....y
X _ [I
H N
LI FIG. 18-Copper phthalocyanine, PB 15.
N
I
D
FIG. 16-Generic structure of but its inferior heat stability and its poorer chemical fastness,
pyrazoloquinazolone (basis of coupled with a price almost three times that of the copper
Pigment Red 251 and 252), containing salt, has resulted in a rapid decline in its con-
sumption for all but very special applications.
Copper phthalocyanine is commercially available in two
Pigment Reds 251 and 252 are both based on the
crystal forms, the alpha and the beta form. The alpha crystal
pyrazoloquinazolone structure as shown in Fig. 16. These
is described as Pigment Blue 15, 15 : 1 and 15 : 2 and is a clean,
pigments are monoazo compounds derived from pyra-
bright red shade blue. The beta crystal is described as Pig-
zolo(5,1-b)quinazolones as the coupling component and sub-
ment Blue 15:3 and 15:4 and is a clean green or peacock
stituted anilines or polycyclic amines as diazo component.
Each pigment exhibits excellent brightness of hue at full shade.
shades, good gloss retention, and high scattering power com- The beta form is the most stable crystal form and readily
bined with good light and weather fastness. As such, they are resists recrystallization. The alpha form, conversely, is the
finding increased use in industrial and automotive coatings. least stable or meta form, which readily converts to the more
Recently a series of novel reds based upon the pyrrolo- stable, green shade, beta crystal. As such the crystal requires
pyrrole structure, Fig. 17, have been marketed into the auto- special proprietary treatments to produce a red shade prod-
motive coatings industry. The first pigment marketed is a uct that is stable to both crystallization and flocculation.
bright red with excellent color intensity that will find use Copper phthalocyanine gives excellent performance in
alongside quinacridones and perylenes in automotive formu- most coatings applications but there is considerable variation
lations. between both the chemical and crystal types available. The
coatings formulator should bear this in mind when choosing
a grade for a specific application. Use of any of the
Blues unstabilized grades in strong solvents or in systems that
Copper Phthalocyanine Blue experience heat during dispersion or application will result in
The most important and most widely used blue throughout a shift in shade to the greener side and a loss of strength as
all applications of the coatings consuming industry is copper recrystallization takes place within the unstabilized crystal.
phthalocyanine blue, Pigment Blue 15, Fig. 18. Pigment Blue 15 (C.L No. 74160) is a red shade, alpha
First described in 1928 by chemists working for the crystal. It is the least stable of the family and as such is
Scottish Dye Works (now part of I.C.I.), this pigment has referred to as crystallizing red shade (CRS) blue.
steadily increased in importance to become a product with Pigment Blue 15 : 1 is a modified alpha crystal also having a
worldwide significance. The only metal derivative of signifi- red shade but with modifications to stabilize the structure
cant commercial use is that of copper, derivatives of other against phase transformation to the beta crystal. Most com-
metals having been shown by research to have less desirable monly the molecule is chlorinated to the extent of one mole-
shade or fastness characteristics. Metal-free phthalocyanine, cule of chlorine per molecule of copper phthalocyanine to
Pigment Blue 16, once found an outlet as a green shade blue, give "monochlor" blue (C.I. No. 74250).
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Pigment Blue 15:2, described as "non-crystallizing non- flocculation-resistant pigment with outstanding fastness
flocculating" (NCNF), red shade blue, is an alpha crystal that properties. This pigment is used in paint systems requiring
is stabilized against both flocculation and recrystallization only small amounts of an intense red shade blue as a shading
using additive technology. Such additives are introduced dur- pigment at low levels where the expense of using indanthrone
ing the manufacturing or blending operation and are essen- blue is justified.
tially derivatives of copper phthalocyanine that confer stabil- Carbazole Violet--Pigment Violet 23, C.I. Number 51319.
ity by a steric hindrance mechanism. A complex polynuclear or heterocyclic, intense red shade
Pigment Blue 15 : 3 represents the most stable crystal, green blue pigment that possesses excellent fastness properties.
shade, beta copper phthalocyanine. Pigment Blue 15:4 is Only the pigment's relatively high cost and hard nature limit
descriptive of a beta blue that has been modified with ph- its more widespread use. The pigment is used at very low
thalocyanine-based derivatives to confer flocculation resist- levels to produce "brighter whites" by imparting a bluer hue
ance to the crystal such that it can safely be used in strong to the undertone of the white.
solvent systems.
Other specialized, more expensive crystal modifications
also exist such as P.B. 15 : 5, a red shade, g a m m a crystal and Yellows
P.B. 15:6, a very red shade, epsilon crystal. Monoarylide Yellows
Copper phthalocyanine is a pigment that offers brightness, Azo pigments whose manufacture is based upon the diazo-
cleanliness, strength, and economy with all round excellent tization and coupling sequence as mentioned when dealing
fastness properties. The only drawback to this pigment is its with azo reds. The structures of the major rnonoarylide yel-
tendency to change to a coarse, crystalline nonpigmentary lows are represented in Fig. 19.
form when used in strong solvent systems if the crystal has Itansa Yellow G - - P i g m e n t Yellow 1, C.I. Number 11680.
not been adequately stabilized and has a tendency to floccu- A bright yellow pigment, made by coupling diazotized 2-
late from white pigments such as titanium dioxide when used nitro-4-methyl aniline onto acetoacetanilide, that has a major
to tint such paint and lacquer systems. Another negative is use in trade sales, emulsion, and masonry paints. Its major
the fact that copper phthalocyanine blues exhibit the phe- disadvantages are its poor bleed resistance in most popular
nomenon of bronzing when applied at masstone levels, deep solvents, poor lightfastness in tint shades, and very inferior
tints, and in metallic systems. bake resistance due to its tendency to sublime.
Hansa Yellow 10G--Pigment Yellow 3, C.I. Number 11710.
Miscellaneous Blues A very green shade yellow made by coupling the diazo of 4-
Indanthrone Blue--Pigment Blue 60, C.I. Number 69800. chloro-3-nitro aniline onto 2-chloro acetanilide. Greener in
Belonging to the class of pigments described as "vat pig- shade than Pigment Yellow 1, this pigment is used in the
ments," indanthrone blue is a very red shade, nonbronzing, same types of applications and suffers from the same deft-
NO2 CH
PY 1
COCH3
I
__~
Hansa G H~C N=N--CH--C--NH PY 75 C1 N = N--C,CO-HN OC2H 5
Jl
O
NOt CI OCH3 H3CO

PY 97 NH--S --(( ))-- N= N--CH--C-- NH--~( )~--C
Hansa 10G II \~-~/ II \~/
0 o r - - o
OCH3 OCH3
NO~ HaCO NO2 CH3

ooo.3
PY 65 H3CO--~ N= N--CHOC#i--NH -- ~ PY 98 c, -LV# -
O o
CI CH3
NO2
COCH
9
H3CO
,--/
i
C-OH
PY 73 Cl N=N--CH--C--NH PY 116 H~NOC N=N--C--COHN NHCOCH 3
II
O
OCH3 HaCO
PY 74 o2N #
o
FIG. 1 9 - S t r u c t u r e s of the major m o n o a r y l i d e yellows.
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ciencies as Pigment Yellow 1 with the exception that Pigment light chrome yellow (PY 34) and shows improved light, heat,
Yellow 3 is suitable for use in exterior applications at high and solvent fastness as compared to the other monoarylide
tint levels. yellows. As may be expected from its shade, this pigments
Miscellaneous Monoarylide Yellows--Pigment Yellow 65, major use is in lead-free coatings.
C.I. Number 11740: A newer monoarylide pigment produced
by coupling diazo 2-nitro-methoxy aniline onto 2-ac- Diarylide Yellows
etacetanisidine. Offering a redder shade than the previous The structures of this commercially important range of
two yellows discussed. Pigment Yellow 65 is used in trade organic yellows are shown in Fig. 20. This figure clearly
sales, latex, and masonry paints. A more recent application is shows the similarity between each of these pigments, which
for road traffic marking paints that are specified as being lead are principally a backbone structure centered on 3,3'-di-
free. The bleed resistance and baking stability are little im- chlorobenzidine with modifications to the shade and proper-
proved over Pigment Yellows 1 and 3. ties by variation of the coupling component used in the diazo-
Pigment Yellow 73, C.I. Number 11738." Prepared by cou- tization reaction. Table 2 gives a summary of the properties
pling diazo 3-chlor-2-nitro aniline onto 2-acetoacetanisidine, of the major diarylide yellow pigments of commercial signifi-
this is a pigment with a shade close to that of Pigment Yellow cance.
1 that finds use in similar applications. Not considered dura- Each of the diarylide yellows offers low-cost, reasonable
ble enough for exterior applications, Pigment Yellow 73 nev- heat stability, and moderate chemical resistance. The major
ertheless plays an important role in interior, intermix systems worldwide market for this class of yellows is the printing ink
due to its stability against recrystallization in the presence of industry. These yellows are approximately twice as strong as
glycols and wetting agents used in latex systems. the monoarylide yellows dealt with previously; furthermore,
Pigment Yellow 74, C.I. Number 11741: A product from the they offer improved bleed resistance and heat fastness. Nev-
coupling of diazo 4-nitro-2-anisidine onto 2-acetoacet- ertheless, none of the diarylide yellows have durability prop-
anisidide which offers the user a pigment suitable for outdoor erties that would allow for their use in exterior situations and
applications that is considerably stronger and somewhat as such should never be considered for an outdoor paint
greener than Pigment Yellow 1. Major outlets, as with all the application.
monoarylide yellows, are in latex, trade sales, and masonry Minor applications in the area of toy enamels and pencil
paints. Additionally a specially opacified grade is available coatings are found for the diarylide yellows, especially if a
that is optimized for its exterior durability although of lower lead-free formulation is specified.
tint strength than the normal more transparent grade. A range of opacified diarylide yellows is available, having
Pigment Yellow 73 and the opaque grades of Pigment Yel- undergone an after treatment that has reduced their surface
low 74 show the least tendency to crystallize in organic sol- area and consequently given increased opacity that has re-
vent containing systems. sulted in these specific types exhibiting improved fastness
Pigment Yellow 75, C.I. Number 11770: A pigment produced properties when compared against their nonopacified coun-
by the coupling of 4-chloro-2-nitroaniline onto acetoaceto- ter parts.
phenetidide. A red shade yellow that has only recently found
considerable application in the coatings industry as a re- Benzimidazolone Yellows
placement for lead containing medium chrome yellow as Illustrated in Fig. 21, these yellows take their name from
used in road traffic marking paints. One of the few diarylide the fact that each features the 5-acetoacetyl-aminoben-
yellows that has been found acceptable from the point of view zimidazolone molecule within its structure. Additionally
of economy and durability, being able to withstand nine each is an azo pigment with an acetoacetylarylamide nucleus.
months exposure on a 100 000 vehicle a day highway. A point The exceptional fastness to heat, light, and overstriping is
worthy of note is that this pigment appears to be inherently attributed directly to the presence of the benzimidazolone
"easy dispersing" since the economics of the traffic paint group within the pigments structure, first described in 1964
industry demand that any pigment used to replace lead and offered to the marketplace in 1969.
chromes must be dispersed into water or solvent systems Used initially for the coloring of plastics, these pigments
with little more than a "Cowles" type disperser. are now finding increased use in the coatings industry where
Pigment Yellow 97, C.I. Number 11767: A yellow derived their excellent fastness properties are demanded. Table 3
from the coupling of diazo 4-amino-2,5-dimethoxybenzene gives a summary of the properties of this class of pigments.
sulphoanilide to 4-chloro-2,5-dimethoxy acetoacetanilide.
Surpassing the Hansa yellows in solvent bleed and tightfast- Heterocyclic Yellows
ness, especially in reduced shades, this newer yellow is find- All these yellow pigments contain a heterocyclic molecule
ing use in high-quality decorating paints. within their structure as shown by the examples presented in
Pigment Yellow 98, C.I. Number 11727: Similar in shade to Fig. 22. In spite of their apparent complexity, these new high-
Pigment Yellow 3, but considerably stronger and more heat performance yellows continue to be introduced to satisfy the
stable, this pigment has only met with limited commercial exacting demands of the coatings industry. Pigments such as
success in trade sales, masonry and decorative paints. Manu- Isoindoline Yellow (PY 139) and Quinophthalone Yellow (PY
facture by coupling diazo 4-chloro-2-nitro aniline onto 4- 138) are typical examples of such complex, novel chromo-
chloro-2-methyl acetoacetanilide. phores introduced as recently as 1979 and 1974, respectively.
Pigment Yellow 116, C.I. Number 11790: A product from the All of these pigments find application in high-quality coat-
coupling of diazo 2-chloro-5-carbamoyl aniline onto 4-ace- ings where the end use can justify the price of these high-
tylamino acetoacetanilide, this pigment is similar in shade to performance products. Table 4 summarizes the properties of
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0o0.3 ~
<~..-c-c.-N=N~ c, 1 I OH. COCH.~. 1
PY 12
I O 2
PY 81
O
CI
2
000.3 I OCH3 CI -}
PY 13
r H NH--C--
O
PY 83 C I ~
OCH3
NH--C-- CH-- N = N ~ J 2
COCH3 COOH,
PY 14
I NH--C--CH-- N=N
O
PY 106 NH--C--CH-- N=N
II
O
PY 16 CI
COCH3
NH--C-- CH-- N=N PY 113
r C I ~
c, co. c#l
NH--C--CH--
N=NII
O 2 O 2
CI
o0~3 0o0.3 ?_~

PY 17
F NH--C--CH--N=N~ c, 1 PY 114
PY 126
PY 127
coc.,
O 2
PY 55 .~ N,-O-c,-H~| PY 152
O ----J2
FIG. 20-Structures of the major diarylide yellows.
the heterocyclic yellows currently available that find some mended in coatings due to the pigments poor solvent fastness
use within the coatings industry. and lightfastness.
Dinitroaniline Orange--Pigment Orange 5, C.I. Number
12075.
Oranges Produced by coupling diazo dinitroaniline onto beta naph-
thol, this pigment offers good lightfastness in full tone and
Table 5 lists those orange pigments that have significance moderate solvent fastness. As such, Pigment Orange 5 finds
in todays marketplace. outlets in latex paints and air dry architectural and industrial
finishes. Its poor baking stability rules out its use in high bake
Azo-Based Oranges enamels.
These oranges show considerable variation in structure as Pyrazolone Orange--Pigment Orange 13, C.I. Number
can be seen from Fig. 23; all, however, have the azo chromo~ 21110.
phore ( - - N = N - - ) featured within the molecule. The benzim- Synthesized by coupling tetrazotized 3,3'-dichloro-
idazolone oranges all feature the azo chromophore in addi- benzidine onto 3-methyl-l-phenyl-pyrazol-5-one, the pig-
tion to all being produced using 5-acetoacetylamino- ment is a bright, clean yellow shade product that may be used
benzimidazolone as the coupling agent. for interior coatings, particularly as a replacement for lead
Orthonitroniline Orange--Pigment Orange 2, C.I. Number based orange pigments.
12060. Dianisidine Orange--Pigment Orange 16, C.I. Number
Prepared by the classical diazotization and coupling tech- 21160.
nique used for all azo pigments, this pigment is the product of A diarylide orange produced by coupling tetrazotized 3,3'-
coupling diazo orthonitro aniline onto beta naphthol. Its dimethoxybenzidine onto acetoacetanilide that finds an out-
major outlet is in printing inks, and its use is not recom- let in baking enamels and interior coatings at full shade.
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TABLE 2--Properties of major diarylide yellows. O

Colour Index H3COC// NH_C ~ O
Name Common Name Properties
PY 12 AAA Yellow Poor lightfastness. Poor bleed PY 120 N=N--CH--~-- NH NH
resistance. Major use in printing
inks H3COC\\
PY 13 MX Yellow Redder shade than PY 12. Improved O ~O
heat stability and solvent fastness. COOH ? OCH3 NH-- I
Major use in printing inks
PY 14 OT Yellow Green shade. Some use in interior

PY 151
finishes. Poor tint lightfastness O
PY 16 Yellow NCG Bright green shade. Improved heat

~O
@ N"-i
and solvent fastness. Used in full
shade for coatings
PY 17 OA Yellow Green shade. Some use in interior =.

PY 154
finishes. Poor lightfastness
O
PY 55 PT Yellow Red shade. Some use in interior
finishes. Poor lightfastness. Isomer
of PY 14 CI NH--C/'~O
PY 81 Yellow H10G Bright green shade. Same shade but
coc. I
much stronger than PY 3 PY 156 N.
PY 83 Yellow HR Very red shade. Improved O ~O

transparency, heat stability and CI N.-- C
lightfastness over PY 12. Some use
in interior finishes
PY 175 N=N--CH--C-- NH NH
II
PY 106 Yelow GGR Green shade. Poor tint lightfastness. O
Major use in packaging inks FIG. 21-Structures of the benzimidazolone yellows.
PY 113 Yellow H10GL Very green shade. More transparent
than PY 12 and offering better heat t h a n i l i d e to p r o d u c e a b r i g h t r e d s h a d e o r a n g e t h a t e x h i b i t s
and solvent fastness. Some interior e x c e l l e n t alkali a n d a c i d fastness. W h e n u s e d in full shades,
finish use
this p i g m e n t also f e a t u r e s a c c e p t a b l e lightfastness. C o a t i n g s
PY 114 Yellow G3R Red shade. Improved solvent and a p p l i c a t i o n s e x t e n d to b a k i n g e n a m e l s , latex, a n d m a s o n r y
lightfastness over PY 12. Major use paints.
in oil-based inks
Clarion | Red--Pigment O r a n g e 46, C.I. N u m b e r 15602.
PY 126 Yellow DGR Similar shade to PY 12 but offering
improved heat and solvent fastness.
Major use in printing inks T A B L E 3--Properties of benzimidazolone yellows.
PY 127 Yellow GRL Bright, red shade. Poor Colour Index

lightfastness. Major use in offset Name Common Name Properties
inks PY 120 Yellow H2G Medium shade. Good solvent
fastness. Excellent lightfastness.
PY 152 Yellow YR Very red, opaque product. Poor Used in industrial finishes
lightfastness. Some use in interior
finishes as a lead chrome PY 151 Yellow H4G Greener shade. Good solvent
replacement fastness. Excellent lightfastness.
Industrial and refinish applications
Tolyl Orange--Pigment O r a n g e 34, C.I. N u m b e r 21115. PY 154 Yellow H3G Green shade but redder than PY 151.
Good solvent fastness. Excellent
A d i a r y l i d e p i g m e n t m a n u f a c t u r e d by c o u p l i n g t e t r a z o 3,3'- lightfastness. Industrial and
dichlorobenzidine onto 3-methyl-l-(4'methylphenyl)-pyraz- automotive refinish applications
ol-5-one. This o r a n g e is a bright, r e d d i s h s h a d e o f f e r i n g m o d -
PY 156 Yellow HLR Redder shade. Transparent. Good
e r a t e l i g h t f a s t n e s s a n d g o o d alkali r e s i s t a n c e b u t p o o r solvent exterior durability in full shade and
fastness. As such, t h e p i g m e n t is u s e d in i n t e r i o r c o a t i n g tint. All exterior coatings and
a p p l i c a t i o n s , p a r t i c u l a r l y w h e r e a l e a d - f r e e f o r m u l a t i o n is refinish applications
specified. PY 175 Yellow H6G Very green shade. Good solvent
Naphthol Orange--Pigment O r a n g e 38, C.I. N u m b e r 12367. fastness. Excellent lightfastness. All
N a p h t h o l O r a n g e is p r e p a r e d by c o u p l i n g d i a z o 3 - a m i n o - exterior coatings and refinish
applications
4-chloro-benzamide onto 4'-acetamido-3-hydroxy-2-naph-
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/ c, o . C -- N-- C2Hs ~ 2 "] O

I
N=N--CH NI /N~ / N\ /~-NxH
PY 60 \# PY139 O=C C=C C=C C=
XN----/~ ~ //~--N/H
'
CH3 H' o ~ _ ? o
Arylide Yellow Isoindoline Yellow
PY 101
? OH
CH=N--N=CH
OH
py, o
H
O
~ N ~~x
O
O
kk NH
~ -//- I ~ H
O
Pyrimidine Yellow
Methlne Yellow O
NH~C -- O
CH,,
CH3 / N ~ fN~
Q Ni.. Q-H
Cl N~ N Cl H--O..# ~ N ~ O
CI. ~ ICl NH[~NH/~.~ (31 PY 153 II C -- NH
11
PY 109 C H 3 - - C - - --~
cl . - ' - . ~ / ~ c ~ \C-'~.y__.~ Cl
/ II I I / 0
CI O O Cl
Nickel Dioxine Yellow
Tetrachloro Isoindolinone Yellow
O%/OCH3
C
--~ N~,X~~N/_ _ c" , [~ OcOH,.,
\\ / O%/OCH3
Cl~C\ ./C ~ C, PY 155 O H
PY 110 /C\\ N " ~
C," t "1~ ~" ~ " C, H3CO O \C / \ N ~ Io1
CI O O CI /n.,.%
I H
Tetrachloroisoindollnone Yellow H3C 0 /C%

H3CO 0
Azo Condensation Yellow
-o" c u ~ + \ ~ a 2
PYl17 ~ CH=N
PY 173
~ N - ~
r~C'NH~H ~0~ 30%R~ = R2 = CI
70%R~ = H, R2 = CI
N%
Azomethine Yellow
"%0 O//,.. v
Isoindolone Yellow
? c,
/C~CI
%cOCH, .~
C% I< )1 ~ H"~
,,N,
O=C C=O
c-'--..7~ c,
O CI
PY ,8~
~ N//N" C'/C~O OCH3
PY 138 _~ c ~2"m.
c, o, H~OO o o~LJ"o
I
CI CI H
Quinophthalone Yellow
Triazinyl Yellow
FIG. 22-Structures of the heterocyclic and azo c o n d e n s a t i o n yellows.
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TABLE 4--Properties of the heterocyclic yellows. were formerly m a d e used the l e a d - b a s e d pigment, M o l y b d a t e
Colour Index Name Properties Orange.
Pigment Orange 60--C.I. N u m b e r 11782.
PY 60 Arylide Yellow. Very red shade. Moderate A transparent, yellow shade orange that also exhibits excel-
light and solvent fastness. Trade sales, latex,
and masonry paints. Good acid and alkali lent h e a t a n d solvent fastness with a n exterior d u r a b i l i t y that
fastness. allows the p i g m e n t to be used in a u t o m o t i v e a n d high per-
f o r m a n c e industrial finishes. M a n u f a c t u r e d b y coupling
PY 101 Methine Yellow, bright yellow. Highly b e n z i m i d a z o l o n e to 4-nitro-aniline.
transparent and exceptionally brilliant.
Industrial finishes and specialty coatings. Pigment Orange 6 2 - - T h e newest of the b e n z i m i d a z o l o n e
Only moderate bleed and alkali fastness. oranges, the structure of this p i g m e n t has yet to be m a d e
public. Again a yellow s h a d e p i g m e n t t h a t has shares the
PY 109 Tetrachloroisoindolinone. Green shade. lightfastness p r o p e r t i e s of PO 36 a n d PO 60 b u t offers inferior
Excellent brightness strength and durability.
Automotive finishes. solvent fastness a n d exhibits slight bleed in alkaline systems.
Currently the p i g m e n t is being used in oil-based inks a n d
PY 117 Greenish yellow copper complex of an artists colors; its use in the coatings i n d u s t r y has still to be
azomethine. Excellent chemical, light, and fully explored.
heat fastness. Specialty finishes.
PY 129 Azomethine Yellow, very green shade.
Miscellaneous Oranges
Excellent chemical, light, and heat fastness. F i g u r e 24 illustrates the structures of those oranges that fall
Industrial and specialty coatings. into a "miscellaneous" category as far as such structures have
PY 138 b e e n declared. Table 6 s u m m a r i z e s the p r o p e r t i e s of this
Green shade Quinophthalone. Clean hue and
excellent overall fastness properties. High series of pigments, each of which is finding increased use
quality industrial and automotive finishes. within the coatings industry.
PY 139 Red shade isoindoline. Similar in masstone to

medium chrome (PY 34). Excellent light and Greens
solvent fastness. Industrial and automotive
coatings. Copper Phthalocyanine Green
PY 150 Pyrimidine Yellow, very green shade. Good W h e n a self shade green is required, r a t h e r t h a n a green
heat and lightfastness. Industrial coatings. p r o d u c e d by mixing blue and yellow, then c o p p e r ph-
t h a l o c y a n i n e is the green of choice. This p i g m e n t is b a s e d
PY 153 Red shade nickel dioxine. Excellent fastness u p o n h a l o g e n a t e d c o p p e r p h t h a l o c y a n i n e using either chlo-
properties. Specialty coatings and baking rine o r a mixture of chlorine a n d bromine, the f o r m e r p r o d -
enamels. Poor acid resistance.
uct being Pigment Green 7 a n d the later, P i g m e n t G r e e n 36.
PY 155 Azo Condensation Yellow, green shade. P i g m e n t Green 7 is a blue shade green m a d e b y i n t r o d u c i n g
Excellent overall fastness properties in full 13-15 chlorine a t o m s into the c o p p e r p h t h a l o c y a n i n e mole-
shade. Industrial and specialty coatings. cule, whereas P i g m e n t Green 36 is a yellow shade green b a s e d
PY 173 Isoindolone Yellow, very green shade. u p o n a structure t h a t involves progressive r e p l a c e m e n t of
Excellent fastness properties. Industrial and chlorine in the p h t h a l o c y a n i n e structure with b r o m i n e . Fig-
specialty finishes.
PY 182 Triazinyl Yellow, medium shade. Excellent TABLE 5--Orange pigments of significance in the coatings
fastness properties at masstone levels. industry.
Industrial finishes. Colour Index Colour Index
Name Number Chemical Type
A m e t a l l i z e d azo p i g m e n t m a n u f a c t u r e d by coupling diazo- PO 2 12060 Azo

PO 5 12075 Azo
tized 2-amino-5-chloro-4-ethyl b e n z e n e sulfonic acid onto PO 13 21110 Bisazo
b e t a n a p h t h o | followed b y reacting this p r o d u c t with b a r i u m PO 16 21160 Bisazo
to yield the b a r i u m salt of the pigment. Not r e c o m m e n d e d for PO 31 20050 Bisazo condensation
PO 34 21115 Bisazo
coatings due to its p o o r lightfastness, inferior alkali resist- PO 36 11780 Benzimidazolone (Azo)
ance, a n d i n a d e q u a t e solvent fastness, this p i g m e n t finds its PO 38 12367 Azo
m a j o r outlet in the printing ink marketplace. PO 43 71105 Perinone
Benzimidazolone Orange--Pigment Orange 36, C.I. N u m - PO 46 15602 Azo
PO 48 n/aa Quinacridone
b e r 11780. PO 49 n/a Quinacridone
The p r o d u c t from the coupling of diazo 4-chloro-2- PO 51 rda Pyranthrone
n i t r o a n i l i n e to 5 - a c e t o a c e t y l a m i n o - b e n z i m i d a z o l o n e , this is a PO 52 n/a Pyranthrone
b r i g h t red shade orange of high tint strength. In its opacified PO 60 11782 Benzimidazotone (Azo)
PO 61 11265 Tetrachloroisoindolinone
form, this p i g m e n t offers excellent fastness to b o t h h e a t a n d PO 62 11775 Benzimidazolone (Azo)
solvents a n d a hue s i m i l a r to Motybdate Orange (PR 104). As PO 64 12760 Heterocyclic Hydroxy
such, the p i g m e n t is u s e d in a u t o m o t i v e a n d high-quality PO 67 12915 Pyrazoloquinazolone
industrial formulations w h i c h m u s t be l e a d free a n d w h i c h an/a = Not assigned.
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NO~ HO ure 25 illustrates the proposed structures of the phtha-

locyanine greens. The most highly brominated product, Pig-
PO 2 ment Green 36, sometimes referred to as "green 6Y" or "green
8G," has an extreme yellow shade and contains 12-13 chlo-
rine atoms.
Both greens exhibit outstanding fastness properties to sol-
OrthonitroanilineOrange vents, heat, light, and outdoor exposure. They can be used
equally effectively in both masstone and tints down to the
NO~ HO very palest depth of shades. Metallic automotive paints may
_._/ k._.._
feature phthalocyanine green at all shade depths. Approxi-
PO 5 O2N--/{'I~"k7-- N= N --~/("~~ mately 50% of the worldwide production of copper ph-
thalocyanine green is consumed by the coatings industry.
Miscellaneous Greens
DinitroanilineOrange Table 7 gives a brief summary of the properties of other
commercially available organic green pigments that may find
some use in the coatings industry. Such inorganic greens as
Brunswick Green (PG 15) and Phthalo Chrome Green (PG
PO 13 N CH--N=N 13), widely used in industrial coatings, are now being re-
',\C/ placed by the more economic organic greens such as ph-
I
CHa 2 thalocyanine green.
Pigment Greens 1, 2, and 4 are triphenyl-methane-based
PyrazoloneOrange
dyes complexed with phospho tungsto molybdic acid (PTMA)
to allow their use as pigments. Their fastness properties are
I CH3 -~ inadequate for most paint applications.
coo., I Pigment Green 8, the bisufite complex of 1-nitroso-2-naph-
PO 16 NH-- C-- CH--N=N ~ _ / / ~
thol reacted with ferrous sulfate and then with sodium hy-
O ~2 droxide is one of the oldest chelate-based pigments that
DianisidineOrange maintains some minor commercial significance as a colorant
for cement. Exhibiting excellent alkali stability this pigment
suffers from poor acid fastness.
-H3C~F- N C #O Cl -] Pigment Green 10, Nickel Azo Yellow, or Green Gold is the
most lightfast azo pigment currently in commercial produc-
PO 34
tion, being lightfast at all range of shade from deep tones to
pale tints. The pigments does, however, show poor overstripe
fastness when used in baking enamels.
Toly!Orange
Health and Environmental Concerns
CI HO C--NH NHCOCH3 The majority of pigments used within the coatings industry
are classified as "nuisance dusts" under controlling OSHA
PO 38 standard 29 CFR 1910.1000 with an 8-h time-weighted aver-
age exposure tolerance of 15 mg/m 3. Most pigments dealt
with in this chapter can be handled in the workplace using
o normal standard practices of good industrial hygiene as asso-
ciated with dusty products. However, there are instances
NaphtholOrange
which call for specific comment since additional information
is available or more specific handling controls are required.
Calcium and Barium Lithol Red, Lithol Rubine, and the
BON Reds have each been tested extensively for any toxic
PO 46 C l ~ N=N Ba2" properties. The LDs0 (rat) for each was estimated at greater
than 5000 mg/kg. The pigments are classed as nonhazardous
SO a - ~ as defined by OSHA 29 CFR 1916.25 and not toxic as defined
by FHSA 16 CFR 1500.3. BON Maroon has an oral LDs0 (rat)
ClarionRed of 10 g/kg. Additionally, in vitro screening tests for muta-
FIG. 2 3 - S t r u c t u r e s of the a z o - b a s e d oranges. genicity proved negative.
Toxicological results for both Pigment Violet 19 and Pig-
ment Red 122 have been reported. Both pigments exhibited
an oral LDs0 (rat) of 5000 mg/kg or higher. The pigments are
thus classified as "non-toxic" under FHSA 16 CFR 1500:3.
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CHAPTER 2 1 - - C O L O R E D ORGANIC PIGMENTS 205
O
II CI
~O
~---------~
N%C~-- C\
PO 43 N
PO 51
o~ ~
Perinone
0
Pyranthrone Orange
O O O CI CI
H II H II II
CI~--CI CHa
II H II II H
0 0 0
PO 48
and PO 61 CI--~CI
PO 49
Quinacridone / Quinacridone Quinone CI CI
(Ratio determines pigment type)
Tetrachloroisoindolinone
FIG. 24-structures of the miscellaneous oranges.
cI cI
PigmentGreen7 C I ~ CI
N=C //C--N
TABLE 6--Properties of the miscellaneous orange pigments.
c, I --. II c,
Colour Index Name Properties
PO 43 Perinone. Red shade. Strong clean vat
pigment with excellent fastness properties. CI / ' ~ "C : C~ " ' ~ ~'Cl
Used in metallized finishes and high grade
paints. Shows slight solvent bleed
c j If
Br Br N=C C--N
PO 48 Quinacridone gold. Yellow shade. Excellent
lightfastness. Lacks brightness in
CI ~ Cl
Pigment C I ~
masstone. Used in metallic finishes Green36~6Y
N=C .~C--N CI CI
PO 49 Quinacridone deep gold. Red shade. Dull Br I \N ~ II
masstone. Excellent durability. Used in ! ~ II r
metallics
PO 51 Pyranthrone orange. Medium shade. Br ~ /

(3 ..c ~ . . . r ~ Br
Excellent solvent, light, and heat fastness. I .-N.. LI
Dull in tint. Exhibits slight solvent bleed. N= C C-- N Br Br
Used in air dry and bake enamels
PO 52 Pyranthrone orange, red shade. Vat

pigment with excellent solvent, light, and
heat fastness. Dull in tints. Slight solvent
N~C C--N
bleed. Used in air dry and bake enamels
Br - , y ~ ' - ~ C"-. --i /c~CI
PO 61 Tetrachloroisoindolinone orange. Medium i I /N--Cu--N II t
shade. Exhibits some solvent bleed. Used
in metallic automotive finishes
c, I II
PO 64 Bright red shade. Excellent solvent and N~C C--N
lightfastness. Used in industrial coatings Pigment
Green36-3Y CI
PO 67 Yellow shade. Excellent brilliance in full
shade. Good gloss retention. Very good Br Br
weather and light fastness in full shade. FIG. 25-Proposed structures for phthalocyanine greens (PG
Used in industrial and automotive coatings
7 and PG 36),
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TABLE 7--Properties of the miscellaneous commercial green m e n t s to the p a r e n t amine, 3,3'-dichlorobenzidine, d u r i n g

pigments. metabolism.
Colour Index Both O r t h o n i t r o a n i l i n e Orange a n d Dinitroaniline Orange
Name Chemical Name Properties are c o n s i d e r e d to have an oral LDs0 of greater t h a n 5000
PG 1 Brilliant Green Brilliant, blue shade. Poor mg/kg (rat) a n d are therefore classified as "non-toxic" as de-
(Triphenylmeth- alkali and soap resistance, fined b y FHSA 16 CFR 1500.3 a n d as "not h a z a r d o u s " u n d e r
ane PTMA) solvent bleed, and OSHA 29 CFR 1916.3. Both p i g m e n t s meet the heavy m e t a l
lightfastness. May be used
in interior finishes content specification u n d e r USAST Z66.1-1964 m a k i n g their
use in toy enamels a n d crayons acceptable.
PG 2 Permanent Green Blend of Pigment Green 1 and P i g m e n t Orange 46 contains 15% b a r i u m as p a r t of its
(Triphenylmeth- Pigment Yellow 18. Bright c h e m i c a l m a k e u p a n d a s such m u s t be checked for w a t e r
ane PTMA) yellow shade. Poor fastness
overall soluble b a r i u m u n d e r ANSI Z66.1 p r i o r to it b e i n g used in toy
e n a m e l s a n d s i m i l a r coatings.
PG 4 Malachite Green Bright, blue shade. Poor The LDs0 for p h t h a l o c y a n i n e greens has b e e n shown to be
(Triphenylmeth- fastness properties overall in excess of 2000 mg/kg a n d the p i g m e n t s can, therefore, be
ane PTMA)
a s s u m e d as not h a r m f u l b y ingestion. N i n e t y - d a y feeding
PG 8 Pigment Green B Yellow shade. Dull hue. Poor trials with b o t h rats a n d mice s h o w e d no adverse effects n o r
(Nitroso) fastness properties. May be evidence of a d s o r p t i o n of the pigment. Mutagenicity tests
used in interior emulsions have also proved negative. Concerns a b o u t the c o n t a m i n a t i o n
Yellow shade. Loses metal in of p h t h a l o c y a n i n e greens with p o l y c h l o r i n a t e d biphenyls
PG 10 Green Gold
(Nickel azo strong acid or alkali. Good (PCBs) have all b u t d i s a p p e a r e d with p i g m e n t s m a n u f a c t u r e d
complex) lightfastness. Moderate within the United States due to today's m u c h i m p r o v e d m a n -
solvent fastness. Used in ufacturing techniques, easily m e e t i n g the 25-ppm limit im-
automotive and exterior p o s e d in the United States.
paints
Testing o f Pigments for Use in Coatings

Additionally, the p i g m e n t s are classified as being "non-haz-
ardous" as defined b y OSHA 29 CFR 1916.25. M a n y tests can be a p p l i e d to a p i g m e n t to assess its suit-
Both the disazo c o n d e n s a t i o n p i g m e n t s a n d the novel high- ability in a coatings formulation. However, it is of p a r a m o u n t
p e r f o r m a n c e reds have such low b i o d e g r a d a b i l i t y t h a t they i m p o r t a n c e that the f o r m u l a t o r is satisfied that the tests have
do n o t pose a n y significant risk to either health or to the a clear relationship to the end use of the coating. It is
environment. pointless to evaluate a p i g m e n t s interior p e r f o r m a n c e only to
t h e n use the p i g m e n t in an exterior application. F o r a pig-
In the 1970s it was discovered that the use of tri-
m e n t to be merely the shade a n d opacity as r e q u i r e d b y the
c h l o r o b e n z e n e as a solvent in the m a n u f a c t u r e of c o p p e r ph-
c u s t o m e r is not an a d e q u a t e safeguard that the p i g m e n t will
t h a l o c y a n i n e crude resulted in the f o r m a t i o n of poly chlori-
p e r f o r m as expected once the p r o d u c t is e m p l o y e d in its
n a t e d biphenyls (PCBs), principally hexachlorobiphenyl.
i n t e n d e d end use. In today's marketplace, m o r e t h a n any
More m o d e r n m a n u f a c t u r i n g techniques n o w p r o d u c e a
o t h e r t i m e in the past, with quality relationships being of
crude with levels of PCBs significantly b e l o w the 25 p p m
such c o m m e r c i a l significance, it is vital t h a t the u s e r a n d
m a x i m u m required by the E n v i r o n m e n t a l Protection Agency
s u p p l i e r have a full u n d e r s t a n d i n g of w h a t is expected of any
(EPA).
coatings f o r m u l a t i o n that is in c o m m e r c i a l production. The
The N a t i o n a l Toxicological P r o g r a m e x a m i n e d c o p p e r ph-
coatings business is u n d e r c o n s t a n t change a n d review a n d it
t h a l o c y a n i n e blue in their long-term b i o a s s a y p r o g r a m , a n d
is in this a t m o s p h e r e of change t h a t care m u s t be taken to
in an a l m o s t u n p r e c e d e n t e d move the p i g m e n t was with- ensure "fitness for use" of any colored organic p i g m e n t is fully
d r a w n from further testing after only 90 days since it failed to explored.
exhibit a n y toxic characteristics d u r i n g this time period. M a n y types of test will be r u n on a p i g m e n t that are not
Both P i g m e n t Yellow 1 a n d 74 have b e e n assessed as nega- specific to an a p p l i c a t i o n b u t w h i c h are a p r o p e r t y of the
tive w h e n evaluated in "in vitro" screening tests for muta- p i g m e n t in question a n d which need to be k n o w n in spite of
genicity. the end use application.
The industrial h a n d l i n g of diarylide yellows has been the
subject of considerable investigation as a result of the rela- Color and Tint Strength (ASTM D 387-60)
t i o n s h i p of the 3 , Y - d i c h l o r o b e n z i d i n e to the k n o w n carcino- The m o s t obvious p r o p e r t y of a p i g m e n t is its hue, that is,
gen, benzidine. As a result, in the United States, 3,3'-di- its color as being distinctly blue, yellow, green, red, etc. a n d
c h l o r o b e n z i d i n e a n d its salts are classified as a n "industrial the finer detail t h a t distinguishes a green shade blue from a
substance suspected of carcinogenic potential for m a n " by r e d shade blue. The o t h e r tinctorial p r o p e r t i e s m a y be taken
the ACGIH a n d as a "cancer suspect agent" by the OSHA (Std. as those t h a t are significant w h e n the p i g m e n t is used in full
29 CFR 1910.1007). tone a n d those of significance w h e n the p i g m e n t is used in
I n a r e p o r t of h e a l t h studies on diarylide yellow pigments, r e d u c e d shades after diluting the full shade with a n o p a q u e
no carcinogenicity was r e p o r t e d from P i g m e n t Yellow 12, 16, white.
or 83 in a two-year feeding study using rats a n d mice. An oral Evaluation of any p i g m e n t m u s t include a test of full color
feeding study using rabbits s h o w e d no r e d u c t i o n of the pig- or m a s s t o n e t h a t requires inspection of the pigment,
www.iran-mavad.com

u n d i l u t e d w i t h white, b u t fully d i s p e r s e d in a m e d i u m that Paint a n d Related Coatings a n d Materials Using Filtered

has relevance to the coatings formulation. I n s p e c t i o n of this O p e n - F l a m e Carbon-Arc Light a n d W a t e r E x p o s u r e A p p a r a -
full color shows the hue, intensity, t r a n s p a r e n c y , cleanliness, tus) to assess the pigment's b e h a v i o r in accelerated exposure
a n d jetness of the pigment. C o m p a r i s o n of this using side-by- using the "Blue Wool Scale" to calibrate the m e a s u r i n g equip-
side evaluation with a s t a n d a r d or specification full color will m e n t (B.S. 1006).
show h o w close the test p i g m e n t comes to the standard. The
full color can t h e n be tinted with a white base such as one Exposure Testing
m a d e f r o m t i t a n i u m dioxide to enable the pigment's tinting It is n o w generally a c c e p t e d within the coatings i n d u s t r y on
strength to be assessed against a previously a p p r o v e d stan- a w o r l d w i d e basis that the true test of a h i g h - p e r f o r m a n c e
d a r d o r control. S u c h a tint is k n o w n a bleached, timed, o r p i g m e n t is t h r o u g h p r o l o n g e d o u t d o o r exposure at specifi-
r e d u c e d d r a w d o w n or display. cally chosen sites in the state of Florida. To this end, m a n y
c o m m e r c i a l e s t a b l i s h m e n t s exist in the state t h a t will provide
Oil Absorption (ASTM D 281-31) a controlled service to expose s p r a y e d panels of p i g m e m e d
A b r o a d definition of oil a b s o r p t i o n is the a m o u n t of an oil coatings angled in a p r e d e t e r m i n e d w a y t o w a r d s the sun for
or vehicle w h i c h p r o d u c e s a u n i f o r m p a s t e w h e n t h o r o u g h l y p e r i o d s up to five years with assessments at intervals d u r i n g
i n c o r p o r a t e d with the test pigment. F o r s t a n d a r d p u r p o s e s it this five-year period. Typically m a n y duplicate panels will be
is the a m o u n t of refined linseed oil, by either weight o r vol- exposed p e r test with a panel being r e t u r n e d to the formula-
ume, necessary to p r o d u c e a coherent paste from 100 g of d r y tor every six m o n t h s such t h a t a m e a s u r e of the system's
pigment. Since the transition p o i n t of going from a p a r t i a l l y w e a t h e r a b i l i t y as a function of t i m e is m a i m a i n e d on r e c o r d
wetted p o w d e r to an c o h e r e n t paste is not a d e a f l y defined for each p i g m e n t a n d each system used in o u t d o o r situations.
measure, this test will always be subject to differences be-
tween labs a n d technicians as to w h e n the test's end p o i n t is Specific Gravity (ASTM D 153: Test Methods for
reached. The figure for oil a b s o r p t i o n is used b y m a n y coat- Specific Gravity of Pigments)
ings f o r m u l a t o r s to give an i n d i c a t i o n of w h a t effect different Defined as the m a s s of a given volume of a substance as
p i g m e n t s will have on the flow p r o p e r t i e s of the system a n d to c o m p a r e d to the m a s s of an equal volume of w a t e r at a
calculate the p i g m e n t l o a d i n g limits. The values are essen- prespecified t e m p e r a t u r e , the specific gravity of a p i g m e n t is
tially a m e a s u r e of particle shape, as a p s e u d o s p h e r i c a l parti- used to arrive at a b u l k density or "bulking volume" of the
cle will have a lower oil a b s o r p t i o n t h a n an a n i s o t r o p i c parti- pigment. This is a subjective test that c a n n o t be exactly com-
cle. p a r e d b e t w e e n technicians a n d b e t w e e n laboratories.
Bleed Test (ASTM D 279-73)

This test gives an i n d i c a t i o n of the extent to w h i c h the REFERENCES
p i g m e n t will dissolve, however minutely, in the solvents the
p i g m e n t is likely to be exposed to during its use. AdditiOnally, [1] NPIRI, Raw Materials Data Handbook, Vol. 4: Pigments, 1983, p.
an overstripe test can be i n c o r p o r a t e d w h e r e the coating 6.
containing the p i g m e n t u n d e r test is overstriped with a white [2] ColourIndex, American Association of Textile Chemists and Col-
p a i n t a n d allowed to dry. The extent of the d i s c o l o r a t i o n of orists, Research Triangle Park, NC, 27709, 1980. Pigments sup-
the white is an i n d i c a t i o n of the pigment's overstripe bleed. plementary volume.
An a t t e m p t can be m a d e to quantify this bleed b y use of the
"Grey Scale for Assessing Change in Color" (B.S. 2662) w h e r e
the bleed is r a t e d from 5, representing no visible bleed, to 1, BIBLIOGRAPHY
r e p r e s e n t i n g c o n s i d e r a b l e bleed.
American Association of Textile Chemists and Colorists, Research
Fastness Tests Triangle Park, NC, 27709.
The t e r m "fastness" is used in this context to relate to h o w Dry Color Manufacturers Association, North 19th St, Arlington, VA,
22209.
susceptible o r d u r a b l e a p i g m e n t is to the p a r a m e t e r u n d e r
Ehrich, F. F., "Pigments," in Encyclopedia of Chemical Technology,
test. As such, the p i g m e n t s fastness to light, heat, solvents, Vol. 15, John Wiley & Sons, New York, 1968.
etc. can all be m e a s u r e d a n d quantified using a "Fastness Fytelman, M., "Pigments," in Encyclopedia of Chemical Technology,
Scale" w h i c h rates a p i g m e n t from 1 (poor) to 5 (excellent) in 3rd ed., Vol. 15, John Wiley & Sons, New York, 1978.
all cases except lightfastness w h i c h is subdivided i m o 1 Geissler, G., Polymers Paint and Colour Journal, 30 Sept. 1981, pp.
t h r o u g h 8, 1 being total failure to 8 being outstanding. 614-623.
Among those p r o p e r t i e s i m p o r t a n t to the f o r m u l a t o r are Hopmeir, A. P., "Pigments," Encyclopedia of Polymer Science Tech-
fastness to solvents, where bleeding is observed by allowing a nology, Vol. 10, Interscience, New York, 1969, pp. 157-193.
q u a n t i t y of the d r y p i g m e n t to stand for 24 h in contact with a Lewis, P. A., "Pigment Handbook," Vol. 1, 2nd ed., John Wiley &
solvent a n d observing any d i s c o l o r a t i o n of the solvent that Sons, New York, 1987.
Lewis, P. A., "Organic Pigments," FSCTMonograph Series, Philadel-
occurs, fastness to heat, w h e r e the effect of stoving t e m p e r a -
phia, PA, 1988.
tures on the p i g m e n t f o r m u l a t e d into a finished coating are Lewis, P. A., "Organic Pigments," Coatings Technology Handbook,
observed, fastness to acidic or alkaline e n v i r o n m e n t s a n d Marcel Dekker, Inc., New York, 1991.
fastness to light, where several tint levels of a f o r m u l a t i o n are Lubs, H. A., "The Chemistry of Synthetic Dyes and Pigments," ACS
exposed in such artificial sources as the X e n o n o r c a r b o n arc Monograph, No. 127, American Chemical Society, Reinhold, New
f a d e - o m e t e r (ASTM D 822: Practice for Conducting Tests on York, 1955.
www.iran-mavad.com

Muzall, J. M. and Cook, W. L., Mutagenicity Research, Vol. 67, Else- Patton, T. C., Pigment Handbook, 3 volumes, John Wiley & Sons,
vier Press, Amsterdam, 1979, pp. 1-8. New York, 1973.
Moser, F. H. and Thomas, A. L., "Phthalocyanine Compounds," ACS Patton, T. C., Paint Flow and Pigment Dispersion, Interscience, New
Monograph No. 157, American Chemical Society, Reinhold, New York, 1964.
York, 1963. Patterson, D., "Pigments, An Introduction to Their Physical Chemis-
try," Elsevier, Amsterdam, 1967.
Mills, W. G. B., Paint Chemists Handbook, Scott Greenwood, Lon-
Parfitt, G. D., Dispersion of Powders in Liquid, 3rd ed., Applied Sci-
don, 1962.
ence, London, 1981.
NPIRI Raw Material Data Handbook, Vol. 4, "Pigments," Lehigh Remington, J. S. and Francis, W., Pigments: Their Manufacture, Prop-
University, Bethlehem, PA, 1983. erties and Use, Leonard Hill, London, 1954.
NPCA Raw Materials Index, Pigments Section, Washington, DC Venkataraman, K., The Chemistry of Synthetic Dyes, Academic Press,
20005. New York, 1952.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Inorganic Colored Pigments

by Peter A. L e w i s 1
C L A S S I F I C A T I O N OF I N O R G A N I C 1. By calcining iron sulfates.

P I G M E N T S BY C H E M I S T R Y
12FeSO4.H20 + 302 >2Fe203 + Fe(SO4)3 + 12H20
BROADLYSPEAKING,the colored inorganic pigments are either 2. From synthetic black oxide by calcining the material in a
lead chromates, metal oxides, sulfides, or sulfoselenides with controlled atmosphere containing oxygen.
a few miscellaneous pigments such as cobalt blue, ultrama-
4FeO.Fe203 + 02 ) 6Fe203
rine blue, iron blue, and bismuth vanadate yellow. This sec-
tion describes the chemistry, manufacture, and properties of 3. Precipitated red oxide can be prepared in an aqueous me-
each of these classes of inorganic pigments. Inorganic whites dium by growing seed nuclei in the presence of a ferrous
such as zinc oxide, titanium dioxide, lithopone, and zinc salt and scrap steel, the lightness/darkness of the resulting
sulfide, while pigmentary in nature and most definitely a part pigment being determined by the crystal size distribution
of the coatings industry, fall outside of the scope of this of the precipitate.
chapter. 4. By calcining synthetic yellow iron oxide to give the dehy-
By chemistry inorganic pigments can be subdivided as drated product, Fe203.
shown in Table 1. In addition to the inorganic pigments listed The wide range of red iron oxide shades available, in addi-
in Table 1, there also exist a series of pigments classed as tion to their acid and alkali resistance and their economy,
mixed metal oxides such as, for example, zinc iron chromite accounts for the large volume of these pigments used in
brown (PBr 33), cobalt chromite green (PG 26), cobalt tita- today's coatings marketplace.
nate green (PG 50), and cobalt aluminate blue (PB 28 and PB
36). These types of inorganic pigments are sometimes also
called ceramic colors because of their widespread use in the Molybdate Orange
ceramics industry. Since they are covered in the next chapter This pigment is, in fact, Pigment Red 104, a very yellow
of this book, no additional consideration will be given to shade of red that has the common name of molybdate orange,
these colors in this chapter. a pigment based upon oxides of lead, chromium, and
molybdenum with the empirical formula of PbCrO4.
xPbMoO4.yPbSO4, a solid solution of lead chromate, lead mo-
C L A S S I F I C A T I O N OF P I G M E N T S BY COLOR lybdate, and lead sulfate.
Molybdate orange is produced by the addition of a solution
Most likely, when searching for a color to fulfill a particular of sodium chromate, sodium molybdate, and sodium sulfate
specification, the coatings formulator is likely to begin the under carefully controlled conditions into a solution of lead
search on the basis of color rather than chemistry. Accord- nitrate at a temperature between zero and 40~ to precipitate
ingly, the remainder of this section will concentrate on the the mixed crystal. Control of particle size, particle-size distri-
classification of inorganic pigments based upon their color bution, and crystalline shape combine to determine the ac-
rather than their chemistry. tual hue of the pigment, from a red shade of yellow to a red
shade of orange with specialty hues such as "chili red."
An opaque pigment with high solvent fastness, moderate
Reds
heat fastness, and good economy, molybdate orange finds its
Iron Oxide Reds major outlet in the coatings industry, particularly industrial
Available as both natural and synthetic products, these pig- finishes. On the negative side, the pigment has poor alkali and
ments also carry such names as haematite, Mars Red, Ferrite acid resistance; nontreated grades also tend to darken mark-
Red, Rouge, Turkey Red, and Persian Gulf oxide. edly on prolonged exposure to the environment. Additionally,
Synthetic iron oxide makes up the largest volume of manu- the pigment is based upon lead, which has been under an
factured iron oxides and is produced by one of four major "environmental cloud" for some years, a fact which has re-
syntheses: sulted in molybdate orange being replaced by more expen-
sive, but less toxic, organic reds in decorative paints and
1Coatings Industry Manager, Sun Chemical Corp., Colors Group, almost all original equipment manufacturer (OEM) automo-
Cincinnati, OH 45232. tive paints made in the United States.
209
www.iran-mavad.com

TABLE 1--Summary of colored inorganic pigments. CdS.xCdSe.yBaSO4

LEAD CHROMATES Cadmium red features excellent stability to heat, alkali,
Pigment Yellow 34 Primrose, medium and dark
PbCrO4.xPbSO4 solvents, and light when used at high tint and masstone
chrome yellow
levels. The pigment offers the formulator a clean bright red
Pigment Red 104 Molybdate orange with high chroma. Use of the pigment in a reduced form as a
PbCrO4.xPbSO4.yPbMo04 light tint is not recommended since the durability will suffer
at weak tint levels.
Pigment Orange 21 Light and dark chrome orange
PbO-xPbCrO4
Mercury Cadmium Red
Pigment Green 15 Chrome green (mixture of lead Pigment Red 113 is yet another calcined co-precipitate. It is
PbCrO4.xPbSO4-yFeNH4Fe(CN)6 chrome and iron blue) mercuric sulfide co-precipitated with cadmium sulfide to give
METAL OXIDES a pigment with the empirical formula CdS.xHgS, offering
Pigment Yellow 42 Yellow iron oxide--synthetic good hiding properties and good solvent resistance with ex-
Pigment Yellow 43 Yellow iron oxide--natural cellent brightness, but the pigment's inferior heat and acid
Fe203.xH20 resistance when compared to Pigment Red 108 has limited its
Pigment Red 101 Red iron oxide--synthetic use in coatings applications.
Pigment Red 102 Red iron oxide--natural
FeaO3
Violets
Pigment Brown 6 Brown iron oxide--synthetic Technically blue shade reds, the two most important inor-
Pigment Brown 7 Brown iron oxide--natural
Fe203 ganic violet pigments are Pigment Violet 15, ultramarine
violet, prepared by the oxidation of ultramarine blue, Pig-
Pigment Green 17 Chromium oxide green ment Blue 29, and Pigment Violet 16, manganese violet, pre-
Cr203 pared when manganese dioxide and diammonium phosphate
Pigment Green 18 Chromium oxide green, are slurried at high temperatures in phosphoric acid.
Cr203.2H20 hydrated Ultramarine violet has good heat and light fastness and a
brilliant red shade. The pigment will react with metals to
SULFIDESAND SULFOSELENIDES form sulfides and finds use in cosmetic applications and spe-
Pigment Yellow 35 Lithopone, cadmium yellow cialty acrylic poster paint and artists colors.
CdS.xZnS.yBaSO4
Manganese violet does not possess the same brightness of
Pigment Yellow 37 Cadmium yellow hue as Pigment Violet 15 and has only moderate opacity and
CdS poor alkali resistance. On the plus side, the pigment has high
lightfastness and superior fastness to solvents and overstripe
Pigment Orange 20 Cadmium lithopone orange
CdS.xCdSe.yBaSO4 bleed. Major uses are in the plastics and cosmetics industry.
Pigment Red 108 Cadmium red

CdS-xCdSe Blues
MISCELLANEOUSTYPES
Iron Blue
Pigment Blue 27 Iron or milori blue Also known as Prussian Blue and Milori Blue, this pigment
Fe(NH)4Fe(CN)6.xH20 is manufactured by reacting ferrous sulfate and sodium fer-
rocyanide in the presence of ammonium sulfite to yield a
Pigment Blue 28 Cobalt blue
COA1204 leucoferricyanide called Berlin White, which is then isolated
and dissolved in sulfuric acid and oxidized with sodium chlo-
Pigment Blue 29 Ultramarine blue rate to yield iron blue.
Na6_sa16si602452_4
Na4Fe(CN) 6 + FeSO 4 + (NH4)2SO4 >
Pigment Violet 16 Manganese violet Fe(NH4)2Fe(CN)6 + 2Na2SO4
MnNH4P207 (Berlin white)
Pigment Yellow 184 Bismuth vanadate/molybdate 6Fe(NH4)2Fe(CN)6 + 3H2SO4 + NaC103
4BiVO4.3BiaMoO6 yellow
6FeNH4Fe(CN) 6 + NaC1 + 3(NH4)2SO4 + 3H20
Differing grades of iron blue exist that offer varying
Cadmium Red masstone, strength, oil absorption, and dispersion character-
istics. Chinese Blue, for example, offers a greener undertone,
Cadmium sulfoselenide red, Pigment Red 108, is a solid
whereas Bronze Blue features a surface bronziness effect that
solution of cadmium sulfide and cadmium sulfoselenide pro-
varies dependent upon the viewing angle.
duced by calcining co-precipitated cadmium sulfide and sul- Iron blue offers good resistance to weak acids but markedly
foselenide, the pigment's hue is determined by the amount of poor resistance to even mild alkali; furthermore, the pigment
cadmium sulfoselenide incorporated into the solid solution has a tendency to "bleach out" on storage, losing almost all its
and, to a lesser extent, the temperature of processing. Pig- color when incorporated into a paint formulation that con-
ment Red 108:1 is a co-precipitate with barium sulfate hav- tains oxidizable vehicles such as linseed oil. The pigment has
ing the empirical formula only acceptable lightfastness properties when used at
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CHAPTER 22--INORGANIC COLORED PIGMENTS 211
masstone levels; extension of the paint with a white such as mate onto barium sulfate to give an extended pigment that
titanium dioxide gives a weak blue tint that will rapidly fade carries the Colour Index name of Pigment Yellow 36: 1.
on exposure. Used primarily in corrosion-inhibiting coatings, its poor
tinctorial strength and poor resistance to acid and alkali se-
Ultramarine Blue verely limits this pigment's use elsewhere.
Going by such varied common names as Laundry Blue,
Dolly Blue, and lapis lazuli, this pigment, made by the con- Cadmium Zinc Yellow
trolled grinding of a mixture of calcined kaolin, soda ash, Yet another solid solution, Pigment Yellow 35 is a cad-
sulfur, coal, and sodium sulfate, is Pigment Blue 29. Empiri- mium solution co-precipitated with zinc sulfide. Calcination
cally the product is Na6A16Si6024S4, and its major use is as a of this product gives pure cadmium zinc sulfide, CdS.xZnS.
component of laundry powders and detergent soaps. Less The hue is readily altered by varying the ratio of the two
than 5% of the production is used in the coatings industry for components of this solid solution. Levels of zinc sulfide of 14
interior emulsion paints that require high alkali resistance to 21% give a green or primrose shade, while 1 to 7% gives a
and lightfastness. redder shade achieving a golden hue. Incorporation of bar-
ium sulfate during manufacture produces a lithopone ver-
Yellows sion, Pigment Yellow 35 : 1.
Cadmium zinc yellows offer bright, clean, opaque pig-
Strontium Yellow ments with excellent resistance to heat, light, and strong
Strontium chromate, SrCrO4, prepared by precipitating a solvents. Their poor fastness to mineral acids and marked
suitably soluble chromate with an appropriate strontium salt, tendency to fade when used at low tint levels limits their use
is Pigment Yellow 32. Finding a primary use in corrosion- within the coatings industry.
inhibiting coatings, this pigment has poor tint strength, low
opacity, and unsatisfactory alkali and acid resistance, which Cadmium Sulfide Yellow
limits its more widespread use in the coatings industry. Calcined calcium sulfide, CdS, is identified in the Colour
Index as Pigment Yellow 37. This pigment can be produced
Chrome Yellow with hues ranging from a green shade to a very red shade by
A co-precipitate of lead sulfate and lead chromate, Pigment simply varying the calcination conditions. Offering excellent
Yellow 34 has the empirical formula PbCrO4.xPbSO 4. Vari- stability to heat, light, acids, and alkali, this pigment's only
ous types exist that differ in the ratio of the lead sulfate to the major drawback is its tendency to fade in the presence of
lead chromate and as such are described as medium chrome, moisture.
primrose, and lemon chrome yellows. A typical primrose
chrome will contain 23 to 30% lead sulfate in the solid solu- Iron Oxide Yellows
tion of the co-precipitate, whereas a medium chrome will As with most of the commercially available iron oxides, this
contain 0 to 6% lead sulfate. During manufacture, proprie- pigment can be obtained as the natural grade, Pigment Yel-
tary techniques are employed such that the orthorhombic low 43, or the synthetic variant, Pigment Yellow 42.
crystal form is produced almost exclusively in preference to The natural yellow oxides, FeO.xH20, will also contain clay
the unstable monoclinic form. and various other minor minerals. Available under several
Many different grades of this type of pigment are available names, often related to the country of origin or the pigment's
to offer such improvements in properties as better chemical history, the natural yellow oxide is also called Indian Ochre,
resistance, decreased tendency to darken on exposure, im- Ocher, Sienna, and limonite.
proved weathering, and as a silica-encapsulated product to The synthetic oxide is produced by direct precipitation us-
minimize solubility of the lead contained within the pigment. ing a m m o n i u m hydroxide and ferrous sulfate, via the
Primrose chrome exhibits a very green shade and offers Penniman-Zoph process using scrap steel and a ferrous salt
good lightfastness, high opacity, and low theology coupled to grow seed particles or by the aniline process where nitro-
with economy of use. The coatings industry, closely followed benzene is reacted with metallic iron to produce iron oxide
by the ink and plastics industry, is the largest consumer of and aniline. The synthetic product has the empirical formula
primrose chrome. Medium chrome is used widely in road- Fe203-xH20, irrespective of the manufacturing process.
marking paints in the United States where the law requires a Iron oxide yellows are economical pigments with excellent
yellow marking line as opposed to white. Grades that have lightfastness, weatherability, opacity, and flow properties. On
been pre-darkened by the use of antimony during the precipi- the downside, they are dull in masstone and exhibit only fair
tation stage offer much increased stability to weathering tinctorial strength and moderate baking stability at best. It is
since these grades will not darken further on exposure to their value in use that has resulted in their widespread accep-
sulfur in the atmosphere. tance throughout the coatings industry.
Zinc Chromate Bismuth Vanadate/Molybdate Yellow
Also called zinc yellow, this pigment is identified as Pig- The most modern of the inorganic pigments discussed in
ment Yellow 36, as opposed to the lithopone version incorpo- this section, Pigment Yellow 184, was introduced into the
rating barium sulfate which is Pigment Yellow 36: 1. It is a marketplace in 1985. Manufactured by dissolving bismuth
bright, green shade of yellow made by the precipitation of nitrate, sodium vanadate, and sodium molybdate in nitric
hydrated zinc potassium chromate from the reaction of so- acid followed by the precipitation of a complex mixture of the
dium bichromate with zinc oxide and potassium chloride. metals, the precipitate is calcined to give a polycrystalline
The lithopone version is merely a co-precipitate of zinc chro- product, 4BiVO4.3Bi2MoO6. It is a green shade of yellow used
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principally for a brilliant solid shade in both automotive Chromium Oxide Green
and industrial coatings. The pigment has excellent Pigment Green 17 is a pure, calcined chromium oxide,
weatherfastness coupled with good hiding power and gloss Cr203, manufactured by reduction of sodium bichromate
retention. Earlier grades suffered from the unusual phenom- with carbon or sulfur:
enon where the color under shadows would darken only to
lighten again once the shadow was removed. More stable Na2Cr207 4- 2C ) CO + N a 2 C O 3 -k Cr203
grades introduced recently do not suffer this drawback. This pigment has a unique use in camouflage paints because
of its ability to reflect infrared light. Otherwise, the product
finds a use where its price can be justified by the resultant
Oranges excellent light and chemical resistance properties the pig-
ment features.
Chrome Orange
A basic lead chromate, Pigment Orange 21, is formed under
alkaline conditions to give a product of empirical formula Hydrated Chromium Oxide Green
PbCrOg.xPbO, shades varying from a yellow shade to red Also known as Viridian Green or Guignets green, Pigment
shade dependant upon the alkalinity maintained during the Green 18 is a hydrated chromic oxide of formula Cr2Oa.2H2O
reaction sequence. from the hydrolysis of the product produced by calcining
As with all lead-containing pigments, the product will sodium bichromate with boric acid. The pigment is a bright,
darken on exposure to the atmosphere, the rate dependant blue shade green with high chroma and outstanding fastness
upon the sulfur content. The pigment offers low cost and properties in both masstone and deep tints.
moderate lightfastness and finds use in the protective coat-
ings marketplace with some use as a shading pigment for
road traffic paints.
Browns
Cadmium Orange Natural Iron Oxides
Pigment Orange 20, cadmium sulfoselenide orange, is a
This is mined from either iron oxide mines operating prin-
solid solution produced by calcining cadmium selenide with
cipally to supply ore as feedstock for blast furnaces with a
cadmium sulfide at approximately 1000~ (1800~ A change
small offtake directed to the pigment industry or pigment
in the ratio of the solid solution components gives pigments
mines which operate solely to supply pigmentary grade ore.
that are bright yellow (PY 35) to bright red (PR 108). Barium
Typically the mined ore is slurried in an aqueous suspen-
sulfate added or produced during the processing will form
sion and washed through a series of stages to remove sand
the lithopone grade, Pigment Orange 20: 1.
and clay after which the slurry passes into a separator tank,
This pigment is used in industrial coatings, for color coding
then through a Dorr bowl rake where the iron oxide ore is
applications, where chemical and heat resistance are princi-
pal requirements. separated and dried as a thin layer on a rotary drum drier.
The dried natural ore is then pulverized and classified to
produce pigmentary iron oxide. Pigment Brown 7 is an iron
Cadmium Mercury Orange
oxide brown that is available in shades ranging from light red
This pigment is a solid solution of mercury sulfide in cad- to deep purple brown. Empirically the product is Fe203. Me-
mium sulfide and is identified as Pigment Orange 23. Again, tallic brown is produced from calcined hematite (PR 102) and
various hues can be obtained by controlling the formation of burnt sienna from calcined limonite (PY 43).
the mixed crystal manufactured by precipitating the sulfides Pigment Brown 7 :x is a ferrosoferric oxide derived from
of cadmium and mercury from a solution of their soluble ores containing 25% manganese dioxide with a distinct com-
salts. Again, the final stage is calcination in an inert atmo- position as Fe2Oa.xMnO with varying proportions of clay.
sphere to give an extremely heat stable pigment with excel- Classical names include such as raw umber, burnt umber,
lent chemical resistance, weatherability, and solvent fastness. and Turkish umber.
Synthetic Brown Oxide

Greens
Also known as brown magnetite iron oxide, Pigment
Chrome Green Brown 6 is produced by controlled oxidation of Pigment
These pigments are merely mixtures of a green shade Black 11. Chemically the product may be represented as
chrome yellow (PY 34) and iron blue (PB 27). As such, Pig- Fe2Oa-xFeO.yH20.
ment Green 15 offers a range of hues with a light yellow shade Pigment Brown 11 is magnesium ferrite from the calcina-
to a deep dark shade, providing good hiding, high tint tion of a blend of ferric and magnesium oxides, MgO.Fe203.
strength, and a moderate chemical resistance at an economi- The volume of all types of brown oxides used in coatings is
cal price. It can be used for bake enamels where the bake generally low since most browns are achieved by mixing yel-
temperature does not exceed 148~ (300~ but is restricted low, red, and black pigments. As a class, these pigments have
to exterior and industrial coatings applications as opposed to good chemical resistance and high tint strength and as such
decorative finishes because of its lead content. find some use in wood stains and furniture finishes.
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CHAPTER 22--INORGANIC COLORED PIGMENTS 213
REFERENCE BIBLIOGRAPHY
[1] Gosselin, R. E. and Smith, R. P. et al., Clinical Toxicology of Com- Fetsko, J. M., Ed., Raw Materials Data Handbook, Vol. 4, Pigments,
mercial Products, 5th ed., Williams and Wilkins, Baltimore, 1984, National Printing Ink Research Institute, Lehigh University, Beth-
p. VI 172. lehem, PA, 1983.
Lewis, P. A., Ed., Pigment Handbook, Vol. 1, 2nd ed., John Wiley,
New York, 1988.
Satas, D., Ed., Coatings Technology Handbook, Marcel Dekker, Inc.,
New York, 1991, p. 62.
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MNL17-EB/Jun. 1995
Ceramic Pigments
by Richard A. Eppler 1
C E R A M I C PIGMENTS ARE C O M P L E X MIXTURES of oxygen-contain- temperature calcination [1 ]. The result is formation of a crys-
ing materials that have been calcined at high temperatures to talline matrix of rutile that has the basic chemical formula
form specific crystalline phases [1]. In most cases, oxide raw (Ti,Ni,Sb)O2. The pigment is used for coloring high-perfor-
materials are carefully mixed and then calcined in either mance industrial coatings, wire coatings, vinyl sidings, auto-
batch kilns or continuous calciners [2]. After calcination, they motive and other exterior paints, as well as for roofing, gran-
are ground to the necessary fineness in mills. Micronizers ules, porcelain enamels, and ceramic bodies.
and/or jet mills are used to break agglomerates. The final Chrome-doped rutile is prepared from a mixture of varying
production step involves careful control of the color tone by amounts of titanium (IV) oxide, chrome (III) oxide, and anti-
adjustment with toners. mony (V) oxide by high-temperature calcination [1]. The
Because these pigments are formed at high temperatures, resultant crystalline ruffle matrix has the basic chemical for-
they generally offer superb thermal stability and are relatively mula (Ti,Cr,Sb)O2. The orange-yellow pigment is used for
inert. This results in excellent weathering and light fastness coloring the same systems as nickel-doped ruffle.
properties. Most of these pigments have superior acid and Manganese-doped rutile is prepared from a mixture of vari-
alkali resistance. They are nonmigrating and nonbleeding in ous amounts of titanium (IV) oxide, manganese (II) oxide,
nature and do not interact with polymer systems [3]. and antimony (V) oxide by high-temperature calcination [1].
The principal disadvantage of ceramic pigments is their The resulting crystalline ruffle matrix has the basic chemical
low tinting strength. In addition, some are relatively high in formula (Ti,Mn,Sb)O2. The brown pigment is used for color-
cost. This is particularly true of cobalt-containing pigments. ing the same systems as nickel-doped futile.
Some of these pigments are difficult to disperse. However, the Spinel brown pigments are an example of the 2-4 inverse
recent development of easily dispersed ceramic pigments spinels [4]. The basic pigment is prepared by a high-tempera-
should eliminate this problem, at least for water-based sys- ture calcination of titanium (IV) oxide and iron (II) oxide [1].
tems. A final concern is the inherent hardness of these pig- The resulting crystalline matrix of spinel is brown in color
ments. Their hardness can lead to processing system damage and has the basic chemical formula Fe2TiO4. The spinel phase
through abrasion. When using ceramic pigments, processing permits extensive substitution, within defined limits, with
system components designed for use with abrasive materials other compounds to provide a variety of shades of brown.
should be considered. Modifiers used for substitution include Al203, CoO, Cr203,
The major use of ceramic pigments is for applications such Fe203, MnO, and ZnO. The pigments are used for coloring
as vinyl siding and automotive paints where the product is high-performance industrial coatings, wire coatings, vinyl
thermally cured and then placed in an outdoor setting. sidings, and automotive and other high-quality exterior
paints.
Titanate green and blue-green pigments are also produced
by high-temperature calcination of mixtures of titanium (IV)
oxide, cobalt (II) oxide, nickel (II) oxide, and zinc (II) oxide to
CERAMIC P I G M E N T S U S E D IN ORGANIC form a crystalline matrix of inverse spinel [1 ]. The pigments
PAINTS have the basic chemical formula (Co,Ni,Zn)/TiO 4. The pig-
ments are used for coloring the same systems as the spinel
The major criterion used in selecting ceramic pigments for brown pigments.
organic paints is hardness. The pigments listed in Table 1 and Cobalt blue pigments are crystalline spinels formed by
discussed below are those that can be used in paint process- high-temperature calcination of cobalt (II) oxide and alumi-
ing equipment without causing excessive wear. Property at- num (III) oxide in varying amounts [1 ]. The basic cobalt blue
tributes of the pigments are given in Table 2. All are compat- pigment (CAS 68186-86-7) has the chemical structure
ible with most polymer systems, with manganese-doped CoAl204. The lighter-colored cobalt blue is prepared by addi-
ruffle especially useful when it is necessary to avoid iron. tion of zinc (II) oxide to the ingredients used for the basic
Nickel-doped ruffle, which is often called Sun Yellow, is pigment. The chemical structure of the resultant material
produced from a mixture of various amounts of titanium (IV) (CAS 68186-87-8) is (Co,Zn)Al204. Blue-green shades are pro-
oxide, nickel (II) oxide, and antimony (V) oxide by high- duced by introduction of chromium (III) oxide, partially re-
placing aluminum (III) oxide in the basic cobalt blue system.
1Eppler Associates, 400 Cedar Lane, Cheshire, CT 06410. It has the chemical formula Co(Al,Cr)204. In addition to being
214
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CHAPTER 2 3 - - C E R A M I C PIGMENTS 215
TABLE 1 - - R e c o m m e n d e d ceramic pigments for use in organic paints.

Pigment
Ceramic Pigment Powder Color Color Index/Name CAS Number
Nickel-doped rutile Yellow 77788/Pigment Yellow 53 71077-18-4
Chrome-doped rutile Orange-yellow 77310/Pigment Brown 24 68186-90-3
or maple
Manganese-doped futile Brown 77899/Pigment Yellow 164 68412-38-4
Spinel brown Brown 77543/Pigment Black 12 68187-02-0
Titanate greens and Green 77377/Pigment Green 50 68186-85-6
bluegreens
Cobalt blue Blue (basic) 77346/Pigment Blue 28 68186-86-7
Cobalt-zinc blue Blue (lighter 77347/Pigment Blue 72 68186-87-8
than basic)
Cobalt chromite blue Blue-green 77343/Pigment Blue 36 68187-11-1
Cobalt phosphate violet Purple 77360/Pigment Violet 14 13455-36-2
Manganophosphate violet Purple -.. 10101-66-3
Ceramic black Jet black 77428/Pigment Black 28 68186-91-4
Ceramic black Jet black 66502/Pigment Black 27 68186-97-0
TABLE 2--Properties of recommended ceramic pigments (see Table 1 for color and pigment reference numbers).
Acid/
Ceramic Heat Weathering Light Alkali Hydrolytically Nonmigrating/
Pigment Stability Properties Fastness Resistance Stable Bleed
Nickel-doped High Excellent Excellent Excellent Yes Yes
rutile
Chrome-doped High Excellent Excellent Excellent Yes Yes
rutile
Manganese-doped High Excellent Excellent Excellent Yes Yes
rutile
Spinel brown High Excellent Excellent Good Yes Yes
Titanate greens High Excellent Excellent Excellent Yes Yes
and bluegreens
Cobalt blue-- High Excellent Excellent Excellent Yes Yes
basic
Cobalt zinc blue High Excellent Excellent Excellent Yes Yes
Cobalt chromite High Excellent Excellent Excellent Yes Yes
blue
Cobalt phosphate High Excellent Excellent Excellent No Yes
violet
Manganophosphate High Excellent Excellent ...a No Yes
violet
Ceramic Jet black High Excellent Excellent Excellent Yes Yes
Ceramic Jet High Excellent Excellent Excellent Yes Yes
black--stronger
~Manganophosphate violet has good acid resistance, but poor alkali resistance.
used to color the s a m e systems as the rutiles, the c o b a l t blues f o r m u l a (Co,Fe)(Fe,Cr)204. The c e r a m i c blacks are used in
are used in c e r a m i c glazes. the s a m e systems as the above-described rutiles.
Cobalt p h o s p h a t e violet is p r e p a r e d b y h i g h - t e m p e r a t u r e Like m o s t pigments, c e r a m i c p i g m e n t s are m a n u f a c t u r e d
calcination of cobalt (II) oxide a n d p h o s p h o r u s (V) oxide to to have a suitable particle size for i n c o r p o r a t i o n into the
form a crystalline p h o s p h a t e [1]. It has the f o r m u l a Co3(PO4) 2. coating, b u t w h e n a p a i n t m a n u f a c t u r e r receives t h e m in bags
It is used for coloring the s a m e systems as the spinels a n d in of dry material, the particles generally have a b s o r b e d mois-
p r i n t i n g inks. M a n g a n o p h o s p h a t e violet is p r o d u c e d by a ture [5]. They are stuck t o g e t h e r in groups by this layer of
p r e c i p i t a t i o n process from a m m o n i u m salts of m a n g a n e s e w a t e r or a b s o r b e d air. Hence, in the dispersing process, these
layers m u s t be d e s t r o y e d a n d the p r i m a r y particles d i s p e r s e d
(IID a n d p h o s p h o r u s (V) [3]. This p i g m e n t has the c h e m i c a l
in the paint.
f o r m u l a NH4MnP207. It is used for inks a n d other applica-
There are a n u m b e r of wetting a n d dispersing agents w h i c h
tions w h e r e h e a t stability is of less i m p o r t a n c e .
can be a d d e d to a p a i n t [5]. Discussion of this topic will be
One c e r a m i c b l a c k is a jet black p o w d e r p r o d u c e d b y calci-
found elsewhere in this m a n u a l . However, one i m p o r t a n t
n a t i o n of mixtures of c o p p e r (II) oxide a n d c h r o m i u m (III) a d d i t i o n a l factor should be noted. Most c e r a m i c p i g m e n t
oxide to form a crystalline spinel [1]. The basic jet b l a c k has m a n u f a c t u r e r s t o d a y offer a line of easily d i s p e r s e d pigments.
the f o r m u l a CuCr204. A m a r g i n a l l y stronger black is pro- These p r o d u c t s are f o r m u l a t e d with a p r o p r i e t a r y dispersant.
d u c e d b y a h i g h - t e m p e r a t u r e calcination of cobalt (II) oxide, Adding the d i s p e r s a n t to the p i g m e n t itself p r o m o t e s opti-
i r o n (III) oxide, a n d c h r o m i u m (III) oxide in varying m u m contact b e t w e e n the d i s p e r s a n t a n d the pigment. These
a m o u n t s , also to form a spinel. The p r o d u c t has the c h e m i c a l d i s p e r s a n t s are p r i m a r i l y designed for w a t e r - b a s e d systems.
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T E S T I N G OF CERAMIC P I G M E N T S erty of a pigment is measured by determining the oil absorp-

tion characteristics of the pigment as described in ASTM Test
Ceramic pigments are usually tested for two important Method for Oil Absorption of Pigments by Spatula Rub-out
properties--particle size and tinting strength. Hardness is (D 281) [6].
essentially a property of the pigment crystal produced and is Tinting strength is the other important characteristic that
insensitive to production details. Hence, handbook values for needs to be evaluated. The determination of the color of a
the crystal are usually adequate for most purposes. pigment requires that it be dispersed into a medium similar
There are three aspects of particle size to be considered: (1) to that in which it is to be used. It is never acceptable to imply
the particle-size distribution; (2) the concentration of coarse application color from the color of a dry pigment. The tech-
particles; and (3) the particle shape as it affects the formula- niques for dispersing a pigment in a suitable vehicle and then
tion of the paint. The measurement and reporting of particle- measuring the color in both masstone and letdown are de-
size distribution of pigments in paints is contained in ASTM tailed in ASTM Test Method for Color and Strength of Color
Practice for Reporting Particle Size Characteristics of Pig- Pigments with a Mechanical Muller (D 387) [6].
ments (D 1366) [6]. The practice covers measurements by
microscopic techniques, sedimentation methods, turbidimet-
ric methods, absorption, and permeability methods. The re- REFERENCES
cent laser dispersion and electric sensing zone techniques are
not yet dealt with in this standard. The procedures described [1] DCMA Classification and Chemical Description of the Mixed Metal
Oxide Inorganic Colored Pigments, 2nd ed., Dry Color Manufac-
in ASTM Test Method for Particle Size Distribution of Alu-
turers' Association, Arlington, VA, 1982.
mina or Quartz by Electric Sensing Zone Techniques (C 690) [2] Eppler, R. A., "Ceramic Colorants," in Ullmann's Encyclopedia of
and ASTM Test Method for Determining Particle Size Distri- Industrial Chemistry, Vol. A5, VCH Verlagsgesellschaft mbH,
bution of Alumina or Quartz by Laser Light Scattering Weinheim, Germany, 1986.
(C 1070) should be applicable to ceramic pigments [7]. [3] Product literature from Shepherd Color Company, Cincinnati,
Determination of the concentration of coarse particles that OH.
may cause defects in a coating is covered by ASTM Test [4] Muller, O. and Roy, R., "The Major Ternary Structural Families,"
Methods for Coarse Particles in Pigments, Pastes, and Paints Springer Verlag, Berlin, 1974.
[5] Calbo, L. J., Ed., Handbook of Coatings Additives, Marcel Dekker,
(D 185) [6].
Inc., New York, 1987, especially pp. 511-539.
The amount of pigment which may be added to a paint [6] ASTM Annual Book of Standards, Part 6.02: Paint--Pigments, Res-
formulation is a strong function of the shape of the pigment ins, and Polymers.
particles. Higher loadings are possible for pseudo-spherical [7] ASTM Annual Book of Standards, Part 15.02 Glass, Ceramic
particles than is possible with plate-like particles. This prop- Whitewares.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Extender Pigments
by Henry P. Ralston 1
COATING FORMULATORS FREQUENTLY USE e x t e n d e r p i g m e n t s t o carefully controlled by altering reaction conditions to yield
reduce the raw material cost of a coating formulation and, in effective extender pigments. Fine-particle-size precipitated
some cases, improve coating performance. Extender pig- grades and fine-ground limestones are utilized as extender
ments are relatively inexpensive compared to titanium diox- pigments.
ide or color pigments and are easily incorporated into a
coating. Most are white or near-white inorganic minerals,
beneficiated to varying degrees, with a coarser particle size Physical Properties
and lower oil absorption (binder demand) than primary pig- Calcium carbonate products are differentiated further by
ments. physical properties such as particle size, brightness, residue,
Extender pigments include inexpensive fillers, such as and, for precipitated grades, oil absorption. Fine-particle-size
coarse calcium carbonate, which are used to reduce cost by products have an average particle size of from less than 1 to
filling coating volume with minimal impact on performance. about 4 ~m with coarse-particle-size grades ranging up to
Other extender pigments such as hydrous and calcined kaolin about 15 ~m. Most are high in brightness, ranging from 90 to
can actually enhance coating performance plus provide very 98, with a pH of 9 to 10. Ground carbonates have low oil
favorable economics by improving the efficiency of a more absorption which correlates with low resin demand in coat-
expensive pigment such as titanium dioxide. ings.
Some extenders have specific features that improve coating
performance, such as better durability, derived from the
unique platy particle shape of talc or mica. Pyrogenic, fumed, Coatings Performance
and diatomaceuos silica are frequently used as functional
additives to control rheology and film gloss. While extender Calcium carbonate is widely used in water-based trade
pigments can vary in form and use, the added value delivered sales architectural coatings since it is less expensive than
to the coatings formulator remains [1-4]. titanium dioxide, a primary pigment in paints and coatings,
and significantly lowers raw material cost. Fine-particle-size
calcium carbonate functions as an extender by spacing tita-
nium dioxide and maintaining or improving optical proper-
CALCIUM CARBONATE ties of the dry coating film at lower titanium dioxide levels.
Higher-oil-absorption (binder demand) precipitated grades
Description may contribute to opacity. Finer-particle-size grades tend to
Calcium carbonate, also known as calcite, whiting, or lime- develop high gloss; high brightness can have a positive effect
stone, has the chemical formula CaCO3. It is produced by dry on the color of the coating.
or wet grinding of limestone or by precipitation via carbon- Coarser grades of calcium carbonate are primarily used as
ization of slaked lime. Product from ground limestone is de- fillers to reduce cost but also contribute to flatting and en-
pendent upon both the initial crude mineral and the subse- hance low sheen control. Some grades may cause frosting
quent degree of processing or beneficiation. Limestone ore is and chalking in exterior applications.
crushed and milled; the dry ground product is air classified to
different particle-size fractions. Wet ground product is milled
as a slurry, undergoes flotation to remove impurities, and is
KAOLIN
then filtered and dried. The coarser dry-ground grades of
calcium carbonate are used as inexpensive fillers.
Description
Precipitated calcium carbonate is produced by heating nat-
ural limestone to form calcium oxide, which is then slaked in Kaolin, also known as china clay, is an aluminum silicate
water and reacted with carbon dioxide to form a low-solids with the chemical formula A12Oa.2SiO2.2H20, which is com-
slurry. The precipitate is vacuum filtered, dried, and ground. mercially available in both hydrous and calcined (anhydrous)
Both particle shape and size of precipitated grades can be forms. Domestic deposits occur primarily in South Carolina
and Georgia. It has a platy particle shape with finer particles
~Technical Service Engineer, Engelhard Corporation, 101 Wood present as individual platelets and coarse particles present as
Avenue South, Iselin, NJ 08830. stacks of platelets or booklets.
217
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The hydrous form is produced by air flotation or water in more air/pigment and air/binder interfaces in the dry paint
washing. Air-floated grades are crushed and ground to a spe- film. These grades develop good flatting, and the harder cal-
cific particle size and air classified. This process is very de- cined particles also improve scrub resistance in interior latex
pendent on the initial ore deposit. coatings [5,6].
Water washing involves processing the mineral in an aque-
ous slurry and separating particles of different size, which
can then be recombined to yield products with controlled TALC
particle-size distribution. These products can also be further
beneficiated by bleaching, ozonation, high-intensity mag- Description
netic separation (HIMS), or chemical flotation to remove im-
purities and improve color. Some grades are subjected to a Talc is a hydrated magnesium aluminum silicate with the
delaminating process that physically separates coarse plate- chemical formula 3MgO.4SiO2.H20. Deposits are found do-
lets from one another. mestically in New York, Vermont, Montana, Texas, and Cali-
Water washing offers a more carefully controlled product fornia. Talc varies widely in purity depending on its source
available in either slurry or dried form. Predispersed spray- and may also contain dolomite, limestone, and silica, among
dried beads offer ease of handling and are suitable for water- others. Western talcs are highly platy, while eastern talcs
based coating systems. Pulverized, acid grades are recom- have an acicular particle shape. Both dry and wet grinding
mended for solvent-based coatings. techniques are used in its beneficiation. Ore flotation pro-
Calcined (anhydrous) forms are produced by subjecting cesses are used to produce high-quality products. Dry pro-
hydrous kaolin to thermal dehydroxylation, which removes cessing includes use of jaw crushers, Raymond mills, and
the water of crystallization and alters the crystal shape. cyclones. Advanced milling technologies eliminate oversized
particles.
Physical Properties
Physical Properties
Kaolins are also differentiated by properties such as parti-
cle size, brightness, residue, and oil absorption. Hydrous Key properties for talc include composition, color, particle
kaolins have an average particle size ranging from an ex- size, water solubility, and oil absorption. Some grades are
tremely fine 0.2 up to 5 ~m depending on the product. Dry available with an average particle size of 1 to 3/~m, but most
brightness ranges from 85 to 90%, and most water-washed are around 5 to 15/~m. Brightness ranges from 70 to 85 for
grades are very low in residue. Acid grades have a pH of 4 to 5, inexpensive grades and 87 to 92 for premium grades. Oil
while predispersed grades are 6 to 7. Kaolins are chemically absorption depends on particle shape and size but in general
inert. Water-washed grades are lower in impurities such as fits in between calcium carbonate and kaolin. Slurry pH is
soluble salts than are air-float grades. basic at 9 to 10. Talcs are hydrophobic and organophilic [7].
Calcined grades range from below 1 to 2.5 p.m in average
particle size and are usually higher in brightness than all
except premium hydrous grades. These grades have a more Coatings Performance
irregular particle shape and higher oil absorption than the Talcs are used in many different types of coatings including
hydrous grades. interior and exterior trade sales paints, primers, traffic paints,
and industrial coatings. Western platy talcs develop good
Coatings Performance flatting and provide good chemical and water resistance due
to high-purity and low-soluble calcium. These are best for
Fine particle-size hydrous kaolins are commonly used in sanding primers because of softness and good sealing proper-
latex and alkyd trade sales paint. Finer particle size improves ties, while coarse grades help develop surface roughness
opacity and allows for cost reduction by extending/reducing ("tooth"). Platy talcs have good flow properties and improve
the amount of titanium dioxide. Finer particle-size products barrier resistance and durability in exterior trade sales paints
also develop higher gloss and are particularly useful in and enamel hold-out in interior applications. Talcs also en-
enamels and semigloss formulations. Chemically modified hance durability of traffic paints. Eastern acicular talcs have
hydrous kaolins are effective in high-solids and water-reduc- better color and develop lower viscosity at high loadings due
ible industrial coatings. to lower oil absorption.
Delaminated grades also develop good opacity, and the
platy particle shape improves barrier resistance and film in-
tegrity. Delaminated grades or coarser hydrous grades are
more suitable for exterior trade sales formulations and ex-
SILICA
hibit more controlled chalking and better overall durability.
Air-floated grades are not used significantly in coatings be-
Description
cause the higher water-soluble salt content can cause viscos- Silica is a general term describing products with the chemi-
ity instability. cal formula SiO2 of which both natural and synthetic types
Calcined kaolins are widely used in interior latex and alkyd are available. Those most widely used in paint and coatings
trade sales fiats to develop dry hiding and reduce cost at lower are crystalline, microcrystalline, diatomaceous, precipitated,
titanium dioxide levels. Dry hiding is due to the higher oil and fumed. They differ in method of production, physical
absorption (binder demand) of the calcined grades, resulting properties, and function.
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CHAPTER 2 4 - - E X T E N D E R PIGMENTS 219
Crystalline silica is produced by crushing, grinding, and binder demand [8]. Precipitated silicas are used as flatting
classifying quartz. Microcrystalline differs from crystalline in agents in solvent-based industrial coatings. Fumed grades,
that its deposits, found principally in Arkansas, have a higher more expensive than precipitated because of high-energy re-
concentration of fine particles. It is produced in a similar quirements during production, are used as rheology modi-
manner as crystalline, but the ore is finer in particle size. Both fiers and flatting agents in industrial coatings.
are decreasing in usage because of reported health and safety
issues related to crystalline silica.
Diatomaceous silica, also known as diatomaceous earth or MICA
simply diatomite, consists of the skeletal remains of single-
celled aquatic plants called diatoms. Domestic deposits are Description
located in California, Nevada, and Washington. The ore is
Mica is a family of hydrous aluminum potassium silicates
crushed, milled, dried, and air-classified. Calcined grades are
of which one, muscovite, has the chemical formula
processed in high-temperature rotary kilns and separated
into selected particle size ranges by air classification. These K20.3A12Oa.6SiO2.2H20. Micas are best known for a very
products have superior color and are preferred for coatings platy particle shape and high aspect ratio. These are coarser
applications. in particle size than most extenders. Higher-aspect-ratio
Synthetic silicas are produced by a number of differing micas are produced by frictional wet grinding. Dry process-
chemical and thermal processes. Precipitated silica is pro- ing in high-pressure air jets to both delaminate and reduce
duced by acidification of sodium silicate to form aggregates the particles results in lower-aspect-ratio mica.
of ultra-fine particles. Aggregate size and degree of struc-
turing are controlled by reaction conditions. Fumed silica, Physical Properties
produced via high temperature hydrolysis of silicon tetra-
chloride with hydrogen, also exists in aggregates of ultra-fine Most coating grades of mica have an average particle size
particles, and particle size and surface area are also depen- of 5 to 50/zm. Residue of 325 mesh varies from less than 1 to
dent on reaction conditions. as high as 50%, depending on the particle size of the product.
Brightness ranges from 65 to 80%, low compared to other
extenders, while pH is 7 to 8. Oil absorption is higher than
Physical Properties other hydrous minerals and is closer to coarse calcined kao-
lins.
Since processing of crystalline silica is essentially a size
reduction operation, particle size and particle-size distribu-
tion are the primary means of differentiating products. Crys- Coatings Performance
talline silicas range from 2 to 10-/~m average particle size.
Mica is best known for its very platy particle shape, which
Microcrystalline grades are easier to disperse and are less
forms layers parallel to the paint film. Mica reinforcement
abrasive than crystalline grades. Brightness is from 85 to 90%
increases durability and resistance to moisture penetration,
and pH from 6 to 7. Oil absorption is intermediate between
corrosion, checking, heat, and chemicals. It helps prevent
calcium carbonate and hydrous kaolins. These extenders ae
cracking in exterior architectural coatings and traffic paint. It
translucent and don't contribute to hiding as do some cal-
prevents cracking and sagging in textured coatings. Mica
cium carbonates and kaolin. Diatomaceous silica is a very
provides good barrier resistance in primers and roof coatings
high oil absorption material found in aggregates ranging in
[9]. Its platy particle shape, however, limits loading levels due
mean particle size of 2 to 20/zm. Calcined grades have a
to rheology constraints.
brightness of 87 to 90%.
The synthetic silicas are differentiated by surface area and
particle size. Surface area of precipitated types is about 60 to
BARIUM SULFATE
300 m2/g, while fumed silica ranges from 50 to 400 m2/g. Ulti-
mate particle size of the individual particles are less than
0.1 /~m for both; however, precipitated may develop larger
Description
aggregates. Fumed silica has a pH of 3 to 4, and precipitated Barium sulfate (BaSO4) is available as barytes, its naturally
is 6 to 8. These grades are often made hydrophobic by reac- occurring form, or as blanc fixe, a synthetic precipitate.
tion with organofunctional silanes to improve performance Barytes has a nodular particle shape with deposits found pre-
in coatings. dominantly in Nevada, Georgia, Missouri, Montana, Tennes-
see, Illinois, and Washington. The ore is beneficiated by flota-
tion techniques and then wet ground to obtain the required
Coatings Performance
particle size and bleached to improve color. Some higher
Crystalline silica is used in trade sales, industrial coatings, quality ores are dry ground and air classified. Blanc fixe is a
and primers. It is an inexpensive extender which contributes very white, fine-particle-size extender not as widely used in
to low sheen control, burnish resistance, and durability with paints and coatings as barytes. It is precipitated to a specific
minimal impact on theology in latex trade sales paints. It is particle size from solutions of barium salts and sodium sul-
also used in powder coatings where its low binder demand fate. Blanc fixe is also used to make lithopone (extended)
does not affect flow properties. grades of pigments. Multistage washing and filtration re-
Diatomaceous silica is primarily used as an inexpensive moves soluble impurities, and the products are then dried
flatting agent in latex trade sales paints because of its high and ground.
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Physical Properties 3Na20.4.5A1203-20SiO2 and is mined and beneficiated in Can-

ada. It has high brightness (95 to 98%) and is relatively coarse
Barytes is best known for its high density and very low oil
in particle size (2 to 16 p.m). Its low binder demand makes it
absorption relative to other extenders. Particle size ranges
particularly effective in exterior trade sales architectural
from about 1 to more than 10/~m depending on the grade.
coatings. Nepheline syenite provides good tint retention and
Brightness also varies from below 70 to greater than 90%
prevents checking and cracking in exterior paints and also
depending on the source and degree of beneficiation. Slurry
develops good scrub resistance in interior latex paints.
pH runs from 4 to 10. Blanc fixe is a more uniform product
with a 1 to 2-~m average particle size and high brightness (95
to 98%). Sodium Aluminosilicates
Synthetic sodium aluminosilicates are produced by react-
Coatings Performance ing aluminum sulfate with sodium silicate to produce a struc-
Barytes is used in industrial and automotive primers and tured extender. These have high brightness (92 to 98%) and
undercoats. Its low oil absorption allows for high loadings relatively coarse particle size of 5 to 6/~m. Sodium alumino-
with less impact on rheology compared to higher binder silicates are used as partial replacements for titanium dioxide
demand extenders. It helps develop a smooth surface with in latex trade sales paints similar to calcined kaolin but at
minimal impact on the gloss of subsequent coats. Because higher cost; some of the highly structured grades are used as
extenders are sold by weight, its high density can be a disad- flatting agents in latex paint.
vantage in trade sales coatings where more weight is needed
to fill a given volume. Higher density relative to other pig- Alumina Trihydrate
ments can increase settling and cause stability problems.
Blanc fixe has been used to develop dry hiding as a partial Alumina trihydrate (ATH) has the chemical structure
replacement for titanium dioxide in trade sales and industrial AI(OH)3 and is produced from bauxite ore as an intermediate
coatings [10]. in aluminum production. It is most commonly used as a
flame retardant and smoke suppressant in thermoplastic and
thermoset polymer applications. ATH has a brightness rang-
OTHER ing from 85 to 98% depending on the grade. Some very fine
particle size grades, less than 1 /~m, may be effective in spac-
Wollastonite ing titanium dioxide in trade sales paints.
Wollastonite is a calcium metasilicate with the chemical
formula CaO-SiO2 of which the primary domestic sources are
COMPARISON OF DIFFERENT E X T E N D E R
New York and California. It has an acicular particle shape
PIGMENTS
and is brown to white in color. It is principally produced by
dry processing. Typical coating grades range from 2 to 10/zm
in mean particle size. Brightness ranges from 80 to 95%, and
Physical Properties
pH is 9 to 10. Its acicular particle shape provides some rein- Physical properties of the pigment extenders described
forcement in coatings, and high pH is effective in buffering above are compared in Tables 1 and 2. Calcium carbonates
latex systems. Surface-modified grades improve performance are available in different particle size grades and are very
in industrial coatings by both reducing resin demand and white in color and high in brightness. Low oil absorption
improving bonding between the mineral and resin [11]. enables high loading levels with minimal influence on rheol-
ogy. High pH makes these products appropriate for latex
Nepheline Syenite paints. Surface-treated grades are available for solvent-based
systems. Precipitated forms are higher in brightness, finer in
Nepheline Syenite is an anhydrous sodium potassium particle size, and have higher oil absorption approaching that
aluminum silicate with the chemical formula K/O. of calcined kaolins.
TABLE1--Physical properties of pigment extenders.

Ground Precipitated
Calcium Calcium Hydrous Calcined Crystalline
Carbonate Carbonate Kaolin Kaolin Talc Silica Mica
Free moisture, % 0.5 0.5 1.0 0.5 0.2-.5 0.3 0.5
Specific gravity 2.71 2.71 2.58 2.63 2.8 2.65 2.82
Brightness, %
Fine 90-95 97-98 88-90 90-95 75-92 85-90 ...
Coarse 85-90 ... 85-88 ... 70-92 85-90 65-80
Ave particle size
Fine,/~rn 1-3 0.5-1.5 0.2-5 0.8-2.5 1-3 2-3 ...
Coarse, /zm 5-12 . . . . . . . . . 5-15 5-10 5-50
pH 9.5 9-10 4-7 4-5 9-10 6-7 7-8
+325 Residue, % 0.01-I <0.05 0.01-.1 0.01 0.01-1 <1-4 1-50
Oil absorption, g/100 g 10-20 30-60 30-50 50-100 25-55 20-30 60-65
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CHAPTER 2 4 - - E X T E N D E R PIGMENTS 221
TABLE 2--Physical properties of pigment extenders.

Sodium
Diatomaceous Precipitated Fumed Alumino- Nepheline
Silica Silica silica Barytes Wollastonite Silicate Syenite
Free moisture, % <1 <1.5 5 <1 <1 <1 <1
Specific gravity 2.30 2.20 2.20 4.40 2.90 2.1-2.3 2.60
Brightness, % 87-90 96 white 80-95 80-95 92-98 95-98
Ave. particle size
Fine,/zm 3-4 0.01-0.05 0.01-0.05 1-4 2-4 ... 2-4
Coarse, /zm 5-10 . . . . . . 8-12 7-10 5-6 7-16
pH 9-10 6-8 3-4 4-10 9-10 7-10 10
+ 325 Residue, % < 1-3 0.01 0.01 <1 <0.1 <0.5 <0.5-6
Oil absorption, g 90-130 100-300 100-400 10-15 20-40 75-115 20-30
oil/100 g
T A B L E 3--Comparative properties of extender pigments in coatings.

Calcium Hydrous Hydrous Calcined
Carbonate, Kaolin, Kaolin, Kaolin, Talc, Silica,
5/zm 0.5/xm 4.8 ~m 1.8 ~tm 8/xm 5 & 10 ~m
Hiding contribution Very low Very high Moderate Very high Moderate Moderate
Gloss Low Moderate Low Low Low Low
Enamel holdout Poor Excellent Very good Poor Fair Poor
Stain removal Poor Excellent Very good Poor Fair Fair
Abrasion resistance Fair Poor Poor Excellent Good Good
Adhesion Poor Very good Very good Fair Good Very good
Water spot resistance Poor Excellent Excellent Excellent Good Excellent
Chemical resistance Very poor Very good Very good Good Good Excellent
Viscosity Very low High Low High High-rood. Low
Stability Poor-very good Excellent Excellent Very good Poor-very good Excellent
Suspension Poor Excellent Very good Very good Very good Poor
Ease of brushing Fair Excellent Excellent~ Good Fair-poor Good
Leveling Excellent Very good Very good Good Fair Very good
TABLE 4 t A S T M Test Methods for extender pigments.

Standard Title
Specifications
D 602-81 Standard Specification for Barium Sulfate
D 603-66 Standard Specification for Aluminum Silicate Pigment (Hydrous)
D 604-81 Standard Specification for Diatomaceous Silica
D 605-82 Standard Specification for Magnesium Silicate (Talc)
D 607-82 Standard Specification for Wet Ground Mica
D 1199-86 Standard Specification for Calcium Carbonate
D 3619-77 Standard Specification for Aluminum Silicate Pigment (Anhydrous)
Analytical
D 715-86 Analysis of Barium Sulfate Pigment
D 716-86 Evaluating Mica Pigment
D 717-86 Analysis of Magnesium Silicate Pigment
D 718-86 Analysis of Aluminum Silicate Pigment
D 719-86 Analysis of Diatomaceous Silica Pigment
Physical Properties
E 70-90 pH of Aqueous Solutions with the Glass Electrode
D 153-84 Specific Gravity of Pigments
D 281-84 Oil Absorption of Pigments by Spatula Rub-out
D 1210-79 Fineness of Dispersion of Pigment-Vehicle Systems
D 1366-86 Reporting Particle Size Characteristics of Pigments (Practice)
D 1483-84 Oil Absorption of Pigments by Gardner-Coleman Method
D 2448-85 Water-soluble Salts in Pigments by Measuring the Specific Resistance
of the Leachate of the Pigment
D 3360-80 Particle Size Distribution of Common White Extender Pigments
D 4139-82 Determining Volatile and Non-volatile Content of Pigments (Guide)
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Hydrous kaolins are the finest particle size naturally occur- categorizing extenders by mineral type and provide some
ring extenders. Neutral predispersed grades are available for general test guidelines. Analytical standards are useful for
latex systems, and acid grades are available for solvent-based chemical analysis of extenders for identification purposes.
systems. These products have very low residue, which im- Standards for measurement of physical properties are very
proves gloss development. The calcined grades have slightly useful in categorizing extenders and for predicting suitability
better color, and higher oil absorption contributes to opacity. for a particular coatings application, Particle size, oil absorp-
Talcs are available in a wide variety of grades depending on tion, fineness of dispersion, pH, and water-soluble salt con-
the source. These are more similar to calcium carbonate in tent are important parameters in determining the suitability
particle size, although brightness is somewhat deficient. Platy of an extender for a particular coatings application. Actual
particle shape is a key parameter. Crystalline silica has lower product specifications should always be mutually agreed
binder demand than kaolin or talc. Coarser grades are effec- upon by supplier and user.
tive flatting agents. Mica is much coarser in particle size than
most extenders. It also has lower brightness and high residue,
which limit the levels at which it may be used.
The high oil absorption of diatomaceous earth makes it an REFERENCES
effective flatting agent. Precipitated and fumed silica, as more
carefully controlled reaction products, are more appropriate [1] Lewis, P. A., Ed., Pigment Handbook, Vol. 1, 2nd ed., John Wiley
& Sons, New York, 1988.
for industrial coatings applications. Barytes, wollastonite,
[2] Kroschwitz, J. I., Encyclopedia of Polymer Science and Engineer-
and nepheline syenite are coarser particle-size products ing, Vol. 7, Wiley, 1987, pp. 53-73.
which are less broadly used than finer particle-size extenders. [3] Katz, H. S. and Milewski, J. V., Handbook of Fillers and Rein-
forcements for Plastics, Van Nostrand Reinhold, New York,
1978.
Comparative Performance in Coatings [4] Madson, W. H., White Hiding and Extender Pigments, Federation
Performance characteristics of the extenders previously Series on Coatings Technology, 1967.
discussed are compared in Table 3. Coarse calcium carbonate [5] Engelhard Technical Literature TI 226, "ASP & Satintone Ex-
tender Pigments--Performance Products for the Paint & Coat-
filler does not provide significant improvement in coatings
ings Industry," Engelhard Corporation, Iselin, NJ, June 1984.
performance and is primarily used to reduce cost. Fine-parti- [6] Engelhard Technical Literature TI 218, "Satintone Specialty
cle-size hydrous kaolin helps develop hiding power and gloss. Pigments in Coating Applications," Engelhard Corporation,
These extenders develop good film properties, help maintain Iselin, NJ, October, 1986.
stability, and aid in coating application. Calcined kaolin also [7] Grexa, R. W., "North American Talc-Competition in Every Di-
contributes to opacity development and is fairly good in rection," Industrial Minerals, June 1987, pp. 52-54.
maintaining film properties, rheology, and application prop- [8] Johns-Manville Technical Literature, "Functional Fillers for In-
erties. Talc develops good film properties but may have an dustrial Applications," Johns-Manville, Denver, CO, January
deleterious effect on rheology, particularly at higher load- 1985.
ings. Coarse amorphous silica is an adequate filler. [9] KMG Minerals Technical Literature, "White Wet Ground
Muscovite Mica," KMG Minerals Inc, Kings Mountain, NC.
[10] Sachtleben Technical Service Note, "Blanc Fixe Micro, a New,
Multi-Purpose Barium Sulphate Extender," Sachtleben Chemie
PERTINENT ASTM TEST STANDARDS GmbH, Duisburg-Homherg, Germany, 1982.
[11] Hare, C. H. and Fernald, M. G., "Wollastonite Extenders in An-
ASTM standards useful in evaluating extender pigments ticorrosive Alkyd Metal Primers," I&EC Product Research &
are shown in Table 4. Standard specifications are useful for Development, 1985, pp. 24, 84.
www.iran-mavad.com

MNL17-EB/Jun. 1995
25
Metallic Pigments
by Russell L. Ferguson 1
METALLICPIGMENTS,INCLUDINGALUMINUM,zinc, gold, bronze, Zinc powders have a similar, but divergent, history. Not
nickel, and stainless steel, provide the paint and coatings being sought after for aesthetic properties, they were first
industry with a variety of aesthetic and functional properties. used in the mid-1800s for anticorrosive functionality and
These pigments, either in flake or powder form, contribute to were referred to as "blue powder." Zinc-gray coatings were
the metallic effects associated with automotive topcoats; gen- used extensively for industrial and marine environments by
eral industrial finishes; silver, gold, and copper finishes; me- the early 1900s. However, it was not until the late 1930s and
tallic ink systems; and many of the high-performance primers 1940s that the industry gained a firm foothold. The manufac-
for coatings systems. In addition to providing metallic and ture of zinc dust is carded out by melting and vaporizing zinc
polychromatic effects, they provide functional, anticorrosive metal followed by a controlled condensation of the vapor in
benefits. an inert atmosphere. The product is collected, screened, clas-
sified, and packaged [2].
History and Manufacturing Methods
The origin of metallic coatings can be traced back to early
Properties
civilizations, who utilized thin, gold sheets to overlay wood, Metallic pigments share similar properties; however, each
bone, or other materials. As the artisans molded these foil is distinct enough to be considered separately.
sheets, the thin edges would break off into flakes. It was soon
discovered that by mixing these flakes in a resinous polymeric Aluminum
material, a similar effect could be achieved. This process was Aluminum pigments are manufactured from aluminum
later continued, and by shredding the foil into flakes, artisans metal with a purity ranging from 99.3 to 99.97%, depending
were able to produce gold and later silver and bronze metallic on the grade being manufactured. Although amphoteric in
effects on ornamental objects. In the middle of the 19th nature, the pigment exhibits a high degree of chemical resist-
century, a mechanical stamping process, along with newly ance. Aluminum pigments owe their aesthetic and functional
developed smelting processes, made gold and silver substi- properties to the geometry of the particle, particle-size, and
tutes more readily available. Aluminum, gold, bronze, and particle distribution. The pigment is a flake-like particle (la-
later stainless steel and nickel became readily accepted sub- mellar) and has either a round or irregular perimeter. Once
stitutes. formulated into a coating, they orient parallel to the substrate
Today, with the exception of zinc powder, most metallic and film surface. This orientation provides for exceptional
pigments utilize the Hall Wet-Ball Milling Method [1]. This barrier properties in the appropriate coating system. Metallic
process carries out the particle-size reduction in the presence or polychromatic coatings containing aluminum flake pig-
of a suitable lubricant and solvent, offering a safer produc- ments, either by themselves or in combination with transpar-
tion method. Eliminating the explosive hazards associated ent colors, offer a two-tone quality often sought after. The
with mechanical stamping processes has allowed the produc- two-tone, or flop, feature is an important characteristic in
tion of finer metallic flakes that find widespread use today. many automotive top coats.
Stamping and dry-ball milling are still utilized in the manu- There are two general types of aluminum pigment: leafing
facture of gold bronze flakes. and nonleafing. Leafing grades are manufactured using a sat-
The post-milling manufacture processes for metallic flakes urated fatty acid as the lubricant (typically stearic acid),
generally include a screening operation to remove undesir- which allows the flakes to float at, or near, the surface of a
able particles, along with tight controls on aesthetic proper- paint film. This continuous layer of flakes provides a solid
ties. Color adjustments, along with polishing and blending silver color, unable to be tinted with other pigments. The
operations, are utilized in the final stages of the manufactur- nonleafing grades utilize an unsaturated fatty acid as the
ing process. The metallic flake pigments are available as a dry lubricant (typically oleic acid) which allows the flakes to
flake or in a wide range of solvents, including aliphatic and orient throughout the paint film. Nonleafing pigmented coat-
aromatic solvents, alcohols, plasticizers, water, and coa- ings can be tinted with organic pigments to offer a polychro-
lescing solvents. matic appearance.
Aluminum flakes range in size from 0.1 to 2.0/~m in thick-
1Vice President of Technical Functions, Silberline Manufacturing ness, and 0.5 to 200/~m in diameter. Generally, aluminum
Co., Inc., R.D. 2, P.O. Box B, Tamaqua, PA 18252. flakes are supplied in a paste form with a typical composition
223
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of 64% aluminum metal, 1% lubricant, and 35% hydrocarbon contain a wide range of grades from very coarse, large flakes
solvent [3]. to very fine, small flakes.
Gold Bronze Leafing Grades

Gold bronze pigments are neither gold nor bronze, but are The standard grade category is composed of a series of
typically manufactured from a composition of copper and grades from very coarse flakes (having water coverage from
zinc alloy. By altering the copper-zinc ratios, four standard 6000 to 9000 cm2/g) to very fine flakes (having water coverage
gold bronze colors can be produced. The standard alloy sub- in the area of 35 000 cm2/g). These grades are used, primarily,
divisions are: (1) copper--100% copper, 0% zinc; (2) pale in trade sales and maintenance coatings. Their leafing values
gold--90% copper, 10% zinc; (3) rich pale gold--85% cop- are traditionally 50% minimum.
per, 15% zinc; and (4) rich gold--70% copper, 30% zinc. The ultra-leafing grades are characterized by very high leaf-
Further oxidative treatments can be utilized to produce spe- ing values (in the area of 90 + %) and exceptional brightness.
cial colored bronzes, varying from brown-golds to oranges Their uses include aerosol coatings and ink applications.
and reds. Additionally, blending of any of the above-men-
Nonleafing Grades
tioned bronze powders will result in an almost unlimited
pallet of gold-bronze colors. The standard grades are represented by a full range of
Gold-bronze pigments are flake-like particles (lamellar) products from very coarse, low-opacity to very fine, high-
with an irregular perimeter. In a coating or ink application, opacity grades. They are used in diverse applications from
they orient parallel to the substrate and film surface [4]. maintenance coatings to general industrial applications and
automotive refinish.
Zinc Pigment The automotive grades are distinguished from standard
grades by possessing improved aesthetics, including brighter,
Zinc dust is the only metallic pigment that is not found in a
more sparkling appearances, with tighter control on particle-
lamellar form. Produced through the condensation of zinc
size distribution. Many subcategories exist under this head-
vapor in an inert atmosphere, the zinc dust is a spherical
ing, including specialized grades for base coat/clear coat sys-
particle averaging about 8/zm in diameter. Zinc dust is pre-
tems, circulation resistance, etc.
dominantly zinc metal (96 to 97%), with some zinc oxide (3 to
Plasticized and polymer-modified grades are represented
4%), and traces of lead, cadmium, iron, and other elements.
by a full range of products designed for end-use systems that
cannot tolerate solvents (mineral spirits). The primary end
Stainless Steel Flake
use is plastic and ink applications.
Stainless steel is a composition of iron, chromium, nickel, The dedusted grade category comprises dry aluminum
manganese, and molybdenum. There are three groups of flakes held loosely together by Teflon bonds, resulting in a
stainless steel alloys available: (1) martensitic, (2) ferritic, nondusting product. These grades are used in some general
and (3) austenitic, differentiated according to alloy composi- industrial coatings; however, the primary application is to act
tion. Of the three groups, austenitic is the most corrosion as a sensitizer for slurry explosives.
resistant and typically used to manufacture stainless steel The surface-treated grades include aluminum flakes whose
flake. Austenitic alloys owe their corrosion resistance to surface chemistry has been altered to allow for improved
higher levels of nickel and molybdenum. Stainless steel pig- aluminum flake performance. These grades are used in pow-
ment has a lamellar geometry and will orient itself parallel in der coatings and some solvent-borne coatings where im-
a coating system. Stainless steel flake has a high degree of provements in flake orientation and performance are desired.
durability and will resist tarnishing, abrasion, and chemical The aqueous grade category consists of aluminum pig-
attack. Additionally, stainless steel flake is able to maintain ments treated with various chemical components to stabilize
stability in water-based systems. the flake for use in waterborne systems. Various levels of
inhibition and performance are available.
Nickel
Nickel pigments can be found in either powder or flake-like Gold Bronze Pigments
form. They are typically composed of nickel metal, with
traces of carbon, oxygen, sulfur, and iron. Nickel flake pow- These pigments are primarily used for coating and ink
ders are available dry, as a paste in mineral spirits, or as a applications. They can be divided into four categories, based
paste in mineral oil. Nickel powders have good electrical on alloy composition:
conductivity [5]. 1. Copper--coppery-red color (100% copper).
2. Pale Gold--reddish gold color (90% copper; 10% zinc).
3. Rich Pale Gold--gold color (85% copper; 15% zinc).
4. Rich Gold--greenish gold color (70% copper; 30% zinc).
METALLIC PIGMENT GRADE
CLASSIFICATION
Zinc Pigment
Aluminum Pigments The zinc pigment, dust and flake, is used in coatings, pri-
Aluminum pigments are more widely used than any other marily for corrosion-resistant properties. The categories
metallic pigment and can be divided into a number of differ- available are:
ent categories. The grade classification is, in general, deter- 1. Regular Zinc Dust--7 to 8-/zm particle-size diameter.
mined by the intended use. Most of the following categories 2. Fine Zinc Dust--5 to 6-p~m particle-size diameter.
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CHAPTER 25--METALLIC PIGMENTS 225
3. Ultra-Fine Zinc Dust--3 to 4-/~m particle-size diameter. the needs of these 100% solids systems. These grades have
4. Zinc Flake--Available in several grades, based on particle- been surface-treated to allow for improved flake orientation,
size. along with modified electrical conductivity. Applied electro-
statically, the surface-treated aluminum flake will perform in
a similar fashion to the powder coating resin.
Stainless Steel Flakes
The application of metallic pigmented coatings and inks
These flakes are used in specialized coatings that require will depend on the system being used. Traditional ink appli-
good resistance to severe environmental conditions. cation methods will apply to both leafing and nonleafing
metallic pigments. In the case of coating systems, leafing
metallic pigments can be applied by brush, roller, or spray
Nickel Powder and Flake
application. Nonleafing grades, however, must be applied us-
The powder and flake are used in coating and plastic sys- ing appropriate spray application techniques. Improper ap-
tems to provide electrical conductivity and corrosion-resist- plication techniques can lead to poor flake orientation which
ance characteristics. will result in reduced aesthetic and functional properties.
F O R M U L A T I O N A N D APPLICATION
GUIDELINES Market Applications
Metallic pigments are widely used in the coating, ink, plas-
Formulation Considerations
tic, and explosive markets. In the coating industry, metallic
Metallic flake pigments, by the nature of their geometry pigments offer both functional and aesthetic properties.
and composition, are malleable and therefore somewhat Those pigments that are lamellar (aluminum, gold bronze,
fragile. The dispersion of these flakes into a coating system is stainless steel, and nickel) are opaque and orient parallel to
critical in maintaining optimum aesthetic and functional per- substrate and coating film surface. Thus, they provide a bar-
formance. The preferred dispersion process involves the ad- rier to ultraviolet (UV) and infrared (IR) light, along with
dition of vehicle or solvent to the metallic pigments, with moisture and oxygen penetration. Zinc pigment, while not a
slow-speed mixing, to gently separate the flakes. Once a thick, flake, possesses superior corrosion protective properties for
uniform slurry of metallic flakes, solvent, and vehicle is steel or iron substrates. Because zinc is higher in the elec-
achieved, the formulator can continue to let down to final tromotive series, it acts as the anode of a corrosion cell. The
product composition. Severe dispersion techniques such as iron or steel substrate is protected by the zinc because of the
Cowles high-speed mixers, sand mills, etc. will destroy the formation of insoluble compounds with lower oxidation
flake integrity, resulting in loss of aesthetic and perhaps func- states.
tional properties. Zinc pigment, which is not a flake, can be The aesthetic benefits of metallic pigments are widely
dispersed using conventional paint dispersion techniques.
known in the coatings industry. In the area of trade sales and
Appropriate selection of vehicle, solvents, and additives
maintenance coatings, aluminum pigments provide very
must also be considered when formulating with metallic pig-
bright, silvery finishes typically found in many roof coatings,
ments. The leafing properties of aluminum and bronze flakes
aerosol applications, and bridges. In general industrial
can be detrimentally affected by such properties as acid value
and automotive coatings, various polychromatic and
of the resin; polar solvents, or solvents with low-surface ten-
sion; moisture in the system; and additives, including driers metallescent appearances are produced utilizing nonleafing
that are good wetting agents. Since most metallic pigments grades.
contain mineral spirits, coating system compatibility must be In the ink and plastic industries, the primary benefits de-
considered. rived are from aesthetic properties. Gold bronze flakes, along
The current trend toward waterborne coatings also poses with aluminum flakes, provide attractive polychromatic fin-
problems in formulation. Dispersion of metallic pigments ishes.
can be accomplished through the correct selection of an ap- The explosives industry utilizes aluminum flake pigment as
propriate coalescing solvent. However, even good dispersion a sensitizer in slurry explosives.
will not guarantee good coating performance. Metallic wa-
terborne coatings have the potential for hydrogen gas genera-
tion. This potential has been addressed by many manufactur-
ers through various inhibiting processes. While many Economics o f Use
inhibited grades are available on the market today, perfor-
mance may vary in different aqueous systems. In addition to The extensive markets for metallic pigments has mandated
the potential for hydrogen gas generation, tarnishing and their use in a wide range of systems for many years. Their
printability have been addressed by manufacturers of gold properties, both functional and aesthetic, along with the tra-
bronze flakes. Stainless steel flakes, because of the very na- ditional economic values associated with their properties,
ture of their composition, can be used in waterborne coating have established them as an important raw material in the
formulations without the possibility of gas generation. coating, ink, and plastic markets. The economics of these
Another solution to the VOC (volatile organic compound) pigments are dependent on a number of factors, including
problem is the use of powder coating systems. Specialized cost of the raw material, degree of sophistication of the pig-
grades of aluminum pigments have been developed to meet ment, and the end product for which it is intended.
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TESTING Acid Spot Test

This test is designed to determine the acid resistance of
ASTM Test Methods aluminum pigments in coating systems. A metallic pig-
ASTM covers various specifications and test procedures for mented coating is tested by placing drops of a 10% solution of
metallic pigments. Included are: hydrochloric acid on the panel. Three rows of three drops are
9 D 962-81--Specification for Aluminum Pigments, Powder placed on the panel and each row is removed after 1-h inter-
vals (Fig. 1). If the aluminum pigment is acid resistant, no
and Paste, for Paints
9 D 480-88--Test Method for Sampling and Testing of Flaked spotting will be apparent after the first or second hour, with
Aluminum Powders and Pastes (includes tests for volatile only slight spotting after 3 h. A nonacid-resistant aluminum
analysis; coarse particles; leafing properties; brushing, will show definite spotting from the acid solution after the
smoothness, lustre properties; and easily extracted fatty first hour.
materials) Particle-Size Analysis
9 D 95-83--Test Method for Water in Petroleum Products
One of the key elements in any metallic pigment is the
and Bituminous Materials by Distillation
9 D 185-84--Test Methods for Coarse Particles in Pigments, particle-size distribution. Instruments are available on the
Pastes, and Paints market today to characterize, or fingerprint, metallic pig-
9 D 235-87--Specifications for Mineral Spirits (Petroleum ments. Unfortunately, most of these instruments are incapa-
Spirits) (Hydrocarbon Drycleaning Solvent) ble of characterizing lamellar-shaped pigments; however,
9 D 267-82--Specifications for Gold Bronze Powder their increased sophistication has allowed for a very close
9 D 520-84--Specification for Zinc Dust Pigment approximation. In addition to providing a distribution of the
9 D 521-81--Test Methods for Chemical Analysis of Zinc particles in a pigment, also provided are surface area, average
Dust (Metallic Zinc Powder) particle size, and percentages at various levels.
9 D 4017-88--Test Method for Water in Paints and Paint Water Coverage
Materials by Karl Fischer Method
This test can be used to determine the particle-size thick-
ness and surface area of leafing and nonleafing metallic flake
Test Methods Not Covered by ASTM pigments. This test has been fully described by Edwards and
Specifications Ray [6]. A dry, metallic pigment is dusted onto a surface of
clean, distilled water, which is contained in a shallow, rectan-
ASTM test methods cover many of the properties of metal- gular pan. The accurately weighed flake metallic pigment is
lic pigments; however, there are additional tests which fur- dusted onto the surface of the water and separated until it is
ther serve to characterize these pigments. Included are: one flake thick. The coverage of metallic flake on the water
TESTING PAINTS FOR ACID RESISTANCE
Remove after 3 hours
Remove after 2 hours
Remove after 1 hour
10% HCI Drop Test

FIG, 1-Testing paints for acid resistance,
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CHAPTER 25--METALLIC PIGMENTS 2 2 7
can then be measured, and total surface area can be calcu- to determine the gas generation potential and stability char-
lated based on the weight of the metallic flake pigment used. acteristics of metallic flake pigmented aqueous coating sys-
The thickness of the metallic flake pigment can also be calcu- tems. Approximately 200 mL/s of a metallic pigmented coat-
lated using simple density and volume calculations. ing is charged into an Erlenmeyer flask. Attached to the flask
is a glass condenser with Tygon tubing coming out of the top
Degradation Test and extending into an inverted buret filled with water. The
This test is designed to determine the level of flake deterio- Erlenmeyer flask is suspended in a hot oil bath, which accel-
ration in a coating system when subjected to severe stress. erates the potential for hydrogen gas evolution. This test is
Automotive coating systems are often circulated through operated for seven days (168 h) at a temperature of 52~ The
pumps, regulators, and long piping and tank systems to keep acceleration of the environmental conditions will allow for
all the components of the coating in suspension. Circulation hydrogen gas generation, which will pass out of the Eden-
may have detrimental effects on the metallic flake integrity, meyer flask, through the Tygon tubing, and into the inverted
causing bending, curling, and even breakage of the metallic buret. The water in the inverted buret is displaced by the
flake. The loss in aesthetic properties due to flake deforma- hydrogen gas and generation can be easily read through this
tion results in a darkening of the coating, along with a change displacement (Fig. 2). The specifications for gas generation
in the flop characteristic. This test is designed to evaluate the should be designed around the metallic flake pigment and
capability of the metallic flake to resist deformation under coating system tested. The specification for gas generation
these stress conditions. should not exceed the volume of the buret (typically,
A metallic pigmented coating is placed into a water- 100 mL/s).
jacketed Waring blender. Using a standard cutting blade, the
blender is operated at high speeds for 5 to 15 min. The metal- Electrical Resistivity~Conductivity
lic coating is a sprayed pre- and post-blender operation, and In waterborne coating systems it is often useful to know the
visual and instrumental comparisons are made. The degree of conductivity or resistivity of the components of the system. In
flake deformation can be translated into numerical data order to measure metallic pigments, it is necessary to dis-
based on the brightness of the metallic coating (face and perse the metallic pigment in an isopropyl alcohol/deionized
flop). water mixture. This mixture should be agitated using an air
mixer for at least 5 min, after which the metallic pigment
Gassing Test should be filtered out. The resultant filtrate can be tested for
Aluminum and other metallic pigments, by their very na- resistivity/conductivity using a conductivity meter (i.e.,
ture, will react with water to generate hydrogen gas. Today, Jenway Conductivity Meter, Model 4010).
due to VOC regulations, more and more coating and ink sys-
tems are moving toward waterborne technologies. Metallic pH Measurement
pigment manufacturers have developed technologies to in- In waterborne coatings and ink systems, it is often neces-
hibit the aluminum flake pigments, and this test is designed sary to know the pH of the components of the system. The pH
Exit W a t e r
t,d
Inlet W a t e r
t't" 25 I
I.IJ II
I'- 20
m 15
..I
m 10
..J
iioii!iiiii!ii ii!iiiii
.j 5 Aluminum !iBa !!!ii!!iiii! _
"- 0 Sample ii::iiiiiiiii!iiiii!iiiiiiiilEiiiiiiiiiii
Water Heater
FIG. 2 - G a s evolution test for metallic coatings.
www.iran-mavad.com

of metallic p i g m e n t s can be evaluated b y a d d i n g the metallic The color attributes from the face a n d flop angles can be
p i g m e n t to a mixture of isopropyl alcohol/deionized water. n u m e r i c a l l y m e a s u r e d . There are a n u m b e r of i n s t r u m e n t s
The slurry should be m i x e d using an air mixer for at least 5 available t o d a y that are capable of m e a s u r i n g reflected
rain. The metallic p i g m e n t should then be filtered out, a n d the light at different angles. All of t h e m are goniospec-
p H of the resultant filtrate can t h e n be evaluated. t r o p h o t o m e t e r s a n d are c a p a b l e of m e a s u r i n g reflected
light on metallic p i g m e n t e d coatings at angles from 10 ~ off
s p e c u l a r to 110 ~ off specular. ASTM Task F o r c e C o m m i t t e e
Aesthetic Properties
E-12.03.02 is currently working on a s t a n d a r d test m e t h o d
Metallic p i g m e n t s are used for the aesthetic p r o p e r t i e s they to evaluate metallic p i g m e n t e d coatings utilizing specified
lend to coating systems. E a c h metallic p i g m e n t grade offers a g o n i o s p e c t r o p h o t o m e t r i c angles.
slightly different a p p e a r a n c e p r o p e r t y to these coatings, a n d
it is necessary to be able to assess these differences. Visual
a n d quantitative d a t a can be generated b a s e d on a n u m b e r of REFERENCES
these properties. F o u r of the m o s t i m p o r t a n t p r o p e r t i e s are:
[1] Hall, E. J., U.S. Patents 1,501,499 (1924); 1,545,253 (1925);
9 The face-color, or head-on-brightness, attribute generally re- 1,569,484 (1926); and 2,002,891 (1935).
fers to the a m o u n t of reflected light f r o m a metallic pig- [2] Ruddick, D. H., "Zinc Pigment," Pigments Handbook, Vol. I,
m e n t e d coating w h e n viewed at a p p r o x i m a t e l y 20 to 25 ~ off Properties and Economics, John Wiley and Sons, New York, 1988,
of specular. pp. 811-817.
9 The flop, flip/flop, or metallic travel angle refers to the [3] Ferguson, R. L., "Aluminum Flake," Pigments Handbook, Vol. I,
a m o u n t of reflected light w h e n viewing a metallic pig-
Properties and Economics, John Wiley and Sons, New York, 1988,
pp. 785-801.
m e n t e d coating at an angle that is 70 to 110 ~ off of specular.
[4] Humphrey, S. A. and Laden, P. J., "Gold Bronze Pigment,"
Metallic travel is often referred to as the degree in change of Pigments Handbook, Vol. I, Properties and Economics, John Wiley
brightness going from the face angle to the flop angle. and Sons, New York, 1988, pp. 803-810.
9 Seed level refers to the degree of p r o t r u s i o n of the metallic [5] Antonsen, D. H., "Nickel Powders and Nickel Flake Powders,"
flake t h r o u g h a coating film surface. Pigments Handbook, Vol. I, Propertiesand Economics, John Wiley
9 DOI (distinctness of image), closely related to gloss, refers to and Sons, New York, 1988, pp. 823-827.
the reflection of an image f r o m a metallic p i g m e n t e d coat- [6] Edwards, J. D. and Wray, R. I., "Aluminum Paint and Powder,"
ing b a c k to the observer. The clearer, o r m o r e distinct, the Reinhold Publishing, New York, 1955, pp. 18-22.
reflected image, the higher the DOI value. Typically, the
finer the pigment, the higher the level of DOI.
9 Patina is the packing a p p e a r a n c e of the metallic flakes in BIBLIOGRAPHY
coating systems. A good p a t i n a is often d e s c r i b e d as having
a smooth, velvety a p p e a r a n c e , lacking individual flake iden- Other literature, with m o r e extensive i n f o r m a t i o n on func-
tity in the coating. If an observer sees only a c o n t i n u o u s tional p r o p e r t i e s a n d applications, is listed below:
metallic film w i t h o u t breaks, protrusion, or individual flake
Hare, C. H. and Fernald, M. G., "Anti-Corrosive Barrier Finishes,"
identity, the metallic coating is c o n s i d e r e d to have a good
Modern Paint and Coatings, Vol. 74, No. 10, 1978, pp. 138-151.
patina. Many coating systems a n d p i g m e n t p a r a m e t e r s af-
Humphrey, S. A. and Laden, P. J., "Stainless Steel Flake," Pigment
fect the p a t i n a of a coating system. Typically, higher solids Handbook, Vol. I, Properties and Economics, 2nd ed., John Wiley
coatings, p o o r a p p l i c a t i o n methods, coarse pigments, a n d and Sons, New York, 1988.
p o o r flake o r i e n t a t i o n c o n t r i b u t e to p o o r e r p a t i n a p r o p e r - Smith, A., Inorganic Primer Pigments, Federation Series on Coatings
ties. Technology, Philadelphia, PA, 1988.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Pearlescent Pigments
by Carl J. Rieger 1
PEARLESCENTPIGMENTS, SOMETIMESREFERREDTO as nacreous 3. Natural pearl essence, guanine, and hypoxanthane purines
pigments, are attempts to create the natural pearl luster ef- from fish scales.
fects seen in pearls or sea shells [1]. These pigments are high- Mainly because of its high cost, natural pearl essence is used
refractive-index coatings on thin transparent flakes. The in cosmetic applications such as fingernail polish, lotions,
high-refractive-index material reflects incident light, and the
and creams.
transparent flakes allow some light to be transmitted through
Titanium-coated mica types of pigments evolved in the
the flakes. Many different grades and types of pearlescent
early 1960s through the work of Linton and others [3-6].
pigments are available. These grades range from materials
Coated mica of both the titanium dioxide and ferric oxide
for soft, satin-like effects from small-particle-size pigments to
types have the dominant share of the pearlescent pigment
materials with sparkle metallic effects from larger-size pig-
market. This market involves uses in plastics, coatings, and
ments. A special type of pearlescent pigment that produces an
inks in addition to cosmetic applications.
iridescent color effect is termed an "interference pigment."
These are very thin films with a high refractive index that
exhibit color through an optical effect called light interfer- MANUFACTURING AND COMPOSITION
ence. This is similar to the "rainbow effect" seen in soap
bubbles or in oil and gasoline slicks [2]. The type mica used in pearlescent pigments is called "wet-
Because of these optical effects, pearlescent pigments can ground mica." This is ground as a water paste in Muller mills
exhibit color without conventional light-absorbing pigments to give a delamination effect in the grinding process. As the
present. The colors arise from light interference effects that mill rollers go over the mica, it becomes thinner and smaller
will be described in more detail later. Other types of in particle-size reducing aspect ratio. These mica flakes are
pearlescent pigments have conventional absorption colors then dried, sieved, and classified into the desired particle-size
added by either depositing these colorants onto the distribution.
pearlescent-pigment surfaces or by mixing colorants with Various particle sizes are available. The coarse particle-size
pearlescent pigments. distributions impart a sparkling, wet-look effect. The fine
particle-size distributions impart a satin, soft appearance.
HISTORY The particle size for use in exterior grade pigments intended
for automotive paints is very carefully controlled so that they
The earliest use of pearlescent pigments is credited to contain no particles greater than 50/xm. This prevents clogg-
French rosary makers in the 17th and 18th centuries. They ing of paint filters in recirculation systems of automotive as-
used the scales of fish to impart pearl effects to the glass sembly plants and is vital for good application characteris-
beads used in making rosaries. The modern era of pearlescent tics.
pigments began in the late 1920s when scales of fish, namely When titanium dioxide-coated types of pearlescent pig-
herring, were used to make simulated pearls for costume ments are made, classified mica is suspended in water. Then,
jewelry. Because "natural pearl essence," as the material ex- under controlled conditions of temperature and pH, titanium
tracted from the fish scales came to be called, was so expen- sulfate or titanium tetrachloride solutions are added slowly
sive, synthetic pearl pigments were developed in the 1930s. to yield uniform deposition of the hydrous titanium dioxide
These early synthetic pearl pigments were mainly lead salts. on the mica flakes or platelets. This suspension is filtered,
They possessed both the high refractive index and thin plate- dried, and calcined at temperatures above 800~ to convert
let shapes required for pearlescent pigments. the hydrous oxide into the crystalline form of titanium diox-
The moderu commercial forms of pearlescent pigments ide (TiO 2) and to increase its refractive index. The normal
consist of: crystal form for these pigments is the anatase form of TiO2,
1. Titanium dioxide and ferric oxide coatings on mica. but conversion to the rutile form may be made by addition of
2. Bismuth oxychloride crystals grown from a solution of small amounts of stannic chloride prior to the calcination
bismuth salts. operation. For the ferric oxide coated mica pigments, a simi-
lar procedure is followed except that ferric chloride solutions
1Vicepresident, The Mearl Corporation, Applications and Develop- are added to the mica-water suspension instead of the tita-
ment Laboratory, 3 Greentown Rd., Buchanan, NY 10511. nium salts. By varying the thickness of the titanium dioxide
229
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or ferric oxide layer on the mica, the various interference 5. Smooth surfaces that give high luster in comparison to
colors can be obtained. rough surfaces that can cause light scattering. Uniformly
Bismuth oxychloride crystals are made by a precipitation dense surfaces also give low surface areas, as measured by
process under controlled crystallization conditions. In this the Brunauer-Emmett-Teller (BET) method, z that can im-
procedure, a bismuth nitrate solution in hydrochloric acid is prove weatherability.
added simultaneously with sodium hydroxide at a constant
pH and temperature to grow flat, hexagonal-shaped platelets
in the particle-size range of 11 to 15/xm. These are very high APPLICATIONS
quality pearlescent pigments because of the narrow particle-
size range, high refractive index, and flat shape of the bis- Industrial Coatings
muth oxychloride platelets. Bismuth oxychloride has about
twice the reflectance of the best titanium dioxide-on-mica Pearlescent pigments have been used in many industrial
types of pearlescent pigments. coating applications. One such use is coil coatings. Polymers
A lower quality and smaller size, 5 to 10/xm, type of bis- often used in these applications, such as fluoropolymers, re-
muth oxychloride is made by a "dump" procedure in which a quire high baking temperatures. Since they have been cal-
bismuth nitrate solution is added to a sodium chloride solu- cined at over 800~ during their manufacturing process,
tion or vice versa. Because of the small size and irregular- pearlescent pigments can tolerate high bake temperatures of
shaped platelets obtained with this process, this type of bis- 500 to 600~ (260 to 315~ without any damage to pigment
muth oxychloride gives less luster on reflection than the 11 to mechanical integrity or optical properties. Not all organic
15-/xm types. pigments can be used in such coil coating applications be-
Several patented post treatments [7,8] are available to cause of temperature limitations.
modify commercial preparations and to give these pearl- Pearlescent pigments find application in ink formulations
escent pigments the weathering resistance needed for exte- such as gravure, silk screen, flexographic, and, to a lesser
rior applications such as automotive paints, outdoor signs, extent, offset printing inks. The particle size of some
and plastics. pearlescent pigments is too large for most offset applications.
Bismuth oxychloride pigments have been used for many
years as coatings on wood furniture to sharply bring out the
OPTICAL PROPERTIES "grain" of the wood. Also, bismuth pigments have been uti-
lized in the costume jewelry industry for coating and dipping
Pearlescent luster is developed by the specular reflection of beads and pearls.
light as it strikes the broad surfaces of the platelets. These Other applications for these pigments include roller and
platelets are dispersed throughout the depth of the paint or knife coating of leather and paper as well as coating of vari-
ink film or plastic article. This reflection of light from ous types of toys and balls. The pigments are also used in the
pearlescent pigment particles dispersed throughout the popular craft industry.
thickness of the coating reinforces the luster and differenti-
ates it from a strictly surface reflection as featured by leafing
aluminum flake.
Automotive Coatings
The requirements for a good pearlescent pigment are: Pearlescent pigments were first used in original-equip-
1. A high refractive index preferably greater than 2. ment-manufacture (OEM) automotive paint in the early
2. An optical thickness, i.e., the geometrical thickness of the 1980s, and they became a major styling tool about 1985
layer multiplied by the refractive index, of approximately [9,10]. Since pearlescent pigments, chiefly the coated mica
100 to 140 nm for pearl (white) pigments. As interference types, are transparent in nature, they do not "gray out" or
pigments are produced by increasing the geometrical "muddy up" the expensive transparent organic coating colo-
thickness, this optical thickness increases to 200 nm for rants used in automotive coatings. These pigments add to the
gold, 250 nm for reds, 300 nm for blues, and 370 nm for chromatic effect of organic pigments and contribute to the
green interference colors. "flop" or polychromatic effect desired in these coatings. Flop
3. A high aspect ratio primarily derived from the mica. the is defined as a change of color as viewing angle changes.
larger the diarueter-to-thickness ratio (the aspect ratio), For the 1991 model year, it is estimated that nearly 40% of
the better the pearl effect. Another way of describing this all U.S. automotive OEM coatings contained pearlescent pig-
would be to term it a "platey" structure. The mica itself ments. European and Japanese paint companies are also us-
plays no role in the optics and functions merely as a sub- ing pearlescent pigments in their OEM paint formulations.
strate upon which the high-refractive-index material is de- Pearlescent pigments have been stabilized by various meth-
posited. ods to give the durability required for automotive end uses.
4. Proper particle-size distributions are needed. Optimum Panels have been weathered outdoors in Florida and Arizona
luster occurs when the size distribution, measured by laser for five or six years with little or no change in color or gloss.
diffraction methods, falls between about 10 to 40/zm. The use of the color base coat and clear top coat now favored
Smaller particles, 5 to 10/zm, act as light scatterers and in the automotive industry has also added to the gloss and
detract from luster. Particles larger than 40/~m give a weathering stability of coatings formulated with pearlescent
grainy effect and reduce opacity. Pearlescent pigments are
essentially transparent pigments and, as such, do not have 2Brunauer, S., Emmett, P. H., and Teller, E., Journal of the Ameri-
good opacity or hiding. can Chemical Society, Vol. 60, 1938, p. 309.
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CHAPTER 26--PEARLESCENT PIGMENTS 231
pigments because the clear top coat affords additional pro- Water-based coatings containing exterior grade pear-
tection for the pigmented coat underneath. lescent pigments have been tested in outdoor exposure in
Another interesting property that pearlescent pigments op- Florida for three years. These show good weatherability with
tically display is referred to as "geometric metamerism," or optimum gloss and color retention.
"goniochromaticity." These terms mean that the color of the
pigments changes as the viewing angle changes. While this is
a very desirable attribute from a styling standpoint, it compli- COLOR MEASUREMENT
cates color measurement of coatings that contain pearlescent
pigments [11-14]. Visual
Instrumental color analysis of coatings pigmented with
Powder Coatings pearlescent pigments is rather difficult. As mentioned earlier,
the phenomenon known as goniochromaticity complicates
Pearlescent pigments have been successfully used in pow- instrumental measurements. As a result, much color observa-
der coatings for a number of years [15]. Since they are non- tion has been done visually using both draw down cards with
metallic in nature, these pigments are free of some of the
nitrocellulose lacquers and coated panels. Comparing a sam-
arcing and flashing problems that occur in electrostatic spray ple and a standard on a black-and-white draw-down card is
application of powder coatings. an effective way of making color comparisons since both the
One limiting factor found with the use of pearlescent pig- interference color and the absorption color can be seen. Due
ments in powder coatings is their inability to be used in the
to the transparency of pearlescent pigments, the color ap-
"melt mix" method of incorporation. This calls for the extru- pears different over the black and the white portions of the
sion of pigments and the powdered polymer to encapsulate
card.
the pigment. The use of an extruder is not the problem since The interference color can be best seen and visually com-
pearlescent pigments are extruded in the plastics industry. pared to the standard by looking at the black portion of the
The problem arises through the use of hammer-mill type mill draw-down card. The absorption color can be best evaluated
used to reduce the size of the polymer mass into a powder
and compared by viewing the white portion of the card. Color
that will spray through an electrostatic spray gun. Pearl-
appears more intense over the black portion because the
escent pigments must retain their platey or flake-like shape to incident light is reflected and the complementary color is
properly reflect light and produce luster. If these pigments
absorbed. On the white portion of the card, the reflected light
are broken or smashed by milling, the pearlescent effect is
and the complementary color are both reflected back to the
greatly reduced. This leaves only dry mixing of the viewer with only a slight diminishing of the specular effect.
pearlescent pigment and the powdered polymer as an alter-
Side-by-side draw downs of samples against a standard
native method of incorporation. Such a technique has certain
batch are so effective that they can be used in process control
drawbacks such as separation due to different specific grav-
with samples taken at various intermediate stages of the man-
ities, different particle sizes, and so on that can take place due
ufacturing process. Also, final quality control judgments can
to vibration during shipping, handling, and application.
be made using visual assessment of side-by-side draw downs.
A new method called the "bonding" method has recently
been used with pearlescent pigments and metallic flakes in
powder coatings. This technique involves "bonding" of the Colorirneters and Spectrophotometers
pigments to the powder by various proprietary methods.
Pearlescent pigments have been used to powder coat auto- The use of colorimeters and spectrophotometers to mea-
motive wheel covers, bicycles, and outdoor furniture. sure the color of pearlescent pigmented coatings results in
only limited information. Most of these instruments measure
at fixed angles of illumination and fixed reflectance angles,
Water-Based Coatings such as 00/45~ or 450/0~ This results in only a portion of the
pearlescent color being measured through diffuse reflection.
Since pearlescent pigments are chemically very inert and These instruments are not capable of measuring at specular
not sensitive to pH, they make ideal pigments for use in or slight off-specular reflection angles. It is at these near-
water-based coatings. Because of their inert nature, they do specular angles that pearlescent pigmented coatings exhibit
not evolve hydrogen gas or react with water-borne systems. most of their color through specular reflection,
Pearlescent pigments are hydrophilic in nature and as such Colorimeters can be used to measure the bulk color of
disperse very well in most water-based systems. pearlescent pigments. Highly concentrated draw downs can
Pearlescent pigments have been successfully used in Can- be made, and the colorimeter readings may be used to deter-
ada in water-based truck-paint finishes for several years. Cur- mine the bulk color of white and pearl pigments. Colorime-
rently they are being used as the automotive industry ters and spectrophotorneters may also be used to measure
switches from high-solids to water-based coatings with lower color on draw-down cards. These data are useful in compar-
volatile organic compound content. ing various batches to each other for quality control and SPC.
Ink formulations based on water-borne systems have also Color loss from test panels used in accelerated weathering
been developed for both the coated mica and bismuth oxy- devices and from actual outdoor exposure may be followed
chloride pigments. These are being used in Europe to replace using colorimeters and spectrophotometers. Loss of gloss
the metallic ink formulation that may be an environmental may be followed in weathering test panels with the use of
problem. gloss meters at the 20 ~ gloss angle.
www.iran-mavad.com

232 PAINT A N D COATING TESTING MANUAL
Goniospectrophotometers conventional 00/45~ colorimeter, the readings would be of a

blue and a green colorant with no information obtained
When the color of coatings with pearlescent pigments or
about the color due to the gold pearlescent pigment.
metallic flake is measured, it is necessary to measure at more
Figures 4, 5, and 6 are reflection data for the color of panels
than one angle. The reason for this is that the color of these
coated with solid color, metallic flake, and pearlescent pig-
types of coatings changes with viewing angle. An instrument
ment, respectively, as a function of viewing angle. These
capable of making multi-angle color measurements is called
curves were obtained at 14 viewing angles from 10 to 110~ off
a goniospectrophotometer. These instruments are usually ca- specular with a research-type goniospectrophotometer. From
pable of changing the angle of incident light (illumination), Fig. 4, it is apparent that the solid color, i.e., nonmetallic or
changing the angle of viewing (reception), or tilting the speci- pearlescent, does not change appreciably with viewing angle,
men under investigation. For most of the commercial quality so conventional colorimeters and spectrophotometers mea-
control instruments, only the angle of viewing is changed and suring at 00/45~ can be used to obtain information about
the other variables are held constant with the incident-light coating color. Figure 5, which contains reflection data for the
angle usually fixed at 45 ~. metallic-flake (aluminum) pigmented coating, has a change
Figure 1 shows the viewing angles used in some of these in the lightness (L) value with angle, but has very little change
commercial instruments. The optics used are called nor- in the chroma values (a and b). Adding organic colorants to
malized reflective angles, which means all viewing angles are metallic flake will increase the chroma change. The reflection
referred to the specular angle that is sometimes called the data in Fig. 6 demonstrates the change in color as a function
gloss angle. Incident light strikes the ample at 45 ~, and thus of viewing angle of a blue interference color pearlescent pig-
the specular angle is also 45 ~. The near specular angles are ment. Changes in the chroma values are readily evident. In
usually 15 to 20~ off the specular angle to exclude any gloss Figs. 4, 5, and 6, L*, a*, and b* are the CIE 1976, International
from affecting the color readings. To completely characterize Commission on Illumination 1976, apparent-color scales,
pearlescent pigmented finishes, it is necessary to measure at ASTM Standard Terminology on Appearance (E 284).
least three angles. This is usually near specular, i.e., about 15 ASTM has a task group under E-12.03.02 developing a
to 20 ~ off specular, at 45 ~ off specular, and at several far specification for visually and instrumentally measuring the
diffuse angles, usually 70 to 115 ~ off specular. All commer- color of metallic and pearlescent pigments. In addition to
cially available goniospectrophotometers will measure re- development of an instrumental method for measuring the
flected light at a minimum of three angles, and several instru- color of such pigments, the task group is also involved in
ments measure at more angles, with one measuring at twelve having a visual method approved. Recently one of the instru-
angles. Research goniospectrophotometers that allow angle ment companies has developed a color-matching booth espe-
variation of about 5~ off specular to 110~ in five-degree inter- cially designed for color matching these types of pigments.
vals are also commercially available. This booth contains a combination of three differently posi-
The importance of measuring at more than one angle is tioned light sources, and rotation of the sample panels
apparent from Figs. 2 and 3. In Fig. 2 the reflection curves through five different angles will provide 15 viewing geome-
taken at near specular angle are nearly identical, whereas in tries ranges from 10 to 110~ off specular. This visual color
Fig. 3, when this same set of panels was measured at a diffuse matching booth should provide color matchers with a new
angle, markedly different reflection curves are obtained. tool for studying metallic and pearlescent pigmented finishes.
These data were obtained using one gold interference
pearlescent pigment to which a small amount of ph-
thalocyanine blue had been added and another gold interfer-
ence pearlescent pigment to which a small amount of ph-
TESTING
thalocyanine green had been added. At the near specular
angle, the gold interference color is apparent, and, since both
Weatherability Testing
coatings used the same gold pigment, the two curves are Weatherability tests with pearlescent pigments take the
nearly identical. However, at the diffuse angle, the colors of form of both accelerated and outdoor testing. Accelerated
the organic pigment added to the pearl finish are now appar- testing includes use of such devices as QUV exposure cham-
ent, with one curve typical of a blue and one curve typical of a bers, condensation testers, and water-bath soaking. Outdoor
green colorant. If this same pair of panels were presented to a testing may include exposure in Florida and/or Arizona at 5~
South or Black Box. Specimens consist of painted metal test
45~ panels, pieces of pearlized plastic film, or injection-molded,
70~ 20~ pigmented parts.
45~ INCIDENT /~ Color and gloss readings are made on the original test
BEAM SPECULAR REFLECTION
' r panels before exposure, and panels are exposed in replicates.
45 ~ /0 o
Panels are removed from the test fences at various times and
110 ~ / tested for changes in color and gloss. Testing with the stabi-
lized exterior grades of pearlescent pigments usually goes on
for at least five years, and the panels are viewed and examined
every six to twelve months. Such testing has shown that exte-
rior-grade pearlescent pigments have the capability of stand-
FIG. 1 - N o r m a l i z e d reflection a n g l e s c h e m a t i c for a c o m m e r - ing up to the weathering stresses found in modern automo-
cial g o n i o s p e c t r o p h o t o m e t e r . tive coatings along with other exterior uses. Accelerated
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41
40
36
30
26 - - - I - - - Blue
Reflectance, %
20
16
10
o : t ! I' I ', ', : I I J I ~ } I

400 440 480 620 660 600 640 680 700
Nanometers
FIG. 2-Reflection as a function of wavelength at near the specular angle for a gold
pearlescent pigment containing a blue or a green colorant.
80
70
6O
60
Reflectance, % 40
30
Blue
2o
10
0 I I I I I I' I I I I I ! l I 'I
400 440 480 620 660 SO0 640 680
Wavelength, nanometers
FIG. 3-Reflection as a function of wavelength at a diffuse angle for a gold pearlescent
pigment containing a blue or a green colorant.
www.iran-mavad.com

40,
L* ~ ~, r A
= =v ~ , ."-. ..,=
. , r ~ r r .. ~-
20
10
i i i i i i i i i i
10 20 30 40 60 60 70 80 90 100 110
50 v
v v v v v
4O
30
a=
2O
10
0 I I I ' I I I I I I
10 20 30 40 50 60 70 80 90 100 110
50 84
40
A
~
C v A. . #Av v r A A v
30 84
b*
20 84
10
0 I I I I I I I I I I
10 20 30 40 50 60 70 80 90 100 110
Viewing Angles Away from Specular
FIG. 4 - V a r i a t i o n of color in a solid color-coated panel as a function of viewing
angle.
weathering has proven to be reliable and capable of differen- i.e., they are flakes with very thin thickness and very broad
tiating between the stabilized exterior grades and the un- surfaces. These pigments are roughly the same size as metal-
treated types generally used in plastics or inks. lic flake pigments, but they are much larger in size than
organic colorants and most inorganic pigments. The most
successful instruments found thus far for measuring particle
Particle S i z e size of these pigments are the laser diffraction types. These
give good relative measurements. The numbers obtained,
Early methods for determining the particle-size distribu-
tion of pearlescent pigments involved manually counting however, are not absolute values since the theory for these
particles viewed under a microscope. The microscopist usu- devices is based on spherical particles and not platelets. Cali-
ally counted about 1000 particles, grouped them in 5-/zm bration of these laser diffraction instruments with standard-
intervals, and then created a distribution curve. The tech- ized glass spheres have shown them to be reliable and repro-
nique was tedious and time consuming, plus it did not give ducible with pearlescent pigments.
enough statistical data about the large particles. As mentioned above, pearlescent pigments are classified
More modern methods that have been tried include the into particle-size distributions for various end uses. Automo-
Coulter Counter, automated sedimenters, and sieving. Most tive coating sizes are carefully controlled by sieving to remove
had difficulties because of the shape of pearlescent pigments, any particles over 50/zm. Such large particles can lead to
www.iran-mavad.com

CHAPTER 2 6 - - P E A R L E S C E N T PIGMENTS 235
140,
120,
100,
L~ 80,
60
40
20
0
10 20 30 40 50 60 70 80 90 100 110
5
4
3
2
I
a*
-1
-2
-3
-4
-5 t I I I I I I I I I
10 20 30 40 50 60 70 80 90 100 110
5,
4,
3
2
1
b* 0
-1
-2
-3
.4
-5
10 20 30 40 50 60 70 80 90 100 110
Viewing Angles Away from Specular
FIG. 5 - V a r i a t i o n of color in a metallic flake-coated panel as a function of viewing
angle.
clogging of filters in automotive painting operations. Very methods usually give less than 20 ppm lead and 3 ppm arse-
fine particle sizes are required for some applications such as nic in pearlescent pigments. Other tests performed include
offset ink formulations and some low solids, water-based conductivity, pH in aqueous solution, specific gravity, bulk
coating systems. Particle sizes of pearlescent pigments range density, and, when a solvent is present, flash point.
from about 5 to 20 p~m for fine grades and up to 100 to
150/.~m for the coarse grades.
Chemical Testing HEALTH AND ENVIRONMENTAL

CONSIDERATIONS
Chemical testing of pearlescent pigments consists of analy-
ses of the chemical composition, i.e., percentage of TiO2 or Pearlescent pigments are nontoxic and nonmetallic materi-
ferric oxide (Fe203), of mica, and of other ingredients. Also, als that do not exhibit the arcing and conductivity usually
trace analyses for heavy metals such as lead, arsenic, Cr +6, associated with metals. Lead and arsenic contents are less
are clone by atomic absorption, ICP instrumentation, and X- than 20 and 3 ppm, respectively. All ingredients are Toxic
ray fluorescence. Both extractions in 0.5 N HC1 and total Substances Control Act (TSCA) listed. The health hazard
dissolution methods are used in these analyses. Extraction rating for dry pearlescent pigments are:
www.iran-mavad.com

100
8O
60
L*
40
2O
0
10 20 30 40 50 60 70 80 90 100 110
75
55
a* 35
-5 60
A A A
~ v v v
-20
b* -40
-60
-80
f
0
Viewing
I
20
Angles
I
30
I
Away
40
from
I
50
P
60
Specular
I
70
I
80
I
90
I
100
I
1 10
FIG. 6-VariaUon of color in a pearlescent pigment-coated panel as a function of

viewing angle.
Health--O REFERENCES
Flammability--O
Reactivity--O A general reference for pearlescent pigments is Greenstein, Leon
Personal P r o t e c t i o n - - E M., Pigment Handbook, Vol. 1, 2d ed., Peter A. Lewis, Ed., Wiley and
Sons, New York, 1988.
If dusting occurs when h a n d l i n g the dry products, a d u s t [1] Simon, H., The Splendor of Iridescence, Dodd, Mead and Co.,
New York, 1971.
m a s k should be worn. Several grades are also available in a
[2] Bolomey, R. A. and Greenstein, L. M., Journal of Paint Technol-
"wetted out" form to p r o d u c e n o n d u s t i n g products. M a n y
ogy, Vol. 44, No. 566, March 1972.
pearlescent p i g m e n t s have been used for years in cosmetic [3] Linton, H. R., U.S. Patent 3,087,828 (1963).
applications. These cosmetic grade p e a r l e s c e n t p i g m e n t s [4] Armanini, L. and Bagala, F., U.S. Patent 4,146,403 (1979).
have FDA approval for use as cosmetic ingredients a n d color [5] Quinn, C.A., Rieger, C.J., and Bolomey, R.A., U.S. Patent
additives. 3,437,515 (1969).
www.iran-mavad.com

[6] Esselborn, R. and Berhanrd, H., U.S. Patent 4,086,100 (1978). 1990,
[7] Rieger, C. J. and Arrnanini, L., U.S. Patent 4,134,776 (1979). [12] Teaney, S., Welker, J., and Rieger, C. J., Detroit Color Council,
[8] Nittz, K., Watanabe, T., and Suzuki, F., U.S. Patent 4,828,623 15 Nov. 1989.
(1989). [13] Hofmeister, F., Paint and Ink International, May 1991.
[9] Rieger, C. J., Industrial Finishing, October 1984. [14] Hofmeister, F. and Pieper, H. I., Farbe & Lack, Vol. 95, 1989, p.
[10] Rieger, C. J., Journal of Polymers Paint Color, October 1986. 557.
[11] Rodrigues, A. B. J., Proceedings, AIC Symposium on Instru-
[15] Rieger, C. J., Reprints ofSPE NATEC, November 1975, p. 155.
mentation for Color Measurement, Berlin, Germany, 4 Sept.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Inorganic Anti-Corrosive
Pigments
by M. Jay Austin 1
W H A T IS C O R R O S I O N ? and mechanisms. For our purposes, we will limit our discus-

sion to examination of the following five mechanisms of pro-
CORROSION IS AN ELECTROCHEMICAL PROCESS t h a t t a k e s p l a c e tecting metals by using coatings:
on the surface of metals, deteriorating them a n d - - i f not 9 Barrier effect of film or vehicle.
halted--destroying them. The process usually occurs in a 9 Barrier pigment effect.
liquid or gaseous environment and may take the form of a 9 Sacrificial pigments.
direct chemical attack, electrochemical reaction, electrolysis, 9 Vehicle enhancement (film formulation and development).
or oxidation. During deterioration, the metal may form com- 9 Active inorganic inhibitive pigmentation.
pounds or be taken into solution. The following factors must
be present for corrosion to take place:
9 A thermodynamically unstable metal. Barrier Effect
9 An electrolytic conductor of ions. Among the oldest inhibitive methods known, barrier coat-
9 An electrolyte (an electrical conductor such as a moist ings provide a protective, physical shield between a metal and
path). air, moisture, or chemicals. While the composition and thick-
9 An electron acceptor. ness of barrier coatings vary widely, they generally have a low
If corrosion is extreme, the metal will, in essence, return to permeability or moisture vapor transmission rate. As a rule,
the more stable composition of its original ore, disintegrating the lower the transmission rate, the less likelihood that oxy-
into oxides, carbonates, and sulfates. For instance, the rust- gen and moisture will reach the substrate. Some common
ing of iron metal occurs naturally under atmospheric condi- barrier coatings include organic paints and lacquers, metallic
tions, since rust, a hydrated form of the common iron ore, coatings (hot dip), and heavy mastics.
ferric oxide, is more stable than iron metal [1]. In this exam-
ple, the unstable iron metal is also an electrical conductor. Barrier Pigment Effect
Salt water is usually the electrolytic conductor of ions, and Pigments not only add color to coatings but can also pro-
dissolved oxygen is the electron acceptor [2]. tect metal from corrosion by reinforcing the film and limiting
Rates of corrosion vary, often depending on the electrolyte. permeability. "Lamellar" pigments, for example, such as mica
Normally, metallic surfaces in contact with acidic solutions and micaceous iron oxide, form a wall of flat, thin particles
(such as salt water [3]) will exhibit the most rapid rate of within a paint film. These resist penetration, forcing water to
corrosion; neutral solutions will be somewhat less corrosive wend a long, tortuous path toward the substrate (Fig. 1).
and alkaline solutions the least corrosive. Metal may also Metallic flakes of aluminum, bronze, or steel produce similar
corrode in the presence of soil or a dissimilar metal [4]. While effects.
many types of corrosion exist, this discussion is limited to the Since not all pigments are compatible with all resin sys-
degradation which occurs when a metal's natural protective tems, care must be taken when adding pigments to a coating.
oxidative film is attacked and worn away. In highly acid or alkaline environments, inert or chemically
Common examples of this sort of corrosion include the resistant pigments should be used.
progressive red rusting of iron, the white rusting of zinc, and
the tarnishing of copper. Sacrificial Pigments
Zinc is a "natural" for use in protective coatings since zinc-
rich coatings offer cathodic protection when applied to
T H E U S E OF COATINGS TO P R O T E C T ferrous substrates, that is, the zinc acts as a cathode during
METALS AGAINST C O R R O S I O N the corrosion process, receiving the attack normally suffered
by the ferrous metal [5]. To some degree, the duration of the
Before the beginning of recorded time and ever afterward, pigment's efficacy is dependent on the thickness of the sacrifi-
mankind has battled corrosion with a multitude of methods cial coating.
Vehicle Enhancement
1Vice President and technical director, HALOX Pigments, a divi-
sion of H a m m o n d Lead Products, 1326 S u m m e r Street, H a m m o n d , The formulation of a coating itself can add greatly to corro-
IN 46320-2240. sion protection. The addition of pigments, for example, can
238
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CHAPTER 27--1NORGANIC ANTI-CORROSIVE PIGMENTS 239
Coating with
Metallic Pigment or Mica Unreinforced Coating
Water Wa~r
[~11 lit
I I
I
OOQ
,
..'--E
I
I
?,
Ill
]
:
I
J l ~
t
I I
=,Ooo~176
Substrate
/11/11111111/111111
Substrate
FIG. 1 -Barrier pigment effect. Water takes a straight path through an unreinforced film,
but is forced to take an extended path through lamellar particles of a metallic flake or
mica-reinforced film (after Alan Smith, Inorganic Primer Pigments [2]).
help reinforce film structure and reduce permeability (as enhancing polarization by raising the concentration of posi-
mentioned earlier). Some pigments, such as red lead, react tively charged hydrogen ions at the cathode.
with components in linseed oil/alkyd primers to produce lead Inhibitive pigments such as zinc chromate, phosphate, sili-
soaps which increase the corrosion resistance of the paint cate, and borate suppress corrosion by enhancing anodic
film [6]. Other additives are used to enhance other coating or passivation in acid solutions. In neutral solution, the pig-
film characteristics, such as drying time, flow, adhesion, and ments are adsorbed onto the metal surface, reducing anodic
mildew resistance. Binder selection and manufacturing activity.
methods may also be adjusted to offer maximum corrosion Oxidativepassivation--Though oxidation is usually thought
prevention. to contribute to the deterioration of a metal, oxidation some-
times creates a protective layer on a metallic surface. Passiva-
Inorganic Inhibitive Pigments tion can occur if a metal is oxidized to a stable compound that
The majority of this chapter will focus on the following is part of the electrolyte [9]. Consider, for example, the pro-
active inorganic inhibitors: borates, chromates, leads, molyb- tective layer of aluminum oxide on aluminum metal. The
dates, phosphates, phosphites, and silicates. These pigments oxide minimizes atmospheric corrosion despite the reactive
help prevent corrosion by increasing the likelihood of a nature of the metal.
chemical reaction which can produce a protective coating on Strong oxidizing conditions are normally required for pas-
the surface of a metal or otherwise foiling the chemical reac- sivation to occur. Take the case of iron and nitric acid.
tion between metal and corrosive solution. The ability to Exposed to concentrated nitric acid, iron will develop a very
render a metal surface passive is called passivation and is thin inhibitive passive film; dilute nitric acid, however, will
covered here in two forms: (1) cathodic/anodic and (2) oxida- attack the metal [10].
tive. Neutralization--Another mechanism of inhibitive pig-
Cathodic and Anodic Passivation--Inhibitive inorganic pigments is neutralization of corrosive substances as sulfates,
ments minimize corrosion in neutral solutions by acting as acids, and chlorides. This can often be achieved through the
polarizing agents to retard the three elements of the corro- use inhibitors in a basic environment, which decrease the
sion process: cathodic reactions, anodic reactions, and ionic corrosive effect of acids and enhance the precipitation of
currents in the solution and the metal itself [7]. corrosive elements.
Since the cathodic and anodic processes are the basis for
the corrosion process, control of these processes can play an
important role in corrosion inhibition. The cathodic process S O M E W E L L - K N O W N I N O R G A N I C ANTI-
consists of electrons passing from the metal to an electron CORROSIVE PIGMENTS
acceptor, such as oxygen or hydrogen ions at the negative
terminal, or cathode. In the anodic process, metal ions pass Coatings industry suppliers are developing high-perfor-
into the solution at the positive terminal, or anode (Fig. 2). mance inorganic pigments to meet the growing demand for
As polarizing agents, inhibitive pigments work in a variety nontoxic inhibitive coatings that are both economical and
of ways. Some slow the electrolytic process by retarding the highly effective. The section that follows discusses the chem-
reactions through resistance polarization, that is, by increas- istries, physical properties, functions, advantages, and disad-
ing a film's electrical resistance on the surface of the anode or vantages of some of the most common inorganic inhibitive
cathode [8]. Some inhibitors, such as zinc, magnesium, and pigments.
manganese, form insoluble deposits with hydroxyl ions in Wherever available, the specific gravity, color, pH, oil ab-
neutral solutions at the cathode. These deposits create a visi- sorption, and water solubility of each pigment is recorded,
ble film on metal surfaces and help increase cathodic resist- supplied in most cases from pigment manufacturers' pub-
ance polarization. Some inhibitors work in acid solutions, lished data. Large discrepancies can exist between such data
www.iran-mavad.com

Current flow Metallic conductor

,n
Anode Cathode
(Metal 1) / (Metal 2)
Oxidation
reaction
occurring . . . .
f
J
/ M1
~
~
Oxygeninelectrolyte
Electrolyte
Reductionreaction
~,. occurring at cathode
at anode
Current flow through electrolyte

FIG. 2-Electrochemical corrosion. A simple cell showing the components required for
cathodic and anodic corrosion processes (after Dean Burger, "Fundamentals and Pre-
vention of Metallic Corrosion," Corrosion and Corrosion Protection Handbook, Philip A.
Schweitzer, Ed., Marcel Dekker, Inc., New York and Basel, 1983).
and actual measurements, and verification of the published TABLE 1--Typical properties of modified barium metaborates.
data is therefore recommended before any formulation Grade I G r a d e II G r a d e III
project is initiated since significant differences in data can
Specific gravity 3.30 3.70 3.30
dramatically affect formulation performance. This author, Color White White White
for example, measured oil absorptions as high as 85 for some pH 10.0 9.1 10.0
zinc chromate samples, although the published data report Oil absorption 30 20 23
an oil absorption of approximately 25. Water solubility 0.3% 0.2% 0.4%
Typical loading levels: 3 to 15%, based on total weight.
For the following pigments, specific gravity is expressed as Some heavy duty maintenance
g/cm3; color indicates general appearance; pH is measured on coatings may require up to 40%
a 10% slurry; oil absorption is expressed as g/100 g and nor-
mally determined by the spatula rubout method, ASTM D
281-84; and water solubility is expressed as percent soluble. tion, and the anodic passivation from the metaborate ion
Recommended loading levels for many of the pigments are adds to the pigment's anti-corrosion performance.
also included for general formulation assistance, and these Barium metaborates are often considered environmentally
are expressed as a percentage of total weight based on typical acceptable alternatives to more traditional, toxic pigments;
paint density of 1200 g/L or 10 lb/U.S, gallon. If paint densi- however, it must be remembered that soluble barium is an
ties vary widely from these figures, simple extrapolations may acute toxicant, and its presence in high levels may cause
be made. pigments to be classified as hazardous wastes.
The pigment has other disadvantages. As a soluble com-
pound, it may be quite reactive with many systems. To con-
Borates trol its solubility, it is often coated with a silica modification.
A. Barium Metaborate (BaO-B203.H20) [11-14] When barium metaborate is formulated with certain acidic
resins or acid-catalyzed baking systems, the resultant coating
The grades shown in Table 1 indicate three grades of com- may exhibit stability problems. Therefore, care must be taken
mercially available modified barium metaborate, the most when formulating water-reducible and latex resin systems us-
commonly used borate inhibitor. Grade I is the primarily
ing this pigment to minimize its solubility and reactivity.
barium metaborate, and Grades II and III are modifications
of Grade I which are said to decrease the reactivity of the
pigment, thus increasing its formulation versatility. Grade II B. Zinc Borate
includes approximately 27% zinc oxide, and Grade III in- Zinc borate, usually used to provide flame retardancy in
cludes approximately 18% zinc oxide and 29% calcium sul- plastics and cellulosic fibers, is not normally thought of as an
fate. inhibitive pigment. However, recent research indicates that
Modified barium metaborates may be used in many kinds zinc borate, used in combination with modified barium me-
of applications in a broad range of solvent and water-based taborate or zinc phosphate, exhibits synergistic performance
resin systems. The pigment's alkalinity contributes to inhibi- properties resulting in enhanced corrosion prevention. This
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CHAPTER 27--INORGANIC ANTI-CORROSIVE PIGMENTS 241
effect is most likely the result of the blended product's de- are applied at fairly low film thicknesses, these wash primers
creased solubility. have very poor hiding ability.
C. Strontium Chromate (SrCrO4)
Chromates Specific gravity 3.70
Color Yellow
Chromates have long been used as inhibitors since the pH 8.5
soluble chromate ion is itself inhibitive and the chromate Oil absorption ~35
passivating ion is among the most efficient passivators Water solubility 0.05%
known. Unfortunately, chromates are less widely used than in
the past since hexavalent chromium pigments are either con- Strontium chromate is mainly used to prevent corrosion on
firmed or suspected human carcinogens [15]. Evidence indi- aluminum, and primers containing this pigment are standard
cates that strontium, calcium, and zinc chromates are among for the aviation industry. Strontium chromate is so effective
the most carcinogenic forms of hexavalent chromium. Also, at low loadings that it is often used to provide inhibition for
lead chromate is considered a suspected carcinogen by the coil coatings despite the fact that it is the most expensive
American Conference of Governmental Industrial Hygienists chromate inhibitor.
(ACGIH), while zinc chromate is considered a confirmed The pigment is sometimes combined with zinc chromate in
carcinogen [16]. water-based formulations. In these cases, to avoid stability
problems, loadings are kept at low levels, about 2% total
A. Zinc Potassium Chromate (4ZnO.6K20.4CrOr3H20) chromate.
Specific gravity 3.45 D. Other Chromate Inhibitors
Color Yellow Barium chromate, calcium chromate, and ammonium di-
pH 7.5 chromate are also used to control corrosion and flash rust,
Oil absorption 25 but their use is very limited and merits no further discussion
Water solubility 0.1% [17] here.
This inhibitive pigment, also known as zinc chromate or
zinc yellow, is the product of reactions among potassium
Leads
dichromate, zinc oxide, and sulfuric acid. Versatile and Lead, though not a direct inhibitor, reacts with certain
highly efficient, zinc chromates are effective inhibitors even resin systems to form lead soaps which are active inhibitors.
at relatively low loading levels. Because of their yellow color, Lead pigments have proven themselves over the years to be
they are generally limited to use as primers. outstanding anti-corrosives which perform particularly well
Although zinc chromates have a threshold limit value of over insufficiently prepared surfaces.
0.001 mg/m 3 and are therefore fairly toxic, these pigments are However, since it accumulates in body tissue, lead is gener-
among the most widely used anti-corrosive products. In the ally considered an acute and chronic toxicant and has be-
United States, they still make up more than 30% of the entire come the subject of strict environmental regulations, espe-
inhibitive pigment market. cially regarding waste disposal and worker protection.
How do zinc chromates prevent corrosion? While the spe- Although they are still used to produce heavy duty mainte-
cific mechanism is not wholly understood, there are several nance coatings and lead chromate colors, regulations have
theories on the subject, i.e.: caused the use of lead pigments to decline.
9 Zinc chromates are anodic inhibitors. A. Red Lead (Pb304)
9 Zinc chromates improve the corrosion protection of the Specific gravity 8.85
existing oxide film [18]. Color Orange
9 The ferrous salts precipitated by zinc chromates contain a pH 6.5
protective mixture of ferric and chromic oxides. Oil absorption 6
Water solubility <0.001%
B. Zinc Tetraoxychromate (ZnCrO4-4Zn[OH]z)
One of the first recorded inhibitors and still one of the most
Specific gravity 3.65
effective, red lead has been widely used in primers for struc-
Color Yellow
tural steel. The pigment is available in four grades containing
pH 7.5
from 85 to 98% Pb304.
Oil absorption 53
While red lead is an oxidizing agent, its inhibitive mecha-
nism is much more complicated than mere oxidation. When
Often referred to as basic zinc chromate, zinc tetra- formulated with linseed oil, red lead forms soaps which, in
oxychromate is commonly used in the manufacture of two- the presence of water, release soluble lead compounds and
package poly(vinyl butyryl) (PVB) wash primers, which con- organic acids. These soaps also improve the mechanical
sist of phosphoric acid and zinc tetraoxychromate dispersed properties of the paint film and promote passivation through
in an alcoholic poly(vinyl butyryl) solution. These primers, three mechanisms:
also called etch primers or tie coats, are used to passivate 9 Anodic adsorption of soluble lead compounds.
steel, galvanized, and aluminum surfaces, improving the ad- 9 Anodic adsorption of acid molecules.
hesion of topcoats. Because they are usually low in solids and 9 Anodic precipitation by oxidation [19].
www.iran-mavad.com

Although soap formation is red lead's chief protective A. Basic Zinc Molybdate [20]
mechanism, use of the pigment is not restricted to oil-based Specific gravity 5.06
paints. Epoxides, chlorinated rubbers, and vinyls are just Color White
some of the "oil-less" systems which are often formulated pH 6.5
using red lead. There are questions regarding whether red Oil absorption 14
lead functions as an inhibitor in these systems. It is more Water solubility <0.01%
likely that the pigment exhibits the low oil absorption, pig- Typical loading levels 5 to 15%
ment packing characteristics, and fine particle size of an ideal
extender. Recommended for use in alkyds, epoxides, epoxy esters,
polyesters, and other solvent-based resin systems.
B. Basic Lead Silicochromate (BLSC)
B. Basic calcium zinc molybdate [21]
Color Orange Specific gravity 3.0
pH Color White
Oil absorption 14 pH 8.5
Water solubility <0.01% Oil absorption 18
Typical loading levels 2.5 to 10%
Developed as a substitute for red lead, BLSC was once
widely used in heavy duty maintenance coatings. It contains Recommended for use in water-reducible and latex-based
two active ingredients: monobasic lead chromate and gamma resin systems as well as two-component polyurethane and
tribasic lead silicate. The former enhances the stability of the epoxy systems.
coating package and contributes a chromate ion, thus im-
C. Basic Zinc Molybdate/Phosphate [22]
proving inhibition; the latter provides exceptional inhibitive
characteristics. Specific gravity 4.0
BLSC offers several advantages over red lead: Color White
9 Reduced density minimizes problems with pigment sus- pH 5.5
Oil absorption 14
pension and settling and lowers the density of finished
paint. Water solubility <0.01%
9 Improved resistance to chalk and carbonation for better Recommendations are the same as for basic zinc molyb-
weather resistance and application in topcoats. date. This product, however, is reported to provide enhanced
9 Lower tint strength for a broader range of color formula- performance over rusted steel substrates.
tion.
Because it contains both lead and hexavalent chromium, D. Basic Calcium Zinc Molybdate/Zinc Phosphate [23]
BLSC is no longer as widely used as it once was. Specific gravity 3.0
Color White
C. Other Lead Pigments pH 7.5
The following lead-based products have been used to in- Oil absorption l8
hibit corrosion in very specific or very limited applications: Typical loading levels 5 to 15%
lead suboxide; basic carbonate white lead and lead cyana- This inhibitor, a mixture of basic calcium zinc molybdate
mide (mirror back coatings); basic lead silicate (electrodepo- and zinc phosphate, is reported to offer improved adhesion
sition primers); tribasic lead phosphosilicate; basic lead sili- over ferrous metals. Recommended for use in both solvent-
cosulfate; dibasic lead phosphite; lead chromosilicate; lead and water-based systems.
sulfate; and calcium plumbate.
Phosphates
Molybdates
A. Zinc Phosphate [Zn3(PO4)2-2HzO]
Molybdate-based pigments are anodic passivators, pre-
venting corrosion by forming a protective layer of ferric mo-
Color White
lybdate on the surface. This layer is insoluble in neutral and
pH 7.5
basic solutions. However, since most commercial molybdate
Oil absorption 25
pigments contain zinc, the formation of inhibitive zinc soaps
in oleoresinous systems may add to the anti-corrosive proper-
Typical loading levels 5 to 10% in water-
ties of molybdate products.
based systems;
Although molybdate inhibitors are free of lead and chro-
5 to 15% in solvent-
mate, they are limited in market value due to their expense.
based industrial systems;
To make these more accessible, molybdate/phosphate com-
10 to 30% in
positions have been introduced, though these are difficult to
maintenance coatings
disperse. Micronized versions of molybdate/phosphate are
available to counteract the dispersion problem. Zinc phosphate's formulation versatility has probably led
Following are the four most popular molybdate inhibitors to its status as one of the most widely used "nontoxic" inor-
available on the market today. ganic inhibitors. Zinc phosphate can be readily used in a wide
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CHAPTER 2 7 - - I N O R G A N I C ANTI-CORROSIVE PIGMENTS 243
variety of resin systems, including high acid number alkyds, TABLE 2--Typical properties of aluminum triphosphate.
water-reducible coatings, high-performance resins and acid- Grade I Grade II Grade III
catalyzed baking systems. The pigment's low reactivity and
low solubility give it a distinct formulating advantage over Color White White White
more basic, less stable nontoxic pigments. pH 6.5 6.5 6.5
Zinc phosphate is thought to inhibit corrosion in three Oil absorption 37 32 30
ways: Water solubility (max) 1% 1% 1%
9 Through phosphate ion donation.
9 By forming a protective anodic film.
9 By forming anti-corrosive extracts in the presence of cer- suitable for water-based coatings. Grade II is modified with
tain oleoresinous vehicles. zinc and silicate.
Zinc phosphate has a creditable track record of effective Grade III--For solvent and water-based systems. Easier
performance in real-world testing, but rates much lower in dispersion makes the pigment more effective in low build
salt spray testing and other accelerated tests. This poor per- coatings. Grade III is modified with zinc.
formance may be explained by the fact that salt water and
high humidity often impair the performance of the pigment.
Phosphites
B. Modified Zinc Phosphates [24,25] A. Zinc Hydroxy Phosphite [[2ZnO(OH)z.
The coating industry has produced several variations of ZnHPaOa].X2H2-O, w h e r e X = 1 to 17] [27]
zinc phosphate that make use of other inorganic inhibitors Specific gravity 3.9
and organic surface treatments to improve the pigment's per- Color White
formance in salt spray testing. The formulation versatility pH 7.0
and recommended loading levels of these modified versions Oil absorption 18
of zinc phosphate are about the same as those of standard Water solubility (Max.) 0.04%
unmodified zinc phosphate. Although the modified zinc Typical loading levels 10-25% in
phosphates appear to offer improved performance in acceler- maintenance applications;
ated testing, there is little evidence to uphold these claims in 5-15% in general
actual commercial applications. industrial and water-
Modified versions of zinc phosphate include: based applications
Aluminum zinc phosphate--The higher phosphate content
and solubility of this aluminum/zinc coprecipitated phos- Zinc hydroxy phosphite (also called zinc phospho-oxide)
phate contribute to its enhanced corrosion inhibition. results from the reaction between zinc oxide and phospho-
rous acid. Anodic passivation of the phosphite ion is the
Basic zinc phosphate hydrate--An organic surface treat-
primary mechanism of inhibition, although the pigment's
ment (claimed to be an electrochemically effective inhibi-
ability to form inhibitive zinc soaps in oleoresinous systems
tor) enhances the performance of this pigment.
also contributes to corrosion prevention. While not recom-
Basic zinc molybdenum phosphate--This pigment makes mended for use in high-acid-number or water-soluble resins,
use of a low level of molybdate (1.5%) to enhance inhibi- the pigment is compatible with a variety of resin systems.
tion.
Zinc silicophosphate hydrate--This pigment appears to be a
complex composite of barium sulfate, silica, magnesium Silicates
oxide, and sodium dichromate. Trace amounts of Silicate pigments contribute to corrosion inhibition in sev-
hexavalent chromium may account for the pigment's im- eral ways, chiefly through anodic and cathodic passivation.
proved performance, but even these very low chromate In addition, in oleoresinous systems, these pigments form
levels could possibly present waste disposal problems. inhibitive soaps of barium, calcium, strontium, and zinc. The
inhibitive value of silicate pigments is further enhanced by
C. A l u m i n u m Triphosphate [26] their alkalinity and solubility.
Available commercially in three grades (Table 2), alumi-
num triphosphate is a relatively recent chromate-free inhibi- A. Calcium Borosilicate [28-30]
tor. A condensation product, it is often modified with zinc ion Available in three commercial grades (Table 3), calcium
or silicate to minimize its solubility and reactivity. Inhibition borosilicate is effective in a range of applications:
is thought to result from the tripolyphosphate ion's ability to a. Grades I and III--Recommended for use in protective
chelate iron ions, as well as higher phosphate levels resulting coating systems-based on traditional alkyd technology,
from the depolymerization of the tripolyphosphate ion into these pigments differ primarily in their B203 content:
orthophosphate ions. These pigments exhibit typical phos- 10.6% for Grade I and 15.6% for Grade III. They are gener-
phate performance relative to loading levels. ally used for such applications as trade sales, industrial
Each grade is recommended for specific applications: maintenance, railroad and tank coatings, and shop
Grade / - - F o r use in solvent-based primers (alkyds and primers. While they can be used in a variety of resin sys-
epoxides). Grade I is modified with zinc and silicate. tems, including medium and long oil alkyds, epoxy-esters,
Grade H - - F o r use in solvent and water-based systems. The and modified alkyds, they are not suited for use in high-
pigment's lower water solubility apparently makes it more acid-number resins, acid-catalyzed systems, water-based
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TABLE 3--Typical properties of calcium borosilicates. tive in thin film applications and in systems requiring a
Grade I Grade II Grade III high gloss.
Color White White White M i s c e l l a n e o u s Inhibitive Pigments
pH 10.1 10.1 10.1
Oil absorption 36 27 41 A. Ion Exchange Pigment
Water solubility 0.35% 0.34% 0.37%
(max) Specific gravity 1.8
Typical loading levels 10-20% 10-20% in primers, 10-20% Color White
2.5-10% in pH 9.2
topcoats and DTM
finishes Oil absorption 50 [35]
Claimed to be effective in all paint systems, this pigment
uses the mechanism of ion exchange with corrosive species to
resins, epoxides, and other high-performance resins, or for prevent corrosion. Loading levels should be half the levels of
immersion or semi-immersion service. typical corrosion-inhibiting pigments.
b. Grade H--This pigment, a low-oil-absorption version of
the other two grades, is used primarily in high solids, B. Zinc Oxide
medium gloss topcoats, direct-to-metal (DTM) coatings, Research has suggested that zinc oxide possesses both pas-
and self-priming alkyd systems. PVC levels range from 40 sivating and cathodic inhibitive capabilities [36,37]. Also,
to 45% in primers and 15 to 25% in topcoats and DTM when used in latex metal primers and certain oleoresinous
coatings. systems (such as SSPC Paint No. 25) [38], zinc oxide exhibits
obvious anti-corrosive action. ~
B. Phosphosilicates [31-34] Often used with more conventional active inhibitors such
Four modifications (see Table 4), each representing a dif- as zinc chromate and calcium borosilicates, zinc oxide ap-
ferent commercial grade, are available for a variety of uses. pears to raise the cross-link density of many paint films,
Calcium Barium Phosphosilicate (Grade/)--This pigment making them harder. Zinc oxide may also absorb ultraviolet
is for use in conventional and high solids solvent-based light, thus protecting the resin. Since the pigment tends to
epoxy systems. The pigment is also used in organic zinc- have seeding problems and can cause film brittleness, care
rich primers as an anti-settling agent. must be taken when using zinc oxide in inhibitive coating
applications.
Calcium Barium Phosphosilicate (Grade II)--A low-oil-ab-
sorption version of this pigment, Grade II is for use in most
water-borne systems, including latexes and water-reduc- Zinc Metal in Primers
ible systems. When formulated in alkyds, this product, like
many other phosphate pigments, will demonstrate excel- The prime focus of this discussion is inorganic inhibitive
lent real-world performance, but poor performance in ac- pigments which function through the mechanism of soluble
celerated testing. inhibitive species; however, zinc metal--which functions
through the mechanism of cathodic protection--deserves a
Calcium Strontium Phosphosilicate (Grade III)--This pig-
brief mention.
ment is for use in most water-based acrylic lacquers, as well
In many applications, including the protection of steel
as water-reducible caulks and sealants. When the product
structures, zinc-rich coatings offer the best corrosion inhibi-
used with zinc phosphate in water-based lacquer systems
tion available, especially when topcoated with either epoxy or
in a 1:1 ratio, a synergistic effect is produced which im-
urethane. Actual particles or flakes of zinc in the paint film
proves performance.
protect the ferrous substrate by acting as the anode and
Calcium Strontium Zinc Phosphosilicate (Grade IV)--This corroding sacrificially. While the correct loading level of zinc
grade is for use in a broad range of resin systems, including metal in zinc-rich primers is still a matter of debate, these
traditional and high-solid alkyds, latexes, epoxides, water- coatings usually contain 80 to 85% zinc metal. Zinc-rich
reducible alkyds, high-acid-number resins, vinylidene chlo- primers can be formulated as inorganic coating systems
ride latexes, and catalyzed baking systems. A recent devel- (ethyl silicate binders) or organic systems (such as epoxides).
opment, Grade IV is the most versatile and effective of the Zinc-rich primers require near-white blast surface prepara-
phosphosilicate inhibitive pigments. Because of its fine tion and must be fully cured before topcoating. Two major
particle size and low oil absorption, this pigment is effec-
problems associated with zinc-rich formulation are pigment
settling and hydrogen gassing.
TABLE 4--Typical properties of phosphosilicate inhibitors.
Grade I GradeII GradeIII GradeIV Barrier Pigments
Specific gravity 2.97 2.97 2.90 3.01 A. A l u m i n u m Flake
Color White White W h i t e White
pH 7.9 8.3 7.8 7.0 Aluminum flake, typically supplied as a slurry, is produced
Oil absorption 44.5 31.5 53.5 26.0 by atomizing molten aluminum and ball-milling the powder
Water solubility 0.02% 0 . 0 2 % 0 . 0 3 % 0.02% into a solvent. The resultant flake is frequently used to im-
Typical loading levels 5-10% 5-10% 5-10% 2.5-15%
prove the appearance and anti-corrosion performance of
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coatings for tanks, bridges, roofs, railroad cars, automobiles, nated with lead and chromate-based pigments. Under these
and office equipment. regulations, containment and disposal of these materials
Coatings containing aluminum flake stand up well to heat could well increase the cost of a typical maintenance repaint-
and moisture. They also resist the damaging effects of ultravi- ing project by tenfold. Regulations concerning the disposal of
olet light, cooling the substrate and preventing deterioration industrial wastes in the United States are strict, due in part to
of the binder. revisions of the Drinking Water Regulations of the Safe
Aluminum flake is available in two grades, leafing and Drinking Water Act, which is an effort to prevent contamina-
nonleafing. A stearate coating on the leafing grade allows the tion of the water supply.
pigment to float on the surface of a paint film. Because this The coatings industry is under legislative pressure to de-
coating is also associated with intercoat adhesion failure in velop environmentally acceptable, high-performance, long-
primer coats, leafing grade aluminum flake is normally used lasting replacements for lead and chromate-based pigments
in topcoat formulations. Typical loadings range from 20 to and reduce levels of VOC. These are not easy tasks. Some of
25%. A disadvantage of using aluminum flake is that the the formulation and application factors which affect the in-
pigment is very reactive with water, and hydrogen gassing dustry's efforts at compliance have already been discussed;
may occur if moisture levels are not maintained below 0.15%. the following is a look at some of the stringent techniques in
use to evaluate the performance of new, less toxic inhibitors
B. Steel Flake and protective coatings.
Stainless steel and a number of steel alloys are sometimes
used to make steel flake, which is used in coatings for applica-
tions requiring m a x i m u m resistance to abrasion. HOW FORMULATION AFFECTS THE
P E R F O R M A N C E OF I N H I B I T I V E
C. Micaceous Iron Oxide (MIO) PIGMENTS
Color Dark Gray When formulating with inhibitors, a host of formulation
Oil absorption 11 factors must be taken account since these factors often deter-
Typical loadings 30-50% mine the selection of inhibitive pigments and greatly affect
the development of inhibitive coatings. The most critical
A naturally occurring form of hematite with an Fe2Oa con- formulation factors include PVC (pigment volume concentra-
tent of about 92 to 95%, MIO has been used in protective tion), selecting an extender pigment, solubility and reactivity
coating formulations for over 100 years. Because of its lamel-
(that is, selecting a vehicle and understanding how its compo-
lar structure, it is typically used in primers to improve their
nents interact), and the complex interrelationships between
barrier resistance. Used in topcoats, MIO enhances resist- all these factors.
ance to ultraviolet light.
Pigment Volume Concentration
Pigment volume concentration (PVC) is the ratio of pig-
ENVIRONMENTAL CONSIDERATIONS ment volume to the total nonvolatile volume in a coating.
Probably the most important formulation factor to consider
Health and safety factors have always been seriously con- when evaluating anti-corrosive pigments, PVC is especially
sidered during the development and evaluation of new crucial when two or more inhibitors are being considered for
protective coatings. Use of lead, hexavalent chromium com- a given application.
pounds, and other toxic pigments is constantly monitored to Essential to the understanding of the importance of PVC is
ensure that current, acceptable limits are met. Environmen- the concept of a "formulation window." This term represents
tal regulations have driven the inhibitive coatings industry to the PVC range at which an inhibitive pigment will give its best
increase efforts to develop and evaluate new, nontoxic prod- performance and is clearly depicted in Fig. 3. Here, the per-
ucts to replace lead, chromates, and traditional inhibitors formance in a salt fog cabinet of three popular chromate-free
with long-standing performance records. inhibitors is compared to that of zinc chromate in a medium
Two primary environmental concerns within the industry oil alkyd primer. Loadings are equal--about 10% of total
are worker protection and waste disposal. Several steps have formula weight--across a PVC ladder at constant volume
been taken to ensure worker safety. For example, all workers solids.
have the right to know the dangers involved with handling the In the figure, the three nontoxic inhibitors each yielded
materials they are exposed to every day and the right to be performance equivalent to zinc chromate, but only within a
offered the capability to handle these materials safely. Be- specific PVC range, a rather narrow formulation window.
cause absorption of toxic pigments through inhalation is a Conversely, zinc chromate offered far greater formulation
major concern, workers are protected by engineering con- versatility, performing over a much broader PVC range.
trols (ventilation), respiratory controls (masks, filters, and The figure illustrates both the importance of addressing the
other equipment), and extensive safety training. The pre- variable of PVC and poses a problem facing the formulator:
ferred option is to completely eliminate the hazardous mate- None of the environmentally acceptable inhibitors--in-
rial and substitute a less toxic pigment, if possible. cluding the three in the figure--come close to matching the
Waste disposal pertains to plant waste produced by paint traditional lead and chromate-based pigments for overall effi-
manufacturing and waste from painting operations. The lat- ciency and formulation flexibility. While each of the three
ter includes overspray and spent blast abrasives contami- chromate-free inhibitors was formulated to equal the per-
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"..\
<><>v .... .~% v<>~ -. ~.
o
\ "...
.-" ,. <>0 ".
a.
\ %'.1
x
~-.~ oo-j
I I I I ~d
J
30 35 40 45 50 55
PVC
INHIBITIVE PIGMENT
m m Zinc Phospho-oxide [] [] [] DModified Barium Metaborate
9999 9 Borosilicate ~ Z i n c Chromate
PVC Loading Levels (Formulation Windows)

of Chromate-free Inhibitors and Zinc Chromate
FIG. 3 - M e d i u m oil alkyd PVC ladder: salt spray performance. Formulation win-
dows of four inhibitive pigments,
formance of zinc chromate, each performed at a much nar- "rule" worked as long as formulators used red lead and other
rower formulation window, thereby severely restricting its lead-based pigments whose very high specific gravities and
use. low oil absorptions permitted relatively high loadings. When
Many factors influence the formulation window of an inhi- large amounts of nonlead inhibitors are used in formulations,
bitive pigment in a given formulation. All these factors must the resulting coatings often perform well in accelerated cor-
be satisfied to maximize the performance of an inhibitor. rosion tests. However, most nonlead inhibitors are much
Crucial factors to consider in association with PVC are: (1) more reactive in vehicle systems than lead-based inhibitive
specific gravity, oil absorption, and other physical properties products, and this reactivity can lower the actual perform-
of an inhibitor; and (2) the effect of these properties on CPVC ance of coatings formulated with high inhibitor loadings.
(critical pigment volume concentration). In general, inhibitor loading should be carefully balanced,
The concept of CPVC, introduced in the late forties, postu- keeping in mind that more is not necessarily better, at least as
lates the existence of a level of pigmentation in a dry paint far as less-toxic, more-reactive inhibitors are concerned.
film at which there is just enough binder to coat the pigment
Comparing inhibitive pigments--Certainly not as straight-
particles and fill the spaces between them [39,40]. Since
forward a matter as comparing apples to oranges, compar-
many nontoxic inhibitors are lower in specific gravity and
ing pigments may be accomplished in several different
higher in oil absorption than more traditional inhibitors, it is
ways: on the basis of equal volume, equal weight, equal
easy to formulate anti-corrosive coatings which exceed CPVC
cost, or equal performance. The choice of method can dras-
and therefore deliver unacceptable levels of inhibition. To
tically affect the results of a formulator's evaluations.
avoid this situation, it is necessary to evaluate inhibitive pig-
ments across a PVC range to achieve optimum performance. Equal Volume--This is the easiest evaluation method and
To do this, coatings should be made at each extreme of the by far the least desirable. Replacing a given volume of one
PVC range; then weight blends of these paints may be used to inhibitor with the same volume of another is simple and
generate the intermediate levels. requires the least number of formulation changes. How-
ever, the wide variations in specific gravities of inhibitors
Inhibitor Loading Levels (from a low of 2.5 to a high of 9.1) and oil absorptions,
In the "old days" of inhibitive coatings formulations, before which vary from 10 to 70, make the results of these evalua-
the advent of environmental regulations, the rule of thumb tions highly questionable.
was to add as much inhibitive pigment as possible. The Equal Weight--This is a valid method of evaluating inhibi-
assumption: if a little was good, then a lot must be better. This tors with loading levels equal to or exceeding 120 g per liter
www.iran-mavad.com

(1 lb/gal). Care must be taken to adjust the levels of ex- problems arising from reactivity and solubility. For example,
tender pigment and vehicle solids when replacing one in- a pigment must have some solubility within a given system in
hibitor with another. This is to ensure that the inhibitors order to participate actively in passivation. Also, a highly
can be compared at a constant loading level over a given reactive pigment can react with binders and other ingredients
PVC range at constant volume solids. in a coating system, causing instability. Adverse chemical
Equal Cost--This method is valid if the inhibitor levels are reactions between the inhibitor and the vehicle in the can or
less than 120 g per liter (1 lb/gal), as long as comparisons the cured paint film can effect coating properties such as
are conducted at a constant loading level over a PVC range viscosity, drying time, cure, adhesion, and weatherability.
at constant volume solids. Therefore, inhibitive pigments must be chosen carefully to
prevent these formulation problems [42].
Equal Performance--The most tedious approach, this
Some chemical reactions, such as the reactions between
method ensures the most cost-effective formulation possi-
basic pigments and acid catalysts, neutralize inhibitive action
ble. Basically a combination of simultaneous evaluations of
by preventing film cure. Some reactions may even accelerate
a PVC ladder and an inhibitor loading ladder, this ap-
corrosion. Others may do good or harm, depending on where
proach permits the formulator to evaluate each inhibitor
they occur. For example, the formation of metallic soaps on a
for its optimum formulation window.
paint film caused by a reaction between red lead and linseed
Extender Pigments oil acids promotes corrosion inhibition; however, if this same
reaction occurs in the paint can, viscosity may increase to the
Although a wide choice of extenders is available for inhi-
point that the liquid paint becomes unusable.
bitive coatings formulation, extender selection traditionally
Generally, inhibitive pigments retard or prevent blistering
has not received much attention. This may be the result of the
caused by corrosion in pinholes or scribes or by moisture
former widespread use of lead and chromate-based inhibi-
drawn into the paint film by electrical activity of the corro-
tors, whose excellent performance masked any flaw contrib-
sion cells. But use of inhibitors may lead to osmotic blister-
uted by an extender. With emphasis on environmentally ac-
ing, especially during humidity and condensation testing. Os-
ceptable (and less effective) inhibitors, however, selection of
motic blistering is caused by the presence of water and
suitable extenders is an important factor in the formulation
soluble pigment at the juncture of the substrate and the
of inhibitive coatings.
coating film [43]. To prevent this condition, low-solubility
Figure 4 contains the results of work in latex maintenance
pigments should be used.
coatings. The data here clearly show that the performance of
extender pigments depends to a great extent on the type of
vehicle and inhibitor used in the formulation, that is, the
performance of extenders will vary from system to system. A P P L I C A T I O N A N D P R O T E C T I V E COATING
Selecting the appropriate extender, therefore, may be as cru- PERFORMANCE
cial to coating performance as selecting the vehicle system or
inhibitive pigment [41]. Coating application (how, where, why, and for how long a
coating will be used) must be carefully considered when for-
Reactivity and Solubility mulating environmentally acceptable alternatives to tradi-
Inhibitors should be carefully selected for compatibility tional toxic inhibitors. The length of time a protective coating
with given coating systems to prevent common formulation can effectively protect a ferrous surface has been said to
10
Calcium Calcium
Clay Carbonate Carbonate
w
O
z 6
<
=E
n-
O
iJ.
n- 4
Ill
a.
Clay
0
ACRYLIC LATEX STYRENE-ACRYLIC LATEX
FIG. 4-Extender performance properties: accelerated performance measure-
ments.
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depend on the following application factors: the environ- EVALUATING INHIBITIVE PIGMENT AND
ment, how the coating is applied, the substrate, and the COATING P E R F O R M A N C E
surface preparation of the substrate [44].
Consider the environment where the inhibitive coating will Pigment and coating evaluation techniques--especially ac-
be used: Will the coating be exposed to harsh chemicals, celerated laboratory tests--are more important now than
abrasion, industrial atmospheres, heavy traffic, high heat, or ever before. The reason: Users and manufacturers alike de-
other extreme conditions? Or will it be used in a rural setting, mand that new inhibitive products not only meet environ-
exposed to the elements? Answering these questions will help mental regulations, but also meet or exceed the performance
determine the proper vehicle system and application tech- standards set by established, environmentally unacceptable
niques to be used with the coating. pigments. This discussion will deal with the two principle
Other factors to consider when deciding how to apply a methods of evaluation used by the coatings industry: acceler-
protecting coating include the type of applicator (brush, ated testing and "real-world" (natural atmospheric) testing.
roller, spray, or dip), adequate and uniform film thickness
[45], drying time, and temperature. Though application tech- Accelerated Corrosion Testing
niques are often given little attention, they can profoundly In real-world applications, protective coatings are often
affect the performance of a protective coating. expected to provide up to 20 years of service. Accelerated
Substrates are also important factors in testing protective testing attempts to predict the life expectancy of a protective
coatings and inhibitive pigments. For example, untreated coating in a short span of time, from half a year to a year. This
cold rolled steel generally shows more undercutting at scribes evaluative "fast forwarding" meets the needs of manufactur-
than sandblasted hot-rolled steel or treated steel. Because it is ers and users alike, who demand prompt development and
easier to differentiate between pigments on untreated steel, commercialization of new products. Though several kinds of
that substrate is frequently used to compare the performance accelerated testing procedures are in use, all have essentially
of different inhibitive pigments. On the other hand, use of a the same purposes: to significantly shorten the time needed
phosphatized substrate seems to improve the performance of for a coating to fail and to evaluate the causes of its failure.
protective coatings, apparently enhancing adhesion, pas- Although accelerated corrosion testing is the most com-
sivating the surface, and improving the coating's inhibitive monly used evaluation method for inhibitive pigments and
properties. protective coatings, the results of accelerated tests correlate
A word of caution: When selecting substrates for testing poorly with the results of real-world testing. Because of this,
inhibitive coatings systems, care must be taken to conduct the validity of accelerated testing, particularly the salt spray
final evaluations of a system on the substrate that the coating test, has been the target of serious doubts and questions. Is
will be applied to in actual use. For screening purposes, accelerated testing relevant to real-world conditions? Do the
however, evaluations m a y be conducted on any appropriate tests accurately predict product performance? Evidence is
substrate. growing to support the theory that many formulation varia-
Protective coatings are frequently applied to the following tions used to enhance a coating's salt spray performance may
ferrous substrates [46]: cold-rolled steel; polished cold-rolled actually detract from the coating's real-world performance.
steel; zinc phosphate-treated cold-rolled steel; iron phos- It has already been demonstrated that, in many cases, ac-
phate-treated cold-rolled steel; hot-rolled steel; abrasive celerated testing is an unreliable predictor of a coating's long-
blasted hot-rolled steel; pre-rusted hot rolled steel, and galva- term protective performance. Figure 5 clearly illustrates this
nized steel. deficiency, depicting salt spray results which totally contra-
No matter what the substrate, the surface preparation of dict the results of natural exposure testing for two protective
the substrate, or its condition, is vital to the evaluation of coatings.
protective coatings and an important factor in determining Despite such strong evidence against the reliability of the
the life expectancy of a coating system. In addition to clean- salt spray test, its popularity continues. For good or bad rea-
ing a surface, improving adhesion, and maximizing the persons, it is the driving force behind the establishment of per-
formance of the inhibitive pigment, surface preparation formance evaluation criteria for many protective coating sys-
helps remove contaminants--such as chlorides and sul- tems and is often the only criterion used to evaluate an
f a t e s - f r o m the substrate's surface [47]. inhibitive coating. In some cases, raw material suppliers are
Though many methods of surface preparation exist, their forced to offer products based solely on their salt spray per-
effectiveness varies widely. For example, studies suggest that formance, often without regard to the coatings' performance
a protective coating will last four times longer on a blasted in the real world. Another section of this book discusses this
surface than on a hand-cleaned or weathered substrate [48]. situation further and details the research the industry is
This improved longevity is attributed to better adhesion and a doing to address the problem.
more intimate contact between substrate and coating, which
allows the inhibitor to maximize its performance. Real-World Corrosion Testing (Natural Atmospheric
Some of the commonly used surface cleaning techniques Exposure Testing
are [49]: centrifugal blasting; metallic and nonmetallic abra- Considered by many researchers to be the most dependable
sives; abrasive air blasting and water blasting; by hand and method of predicting the performance of a protective coating,
power tools; chemicals; pickling. Less common methods in- real-world testing exposes products to real-time, actual atmo-
clude hot gas, flame, bacterial, zinc shot, ice particles, and spheric conditions. In essence, the tests approximate the
ultrasonic. types of environments for which the coatings were designed.
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CHAPTER 2 7 - - I N O R G A N I C ANTI-CORROSIVE PIGMENTS 249
thicknesses. Neither of these procedures are effective,

however, since neither represents the application for
which the coating was designed.
2. Lack of Controls--Establishing controls and measuring a
coating's consistency of performance is a real challenge in
real-world testing. In outdoor exposures, environmental
factors such as temperature and humidity change from
year to year at the same site, making reproducible results
next to impossible.
3. Multiple Stresses--Because a coating exposed to an out-
door environment encounters many stresses, it is not easy
to determine the effects of each individual stress.
4. Varying Environments--In outdoor testing, establishing a
standard test environment is virtually impossible. Environ-
ments vary dramatically from one part of the country to
the other, from desert to seashore, from mountains to
alluvial plains. Local industries and fluctuations in
weather patterns also contribute to the problem.
In spite of these drawbacks, real-world testing is emerging
as a viable alternative to traditional accelerated testing. Even
comparatively brief exposures of six to eight months can yield
important data. However, the value of these data depends on
sound experiments and proper evaluation techniques. For-
mulators can no longer depend on "one paint/one panel" test
designs.
Statistical Analysis
Another method of correlating performance data and pre-
dicting coating performance is the use of statistical analysis,
which is growing in popularity. Various techniques used to
design more meaningful, accurate evaluations include corre-
lation methods, survival analysis, curve fitting, time series
analysis, and reliability and life analysis.
Several techniques have been developed for assessing mac-
roscopic damage to protective coatings. Though coatings
have traditionally been assessed by visual inspection, these
procedures can apparently detect early stages of corrosion,
giving more relevant, accurate information in a shorter expo-
sure period.
RECENT TRENDS AND DEVELOPMENTS
New Product Development

The Federation of Societies for Coatings Technology
(FSCT) monitors the development and performance evalua-
tions of many new products, many of which reflect the trend
FIG. 5-Protective coating performance data. toward less toxic inhibitors [51]. Another growing trend is the
development of products with lower oil absorption, necessary
for the formulation of high solids vehicles.
Despite their excellent ability to measure and predict anti- Because proper use of auxiliary extenders can enhance in-
corrosive coating performance, outdoor exposure tests have hibitive properties of protective coatings (especially those in-
four obvious disadvantages compared to accelerated tests corporating nontoxic inhibitors), the trend toward develop-
[50]: ing auxiliary extender pigments is likely to continue.
1. Long Duration--Monitoring the degradation of protective Auxiliary pigments are standard extenders modified by sur-
coatings is a marathon task lasting from 5 to 20 years. To face treatments of silanes, titanates, ziconates, and other
accelerate the rate of failure in outdoor exposures, testing compounds. Some commonly used auxiliary pigments in-
labs have exposed the paints to very harsh environments or clude calcium carbonates, clays, talcs, silicas, and wol-
applied the coatings at lower-than-recommended film lastonite.
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O t h e r Testing Procedures ing Practice, 2nd ed., J. D. Kean, Ed., Steel Structures Painting
Council, Pittsburgh, PA, 1982.
Driven by changing r e g u l a t o r y s t a n d a r d s a n d the industry's [7] Shreir, L. L., Corrosion, Vol. 2--Corrosion Control, John Wiley
need for p r o m p t p r o d u c t development, a variety of alterna- and Sons, Inc., New York, 1963.
tive accelerated testing p r o c e d u r e s are being r e s e a r c h e d a n d [8] Shreir, L. L., Corrosion, VoL 2--Corrosion Control, John Wiley
developed. The challenge is to m a k e accelerated testing accu- and Sons, Inc., New York, 1963.
rately reflect real-world conditions a n d yield meaningful, re- [9] Scully, J. C., The Fundamentals of Corrosion, 2nd ed., Pergamon
alistic results. The Corrosion C o m m i t t e e of the F e d e r a t i o n of Press, Oxford and New York, 1975.
Societies for Coating Technology (FSCT) c o m m i s s i o n e d a [10] Scully, J. C., The Fundamentals of Corrosion, 2nd ed., Pergamon
survey [52] on this subject directed to m a n u f a c t u r e r s a n d Press, Oxford and New York, 1975.
users of protective coatings. The results of the survey s h o w e d [11 ] Technical Bulletin RTP-771010, Buckman Laboratories, Mem-
that the p a r t i c i p a n t s were exploring the use of the following phis, TN.
Technical Bulletin B1, Buckman Laboratories, Memphis, TN.
kinds of modified accelerated testing techniques: (1) cyclic [12]
Technical Bulletin B23W, Buckman Laboratories, Memphis,
tests; (2) cyclic n a t u r a l exposures; (3) electrochemical testing; [13] TN.
a n d (4) physico-chemical, physical, a n d m e c h a n i c a l testing [14] Technical Bulletin PC-23W, Buckman Laboratories, Memphis,
procedures. TN.
The Steel Structures Painting Council (SSPC) is evaluating [15] Levy, L. S. and Martin, P. A., "Effect of a Range of Chromium
the m o s t p r o m i s i n g of these accelerated cyclic c o r r o s i o n Containing Materials on Rat Lung," unpublished multi-sponsor
tests. The survey itself is too extensive to be included here b u t study, University of Aston, Birmingham, England, July 1983.
is readily available from the FSCT. [16] American Conference of Governmental Industrial Hygienists,
"Threshold Limit Values for Chemical Substances and Physical
Agents and Biological Exposure Indices (pamphlet)," 1990-
1991.
CONCLUSION [17] Raw Materials Index, National Paint & Coatings Association,
Washington, DC.
Before the b e g i n n i n g of r e c o r d e d history a n d ever since, [18] Jordan and Whitby, 16th Bulletin Research Association of Brit-
p r o t e c t i n g ferrous surfaces from the disintegrating effects of ish Paint, Colour and Varnish Manufacturers, Teddington, En-
c o r r o s i o n has been one of m a n k i n d ' s m o s t c o m m o n a n d per- gland, 1936.
plexing battles. F r o m the lead c o m p o u n d H o m e r ' s black- [19] Appleby, A. J. and Mayne, J. E. O. in Journal of Oil Colour
smiths s m e a r e d on their w a g o n wheels to the sophisticated Chemists' Association, Vol. 50, 1967.
protective coatings used today, the science of preventing cor- [20] Technical Bulletin X65 ZM 0101, Sherwin-Williams Chemicals,
Coffeyville, KS.
r o s i o n is as complex as the corrosion process itself. Over the
[21] Technical Bulletin X65 ZM 0212, Sherwin-Williams Chemicals,
years, m a n y factors have arisen w h i c h d e m a n d consider- Coffeyville, KS.
ation: s u b s t r a t e selection, surface p r e p a r a t i o n , vehicle a n d [22] Technical Bulletin X65 ZM 0332, Sherwin-Williams Chemicals,
p i g m e n t selection, a n d PVC, to n a m e just a few. Coffeyville, KS.
N o w the coatings i n d u s t r y is engaged in a new a p p r o a c h to [23] Technical Bulletin X65 ZM 0425, Sherwin-Williams Chemicals,
the age-old c o r r o s i o n - p r o t e c t i o n problem: developing effec- Coifeyville, KS.
tive n e w nontoxic inhibitors to take the place of t r a d i t i o n a l [24] Heubach Technical Bulletin 10/84, Hans Heubach GmbH and
lead a n d c h r o m a t e - b a s e d pigments. The r e s e a r c h is well un- Co., Longelsheim, Federal Republic of Germany.
derway, a n d the next ten years m a y well see the w i d e s p r e a d [25] Heubach Technical Bulletin h 86-7, Hans Heubach GmbH and
a c c e p t a n c e of these safe, h i g h - p e r f o r m a n c e alternatives. This Co., Longelsheim, Federal Republic of Germany.
[26] Technical Bulletin "K-White Aluminum Triphosphate," Tayca
progress will b e a c c o m p l i s h e d not by scientific curiosity o r
Corp., Osaka, Japan.
c o m m e r c i a l d e m a n d alone, b u t also b y c o n c e r n for the pro- [27] Technical Bulletin PB 173 MGW, NL Chemicals, Hightstown,
tection of o u r fragile h u m a n habitat. NJ.
[28] Technical Bulletin "HALOX CW-22/221," HALOX Pigments,
Hammond, IN.
REFERENCES [29] Technical Bulletin "HALOX CW-291," HALOX Pigments,
Hammond, IN.
[1] Chilton, J. P., Principles of Metallic Corrosion, The Royal [30] Technical Bulletin "HALOX CW-2230," HALOX Pigments,
Institute of Chemistry, W. Heifer and Son LTD, Cambridge, Hammond IN.
England, 1964. [31] Technical Bulletin "HALOX BW-111," HALOX Pigments,
[2] Smith, A., Inorganic Primer Pigments, Federation Series on Hammond, IN.
Coatings Technology, Federation of Societies for Coatings Tech- [32] Technical Bulletin "HALOX BW-191," HALOX Pigments,
nology, Philadelphia, PA, 1988. Hammond IN.
[3] Chilton, J. P., Principles of Metallic Corrosion, The Royal Insti- [33] Technical Bulletin "HALOX SW-111," HALOX Pigments,
tute of Chemistry, W. Heifer and Son LTD, Cambridge, England, Hammond, IN.
1964. [34] Technical Bulletin "HALOX SZP-391," HALOX Pigments,
[4] Schweitzer, P. A., What Every Engineer Should Know About Hammond, IN.
Corrosion, Marcel Dekker, Inc., New York and Basel, 1987. [35] Technical Bulletin "Shieldex News," W. R. Grace & Co., Balti-
[5] Gleekman, L. W., "Selecting Materials of Construction," more, MD.
Corrosion and Corrosion Protection Handbook, P. A. Schweitzer, [36] Mayne and Van Rooyen, in Journal of Applied Chemistry (Lon-
Ed., Marcel Dekker, Inc., New York and Basel, 1983. don), Vol. 4, July 1954, p. 384.
[6] Eickhoff, A. J,, "Corrosion Inhibitive Pigments and How They [37] Evans, U. R., Metallic Corrosion, Passivity and Protection,
Function," Steel Structures Painting Manual, Vol. 1, Good Paint- Longmans Green and Co., New York, 1945.
www.iran-mavad.com

[38] Steel Structures Painting Manual, Vol. II, Systems and Specifica- Austin, M. J. and DeVaney, J. G., "Extender Pigments for Latex
tions, Steel Structures Painting Council, Pittsburgh, PA. Coatings: Do They Make a Difference?" Journal of Protective
[39] Asbeck and Van Loo, "Critical Pigment Volume Relationships," Coatings & Linings, Vol. 7, No. 6, June 1990.
Industrial and Engineering Chemistry, Vol. 41, 1949, p. 1470. Appleiaaan, B, R., "Survey of Accelerated Test Methods for Anti-
[40] Wicks, Z. W. Jr., Corrosion Protection by Coatings, Federation Corrosive Coating Performance," Journal of Coatings Technology,
Series on Coatings Technology, Federation of Societies for Coat- Vol. 62, No. 787, August 1990.
ings Technology, Philadelphia, PA, 1987. Burns, R. M. and Bradley, W. W., Protective Coatings for Metals,
[41] Austin, M. J. and Devaney, J. G., "Inhibitive Pigments for Latex Reinhold Publishing Corporation, New York, 1955.
Coatings: Do They Make a Difference?," Journal of Protective Chilton, J. P., Principles of Metallic Corrosion, The Royal Institute of
Coatings & Linings, Vol. 7, No. 6, June 1990. Chemistry, W. Heifer and Son LTD, Cambridge, England, 1964.
[42] Smith, A. Inorganic Primer Pigments, Federation Series on Coat- Collie, M. J., Ed., Corrosion Inhibitors, Noyes Data Corp., Parkridge,
ings Technology, Federation of Societies for Coatings Technol- NJ, 1983.
ogy, Philadelphia, PA, 1988. Eickhoff, A. J., "Corrosion Inhibitive Pigments and How They Func-
[43] Smith, A., Inorganic Primer Pigments, Federation Series on tion," Steel Structures Painting Manual, Vol. 1, Good Painting Prac-
Coatings Technology, Federation of Societies for Coatings Tech- tice, 2nd ed., J. D. Kean, Ed., Steel Structures Painting Council,
nology, Philadelphia, PA, 1988. Pittsburgh, PA, 1982.
[44] Eickhoff, Arnold J., "Corrosion Inhibitive Pigments and How Fontana, M. G., Corrosion: A Compilation, The Press of Hellenbeck,
They Function," Steel Structures Painting Manual, Vol. 1, Good Columbus, OH, 1957.
Painting Practice, 2nd ed., J. D. Kean, Ed., Steel Structures Hare, C. H., Anti-Corrosive Barriers and Inhibitive Primers, Federa-
Painting Council, Pittsburgh, PA, 1982. tion Series on Coatings Technology, Unit 27, Federation of Socie-
[45] Steel Structures Painting Council, "Minimum Paint Film Thick- ties for Coating Technology, Philadelphia, PA, 1979.
ness for Economical Protection of Hot Rolled Steel Against Hitzrot, H. W., "Surface Preparation," Steel Structures Painting Man-
Corrosion," Pittsburgh, PA. ual, Vol. 1, Good Painting Practice, 2nd ed., J. D. Deane, Ed., Steel
[46] Smith, Alan, Inorganic Primer Pigments, Federation Series on Structures Painting Council, Pittsburgh, PA, 1982.
Coatings Technology, Federation of Societies for Coatings Tech- Jackson, M. A., "Guidelines to Formulation of Water-Borne Epoxy
nology, Philadelphia, PA, 1988. Primers: An Evaluation of Anti-Corrosive Pigments," Journal of
[47] Steel Structures Painting Council, Guide 5, Guide to Mainte- Protective Coatings and Linings, April 1990.
nance Painting Programs, Pittsburgh, PA. Mansfield, F., Corrosion Mechanisms, Marcel Dekker, Inc., New York
[48] Burns, R. M. and Bradley, W. W., Protective Coatings for Metals, and Basel, 1987,
Reinhold Publishing Corporation, New York, 1955. Munger, C. G., Corrosion Protection by Protective Coatings, National
[49] Hitzrot, H. W., "Surface Preparation," Steel Structures Painting Association of Corrosion Engineers, Houston, TX, 1984.
Manual, Vol. 1, Good Painting Practice, 2nd ed., J. D. Deane, Ed., Schweitzer, P. A., Ed., Corrosion and Corrosion Protection Hand-
Steel Structures Painting Council, Pittsburgh, PA, 1982. book, Marcel Dekker, Inc., New York and Basel, 1983.
[50] Appleman, B. R., "Survey of Accelerated Test Methods for Anti- Schweitzer, P. A., What Every Engineer Should Know About Corro-
Corrosive Coating Performance," Journal of Coatings Technol- sion, Marcel Dekker, Inc., New York and Basel, 1987.
ogy, Vol. 62, No. 787, August 1990. Scully, J, C., The Fundamentals of Corrosion, 2nd ed., Pergamon
[51] Hare, C. H., Anti-Corrosive Barriers and Inhibitive Primers, Fed- Press, Oxford and New York, 1975.
eration Series on Coatings Technology, Unit 27, Federation of Shreir, L. L., Corrosion, Vol. 2: Corrosion Control, John Wiley and
Societies for Coating Technology, Philadelphia, PA, 1979. Sons, Inc., New York, 1963.
[52] Appleman, B. R., "Survey of Accelerated Test Methods for Anti- Smith, A., Inorganic Primer Pigments, Federation Series on Coatings
Corrosive Coating Performance," Monograph prepared for the Technology, Federation of Societies for Coatings Technology, Phil-
Corrosion Committee of the Federation of Societies for Coatings adelphia, PA, 1988.
Technology, Philadelphia, PA, June 1990. Speller, F. N., Corrosion--Causes and Prevention, McGraw-Hill Book
Co. Inc., New York and London, 1951.
Suzuki, I., Corrosion-Resistant Coatings Technology, Marcel Dekker,
New York, 1989.
BIBLIOGRAPHY Uhlig, H. H., Ed., The Corrosion Handbook, John Wiley and Sons,
Inc., New York.
American Conference of Governmental Industrial Hygienists, Wicks, Z. W., Jr., Corrosion Protection by Coatings, Federation Series
"Threshold Limit Values for Chemical Substances and Physical on Coatings Technology, Federation of Societies for Coatings
Agents and Biological Exposure Indices," pamphlet, 1990- 1991. Technology, Philadelphia, PA, 1987.
www.iran-mavad.com

MNL17-EB/Jun. 1995
28
Oil Absorption of Pigments*
by Joseph V. K o l e s k e I
MIXING A PIGMENT WITH LINSEED OIL and m a k i n g a paste is a have an acid n u m b e r of 3 _+ 1, is used. More extended
p r e l i m i n a r y test a p p l i e d to p i g m e n t s that has been in use in a discussions of oil a b s o r p t i o n t h e o r y a n d practice can be
systematic m a n n e r for a l m o s t a century a n d p e r h a p s even f o u n d in the literature [6-10].
longer in a less defined m a n n e r . Results from the test are
usually qualitative in c h a r a c t e r a n d give an a p p r o x i m a t i o n of
color a n d texture. If the test is c o n d u c t e d in a quantitative M E T H O D S F O R D E T E R M I N I N G OIL
m a n n e r , the a m o u n t of oil n e e d e d to m a k e a stiff paste is ABSORPTION
obtained. It has been felt that the oil a b s o r p t i o n test is a
m e a s u r e of an oil-based paint's resistance to flow or consis- There are two ASTM m e t h o d s for d e t e r m i n i n g oil absorp-
tency. F o r example, Mills [2] i n d i c a t e d that if equal volumes tion that will be d e s c r i b e d briefly as well as related m e t h o d s
of "oil a b s o r p t i o n paste" are m i x e d o r t h i n n e d with equal that, for the m o s t part, are t a b u l a t e d and referenced (Ta-
volumes of thinners, the paints p r e p a r e d have equal resist- ble 1).
ance to flow, viscosity, or consistency. Also, Stieg [3] f o u n d
that if the oil a b s o r p t i o n value is d e t e r m i n e d by the ASTM
r u b - o u t m e t h o d (described below) a n d expressed on a volume Gardner-Coleman M e t h o d
basis, it is p r o p o r t i o n a l to the critical p i g m e n t volume con-
centration. This test is also related to the p i g m e n t packing This classical m e t h o d or some variation of it [11] has been
factor (PPF) a n d critical p i g m e n t volume c o n c e n t r a t i o n in use for a b o u t three quarters of a century. The c u r r e n t
(CPVC). m e t h o d , ASTM D 1483: Test M e t h o d for Oil A b s o r p t i o n of
Pigments by G a r d n e r - C o l e m a n M e t h o d [12], has been in use
for over 32 years. In this test, a soft paste is f o r m e d from the
p i g m e n t by drop-wise a d d i t i o n of r a w linseed oil with an acid
MECHANISM n u m b e r of 3 _+ 1 from a b u r e t t e to the gently stirred pigment.
As the oil is slowly added, the mixture is c o n t i n u o u s l y stirred
W h e n the oil a b s o r p t i o n test is performed, the surface of a n d folded so the oil strikes d r y p i g m e n t as long as any
each p i g m e n t particle is wet a n d s a t u r a t e d to a certain extent
remains. The mixture is not vigorously r u b b e d as in the rub-
with oil a n d thus is encased in a n oil shell that has been
out method. Eventually the mixture collects in small l u m p s
e s t i m a t e d to be as thick as eight molecules [3, 4]. The a m o u n t
that gradually coalesce. The rate of oil a d d i t i o n is r e d u c e d as
of oil n e e d e d d e p e n d s on the specific p i g m e n t area, w h i c h is a
the end p o i n t is reached. The a m o u n t of oil r e q u i r e d to form a
function of particle size, roughness, and porosity. W i t h tem-
paste is used to calculate the oil a b s o r p t i o n value. The end
p e r a t u r e a n d h u m i d i t y constant, the oil a d s o r p t i o n value
p o i n t for paste f o r m a t i o n is t a k e n to be the p o i n t w h e n the
d e p e n d s on the d u r a t i o n a n d vigor of the r u b b i n g o p e r a t i o n
l u m p s of wet p i g m e n t form a single ball or w h e n an excess of
a n d on the affinity of the oil for the pigment. As oil is a d d e d
oil s m e a r s the wall of a c o n t a i n e r (Fig. 1). This will take place
b e y o n d the particle e n c a s e m e n t stage, the interstices b e t w e e n
within one or two d r o p s of oil. It is i m p o r t a n t that there is no
the oil-encased particles b e c o m e filled with oil. The a m o u n t
r u b b i n g o r grinding w h e n this test is carried out. 'Mthough
of oil r e q u i r e d for this stage of the test is a function of the type
the c u r r e n t test calls for use of a steel spatula with p a r t i c u l a r
packing taken on b y the particles. Packing can range f r o m
d i m e n s i o n s a n d a glass flask for the test, variations of these
r h o m b e h e d r a l to cubic. In addition, the presence of aggre-
tools have been used [13,14].
gates, which are clusters of p i g m e n t not b r o k e n up b y the
Oil Absorption, A, is expressed as g r a m s of oil p e r 100 g of
r u b b i n g process, a n d agglomerates, which are clusters of pig-
p i g m e n t a n d is calculated as follows
m e n t f o r m e d after the p i g m e n t has been wet, have a n effect
on the a m o u n t of oil needed. A g g l o m e r a t i o n is affected by the
n a t u r e of the oil, a n d linseed oil that meets ASTM D 234:
Specification for R a w Linseed Oil [5], except that it should
where M is the m L of oil used, P is the a m o u n t of p i g m e n t
used in grams, a n d 0.93 is a c o n s t a n t that represents the
*This chapter is an abridged and modified version of the chapter
with the same title found in the previous edition of this manual [1]. density of the linseed oil. Test results by a single o p e r a t o r a n d
1Senior consultant, Consolidated Research, Inc., 1513 Brentwood b e t w e e n o p e r a t o r s in different laboratories t h a t differ by
Road, Charleston, WV 25314-2307. m o r e t h a n 9.9 a n d 15.3%, respectively, are suspect. Oil ab-
252
www.iran-mavad.com

CHAPTER 2 8 - - 0 I L ABSORPTION OF PIGMENTS 253
TABLE 1--Various non-ASTM methods for determination of oil sorption values obtained by this test and the above Gardner-
absorption values. Coleman test are given in Table 2.
Method Comment Reference
Azam Method same as ASTM D 281 15 Azam M e t h o d
except end point is where paste
just adheres to the spatula. See The Azam Method [15] is essentially the same test as ASTM
text. D 281 with the main difference being a more rigorously de-
fined end point. The end point is defined as the point where
Bessey-Lammiman An indirect method. Pore volume 8
of a compressed pigment wafer the paste just adheres to the spatula and the paste was termed
is determined. From this, an a "complete" paste. Azam found that a complete paste ab-
oil adsorption number is sorbed no more oil when immerse in oil, but an "incomplete"
calculated. paste would absorb oil in an amount sufficient to make it a
British Standards Method is similar to ASTM 16 "complete" paste. The end point check was made by immers-
Institution D 281, but differs mainly in ing the rub-out mass in a known amount of oil and then
acid value of oil, 7.5-8.5; determining the change after two or three days.
rubbing is done for 20-25 min.
Density End Point Assumesdensity of pigment and 17
oil are additive. Can have void PLASTICIZER ABSORPTION BY PIGMENTS
volume errors associated with
it. Although linseed oil is used to obtain the oil absorption
National Lead Method is similar to ASTM D 281 18 values, it is obvious that a variety of liquids can be absorbed
Company and Azam methods, but an by pigments. Typical data for selected plasticizers as well as
attempt is made to regulate raw linseed oil are given in Table 3.
rubbing pressure and contact
area of spatula and rubbing
plate.
CRITICAL PIGMENT VOLUME
Smith-Stead Pigment is added to oil in this 19
method, and a mechanical For a long time, the paint industry formulated on a weight
muller is used to better define basis. In 1926 Calbeck [20] concluded from a statistical study
the rubbing effort.
of house-paint test results that the pigment/binder system
should contain at least 28 vol% pigment. Not long after this,
Wolff [21,22] related optimum performance of exterior
sorption values obtained by this method and the following
paints to their critical oil contents, and simple graphical
rub-out method are given in Table 2.
methods for determining this parameter were devised [23].
When Elm [24] investigated this concept, he confirmed
Wolff's findings, but found it necessary to reverse the point of
Spatula Rub-Out Method
reference so it expressed the critical composition in terms of
ASTM D 281: Test Method for Oil Absorption of Pigments pigment content as in the work of Calbeck. Later Vannoy [25]
by Spatula Rub-Out [12] is another classical test that was first studied the matter and concluded that replacement of certain
published by ASTM in 1928 and updated from time to time pigments by others on a volume basis was the manner in
with the latest reapproval in 1989. It is approved for use by which formulating should be approached. From such studies,
agencies of the U.S. Department of Defense. In this test, a the relationship known as the pigment volume concentration
stiff, putty-like paste is formed by adding linseed oil in a drop- (PVC) came into use. It is a simple percentage calculated in
wise manner to the pigment while it is being thoroughly the following manner:
rubbed with a spatula. It differs from the prior method in that
[ Pigment Volume ]
ASTM D 1483 requires only gentle folding and stirring,
PVC = [Pigment Volu--m--ee~ Solids Volume_] [ 100%]
whereas the rub-out test requires a thorough rubbing action
of the pigment and oil with a steel spatula. Studies such as these led to the critical pigment volume
Raw linseed oil that meets ASTM D 234 but with an acid concentration (CPVC) concept, and its importance to paint
number of 3 + 1 is slowly added in a drop wise manner to a formulation was established by Asbeck and Van Loo [26].
known amount of pigment. After the addition of each drop of When there is just sufficient binder present to fill the voids
oil, the oil is incorporated into the pigment by working or between pigment particles in the dry paint, the paint is said to
rubbing the two together with the spatula. The end point is be at the CPVC. This is the point of commonality at which a
taken to be the point where sufficient oil has been incorpo- variety of properties show marked change. These properties
rated into the pigment to produce a very stiff, putty-like paste include corrosion resistance as evidenced by blistering and
that does not break up. Various stages in the spatula rub-out rusting, ease of stain removal, gloss, hiding, scrub resistance
test are described in Fig. 2. The weight of oil is determined, or washability, water-vapor permeability, as well as others.
and the oil adsorption value is calculated as the grams of oil For example, it is readily understood that gloss decreases
used per 100 g of pigment. Test results by a single operator as pigment volume increases, that permeability and rusting
and between operators in different laboratories that differ by are relatively constant until the pigment concentration
more than 14.3 and 38.0%, respectively, are suspect. Oil ab- reaches relatively high values after which marked decreases
www.iran-mavad.com

FIG. 1 [/]-Critical states in the Gardner-Coleman test. Left photograph is the oil/
pigment mass just before the end point where the mass retains its rigidity. The right
photograph is the mixture at the end point where the mass undergoes slight flow and
smears the glass.
TABLE 2--Oil absorption values, grams of oil/100 g of pigment, weight of a gallon of water or 8.33 (1 kg/L). For example, if a
of some common pigments [1]. pigment has a specific gravity of 2.0, its bulk can be calculated
Gardner-Coleman SpatulaRub-Out as follows
Pigment Test Test
[2.0g/cc] [8.33 lb]- 16.661b 2 . 0 k g
Barytes 13.5 ...
Basic carbonate of white lead 18 13.0 BULK = L 1.0 g/cc_] L gal _] gallon - litre
Basic sulfate of white lead 30 12.8 Since the paint industry is usually interested in gallons of
Blanc fixe 30 15.0
China clay 51 30.0 product, the bulk is often expressed as the reciprocal of this
Gypsum 33.5 ... n u m b e r or 0.06 gal/lb (0.5 L/kg) or as bulk per 100 lb,
Lithopone 33 21.5 100/16.66 = 6.00 gal/100 lb in this example. From this exam-
Silica, crystalline 23 ... ple, it is apparent that the higher the bulking value of a
Silica, amorphous 32 29.0
Talc 60 ..- pigment, the more advantageous it is from a cost standpoint.
Titanox 26 18.5 If pigment is lower in cost than vehicle, and assuming equiva-
Whiting 32 17.5 lent performance, a pigment with a higher bulking value over
Zinc oxide 52 19.5 another would be selected.
in performance takes place, and so on. It is at the CPVC that Asbeck-Van Loo M e t h o d o f D e t e r m i n i n g CPVC
the marked changes take place. When two vehicles--latex,
The Asbeck-Van Loo [9,26] method of directly determining
oil-base, etc.--are compared in a given formulation, one m a y the CPVC is based on the observation that the packing pattern
have a higher CPVC than the other. Predictably, the one with of a pigment in a paste persists when the dispersion is diluted
a higher CPVC formulation should have better permeability for sedimentation tests if nonpolar liquids are used for the
characteristics, such as stain and scrubbability, than the dilutions. Thus, to measure the voids in a dry paint film, it is
other. Pigment or vehicle could be added to one paint or the only necessary to obtain the pigment in the form of a filter
other, and a paint with comparable properties can be pre- cake and measure the volume of the cake. Then, the cake
pared. The selection of which paint to modify by increasing volume is subtracted from the actual volume of the pigment
pigment or vehicle is made on the basis of additive econom- calculated from density data. The ratio of the actual volume
ics. of the pigment to the volume of the cake is the CPVC.
Different end-use requirements impose different pigment
volume concentrations that are above or below the CPVC. For Pigment Packing Factor
example, a ceiling paint does not need to have excellent Asbeck and coworkers [9] proposed the term "pigment
washability, and usually this paint type only requires low to packing factor" (PPF) as a name for a pigment parameter that
moderate gloss. Therefore, a paint such as this can be for- replaces or supplements the oil absorption value. PPF is the
mulated at or even above the CPVC. In contrast, m a n y exte- CPVC for a single pigment in a standard vehicle with the term
rior paints that have a high gloss as well as glossy enamels are CPVC being applied to a single or mixture of pigments pres-
formulated well below the CPVC, and it is PVC rather than ent in a paint. The investigators suggested a blend of 4 mL of
CPVC that has significance. Although the parameter was de- heat-bodied linseed oil and 50 mL of naphtha as the dispers-
vised for oil-based paints, the concepts involved are impor- ing vehicle. The PPF is determined by placing 54 mL of the
tant to other types of coatings. vehicle in a 1/4-pt can or glass jar that is half filled with steel
The pigment volume is often expressed as bulk, which is balls. To this, 6 mL of pigment (the weight in grams of pig-
the volume occupied by a given weight of pigment. It is ment equal to the specific gravity times 6) are added. The
calculated by multiplying pigment specific gravity by the system is dispersed by machine shaking for exactly 3 min.
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FIG. 2 [ I ] - A , B, and C in the top photograph represent 1 g of zinc oxide that has
been mixed with increasing amounts of linseed oil. Rub-Out A (top) is crumbly and
breaks up when an attempt is made to lift it with a spatula. Rub-Out B (lower left) is
coherent and tends to form a roll when deformed with the spatula. Rub-Out C (lower
right) contains too much oil and does not roll. It can be lifted as a sheet and the
mixture is beyond the end point. The bottom two photographs are additional exam-
ples of the mixture condition just before the end point is reached. A single drop of oil
will convert the crumblings into coherent masses,
Twenty millilitres of the dispersion are then used to deter- on the fact that below the CPVC dry film volume, V, is a sum
mine the PPF using the same procedure as that used for of the pigment, Vv, and binder solids, Vb volumes
CPVC. If the PPF is to be compared with oil absorption
values, it must be converted to a weight basis, PPFweight, by
v=vp+vb
means of and that above the CPVC the volume of the voids must also be
considered with
F(100 - PPF)(specific gravity of oil)]
PPVweight = "[_( - - P P F - ) ( ~ y ~ _]" (100) V = PVp
where P is the relative pigment packing factor (the ratio of

bulk volume to true volume). Two graphical and calculation
C o l e M e t h o d f o r CPVC methods were used to obtain CPVC.
The CPVC depends on pigment particle packing or orienta-
Pierce-Holsworth M e t h o d f o r CPVC
tion [9,26], and Cole [27] noted that spherical particles may
pack similarly in both liquid and dry films. To demonstrate This method [28] also used paint films, but it treated the
this, a dry-film method was developed. The method is based data in a different manner by introducing specific volume
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TABLE 3--Plasticizer absorption for some typical pigments [1]. line with the previously described straight line should occur
Absorption,g, Plasticizer/100g Pigment at a value of fv corresponding to the CPVC. Results o b t a i n e d
Tricresyl Dibutyl Raw Linseed by this method are presented in Table 4 along with the CPVCs
Pigment Phosphate Phthalate Oil o b t a i n e d by tensile strength, elongation, a n d water vapor per-
meability. The good agreement is apparent.
Barium titanox 27.6 24.2 17.0
Carbon black, super 179.0 147.0 106.0 A n u m b e r of papers detailing studies of CPVC a n d its im-
Calcium titanox 37.2 39.4 22.0 portance [29-34] as well as i n f o r m a t i o n relating CPVC, OA,
CP cadmium red 26.0 26.2 14.0 a n d viscosity [35,36] can be found in the literature.
CP cadmium yellow 48.4 50.5 37.2
CP Chinese blue 145.0 136.5 41.1
CP chromium oxide 29.5 24.7 17.0
CP chrome orange, medium 19.5 21.0 7.5 CRITICAL PIGMENT VOLUME
CP glen green DD 78.0 72.5 28.9 CONCENTRATION AND OIL ABSORPTION
Chromium hydroxide, green 80.0 76.6 53.0
Lampblack 118.0 126.0 145.0
Oil absorption and CPVC are accepted to be interrelated
Lithol toner 65.0 50.5 50.0
Lithopone, high strength 35.4 32.5 24.0 [29-31] a n d actually are two ways of stating the same con-
Madder Lake 106.0 81.0 51.4 cept: i.e., CPVC is the c o n c e n t r a t i o n of p i g m e n t in a pigment-
Titanium dioxide 54.3 47.2 22.5 b i n d e r system that contains just sufficient b i n d e r (oil) to fill
Toluidine red 31.9 20.0 35.0 the space between the p i g m e n t particles [1 ]. If the parameters
Ultramarine blue 65.0 55.0 31.6
Zinc Oxide 28.3 25.2 14.5 are to be equated, it is necessary to determine the oil absorp-
Zinc Sulfide 37.2 34.1 15.7 tion value (OA) by the spatula m e t h o d a n d to express the
results in volume terms. If OA is expressed as X v o l u m e s of oil
per Y volumes of pigment, then
concepts. The specific volume, v, of a dry p a i n t film can be Y
expressed as CPVC -
X+Y
V V W h e n OA is expressed as the fraction X/Y a n d Y is set to one,
v- - - - - v J ~ + vdb
w wp+wb then X/Y = X a n d
where V is the dry film volume, v, vp, a n d Vb are specific CPVC
volumes of the dry film, pigment, a n d binder; W, Wp, and Wb
OA-
1 - CPVC
are weights of dry film, pigment, a n d binder; a n d fp a n d fb are
weight fractions of p i g m e n t a n d binder, respectively. Since and
the s u m of fp a n d fb is unity, the expression can be arranged to 1
CPVC - - -
v = % , - v~)f,, + vb I +OA
I f v is plotted as a f u n c t i o n offp, a straight line of slope (vp - The PPF a n d OA values are compared in Table 5. If values are
Vb) a n d intercept of Vb should result. ranked from highest to lowest, the values calculated from the
Above the CPVC, the volume of the film is given by PPF are highest, those from G a r d n e r - C o l e m a n fall next, a n d
those from the spatula r u b - o u t test are lowest. Explanations
V = PvpWp
[1, 9] for the difference based o n conditions existing at the end
where P is a packing factor. If both sides of this expression are point are tabulated in Table 6.
divided by W, the expression Investigation of the effect of p i g m e n t a t i o n o n selected
properties of flat wall paints has indicated that o p t i m u m
V = Pvpfp levels of p i g m e n t c o n c e n t r a t i o n for color u n i f o r m i t y a n d
is obtained. If dry film specific volume, v, is plotted against e n a m e l holdout corresponded to the CPVC [32,33]. I n addi-
the weight fraction of pigment, fv, a straight line of slope Pvp tion, the study indicated that r u b - o u t OA values are a good
passing through the origin results. The intersection of this indication of the CPVC. Stieg [31] points out that any one
TABLE 4--[1] Comparison of the critical pigment volume concentration calculated by the
Pierce-Holsworth method [28] and comparison with results from physical property
measurements.
Critical PigmentVolume Concentration
Pierce- Tensile Elongation WaterVapor
Holsworth Strength at Break Permeability
Paint System Method Method Results Results
Acrylic latex exterior House Paint A 47 47 42 46
Acrylic latex exterior House Paint B 41 42 4l 42
Poly(vinyl Acetate) latex masonry paint 44 44 44 45
Acrylic exterior masonry paint (from House 48 47 44 48

Paint A above)
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TABLE 5--Comparison of pigment packing factors, calculated pastes with s o m e being long, stringy, a n d soft in character.
and experimentally determined oil absorption values [1]. Others are tough a n d short, others have a high gloss, others
Oil Absorption Values have a dull a p p e a r a n c e , others are soft a n d easy to spread,
Gardner- Spatula a n d still others are stiff a n d require a large p r e s s u r e s p r e a d or
Calculated Coleman Rub-Out flatten. The a m o u n t of oil n e e d e d is not closely related to
Pigment PPF from PPF M e t h o d Method
these attributes, a n d one is led to the conclusion t h a t pig-
Carbon black, medium 10 456 212 124 m e n t s with essentially the s a m e oil a b s o r p t i o n value can yield
Chrome green 34 41 33 20
Chrome yellow 27 46 33 24 pastes with m a r k e d l y different character.
Iron oxide, light red 37 32 24 19 Daniel a n d G o l d m a n [38] developed a s c h e m e for evaluat-
Lampblack 29 128 70 51 ing d i s p e r s i o n c h a r a c t e r b y using the p a s t e o b t a i n e d at the
Magnesium silicate 39 50 27 25 end of the spatula r u b - o u t test. The a m o u n t of liquid n e e d e d
Midori blue 33 104 87 51
Phthalocyanine blue 20 225 55 34 to wet the p i g m e n t a n d p r o d u c e flow are d e t e r m i n e d . F r o m
Silica, diatomaceous 24 131 105 65 this i n f o r m a t i o n a n d the types of flow exhibited by the pastes,
Toluidine red toner B 25 199 62 48 dispersions are classed as good, fair, or poor. F r o m 10 to 20 g
Zinc oxide 27 45 19 12 of d i s p e r s i o n is w o r k e d with a fairly stiff steel s p a t u l a in the
test. The oil a b s o r p t i o n value is called the wet point. F r o m this
o p e r a t o r of the s p a t u l a r u b - o u t test can reproduce p e r s o n a l point, oil a d d i t i o n is c o n t i n u e d until the flow point is reached.
test results with a r e a s o n a b l e degree of accuracy. It seems In well-dispersed systems, the flow p o i n t is the stage w h e r e a
that i n t e r p r e t a t i o n of the e n d p o i n t a n d not r e p r o d u c i b i l i t y is substantial p o r t i o n of the paste flows from a vertically held
the source of variation b e t w e e n o p e r a t o r s in these tests. Oil spatula w i t h o u t leaving jagged flow edges. In p o o r l y dis-
a d s o r p t i o n of p i g m e n t mixtures has b e e n treated b y Arm- p e r s e d or flocculated systems, the flow p o i n t is the stage
strong and M a d s o n [37]. w h e r e the paste d r o p s from a vertically held spatula. Cases
i n t e r m e d i a t e to these two are difficult to define. At the i n s t a n t
CHARACTERIZATION OF D I S P E R S I O N S AT w h e n paste d r o p s from the spatula, it elongates at the edge. If
T H E OIL A B S O R P T I O N P O I N T a p a s t e does not flow after a d d i t i o n of 10 to 20% m o r e liquid
t h a n is r e q u i r e d for the wet point, a p o r t i o n of the diluted
E x a m i n a t i o n of the d i s p e r s i o n s (pastes) f o r m e d b e t w e e n paste is placed on the tip of a h o r i z o n t a l l y held spatula. The
oil a n d p i g m e n t at the oil a b s o r p t i o n p o i n t is a source of s p a t u l a is then t a p p e d n e a r the h a n d l e w i t h a finger. The
considerable information. Large differences exist in such t a p p i n g is gentle at first a n d t h e n m o r e vigorous. The p a s t e
TABLE 6--Physical conditions that exist at the end points of pigment packing factor and oil absorption test [1,9].
Parameter PPF Gardner-Coleman Spatula Rub-Out
Dispersion Aggregates are completely broken Only a few of the largest More aggregates are broken
down, aggregates are broken down down than in the Gardner-
and the interstices are filled Coleman methods and the
with oil. interstices are filled with oil.
Electrokinetic equilibrium Agglomeration is complete because Agglomeration is incomplete Agglomeration is incomplete

of high system fluidity, because of low system fluidity. because of low system fluidity.
Pigment surface requirements Satisfied Not completely satisfied Substantially satisfied
Work of dispersion Defined and very high (approaching Undefined but low Undefined but relatively high
maximum)
Work of packing Defined and very low (approaching Undefined but low Undefined but relatively high
zero)
TABLE 7--Characteristics of pastes from oil absorption studies [1].

Observation Point Good Dispersion Fair Dispersion Poor Dispersion
At wet point Shines without tapping or with light Shines when sharply tapped Remains dull even when sharply
tapping; dry and difficult to knead tapped
At intermediate stage .-. Flows only on tapping; Rises on tapping; has no
occasionally has a resistance resistance to suddenly applied
to suddenly applied pressure pressure; has a high yield value
At flow point Flows without tapping; offers Falls with elongation at Falls without elongation at
resistance to suddenly applied breaking line; no resistance breaking line
pressure to suddenly applied pressure;
has visible thixotropy
Gap between wet and Very small -.. Very large
flow points
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m a y then become glossy a n d flow over the edge of the spatula, [20] Calbeck, J. H., "Application of the Statistical Method in Testing
in which case it is passively dilatent, or it m a y tend to rise or Paints for Durability," Industrial and Engineering Chemistry,
otherwise decrease the interface between it a n d the blade, i n Vol. 18, 1926, p. 1220.
which case it is flocculated. Characteristics of pastes tested in [21] Wolff, H., "Oil Absorption of Pigments," Farben Zeitung, Vol. 34,
this m a n n e r are given in Table 7. A test such as this c a n yield 1929, p. 2940.
practical rheological results without sophisticated testing [22] Wolff, H., "The Critical Oil Content of Paints," Farben Zeitung,
equipment. Vol. 37, 1931, p. 374.
[23] Wolff, H. and Zeidler, G., "Rapid Method for Determination of
Critical Oil Requirements," Paint and Varnish Production Man-
ager, Vol. 12, No. 6, 1935, p. 7.
REFERENCES [24] Elm, A. C., "Paint Durability as Affected by the Colloidal Proper-
ties of the Liquid Paint," Industrial and Engineering Chemistry,
[1] "Oil Absorption of Pigments," Chapter 3.5, Paint Test Manual, Vol. 26, 1934, p. 1245.
13th ed., G. G. Sward, Ed., The American Society for Testing
[25] Vannoy, W. G., "Extenders in Outside House Paints," Official
and Materials, Philadelphia, PA, 1972.
Digest, Federation of Paint and Varnish Production Clubs, Vol.
[2] Mills, G., "Pigment Surfaces," Journal of the Oil and Colour
33. 1961, p. 1215.
Chemists' Association, Vol. 34, 1951, p. 497.
[3] Stieg, F. B., Jr., "Color and CPVC," Official Digest, Federation of
[26] Asbeck, W. K. and Van Loo, M., "Critical Pigment Volume Rela-
Paint and Varnish Production Clubs, Vol. 38, 1956, p. 695. tionships," Industrial and Engineering Chemistry, Vol. 41, 1949,
[4] Long, J. S., "Creative Imagination as it Applies to the Decorative p. 1470.
and Protective Industry," Official Digest, Federation of Paint and [27] Cole, R. J., "Determination of Critical Pigment Volume Concen-
Varnish Production Clubs, Vol. 32, 1954, p. 989. tration in Dry Surface Coating Films," Journal of the Oil and
[5] Annual Book of ASTM Standards, Vol. 06.03. Colour Chemists' Association, Vol. 45, 1962, p. 776.
[6] Marsden, E., "Oil Absorption: A New Assessment, Part I," Jour- [28] Pierce, P. E. and Holsworth, R. M., "Determination of Critical
nal of the Oil and Colour Chemists'Association, Vol. 42, 1959, p. Pigment Volume Concentration By Measurement of Density of
119. Dry Paint Films," Official Digest, Federation of Paint and Varnish
[7] Mill, C. C. and Bank, H. W., "An Interpretation of the Oil Ab- Production Clubs, Vol. 37, 1965, p. 272.
sorption of Pigments," Journal of the Oil and Colour Chemists' [29] Smith, A., "Inorganic Primer Pigments," Federation Series on
Association, Vol. 32, 1949, p. 599, Coatings Technology, Federation of Societies for Coatings Tech-
[8] Bessey, G. E. and Lammiman, K. A., "The Measurement and nology, Philadelphia, 1988.
Interpretation of Oil Absorption," Journal of the Oil and Colour [30] Philadelphia Paint and Varnish Production Club, "Determina-
Chemists' Association, Vol. 34, 1951, p. 519. tion of CPVC by Calculation," Official Digest, Federation of Paint
[9] Asbeck, W. K., Laiderman, D. D., and Van Loo, M., "Oil Absorp- and Varnish Production Clubs, Vol. 33, 1961, p. 1437.
tion and Critical Pigment Volume Concentration," Official Di- [31] Philadelphia Paint and Varnish Production Club, "Determina-
gest, Federation of Paint and Varnish Production Clubs, Vol. 30, tion of the Oil Absorption and Critical Pigment Volume Concen-
1952, p. 156. tration of Multicomponent Pigment Systems," Official Digest,
[10] Davidson, R. R., "Whiting Dispersions, Particle Packing, and Federation of Paint and Varnish Production Clubs, Vol. 31, 1959,
Surface Adsorption," Journal of the Oil and Colour Chemists p. 1491.
Association, Vol. 43, 1960, p. 307. [32] Stieg, F. B., Jr., "The Determination of CPVC by the OA Test,"
[ll] Gardner, H.A. and Coleman, R. E., "Oil Absorption of Pig-
American Paint Journal, Vol. 45, No. 4, 1958, p. 41.
ments," Scientific Section Circular, No. 85, National Paint, Var-
[33] Stieg, F. B., Jr., "A Complex Problem and a Simple Answer,"
nish, and Lacquer Association, Washington, DC, 1920.
[12] Annual Book of ASTM Standards, Vol. 06.02. Official Digest, Federation of Paint and Varnish Production Clubs,
[13] Haugen, O.A. and Hentzen, H. D., "Oil Absorption of Paint Vol. 28, 1956, p. 695.
Pigments," Chemical and Metallurgical Engineering, Vol. 29, [34] Stieg, F. B., Jr., "Effects of Pigmentation on Modern Flat Wall
1923, p. 840. Paints," Official Digest, Federation of Paint and Varnish Produc-
[14] van Wullen-Scholton, W., "Oil Absorption of Pigments," Farben tion Clubs, Vol. 26, 1954, p. 81.
Zeitung, Vol. 344, 1929, p. 2940. [35] Dinenfass, L., "Selective Polar Adsorption and Some Rheo-
[15] Azam, M., "Oil Absorption of Pigments, Industrial and Engi- logical Phenomena in Paint Systems," Journal of the Oil and
neering Chemistry," Analytical Edition, Vol. 14, 1942, p. 545. Colour Chemists' Association, Vol. 41, 1958, p. 25.
[16] British Standards Institution, Standard 3483, 1962, p. 11. [36] Stieg, F. B., Jr., "Particle Size as a Formulating Parameter,"
[17] Bessey, G. E. and Lammiman, K. A., "Oil Absorption of Pig- Journal of Paint Technology, Vol. 39, 1967, p. 703.
ments and Extends," Journal of the Oil and Colour Chemists' [37] Armstrong, W. G. and Madson, W. H., "The Effect of Pigment
Association, Vol. 33, 1950, p. 411. Variation on the Properties of Flat and Semigloss Finishes,"
[18] "Oil Absorption," Brochure No. TP-P-OA, National Lead Com- Official Digest, Federation of Paint and Varnish Production Clubs,
pany, Titanium Division, New York, 10 April 1953. Vol. 19, 1947, p. 321.
[19] Smith, F. M. and Stead, D. M., "Determination of Oil Absorp- [38] Daniel, F. K. and Goldman, P., "Evaluation of Dispersions by a
tion: A New Method," Journal of the Oil and Colour Chemists' Novel Rheological Method," Industrial and Engineering Chemis-
Association, Vol. 37, 1954, p. 194. try, Analytical Edition, Vol. 18, 1946, p. 26.
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Part 7: Additives
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MNL17-EB/Jun. 1995
Bactericides, Fungicides, and 29

Algicides
by Vanja M. King 1
THE VARIED METABOLIC CAPABILITIES o f microorganisms enable 9 Toxicity is the deleterious effect on organisms other than
them to cause many problems in paints and coatings, from the target organism, Aquatic toxicity of a fungicide would
manufacture through storage and application. These prob- be an example of a fungicide's effect on fish, etc.
lems can usually be controlled with the effective use of mi- 9 Efficacy is the effect of a microbicide on the target organism
crobicides (bactericides, fungicides, and algicides). The or- or group of organisms. Efficacy could be measured in per-
ganisms involved are also discussed elsewhere in this man- cent kill compared to control, but should be defined in the
ual. Knowing the type of organisms against which a test method, The result is usually expressed as the mini-
microbicide is to provide protection is very important in mum inhibitory concentration (MIC) against a specific or-
selecting the best types of chemicals to use. ganism.
Other considerations in the selection of the treatment 9 Colonization refers to the establishment of growth of organ-
chemicals include the intended application of the end prod- isms on a surface.
uct, the composition of the product being preserved, and the 9 Spectrum is a term describing the efficacy of a microbicide;
desired level of performance. The physical parameters are broad spectrum means that the microbicide is effective
also of great importance. Some types of organics and inor- against more than one group of microorganisms.
9 Microbial pigments refers to colored substances produced
ganics, pH levels, temperature at the time of addition, and
by microorganisms. These include both water-soluble and
ultraviolet (UV) exposure of the film may deactivate the
water-insoluble compounds.
biocide used [1,2]. A thorough knowledge of the biocides
available will help the chemist select the proper materials for
his or her system and help minimize the occurrence of un-
pleasant surprises.
DESCRIPTION OF MICROBIAL PROBLEMS
Environmental considerations and public opinion are also
of great importance. Strong feelings have evolved about anti-
In-can Preservation
microbials like mercury and tin. Some toxicological concerns
regarding biocides are: exposure during manufacturing, stor- Problems frequently associated with unpreserved, water-
age, application, clean up (washing), and disposal of wash based paints have increased in recent years, mainly because
waters. water-based paints have become much more common. These
formulations are susceptible to attack by bacteria and unicel-
lular fungi (yeasts) and occasionally filamentous fungi. There
are several food sources available for growth of microorgan-
Definition o f Terms
isms in common coatings formulations; cellulosic thickeners,
Following are definitions of the terms used: surfactants, and defoamers are all molecules used as a carbon
9 A biocide is a substance that kills organisms. The use in this source by microorganisms. Good discussions can be found in
section is synonymous with microbicide. Occasionally the Refs 3-5. The problems most commonly encountered in wa-
terms are further defined (bactericide, fungicide, algicide) ter-based paints include those shown in Table 1.
to include the types of organisms killed. To prevent these problems from occurring, an effective
9 A microbiostatic agent is one that prevents the growth of biocide should be incorporated into the coating. It must be
microorganisms and their spores, but does not necessarily cost effective, be compatible with coating ingredients, impart
kill them. no color to the formulation, have no objectionable odor, be
9 A preservative is an agent that slows down the bio- nonyellowing in the dried film, and be environmentally ac-
deterioration of a material. (An important factor to remem- ceptable in manufacture, handling, and release into the envi-
ber is that bacterial endospores only need to be kept from ronment.
germination and outgrowth because endospores are The best understood problem in coating film preservation
nonmetabolizing and cannot cause deterioration or spot- is the disfiguring growth of organisms on the exterior surface
age.) of the film itself [6, 7], such as on ships, bridges, and interior
and exterior walls of buildings. Less understood are problems
~Chief research microbiologist, Buckman Laboratories Interna- associated with loss of adhesion from fungi growing under-
tional, Inc., 1256 N. McLean Blvd., Memphis, TN 38108. neath the coating film and the corrosion problems on equip-
261
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TABLE 1--Problems caused by contamination of water-based TABLE 2--Problems in paint and coating film preservation.
paints. Type of Problem Common Cause
Type of Problem Common Cause Discoloration/dirt Algae and/or fungi.
Gassing--swelling CO2 released by bacteria or entrapment
or exploding yeasts. Loss of adhesion Fungi.
cans
Corrosion Moisture produced by fungi.
Viscosity loss Cellulase enzymes produced by
bacteria or fungi attacking Need for sanitizing agents in Microorganisms on hospital walls.
thickeners. film
Odors Organic acids and other metabolic Antifouling paints on marine Bacteria, fungi, algae, barnacles,
byproducts of microbial crafts and structures hydroids, etc.
metabolism. Production of growth Algae and fungi.
pH change/physical Organic acids produced can lower promoting substances
instability pH of paint. Destruction of cultural Algae, fungi, and bacteria growing
Loss of paint film Pseudomonas sp. bacteria are well objects on paintings, statues, and
fungicide/algicide known for detoxifying buildings.
antimicrobials; Cladosporium
resinae is reported to deactivate
methylparaben. G R O U P S OF M I C R O O R G A N I S M S R E L A T E D
Gelation Pseudomonas sp. have been TO BIOCIDAL EFFICACY
implicated.
Discoloration Both bacteri and fungi/yeasts It is i m p o r t a n t to k n o w the activity of a p a r t i c u l a r preserva-
growing in and on in-can tive/biocide against the types of o r g a n i s m s e n c o u n t e r e d by
materials can produce water- the formulation. F o r this purpose, the m o s t i m p o r t a n t groups
soluble and insoluble pigments.
of m i c r o o r g a n i s m s are:
Slime formation Biofilm formation by slime-
forming bacteria and fungi can
produce clumps in the liquid Bacteria
and slime on the sides of pipes Aerobic b a c t e r i a
and cans. G r a m positive b a c t e r i a
endosporeforming bacteria
m e n t from the m o i s t u r e p r o d u c e d by the r e s p i r a t i o n of fungi. G r a m negative b a c t e r i a
Fungicides are n e e d e d to control these p r o b l e m s . Anaerobic b a c t e r i a
There is a continuing need for sanitizing a n d disinfecting G r a m positive b a c t e r i a
p a i n t films. In this case, there is m o r e n e e d for a b a c t e r i c i d e endosporeforming bacteria
t h a n a fungicide. F o r example, the hospital e n v i r o n m e n t con- G r a m negative b a c t e r i a
tinues to be conducive to so-called n o s o c o m i a l infections Fungi
(those acquired in the hospital) and, with the rise in n u m b e r s Multicellular (molds)
of i m m u n o c o m p r o m i s e d a n d elderly patients, paints contain- Unicellular (yeasts)
ing long-lasting bactericides are needed. M a n y c o m p o u n d s
m a y n o t r e m a i n active the length of t i m e n e e d e d for t h e m to Algae
work, Green algae
Microbicide toxicity a n d efficacy are often concerns w h e n Blue-green algae (cyanobacteria)
preserving coating films. Fungicides a n d algicides are fre-
quently m o r e toxic t h a n m o s t c o m m o n bactericides since NOTE: All of these o r g a n i s m s are described in m o r e detail
fungal a n d algal cells share m a n y similarities with cells from elsewhere.
higher organisms, while b a c t e r i a l cells a r e distinctly differ-
ent. Most m i c r o b i c i d e s are limited to efficacy against one
group, a n d s o m e of the m o r e effective a n t i m i c r o b i a l s target
M O D E OF ACTION OF M I C R O B I C I D E S /
specific m e t a b o l i c p a t h w a y s u n i q u e to one group of organ- S P E C T R U M OF ACTIVITY
isms.
Several recent studied [8, 9] have s h o w n a relationship be- It is very i m p o r t a n t to note the difference in the activity of a
tween bacterial growth, their polysaccharides, a n d subse- p a r t i c u l a r biocide a g a i n s t the different o r g a n i s m s w i t h i n a
quent colonization of surfaces by fungi o r other organisms. It group, a n d differences are to be expected. The m o s t i m p o r -
a p p e a r s that colonization succession occurring on dry films is tant c o n s i d e r a t i o n is to k n o w w h i c h o r g a n i s m s one is trying
s i m i l a r to that occurring on ship bottoms. This implies that to protect against a n d to use an effective agent. W h e n the
there should be a bactericide and a fungicide i n c o r p o r a t e d for m o d e of action of a biocide has b e e n elucidated, it frequently
coating film protection. S o m e biocides can provide b o t h explains the differences in activity. The lists below are not
functions. In tropical climates, disfiguring g r o w t h of algae on m e a n t to b e comprehensive. They describe s o m e m a t e r i a l s
the exterior of the films is also a p r o b l e m [10,11]. Table 2 well k n o w n to the industry a n d r e p o r t on the o r g a n i s m s
indicates p r o b l e m s in p a i n t a n d coating film preservation. against which the c o m p o u n d s are m o s t effective [12-14].
www.iran-mavad.com

CHAPTER 29--BACTERICIDES, FUNGICIDES, AND ALGICIDES 263
Another important factor related to the spectrum of activ- For an excellent summary of the chemistry of many of the
ity is concentration. Some biocides are effective against bac- compounds shown in Table 4, please see Ref 16.
teria in one concentration and effective against fungi in a Table 5 indicates some nitrogen and/or sulfur-containing
much higher concentration; the reverse can also be true. microbiocides used in paints and coatings. Many of the
Furthermore, a biocide may be microbiostatic in a low con- biocides listed in Table 5 are important to this industry,
centration and microbicidal in another. The general defini- especially from a general housekeeping standpoint. The im-
tion of "microbiostatic" is that it interferes with some activity portance of cleanliness in the production of all types of mate-
rials should be emphasized since heavy contamination of a
of the organisms without necessarily killing them. A "-cidal"
product is difficult to overcome with any preservative. Disin-
compound kills the organisms. The definition of a micro-
fection of pipes and vessels along with a general washup will
biostatic/microbicidal compound is here broadened to in-
remove the surviving, more resistant organisms.
clude concentration. The underlying principles to the mode
of action are generally agreed upon to be one of two mecha-
nisms:
M O D E OF ACTION OF S O M E
1. Membrane-active compounds such as quaternary com- ANTIMICROBIAL AGENTS
pounds.
2. Electrophilic agents (react with nucleophilic groups on or The following is not intended to explain all possible modes
within cells). of action, but to give a general overview of the terms used in
Table 3 shows some metal microbicides used in paints and the biocide listings. More detailed explanations can be found
coatings. in the references listed at the end of this chapter.
Because of environmental concerns, the use of many
heavy-metal-containing biocides traditionally incorporated Agents that React with Acetylacetone
in coatings has become more limited [15]. An example is the
recent (1988) ruling by the EPA regarding the maximum re- This term describes chemicals that, when treated with ace-
lease of tributyl tin. The Organotin Antifouling Paint Control tylacetone (Nash's reagent), will yield formaldehyde. Some of
Act essentially restricts the use of organotin antifouling these act as preservatives by releasing formaldehyde, while
paints to commercial and military crafts. In 1990, the U.K. others (manufactured through condensation reactions with a
revoked the use of tributyl-tinoxide (TBTO) in surface starting compound and formaldehyde) may not necessarily
biocides for professional and amateur use. Mercury-type act through the release of formaldehyde. The release of form-
compounds are losing favor with a large segment of the aldehyde is also related to pH. At alkaline pH, little or no
coatings industry and the public, and it appears likely their formaldehyde is released.
use will continue to decrease as nonmercurials replace them Formaldehyde interacts with amine groups on proteins in a
in the future. The toxicity of some mercurial compounds, condensation reaction, thereby deactivating them. Proteins
notably methyl mercury, also makes them very potent and are common on the outer layers of microorganisms and many
long lasting preservatives with a broad spectrum of activity. also produce extracelfular proteins (enzymes) for metabolism
Some positive effects of the metal compounds on the prop- of large molecules like cellulose. Deactivated proteins hinder
erties of coatings should also be noted. Barium metaborate, a metabolism or growth or may actually kill the organism. A
pigment, has been reported [2] to act as a corrosion inhibitor common result is the leakage of the contents of the cell into
and a UV light stabilizer. Zinc oxide further enhances drying the environment.
of the paint film (which is a desirable property) and makes it Because of the current public unease concerning formalde-
more resistant to fungi [12]. Table 4 shows some nitrogen hyde, few biocide producers like to call their products formal-
and/or sulfur-containing microbicides used in paints and dehyde releasers. However, this is probably the most com-
coatings. mon mode of action among the bactericides. It is very
TABLE 3--Some metal microbicides used in paints and coatings.

Composition Effective Against Putative Modeof Action
Barimn metaborate Broad spectrum Enzyme inhibition
Copper (II) 8-quinolinolate Fungi General coagulation
Phenylmercuric acetate and Broad spectrum Protein deactivation
other organo-mercurials (coagulation), etc.
Tributyl tin oxide and other Broad spectrum, except Chelation, enzyme inhibition
tributyl tins gram negative
bacteria
Zinc oxide Fungi, algae Chelation, protein inhibition
Zinc-dimethyl Fungi Chelation of necessary
dithiocarbamate + Z n 2- metals; possibly interferes
mercaptobenzothiazole with oxidative
phosphorylation
Zinc 2-pyridinethiol-N-oxide Fungi Chelation of necessary metals
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TABLE 4--Some nitrogen and/or sulfur-containing microbicides used in paints and coatings.
Composition Effective Against Putative Mode of Action
4,4-dimethyl-oxazolidine + Bacteria Reacts with acetylacetone
3,4,4-trimethyloxazolidine
5-hydroxy-methyl-1-aza-3,7- Bacteria Reacts with acetylacetone
dioxabicyclo (3.3.0.) octane*
2(hydroxymethyl)- Bacteria Inhibits active transport; coagulates protein
aminoethanol
2 [(hydroxymethyl)-amino]-2- Bacteria Reacts with acetylacetone
methyl- 1-propanol
Methylenebis(thiocyanate) Bacteria/fungi/algae Attacks cellular thiols; inhibits oxidative phosphorylation
1,2-dibromo-2,4- Bacteria/fungi/algae Has several highly electron withdrawing centers
dicyanobutane
2-(4-thiazolyl)benzimidazole Fungi Low: inhibits ergosterol synthesis
High: membrane damage; interacts with DNA synthesis;
blocks oxidative phosphorylation
2-mercaptobenzo-thiazole Fungi/bacteria (?) Chelation of necessary metals
1,2 -benzisothiazoline-3-one Bacteria/fungi/yeast Interacts with nucleophilic components
5-chloro-2-methyl-3(2H)- Fungi/bacteria At physiological pH, reacts oxidatively with thiol-containing
isothiazoline + 2-methyl- Bacteria compounds; thio-acyl chloride formation
3(2H)-isothiazolone
4-(2-nitrobutyl)-morpholine + Fungi/bacteria Interferes with membrane synthesis (fungi); ergosterol
4,4'-(2-ethylnitrotrimethylene synthesis
dimorpholine
Zinc 2-pyridinethiol-N-oxide* Fungi Chelation of necessary metals
Tetra-hydro-3,5-di-rnethyl- Bacteria/fungi Detected with acetylacetone
2H-1,3,5-thiadiazine-2-thione
N-trichloromethyl-thio-4- Fungi Reacts with thiols = disulfide; inhibits respiration
cyclohexene-l,2-
dicarboximide
Hexyhydro- 1,3,5 -tri-ethyl-s- Bacteria Detected with acetylacetone
triazine
2 -n-octyl-4-isothiazoline-3- Fungi Reacts with thiol-containing compounds
one
1-(3-chloroallyl)-3,5,7-triaza- Bacteria Detected with acetylacetone

1-azonia-adamantane chloride
1-methyl-3,5,7-triaza-1- Bacteria Detected with acetylacetone
azonia-adamantane chloride
2,4,5,6-tetrachloro- Fungi Reacts with thiols; inhibits oxidation of glucose
isophthalonitrile
3-iodo-2-propynyl butyl Fungi Chelation?
carbamate
N-(trichloromethyl- Fungi Reacts with thiols = disulfide; inhibits respiration
thio)phthalimide
2-(thiocyanomethyl- Fungi/anaerobic; bacteria/ Reacts with thiols/inactivation of metal enzyme complexes
thio)benzothiazole algae
Diiodomethyl-p-tolyl sulfone Fungi ?
Potassium N-hydroxy-methyl- Fungi Chelates necessary metals
N-methyl-dithiocarbamate
2 -(thiocyanomethyl- Bacteria/fungi/algae/anaerobic Uncouples oxidative phosphorylation; reacts with SH-groups
thio)benzothiazole + bacteria/mollusks
methylenebis (thiocyanate)
Sodium 2-pyridinethiol-i- Fungi Chelation; ATP; transport; protein synthesis
oxide
*Other actives also present in the formulation.
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TABLE 5--Some other microbicides used in the coatings Other Mechanisms

industry.
Reported Effective PutativeMode of Coagulation is a term denoting a general deactivation of
Composition Against Action proteins or cells without specifying the molecular action.
Interference with active transport (of food molecules into
Glutaraldehyde Bacterial Reaction with
spores, proteins cells) may be from deactivation of transport proteins or by
bacteria, adsorption of molecules onto the cell surface, blocking the
fungi, algae transport proteins. Ergosterol is an important lipid compo-
Parabens (ethyl, or Fungi Membrane activity nent of the fungal membrane, and interference with its syn-
propyl, methyl, or and integrity thesis would be fungistatic in low concentrations and fungici-
butyl dal in high. Inhibition of respiration (oxidative phos-
parahydroxybenzoate)
phorylation) results in the cell being unable to generate
Quarternary Bacteria, a l g a e Generalized energy (ATP or adenine triphosphate) through metabolism,
ammonium membrane eventually killing it. Interference with DNA (deoxyribose nu-
compounds damage
cleic acid; chromosome material), RNA (ribose nucleic acid),
Chlorine biocides Broad spectrum Deactivation of or protein synthesis would hinder reproduction and metabo-
proteins
lism, eventually killing the cell.
effective against bacteria, but it is less effective against yeasts

and multicellular fungi.
STRATEGIES FOR MINIMIZING
Formaldehyde in its mode of action could also be classed RESISTANT STRAINS
with the electrophilic agents, which are agents that react with
nucleophilic components of a cell. The topic of resistance to antimicrobials is mentioned fre-
quently in industrial preservation discussions, probably be-
cause we are all familiar with resistance of disease-producing
Agents that React with Nucleophilic Groups microorganisms to therapeutic antibiotics. The issue of re-
Thiols are nucleophilic groups on amino acids (building sistance seems less obvious when dealing with industrial
blocks of proteins) or proteins found in all living cells; some biocides.
are reducing agents containing S groups. The cytoplasm of The most important factor for minimizing contamination
cells of all types of organisms contain a pool of amino acids and resistant strains is general housekeeping. Leaving water
and proteins. Biocides that contain electrophilic groups react in pipes and vessels that previously contained preserved ma-
with the nucleophilic areas of the cell, and deactivation of the terial would provide diluted biocide in nonlethal concentra-
organism occurs. tions to which microorganisms could become resistant.
Such biocides can also react with coating components that There are different opinions regarding genetic resistance to
contain nucleophilic groups. This results in the loss of some disinfectants and antimicrobials. It frequently appears that,
activity commensurate with the concentration of each reac- when an organism becomes resistant to one biocide (such as
tant. Reversal of biocidal activity or deactivation could result, quarternary ammonium compounds), it will also be resistant
from the addition of such materials. As the biocide reacts, it is to several, chemically unrelated biocides (such as thia-
being used up and unavailable for further activity. zolinones) [17]. This, of course, happens more readily when
A review of the chemistry of a preservative molecule could similar biocides are used (such as formaldehyde releasers).
reveal one or more electron withdrawing centers that would Therefore, changing the biocide may not be the solution to
be able to react with nucleophilic groups. There are many resistant organisms; rather, it may make matters worse by
compounds in this category. widening the materials to which resistance is observed.
Testing of biocides should utilize organisms isolated from
the manufacturing plant and spoiled materials. Plant isolates
Agents that Chelate Metals are almost always more resistant to biocides than stock cul-
tures maintained on artificial media. Also, selection of a good
Metals are necessary as trace elements for organisms. The
broad spectrum biocide minimizes the possibility of resistant
metals are frequently parts of enzymes or vitamins needed for
organisms. Finally, a thorough knowledge of the chemistry of
growth and metabolism. It is postulated that chemicals that
available biocides will keep one from using products with
chelate metals would deactivate microorganisms by with-
similar modes of action consecutively.
drawing the metals needed for life.
Cationic Agents ANALYSIS AND DECONTAMINATION

Cationic polymerics are frequently used as sanitizing It is of considerable importance to be able to accurately
agents. Such molecules would react with anionic constitu- analyze for the presence and concentration of the antimicro-
ents, inorganic and organic (such as those present on the bial agent. One reason is the ability to ascertain that the
surface of the microbial cell wall). The cationic material material was, in fact, added and in the right concentration
causes leakage of materials from the cell through the destabi- both as a quality control measure parameter and in case of a
lized cell wall, causing death of the cell. failure in the field.
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Available m e t h o d s vary with the type of active ingredient m a n y of the same factors are also i m p o r t a n t b ec a us e of their
utilized. Preferably, the m o l e c u l e should be d e t e r m i n e d with- i m p a c t on the activity of biocides. The i m p a c t is frequently
out e m p l o y i n g a destructive m e t h o d since one could not de- d e t r i m e n t a l [18], b u t can also be positive. S o m e factors are
t e r m i n e if b r e a k d o w n h a d o c c u r r e d in the c o n t a i n e r or if described in Tables 6 and 7.
b r e a k d o w n o c c u r r e d because of the m e t h o d of analysis. F o r
example, it w o u l d be preferable to d e t e r m i n e the intact mole-
TABLE 7--Factors that decrease biocidal efficacy.
cule of a f o r m a l d e h y d e releaser r a t h e r than d e t e r m i n i n g the
f o r m a l d e h y d e present after breaking up the molecule. The pH Knowledge of the chemistry of a biocide
f o r m a l d e h y d e release could have o c c u r r e d before analysis should include its activity at different pHs.
It is easier to find a biocide that is effective
was attempted. Nondestructive m e t h o d s include N M R (nu- and stable at acid pH than at alkaline, but
clear m a g n e t i c resonance) methods. many are described as being alkaline stable/
The i n f o r m a t i o n literature on a preservative p r o d u c t fre- effective. However, many are considerably
quently contains p r o c e d u r e s for deactivation of the biocide. less effective at alkaline pH, making an
increased concentration necessary. Stability
This i n f o r m a t i o n is necessary for several reasons. A spill can is not to be equated with efficacy since a
always occur, and a puddle of c h e m i c a l w o u ld need to be biocide that is stable at alkaline pH (such as
neutralized an d cleaned w i t h o u t d a n g e r to personnel. In ad- many dithiocarbamates) may not have much
dition, w h e n testing for efficacy of preservatives, small con- efficacy at alkaline pH, except after a long
centrations r e m a i n i n g even after dilution for e n u m e r a t i o n period of time.
m a y be at m i c r o b i o s t a t i c levels. If the o r g a n is m s h a d not been Addition Examples of biocides affected by addition
killed, there is a chance for r e g r o w t h and spoilage. A m e t h o d temperature temperatures are the parabens, which need
to be added at temperatures below 50~ It
for neutralizing the biocide should, therefore, always be used is typical of biocides that they are
in the growth m e d i u m w h e n p e r f o r m i n g preservative efficacy deactivated to various degrees based on
tests. temperature, although this temperature
effect varies considerably from biocide to
biocide. Increased concentration may
alleviate this problem. Typically, increase in
FACTORS THAT IMPACT T H E EFFICACY OF pH and increase in temperature is
S O M E C O M M O N ANTIMICROBIAL A G E N T S synergistic in deactivating sensitive biocides.
Nonionic Biocides that are deactivated by these include
The i m p o r t a n c e of physical and c h e m i c a l factors on the surfactants the parabens, phenolics, organic acids, and
aromatic alcohols.
g r o w t h of m i c r o o r g a n i s m s is discussed elsewhere; however,
Low solubility Preservatives need to be water-soluble to the
concentration needed for efficacy. This
means that the solubility should not be too
high, or that a combination of a soluble and
T A B L E 6--Factors that positively influence biocide efficacy. less soluble agent would be most effective.
Inclusion of pigments that Such components could possibly Leachability A coating film preservative must maintain an
have antimicrobial activity. cut down on the amount of effective concentration within the film to
preservative needed. remain antimicrobial. Water-soluble
Inclusion of other materials in Some components are less readily materials would be quickly compromised in
the formulation that have used as a food source (e.g., this situation. However, some movement
antimicrobial activity (e.g., choices of may be necessary to transport the
propylene glycol) or resist carboxymethylcelluloses). antimicrobial through dirt layers that
degradation accumulate. This balance may be hard to
maintain.
Many biocides are more Adjusting the pH to suit the
effective at acid pH, while biocide, if no effects are seen in Can components Can components could adsorb the
others are more active at an the formulation, could be antimicrobial agent from the content.
alkaline pH. helpful. Formulation Formulation components could deactivate the
Difference in solubility of Combining biocides with different components biocide. Such components are proteins for
different biocides. solubilities may increase formaldehyde releasers and thiols for
efficacy. An example of this is to electron withdrawing biocides.
use several different parabens, Stabilizing Inclusion of components may keep other
each of which has its own agents biocides from yellowing the film. Sodium
independent solubility. sulfite reportedly decreases the chance of
Synergism resulting from This effect, in most cases, appears 1-(3-chloroallyl)-3,5,7-triaza- 1-azonia-
combining biocides with to be additive instead of true adamantane chloride yellowing the paint
different spectra of activity. synergism (when the whole is film. However, such components may
more than the individual deactivate biocides since they are frequently
components together). listed as neutralizing materials in
Whichever case, antimicrobial preservative brochures.
agents are frequently UV light UV light frequency decomposes coating film
complemented by combination, frequency fungicides and algicides. The photolysis
e.g., the isothiazolones and products are less effective and efficacy is
methylene bis(thiocyanate)/2- lost. The inclusion of products that make
(thiocyanomethylthio)benzothia- the film more UV stable alleviates this
zole). problem.
www.iran-mavad.com

M E T H O D S F O R D E T E R M I N A T I O N OF [3] Ross, R. T., "Biodeterioration of Paint and Paint Films," Journal

B I O C I D E EFFICACY of Paint Technology, Vol. 42, No. 531, April 1969, pp. 266-274.
[4] Opperrnann, R. A. and Goll, M., "Presence and Effects of Anaer-
There are n u m e r o u s m e t h o d s d e s c r i b e d in the literature for obic Bacteria in Water-Based Paints," International Journal of
Coatings Technology, Vol. 56, No. 712, 1984, pp. 51-56.
d e t e r m i n i n g the efficacy of a p r o p o s e d biocide, b o t h for in-
[5] Jakubowski, J. A., Simpson, S. L., and Gyuris, J., "Microbiologi-
can preservation a n d for p a i n t film use. The a p p r o p r i a t e cal Spoilage of Latex Emulsions: Causes and Prevention," Jour-
ASTM m e t h o d s are: D 2574-86, Test M e t h o d for Resistance nal of Coatings Technology, Vol. 54, No. 685, 1982, pp. 39-44.
of E m u l s i o n Paints in the Container to Attack b y Microorgan- [6] Gillat, J. and Wood, B., "Prevention of Organic Growth on Coat-
isms; D 3273-86, Test M e t h o d for Resistance to G r o w t h of ings," Polymers, Paint & ColourJournal, Vol. 180, 1990, p. 4266.
Mold on the Surface of I n t e r i o r Coatings in an E n v i r o n m e n - [7] Hoffman, E., "Inhibition of Mold Growth by Fungus-Resistant
tal Chamber; a n d D 3456-86, Practice for D e t e r m i n i n g by Coatings Under Different Environmental Conditions," Journal
Exterior E x p o s u r e Tests the Susceptibility of Paint F i l m s to of Paint Technology, Vol. 43, 1971, pp. 54-59.
Microbiological Attack. These m e t h o d s are c o n t a i n e d in [8] Jackson, S. M. and Jones, E. B. G., "Fouling Film Development
on Antifouling Paints with Special Reference to Film Thick-
Section III, "Microbiological C o n t a m i n a t i o n a n d Biode-
ness," International Biodeterioration, Vol. 24, 1988, pp. 277-287.
t e r i o r a t i o n Assessment," of ASTM Standards on Materials and [9] O'Neill, T.B., "Succession and Interrelationships of Micro-
Environmental Microbiology, first edition, 1987 [19]. Several organisms on Painted Surfaces," International Biodeterioration,
o t h e r m e t h o d s in this section are also of interest. A c o m p l e t e Vol. 24, 1988, pp. 373-379.
fungicide testing p r o g r a m is d e s c r i b e d in Ref 20, a n d an [10] John, D. M., "Algal Growth on Buildings: A General Review and
electronic r a p i d m e t h o d for d e t e r m i n i n g c o n t a m i n a t i o n in Methods of Treatment," Biodeterioration Abstracts, Vol. 2, No. 2,
coating r a w m a t e r i a l s (and b y extension, preservation ef- 1988, pp. 81-102.
ficiacy) has recently b e e n p u b l i s h e d [21]. Other m e t h o d s are [I 1] Wee, Y. C., "Growth of Algae on Exterior Painted Masonry Sur-
d e s c r i b e d in Ref 22. Testing of algicides for tropical locations faces," International Biodeterioration, Vol. 24, 1988, pp.
367-371.
is d e s c r i b e d in Ref 23.
[12] Block, S. S., "Preservatives for Industrial and Miscellaneous
Products," Chap. 52 in Disinfection, Sterilization, and Preserva-
tion, 4th ed., S. S. Block, Ed., Lea & Febiger, Philadelphia, PA,
1991.
CONSIDERATIONS FOR THE FUTURE
[13] Lukens, R. J., "Microbial Agents Used in Agriculture," Chap. 44
D E V E L O P M E N T OF A N T I M I C R O B I A L in Disinfection, Sterilization, and Preservation, 4th ed., S. S.
AGENTS Block, Ed., Lea & Febiger, Philadelphia, PA, 1991.
[14] Sharpell, F. H., Biocides in Specialty Products, Vol. 9, No. 4,
While it is clear the d e v e l o p m e n t of new m i c r o b i c i d e s is 1989, pp. 233-236.
b o t h expensive a n d full of frustrations [24], some i m p o r t a n t [15] Review of Tributyltin Oxide (TBTO) Wood Preservatives and
results could ensue. The public is well a w a r e of the potential Surface Biocides, The Pesticide Register, No. 5, 1990, pp. 1-2.
h a r m to w h i c h people a n d the e n v i r o n m e n t have recently [16] Rossmore, H. W., Chap. 17 in Disinfection, Sterilization, and
been exposed a n d is p r e s s u r i n g the i n d u s t r y to move a w a y Preservation, 4th ed., S. S. Block, Ed., Lea & Febiger, Philadel-
from such products. However, few p e o p l e will accept the pur- phia, PA, 1991.
[17] Brozel, V, S. and Cloete, T. E., "Resistance of Bacteria from
chase of a d e t e r i o r a t e d material, a n d c o n s u m e r s expect the
Cooling Waters to Bactericides," Journal oflndustrial Microbiol-
p r o d u c t to p e r f o r m adequately once in use. Therefore, poten- ogy, Vol. 8, 1991, pp. 273-276.
tially less e n v i r o n m e n t a l l y negative preservatives w h i c h are [18] Hugo, W. B., "The Degradation of Preservatives by Microorgan-
still effective have a place in the m a r k e t a n d should be devel- isms," International Biodegradation, Vol. 27, 1991, pp. 185-186.
oped. Since the expense is exorbitant, this is going to be a [19] ASTM, Standards on Materials and Environmental Microbiology,
slower process t h a n one w o u l d like b u t should, nevertheless, 1st ed., 1987, Section III: "Microbiological Contamination and
proceed. The costs c o m e f r o m m a i n t a i n i n g r e s e a r c h a n d de- Biodeterioration Assessment," American Society for Testing and
v e l o p m e n t d e p a r t m e n t s , as well as a p p l i c a t i o n a n d develop- Materials, 1916 Race St., Philadelphia, PA.
m e n t costs. The highest costs are i n c u r r e d from r e q u i r e d a n d [20] Hollis, C. G., "Methods of Testing Fungicides," Chap. 61 in Dis-
infection, Sterilization, and Preservation, 4th ed., S. S. Block, Ed.,
necessary toxicology testing. W i t h the goal of developing less
Lea & Febiger, Philadelphia, PA, 1991.
toxic a n d m o r e e n v i r o n m e n t a l l y friendly biocides, these costs [21] Jaquess, P. A. and McLaurin, M. C, "An Efficient Impedimetric
will surely increase with b r o a d e r testing. Procedure to Demonstrate Bacterial Contamination in Water-
Based Coatings and Their Raw Materials," Journal of Coatings
Technology, Vol. 65, No. 823, 1993, pp. 77-81.
[22] Gillatt, J., "Methods for the Efficacy Testing of Industrial
REFERENCES Biocides--1. Evaluation of Wet-State Preservatives," Interna-
tional Biodeterioration, Vol. 27, 1991, pp. 383-394.
[1] Gabriele, P. D. and Iannucci, R. M., "Protection of Mildecides [23] Drisko, R.W. and Crilly, J. B., "Control of Algal Growth on
and Fungicides from Ultraviolet Light-Induced Photo-Oxida- Paints at Tropical Locations," Journal of Paint Technology, Vol.
tion," Journal of Coatings Technology, Vol. 56, 1984, pp. 33-48. 46, No. 595, 1974, pp. 48-55.
[2] McLaurin, M. C., Modified Barium Metaborate in Properties and [24] Dalton, D. L., "Introduction of a Novel, Nonmetallic Fungicide
Economics, Vol. 1, 2nd ed., John Wiley & Sons, Inc., New York, for the Coatings Industry," Journal of Coatings Technology, Vol.
1988. 60, No. 761, 1988, pp. 45-53.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Thickeners and Rheology 30

Modifiers
by Gregory D. Shay 1
LIST OF A B B R E V I A T I O N S pEO Polyethylene oxide

PG Propylene glycol
AQ Aqueous PVC Pigment volume concentration
ASE Alkali-swellable and/or soluble emulsion RM Rheology modifier
ATRM Associative thickener and/or rheology modi- SOLV Solvent
fier T Thickener
BCARB Butyl Carbitol | TRM Thickener and/or rheology modifier
BP Biopolymer VOC Volatile organic components
CMC Carboxymethyl cellulose XCPS Xanthamonas campestris polysaccharide
CTRM Conventional thickener and/or theology mod- (Xanthan gum)
ifier
DS Degree of substitution
DUEV Dynamic uniaxial extensional viscosity INTRODUCTION
EHEC Ethyl hydroxyethyl cellulose
HASE Hydrophobe modified alkali-swellable/solu- DEMANDS ON THE APPLICATIONand flow properties of coatings
ble emulsion have increased substantially, and because thickeners and rhe-
HBMC Hydroxybutylmethyl cellulose ology modifiers (TRMs collectively) play a key role in per-
HEC Hydroxyethyl cellulose formance, they are among the most important components in
HEEASE Hydrophobe modified ethoxylate ester alkali- a coatings system. Although TRMs are used in minor
swellable/soluble emulsion amounts in most formulations and are generally considered
HEMC Hydroxyethylmethyl cellulose additives, aqueous coatings usually contain at least one, often
HENN Hydrophobe modified ethoxylate nonionic two, and sometimes several to obtain the desired balance of
non-urethane properties. Due to present-day environmental concerns and
HEUR Hydrophobe modified ethoxylate urethane the use of TRMs predominantly in aqueous coatings, the
HEURASE Hydrophobe modified ethoxylate urethane focus of this chapter is on water-borne, and especially latex-
alkali-swellable/soluble emulsion based systems. TRMs also find utility in solvent-borne coat-
HMC Hydrophobe modified cellulosic ings where they function primarily as flow modifiers and
HNS Hydrophobe modified nonionic synthetic thixotropes. These products are discussed in later sections of
HMEHEC Hydrophobe modified ethyl hydroxyethyl cel- this chapter.
lulose
HMHEC Hydrophobe modified hydroxyethyl cellulose
HPG Hydroxypropyl guar Thickeners
HPMC Hydroxypropylmethyl cellulose Thickeners, as traditionally defined, are components that
HSV High-shear viscosity substantially increase viscosity (resistance to flow) at rela-
ITRM Inorganic thickener and/or rheology modi- tively low concentrations. For coatings, thickeners are nor-
fier mally used to increase viscosity at moderate shear rates
LIQ Liquid approximating those encountered during pouring, stirring,
LSV Low-shear viscosity or mixing. The viscosity in this shear rate range is often
MC Methyl cellulose referred to as the coating "consistency" or medium-shear vis-
MS Molar substitution cosity (MSV). To be effective, a thickener should produce the
MSV Medium-shear viscosity desired consistency at a low-use level that is often expressed
NA Data not available in units of lb thickener solids per 100 gal of liquid coating (g/L
ORG Organo or organic where metric units are used). For architectural coatings, the
PAA Polyacrylic acid total amount of thickener typically used is less than about 15
lb/100 gal ( - 1 8 g/L) and can be as low as 3 lb/100 gal ( - 4 g/L)
ITechnology manager, Thickeners and Rheology Modifiers, Union or less, depending on coating solids, pigment volume concen-
Carbide Corp., UCAR Emulsion Systems, 410 Gregson Drive, Cary, tration (PVC), vehicle type, and other components present in
NC 27511. the formulation. As discussed later, selection of components
268
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Copyright 1995 by ASTM lntcrnational
9
www.astm.org

CHAPTER 3 0 - - T H I C K E N E R S AND R H E O L O G Y MODIFIERS 269
is particularly important with associative thickeners. The plies to associative rheology modifiers where strong interac-
units of shear rate are reciprocal seconds (s-1), and the shear tions occur between the TRM and other coating components.
rate range for measurement of consistency is about 10 to
1000 s -1 and more typically about 100 s -1.
A change in a coating's consistency can be sensed subjec- INCORPORATION OF TRMs
tively. For example, the depth of fluid vortex in a container at
a given mixing speed can be observed visually, or the increase Coating manufacturing operations generally consist of
in resistance to flow during hand stirring can be felt. The several stages of processing, and TRMs are important in each.
consistency of the coating can also be measured using an Some common stages are the "premix" (ingredients added
appropriate viscometer or rheometer that operates in the prior to pigments), "grind" (pigment added and reduced in
medium shear rate range (such as at 10 to 1000 s- 1). The high size for optimum dispersion), and "letdown" (where polymer
end of this range also correlates with "pumpability," which is or latex is normally added). Some but usually not all of the
critical in some automated manufacturing operations. Sev- thickener is added to the premix to increase viscosity in the
eral popular instruments for measuring consistency are de- grind for improved pigment dispersion (deagglomeration).
scribed later in this chapter under Coating Consistency Under laminar flow conditions, rate of shear during grinding
(Medium-Shear Viscosity). is set by the tip speed of the impeller and the depth of the
shear gradient. One theory suggests that increased viscosity
allows better energy transfer by decreasing turbulence at the
Rheology Modifiers impeller, which, in turn, increases the shearing collisions that
attrite the pigment agglomerates. However, too much thick-
Presently, there is no universally accepted definition of the ener at this stage impedes mixing and actually slows down
term "rheology modifier." In fact, the terms "thickener" and the grinding process. The remaining thickener is usually
"rheology modifier" are often used interchangeably in com- added to the letdown to provide proper suspension and prod-
merce, especially for associative TRMs. All thickeners modify uct consistency. Finally, post-adjustments with additional
rheology to varying degrees when incorporated; conse- thickener or rheology modifier may be required to bring the
quently, all thickeners, technically, are also rheology modi- product "into specification" for application and appearance
fiers. Some modify rheology in a positive way, and others properties.
modify rheology adversely depending on the desired effect.
Although all thickeners can be considered theology modi-
fiers, not all rheology modifiers are considered thickeners,
RHEOLOGY AND VISCOSITY
and herein lies a distinction. For purposes of classification,
rheology modifiers are defined here as additives which influ-
Because viscosity and rheology modification are the very
ence viscosity at high and/or low shear rate (generally above
essence of primary TRM function, a basic understanding of
1000 s -1 or below 10 s -1) but contribute little to consistency
rheological concepts is helpful to fully appreciate differentia-
(that is, they change rheology but are inefficient thickeners). tion in product performance. A thorough treatment of this
If a rheology modifier as defined was used as the sole thick- subject is found elsewhere in this book. The following subsec-
ener for consistency, typically more than about 15 lb/100 gal tions provide a general overview of the two primary types of
( - 1 8 g/L) would be required, and 30 to 60 lb/100 gal ( - 3 5 to flow encountered during the preparation, storage, and appli-
75 g/L) would not be unusual. When used as primarily in- cation of coatings that are affected by the choice and amount
tended (as a rheology modifier with one or more other thick- of TRM present [1-5].
eners present), amounts much less than this normally suffice.
Like thickeners, rheology modifiers may also influence the
elastic or elongational (extensional) properties of coatings, Shear Flow
which can be measured on some relatively sophisticated Most low, medium, and high shear rate coating phenom-
rheometers. Frequently, a single thickener or combination of ena involve shear flow that is normally characterized in the
thickeners is effective in meeting all of the rheological re- laminar regime (where the shear field produces Reynold's
quirements (low, medium, and high-shear) of a given coating Numbers below the critical characteristic for the fluid). Shear
formulation, and a rheology modifier is not needed in this flow in the Turbulent regime (high Reynold's Numbers) is not
situation. If the rheological requirements cannot be met with normally characterized, since most parameterizing equations
thickeners alone, a rheology modifier is often included to fail here. The vast majority of viscometers produce shear flow
augment flow properties. A common example of this is the and measure the ratio of shear stress to shear rate (viscosity).
incorporation of a rheology modifier to raise the high-shear With coatings, it is useful to determine viscosity at several
viscosity (HSV) of a coating. This increases viscosity on appli- shear rates to obtain a complete rheology profile which is
cation which, in turn, provides increased film build (film normally represented in log-log form. These profiles are also
thickness) for improved substrate protection or one-coat hid- conveniently divided into three shear rate regions--"at rest,"
ing. "processing," and "application," which correspond to the low-
In some situations, a rheology modifier is efficient enough shear, medium-shear, and high-shear regions, respectively,
to function as an effective thickener such as in the presence of as depicted in Fig. 1. Optionally, the viscosity profile can be
a small-particle-size latex, water-insoluble coalescing aids, at approximated by single-point measurements of low-shear
high binder concentrations, or at high-volume solids. This viscosity (LSV), medium-shear viscosity (MSV), and high-
effect, which will be discussed in detail later, especially ap- shear viscosity (HSV). Some of the coating processes and
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VISCOSITY (Pa.s)
10,000
AT REST PROCESSINO APPLICATION
1,000
LOW S H E A R MID S H E A R HIGH S H E A R
100
BRUSHING
10
ROLLING
LEVELING SPRAYING
SAGGING TROWELING
SETTLING MIXING
0.1 CONSISTENCY
SYNERESIS
APPEARANCE
0.01
PUMPING
0.001 I I I IIIlll I I I IIIII I I I III111 I I ~ IIIIli I I I Illlll I I I IIII
0.1 1 10 100 1,000 10,000 100,000
SHEAR RATE (s-l)

FIG. 1 - A typical architectural coating viscosity profile, three important shear rate
ranges, and the coating parameters affected and operating in each shear rate range.
properties affected in each region are also shown in Fig. 1 and measurement of DUEV on disperse phase coating systems
are further discussed later in this chapter under TRM FUNC- was difficult; however, a commercial instrument is now avail-
TIONS. able for measuring DUEV on undiluted coatings directly. As a
Time-dependent shear thinning (thixotr0py) and zero- class, associative thickeners tend to impart lower DUEV than
shear yield value are two other rheological coating properties conventional (nonassociative) thickeners, which improves
that may be very important. For example, a thixotropic fluid some of the application properties described. Comparative
with high yield value may exhibit good leveling if the time representations of shear and elongational (extensional) flow
required to rebuild viscosity is long compared to the time are depicted in Fig. 2.
needed for flowout. The viscoelastic properties of a coating
may also be important. The elastic component of shear can be
determined on some advanced cone-plate or parallel plate TRM CLASSIFICATION
rheometers either by measuring the shear storage modulus
(G') in oscillatory simple shear or by measuring normal Polymeric organic thickeners for aqueous media are often
forces (for example, first normal stress difference, N]), which classified into two basic types: "conventional," which thicken
are perpendicular to the plane of shear. predominately by hydrodynamic and flocculative mecha-
nisms, and "associative," which thicken predominantly by as-
sociative mechanisms. Unfortunately, these are mechanistic
Elongational Flow
In addition to the simple shear flow fields generated during
the mixing and application of coatings, elongational (exten-
sional) flows may also be induced during the application
processes of spray, roll, or blade coating. The study of exten-
sional flows and their importance in coatings has been exam-
ined [6-11]. During these application processes, the fluid is
accelerated as it approaches the applicator orifice or nip, and
the TRM polymer molecules become stretched and aligned.
The viscosity related to the induced elongational flow is
termed by Glass [7] as the "dynamic uniaxial extensional
viscosity" (DUEV). One coating property that has shown
some correlation with DUEV is roller spatter that can be
rated using ASTM Test Method for Measurement of Paint
Spatter Resistance to Roller Application (D 4707-87). Other
properties that have shown some correlation with DUEV are
ribbing, web formation, and misting in roll coatings, and the
atomization process in spray coatings. Until recently, the FIG. 2-Types of induced flow in coatings.
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CHAPTER 30--THICKENERS AND RHEOLOGY MODIFIERS 271
definitions that are subject to some variability and exception. TABLE 1--Thickening mechanisms for organic polymers in
A clear distinction, however, can be made for purposes of aqueous media.
classification based on composition. Conventional (non- I. Hydrodynamic (CTRMs)
associative) thickeners (CTRMs) are defined here as high- (A) High MW soluble polymers
molecular-weight water-soluble polymers with relatively uni- (B) Insoluble swellable polymers
II. Associative (ATRMs)
form hydrophilic backbones lacking hydrophobic groups. (A) Hydrophobe interactions
Lower-molecular weight species of similar chemical compo- (B) Ion-dipole interactions
sition (analogs) are less efficient as thickeners but may serve III. Flocculative (CTRMs and ATRMs)
as rheology modifiers. Associative thickeners (ATRMs), on (A) Depletion flocculation
(B) Bridging flocculation
the other hand, are defined here as water-soluble polymers of
comparatively lower molecular weight which contain hydro- NOTE:The flocculativemechanismsoccurin dispersephasesystemsonlyand
almost exclusivelyin the presence of CTRMs.
phobic groups at the ends within or pendant to the hydro-
philic backbones. The hydrophobes in these polymers are
capable of nonspecific hydrophobic associations similar to The H y d r o d y n a m i c M e c h a n i s m
those of conventional surfactants, and these associations are Prior to the introduction of associative thickeners, nearly
primarily responsible for generation of viscosity with these all organic thickeners used for aqueous coatings were water-
thickeners. Variation in chemical architecture, the number of soluble polymers of high molecular weight (MW) without
hydrophobes present, and a further reduction in molecular hydrophobe modification, which is the collective criteria for
weight can produce associative polymers which function pri- their classification as conventional thickeners. The molecular
marily as rheology modifiers. It becomes readily apparent weights of the conventional polymers that function as thick-
that, with proper hydrophobe modification, virtually any eners for water-borne coatings are generally greater than
CTRM can be converted to an associative polymer, and this is about 105 and can be as high as 106 or more. Polymers with
what has been done in the design of several commercial stiff backbones (for example, cellulosics) at the lower end of
ATRM products. The advantages and disadvantages of the MW range are as effective in thickening in the high end of
CTRMs and ATRMs have been reviewed in the literature this range with flexible backbones (for example, polyethylene
[12,13] and will become more apparent in the following sec- oxide). When conventional thickeners dissolve in water, the
tions. A clearer distinction between these two major classes polymer chains occupy a large hydrodynamic volume in solu-
of TRMs will be apparent on examination of the thickening tion and immobilize large volumes of water within the coils
mechanisms involved. Although nearly all inorganic thick- of their backbones. This increases viscosity of the continuous
eners are conventional with respect to their thickening mech- water phase dramatically. For a given polymer type, higher
anisms, these TRMs will be treated separately later of this molecular weight generates higher viscosity. In fact, the solu-
chapter under INORGANIC T H I C K E N E R S FOR AQUE- tion viscosity of conventional polymers in water or nonaque-
OUS AND SOLVENT-BORNE COATINGS. ous solvents is one of the common methods used for
determination of molecular weight. As previously stated, suf-
ficiently low-molecular-weight polymer analogs can function
as true rheology modifiers since they do not contribute appre-
THICKENING MECHANISMS ciably to consistency (MSV). However, these have been re-
placed to a large degree with associative rheology modifiers
The three primary thickening mechanisms for polymeric in many coatings applications.
water-borne thickeners are "hydrodynamic," "flocculative," Some conventional thickeners are lightly cross-linked to
and "associative." Each of these mechanisms may be further make them water-swellable rather than water-soluble. In
divided into subclasses, if desired, which have their own indi- aqueous media, these polymers swell significantly to produce
vidual rheological and coating characteristics. Consequently, viscosity by a hydrodynamic mechanism. When the polymers
it is important to consider these mechanisms when making are made by emulsion polymerization, they may swell to
TRM selection for increasing coating consistency, for rheol- many times their original particle size. Examples of conven-
ogy modification, or for other coating properties. tional water-soluble or water-swellable thickeners used
Thickening is often a complex process. For example, the extensively in coatings are hydroxyethyl cellulose,
flocculation mechanism is frequently a byproduct of hydro- hydroxypropyl methyl cellulose, and alkali-swellable/soluble
dynamic thickening but may also occur in associative sys- copolymer emulsions (ASEs). These and some other CTRMs
tems that are improperly formulated or in those where a are discussed later in this chapter under CONVENTIONAL
controlled degree of flocculation is desired. Some associative TRMs (CTRMs).
thickeners (for example, alkali-swellable types) are suffi-
ciently high in molecular weight that an appreciable
Flocculative Mechanisms
hydrodynamic component of thickening is also present.
Depending on their chemical architecture, strength of the Because CTRMs take up so much volume in solution, they
hydrophobic associations, and other formulation compo- induce flocculation in coatings, forming latex-rich and thick-
nents present, some ATRMs actually function to varying ener-rich domains by a mechanism commonly referred to as
degrees with several associative and nonassociative mecha- 'volume restriction," "volume exclusion," or "depletion" floc-
nisms at the same time. Outlined in Table I are some possible culation. This process is now recognized as the primary mode
thickening mechanisms for conventional and associative of thickening for conventional thickeners in disperse phase
thickeners. systems (such as, in coatings with pigment or latex particles
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present) and has been examined in both experimental than conventional thickeners. To be viable in commerce,
[14-16] and theoretical treatments [17,18] and more recently ATRMs usually have a few repeat hydrophile-hydrophobe
modeled by computer simulation [19]. The process begins units to increase molecular weight, thereby increasing the
when latex particles randomly approach each other, and hydrodynamic contribution and also the association effi-
when they are close enough (on the order of a random-coil ciency.
thickener molecular diameter), thickener molecules are "ex- Another aspect of ATRMs is their interaction with colloidal
cluded" from the interparticle region. The concentration components in a coating formulation. Whenever latex parti-
gradient formed causes water to be osmotically "pumped" cles or hydrophobic pigments are present in a coating formu-
from between the particles driving them even closer together, lation, the hydrophobes on the associative thickeners can
which further concentrates the thickener molecules in the adsorb onto the hydrophobic particle surfaces, which results
aqueous phase. Eventually, the latex particles touch, forming in a further increase in system viscosity and possible modifi-
flocs which are readily observable on microscopic examina- cation of rheology. The strength of the association is impor-
tion. This mechanism of thickening can adversely affect gloss tam, and depending on degree, a polymer can induce several
and hiding and also may impart more shear thinning charac- types of equilibrium phase behavior including nonassociative
ter and more viscoelasticity. Since these polymers are of high volume restriction and associative bridging flocculation [26].
molecular weight, they also tend to impart high extensional For comparison, diagrammatic representations of a conven-
viscosity to coatings. The combination of viscoelasticity and tional thickener and an associative thickener in the presence
high extensional viscosity results in a tendency for spatter of latex particles are depicted in Figs. 3 and 4, respectively.
and increased rib pattern in roll coatings [20]. Although hydrophobe interaction is the predominate asso-
Another flocculative mechanism is '~oridging" flocculation. ciative mechanism for ATRMs, some evidence suggests an
In this mechanism, the polymer molecules partially adsorb additional associative mechanism which is hydrophilic
onto latex or pigment particles. If the thickener molecules are rather than hydrophobic in nature. The proposed hydrophilic
sufficiently long and have a strong affinity for other particles, association is an ion-dipole interaction between surface car-
bridging can occur, forming flocs. boxyl groups on the latex with the polyethylene oxide (pEO)
segments in the associative thickeners [25]. When the ATRMs
contain both carboxyl and ethoxylate functionality in the
ASSOCIATIVE MECHANISMS same molecule (for example, associative alkali-swellable/sol-
uble polymers), both intermolecular and intramolecular ion-
The primary thickening mechanism for ATRMs is via dipole associations are theoretically possible.
intermolecular hydrophobic association and association
of the thickener hydrophobes with disperse phase (colloidal
phase) hydrophobic components in the coating formulation TRM FUNCTIONS
[21-24]. When a water-soluble polymer contains both hydro-
philic and hydrophobic moieties, the potential for associative The primary function of TRMs are the control of viscosity
interaction exists. Among the simplest associative structures and rheology throughout the applicable shear rate spectrum:
are nonionic surfactants. These molecules have a hydrophilic consistency is measured and adjusted in the medium-shear-
polymer segment on one end (usually polyethylene oxide) rate range, application properties in the high-shear-rate
and a hydrophobic group on the other (typically a long chain range, and film formation and container storage properties in
alkyl or alkyl aryl group). At a sufficiently high concentration the low-shear-rate range. The viscosities associated with
known as the critical micelle concentration (CMC), these sur- these ranges may be referred to as the medium-shear viscos-
factants spontaneously form micelles in aqueous solution. At
or above this concentration, the hydrophobes aggregate at
the interior of the micelle, and the hydrophilic tails orient
outward into the water phase. The key driving force for mi-
cellization is not the London Van der Waals attractive forces
between hydrophobes, but rather the change in free energy
on transfer of a hydrophobe in the aqueous phase to a more
oil-like environment at the interior of the micelle.
If a hydrophobe is chemically attached to the other end of a
nonionic surfactant, a simple associative thickener is formed.
However, because the thickener has a hydrophobe at each
end, micelle formation is not a favorable process and is not
observed except for certain chemical architectures at ex-
tremely low concentrations. Instead, the associative mole-
cules aggregate into a three-dimensional network structure
that inhibits flow and raises the viscosity of the aqueous
solution or coating. The driving force is similar to that for
micelle formation. Although each associative polymer type
has an optimum molecular weight, high molecular weight is
not a requirement of associative thickeners, and most are FIG. 3-Conventional (nonassociative) thickener molecules in
significantly lower in molecular weight (typically <50 000) the presence of aqueous latex particles.
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in the medium-shear range by varying the amount of thick-

ener added. The target viscosity is normally based on prior
experience or on a previously established specification range
for a particular type of coating. One popular rheometer used
for measuring and facilitating consistency adjustment in ar-
chitectural coatings is the Stormer ~ viscometer. Viscosity de-
termination with this instrument is conducted in accordance
with ASTM Test Method for Consistency of Paints using the
Stormer Viscometer (D 562). This rheometer provides a pad-
dle-type mixing action during measurement that is similar to
stirring, and viscosity is expressed in Krebs Units (KU). Many
coatings fall within the range of 60 to 120 KU, and a typical
specification range for a semigloss architectural coating, for
example, might be 90 to 95 KU.
The Brookfield | viscometer is another popular instrument
for determination of consistency when operated at higher
FIG. 4-Associative thickener molecules in the presence of speeds (for example, 20 to 100 rpm). It is also useful at lower
aqueous latex particles. speeds (for example, 0.3 to 5 rpm) for determination of low-
shear processes such as leveling [see later in this section
ity (MSV), high-shear viscosity (HSV), and the low-shear vis- under Leveling, Sag, Syneresis, Settling (Low-Shear Vis-
cosity (LSV), respectively. Several film properties are also cosity)]. Both of these measurements can be conducted in
affected and may be manipulated by the appropriate choice accordance with ASTM Test Method for Rheological Proper-
and amount of TRM in the coating [27]. Two examples of ties of Non-Newtonian Materials by Rotational (Brook:field)
coatings improperly formulated with TRMs are represented Viscometer (D 2196). Both the analog and digital Brookfield
in Fig. 5. A clear understanding of the rheology profiles de- models provide viscosity in centipoise (mPa-s), and cylindri-
picted and their impact on application and film properties cal spindles are commonly used for the measurement. An-
will become apparent in the following subsections. other Brookfield viscometer recently introduced has a paddle
configuration similar to the Stormer viscometer. Readout on
this model is in Krebs Units.
Coating Consistency (Medium-Shear Viscosity) The Rotothinner ~ is another viscometer which can be used
Measurement of MSV in the previously defined medium- to determine consistency. It provides an even greater mixing
shear domain provides an indication of the consistency of a action that is capable of stirring the entire container contents
coating that relates to its appearance and feel on mixing. It is while the viscosity measurement is being made. While this
common practice for formulators to adjust coating viscosity instrument can be used for more conventional coatings, it is
VISCOSITY (Pa.s)
10,000
! AT REST PROCESSING APPLICATION
1,000 __=
POOR LEVELING
100
10
SAG & SETTLING HIGH BRUSH DRAG

1 ==
FORMULATED TO
0.1 -_=
SAME CONSISTENCY
0.01 -
LOW FILM BUILD
0.001 I t i liIlll I I IIIIII i t I lltlll i I ililSl i I i iilfli I i I llili
0.1 1 10 100 1,000 10,000 100,000
SHEAR RATE (s-l)

FIG. 5-Shear profile examples of inadequate TRM formulation for a premium archi-
tectural coating.
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ideally suited for breaking down the structure of thixotropic leveling. In architectural coatings, LSVs that are too high
fluids to obtain a sheared viscosity. result in poor leveling, and brush or roller pattern is very
apparent. The degree of leveling is often determined by sim-
ple inspection of brush marks or roller pattern after the
Application Properties (High-Shear Viscosity) applied film has dried. Optionally, a notched applicator on a
Most brush, spray, or blade coating operations are rela- horizontal surface may be used in accordance with ASTM
tively high-shear processes. This is also true for roll coating Test Method for Leveling of Paints by Draw-Down Method
applications when the circumferential velocity of the roll is (D 4062). In contrast, LSVs that are too low may allow sag-
significantly different than the linear velocity of the substrate. ging on vertical surfaces and in-can settling or syneresis. Sag
The shear on application for these operations is generally ratings are often conducted in accordance with ASTM Test
greater than about 103 s -1 and is typically about 104 s -1 for Methods for Sag Resistance of Paints using the Multinotch
brushing and as high as 106 s -1 for some high-speed roll Applicator (D 4400).
coating, blade coating, and spray operations. There are sev- A variety of viscometric techniques have shown some cor-
eral high-performance rotational rheometers for measuring relation with leveling. Among these is a stress-relaxation pro-
the HSV, and most use cone/plate or plate/plate geometry. cedure [28]. In this method, the coating is first sheared at a
One general purpose instrument that is popular for labora- moderately high rate to break down structure to simulate
tory and quality control of HSV measurement is the ICI cone- brushing or rolling. The shearing is then stopped, and the
plate viscometer by ASTM Test Method for High-Shear Vis- declining shear stress versus time is recorded. The area under
cosity Using the ICI Cone/Plate Viscometer (D 4287-88). This the relaxation curve is then integrated to obtain a "leveling
instrument has a fixed shear rate of 104 s -1, and viscosity viscosity" (that is, the product of stress and time has the
measured is a good predictor of film build when a coating is dimensions of viscosity).
applied by brush or paint roller. The higher the ICI viscosity, A relatively simple one-point technique which generally
the more resistance a brush or roller encounters on applica- provides good correlation with leveling is a viscosity mea-
tion, which results in a thicker applied film. HSVs at this surement at low rpm (for example, 0.3 rpm on a Brookfield|
shear rate are typically from about 0.5 to 2.5 P (50 to 250 viscometer), At the low shear rate produced at this speed,
mPa s) for architectural coatings. If the HSV is too high, the excellent leveling would be indicated for coatings with mea-
coating will require too much effort to apply, will have a low sured viscosities of less than about 250 P (25 Pa.s) as might
spread rate, and may sag. If the HSV is too low, a second coat be obtained with a high-performance associative thickener.
may be required to hide the substrate. Subjective brush drag Too much flow would be indicated below about 100 P
by actual application is often conducted in accordance with (10 Pa.s), and sag would be predicted on vertical surfaces. By
ASTM Test Method for Comparison of Brush Drag in Latex the same technique, poor leveling would be indicated at
Paints (D 4958). about 1000 P (100 Pa.s) as might be obtained from a moder-
Conventional thickeners generally produce coatings with ately high MW conventional thickener, and little or no flow at
low HSV, while most associative thickeners and particularly 2000 to 3000 P (200 to 300 Pa.s) for some very high MW
associative rheology modifiers produce high HSV. Although conventional or special associative thickeners. Another com-
not common, some associative thickeners produce low HSV mon method conducted on a Brookfield | viscometer is the
that may be desirable depending on the application and film measure of "pseudoplastic index." This is a two-point deter-
thickness desired. These thickeners tend to be very efficient in mination that is the ratio of two viscosities a decade apart in
the medium-shear region, and the low HSV is primarily a shear rate (for example, 0.3 rpm/3.0 rpm or most commonly 6
consequence of less thickener being used. As a general rule rpm/60 rpm). LSV is probed by extrapolation of viscosity to
for a given thickener type, the more thickener required to lower shear rates (lower rpm).
obtain desired consistency (MSV), the higher the HSV will be. From the prior discussion, it follows that a high LSV is
Therefore, if an increase in HSV is desired, a less efficient generally needed for suspension or low flow characteristics,
thickener or a rheology modifier may be needed. As an option while a low LSV or low yield value is needed to promote flow
with associative thickeners, efficiency in the medium-shear and leveling. Due to the associative mechanism, most, but not
region can be suppressed or enhanced by adjustment of other all, ATRMs provide low LSVs to impart excellent leveling
components in the coating formulation. By proper TRM se- characteristics. However, some alkali-swellable associative
lection or TRM blending, the desired HSV can be obtained thickeners impart uncharacteristically high LSVs, and like
without adversely affecting MSV or LSV. very high MW CTRMs, these thickeners have utility as antisag
or antisettling agents or for use in highly structured coatings
(for example, texture paints). Although these thickeners are
Leveling, Sag, Syneresis, Settling (Low-Shear
definitely associative by examination in aqueous solution,
Viscosity)
their unusual behavior in coatings may be due to their ability
After a coating has been made or applied, an appropriate to impart a degree of flocculation. Although not as low as
LSV is needed to prevent container separation (pigment CTRMs, lower gloss levels observed for some of these thick-
settling and syneresis) and to promote film formation eners support this conclusion. However, some of these thick-
(leveling and sag resistance). The applicable shear rates for eners actually produce very high gloss levels, which suggests
LSV are generally less than about 10 s- 1and more practically that aqueous phase networking has a larger influence on
in the range of 10~to 10 3 s- 1. The low-shear applied in these rheology than expected and/or that the dispersant character
processes is primarily due to the effects of gravity for con- for these thickeners is greater than expected. Conventional
tainer separation and sagging and due to capillary pressure thickeners, on the other hand, nearly always are highly shear
(generated by surface tension and surface curvature) for thinning with high LSVs due to the hydrodynamic and floc-
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culative mechanisms operating. Consequently, the gloss and TABLE 2--Conventional water-soluble thickeners for coatings and
hiding imparted from these thickeners tends to be lower. noncoatings applications.
Cellulosic polysaccharides
Carboxymethyl cellulose (CMC)
CONVENTIONAL TRMS (CTRMS) Carboxymethyl hydroxyethyl cellulose
Ethyl hydroxyethyl cellulose (EHEC)a
In the broadest definition, conventional TRMs (CTRMs) Hydroxyethyl cellulose (HEC)b
are water-soluble polymers lacking hydrophobe modification Hydroxypropyl methyl cellulose (HPMC)b
Methyl cellulose
(that is, they are nonassociative). The higher-molecular- Biopolymer polysaccharides
weight polymers function primarily as thickeners, and the Gellan gum
lower-molecular-weight polymers function as theology modi- Rhamsan gum~
fiers. Their primary thickening mechanisms are hydrody- Whelan gum
namic and flocculative. Although there are many different Xanthan gum (XCPS)~
Other potysaccharides
types of water-soluble polymers which could be used as Guar gum
TRMs in architectural and industrial coatings, only a few Hydroxypropyl guar (HPG)a
have been accepted for use due to factors relating to econom- Sodium alginate
ics, bio-stability, water sensitivity, compatibility, production Synthetic hydrocarbonpolymers
Poly acrylamide and copolymers
quality, ease of handling, or rheology. Those CTRMs which Poly ethylene oxide (PEO)
are currently used in coatings, some widely and others infre- Poly hydroxyethyl (meth)acrylate
quently, are discussed in the subsections which follow. These Poly (meth)acrylic acid copolymers (ASE)b
fall into two major categories: polymers of biological origin Poly olefinic sulfonate copolymers
Poly vinyl alcohol (PVOH)
(polysaccharides) and the synthetic alkali-swellable/soluble Poly vinyl pyrolidonea
emulsions (ASEs). The polysaccharides may be further subdi- Poly styrene/maleic anhydride (SMA)
vided into modified cellulosics, guar derivatives, alginates, Poly methylvinyl ether/maleic anhydride
and "biopolymers." The bipolymers are of more recent origin NOTE:"These have some use in architectural coatings. ~Thesehave signifi-
and employ microorganisms as a means of production or cant use in architectural coatings. All others have little or no current use in
modification. Table 2 lists conventional water-soluble poly- architectural coatings.
mers used as thickeners in both coatings and noncoatings
applications. With respect to coatings only, nearly all have for a given polymer type, the amount of thickener required
been tried, many were found unacceptable, some are cur- for constant MSV decreases (thickening efficiency improves).
rently used, some have been used in the past, and others may At the same time, LSV increases and HSV decreases. The
have future potential particularly if modified with hy- effect on film build is predictable (lower); however, some
drophobes for conversion to ATRMs. Table 3 details some investigators have actually reported improved leveling with
important domestic (U.S.) suppliers of CTRMs and their re- higher MW cellulosics. The modifications are defined in two
spective products. ways: the degree of substitution (SD), which is the average
number of hydroxyl groups which have been substituted per
Cellulosics anhydroglucose unit, and the moles of substitution (MS),
which is the average number of moles of substituents per
Prior to the introduction of ATRMs, conventional cellulos-
anhydroglucose unit for those substituents which generate
ics were by far the most commonly used TRMs in aqueous
repeating units (such as ethylene oxide in HEC).
coatings. They still dominate, but their use is in decline today.
The reduction has been somewhat offset with the introduc-
tion of associative cellulosics, which are discussed later in
HEC
this chapter under Hydrophobe Modified Cellulosics Of the cellulosics, hydroxyethyl cellulose unquestionably
(HMCs). Cellulose (C6H1005)n is a naturally occurring poly- has been the most popular TRM used in coatings. HEC is a
saccharide composed of repeating anhydroglucose units. Be- nonionic polysaccharide manufactured by reacting ethylene
cause of its relatively straight and stiff polymer chain and oxide with the reactive hydroxyls on the anhydroglucose
strong intermolecular and intramolecular hydrogen bonding, units of cellulose. The ethylene oxide also reacts with previ-
the polymer itself is highly crystalline and consequently insol- ously substituted hydroxyls, resulting in short pEO side
uble in water. Nonetheless, with chemical modification, cel- chains (usually two or three units in length). The ratio of
lulose can be readily converted to amorphous water-soluble molar substitution (MS) to degree of substitution defines the
polymers. Hydroxyethyl cellulose (HEC), hydroxypropyl number of EO groups per side chain. The most popular prod-
methyl cellulose (HPMC), carboxymethyl cellulose (CMC), ucts have MS values in the range of 1.5 to 3.0 and DS values of
and ethylhydroxyethyl cellulose (EHEC) are among those about 0.85 to 1.35. Optimizing reaction conditions results in
that have been used in aqueous coatings. a more uniform distribution of substitution to produce bio-
The reactions used to produce water-soluble cellulose poly- resistant polymer grades.
mers are relatively uncomplicated. They typically involve Presently there are two major international producers of
treatment of cellulose with alkali to swell the polymer, fol- HEC, and the products are available in several regular and
lowed by the chemical addition of the appropriate substitu- enzyme-resistant grades. Of these, the medium- and high-
ent. Each of the commercial polymer types is available in a molecular-weight bio-resistant grades have been of greatest
variety of grades that are differentiated by molecular weight, utility in coatings as thickeners. Low-molecular-weight
levels of substitution, uniformity of substitution, and treat- grades are used as secondary TRMs to modify rheology (im-
ment for ease of dispersion. As molecular weight increases prove flow or film build). Some grades also have surface treat-
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TABLE 3 - - C o n v e n t i o n a l TRMs (CTRMs)--U.S. suppliers a n d trade names for aqueous architectural and industrial coatings.
Typical
Company TRM Viscosity, Water in
Code Trade Name TRM Code TRM Class Solids, % mPa-s Co-solvent Volatiles, %
1 Alcogum | L- 11 ASE 28.0 14 None 100
1 Alcogum | L-27 ASE 20.0 50 None 100
2 Aqualon | 7 Series CMC 100.0 Solid None ...

2 Aqualon | 9 Series CMC 100.0 Solid None ...
2 Natrosol | 250R Series HEC 95.0 Solid None .-.
2 Natrosol | 250B Series HEC 95.0 Solid None ..-
2 Natrosol | FPS | HB HEC 20.0 7000 None 100
2 Natrosol | FPS | MB HEC 20.0 7000 None 100
2 Natrosol | FPS | G HEC 25.0 7000 None 100
6 Methocel | J Series HPMC 100.0 Solid None

6 Methocel | K Series HPMC 100.0 Solid None
10 Carbopol | 600 Series PAA 100.0 Solid None

10 Carbopol | 900 Series PAA 100.0 Solid None
13 Aqua Thix | ... HPG 100.0 Solid None
14 Rhamsan K7C233 BP 100.0 Solid None

14 Welan K 1A96 BP 100.0 Solid None
14 Kelzan | Xanthan XCPS 100.0 Solid None
14 Kelzan | S Xanthan XCPS 100.0 Solid None
14 Kelgin | F, MV, HV Algin 100.0 Solid None
15 Flocon | 4800 XCPS 4.0 4000 None 100

15 Flocon | 4800C XCPS 13.5 13000 None 100
18 Colloid | 1560 ASE 28.0 5 None 100
19 Acrysol ~ ASE-60 ASE 28.0 4 None 100

19 Acrysol ~ ASE-75 ASE 40.0 20 None 100
19 Acrysol | ASE-95 ASE 18.0 50 None 100
19 Acrysol ~ ASE- 108 ASE 20.0 200 None 100
19 Acrysol ~ G-1 l0 ASE-NH4 22.0 130 None 100
19 Acrysol | GS ASE-Na 12.5 15000 None 100
19 Acrysol | HV- 1 ASE-Na 10.0 17500 None 100
23 Cellosoze | QP Series HEC 100.0 Solid None

23 Cellosoze | ER Series HEC 100.0 Solid None
25 Rhodopol | 23 XCPS 87.0 Solid None

25 Rhodopol | 50MD XCPS 87.0 Solid None
ments to slow down the rate of hydration to minimizes lulose (HBMC). Grades of HPMC vary in molecular weight
lumping. Until recently, HEC was only available in solid [29], t h e r a t i o o f m e t h y l t o h y d r o x y p r o p y l s u b s t i t u t i o n o n t h e
form. Moderately viscous "fluidized dispersions" are now cellulose backbone, and the degree of substitution. Commer-
available which improve handling and increase the rate of cial g r a d e s of H P M C h a v e a v e r a g e D S f o r t h e m e t h y l g r o u p s
i n c o r p o r a t i o n . To m i n i m i z e t h e d i s p e r s i o n v i s c o s i t y o f t h e i n t h e r a n g e o f 0.9 t o 1.8 a n d M S f o r h y d r o x y p r o p y l g r o u p s i n
supplied product, proprietary salts are incorporated. Various t h e r a n g e o f 0.1 t o 1.0. V a r i a t i o n s i n t h e s e p a r a m e t e r s a f f e c t
test methods for HEC are found in ASTM Test Methods for solubility, thermal properties, and resistance to enzymes.
H y d r o x y e t h y l c e l l u l o s e (D 2364). Both MC and HPMC exhibit lower critical solution tempera-
t u r e s (i.e., t h e y p o s s e s s t h e s o m e w h a t u n u s u a l p r o p e r t y o f
HPMC being soluble in cold water and insoluble in hot water). Solu-
H y d r o x y p r o p y l m e t h y l cellulose, a d e r i v a t i v e o f w a t e r - s o l u - t i o n s o f t h e s e p o l y m e r s f o r m gel s t r u c t u r e s o n h e a t i n g . W i t h
b l e m e t h y l c e l l u l o s e (MC), is a n o t h e r n o n i o n i c p o l y s a c c h a - m o d i f i c a t i o n s i n p r o c e s s i n g , DS, M S , t h e gel t e m p e r a t u r e ,
ride which has wide acceptance in coatings. Two other lesser a n d gel t e x t u r e a r e a l t e r e d . B e c a u s e o f its s t r u c t u r e , H P M C is
known water-soluble analog derivatives of MC are hydroxy- also inherently more resistant to bio-organisms compared to
e t h y l m e t h y l c e l l u l o s e ( H E M C ) a n d h y d r o x y b u t y l m e t h y l cel- some other polysaccharides. Various test methods for the
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characterization of HPMC may be found in ASTM Test Meth- used as either primary or secondary thickeners to provide
ods for Hydroxypropyl Methylcellulose (D 2363). suspension characteristics. Commercial biopolymers are
polysaccharides; however, they differ from the cellulosic and
EHEC guar products described above in that they are enzymatically
Ethyl hydroxyethyl cellulose is another water-soluble poly- produced rather than being made by chemical modification.
mer with utility in water-borne paints with many properties The biopolymer synthesis is typically conducted in a fermen-
similar to HPMC. The principal commercial product line tation broth with bacterium or yeast. Seemingly common to
consists of two series where the degree of molar substitution the biopolymers is their ability to suspend or gel, their salt
for the hydroxyethyl group is 0.8 and 2.1, respectively, and tolerance, and their stable viscosity over a wide temperature
the ethyl group is the same for all grades with DS of approxi- range. As with HPG, a limitation is that there are only one or
mately 0.8. All grades are also available with surface treat- two grades available from each supplier. Among the commer-
ment for fast dispersion and adjustable dissolution rate. Like cial biopolymer products which are available are Xanthan
HPMC, EHEC is soluble in cold water and insoluble in hot gum, Rhamsan gum, Welan gum, and Gellan gum.
water. Increasing hydroxyethyl substitution increases water
solubility, improves salt tolerance, and decreases the ten- Xanthan Gum
dency for gellation on heating. Perhaps the most well known and commercially important
biopolymer is Xanthomonas campestris polysaccharide
CIVIC (XCPS), better known as Xanthan gum. This polymer was
Sodium carboxymethyl cellulose (CMC) is an anionic wa- initially "cultured" in USDA laboratories using fermentation
ter-soluble polymer which has been of limited use in coatings technology with the bacterium Xanthomonas campestris [30].
because the modification constituent (sodium carboxylate) Xanthan gum is a high-molecular-weight (approximately 2
leaves the dried films more water-sensitive than most non- 106), branched polysaccharide which is characterized as hav-
ionic polysaccharides. CMC is prepared by reaction of cellu- ing high yield values and a high degree of pseudoplasticity
lose with monochloroacetic acid after treatment with alkali. (high LSV and low HSV). Total and immediate recovery of
Commercial grades have DS for carboxylate substitution viscosity after sheafing is also characteristic. Other features
ranging from 0.4 to 1.4, and the most popular products are are its relative insensitivity to pH, temperature, and the pres-
MS 0.7 to 0.8. As with most other conventional polysaccha- ence of most salts. Applications for Xanthan are similar to
rides, the viscosity is primarily controlled by varying the mo- those for HPG with somewhat better efficiency and even
lecular weight of the cellulosic chain. Some technical grades more shear thinning rheology (higher LSV). Xanthan gum is
of CMC contain by-product salts (primarily sodium chloride normally sold as a solid; however, liquid versions of this
and sodium glycolate) that further limits their use in coatings polymer (Xanthan broths) are now available that are easier to
applications (for example, to dry-mix paints where the CMC handle--supplied at relatively low concentrations (3 and
functions to control viscosity and wet edge). A purified grade 15%) with viscosities of about 4000 and 14 000 mPa.s, respec-
referred to as cellulose gum is preferred for use in latex tively. The side-chain functionality of the fluid polymer is
paints. Various procedures for characterization of CMC may significantly different (much higher in pyruvate content)
be found in ASTM Test Methods for Sodium Carboxymethyl- from conventional solid Xanthan, but the rheology is still
cellulose (D 1439). very shear thinning. The active biopolymer in these products
is also claimed to be a more effective viscosifier than solid
Xanthan.
Hydroxypropyl Guar (HPG)
Of the noncellulosic polysaccharides available for use in Rhamsan Gum
coatings, only hydroxypropyl guar (HPG) has found signifi- Rhamsan gum is another biopolymer that has some appli-
cant application. HPG is a chemical modification of guar gum cation in coatings. One of the more outstanding characteris-
which is a high-molecular-weight galactomannan obtained tics of this polymer is its exceptional suspending power
from the seeds of two leguminous plants (Cyamopsis tetrago- (produces very high LSV in coatings). In approximate order
nalobus and psoraloides). Like the biopolymers described be- of decreasing suspending ability are Rhamsan gum >
low, this polymer produces coatings which are more shear Xanthan gum > HP guar > CMC > HEC < CMC. Rhamsan
thinning (more pseudoplastic) than the cellulosic products. gum also reportedly has good salt tolerance and improved
Hence, compared to cellulosics, HPG tends t o have better stability to high-shear mixing.
suspension and antisag characteristics but produces more
roll spatter and is less bio-resistant. Another limitation for
HPG is that it is available in only one grade. Compared with
Alkali-Swellable/Soluble Emulsions (ASEs)
its parent (guar gum), solutions of HPG are more bio-resis- ASEs are among the few conventional synthetic hydrocar-
tant, less electrolyte sensitive, and have improved solubility bon thickeners to be used in substantial amounts in coatings.
and clarity. Utility of HPG is primarily as a secondary thick- Conventional ASEs are carboxyl functional copolymers pro-
ener or for use in flat, texture, and dripless paints. duced by the free-radical emulsion polymerization of ethyl-
enically unsaturated monomers [31]. They are low-viscosity
Biopolymers water-insoluble latexes at low pH as supplied, but exhibit
thickening on dissolution or swelling of the latex particles
The use of biopolymers in paints and coatings has also when the pH is raised (generally above pH 5.5). Copolymers
been limited; nonetheless, at least two products are being of methacrylic acid and ethyl acrylate are most common and
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may contain a small amount (generally less than 1%) of a groups [25,37], surfactants and cosolvents [38], coalescing
polyfunctional monomer to lightly cross-link the polymer to aids [39], and some clay pigments [40,41]. The steady shear
enhance swellability. Since most coating formulations are and linear viscoelastic properties of associative thickener
finished on the basic side, the ASE polymers are fully neutral- solutions have also been characterized [42].
ized in most applications. They achieve their m a x i m u m vis-
cosities above about pH 7, and, ideally, viscosity generated
should be constant between about pH 7 to 10 so that slight
Hydrophobe Modified N o n i o n i c Synthetics (HNS)
changes in pH have little effect on coating consistency. Al- The HNS ATRMs are nonionic condensation polymers of
though ASEs impart rheology similar to other conventional synthetic origin. Common to these polymers are hydrophilic
thickeners, their primary advantages compared to the poly- pEO segments which alternate with hydrophobic groups. The
saccharides are in ease of handling and bio-stability. ASEs polymers tend to be much lower in molecular weight than
may be more water sensitive than most nonionic polysaccha- conventional thickeners, and the repeat units (pEO segment
rides; however, unlike CMC, which is supplied as a sodium plus hydrophobe) are generally less than about 20. Main
salt, neutralization of ASEs is normally with ammonia or chain ends and any side chains are typically terminated with
volatile aminoalcohols which leave the film on drying. Hy- hydrophobic groups. The two principal subclasses are
drophobe modification of conventional ASEs to produce as- hydrophobe-modified ethoxylate urethanes (HEUR) and
sociative TRMs (HASEs) has greatly increased the popularity hydrophobe-modified nonionic nonurethanes (HENNs).
of the emulsion thickeners. These are discussed later in this Differentiation in this classification scheme is simply the
chapter under H y d r o p h o b e Modified ASEs (HASE). presence or lack of urethane functionality.
HEUR (Subclass o f HNS)

ASSOCIATIVE TRMS (ATRMS) The HEUR polymers are the major subclass of the nonionic
synthetics (HNS). They are among the most popular ATRM
Because of the increasing importance of rheology modifi- products, and presently there are several domestic and inter-'
cation in coatings, the use of ATRMs continues to grow with national suppliers. Common to all HEUR polymers are the
m a n y product offerings now available. Presently, three broad presence of three chemical components (terminal hy-
classes of commercial ATRMs represent m a n y older and drophobes at the ends of side or main chains, internal hydro-
newer products. They are hydrophobe-modified nonionic philic pEO segments, and urethane linkages). The HEUR
synthetics (HNS), hydrophobe-modified cellulosics (HMC), polymers are generally considered to be among the best of the
and hydrophobe-modified alkali-swellable/soluble emulsions associative products with respect to rheology modification.
(HASE). Contained within the major classes are important Being low in molecular weight and highly associative, they
subclasses all of which are discussed in detail below. Table 4 tend to provide the most Newtonian rheology (low LSVs and
summarizes the commercial product classification scheme high HSVs) for superior flow/leveling and film build and also
for ATRMs, principal subclass examples, and the designated impart low extensional viscosity and low viscoelasticity for
acronyms. Those acronyms that are prominent in the litera- superior spatter resistance.
ture as well as those which are newly assigned are indicated. Nearly all HEUR polymers are supplied as moderately vis-
Table 5 lists some important U.S. suppliers of ATRMs, their cous solutions in a combination of water and cosolvent (for
representative products, and the product's classification. example, Butyl Carbitol | or propylene glycol). The cosolvent
Coating components and coating formulation variables are is present to suppress viscosity for ease of handling. Since
HEURs are nonionic, they should have inherently low water
known to affect the rheological performance of associative
sensitivity. However, they are generally less efficient than
thickeners [32,33]. Some specific parameters which have
been examined are volume solids [34], type of latex binder cellulosics or ASEs, and they are also much lower in molecu-
lar weight, which may limit their use in some exterior appli-
[35,36] latex binder particle size [14,15], particle surface acid
cations. Because the HEUR products have very low LSVs for
superior flow, they may permit sagging, syneresis, or pigment
TABLE 4--Classification of associative thickener/rheology
modifiers (ATRMs). settling, particularly when used as the sole thickener. They
are also very sensitive to other coating components, and
HNS--Hydrophobe modified nonionic synthetic proper formulation balance is necessary for optimum per-
Subclass Example: formance. The HEUR products have been the subject of nu-
HEUR--Hydrophobe modified ethoxylate urethane
HENN--Hydrophobe modified nonionic non-urethane merous technical investigations [43-45].
HMC--Hydrophobe modified cellulosic
Subclass Example: H E N N (Subclass o f HNS)
HMHEC--Hydrophobe modified hydroxyethyl cellulose Synthetic nonionic associative thickeners lacking urethane
HMEHEC--Hydrophobe modified ethyl hydroxyethyl
cellulose functionality are the latest entry into the ATRM arena. At this
HASE--Hydrophobe modified alkali-sweUable/solubleemulsion writing, there is one commercial offering and two develop-
Subclass Example: mental products. Being synthetic, nonionic, and containing
HEEASE--Hydrophobe modified ethoxylate ester alka]i- terminal hydrophobes, the chemical makeup of HENN poly-
swellable/soluble emulsion
HEURASE--Hydrophobe modified ethoxylate urethane alkali- mers is generally similar to HEUR with the exceptions that
swellable/soluble emulsion the polyether segments may not be limited to ethylene oxide
alone (that is, EO-PO blocks may be present), the molecular
NOTE:HNS,HENN,and HEEASEare new acronymsfor which there were
none previously.All others are those of general acceptancein ACS and other weights may be lower than some HEURs, and the products
technical publications. lack urethane linking groups (may contain ether, amide, or
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TABLE 5--Associative TRMs (ATRMs)--U.S. suppliers and trade names for aqueous architectural and industrial coatings.
Total Typical
Company TRM TRM TRM TRM TRM Solids, Viscosity, Water,
Code Trade Name Code Class Subclass Type % mPa.s Co-solvent %
1 Alcogum| PT-33 HASE HEEASE T 30.0 20 None 100
1 Alcogum| SL-70 HASE HEEASE T 30,0 20 None 100
1 Alcogum| SL-76 HASE HEEASE T 30,0 20 None 100
1 Alcogum| SL-98 HASE HEEASE T 30.0 20 None 100
2 Natrosol | Plus 330 HMC HMHEC T 95.0 Solid None 100

2 Natrosol | Plus 430 HMC HMHEC T 95.0 Solid None 100
2 Natrosol | FPS | Plus 330 HMC HMHEC T 25.0 7000 None 100
2 Natrosol | FPS | Plus 330 HMC HMHEC T 25,0 7000 None 100
11 DSX 1514 HNS HEUR T 40.0 3000 NA NA

11 DSX 1550 HNS HEUR T 40.0 1500 NA NA
17 Rheolate | 1 HASE HEEASE T 30.0 30 None 100

17 Rheolate | 101 HASE HEEASE T 100.0 Solid None 100
17 Rheolate | 300 HNS HENN T 32.0 2400 BCARB 82
19 Acrysol| RM-3 HASE HEEASE RM 30.0 50 None 100

19 Acrysol| RM-825 HNS HEUR T 25.0 2500 BCARB 75
19 Acrysol| RM-1020 HNS HEUR RM 20.0 2500 BCARB 88
19 Acrysol | RM-2020 HNS HEUR RM 20.0 3000 None 100
19 Acrysol| QR-708 HNS HEUR T 35.0 3500 PG 40
19 Acrysol| TT-615 HASE HEEASE T 30.0 110 None 100
19 Acrysol| TT-935 HASE HEEASE T 32.0 30 None 100
19 Acryso] | TT-950 HASE HEEASE T 30.0 40 None 100
19 Acrysol | SCT-200 HNS HEUR T 20.0 4800 BCARB 80
19 Acrysol| SCT-215 HNS HEUR T 15.0 10000 BCARB 80
19 Acrysol| SCT-270 HNS HEUR T 20.0 10000 BCARB 80
19 Acrysol | SCT-275 HNS HEUR T 17.5 3000 BCARB 75
22 Ucar | Polyphobe | 101 HASE HEURASE T 25.0 50 None 100

22 Ucar | Polyphobe | 102 HASE HEURASE T 25.0 50 None 100
22 Ucar | Polyphobe | 103 HASE HEURASE T 25,0 50 None 100
22 Ucar* Polyphobe | 104 HASE HEURASE T 25.0 50 None 100
22 Ucar | Polyphobe| 107 HASE HEURASE T 25.0 50 None 100
22 Ucar | Polyphobe | 106HE HASE HEURASE T 25.0 50 None 100
22 Ucar* Polyphobe | 111 HASE HEURASE T 25.0 50 None 100
23 Ucar | Polyphobe| 9820 HASE HEURASE T 25.0 50 None 100
23 Ucar* Polyphobe | 9823 HASE HEURASE RM 25.0 50 None 100
23 Cellosize| 100 HMC HMHEC T 95.0 Solid None 100

Spatter Guard |
s o m e other linkage). Like the H E U R polymers, H E N N thick- r ap i d viscosity equilibration, lack of cosolvents (0 o r low
eners co n t ai n cosolvent and are supplied as m o d e r a t e l y vis- VOC), and low-viscosity liquid f o r m as supplied. Like ASEs,
cous aq u eo u s solutions. Little i n f o r m a t i o n is currently the HASE products are synthetic addition polymers pro-
available; however, based on advertising claims for c h e m i c a l d u c e d by e m u l s i o n p o l y m e r i z a t i o n of carboxyl functional
c o m p o s i t i o n an d p e r f o r m a n c e , the rheological characteris- m o n o m e r s . Consequently, they are of relatively high mol e c u-
tics of these products are expected to be similar to H E U R lar weight (higher t h a n H N S b u t l o w er t h a n c o n v e n t i o n a l
ATRMs. The c h e m i c a l c o m p o s i t i o n a n d physical f o r m w o u l d thickeners) an d thicken by a h y d r o d y n a m i c m e c h a n i s m in
also suggest that the handling a n d p e r f o r m a n c e limitations addition to the associative m e c h a n i s m . The p r e d o m i n a t e
are similar to those of HEURs. I m p r o v e d color acceptance, m e c h a n i s m operating depends on several factors including
color stability, and block resistance are c l a i m e d for the com- the m o l e c u l a r weight an d the a m o u n t and type of associative
me rc i al product, and i m p r o v e d shear stability d u e to l o w er functionality.
m o l e c u l a r weight is c la im e d for the d e v e l o p m e n t a l p r o d u c t s Typically, H A S E p r o d u c t s are terpolymers of ethyl acrylate,
but at the expense of thickening efficiency [46]. m et h acr y l i c acid or itaconic acid, an d an associative mac-
r o m o n o n e r . The m a c r o m o n o m e r usually contains pE O units
(typically 10 to 100 tool ethylene oxide) t e r m i n a t e d with a
Hydrophobe Modified ASEs (HASE)
h y d r o p h o b e (typically alkyl or alkylaryl). The associative side
The H A S E polymers w e r e a m o n g the first ATRMs to be ch ai n linkage to the m a i n chain b a c k b o n e is p r e d o m i n a t e l y
developed, and their c o m m e r c i a l significance dates back to either ester (HEEASE) or u r e t h a n e ( H EU RA S E) pe r the clas-
the late 1960s [47-49]. The popularity of these products con- sification s c h e m e of Table 4. The patent literature does de-
tinues d u e to their relatively good economics, bio-stability, scribe other linkages, an d although s o m e have b e e n used in
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the past, they are not commercial today (for example, prod- Hydrophobe Modified Cellulosics (HMCs)
ucts with ether linkages were marketed in the 1960s but were
Like the HNS polymers, hydrophobe-modified cellulosics
later discontinued). Like ASEs, the HASE polymers may also
are condensation polymers but of biological origin. These
be cross-linked to varying degrees with small amounts (typi-
polymers are prepared by modifying standard or special
cally less than 1%) of a polyfunctional m o n o m e r to increase
swellability. Although HASE polymers are anionic and, there- grades of conventional cellulosics with hydrophobes. And,
fore, predicted to be more water sensitive than nonionic like the other ATRMs described above, the hydrophobes are
ATRMs, many HASE products are more efficient (less thick- typically alkyl or alkylaryl, but the pEO chains are compara-
ener is required for consistency), which minimizes the effect tively very short. Presently there are two commercial sub-
of the anionic character. Additionally, performance of classes of HMCs: hydrophobe-modified hydroxyethyl cel-
HASEs in exterior coatings can be improved with ZnO or zinc lulose (HMHEC) and hydrophobe-modified ethyl hydroxy-
complexes which cross-link the carboxyl functionality pres- ethyl cellulose (HMEHEC). These HMCs are presently all
ent [50,51], which is lacking in the HNS polymers. Being nonionic; however, the potential exists for future products
polyanionic, the HASE polymers also have dispersant charac- which may be either nonionic [for example, hydrophobe-
ter that contributes to hiding and gloss. The carboxyl groups modified hydroxypropyl methyl cellulose (HMHPMC) and
in HASE polymers can also covalently cross-link with mela- the like] or anionic [for example, hydrophobe-modified car-
mine, urea, and epoxy resins in thermoset coatings, and being boxymethyl cellulose (HMCMC) and the like].
acidic, they catalyze the cross-linking process.
HMHEC (Subclass of HMC)

HEEASE (Subclass of HASE)
The first commercial associative cellulosic thickener on the
The HEEASE polymers are one of two major HASE sub-
market in the late 1980s was hydrophobe-modified hydroxy-
classes. Prior to the recent introduction of HASEs containing
urethane linkages, the many commercial HEEASE polymers ethyl cellulose (HMHEC). This product has overcome many
were the only representatives of the HASE class. Conse- of the limitations of conventional HEC including improved
quently, HASE usually implied HEEASE in the literature. film build, improved leveling, and better spatter resistance
Since there are now several commercial urethane functional [56]. The associative behavior (adsorption onto latex and pig-
HASE polymers, subclassification was needed, and like the ment particles) and the rheology of this polymer have been
HEUR and HENN polymers, differentiation here relates to characterized [57] along with various solution properties
the presence or lack of urethane linking functionality. The [58]. The improvement in rheology (more Newtonian for bet-
associative side chains of HEEASE polymers contain ester ter leveling and increased film build) over HEC is generally
linkages, and like most other ATRMs, some HEEASE poly- similar to the HEEASE thickeners, but since HMHEC is non-
mers are true rheology modifiers [48], and others are primar- ionic, the water sensitivity of coatings made with it tends to
ily thickeners providing relatively good associative rheology be better. The methods of preparation and solution proper-
[37,52]. Because of the dual thickening mechanisms, the mo- ties of HMHEC have also been described [59,60]. HMHEC is
lecular weight and type and amount of associative functional- prepared by attaching hydrophobes to conventional HEC via
ity are among the processing variables that can be altered to the hydroxyl groups along the polymer backbone. The degree
effect change in performance. With respect to rheology, the of substitution and molecular weight grade of HEC chosen
HEEASE thickener performance is generally similar to the for this modification are important. Presently, there are two
associative cellulosics. domestic commercial suppliers of HMHEC. One employs
alkylaryl hydrophobe modification and the other aliphatic
HEURASE (Subclass of HASE) hydrophobe modification. Unlike other classes of ATRMs, the
The HEURASE ATRMs are a relatively new technology, ethoxylate content between hydrophobe and HEC backbone
combining much of the chemical architecture and advantage is small (generally one to a few units). Because HMHEC is a
features of the anionic ASE and nonionic HEUR thickeners solid, the handling limitations are similar to those of HEC
[53-55]. Like conventional ASEs, HEURASE polymers are and other solid thickeners. To party overcome this limitation,
prepared by emulsion polymerization and supplied as low- developmental fluidized aqueous dispersions of HMHEC are
viscosity, low-pH latexes. However, the associative side now available which are analogous to those now commercial
chains in HEURASE contain the same three functional com- for conventional HEC. The viscosity of the fluidized products
ponents found in HEUR thickeners (terminal hydrophobes, as supplied is still moderately high and similar to that of the
pEO segments, and urethane linkages). Because of this and HEUR and HENN products.
the relatively high level of associative m o n o m e r present in
these terpolymers, rheology modification approaching that of
the premium HEUR thickeners is claimed without many of HMEHEC (Subclass of HMC)
the HEUR and HENN limitations. Although most HEURASE Associative EHEC polymers were introduced in 1992 and
thickeners provide the expected Newtonian rheology, some are the most recent HMC products. Being relatively new, little
atypically impart suspension characteristics (high LSV) for is known about them; however, their chemical construction
use in antisag, antisettling, or texture paint applications. The and performance is expected to be similar to HMHEC. At this
extensional viscosity imparted by HEURASE products is low writing, there is currently only one nondomestic supplier of
and comparable to some HEUR thickeners [54]. these products.
www.iran-mavad.com

INORGANIC THICKENERS FOR AQUEOUS particle surface, w h i c h is often modified with organic treat-
AND SOLVENT-BORNE COATINGS m en t s to r e n d e r it hydrophilic (usually for w a t e r - b o r n e coat-
ings) or h y d r o p h o b i c (usually for solvent-borne coatings).
Most inorganic thickeners and rheology modifiers (ITRMs) ITRMs are also s o m e t i m e s ad d ed to aq u eo u s f o r m u l a t i o n s as
are supplied as powders. W h e n they are properly dispersed seco n d ar y thickeners to i m p a r t s o m e degree of antisag, an-
into a coating, they usually function as suspending or gelling tisettling, or antisyneresis to coatings containing p r i m a r y
agents and s o m e m a y have secondary utility as extender pig- conventional or associative thickeners. The m o s t c o m m o n
ments. Rheologically, ITRMs tend to have high yield values types of modified and u n m o d i f i e d ITRMs are attapulgite
and are ch aract er i ze d as "thixotropes." The viscosity of the clays, b en t o n i t e clays, organoclays, and treated and u n t r e a t e d
coating decreases with t i m e u n d e r constant s h e a r as its gel synthetic silicas [61]. Table 6 details s o m e i m p o r t a n t domes-
structure is b r o k e n down. W h e n the shear is removed, the tic (U.S.) suppliers of modified and unmodified ITRMs for
coating gradually recovers to its original viscosity. The rate of aq u eo u s and solvent-borne coatings systems.
recovery can be very rapid (complete w i t h i n seconds) or can
take several m i n u t e s or even h o u r s d e p e n d in g on the degree
of thixotropy an d p r i o r shear history. Certain grades or min-
Attapulgite Clays
eral types of ITRMs are useful for thickening a q ueo u s sys- The attapulgite clays are the m o s t c o m m o n l y used ITRMs
tems an d others for solvent-borne coatings. Utility in one in latex paints because they are e c o n o m i c a l an d also function
m e d i a or the o t h er is mostly a function of the thickener's as extender pigments. The principal m i n er al in attapulgite
TABLE 6--Inorganic TRMs (ITRMs)--U.S. suppliers and trade names for aqueous and solvent-borne architectural & industrial coatings.
TRM TRM TRM System Form, Total
Company Trade Name Code Class Use mPa.s Solids, %
3 Cab-o-sil | L, M, H Series Fumed Silica AQ/SOLV Solid 100
3 Cab-o-sil| TS Series Treated Fumed Silica AQ/SOLV Solid 100
3 Cab-o-sperse | A Series Fumed Silica AQ LIQ 12
4 Neosyl| TS Precipitated Silica AQ/SOLV Solid 100

4 Gasil DP Precipitated Silica AQ/SOLV Solid 100
5 Aerosil| 130-380 Fumed Silica AQ Solid 100

Series
5 Aerosil| R972, R974 Fumed Silica SOLV Solid 100
7 Korthix| Regular Refined Bentonite AQ Solid 100

7 Korthix| H Refined Modified Bentonite AQ Solid 100
8 Attagel| 40 & 50 Attapulgite Clay AQ/SOLV Solid 100
9 Minugel | AR Attapulgite Clay SOLV Solid 100

9 Minugel| LF Attapulgite Clay AQ/SOLV Solid 100
9 Minugel| 200, 400 Attapulgite Clay AQ/SOLV Solid 100
12 Zeothix| 177 & 265 Precipitated Silica AQ/SOLV Solid 100
16 Hi-sil| T-600 & T-700 Precipitated Silica AQ/SOLV Solid 100

16 Hi-sil| 200 Fumed Silica .-. Solid 100
16 Hi-sil| M5 Fumed Silica .-. Solid 100
17 Benaqua | 4000, 8000 Hectorite Clay AQ Solid 100

17 Bentone | 27, 34 & 38 Organoclay SOLV Solid 100
17 Bentone | SD-1, 2 & 3 Organoclay SOLV Solid 100
17 Bentone | EW Smectite Clay AQ Solid 100
17 Bentone | LT Bentonite Clay AQ Solid 100
20 Aquamont | 600 Modified Bentonite AQ Solid 100

20 Bentolite| ... Purified Bentonite AQ Solid 100
20 Claytone| Series Organo-mod. Montmorillonite SOLV Solid 100
20 Laponite | Series Synthetic Hectorite Clay AQ Solid 100
20 Lapomer e 40 Laponite Clay + Org Polymer AQ Solid 100
21 Troythix| A-SS Organoclay Solid 100

21 Troythix| A-S Silicate Solid 100
24 Tixogel| VP & VZ Organoclay SOLV Solid 100

24 Tixogel| LX Organoclay AQ Solid 100
25 Van gel| B Refined Colloidal Clay AQ Solid 100
www.iran-mavad.com

clays is attapulgite, which is chemically described as hy- ment. The chemical activator serves to disperse the orga-
drated magnesium aluminum silicate. The lath-shaped parti- noclay and also carries water into the hydrophobic organic
cles of this mineral as supplied are colloidal (less than 0.5 solvent to insure full hydrogen bonding. Some newer prod-
t~m), and the crystal structure is chain-like. In an aqueous ucts still require wetting and shear but are functional without
environment, attapulgite is nonswelling and essentially inert. the chemical polar activator. Although not essential, elevated
Thus, coatings containing attapulgite clay thickened not by temperatures are preferred for efficient processing. High-per-
swelling, but instead by the structured reflocculation of the formance organoclays have recently been developed with
pigment particles into a colloidal interaction network after greater thixotropy and improved sag resistance [62].
shearing. In coating preparation, attapulgite clays can be Special grades of organoclays (organophilic clays) have
added as powders or as pregelled dispersions throughout the also been designed for aqueous coatings. Some of these de-
formulation process. However, they are normally added in pend on shear, wetting, and hydration for full rheological
the grind using high-speed mixers for dispersion and hydra- performance, while others are available in readily activated
tion. The thickening power of these clays is high, and salts slurry form. The efficiency of these products is generally
have little or no effect on viscosity. However, like many other independent of pH [63].
ITRMs, the amount of attapulgite clay required for thicken-
ing is generally higher than for organic TRMs, and the water
demand is high (water is pulled from the aqueous phase to
Synthetic Silicas
wet the particle surface, thereby increasing effective coating Another class of inorganic thickeners are certain types of
solids). synthetic amorphous hydrophilic and hydrophobic silicas.
Both are widely used in solvent-borne coatings; however,
excessive hydration generally limits the utility of the hydro-
Bentonite Clays
philic silicas in aqueous media. Two forms of amorphous
Bentonite clay is obtained from the mineral mont- hydrophilic silica are commercially available and get their
morillonite (a Fuller's earth mineral), which is described as names, "precipitated silica" and "fumed silica," from the
an aluminum silicate with varying degrees of aluminum re- manufacturing processes. A proposed thickening mechanism
placement with magnesium, calcium, and sodium. The crys- for these silicas is based on hydrogen bonding between the
tal structure is a three-layer sheet which forms flake-like silica particles and with other coating components to form a
colloidal particles of less than 0.5 p,m. In aqueous media, three-dimensional structure. High water demand may also
bentonite is naturally hydrophilic and readily dispersible. contribute to thickening with these products.
The water is taken up between the mineral laminae, causing
the lattice structure to stretch and swell. Thickening is due to Precipitated Silica
a combination of swelling and particle network interaction, Precipitated silica is obtained in a wet process by the neu-
and purified forms of unmodified bentonite are highly effec- tralization of sodium silicate solution. This results in a polar,
tive as thickeners in aqueous coatings. Although the thicken- fully hydroxylated surface. Consequently, hydrogen bonding
ing mechanism is rather different than that of attapulgite is strong, and excellent thickening comparable to that of
clays, most bentonite clays also require wetting, high-shear fumed silica is obtained especially in nonpolar media. How-
for dispersion, and time for complete hydration. Some modi- ever, because of the competition between hydroxyls on the
fied grades are, however, readily dispersible with conven- silica and those in the continuous phase, precipitated silica
tional agitators. For effective incorporation, pH must be tends to be less efficient than fumed silica in polar (for exam-
carefully regulated. If it is too high, excessively rapid hydra- ple, aqueous) media.
tion occurs, and if it is too low, hydration times are long with
loss in thickening efficiency. The presence of salts (electro- Fumed Silica
lytes) may cause flocculation, rendering bentonite ineffective Fumed silica is fumed silicone dioxide which is prepared
in highly ionic environments. by hydrolysis of silicon tetrachloride vapor in a hydrogen-
oxygen flame. The product gets its name from the smoke-like
appearance as it forms in the flame. In the fuming process, a
Organoclays
partially hydroxylated surface containing silanol, siloxane,
Many different grades of organoclays are available for both and hydroxyl groups is generated, which is somewhat less
solvent-borne and aqueous coatings. Although these products polar than that of precipitated silica, pH does have a signifi-
differ in modification, the mechanism for thickening and cant effect on the thickening efficiency of fumed silica in
rheology control is substantially the same. Bentonite clay is aqueous systems. To be effective, pH must be below about pH
one of the principal minerals used to prepare organoclays, 7.5. Above this pH, electrostatic repulsion keeps the particles
and, being both hydrophilic and oleophobic in its natural far enough apart to inhibit hydrogen bonding.
form, it must be modified for dispersion in organic solvents.
Only after a sophisticated purification process followed by Organosilica
cation exchange with organic a m m o n i u m bases is the surface Hydrophobic silica is produced when freshly manufac-
rendered sufficiently organophflic for use in nonaqueous me- tured hydrophilic fumed silica is treated with organosilane or
dia. As supplied, organoclay thickeners are in the form of organosiloxane compounds [64]. This is a chemical modifica-
agglomerated platelet stacks. Conventional organoclays re- tion in which many of the surface hydroxyl groups are re-
quire wetting and shear for deagglomeration and the addition placed with organic functionality. After treatment, these
of a chemical polar activator for full theological develop- products have minimal surface silanol groups left for hydro-
www.iran-mavad.com

gen bonding, a n d the a m o u n t of c a r b o n i n c o r p o r a t e d into the [10] Barnes, H. A., "The Role of Molecular Morphology in Establish-
f u m e d silica (on the surface) is typically on the o r d e r of 1 to ing the Extensional (Elongational) Viscosity of Polymer Solu-
5%. H y d r o p h o b i c silicas are generally s u p e r i o r to h y d r o p h i l i c tions and Melts--A Review," Proceedings of the ACS Division of
silicas in water-reducible systems; however, o r d e r of a d d i t i o n Polymeric Materials: Science and Engineering, Inc., Vol. 61, 1989,
pp. 30-37.
can be i m p o r t a n t .
[11] Soules, D. A., Dinga, G. P., and Glass, J. E., "Elongational Vis-
cosity of Filled Systems by the Vacuum Draw Technique," Pro-
ceedings of the ACS Division of Polymeric Materials: Science and
ORGANIC T R M s F O R S O L V E N T B O R N E Engineering, Inc., Vol. 61, 1989, pp. 43-46.
COATINGS [12] Schwab, F. G., "Advantages and Disadvantages of Associative
Thickeners in Coatings Performance," Chapt. 19 in Water-Solu-
Besides the inorganic p r o d u c t s described above, a variety ble Polymers, ACS Advances in Chemistry Series No. 213, J. E.
of organic additives also function as thickeners, rheology Glass, Ed., 1986, pp. 369-373.
modifiers, a n d thixotropes in solvent-borne systems. These [13] Hall, J. E. et al., "Influence of Rheology Modifiers on the Per-
p r o d u c t s are mostly available in liquid p a s t e a n d p o w d e r formance Characteristics of Latex Paints," Journal of Coatings
form. M a n y require s o m e d i s p e r s i o n a n d activation for thick-
Technology, Vol. 58, No. 738, July 1986, pp. 65-73.
[14] Sperry, P. R., "Morphology and Mechanism in Latex Floccu-
ening, a n d the r e c o m m e n d e d process t e m p e r a t u r e s often de-
lated by Volume Restriction," Journal of Colloid and Interface
p e n d on the strength of the solvent p r e s e n t in the coating Science, Vol. 99, May 1984, pp. 97-108.
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avoid seeding, "false body," or loss in thickening efficiency. lation and Rheological Characteristics of Mixtures of Latices
A m o n g the m a n y types of organic p r o d u c t s available for use and Water-Soluble Polymeric Thickeners," Proceedings: Elev-
as thickeners a n d flow control agents for solvent-borne sys- enth International Conference Organic Coatings Science Technol-
t e m s a r e c a s t o r oil derivatives [62], modified acrylic copoly- ogy, 1985, pp. 371-388.
mers, polyethylene glycol, p o l y a m i d e s [65], p o l y m e r i z e d oil [16] Belbin, D., Buscall, R., Mumme-Young, C. A., and Shankey,
derivatives, organic esters, c o m p l e x polyolefins, a n d a r a m i d J. M., Polymer Latex II, Proceedings, Plastics and Rubber Insti-
p u l p fibers [66]. Because of the n u m b e r of products, their tute, London, 1985.
[17] Gast, A. P., Hall, C. K., and Russel, W. B., Faraday Discussions,
diverse nature, a n d the fact t h a t little i n f o r m a t i o n is available
Chemical Society, Vol. 76, 1983, p. 338.
on m a n y due to their p r o p r i e t a r y status, no a t t e m p t will be
[18] Dickinson, E., "A Model of a Concentrated Dispersion
m a d e here to classify o r categorize these p r o d u c t s a n d their Exhibiting Bridging Flocculation and Depletion Flocculation,"
suppliers. Resources for this i n f o r m a t i o n are available else- Journal of CoUoidand Interface Science, Vol. 132, 1 Oct. 1989, pp.
w h e r e (for example, see McCutcheon's F u n c t i o n a l Materials 274-278.
in the Bibliography). [19] Heyes, D. M., McKenzie, D. J., and Buscall, R., "Rheology of
Weakly Flocculated Suspensions: Experiment and Brownian
Dynamics Simulation," Journal of Colloid and Interface Science,
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presented at the Spring Meeting of FSCT, Philadelphia, 1991.
11, November 1984, pp. 279-283.
[55] Shay, G. D., Kravitz, F. K., and Brizgys, P. V., "Effects of Pro-
[37] Glancy, C. W. and Bassett, D. R., "Effect of Latex Properties on
cess Variables on the Emulsion and Solution Properties of Hy-
the Behavior of Nonionic Associative Thickeners in Paint," Pro-
drophobically Modified Alkali-Swellable Emulsion Thickeners,"
ceedings of the ACS Division of Polymeric Materials: Science and
Chapt. 7 in Polymers as Rheology Modifiers, ACS Symposium
Engineering, Inc., Vol. 51, 1984, pp. 348-352.
Series No. 462, J. E. Glass and D. N. Schulz, Eds., 1991, pp.
[38] Thibeault, J. C., Sperry, P. R., and Schaller, E. J., Chapt. 20 in
121-141.
Water-Soluble Polymers, ACS Advances in Chemical Series No.
213, J. E. Glass, Ed., 1986, pp. 376-389.
[56] Goodwin, J. W. et al., "The Rheological Properties of a Hydro-
[39] Alahapperuma, K. and Glass, J. E., "Influence of Coalescing Aids phobically Modified Cellulose," Chapt. 19 in Polymers in Aque-
in Associative Thickener Dispersions," Journal of Coatings Tech- ous Media: Performance Through Association, ACS Advances in
nology, Vol. 63, No. 799, August 1991, pp. 69-78. Chemistry Series No. 223, J. E. Glass, Ed., 1989, pp. 365-378.
[40] Chang, S. H., Ryan, M. E., and Gupta, R. K., "Competitive Ad- [57] Fu, E. and Young, T.-S., "Associative Behavior of Hydro-
sorption of Water-Soluble Polymers on Attapulgite Clay," phobically Modified Hydroxyethyl Cellulose in Latex Coatings,"
Journal of Applied Polymer Science, Vol. 43, 1991, pp. 1293- Proceedings of the ACS Division of Polymeric Materials: Science
1299. and Engineering, Inc., Vol. 61, 1989, pp. 614-618.
[41] Young, T. S. and Fu, E., "Associative Behavior of Cellulosic [58] Goodwin, J. W., Lain, C. K., and Reed, C., "Water-Soluble and
Thickeners and its Implications on Coating Structure and Rhe- Water-SweUable Polymers: The Solution Properties of a Hydro-
ology," Tappi Journal, April 1991, pp. 197-207. phobically Modified Cellulose," Proceedings of the ACS Division
[42] Jenkins, R. D., Silebi, C. A., and E1-Aasser, M. S., "Steady Shear of Polymeric Materials: Science and Engineering, Inc., Vol. 57,
and Linear Viscoelastic Material Properties of Associative 1987, pp. 502-505.
Thickener Solutions," Chapt. 13 in Polymers as RheoIogy Modi- [59] Landoll, L. M., "Nonionic Polymer Surfactants,"JournalofPoly-
fiers, ACS Symposium Series No. 462, J. E. Glass and D. N. mer Science, Polymeric Chemistry Edition, Vol. 20, 1982, pp.
Schulz, Eds., 1991, pp. 222-233. 443-455.
[43] Glancy, C.W., "New Associative Thickeners Advance Latex [60] Sau, A.C., "Synthesis and Solution Properties of Hydro-
Paint Technology," American Paint and Coatings Journal, 6 Aug. phobically Modified Water-Soluble Polymers," Proceedings of
1984, pp. 48-53. the ACS Division of Polymeric Materials: Science and Engineer-
[44] Karunasena, A., Brown, R.G., and Glass, J.E., "Hydro- ing, Inc., Vol. 57, 1987, pp. 497-501.
phobically Modified Ethoxylated Urethane Architecture: Impor- [61] Griffith, K.A., Leipold, D. P., and Burrneister, L.A., "Rheo-
tance for Aqueous and Dispersed-Phase Properties," Chapt. 26 logical Modifiers in Aqueous Systems," Journal of Water-Borne
in Polymers in Aqueous Media: Performance Through Associa- Coatings, Nov. 1987, pp. 2-16.
tion, ACS Advances in Chemistry Series No. 223, 1989, pp. [62] "Rheological Control Using Organoclay Technology," European
495-525. Polymers, Paint and Colour Journal, Vol. 183, No. 4321, 13/27
[45] Concannon, A. J. and Kossman, H. H., "New Diurethane Thick- Jan. 1993, pp. 19-20.
eners for Emulsion Paints and Textured Finishes," Australian [63] Tso, S. C., Beall, G. W., and Gordon, J., "New Generation of
Oil and Colour Chemists Association Proceedings and News, Jan- Water-Based Thickener," Journal of Water-Borne Coatings, Au-
uary-February 1980, pp. 6-15. gust 1987, pp. 3-8.
www.iran-mavad.com

[64] Nargiello, M. and Chasse, D., "Improved Rheological Character- 7. Dry Branch Kaolin Co., Kaopolite Inc., R.R. 1, P.O. Box
istics of Water-Reducible Coatings with Hydrophobic Fumed 468-D, Dry Branch, GA 31020-9798.
Silicas," American Paint and Coatings Journal, 1 July 1991, pp. 8. Engelhard Corp., Specialty Minerals and Colors Group,
38-45.
[65] Nae, H. N. and Reichert, W. W., "Rheological Properties and 101 Wood Ave, Iselin, NJ 08830-0770.
Thickening Mechanisms of Polymeric Rheology Modifiers," Pro- 9. Floridin Co., 1101 N. Madison St., Quincy, FL 32351.
ceedings of the ACS Division of Polymeric Materials: Science and 10. B. F. Goodrich Co., Specialty Polymers & Chemicals,
Engineering, Inc., Vol. 61, 1989, p. 628. 9911 Brecksville Rd., Brecksville, OH 44141.
[66] Frances, A. and Dottore, J., Adhesives and Sealants Council 11. Henkel Corp., Functional Product Grp., Coatings &
Seminar, Fall 1987. Inks, 300 Brookside Ave., Ambler, PA 19002.
12. J. M. Huber Corp., Chemicals Division, P.O. Box 310,
Havre de Grace, MD 21078.
BIBLIOGRAPHY
13. Hills America Inc., 80 Centennial Ave., P.O. Box 456,
Handbook of Coatings Additives, L. J. Calbo, Ed., Marcel Dekker Inc., Piscataway, NJ 08854.
New York, Vol. I, Chapts. 1-5, 1987, pp. 1-147. 14. Kelco, Division of Merck & Co. Inc., 8355 Aero Dr., San
Handbook of Coatings Additives, L. J. Calbo, Ed., Marcel Dekker Inc., Diego, CA 92123.
New York, Vol. II, Chapt. 4, 1992, pp. 105-164. 15. Pfizer Chemical Div., 235 E. 42nd St., New York, NY
Handbook of Water-Soluble Gums and Resins, R. L. Davidson, Ed., 10017.
The Kingsport Press, Chapts. 4, 6, 12, 13, 17, and 24, 1980. 16. PPG Industries, Specialty Chemicals Bus. Unit, 3938
McCutcheon's Functional Materials, Vol. 2: North American Edition,
McCutcheon Division, MC Publishing Co., 1993. Porett Dr., Gurnee, IL 60031.
Polymers as Rheology Modifiers, ACS Symposium Series No. 462, J. E. 17. Rheox Inc., P.O. Box 700, Wyckoffs Mill Rd.,
Glass and D. N. Schulz, Eds., No. 462, Chapts. 1-4, 1991, pp. 2-87. Hightstown, NJ 08520.
Polymers in Aqueous Media: Performance Through Association, ACS 18. Rhone-Poulenc Corp., Colloids Div., 1525 Church St.,
Advances in Chemistry Series No, 223, J. E. Glass, Ed., 1989. Marietta, GA 30060.
19. Rohm and Haas Co., Rohm and Haas Building, Inde-
pendence Mall, West, Philadelphia, PA 19106.
LIST OF P R O D U C E R S A N D S U P P L I E R S 20. Southern Clay Products Inc., Division of Laporte Absor-
bents, 1212 Church St., P.O. Box 44, Gonzales, TX 78629.
*Company Reference Numbers for Tables 3, 5, and 6
21. Troy Chemical Corp., P.O. Box 366, 72 Eagle Rock Ave.,
1. Alco Chemical Corp,, Div. of National Starch & Chemi-
East Hanover, NJ 07936.
cal, 909 Mueller Dr., P.O. Box 5401, Chattanooga, TN 37406-
0401. 22. Union Carbide Chemicals and Plastics Co., UCAR
2. Aqualon, 1313 N. Market St., P.O. Box 8740, Wilming- Emulsion Systems, 410 Gregson Dr., Cary, NC 27511.
ton, DE 19899-8740. 23. Union Carbide Corp., Specialty Chemicals Division, 39
3. Cabot Corp., Cab-O Sil Division, P.O. Box 188, Tuscola, Old Ridgebury Rd., Section H-2375, Danbury, CT 06817-
IL 61953-0188. 0001.
4. Crosfield Co., 101 Ingals Ave., Joliet IL 60435. 24. United Catalysts Inc., Rheologicals and Performance
5, Degussa Corp., Pigments Div., 425 Metro Place North, Minerals Group, subsidiary of Sild Chemie AG, P.O. Box
Dublin, OH 43017. 32370, Louisville, KY 40232.
6. Dow Chemical USA, Larkin Lab, 1691 N. Sweede Rd., 25. R. T. Vanderbilt Co, Inc., 30 Winfield St., Norwalk, CT
Midland, MI 48674. 06855.
www.iran-mavad.com

Part 8: Physical Characteristics of Liquid
Paints and Coatings
www.iran-mavad.com

MNL17-EB/Jun. 1995
31
Density and Specific Gravity
by Raymond D. Brockhaus 1
INTRODUCTION formula loading target. Quick approximate estimations of

density can be done with inexpensive equipment that acts as a
Why Concern Ourselves with Density? screening tool, catching special-cause errors like wrong ma-
terial shipped. Common-cause errors of minor contamina-
The World of the Producer and the Customer tion are usually not caught this way.
MATERIALS ARE EXCHANGED FOR AN agreed-upon value based The use of density measurements as a measure of quality is
upon a "cost per unit material." The "unit of material" is in declining in favor of testing tuned to providing measure-
terms of what the user wants to do with the material ex- ments of ingredient concentrations and chemical functional-
pressed in physically measurable units such as volume or ity. This is most often a balance between spending time,
weight. The customer does not want to be shorted, and the money, and manpower on testing and risking the liability of
provider does not want to give away material. Accurate mea- inadequate product performance.
surements are expected to keep both parties happy. When a
customer wants a gallon of paint, the manufacturer blends Regulatory Concerns
the component materials together by weight and fills out by In addition to customers and producers, government can
weight. Balances are easy devices to place and use with filling express concerns in the exchange of materials. Government's
lines. Delivery of constant volumes, on the other hand, is not concern is for regulation. Paints or other similar heteroge-
an easy task, as will be explained later. Measurement of the nous materials are mixtures in which only the nonvolatile
weight of a known volume of the paint generates a relation- portion of the bulk material being exchanged is of true value
ship defined as density. With this relationship, the producer to the customer. The "carrier" portion of the bulk material
can fill by weight and then sell to the customer on a by volume must be accounted for because it is a discarded material and
basis. The customer wants volume; the producer wants to thus a "pollutant." The carrier portion, solvents, and viscosity
work in weights. The relationship--density--enables the reducers are used to aid in transporting the solids to the work
transformation to make life easier for both groups. surface to form a thin film. These pose disposal problems and
impact landfills, air and water quality, which are under gov-
Measure of Quality erument regulations. Paint volume solids and critical pig-
In the open marketplace, the business person and the cus- ment volumes are two significant concepts which must be
tomer have this rule of thumb--let the buyer beware. Testing understood and accounted for when dealing with modern
for quality of the shipment is best done on-the-spot, quickly, government regulations [1].
and in a way that is highly reliable. If you are in charge of the
wine and ale stocks of a restaurant, one method of determin-
ing the quality of the goods obtained would be verification of Definitions--Density--Static and Dynamic
the density with flotation probes called hydrometers. Simi- Mathematical Models
larly, the purchasers of metals such as gold, lead, silver, and Static Model
copper could use various methods of determining density to
Density is the weight in vacuo, that is, the mass of a unit
keep from being cheated and assuring quality.
volume of a material at any given temperature [2]. In vacuo is
In our more modern world, with instruments capable of
specified because measurement of weights in gaseous or liq-
assaying individual chemical compounds in complex mix-
uid environments may require a buoyancy correction. If the
tures, verification of density has become a manufacturing
volume of the mass being weighed is large, a correction must
tool for in-process control. Density measurement becomes an
be made for displacement of the environmental media (air or
indirect assurance that the ingredient(s) of interest exists in
a liquid).
the material of exchange at the proper concentration. For
For some samples, however, vacuum conditions will cause
paint, ingredients such as solvents, polymers for binders, and
vaporization of the sample. Therefore, "in vacuo" is usually a
pigments have a different range of density typical of that
theoretical condition rather than a normally experienced one
material. Partial omission of a major component, for exam-
and deals with the surrounding environment. The balance
ple, a solvent, can make the paint density change from the
used to weigh the sample must also be in vacuo.
The Greek letter p (rho) is used to denote density.
1Research Associate, E. I. Du Pont, Automotive Products, 400
Groesbeck Highway, Mt. Clemens, MI 48043.
289
www.iran-mavad.com

w h e r e m is mass, a n d V is volume expressed in units consis- Relative Density, also referred to as specific gravity, is the
tent with the m a s s units. ratio of a density d e t e r m i n e d for Material A at T e m p e r a t u r e
T I divided by the density of a reference m a t e r i a l at s o m e
p = (W/V) (2)
t e m p e r a t u r e , T2. F o r solids a n d liquids, the reference m a t e r i a l
where W is weight (a function of mass), a n d V is v o l u m e is p u r e water. F o r gases, the reference m a t e r i a l is air.
expressed in units consistent with the m a s s units.
DensityRelative g = D e t e r m i n e d Density A at T 1 (3)
Dynamic Model D e t e r m i n e d Density W a t e r at 0~
Density is a m a t h e m a t i c a l value describing a b a l a n c e of If a Liquid A has the s a m e density as w a t e r at T~, w h e n
physical forces acting on a m a t e r i a l called m a s s occupying a d e t e r m i n e d by a b o u y a n c y device, then the density can be
k n o w n v o l u m e of space u n d e r k n o w n t e m p e r a t u r e condi- d e t e r m i n e d from a table of k n o w n density values established
tions. This e q u a t i o n is identical to that given in the static for p u r e w a t e r over a range of t e m p e r a t u r e s .
model. Density is expressed as a single value, b u t is really an W h e n T2 equals 4.0~ the relative density for p u r e w a t e r
average value of forces d y n a m i c a l l y fluctuating, b o t h internal equals the m e a s u r e d density. As t e m p e r a t u r e increases, w a t e r
to the m a t e r i a l a n d external as the s u r r o u n d i n g environment. expands. F o r a c o n s t a n t volume, the mass of w a t e r m u s t be
Two definitions are included here. The first (static) is the d e c r e a s e d to fit into a given volume. Thus, water's density
t r a d i t i o n a l model. It has c h a n g e d only slightly over the ages, value m u s t decrease with increasing t e m p e r a t u r e . Relative
being u p g r a d e d with the t e r m s "mass" in place of weight a n d density is a ratio of two values carrying the s a m e units. There-
"in vacuo" after v a c u u m bell j a r s were developed. The s e c o n d fore, relative density is a unitless n u m b e r .
(dynamic) is a m o r e f u n d a m e n t a l model, dealing with m a t e r i - Specific Gravity--An old term; the t e r m relative density is
als on a m o l e c u l a r level, w h e r e the concepts of c h e m i c a l identical a n d is less misleading [4].
functionality, kinetic a n d potential energy, a n d interfacial Apparent Density--A density value for p o w d e r s a n d m a c r o -
b o u n d a r i e s c o m e into play. W i t h the second model, we can scopic p a r t i c u l a t e solids w h i c h are c o m p a c t e d by vibration.
u n d e r s t a n d a n d deal with mixtures of c h e m i c a l s a n d m a t h e - Air is still p r e s e n t in the voids b e t w e e n the particles a n d in
m a t i c a l l y deal with h o w a single c o m p o n e n t ' s densities inter- pockets o r voids at the irregular surface of the m a c r o s c o p i c
act w h e n mixed. particles. This m e a n s the v o l u m e is greater t h a n just for the
The attractive forces exerted on a p r i m a r y m a s s o r collec- solids, a n d the density is s m a l l e r in value t h a n if the m a t e r i a l
tion of particles by a second m a s s m u c h larger t h a n the first was a liquid o r c o m p a c t e d such that no voids existed. Pig-
m a s s is called weight. This is a n attractive action, resulting in m e n t s used in p a i n t are m e c h a n i c a l l y w o r k e d with solvents
c o m p r e s s i o n a n d increasing the density of the p r i m a r y mass. a n d resins to fill in these voids. The true density of the pig-
The dispersing forces are caused b y t h e r m a l energy a b s o r p - ment, w h i c h is n e e d e d in p a i n t calculations, is that o b t a i n e d
tion, resulting in particles of increasing m o t i o n or kinetic w i t h o u t a n y of the air (void) contribution.
energy. This manifests as t e m p e r a t u r e of the material.
The volume of space o c c u p i e d by a m a s s of particles that
exists at an average kinetic energy level expressed as the
t e m p e r a t u r e of the physical m a t e r i a l is the volume. This in- Fundamental Concepts--Material, Objects,
cludes the voids of space b e t w e e n the particles on a m o l e c u l a r Volumes, Masses, and Weights--What Really is
level. Density?
The average kinetic energy level of the m a t e r i a l is expressed Density is m o r e t h a n just the m a t h e m a t i c a l n u m e r i c a l
in the m o t i o n of the particles of the material. Material is value identified above. It also i n c o r p o r a t e s units of m e a s u r e
m a d e u p of m a n y small particles that are i n d e p e n d e n t in t h e i r w h i c h are, in turn, b a s e d u p o n m o r e general a n d f u n d a m e n -
motion. These m o t i o n s are r a n d o m , such that the overall tal concepts. These units of m e a s u r e a s s u m e a set of defini-
m o t i o n in the X, Y, a n d Z directions cancel each o t h e r a n d the tions which will be explored in very general terms. These
net m o t i o n of the total m a s s is zero. As the kinetic energy
level, expressed as t e m p e r a t u r e , increases, the distances be- TABLE 1--Density of water, grams per cc [2].
tween particles increase a n d the m a t e r i a l is identified as ex-
Temperature, ~ Density, g/cm3
panding.
Special cases used as s t a n d a r d m e a s u r e m e n t reference 15 0.999 099
points: 16 0.998 943
17 0.998 744
9 One cubic c e n t i m e t r e (cm 3) of p u r e w a t e r (H20) at 4.0~ is 18 0.998 595
defined to weigh 1.0000 g. 19 0.998 405
20 0.998 203
Densitywater = 1.000 g/1.000 c m 3 21 0.997 992
22 0.997 770
9 1.000 mole of a gaseous c o m p o u n d occupies 22.4 L of vol- 23 0.997 538
u m e at 0~ (273~ at 1.000 a t m o s p h e r e p r e s s u r e (a m o l a r 24 0.997 296
volume). 25 0.997 044
26 0.996 783
F o r air, whose c o m p o s i t i o n is 22% by weight oxygen a n d 78% 27 0.996 512
by weight nitrogen (ignoring o t h e r gases), 1 m o l e weight = 28 0.996 232
(32 g 0.22) + (28 g 0.78) = 28.88 g. Density = 28.88 29 0.995 944
g/22 400 c m 3 = 0.001 29 g/cm 3 or 1.29 g/L [3]. 30 0.996 565 6
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CHAPTER 3 1 - - D E N S I T Y AND SPECIFIC G R A V I T Y 2 9 1
units are crucial to u n d e r s t a n d i n g the d y n a m i c m o d e l of be u s e d for filling by volume. P r o d u c e r s s e l d o m can o r w a n t

density a n d in allowing m i c r o s c o p i c concepts to he explored. to control t e m p e r a t u r e d u r i n g packaging. T e m p e r a t u r e con-
Material--Anything (a physical entity) w h i c h exists for a trol devices will a d d expense w i t h o u t m a k i n g a difference in
d u r a t i o n of time, occupies space, a n d has mass. Mass is a the material's p e r f o r m a n c e . W i t h o u t t e m p e r a t u r e control,
stable configuration of a t o m s individually loosely o r g a n i z e d filling at a c o n s t a n t v o l u m e will p r o d u c e units of varying
as elemental a t o m s or j o i n e d together chemically to form a m o u n t s of material. Use of density overcomes these p r o b -
molecules. lems a n d p e r m i t s correct volumes to b e filled out.
Object--A collection of materials, h o m o g e n e o u s or hetero-
geneous, localized to a p o r t i o n of v o l u m e (space). The mate-
rial can b e in any one of three states: solid, liquid, o r gaseous. Weight and Mass
The shape of the volume of space o c c u p i e d by the object plays
A f u n d a m e n t a l attribute of a physical entity is mass. This is
a role in dealing with density b u t does n o t define the object
one of the indefinable m e c h a n i c s [4]. Two physical objects
itself.
exhibit an a t t r a c t i o n for each o t h e r in p r o p o r t i o n to the
Volume is b a s e d u p o n m e a s u r e m e n t of distance in three
q u a n t i t y of m a s s in each object. The greater the mass, the
directions at right angles to each o t h e r as in Fig. 1.
greater the attraction. W h e n the ratio of two masses is grossly
The physical universe in w h i c h we live is often d e s c r i b e d in
unequal, such as the p l a n e t E a r t h a n d an object on its surface,
three d i m e n s i o n s in t e r m s of distance, w h i c h is a scalar p r o p -
the larger m a s s is a s s u m e d to be c o n s t a n t a n d the s e c o n d
erty. W h e n dealing with three d i m e n s i o n s , the t e r m distance
object is d e s c r i b e d to have a "weight" relative to this larger
is d e s c r i b e d as length, width, a n d depth. An object having all
object. The m a s s of the p l a n e t is effectively u n c h a n g i n g a n d
three is d e s c r i b e d as having volume. The m a t h e m a t i c a l value
thus constant. Our m o o n is also a very large object, b u t
for volume is the p r o d u c t of m u l t i p l i c a t i o n of the three scalar
s m a l l e r t h a n the earth, thus its a t t r a c t i o n to a second object
values. Volume can exist w i t h o u t objects occupying that
w o u l d be w e a k e r t h a n for the Earth. Mass is the unchanging,
space. This c o n d i t i o n is called a vacuum. V a c u u m ' s v o l u m e
f u n d a m e n t a l property.
a n d object's volume can b o t h be of very irregular a n d
But we are h u m a n , a n d we deal in the m e a s u r e m e n t of
n o n m a t c h i n g shapes, yet they can equal in the scalar value of
weight, w h i c h is a force. While weight is a vector q u a n t i t y
the volumes. E x a m p l e s are s h o w n in Fig. 2.
having b o t h scale a n d direction, the direction p o r t i o n is t a k e n
Problems with Volume Measurements for g r a n t e d a n d weight is usually treated as only a scalar
value. Figures 3 a n d 4 graphically depict this issue.
Customers often m a k e use of m a t e r i a l b a s e d on volume as Weight, w, is defined as a force of gravity, Fg, [4].
a p p l i e d a n d w a n t to p u r c h a s e these p r o d u c t s in containers
recognized to hold s t a n d a r d volumes. Materials have the G mine
p r o p e r t y of r e s p o n d i n g to t e m p e r a t u r e changes with expan-
w = Fg = T = mg (4)
sion or c o n t r a c t i o n of their volume. Products that experience
wide t e m p e r a t u r e ranges d u r i n g filling, shipping, storage, or where
in use m u s t also have extra unfilled v o l u m e to a c c o m m o d a t e G = a gravitational c o n s t a n t for E a r t h -- 6.670
e x p a n s i o n or the m a t e r i a l forces leak a n d m a t e r i a l is lost. 10 -11 N.m2/kg m 2,
This p r o b l e m is m o s t severe with liquid materials. Material mE -- m a s s of the E a r t h = 5.98 1027 g, a n d R is the
suppliers use containers w i t h larger t h a n exact volume re- r a d i u s of the E a r t h = 6370 km,
quired to allow for expansion. These vessels m u s t be m a r k e d m -- m a s s of a second b o d y (Newton's law) [5],
in s o m e w a y to indicate the volume i n c r e m e n t s if they are to gE = 9.80 m/s 2 o r 32.0 ft/s 2, a n d
gMoon 5.333 f t / s 2 o r 1/6 that for Earth.
=
u gDist. . . . from Earth = 1.0 106 k m = gE/[(1.0064 106 kin)2/

(6370 km) 2] -- 0.004g E
l These values are given as constants in physics calculations

b u t actually r e p r e s e n t average values. In the real world, the
/;
m X
value of g varies from l o c a t i o n to location for a variety of
reasons. Table 2 a n d Figs. 5 a n d 6 a b o u t m o u n t a i n s a n d dense
I b u r i e d m a s s e s of r o c k d e m o n s t r a t e this.
FIG. 1-Coordinates in three Example 1: A gallon of p a i n t p r o d u c e d in Galvaston, Texas
dimensions. has a weight of 10.000 lb/gal. The p r o d u c t finds its w a y to
FIG. 2-Examples of physical objects.
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G

292 P A I N T AND COATING TESTING MANUAL
Plumbline
SmallObject-- ~ m rge~
ry massive object
agallonof liquid
\
l eters
a orn 3822
c mieels \
Center of gravity
9b)of Earth
FIG. 6-Large buried mass con-
centration effects on objects on the
earth. From The New Book of Popu-
lar Science, 1993 Edition. Copyright
1993 by Grolier Incorporated. Re-
printed by permission.
Eagle City, Alaska. Here it has a gallon weight of 10.03 lb/gal.

FIG. 3-Moderate distance to large body center. The difference is m i n o r b u t real. If the p a i n t specification is a
density in the range of 9.90 to 10.10 lb/gal, the + 0.03 lb leaves
only 0.07 lb for testing errors before the m a t e r i a l is identified
as o u t of specification. As e n v i r o n m e n t a l regulations on the
volatile o r g a n i c content (VOC) increase in i m p o r t a n c e , these
O m i n o r differences will play a larger role a n d should not be
SmalObject--
l overlooked for their c o n t r i b u t i o n s to relationships such as
agallonofliquid density.
The pull of gravity is not as strong at a m o u n t a i n t o p , A, as it
is on the plain, B. The r e a s o n is b e c a u s e A is at a greater
distance from the center of gravity t h a n B. The p l u m b line in
FIG. 4-Vast distance to large body center. Fig. 6 does not p o i n t exactly to the earth's c e n t e r of gravity
b e c a u s e it is a t t a c h e d to A, w h i c h is a dense p a r t of the earth's
A crust [5].
Example 2: The weight of a gallon of p a i n t in New York City
is r e c o r d e d at 9.5 lb. The distance from the c e n t e r of the E a r t h
is 6370 k m at this location. At a distance of one million
kilometres from the earth, the s a m e gallon of p a i n t w o u l d
weight 0.003 78 lb.
Has the a m o u n t of m a s s changed? No. Has the weight
changed? Yes, b e c a u s e of distance. Has the v o l u m e of the
m a t e r i a l changed? Possibly. If the gallon c o n t a i n e r is sur-
r o u n d e d by air at 1 arm, the c o n t a i n e r shape is r e t a i n e d a n d
FIG. 5-Height effects on objects the m a t e r i a l in it will n o t overflow. But, in the n e w location,
on the earth's surface. From The
the fluid does not w a n t to r e m a i n together. It forms droplets
New Book of Popular Science, 1993
Edition. Copyright 1993 by Grolier a n d w a n t s to float off in all directions. It has lost the cohesive-
Incorporated. Reprinted by permis- ness p r o v i d e d by gravity. Has the density of the m a t e r i a l
sion. changed? By definition, yes, drastically! By fact, little. The
s a m e physics rules a p p l y in b o t h locations, b u t the environ-
m e n t has c h a n g e d and with it o u r a p p r e c i a t i o n for the t e r m
mass.
TABLE 2reValues of g, the acceleration due to gravity [5].

Place Value~ Place Valuea
Cambridge, Massachusetts 980.398 Denver, Colorado 979.609
Eagle City, Alaska 982.183 Galveston, Texas 979.272
Greenwich, England 981.188 Honolulu, Hawaii 978.946
Madras, India 978.281 New Orleans, Louisiana 979.324
Panta Delgada, Azores 980.143 Reykjavik, Iceland 982.273
aCentimetres per second per second. Use of centimetres emphasizes the differences which are occurring in the second through sixth numerical place.
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CHAPTER 3 1 - - D E N S I T Y AND SPECIFIC GRAVITY 2 9 3
Example 3: A 1.00 m 3 S t y r o f o a m cube of m a t e r i a l is created

on e a r t h in o u r a t m o s p h e r e (air) at 20~ a n d 1.0 atm. This is a
heterogeneous m a t e r i a l b e c a u s e it has t r a p p e d air in the
foam. Let's say it weighs 900 g on a b a l a n c e on an open desk
top.
Densitye~rth = 900 g + 1.00 m 3 = 900 g/m 3
Next, this cube is taken to the m o o n (gravitational factor = FIG. 7-Simple model of particles of matter
1/6 Earth) a n d kept inside a building with 1.0 a t m at 20~ in solid state.
Density . . . . = (900g 1/6 + 1.00m 3) = 150g + 1.00m 3 -=
150 g/m 3 Liquids--In a liquid as d e p i c t e d in Fig. 8, the particles are
m o l e c u l a r o r a t o m i c in scale. Distances b e t w e e n particles are
Next, the cube is taken out onto the m o o n ' s open surface, not constant. Kinetic energy is greater t h a n in solids. Exter-
where there is no a t m o s p h e r e (vacuum conditions). nal p r e s s u r e can s h o r t e n the distance between particles. E a c h
Now, two t h i n g s h a p p e n to this cube. m a t e r i a l has a characteristic c o m p r e s s i b i l i t y factor. All liq-
1. There is no air to displace w h e n weighing the cube. It can uids behave elastically, flowing b a c k a n d filling in. The p o p u -
thus exhibit a heavier weight since there is no b u o y a n c y lation of particles has a d i s t r i b u t i o n of kinetic energy values,
correction: l m 3 of air weighs 1.29 g on E a r t h a n d 0.215 g with s o m e being greater t h a n the surface energy. The p o r t i o n
on the Moon. So the weight would be 150.215 g. of the p o p u l a t i o n which has a kinetic energy greater t h a n the
2. The m a t e r i a l can also lose the air e n t r a p p e d in the foam. surface energy escapes a n d is called vapor.
This m a y be a slow process, b u t it can happen. N o w the F o r ideal conditions a n d "conceptual" materials, no inter-
cube will a p p e a r to lose weight. Let's say it loses 0.050 g by actions occur between the materials, the testing containers,
m o o n weight a n d n o w weighs 150.215 - 0.050 g. a n d the s u r r o u n d i n g environment. The m a t e r i a l investigated
is well behaved. W h e n such m a t e r i a l s are m i x e d together, the
Densityv . . . . . . . . = 150.165 g + 1.00 m 3 = 150.165 g/m 3
weight of each m a t e r i a l times the individual material's den-
R e t u r n the cube b a c k into the building on the m o o n with sity will a d d together as a l i n e a r sum.
1.0 a t m a n d the weight m i g h t n o w be 149.95 g if the f o a m Gases--In a gas, as d e p i c t e d in Fig. 9, the particles are
structure is strong enough to retain the cubic shape without m o l e c u l a r o r a t o m i c in scale b u t m o r e widely separated.
crushing from the external pressure. Its density is n o w 149.95 Distance between particles is irregular. Kinetic energy is even
g/m 3. h i g h e r t h a n in liquids. External p r e s s u r e can shorten the
Density is a very simple, s t r a i g h t f o r w a r d concept a n d rela- distance b e t w e e n particles. E a c h m a t e r i a l has a characteris-
tionship. Still, as n o t e d before, physical reality can a n d does tic c o m p r e s s i b i l i t y factor.
i m p a c t on it, a d d i n g subtle p e r t e r b a t i o n s that should be Weighing solid o r liquid m a t e r i a l in a c o n t a i n e r o r as a
understood. W h a t a p p e a r s to be h o m o g e n e o u s m a y not be. solid object is an easy task. I n s t r u m e n t s for this task keep
Physical reality is a source of variability, a n d affects m u s t be i m p r o v i n g in accuracy, precision, ease of use, a n d lower cost.
taken into c o n s i d e r a t i o n w h e n arriving at results we will F o r gas-phase material, vessels of a c c u r a t e l y d e t e r m i n e d
share with one another. volume can be p u r c h a s e d a n d used. Materials of c o n s t r u c t i o n
for d u r a b i l i t y a n d reuse are of concern. If the t e m p e r a t u r e of
testing is controlled within the tolerance of the c a l i b r a t i o n of
Solids, Liquids, and Gases--As Concepts and these vessels, e x p a n s i o n is not a concern. Since gases are
Under Ideal Conditions s e l d o m i n c o r p o r a t e d into a p a i n t system, this topic will b e
p a s s e d over.
Materials exist in one of three states: solids, liquids, o r
gases. F o r an equal a m o u n t of weight, solids usually o c c u p y
less volume t h a n liquids, w h i c h occupy m u c h less volume Further Discussion of Liquids and Solids
t h a n a gas. Solids also retain a shape a n d flow o r distort very F o r liquids, containers can be c o n s t r u c t e d to hold a k n o w n
slowly. Liquids take on the form of a c o n t a i n i n g vessel. Gases volume. These vessels can be m a s s p r o d u c e d with a d e q u a t e
have no shape a n d are b o u n d e d a n d s h a p e d by their con-
tainer. Techniques exist to d e t e r m i n e densities for all three Escaping Vapor
states.
Solids--Figure 7 is a d e p i c t i o n of a solid in w h i c h the
particles are a t o m i c or m o l e c u l a r in scale. The distance be-
tween particles is a regular, r e p e a t a b l e distance. Most kinetic
energy is gone. Only external p r e s s u r e can shorten the dis-
O O
tance between particles. This shortening is called c o m p r e s -
sion a n d affects the ratio of weight p r e s e n t a n d the actual
volume o c c u p i e d by that m a s s of material. If the solid re- 8O OO
o b8
m a i n s c o m p r e s s e d after the external p r e s s u r e is released, the
m a t e r i a l is called inelastic. If it r e t u r n s to the original volume,
it is elastic. Density of solids can d e p e n d on the processing
history. FIG. 8-Simple model of particles of matter in liquid state.
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and calculate the volume or use the solid to displace a mate-

0 O0
0 0 0 rial such as a liquid or a gas which has a known density. The
solid can be shaped by mechanical, thermal, or chemical
0 0 0 0 O0 O0 means. Mechanical means can be employed to cut, carve, and
shape, then weigh. Thermal shaping is changing the solid into
0 0 0 0 0 a liquid using heat to melt the solid, pouring the liquid into a
0 0 0 0 0 0 mold, cooling to form a solid, and then weighing. Chemical
shaping is dissolving the solid in a "carrier" liquid (solvent),
0 O0 0 0 pouring the solution into an open mold, and evaporating the
solvent, leaving behind a solid property shaped to accommo-
00 0 0 0 O0 date testing. The drawbacks of this technique are:
FIG. 9-Simple model of particles of matter in gas I. Complete solvent removal is often difficult.
state. 2. Chemical reshaping of solids can cause problems if the
original solid had small air pockets or if the solvent used is
trapped in these voids, thus actually changing the solid and
accuracy to allow large numbers of users to have access. affecting its apparent density. Solids which demonstrate
These are called liquid pycnometers. Some are also called the latter behavior have a bulk density different than their
gallon weight cups. Within the temperature range of 1~ and skeletal density.
99~ the density of water can be determined. More detail will The principle of buoyancy, discovered in the third century
be given in the section entitled "Liquids." Devices that can by Archimedes, provides a means to determine volume [5].
float in water can be calibrated to show a scale calibrated Determination of volume by displacement requires acquiring
directly in density. When these floats are used along with a a weight in air and a weight in a liquid of known density at the
scale for weighing, the volume of material can be determined testing temperature. Complete submersion of the solid object
[6,7]. or a representative portion of the material in a liquid of
Figure 10 contains drawings of several pycnometers as known density is required while determining the material's
seen in a commercial scientific supplies catalog. The catalog apparent weight. See Fig. 11. The weight difference is equal
text descriptions for two pycnometers have been included to to the weight of the volume of liquid displaced. Knowing the
inform you as to sizes, capacities, materials of construction, liquid's density and the weight difference, the volume for the
etc. The features discussed identify attributes of importance tested portion can be calculated by the following formula:
to the end user.
(6370 km) 2
Liquids have other properties that can be used to test for gDist.... fromEarth ~ 1.0 x 106 km = gE
density. One of these is sound transmission. Replacement of (1.0064 x 106)2
air with a liquid in a container will cause that container to = O.O04g E (5)
shift a tone impulse to higher frequencies. The extent of the
shift is related to the liquid's density and can provide a direct
Solids, Liquids, and Gases as Concrete Materials
measurement with different degrees of accuracy depending
in a Physical World
on the sophistication of the instrument.
For solids, the task is more complex. Two paths are avail- A vast variety of materials exist, and interactions are possi-
able. Either shape the solid into a known geometric figure ble between any of the different types of materials. When an
PYREX | Hubbard-Carmick Specific

Gravity Bottle (Corning No. 1620)
9 1[ Stopper I ASTM
For use in place of $2335 in accordance with ASTM D70;
especially for viscous fluids and semisolid samples.
Conical shape with wide bottom for increased stability and
$2305-05 S2335 S2365 S2367
ground solid stopper, concave on bottom. Capacity, 25
mL; bottom diameter, 40 ram; diameter of mouth, 25
ASTM Crude and Fuel Oil Sampler ram; height without stopper, 45 ram; weight empty, less
As specified in ASTM D270 for sampling light lubricating than 40 grams. With 24112 short length g grinding and
and crude oils, nontransparent gas oils, and fuel oils in 1.6 mm hole in stopper to allow air to escape.
sewage tanks. Copper with 19 mm (0.75 in.) diam neck S2365 . . . . . .
opening and 430 cm (17 in.) brass handle; body ODxH,
95x356 mm (3.75x14 in.); capacity, 950 mL (1 qt).
S2305-05 . . . . . . . . .
FIG. 10-Specific gravity testing--pycnometers. (Courtesy of Sargent-Welch).
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CHAPTER 3 1 - - D E N S I T Y AND SPECIFIC G R A V I T Y 2 9 5
FIG. 11-Displacement technique--A block of wood weighs 5 oz (A). The wood

block is placed in an overflow can filled with water up to the spout (B). The displaced
water flows into the container at the side of the can (C). The weight of the displaced
water equals the weight of the block if the block's density is less than or equal to the
water. If the density of the block is greater than water, the entire volume of the block
is displaced and the weight of the water equals the volume of the block (if tempera-
ture = O~ [5]. From The New Book of Popular Science, 1993 Edition. Copyright
1993 by Grolier Incorporated. Reprinted by permission.
attribute, like density, can be directly m e a s u r e d , it is possible geneous, the density is also a fixed value for a fixed t e m p e r a -
to identify two types of these interactions. The first is ideal ture. W h e n two different materials, h o m o g e n o u s o r het-
b e h a v i o r with respect to the a t t r i b u t e u n d e r investigation a n d erogeneous, are m i x e d together, they b e c o m e a new, hetero-
the a m o u n t of m a s s used. These interactions are well b e h a v e d geneous material, a n d the resultant density is a n e w fixed
a n d p r o d u c e p r e d i c t a b l e a t t r i b u t e changes. The s e c o n d type value for a fixed t e m p e r a t u r e . Depending on w h e t h e r the in-
is nonideal a n d m e a n s t h a t o t h e r interactions are taking place teractions are ideal or nonideal, the density c a n be p r e d i c t e d
t h a n just t h a t of m a s s - t o - m a s s attraction. Materials are ideal b y calculation or a deviation in the density will result. Paints
if w h e n m i x e d t o g e t h e r the s u m of the weight fraction of each are f o r m u l a t e d as ideal mixtures, b u t they d o n ' t always follow
m a t e r i a l times the material's density equals the density deter- this a s s u m p t i o n . The relationships b e t w e e n these values are
m i n e d for the entire mixture. Materials are n o n i d e a l if w h e n given b e l o w [8].
mixed together the s u m of the weight fraction of each mate- , w~pA + wAp~
A + A has A s density w h i c h is (6)
rial times the material's density does not equal the density WA + WA
d e t e r m i n e d for the entire mixture.
S o m e solids can exist with varying degrees of crystallinity B + B has B's density which is WsPB + WBPB (7)
WB+WB
i n c o r p o r a t e d into their solid form. As t e m p e r a t u r e s cycle up
A + B has a n e w density w h i c h m a y be = , >, o r < that of
a n d d o w n in the s u r r o u n d i n g e n v i r o n m e n t of these solids, the
solids will change density as their degree of crystallinity A o r B a n d is WAPA + WspB (8)
changes a n d they move t o w a r d a t h e r m o d y n a m i c a l l y stable w~+w~
form of the solid. where
Finally, m a t e r i a l s can chemically interact w h e n mixed, W = weight of c o m p o n e n t ,
p r o d u c i n g o r a b s o r b i n g h e a t a n d generating a n entirely new p = density of the c o m p o n e n t .
m a t e r i a l with its own u n i q u e attributes. M a n y i m p o r t a n t m a t e r i a l s are available as c o m p l e x mix-
These actions are n o t b a d o r good, b u t they basically exist tures in today's world. These mixtures can be h e t e r o g e n e o u s
and m u s t be t a k e n into c o n s i d e r a t i o n when dealing with mix- in t e r m s of phase. Gasoline for the car a n d lawn m o w e r can
tures such as liquid p a i n t s a n d solid coatings. c o n t a i n b u t a n e dissolved into the heavier h y d r o c a r b o n s .
W h e n a m a t e r i a l (A) is h o m o g e n e o u s , the density is a fixed Paints, inks, a n d c e m e n t s c o n t a i n liquids a n d solids, with t h e
value for a fixed t e m p e r a t u r e . W h e n a m a t e r i a l (B) is hetero- liquid p h a s e either n e u t r a l or reactive. If the liquid's role is
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neutral, it can be a solvent or carrier or plasticizer. If the M E A S U R E M E N T S Y S T E M UNITS,

liquid's role is reactive, it is called a binder, reactive diluent, C O N V E R S I O N S , D E N S I T Y , A N D RELATIVE
or catalyst. DENSITY
Modern paints contain chemically reactive, low-molecular-
weight polymers that, when heated, produce a crossed-linked Today's world uses three systems of measurement [4].
solid and usually volatile by-products. When chemical 1. International System of Units (SI), previously referred to
changes occur, the linear density addition model is correct as the metric system, based upon powers of ten. This was
only by chance. Usually the volume is reduced from chemical called the MKS system, standing for meters (distance),
bonds forming, and as a result, the density goes up. kilograms (force), and seconds (time). A common form of
Theoretical volume solids have been calculated for years in this system uses millimetres, grams, and seconds as the
the coating industry using the linear model. This worked well units. By universally accepted definition, 1.0000 g of dis-
for lacquers, varnishes, and other systems where chemical tilled water occupies 1.0000 cm 3 (or 1.0000 mL) at 4.00~
reactions took place at low levels and were of the oxygen up- 2. The British system uses the British yard (distance), pound
(force), and second (time).
take type, making the final film heavier from oxygen addition.
3. The United States (U.S.) system uses the U.S. yard (dis-
Modern paints react internally, generate by-products of low
tance), pound (force), and second (time).
molecular weight, and actually lose weight during cross-link-
ing and film formation. But, because there has been no good The British and U.S. systems use the same basic linear
way to determine the volume of paint films that is repeatable distance and force units, but, when measuring volumes, the
and reproducible, the practice of calculating volume solids is systems do not have equivalency. A British gallon of water
(volume) weighs 9.993 lb at 77~ (25~ while a U.S. gallon of
still used in the 1990s. (Repeatable means in the same lab,
water weighs 8.321 lb at 77~ (25~ [7].
with the same instrument, time after time, and reproducible
Conversion between the three systems can be accom-
means between different sites or labs using similar but physi-
plished using the following relationships:
cally different instruments like balances, ovens, etc.)
2.54 cm = 1.00 in.
231 in. 3 = 1.00 U.S./gal
453.6 g = 1.00 lb
or
Definitions Related to Density and Specific
277.4 in. 3 = 1.00 British (Imperial) gallon
Gravity
Bulk Density = From SI to U.S.:
Total weight of object including air or water
(9) (2.54 cm/in.)3(231 in)/U.S, gal)/453.6 g/lb
Total volume occupied including air or water = 8.345 cm3.1b/U.S, gal.g (11)
Skeletal Density = (2.54 cm/in.)3(277.4 in.3/British gal)/453.6 g/lb
Total weight of object less air or water = 10.02cm3.1b/Britishgal.g (12)
(10)
Total volume of actual material less air or water
These are conversion factors, which carry particular units.
Surface interactions--These interactions involve wetting of They are used to convert density values for a material at any
solid surfaces by liquids during liquid displacement testing. temperature into a second set of units at that same tempera-
In determining the volume of a material due to displacement ture. The 8.345 factor for conversion to U.S. pounds per
of a liquid, the liquid must come in close contact with the gallon is sometimes confused with the 8.320 value for a U.S.
material surface. When the liquid meets or wets the surface gallon of water at 25~ (77~ [2].
without penetration into the bulk of the material, the volume Density (in the SI system) at any temperature -- density (in
of liquid displaced is equal to the bulk volume of the material the U.S. system) 8.345 at the same temperature.
being tested. When the liquid does not contact and wet the Example for pure water at $~ (39.2~
surface, a thin layer of air exists between solid and liquid.
This also displaces liquid, making the apparent volume of the 1.000 g (SI) = 1.000 8.345 (conversion)
1.000 cm 3
material larger. In tests like ASTM D 2965, where the volume
lb
of paint film being tested is very low, this error can be signifi- = 8.345 at 4~
U.S. gallon
cant. Materials called surfactants can be added to increase
wetting, but they affect the density of the liquid. Where sur- for pure water at 25~ (77~
factants cannot be used, another liquid must be used.
Permeation--When the liquid meets or wets the surface 0.997 04 g (SI) = 0.997 04 8.345 (conversion)
1.000 cm s
with total penetration into the bulk of the material, the vol-
lb
ume of liquid displaced is equal to the skeletal volume of the = 8.321 at 25~
material being tested. If there are small molecular weight U.S. gallon
molecules left inside the bulk of the solid, these can migrate Note in these examples that the volume of space (container
out, leaving the testing liquid in its place. These will change internal volume) has not changed with temperature. But, the
the bulk testing liquid's density as they accumulate. amount of material which can fit into that volume has
www.iran-mavad.com

CHAPTER 31--DENSITY AND SPECIFIC GRAVITY 2 9 7
changed with temperature! Using known volume devices pro- attached to a balance and submerged into a liquid to displace
vides only density values. Temperature must be stated as a some of the liquid's volume. The change in weight is attrib-
significant variable. uted to the weight of the displaced liquid. The plummet's
volume is known, and it is related to displacement of water.
These are related back to water as a calibration liquid, so they
LIQUIDS provide a relative density rather than a true density. With this
device, the sample does not need to be clear because there are
Densities of Liquids--Methods of Determination no markings on the plummet. The devices also allow the
liquid to be at temperatures other than 4.0~ This type of
Buoyancy-Hydrometers device is good for solvents and low-volatility materials. Two
Hydrometers are flotation devices that are calibrated using balances are shown in Fig. 14 and are from recent scientific
water at various temperatures. When placed in clear liquids, lab supplier catalogs [11]. The catalog descriptions have been
the relative density is read directly from the scale on the included because they are concise statements about the de-
hydrometer. The hydrometers range from low-cost, low-pre- vices, their operating principles, ranges, and other relevant
cision, to expensive, high-precision devices. Better-grade hy- information.
drometers also have incorporated thermometers for tem- ASTM method using submersion:
perature corrections and greater independence of reading Test Method for Specific Gravity (Relative Density) and Den-
liquids in an as-is condition. A balance or a known volume sity of Plastics by Displacement (D 792)
device is not needed with this technique. Simplicity is the
advantage of this technique. Shown in Figs. 12 and 13 are two
types of hydrometers. The catalog text has been included to Displacement--Fluid External Media
explain ranges and features unique to these devices. This is a device where the sample-holding chamber is not of
ASTM methods using hydrometers are [9,10] a known, calibrated volume. A helium gas pycnometer can be
Test Method for Apparent Density of Industrial Aromatic Hy- used to determine the volume of a liquid in a metal or glass
drocarbons (D 2935) container. The pycnometer's test chamber volume is first es-
Test Method for Calculation of Volume and Weight of Indus- tablished by determination of gas pressure differences in a
trial Aromatic Hydrocarbons (D 1555) sample chamber and after expansion into a connecting ex-
pansion chamber. Then an independent, empty sample con-
Displacement--Submersion--Specific Gravity tainer is introduced into the gas pycnometer test chamber
Balances and tested. The reduction in volume is allocated to the empty
A specific gravity balance is similar to the hydrometer. It is sample container. The independent sample container's
actually a balance which measures the counter weight ap- weight is measured on an analytical balance. The sample is
plied to balance a plummet submerged in the liquid sample. added to the sample container and weighed. The container
The weight and volume of a mercury-filled elongated glass and sample are tested again to establish a new volume.
bulb (plummet) is determined by comparison with standards The sample volume is (sample + container volume) -
established by regulatory agencies and traceable back to well- container volume. The sample weight is (sample + container
characterized standards, referred to as primary standards, weight) - container weight. Density is (sample weight/sam-
established by national scientific bureaus. The plummet is ple volume). The test is fairly fast. Containers of predeter-
..~i.. =~= . s-w see ~ 7o - _ . . . . . oo
Precision Hydrometers for Light and (~at. NO. Ronqo

Heavy Liquids--175 mm S41885-F 1.000 to 1.070
$41885-G 1.060 to 1.130
A series of short range hydrometers with an accuracy of 0.001, S41885-H 1.120 to 1.190
calibrated 60 ~176 Design corresponds with ASTM S41885-1 1.180 to 1.250
specification E l 0 0 for plain hydrometers. With smooth, easily S41885-K 1.240 to 1.310
cleaned shapes, solid metal ballist, and cemented paper scales. S41885-L 1.300 to 1.370
Subdivisions, 0.001. S41885-M 1.360 to 1.430
FIG. 12-Hydrometers--specific gravity scale--plain design [6].
Sugar Hydrometers with Brix Scale and Enclosed Thermometers--380 mm

Hydrometers are similar to $42436, but provided with a Cat. No. R~nQo
thermometer, range 0 ~ to 50~ in 1~ subdivisions, and with S42440-B 0 to 12
scale of correction values in red. $42440-C 9 to 21
FIG. 13-Hydrometer--sugar with Brix scale and enclosed thermometer [6].
www.iran-mavad.com

both the light weight of glass and the ruggedness of metal, a

"featherweight" construction of anodized, high-tensile air-
craft alloy is employed at a cost consistent with the use of
specialized materials of construction. The Monk cup is a
special design (Fig. 15) and discussed under the topic of
handling entrapped air in samples.
Liquid pycnometers or gallon weight cup vessels are built
with a main body or container volume, a cap or lid with a vent
hole, and sometimes a tare weight object. The tare weight is
used as a counter weight for dual pan balances. The weight
read after correcting for the tare weight is attributed to the
material contained in the vessel at a level which reaches the
top of the vent hole in the cap (see Fig. 16).
Both the vessel and a sample of the material to be tested are
equilibrated to room temperature or a constant temperature
bath temperature by immersion in the bath. Common tem-
peratures for paint and solvent testing are 20~ (68~ and
25~ (77~ because these are temperatures in the human
comfort range. Temperatures greater than these would drive
off solvents. Moisture is not likely to condense out on sur-
faces from being too cool (weight gain drift during weighing),
and volatile materials will not evaporate at a rate that signifi-
cantly affects the weight readings taken (weight loss drift
during weighing). Temperatures colder than these are easily
obtained, but are less comfortable for the tester. However,
any temperature can he used if the temperature is noted and
the vessel volume is corrected for that temperature. If the
bath is used, the vessel exterior must be dried off. This has to
be done with minimum handling to prevent temperature
Chain Balance changes from heat exchange by hands or drying materials.
For liquid densities from O.0001 to 2.110 Next, a portion of the tempered sample is poured into the
Chain gravitometer balance determines specific gravity of liquid with vessel up to the top rim. The lid is carefully placed on the
high degree of accuracy. Uses both plummet displacement principle vessel so that the excess liquid is forced up through the vent
and chain weight system for weighings. No calculations or riders are hole in the lid without coming out around the lid lip. The
needed. excess is carefully cleaned off the surface of the lid and from
Instrument is prebalanced at zero reading by adjusting counter-
around the lid lip. This is a cleaning, not merely a wiping off.
balance weights, Plummet is immersed in liquid sample, Balance is
zeroed again. Single roller-type weight is moved to notch on beam Wiping leaves residues, which affect the results obtained. The
where equilibrium is approached; final adjustment is accomplished by sample-containing vessel is then carefully weighed.
raising or lowering one end of rhodium-plated bronze chain. Specific Afterwards, the vessel and lid are cleaned as soon as possi-
gravity is determined by adding rider and chain-support readings. ble and as well as possible to prevent buildup of residues,
FIG. 14-Specific gravity balances--chain balance and Mohr which will change the vessel's volume. A verification should
Westphal balance with catalog text instruction and comments be performed at frequent intervals with distilled water to
[11]. (Courtesy of Fisher Scientific)
catch inaccuracies from poor cleaning or damage to the ves-
sel surfaces. For improved accuracy, the vessel can be cali-
mined volume can be kept available to help shorten testing brated using pure water at normal reading temperatures.
time. Precision and accuracy are good. No ASTM test exists Divide the gram weight of distilled water by the weight deter-
as yet for this technique [12]. mined by direct testing. This produces a correction factor.
This factor number is multiplied by the weight of the gallon
weight found for an unknown liquid or mixture. If the deter-
Displacement--Known Volume Devices--Fluid
mined density of water was less than expected, a factor
Internal Media
greater than 1.000 is generated. As a result, the vessel's vol-
These are devices of known, internal volume. They have ume is less than expected. Tracking the factor value will alert
many names such as liquid pycnometers, U.S. standard the tester to problems arising from poor cleaning or rough
weight per gallon cups, U.S. mini weight per gallon cups, handling that can damage and alter the testing vessel.
British standard weight per gallon cups, "featherweight" type Sample sizes range from 10 to 84 mL. The combined
weight cups, and Monk cup [7,13]. Liquid pycnometers come weight of the vessel, lid, and sample affect the type of balance
in a variety of sizes, shapes, volumes, and materials of con- which can be used to provide good repeatability and repro-
struction. For precision, glass (inert, light weight, and trans- ducibility. The larger the size, the easier to get a sample
parent) is usually used. For testing demanding repeated use, representative of the bulk material. But the larger the size, the
other materials with reasonable inertness or resistance to harder to remove entrapped air bubbles from the sample
chemical attack, such as stainless steel, are used. To combine introduced during sample collection or preparation. For very
www.iran-mavad.com

CHAPTER 3 1 - - D E N S I T Y AND SPECIFIC G R A V I T Y 299
FIG. 15-Monk cup (weight per gallon cup) (courtesy of C. J. Monk and Journal of
Oil and Color Chemists' Association) [2]. See Ref 2for a discussion of Parts A to M.
volatile solvents, use of larger size vessels offsets the weight u n d e r p r e s s u r e does reduce the e r r o r b u t the e r r o r is far from
drift seen d u r i n g weighing. e l i m i n a t e d as the e n t r a p p e d air is n o r m a l l y not removed, b u t
The p r o b l e m of e n t r a p p e d air can be c o u n t e r e d in two only c o m p r e s s e d as shown in Figs. 17 a n d 18."
ways: "Most materials that are difficult to evaluate can be s i m p l y
a n d a c c u r a t e l y m e a s u r e d b y the following d e p i c t e d proce-
1. The M o n k cup is designed to pressurize the s a m p l e to 150
dure."
lb/in. 2 in a k n o w n volume of space. This p r e s s u r e com-
"A m e a s u r e d weight of the u n k n o w n m a t e r i a l is t h o r o u g h l y
presses the e n t r a p p e d air in the s a m p l e to such an extent
b l e n d e d with the weight of a k n o w n diluent from a full weight
t h a t o c c l u d e d a i r b u b b l e s a r e r e d u c e d to a negligible vol-
p e r gallon cup. The b l e n d is then p l a c e d in the cup a n d the
ume. E n t r a p p e d air of up to 10 vol% can be dealt with by
weight per gallon is d e t e r m i n e d . The value of the u n k n o w n
this technique. The v o l u m e p r o d u c e d is still larger t h a n the
m a t e r i a l is calculated from the f o r m u l a given above. The
true volume, a n d a density e r r o r is still present. E n t r a p p e d
diluent liquid m u s t be c o m p a t i b l e with the m a t e r i a l contain-
air should n o t be a c c o u n t e d for if the air escapes before use
ing the e n t r a p p e d air a n d it m u s t be thin e n o u g h in viscosity
or the air is a n artifact of s a m p l e mixing before testing. The
to allow e n t r a p p e d air to rise to the blend's surface a n d
M o n k cup is large a n d heavy a n d requires use of n o n a n a -
lytical b a l a n c e s [2]. Figure 15 is a s c h e m a t i c d i a g r a m a n d escape. In the case of particulate, such as pigment, the liquid
picture of a M o n k p r e s s u r e weight-per-gallon cup. m u s t be able to wet the particle surfaces a n d displace air in
2. An alternative technique is to mix a m e a s u r e d weight of the pockets o r depressions on the surface."
u n k n o w n density m a t e r i a l with the weight of a k n o w n ASTM m e t h o d s using k n o w n volume devices are [13,14]:
diluent from a full weight p e r gallon cup. The blend is t h e n Test M e t h o d for Density or Relative Density of Pure Liquid
p l a c e d b a c k into the cup and then weighed. The following, Chemicals (D 3505)
enclosed in quotes, is copied directly from the GARDCO Test M e t h o d for Density of Paint, Varnish, Lacquer, a n d Re-
m i n i c a t a l o g N u m b e r 9, including the diagrams, with per- lated Products (D 1475)
m i s s i o n from GARDCO [7].
X ~ WunknownBlend wt per gallon =

Sonic Frequency Shifts
(Wunk. . . . + Wdiluentcup weight -- 10 Blend wt per gallon) Waves of air r e a c h i n g a h u m a n ear are r e c o g n i z e d as
WB sound. The p i t c h of a s o u n d is related to h o w m a n y waves
(13)
(W + a - 10B) r e a c h o u r ear p e r unit of time. This unit of t i m e is referred to
as frequency. Waves are m a d e b y an object moving in the
w h e r e A = Wdiluent cup weight media: air or liquids o r even solids. The m e d i a t o u c h e d by the
"Heavy-bodied m a t e r i a l s w h i c h e n t r a p air p r e s e n t a prob- wave can pass this m o v e m e n t t h r o u g h itself, W h e n a b o u n d -
lem in true weight p e r gallon (density) m e a s u r e m e n t s . Air ary between two m e d i a of different densities is e n c o u n t e r e d
e n t r a p m e n t causes the a p p a r e n t vo]ume of a m a t e r i a l to be by the wave, two actions occur: (1) s o m e waves are reflected
g r e a t e r t h a n actual a n d density o r weight p e r gallon calcula- back; (2) a p o r t i o n of the waves are passed into the new m e d i a
tions are low a n d erroneous. The practice of m e a s u r e m e n t b u t with their frequency changed.
www.iran-mavad.com

STAINLESS STEEL
MINI WEIGHT PER GALLON CUPS
METHOD OF USE
1. Determine the weight.of a clean cup in grams. As an alternative, the cup
may be supplied with an accurate tare weight for use with two-pan
laboratory balances. Note: Do not interchange tare weights between
cups as each cup and tare weight is matched.
2. Remove cover and fill to within 1.7mm of rim with material to be tested.
3. Carefully replace cover so that the air and excess material is expelled
through vent.
4. Wipe over cover to remove surplus and reweigh. By subtracting the
original weight of the cup, the weight of the contents will be found. If
a tare weight was used at the start, the balance will show the weight of
the contents. Clean thoroughly immediately after use.
TEMPERATURE WEIGHT
C. F. Grams
21 69.8 8.329
22 71.6 8.327
23 73.4 8.325
24 75.2 8.323
25 77.0 8.321
26 78.8 8.319
27 80.6 8.316
DETERMINING ACCURATE CUP FACTOR

Comparative results on different materials measured in the same cup are accurateto within
the limits of sensitivity of the balances used. Comparative results between cups may be
improved by determining a cup factor as follows: Divide 99.925 by the gram weight of
distilled water held by the cup at 25~ to determine the cup factor. For example, if the weight
of water held by the cup is 99.800 grams, divide 99.925 by 99.800 which is 1.0013. Multiply
all cup readings by this factor. In the same manner, if the cup holds 100.200 grams, divide
99.925 by 100.200 which is 0.9973 and aH cup readings should be multiplied by this factor.
FIG. 16-Mini-weight per gallon cups [7].
Changes in density also lead to changes in frequency. This

can be d e m o n s t r a t e d b y filling a m a t c h e d set of w a t e r glasses
to different levels with water, t h e n striking each glass lightly
to p r o d u c e a sound. The h i g h e r the w a t e r level, the higher the
tone. Just as the frequency changes from a n e m p t y glass (air,
less dense) to a high frequency tone w h e n filled with w a t e r
( m o r e dense), the r e p l a c e m e n t of liquids of differing densities
also shifts the frequency for glasses filled to the s a m e level.
I =:s L :RAMs
I
This is the principle for several digital density meters com- W A B
mercially available today. FIG. 18-Diagram for mixing known and unknown density ma-
terials [7]. Figure provided by Paul N. Gardner Co., Inc.
PRESSURE
i i i APPAREN T
VOLUME Measuring devices have been devised using a glass tube, an
UNDER
cPRESSUR] oscillator, a n d a sensor. The oscillating frequency of the tube
changes w h e n air is r e p l a c e d with a liquid. The i n s t r u m e n t
) TRUE can use air a n d w a t e r to establish a set of constants, called A
VOLUME
WITHOUq a n d B, for the following relationships [15]
AIR
A = (T2 - T~z) + (dw - da) (14)
FIG. 17-Liquid with entrapped air [7]. Figure provided by
Paul N. Gardner Co., Inc. B = T 2 - (A .da) (15)
www.iran-mavad.com

CHAPTER 31--DENSITY AND SPECIFIC GRAVITY 301
where SOLIDS
Tw = observed period of oscillation for cell con-
taining water, Densities of Solids--Methods of Determination
Ta = observed period of oscillation for cell con- With solids, determining the volume for a k n o w n weight of
taining air, the material is a challenge for several reasons. First, the form
dw = density of water at test temperature, is fixed and direct, accurately known volumes are the excep-
da = density of air at test temperature, tion rather than the rule. Second, solids are seldom homoge-
t = test temperature expressed in degrees Kel- neous in their density. Processing often introduces voids or
vin, regions of differing degrees of crystallinity, both of which
p = test barometric pressure expressed in t o m effect density. For large objects, displacement techniques as
da (g/mL) = 0.001 293 (273 + t) x (p + 760) well as sonic shifts are useful. For powders and small parti-
dw (g/mL) = 0.997 04 at 25~ (273 + 25 = 298~ cles, displacement and density by mixing with liquid diluent
Constant A is used by the instrument's c o m p u t e r to calcu- are the most c o m m o n techniques. For thin films, only dis-
late constants Kc and Kcr. Constant B is used by the instru- placement techniques are useful.
ment's computer to return the reading for air density.
Modern digital density instruments are equipped with
heating and cooling devices internal to the instrument, such Direct Volume Measurement by Pycnometer
that the sample can be equilibrated within the instrument in Pigments are insoluble, solid particles used to impart color
a matter of seconds. This leaves the pressure term, P, as a or light reflectance in paints. To provide more than an appar-
visible variable. Pressure changes can occur over a period of ent density, special steps must be taken. ASTM Method for
time due to weather changes. Specific Gravity of Pigments (D 153) is a set of three varia-
The sample tube must be cleaned after each use. The tube's tions on the diluent pycnometer technique described in Fig.
condition needs monitoring to verify that it is at original 18. It uses a v a c u u m p u m p and v a c u u m desiccator or bell jar
condition. Frequent calculation of the instrument cell con- to reduce the pressure on a sample of solid pigment. Varia-
stant Kc overcomes both of these problems. tion A places a weighed sample of pigment in a dry, weighed
For density values glass pycnometer. White kerosene is then added to cover the
1 d~-d~ pigment. The pycnometer and sample is then placed in the
K~ - - - - (16) dessicator or bell jar and slowly evacuated to remove air en-
A r~w- T~ trapped on the irregular surfaces of the pigment. This is a
dmaterial -- dw + Kc.(T~ - T2) (17) method to wet the pigment surface and remove the contribu-
tion of entrapped air in the pigment. After all bubbling stops,
For relative density values
air is let back into the jar and the pycnometer is filled to the
1 . 0 0 0 0 - d~ top with kerosene and weighed. Variation B evacuates the
Kc, - (18) pycnometer before the kerosene is added. Most of the kero-
r~w- T~
sene is added to the pycnometer while it is under vacuum.
dmatc,iaI -- 1.0000 + Kcr.(T2 - T~) (19) The pycnometer is topped off with kerosene after r e t u m i n g to
where normal pressure. Variation C uses a measuring burette to add
the kerosene so that volume of kerosene added is k n o w n [2].
observed period of oscillation for cell con-
ASTM methods using pycnometer are [2,16]:
taining water,
Ts = observed period of oscillation for cell con- Test Methods for Specific Gravity of Pigments (D 153)
taining sample, Test Method for Density (Specific Gravity) of Solid Pitch
Kc ~-" instrument constant for density,
(O 2320)
K~r -- instrument constant for density,
d~ (g/mL) = 0.997 04 at 25~ (273 + 25 = 298 K) density Displacement of Liquids
of water at test temperature, and
t = test temperature expressed in degrees Kel- This was discussed in the section on Solids, Liquids, and
vin. Gases as concepts and under ideal conditions.
Small process computer chips built into commercially Density gradient column systems (Fig. 19) are another
form of submersion test methodology, inverted from the
available instruments handle all the necessary calculations.
plummets of the density balances. Here the fluid is the cali-
Small sample volumes (1.0 to 2.0 mL) are used so heteroge-
brated, k n o w n test media, and the solid is the unknown. A
neous samples like paint must be well mixed. The samples
vertical column tank with black background is carefully filled
must be free of entrapped air. Small amounts of air cause
with a mixture of liquids in a very strict order to establish a
fluctuations in the readings. Use of dilution with a compatible
heavy-to-light liquid density gradient. Measurements are
solvent (of k n o w n density) to thin the sample can be used if
made by adding in both u n k n o w n solid materials such as
the thinning does not cause pigment dropout. The contribu-
fibers, film pieces, powders, and glass particles and reference
tion of the thinner solvent can be calculated and backed out. materials of known density. The particles will sink to the level
The ASTM method using the digital density meter is [15]: of their own density. Using the proper reference materials,
Test Method for Density and Relative Density of Liquids By exact matches can be established within 0.0001 g/mL. There
Digital Density Meter (D 4052) is a problem when the sample interacts with the fluids and
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For accurate density determi- The main problem is to provide a sufficient amount of free
nation of small solid samples to paint film to test at a valid film thickness. Films that are too
0.001g/mL. Conform to ASTM thick can retain solvents. Films that are too thin are very hard
D1505-68 for testing plastics.
Measurements are made with to handle. Free films develop static charge buildups which
reference to standard glass further complicate the testing procedure.
floats calibrated within Dry powders are a second candidate for this technique.
___0.0001g/mL. Fibers, irregular Helium gas displacement eliminates the need for the vacuum
fragments, pieces of film, pow-
ders and glass are suitable. pump and the kerosene used in ASTM Method D 153, Test
Several determinations can be Methods for Specific Gravity of Pigments, to replace the air in
made at same time. the voids and available surface cavities. The drawback is that
In wide use for testing poly- the fine powder is easily blown around. The instrument must
olefins, fluorocarbon polymers,
nylons, PVC. Can separate be designed to eliminate powder travel and to keep the fine
natural and synthetic fibers. particles from the valves and seals. Helium pycnometery may
Can assay factors affecting become the method of choice as methods are developed and
density such as degree of crys-
exchanged in the standard testing methods arena [2].
tallinity of plastics, concentra-
tion of isotopic content, pres- ASTM methods using Helium Pycnometery [21]:
ence of trace amounts of boron Test Method for Density of Solid Pitch (Helium Pycnometer
in silicon.
Method) (D 4892)
Sonic Frequency Shifts

The sonic frequency shift, principle and equations, has
been discussed previously. Use of the sonic technique is lim-
ited to continuous objects which can be cut and shaped.
Powders and small particles can he suspended in liquids and
FIG. 1 9 - D e n s i t y gradient column systems with text from sup-
tested using the equipment discussed previously and using
plier catalog [6]. (Courtesy of Fisher Scientific) the equations noted earlier under Sonic Frequency Shifts.
When the instrument uses solids instead of liquids, several
considerations change. A glass tube is no longer used. The
absorbs them or interacts in other chemical ways which per-
solid specimen must be cut into a rectangle with a smooth
turb the normal test action as with inert materials such as
glass or plastics. Powders with irregular surfaces can also surface. Surface flaws will introduce errors in the readings.
experience surface wetting problems and air pocket en- A sonic sensing head is attached to the solid specimen
trapment. Densities can be determined from 0.79 to 2.89 (approximately 75 mm in thickness), and measures the veloc-
g/mL with this technique [24]. ity of sound transmitted through the specimen. Solid speci-
The test is of long duration, requiring a settling time of mens require a minimum conditioning time period under
usually several hours. Several caution notes are included controlled temperature and humidity conditions before test-
concerning thin film samples and their handling which could ing. A calibration curve can be established using materials of
change the density. Potential users should review ASTM known density. The published use is limited to polyethylene
D 1505 to assess the applicability of this technique to their plastics. Alternative methods are probably cheaper or less
own personal needs and use. time/labor consuming.
ASTM methods using displacement of liquid and gases are ASTM method using Ultrasound [20]:
[17-19]: Standard Method for Density of Polyethylene by The Ultra-
Standard Test Method for Volume Nonvolatile Matter in sound Technique (D 4883)
Clear or Pigmented Coatings (D 2697)
Test for Specific Gravity (Relative Density) and Density of
Plastics by Displacement (D 792)
Standard Test Method for Density of Plastics by the Density- Apparent Density
Gradient Technique (D 1505)
Many pigments or powders are tested without regard to the
Displacement--Gases air entrapment on the particle surfaces or in the voids be-
tween where the particles touch. These materials are placed
Helium pycnometers have been available for a number of
in a graduated transparent container, and a vibrator is
years with many people expressing interest in using these
touched to the container wall. The particles pack down, and a
devices to determine the volume of solids of known weight.
weight is taken. This is referred to as apparent density.
These instruments are usually relatively expensive and only
ASTM methods based on apparent density include [22-24]:
recently have become sufficiently automated to reduce the
intense manual labor required to do a good job. Test method Test Methods for Methylcellulose (D 1347)
activities are being pursued with ASTM paint committee Test Methods for Sodium Carboxy Methylcellulose (D 1439)
D 01.21 for thin film (ASTM D 2697) volume solids [1,12]. Test Methods for Hydroxypropyl Methylcellulose (D 2363)
www.iran-mavad.com

CHAPTER 31--DENSITY AND SPECIFIC GRAVITY 303
Below Critical Pigment Volume At or Above Critical Pigment Volume
///////
FIG. 20-Pigment volume relationships.
PAINT VOLUME SOLIDS c a r r i e r such as a metal disk or a l u m i n u m foil. W h e n the film

is a free film, static charges c a n build up a n d cause s a m p l e
Paint is a m i x t u r e of m a t e r i a l s that is designed to p r o t e c t l o a d i n g a n d h a n d l i n g problems. The test i n s t r u m e n t is n o t
a n d beautify a substrate. W h e n p a i n t is sold, it is sold by inexpensive, b u t it is highly a u t o m a t e d a n d m i n i m i z e s the
v o l u m e as gallons or liters. W h a t the c o n s u m e r wants is the h u m a n l a b o r r e q u i r e d to a b o u t 5 m i n p e r test.
m o s t coverage for the money. C o m m e r c i a l painters a n d origi-
nal e q u i p m e n t m a n u f a c t u r e r s p a i n t surfaces to a m i n i m u m
thickness called "hiding." They k n o w the square footage o r
square m e t e r surface a r e a they need to cover. W i t h the thick-
CRITICAL P I G M E N T V O L U M E S
ness for hiding known, a v o l u m e of solids n e e d e d for p a i n t i n g
a h o u s e o r a n a u t o m o b i l e can be calculated. G o v e r n m e n t
Definition
regulators w o u l d like to k n o w the volume of volatile o r g a n i c A c o n d i t i o n w h e n a p a i n t has too m u c h p i g m e n t a n d too
m a t e r i a l i n c l u d e d in a gallon of paint. A ratio of volume little p o l y m e r such that internal voids are c r e a t e d w h i c h t r a p
volatiles to volume solids w o u l d be a m e a s u r e to c o m p a r e air o r solvent in the v a p o r state [1].
p a i n t p r o d u c t s in t e r m s of pollution contribution.
Effect
Theoretical Calculations o f Paint Volume Solids
A solid is c r e a t e d w h i c h has a h i g h e r a p p a r e n t v o l u m e t h a n
F o r m a n y p a i n t systems in c o m m e r c i a l use today, a straight really exists. See Fig. 20.
calculation of solids content can be p e r f o r m e d with g o o d
results using the densities a n d weight p e r c e n t content of ma-
terials w h i c h c o n t r i b u t e solids to the final product. F o r m a n y Relationship to Volume Solids
o t h e r systems, however, this calculated a n s w e r does not ac-
count for a d d i t i o n a l r e a c t i o n b y - p r o d u c t s o r provide infor- The p r e s e n t volume solids test uses liquids w h i c h are un-
m a t i o n a b o u t h o w the density of the m a t e r i a l has c h a n g e d able to p e n e t r a t e into the void areas. A larger v o l u m e of w a t e r
w h e n cross-linking occurs. F o r these systems a n analytically will be displaced, a n d the a p p a r e n t weight loss will be greater
tested a n s w e r is needed. The a n s w e r w o u l d relate to the pres- in water. The resin is s p r e a d out over the p i g m e n t surfaces
ent U.S. E n v i r o n m e n t a l Protection Agency's (EPA) Reference a n d will experience less o p p o r t u n i t i e s to cross-link o r tangle.
M e t h o d 24: Guidelines of Testing for VOC at 110~ for 1.00 The b i n d e r will not cure well, a n d the d u r a b i l i t y will be poor.
H o u r Bake [1].
Analytical Determination o f Paint Volume Solids REFERENCES

Test M e t h o d for Volume Nonvolatile M a t t e r in Clear o r [1] Manual on Determination of Volatile Organic Compounds,
P i g m e n t e d Coatings (D 2697) is the latest version of this test. MNL4, J. J. Brezinski, Ed., ASTM, Philadelphia, 1989, pp. 1-13.
The test is b a s e d on d i s p l a c e m e n t of liquids, usually w a t e r o r [2] Paint Testing Manual, ASTM STP 500, G. G. Sward, Ed., ASTM,
kerosene. Complications b y c u r e d p a i n t surfaces cause this Philadelphia, 1972, pp. 165-172.
test m e t h o d to be suspect a n d is not accepted by EPA for their [3] Lee, G. L., Principles of Chemistry--A Structural Approach, In-
r e g u l a t o r y purposes. A n e w m e t h o d b a s e d on volume deter- ternational Textbook Co., Scranton, PA, 1970, p. 40, "Gases," pp.
m i n a t i o n by gas (helium) d i s p l a c e m e n t is u n d e r d e v e l o p m e n t 64-88, "Solids and Liquids."
[4] Sears, F. W. and Zemansky, M. W., University Physics, 3rd ed.,
a n d evaluation [1]. The h e l i u m is a pervasive gas that behaves
Part 1, Addison-Wesley Publishing Co., Palo Alto, CA, 1963, pp.
closely to an ideal gas. W h e r e p a i n t surfaces are h a r d to wet 102-107.
with water, the h e l i u m has no p r o b l e m getting very close to [5] The Book of Popular Science, Vol. 2, Grolier Society Inc., New
the p a i n t surface a n d displacing air residing at the surface. York, 1966, pp. 30-32, 317-318.
The test c h a m b e r s are usually from 5.0 to 30 c m 3 in volume. [6] Sargent-WelchCatalog, 1992, pp. 39, 104, 149, 752,756 (Pycnom-
The p a i n t s a m p l e is i n t r o d u c e d as a free film o r a t t a c h e d to a eters and Hydrometers).
www.iran-mavad.com

[7] Gardco New Paint Testing Instruments, Mini-Catalog No. 9, Paul [16] Test Method for Density (Specific Gravity) of Solid Pitch
N. Gardner Co., Inc., Pompano Beach, FL, 1992, pp. 36-38, (D 2320-87), Vol. 04.04, ASTM, Philadelphia, 1992, pp. 168-169.
231-239. [17] Test Method for Volume Nonvolatile Matter in Clear or Pig-
[8] Practice for Calculating Formulation Physical Constants of mented Coatings (D 2697-86), Vol. 06.01, ASTM, Philadelphia,
Paints and Coatings (D 5201-91), Vol. 06.01, ASTM, Philadel- 1993, pp. 168-169.
phia, 1992, pp. 998-1001.
[18] Test Method for Specific Gravity (Relative Density) of Plastics by
[9] Test Method for Apparent Density of Industrial Aromatic Hy-
Displacement (D 792-91), Vol. 08.01, ASTM, Philadelphia, 1992,
drocarbons (D 2935-91), Vol. 06.03, ASTM, Philadelphia, 1992,
pp. 647-651. pp. 288-291.
[10] Test Method for Calculation of Volume and Weight of Industrial [19] Test Method for Density of Plastics by the Density Gradient
Aromatic Hydrocarbons (D 1555-91), Vol. 06.03, ASTM, Phila- Technique (D 1505-90), Vol. 08.03, ASTM, Philadelphia, 1992,
delphia, 1992, pp. 596-601. pp. 455-460.
[11] Fisher Scientific Catalog, 1992, pp. 1448-1449 (Chain Balances [20] Test Method for Density of Solid Pitch by Helium Pycnometer
and Den, Gradients). Method (D 4892-89), Vol. 04.04, ASTM, Philadelphia, 1992, pp.
[12] D01.21.26 Sub Task Group Investigating Helium Gas Pycnom- 354-355.
etry for Paint Volume Solids, 1990-1992, author's personal [21] Test Method for Density of Polyethylene by the Ultrasound
involvement in D01.21. Technique (D 4883-89), Vol. 06.02, ASTM, Philadelphia, 1992,
[13] Test Method for Density or Relative Density of Pure Liquid
pp. 669-670.
Chemicals (D 3505-91), Vol. 06.03, ASTM, Philadelphia, 1992,
pp. 677-687. [22] Test Method for Methylcellulose (D 1347-89), Vol. 06.02, ASTM,
[14] Test Method for Density of Paint, Varnish, Lacquer, and Related Philadelphia, 1992, pp. 226-231.
Products (D 1475-90), Vol. 06.01, ASTM, Philadelphia, 1992, pp. [23] Test Methods for Sodium Carboxymethylcellulose (D 1439-89),
178-180. Vol. 06.02, ASTM, Philadelphia, 1992, pp. 253-260.
[15] Test Method for Density and Relative Density of Liquids by [24] Test Methods for Hydroxypropyt Methylcellulose (D 2363-89),
Digital Density Meter (D 4052-86), Vol. 05.01, ASTM, Philadel- Vol. 06.02, ASTM, Philadelphia, 1992, pp. 355-363.
phia, 1992, pp. 226-229.
www.iran-mavad.com

MNLI7-EB/Jun. 1995
32
Particle-Size Measurements
by George D. Mills I
PARTICLE-SIZEMEASUREMENTASSOCIATEDWITH the paint and age particle size of the manufactured powder. Often, of equal
coatings industry has broadened in scope considerably over importance, is the amount of very small particles present.
the past few decades. Not only must we evaluate the size, These "fines" affect fluidization and electrostatic application
shape, and size distribution of the pigments, fillers, and emul- characteristics of the powder. Although an understanding of
sified resin particles used in the formulation of the coating the relationships of powder properties to product application
system, but major efforts are now put forth to address envi- characteristics and performance is important, quality
ronmental and applicator's health problems that are specific assurance/quality control (QA/QC) requirements demand
to particle size and nature. Environmental and economic high-speed, on-line (real-time) monitoring. This demand for
concerns have been a substantial driving force in the develop- rapid, accurate analysis of particle characteristics has been a
ment of powder coating technology, which requires monitor- driving force in the development of current instrumentation.
ing finished powder size and size distribution to ensure con- The availability of low-cost computers and pertinent software
sistent application parameters. as well as highly reliable and stable energy power sources and
We have learned that the size, shape, and nature of dust detectors have allowed the development of fast, accurate,
particles in the air we breathe during the manufacture, appli- broad spectrum, and "in-process" instrumentation. The de-
cation, and abrasive removal of paints are of utmost concern velopment of robust solid-state laser diodes has allowed the
to our health. Airborne dusts of silica, asbestos, as well as replacement of bulky gas lasers, which required optical table
lead- and chromium-laden paint debris generated during stability. Further, the development of fiber optics, as well as
abrasive blasting are serious health threats. In an effort to the technology associated with its ease of alignment, has
protect the general public, government regulations now ad- assisted in downsizing the footprint of some current genera-
dress the monitoring of small respirable dust particles of less tion instrumentation.
than 10/xm ("RI0" particles) during the abrasive removal of A major objective of this chapter is to provide an under-
certain coatings. standing of the various methodologies available for evaluat-
In the production of electronic microcircuits, chips, and ing particle size, shape, and distribution. The hiding power
semiconductors, photo-resist coatings are applied to silicon and light transmission characteristics of coatings are greatly
wafers with line-to-line resolution of fractions of a micron. affected by the particle size of included pigments and fillers.
Dust particles, which are a fraction of this size, if allowed to Tensile strength of the cured system, water and gas vapor
contaminate the coated surface, will cause the production of transmission coefficients, chemical resistance, and interface
defective chips. Dust has forced the development of more anticorrosive activity are only a few areas impacted by the
sophisticated clean-room technology in recent years. The re- size, shape, nature, and size distribution of the pigments and
ject rate of produced microchips caused by defects in the fillers formulated into the coating.
coating as a result of ultra-small particles of dust is a major This chapter will allow an educated choice of technologies
problem. based on the size-dependent measurement most related to
As technology advances in the evaluation of smaller-size the desired property of importance. An appreciation of the
particle systems, materials used to standardize and calibrate mathematics involved will aid in determining and under-
the measuring/monitoring equipment must be developed. standing the limitations and potential errors inherent in the
The necessity for standard traceable test materials, i.e., from measurement.
the National Institute of Standards and Technology (NIST),
formerly NBS, which are required to ensure the reliability of
the measurements, has led to secondary industries that pro-
History of Particle-Size Analysis
duce these standards from various materials. The earliest reported particle sizing was about 150 B.C. in
Due to pressing global concerns with solvents emissions as Greek and Roman mining manuals using sieves made of lea-
well as the associated economic benefits, powder coatings as ther, woven hair, and planks. The Germans introduced wire-
a class have grown at a very fast rate over the past 20 years. woven screens in the 15th Century. Microscopes were report-
Many properties impacting the production, delivery, applica- edly used in the 1700s for size analysis. Automated ma-
tion, and film-forming characteristics are related to the aver- chinery was developed in the 1800s for weaving metal-wire
sieve fabric. In the late 1800s to early 1900s, standards were
~President, George Mills & Associates International, Inc., P.O. Box developed defining sieve sizes. The first apparatus of record
847, Humble, TX 77347-0847. used for classification of pigment particles into different sizes
305
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was reported by Thompson [1] in 1910. Oden proposed the ticle size and shape of pigments and extenders on the optical
use of gravity sedimentation as early as 1916 [2,3]. and physio-chemical properties of coating systems.
Energy sources of various wavelengths, employing many Many surface properties are impacted by the pigment's and
different configurations, have been used to measure particle filler's particle size and nature of which gloss is one of the
size. Visible light photometry was reported by Stutz and most prevalent. While the larger-size particles can "protrude"
Pfund [4] in 1927. Gamble and Barnett [5] employed radi- through the surface of the coating, causing a surface
roughness related to the size of included particles, extremely
ation in the near-infrared region. Atherton and Peters re-
fine particles can affect gloss by adsorbing binder to a point
ported using light-scattering techniques in 1953 [6]. The elec-
that the gloss is decreased due to a lack of available binder at
tron microscope found use in the 1940s for characterizing the coating surface. The "oil adsorption" of the pigment is a
very small particles as well as to define the corresponding function of its surface area and increases as the average
surface topography. The invention of the laser and diode particle size decreases. The "critical pigment volume concen-
array detectors opened the way for developing the fast light- tration" (CPVC) exists at a pigment loading at which there is
scattering and blocking instruments widely used in the 1990s. insufficient binder solids to completely wet out the included
filler and pigment particles. Coatings formulated above the
CPVC cannot be glossy. Abrasion resistance of the coating
Importance of Particle-Size Analysis may be increased by the addition of hard fillers such as silica.
As the physical properties of paints, coatings, and polymers The relationship between particle dimensions and film prop-
in general are impacted by the size, shape, and size distribu- erties is depicted in Fig. 2. The National Paint, Varnish, and
tion of the fillers included in the formulation, it is imperative Lacquer Association has published a Pigment Index that
that characterization of the pigment and filler system be cor- gives information on the particle size of many of the pigments
related with the physical properties of the coating. available on the American market [12].
Because of the early importance of zinc oxide as a pigment Other coating properties impacted by variations in particle
in oil-based paints and its existence in multi forms and size and shape include the efficiency of contained UV block-
shapes, this material was studied in the 1920s and 1930s. ers and absorbers such as carbon black pigments. The use of
Bunce [7] found that as the average diameter of zinc oxide in acicular pigments such as Wollastonite (asbestos free) are
a paint increased from 0.19 to 0.31/zm, the elongation of the popular in many types of coatings. The tensile and compres-
film increased and the load at the breaking point decreased sive strength of coatings also can be modified by judicial
(Fig. 1). Eide [8] showed that coarse acicular zinc oxide choice of particle size and shape, and gas vapor and molecu-
imparted greater durability to a paint than did "round" zinc lar water transmission of a coating can be altered with the
oxide. In related studies, Morris [9] and Nelson [10] found proper choice of pigment loading and size.
evidence that acicular asbestine of a wide distribution of sizes The coalescent and film-forming characteristics of emul-
favorably influenced the durability of paints, and a review by sion binders are impacted by the particle size of the dispersed
Jacobsen [11 ] cites many examples of the significance of par- resin particles. Cold touch up, brushability, and mechanical
3c .SO~ Z/NC OXIDE 50Z 8 C W L P/I/NTS

-- -- 807.Pel Hum
P/~ 57:. - Veh 45:.
Vgh- :?~w (/#(/Med/urnBod/ed(J.SZ)L/nseed0/I~. Des~ca/ed
SzY1~[ ~:P4RTKLE 31ZEf'~
I .19
9 25
3 .51
Sc~n~,stre~/e~~ follows
6 Days in ca~net(25"C }5~/I) 13
/c~ L~_~/s on roof (Ou/doorEx )
I D E I/POT Con~2///on/n:
II /2
I j , ,
/ I/ /'5
I / 9
/ / I ~ ;
jJ l / ,iJ
5 /: :/I: / I
/1" i ~
J
0 5 /0 20 ~5 50
L o # d - ~ / o g m m s p e r S y Cm
FIG. 1-Stress-strain curves of some paint films. These illustrate the effect of the
particle size of zinc oxide on the strength of paint films.
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CHAPTER 32--PARTICLE-SIZE MEASUREMENTS 307
Icm
DETECTION TYPE OF
I DISPERSION
.I cm mm
ULTIMATE SIZE OF uJ
o w
-->.
HEGMAN COATING TYPICAL PIGMENT <,,,
~ IOMIL GRIND APPEARANCE PARTICLES z
,01 cm O0~u =o
:- 4 VISIBLY COARSE
I MIL
9 f ~(OPENING OF 325 MESHSCREEN)--~
6 INCREASING z
.O01cm O~ 7 TEXTURE LtJ
13.
o
71/2 1 MAGNESIUM SILICATE ( T A L C )

0 z
bJ
.I MIL 7 3/4
DECREASING CALCIUM CARBONATE ~_j~r
o O.
tO
GLOSS CALCIUM SULFATE
.0001 c m ~u BARIUM SULFATE 3E
t IRON OXIDE , ZINC OXIDE
IO-Scm I,u 8
PERFECT
GLOSS
LEAD S U L F A T E , LITHOPONE
TITANIUM DIOXIDE
z~
oo
t~J
4QcJ~
PHTHALOCYANINES p-u~ 5Q:
IO'Scm )m,u Do
ujn~
DYES it.) z o r
o foQ
10"Tcm ~/u (10/~)

CARBON BLACKS
3_
iO-acm ~,
FIG. 2-Dimensions of granular pigments and their relation to surface properties (from Ref 12). (Courtesy of the Journal of Paint
Technology.)
stability during pigment dispersion are a function of proper- chance that the sample selected will be identical to the bulk
ties that are related, in part, to polymer particle size. Surfac- material.
tant demand and effectiveness are a function of polymer par-
ticle size (as well as other binder variables). Because of the
Theoretical Considerations of Variance in
importance (dependence) of many coating properties on the
Sampling
small finite size of the pigment, fillers, catalysts, and poly-
mers formulated into the coating, the demand for rapid, To obtain a representative sample, the sampling process is
accurate analysis of particle characteristics has lead to the usually divided into several steps during which a conscious
refinement of many techniques. effort is made to reduce bias. The bulk material is usually
obtained in huge, ton lots. The first sample reduction pro-
vides the "gross" sample, which is on the order of kilograms.
This sample is then reduced to the "laboratory" sample,
CONSIDERATIONS IN SAMPLING which is on the order of grams. The actual evaluation sample
TECHNIQUES introduced to the instrument is on the order of milligrams.
The reduction process will almost always introduce some
Normally, when a particle-size determination is made, one bias, depending on the actual spread in the distribution. This
will not work with the total collection of particles comprising bias will diminish as the consistency approaches unity, i.e.,
the bulk sample. A "representative" collection of particles is all particles approach being identical. The bias exists because
usually chosen. This sample is then reduced in size a few the physical forces acting on the particles in a collection are
more times until only a few milligrams remain for the actual not the same, but are, in fact, size dependent. The "fines" act
instrumental testing. The assumption is usually made that differently in a pile than will the course particles. Their angle
the fraction actually evaluated is, in fact, "identical" in parti- of repose is different, often resulting in particle stratification
cle size, size distribution, shape, and nature to the total of the and some segregation.
bulk material. This sample test fraction, which usually does There are some established rules that must be followed to
not exactly represent the bulk, can be a major source of error, minimize this bias. The "perfect" sample is one in which the
introducing considerable bias and distortion to the results. differences seen between the evaluated characteristics and
The reliability of any measurement depends on the degree of those that actually exist in the bulk can be ascribed to the
representitiveness of the test sample. Thus, the sampling expected number variations described by statistics. For a
technique is as important (if not more so) than the actual sand (A) and sugar (B) mix, the probability that the n u m b e r
particle-size measurement, though in reality there is little fraction, p, of (A) in the bulk actually is represented by the
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number fraction (Pi) in the sample is computed from the 1 show the values obtained via each method as well as the
number of actual particles in the bulk (N) and the reduced expected standard deviation from the known sample.
sample (n) [13]. The equation is as follow Cone and quartering is a procedure in which the powders
are piled into a cone. The cone heap is then carefully pushed
Var(pi)-P(1--P) (1) down fiat and divided into four equal sections. The assump-
tion is that the cone will be symmetrical about its central axis
Theoretically, the expected deviation (i.e., standard devia- and the flattened sections will all be representative of the bulk
tion), ~, is the square root of the variation. Since the use of mixture. A problem exists as it is very difficult to produce
the weight fraction is often more convenient, the equation for perfect symmetry, which results in some size segregation
variance is given by from the center out. The technique is also operator depen-
dent, and tests showed this technique to give the largest stan-
Var(Pi)-P(1-P)[PWn+w (I--P)WA]( 1 - W ) (2) dard deviation of the five techniques evaluated (see Table 1).
Scoop sampling entails randomly dipping into and pulling
where the weight fraction in the sample and bulk are Pi and P, a scoopful of powder from a pile of the material to be evalu-
respectively, W and w are the bulk weight and sample weight, ated. Because the pile is usually not totally symmetrical and
respectively, and wa and w8 are the weights of individual evenly distributed throughout, the technique is prone to
grains of A and B, respectively. errors. Since in this procedure the powder is not caught while
Even with the "perfect" sample, there is a finite probability moving, it will not be typical of the bulk lot of material.
that the measured sample will deviate from the actual bulk by Table sampling (Fig. 3) utilizes a tilted surface over which a
some predictable value. To minimize this "guaranteed" devia- powder sample is allowed to slide. A series of splitting wedges
tion, a minimum sample size is required. One may calculate cut the sample into numerous sections where some portions
the minimum sample size required to yield values within fall through openings and are discarded. Ultimately, a de-
preset statistical limits [13]. The equation relating the mini- creased quantity of sample is collected, although it is neces-
mum sample weight of a gross sample is given by sary that the incoming powder be uniform and consistent.
Chute splitting utilizes a funneling or channeling device
Ms = 89 - 2]d 3 x 103 (3) capable of alternately placing the powder sampling stream
where into one of two collection hoppers. The technique is subject
to error and operator bias if segregation is allowed to occur in
Ms = the limiting weight in grams,
loading the bulk sampling trough. Such error is present when
p = the powder density in g/cm 3,
the two collected portions are not the same size.
02 = the variance of the tolerated sampling error,
Spinning rifflers (Fig. 4) utilize a series of smaller collec-
wx = the fractional mass of the coarsest size class being
tion tubes or holders mounted in a way to collect a flowing
sampled,
powder stream over a very short time period. This technique
d 3 = the arithmetic mean of the cubes of the extreme
was found to be the most reliable method for sampling and,
diameter in the size class in cm a.
when tested with different operators, showed little operator
The collection methods used in obtaining the sample are bias. Such was not the case for the other techniques investi-
important. Depending on the nature of the material being gated.
tested, samples should be gathered so as to minimize the
introduction of bias. There are two "golden rules" of sampling
that should be followed when possible [14]. These are:
PARTICLE CHARACTERIZATION
9 The sample should be collected while in motion. METHODOLOGY
9 All of the stream should be collected for a short period of
time rather than a portion of the stream for a longer period
Particles that are perfect spheres can be described by a
of time.
single value representing the sphere's diameter. Calibrated
This procedure will assist in minimizing the probability of microscopes are useful in reading such values directly from
error generated by stratification and segregation due to dif- the reticule. They have some utility with spherical resin parti-
fering weights of the particles within the stream and of the
way they act within the collective mass of the sample during
transport. Special collection devices are available for affect- TABLE l--Standard deviation in particle size determination of a
ing the sample collection. sugar-sand mixture as a function of sampling techniques.
Standard Deviation(tr)1
Sampling Techniques and Equipment Sugar-Sand Sand-Sand
Cone and quarter (worst) 5.762 6.812
Sampling techniques have been developed to minimize the Scoop sampling 6.312 5.142
systematic errors introduced both in collecting the gross sam- Table sampling 2.11% 2.09%
ple and in reducing its size to the analytical sample. In the Chute riffler 1.10% 1.01%
work done by Allen and Khan [15] using sand-sugar and Spinning riffler (best) 0.27% 0.132
Random variation 0.09% 0.08%
sand-sand, mixtures were evaluated utilizing different collec-
tion techniques. These techniques included; (1) cone and IBinarymixtures of sand-sandand sand-sugarwereused, and all particles of
quartering; (2) scoop sampling; (3) table sampling; (4) chute one componentand none of the other wouldpass through a designated sieve.
Density of sand and sugar, respectively,is 2.65 and 1.64g/mL.From Allen, T.
riffling; and (5) spinning riffling. The data presented in Table and Khan, A.A., 1970,ChemicalEngineering,Vol. 238, pp. 108-112.
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FIG. 3-Table sampler: A 16 to I reducer with removable legs

for portability. (Courtesy of Gilson, Inc.)
cles and with visual measurement of standardized test mate- FIG. 4-The spinning riffler. (Courtesy of Brinkman Instru-
ments, Inc.)
rials. Classification of most powders, on the other hand, must
address particles of various shapes and sizes.
A particle-size determination utilizes some size-dependent available for determining particle size take advantage of
property that can be measured and then relates this property m a n y different characteristics of the powder particle.
to a linear dimension. The measurement derives either from
individual particles or as a property of the collection of parti- Definitions of Particle Size and Shape
cles that is often expressed as a diameter of sorts. Measure- Particle shapes are everything but spherical for pigments
ment of a single individual particle can have m a n y different and fillers, which are produced, essentially, by crushing and
"diameters" depending on the direction and m e t h o d of view. shattering. As the sizes get smaller, the actual particle shape
Particle characterization, therefore, m a y involve determining plays an increasingly important role in its use in a coating as
the rate of a particle's travel through a fluid (either under the well as on the physical laws employed for its characteriza-
influence of gravity or while being subjected to angular accel- tion. From the diagram in Fig. 5, the same particle m a y be
eration due to rotation), its actual surface area, its ability to defined in a n u m b e r of ways [16]. Some of these include the
pass through a screen of square or r o u n d holes, or its ability following:
to scatter light of various wavelengths in various directions.
It is convenient to use the term "equivalent diameters" Martin's Diameter--the distance between opposite sides of
when comparing sizes. The value so determined for a given a particle measured on a line bisecting the projected area. To
collection of irregular particles will vary somewhat depend- ensure statistical significance, all measurements are made in
ing on the technique used (i.e., the size-dependent variable the same direction regardless of particle orientation.
being measured). The definition of some of these "diameters" Feret's Diameter--the distance between parallel tangents
are presented in Table 2 along with their mathematical repre- on opposite sides of the particle profile. Again, to ensure
sentation. Table 3 lists some of the methods, the nominal statistical significance, all measurements are made in the
particle-size range, and the size measured. The methods same direction regardless of particle orientation. Note: Both
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TABLE 2--Definitions of particle size.

Symbol Name Defufition Formula
d~ Volume diameter Diameter of a sphere having ~" 3
the same volume as the V = - dv
6
particle
ds Surface diameter Diameter of a sphere having S = Ird2
the same surface as the
particle
dsv Surface volume Diameter of a sphere having dv3
diameter the same external surface dsv -
to volume ratio as a d2
sphere
dd Drag diameter Diameter of a sphere having V2
the same resistance to F~ = C~.p~-
motion as the particle in
where CnA = f(dd)
a fluid of the same Fo = 31rdarlv
viscosity and at the same Re < 0.2
velocity (da approximates
to ds when Re is small)
dr Free-falling Diameter of a sphere having
diameter the same density and the
same free-falling speed as
the particle in a fluid of
the same density and
viscosity
dst Stokes' diameter The flee-falling diameter of d3
a particle in the laminar dst 2 -
flow region (Re < 0.2) da
da Projected area Diameter of a circle having
diameter the same area as the A = -~ d~
4
projected area of the
particle resting in a stable
position
dp Projectedarea Diameter of a circle having Mean value for all
diameter the same area as the possible orientations
projected area of the d, = ds for convex
particle in random particles
orientation
de Perimeter Diameter of a circle having
diameter the same perimeter as the
projected outline of the
particle
dA Sieve diameter The width of the minimum
square aperture through
which the particle will
pass
dr Feret's diameter The mean value of the
distance between pairs of
parallel tangents to the
projected outline of the
particle
dM Martin's diameter The mean chord length of
the projected outline of
the particle
dn Unrolled The mean chord length 1 2
diameter through the center of E(de) = - fo ~ dndOR
'IT
gravity of the particle
M a r t i n ' s a n d Feret's d i a m e t e r s a r e g e n e r a l l y u s e d for p a r t i c l e - ing is involved. This d i a m e t e r is d e t e r m i n e d , in effect, b y

size analysis by o p t i c a l a n d e l e c t r o n m i c r o s c o p y . m e a s u r i n g t h e b e h a v i o r of t h e i r r e g u l a r p a r t i c l e in a c e r t a i n
c i r c u m s t a n c e a n d r e l a t i n g t h a t to t h e b e h a v i o r of a s p h e r e of
Equivalent Circle D i a m e t e r - - t h e d i a m e t e r of t h e circle hav-
otherwise identical properties.
ing a n a r e a e q u a l to t h e p r o j e c t e d a r e a of t h e p a r t i c l e in
r a n d o m o r i e n t a t i o n . This d i a m e t e r is u s u a l l y d e t e r m i n e d Sedimentation (Stokes') E . S . D . - - t h e d i a m e t e r of a s p h e r e of
s u b j e c t i v e l y a n d m e a s u r e d b y o c u l a r m i c r o m e t e r s called t h e s a m e d e n s i t y as t h e p a r t i c l e a n d h a v i n g t h e i d e n t i c a l free-
graticules. fall v e l o c i t y of t h e particle.
Equivalent Spherical Diameter (E.S.D.): T h i s o f t e n affords a Volume E . S . D . - - t h e d i a m e t e r of a s p h e r e h a v i n g t h e s a m e
m o r e useful m e a s u r e , p a r t i c u l a r l y w h e r e i n d u s t r i a l p r o c e s s - v o l u m e as t h e particle.
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TABLE 3mComparison of particle-sizing methods.

Nominal Range, /zm Size Determined
Gas Permeability 0.1-40 Mean
Gas Adsorption 0.005-50 Mean
Brownian Motion 0.01-3 Mean
Sieving
Dry >10 Passing through
Wet 2-74 minimum opening
Microscope
Optical 0.5-500 Martin's, Feret's, or
Electron 0.002-15 equivalent circle diameter
Zone sensing
Resistivity 0.05-500 Volume or area
Optical 1-500
Elutriation
Laminar flow 3-75 Equivalent spherical
Cyclone 8-50 diameter (E.S.D.)
Centrifugal classification 0.5-50 E.S.D.
Mercury intrusion 0.01-200 E.S.D.

Centrifugal sedimentation E.S.D.
Mass accumulation 0.05-25
Photo extinction 0.5-100
X-ray 0.01-5
Gravity sedimentation E.S.D.
Pipettes & hydrometers 1-100
Photo extinction 0.05-100
X-ray 0.1-130
Hydrodynamic chromatography
Packed column 0.03-2 E.S.D,
Capillary column 0.1-60
Cascade impactor 0.05-30 Aerodynamic diameter
DIAMETER DEFINITIONS Particle Size From Surface Area

It is often useful to use the a p p r o x i m a t i o n of size from
,t---.-- Martin's surfaces to evaluate o t h e r p a r a m e t e r s derivable f r o m the vol-
Diameter u m e function, such as specific surface a r e a a n d density. The
b a s i c equations that describe a sphere's surface a r e a a n d vol-
u m e are given by
Area of a sphere = ~D 2 (4)
Volume of a sphere = ~rD3/6 (5)
n ~ 2.'%':5.,~:.~:x-.',::,~ These relationships alIow d e t e r m i n a t i o n of the m e a n parti-
cle d i a m e t e r if the specific surface (area) is known, Particle-
size c h a r a c t e r i z a t i o n s t h a t e m p l o y surface a r e a techniques in
the size d e t e r m i n a t i o n yield average diameters. The surface
Equivalent a r e a of a p o w d e r m a y be d e t e r m i n e d from gas a d s o r p t i o n
experiments. By a s s u m i n g uniform-size n o n p o r o u s a n d
"~-Diameter'-~
spherical particles, the m e a n particle size m a y b e d e t e r m i n e d
from the surface a r e a data. The F i s h e r subsieve sizer is an
example of an i n s t r u m e n t of this type (Fig, 6). The "specific
Feret's surface" o b t a i n e d equals the d e t e r m i n e d surface a r e a divided
|- Diameter =1 b y the p r o d u c t of the particle v o l u m e and density. W i t h ap-
FIG. 5-The relationship of some stated diameters
p r o p r i a t e units conversion,
and the physical size of the particle. D = 6/[oA] (6)
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1. Perspective of Operating Principles

FIG. 6-The Fisher subsieve sizer. (Compliments of Fisher Scientific.)
where Perfectly spherical particles are seldom encountered in

D = particle diameter, ~m, mineral pigments and fillers used in paint and coating appli-
p = particle density, g/cm 3, and cations since these particles result from shattering by crush-
A = specific surface area, m2/g. ers and high-speed pulverizers. Crystalline materials fracture
Any shape other than a sphere, either regular or irregular, along crystal planes, while some pigments are acicular (like
has a greater ratio of surface to volume, and consequently the needles). With the many shapes of particles to be evaluated
particles will be smaller than calculated. Cracks, crevices, and characterized, instruments that operate on different
and pores are other factors leading to an increase in specific principles "see" different values of the size-dependent vari-
surface area and to a corresponding decrease in calculated able being monitored. As a result, a sample characterized by
particle size. one machine may yield a somewhat different value when
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evaluated using a different technique. For this reason, the

practitioner must be aware of the size-dependent variable to Silica ~--Cap
which his machine is sensitive.
Methods [17] for determining specific surface include ad-
Helix~,.~ ~=~.,
sorption of gases by the pigment, adsorption of solutes from
solutions by the pigment, and permeability of pressed pig-
ment particles to gases or liquids.
"--': ITo~--~ I'I ] ~Water JaCv::~um
Adsorption of Gases
This method is based on determining the number of gas
molecules that will adsorb as a monomolecular layer on the
surface of the particles. Knowing the area occupied by one
molecule and the number of molecules, the specific surface
11
area of a specimen of pigment may be calculated from
s = nNA (7)
where
E = specific surface area in cm 2,
n =
N =
number of moles of gas per gram of pigment,
Avogadro's number, 6.02 1023, and
~ Sample
A -- area covered by each molecule.
Knowing the specific surface, the surface mean diameter
may be calculated.
Brunauer-Emmett-Teller (BET) Method--The general pro-
cedure for this method [18,19] includes introducing the spec-
imen into an enclosed space of known volume followed by
degassing with heat and evacuation. A known amount of gas
is admitted to the system, and its pressure is determined. The Mercury
gas is then compressed to a new volume, and the correspond-
ing pressure is determined. The procedure is repeated until Manometer
FIG. 7-The Components of a basic gravimetric adsorption
enough data for the preparation are obtained. By means of
apparatus.
the BET equations, the surface area is found, and from it the
average particle size may be calculated.
Continuous Flow Method--This method makes use of the Adsorption of Nongaseous Molecules
BET equation, but the adsorbed gas is determined by concen-
Adsorption of molecular species other than typical gaseous
tration measurements in a continuous flow system [20]. Ni- molecules is possible also. These include the adsorption of
trogen gas is adsorbed by the specimen at liquid nitrogen solvents and surfactants in special cases.
temperature from a stream of nitrogen and helium gas and is Adsorption of Solutes onto Pigments--This method de-
later eluted by warming the specimen. The amount of nitro- pends on the adsorption of solute molecules onto a particle
gen liberated is estimated by thermal conductivity. For de- when it is wet out by a solution containing the dissolved
tecting changes in the amount of adsorbed nitrogen, surface active solute [23]. The process requires that the ad-
Beresford et al. [21] used the Perkin-Elmer-Shell sorptometer sorbent be thermodynamically more active than the solvent
with conductivity bridge and potentiometric recorder. and the kinetics be such that wet-out times be reasonable.
Gravimetric Method--In addition to the volumetric meth- Typical systems used are stearic acid in benzene, dyes in
ods, a gravimetric method using balances patterned after that benzene, and wetting agents in water. The amount adsorbed
of McBain and Bahr [22] can be used. The procedure is much will asymptotically approach a constant value with time. At
simpler but requires care as the apparatus is very fragile and this value it is assumed that the surface of the particles is
the changes in weight are very small. covered with a mono-molecular layer of solute. The area oc-
An essential part (Fig. 7) of the gravimetric method is a cupied by a single molecule of solute may be obtained from
fused silica spring balance from which a small glass "bucket" tests made with solids of known areas. The amount adsorbed
for the specimen is hung. The balance assembly is located in a is obtained by analysis of the solution before and after ad-
glass housing connected to a source of gas and to a manome- sorption.
ter for determining the pressure. The bucket is hung on the A disadvantage of the method is uncertainty about the size
balance, the housing is closed, and the specimen is degassed and orientation of certain types of molecules. On the other
by evacuation. The zero point of the balance is recorded. Gas hand, the method is rapid and easy to perform. For this
is admitted to the housing, and the change in weight of the reason it is suited to routine tests where its reliability has
specimen is determined by noting the change in the elonga- been established.
tion of the balance with a traveling microscope. Details are Soap Titration of Emulsion Particles--Maron et al. [24] de-
set forth in Ref 17. termined surface area and particle size of a synthetic latex by
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titrating with a soap until the critical micelle concentration of ter, (3) a capillary specimen tube, and (4) a leveling bulb
the soap in the solution was attained. From the effective containing mercury.
molecular surface area of the adsorbed soap and the amount To provide the constant volume of air, the U-tube is in-
adsorbed, surface area and particle size are calculated. The verted and filled through the stopcock at the bend. Then, with
method is calibrated with electron micrographs. Brodnyan a capillary eyedropper, a weight of mercury equivalent to 1
and Brown [25] also studied the technique. mL is removed, leaving an equal volume of air after which the
stopcock is closed and sealed. The mercury does not pass
Permeation Through Packed Powders through the sintered glass disk at the pressure used in the
test. To make a test, a plug of pigment is formed inside the
In this method, a gas, usually air, is forced through a specimen tube using the special press. The weight of the spec-
compacted bed of the pigment. The rate of flow is a function imen is a function of its density and the desired porosity of
of voids (pore space), pressure drop through the bed, specific the plug (usually about 0.5). With the leveling bulb in the
surface of the pigment, and viscosity of the gas. A knowledge lower position, the specimen tube is attached to the side arm
of all the other factors allows calculation of the specific sur-
of the apparatus, and a vacuum is applied by opening the
face area and, from it, the mean surface diameter. The
stopcock at the upper right-hand corner. The vacuum is ad-
method is fairly simple and is suitable for routine determina-
justed, and simultaneously the stopcock is closed, timing is
tions of spherical or near-spherical particles.
started, and the leveling bulb is raised to its upper position,
Gooden-Smith Method--Using air as the gas, Gooden and
which forces the 1 mL of air into the system. The timing is
Smith [26] designed a permeation method with two special
features: (1) the weight of specimen used in grams is numeri- stopped when the manometer returns to zero. The stopcock is
cally equal to its density and (2) every specimen is packed to then opened, and the bulb is returned to its lower position for
the same volume (Fig. 8). Together with a graphic calculator, another run.
these features greatly simplify the test and make it attractive
for routine testing or research in the particle-size range 0.2 to
50/xm.
Separation and Collection: Particle Size by
Hutto-Davis Method Elutriation
The principle differences between this and the preceding
method are: (1) the weight of the powder used to make the This approach is primarily a means for separating or frac-
compacted pellet is calculated to give a definite porosity, and tionating a quantity of pigment into portions according to
(2) the volume of air is kept constant for all plugs. particle size rather than providing a value of the sizes sepa-
Hutto and Davis [27] modified the apparatus of Carman rated. Size determinations may then be made on the sepa-
and Malherbe [28] by providing an improved manometer, rated fractions. The technique has utility in evaluating the
better control of the volume of air, and an improved press for influence of pigment and filler particle size on the properties
preparing the specimen. They also designed a nomograph for of the formulated product. After standardizing operating con-
calculating specific surface and surface area. The apparatus ditions for a material and measuring sizes by an independent
consists of: (1) a U-tube with legs of unequal length and method, approximate size distribution may be estimated for
closed at each end with a sintered glass disk, (2) a manome- additional material.
air
t nlet sorew clamp
i ~ ao iurt
oo.I
valve
//
/]
//
/ / ample-/
//
/ / plusJ ~
//
// I t /
// /
diffuser t~bes
// /
// /
//
//
//
// back a J
//
// f r o n t aria ~P---levoliN
//
//
/~ tube
l~re samva r e ~ d a t o ~
FIG. 8-Gooden-Smith apparatus for surface area. (Courtesy of Official Digest.)
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Roller Particle-Size Analyzer <

This device [29] uses elutriation by air to separate pigments
into sizes. The glass U-tube at the bottom of Fig. 9 is charged
with the specimen of pigment. Air under pressure is admitted
through a nozzle that extends to the bottom of the tube. The To filter system ~ i :.!:!!)!i ~
other arm of the tube is connected to the metal settling tube. to removefine j : ::!i:ili::j:
By proper selection of size of nozzle, size of settling tube, and particles from ] ~4k?~": ~
stream J::., : Sievieg
velocity of the air, separation into desired fractions is ob-
tained. The fractions are collected in paper extraction thim-
bles connected with a gooseneck to the settling tube. During
.L Finerparticles
passthrough Flow from
reservoir
the separating, the U-tube and the settling tube are vibrated
vigorously. Using 25-g charges, the average time required for sieve
separations ranges from 62 rain for particles up to 5/~m in
diameter to 11 min for particles from 40 to 80/~m in diame- EIMdatlen f
ter. Largerparticles
tend to settle Powderto be
Felvation f " fractionated
This method [30] combines elutriating and sieving for frac- '% Coarse
tionating fine powders. The basic apparatus (Fig. 10) consists wire screen
of a column about 4 in. (10 cm) in diameter and 24 in. (61 cm)
in height. The specimen is placed in the narrow tube at the
Flu|dizatiee
right. Fluid is introduced and allowed to pass through at a
Powderfluidizedby flow
relatively low rate. The powder soon becomes fluidized in the
conical base of the column. The flow of the liquid is increased FIG. 10-Felvation. Fractionating powders into different sizes
by a combination of fluidization, elutriation, and sieving. (Cour-
gradually. The smaller particles reach the sieve and pass
tesy of Chemical and Engineering News.)
through it. The throttling action of the sieve increases the
flow through it. Hence, particles that have passed through do
not fall back and clog the screen. Eventually, particles just rapid. Complete fractionations can be run in a period as short
larger than the sieve openings reach the sieve, but they do not as 10 min.
block the screen as they reduce the flow around them and
then tend to fall from the sieve.
The sieve functions only as a gage. It does not support the Individual Particle S e n s i n g
powder. Highly accurate electroformed sieves are used, but, In this technology, individual particles are separated from
because of their small size (1 in. (2.5 cm) in diameter), their each other by a diluted suspension in either air (by fluidiza-
cost is reasonable. Beside being economical, the method is tion followed by entrainment in a flowing stream) or a con-
stantly stirred conductive solution. The particles are then
forced to pass through the sensing zone. In one air-fluidized
instrument, the time of flight between two precisely placed
laser light sources and detectors is used to calculate size. In
another, the attenuated light as detected by a photodiode is
used to calculate a size. In the liquid suspension instrument,
a change in the established electrical resistivity through an
electrolytecircuit is measured as a particle passes through a
small orifice.
Time of Flight from Light Blockage

An instrument based on aerodynamic time-of-fight tech-
nology was developed by Dahneke [31]. The measurement
range is reported to be from 0.2 to 200/xm, with 150 channels
per decade and a count rate of up to 100 000 particles per
second. Output may be reported in either geometric or aero-
dynamic diameter. In this instrument, a gas (usually air for
pigment particles) is used to break down agglomerate mate-
rial and entrain them in a controlled flow; a specially de-
signed "pulse-jet dispenser" is used where a controlled flow of
air is directed down onto a sample placed into a small cup
(Fig. 11). Depending on the nature of the sample, the operator
sets the computer values for particle count rate, flow pres-
sure, and pulse pressure. The disperser flow pressure control-
FIG. 9 - T h e roller particle-size analyzer. ling the carrier gas usually remains constant. The disperser
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PULSE
JETDISPERSER
~~..~ TM
heath
It~J/~/I Toroidal Pulse Jet
Swirl
FIG. 11-A diagram of the operation of the dry-powder pulse jet disperser. (Cour-
tesy of Amherst Process Instruments, Inc.)
pulse pressure determines the number of particles fed particles in the air stream moving at about 6 L per minute.
through the analyzer. There is no operator involvement during the I to 5-min deter-
Measurements are made over 2-s intervals to ensure that mination. Two laser beams set at a discrete distance apart
the minimum count rate is met. Should the count rate fall and directed onto two photomultipliers make up the "sensing
below the predetermined count rate, the pressure is in- zone" (Fig. 12). As the particle passes through the set of laser
beams, light that is attenuated and scattered is monitored by
creased. Should the count rate exceed the maximum allowed,
the detectors. Signal analysis using cross-correlation tech-
the pressure is dropped by a factor of 2, thus maintaining the
niques give the particle's time-of-flight (TOF) with a resolu-
number of counts between the allowed maximum and mini-
tion of 25 ns. The technique is reported to be able to
mum.
discriminate between particles with only a 10% size differ-
The particles are deaggregated to primary size and fed into ence. Attachments to the instrument also allow the investiga-
the injection tube of the sonic nozzle suspended as single tion of sprayed aerosol droplets as well.
Electrical Resistance
According to the Coulter principle [32-34], when a particle
suspended in an electrically conductive liquid enters a con-
stricted path between electrodes, it changes the pathway elec-
trical resistance between the electrodes. This change
produces a fluctuation in the applied voltage that, under
proper conditions, is inversely proportional to the volume of
the particle. When the dispersion is made to pass through a
hole small enough to pass the particles one by one, the resul-
tant series of voltage fluctuations may be electronically am-
plified, scaled, and counted.
A functional diagram is shown in Fig. 13. The beaker and
tube contain the suspension. When the stopcock is opened, a
controlled vacuum starts flow of the suspension from the
beaker into the tube and also unbalances the mercury in the
manometer. The stopcock is then closed, and the mercury
siphon continues the flow of the suspension. Electrical con-
tacts in the manometer start and stop the counting of the
particles. The volume of the manometer tube between the
contacts determines the volume of the specimen. This ranges
from 0.02 to 5 mL. A fresh volume is drawn for each count. A
typical count requires from 3 to 30 s, depending on the size of
the hole and the volume between the contacts in the manom-
FIG. 12-Schematic of the aerosol beam generator and detec- eter. The Coulter counter was found to be useful by Princen et
tion mechanism. (Courtesy of Amherst Process Instruments, al. [35] for particle-size determination of emulsified oil sys-
Inc.) tems.
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COULTER PRINCIPLE sieves in the U.S. Series. Especially useful for sizes under 100
/zm is a sieve made by a photoengraving and electroplating
process [39]. Such sieves are intended to serve mainly as
primary reference standards [see ASTM Specification for Pre-
cision Electroformed Sieves (Square-Opening Series) (E-
S
A CURRENT
{ 161)].
PULSEDETECTION, ~ ~. ION Hand Sieving
If the sieves are used singly, the following directions that
appear in several ASTM test methods, among them D 546,
Sieve Analysis of Mineral Filler for Road and Paving Materi-
als, may be used.
After transferring the specimen to the sieve, "Hold the
ELECTROLYTE~ ~ \\ . ~ ' ~ 1 1 sieve, with pan and cover attached, in one hand in a
WITHDISPERSED \\ / > - ~ J l l slightly inclined position so that the specimen will be
PARTICLES ~ / " well distributed over the sieve, and at the same time
gently strike the side about 150 times per minute against
J
the palm of the hand on the upstroke. Turn the sieve
every 25 strokes about one sixth of a revolution in the
same direction each time. Continue the operation until
FIG. 1 3 - T h e Coulter principle: A fluctuation in not more than 0.05 g passes through the sieve in 1 minute
current flow occurs when a particle paretically blocks of continuous sieving."
the small opening between the electrodes. The size of
the particle is related to the amount of change in cur- Sources of error in hand sieving are operator fatigue and
rent flow, casual attention to directions. While machine sieving elimi-
nates these errors, some specifications still require hand siev-
ing unless it can be shown that machine sieving gives the
The principle utilized to determine individual particle size same results.
is the electrical resistance of the particle as it is forced to pass
through a small hole in a glass envelope through which an Machine Sieving
electrical potential exists. Machine sieving has the advantages of uniformity of treat-
ment and saving time since the operator is free to perform
Particle Size by Sieving other tasks while the machine is working. Several types of
machines are available. The conventional ones impart an
Sieving appears to be a simple means for separating pig- oscillating or rotating motion (or both) to the sieve, with
ments into fractions according to size. A significant addition regular tapping. None appear to reproduce the motions of
to the physical laws governing the process has been made by hand sieving.
Whitby [36], who investigated variables such as size distribu- Ro-Tap Sieve Shaker--This machine [37] (Fig. 14) manipu-
tion, mesh size, sieve loading, sieve motion, sieve material, lates a series of sieves, graduated with respect to mesh size, so
and relative humidity. A comprehensive manual on sieving as to permit separation of a specimen into sizes. As the name
methods has been published by ASTM [37] and the W. S. implies, the sieves are given a special rotary motion accompa-
Tyler Company [38]. nied at regular intervals by a tap. The nature of the specimen
For routine testing, sieves conforming to ASTM Specifica- dictates the size of the sieve openings and the timing cycle.
tion for Wire-Cloth Sieves for Testing Purposes (E-11) are This type of machine is recommended in ASTM Test Method
useful. These sieves are made of woven wire cloth, supported for Particle Size or Screen Analysis at No. 4 Sieve (4.75-mm)
in frames of up to 12 in. (30 cm) in diameter. A skirt protrudes and Finer for Metal Bearing Ores and Related Materials (E-
slightly below the sieve, allowing it to nest into the frame of 276).
the next size sieve. The openings in successive sieves progress Sonic Sifter--In the Allen-Bradley sonic sifter [40] (Fig.
from a base of 1.00 mm in the ratio of the square root of 2 to 1 15), the sieves are stationary, and agitation is imparted to the
(i.e., 1.414:1). When selecting a range of sieves from the particles by an oscillating column of air. Sieve wear and
series, it is recommended that each sieve, each alternate particle attrition are said to be minimal. The sonic sifter
sieve, or each fourth sieve be taken. In this way, the basic consists of a sieving chamber, a diaphragm at the top vibrat-
ratio between successive sieves remains constant. ing at 60 Hz, and a motor with the necessary controls. The
The U.S. Series of sieves is patterned after the Tyler Series amplitude of vibration is adjustable to the nature of the speci-
that was introduced in 1910 [38]. In fact., the two are now men. A determination may require no more than 60-s opera-
interchangeable, the only difference between them being the tion of the machine.
designations of the individual sieves. Those in the U.S. Series To make an analysis, the sieves, in descending order from
are identified preferably by the sizes of the openings in milli- top to bottom, are assembled in the holder, and the specimen
meters or micrometers, while an alternate means is by a (not more than 30 g or 10 mL) is transferred to the top sieve.
number approximately equal to the mesh. Tyler sieves are The cone, coupling unit, and the diaphragm are added, and
identified by mesh. Equivalent sieves are available in both the stack is latched within the chamber. The complete assem-
series. The sieves proposed as standard by the Internationat bly is positioned in the machine, the power level and the time
Standards Organization (ISO) correspond to many of the interval are set, and the operation is started. After the sift
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FIG. 14-Ro-tap resting sieve shaker. (Courtesy of W. S. Tyler Co.)
interval, the stack is removed and opened, and the fractions the component parts. The complete operational unit includes
are weighed and computed in the usual manner. a vacuum cleaner. The hose of the vacuum cleaner is fastened
Air-Jet Sieve--A cross section of the air-jet sieve [41] is to the outlet at the lower left. The specimen is placed on the
shown in Fig. 16. A specimen is seen being processed through sieve, and the air, which comes from the rotating split nozzle
on its way to the vacuum cleaner, agitates the specimen. The
finer particles pass the sieve and are collected in a tared filter
bag; the coarse particles are retained on the sieve. Sieves with
different meshes are used for additional fractionations, and
the procedure is repeated. New tared filter bags are used for
Lock upport each fractionation if retention of the fractions is desired. Air
Air C0h
Sieve S velocity must be regulated, and a manometer is used to indi-
Light m cate the vacuum in the housing.
6 Standat Direct M i c r o s c o p i c M e a s u r e m e n t
or 3 Dee older
Microscopes, both optical and electron as well as auto-
mated image analyzers, are used to measure particle size
directly. Optical techniques suffer somewhat from an inabil-
M(
P~ ity to focus on the "edge" of a particle at very high magnifica-
tions due to a depth of field problem. The lower limit is set by
I its resolving power and the upper limit by its depth of focus.
[tude The microscope is especially useful for measurement of plate-
flitude like and needle-shape particles that do not obey Stokes' law,
on which the sedimentation methods are based. Disadvan-
Di'. . . . . . . . . . . ~ot
. . . . . . . tages of the method are that it is slow and laborious. Hence, it
FIG. 1 5 - D i a g r a m of the Allen-Bradley sonic 'sifter. is used chiefly for the calibration of the more rapid relative
(Courtesy of Allen-Bradley Co.) methods. ASTM Practice for Particle-Size Analysis of Particu-
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CHAPTER 32--PARTICLE-SIZE MEASUREMENTS 3 1 9
The use of the electron microscope for particle character-

ization is now a routine practice. The resolving power is
many times that of the light microscope and may be used in
scanning as well as transmission mode. With state-of-the-art
surface analysis tools such as energy dispersive X-ray (EDX)
built into the scanning electron microscope (SEM) equip-
ment, elemental analysis of a single-pigment particle within
the coating matrix can be done conveniently while the coat-
ing sample is in the instrument.
Array Method Using Optical Microscope

The array method of particle sizing lends itself to systems
of monodispersed spheres, as in Fig. 17 (from Duke [48]).
These are highly uniform with respect to diameter. When
placed on a flat plate, the spheres tend to align themselves
into hexagonal arrays. These are characterized by straight
rows of the particles. Because of this, the rows can be mea-
sured, and the diameter of the particles may be derived by
dividing by the number in the row.
Transmission Electron Microscopy (TEM)

TEM is useful for the measurement of latex microspheres
of 200 nm and larger [49,50]. The procedure usually utilizes
the magnification factor of the microscope in the size deter-
mination from photomicrographs. Because this factor is not
always dependable, photographs are sometimes made
against a replica diffraction grating of known spacing. Figure
18 shows 100-nm latex microspheres on a 2160-1ine/mm
grating. Sources of error include uncertainty in the accuracy
of the line spacing, the roughness of the lines, and the line
thickness relative to the size of the particles. Duke [51] has
used an internal standard of NIST traceable materials, as
shown in Fig. 19, and reports accurate sizing to as small as 50
FIG. 16-Alpine air-jet sieve. (Courtesy of Gilson, Inc.) nm.
late Substances in the Range of 0.2 to 75 p,m by Optical

Particle Size by Sedimentation
Microscopy (E 20) and a paper by Loveland [42] are good The use of the principle that a particle will "fall" through a
references. Dark field illumination can use the detecting liquid medium at a rate dependent on its diameter (as well as
power of the microscope rather than the resolving power for other variables) is a popular sizing technique. By this
sizes below the resolving power of the optical microscope.
Green [43] was the first investigator to systematize the use
of the microscope for direct measurement. He dispersed the
pigment in a medium on a microscope slide, photographed
the dispersion at a known magnification, and projected the
image on a screen to increase the magnification for measure-
ment. Dunn [44] bypassed the photomicrograph by project-
ing the image of the particles directly from the slide on the
screen.
Ideally, the pigment should be dispersed in the medium in
which it is used, but this is rarely done. Green used turpen-
tine, Allen [45] recommended a viscous vehicle, and Eide [46]
used fused resins. Gehman and Morris [47] milled the pig-
ment in rubber, dissolved the mix in a solvent, and applied
the suspension to the slide.
Microscopes equipped with view-through linear scales, cir-
cles or ellipses in graduated sizes, may be used as a direct
measurement method [42]. The comparison scale may be a
micrometer eyepiece, an eyepiece reticle, or a scale engraved FIG. 17-Microphotograph of 9.87-v.m spheres in arrays.
on the microscope side. (Courtesy of Stan Duke.)
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Stokes' L a w
For essentially spherical particles, one assumes that Stokes'
law will be followed when particles are falling in a fluid under
some accelerating potential such as gravity or centrifugal
force. This assumption requires that the particles will fall
freely under laminar flow conditions [52]. For a perfect
sphere, the diameter can be calculated simply from the
Stokes' equation.
-~) (8)
where
D -- diameter of sphere,
/z = medium viscosity,
FIG. 18-Microphotograph of 100-nm latex spheres against a v = velocity of fall under influence of gravity,
2160-1ine/mm grating. (Courtesy of Stan Duke.) g = gravitational constant,
pp -- sphere density, and
p = medium density.
method, the pigment particles are dispersed in a liquid and Most often, the particles are not exactly spherical. Because
then allowed to settle under the influence of gravity or centrif- of this, it is difficult to relate a particle's dimensions directly
ugal force. The rate of particle movement through the liquid to the observed settling rate. The usual procedure is to use
then gives the particle diameter. Among the methods for Stokes' equation to determine the values for d from the sedi-
measuring the rate of particle movement in a fluid are: (1) mentation distance and its corresponding time. The value so
collecting the particles on a balance pan suspended in the determined is then the "Stokes' diameter" of the particle. The
dispersion, (2) analyzing specimens withdrawn with a pipet definition then becomes "the diameter of a sphere that has
from different levels, (3) determining density with hydrome- the same density and free falling velocity (in a given fluid) as
ters or "divers," and (4) measuring attenuated light transmis- the particle being investigated (within the range of Stokes'
law)."
sion through the dispersion. With low-cost computers and
This practice avoids the problem of variations in free fall
extremely stable rotational control provided by advanced
velocities caused by shapes which differ from being a sphere.
electronic feedback circuits, the sedimentation methods us-
The assumption holds and permits useful comparisons of the
ing centrifugal acceleration have become popular.
size distributions when similar types of materials are evalu-
A prerequisite to analysis by the sedimentation process is
ated. The size distribution of particles of different shapes may
that the particles must be at their primary size. Vigorous
he compared provided that the phenomenon being studied is
stirring, usually with a dispersant agent or surfactant, both
dependent on its behavior in the fluid.
with and without ultrasonics, is often necessary. Agents to While the concept of the Stokes' diameter is useful, it is
prevent flocculation may be required, and adjustments in necessary to appreciate its limitations. One should not equate
solution pH may be necessary to stabilize the system. These the Stokes' diameter to a sphere of equal volume or other
additives must be evaluated at different levels to determine related quantity. Two types of errors may be introduced. In
impact on the derived values. the first case, errors arise when the particle's movements
depart from Stokes' law and, in the second case, errors are
introduced by the experimental technique itself.
Departure from Stokes' law can occur when flow condi-
tions are not met. Stokes' equation is valid under laminar
flow only. Consequently, there is an upper limit to the size of
a particle that can be evaluated in a given liquid. Large parti-
cles can experience too high a velocity in the liquid and create
turbulent flow. Vortexes in the liquid in the vicinity of other
particles also introduce errors. Laminar flow is determined
by the Reynolds number experienced by the particle/fluid
system at the fall rate. The Reynolds number, Re, is defined as
Re - vdp (9)
where v is the velocity in the fluid, d is the diameter in

centimeters, p is density of the particle in grams per milliliter,
and ~ is the viscosity in poise. According to B.S. 3406 [53], the
FIG. 19-The use of an internal standard of known size. (Cour- value of Re cannot exceed 0.2 if the introduced error from
tesy of Stan Duke.) Stokes' law deviation is to be less than 5%. This would imply
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that the upper limit of particle size would depend on both the developed in large part by Bauer [59], is TAPPI Method
viscosity and density of the fluid. For water, this value would T649sm, Determination of Particle Size of Clay. Included in
place an upper limit of about 60/~m. However, as might be the method is a nomograph by Casagrande [60] to aid in the
anticipated from the Reynolds equation, this limit may be calculations. The same nomograph is found in Test Method
stretched somewhat when using either more dense or more for Particle Size Distribution by Hydrometer of the Common
viscous liquid media than water. White Extender Pigments (D 3360) [61].
Another problem arises when the concentration of parti- Radioactivity Method--Connor and Hardwick [62] report
cles is too great. The Stokes' equation assumes single parti- on this method for determining the height of the sedimenta-
cles having no influence from the wall of the vessel or other tion. The radioactivity is either induced in the specimen or is
particles in close proximity. Wall effects are minimized by used as an external probe. The technique avoids disturbing
employing properly sized vessels. While some investigators the suspension by periodic sampling and can be used with
have recommended that the volume concentration should be both gravity and centrifugal sedimentation.
kept less than 0.05%, others recommend concentrations of up
to about 0.5 to 1% by volume. Certain investigators feel that Centrifugal Sedimentation
this compromise introduces systematic errors and renders The centrifuge is used to provide an accelerating force for
the method inappropriate as an absolute measure, although sedimentation analysis. Configurations exist using rotating
it is suitable as a routine control method. The flocculating disks with "see-through" ports as well as holders of small see-
nature of the powder in the test fluid will impact the maxi- through cells.
mum concentration that can be used. B.S. 3406 recommends Disk Centrifuge--The technique for the disk centrifuge was
a concentration of 1% by volume, although it cautions that, developed by Atherton et al. [63]. The apparatus might be
under certain circumstances, a small interference may occur. considered to be a direct descendant of the single cell centri-
Because of the potential introduction of systematic errors at fuge of Donoghue [64] and the scratch start technique of
higher concentrations, efforts to refine the technique so that Marshall [65]. The range is from 0.01 to 0.5/~m.
reduced concentrations are used are underway. Precision The apparatus consists of a centrifuge unit, a sampling
with differentials no more than 4% are usually expected. unit, and an electronic control unit [66]. The rotor of the
Another problem that must be addressed is the tempera- centrifuge is a cell (hollow disk) of plastic or glass that rotates
ture stability of the liquid. Not only is there a change in the on a horizontal axis (Fig. 20). The back wall is attached to the
liquid viscosity, but thermally produced convection currents shaft of the rotor. The front wall has a hole in the middle that
grossly impact the sedimentation process. Because of the dif- serves as an access port. The inside diameter of the standard
ficulty in maintaining thermostatic control over the long pe- cell is 10 cm, and the width is 1 cm. In operation, the cell
riods required for gravitational settling, there is usually a takes liquid up to a minimum radius of 2.3 cm. The speed
lower particle-size limit of about 2/~m when water is used as ranges from 500 to 8000 rpm.
the suspending liquid. The sampling unit (Fig. 21) consists of a probe connected to
collection flask and a clock motor. The probe is an L-shape
Gravity Sedimentation thin-wall steel tube arranged to rotate about the axis of one
The analysis of particles by sedimentation is possible be- arm. The other arm terminates in a sharp bevel for scooping
cause of Stokes' law, which states that the time of fall of a up the contents of the cell in a manner analogous to that of an
particle through a viscous medium is proportional to the inside cutter in a lathe. The center of rotation of the probe lies
particle's density (the difference between it and the medium) below the center of the rotor.
and its diameter. Of course, if the density of the medium were To make a test, an appropriate volume of "spin fluid,"
greater than the particle, the particle would float. Another typically a 4% sucrose solution, is transferred to the rotating
requirement is that all of the particles must have a common cell. After swirling stops (20 to 30 s), the specimen--usually
density. This rules out mixtures of different minerals and 0.5 mL of a 0.5% dispersion--is expelled from a syringe
pigments having different densities since they cannot be de- against the back wall near the center of rotation. The speci-
termined together. men flows outward over the wall unit it reaches the free
Because of the time required for sedimentation to occur, surface of the spin fluid, where it forms a band about 1 mm
the simple gravimetric method and the photometric method thick. The spin fluid and the dispersion do not mix because of
appear to be limited to pigments of sizes above 0.5 to 1.0/~m. the higher density of the former. Thus, zero time for the
Cadle [53.1] and Orr and Dallavalle [54] have reviewed the measurement is defined rather accurately.
many variations of the method. Gravity settling was first pro- After the desired time, spin fluid is withdrawn from the cell
posed by Oden [55,56]. Calbeck and Harner [57] were among with the probe, which is driven by a clock motor at 1 rpm.
the first to use the technique for paint pigments; Jacobsen With the pickup end of the probe in the 12 o'clock position,
and Sullivan [58] brought the method to a higher degree of the motor is started automatically. All but 5 mL of the spin
refinement by using an analytical balance with one of the fluid is removed for measurement of the undersized fraction
pans replaced with a cup submerged in the suspension. of the dispersed powder.
Hydrometer Method--The density of a dispersion is propor- The development of detector systems must consider the
tional to the concentration of the dispersed material, and action on a transmitted light beam. Light-scattering theory
methods for particle-size analysis based on the use of the dictates that when light of intensity I0 attempts to pass
hydrometer have been developed. One such method is ASTM through a dilute suspension (i.e., no multiple scattering) of
Method for Particle-Size Analysis of Soils (D 422). Another, particles, it is lost or extinguished to an extent that It makes it
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FLUID
SAMPLE LAYER
MOTOR SHAFT ENTRY PORT
~ i, ' f I ~ INJECTION HEAD AND SYRINGE

i~!~ii~~"i SAMPLE INJECTION NEEDLE
BOSS
9 9 ,pf~
~ P E R S P E X ROTOR
i 84
FIG. 20-Diagram illustrating the principle of the disk centrifuge. (Courtesy of Joyce, Loebl
& Company, Ltd.)
tBE PIVOT
PATH DESC
BY PROBE "
LE
FINAL COLLECTION POINT
FIG. 21-Relationship of disk and probe of disk centrifuge sampling. (Courtesy of
Joyce, Loebl & Company, Ltd.)
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through. Mathematically [67,68], the transmitted light is ing of the reference cell, the sample cell, and the rotor speed
given by (Fig. 23). Data are displayed in real time on a built-in CRT as
well as printed out on tape after the analysis for a permanent
/t = I0 exp( - a~xtL) (10)
record. Graphs are presented indicating the absorbance ver-
where L is the length through the suspension, and O/ext is the sus time, frequency distribution, and cumulative distribution
attenuation coefficient (turbidity). The value of O/ext is related (either percent undersize or percent oversize).
to the number concentration of particles, N per unit volume,
by
Light A t t e n u a t i o n a n d S c a t t e r i n g T e c h n i q u e s
Otext = N C e x t (11)
Spectrophotometric Techniques
where Cext is the extinction cross section of the particles. The Gamble and Barnett [71] developed a method for measur-
extinction efficiency of a particle of cross-sectional Area A is ing particle-size distribution by the scattering of light in the
conveniently expressed as near infrared. The pigment is dispersed in low concentration
a = Cext/Qext (12) and placed in a transmission cell for spectrophotometric
measurement. From the shape of the spectrophotometric
This yields the relationship curve, the relative size and size distribution characteristics of
N 1rd2Qext an unknown pigment are obtained in terms of calibrated
Ctext -- (13) samples (Fig. 24).
4
Bailey [72] also developed a spectral transmission method
Photo extinction detectors on modern turbidity instruments using infrared wavelengths from 0.4 to 2/~m. The spectro-
essentially determine aext. The internal calculation of Qext photometric curve was related to size by graphic comparison
requires knowledge of the particle refractive index, size, with specimens of known sizes.
shape, orientation, state of polarization, and wavelength of Atherton and Peters [73] measured light scattering by
the scattered light as well as the refractive index of the sus- polydispersed system of spherical particles. The size distribu-
pending liquid. Using Mie theory [67-69], size may be tion curves for the materials compared favorably with direct
deduced. Oppenheimer [70] has pointed out that a source of measurement with the electron microscope.
potential error is that the refractive index of the suspending Leobel [74] used a spectrophotometer to obtain the effect
liquid and particles must be known for each wavelength. of wavelength on turbidity in the determination of the size of
Rotating Cell Holder Centrifuge--Real time monitoring is latex particles. The sizes of particles used for calibration were
provided on some instruments and is advantageous when determined from electron micrographs.
irregular measurements force an abort. One such instrument
can perform centrifugal as well as gravity analysis using the Light-Scattering Techniques
same on-board computers. With ten different rotor speeds When solid particles pass through a light beam, the light
switchable from 300 to 10 000 rpm, an accelerating potential will interact with the particles in one or more ways. It can
of up to 9000 g is available. Particles as small as 0.01/zm are either be reflected, refracted, diffracted, or adsorbed and re-
reported to be measurable. radiated. This is shown schematically in Fig. 25. The scat-
The instrument uses two small, transparent rectangular tered radiation will present a pattern that is dependent on the
cells (Fig. 22) mounted opposite each other on the balanced shape and size distribution of the particles. By evaluating the
rotor. While they counterbalance each other, one serves as a scattered radiation detected at different locations relative to
reference for the suspension liquid, and the other holds the the beam direction and in different positions, much can be
particle suspension system under analysis. Three photocells learned about the scattering media. Figure 26 depicts some of
in the top monitor three opposite light-emitting diodes (LED) the angular intensities of scattered light produced by parti-
on the back side of the rotor. This allows real-time monitor- cles of various size. With low-cost computers and stable de-
FIG. 22-Reference cells used in a centrifuge. (Courtesy of Horbia Instruments,

Inc.)
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SYSTEM DIAGRAM PHOTOCELLS

1.SYNCHRO-SIGNAL(REF)
2.ANALOG-SIGNAL
;;;
3.SYNCHRO-SIGNAL(SAMPLE)
,~~2OCELL (REFERENCE)
(OPTION) (OPTION)
The CAPA-700 system is comprised of an optical system, a centrifuge, computation cir-

cuitry and input/output functions. The rotating disc in the horizontally mounted centri-
fuge is connected directly to the motor to minimize gravitational effects, and electronic
control keeps the rotational speed stable at the set value. The CPU monitors and controls
automatic checking for fluctuations in rotational speed, computation formulae and
deterioration of the light source and detector, assuring precision data at all times. In the
optical system, a reference cell guarantees both optical and mechanical balance for each
revolution, which, after CPU processing, gives even higher precision particle size distribu-
tion analysis.
FIG. 2 3 - A modern instrument for determining particle size in real time.
tectors, instruments have been developed that can monitor

this scattered radiation, giving fast and reliable data.
Angular dependence techniques, which include detection
and manipulation of signals from front (reflection) as well as
side and rear (diffraction), have been integrated into a single
instrument. Angular-dependence, light-scattering techniques
have been widely studied for information concerning the
sizes of both pigmentary and nonpigmentary particles. In the
latter class, polymeric organic materials from molecular to
latex sizes have been included. Debye and Bueche [75] de-
scribed how to characterize the optical inhomogeneities re-
LO lated to size from information concerning the way a system
z0 B
80 scatters light.
Angular-dependence techniques include the work of Brice
et al. [76], who designed a photoelectric photometer for mea-
surement of molecular weight by applying the Debye theory.
~- 40
D-
Aughey and Baum [77] note that particles in the size range
Z of large molecules produce variations in the intensity of light
~cg ao scattered at large angles to the illuminating beam. Progres-
sively larger particles produce significant variation in the
0 light scattered at small angles. The light source is a well-
o LO a.o 3.o 4.0 defined monochromatic beam. The cell containing the dis-
WAVE LENGTH IN MICRON e.
FIG. 2 4 - P a r t i c l e s i z e m a y b e deter- persion is stationary, and the photoelectric tube travels
mined from the scattering of radiation in around the cell in an arc that covered a useful range from 0.05
the near infrared region of the s p e c t r u m . to 140 ~ Scattered light reaches the tube through a small aper-
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Reflected
Absorbed and
Reradiated
>
~" ~'- Refracted
Diffracted
FIG. 2 5 - P o s s i b l e interactions w h e n light strikes a particle.
ture in the housing for the tube. The radii of the optical on the intensity distribution of the diffracted laser beam.
inhomogeneities range from 0.1 to 100/~m. Modern diode Since the intensity pattern is a function of the actual particle
array detectors are now available to do similar tasks without size, mixtures of particles having different densities may be
the movement. measured together, unlike those relying on Stokes' law. The
Diffraction of Laser Light--Instruments using diffraction of instrument is reported to address 0.1 to 200-p.m particles.
single-wave-length laser light have been made possible by the Total Light Scattering--Instruments capable of monitoring
development of low-cost, highly stable lasers and diode array light from all sides can effectively measure particles even
detector technology. By fluidizing the particles in a stream of smaller than the usual limit of 0.1/xm. This limit is imposed
air, they are directed through a cell being illuminated by a because of the physics relating the wavelength of the incident
laser source. The He-Ne laser, emitting a coherent beam of radiation and the interacting particles. By taking advantage
632.8-nm wavelength is often used. To increase the cross- of a set of detectors located strategically around the scatter-
sectional area of the beam, expanders are often employed ing cell, data relating to even very small particles less than 0.1
(Fig. 27). /xm are determined. As the size of the particle decreases, the
The diffraction pattern that is seen by the detector is a intensity of the scattered light obscures critical differences in
pattern of rings varying in darkness depending on the size the angular distribution. In practice, this difficulty in treat-
distribution of the passing particles. On-board computers use ment of data leads to the so-called laser-diffraction measure-
both the Fraunhofer diffraction and Mie scattering theories ment barrier.
to calculate the particle-size distribution of the sample. These Since there is an increase in both the side and rear
methods allow the determination of size distribution based scattering with very small particles, it is possible to take
advantage of the phenomenon. Figure 28 is an instrument
Incident ~---=--:..~_~.~_ diagram with an arrangement of detectors that allow a single
~-~---~,,,.~
Beam ~ ~ ; ,~, . ,~~, .,~-~-
-'~" instrument to measure a broad range of sizes. Light irra-
diating the particles is scattered at various angles. For rela-
tively large particles, light is scattered in the forward
Sphere Smaller than 0.1 the Light Wavelength
direction, while, for smaller particles, the light tends to be
scattered in all directions. By arranging a lens system and
manipulating data from the detectors, the particle-size distri-
Incident bution is calculated from the Mie theory. Since the size of the
Beam ~'~2 ~- ~ . particles measured is a function of the wavelength of the
impinging radiation, the instrument uses a beam of filtered
blue light to expand the range.
Sphere about 0.25 the Light Wavelength
X-Ray Scattering
The Debye-Scherrer small angle X-ray scattering technique
for observing interference effects related to particle size is
Beam
-~---~-.- ' . " - - ~ - ~ ,, L '..2__
well known [78]. Some generalizations on the use of the
technique were addressed by Debye [79].
Yudowitch [80] and Danielson et al. [81] both employed the
Sphere larger than t h e Light Wavelength "diffraction peak" procedure for the determination of latex
FIG. 26-Angular intensity of scattered light after striking a particle size. For control they used a latex whose size had
particle. been determined under the electron microscope.
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sampleparticle
/ diffracted lightpattern
He-Nelaser
beamexpander condenser I) photo-cell

lens Ycletector
Principle of Operation
The He-hie laser emits a beam of 632.8 nm whose flux is enlarged by a beam ex-
pander and radiated upon the particles suspended in the liquid. After it has been
diffracted and dispersed by the particles, the laser beam passes through the
condenser lens and its image is formed at the photo-cell detector located at the
focal point of the lens.
The diffraction pattern that appears at the detector is a pattern of light and dark
concentric rings that corresponds to the particle size distribution of the sample.
Now, using both of the Fraunhofer diffraction and Mie scattering theories, the
intensity values are used to calculate the particle size distribution of the sample.
tungstenlamp sampleparticle
~ condenser detector scatteredlightpattern
He-Nelaser ~ filter I\ lens [~
~ r - --- ",~......... - ~ % ~
rear ~- detector
detector side
detector
Here is how the LA.900 works.

Light irradiating the particles is scattered at various angles. If the particles are
comparatively large, this scattering tends to be concentrated in a forward direction. As
the size of the particles decreases, the light is scattered in all directions. Therefore, to
measure larger particles, data from a small angle of scatter is required; to measure
smaller particles, a larger angle of scatter is required.
On the LA-900, to measure the distribution of low angle scattered light, a condenser
lens is used with an array detector at the focal point of the lens. To measure large angle
scattered light, detectors are used at the front and rear of the sample chamber. From
angular measurement of the scattered light by all of these detectors, the particle
distribution is calculated from Mie theory.
It is also true that as the wavelength of the light becomes shorter, so does the
measurement size of the particles. Therefore the LA-900 uses a He-Ne laser beam and
a red light beam and a blue light beam obtained by filtering a tungsten lamp to expand
the measurable range.
FIG. 27-Schematic layout for the large-particle system. (Courtesy of Horbia Instru-
ments, Inc.)
Drawdown Techniques for Texture and O v e r s i z e are not ground but are only wet out and dispersed to their
"primary" size. This primary size is the smallest possible size
During the manufacturing of paints and coatings, there is a
supplied from the producer.
need for rapid, "on-the-floor" testing to determine whether a
dispersion has reached its maximum grind. The "grind" gages
were developed to provide quick, on-the-spot answers. Some Thin-Film Drawdown for Oversize Particles
of the tests could be done in the factory at the disperser This test [82] is suited particularly for detecting oversize
during the grinding stage of production. Actually, during the particles that adversely affect the gloss of high-gloss indus-
production of paints and pigmented coatings, the pigments trial enamels. A 2-mL wet film of the enamel is spread on a
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Flow Schematics
reservoir unit (option)

auto-sampler (option) ....................... -~
......................... "I I l
I i
I ? === I !
,=,,,
printer
light soure~...~",",,J,'~:',T': ...... ",,'T' ,, , "'",',"', . . . . . . "1"". . . . . . II
9 _lL'-e I. . . . . 1
Y II I ~/~_- ' detector scattered light -
ultra-sonicl'~ J ~ / ~""~:. -I"I ' I ainnal
mirror II ~ J],"l"~. ~_~y~" / ~ I I ~ IA/D converter
.... flow cell
m'~or~
9 ;'H-/-Nelase
He " jH' T [ _ lens / / I .....CPU
1 +ra,
tecto,
I
circulation valve II RS-232C mouse
ouoo I
drain ,at>
panel keys
FIG 28-Schematic layout for a system m e a s u r i n g both large and small p a r t i c l e s (Courtesy of Horbia
Instruments, Inc.)
glass plate with a Bird applicator blade. Inspection of the film St. Louis Gage--This [83], the first of the dispersion gages,
is best made in a dimly lit room with the operator facing a was designed to facilitate the use of the North Standards. The
light source such as a window or under a florescent light with channel is 2 in. (51 cm) long and 0.005 in. (0.13 mm) deep at
a grid that can be reflected from the wet paint sample. With the deep end. The sample and the selected North Standard
the eye focused on the silhouetted image of the window sash are placed side by side in the deep end, drawn by a scraper
or the reflected pattern from the light or ceiling, extremely toward the shallow end, and compared.
fine particles may be detected and compared with a visual Hegman Gage--The Hegman gage [84,85] (Fig. 29) made
standard. They appear as a roughness to the wet surface. the North standards and the St. Louis gage obsolete. It is
A variation of this approach is to illuminate the specimen essentially a St. Louis gage with the addition of a scale to
at grazing incidence with a spotlight and view the film show the depth of the channel or the distance from the deep
through a magnifier parallel to the specimen. Still another end. Instead of evaluating the dispersion in terms of the
version is the use of wedge-shape or step-wise multithickness North standards, the distance from the deep end is reported.
films. The finer the dispersion, the greater the distance. This is the
reverse of the North standards, where the finer the disper-
Fineness-of-Dispersion Gages sion, the lower is the number of the standard.
ASTM Gage--The gage specified in ASTM Test Method for
Drawdown tests for the detection of oversize particles led Fineness of Dispersion of Pigment-Vehicle Systems (D 1210)
to development of fineness-of-dispersion gages, or, as first is almost identical to the Hegman. The steel block (Fig. 30) is
called, fineness-of-grind gages. The gage is a steel block in about 180 m m long, 63.35 mm wide, and 12.7 mm thick. The
which is cut a wedge-shape channel, tapering usually from 4 channel is 100/~m deep at the heel. The gage is calibrated
mils at the deep end to zero at the other end, though other according to depth in steps of 10/~m along one edge and to
depths and different widths and lengths of the channel are the corresponding nearest 0.1 mil along the other. The di-
available. Some gages have twin channels. An excess of the mensions of the scraper are shown in the diagram.
sample is placed in the deep end of the channel, and the Experience has shown that the speed of drawdowns and
excess is drawn to the shallow end with a scraper. At some the angle at which the scraper is held have no important
point along the channel, coarse particles or agglomerates effect on the results. However, the time lapse between the
become visible. The results are interpreted by reference to drawdown and reading, as well as operator technique, are
standard reference patterns. The addition of slow-evaporat- important [86]. Readings should be made within 10 s after
ing solvents may be required to thin down the system to allow completion of the drawdown, especially for dispersions with
more time for reading the gage without experiencing volume a rating of seven or better due to the volume loss from solvent
loss by evaporation. evaporation. Good practice suggests three drawdowns using
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Elimination of operator variance is aided by the use of six

standard patterns. Figure 31 illustrates reading of the end
points, and the scales show the depth of the channel. This
scale appears to have some advantage over both the North
and the Hegman scales as it is related directly to the dimen-
sions of the oversize particles. Other scales in use include the
FSCT (Federation of Societies for Coatings Technology)
scale, which divides the distance into ten parts.
Constant Depth Gage--The channels in this gage are of
constant depth rather than tapered as in the gages previously
described. The gage most often used has four channels, 1/2 in.
(1.3 cm) wide and 6 in. (15 cm) long, having depths of 0.002
(0.005 cm), 0.0015 (0.0038 cm), 0.0010 (0.0025 cm), and
0.0005 in. (0.004 cm) equivalent to Hegman values of 4, 5, 6,
and 7, respectively. Other depths can be supplied. The advan-
tage of this type of gage is the long path available for inspec-
tion, a condition that should minimize the influence of
bubbles and foreign matter on the ratings.
NPIRI Grindometer--Printing ink films are much thinner
than those of paints or coatings. Relatively fine particles in
the latter would be considered relatively coarse in the ink.
Because of this, the printing ink range is addressed with a
gage designed by the National Printing Ink Research Institute
FIG. 29-Hegman fineness-of-dispersion gage. (Compliments (NPIRI) called the Grindometer [87,88]. The channel of this
of Lynn Shirey.) gage is only 0.001 in. deep at the deep end, is 1 in. (2.54 cm)
wide, and the scale is graduated in steps of 0.0001 in.
(0.000 25 cm).
fresh material each time. The first drawdown allows accom-
modation to the light source and a rough estimate of the X-Ray Microradiography Technique
dispersion pattern and the end point. Subsequent readings This technique detects undispersed clumps of pigment (in-
may then he made within 3 or 4 s. ASTM directs viewing the organic types only) in paint. It uses low-energy X-rays [89] to
drawdown with the line of vision at a right angle to the long resolve oversize material in the range of 1 ~M or less, which is
dimension of the channel and at an angle between 20 and 30 ~ below the range detectable with fineness-of-dispersion gages.
with the face of the gage in a light that renders the pattern A thin film of paint is spread over the surface of photo-
readily visible. Diffuse subdued light is preferred. graphic-sensitized, fine-grain film. The specimen is exposed
/
MILS MICRONS
4- -I00
- 80
3-
-60
2-
-40
I-
-20
0 0
f J
FIG. 30-ASTM dispersion gage and scraper.
www.iran-mavad.com

mils microns where

Vr = liquid velocity at radius, r,
4-- --I00 (P0 - P/.)= pressure drop for the distance, L,
R = inside radius of capillary,
r= effective radius of liquid at Vr,
= viscosity of fluid in flow, and
- 80 L = length of capillary.
3-- Because the larger particles tend to have statistically more
volume in the fluid away from the wall, the larger particles
are under a greater influence of the faster-moving fluid away
--60 from the wall more so than the smaller particles, which can
physically fit in the slower-moving layer nearer the wall.
2 Thus, the larger particles advance faster than the smaller
ones affecting the separation.
- 40
THE ROLE OF PARTICLE-SIZE
REFERENCE TEST MATERIAL
Carefully prepared particles of known size and composi-

tion have become an important part of testing for emulsions,
[ ;Piiil -- powders, film, and processes. When properly used, reference
particles are an important factor in demonstrating compli-
0 ---J - 0 ance with standards such as ISO-9000, FDA Good Manufac-
4 0 microns
1.6 mils turing Practices and various military specifications [91]. In
FIG. 31-Typical pattern pro- the past two decades, the need for instrument calibration has
duced by a dispersion gage. prompted the establishment of several businesses special-
izing in the production and supply of reference particles,
which are available in assortment of materials of various
to X-rays and the film developed after removal of the paint. sizes, densities, and grades.
The film is enlarged optically to reveal silhouettes of the A brief discussion of some typical applications will illus-
oversize materials on a photographic negative. Determina- trate the usefulness of these test reference particles. They are
tion of size may be made following the methods used for light used for instrument calibration, filter checking, flow tracing,
and electron microscopy. and evaluation of processes such as blending, cleaning, and
spraying, to name a few.
Instrument calibration and checking covers two broad
Hydrodynamic Chromatography: Angstrom classes: (1) particle-size analyzers and (2) particle contamina-
Particle Sizing tion analyzers. Both types of instruments are calibrated or
controlled by spherical particle-size standards, primarily
The separation of angstrom-sized particles may be affected polystyrene microspheres, which are normally measured and
by the use of hydrodynamic chromatography. In this tech- calibrated by methods traceable to the National Institute of
nique, the mixture of very small particles is allowed to trans-
gress a long capillary tube in which the liquid medium is
flowing in laminar flow. It is welt known that fluids, both
sasses and liquids, will experience a pressure drop as a func-
tion of distance traveled and of the diameter of the tubing
that occurs because the fluid in actual contact with the wall of
the tube does not flow and is stationary. For noncompressible
fluids, (i.e., liquids), this variation in flow velocity from wall
to center of tube may be used to separate particles of differing r
size.
f
For laminar flow, the velocity of flow through the cross
section of the tube increases from the wall to the center,
essentially in concentric "layers" [90]. This may be repre-
sented by the vectorial diagram in Fig. 32 of the flow velocity >
profile. The actual velocity of flow of one of the "concentric
circular layers" will be a function of its distance from the wall
of the tube. The flow velocity gradient is given by
Vr _ _ (Po - PL)R2 [1 - (r/R) 2] (14) FIG. 32-Vectorial representation of the veloc-

4~L ity of a fluid in laminar flow.
www.iran-mavad.com

S t a n d a r d s a n d Technology (NIST). The spherical c a l i b r a t i o n [5] Gamble, D. L. and Barnett, C. E., "Scattering in the Near Infra-
particles have fairly p r e d i c t a b l e i n s t r u m e n t responses a n d red; A Measure of Particle Size and Size Distribution," Industrial
are available as aqueous s u s p e n s i o n s of highly u n i f o r m parti- and Engineering Chemistry, Analytical Edition, Vol. 9, 1937, p.
cles in discrete sizes (diameters) from 0.02 to 2000/zm. I n 310.
[6] Atherton, E. and Peters, R. H., "Light Scattering Measurements
a d d i t i o n to polystyrene spheres, w h i c h m a y be non-
on Polydispersed Systems of Spherical Particles," British Jour-
fluorescent o r m a y c o n t a i n various fluorescent dyes, calibra-
nal of Applied Physics, Vol. 4, 1953, p. 344.
tion spheres are c o m p o s e d of silica a n d glass. N o n s p h e r i c a l [7] Bunce, E. H., "Zinc Oxide in Exterior Mixed Paints," Scientific
m a t e r i a l s such as alumina, quartz, a n d various milled pow- Section Circular, National Paint, Varnish, and Lacquer Associa-
ders are available as e x p e r i m e n t a l m a t e r i a l s or controls. tion, No. 319, 1927, p. 541.
Particle-size s p e c t r o m e t e r s are used to m e a s u r e the parti- [8] Eide, A. C., "Properties of Zinc Oxide Influencing the Weather-
cle-size d i s t r i b u t i o n of powders, suspensions, emulsions, a n d ing of Paints," Official Digest, Federation of Paint and Varnish
aerosols. Other t h a n c o m p o s i t i o n , particle-size d i s t r i b u t i o n is Production Clubs, Vol. 7, 1935, p. 164.
p r o b a b l y the m o s t i m p o r t a n t variable in p r o d u c t quality and [9] Morris, H. H., "Titanium Dioxide, Lithopone, and Leaded Zinc,"
p e r f o r m a n c e . The m a j o r class of instruments, particle Official Digest, Federation of Paint and Varnish Production Clubs,
counters, are used to m e a s u r e trace a m o u n t s of particle con- Vol. 6, 1934, p. 8.
[10] Nelson, H. A., "Zinc Sulfide Pigments for Interior Paints,"
t a m i n a t i o n in air, water, chemicals, beverages, a n d medi-
Official Digest, Federation of Paint and Varnish Production Clubs,
cines. A recent variation of the particle c o u n t e r can m e a s u r e
Vol. 7, 1935, p. 177.
particle c o n t a m i n a t i o n on flat surfaces, such as silicon waf- [11] Jacobsen, A. E., "Significance of Pigment Particle Size and
ers, a n d a variety of optical a n d electronic parts. All these Shape," Canadian Chemical Process Industries, Vol. 33, 1949, p.
instruments, as well as optical a n d electron microscopes, 124.
require calibration a n d reference particles to assure b o t h the [12] Pigment Index, National Paint, Varnish, and Lacquer Associa-
quality a n d traceability of m e a s u r e m e n t s . tion, Washington, DC.
In a d d i t i o n to i n s t r u m e n t evaluation a n d calibration, refer- [13] Allen, T., Particle-Size Measurement, 4th ed., Chapman and Hall,
ence particles a r e used to verify r e t e n t i o n ratings a n d pore- New York, 1990, p. 5.
size d i s t r i b u t i o n of a i r a n d liquid filter media. Using aerosol [14] Allen, T., Particle-Size Measurement, 4th ed., Chapman and Hall,
particle generators and p r e c i s i o n particle counters up a n d New York, 1990, p. 9.
d o w n stream, high-efficiency p a r t i c u l a t e air (HEPA) filters [15] Allen, T. and Khan, A. A., Chemical Engineering, Vol. 238, 1970,
pp. 108-112.
can be certified for use in ultraclean m a n u f a c t u r i n g opera-
[16] HORIBA: PARTICLE SIZING SEMINAR, Notes and Workbook,
tions for rigorous c o n t a m i n a t i o n control. Polystyrene Horiba Instruments, Inc., (714) 250-4811, Irvine, CA, 1992, p. 5.
spheres with a p p r o x i m a t e l y a 0.25-/zm d i a m e t e r are fre- [17] Fries, R., "The Determination of Particle Size by Adsorption
quently used for this purpose. Methods," Particle-Size Measurement, STP 234, American Soci-
Another b r o a d class of reference particle a p p l i c a t i o n is for ety for Testing and Materials, Philadelphia, 1958, p. 259.
validating processes, such as for cleaning, blending, dispers- [18] Brunauer, S., Emmett, P. H., and Teller, E., "Absorption of
ing, separation, a n d spraying. F l u o r e s c e n t particles, which Gases in Multimolecular Layers," Journal, American Chemical
have b r i g h t a n d distinctive colors t h a t can be c o n t r a s t e d with Society, Vol. 60, 1938, p. 309.
o t h e r b a c k g r o u n d materials, are frequently used to follow the [19] Emmett, P. H., "A New Method for Measuring the Surface Areas
flow or direction of a process. Other m a t e r i a l s such as pol- of Finely Divided Materials and for Determining the Size of
lens, g r o u n d walnut shells, refractory powders, or other ma- Particles," Particle Size Determinations in the Subsieve Range,
STP 51, American Society for Testing and Materials, Philadel-
terials of the d e s i r e d particle size a n d specific gravity are
phia, 1941, p. 95.
available as m o d e l systems for evaluating processes.
[20] Nelsen, F. M. and Eggersten, F. T., "Determination of Surface
In conclusion, reference particles are a key ingredient of Area. Adsorption Measurement by Continuous Flow Method,"
m o d e r n testing methods, a n d their use should be c o n s i d e r e d Analytical Chemistry, Vol. 30, 1958, p. 1387.
at a n early stage in a n y QA/QC p r o g r a m as quality m a n a g e - [21] Beresford, J., Carr, W., and Lombard, G. J., "Surface Area of
m e n t p r o g r a m s require the r e g u l a r a n d t i m e l y evaluation a n d Pigments," Journal of the Oil and Colour Chemists' Association,
s t a n d a r d i z a t i o n of particle-sizing equipment. Vol. 48, 1965, p. 293.
[22] McBain, J. W. and Bahr, A.M., "A New Sorption Balance,"
Journal of the American Chemical Society, Vol. 48, 1926, p. 690.
[23] Ewing, W. W., "Specific Surface of Pigments by Adsorption from
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Physical Chemistry of Clays and Precipitates," Colloid Chemis- [26] Gooden, E. L. and Smith, C. M., "Measuring Average Particle
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[4] Stutz, G. F. A. and Pfund, A. H., "A Relative Method for Deter- [27] Hutto, F. B., Jr. and Davis, D. W., "An Improved Air Permeability
mining Particle Size of Pigments," Industrial and Engineering Apparatus," Official Digest, Federation of Paint and Varnish Pro-
Chemistry, Vol. 19, 1927, p. 51. duction Clubs, Vol. 31, 1959, p. 429.
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[31] Dahneke, B. E. and Cheng, Y. S., "Properties of Continuum millan, New York, 1959.
Source Particle Beams. L Calculation Methods and Results," [55] Oden, S., "A New Method for Determination of Particle Size in
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[32] Berg, R. H., "Electronic Size Analysis of Subsieve Particles by [56] Oden, S., "Sedimentation Analysis and Its Application to the
Flowing Through a Small Liquid Resister," Particle-Size Mea- Physical Chemistry of Clays and Precipitates," Colloid Chemis-
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Philadelphia, 1958, p. 245. 1926, p. 861.
[33] "Theory of the Coulter Counter," Coulter Electronics Industrial [57] Calbeck, J. H. and Harner, H. E., "Particle Size and Distribution
Division, 2601 N. Mannheim Road, Franklin Park, IL 60131. by Sedimentation Method," Industrial and Engineering Chemis-
[34] Valentine, L., "Measurement of Particle Size with the Coulter try, Vol. 19, 1927, p. 58.
Counter," Peintures, Pigments, Vernis, Vol. 39, 1963, p. 214. [58] Jacobsen, A. E. and Sullivan, W. F., "Method of Particle Size
[35] Princen, L. H., Stolp, J. A., and Kwolek, W. F., "Emulsificationof Distribution for the Entire Subsieve Size Range," Industrial and
Linseed Oil. I. Effects of Oil Viscosity, Temperature, Time of Engineering Chemistry, Analytical Edition, Vol. 19, 1947, p. 855.
Agitation, and Age of Emulsions on Particle Size Distribution," [59] Bauer, E. E., "Recent Developments in the Hydrometer Method
Journal of Paint Technology, Vol. 39, 1967, p. 183. as Applied to Soils," Particle-Size Measurement, STP 234, Ameri-
[36] Whitby, T., "The Mechanism of Fine Sieving," Particle-size Mea- can Society for Testing and Materials, Philadelphia, 1958, p. 89.
surement, STP 234, American Society for Testing and Materials, [60] Casagrande, A., Die Araometer Method zur Bestimmung der
Philadelphia, 1958, p. 3. Kornverteilung yon Baden and anderen Materialen, Julius
[37] Manual on Test Sieving Methods, STP 447, American Society for Springer, Germany, 1934.
Testing and Materials, Philadelphia, 1969. [61] Annual Book of ASTM Standards, Vol. 02.05, ASTM, Philadel-
[38] "Testing Sieves and Their Uses," Handbook 53, W. S. Tyler Co., phia, 1993.
Cleveland, 1991. [62] Connor, P. and Hardwick, W. H., "The Use of Radioactivity in
[39] Daescher, H. W., Siebert, E. E., and Peters, E. D., "Application of Particle Size Determination," Industrial Chemistry, Vol. 36,
Preformed Micromesh Sieves to the Determination of Particle
1960, p. 427.
Size Distribution," Particle-Size Measurement, STP 234, Ameri-
[63] Atherton, E., Copper, A. C., and Fox, M. R., "The Measurement
can Society for Testing and Materials, Philadelphia, 1958, p. 26.
of Particle Size and Its Practical Significance in Vat-Dye Qual-
[40] "Allen-Bradley Sonic Sifter," Publication 6801, Allen-Bradley
ity," Journal of the Society of Dyers and CoIourists, Vol. 80, 1964,
Co., Milwaukee, WI, 1965.
p. 521.
[41] "Air-Jet Sieve," Bulletin l-A, Alpine American Corp., 3 Michigan
[64] Donogue, J. K. and Bostock, W., "New Technique for Particle
Drive, Natick, MA 01760.
Size Analysis by Centrifugal Sedimentation," Transactions, In-
[42] Loveland, R. P., "Methods of Particle Size Analysis," Particle-Size
stitute of Chemical Engineering, Vol. 33, 1953, p. 72.
Measurement, STP 234, American Society for Testing and Mate-
[65] Marshall, C. E., "The Degree of Dispersion of the Clays, I. The
rials, Philadelphia, 1958, p. 57.
Technique and Accuracy of Mechanical Analysis Using the Cen-
[43] Green H., "A Photographic Method for Determination of Parti-
trifuge," Journal, Society of Chemical Industry, London, Vol. 50,
cle Size of Paint and Rubber Pigments," Journal, Franklin
Institute, Vol. 192, 1921, p. 637. 1931, p. 444.
[44] Dunn, E. J., Jr., "Microscopic Measurement for the Determina- [66] Beresford, J., "Size Analysis of Organic Pigment Using the ICI-
tion of Particle Size of Pigments and Powders," Industrial and Joyce Loebl Disc Centrifuge," Journal, Oil and Colour Chemists'
Engineering Chemistry, Analytical Edition, Vol. 2, 1930, p. 59. Association, Vol. 50, 1967, p. 594.
[45] Allen, R. P., "Preparation of Pigment Mounts for Microscopy," [67] Kerker, M., The Scattering of Light and Other Electromagnetic
Industrial and Engineering Chemistry, Analytical Edition, Vol. 14, Radiation, Academic Press, New York, 1969.
1942, p. 92. [68] Bohren, C. F. and Huffman, D. R., Absorption and Scattering of
[46] Eide, A. C., personal communication to G. G. Sward, 1945. Light by Small Particles, Wiley-Interscience, New York, 1983.
[47] Gehman, S. D. and Morris, J. C., "Measurement of Average [69] Mie, G., "Beitrage zur Optik truber Modien, spezeill Kollaidaler
Particle Size of Fine Pigments," Industrial and Engineering Metallosungen," Annalen der Physik 25, Vol. 3, 1908, pp. 377-
Chemistry, Analytical Edition, Vol. 4, 1932, p. 157. 445.
[48] Duke, S. D. and Layendecker, E. B., "Improved Array Method for [70] Oppenheimer, L. E., "Interpretation of Disk Centrifuge Data,"
Size Calibration of Monodispersed Spherical Particles by Opti- Journal of CoUoid Interface Science, Vol. 92, 1983, p. 350.
cal Microscope," Particle Science and Technology, Vol. 7, 1989, [71] Gamble, D. L. and Baranett, C. E., "Scattering in the Near
pp. 209-216. Infrared; A Measure of Particle Size and Size Distribution,"
[49] Maron, S. H., Moore, C., and Powell, A. S., "Electron Microscopy Industrial and Engineering Chemistry, Analytical Edition, Vol. 9,
of Synthetic Lattices," Journal of Applied Physics, Vol. 23, 1955, 1937, p. 310.
pp. 900-905. [72] Bailey, E. D., "Particle Size by Spectral Transmission,"
[50] Bradford, E. B. and Vanderhoff, J. W., "Electron Microscopy of Industrial and Engineering Chemistry, Analytical Edition, Vol. 18,
Monodispersed Latexes," Journal of Applied Physics, Vol. 26, 1946, p. 365.
1955, pp. 864-870. [73] Atherton, E. and Peters, R. H., "Light Scattering Measurements
[51] Duke, S. D. and Layendecker, E. B., "Internal Standard Method on Polydispersed Systems of Spherical Particles," British Jour-
for Size Calibration of Sub-Micrometer Spherical Particles by nal of Applied Physics, Vol. 4, 1953, p. 344.
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[74] Loebel, A. B., "Determination of Average Particle Size Synthetic [82] Pigments Division, duPont Co., White Pigments for Paint, Sec-
Lattices by Turbidity Measurements," Official Digest, Federation tion II, 1956, p. 11.
of Paint and Varnish Production Clubs, Vol. 31, 1959, p. 200. [83] St. Louis Paint and Varnish Production Club, "Effects of Wet-
[75] Debye, P. and Bueche, A. M., "Scattering by an Inhomogeneous ting Agents upon Pigment Dispersion," Scientific Section
Solid," Journal of Applied Physics, Vol. 20, 1949, p. 518. Circular, National Paint, Varnish, and Lacquer Association, No.
[76] Brice, B. A., Halwer, M., and Speiser, R., "Photoelectric Light- 471, 1934, p. 429.
Scattering Photometer for Determining High Molecular [84] Fasig, E. W., "The Hegman (Sherwin-Williams)Fineness Gage,"
Weights," Journal, Optical Society of America, Vol. 40, 1950, p. Drugs, Oils, and Paints, Vol. 54, 1938, p. 438.
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Scattering--A High Resolution Recording Instrument for the
[86] Doubleday, D. and Barkman, A., "Reading the Hegman Grind
Angular Range 0.05-140," Journal, Optical Society of America,
Gage," Official Digest, Federation of Paint and Varnish Produc-
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[78] Marculaitis, W. J., "Particle Size and Particle Size Distribution tion Clubs, Vol. 22, 1950, p. 598.
of Pigments by Small Angle X-Ray Scattering," Journal of Col- [87] National Printing Ink Research Institute, "The NPIRI Produc-
loid Science, Vol. 12, 1957, p. 581. tion Grindometer," Project Report 12, 1949.
[79] Debye, P., "Light Scattering as a Tool," OfficialDigest, Federation [88] Walker, W. C. and Zettlemoyuer, A. C., "Fundamentals of
of Paint and Varnish Production Clubs, Vol. 36, 1964, p. 518. Grindometers," American Ink Maker, Vol. 28, No. 7, 1950, p. 31.
[80] Yudowitch, K. L., "Latex Particle Size from X-ray Diffraction [89] Venuto, L. J. and Hess, W. M., "A New Look at Carbon Black,"
Peaks," Journal of Applied Physics, Vol. 22, 1951, p. 214. American Ink Maker, Vol. 45, No. 10, 1967, p. 42.
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www.iran-mavad.com

MNL17-EB/Jun. 1995
33
Rheology and Viscometry
by Richard R. Eley I
Nomenclature G~ Plateau m o d u l u s
G* Complex s h e a r m o d u l u s
ap Fluidity integral, Eq 64
G' Storage m o d u l u s
a Rate of decay of r o u g h n e s s amplitude, s- l
G" Loss m o d u l u s
/3 Time c o n s t a n t characteristic of a critical shear rate, s
K Consistency in p o w e r law model; c o n s t a n t in viscos-
7 Dimensionless shear strain
ity-molecular weight equation
S h e a r strain rate, s-1
L Capillary tube length
~w Wall s h e a r rate in t u b e flow, s 1
M w Weight-average p o l y m e r m o l e c u l a r weight
8 Phase shift; thickness of a d s o r b e d p o l y m e r layer
M c Critical (entanglement) p o l y m e r m o l e c u l a r weight
Extensional (Hencky) strain, dimensionless
P Pressure
Extensional (Hencky) strain rate, s-1
Q Volumetric flow rate
Coefficient of viscosity
R Capillary tube radius; particle radius; air b u b b l e ra-
T0 Zero-shear viscosity
dius
~/| H i g h - s h e a r limiting N e w t o n i a n viscosity
T Absolute t e m p e r a t u r e
~d Dispersion viscosity
Tg Glass t r a n s i t i o n t e m p e r a t u r e
Tie Extensional viscosity
a Curvature p a r a m e t e r in Eq 15; a m p l i t u d e of coating
~l Liquid-phase viscosity
surface striations
"Or Relative viscosity, ~d/~t
a0 Time-zero a m p l i t u d e of coating surface striations
~' D y n a m i c viscosity
e Base of the n a t u r a l l o g a r i t h m i c scale = 2.718 28
[~] Intrinsic viscosity (limiting viscosity n u m b e r )
f Frequency, Hertz
0 Angle of inclination with respect to the vertical
g Gravitational acceleration
)t Wavelength of coating surface striations; elastic
h Film thickness
stress relaxation t i m e c o n s t a n t
k B o l t z m a n n ' s constant; general rate c o n s t a n t
v K i n e m a t i c viscosity
l Length
Ratio of c i r c u m f e r e n c e of a circle to its d i a m e t e r
m Kinetic energy correction t e r m for capillary tube
p Density
flow, Eqs 72 a n d 73
tT Surface tension; generalized stress
n Power law exponent
(r0 Initial i m p o s e d stress
t Time
~r Tensile stress
v Velocity
~- Shear stress; viscosity-kinetic time constant for dry-
x Coordinate parallel to substrate
ing, wicking, or t h i x o t r o p y
y Coordinate n o r m a l to substrate
% Yield stress
Zs Tangential surface s h e a r stress
% Wall s h e a r stress
Volume fraction of internal (dispersed) p h a s e of a
INTRODUCTION
dispersion
THE VALUEOF RHEOLOGICALSCIENCEis increasingly being real-
the Effective volume fraction for a d i s p e r s i o n
ized in the coatings laboratory. One r e a s o n is economic: As
thin M a x i m u m packing fraction of a dispersion, where
m u c h as half the cost of new p r o d u c t d e v e l o p m e n t c a n be
~r ---~ ~ c o n s u m e d in solving rheology-related p r o b l e m s of m a n u f a c -
tO Angular frequency ( = 2wf)(rad/s)
ture or p e r f o r m a n c e . Moreover, the rheology of an estab-
A Area of s h e a r face
lished p r o d u c t can go a w r y due to r e f o r m u l a t i o n or a r a w
De D e b o r a h n u m b e r ( )t/t )
m a t e r i a l or process change, a n d such p r o b l e m s are generally
F Force
in urgent need of solution. Rheological analysis can be a cost-
Fg Force of gravity
effective aid to the coatings f o r m u l a t o r in u n d e r s t a n d i n g a n d
G Shear modulus
solving p r o d u c t a n d process difficulties.
Traditionally, m e a s u r e m e n t of the viscosity or "consis-
lThe Glidden Company (member ICI Paints), Glidden Research tency" of p a i n t s a n d coatings h a d b e e n b a s e d on a n u m b e r of
Center, 16651 Sprague Road, Strongsville, OH 44136.
test m e t h o d s having certain perceived virtues: They were
333
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undemanding in operator skill, required inexpensive equip- commercial instruments are capable of viscoelastic charac-
ment, and the result was usually a single number requiring no terization of materials.
interpretation. These tests proved useful enough, especially Finally, in the words of Professor Ken Walters, "Rheology
as tools of the experienced formulator or bench chemist. This is a difficult subject." This is certainly true, combining as it
was partly because, in the times when many industrial coat- does several disciplines under one banner: mathematics,
ings were solvent-borne and relatively low in solids, the prod- physics, physical chemistry, colloid and polymer science,
uct rheology was seldom far from Newtonian. In the latter continuum mechanics, etc. This is not to mention the special
case, any test serves as well as any other. The advent of complexities of the experimental methods used. Further-
environmentally compliant technologies, such as water- more, rheology requires mastery of concepts peculiar to the
borne, higher solids, and powder coatings, changed this situ- science with which most persons have had limited opportu-
ation. With the new formulations, non-Newtonian, time-de- nity to become familiar in the normal course of a technical
pendent, and viscoelastic behaviors were encountered. Here, education. Nevertheless, it is quite possible for the
the traditional methods were inadequate for the reasons that nonspecialist to acquire a useful working knowledge of the
many of the latter tests yield only a single-point measure- principles and practice of rheology and to use this profitably
ment, use arbitrary (rather than absolute) viscosity units, or in linking formulation and performance for coatings.
use a flow field which is "nonviscometric. "2 Any of these
shortcomings render a method inappropriate for non-New-
tonian materials. DEFINITIONS OF BASIC TERMS
A recurrent failing in product viscosity testing is the em-
ployment of methods not relevant to the performance prop- Rheology
erty in question. This deprives the test of any analytical or The derivation of the term theology is from the Greek rhein,
predictive power relative to paint performance. Thus, for ex- "to flow." The classical definition of the science of rheology is
ample, a low-shear viscosity measured using a spindle vis- "the study of the deformation and flow of matter." Some have
cometer, paddle viscometer, or orifice cup bears no relation pointed out a redundancy in this definition since flow is a
to the performance of a paint during application, generally a subset of deformation, as we shall see. An operational defini-
high-shear process. Part of the aim, therefore, is the develop- tion of rheology would be "the study of the response of certain
ment of tests which are related specifically to the critical materials to the stresses imposed on them."
processes paints must undergo. In order to quantify the deformation and flow behavior of
Rheological factors play a key role in all stages of a coat- materials, three basic terms must be defined. The first two of
ing's lifetime, from manufacture to the final career of a pro- these relate to the measurement of the deformation (strain
tective, decorative film. The many processes embodied in that and strain rate) and the third to the measurement of the force
history involve broad aspects of the science of rheology. Table required to deform the material (stress).
1 lists some coatings processes, each process having associ-
ated with it several distinct deformation characteristics. For Deformation (Strain)
each deformation type, a specific rheological test is required
to measure its effect on the process. Many of these measure- A deformation is a change in shape and/or volume of a
ment quantities are independent, i.e., they cannot be inferred material in response to an applied stress. The equivalent
from another rheological property. Obviously, if one were to engineering term is strain. During the lifetime of a coating,
measure only steady-shear viscosity, and over a limited range the deformation history may be complex (see Table 1), with
of shear rate at that, the real cause of a performance problem the most important components being simple shear and ex-
may be missed. Thus, the characterization necessary for com- tension. For purposes of definition, we will limit our discus-
plete understanding of rheology-controlled behavior may re- sion to simple shear. Simple shear deformation is exactly
analogous to the spreading of a deck of playing cards, each
quire the use of more than one instrument and technique.
card representing a thin volume element (or shear plane)
Notwithstanding, many problems can be solved from shear
displaced relative to its nearest neighbor (Fig. 1). If a force F
viscosity and viscoelastic data alone provided the experi-
is applied to the uppermost volume element (thickness dy),
ments performed are well designed and the results properly
the material will deform by the displacement of adjacent vol-
interpreted.
ume elements by a distance dx. The total thickness is Ay, and
In order to take full advantage of the capabilities built into
the total displacement is Ax. The shear strain, % is the ratio of
the sophisticated rheological instruments now being widely the net displacement, Ax, to the distance of separation of the
used in the coatings industry, more than a passing knowledge confining surfaces, Ay.
of the subject of rheology is required. This chapter is there-
fore somewhat tutorial in style, endeavoring to provide the Ax
V- (1)
novice an entry point to the discipline. Certain concepts are ay
discussed at some length because of their importance or
complexity. One of these is viscoelasticity. It is worth the time
Strain Rate
because (a) it is established that viscoelasticity exerts control
over coating processes when present, and (b) a number of In order to measure the viscosity, or resistance to flow, of a
fluid, we must know not only the extent, of deformation
2"Viscometric" shear flow requires that the flow be "everywhere (strain), but also the rate of deformation (strain rate). The
indistinguishable from steady simple shear" [1]. strain rate is the change in strain per unit time, or the time
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CHAPTER 33--RHEOLOGY AND VISCOMETRY 335
TABLE 1--Rheological components of coatings processes.

Deformation Rheological Non-Rheological
Process Type or Attribute Property Effects
Roll Coating Squeezing flow Biaxial extensional viscosity Drying
Stretching flow Uniaxial extensional viscosity
Shearing flow Shear viscosity
High strain rate High shear viscosity
Large accelerations Elasticity (G')
Large decelerations G' recovery
Surface area transients Dynamic surface tension
Spray High shear rate High shear viscosity Flash-off

Large accelerations Elasticity (G')
High-strain-rate Extensional viscosity/elasticity
extensional flow
Brushing/rolling Medium shear rate Shear viscosity
Stretching flow Extensional viscosity/elasticity
Leveling/sagging Slow shear flow Low shear stress viscosity Wicking
Surface-stress driven Dynamic surface tension Drying
Transient Structure recovery kinetics
Curtain coating Extensional flow Extensional viscosity/elasticity
Shear (pumping, Shear viscosity
extrusion)
F dv Stress
Shear Stress ('r) - A Shear Rate (5') -
dy Force a p p l i e d to a m a t e r i a l creates a state of stress w i t h i n
the material. Stress can be expressed in units of force p e r unit
7 a r e a (e.g., dyne/cm2), or, equivalently, energy p e r unit v o l u m e
Shear Strain (3') - Ax Viscosity (~/) = "it
Ay (e.g., erg/cma). In t e r m s of Fig. 1, the s h e a r stress, T, is the
force, F, necessary to m a i n t a i n steady shearing m o t i o n
Y against the resistance of the confined fluid divided b y the a r e a
of the s h e a r face, A.
F
r - (3)
dv = dx/dt A
F
A
~y Viscosity
~
The viscosity of a fluid characterizes its resistance to flow.
" EXx
The resistance to flow is, in turn, a m e a s u r e of the friction
b e t w e e n the flow units of the fluid (e.g., molecules) o r m a y
X
also be a m e a s u r e of the attractive forces b e t w e e n the flow
FIG. 1-Basic term definitions for simple shear. units. Thus, a "viscous" fluid (one reluctant to flow) m a y be so
b e c a u s e of high m o l e c u l a r weight (as in m o t o r oil) o r be of
derivative of the strain, s y m b o l i z e d ~, w h e r e the "dot" sig- relatively low m o l e c u l a r weight, b u t having strong i n t e r m o -
nifies "time derivative of." Therefore, from Fig. 1 lecular interactions (e.g., h y d r o g e n bonds, as b e t w e e n sugar
molecules in honey).
_ A~, _ A ( ~ / A y ) _ A(~/At______) _ A v (2)
The s e p a r a t i o n of molecules in flow dissipates energy,
At At Ay Ay chiefly as frictional heat. Flow, therefore, is a process w h i c h
If the d e f o r m a t i o n is simple shear, the strain rate is t h e n costs energy, of w h i c h the viscosity is a measure. F o r the case
called the s h e a r rate. The d i m e n s i o n a l i t y of y is L T - 1 L - 1 (e.g., of s h e a r d e f o r m a t i o n , the viscosity, a?, is calculated as the
cm/s p e r cm). Unit cancellation leaves reciprocal t i m e (s 1)as ratio of s h e a r stress to s h e a r rate. The viscosity, therefore, is
the energy p e r unit volume dissipated to a t t a i n a unit velocity
the unit of s h e a r rate. It is conceptually helpful, however, to
gradient.
r e m e m b e r that, as s h o w n b y Eq 2, the s h e a r rate is actually a
velocity g r a d i e n t (change in velocity p e r unit gap b e t w e e n T
rl = -7 (4)
shearing surfaces, A v / A y ) . Y
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Modulus of t e m p e r a t u r e , pressure, a n d concentration. If the viscosity

of such a m a t e r i a l is m e a s u r e d at any s h e a r rate o r s h e a r
Materials c o m p l y with an a p p l i e d stress b y deforming, o r
stress, the viscosity u n d e r all conditions of d e f o r m a t i o n is
u n d e r g o i n g strain. F o r ideal H o o k e a n materials, the strain
known.
will be p r o p o r t i o n a l to the a p p l i e d stress. The m o d u l u s is the
p r o p o r t i o n a l i t y constant b e t w e e n the stress a n d strain. F o r
example Non-Newtonian Fluids
T Of m a t e r i a l s e n c o u n t e r e d in the coatings industry, only
C - (s)
Y dilute o r low-molecular-weight p o l y m e r solutions or stable
dispersions of low c o n c e n t r a t i o n are likely to be Newtonian.
w h e r e the s h e a r modulus, G, is equal to the ratio of the s h e a r In general, p o l y m e r solutions, colloids, dispersions, a n d sus-
stress a n d s h e a r strain. Most p o l y m e r i c m a t e r i a l s a n d m o s t pensions of particulate solids will be non-Newtonian. F o r
coatings systems as well are non-Hookean, i.e., the m o d u l u s n o n - N e w t o n i a n materials, the viscosity is no longer a mate-
is not a m a t e r i a l constant, b u t will d e p e n d on b o t h rate a n d rial constant, b u t is called a m a t e r i a l f u n c t i o n - - i n this case, a
extent of deformation. "function" of the s h e a r rate (or s h e a r stress). F o r non-New-
t o n i a n fluids, a viscosity m e a s u r e d at a single s h e a r rate is not
an a d e q u a t e r e p r e s e n t a t i o n of the rheology of the system.
Units
Various systems of units for rheological variables are in use
a n d m a y be e n c o u n t e r e d in the literature. Until recently, the
m o s t c o m m o n system of units for rheological t e r m s was the C L A S S E S OF N O N - N E W T O N I A N B E H A V I O R
cgs (centimeter-gram-second), o r "smaLl metric" system.
However, m a n y technical p u b l i c a t i o n s a n d scientific j o u r n a l s In the following sections, the various types of non-New-
n o w specify that Systeme Internationale (SI) units be a d h e r e d t o n i a n flow behavior will be outlined. At the s a m e time,
to. The SI system is b a s e d on the "large metric," o r MKS several m a t h e m a t i c a l expressions which can describe non-
(meter-kilogram-second) units, with s o m e a d d i t i o n a l n a m e d N e w t o n i a n flow will be introduced. M a t h e m a t i c a l m o d e l s are
units. The units associated with the above variables, accord- useful for s u m m a r i z i n g flow b e h a v i o r quantitatively. To be
ing to the various systems, are given in Table 2. sure, m a t e r i a l s m a y be evaluated by qualitative c o m p a r i s o n
of flow curves (e.g., b y visual inspection), b u t the m a t h e m a t i -
cal analysis of a flow curve has significant value. F o r one
thing, the m o d e l constants m a y have physical significance.
CLASSES OF RHEOLOGICAL B E H A V I O R
F o r example, s o m e of the m o d e l s contain a yield stress t e r m
(see P l a s t i c (Yield) B e h a v i o r ) as a fitted p a r a m e t e r . The
Newtonian Fluids
m a g n i t u d e of this p a r a m e t e r m a y be coupled to sag o r
I s a a c Newton p o s t u l a t e d that the force resisting m o t i o n of leveling p e r f o r m a n c e [2]. A later section of this chapter,
liquids is p r o p o r t i o n a l to the rate at which one a t t e m p t s to LEVELING, gives examples of h o w sagging can be p r e d i c t e d
"separate the parts" of the liquid. In t e r m s of o u r defined for n o n - N e w t o n i a n fluids using constants from m o d e l s dis-
quantities, this w o u l d be expressed as cussed below. F u r t h e r m o r e , the values of m o d e l p a r a m e t e r s
m a y be associated with f o r m u l a t i o n variables, allowing one,
r ~ v (6)
in principle, to o p t i m i z e rheology b y adjusting c o m p o s i t i o n
or in a rational way.
It should be u n d e r s t o o d t h a t the models a b o u t to be dis-
r = n~/ (7)
cussed are actually idealizations a n d therefore limited in
w h e r e "0 is a c o n s t a n t of proportionality, called the coefficient their ability to r e p r e s e n t the b e h a v i o r of real materials. The
of viscosity o r simply the viscosity. models can describe real b e h a v i o r at least over a limited
E q u a t i o n 7 is the simplest example of a flow model, a n range of stress or strain rate. Thus, a second use of m a t h e -
expression w h i c h allows one to predict the flow p r o p e r t i e s of matical m o d e l s of flow is to m a k e p r e d i c t i o n s of flow behav-
a m a t e r i a l in response to an a p p l i e d stress. Fluids w h i c h obey ior, b e a r i n g in m i n d that it is d a n g e r o u s to extrapolate the
Eq 7 over a range of shear rate are said to be N e w t o n i a n over m o d e l s b e y o n d their range of validity.
t h a t range. The viscosity of N e w t o n i a n fluids is a m a t e r i a l As m e n t i o n e d above, the simplest flow m o d e l is the New-
c o n s t a n t a n d d e p e n d s only on the t h e r m o d y n a m i c variables t o n i a n expression, which has only one constant, the coeffi-
TABLE 2--Units.
Variable CGS MKS SI
Strain Dimensionless . . . . . .
Strain rate s- ~ s- 1 s-
Stress Dyne/cm2 N/M 2 Pascal (Pa)( = 1 N/M z)
Viscosity Poise (P)(= 1 dyne 9 s / c m 2 ) ... Pa - s (= 10 P) or
or centipoise (cP) (1 cP millipascal-second
= 0.01 P = 1 mPa 9 s) (mPa 9s)(= 1 cP)
Modulus dyne/cm 2 N/M2 Pa
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CHAPTER 3 3 - - R H E O L O G Y A N D V I S C O M E T R Y 337
cient of viscosity, 4. To describe m o r e c o m p l i c a t e d behavior,

we wilt have to a d d a d d i t i o n a l coefficients a n d terms, the
physical significance of w h i c h will be given w h e n possible.
Shear-Dependent Viscosity
Materials in w h i c h the viscosity falls with increasing shear
rate 3 are d e s i g n a t e d shear thinning. S i m p l e shear t h i n n i n g
b e h a v i o r w i t h o u t either t i m e d e p e n d e n c e (see u n d e r T i m e - ~p
D e p e n d e n t Fluids) o r a yield stress (see u n d e r Plastic
(Yield) B e h a v i o r ) is termedpseudoplastic, a c o m m o n type of
rl
n o n - N e w t o n i a n b e h a v i o r in coatings systems. Viscosity rising ~HB
with increasing rate of s h e a r is called shear thickening. The
t e r m dilatancy (see u n d e r Shear Thickening Fluids) is often N ~ ~ PL (n> 1)
a p p l i e d to s h e a r thickening behavior, although this refers
strictly to s h e a r thickening a c c o m p a n i e d b y a v o l u m e in-
PL (n< 1)
crease, as the t e r m implies. Figure 2 shows curves illustrating
viscosity-shear rate relationships for N e w t o n i a n a n d non-
N e w t o n i a n fluids.
As stated, N e w t o n i a n b e h a v i o r is the simplest of all a n d is
described b y Eq 4. The viscosity, 4, is a m a t e r i a l c o n s t a n t FIG. 2-Viscosity-shear rate curves for simple flow models.
i n d e p e n d e n t of s h e a r rate (Contour N, Fig. 2). More compli- Symbols represent the following fluid models: N = Newtonian;
cated viscosity-shear rate b e h a v i o r requires a m o r e c o m p l e x B = Bingham (~b, = plastic viscosity); HB = HerscheI-Bulkley;
expression to m o d e l it. The first level of complexity is to a d d PL = power law (n = exponent).
yield b e h a v i o r (see u n d e r P l a s t i c (Yield) B e h a v i o r ) to the
N e w t o n i a n model, resulting in the B i n g h a m equation [3]
from a Casson analysis are not necessarily true m a t e r i a l con-
,r- r0 = 4// (8) stants. F o r example, b e c a u s e the analysis of flow d a t a is sim-
E q u a t i o n 8 says that, above the yield stress (%), the shear ply curve-fitting, a finite yield stress will generally be o b t a i n e d
stress (minus the yield stress) is directly p r o p o r t i o n a l to s h e a r w h e t h e r o r not the m a t e r i a l really possesses yield behavior.
rate. 4 It is a c o m m o n m i s c o n c e p t i o n that this c o r r e s p o n d s to The next c o m p l i c a t i o n we will i n t r o d u c e is to let the expo-
N e w t o n i a n b e h a v i o r above the yield stress. Figure 2, Curve B nent of the s h e a r rate in the N e w t o n i a n law be other t h a n
shows that the B i n g h a m m o d e l displays power-law-like be- unity. In o t h e r words, the s h e a r stress now will d e p e n d on
havior, b u t deviates from the p o w e r law (Curve PL) at higher s o m e p o w e r of the s h e a r rate
s h e a r rate, a p p r o a c h i n g the plastic viscosity, ~/e, as a limit.
Casson [4] modified B i n g h a m ' s equation by taking the square ' r = K * '~ (11)
r o o t of all t e r m s E q u a t i o n 11 is k n o w n as the p o w e r law or Ostwald-
'T 1/2 - - "1"1/2 = 41~:,/2' 1/2 (9) deWaele model. Here, K is a constant, s o m e t i m e s called the
"consistency, "s w h i c h has r e p l a c e d the coefficient of viscos-
The Casson m o d e l is n o t empirical, b u t was theoretically ity, 4. This is necessary b e c a u s e the exponent n can be o t h e r
derived specifically for systems whose p r i m a r y flow units are
t h a n unity, in w h i c h case K will not have p r o p e r viscosity
rigid rods. Casson's equation is r e p u t e d to hold for a variety of
units associated with it. The p o w e r law exponent, n, has b e e n
p a i n t systems, particularly as modified b y Asbeck [5]
t e r m e d the "flow index." Its value is characteristic of the
,~1/2 _ ,01/2 = ,/1/2,-1/2 (10) d e p e n d e n c e of viscosity on s h e a r rate, i.e., w h e t h e r the viscos-
which is somewhat surprising since few paints utilize rod- ity rises or falls with increasing shear. Dividing Eq 11 t h r o u g h
shaped particles as fillersor pigments. In fact, this author's b y , yields a form of the p o w e r law which relates the viscosity
experience is that frequently the Casson model does not rep- to the s h e a r rate
resent paint flow as well as certain other models (see below). 4 = K'* n-I (12)
In Eqs 9 a n d 10, q~, s o m e t i m e s called the Casson viscosity, is
not truly an "infinite-shear viscosity," b u t is a limit t h a t is w h e r e K' = (l/K) ira. Obviously, i f n = 1 in Eqs 11 a n d 12, the
a p p r o a c h e d , c o r r e s p o n d i n g to s o m e u n k n o w n high shear p o w e r law reduces to the N e w t o n i a n law. A value of n < 1
rate. The value o b t a i n e d for the Casson viscosity will d e p e n d c o r r e s p o n d s to s h e a r thinning b e h a v i o r a n d n > 1 to s h e a r
on the m a x i m u m e x p e r i m e n t a l s h e a r rate. As with all such thickening (Fig. 2 curves PL).
models, the u s e r m u s t be a w a r e that the constants resulting The next c o m p l i c a t i o n we shall consider is to a d d a yield
stress t e r m to the p o w e r law expression
3Any definitions or descriptions of shear rate-dependent behavior r - ro = K , " (13)
may likewise be stated in terms of shear stress dependence.
41n the Bingham expression and in other models incorporating a
yield stress term, it is important to note that the equations describe 5Mathematically, K corresponds (in numerical magnitude but not
flow behavior only when r > %. When r -< %, 5' = 0 (i.e., "q = co),and dimensionally) to the viscosity at unit shear rate (1 reciprocal sec-
there is no flow. ond).
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which is known as the Herschel-Bulkley equation. This model "qo -- "r/~

describes power law behavior above the yield point (Curve = ~ -~ (1 + [/37],)(,-,)/a (15)
HB, Fig. 2).
Figure 3 shows a generalized equilibrium flow curve [6, 7]. Here, T0 is the first Newtonian plateau viscosity and a is a
constant that determines the curvature of the transition re-
This figure represents the general features of the shear rate
gion between the lower Newtonian regime and the power law
dependence of viscosity for non-Newtonian fluids with any
regime. The value of a can be a measure of the breadth of the
time-dependent or relaxation behavior removed. It consists
molecular weight distribution of a polymer [10] or perhaps
of a low shear rate Newtonian regime, Region I, an exponen-
the particle-size distribution of a colloidal dispersion. Setting
tial shear thinning regime, Region II, a high-shear Newtonian
a = 1 - n in the above expression yields the Cross equation;
regime, Region III, and m a y include a shear-thickening re-
setting a = 2 gives the Carreau-B model. The parameter n has
gime, Region IV. The figure is explained in detail (see S h e a r - the identical meaning as in the simple power law model (Eqs
Thinning Fluids). The chief limitation of the power law 11 and 12), i.e., it is the slope of the power law region in a log-
models is that they are valid only over a limited range, log plot of shear stress versus shear rate. The constant/3 has
namely, the linear portion of Region II of Fig. 3. They cannot the dimension of time and is actually a time constant repre-
account for the upper or lower Newtonian regions and, in senting a characteristic time of the system. This time con-
fact, predict infinite viscosity at zero shear rate and zero stant m a y be related to, for example, the diffusional or
viscosity at infinite shear rate, both unrealistic limiting be- rotational relaxation time of the flow units (be they colloidal
haviors. Nevertheless, the power law models are found to be particles or polymer chains) or to the time for rupture of
quite useful within their limitations, particularly for engi- particle flocs or aggregates under shear. The location of the
neering-type calculations. The Herschel-Bulkley equation has transition from the initial Newtonian plateau (Region I) to
been found to be superior to a n u m b e r of other models in the shear thinning regime (Region II) in Fig. 3 is governed by
describing the flow behavior of a wide variety of coatings the value of/3 in an inverse sense: increasing/3 decreases the
materials over a useful range of deformation conditions [8]. shear rate of the onset of shear thinning and vice versa. In
Extending the range of validity beyond Region II in Fig. 3 other words, /3 defines a characteristic shear rate of transi-
requires more elaborate models. A simple extension of the tion, "]/,r [11-13].
power law model is to add an upper Newtonian limiting
1
viscosity, 7]~ ~ltr - (16)
/3
= ~ + K'~, "-1 (14)
It is tempting to postulate that /3 corresponds to the time
This expression is known as the Sisko model [9] and in- constant for Brownian diffusion of the primary flow units of a
cludes Regions II and III of Fig. 3. fluid. Stokes-Smoluchowski-Einstein theory gives us the
Of several proposed models encompassing Regions I, II, value of/3 for a particulate dispersion from
and III inclusively, two in particular have perhaps found
48w~R 3
wider acceptance and utility in the literature. These are the /3 - - - (17)
Cross and Carreau models. Hieber et al. [10] recently wrote a kT
general form of which the Cross and Carreau models are where r/ is the viscosity of the continuous phase, R is the
special cases (here modified to include Region III) particle radius, k the Boltzmann constant, and T absolute
temperature. For a typical aqueous latex dispersion, R = 125
nm, ~1 = 0.05 P, for which (at 25~ = 0.36 s, corresponding
to "Ytr = 2.8 s - l .
~/0 When the experimental shear rate equals 1//3, the shear-
ordering effect begins to dominate the randomizing effects of
Brownian motion, and onset of shear thinning is seen [14]
(see S h e a r - T h i n n i n g Fluids). This event corresponds to
log "17 Point c in Fig. 3. Equations 16 and 17 show how the transition
from Newtonian to shear thinning behavior m a y be con-
trolled. Any variation which increases the value of/3 (such as
increasing the effective particle size, the continuous-phase
viscosity, or lowering the temperature) will move the shear
thinning transition to lower shear rates. Decreasing/3 extends
I[I Newtonian behavior to higher shear rates. While Eq 17 is
strictly valid only for very dilute dispersions, it still provides
log "Y qualitative guidelines for manipulating the rheology of dis-
persions. For concentrated dispersions, "Oshould be taken as
FIG. 3-Generalized equilibrium flow curve: rio is the zero-
shear viscosity (random structure, maximum disorder); ~q| is the viscosity of the dispersion [15-17].
the high-shear limiting viscosity (maximum order). Region I is It follows from the above discussion that the broader the
the first Newtonian plateau; Region II the power law regime; size distribution of the flow units, the wider the spectrum of
Region III the second Newtonian plateau; Region IV the shear- relaxation times and the more gradual the transition from
thickening regime. (Adapted from Ref 6.) Region I to Region II (corresponding to a smaller value of a).
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The shear rate of transition is fixed by/3 (a mean relaxation shear rate depending on dispersion concentration [21], so
time), while a represents the distribution of relaxation times. that one or more of the other regimes are obliterated. That is,
the equilibrium flow curve may consist of Regions I to IV, I,
II, and IV only, I and IV only, or IV only.
Shear-Thinning Fluids Note, once again, that structural order and viscous dissipa-
tion are inversely related. An increase in order means de-
The term pseudoplastic has been applied t o fluids which
creasing viscosity (Region II), while a decrease in order
decrease in viscosity with increasing shear rate (or shear
results in an increase in viscosity (Region IV) [22]. It follows
stress) and implies shear-thinning behavior without yield
that, for Newtonian behavior, no change must occur in struc-
stress. However, the term is passing out of use in favor of the
tural ordering with shear. If the disperse system is unstable,
more general description shear thinning. Particulate disper-
i.e., tending to flocculate, the dotted curve may be followed
sions, polymer colloids, and polymer solutions can display
(Fig. 5) instead of displaying a low-shear Newtonian regime
this behavior above a certain concentration threshold.
[7]. Some systems may possess an apparent yield stress (see
Viscosity is a measure of the dissipation of energy or the
"energy cost" to flow. Shear thinning behavior, therefore,
Plastic (Yield) Behavior). (See DISPERSION RHEOLOGY
for additional discussion of particulate system rheology.)
implies that an increase of shear rate causes a structural
As a general statement, the range of accurate measurement
change in the fluid that allows it to flow more efficiently,
of most laboratory viscometers (for typical coatings fluids) is
consequently with less energy loss. The mechanism 6 involves
in the power law region. It may require extraordinary meth-
a shear-induced increase in order, or anisotropy, within the
ods or special instrumentation to characterize fluid behavior
system. Thermal (Brownian) motion tends to keep systems
in Regions I or III.
disordered (of random order). Shear forces work against this,
tending to impose orderliness. If shear rates are low, the
randomizing forces win out and the viscosity does not change Shear-Thickening Fluids
for small increases of shear rate (Point a to Point b in Fig. 3).
Since the structure is no less random anywhere in Region I We have seen above that shear thinning involves a shear-
than at zero shear rate, the viscosity equals ~?o,the zero-shear induced increase in order of a system. This allows the ele-
value. As the shear rate approaches a critical magnitude (see ments of a fluid to move or flow with minimum expenditure
Shear-Dependent Viscosity), the competition of thermal of energy. Conversely, shear thickening evidences that shear
randomizing and shear ordering starts to favor ordering has caused a decrease in order of a system. The resulting
(Point c in Fig. 3). In the case of polymers in solution, ran- disordered system dissipates more energy during flow and
domly coiled polymer chains tend to stretch in the direction hence is more viscous. An example of this is provided by the
of shear, partially uncoil, and align in more or less parallel catastrophic increase in viscosity observed by Hoffrnan [19],
fashion depending on the strength of the shear field. The resulting from the "buckling" or "log-jamming" of ordered,
particles of a dispersion tend to line up like "strings of pearls" layered arrays of particles.
(Fig. 4) and eventually in ordered planes perpendicular to the One frequently encountered type of shear thickening be-
shear gradient [18-20]. The result is a steadily decreasing havior is dilatancy. Properly, dflatant behavior is shear thick-
viscosity with increasing shear rate as the degree of order ening accompanied by an increase in volume of the fluid. It is
increases. Ultimately, if the shear rate is high enough, the most commonly observed in relatively concentrated disperse
maximum amount of shear ordering possible is attained and systems. In a dilatant system, the disperse phase particles are
the viscosity again becomes independent of shear rate (New- "wetted" with the minimum amount of liquid continuous
tonian). phase. Furthermore, at rest, the particles of the disperse
Figure 3 shows the overall way in which viscosity varies phase are in a random close-packed structure for which the
with shear rate for systems such as those described above interstitial volume is relatively minimal (Fig. 6). If the disper-
where Region I is the low-shear Newtonian regime (where sion moves only slowly, adequate time exists for the meager
Brownian motion controls structure). Region II is the shear- liquid phase to flow sufficiently to maintain the dispersed
thinning segment of the flow curve (where shear forces con- phase in a "wetted" state, and the system is able to maintain
trol the structure). It is found that the viscosity decreases its close-packed structure. Faster or more forceful motion
exponentially with shear rate here; hence, it is often referred causes a liquid-starved condition because the interstitial vol-
ume increases when the system is deformed or made to flow
to as the "power law" regime. Region III is the high-shear
(Fig. 6). There is no longer enough liquid to lubricate the
Newtonian regime. Here, the maximum degree of shear or-
system. The particles are, therefore, incompletely wetted, and
dering has been attained; thus, the viscosity is once again
forced flow would ultimately create microscopic voids, lead-
independent of shear rate. The high-shear limiting New-
ing to fracture of the material. The surface of a dilatant
tonian viscosity is usually given the symbol ~ . Region IV is a
material may appear dry when stressed due to the withdrawal
shear-thickening region which is occasionally seen, espe-
of surface liquid into the increased interstitial volume. This is
cially with concentrated dispersions. In actuality, shear thick-
seen when walking on wet sand on the beach. The resistance
ening in dispersions may occur at virtually any magnitude of
to deformation of the material can increase tremendously
with increased deformation rate due to these effects.
6The following discussion applies strictly to "stable" systems, i.e., During the course of a pigment grind operation, a fairly
those in which the net force between flow units is repulsive and
therefore which do not flocculate. The shear-thinning mechanism for sudden maximum in viscosity is often seen and is an indica-
unstable systems (net interparticle force attractive) is discussed in tion that a good grind (i.e., to primary particles) has been
the subsection entitled Mechanism of Thixotropy. achieved. In fact, the surge in viscosity and power draw result
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o o 0
o oO 0 9 9 0 0
9O 0 9
o 0 ooooo
9 o O0 0Ooooo o
o o o @
Q
o 0 9 0 ooooo0
O0 o o
o o o
o 0 ooo
o
o 9 0 o o
0 9 o o
0 o
0 o~ 9 9 ooo
0 Oo
0 o
o 9 o 9 o oooo
o
o ooo o
o 9 9
0 o o
0
~) ~)
0
o~
oo0oOOOOO o
oooo
oor
(c) (d)
FIG. 4-Dilute suspension of glass spheres in a polymer solution confined between glass plates with small plate
separation: (a) just after loading, particles are randomly distributed; (b)-(d) after being sheared in a side-to-side
direction at both increasing duration and shear rate. (By permission from J. Michel, R. P~tzold, and R. Donis,
R h e o l o g i c a Acre, Vol. 16, 1977, p. 317. Cited in Ref 20.)
03 permit flow under even very low stresses. For this reason,
paints in a dilatant state may suffer from rapid settling and be
difficult to redisperse. For most coatings operations, dil-
~X atancy is, in fact, undesirable. Pumping of dilatant disper-
\\
\\
sions may result in high back-pressure in lines, excessive
X\
\n \
log "~ \\ Dilatant Behavior
log
FIG. 5-Flow curve seen for unstable (flocculating) disper-
sions is indicated by the ascending curve going toward infinite
viscosity at low shear rate.
random
close-packed under shear
from the grind having become dilatant. The dilatancy is desir-
able here because it facilitates energy transfer throughout the Volume Expansion Under Shear
grind. Thus, dilatancy is frequently an indicator of achieve- FIG. 6-Dilatant behavior-volume expansion under shear.
ment of a stable dispersion to primary particles. Dilatant Random close-packed structure gives way to less-efficient
systems, in general, are not also thixotropic and therefore packing with necessary volume dilation.
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wear of system components, high power consumption, and shear thickening materials has been called rheopexy (a rather
loss of metering. In industrial rollcoating, dilatancy shortens rare phenomenon). The preferred term now for the latter is
coating lifetime on the roll, causing "dry edges" and loss of antithixotropy.
film thickness control.
Dilatancy is very sensitive to dilution and can be dramati- "Thixotropic Index" Test
cally reduced or eliminated by a small reduction in paint We emphasize that the most important characteristic of
solids. Also, addition of flocculants, electrolyte, a particulate thixotropic behavior is not shear thinning alone, but time
phase of different particle size, or warming can alleviate un- dependence. The relatively slow change of Viscosity provides
desirable dilatancy. Flow curve measurement provides an ex- a means of control of flow behavior and is the reason
cellent means of quantifying the degree of reduction of thixotropy is formulated into coatings. Hence, it is important
dilatancy achieved by these measures. to correctly characterize the time-dependent aspect of the
behavior. For this reason, the so-called "Thixotropic Index"
test is of limited benefit for characterization of such systems.
Time-Dependent Fluids We will digress for a moment to discuss the Thixotropic
Time-dependent fluids are those whose viscosity is a func- Index test since it is very widespread in practice. This
tion of both shear rate (or shear stress) and time. The most misnamed test determines the ratio of viscosities measured at
common such behavior encountered in coatings is time-de- arbitrary high- and low-shear conditions. ASTM Test Method
pendent shear thinning or thixotropy [23]. At constant shear D 2196 specifies taking the ratio of viscosities measured on
rate and temperature, the viscosity of thixotropic fluids will the Brookfield Synchro-Lectric viscometer at two speeds, rep-
fall, eventually reaching a constant value. If the shear rate is resenting a ten-fold speed ratio. Since only equilibrium vis-
changed, the viscosity will approach a new equilibrium value cosities are measured, the test yields no information about
at a characteristic rate. This behavior is illustrated in Fig. 7, time dependence and should be called the "Shear-Thinning
showing the way viscosity changes for a time-dependent sys- Index" instead (it is so termed in ASTM D 2196). Its value,
tem when the imposed shear rate (or shear stress) is changed like many quality-control tests, is in its simplicity and "quick-
in steps. Initially, the shear rate is zero, and the viscosity is and-easy" character, requiting no interpretation. As long as a
very high or infinite for a thixotropic system. As a shear rate given coating formulation changes little, so that the hidden
greater than zero is imposed (%), the viscosity drops expo- kinetic factor would be expected to change little, the "Thix
nentially, reaching a constant value. Increasing the shear rate Index" can reveal when something has gone awry (i.e., can be
to ~/2 decreases the viscosity further to a new equilibrium useful as a gross indicator whether a formulation error has
value. A decrease of the shear rate to % results in an exponen- occurred). However, it is always possible that the recovery
tial rise of viscosity to a higher equilibrium value. If, instead kinetics of the system have changed, which would go com-
of a multiple steady-shear experiment, just described, we pletely unnoticed if the "Thix Index" were the only test used to
were to carry out a shear rate (or shear stress) ramp experi- evaluate the rheology. Below, we will present test methods
ment (Fig. 8a), the time dependence would result in a loop which can be virtually as simple as the "Thix Index," but
(Fig. 8b). The explanation of the loop is given below, but has which give more useful, relevant, and complete information
to do with the fact that in a ramp experiment the equilibrium about thixotropic systems.
structure is never attained. The circuit in Fig. 8b is called a
thixotropic loop. Roughly bisecting the loop is the equilib- Mechanism of Thixotropy
rium-structure curve generated from the equilibrium viscos- Thixotropy is formally defined as an isothermal, reversible
ity data of Fig. 7. The analogous time-dependent behavior for sol-gel (fluid-solid) transformation [24]. As stated, it is experi-
enced as a viscosity which is both time- and shear-dependent.
Its origin is the breakdown, under shear, of internal fluid
"Y--o "YI>0 >4,1 "Y3 < "ir 1

structure to smaller flow units or the reassembly of structure
from smaller units when shear is relaxed.
The mechanism of shear thinning in thixotropic (time-de-
pendent) systems is different from pseudoplastic (time-inde-
r/ pendent) systems. In pseudoplastic systems, shear thinning is
the consequence of order externally imposed by shear [14]. In
thixotropic systems, an internally imposed, viscosifying
structure exists at rest, and the viscosity falls because of the
collapse of that structure under shear. (Flocculated systems
possess extra mechanisms of energy dissipation [25]; there-
fore, their viscosity will be higher than that of a deflocculated
dispersion of the same composition.) A further important
difference between the two is in the amount of time the
structure requires to respond to changes in shear rate. In the
Time case of time-independent systems, rapid structural equilibra-
FIG. 7-Time-dependent fluid behavior. At ~, = 0, viscosity is tion quickly accommodates to changes in shear rate. The
high (or infinite), Imposing ~'1 > 0 causes viscosity to fall expo- accommodation process essentially is particle diffusion,
nentially, reaching new equilibrium value. Subsequent changes which is quite rapid for submicron particles (see Shear-De-
in ~, result in re-equilibration of structure, hence viscosity. pendent Viscosity). The viscosity (a measure of structure)
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T
OT
A
= o,T
T
~ gRLr~ C~'Vr
Time ~1 ~p
time
FIG. 8-(A) Shear rate or shear stress ramp experiment. Shear rate or stress increases linearly
(sometimes logarithmically, optionally) to preselected maximum over a selected sweep time
period, resulting in a given acceleration gradient (~) or stress rate (~-); (B) Thixotropic loop.
Equilibrium structure curve (approximately bisecting loop) corresponds to data from an experi-
ment like that in Fig. 7.
thus always "keeps up" with changes in shear rate for such
systems. For thixotropic systems, the rate of structural reor-
ganization is slower than the experimental rate of change of
+--o ')'1> 0 ~t2< ~1
shear rate (~) or slow with respect to the time of observation
at constant shear rate. In a "shear rate ramp" experiment (see f f --~/00
below), the structural breakdown always lags behind the
ever-increasing shear rate, so that the viscosity on the "up"
r a m p will be higher than the equilibrium viscosity at a given
shear rate. On the "down" side of the ramp, the rebuilding
structure lags behind the rate of reduction of shear rate, so
that the measured viscosity is always lower than the equilib-
rium value. Thus, a "thixotropic loop" is seen, the size of
which should be proportional to the structural time constant
(
for a given r a m p time. Holding the shear rate constant, as in 7
the description above, allows the structure breakdown pro-
cess to "catch up." The viscosity then continues to change Time
until an equilibrium between structural breakdown and re- FIG. 9-Step-shear method for thixotropic recovery. High
shear rate ~'1 simulates application process, followed by low
covery rates is achieved (see Fig. 7).
shear rate ~'2, emulating film after application. Viscosity re-
covers from zero-time value ~1(o)with a characteristic time con-
Thixotropy Test Methods stant 7, eventually reaching final level ~(|
Two c o m m o n test methods for experimental characteriza-
tion of thixotropy are the "Thixotropy Index" test, and the test (Fig. 9). In it, a high shear rate (order of 104 s -1 desir-
"Thixotropic Loop" test, described above. In the latter, a able) is applied to the material, allowing time for the viscosity
p r o g r a m m e d increase and decrease of shear rate (or shear (hence, structure) to reach equilibrium; then the shear rate is
stress) is applied to a material (Fig. 8A), resulting in the suddenly reduced to a very low value (order of 1 s-1). The
generation of a loop (Fig. 8B). The size of the loop can be equilibrium a m o u n t of structure which can exist at the lower
obtained by numerical integration and is taken as an indica- shear rate is greater than at the previous high shear rate, so
tor of the rate of structural breakdown and recovery for a reassembly of fluid structure occurs, accompanied by an ap-
given r a m p time (the larger the loop, the slower the break- proximately exponential rise of viscosity. Meaningful physi-
down-recovery rates)9 This m e t h o d is a difficult one to do cal constants can be extracted from the data by fitting the
correctly, however, and is more complex than first appears 9 following equation to the recovery curve
The result (loop size) depends on the shear history of the
-q(t) = ~/(0) + [~(o0) - n(0)] [1 - e -t/v] (18)
s a m p l e - - t h e time interval since its last shear experience--
and the magnitude of the shear undergone 9 It also depends on where ~(t) is the viscosity as a function of time, t, "O(0) the
the shear rate (or shear stress) m a x i m u m in the loop experi- sheared-out viscosity (at time zero), ~(~) the infinite-time
m e n t and the r a m p rate (# or ~). recovered viscosity level, and 9 the time constant describing
A better m e t h o d is one which puts the thixotropic material the recovery rate9 The ratio ~(~)/~, which we have termed the
into a k n o w n state, i.e., having had a controlled shear experi- Recovery Parameter, has been found in our laboratories to
ence, followed by the test9 Such a method is the step-shear correlate well to thixotropy-related properties such as sag
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CHAPTER 3 3 - - R H E O L O G Y AND V I S C O M E T R Y 343
TABLE 3--Gel coat thixotropy test data comparison: z is the

recovery time constant and ~(~) the recovered viscosity level from High Steady-Shear Rate
a step-shear experiment; ~(m)/r is the recovery parameter.
~(~)/~, Thix
Composition ~, s r/(00),p P/s Index Sag?
With additive 8.9 116 13 4.04 No
Without additive 18.2 97.3 5.4 4.24 Yes
resistance a n d air e n t r a i n m e n t [26]. Table 3 shows d a t a for

two gel coat formulas, o n e sagging a n d one nonsagging. The Small-Amplitude
conventional "Thix Index" results do not predict the sag be-
havior and, in fact, are o p p o s i t e w h a t w o u l d be expected from Viscoelastic Measurement
the observed behavior. The s t e p - s h e a r e x p e r i m e n t a l p a r a m e -
ters T a n d ~(~) are given, along with their ratio. The nonsag-
ging f o r m u l a ("with additive") has b o t h a s h o r t e r recovery
t i m e a n d a higher final recovered viscosity, a n d the recovery
p a r a m e t e r takes b o t h of these into account to p r e d i c t signifi-
Time
cantly b e t t e r sag resistance t h a n for the "without additive" FIG. lOa-Viscoelastic characterization of structural recovery
by step-shear method using small amplitude oscillatory strain
material.
for recovery phase.
The step-shear test puts useful t h i x o t r o p y c h a r a c t e r i z a t i o n
within r e a c h of a n y d e v e l o p m e n t lab, for it can be p e r f o r m e d
on a n inexpensive v i s c o m e t e r (such as the Brookfield Syn-
chro-Lectric o r Wells-Brookfield Cone/Plate Viscometer) as ts
r--t
well as on m o r e s o p h i s t i c a t e d i n s t r u m e n t a t i o n . The latter
offer advantages, of course, p a r t i c u l a r l y if possessing visco-
elastic c h a r a c t e r i z a t i o n capability. The ideal way to charac-
terize thixotropic recovery is to b r e a k d o w n the structure
u n d e r high, steady shear (as in the step-shear method), t h e n E
step d o w n to a s m a l l - a m p l i t u d e (small strain) oscillatory-
s h e a r test, as described by Dodge [27] (Fig. 10a). The
r e b u i l d i n g of structure can then be followed b y m e a n s of the q
viscoelastic p a r a m e t e r s , w h i c h are sensitive p r o b e s of the S
v
fluid structure responsible for thixotropy. This m e t h o d m o r e
2
faithfully m i m i c s processes o c c u r r i n g in the relatively quies-
cent film after application. Figure 10b shows the recovery o
curves of the viscoelastic m o d u l i G' a n d G" (see The Viscoelas-
O
tic Parameters and Their Measurement) from such a step-shear O~
O3
experiment. b 7
cY
CL
Plastic (Yield) Behavior ~-3 <
I
An ideal plastic m a t e r i a l behaves as an elastic solid until a o I I

critical stress is applied, w h e r e u p o n it will "yield" a n d be- O 0.0 2.5 5.0 7.5
c o m e fluid. This critical stress is the yield stress, the mini- TIME (minutes)
m u m stress necessary to initiate flow. Ideally, the p r o p e r t i e s FIG. lOb-Experimental curves of G' (elastic modulus, []) and
of a m a t e r i a l exhibiting yield b e h a v i o r w o u l d be those of an G" (viscous modulus, O) versus time for a viscoelastic step-
elastic, or "Hookean," solid, b e l o w the yield stress. F o r such shear experiment.
materials, t h e steady-shear viscosity w o u l d be infinite (or un-
defined), the d e f o r m a t i o n l i n e a r with stress, a n d the yield
value a m a t e r i a l constant. F o r m o s t real materials, however,
d e f o r m a t i o n b e l o w the yield p o i n t is a c o m b i n a t i o n of elastic
Barnes a n d Walters [29] have c l a i m e d that m o s t m a t e r i a l s
strain a n d viscous flow. This is b e c a u s e interparticle forces
("secondary bonds") are of a range of types with a corre- with an a p p a r e n t yield stress will be found, in reality, to have
s p o n d i n g range of r e l a x a t i o n times [28]. As a consequence, a high b u t finite viscosity if m e a s u r e d at sufficiently low stres-
the m e a s u r e d yield value will d e p e n d on the rate at w h i c h the ses. In practical terms, yield stress b e h a v i o r can have i m p o r -
stress is i n c r e a s e d up to the p o i n t w h e r e flow occurs (the tant c o n s e q u e n c e s for the processing, stability, a n d ap-
faster the rate of stress increase, the h i g h e r the m e a s u r e d plication of coatings. There is quite obviously s o m e sort of
yield value). 7 flow d i s c o n t i n u i t y that occurs at low stresses, the m a g n i t u d e
of w h i c h is a p p a r e n t l y related to the n u m b e r a n d strength of
7For this reason, yield stress values cited in the literature are mean- interparticle attractive forces [28,30]. The yield stress is
ingless unless the exact experimental methodology is provided. therefore a n "engineering reality" [31 ] that m u s t be taken into
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account when formulating paints or dispersions. A yield "freeze." Coatings with significant yield stresses m a y exhibit
stress m a y be desirable or undesirable depending on the poor leveling [2] since, as the shear stress decreases during
process in question. Materials with a yield stress will often the course of the leveling process, the material effectively
exhibit thixotropy and viscoelasticity as well. becomes immobile when the dynamic yield stress is reached.
On the other hand, a small yield stress can be of great value
Static Versus D y n a m i c Yield Stress in inhibiting settling of particulate suspensions. One can eas-
There are two types of yield stress which m a y be measured. ily calculate the shear stress exerted on the surrounding me-
The first is the static yield stress, measured by the startup of dium by a spherical particle falling under the influence of
flow from nonflowing conditions. The second is the dynamic gravity
yield stress, which is the shear stress at which a presently Fg _ Force of gravity on particle
fluid material suddenly turns solid (or exhibits a flow discon- T--
tinuity). Experimental methods exist for measuring both A Surface area of particle
[32], and the type which is relevant to the particular process
Fg = 4 7rR3(pp _ Pl)g;A 4~rR2
in question should be the one measured. For example, for
long-term suspension of solids or for start-up flow in pumps,
the static yield stress is relevant. Postapplication leveling and ~- = -~ (pp - p~)g
sag behavior would be governed by dynamic yield stress
characteristics, including the kinetics of structural recovery
where R is the particle radius, pp the particle density, and Pl
(see thixotropy in T i m e - D e p e n d e n t Fluids). Some have used
the liquid density.
curve-fitting techniques to obtain a value for the yield stress
For a titanium dioxide particle of radius 0.2 m m and den-
by fitting a mathematical model for flow to a rheological flow
sity 4 g/cm 3, the shear stress due to gravity acting on the
curve. The Bingham, Herschel-Bulkley, and Casson models
particle is about 0.2 dyne/cm z. To prevent settling of such a
contain a yield stress term and have been c o m m o n l y used to
particle, the surrounding m e d i u m need only resist with an
obtain a yield stress from measured flow behavior. Such
opposing stress of greater than 0.2 dyne/cm z. Even this, alas,
methods are questionable, however, since one is attempting
is impossible for a Newtonian liquid, be it water or honey,
to infer a property of the solid state from behavior of the fluid
since it will flow under all stresses no matter h o w slight (it is
[25,33].
only a question of how slowly). A pigment particle will inevi-
Yield Stress Test M e t h o d s tably settle out of such a fluid, especially for viscosities of
practical magnitudes. However, if the suspending m e d i u m
Startup-of-flow methods include the use of penetrometer-
possesses a yield stress equal to or greater than the particle
type instruments such as a thermomechanical analyzer,
shear stress, the particle "thinks" it is suspended in a solid
where increasing force is applied to a standard probe. The
and will be suspended indefinitely. This a r g u m e n t assumes
yield stress is determined as the break point of a force-
more or less ideal yield behavior, which, as described above,
penetration curve [34].
m a y rarely be encountered. A m e d i u m with a measured yield
In recent years, a new type of instrument known as a
stress of apparently sufficient magnitude m a y or m a y not
controlled-stress rheometer has become commercially avail-
permit the particle to settle over long periods of time due to
able that is well-suited to measurement of yield stress and
the possibility of viscous flow below the apparent yield point.
other properties of structured materials. For this instrument,
Therefore, to ensure adequate practical stability, one should
the shear stress is the independent (or controlled) variable,
build in a higher yield value than that calculated from the
while the dependent (or measured) variable is the shear rate.
above.
This allows an experiment to be done whereby the stress is
gradually increased from zero or a very low value, registering
zero shear rate (i.e., infinite viscosity) until the applied stress Elastic Liquids (Viscoelasticity)
reaches the yield value, whereupon the viscosity becomes
finite. The instrument reports this value as the measured In ideal viscous flow, all energy input is converted either to
yield stress. Another recent method employs a special vaned heat or energy of motion. None is stored (i.e., none is con-
rotor to remedy problems of slip with yield-stress materials verted into potential energy). Therefore, viscous flow results
[35-37]. The vaned rotor consists of rectangular blades or in irreversible deformation. Newtonian liquids show essen-
vanes fixed to a rotating shaft. Advantages of this geometry tially ideal viscous (also called "inelastic") behavior over a
are: (1) there is little disturbance of the sample when this type wide range of deformation rate. For ideal elastic CHookean")
of probe is inserted, and (2) when the rotor turns, the mate- substances, all the energy of deformation is stored, similar to
rial moves as a solid "cylinder." Thus, the shear surface is a stretched rubber band. Consequently, elastic deformation is
within the material itself, avoiding problems of wall slip. not permanent, but is in fact completely reversible. Real
fluids can display elasticity, but mixed with viscous charac-
Practical Aspects o f Yield B e h a v i o r ter, in varying degrees. Hence, the term viscoelastic is applied
Some of the practical consequences of yield behavior occur to such materials. Not all non-Newtonian fluids have signifi-
in the processing of, for example, pigment dispersions. Dis- cant elastic properties, but m a n y do. The presence of signifi-
persions with high yield stresses m a y be difficult to dispense cant elasticity in colloidal systems generally means there is a
accurately or reproducibly via automatic metering systems. microscopic three-dimensional structure, or association net-
Pumps m a y actually refuse to move or m a y cavitate while work (rnicrostructure), within the fluid. Elementary flow
attempting to p u m p such materials; solenoid valves m a y units are linked together in some fashion such that the struc-
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tural relaxation time (see below) is measurably long. This

structure, and particularly the destruction and rebuilding rubber band
process that occurs during and after coating application, can
have great consequences for application and film formation
processes. An example of this is the influence of elasticity on oB
leveling of an applied coating [38] (see also Massouda [39]
and Glass [40]).
As the term implies, viscoelasticity refers to a material viscoelastic material
response which is a combination of viscous and elastic behav-
ior. Viscous flow superimposed on elastic strain results iia the
"relaxation," or gradual disappearance, of stress within the
strained object. This is manifested as an imperfect, or fading,
stress memory. Figure 11 illustrates the material response to time
an applied elongational stress for a material with permanent FIG. 11-Viscoelastic stress-memory loss: stretch-force ex-
stress m e m o r y (e.g., rubber band) and one with fading stress periment. Rubber band is cross-linked polymer, does not relax
m e m o r y (e.g., "bouncing putty"). stress ((rE) when stretched. Viscoelastic material can accom-
modate to strain by molecular motion (viscous flow), allowing
The Viscoelastic P a r a m e t e r s a n d Their M e a s u r e m e n t elastic stress to decay.
A convenient way of experimental characterization of vis-
coelastic materials is by alternating the direction of strain (or
6=o ~
stress). Most often, a sinusoidal deformation is employed
(Fig. 12). The strain amplitude must be kept small so that the
material response remains in the linear viscoelastic region Stress response,
where stress and strain are linearly related. 8 In perfectly elas- elastic solid
tic behavior (Hookean spring), the stress and strain are "in
phase" with each other, that is, u p o n deformation, the maxi- 6=90 c
m u m stress and m a x i m u m strain occur at the same instant in
time. If there is any viscous (energy-loss) component in the Stress response,
material response, the stress and strain maxima will not be viscous liquid
coincident, but will be "out of phase." This happens because
viscous flow relieves the stress within the material, causing
the stress m a x i m u m to occur before the strain maximum.
That is, as the rate of strain decreases near the m a x i m u m (or
m i n i m u m ) of the strain sine wave, stress relaxation "catches
up" and overtakes the stress-building effect of the strain. The
separation in time of the stress and strain maxima is called Time
the phase shift (orphase angle, the fraction of a complete cycle FIG. 12-Phase shift/~ for ideal viscous and elastic bodies.
in degrees or radians that the phase shift represents). The
phase shift is often given the symbol g. The faster the viscous
stress-relaxation process, the earlier in the cycle the stress that when 8 is zero, G* = G', and when 6 = 90 ~ G* = G". The
m a x i m u m will occur, i.e., the larger the phase shift will be. physical meaning is that, when 8 = 0, all of the measured
The limiting value of the phase angle for purely viscous liq- modulus is due to elastic effects, and when 6 = 90 ~ the
uids is 90 ~ (see Fig. 12). The reason is that, for sinusoidal modulus consists entirely of viscous effects. This follows
deformation, the m a x i m u m strain rate (maximum slope of from the discussion of the phase shift, above. By trigonome-
the strain sine wave) occurs 90 ~ ahead of the m a x i m u m try, G' = G* cos 6 and G" = G* sin 6. Alternately stated, G' is
strain, and that, for Newtonian liquids, the stress is propor- the c o m p o n e n t of the complex shear modulus which is in
tional to strain rate. Therefore, the m a x i m u m stress must phase with the strain. G' therefore represents the elastic part
occur at the m a x i m u m strain rate, which corresponds to a of viscoelastic behavior. The viscous c o m p o n e n t (G"), on the
phase shift of 90 ~. other hand, is derived from the part of the modulus which is
The derivation of viscoelastic parameters from a sinusoidal out of phase with the strain, but in phase with the strain rate.
shear experiment begins with the calculation of the complex Consider a dynamic test in which a sinusoidally varying
shear modulus, G* (refer to Fig. 13). This is simply the ratio of strain is applied to a viscoelastic material. The angular fre-
the m a x i m u m stress, ~o, to the m a x i m u m strain, 70 (G* = quency of the deformation is given by to -- 2~'f, where f i s the
%/70). F r o m G* m a y be separated G', the modulus of elastic- frequency of oscillation (s i) and to is in rad/s. Now, the
ity (storage modulus), and G", the viscous modulus (loss mod-
amplitude of the strain with time is given by
ulus). Figure 13 demonstrates the geometric relationship of
G* to its in-phase and out-of-phase components, G' and G", 7 = 7oCOS tot (19)
governed by the phase angle, 6. It is obvious from geometry
which describes a cosine wave of m a x i m u m amplitude 3'o and
period 1/to. The strain rate experienced by the material is then
8This is a requirement because the equations used are valid only in
the linear viscoelastic region. j, = - my o sin 0Jt (20)
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Complex G* = s h e a r stress O0
modulus shear strain - 'YO
out-of- T
phase axisl
Storage G' = G ' c o s
modulus
Loss G" = G'sin (~

modulus
G' in-phaseaxis
I " Dynamic
viscosity 'J~'--
G I!
FIG. 13-Viscoelastic relationships in the complex plane.
The oscillating strain p r o d u c e s a stress response c o m b i n a t i o n of two idealized behaviors: H o o k e a n elasticity

and N e w t o n i a n viscosity. The m e c h a n i c a l a n a l o g u e of
o- = o-oCOS (cot + 8) (21)
H o o k e a n b e h a v i o r is a spring of force c o n s t a n t G, a n d t h a t of
w h e r e 8 is the p h a s e shift, advancing the p h a s e of the stress N e w t o n i a n flow is a "dashpot" (a piston-in-cylinder filled with
relative to the strain. E q u a t i o n 21 m a y be equivalently w r i t t e n a viscous fluid of viscosity "O).These elements are c o m b i n e d in
[96] various ways to m o d e l viscoelastic m e c h a n i c a l response.
o-* = % cos 8 cos cot - o-0sin 8 sin cot (22) To build o u r first model, we will connect a spring and
d a s h p o t in series (Fig. 14), an a r r a n g e m e n t k n o w n as the
w h i c h describes a complex stress, where, by complex plane Maxwell model. To i m a g i n e w h a t response the m o d e l has,
relationships analogous to Fig. 13, o-0 cos 8 is the stress com- let's a p p l y a c o n s t a n t stress, o-0, to one end, the o t h e r being
p o n e n t in-phase with strain a n d o-osin 8 the stress c o m p o n e n t
fixed. By the way, o u r d a s h p o t is c o n s i d e r e d to be infinitely
w h i c h is out-of-phase with the strain (but in-phase with the
long so that the piston never r u n s out of travel. This being the
strain rate). We therefore can define a d y n a m i c viscosity, "o',
case, one can see that an e q u i l i b r i u m strain w o u l d never be
as the quotient of the stress in-phase with the strain rate
reached, b u t the d a s h p o t w o u l d continually move as long as
divided by the strain rate
the stress is applied. Since the m o d e l can "flow" w i t h o u t limit,
7' o-osin 8 o-o sin 8 G* sin 8 G" this is obviously a m o d e l for viscoelastic liquids ( s o m e t i m e s
. . . . . . (23)
~o Y0co co co called "elasticoviscous"). We have just d e s c r i b e d w h a t is
k n o w n as a creep experiment, in w h i c h a s u d d e n stress o-0 is
The above expression is o b t a i n e d using the relationships %
applied, a n d the evolution of strain, or d e f o r m a t i o n , is fol-
(strain-rate a m p l i t u d e ) = Y0coa n d G* = o-0/Y0.
lowed with time. The creep of a Maxwell liquid is not very
The m a g n i t u d e s of G" a n d G' reveal the relative i m p o r t a n c e
interesting, however. The strain-time curve consists m e r e l y of
of viscous a n d elastic b e h a v i o r in the m e c h a n i c a l response of
a material. In Fig. 13, again by trigonometry, the t a n g e n t of a straight line with intercept equal to o-0/G a n d slope of o-0/~
the p h a s e angle equals the ratio G'TG'. Thus, t a n 8 quantifies (Eq 26).
the b a l a n c e of energy loss to energy storage m e a s u r e d u n d e r We will use the Maxwell m o d e l to illustrate h o w equations
certain conditions of t e m p e r a t u r e , pressure, a n d frequency o r describing viscoelastic b e h a v i o r m a y be derived. Just as the
rate of d e f o r m a t i o n . F o r solids, t a n 8 can be useful to p r e d i c t stress is the s a m e in every p a r t of a stretched string, so is the
the likelihood of brittle o r ductile failure of a p o l y m e r or the stress the s a m e on b o t h elements for the Maxwell model, a n d
s o u n d a b s o r p t i o n o r v i b r a t i o n d a m p i n g properties. F o r liq- also, therefore, the rate of change of stress is identical as well.
uids, t a n 8 can m o n i t o r the progress of fluid r e s t r u c t u r i n g in
O'Total = o-Elastic = O-Vi . . . . . ( = O-0) (24)
thixotropic recovery. The latter m a y be useful in c o m p u t i n g
sag resistance for w h e n t a n 8 b e c o m e s less t h a n unity, the and
system has essentially b e c o m e i m m o b o l i z e d (i.e., r e a c h e d a
o"T = 6-e = ou (25)
" d y n a m i c yield point"). W h e n t a n 8 > 1, viscous flow (i.e., a
steady-state viscosity) is possible. W h e n t a n 8 < 1, however,
the m a t e r i a l is m o r e elastic t h a n viscous (i.e., a p e r c o l a t i n g \ G
n e t w o r k extends t h r o u g h o u t the bulk, a n d it is essentially an \
elastic solid).
\
Viscoelastic Models \
It turns out that viscoelasticity can be r a t h e r realistically \
m o d e l e d b y simple m e c h a n i c a l analogues. These are useful
not only as an aid to c o n c e p t u a l i z a t i o n of viscoelastic behav- FIG. 14-Maxwell model. G is force constant of
ior, b u t also in helping to u n d e r s t a n d the e l e m e n t a r y m a t h e - spring; ~ the viscosity of dashpot fluid; ~ro is the
matics of viscoelasticity. As we have said, viscoelasticity is a applied stress.
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CHAPTER 33--RHEOLOGYAND VISCOMETRY 347
F u r t h e r m o r e , the total strain is clearly the s u m of the strains Stress

u n d e r g o n e by the two elements
7r = 3`E + 3`v = 0-E + 0-_~# (26) a0

G B
The expression on the right follows f r o m the definition of the
m o d u l u s (G = 0-/3,), Eq 4, a n d the fact t h a t 3` = ~/t. It is also
true that
~T = 7E + ~v = 0-E + 0-v (27) a0

G B e
An alternative to the creep m e t h o d that is p a r t i c u l a r l y useful
for viscoelastic solids is to apply a s u d d e n d e f o r m a t i o n a n d
follow the decay of stress w i t h time. This is similar to the
e x p e r i m e n t d e p i c t e d in Fig. 11 a n d is k n o w n as stress relaxa-
tion. S u d d e n i m p o s i t i o n of a strain 3`o results in instanta- X (='r//e) TEe
neous lengthening of the spring. The d a s h p o t experiences, in relaxation
turn, an initial stress 0-0 from the extended spring, causing a time constant
g r a d u a l m o v e m e n t of the d a s h p o t ' s piston, resulting in relax- FIG. 15-Stress relaxation (constant strain) experi-
a t i o n of the stress. By m a n i p u l a t i o n of the above equations, ment. initial elastic stress r o relaxes viscously with a
we can arrive at a quantitative w a y of describing this relaxa- time constant ,1 ( = ~q/G). A corresponds to the point
tion process. where stress has fallen to a value ~role.
Since the strain in a stress-relaxation e x p e r i m e n t is con-
stant (3`0), the total strain rate, 7T = 0. Therefore, f r o m Eq 27 m e n t s - - s e e below.) E q u a t i o n s derived for the Maxwell m o d e l
[42,43] show how the viscoelastic t i m e constant, X, m a y b e
0-v _ oE _ d0-/dt
(28) o b t a i n e d from the oscillatory d a t a
B G G
G~0X
rearranging B'co = G . . . . (31)
1 + 602)i 2
do"_ G dt (29)
and
0-v B
G~2,~. 2
Integrating Eq 29 from t i m e 0 to t i m e t results in the Maxwell G' - - - (32)
1 + ~o2h 2
stress relaxation expression
or = 0-oe - ~ " " (30) from w h i c h
Figure 15 illustrates the decay of stress in a c o n s t a n t strain or G" 1

tan 6 - - (33)
stress relaxation e x p e r i m e n t for the Maxwell model, de- G' ~0h
scribed b y Eq 30. Note that the quantity B/G has the d i m e n -
w h e r e G~ is the p l a t e a u m o d u l u s (limiting value of G ' r e a c h e d
sion of time. We will assign to this q u a n t i t y the symbol A a n d
at high frequency = Maxwell spring constant). E q u a t i o n 33
refer to A as the stress-relaxation time constant. It can be seen
from Eq 30 t h a t w h e n t = B/G, or = 0-o/e.~Therefore, A repre- says that w h e n G' a n d G" cross over (tan 6 = 1), X = l/c0c (~0C
sents the time r e q u i r e d for the stress to fall to 1/e of its initial is the crossover frequency). The p l a t e a u m o d u l u s can be ob-
value (Fig. 15) a n d gives a convenient w a y of quantifying the t a i n e d from Eq 32, as well, since at the crossover p o i n t G~ =
rate of d e c a y of stress in viscoelastic materials. 2G'. Similarly, at crossover, the zero-frequency p l a t e a u vis-
The t i m e constant, h, could also be called the stress m e m - cosity, B0 = 2B' (from Eq 31).
o131 t i m e c o n s t a n t since it is related to the t i m e it takes for a If the m e c h a n i c a l elements are c o n n e c t e d in parallel r a t h e r
viscoelastic m a t e r i a l to "forget" its initial elastic stress level t h a n series, they each experience identical strain, b u t the
w h e n subjected to a c o n s t a n t strain. As such, X d e t e r m i n e s stresses are n o w additive. This a r r a n g e m e n t is called the
the role t h a t viscoelasticity plays in a n industrial process. Kelvin-Voigt m o d e l (Fig~ 16). Because the elements are n o w
That is, elastic m a t e r i a l s generate a n "extra (elastic) stress" in parallel, the Kelvin-Voigt m o d e l can only u n d e r g o finite
w h e n deformed, w h i c h m a y result, for example, in the stabili- strain, limited b y the extensibility of the spring. Therefore,
zation of fluid structures w h i c h w o u l d o r d i n a r i l y collapse t o o this is a m o d e l for a viscoelastic solid b e l o w its yield point.
quickly to be i m p o r t a n t . These include, for example, liquid E q u a t i o n s for creep, stress relaxation, a n d t a n 8 for the
fibers a n d webs, w h i c h result in roller s p a t t e r [41]. The mag- Kelvin-Voigt m o d e l are
n i t u d e of the u n d e s i r a b l e effect will d e p e n d on the rate at Kelvin-Voigt creep
w h i c h the elastic extra stress decays or "relaxes," as we'll see
below.
3' = G (1 - e -t/a) (34)
In m o d e r n rheometers, sinusoidal oscillation is the m o s t
c o m m o n m e t h o d of viscoelastic characterization. (Creep is
Kelvin-Voigt stress relaxation
also available as a viscoelastic test m o d e for controlled-stress
i n s t r u m e n t s a n d stress relaxation for controlled-rate instru- or = ToG (35)
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G 71
\
\
\
\
\
0
/ G1
72
II
FIG. 18-Burgers model. Symbol definitions same as Fig. 13.

y
Subscript 1 refers to the Voigt element, 2 to the Maxwell ele-

ment.
then be extracted from the data by analysis according to one

FIG. 16-Kelvin-Voigt model. Symbol definitions or more of the above models.
same as Fig. 14.
Viscoelasticity and Industrial Processes
tan 6 = toh (36) Now, since industrial processes are of m a n y types, how do
These equations describe an exponentially increasing strain we assess the effect of elasticity on a given process? That
at constant stress (see Fig. 17 and Eq 34) and a nonrelaxing depends in part on the length of time the process stress is
stress at constant strain (Eq 35), respectively. applied to the material. That is, what's most important is not
The Maxwell and Voigt models, by themselves, are too how rapidly a stress is applied nor even the magnitude of the
simple to describe accurately most real viscoelastic materials. stress, but for how long the stress is applied relative to the
However, a Maxwell element connected in series with a time required for any elastic "extra" stress to decay. This
Kelvin-Voigt element turns out to model the linear viscoelas- suggests taking a ratio of the stress relaxation time, A, to the
ticity of m a n y real systems rather well. Figure 18 shows such time (duration) of the process stress, t
an arrangement, known as the Burgers model. For complete- A
ness (and also because an error in the Burgers stress-relaxa- De - (39)
tion expression has crept into the literature), equations t
describing creep and stress relaxation behavior for the This ratio is a defined theological term known as the Deborah
Burgers model are given number, De. It is n a m e d for the Biblical prophetess Deborah,
Burgers creep who prophesied that the "mountains flow before the Lord"
[44]. This is a perfectly accurate statement, made long before
% + ~r~ + ~11(1 - e -t/A') (37) being verified by the science of geology, of the fact that, on
= G--2 ~2 God's time scale, rock formations can be observed to undergo
Burgers stress relaxation permanent deformation, or flow. In other words, if the stress
time scale, t, greatly exceeds the relaxation time, h (De ~ 1),
tr = ~/oG2e-t/'x2 + ~0G1 (38)
the material will respond as a viscous fluid (because elastic
where hi = ~1/GI and h2 = ~2/G2. The creep and stress stress has time to decay). Conversely, if De ~ 1, the stress
relaxation behavior for the Burgers model are shown in Figs. duration is too brief to provide an opportunity for viscous
19 and 20. Modern rheometers of the type known as "con- relaxation, and the material behaves as if an elastic solid.
trolled stress" (see Rotational Instruments) are capable of Thus, the Deborah n u m b e r quantifies the proportion of elas-
performing creep measurements. Viscoelastic constants can tic to viscous control of a process. This is one reason why a
determination of the viscoelastic properties of paints and
Strain, coatings is important. The results of an analysis by Keunings
[38] of the effect of viscoelasticity on leveling can be adapted
3'
/
retarded spring to the situation of a typical paint, and the influence of the
motion: elastic-stress relaxation time constant on leveling rate is
shown in Table 4. To be sure, real materials m a y not exhibit
"Y(t)= ~0 (l_e-t/X) simple exponential stress decay (i.e., a single relaxation time),
but rather m a y possess a spectrum of relaxation times. How-
ever, the mechanical response will be dominated by a "mean"
relaxation time (or sometimes the longest relaxation time
[38]), obtained from experiments such as described in forego-
ing sections. Simple viscoelastic dispersions can show Max-
wellian behavior with a single relaxation time [45,46].
Time One of the reasons that associative thickeners (ATs) have
FIG. 17-Kelvin-Voigt creep (constant stress) experiment. At been so successful in being able to thicken paints without at
constant applied stress ~ro,strain increases exponentially with the same time adversely affecting flow and leveling is no
time constant A ( = -q/G). doubt due in part to their low elasticity. Even though ATs
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slope = strain rate, dT/dt

Strain,
3'
t viscous
flow:
77 = O~QO or,
- .y
instan- t/x) "Y(t)= ~t

taneous O0 {
strain: G22
Time
FIG. 19-Burgers creep (constant stress) experiment. Under applied stress ~0, the
Burgers model undergoes instantaneous deformation equal in magnitude to (rolG. In
next segment of curve ("retarded spring motion") strain increases exponentially
with time. Finally, spring is fully extended and viscous flow occurs with a constant
strain rate.
O viscous
relaxation:
"Y0G2e-t/x2
_~ unrelaxed stress:
oGi
time
FIG. 20-Burgers model stress relaxation (constant strain). Stress generated by
initial strain ~'o decays exponentially governed by the relaxation time ~ ( = ~/~G2).
Voigt element contributes unrelaxed stress ~r| = ~'oG1.
TABLE 4--Leveling rate dependence on Maxwell relaxation time, As stated before, the process consequences of viscoelastic-
h. c~ = da/dt, where a = roughness amplitude, and tl/2 = time for ity stem partly from the stabilization of otherwise unstable
a ~ 0.5ao (initial amplitude).
liquid structures by the elastic "extra stress." Thus, liquid
;t, s 0.0 0.1 1.0 10.0 50.0 100.0 fibers and "webs" which would ordinarily collapse by surface
c~, s -t 34.5 7.75 0.972 0.0997 0.02 0.01 tension are stabilized, producing, for example, excessive
tl/2 0,020 0.09 0.67 6.95 34.7 69.3 rollcoat spatter (or "misting") and ribbing, and inhibiting at-
omization of sprayed materials. The importance of viscoelas-
generate a three-dimensional network structure within the ticity for a particular process is gauged, using the Deborah
fluid, 9 they typically would have negligible G' values, in con- number, by the ratio of the stress-relaxation time constant to
trast to typical cellulosic thickeners, for example. This is be- the time duration of the process stress. Of course, both the
lieved to be due to the extreme lability of the micellar magnitude and lifetime of the elastic stress will be important,
junctions of the associative network, resulting in very short for together they will govern the degree of stabilization.
network relaxation times [46,47]. Thus, the decay of elastic The analysis of the problem is complicated by the fact that
stress in ATs is so rapid that such stresses are virtually unob- m a n y processes, particularly of coatings application, involve
served (De ~ 1). strain magnitudes outside the range of linear viscoelasticity.
Approaches to nonlinear viscoelasticity exist, but are beyond
9See Chapter 30--Thickeners and rheology modifiers. the scope of this chapter. Quantitative prediction of viscoelas-
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tic effects would require the use of a model for the fluid strain rate thickening. For example, Lu [48] observed that
behavior, or viscoelastic constitutive equation, also outside polyacrylamide thickeners in latex paint systems showed ex-
the scope of this presentation. However, it is often possible to tensional thickening behavior, whereas hydroxyethylcellu-
build experimental correlations between coating elasticity lose-type thickeners did not. Coatings application processes
and performance problems, so that guidance may be pro- are generally high strain rate, so it is clear that ~/e can domi-
vided for formulation efforts to solve them. nate the mechanical response, generally leading to detrimen-
For most modern coatings, in particular, the origin of elas- tal consequences. Extensional stresses can stabilize liquid
ticity is likely to be an associated structure built up from a "webs" and fibers, such as form in direct rollcoating, allowing
dispersed phase rather than polymeric entanglement. Such them to grow large instead of dissipating. This can result in
particulate flocs are generally shear-sensitive and are reduced heavy ribbing and "misting" (roll spatter) [49]. On the other
or destroyed by high-shear application processes. The elastic hand, the breakup of a liquid jet to form atomized droplets in
modulus G' will be seen to decrease with increasing strain spray application is suppressed by a high extensional viscos-
and strain rate outside the linear regime. Thus, in most cases, ity because the liquid fibers formed intermediary to droplet
G' is a measure of structure that has its greatest effect at low formation are inhibited from disintegration. J. E. Glass has
strain and strain rate (unless the elastic character is high- been the chief proponent of the study of extensional viscosity
polymeric in origin). Therefore, under most conditions of in relation to paint performance, correlating it to roller spat-
application, structure (therefore elasticity) is destroyed and ter [41] and the performance of sprayed coatings [50].
must rebuild in the applied film. Herein, it is seen that Massouda did a clever and, unfortunately overlooked study of
thixotropy and viscoelasticity are kindred phenomena. the relationship of extensional stress measurements to visco-
elastic relaxation kinetics and thence to spattering of paints
[39].
EXTENSIONAL RHEOLOGY
Extensional Viscosity Measurement
The other important deformation occurring in coatings
besides simple shear is extensional (or elongational) defor- There are, unfortunately, few commercial instruments
mation. Extensional or "stretching" deformation causes an suitable for extensional measurement on coatings. Carri-Med
increase in length and decrease in cross section of an object. (division of TA Instruments) markets the Spin-Line
In a simple shear field, particles or polymer coils (i.e., the flow Rheometer (SLR) utilizing the fiber-spinning geometry.
units) rotate with a velocity ~/2. The rotational motion lessens Rheometrics' RFX rheometer is probably better suited to low-
the friction between the solvent and solute particles. In an viscosity fluids, using opposed-nozzle flow to measure exten-
extensional flow, this rotational accommodation to the flow sional forces (the latter instrument offers dual high-shear and
field is not possible because there is no velocity gradient nor- extensional measurement capability). With the necessary
mal to the flow direction. The separation of flow units is thus electromechanical design and fabrication resources, one
more costly in terms of energy dissipation due to friction. might attempt to build a simple extensional rheometer, per-
Thus, the viscosity of a Newtonian fluid in extension turns out haps patterned after that of Gupta [51]. The relatively simple
to be three times greater than its viscosity measured in shear technique of convergent flow analysis was used by Lu for
(Trouton rule). measuring extensional properties of latex paints [48]. An
The extensional viscosity (~e) is calculated as the ratio of overview of extensional rheometry has recently been pub-
tensile stress to extensional deformation rate lished by James and Walters [52].
~e - (40)
POLYMER MELT AND SOLUTION
The strain in extension is usually defined as a Hencky strain, 9 RHEOLOGY
= Al/lo, where l0 is the original length and Al the increase in
length under tensile stress tre. The Hencky strain rate is then High-polymer solution rheology is a subject of relatively
the time derivative of the strain or little interest with respect to coatings due to the shift from
solvent-borne to environmentally compliant technologies,
1 dl d(lnl) such as water-borne, higher solids, and powder coatings. The
- - (41)
l dt dt polymers used for high solids and powder coatings are little
more than oligomers in order to achieve necessary flow for
E x t e n s i o n a l V i s c o s i t y in C o a t i n g s P r o c e s s e s satisfactory processing and film formation. Even the modest
molecular weight polymers used in solvent-borne varnishes
Many coatings processes involve stretching (elongational) and paints are below the entanglement molecular weight, Me,
flows (Table 1), and when coatings can support large exten- hence, both their neat and solution rheology are Newtonian.
sional stresses (i.e., high extensional viscosity) performance Similarly, powder coating melts are Newtonian until near
can be dominated by such flows. As mentioned, the viscosity gelation [53]. The viscosity of polymer solutions below Mc is
of a Newtonian liquid in extension is three times that mea- proportional to the weight-average molecular weight, Mw,
sured in shear. For non-Newtonian fluids, the Trouton ratio
[~(~)/~(~)] can be as much as 10 4. Furthermore, whereas the "qo = KMw(Mw < Mc) (42)
shear viscosity is usually a decreasing function of shear rate, where K is a constant dependent on chain flexibility (Tg),
extensional viscosity frequently displays strong extensional polymer-solvent interaction, temperature, etc. If Mw > Mc,
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CHAPTER 3 3 - - R H E O L O G Y AND VISCOMETRY 351
the motion of entangling polymers becomes much more com- It is reasonable that the viscosity of a liquid will be aug-
plex, and the viscosity now depends on M~ raised to the mented by a factor equal to the product of the particle intrin-
power of approximately 3.4 [54]. sic viscosity and the concentration of particles.
Trl0-----KMw34(Mw > Mc) (43) n, = I + [n]~' (45)
The viscosity of polymer melts follows a similar relationship. Einstein [56] was the first to calculate the intrinsic viscosity
It should be noted that polymers having highly polar or hy- for noninteracting rigid spheres in a Newtonian liquid and
drogen-bonding functionalities (such as commonly used in obtained the number 2.5
high-solids formulations) can show nonlinear dependence of
~]r = 1 + 2.5~b (46)
viscosity on molecular weight even below M~ due to transient
intermolecular associations [55]. The intrinsic viscosities of other particle shapes (e.g., prolate
The sole use of high-polymer binders in coatings today is and oblate spheroids--discs and rods) have been calculated
where they exist as a separate phase dispersed in a liquid [57] and are always greater than 2.5. This means that any
carrier medium, m Such materials are known as polymer la- deviation from spherical particle shape will increase disper-
texes, or latex dispersions. Because the latex polymer is segre- sion viscosity. Equation 46 is valid only in the very dilute
gated from, and therefore noninteracting with, the solvent, regime (d~ < 0.05). Batchelor [58] extended the rigorous treat-
the rheology of latexes is much simpler than that of the same ment to somewhat higher volume fractions by using a sec-
high polymer in the solution state. The rheology of polymer ond-order expression in
dispersions will be discussed below.
~]r = 1 + 2.5q6 + k~ 2 (47)
The value of k ranges from 5.2 to 6.2. Figure 21 illustrates the
DISPERSION RHEOLOGY typical dependence of 7It on 4~ for actual dispersions (using
data of Eilers [59]) and shows curves corresponding to the
A dispersion (or suspension) consists of a suspended or predictions of Einstein's and Batchelor's equations. It can be
dispersed discontinuous phase contained in a continuous seen that Batchelor's equation predicts a finite viscosity at 4~
phase. As an example, for coatings in particular, this might be = 1, which is not realistic. Also in Fig. 21, it is seen that ~],
a system in which a fine particle size solid is wetted by and rises toward infinity at a volume fraction considerably
thoroughly mixed in a liquid. However, the dispersed phase smaller than unity. The volume fraction corresponding to ~r
may be a liquid or semisolid (or gaseous) as well. The dividing oo is denoted thin, the m a x i m u m volume fraction, or maxi-
line between dispersions and suspensions is essentially one of m u m packing fraction. At ~ = thin, the density of particle
particle size. Dispersions are generally of colloidal dimen- packing is such that the dispersion can no longer flow. The
sion, about 10 nm to 1/.~m. Due to their small size and mass, value of ~,, will be system-dependent and will be determined
colloidal particles are very slow settling or nonsettling be- by particle shape, particle-size distribution, the ionic strength
cause Brownian motion effectively keeps them randomly sus- of the medium, the degree of particle flocculation, and the
pended. Suspensions range in size above 1/~m and generally exact manner in which the particles arrange themselves
exhibit rapid setting because Brownian forces are ineffective (pack) in three-dimensional space.
with such massive particles, and also because Van der Waals Numerous models have been proposed to take account of
attractive forces increase in proportion to particle size. the limiting concentration parameter q~,,, [15,59-61]. Proba-
Addition of a particulate phase to a liquid modifies its bly the model which has been most successful in fitting a
viscosity and sometimes its rheology. The modification to the variety of data is the Krieger-Dougherty equation [62]
continuous-phase viscosity made by an added particulate
phase depends on characteristics of the particle and on the
particle concentration. The contribution of a single particle
,, = ( 1 - g-~! (48)
to the viscosity of a dispersion is characterized by its intrinsic
Figure 21 shows the fit of the Krieger-Dougherty model to
viscosity (or limiting viscosity number), [~]. The primary fac-
some data of Eilers [59] with a value of [~] close to the
tors governing [~] are particle shape and deformability. The
Einstein value. The m a x i m u m packing fraction will, in fact,
influence of particle concentration on viscosity is expressed
have different, unique values at low and high shear rates
by the volume fraction (or internal phase volume) 4, the frac-
because the strength of the shear field determines the way
tion of the total volume of the suspension occupied by the
particles pack together. Recent reviews of the rheology of
suspended material and which is a dimensionless number. A
polymer colloids are recommended for further reading
convenient way of expressing the effect of a dispersed phase
[6,14].
on the viscosity of a liquid is by normalizing the dispersion
It should be noted here that, although the dispersion rheol-
viscosity to the pure-liquid viscosity. This ratio is termed the
ogy is controlled by the disperse-phase volume fraction, (b,
relative viscosity ~r and is also dimensionless.
the effect of the particle phase on the rheology may be greater
than expected on the basis of the volume of material added to
~r - a~d (44)
~z make up the dispersion. This is because the disperse-phase
volume may be augmented by various effects tending to in-
crease the effective particle radius. It is the "hydrody-
~~ high-molecular-weight, water-soluble polymers are used
as thickeners. However, they are used at low levels, and their effects namically effective" particle volume that determines the
on rheology are mainly colloidal/osmotic rather than as solution rheology. Thus, the rheological behavior will be found to
polymers. scale with the "effective" volume fraction, ~e, rather than with
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[] Eile'rs' relative viscosity data ] latex spheres (4 = 0.4) decreased from 106 to 10 for a two-
....... Einstein model / orders-of-magnitude increase in concentration of electrolyte
--! Batchelor model 1 [66]. In that study, the low-electrolyte latexes exhibited ap-
Krieger-Dougherty fit
parent yield stress behavior, a consequence of the increase of
the effective volume fraction of the latex particles due to the
expansion of the repulsive electrostatic field. The effect is so
~-
great that the particles are actually "locked" into crystalline
arrays that can diffract light, producing striking iridescent
colors. As the electrolyte concentration is increased, the
counterion "cloud" both shrinks the electrostatic field and
~.
shields particle fields from each other. Consequently, the vis-
o
cosity drops dramatically (remember that the volume change
depends on the cube of the radius change).
Rheology is particularly useful for dispersion characteriza-
Lt~ ~
tion because of its sensitivity to microstructure. Dispersion
rheology has two broad aspects: (1) the dependence of viscos-
ity on the concentration of the dispersed phase, and (2) the
~[ dependence of viscosity on shear stress and shear rate, dis-
: I I I cussed in CLASSES OF NON-NEWTONIAN BEHAVIOR.
0.00 0.15 0.30 0.45 0.60 0.75
Volume Fraction, ~o To the foregoing are added effects of particle shape, rigidity,
FIG. 21 -Relative dispersion viscosity data of Eilers, together particle size and particle size distribution, and interparticle
with best-fit curves for the Einstein model, Batchelor model, forces, both attractive and repulsive. All these factors com-
and the Krieger-Dougherty model. bine to determine the microstructure of the dispersion and
hence its rheology.
the formulated volume fraction, 4~. The effective particle ra- Dispersions can exhibit the full range of rheological behav-
dius can be increased in a number of ways, often as a conse- ior mentioned previously, including Newtonian, shear-de-
quence of employing various methods of achieving sta- pendent, time-dependent, plastic, and elastic behavior. A
bilization of dispersions. Adsorption of a polymeric stabilizer dispersion of noninteracting spherical particles will be New-
onto the surface of a particle adds the thickness of the stabi- tonian up to about q~ = 0.2 [15]. Above this point, onset of
lizer layer to the particle radius. This layer prevents the close non-Newtonian character begins due to particle interactions
approach and flocculation of particles by steric interactions and hydrodynamic factors. Mechanisms for these effects are
between stabilizer layers, resulting in steric stabilization. If discussed in the section entitled Shear-Thinning Fluids.
the thickness of the steric stabilizing layer on the particle is 6,
the effective volume fraction is [63]
SAGGING
~e= q~[1-t- ( ~ ) 3 1 (49)
A coating layer on any but a horizontal surface will experi-
ence a tangential shear stress due to gravity of magnitude
where R is the original particle radius. Quantitative viscomet-
tic methods have been developed for inferring the adsorbed- "r = pgh cos 0 (50)
layer thickness [63,64].
where p is the liquid density, g the gravitational acceleration,
Aqueous dispersions are often stabilized by association of
and h the uniform layer depth. 0 is the angle of inclination of
repulsive electrical charge with the particle, known as elec- the substrate to the vertical. For a vertical substrate, ~- = pgh
trostatic stabilization. The charge may be due to adsorption (Fig. 22).
of ions, anionic or cationic surfactants or polyelectrolytes, or, The shear stress on any layer within a coating will be equal
in the case of polymer colloids, to the presence of ionizable to the load from the outer layers. For a vertical surface
groups which are part of the polymer molecules. (In the case
of functionalized polymer latexes, such groups tend to mi- r = pg(h - y) (51)
grate to the particle surface.) The surface ionic charge propa- is the shear stress acting on a layer a distance y from the
gates an electrical potential field into the aqueous phase, substrate due to the weight of the outer layer of thickness
depending on the ionic strength of the medium. In the pres- h - y (Fig. 22).
ence of dissolved counterions, an ionic "atmosphere" devel- Coating layers having a yield stress % (see Plastic (Yield)
ops around the charged particle. These phenomena are the Behavior) will not sag unless the gravitational shear stress
origin of the so-called electroviscous effects, which have to do exceeds the yield value. The shear plane where yield occurs
with the way the electrical field surrounding the particle will therefore be at y' (for ideal yield behavior) when the
affects the effective volume fraction or collision cross section, following expression is satisfied
and the nature of the hydrodynamic interaction between
% <- og(h - y') (52)
particle and surrounding liquid [57,65]. Dispersion rheology
can be greatly altered as a consequence of these effects, as the Since only layers deeper than y' experience sufficient stress to
solution ion concentration or pH are varied. Krieger and flow, it follows that the layer h - y' (from y' to the free
Eguiluz showed the ~/r of a dispersion of uniform polystyrene surface) is solid and slides as a solid sheet over the flowing
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Y The sagging of a coating is similar to the problem of drain-

\ Tangential Gravitational Shear Stress age of a liquid layer from an inclined surface. The difference
\ between the two is that, in sagging, the coating layer is as-
T = p g h cosO sumed infinite in extent; hence, sagging causes no change in
\ the local coating thickness. If this assumption is not perti-
\ nent, then gravitational flow will result in thinning of the
(cosO= 1 for vertical)
\ coating layer at the top and thickening at the bottom of a
\ finite substrate. The distinction between the two processes
x j, Shear Stress on a Layer at Distance y may be useful for those desiring to calculate, for example, the
degree of "wedging" on a dipcoated part as against simply
\
calculating a sag length or sagging velocity. Again, in the case
T = pg(h-y) cosO of sagging, h is assumed constant and a sagging distance x
~-h~ may be calculated, whereas, for drainage, the thickness h
FIG. 22-Sagging, driven by gravitational shear stress. varies with distance x down the substrate. The equations
describing the flow are otherwise identical and interchange-
inner layers. For a coating with a large yield stress, the load able. By a derivation similar to that of Wu [68, 72] for sagging,
necessary to cause yield and flow is greater. Therefore, the the expressions below, describing drainage, can be obtained.
yield plane moves deeper into the coating layer, leading to a For a Newtonian liquid, the thickness at time t at a distance
phenomenon known as slumping. Slumping, therefore, is di- x down from the upper edge of the liquid layer is given by
agnostic of the presence of a significant yield stress. Figure 23
h = ~/ fix (54)
illustrates the effect of a yield stress on sagging, leading to
pgt cos 0
plug flow (slumping). Croll [67] showed direct evidence of
plug flow in a sagging coating possessing a yield stress. The angle 0 is as defined above. Most coatings are non-New-
The surface velocity of a sagging Newtonian liquid is tonian, however, which will have great impact on the drain-
pgh 2 age behavior. For example, shear thinning fluids will drain to
v- (53) a much more uniform film thickness than Newtonian fluids.
27 The gravity drainage of a power law fluid (see Shear-Depen-
(Wu [68] gives sagging velocity expressions for various non- dent Viscosity) is given by
Newtonian rheologies.) Sagging transmits substrate imper-
fections to the surface and amplifies them [69]. This is be-
cause any surface irregularity causes fluctuations in the
effective local coating thickness normal to gravity and there- In the above, K is the "consistency" term and n the exponent
fore in the local sagging shear stress. Furthermore, any local in the power law expression (see Shear-Dependent Viscos-
variations in film thickness due to application or to substrate ity). Here we see a practical application of mathematical flow
features (e.g., a hole or a corner) can produce local accelera- models. The parameters obtained from fitting the power law
tions of sagging in which thicker elements overtake thinner to an experimental flow curve can be inserted into the above
elements. This is a self-accelerating process, leading to drips, equation and the sagging behavior of a coating formula can
"tears," runs, or "curtaining" [70]. Such undesired flows can be calculated and graphed. Figures 24a and 24b compare the
be minimized by proper characterization and control of rhe- drainage behavior of a Newtonian and a shear thinning liquid
ology [71]. layer, showing film thickness as a function of both time and
height on a vertical substrate (calculated with Eqs 54 and
55).1~ The improved uniformity of the non-Newtonian coat-
Y ing can clearly be seen. For shear-thinning fluids with yield
\ Condition for slumping: stress, the drainage equation is
\ 7"0 <_.p g ( h - y ' )

The constants n, K, and % are obtained by fitting the Her-
xl / Thickness of slumping layer:
(h-y') -
z0
schel-Bulkley flow model to the experimental flow curve (see
Shear-Dependent Viscosity).
As with leveling, a realistic description of sagging must
include not only non-Newtonian effects, but also effects of
drying, geometry of the applied film, and the instantaneous
Pg rheological state of the applied film. A recent review, analysis,
and experimental study of sagging examines these effects
~-hq~ [67].
FIG. 23-Slumping (plug flow), caused by the presence of a
yield stress, ~o- l~Note that t = 0 is excluded, since h = ~.
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ufactured by Leneta) spreads paint stripes of graduated thick-

nesses over a nonabsorbent substrate. Sag is rated according
to the thickest stripe that does not show sag (Fig. 25). A
similar but somewhat simpler test involves the use of a wire
device that scribes two lines, of 1//8 and 1/4 in. (0.32 and
0.64 cm) width across a 3-wet-mil paint stripe, which is then
o hung vertically, and sagging is visually evaluated on the dry
paint film. 12The method is illustrated in Patton [73]. Another
device which has apparently met with some success is the so-
hf)
o ~--4
called "sagging balance" [74], which uses an electronic bal-
ance to measure the shift in mass accompanying drainage of
a coating applied to an inclined plate.
Sagging is, of course, driven by gravitational shear stress.
~ The sagging shear stress magnitude depends entirely on the
wet film thickness and density (Eq 50). The resulting shear
rate of sagging is determined by the rheology profile of the
paint in question. It is imprecise to attempt to predict sagging
from viscosity measurements at an arbitrary "sagging shear
rate" and may lead to incorrect estimates of relative sagging.
Film Thickness (cm) The proper way to predict relative sagging tendency is to plot
viscosity as a function of shear stress rather than shear rate.
Shear stress levels corresponding to the desired wet film
thickness can be calculated, and the magnitude of the viscos-
ity controlling sagging (~sag) determined from the graph. Fig-
ure 26 compares two paints in this manner, with indicated
gravitational shear stress levels corresponding to wet film
thicknesses of 3, 6, and 12 mils film thickness indicated. Fig-
ure 27 shows flow curves for the same two paints plotted as a
function of shear rate, with the calculated sagging shear rates
at 3, 6, and 12 mils indicated ( ~ / s a g = T s a g / ' / J s a g ) 9 The solid line
hO in Fig. 27 indicates approximately the shear rate of the
~
Stormer TM paddle viscometer. The ratio of the viscosities of
the two paints at the Stormer TM shear rate is less than 2,
whereas the ratio computed at the true sagging shear rates is
as high as 6. Clearly, comparison of viscosities measured at
~
an arbitrary shear rate can lead to incorrect predictions of
relative sagging behavior, particularly if flow curves should
cross over.
LEVELING
v .; i The mechanics of coating application generally cause the

applied coating layer to be initially rough and consequently of
varying thickness. Uniform film thickness is desired both for
FIG. 24-(a) Drainage behavior for Newtonian fluid is repre- reasons of appearance (color and hiding uniformity) and for
sented three-dimensionally as film thickness versus vertical substrate protection (necessary minimum film thickness).
height versus time. Note that thickness varies strongly with The process of smoothing of the initial rough surface is called
height, known as "wedging"; (b) Drainage behavior for non- leveling. Adequate leveling is of obvious critical importance to
Newtonian (shear thinning) fluid is represented three-dimen-
the success of a protective or decorative coating; hence, a very
sionally as film thickness versus vertical height versus time.
Note that thickness is nearly constant with height, showing that large number of studies of the subject have been published
shear thinning rheology can achieve improved film uniformity (e.g., Refs 2,38,75-82). Despite this, there is not complete
in dip coating. agreement on how best to predict leveling behavior from
rheological measurements. Leveling generally correlates rea-
sonably well to low-shear viscosity, but not always because of
Measures of Sagging
complicating factors such as viscoelasticity, time depen-
A number of laboratory methods for evaluating sagging dence, volatilization, wicking, and surface tension gradients,
have been used, some of which measure some rheological which can greatly confuse the picture. The leveling and film
property related to sagging behavior [80] and some of which formation of a paint layer is so complex that, in the opinion of
measure sagging directly. Among the latter are ASTM
D 4400, in which a drawdown blade with multiple slots (man- 12Federal Test Method 4493, September 1965.
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CHAPTER 3 3 - - R H E O L O G Y AND VISCOMETRY 355
i ..... 3ii II .... 9 9149 :: : ..... 9 :
c~
o
9
i
: i i J i 84 84 :
i
! :!:ii ..... i
~:
i
i
I ......
:~i
....
i
1
0~
o
v
FIG. 25-Sagging evaluated by Leneta drawdown blade.

Sagging is rated by the thickest paint stripe that does not o
show sag. 0~
~>
9i i
O
o
Shear R a t e ( s e c -1)
FIG. 27-Viscosity versus shear rate for two paints, together
with lines indicating sagging shear stress acting on films of 3,
6, and 12 wet mils thickness. Solid line is approximate shear
rate of the Stormer viscometer.
The mechanics of leveling is illustrated in Fig. 28 for a

liquid without surface tension gradient, having a sinusoidal
surface profile. The sum of all surface tension vectors in the
curved surface produces a net force downward at the "peaks"
and upward in the "valleys," the liquid-air interface acting as
9 . 9 : " ......
,if it were a stretched elastic membrane. Forces due to liquid
surface curvature are called capillary forces and result in
i............ i , capillary pressure variations within the liquid layer. Thus,
leveling is driven primarily by capillary pressure gradients
C
arising from local surface curvature under conditions of uni-
101_1J J JJJHIIoJO-~ J JIIJJ{lOJ 1 I J I~HIIIoI2 I , JlllllloI3 J l iJlJl [0 4 form surface tension. Liquid is "pumped" from the peaks into
Shear Stress (dyne/em 2) the valleys, ultimately producing a level surface. For thin
FIG. 26-Viscosity versus shear stress for two paints, to-
films, gravity is of negligible effect on leveling unless a critical
gether with lines indicating sagging shear stress acting on roughness wavelength is exceeded. For a typical paint, the
films of 3, 6, and 12 wet mils thickness. Relative sagging behav- critical wavelength is of the order of 1 cm [84].
ior is indicated by the ratio of viscosities at the appropriate film The quantitative prediction of leveling from physical prop-
thickness. From this, #sag = %ag/~sag. erties requires the use of some mathematical model of the
process. Smith, Orchard, and Rhind-Tutt [2] derived such a
this author, only computer modeling has the potential to model by a linear lubrication approximation-type analysis,
provide a wholly satisfactory method of analysis and predic- assuming a uniform sinusoidal surface profile. (The Los An-
geles Paint Club obtained a similar equation in 1953 [83] for
tion (see, for example, Schwartz and Eley [79]). However,
surface roughness approximated by semicircular arcs.)
such modeling capability is not readily available to most
Orchard later [85] developed a complicated expression for
practitioners, so we will review some of the analytical models the leveling of a more realistic, arbitrarily rough surface pro-
of leveling. These can provide at least qualitative understand- file in terms of a Fourier series. However, the expression
ing of the role of rheology and other factors in leveling. simplifies considerably when the coating thickness is as-
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is warranted, taking into account other film properties and

Ao processes that affect leveling significantly. A step was taken
-0 by Murphy [86] (see also Refs 87 and 76), who rederived the
Ax Orchard equation for pseudoplastic paints assuming power
law behavior (see Shear-Thinning Fluids)
-AP AP
u~0
Ax = a 0" '"'
1 Ao
This expression contains the power law coefficients, K and n,
all other terms retaining the same definitions as above. Note
that the leveling rate increases as the power law exponent, n,
decreases (i.e., as the paint becomes more shear thinning). As
-0
Ax expected, the leveling rate decreases with increasing K (con-
sistency). Lu [48] found the Murphy equation valid for corre-
AP lating the change of brushmark amplitude with time for
-0 systems where the leveling was clearly dominated by the
Ax viscosity. However, the Murphy equation still assumes that
viscosity depends only on shear rate and that surface tension
does not change during the leveling process. In reality, both
X D will change due to evaporation of the volatile phase of the
FIG. 28-Surface tension-driven leveling. Curvature of liquid coating or to wicking. The Murphy equation may be modified
surface generates capillary overpressures and underpres- to take account of time-dependent viscosity increase by in-
sures, P, which drive fluid flow to level the surface. There is no cluding a time-integral expression for the viscosity
surface tension gradient along the film coordinate (O~rl#x = 0).
Pressure is not uniform, however (OPIOx -4: 0). a('~-~/'~176176 2n+--n-l~
sumed to be small relative to the roughness wavelength. As-

suming a single sinusoidal wavelength (which is a reasonable s
approximation since the leveling behavior will be dominated
by the longest wavelength), the Orchard equation is where o(t) is some time function of viscosity relating effects
In at - 16~4h3trt (57) of thixotropy, drying, wicking, etc. The effect of time-depen-
a0 3)t40 dent viscosity on leveling is dramatic, as shown in Fig. 29.
Here, for two different paints, the decay of surface amplitude
for constant surface tension tr and viscosity 0. The equation is calculated using Eq 58 (Curves A) and Eq 59, together with
indicates that the logarithmic ratio of surface wave amplitude an experimentally determined expression for the increase of
a at time t to its initial amplitude a0 depends on the coating viscosity with time due to drying (Curves B). Camina [76]
layer thickness h to the third power and inversely on the reported that the viscosity of a drying paint increases expo-
wavelength of the surface roughness h to the fourth power. nentially in the initial stages. Therefore, an expression such
For roughness geometry other than sinusoidal, the constant as the following would fit drying-viscosity data
term (16zr4/3) will take on other values.
The Orchard equation, as written above, is only an approxi- o(t) = ooekt (60)
mation to the leveling behavior of most real paints because where 00 is the viscosity before drying has begun, k a drying
it assumes Newtonian fluid behavior and neglects time- rate constant, and t the time. Such an expression can be
dependent (and other 13) effects. The latter effects include inserted into Eq 59 in place of O(t) and integrated TM to calcu-
thixotropy and changes in rheology from loss of solvent due late the leveling curve for a paint whose viscosity is increasing
to drying and also due to "wicking" (absorption) of the liquid with time due to solvent loss. In fact, Eq 60 can account for all
phase into a porous substrate. Nevertheless, the Orchard time-dependent effects if k is understood as the reciprocal of
model conveys the importance of film geometry and physical a sum of time constants representing all time-dependent pro-
properties on leveling rates and allows an estimation of the
cesses [78]
order of magnitude of effects of changes in these variables.
For example, it should generally hold, despite complicating 1
k = (61)
factors, that doubling the wet film thickness will increase the Tall31 nt- Twick -~ T, hix
leveling rate eight-fold. However, a more realistic description
Here, rd~y is the time constant (inverse of rate constant) for
drying. Similar time constants can, in principle, be obtained
13Overdiep [78] has demonstrated that, for some solvent enamels
whose leveling is influenced by surface tension gradients, the
Orchard equation fails even to give a qualitative description of behav- 14provided that the viscosity during drying is measured at unit
ior. shear rate, K, in Eq 58 becomes ~ in Eq 59.
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~a
~d
k.---I
<~
~c5
mS I I I I
o 0 40 8 0 120 160
TIME (see)
FIG. 29-Calculated brushmark leveling for two paints, with and without effects of
drying. Curves calculated using Eqs 59 and 60: FI--Paint A, with drying; OmPaint A,
without drying; A--Paint B, with drying; 0 rePaint B, without drying.
for solvent loss through wicking (%ick) and for viscosity in- + Ao -Ao + 4o 4o
crease due to thixotropy (Tthix) (see Thixotropy Test Methods).
Quach [84] has discussed and summarized the shortcom- ' ' Ax r
1 D
ings of various laboratory methods of leveling evaluation. As
noted by Quach, much work on leveling has been done with- ~'- -'* AP
out adequately taking into account the numerous interacting 4k ,1~ --0
subprocesses whose final result is the dried film profile. An
Ax
additional important factor recently dealt with experimen-
tally and theoretically is the influence of surface tension
gradient-driven flows (Marangoni flows) [78,88,90]. Surface
tension gradients may arise due to a number of causes during
film formation and when present can have consequences for
the course of film leveling, among other things. Figure 30
illustrates the mechanism of surface tension gradient-driven
1
flow, which can result in the deleveling of an initially level
liquid layer. Local surface tension gradients may develop due
to differential evaporation or to temperature gradients (or f AO
other causes). This results in a surface flow from regions of Ax - 0
low surface tension toward regions of high, in an attempt to
reach surface equilibrium. The moving surface "drags" sub- AP
surface liquid along, creating a bulk flow. This is the Ax ~0
Marangoni effect. The driving force for Marangoni flow in the
case of differential evaporation is a shear stress tangent to the
film surface, %, proportional to the strength of the depen-
dence of surface tension on solvent concentration, Oo'/O[S], X D
and to the magnitude of the solvent concentration gradient, FIG. 30-Deleveling by Marangoni (surface tension gradient-
O[S]/Ox (x is the film coordinate). Hence driven) flow. Surface tension gradient (~r/Ox ~ 0) drives sur-
face flow, resulting in bulk flow and deleveling of initially level
O~r a[S] O~r surface.
~s - - - - - - (62)
o[s] Ox Ox
the surface tension gradient Oo'/Ox drives the flow. For the will result in an appearance defect. Overdiep [78] demon-
case of Marangoni flow driven by thermal surface tension strated (for solvent-based paints) that Marangoni flows ini-
gradients, replace O[S] by OT in the above. Persistence of tially enhance the leveling rate, but can produce a "rebound"
surface tension gradients until the film is incapable of reflow effect that ultimately worsens film roughness. Wilson [90]
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recently modeled this behavior by a linear perturbation anal- the best rheological test for leveling should most closely sim-
ysis. Other authors have discussed the importance of ulate the application experience of the paint. This means: (1)
Marangoni flows for waterborne, cosolvent-containing coat- the paint should experience shear rates/stresses of similar
ings [79,89]. magnitude and duration to those of the application process;
The role of viscoelasticity in leveling has been a subject of (2) the shear rate/stress should then be step-changed to values
some debate, with some authors concluding that elasticity representative of the leveling process; (3) the change of vis-
enhances leveling [91] and some that it retards leveling cosity with time should then be followed under the latter
[38, 92]. The evident link between elasticity and the under- conditions. This protocol is essentially identical to the "step-
lying structural rheology for coatings (see Viscoelasticity shear" method of characterizing thixotropic recovery de-
a n d Industrial Processes) suggests the presence of a gel-like scribed in Thixotropy Test Methods. This kind of procedure
structure of some sort in systems possessing significant elas- is most easily accomplished by employing a rheometer capa-
ticity. Such a structure would be expected to inhibit flow at ble of "job streaming" or "linked methods." However, the
low stress levels so that coatings which exhibit elasticity foregoing method still suffers from the limitation that the
should also show poorer leveling. In any case, the leveling effect of drying on viscosity during the leveling period is
behavior of viscoelastic systems has been modeled by Keun- neglected. Figure 29 demonstrates that this can be a very
ings [38] and the presence of viscoelastic relaxation shown to significant effect. Paints "A" and "B" were commercial for-
retard leveling. The leveling rate, a, as a function of the New- mulas which differed markedly in leveling performance. The
tonian leveling rate, O/Newt, was shown to be increase of viscosity with time during drying of a film of
typical applied thickness was measured for both and found to
O/ -- O/Newt (63) obey Eq 60. The latter expression was then inserted into Eq
1 + ~tffNewt 59 as the time-integral function for viscosity (as described in
where a = da/dt (rate of change of roughness amplitude, a, in the previous section) and the leveling curves in Fig. 29 were
s-~), and X is the elastic stress memory time constant (or calculated. There are two curves for each paint, one showing
relaxation time) (see Viscoelastic Models). In Eq 63, the New- how the paint levels without the effect of drying, and one
tonian leveling rate is always positive, hence elasticity (X > 0) calculated taking the increase of viscosity due to drying into
always retards leveling. Interestingly, if surface tension account. The effect of drying is most dramatic on Paint B,
gradients are present, aNewt may actually become negative where the reduction of surface roughness achieved after 3
(i.e., deleveling, or crawling). In such cases, late-developing min decreases from 50 to 10%.
elasticity will be of benefit by retarding the deleveling. Table 4 It is established that leveling shear stress decays expo-
shows the results of a calculation similar to that of Keunings nentially as leveling progresses [80]. A controlled-stress
adapted for the case of a typical paint. It is seen that the rheometer with programmable logarithmic stress ramps of-
leveling rate dramatically decreases and the leveling half- fers the ability to simulate the variation of viscosity with
time increases (by a factor of 3500), relative to the Newtonian realistic shear-stress decay using variable ramp times.
(2, = O) values, for ?t = 100 s. Leveling efficiency might then be judged by numerically inte-
grating the fluidity over the "leveling" period.
Measures of Leveling
| =
do~
(64)
Visual evaluation of leveling is common practice. However,
it is generally agreed that visual rating is subjective to the The leveling might be expected to be logarithmically related
degree that leveling rankings are often found to be operator- to the fluidity integral [81].
dependent. Numerous objective methods and standards have A very promising method for direct observation of paint
been published. Quach [84] reviewed aspects of both scien- leveling has been described by I~arskov [82]. It is an optical
tific and laboratory practical studies of leveling. For the lat- interferometric method which is simple but quite precise for
ter, special drawdown blades have been used such as the real-time surface profile measurement, having a vertical reso-
NYPC leveling test blade (ASTM D 2801), which has pairs of lution of a fraction of a micron. At present, unfortunately,
notches over a range of depths. Leveling is judged by the there is no commercial instrument based on Klarskov's
flowing together of adjacent paint stripes. This method has method.
been criticized by Quach and others [27] because the paint ATI Systems15 offers a relatively inexpensive noncontacting
passing through the notches experiences a varying shear rate Laser profilometer. Laser confocal microscopes can also
due to varying notch depth, resulting in a different shear measure the real-time evolution of surface profile during
history for each stripe, and because the shear rate achieved is leveling, but are quite expensive.
unrealistically low. The latter test has been superseded by
ASTM D 4062, based on a grooved drawdown rod. In this
method, the paint is presheared, simulating brushing shear RHEOLOGY INSTRUMENTATION
rates, by ejection from a syringe and 15-gauge needle prior to
drawdown. The leveling quality is then estimated by visual There are a great many instruments that have been devised
comparison of the dried film with plastic leveling standards to measure viscosity or "consistency." However, a number of
viewed against oblique lighting. them have in common a serious limitation in their design
Kornum [93] gives a good discussion of issues of measure-
ment under test conditions approximating real paint pro- 15ATISystems, Inc., P.O. Box 71460, 32355 Howard Street, Madi-
cesses, including leveling. Dodge [27] also emphasizes that son Heights, MI 48071.
www.iran-mavad.com

CHAPTER 3 3 - - R H E O L O G Y AND V I S C O M E T R Y 3 5 9
which makes them generally unsuitable for measurements of Efflux Devices (Orifice flow)
non-Newtonian fluids. The importance of this issue becomes
Effiux devices, or orifice cups, come in a variety of types,
apparent when it is realized that the majority of coatings and
but share one principle: measuring viscosity by flow from a
coatings components are non-Newtonian, yet m a n y laborato-
reservoir or cup through a restriction of some type. In most
ries continue to use methods which are not suited for such
cases, the restriction is simply a hole in the b o t t o m of the
materials. The difficulty with m a n y of the "traditional" labo-
reservoir, but in some it is a short tube. These devices have
ratory viscometers is that the "flow field" (the total descrip- the advantages of low cost, ease of cleaning, durability, and
tion of the trajectories of the fluid elements) is complex and simplicity in the measurement, which is simply the time to
not subject to practicable mathematical description. The re- empty (in whatever m a n n e r "empty" is defined). They also
suit is that an accurate strain rate cannot be calculated. have, however, a n u m b e r of limitations. The first is that the
Therefore, even if the stress is known, the true viscosity can- flow is never viscometric. Even when a short capillary tube is
not be obtained. Furthermore, the shear field is often so non- the exit, the length-to-diameter ratio is too small for proper
uniform that, for non-Newtonian materials, the viscosity of tube flow to develop, so that the flow is dominated by en-
the material itself varies within the test sample. For complex trance effects. In fact, the orifice cups have been described as
flow fields, such an error cannot be corrected. The measure- "poor capillary viscometers." Since substantial shear stress is
ment error will be in proportion to the deviation from New- not developed in the exit hole, orifice cups are not suitable for
tonian character. Nevertheless, such instruments have been very thin liquids because a significant fraction of energy is
in use throughout the industry for decades and no doubt will dissipated not in viscous flow, but merely in accelerating the
continue to be used for the foreseeable future. The approxi- fluid. In other words, measurements on low viscosity fluids
mate measurement given is s o m e h o w related by the practi- are subject to significant fluid inertia errors. Thus, for the
tioner to something believed relevant to the performance. Ford No. 4 Cup (ASTM Method D 1200), liquids with an
One suspects that when the result is contradictory, as is prob- efflux time of less than 20 s should not be used. The flow in
ably often the case, it is either ignored or "worked around." efflux cups is stress-driven, controlled by the hydrostatic
We shall refer to this type of device as a "Q/C (quality control) head, i.e., the fluid depth in the cup. The pressure varies as
instrument" or a "qualitative viscometer." It should be em- the liquid drains; consequently, the flow rate (shear rate)
phasized that these instruments are accurate for Newtonian varies during the test. The viscesity of shear-thinning liquids,
or near-Newtonian materials and are generally useful as Q/C therefore, will increase in the course of the test, and in ex-
test devices even when the measurement is approximate. treme cases such materials m a y not fully drain from the cup.
However, the practitioner should be alert to situations where Because the flow field is complex, the shear rate cannot be
their deficiencies can be of significance. calculated, and from the previous argument will depend on
the viscosity-shear stress relationship for non-Newtonian ma-
In years past, m a n y coating fluids were nearly Newtonian,
terials. For the above reasons, it must be concluded that
which accounts in part for the success of Q/C-type instru-
orifice cups are really only suitable for viscosity measure-
ments. As alluded to before, it is very easy to characterize a
ments of Newtonian liquids of moderate viscosity. Non-New-
Newtonian fluid. Virtually any type of flow measurement de-
tonian liquids should not be tested unless only mildly shear-
vice m a y be used to obtain accurate information on the vis- dependent. Materials with possible yield stress (meaning any
cosity of such a material provided the device used is thixotropic materials) should not be tested with efflux de-
calibrated with known standard fluids and the temperature is vices. A final caution for these devices is that, unless the
controlled. It is not even necessary to know the shear rate of temperature of the cup is controlled by means of a water
the measurement since Newtonian fluid viscosity is indepen- jacket, large errors are likely to result. Even if the test liquid is
dent of the shear rate. Consequently, Newtonian viscosity thermostatted in a water bath prior to test, it can rapidly
measured by any test is valid for all process conditions (exchange in temperature and viscosity when placed in a cup
cept turbulent flow). Even instruments which measure vis- which is at the temperature of the room. Figure 31 shows
cosity according to some arbitrary scale m a y be used since data for replicate measurements on cups with and without
they m a y be calibrated in absolute units using Newtonian temperature control. Obviously, the errors in the data taken
standard fluids. with the standard cup would hide the real batch-to-batch
A requirement for an instrument to measure non-New- differences of the product. A good Q/C test should reveal, not
tonian fluids properly is that the flow field within the test fluid obscure, product variability.
be viscometric, defined as "everywhere indistinguishable
from steady simple shear" (or other ideal deformation) [1]. Rotational Devices
Instruments which measure under such well-controlled con- Stormer TM Viscometer
ditions we will call "research instruments." Nonviscometric
The widely-used Stormer 16 Viscometer was one of the earli-
flows such as tube flow can be used for non-Newtonian fluids
est controlled-stress rotational viscometers. Rotors of various
when necessary corrections are applied.
geometries are available, but the "paddle" rotors, in which
two paddles are attached in offset fashion to a rotating shaft,
Q/C INSTRUMENTS are exclusively used for the measurement of the consistency
of paints. During a measurement, the rotation is driven by a
These are of three types: (1) efflux devices, (2) rotational
devices, and (3) obstructed-flow devices (following Barnes 16The name "Stormer" is a trademark of the Thomas Scientific
et al. [94]). Company.
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[] STANDARD FORD #4 CUP for a process which is far removed from the flow kinematics
O JACKETED CUP, BATCH 1 of the instrument.
JACKETED CUP, BATCH 2
Thomas-Stormer TM Viscometer Model ETS- I O00
This instrument is an electronic implementation of the
Stormer paddle viscometer by the Thomas Scientific Com-
pany. TM Weights are done away with, as the instrument is
motor-driven. A selector switch allows a digital readout to
O display the measured viscosity in centipoise, Krebs Units, or
in grams (for comparison to the standard Stormer instru-
ment).
O
Brook-field Digital Viscometer Model KU-1
The Brookfield Model KU-1 is likewise an electronic paddle
viscometer, similar to the Stormer, by Brookfield Engineer-
ing Laboratories. A digital panel readout displays either the
O
weight in grams corresponding to the applied motor torque
or the viscosity in Krebs units (KU).
ICI Rotothinner
The Rotothinner, originally developed by ICI Paints, is
driven by a constant-speed motor and utilizes a large, disk-
shaped rotor which is immersed in the sample under test. A
standard sample container is used, which is held magneti-
cally to a turntable. The torque transmitted through the sam-
ple rotates the turntable until a steady position is reached.
I I I I I
5 10 15 20 25 (The rotary motion is resisted by a spring.) The turntable is
Measurement Number graduated in poise units, and the viscosity is indicated by a
FIG. 31 -Ford cup viscosity data taken with and without tem- pointer attached to the instrument base. The viscosity range
perature control of the cup. Test temperature was 130~ (54~ of a given model is somewhat narrow, and measurement over
a wide viscosity range necessitates purchase of separate in-
free-falling weight attached to a string and pulley arrange- struments. The instrument is calibrated for use only with
ment, the string being wound around a drum. The shear standard containers. There is no provision for temperature
stress is varied by use of different weights. A counter tallies control of the specimen. For "rheologically structured" mate-
up the number of revolutions as the weight falls. After the first rials, the manufacturer recommends to allow up to 4 min
ten revolutions, the time required for the next 100 is mea- under shear for the reading to become steady, thus providing
sured. (Stroboscopic timers are available.) The apparent vis- for a more or less constant shear history. However, tempera-
cosity is calculated from a plot of applied torque versus rotor ture may vary during this period due to the input of energy
rpm. The measurement is also made in terms of the weight, resulting from the 575-rpm rotor speed.
W, required to achieve a rotational speed of 200 rpm. The Although the instrument has a scale graduated in poise
viscosity is obtained according to an arbitrary scale called units, the shear rate of test is unknown since the flow field is
"Krebs Units" (KU). A conversion table of W versus KU is not viscometric. Flow in the vicinity of a rotating disk can be
supplied. As with any viscometer whose measurement geom- quite complex, especially for non-Newtonian and viscoelastic
etry is complex, an absolute viscosity (i.e., in engineering materials. Consequently, the apparent Rotothinner viscosity
units of poise or pascal-seconds) cannot be calculated with must be considered only approximate and the scale gradu-
this instrument for non-Newtonian fluids. The Stormer vis- ations arbitrary for such materials.
cometer is specified in a number of standard test methodsJ 7 The Rotothinner is manufactured by Sheen Instruments,
For its purpose, i.e., to measure the in-can "feel" of paint, Ltd. and is widely used in Europe.
the Stormer is a very good viscometer, that is, the Stormer
measures while stirring the paint with a constant force, just Obstructed-Flow Devices
as the consumer would. Thus, the instrument satisfies the
criterion of measuring under conditions closely approxi- These are gravity-driven instruments in which flow is due
mating those of the process. This justifies the use of an arbi- to density differences between the test fluid and a falling
trary measurement scale, in this case, and makes the Stormer object (falling ball viscometer, falling needle viscometer) or a
a valuable component of the paint laboratory. The only ca- rising bubble (bubble tube viscometer). In each case, the fluid
veat would be not to violate the above-mentioned principle by has to flow around the moving object; hence, they are classed
attempting to use Stormer data to predict paint performance as obstructed-flow devices. In the falling ball and rising bub-
ble instruments, the flow field is complex with the conse-
17Testmethods include ASTMD 115,D 562, D 816, D 856, D 1084,
D 1131, D 1337, D 1338, and Federal Test Methods 3011.1, 3012, 18The Thomas-Stormer ETS-1000 is available from the Cannon
3018, 3019, 3022, and 4281. Instrument Company.
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quence that these devices are generally not useful for non- by means of tables. Bubble tubes can be used also to measure
Newtonian fluids. The falling needle viscometer, however, resin color. For process resins nearing the gelation point, the
possesses a well-defined flow field [95], is therefore suitable bubble can display a pointed "tail," or p r o n o u n c e d "teardrop"
for non-Newtonian materials, and will be discussed in the shape, an indication of the onset of viscoelasticity. As a refer-
section on Research Rheometers. ence for the use of the Gardner-Holdt method, see ASTM
D 803.19
Falling Ball Viscometer
A ball falling in a viscous fluid will reach a terminal, or
constant, velocity U~, which depends on the density differ- RESEARCH RHEOMETERS/VISCOMETERS
ence of the sphere and the liquid, the diameter of the ball, d,
and the fluid viscosity, -q. The viscosity of an u n k n o w n fluid Research-quality rheometers are of several types, chiefly
m a y be calculated from the Stokes equation employing: (1) steady rotational shear, (2) dynamic (oscil-
(Ps - P,)gd2 latory) shear, and (3) capillary tube flow. Acoustic wave de-
~l - (65) vices constitute a fourth, less c o m m o n , type. Useful
18U=
summaries of instrumentation and methods are found in
where g is gravitational acceleration. This deceptively simple Refs 96-98. Although dated, Van Wazer's book is still a valu-
method has several drawbacks, however. For one, the Stokes able source [42]. Appendix A lists vendors of research
solution is only valid for low Reynolds numbers (viscous rheometers and viscometers.
forces controlling, rather than fluid inertia, i.e., slow flow),
and for low-viscosity fluids the ball density must be small Rotational Instruments
enough to produce correspondingly slow rates of fall. For
another, a wall correction m a y be needed to account for the Controlled Stress and Controlled Rate
interference of the container wall with the flow field of the There are two basic types of rotational viscometers, which
ball and hence its falling rate. Perhaps the greatest difficulty, work in the following ways: (1) apply a controlled rotation
however, is the fact that the flow field around a moving rate and measure the opposing viscous torque, or (2) apply a
sphere is complex, and when the fluid is non-Newtonian the controlled torque and measure the resulting rate of rotation.
complexity becomes mathematically intractable. Therefore, In the first case, which m a y be termed "controlled-rate," the
for non-Newtonian fluids, the falling-ball apparatus will not applied angular velocity is the independent variable and the
yield absolute viscosity, and the results would not be expected viscous drag torque the dependent variable. In the second
to correspond with those from an instrument having visco- case, termed "controlled-stress," the applied torque is the
metric flow geometry. A solution to the above problems is independent variable and the measured angular velocity the
provided by a relatively new instrument called the falling dependent variable. Instruments of the controlled-rate type
needle viscometer (see below). include, for example, the Brookfield Synchro-Lectric Viscom-
eter, Haake CV, Rheometrics RFS, and Bohlin VOR instru-
Rising-Bubble Viscometers
ments. Instruments of the controlled-stress type include the
If certain flow field assumptions are made for a rising air Carri-Med CSL, Rheometrics DSR, Bohlin CS, Haake RS, and
bubble in a liquid, the viscosity of the liquid can be calculated Physica MC rheometers.
from [42] The choice between the two types of instruments depends
1 pgR 2 on the material under test and the kind of results desired. For
- (66) characterizing highly structured materials or "weak gels"
3 v
(e.g., thixotropic alkyds and unstable colloidal systems such
where p is the liquid density, R the radius of the air bubble, as some pigment dispersions, thixotropes, etc.), the con-
and v the rising velocity. However, the calculation is only trolled-stress instruments are likely to be more appropriate.
approximate because the air bubble shape often deviates The reason is that controlled-rate instruments impose a shear
from the assumed sphericity due to buoyancy. Furthermore, field upon the specimen over a relatively short time scale, say,
if the liquid phase were non-Newtonian, significant errors in the course of a shear rate r a m p experiment. The resulting
would result for which there is no correction available. relatively rapid deformation tends to destroy shear-sensitive
The Gardner-Holdt bubble tubes provide a rapid means of structure very quickly, making it difficult to gather m u c h
estimating the kinematic viscosity (see Capillary Viscome- information about the structure. In contrast, with controlled-
ters) of transparent liquids such as varnishes and resins stress instruments, the applied stress can be gradually in-
using the rising bubble principle. These consist of a series of creased, allowing the specimen to "obey its own rules" of
sealed glass tubes containing mineral oils comprising a range stress-strain (theological) behavior, thus resolving the maxi-
of standard viscosities. The test liquid is placed into a similar m u m a m o u n t of information. This is particularly true when
tube (ensuring the contained air bubble is the same volume) one is concerned with materials possessing an apparent yield
and thermostatted in a water bath. The test material and a stress. Controlled-stress instruments can, in principle, di-
rack containing the standard tubes are inverted, and the test rectly measure the stress at the onset of yield, avoiding errors
viscosity is identified according to the letter (or sometimes associated with indirect methods of yield stress measurement
number) designation of the standard tube whose rate of bub- (see Yield Stress Test Methods).
ble rise is nearest the same. Interpolation between the stan-
dards is sometimes done. Bubble tubes are disposable, easy 19Additional standard test methods using bubble tubes are: ASTM
to use, and the results can be converted to kinematic viscosity D 1131, D 1545, D 1725, and Federal Test Method 4271 (141-a).
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In selecting the a p p r o p r i a t e i n s t r u m e n t type, one s h o u l d %(r _ "~o,8

take into a c c o u n t also the type of coatings process in ques- (68)
~/B(T) ~0.~
tion. S o m e coatings processes are stress-controlled (or stress-
limited), a n d s o m e are rate-controlled (or rate-limited). A The value of this fact to experimentalists is considerable. F o r
stress-controlled process is one whose s h e a r rate is deter- example, it is often difficult to accurately m e a s u r e "O0for very
m i n e d by the rheology of the material; that is, a relatively low- or very high-viscosity fluids b e c a u s e of l i m i t e d instru-
small a m o u n t of force drives the process, a n d the rate of the m e n t range, sensitivity, or accuracy. Let us s u p p o s e "O0,Ais
process is therefore d e t e r m i n e d b y the viscosity of the mate- m e a s u r a b l e b u t "rl0.Bis not. However, reliable d a t a for Mate-
rial at the process shear stress. F o r example, different p a i n t s rial B are o b t a i n a b l e at h i g h e r (or lower) s h e a r stresses,
at a given wet-film thickness experience a c o n s t a n t gravita- where the i n s t r u m e n t is accurate. E q u a t i o n 68 allows us t h e n
tional shear stress, b u t will sag at different velocities d e p e n d - to calculate the u n k n o w n zero-shear viscosity, ~1o.8- As an-
ing on their viscosities at the sagging s h e a r stress. A rate- o t h e r example, m a n y dispersions, p a r t i c u l a r l y those of ira-
controlled process is one w h o s e s h e a r rate is i n d e p e n d e n t of p o r t a n c e to coatings, are colloidally unstable with the result
the m a t e r i a l rheology, that is, the available driving force is so that the zero-shear viscosity m a y not be m e a s u r a b l e (see
large t h a t the process rate o r t h r o u g h p u t is essentially not S h e a r - T h i n n i n g F l u i d s a n d Fig. 5). A similar technique to
affected by viscosity. E x a m p l e s of stress-controlled coatings the above m a y obviously be used to o b t a i n a n inferred value
processes a n d their driving forces include sagging (gravity), of 7o for such a system as it w o u l d be in the a b s e n c e of the
leveling (surface tension), particle settling (gravity), a n d instability by c o m p a r i s o n to another, colloidally stable mate-
airless spraying (hydrostatic pressure). An e x a m p l e of a rate- rial.
controlled process w o u l d be industrial rollcoating. Gleil~le also s h o w e d that the local flow exponent, n (see
Since m a n y coatings processes are stress-controlled o r Shear-Dependent Viscosity), is c o n s t a n t at c o n s t a n t s h e a r
stress-limited, the controlled-stress r h e o m e t e r offers the ad- stress, i n d e p e n d e n t of differing m a t e r i a l rheology. As a conse-
vantage of m o r e convenient s i m u l a t i o n of these processes. quence of this, the W e i s s e n b e r g - R a b i n o w i t s c h c o r r e c t i o n to
F o r example, a c o n s t a n t stress (simulating sagging) o r a pro- the capillary viscosity for n o n - N e w t o n i a n fluids b e c o m e s a
g r a m m e d exponential stress decay (simulating leveling) m a y constant at a given shear stress, i n d e p e n d e n t of m a t e r i a l
be conveniently a p p l i e d with the latter-type instrument. One rheology, since it d e p e n d s only on the value of n (see Capil-
capability unique to controlled-stress r h e o m e t e r s is the creep lary V i s c o m e t e r s a n d Eq 11). 21 Gleil~le's findings are ap-
test, w h e r e b y a c o n s t a n t l o a d is a p p l i e d to the m a t e r i a l a n d p a r e n t l y e m p i r i c a l a n d will need to be verified for systems
the d e f o r m a t i o n is r e c o r d e d with time. 2~ Creep has been other t h a n the ones reported.
f o u n d to be very useful, b o t h for c h a r a c t e r i z i n g viscoelastic
m a t e r i a l s (see V i s c o e l a s t i c M o d e l s ) a n d for d e t e r m i n i n g Re- Inertia Correction
gion I of the e q u i l i b r i u m flow curve (see S h e a r - T h i n n i n g It can be p a r t i c u l a r l y i m p o r t a n t for r o t a t i o n a l r h e o m e t e r s
F l u i d s ) . The latter is o b t a i n e d by applying a series of very low of the controlled-stress type to correct the d a t a for inertia
torques a n d m e a s u r i n g the e q u i l i b r i u m strain rate. The equi- error. If the test fluid is low in viscosity, and/or the test r o t o r
l i b r i u m flow m e t h o d p e r m i t s viscosity m e a s u r e m e n t s to be has a large m o m e n t of inertia, a n d / o r the acceleration is too
m a d e at the lowest possible rate of shear. A limiting factor in high (short r a m p time), a significant p o r t i o n of the applied
the a c c u r a c y of such methods, however, is the ability to mini- torque is dissipated not viscously, b u t in the acceleration of
mize or correct for spurious air b e a r i n g torque. the rotor. A c o r r e c t i o n for this e r r o r has been p u b l i s h e d by
Other advantages of controlled stress over controlled rate Krieger [100]. S o m e c o m m e r c i a l controlled-stress instru-
have been p o i n t e d out b y Gleil~le [99]. F o r example, using m e n t s n o w feature on-line inertia correction.
d a t a for p o l y m e r melts, he d e m o n s t r a t e d that m e a s u r e m e n t s
at c o n s t a n t stress are of greater sensitivity a n d better able to
d i s c r i m i n a t e a m o n g m a t e r i a l s t h a n m e a s u r e m e n t s at con- Brookfield Viscometers
stant s h e a r rate. F u r t h e r m o r e for controlled stress, the sensi-
Brookfield Synchro-Lectric
tivity, in terms of b o t h absolute a n d relative m e a s u r e d
viscosity differences a m o n g materials, is i n d e p e n d e n t of the The Brookfield Synchro-Lectric v i s c o m e t e r utilizes a set of
stress level chosen, unlike for controlled rate. In fact, the spindles o r disks as the rotor/sensor, w h i c h are r o t a t e d in the
ratios of viscosities of two different materials, A a n d B, are test fluid at selected rpm's, so that the a p p a r e n t viscosity m a y
i n d e p e n d e n t of the s h e a r stress be m e a s u r e d at several s h e a r rates to o b t a i n a flow curve. Its
advantages include low cost, simplicity of use, ease of clean-
~A0-1) _ ~A(T2) (67) ing, a n d durability. The i n s t r u m e n t is in wide use t h r o u g h o u t
the i n d u s t r y a n d is the basis for a n u m b e r of ASTM test
methods. 22 It is i n c l u d e d here in the list of "research quality"
w h e r e ~1 a n d ~2 are two a r b i t r a r y stress levels. Since this
viscometers b e c a u s e the viscosity can be r e p o r t e d in absolute
w o u l d also hold true at low stress levels w h e r e the viscosity is
units over a range of s h e a r rate, a l t h o u g h often it is not (see
constant, we are led to a very useful relationship: t h a t the
below). Its limitations include the latter fact, plus that tem-
ratio of the s h e a r rates for A a n d B, m e a s u r e d at a given s h e a r
stress, gives the inverse ratio of the zero-shear viscosities of
the two materials. 21This would also hold true of the Burgers correction to the paral-
lel-plate viscosity of non-Newtonian fluids for the same reason.
22These include ASTM D 115, D 816, D 1076, D 1084, D 1286,
2~ only controlled-rate instruments can perform a D 1337, D 1338, D 1417, D 1439, D 1638, D 1824, D 2196, D 2364,
step-strain or stress relaxation test. D 2393, D 2556, D 2669, and Federal Test Method 4287.
www.iran-mavad.com

perature control is not integral to the instrument. The Syn- ICI cone and plate viscometer, but represents an improve-
chro-Lectric is available with digital output, automatic ment in that it is capable of variable shear rate m e a s u r e m e n t
viscosity calculation, and computer-interfaced versions with (to 24 000 s - 1). It also provides a digital display of viscosity
analysis and graphing software. and temperature as well as a data interface to a personal
Brookfield spindle viscometer measurements suffer from c o m p u t e r or data logger with applications software.
the use of arbitrary or nonfundamental units in reporting the
result. Even though the viscosity is reported in absolute units
(cP or mPa.s), the shear rate is not. Thus, both the spindle Falling-Needle V i s c o m e t e r
speed (rpm) and the spindle identity must be reported along This is an "obstructed-flow" device which utilizes a long,
with the measured viscosity. The measured viscosity can be slender needle as the falling object. In so doing, it overcomes
different at the same rpm if a different size spindle is used. the objections to the falling ball viscometer while retaining
Without knowing the actual shear rate of measurement, a the latter's simplicity of operation and relatively low cost
true flow curve cannot be constructed from the results. The [103]. The needle is hollow (allowing a wide range of needle
true flow curve is desirable for several reasons, a m o n g them densities) with hemispherically capped ends. E n d effects due
the possibility of comparison with results from other instru- to the finite needle length are mathematically correctable.
ments, the quantitative description of the sample rheology by This geometry produces a well-behaved flow field known as
use of mathematical flow models and the subsequent applica- "annular-ducted flow," with the central tube (needle) moving
tion of such models to predict paint performance (see at constant velocity. Because of the well-defined flow field, the
L E V E L I N G and SAGGING for example). Methods for calcu- true velocity gradient between the needle and container wall
lation of the corrected shear rate for Brookfield RVT spindles can be obtained, and the instrument therefore is suitable for
were given by Williams [101] and also Pierce [102]. Smith measurements of non-Newtonian fluids [104]. The falling-
[87] has given a simplified method. (See also Ref 22, pp. needle viscometer m a y be especially useful for determination
28-31.) Some of the foregoing issues are at least partially of very low shear stress or shear rate behavior of non-New-
answered with certain accessories available from Brookfield. tonian fluids, for example the zero-shear viscosity (Region I
These include options which have small-gap bob-in-cup ge- of Fig. 3) and measurement of yield stresses [105]. 23
ometry and temperature control, e.g., the small-sample
adapter.
Capillary V i s c o m e t e r s
WeUs-Brookfield Cone a n d Plate Viscometer
Capillary tube flow is a classical viscometric method which
Brookfield also offers an instrument possessing a well-de- is useful for coatings in two main ways. Capillary viscometry
fined geometry and good temperature c o n t r o l - - t h e Wells- is the method of choice for measurement of intrinsic viscosity
Brookfield cone and plate viscometer. Its operation and ap- (ASTM Method D 445) (see also D I S P E R S I O N R H E O L -
pearance are very similar to the Synchro-Lectric, except the OGY) and also the measurement of very high shear rate
lower end has been modified to m o u n t a cone and plate rheological properties (see below).
geometry with integral temperature control via a water For fluid flowing through a tube, the shear stress at the tube
jacket. Because the true shear rate can be calculated from the wall is
cone geometry and rpm, the viscosity of non-Newtonian ma-
terials can be measured in absolute units and an equilibrium APR
rw - (69)
flow curve determined. This instrument, therefore, is recom- 2L
mended over the standard Synchro-Lectric for routine viscos- where Ap is the decrease in pressure occurring over tube
ity measurement. length L of radius R. The shear rate at the tube wall for a
Newtonian fluid is given by
ICI Cone a n d Plate V i s c o m e t e r 4Q
~/w - (70)
The ICI cone and plate viscometer is a relatively high shear ~rR3
rate instrument capable of absolute viscosity measurement.
where O is the volumetric flow rate (cmS/s). The viscosity is
It is normally sold in a room-temperature, single-speed con-
figuration. Temperature control is integral to the instrument, then
but there is no provision for control of solvent loss from the rw r
sample. This can be improvised, if desired. A high-tempera- rl - - - - (71)
Tw 8LQ
ture version is available, which is useful for resin melt viscos-
ity measurement. The chief use of the instrument has been which is the well-known Hagen-Poiseuille equation. For ap-
the measurement of viscosity at a shear rate of approximately plied pressure-driven capillary flow, particularly for high-
10 000 s 1 for the prediction of brushability. (See ASTM shear measurements, a correction to Eq 71 is required be-
method D 4287 for high-shear viscosity by ICI cone and cause the fluid undergoes a large acceleration as it enters the
plate.) capillary. Therefore, part of the energy loss represented by
the pressure drop Ap is in accelerating the fluid. This would
result in a calculated viscosity which is too high and so
Brookfield CAP 2000 V i s c o m e t e r necessitates a subtractive term or kinetic energy correction
The Brookfield CAP 2000 multispeed digital cone-plate vis-
cometer was very recently introduced. It is very similar to the 23A new ASTM method for falling-needle viscometry is D 5478.
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7rR4Ap mpQ High-Shear Capillary Rheometry

n - - - (72)
8LQ 8~rL It has b e e n claimed by s o m e that the m e a s u r e m e n t of very
high s h e a r rate viscosity is not necessary b e c a u s e it m a y be
w h e r e p = fluid density a n d m is a c o n s t a n t w h i c h is equal to
e s t i m a t e d from m o d e r a t e - s h e a r data. This is true to an extent,
u n i t y for N e w t o n i a n fluids. F o r n o n - N e w t o n i a n fluids obey-
especially if one can o b t a i n an a d e q u a t e d e s c r i p t i o n of the
ing the p o w e r law (see S h e a r - T h i n n i n g F l u i d s ) , m is calcu- general flow curve b y use of one of the flow m o d e l s contain-
lated from ing the high-shear limiting N e w t o n i a n viscosity, ~ (e.g., the
3(3n + 1) 2 Sisko, Cross, or Carreau models). If a g o o d fit to e x p e r i m e n t a l
m = (73) d a t a can be obtained, the latter m o d e l s can be extrapolated to
(4n + 2)(5n + 3)
predict viscosity b e y o n d the e x p e r i m e n t a l range of shear rate
where n is the p o w e r law exponent. Various a d d i t i o n a l with caution. The p o w e r - l a w - b a s e d models should not be
corrections for capillary flow a r e d e s c r i b e d in van W a z e r [42]. used for e s t i m a t i o n of high-shear viscosity since they p r e d i c t
The pressure head Ap can be o b t a i n e d two ways: by pres- unrealistic high-shear b e h a v i o r (see S h e a r - D e p e n d e n t Vis-
surizing the delivery vessel or by relying on a gravitational cosity). However, u n d e r the best of circumstances, d a t a
h y d r o s t a t i c h e a d to drive the flow t h r o u g h the capillary. In should be extrapolated no further t h a n a b o u t a decade of
s h e a r rate. This m e a n s that, in general, shear rates of less
the latter case, the density of the fluid b e c o m e s an i m p o r t a n t
t h a n 10 s s - 1 can be reached, even by e x t r a p o l a t i o n methods.
p a r t of the m e a s u r e m e n t b e c a u s e the rate of flow will d e p e n d
It should be p o i n t e d out here that the onset of s h e a r thicken-
b o t h on the fluid's viscosity a n d on the m a g n i t u d e of Ap, ing (Region IV, Fig. 3) c a n n o t be p r e d i c t e d by extrapolation,
w h i c h now d e p e n d s on the fluid density, p, a n d on the height yet can cause d i s a s t r o u s consequences in high-shear applica-
of the fluid above the capillary, h (Ap = pgh). The role of the tion processes. F o r precise c o m p a r i s o n s of materials, extrap-
fluid density is t a k e n into a c c o u n t b y the k i n e m a t i c viscosity, olation will be unsatisfactory in any case. I n fact, several
defined as industrial processes involve s h e a r rates of 105 to 106 s -~.
~q These include airless s p r a y a n d reverse rollcoating, for exam-
v- (74) ple. P e r f o r m a n c e p r o b l e m s of coatings exposed to such high
p s h e a r will be difficult to resolve w i t h o u t direct e x p e r i m e n t a l
That is, the k i n e m a t i c viscosity is equal to the shear viscosity m e a s u r e m e n t u n d e r the a p p r o p r i a t e d e f o r m a t i o n conditions.
divided by the density. The viscosity o b t a i n e d from gravity- Such severe conditions of s h e a r can cause a f u n d a m e n t a l
change in a material, such as gross coagulation of an emul-
driven capillary flow is in units of stokes (stoke -- P/g/cm3).
sion, with a possible deleterious effect on rheology a n d hence
The absolute shear viscosity can then be calculated from ~ =
on p o s t a p p l i c a t i o n film f o r m a t i o n behavior. It is recom-
up.
m e n d e d , therefore, to c h a r a c t e r i z e m a t e r i a l s exposed to high-
The velocity profile in tube flow is p a r a b o l i c in shape for s h e a r processing by high-shear rheometry.
N e w t o n i a n liquids (as can be p r o v e n by integration of Eq 70), There are some c o m m e r c i a l high-shear viscometers w h i c h
with the m a x i m u m shear rate at the walls a n d zero s h e a r rate use small-gap bob-in-cup geometry. Problems with this ge-
in the tube center. If n o n - N e w t o n i a n fluids are used, the o m e t r y include p o o r t e m p e r a t u r e control due to viscous heat-
velocity profile b e c o m e s n o n p a r a b o l i c a n d even m o r e c o m - ing a n d a t e n d e n c y t o w a r d flow-field instabilities. Capillary
plex. As a result, the viscosity of n o n - N e w t o n i a n m a t e r i a l s v i s c o m e t r y has s o m e advantages in b o t h regards. The very
will vary across the d i a m e t e r of the tube. N o n - N e w t o n i a n short residence time in the capillary at high flow rates mini-
fluid m e a s u r e m e n t s m a y be m a d e accurately only if the Weis- mizes t e m p e r a t u r e rise, and, for l e n g t h - t o - d i a m e t e r (L/D) ra-
tios of 50 or greater, entrance effects are negligible a n d the
s e n b e r g - R a b i n o w i t s c h correction is a p p l i e d [106], w h i c h cor-
flow field will be essentially uniform.
rects for the variations in viscosity across the capillary arising
By use of short, s m a l l - d i a m e t e r capillaries a n d high pres-
from the n o n u n i f o r m s h e a r field. sures, s h e a r rates of a p p r o x i m a t e l y 106 s-~ are achievable for
[ l d ( l o g ~ a ) ] -1 fluids in the range of viscosities typical of paints. At this
"q = na 1 -- (75) writing, we are a w a r e of only three c o m m e r c i a l r h e o m e t e r s
4 d(log %) d
which m a y he suitable for high-shear rate m e a s u r e m e n t of
w h e r e "qo is the u n c o r r e c t e d a p p a r e n t viscosity, z4 The second coatings fluids. One is the ACAV High S h e a r Capillary
t e r m inside the brackets is o b t a i n e d by calculating the slope Rheometer, m a r k e t e d by ACA Systems Oy, Finland. Another
of a log-log plot of the m e a s u r e d viscosity versus wall s h e a r capillary i n s t r u m e n t c a p a b l e of very high-shear m e a s u r e -
stress. m e n t s is the Paar-Physica HVA-6. The third is the
Tube flow is i n a p p r o p r i a t e for materials with yield behav- R h e o m e t r i c s RFX, w h i c h uses very n a r r o w - g a p a n n u l a r flow
ior. Reviews by Schoff [97,98] describe the a p p l i c a t i o n of in o r d e r to attain high shear rates at lower flow rates (Table
capillary v i s c o m e t r y to coatings. 5).
24The "apparent viscosity" is simply the quotient of the apparent Rank Pulse Shearometer
(experimentally measured) shear stress and the apparent shear rate.
The "true" values of the foregoing, however, may be different from This i n s t r u m e n t is a relatively inexpensive a n d easy-to-use
the apparent, where corrections are necessary, say, for flow fields viscoelastometer. A fixed-frequency acoustic wave pulse is
where the shear rate may be varying across the field and must be p a s s e d t h r o u g h a test s a m p l e a n d the signal detected by a
corrected for non-Newtonian effects.
receiving transducer. The p r o p a g a t i o n velocity v is m e a s u r e d
www.iran-mavad.com

T A B L E 5 - - C o m m e r c i a l r e s e a r c h r h e o m e t e r s a n d viscometers.
Manufacturgr/ Price Viscosity Shear Rate Test Temperature
Instrument Vendor~ Rangeb RangC (mPa.s) RangC (s-l) Geometrya Range, ~
ACAV H i g h - S h e a r ACA S y s t e m s Oy E 1-55 000 to 106 Tube flow 20-90
Capillary R h e o m e t e r
Bohlin VOR e Bohlin E 0.1 - 1011 10 - 3_ 104 CP,PP,CC - 150- 350
Instruments
Bohlin CSM e Bohlin E 0.1-108 10 5-104 CP,PP,CC - 15-250
Instruments RT-400
Brookfield S y n c h r o - Brookfield A 1- l06 ca. 1-102 CP,CC RT
Lectric Engineering RT-300 f
Brookfield CAP2000 Brookfield B 5 0 - 3 0 000 150-24 000 CP 5-75
Engineering
Carri-Med CSL e TA I n s t r u m e n t s E 0.1 - 109 10- 6_ 10 4 CP,PP,CC - 100-400
Contraves LS40 ~ Mettler E 10 3_ 10 s 10- 4-260 CC 0-150
Contraves R h e o m a t Mettler C 3 - 3 7 800 26-1290 CC 0-80
108E/R
Contraves R h e o m a t Mettler D 0.6-106 0.06-10 500 CP,CC -10-400
115A
H a a k e CV S y s t e m ~ Haake/Fisons E 0.1 - 107 0.01 - 103 CC 5-95
Haake M System Haake/Fisons E 0.1-108 1-40 000 CP,PP,CC -50-300
H a a k e RS100 e Haake/Fisons E 0.1-6 108 10-2-3000 CP,PP,CC -50-350
Haake VT500 Haake/Fisons D 1-107 4-6000 CP,CC - 30-200
Irvine-Park FNV Stony Brook B 0.3 - 10 4 10- 4_ 103 A n n u l a r flow - 40-150
Falfing-Needle Scientific
Viscometer
P a a r HVA-6 Capillary Paar-Physica D 0.8-107 102-106 T u b e flow -20-150
Rheometer
Physica Viscolab LC-3, Paar-Physica C-D 1-3 107 0 . 1 - 5 0 000 CP,PP,CC -60-500
LC-10, LC-100
Physica R h e o l a b Paar-Physica D-E 1-3 1012 10- 3_ CP,PP,CC - 60-500
MC10-MC120 e 50 000
Vilastic V-Ee Bohlin D 0.005-5000 0.1-1000 Tube flow 0.4-95
Instruments
Weissenberg TA I n s t r u m e n t s E 1-10 la 10 4_ 104 CP,PP,CC - 100-500
Rheogoniometeff
Wells-Brookfield Cone Brookfield A 5-1.5 )< 106g 0.6-750 CP - 15-100
& Plate Engineering
R a n k Pulse Pen-Kern C ... 250 h Acoustic 10-60
Shearometer~ wave
R h e o m e t r i c s DSR e Rheometrics D-E 0.1-109 10 5-104 CP,PP,CC -40-150
RT-350
R h e o m e t r i c s RFS I F Rheometrics E 1- 10 s 10 2_ 104 CP,PP,CC 0-100
R h e o m e t r i c s RFX Rheometrics D 30-106 10- 2_ 104(~) O p p o s e d jets 0-100
1-105(~) a n n u l a r flow
aSee Appendix A for full address.
bprice key--A: $1,000-$5,000; B: $5,000-$10,000; C: $10,000-$25,000, D: $25,000-$50,000; E: $50,000-$100,000.
~Ranges cited are approximate and may require purchase of special accessories to achieve.
dCP = cone and plate; PP = parallel plate; CC = concentric cylinder (includes couette, bob-and-cup, double-gap concentric cylinder, coni-cylinder, etc.).
~v'iscoelastic characterization capability.
fWith Thermosel9
gFull range for Models LV through HB.
hpulse frequency. Small oscillatory strain provides essentially zero-shear measurement.
from the signal transit time and used to calculate the shear APPENDIX
elastic modulus according to
G' = pv2 (76)
The signal wave is of high frequency but very small amplitude Instrument Manufacturers and Vendors
(10 -4 rad), so that weak gels are not disturbed (the induced ACA Systems Oy
strain will likely be within the linear viscoelastic regime). Chemical Analysis & Paper Applications
Because of the high frequency used, the measured shear Tekniikantie 12
modulus corresponds to the plateau modulus, G= (see Visco- 02150 Espoo, FINLAND
elastic Models). This gives a useful measure of the gel (ATTN: Ilkka Mustonen)
strength of even weak gels and has an advantage in this
Bohlin Instruments, Inc.
regard over instruments which subject the sample to uncon-
2540 Route 130
trolled s h e a r u p o n c l o s u r e .
Cranbury, NJ 08512
www.iran-mavad.com

(609) 655-4447 TA I n s t r u m e n t s , Inc.

109 Lukens Drive
Brookfield Engineering Laboratories, Inc.
New Castle, DE 19720
240 Cushing Street
(302) 427-4000
Stoughton, MA 02072
(617) 344-4310 o r 344-4313 T h o m a s Scientific
99 High Hill R o a d
C. W. B r a b e n d e r I n s t r u m e n t s , Inc.
P.O. Box 99
50 E. Wesley Street
Swedesboro, NJ 08085-0099
P.O. Box 2127
(609) 467-2000
S o u t h Hackensack, NJ 07606
(800) 345-2100
(201) 343-8425
BYK-Gardner, Inc.
1100 East-West H i g h w a y
Silver Spring, MD 20910
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(301) 589-4747
[1] Dealy, J. M., Rheometers for Molten Plastics, Van Nostrand
(800) 343-7721 Reinhold Co., New York, 1985.
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P.O. Box 16 of the Oil and Colour Chemists Association, Vol. 44, 1961, p.
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2138 High Tech R o a d
[3] Bingham, E. C., U.S. Bureau of Standards Scientific Paper No.
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(800) 533-6232 [4] Casson, N., in Rheology of Disperse Systems, C. C. Mill, Ed.,
Haake/Fisons, Inc. Pergamon Press, New York, 1959.
[5] Asbeck, W. K., Official Digest, Federation of Societies for Paint
53 W e s t Century R o a d
Technology, Vol. 33, No. 432, 1961, p. 65.
P a r a m u s , NJ 07652 [6] Krieger, I. M., "Rheology of Polymer Colloids," Polymer Col-
(201) 265-7865 loids, R. Buscall, T. Corner, and J. F. Stageman, Eds., Elsevier
Kayeness, Inc. Applied Science, New York, 1986.
[7] Choi, G. N., "Rheology of Sterically-StabilizedModel Colloidal
115 T h o u s a n d Oaks Blvd.
Dispersions," Ph.D. thesis, Case Western Reserve University,
Suite 101, P.O. Box 709 Cleveland, OH, 1982.
Morgantown, PA 19543 [8] Lapasin, R. and Torriano, G., "Rheological Models Suitable for
(215) 286-9396 Application in the Paint Field," Proceedings, 18th FATIPEC
Congress, Venice, Vol. 4, 1986, p. 1.
Mettler I n s t r u m e n t C o r p o r a t i o n
[9] Sisko, A. W., Industrial and Engineering Chemistry, Vol. 50,
Princeton-Hightstown Road 1958, p. 1789.
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Hightstown, NJ 08520-0071 Modeling of Polymer Melt Viscosity," Polymer Engineering and
(609) 448-3000 Science, Vot. 32, No. 14, 1992, p. 931.
[11] Sorbie, K. S., Clifford, P. J., and Jones, E. R. W., Journal of
Paar-Physica USA, Inc. Colloid and Interface Science, Vol. 130, No. 2, 1989, p. 508.
400 R a n d a l W a y B-207 [12] Laven, J. and Stein, H. N., Journal ofRheology, Vol. 36, No. 3,
Spring, TX 77388 1992, p. 497.
(713) 350-3576 [13] Jenekhe, S. A., Polymer Engineering and Science, Vol. 23, No.
15, 1983, p. 830.
Pen Kem, Inc. [14] Mewis, J. and D'Haene, P., "Prediction of Rheological Proper-
341 A d a m s Street ties in Polymer Colloids," Makromolecular Chemistry, Macro-
Bedford Hills, NY 10507 molecular Symposium, Vol. 68, 1993, p. 213.
(914) 241-4777 [15] Krieger, I. M. and Dougherty, T. J., "A Mechanism for Non-
Newtonian Flow in Suspensions of Rigid Spheres," Transac-
Rheometrics, Inc. tions of the Society of Rheology, Vol. 3, 1972, p. 137.
One P o s s u m t o w n R o a d [16] Boersma, W. H., Baets, P. J. M., Laven, J., and Stein, H. N.,
Piscataway, NJ 08854 Journal ofRheology, Vol. 35, No. 6, 1991, p. 1093.
(201) 560-8550 [17] Toussaint, A., "Choice of Rheological Model for Steady Flow,"
Progress in Organic Coatings, Vol. 21, 1992, p. 255.
S h e e n I n s t r u m e n t s Ltd. [18] Petit, L. and Noetinger, B., Rheologica Acta, Vol. 27, 1988, p.
Sheendale R o a d 437.
Richmond, Surrey [19] Hoffman, R. L, Transactions of the Society of Rheology, Vol. 16,
E n g l a n d TW9 2JL 1972, p. 99.
[20] Boger, D. V. and Waiters, K., Rheotogical Phenomena in Focus,
S t o n y B r o o k Scientific Elsevier, New York, 1993, p. 147.
914 F i l l m o r e Rd. [21] Cheng, D. C.-H., "Viscosity-Concentration Equations and Flow
Norristown, PA 19403 Curves for Suspensions," Chemistry and Industry, 17 May 1980,
(215) 584-9632 p. 403.
www.iran-mavad.com

[22] Barnes, H. A., Hutton, J. F., and Waiters, K., An Introduction to [51] Gupta, R. K. and Sridhar, T. in Rheological Measurement, Vol.
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www.iran-mavad.com

MNL17-EB/Jun. 1995
Surface Energetics
by Gordon P. Bierwagen 1
NOMENCLATURE v Velocity
V Volume
a Integration limit, distance from surface into bulk W Weight
of material, Eqs 3 and 6 7 Liquid surface tension
A Surface area F, Fi Surface excess concentration, of i th species
b Variable in Eq 18, the difference in m a x i m u m and 8f Final film thickness in dip coating
m i n i m u m diameters in elliptical orifice A Difference
c Surfactant concentration Dielectric constant
c~ Concentration of species i ~1 Viscosity
Cio Concentration of species i in the bulk A Wavelength
D Diffusion coefficient /xi Chemical potential of species i
% Surface elasticity ~r 3.141 59
f Correction factor in Eq 15 0 Contact angle
g Acceleration of gravity O Density
G Gibbs free energy
h Variable defined in Eq 9
h Height in capillary rise measurements INTRODUCTION
i Index identifying species i
k Wave n u m b e r = 27r/A (X = wavelength, see below) SURFACES ACT AND PERFORM differently from bulk materials
l Subscript indicating liquid phase because they have two distinct properties that are not true of
l Length of capillary pore path in Eq 23 bulk materials. First, because of unbalanced forces on mole-
n Normal vector to surface, Eq 3 cules or atoms at a surface as compared to the bulk, those in
n Exponent in Eq 4 the surface have an excess free energy [1] (i.e., they are in a
n Most probable n u m b e r of drops from breakup of higher state of potential energy). This excess energy per unit
charged drop, Eq 31 area is the t h e r m o d y n a m i c cost of forming a new surface and
n, N u m b e r of moles of component i, Eq 2 has the units of energy/area, or force/length. These latter
0 Subscript indicating zeroth or bulk phase, or refer- units are those of tension, and the surface excess free energy
ence value is often known as surface tension and can be measured for
p Pressure liquids as such. (A more detailed discussion of this excess free
p Pressure tensor in the bulk phase, Eq 3 energy identified with a surface, including the thermody-
pr Tangential pressure tensor, Eq 3 namic definition of surface tension, is given below.) Second,
Perimeter length there is a preferred direction normal to the surface that can
Q Liquid flux, volume/second be defined in the mechanical definition [2] of surface tension.
q Charge on drop This directional effect of surfaces can be observed in molecu-
r Variable in Eq 18, sum of m a x i m u m and m i n i m u m lar directionality in adsorption phenomena, surface area
radii in elliptical orifice minimization by surface tension effects, and molecular or-
r Radius dering in Langmuir-Blodgett films deposited from ordered
R Ring radius in Du Nouy ring surface tension mea- mono-molecular layers (monolayers).
surement Surfaces occur only when there is an energetic cost to
RI, R 2 Principal radii of curvature creating an interface between two dissimilar materials or
s Subscript indicating solid phase phases. Thus, there are no stable interfaces between gases,
T Temperature between supercritical fluids, nor a m o n g phases in a material
L Critical temperature above its critical point. However, surfaces can occur between
X Distance from surface in Eq 6 gas and liquid (g/l), liquid and liquid (1/1), gas and solid (g/s),
V Index indicating vapor phase, Eq 10 liquid and solid (l/s), and between solid and solid (s/s). An
example of a gfl interface is the surface of a pool of water, and
1Professor of Polymers and Coatings, Department of Polymers and so forth. Liquid surface energy p h e n o m e n a can be analyzed
Coatings, North Dakota State University, Fargo, ND 58105. directly by equilibrium thermodynamics because a liquid
369
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surface cannot support a stress. For a solid, surface energy modified when the system under consideration contains a
and surface stress must both be considered in analyzing the surface. The defining equation for liquids is
properties of an interface, since the past history of the solid
dG = - S d T + Vdp + Edz,dn i + 3"dA (2)
will affect the properties of a solid surface [3]. Even though
this is well known, there has not been as much concern given where G, T, S, V, p, P-i and ni are the thermodynamic quan-
to the surface history of solids in considering their surface tities Gibbs free energy. Temperature, entropy, volume, pres-
properties as often necessary. sure, chemical potential of component i, and the number of
Surface effects relative to bulk properties become more moles of component i, respectively, and 7 and A are the sur-
important as the surface area to volume ratio for materials face tension and surface area. The other equations of thermo-
becomes larger. In the simplest case, a sphere, this ratio is dynamics can be similarly modified. As can be seen, the
given by energetic cost of expanding a liquid surface is the 7dA term.
As pointed out above, this use of 3' is valid only for liquid
interfaces. Another equation for 7 is the mechanical defini-
tion of Ref 2, also discussed by Adamson [1] and reviewed by
Burshtein [7] and Navascues [8] as
Surface effects thus increase in importance as the size of the
object being considered becomes smaller. Statistical thermo-
v=f_~a(p- pr)dn (3)
dynamics and molecular dynamics considerations indicate where + a and - a are distances in either direction of the
that the range of the range of surface effects as 2 to 5 molecu- surface such that molecules at these positions are in the bulk
lar diameters [4]. An interesting feature of this type of analy- phases, p and pr are the bulk pressure and the tangential
sis of surface effects and their ranges is that the distance of pressure tensors, respectively, and n is the normal vector to
propagation of surface effects into the bulk from a polymer the surface. This is shown schematically in Fig. 1. The direc-
adsorbed at an interface can be quite large in atomic dimen- tion of n is the preferred direction of a surface referred to
sions. In effect, the interface is a site of pinning one end of the above. Even if it is not commonly included in introductory
polymer, taking away one of its degrees of freedom of motion, discussions of surface phenomena, it is important to consider
and thus making the interface a location of a layer of polymer Eq 3 when considering the thermodynamics of surfaces be-
of different thermomechanical properties than the rest of the cause it is the relationship between the bulk mechanical
polymer. This is exceptionally important when analyzing the properties of the system and the almost "distincontinuous"
adhesion of polymeric films to bulk substrates. The strength behavior of the system properties at an interface. This expres-
of the adhesive bond can be influenced by these directionality sion describes the directionality that an interface possesses
effects and can be even more important if the substrate is a and is very crucial to modern theories of capillarity [9].
plastic (polymer), where the ordering effects propagate on In general, the surface tension, % of pure liquids decreases
both sides of the interface. The directionality and ordering of with increasing temperature. An approximate form of this
surrounding polymeric bulk media by an interface can extend temperature dependence is [10]
unexpectedly large distances. Many of the properties of self-
ordering systems have these effects as their origin. This will 3' = 3/0 1 - (4)
be commented upon further in the discussion of surface
effects in pigment dispersion and emulsions. where 7~ is the surface tension at T = 0, Tc is the critical
All who deal with coatings must realize that surface effects temperature of the material, and n is an empirical exponent,
are very important in all stages of coatings preparation, appli- 11/9 for organic liquids.
cation, and utilization. Coatings are thin films with a high The other important thermodynamic relation for surfaces
surface-to-volume ratio. Pigments have large surface-to-vol- is the Gibbs equation. In multicomponent systems, one must
ume ratios, and their surfaces are often chemically reactive or consider the effects of materials absorbing at the interface.
catalyze reactions [5]. Latex polymers also occur in fine par- When these are properly taken into account, the Gibbs equa-
ticulate form, and their use and stability depend on surface- tion (at constant T and p) results
dominated effects. Foaming, cratering, and other defects in
coatings come about through surface-mediated events [6]. d3" = - "~,iridl.J,i (5)
Wetting and coverage of substrates by coatings and the adhe- where Fi is the surface excess concentration value for compo-
sion of coatings to these same substrates are also strongly nent i [11]. This equation gives the relationship between the
affected by surface effects. Adsorption at surfaces of particu- surface tension of a fluid interface and the amounts of surface
late materials in a coating, be they pigments or polymer active materials (hereafter referred to as surfactants) in the
particles, is controlled by the energetics of the interface be- solution (component i). The surface excess concentration F i
tween the particles and the suspending liquid. is the difference between the actual and bulk concentrations,
c~ and ci0, of component i and can be calculated in a manner
analogous to Eq 3 as
SURFACE T H E R M O D Y N A M I C S ~ B A S I C S
ri =
f_aa
(Ci - Cio) dx (6)
Liquid Surfaces
where x is again the direction normal to the interface and + a
To understand surface energetics in coatings, one must and - a are locations equidistant from the interface in the
first understand the basics of the thermodynamics of surfaces bulk of the material. This is shown schematically for a single
and interfaces. The definition of the Gibbs free energy is surfactant in Fig. 2. In adsorption of materials to an interface,
www.iran-mavad.com

CHAPTER 3 4 - - S U R F A C E E NE R G E T IC S 371
iiii)Vapor
]ii i!i i i i!i i i i i i i i i i i !i i i i l~
~+a::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::l I:) I
n-direction
iiiiii!iiiiiiiiiiiiiiiiil ........ i!iiiiiiii!,,ii _ '

TangentialPressure Jiiiiiiiiiii!~iiiiiiiiiiiiiiiiililili~i~~ I
aegionby Interface ii i i i!!i!i ii i i i i i i i i i i!!ii i i i i ii i i i i i i i i i:::
iiLiquidiiiiiiiiiiiiiiiii!!iiiiiiiiiiiiiiiii!iiiiiiiiiiiiiiiiiiiiiiii
~,-ffl~-#)an
FIG. 1-Schematic of local pressure changes at surface giving surface tension.
the local concentration in the neighborhood of the interface actions between unlike molecular components. The terms
can be much larger (by factors of up to 108 or larger--see Ref often used to describe the compositional differences in sur-
1, Chapter III for further details) than that in the bulk. The factants are polar/nonpolar or hydrophobic/hydrophilic. Ma-
net energy of the system is minimized by the surfactant mole- terials that act as surfactants are those that have a distinct
cules adsorbing and orienting at the interface to reduce inter- difference between different parts of their molecules, the
Interracial Layer
C It
0
n
Q
)
nc(x)
t
r
i<
t Overlying Fluid
Bulk Liquid
i
0
n %
x > +
Distance Perpendicular to Surface
FIG. 2-Schematic of surface excess concentration as calculated as difference for bulk concentra-
tion.
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classic example being soaps, with an alkyl nonpolar group ize the properties of m o n o m o l e c u l a r layers at surfaces [16]. If
and a [carboxylate + metal ion] polar group. there are diffusional effects due to soluble surfactants (see
In concentrated systems of surface-active materials, espe- below, "Dynamic Properties of Surfaces"), they will reduce
cially those of low inherent solubility in the liquid phase, at a the surface elasticity, effectively short circuiting the surface
certain concentration the addition of further surfactant no tension changes by surface replenishment [17-19]. In these
longer depresses the surface tension, as the surface is satu- cases, Eq 7 should be modified to read
rated, and the molecules of the surfactant begin to form self-
%= - (d~,/d In F) (8)
ordered structures in the bulk liquid called micelles [12].
Micelles are aggregates of surfactant molecules that form in [1 + (h/2)(dc/dF)]
solution to minimize the total system energy. In water they where c is the surfactant concentration and h is given by the
orient with the hydrophobic portion of the molecule directed relationship
toward the interior of the micelle, and in nonaqueous systems
they have the polar end in the interior. At the concentration of h = 2 ~/D (9)
surfactant that micelles just begin to form, m a n y of the solu-
tion properties also undergo rapid change, and this break-
where D is the surfactant diffusion coefficient, and to is the
point in surfactant solution properties is k n o w n as the critical
frequency of the surface motion [18]. Surface elasticity ef-
micelle concentration (CMC) (Fig. 3). The CMC is a unique
fects are a major consideration in foam stability [20] and in
concentration for a surfactant/solvent combination at a spec-
coating application processes [21], where there are rapid sur-
ified temperature. The book by Rosen [13] gives an expanded
face area changes and creation of new surfaces.
discussion of surfactant behavior, and Tanford's book [14]
gives an expanded description of micellar behavior in aque-
ous systems. These texts also describe the complex aggregates
Liquid/Solid Interfaces: Wetting and Contact
that form in surfactant/solvent mixtures, including mem-
brane-like structures and liquid crystals.
Angles
As Gibbs first noted, the presence of a material adsorbing W h e n a liquid solution is in contact with a bulk solid, the
preferentially at an interface imparts an elasticity to the sur- Young equation holds true as
face, as it will tend to resist expansion and contraction. This
surface elasticity is given by %l - %v + ~v cos O = 0 (10)
where %t, %v, and 7zv are the solid/liquid, solid/vapor, and
%_ dv _ dv (7) liquid/vapor surface tensions, respectively, and O is the con-
dlnA dlnF tact angle formed between the liquid and solid [9,22]. This is
where A is the surface area. This elasticity is the resistance to shown in Fig. 4 and discussed extensively in the references
disturbance of a film by the presence of a surfactant. The given above. The contact angle between a liquid and a solid is
effects of this surface elasticity have been reviewed with rein some ways a measure of the difference in surface energies
spect to its effects in liquid films and liquid threads [15]. of the solid and liquid. If a liquid "wets" a solid, the contact
Surface elasticity measurements have been used to character- angle is zero, and the liquid spreads spontaneously over the
surface of the solid, displacing air in contact with the solid
surface. If the contact angle is greater than zero, a liquid will
CMC not wet and spread on a solid. An extreme example of this is
found with Teflon TM, which is of such a low surface energy
that it is wet by few pure liquids or solutions. In general, pure
J
Physioal
Property 2-OsmoticPressure
~ 3_SurfaceTension
~N~4-Equlval.entvlty
~
C C
Surfaotant Concentration
FIG. 3-Schematic of physical property changes in surtactant
solution at critical micelle concentration (CMC). FIG. 4-Schematic of contact angle in G/L/S system.
www.iran-mavad.com

CHAPTER 3 4 - - S U R F A C E E N E R G E T I C S 373
hydrocarbon and fluorocarbon interfaces that are nonpolar D Y N A M I C P R O P E R T I E S OF LIQUID

in nature have very low surface energies and are difficult to SURFACES
wet, while polar materials such as metals and metal oxides
have high surface energies and are easily wet. Oils or other When fresh surfaces are formed in a liquid solution, such
impurities on the surface of a polar substrate will cause the as in coatings application processes, manufacture, etc., the
material to act as a low surface energy solid, making it diffi- surface tension and composition of the fresh surface of a
cult to wet. There is extensive qualitative discussion in the solution will be different from the equilibrium value. At the
literature concerning polar and nonpolar contributions to time of new surface creation, the surface tension of the liquid
surface energetics, much of it of value only in a qualitative will be nearly equal to the surface tension of the pure solvent
sense as a guide to interpreting the wetting behavior of pure at the instant of the surface formation. The surface tension
liquids. Good and Fowkes have both published extensively in then decreases as the surfactant in the solution diffuses to the
this area (see Refs 1 and 23 for a more complete listing of interface. The dynamics of the diffusion from bulk to inter-
these citations), and the literature is full of equations of face, or vice versa in the case of surface compression, has
arguable theoretical value invoking empirical relations be- been well studied, initially by Ward and Tordai [31] and later
tween composition and surface energetics, including acid- by Sutherland [32], Hansen [33], Joos [34], and others. There
base interactions [23]. In coatings application, it is very cru- are also possible complicating effects if the adsorbing mate-
cial to have the liquid coating wet the substrate. Substrate rial is polymeric, for which case additional time-dependent
cleaning and the use of surfactants to depress the liquid changes in the surface tension may occur as the polymer
coating surface tension and reduce the contact angle to zero molecules relax to their equilibrium conformation at the sur-
are two of the most common steps to achieve this. It is face, or if there is an energy barrier to adsorption of the
essential to have this wetting of the substrate to obtain good material [35,36]. Special methods have been developed to
adhesion of the coating to the substrate, hence the impor- measure dynamic surface tension, and these are discussed
tance of proper surface preparation for coatings use. below, along with static surface tension measurement meth-
Rough surfaces tend to have lower contact angles than ods. It is especially important to consider and eliminate dy-
smooth surfaces of the same composition [24]. This is why namic surface tension effects if one is trying to measure the
equilibrium value of ~7(t) for t --~ o0],meaning for example, a
sanding or other surface roughening will give better wetting
Wilhelmy plate rather than a Du Nuoy ring is the appropriate
of a material by a coating. There is also often a difference in
measurement for systems that are other than pure liquids.
the contact angle measured by an advancing drop and a
These dynamic effects are especially important in coating
receding drop, the advancing angle being the larger. This is
application processes and all coating operations that gener-
often due to surface roughness, causing a hysteresis in the
ate fresh surfaces [37]. There are also dynamic effects in the
contact angle [25]. Surface compositional differences and
wetting of surfaces that must be considered for coating appli-
their scale have also been shown to give hysteresis, both by
cation operations. The first is the dynamics of wetting in thin
themselves and together with surface roughness [26]. These
film spreading as discussed by de Gennes [38]; the other is the
literature references, plus many others (see Ref I for a more
dynamics of contact angles on moving substrates [39].
complete discussion), indicate the difficulties in obtaining
completely unambiguous contact angle measurements, espe-
cially when considering both advancing and receding drops
M E A S U R E M E N T OF T H E S U R F A C E
on solid surfaces. Zisman and coworkers have also shown
T E N S I O N OF L I Q U I D S
that there is a "critical surface tension" characteristic of a
given surface [27]. This is determined by plotting the cosine Introduction
of the contact angle O versus surface tension and extrapolat-
ing to cos O = 1 (zero contact angle) and determining the There are many ways of measuring surface tension, but in
surface tension at this value. This is often used to determine essence, they are all related to two effects of capillarity. The
the relative surface energy of a solid and the surface tension first effect is the excess pressure due to surface tension at a
required of a wetting liquid for that surface. Pure liquids can curved interface. This is described by the Young-Laplace
be used as test liquids for the measurement of critical surface equation as
tension, or surfactant solutions can be utilized [13,28]. Some Ap -= T(1/R, + 1/R2) (11)
precautions need to be taken on the choice of test liquids as
the polarity of the test liquid may influence measurements where Ap is the excess pressure due to the curved interface,
and thus the extrapolation procedure used to estimate the and R1 and R2 are the two principal radii of curvature of the
critical surface tension (see Ref 1 for further details). interface. In the case of a sphere of radius r, where the radii of
Exposure to exterior weathering has been noted to de- curvature are both equal to r, this equation reduces to
crease contact angles of organic coatings and other polymeric Ap = 2T/r (12)
films [29]. Similar effects are noted when these surfaces are
The other capillary effect is that the surface tension of a liquid
modified by corona or flame treatment, and these treatments
exerts a force on a solid body immersed in it equal to the
are often used to give wetting and adhesion of coatings to
surface tension times the perimeter of the body times the
hard-to-wet plastic substrates such as polyethylene and poly-
contact angle the liquid makes with the solid. If one is using a
propylene. In addition to these surface treatments, it has been
balance, one can write
found that certain chlorinated olefinic polymers improve the
wetting and adhesion of coatings to polyolefin plastics [30]. AW = ~ , c o s O (13)
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where ~ is the perimeter and O is the contact angle, and AW is

the extra force on the solid body due to surface tension. These
two effects yield, together with various modifications of ge-
ometry, etc., m a n y methods to measure static and dynamic
surface tension. The most widely used methods are described
below.
<--r
In all measurements of surface tension, the cleanliness of
all apparatus and the purity of all materials is of utmost
importance. Organic impurities in aqueous systems will have
drastic effects in reducing the surface tension values mea-
sured. The concentration levels necessary to alter surface
tension measurements are as little as i0 -s M. Trace a m o u n t s _ _ i _ _ ~
of impurities on solid apparatus surfaces can alter contact

angles and, as will be shown, the measured surface tension
values. All water used in surface tension measurements
should be at least double distilled, and often the presence of a
strong oxidizing agent in one step of the distillation ensures
that trace surfactants are removed. The water should be used FIG. 5-Schematic of capillary rise method of
fresh, as surface active impurities can be leached from glass measuring surface tension.
and plastic containers. The same holds true for all solvents
used in surface characterization studies. Du Nuoy Ring
Applying Eq 13 to the case where the object is a ring being
pulled from the surface of a liquid, one has
Static Surface T e n s i o n M e a s u r e m e n t s W = Wnng + 41r?R (16)
There is a group of surface tension measurement methods where W is the total weight sensed by a balance, Wringis the
that apply well only to a static system. These methods must ring weight, and R is the ring radius as shown in Fig. 7.
thus be used on systems where there is no formation of fresh However, this formula requires correction to be accurate and
surfaces, or with pure liquid. holds only for a zero contact angle between the ring and test
Capillary Rise
/
There will be a pressure on a liquid in a small capillary tube / /
relative to the pressure on a large vessel of the liquid. Using /---/
Eq 12 and allowing for the contact angle between the liquid /- -/
and the capillary, we have at equilibrium between the force of /_--_/
/ - /
gravity and the capillary pressure / - - /
/- -
/
Apgh - 2 ? c o s O (14) / -- /
/-_-/
r /- -/
/ -- /
where Ap is the density difference between the liquid and air, /-- /
g is the acceleration of gravity, h is the height of the capillary /- -/
-- /
rise, and the rest of the terms are defined above. This equa- / -- /
tion allows one to measure the surface tension from a simple /--1
measurement of the height of the rise of the liquid in a /--I
/_--/
capillary of known radius and contact angle with the test /-- I
liquid. This m e t h o d is shown schematically in Fig. 5. /--/
~--~_<z~
r
Drop Weight
The weight of a drop when it is formed slowly is the weight
just to exceed the force of surface tension times the radius of
the capillary tip from which it is formed, with a correction
factor required for the formation of small satellite drops.
Thus, one has
J
W-- 2r (15)
where W is the weight of the drop and f is the correction
factor which is discussed in Adamson [1]. This method is
simple to use and accurate if precautions are taken for clean-
liness and very slow flow rates of the liquid in the formation FIG. 6-Schematic of drop weight method of mea-
of drops. The method is shown schematically in Fig. 6. suring surface tension.
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CHAPTER 34--SURFACE ENERGETICS 375
To a force m e a s u r i n g
balance
FIG. 7-Schematic of Du Nuoy ring method of measuring surface tension.
liquid. Again, see A d a m s o n [1] for further details. The force tension. Again cleanliness is m o s t crucial, a n d a r o u g h e n e d
m e a s u r e d by the balance is that force just at d e t a c h m e n t of p l a t i n u m plate cleaned in a Bunsen b u r n e r flame is often
the ring a n d so involves m o t i o n of the sensor; the m e t h o d is used to give a clean plate that is wet by m o s t liquids. As there
thus not a n a p p r o p r i a t e technique to use in studying solu- is no m o t i o n of the plate in the m e a s u r e m e n t , this m e t h o d
tions. can be used to m e a s u r e d y n a m i c as well as static values of 7.
This technique m a y be used as well with a r o d [40] o r cone
Wilhelmy Plate [41] instead of a plate a n d m a y also be used to m e a s u r e the
contact angle of a liquid of k n o w n surface tension against a
If one uses a thin plate instead of a ring a n d m e a s u r e s the specific plate, fiber, o r c o n e - s h a p e d substrate (see later in this
force exerted on the plate just touching the surface of a liquid, c h a p t e r u n d e r CONTACT A N G L E M E A S U R E M E N T S ) .
one has Also, the m e t h o d does not need corrections as with the d r o p
W ~--- Wplate -]- " ~ (17) weight o r the Du Nuoy ring methods.
w h e r e ~ is the p e r i m e t e r of the plate. If the liquid does not Sessile or Pendant Drop Shape Methods
perfectly wet the plate, the expression If the shape of a sessile or p e n d a n t d r o p is m e a s u r e d photo-
W = Wplate + 3 ~ cos O (17a) graphically o r a digitizing camera, a solution of Eq 11 for t h e
specific shape of the d r o p in the presence of a gravitational
m u s t be used as illustrated in Fig. 8. The p e r i m e t e r of the field can be used with the m e a s u r e m e n t s of the d r o p profile to
plate m a y be d e t e r m i n e d in practice as a n e x p e r i m e n t a l con- b a c k calculate the surface tension of the drop. Figure 9 gives a
stant from ~ / m e a s u r e m e n t s with liquids of k n o w n surface s c h e m a t i c of the m e t h o d . This m e t h o d works well at liquid-
air o r liquid-liquid interfaces a n d can also be used to m a k e
d y n a m i c m e a s u r e m e n t s if the c a m e r a response is c o n t i n u o u s
To Force a n d r a p i d [42]. A variation of the d r o p - s h a p e m e t h o d of m e a -
s u r e m e n t is used w h e r e i n the d r o p is d e f o r m e d by a centrifu-
Balance gal field or an electric field. The former, the spinning d r o p
shape method, allows very small interfacial tensions to be
-]
m e a s u r e d b e t w e e n two liquids [43].
Maximum Bubble Pressure Methods

If one forms a b u b b l e w i t h i n a liquid by forcing a gas out
the end of a capillary, the m a x i m u m pressure on the b u b b l e
can be used to m e a s u r e surface tension by Eq 12. This m e a -
s u r e m e n t p r o c e d u r e is illustrated in Fig. 10. However, the
m e a s u r e m e n t m u s t be c o r r e c t e d for the n o n s p h e r i c a l s h a p e
of the bubble. W i t h r a p i d f o r m a t i o n of the b u b b l e s a n d accu-
rate differential pressure m e a s u r e m e n t , the technique m a y
I _~_. . . . . . be used to m a k e d y n a m i c m e a s u r e m e n t s [44]. If capillaries of
two different radii are used s i m u l t a n e o u s l y a n d the p r e s s u r e
difference b e t w e e n the bubbles f o r m e d at the two capillaries
is m e a s u r e d , a rapid, accurate m e a s u r e m e n t of surface ten-
sion can be m a d e a n d has been used as a process m o n i t o r in
FIG. 8-Schematic of Wilhelmy plate method of e m u l s i o n p o l y m e r i z a t i o n [45]. This is k n o w n as the differen-
measuring surface tension. tial b u b b l e p r e s s u r e m e t h o d a n d is illustrated in Fig. 11.
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///.
. / / ,
f///
i/.-/~
i-//~ I
~ ~ ._____ _
Sessile drop profile P e n d a n t drop profile

FIG. 9-Schematic of sessile and pendant drop methods of measuring surface tension,
To Pressure Tranducer circular shape, as shown in Fig. 12, eventually breaking up

into droplets. The oscillations are periodic, and measurement
of their wavelength can be used to determine 3, as given by
40~
[ 37b2~
I ~1 + 2 - - ~ ] (18)
3'app =
6rh 2 (1 + 5w2ral3h
2 ]
where p is the liquid density, vis the velocity of the jet, h is the
wavelength of the oscillation, r is the sum of the minimum
and maximum diameters, and b is their difference [1]. This
dynamic measurement of 3' has been considered by Vijian
and Ponter [46], who give references to the earlier work of
Rayleigh, Bohr, Sutherland, Hansen, and others.
gas flow
FIG. 10-Schematic of maximum bubble pressure
method of measuring surface tension. J
Dynamic Surface Tension Methods
If one is concerned with surface tension effects that occur
in freshly formed surfaces, in flow systems, or in polymer.
solutions where the time for equilibrium may be quite long,
one must consider methods that properly measure dynamic
surface tension. As mentioned above, bubble pressure and
drop-shape methods as well as the Wilhelmy plate method
can be used for static as well as dynamic 3, measurements.
These methods are appropriate only for relatively slow
changes in 3,, but we discuss them briefly below and provide
literature references that discuss their use in characterizing
_~h
3,(t) effects. There are techniques to measure 3, that have been
developed specifically for short-time scales and fresh, rapidly
changing surfaces.
Oscillating Jet
If a liquid leaves as a jet through an elliptical orifice, it is FIG. 11-Schematic of differential bubble pressure
mechanically unstable and will begin to oscillate about a method of measuring surface tension.
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I_
~ f 5,'/'~- " I / K / . 5Pld
FIG, 12-SchemaUc of oscillating jet method of measuring surface tension.
Falling Curtain
In an analysis of curtain coating, Brown [47] observed that
the angle O in the falling curtain formed by the break around
a small, nonwettable obstacle could be used to measure sur-
face tension as
sin O - 27 (19)
Qu
where Q is the mass flow rate per unit orifice slit length in the
curtain and u is the velocity of the liquid. This can enable one
to calculate the dynamic surface tension in the falling film at
the point where the obstacle intersects the falling curtain if
the velocity u is greater than the "bursting velocity" of the
falling sheet. A schematic of this method is given in Fig. 13.
This has been considered further by Van Havenburgh and
Joos [48]. Antoniades et al. [49] reconsidered the work of
Brown and suggest that Eq 19, when derived correctly,
should be written as
FIG, 13-Schematic of falling film method of measuring sur-
sin 2 0 - 27 (19a) face tension.
Qu
and give experimental evidence for this corrected equation. The Falling Meniscus Method
The measurement of the height of a column of liquid in a
tube with a small opening on top can be used to measure the
Capillary Waves
dynamic surface tension of aqueous systems. The height
The properties of capillary waves, small wavelength waves measurement versus time may be analyzed to calculate the
on the surface of a liquid with the dominant restoring force surface tension as a function of time. This is discussed in
being surface tension, can be studied to provide a measure- further detail, together with a full description of the experi-
ment of surface tension, surface elasticity, and other dynamic mental apparatus and analytical equations, by Defay and
surface properties. For clean surfaces of an inviscid liquid, Hommeln [53].
Kelvin [50] determined that on a liquid of density p, waves of
frequency 0~, and wave number k, the surface tension is given Modified Static Surface Tension Measurements
for small wavelengths
Maximum Bubble Pressure--If one can monitor the time
Pc~ (20) response of pressure to the time-dependent surface tension,
7 - - k3 one can use the maximum bubble pressure technique de-
scribed above to measure dynamic surface tension [44]. The
The situation for interfaces in real systems, viscous liquids equipment required for such measurements is the same as
with surfactants present, has been studied in detail [8, 9], and the static maximum bubble technique plus instrumentation
the use of mechanically generated capillary waves for study- for time-dependent measurement of the bubble pressure.
ing interfaces has been reviewed by Hansen and Ahmad [51]. Various authors have examined the theoretical and experi-
The capillary waves generated by temperature fluctuations at mental aspects of this method [34,54].
a surface can be measured by laser-light scattering tech- Wilhelmy Plate--If a time-recording balance is used to
niques, and these data can be used to generate very accurate monitor the force of surface tension pulling on the immersed
values of surface and interfacial tensions [52]. Capillary wave plate, the Wilhelmy plate technique can be used for charac-
studies can be used to study the time dependence of 7 in some terizing dynamic surface tension. As discussed above, the
detail and are probably the most accurate and complete of the method is not useful for short times, but for slowly varying
methods for measuring all dynamic surface properties. 7(0 values. The method is used considerably with Langmuir
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film balances and has been applied to various other problems Capillary Rise Method
[55].
In a similar manner, the equation for capillary rise for a
Other Methods--If a sensing technique that can be time
nonzero contact angle can be modified to read
resolved is coupled to a specific static surface tension mea-
surement, 7(t) data can be acquired. Reference 42 discusses cos O - Aprgh (22)
this for drop-shape methods, and Jho and Burke [56] present 27
a modification of the drop weight technique for T(t) charac-
terization.
Rate o f Penetration
Washburn of the National Bureau of Standards (now
CONTACT ANGLE M E A S U R E M E N T S NIST) has developed an equation from the capillary rise
equation which relates the rate of penetration of liquid into a
Optical Measurement Methods bulk sample of powdered material to the surface tension of
the penetrating liquid and the contact angle between the liq-
Contact angles are often measured by some form of optical uid and the powder [61]. This equation can be used with
measurement technique, either directly by a contact angle
known materials to back calculate the contact angle as
goniometer, by a measurement on a photograph of a drop
shape, or digitally on a video image of the drop. A diagram of cos O - 4v~l (23)
a contact angle goniometer is given in Fig. 14. This measure- 7r
ment often is done with the aid of a microscope. [57]. One can
also calculate the contact angle from the dimensions of a drip where l is the length of the capillary path in the powder, r is
on a solid surface. The corrections and information given in the average pore size, v is the velocity of penetration, and ~ is
sessile drop, etc., measurement descriptions inherently con- the viscosity of the penetrating liquid. This equation can be
tain information on the drop profiles, including the contact used to estimate wetting properties and kinetics in the disper-
angle [38,39]. A more complete discussion of contact angle sion of pigments. A more recent discussion of this problem is
measurements is given by Neuman and Good [58], and given by Letelier et al. [62].
Adamson [1] also surveys these measurements. Sell and
Renzow [59] have reviewed the application of contact angle
studies to pigments and give comments on the measurement S O M E SPECIFIC APPLICATIONS OF
of contact angles in pigments. The relation of wetting and the S U R F A C E E N E R G E T I C S TO ORGANIC
thermodynamics of liquid-solid interfaces to adhesion are COATINGS
discussed in some detail in the monograph edited by Lee [60].
Coatings Application and Defects
Wilhelmy Plate Method Flow phenomena, and their control, at surfaces are very
important to coatings film application technology [6, 63]. The
Using the solid substrate material to be coated as the plate creation of uniform thin films at high speeds involves many
and a liquid of known surface tension as the test liquid, the problems that are determined by a combination of the appli-
Wilhelmy Plate method (Eq 17) can be modified to give cation geometry, the velocity of the substrate relative to the
liquid coating, the physical properties of the liquid coating,
cos 0 = AW/7~ ' (21)
especially the energetics of the surface of the liquid coating,
Figure 8 illustrates the principles of this procedure. the surface of the substrate, and the new liquid/solid and gas/
- Syringe
Therm0statted Cell
G0ni0meter Microscope ~-, ~/ Light Filter
Eyepiece Op/ties Liquid 11~ ~//
~//r Drop v ii ~.+Lilht~ourco_. I
FIG. 14-Schematic of contact angle goniometer.
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liquid interfaces created in the application processes. Analy- has yielded a measurement method for dynamic surface ten-
sis of several application techniques is given below to illus- sion. In the analyses of this problem, Brown [45] and Ha-
trate the importance of the use of concepts discussed in the venburgh and Joos [46] both modeled curtain coating by a
prior portion of this chapter. falling liquid film held in place by two vertical wires (see Fig.
16). The flux Q of falling liquid is
Dip Coating
Q = voho (25)
Dip coating is a coating method in which a sheet of mate-
rial is constantly withdrawn vertically from a coating liquid where v0 is the velocity of the falling film and ho is the width of
bath at constant velocity, producing a constant film thickness the falling film at time zero at the slot through which the
coating adhering to the sheet, which is usually then dried or liquid exits. The velocity of the falling film at a position x from
cured to produce the final coating on the sheet (see Fig. 15). the slot is given by
This problem was originally analyzed by Landau and Levich u2 = ~ + 2 g x (26)
[64], and its solution has been given in modern form by
Probstein [65]. Only the solution of the problem will be given where g is the acceleration of gravity. Since the flux of mate-
here, but it is representative of the problems identified by rial is constant through the slot, we know that
chemical engineers as coating flows. In these cases, the geom- Q = voh o = hv (27)
etry of the coating device, the relative velocity, v, of the object
to be coated, and the physical properties of the coating fluid and therefore
(surface tension, -/; viscosity, ~1;density, p; and acceleration of Q
gravity, g) fix the solution to the coating flow problem. In this h(x) - (28)
case, the limiting film thickness, 8f, at large distances from k / ~ o + 2gx
the coating bath surface, is given by This equation gives the user a description of the thickness of
liquid film as a function of distance from the slot of the
8f = 0.946 (7/2)2/3 (24) curtain coater. This can also be used to estimate the surface
tension at a given position x [46] by the following relation
This solution is derived from the physical effects of surface
y(x) - ph(x)u~~ (29)
tension, as described above, plus the Navier-Stokes equation 2
fluid mechanics. These authors assume Newtonian viscosity
behavior of the liquid, i.e., the viscosity, ~, is independent of These equations give the application engineer a reasonably
shear rate, time-independent surface tension, and an absence complete description of the curtain coating process.
of surface tension gradient-driven flows (Marangoi flows),
Electrostatic S p r a y
with the appropriate boundary conditions determined by the
coating process. This solution can be used by the coating The application of surface energetics to the problem of
designer and user to establish a first order estimate of the film charged liquid droplets was first done by Rayleigh [66]. In
thickness of the liquid film by the properties of the coating this study, the electrical repulsion forces between charges on
and the velocity of sheet withdrawal. a drop are equated to the surface tension forces holding a
drop together to give the following equation as an estimate of
Curtain Coating the upper limit on the charge that can be held on a drop
As described above in the section on measurement of dy- q = ~/16~re~ (30)
namic surface tension, analysis of the curtain coating process
where 9 is the dielectric constant of the drop and r is the drop
radius. This can be used to gain an estimate of the drop size in
electrostatic spray of liquid paints. Further stability analysis
FIG. 15-Schematic of dip coating process. FIG. 16-Schematic of curtain coater.
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of this problem indicates that if a drop at this charge limit often involve the deposition or creation of a rough-surfaced
breaks up, the total energy of the system will be minimized if crystalline layer of metallic phosphates which give an easily
it does so into n droplets, where n is given by wetted surface.
q2
n - (31)
4~re~ SUMMARY
where r0 is the radius of the original drop [67]. This charge
limit has been studied and verified experimentally by several The concepts of surface energy, surface tension, and wet-
workers [68,69] and also applied to problems of spray paint- ting and contact angle p h e n o m e n a are of exceptional impor-
ing [70]. All of this work further illustrates the importance tance to the science and technology of organic coating. Their
and extensive applications of surface energetics to coatings understanding is vital for the proper formulation and appli-
use. cation of coating. Many of the features of the final organic
coating/substrate system are controlled by proper under-
standing of the surfaces of the liquid coating and the sub-
Cleaning and Pretreatment of Substrates for strate, as well as creation of a proper coating/substrate
Coating interface. Both the static and dynamic aspects of liquid sur-
A very important step in the total process of creating a high face properties should be considered and the dynamic as-
performance organic coating/substrate system is the cleaning pects properly accounted for in coating production and
and pretreatment of the substrate prior to the coating appli- application. These concepts have been reviewed, and refer-
cation step. The specific purpose of cleaning and pretreating ences to further reading in this important area of organic
substrate surfaces is to control and/or modify the surface coatings science have been given.
energy of the substrate so that a coating m a y be successfully
applied to the substrate and that the coating will subse-
quently adhere properly to the substrate and provide the REFERENCES
performance desired. Cleaning, as a general rule, involves the
[1] Adamson, A. W., Physical Chemistry of Surfaces, 5th ed., Wiley,
removal of substances foreign to the substrate by a surfac-
New York, 1990, Ch. II-III.
tanffdetergent solution, followed with rinsing by a solvent [2] Bakker, G., "Kapillarit~t und Oberflachenspannung," Handbuch
that leaves the substrate surface clean of contaminants. This der Experimentalphysik, Vol. VI, Akadem, Verlag, Leipzig, 1928.
m a y have to be preceded by a mechanical sandblasting, [3] Wolf, D. E., Griffiths, R. B., and Tang, L., "Surface Stress and
grinding, sanding, scrubbing, etc., to remove thick layers of Surface Tension for Solid-Vapor Interfaces," Surface Science,
mil scale, rust, scum, and other built-up material on what is Vol. 162, 1985, p. 114.
the real substrate. Vapor or organic solvent degreasing/clean- [4] Walton, J. P. R. B., Tildesley, D. J., and Rowlinson, J., Molecular
ing is also often used to yield a clean surface for coating. Physics, Vol. 50, 1983, p. 1357.
These mechanical cleaning steps, along with the cleaning and [5] Braun, J. H., "Titanium Dioxide's Contribution to the Durability
rinsing of the surface with low surface tension solutions that of Paint Films," Progress in Organic Coatings, Vol. 15, 1987, pp.
249-260.
leave no residue, are best done just before the coating step
[6] Bierwagen, G. P., "Surface Defects and Surface Flows in Coat-
lest the surface become recontaminated while stored waiting ings," Progress in Organic Coatings, Vol. 19, 1991, pp. 59-68.
for the coating step. The goal of all these cleaning procedures [7] Burshtein, A. I., "Simple Liquid Surface Structure and Surface
is to insure a uniform surface that has a uniform contact Tension," Advances in Colloid Interface Science, Vol. 11, 1979,
angle, usually and desirably zero, for wetting by the coating, pp. 315-374.
and to insure the interface created is the coating liquid/sub- [8] Navascues, G., "Liquid Surfaces: Theories of Surface Tension,"
strate interface only. The mechanical sanding, polishing, etc., Reports of Progress in Physics, Vol. 42, 1979, pp. 1132-1186.
will also contribute to a lower contact angle by the surface [9] Rowlinson, J. S. and Widom, B., Molecular Theory of Capillarity,
roughness effect discussed above. Oil, dirt, rust, or other Clarendon Press, Oxford, UK, 1982, Ch. 2-4.
contaminants will give poor and incomplete wetting and poor [10] Guggenheim, E. A., Journal of Chemical Physics, Vol. 13, 1945,
p. 253.
adhesion of the coating at the contaminated sites. Complete
[111 Pitzer, K.S. and Brewer, L., Thermodynamics, 2nd ed.,
wetting is further assisted by insuring the surface tension of McGraw-Hill, New York, 1961, Ch. 29.
the coating liquid is low so that all air is displaced by the [12] Meyers, D., Surfactant Science and Technology, VCH Publishers,
coating and the contact angle between the liquid coating and 1988, Ch. 3.
the substrate is zero, or near to it. The surface tension of the [13] Rosen, M. J., Surfactants and Interfacial Phenomena, Wiley &
liquid coating is best lowered by the polymer of the system or Sons, New York, 1978.
by surfactant additives to the liquid system. Attempts to con- [14] Tanford, C., The Hydrophobic Effect, Wiley & Sons, New York,
trol the surface tension by the solvent can cause problems in 1980.
having the surface tension increase as the solvent evaporates. [15] Rusanov, A. I. and Krotov, V. V., "Gibbs Elasticity of Liquid
Substrate pretreatment is usually performed just after the Films, Threads, and Foams," Progress in Surface and Membrane
Science, Vol. 13, J. Danielli, Ed., Academic Press, New York,
cleaning discussed above and is done to further insure com-
1979.
plete wetting and adhesion of the coating, as well as, in the [16] Lucassen-Reynders, E. H., Lucassen, J., Garrett, P. R., Giles, D.,
case of metallic substrates, to deposit a corrosion inhibitive and Hollway, F., "Dynamic Surface Measurements as a Tool to
layer. In the case of plastic substrates, the pretreatment m a y Obtain Equation-of-State Data for Soluble Monolayers," Ch. 21,
be corona or flame modification to oxidize the surface layer Advances in Chemistry Series, No. 145, American Chemical Soci-
and lower the contact angle to near zero. Metal pretreatments ety, Wash., DC, 1975, pp. 275-285.
www.iran-mavad.com

CHAPTER 3 4 - - S U R F A C E E N E R G E T I C S 381
[17] Hansen, R. S. and Mann, J. A., "Propagation Characteristics of [39] Ishimi, K., Hikita, H., and Esmail, M., "Dynamic Contact Angles
Capillary Ripples," Journal of Applied Physics, Vol. 35, 1964, pp. on Moving Plates," American Institute of Chemical Engineering
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[18] Hansen, R. S., Lucassen, J., Bendure, R. L., and Bierwagen, [40] Lyons, C. J., Elbing, E., and Wilson, I. R., "The Rod-in-Free
G. P., "Propagation Characteristics of Interfacial Ripples," Jour- Surface Technique for Surface-Tension Measurement Using
nal of Colloid and Interface Science, Vol. 26, 1968, p. 198. Small Rods," Journal of Colloid and Interface Science, Vol. 101,
[19] Lucassen, J. and Hansen, R. S., Journal of Colloid and Interface 1984, pp. 292-294.
Science, Vol. 22, 1966, p. 32. [41] Ugarcic, Z., Vohra, D. K., Atteya, E., and Hartland, S., "Measure-
[20] Lucassen, J., "Dynamic Properties of Free Liquid Films and ment of Surface Tension Using a Vertical Cone," Journal of
Foams," Ch. 6, E. H. Lucassen-Reynders, Ed., Physical Chemis- Chemical Society, Faraday Transaction I, Vol. 77, 1981, pp.
t~ of Anionic Surfactants, Vol. 6 in Surfactant Science, series, M. 49-61.
Schiff, Ed., Marcell Dekker, New York, 1981. [42] Girault, H. H., Schiffrin, D. J., and Smith, B. D. V., "Drop Image
[21] Benney, D. J., Gutoff, E. B., and Foley, J. A., "The Effect of Processing for Surface and Interracial Tension Measurements,"
Surface Elasticity on the Stability of Flow Down an Inclined Journal of Electroanalyticat Chemistry, Vol. 137, 1982, pp.
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Fluid Mechanics, 72nd Annual Meeting, American Institute of [43] Seeto, Y. and Scriven, L. E., "Precision Spinning Drop Interra-
Chemical Engineering, San Francisco, 25-29 Nov. 1979. cial Tensiometer," Review of Scientific Instruments, VoL 53,
[22] Adamson, Ref. 1, Ch. X. 1982, pp. 1757-1761.
[23] Lee, L.-H., Ed., Fundamentals of Adhesion, Plenum Press, New [44] Bendure, R. L., "Dynamic Surface Tension Determination with
York, 1991, Chapters 2 and 3. the Maximum Bubble Pressure Method," Journal of Colloid and
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Wetting (Theoretical)," Journal of Colloid and Interface Science, [45] Shork, F. J. and Ray, W. H., "On-Line Measurement of Surface
Vol. 60, 1977, pp. 11-38. Tension and Density with Applications to Emulsion Polymeriza-
[25] Bracke, M., De Bisschop, F., and Joos, P., "Contact Angle Hyster- tion," Journal of Applied Polymer Science, Vol. 28, 1983, pp.
esis due to Surface Roughness," Progress in Colloid and Polymer 407-430.
Science, Vol. 76, 1988, pp. 251-259. [46] Vijian, S. and Ponter, A. B., "Dynamic Surface Tension Studies
[26] Joanny, J. F. and de Gennes, P. G., "A Model for Contact Angle Using an Oscillating Jet," Indian Journal of Chemical Engineer-
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552-562. [47] Brown, D. R, "A Study of the Behaviour of a Thin Sheet of
[27] Zisman, W. A., Advances in Chemistry Series, Vol. 43, American Moving Liquid," Journal of Fluid Mechanics, VoL 10, 1961, pp.
Chemical Society, Wash., DC, 1964. 297-305.
[28] Liao, W.-C. and Zatz, J. L., "Surfactant Solutions as Test Liquids [48] Van Havenburgh, J. and Joos, P., "The Dynamic Surface Tension
for Measurements of Critical Surface Tension," Journal of Phar- in a Free Falling Film," Journal of Colloid and Interface Science,
maceutical Science, Vol. 68, 1979, pp. 486-488. Vol. 95, 1983, pp. 172-182.
[29] Croll, S. G., Progress in Organic Coatings, Vol. 15, 1987, pp. [49] Antoniades, M. G., Goodwin, R., and Lin, S. P., Journal of Col-
223-248. loid and Interface Science, VoL 77, 1989, p. 583.
[30] Lawniczak, J., Greene, P., Evans, R., and King, G., "Water- [50] Kelvin, Lord (W. Thomson), Philosophical Magazine, Vol. 42,
1871, p. 368.
Reducible Adhesion Promoters for Coatings on Polypropylene-
Based Substrates," Proceedings, 19th Water-Borne, Higher-Sol-
[51] Hansen, R. S. and Ahmad, J., Progress in Surface and Membrane
Science, Vol. 4, Academic Press, New York, 1971.
ids, and Powder Coatings Symposium, R. Storey and S. Thames,
[52] Lofgren, H., Neuman, R. D., Scriven, L. E., and Davis, H. T.,
Eds., New Orleans, 26-28 Feb. 1992, Univ. of Southern Missis-
"Laser Light-Scattering Measurements of Interracial Tension
sippi, pp. 63-74.
Using Optical Hetrodyne Mixing Spectroscopy," Journal of Col-
[313 Ward, A. F. H. and Tordai, L., Journal of Chemical Physics, Vol.
14, 1946, p. 453.
loid and Interface Science, Vol. 98, 1984, pp. 175-183.
[53] Delay, R. and Hommeln, J., "II. Measurement of Dynamic Sur-
[32] Sutherland, K. L., "The Kinetics of Adsorption at Liquid Sur-
face Tensions of Aqueous Solutions by the Falling Meniscus
faces," Australian Journal of Scientific Research A5, 1952, pp.
Method," Journal of Colloid Science, Vol. 14, 1959, pp. 401-410.
683-696.
[54] Lunkenheimer, K., Serrien, G., and Joos, P., "The Adsorption
[33] Hansen, R. S., Journal of Physical Chemistry, VoL 64, 1960, p. Kinetics of Octanol at the Air Solution Interface Measured with
637.
the Oscillating Bubble and Oscillating Jet Methods," Journal of
[34] Joos, P. and Rillaerts, E., "Theory on the Determination of the Colloid Interface Science, Vol. 134, 1990, pp. 407-411.
Dynamic Surface Tension with the Drop Volume and Maximum [55] Montgomery, D. D. and Anson, F. C., "Time-Resolved Measure-
Bubble Pressure Methods," Journal of Colloid and Interface Sci- ment of Equilibrium Surface Tensions at the Electrified Mer-
ence, Vol. 79, 1981, pp. 96-100. cury-Aqueous NaF Interphase by the Method of Wilhelmy,"
[35] Bois, A. G., Baret, J. F., and Roux, R., "Adsorption at the Oil- Langmuir, Vol. 7, 1991, pp. 1000-1004.
Water Interface: Both Energy Barrier and Diffusion Controlled [56] Jho, C. and Burke, R., "Drop Weight Technique for the Measure-
Kinetics," Kolloid Zeitschrift und Zeitschrift fi~r Polymere, Vol. ment of Dynamic Surface Tension," Journal of Colloid and Inter-
249, 1971, pp. 1144-1147. face Science, Vo]. 95, 1983, pp. 61-71.
[36] Borwankar, R. P. and Wasan, D. T., "Equilibrium and Dynamics [573 Farnarier, C., Capo, C., Balloy, V., Benoliel, A.M., and
of Adsorption of Surfactants at Fluid-Fluid Interfaces," Chemi- Bongrand, P., "Simple Microscopical Measurement of Contact
cal Engineering Science, Vol. 43, I988, pp. 1323-1337. Angles on Transparent Substrates," Journal of Colloid and Inter-
[37] Bierwagen, G. P., "Surface Dynamics of Defect Formation in face Science, Vol. 99, 1984, pp. 164-167.
Paint Films," Progress in Organic Coatings, Vol. 3, 1975, p. 101, [58] Neuman, A. W. and Good, R. J., "Technique of Measuring Con-
and Bierwagen, Ref 5. tact Angle," Ch. 2, Surface and Colloid Science, Vol. H
[38] de Gennes, P. G., "The Dynamics of Wetting," Ch. 5, Fundamen- Experimental Methods, R. J. Good and R. R. Strornberg, Eds.,
tals of Adhesion, L.-H. Lee, Ed., Plenum Press, New York, 1991. Plenum Press, New York, 1979.
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[59] Sell, P.-J. and Renzow, D., "Bestimmung des Benet- [65] Probstein, R. F., Physicochemical Hydronamics, Butterworths,
zungsverhaltens von Pigmenten," Progress in Organic Coatings, London, 1989, pp. 280-289.
Vol. 3, 1975, pp. 323-348. [66] Rayleigh, Lord, "On the Equilibrium of Liquid Conducting
[60] Lee, L.-H., Ed., Fundamentals of Adhesion, Plenum Press, New Masses Charged with Electricity," Philosophical Magazine, Vol.
York, 1991. 14, 1882, pp. 184-186.
[61] Washburn, E. D., Physical Reviews, Vol. 17, 1921, p. 374. [67] Gopal, E. S. R., Ch. 1, Emulsion Science, P. Sherman, Ed., John
Wiley, New York, 1963.
[62] Letelier, M., Leutheusser, H. J., and Rosas, C., "Refined Mathe-
[68] Richardson, C. B., Pigg, A. L., and Hightower, R., "On the Sta-
matical Analysis of the Capillary Penetration Problem," Journal
bility Limit of Charged Droplets," Proceedings of the Royal Soci-
of Colloid and Interface Science, Vol. 72, 1979, pp. 465-470. ety of London, A, Vol. 422, 1989, pp. 319-328.
[63] Bierwagen, G, P., "Film Coating Technologies and Adhesion," to [69] Schweitzer, J.W. and Hanson, D.N., "Stability Limit of
appear in Electrochimica Acta. Charged Droplets," Journal of Colloid and Interface Science, Vol.
[64] Landau, L. D. and Levich, V. G., "Dragging of a Liquid by a 35, 1971, pp. 417-423.
Moving Plate," Acta Phyicochimica URSS, Vol. 17, 1942, pp. 42- [70] Hines, R. L., "Electrostatic Atomization and Spray Painting,"
54. Journal of Applied Physics, Vol. 37, 1966, pp. 2730-2736.
www.iran-mavad.com

MNL17-EB/Jun. 1995
|
Solubility Parameters
by Charles M. Hansen 1
NOMENCLATURE The solubility parameter approach has been used for m a n y

years to select solvents for coating materials. The lack of total
C Dispersion cohesion energy from Fig. 2 and Fig. 3 success has stimulated research. The skill with which sol-
D Dispersion cohesion (solubility) p a r a m e t e r - - i n ta- vents can be optimally selected with respect to cost, solvency,
bles and computer printouts workplace environment, external environment, evaporation
D M Dipole m o m e n t - - D e b y e s rate, flash point, etc. has improved over the years as a result of
~k~d Dispersion cohesion energy a series of improvements in the solubility parameter concept
AEp Polar cohesion energy and widespread use of computer techniques. Most, if not all,
AEh Hydrogen bonding cohesion energy commercial suppliers of solvents have computer programs to
AEv Energy of vaporization ( = ) cohesion energy help with solvent selection. One can now easily predict how
AG M Molar free energy of mixing
to dissolve a given polymer in a mixture of two solvents,
H Hydrogen bonding cohesion (solubility) parame- neither of which can dissolve the polymer by itself.
t e r - i n tables and computer printouts This contribution to the paint testing manual unfortunately
d~"l v Molar heat of vaporization can not include discussion of all of the significant efforts
A H M Molar heat of mixing
leading to our present state of knowledge of the solubility
P Polar cohesion (solubility) p a r a m e t e r - - i n tables
parameter. An attempt is made to outline developments, pro-
and computer printouts
vide some background for a basic understanding, and give
R Gas constant (1.987 cal/mole-~
examples of uses in practice. The key is to determine which
R~ Distance in Hansen space
affinities the important components in a system have for each
R0 Radius of interaction sphere in Hansen space
other. For coatings, this means affinities of solvents, poly-
RED Relative energy difference, R,/Ro
AS M Molar entropy of mixing mers, pigment surfaces, additives, and substrates.
T Absolute temperature
It is noteworthy that the concepts presented here have
1; (Normal) boiling point developed toward not just predicting solubility, which re-
quires high affinity between solvent and solute, but to predict
L Critical temperature
v,,, Molar volume affinities between different polymers leading to compatibil-
Ar Lydersen critical temperature group contribution ity, and affinities to surfaces to improve pigment dispersion
O/ Thermal expansion coefficient and adhesion. Attempts are also being made to extend these
~d Dispersion cohesion (solubility) parameter developments, largely attributable to the coatings industry, to
~h Hydrogen bonding cohesion (solubility) parameter understand affinities and phenomena for a large number of
Polar cohesion (solubility) parameter other materials not specifically related to coatings. In these
8r Total cohesion (solubility) parameter applications the solubility parameter has become a tool, us-
6, Volume fraction of component "i" ing well-defined liquids as energy probes, to measure the
X Polymer-liquid interaction parameter (Flory- similarity, or lack of same, of key components. Materials with
Huggins) widely different chemical structures may be very close in
affinities. Only those materials which interact differently
with different solvents can be characterized in this manner.
INTRODUCTION Many inorganic materials, such as fillers, do not interact
differently with these energy probes since their energies are
SOLUBILITYPARAMETERSAREUSEDin the coatings industry to very much higher. Changing their surface energies by various
select solvents. Liquids with similar solubility parameters treatments can lead to a surface which can be characterized.
will be miscible, and polymers will dissolve in solvents whose Solubility parameters are cohesion energy parameters
solubility parameters are not too different from their own. since they derive from the energy required to convert a liquid
The basic principle is "like dissolves like." Solubility parame- to a gas. The energy of vaporization is a direct measure of the
ters help put numbers into this simple qualitative idea. total (cohesive) energy holding the liquid's molecules to-
gether. All types of bonds holding the liquid together are
~FORCE Institute, Division for Mechatronic and Sensor Technol- broken by evaporation, which has led to the concepts de-
ogy, Park Alle 345, DK-2605 Broendby, Denmark. scribed in more detail below. The term cohesion energy pa-
383
www.iran-mavad.com

rameter is more appropriately used when referring to surface this purpose and because of the lack of accuracy with which
phenomena. the solubility parameters can be assigned.
A more detailed description of the theory presented by
Hildebrand and the succession of research reports which
HILDEBRAND PARAMETERS have attempted to improve on it can be found in Barton's
extensive handbook [3]. The slightly older excellent contribu-
The term solubility parameter was first used by Hildebrand tion of Gardon and Teas [4] is also a good source, particularly
and Scott [1,2]. The solubility parameter is the square root of for coatings and adhesion phenomena. The approach of Bur-
the cohesive energy density rell [5], who divided solvents into hydrogen bonding classes,
has found numerous practical applications, and the approach
8 = (c.e.d) 112 =
\( ~VM
v l l / 2] ( c a ] / c m 3 ) l / 2 o r M P a l / 2 (1) of Blanks and Prausnitz [6], who divided the solubility pa-
rameter into two components, nonpolar and "polar," are wor-
where Vu is the molar volume and AEv is the (measurable) thy of mention, however, in that these have found wide use
energy of vaporization (see Eq 12). The solubility parameter and greatly influenced the author's earlier activities, respec-
is an important quantity in predicting solubility relations, as tively.
can be seen from the following brief introduction. It can be seen from Eq 2 that the entropy change can be
Thermodynamics requires that the free energy of mixing considered beneficial to mixing. When multiplied by the tem-
must be zero or negative for the solution process to occur perature this will work in the direction of promoting a more
spontaneously. The free energy change for the solution pro- negative free energy of mixing. Higher temperatures will also
cess is given by the relation promote this more negative free energy change. The entropy
changes associated with polymer solutions will be smaller
A G u = z3J4M - T A S M (2) than those associated with liquid-liquid miscibility, for exam-
where A G M is the free energy of mixing, A H M is the heat of ple, since the "monomers" are already bound into the config-
mixing, T is the absolute temperature, and A S M is the entropy uration dictated by the polymer they make up. They are no
change in the mixing process. longer free in the sense of a liquid solvent and can not mix
The heat of mixing, ~d-/M, is given by Hildebrand and Scott freely to contribute to a larger entropy change. This is one
as reason polymer-polymer miscibility is difficult to achieve.
The free energy criterion dictates that the polymer solubility
z3J-Iu - ~ A E M = d~,,I,2VM(8, - 82)2 (3) parameters match extremely well since there is little help
where the ~b's are volume fractions and VM is the average from the entropy contribution when progressively larger mol-
molar volume of the solvent. It is important to note that the ecules are involved. However, polymer-polymer miscibility
solubility parameter, or rather the difference in solubility can be promoted by introduction of suitable copolymers or
parameters for the solvent-solute combination, is important comonomers which interact specifically within the system.
in determining the solubility. It is clear that a match in solu-
bility parameters leads to a zero heat of mixing, and the
entropy change should ensure solution. The maximum differ- H A N S E N SOLUBILITY P A R A M E T E R S
ence in solubility parameters which can be tolerated where
solution still occurs is found by setting the free energy change A widely used solubility parameter approach to predicting
equal to zero in Eq 2. It is, in fact, the entropy change which polymer solubility is that proposed by the author. The basis
dictates how closely the solubility parameters must match of these so-called Hansen solubility parameters is that the
each other. It can also be seen that solvents with smaller total energy of vaporization of a liquid consists of several
molecular volumes promote lower heats of mixing, which, in individual parts [ 7 - 1 1 ] . Needless to say, without the work of
turn, means that smaller solvent molecules will be thermody- Hildebrand and Scott [1,2] and others not specifically refer-
namically better than larger ones when their solubility pa- enced here such as Scatchard, this postulate could never have
rameters are equal. A practical aspect of this effect is that been made. The total cohesive energy, A E t, can be measured
solvents with relatively low molecular volumes, such as meth- by evaporating the liquid, i.e., breaking all the cohesive
anol and acetone, can dissolve a polymer at larger solubility bonds. It should also be noted that these cohesive energies
parameter differences than expected from comparisons with arise from interactions of a given solvent molecule with an-
other solvents with larger molecular volumes. The converse is other of its own kind. The basis of the approach is, therefore,
also true. Larger molecular species may not dissolve, even very simple, and it is surprising that so many different appli-
though solubility parameter considerations might predict cations have been possible over the past 25 years. A number
this. This can be a difficulty with plasticizers. of applications are discussed below. A lucid discussion by
A serious shortcoming of the Hildebrand approach is that Barton [12] enumerates typical situations where problems
negative heats of mixing are not possible. Likewise, the ap- occur when using solubility parameters. These are most often
proach is limited to regular solutions as defined by where the environment causes the solvent molecules to inter-
Hildebrand and Scott [2] and does not account for associa- act with or within themselves differently than when they
tion between molecules, such as polar and hydrogen bonding make up their own environment, i.e., as pure liquids.
interactions would require. The latter problem seems to have Materials having similar (Hansen) solubility parameters
been largely solved with the use of multicomponent solubility have high affinity for each other. The extent of the similarity
parameters. The price has been that no thermodynamic cal- in a given situation determines the extent of the interaction.
culations of the heat of mixing in the traditional sense seem The same can not be said of the total or Hildebrand solubility
possible. This is both because of a lack of detailed theory for parameter [1,2]. Ethanol and nitromethane, for example,
www.iran-mavad.com

CHAPTER 35--SOLUBILITY PARAMETERS 385
have similar total solubility parameters (26.1 versus 25.1 ever type of separate energy can be defined. Hansen stopped
MPa 1/2, respectively), but their affinities are quite different. with the three major types found in organic molecules. It was
Ethanol is water soluble, while nitromethane is not. Indeed, and is recognized that additional parameters could be as-
mixtures of nitroparaffins and alcohols were demonstrated in signed to separate energy types. The description of organo-
many cases to provide synergistic mixtures of two nonmetallic compounds could be an intriguing study, for
solvents which dissolved polymers [7]. example. This would presumably parallel similar characteri-
There are three major types of interaction in common or- zations of surface-active materials, where each separate part
ganic materials. The most general are the "nonpolar" of the molecule requires separate characterization for com-
interactions, which derive from atomic forces. These have pleteness. The Hansen parameters have mainly been used in
also been called dispersion interactions in the literature. connection with solubility relations, mostly, but not exclu-
Since molecules are built up from atoms, all molecules will sively, in the coatings industry.
contain this type of attractive force. For the saturated ali- Solubility and swelling have been used to confirm the solu-
phatic hydrocarbons, for example, these are essentially the bility parameter assignments of many of the liquids. These
only cohesive interactions, and the energy of vaporization is have then been used to derive group contribution methods
assumed to be the same as the dispersion cohesive energy, and suitable equations based on molecular properties to ar-
AEd. Finding the dispersion cohesive energy as the cohesion rive at estimates of the three parameters for additional liq-
energy of the homomorph, or hydrocarbon counterpart, is uids. The goal of a prediction is to determine similarity or not
the starting point for the calculation of the three Hansen pa- of the cohesion energy density parameters. The strength of a
rameters for a given liquid. particular type of hydrogen bond or other bond, for example,
The permanent dipole-permanent dipole interactions is important only to the extent that it influences the cohesive
cause a second type of cohesion energy, the polar cohesive energy density.
energy, AEp. These are inherently molecular interactions and Hansen parameters do have direct application in other sci-
are found in most molecules to one extent or another. The entific disciplines of interest to the coatings industry, such as
dipole moment is the primary parameter in calculating these surface science, where they have been used to characterize
interactions. A molecule can be primarily polar in character the wettability of various surfaces and adsorption properties
without being water soluble, so there is misuse of the term of pigment surfaces [4, 8,10,17-19]. Many other applications
"polar" in the general literature. The polar solubility parame- of widely different character have been discussed by Barton
ters referred to here are well-defined, experimentally verified, [3] and Gardon [20]. Surface characterizations have not been
and can be estimated from molecular parameters as de- given the attention deserved in terms of a unified similarity-
scribed below. As noted above, the polar solvents include of-energy approach. The author can certify that thinking in
those with relatively high total solubility parameters which terms of similarity of energy, whether surface energy or cohe-
are not particularly water soluble such as nitroparaffins, pro- sive energy, can lead to rapid decisions and plans of action in
pylene carbonate, tri-n-butyl phosphate, and the like. In- critical situations where data are lacking. In other words, the
duced dipoles have not specifically been treated by Hansen, everyday industrial crisis situation can often be reduced in
but are recognized as a potentially important factor, particu- scope by appropriate systematic approaches based on simi-
larly for solvents with zero dipole moments. larity of energy.
The third major cohesive energy source is hydrogen bond- The basic equation which governs the assignment of
ing, AEh. Hydrogen bonding is a molecular interaction and Hansen parameters is that the total cohesion energy, AEt,
resembles the polar interactions in this respect. The basis of must be the sum of the individual energies which make it up
this type of cohesive energy is attraction among molecules
because of the hydrogen bonds. In this perhaps oversim-
~kE t = ~kEd d- ~ p -~- z~kEh (4)
plified approach, the hydrogen bonding parameter has been Dividing this by the molar volume gives the square of the total
used to more or less collect the energies from interactions not (or Hildebrand) solubility parameter as sum of the squares of
included in the other two parameters. Alcohols, glycols, car- the Hansen D, P, and H components.
boxylic acids, and other hydrophilic materials have high hy-
drogen bonding parameters. Other researchers have divided AE~ _ AEd + AEp + AEh (5)
this parameter into separate parts, for example, acid and base v~ v~ v~ v~
cohesion parameters, to allow both positive and negative St= 82 + 82 + 82 (6)
heats of mixing. These approaches will not be dealt with here,
but can be found described in Barton's Handbook [3], and = D 2 + p2 + H 2 (computer printouts)
elsewhere [13-15]. The most extensive division of the cohe-
sive energy has been done by Karger et al. [16], who devel-
oped a system with five parameters: dispersion, orientation, M E T H O D S AND P R O B L E M S IN T H E
induction, proton donor, and proton acceptor. The Hansen D E T E R M I N A T I O N OF PARTIAL
hydrogen-bonding parameter may be termed an electron in- SOLUBILITY P A R A M E T E R S
terchange parameter as well. As a single parameter it has
remarkably well accounted for the experience of the author The best method to calculate Hansen solubility parameters
and keeps the number of parameters to a level which allows depends to a great extent on what data are available. Hansen
ready practical usage. originally adopted an essentially experimental procedure and
It is clear that there are other sources of cohesion energy in established numbers for 90 liquids based on solubility data
various types of molecules arising, for example, from induced for 32 polymers [7]. This procedure involved calculation of
dipoles, metallic bonds, electrostatic interactions, or what- the nonpolar parameter according to the procedure outlined
www.iran-mavad.com

by Blanks and Prausnitz [6]. This calculational procedure is The exact reason for the constant 4 in Eq 7 is not clear, but
still in use and is considered the most reliable and consistent it is currently considered more as an experimental result
for this parameter. It is outlined below. The division of the related to the entropy changes in the systems described
remaining cohesive energy between the polar and hydrogen rather than a theoretically well-defined constant. The author
bonding interactions was done by trial and error to fit experi- has also found in unpublished studies that values close to 5
mental polymer solubility data. A key to parameter assign- represented solubility data equally well for the cases studied.
ments in this initial trial and error approach was that It is thought that this constant especially reflects the entropy
mixtures of two nonsolvents could be systematically found to change beneficial to the solution process when the molecular
synergistically (but predictably) dissolve given polymers. interactions characterized by the ~p and 6h parameters are
This meant that these had parameters placing them on oppo- involved. The order in the pure liquids is reduced when they
site sides of the solubility region, a spheroid, from each other. dissolve a polymer of lower solubility parameter (degree of
Having a large number of such predictably synergistic sys- order). This entropy change favors the dissolution process.
tems as a basis, reasonably accurate divisions into the three Thus more polar and hydrogen bonded liquids can dissolve
energy types were possible. polymers of lower polar and hydrogen bonding character.
Using the experimentally established, approximate, 8p and The differences in solubility parameters between the solvent
8h parameters, Skaarup [9] found that the B6ttcher equation and solute in the polar and hydrogen bonding parameters are
could be used to calculate the polar parameter quite well, and larger by a factor of two than is tolerated when nonpolar
this led to a revision of the earlier values to those now in wide solvents dissolve the same polymer. This factor of 2 is
use for these same liquids. These values were also consistent squared to give the "4" in Eq 7.
with the eperimental solubility data for 32 polymers available Another way to view this is as follows. It is assumed that the
at that time and Eq 6. Furthermore, Skaarup developed the (center-of-the-sphere) partial solubility parameters assigned
equation for the solubility parameter "distance," Rs, between by computer optimization techniques to polymers using Eq 7
two materials based on their respective partial solubility pa- are the theoretically correct ones. A solvent with parameters
rameter components corresponding to the center is to be changed in quality. If the
nonpolar parameter difference only is changed by one unit,
Rs = 4(3d I -- ~d2) 2 q- (~Pl -- ~P2 )2 q- (~hl -- ~h2 )2 (7)
the effect on Rs is four units. If the polar or hydrogen bonding
This equation was developed from plots of experimental parameter difference is changed by one unit, the effect on R s
data where the constant 4 was found convenient and cor- is also one unit. The entropy changes associated with the
rectly represented the solubility data as a sphere encompass- polar and hydrogen interactions have reduced the total (free
ing the good solvents. When the scale for the dispersion energy change) effect by a factor of 4 and are thus four times
parameter is doubled compared with the other two parame- larger than those associated with the nonpolar interactions.
ters, essentially spherical rather than spheroidal, regions of What is more probable is that the entropy changes on solu-
solubility are found. This greatly aids two-dimensional plot- tion from the polar and hydrogen bonding interactions are
ting and visualization. There are, of course, boundary regions some function of the solubility parameters and, in. fact, in-
where deviations can occur. These are most frequently found crease with increasing polar or hydrogen bonding parameter
to involve the larger molecular species being less effective difference between solvent and solute. If this is, indeed, true,
solvents compared with the smaller counterparts which de- then the currently assigned polar and hydrogen bonding pa-
fine the solubility sphere. Likewise smaller molecular species, rameters for the polymers are too high. Exactly what they
such as acetone and methanol, often appear as outliers in that should be from a theoretical point of view remains to be
they dissolve a polymer even though they have solubility pa- elucidated by future research. This is one reason the calcula-
rameters placing them at a distance greater than the solubil- tion of partial polymer solubility parameters by group contri-
ity sphere radius, Ro. This dependence on molar volume is butions has not provided good agreement with the computer
inherent in the theory developed by Hildebrand and optimizations of experimental data.
Scatchard as discussed above. Smaller molar volume favors The discussion above follows from the fact that the bound-
lower heats of mixing, which in turn promotes solubility. aries of the regions of solubility are characterized by a free
Such smaller molecular volume species which dissolve "bet- energy change of zero for the solution process. The Flory-
ter" than predicted by comparisons based on solubility pa- Huggins limiting chi parameter, X, of about 0.5 is also charac-
rameters alone should not necessarily be considered outliers. teristic for the boundary of the solubility region. Patterson
This statement is justified by Eq 3, where it can be seen that [21], in particular, has been instrumental in showing the
the molar volume and the square of the solubility parameter relations between the chi parameter and solubility parame-
difference are weighted equally in estimating the heat of mix- ters. A polymer of molecular weight approaching infinity will
ing in the Hildebrand theory. have a chi parameter of 0.5 and just be soluble [4,6,22]. This
The molar volume is frequently used as a fourth parameter is strictly valid only for the interactions described by this
to describe molecular size effects. These are especially impor- theory. So-called theta solvents will also be located in bound-
tant in correlating diffusional phenomena with the solubility ary regions on solubility parameter plots with these same
parameter, for example. The author has preferred to retain restrictions. Much polymer research has focused on these
the three, well-defined, partial solubility parameters with a boundary regions only, for the above reasons and because
separate, fourth, molar volume parameter, rather than to relatively small changes in temperature, molecular weight,
multiply the solubility parameters by the molar volume solvent quality, etc. give large easily measureable changes in
raised to some power to redefine them. other quantities.
www.iran-mavad.com

The approach of computer optimizing solubility data to phenomena based on specific interactions among the compo-
spheres which is currently in use still seems most favorable, nents of the mixtures. Barton has recently discussed some of
at least until an improvement is offered by an improved these situations and points out that Hildebrand or Hansen
theory. Plotting experimental solubility data defines bound- parameters must be used with particular caution where the
aries of solubility, which in fact are fixed by the free energy of extent of donor-acceptor interactions, and in particular hy-
mixing being experimentally equal to zero. It should be recog- drogen bonding within a compound, is very different from
nized that using solubility parameters, which relate to the that between compounds [12]. Amines, for example, are
heat of mixing only, emphasizes the practical/empirical na- known to associate with each other. Pure component data
ture of this practical approach and reinforces the use of the can not be expected to predict the behavior in such cases.
term cohesion parameters. Still another reason for difficulties is the large variation of
Equation 7 is readily used on a computer (or on a hand dipole moments reported for the same liquid. The dipole
calculator), and supplementary relations allow easier scan- moment for some liquids depends on their environment, as
ning of large sets of data. It is obvious that solubility, or high discussed below. A given solvent can be listed with different
affinity, requires that Rs be less than R0. The ratio Rs/Ro has values in files to keep these phenomena in mind.
been called the RED number, reflecting the Relative Energy Large data sources greatly enhance searching for similar
Difference. A RED number of 0 is found for no energy differ- materials and locating new solvents for a polymer based on
ence. RED numbers less than 1.0 indicate high affinity, RED limited data, for example. Unfortunately, different authors
equal to or close to 1.0 is a boundary condition, and progres- have used different group contribution techniques, and there
sively higher RED numbers indicate progressively lower is a proliferation of different "Hansen" parameters for the
affinities. Scanning a sizeable (the author has Hansen solubil- same chemicals in the literature. This would seem to be an
ity parameters for about 850 liquids) computer output for unfortunate situation, but may ultimately provide benefits. In
RED numbers less than 1.0, for example, rapidly allows loca- particular, partial solubility parameter values found in Hoy's
tion of the most interesting liquids for a given application. extensive tables [3, 31] are not compatible with the customary
The revised set of parameters for the 90 solvents was the Hansen parameters reported here. Hoy has provided an ex-
basis for group contribution procedures developed by (most cellent source of total solubility parameters. He indepen-
notably) Van Krevelen [23] and Beerbower [11,24], who also dently arrived at the same type division of cohesion energies
used Fedors work [25]. These various developments have as Hansen, although the methods of calculation are quite
been summarized by Barton [3], although Beerbower's latest different.
values have only appeared in the NASA document [24]. Table Many solvent suppliers have also presented tables of sol-
1 is an expanded table of Beerbower group contributions vent properties and/or use computer techniques using these
which was distributed among those who were in contact with in their technical service. Partial solubility parameters not
Beerbower in the late 1970s. Beerbower also developed a taken directly from earlier well-documented sources should
simple equation for the polar parameter [11 ], which involved be used with caution. In particular it can be noted that the
only the dipole moment and the square root of the molar Hoy dispersion parameter is consistently lower than that
volume. This is also given below and has been found quite found by Hansen. Hoy subtracts estimated values of the polar
reliable by Koehnen and Smolders [26]. This equation has and hydrogen bonding energies from the total energy to find
also been found reliable by the author as well, giving results the dispersion energy. This allows for more calculational
generally consistent with Eq 6, which, again, is the basis of error and underestimates the dispersion energy since the Hoy
the whole approach. Koehnen and Smolders also give corre- procedure does not appear to fully separate the polar and
lation coefficients for other calculational procedures to arrive hydrogen bonding energies. The Van Krevelen dispersion pa-
at the individual Hansen parameters. rameters appear too low. The author has not attempted these
A sizeable number of liquids have now been assigned calculations, being completely dedicated to the full procedure
Hansen parameters using the procedures described here. described here, but values estimated independently based on
Many of these have not been published. Exxon Chemical the Van Krevelen dispersion parameters are clearly low. A
Corporation [27,28] has indicated a computer program with comparison with related compounds, or similarity principle,
data for over 500 solvents and plasticizers, 450 resins and gives better results than those found from the Van Krevelen
polymers, and 500 pesticides. The author's files contain the dispersion group contributions.
three parameters for about 850 liquids, although several of In the following, calculational procedures and experience
them appear with two or three sets of possible values await- are presented according to the procedures found most reli-
ing experimental confirmation. In some cases this is due to able for the experimental and/or physical data available for a
questionable physical data, for example, for latent heats of given liquid.
vaporization or wide variations in reported dipole moments.
Another reason for this is that some liquids are chameleonic
[29] as defined by Hoy in that they adopt configurations CALCULATION OF T H E D I S P E R S I O N
depending on their environment. Hoy [29] cites the forma- SOLUBILITY P A R A M E T E R , 8,~
tion of cyclic structures for glycol ethers with (nominally)
linear structure. The formation of hydrogen bonded tetra- The 8d parameter is calculated according to the procedures
mers of alcohols in a fluoropolymer has also been cited [30]. outlined by Blanks and Prausnitz [6]. Figures 1, 2, or 3 can be
The term "compound formation" can be found in the older used to find this parameter depending on whether the mole-
literature, particularly where mixtures with water were in- cule of interest is aliphatic, cycloaliphatic, or aromatic. These
volved, and structured species were postulated to explain figures have been inspired by Barton [3], who converted
www.iran-mavad.com

00
O0
TABLE 1--Group contributions to partial solubility parameters.
Electron Transfer
Molar Volumef London Parameter, Polar Parameter, Parameter, Total Parameter
Functional AV (cm3/mol) AV6~ ( c a l / m o l ) AV8 2 ( c a l / m o l ) AV~ 2 (cal/mol) AV,52 ( c a l / m o l )
Group Aliphatic Aromatic ~ Alkane Cyclo Aromatic Alkane Cyclo Aromatic Aliphatic Aromatic Aliphatic Aromatic (.~
CH~- 33.5 Same 1125 Same Same 0 0 0 0 0 1 125 Same

CH2< 16.1 Same 1180 Same Same 0 0 0 0 0 1 180 Same
CH< - 1.0 Same 820 Same Same 0 0 0 0 0 820 Same
>C< - 19.2 Same 350 Same Same 0 0 0 0 0 350 Same
C H 2 = olefin 28.5 Same 850 _+ 100 ? ? 25 + 10 ? ? 180 75 ? 1 030 Same
- - C H = olefin 13.5 Same 875 + 100 ? ? 18 5 ? ? 180 75 ? 1 030 Same
> C = olefin -5.5 Same 800 100 ? ? 60 _+ 10 ? ? 180 _+ 75 ? 1 030 Same
Phenyl . . . . 71.4 . . . . . . 7530 . . . . . . 50 -+ 25 --- 50 50 a ... 7630
C-5 r i n g 16 . . . . . . 250 ... 0 0 ... 0 ... 250 -..
(saturated)
C-6 r i n g 16 Same ..- 250 250 0 0 0 0 0 250 250
--F 18.0 22.0 0 0 0 1000 150 ? 700 +_ 100 0 0 1 000 800 e
=F 2 twin d 40.0 48.0 0 0 0 700 -+ 250 ~ ? 500 -+ 250 ~ 0 0 1 700 1360 e
~ F 3 triplet d 66.0 78,0 0 0 0 ? ? ? 0 0 1 650 1315 e
CI 24,0 28.0 1400 + 100 ? 1300 +- 100 1250 + 100 1450 100 800 + 100 100 20 a Same 2 760 2200 e
~C12 twin d 52.0 60.0 3650 160 ? 3100 _+ 175 a 800 _+ 150 ? 400 150 ~ 165 _+ 10a 180 10 a 4 600 3670 e
~ C I 3 triplet d 81.9 73.9 4750 _+ 300 a ? ? 300 _+ 100 ? ? 350 -+ 250 a ? 5 400 4300 e
--Br 30.0 34.0 1950 + 300 a 1500 175 1650 _+ 140 1250 100 1700 _+ 150 800 100 500 100 500 + 100 3 700 2960 ~
=Br 2 twind 62.0 70.0 4300 _+ 300 a ? 3500 300 a 800 _+ 250 a ? 400 +_ 150 a 825 2 0 0 ~ 800 _+ 250 a 5 900 4700 e
~ B r 3 triplet d 97.2 109.2 5800 _+ 400 a ? ? 350 150 a ? ? 1500 300 a ? 7 650 6100 e
I 31.5 35.5 2350 250 ~ 2200 250 a 2000 _+ 250 a 1250 + 100 1350 _+ 100 575 + 100 1000 200 a 1000 200 a 4 550 3600 e
=I 2 twind 66.6 74.6 5500 _+ 3 0 0 a ? 4200 + 300 a 800 _+ 250 a ? 400 150 a 1650 2 5 0 a 1800 _+ 250 a 8 000 6400 e
~ I 3 triplet d 111.0 123.0 ? ? ? ~ ? ? ? ? 11 700 9350 e
--O--ether 3.8 Same 0 0 0 500 150 600 150 4 5 0 _+ 150 450 _+ 25 1200 100 800 (1650 +- 150)
>CO ketone 10.8 Same ...c 2350 400 2800 325 (152 000 + 7%)/V 1000 300 950 _+ 300 800 250 b 400 125 a 4 150 Same
CHO (23.2) (31.4) 950 _+ 300 ? 550 _+ 275 2100 + 200 3000 500 2750 _+ 2 0 0 1000 200 750 _+ 150 (4 050) Same
COO-ester 18.0 Same ...c ? ...c (56 000 + 12%)/V ? (338 000 + 10%)/V 1250 150 475 100 a 4 300 Same
--COOH 28.5 Same 3350 300 3550 250 3600 400 500 _+ 150 300 + 50 750 350 2750 _+ 250 2250 250 ~ 6 600 Same
OH 10.0 Same 1770 _+ 450 1370 ~_ 500 1870 _+ 600 700 + 200 1100 x 300 800 _+ 150 4650 400 4650 _+ 500 7 120 Same
~ ( O H ) 2 twin or 26.0 Same 0 ? ? 1500 100 ? ? 9000 600 9300 + 600 10 440 Same
adjacent
--CN 24.0 Same 1600 850 a ? 0 4000 + 800 a ? 3750 _+ 300 a 500 200 b 400 _+ 125 a 4 150 Same
--NO 2 24.0 32.0 3000 -+ 600 ~ 2550 125 3600 + 600 ? 1750 + 100 400 -+ 50 b 350 + 50 a 7 000 (4400)
NHz amine 19.2 Same 1050 300 1050 -+ 450 a 150 _+ 150 ~ 600 200 600 + 350 a 800 200 1350 200 2250 _+ 200 b 3 000 Same
>NH 2 amine 4.5 Same 1150 225 ? ? 100 50 ? ? 750 200 ? 2 000 Same
NH2 a m i d e (6.7) Same ? ? ? ? ? ? 2700 550 a ? (5 850) Same
) P O 4 es t e r 28.0 Same ...c ? ? (81 0 0 0 + 10%)/V ? ? 3000 500 ? (7 000) Same
aBased on very limited data. Limits shown are roughly 95% confidence; in many cases, values are for information only and not to be used for computation.
blncludes unpublished infrared data.
C U s e f o r m u l a i n A V g p2 c o l u m n t o c a l c u l a t e , w i t h V f o r t o t a l c o m p o u n d .
dTwin and triplet values apply to halogens on the same C atom, except that AV~2 also includes those on adjacent C atoms.
~These values apply to halogens attached directly to the ring and also to halogen attached to aliphatic double-bonded C atoms.
f F r o m R . F. F e d o r s [ 2 5 ] .
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CHAPTER 3S--SOLUBILITY PARAMETERS 389
nED kJ/mol
50 i/ ,_~ I 0;,;~~ ,,,s .-
40 - ss- ~.~" i'" ~.s "'~
30
~ L...~
20
io ///,/~
50 100 150 200 250 V, ~mS/mo l

FIG. 1-Energy of vaporization for straight chain hydrocarbons as a function of molar volume and reduced
temperature.
85o ~ ~ . . . . . . -I o.~
. . . . . . .
600 ~ ~ ,. . . . . . . 4 0.50
600 - - ~
o. o 0.65
~
~ i , j ~ , - - ~ o.,o
~50- 0.60 80 90 100 110 120 130 140 150 160 170
0.65 V, c m ~ / m o l
0.70
FIG. 3-Cohesive energy density for aromatic hydrocarbons
50 80 70 80 90 100 110 120 130
as a function of molar volume and reduced temperature.
V, em~/mol
FIG. 2-Cohesive energy density for cycloalkanes as a func-
report the dispersion cohesive energy density, c. The latter is
tion of molar volume and reduced temperature.
much simpler to use since one need only take the square root
of the value found from the figure to find the respective
earlier data to SI units. All three of these figures have been
partial solubility parameter. Barton also presented a similar
straight line extrapolated into a higher range of molar vol-
figure for the aliphatic solvents, but it is inconsistent with the
umes than that reported by Barton. Energies found with
these extrapolations have also provided consistent results. energy figure and in error. Its use is not recommended. When
The solubility parameters in SI units, MPa 1/2, are 2.0455 substituted cycloaliphatics or substituted aromatics are con-
times larger than those in the older centimeter, gram, second sidered, simultaneous consideration of the two separate parts
system, (ca]/cc)1/2, which still finds extensive use in the United of the molecules is required. The dispersion energies are
States, for example. evaluated for each of the types of molecules involved, and a
The figure for the aliphatic liquids gives the dispersion weighted average for the molecule of interest based on num-
cohesive energy, AEd, whereas the other two figures directly bers of significant atoms is taken. For example, hexyl benzene
www.iran-mavad.com

would be the arithmetic average of the dispersion energies for (i.e., its homomorph), and it has a higher dispersion solubil-
an aliphatic and an aromatic liquid, each with the given ity parameter without any special need for corrections.
molar volume of hexyl benzene. Liquids such as chloroben- The careful evaluation of the dispersion cohesive energy
zene, toluene, and ring compounds with alkyl substitutions may not have major impact on the value of the dispersion
with only two or three carbon atoms have been considered as solubility parameter itself because of the taking of square
cyclic compounds only. Such weighting has been found nec- roots. Larger problems arise because of Eq 4. Energy as-
essary to satisfy Eq 6. signed to the dispersion portion can not be reused when
The critical temperature, To, is required to use the disper- finding the other partial parameters using Eq 4 (or Eq 6). This
sion energy figures. If the critical temperature cannot be is one reason group contributions are recommended in some
found, it must be estimated. A table of the Lydersen group cases below.
contributions, AT, [32] as given by Hoy [31] for calculation of
the critical temperature, is included here as Table 2. In some
cases the desired groups may not be in the table, which CALCULATION OF T H E POLAR SOLUBILITY
means some educated guessing is required. The end result PARAMETER, ~
does not appear too sensitive to these situations. The normal
boiling temperature, Tb, is also required in this calculation. The earliest assignments of a "polar" solubility parameter
This is not always available, either, and must be estimated by were given by Blanks and Prausnitz [6]. These parameters
similarity, group contribution, or other technique. The were in fact the combined polar and hydrogen bonding pa-
Lydersen group contribution method involves the use of Eqs rameters as used by Hansen and cannot be considered polar
8 and 9. in the current context. The first Hansen polar parameters [7]
were reassigned new values by Skaarup according to the
Tb/Tr = 0.567 + s - (EAT)2 (8) B6ttcher equation [9]. This equation requires the molar vol-
and ume, the dipole moment, DM, the refractive index, and the
dielectric constant. These are not available for many com-
T~ = T/T~ (9) pounds, and the calculation is somewhat more difficult than
where T has been taken as 298.15 K. using the much simpler equation developed by Beerbower
The dispersion parameter is an atomic force parameter. [11]
The size of the atom is important. It has been found that 37.4
corrections are required for atoms significantly larger than 8p - ( ~ ) ~ d (DM) (10)
carbon, such as chlorine, sulfur, bromine, etc., but not for
oxygen or nitrogen, which have a similar size. The carbon The constant 37.4 gives this parameter in SI units.
atom in hydrocarbons is the basis of the dispersion parame- Equation 10 has been consistently used by the author over
ter in its present form. These corrections are applied by first the past few years, particularly in view of its reported reliabil-
finding the dispersion cohesive energy from the appropriate ity [26]. This reported reliability appears to be correct. The
figure. This requires multiplication by the molar volume for molar volume must be known or estimated in one way or
the cyclic compounds using data from the figures here, since another. This leaves only the dipole moment to be found or
these figures give the cohesive energy densities. The disper- estimated. Standard reference works have tables of dipole
sion cohesive energy is then increased by adding on the moments, with the most extensive listing still being McClel-
correction factor. This correction factor for chlorine, bro- lan [33]. Other data sources also have this parameter as well
mine, and sulfur has been taken as 1650 J/tool for each of as other relevant parameters and data such as latent heats
these atoms in the molecule. Dividing by the molar volume and critical temperatures. The so-called DIPPR database has
been found useful for many compounds of reasonably com-
and then taking the square root gives the (large atom cor-
mon usage, but many interesting compounds are not in-
rected) dispersion solubility parameter.
cluded in DIPPR. This abbreviation is for Design Institute for
The need for these corrections has been confirmed many
Physical Property Research, 2 Project 801 of the American
times, both for interpretation of experimental data and to
Institute of Chemical Engineers at the Pennsylvania State
allow Eq 6 to balance. Research is definitely needed in this
University [34]. When no dipole moment is available, similar-
area. The impact of these corrections is, of course, larger for
ity with other compounds, group contributions, or experi-
the smaller molecular species. The taking of square roots of mental data can be used to estimate the polar solubility
the larger numbers involved with the larger molecular species parameter.
reduces the errors involved in these cases since the correc- It must be noted that the fact of zero dipole moment in
tions themselves are relatively small. symmetrical molecules is not basis enough to assign a zero
It can be seen from the dispersion parameters of the cyclic polar solubility parameter. An outstanding example of varia-
compounds that the ring also has an effect similar to increas- tions of this kind can be found with carbon disulfide. The
ing the effective size of the interacting species. The dispersion reported dipole moments are mostly 0 for gas phase measure-
energies are larger for cycloaliphatic compounds than for ments, supplemented by 0.08 in hexane, 0.4 in carbon tetra-
their aliphatic counterparts, and they are higher for aromatic chloride, 0.49 in chlorobenzene, and 1.21 in nitrobenzene.
compounds than for the corresponding cycloaliphatics. Simi-
lar effects also appear with the ester group. This group ap- 2Design Institute for Physical Property Research, Department of
pears to act as if it were, in effect, an entity which is larger Chemical Engineering, 167 Fenske Laboratory, The Pennsylvania
than the corresponding compound containing only carbon State University, University Park, PA 16802.
www.iran-mavad.com

TABLE 2 - - L y d e r s e n group constants.
Aliphatic, Cyclic, Aliphatic, Cyclic,

Group AT AT Aer AP b5'
CH3 0.020 ... 0.0226 0.227 ...

CH 2 0.020 0.013 0.0200 0.227 0.184
>CH-- 0.012 0.012 0.0131 0.210 0.192
>C< 0.000 - 0.007 0.0040 0.210 0.154
~CH2 0.018 --- 0.0192 0.198 ---
=CH-- 0.018 0.011 0.0184 0.198 0.154
=C< 0.000 0.011 0.0129 0.198 0.154
~CH aromatic . . . . . . 0.0178 . . . . . .
=CH aromatic . . . . . . 0.0149 . . . . . .
--O-- 0.021 0.014 0.0175 0.16 0.12

>O epoxide . . . . . . 0.0267 . . . . . .
--COO-- 0.047 ... 0.0497 0.47 ...
>C~O 0.040 0.033 0.0400 0.29 0.02
--CHO 0.048 ... 0.0445 0.33 ...
--COzO . . . . . . 0.0863 . . . . . .
--OH--~ . . . . . . 0.0343 0.06 ...

--H-o . . . . . . . 0.0077 . . . . . .
--OH primary 0.082 ... 0.0493 . . . . . .
--OH sec . . . . . . . 0.0440 . . . . . .
--OH tert. 9. . . . . 0.0593 . . . . . .
--OH phenolic 0.035 ... 0.0060 - 0.02
--NH 2 0.031 .-. 0.0345 0.095 ...

--NH-- 0.031 0.024 0.0274 0.135 0.09
>N-- 0.014 0.007 0.0093 0.17 0,13
--C~-~N 0.060 ... 0.0539 0.36 ...
--NCO . . . . . . 0.0539 . . . . . .
HCON< . . . . . . 0.0546 . . . . . .
--CONH . . . . . . . 0.0843 . . . . . .
--CON< . . . . . . 0.0729 . . . . . .
--CONH2 . . . . . . 0.0897 . . . . . .
--OCONH . . . . . . . 0.0938 . . . . . .
--S-- 0.015 0.008 0.0318 0.27 0.24

--SH 0.015 . . . . . . . . . . . .
- - C I 1~ 0.017 ... 0.0311 0.320 -..

--C1 2 ~ 9. . . . . 0.0317 . . . . . .
C12 t w i n . . . . . . 0.0521 . . . . . .
C1 a r o m a t i c . . . . . . 0.0245 . . . . . .
--Br 0.010 ..- 0.0392 0.50 ...

--Br aromatic . . . . . . 0.0313 . . . . . .
--F 0.018 ... 0.006 0.224 ...

--I 0.012 . . . . . . 0.83 ...
Conjugation . . . . . . 0.0035 . . . . . .
c is double bond . . . . . . . 0.0010 . . . . . .
trans double bond . . . . . . . 0.0020 . . . . . .
4 Member ring . . . . . . 0.0118 . . . . . .

5 Member ring . . . . . . 0.003 . . . . . .
6 Member ring . . . . . . . 0.0035 . . . . . .
7 Member ring . . . . . . 0.0069 . . . . . .
Ortho . . . . . . 0.0015 . . . . . .
Meta . . . . . . 0.0010 . . . . . .
Para . . . . . . 0.0060 . . . . . .
Bicycloheptyl . . . . . . 0.0034 . . . . . .
Tricyclodecane . . . . . . 0.0095 . . . . . .
www.iran-mavad.com

There is a clear increase with increasing solubility parameter SUPPLEMENTARY CALCULATIONS AND
of the media. The latter and highest value has been found PROCEDURES
experimentally most fitting for correlating permeation
through a fluoropolymer film used for chemical protective The procedures listed above are those most frequently used
clothing [35]. Many fluoropolymers have considerable polar- by the author in calculating the three partial solubility pa-
ity. The lower dipole moments seem to fit in other instances. rameters for liquids where some data are available. There are
Diethylether has also presented problems as an outlier in a number of other calculations and procedures which are also
terms of dissolving or not, or rapid permeation or not. Here helpful. Latent heat data at 25~ have consistently been found
the reported dipole moments [33] vary from 0.74 to 2.0 with a from latent heats at another temperature using the relation
preferred value of 1.17, and with 1.79 in chloroform. given by Fishtine [38].
Choosing a given value seems rather arbitrary. The chame-
leonic cyclic forms of the linear glycol ethers would also seem
to provide for a basis of altered dipole moments in various
media [29].
1 ~
When Eq 10 can not be used, the polar solubility parameter
has been found using the Beerbower table of group contribu-
tions, by similarity to related compounds, and/or by subtrac- This is done even if the melting point of the compound being
tion of the dispersion and hydrogen bonding cohesive considered is higher than 25~ The result is consistent with
energies from the total cohesive energy. The question in each all the other parameters, and to date no problems with partic-
case is: "Which data are available and judged most reliable?" ularly faulty predictions have been noted in this respect, i.e.,
New group contributions have also been developed from re- it appears as if the predictions are not significantly in error.
lated compounds where their dipole moments are available. When the latent heat is given in cal/mole, the above equation
These new polar group contributions then become supple- is used to estimate the latent heat at 25~ RT equal to 592
mentary to the Beerbower table. cal/mole is then subtracted from this according to Eq 12 to
For large molecules, especially those with long hydrocar- find the total cohesion energy, ~ v , in cgs units at this tem-
bon chains, the accurate calculation of the relatively small perature:
polar (and hydrogen bonding) contributions present special
difficulties. The latent heats are not generally available with Mq.,, = z~E, = AH~, - a T (12)
sufficient accuracy to allow subtraction of two large numbers Only very limited attempts have been made to calculate
from each other to find a very small one. In such cases the solubility parameters at a higher temperature. Solubility pa-
similarity and group contribution methods are thought best. rameter correlations of phenomena at higher temperatures
Unfortunately, latent heats found in a widely used handbook have generally been found satisfactory when the established
[36] are not clearly reported as to the reference temperature. 25~ parameters have been used. Recalculation to higher
There is an indication that these are 25~ data, but checking temperatures is possible, but has not been found necessary.
indicated many of the data were identical with boiling point In this direct but approximate approach it is assumed that the
data reported elsewhere in the literature. A more recent edi- parameters all demonstrate the same temperature depen-
tion of this handbook has a completely different and less dence, which, of course, is not the case. It might be noted in
voluminous section for the latent heat of evaporation [37]. this connection that the hydrogen bonding parameter, in
Again, even moderate variations in reported heats of vapor- particular, is the most sensitive to temperature. As the tem-
ization can cause severe problems in calculating the polar (or perature is increased, more and more hydrogen bonds are
hydrogen bonding) parameter when Eqs 4 or 6 are strictly progressively broken, and this parameter will decrease more
adhered to. rapidly than the others.
The gas phase dipole moment is not temperature depen-
dent, although the volume of the fluid does change with
CALCULATION OF THE HYDROGEN temperature, which will change its cohesive energy density.
BONDING SOLUBILITY PARAMETER, 8h Beerbower has suggested relations to predict the changes of
the partial solubility parameters with temperature [11]. The
In the earliest work, the hydrogen bonding parameter was coefficient of thermal expansion, ~, appears in all of these
almost always found from the subtraction of the polar and relations. These are
dispersion energies of vaporization from the total energy of
vaporization. This is still widely used where the required data d(~a) _
1.25 a8 d (13)
are available and reliable. At this stage, however, the group dT
contribution techniques are considered reasonably reliable
for most of the required calculations and, in fact, more reli- d(Sp) _ 0.5 asp (14)
able than estimating several of the other parameters to ulti- dT
mately arrive at the subtraction step just mentioned. d(8,,) _
Therefore, in the absence of reliable latent heat and dipole ~h (1.22 x 10 -3 + 0.5 ~) (15)
dT
moment data, group contributions are judged to be the best
alternative. Similarity to related compounds can also be used, A computer program has been developed by the author to
of course, and the result of such a procedure should be assign the three Hansen parameters for solvents based on
essentially the same as for using group contributions. experimental data alone. This has been used in several cases
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CHAPTER 3 5 - - S O L U B I L I T Y PARAMETERS 393
where the parameters for the given liquids were desired with APPLICATIONS
a high degree of accuracy. The procedure is to enter solvent
quality, good or bad, into the program for a reasonably large There are many applications documented in the literature
number of polymers where the solubility parameters and where solubility parameters have aided in selection of sol-
appropriate radius of interaction for the polymers are known. vents, understanding and controlling processes, and, in gen-
The program then locates that set of 6d, 8p, and ~h parameters eral, offered guidance where affinities among materials are of
for the solvent which best satisfies the requirements of a prime importance. To find the optimum solvent for a polymer
location within the spheres of the appropriate polymers using solubility parameters, it is most desirable to have the
where solvent quality is good and outside of the appropriate solubility parameters for the polymer. Matching the parame-
spheres where it is bad. ters of an already existing solvent or combination of solvents
An additional aid in estimating the Hansen parameters for can be done, but does not necessarily optimize the new situa-
many compounds is that these parameters can be found by tion. The optimum depends on what is desired of the system.
interpolation or extrapolation, especially for homologous se- A solvent with highest possible affinity for the polymer is both
ties. The first member may not necessarily be a straight line expensive and probably not necessary.
extrapolation, but comparisons with related compounds Most coatings applications involve solvents safely within
should always be made where possible to confirm assign- the solubility limit with a maximum of cheaper hydrocarbon
ments. Plotting the parameters reported in Table 3 for homol- solvent. Some safety is advised because temperature changes,
ogous series among the esters, nitroparaffins, ketones, potential variations in production, etc. can lead to a situation
alcohols, and glycol ethers will aid in finding the parameters where solvent quality changes in an adverse manner. Balance
for related compounds. of solvent quality on evaporation of mixed solvents is also
Table 3 contains Hansen solubility parameters for a large necessary. Here again computer approaches are possible.
number of liquids and plasticizers. These are given in SI An oxygenated solvent frequently added to hydrocarbon
units. solvent and which has been cost effective in increasing the
very important hydrogen bonding solubility parameters has
been n-butanol. The mixture of equal parts xylene and
n-butanol can be used in conjunction with many polymers,
but a third solvent, such as a ketone or ester, is often included
in small amounts to increase the polar parameter/solvency of
SOLUBILITY PARAMETERS FOR the mixture. Glycol ethers can also be added to hydrocarbon
POLYMERS
solvents with advantage, and the polar and hydrogen bonding
parameters are higher than had n-butanol been added to the
The solubility parameters for numerous polymers and film
same concentration. There are many possibilities, and a solu-
formers are given in Table 4. Suppliers and trademarks are
bility parameter approach is particularly valuable in quickly
given in Table 5. These data are based on solubility determi-
limiting the number of candidates.
nations unless otherwise noted. There are four parameters,
Coalescing solvents in water-reducible coatings are often
the three describing the nonpolar, polar, and hydrogen bond-
those with somewhat higher hydrogen bonding parameters
ing interactions as for the liquids, and the fourth, R0, a radius
than the polymer, which also means they are water soluble or
of interaction for the type of interaction described. Most of
have considerable water solubility. The distribution between
these are taken from a report [39] from the Scandinavian
the water phase and the dispersed polymer phase depends on
Paint and Printing Ink Research Institute. (This institute un-
the relative affinities for water and the polymer. Solvents
fortunately no longer exists.) Additional values have been
which are not particularly water soluble will preferentially be
contributed according to the notes in the table to indicate the found in the polymer phase. Such coalescing solvents may be
types of data which have been correlated with these tech- preferred for applications to porous substrates, making cer-
niques. Barton [40] has also provided solubility parameters tain they are where they are needed. Otherwise a water-solu-
for many polymers in a recent handbook. ble coalescing solvent would tend to follow the aqueous phase
Experimental determination of polymer solubility parame- penetrating the substrate and not be available to do its job in
ters involves trying to dissolve the polymer at a given concen- the film itself.
tration, usually 10% by weight, in a selection of solvents When water evaporates the solvent must dissolve to some
intended to maximize information regarding all types of in- extent in the polymer to promote coalescence. This can be
teraction. Whenever possible the author uses a set of parame- determined and adjusted by either increasing or decreasing
ters indicated with an "*" in Table 3. The "yes" or "no" the affinity for the polymer.
solubility data can be plotted by hand or processed by com- Amines are frequently added in water-reducible coatings to
puter to yield a "spherical" characterization as described neutralize acid groups in polymers, thus providing a water-
above. Teas [41] has developed a triangular plotting tech- solubilizing amine salt. Amine in excess of that required for
nique which helps visualization of three parameters on a total neutralization acts like a solvent. Such amine salts have
plane sheet of paper. Examples are found in Ref 3 and Ref 4 been characterized separately to demonstrate that they have
as well. higher solubility parameters than either (acetic) acid or or-
Swelling, weight gain, solvent resistance, and surface at- ganic bases [42]. These salts are hydrophilic and have very
tack have also been used as a primary data to characterize little affinity for coatings polymers, which means they are to
polymers. be found in a stabilizing role in interfaces in the aqueous
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TABLE 3 - - H a n s e n solubility parameters for selected liquids. The solvents in alphabetical order.
Hydrogen Molar
No. Solvent Dispersion Polar Bonding Volume
1 Acetaldehyde 14.7 8.0 11.3 57.1
2 Acetic acid 14.5 8.0 13.5 57.1
3 Acetic anhydride 16.0 11.7 10.2 94.5
4 *Acetone 15.5 10.4 7.0 74.0
5 Acetonitrile 15.3 18.0 6.1 52.6
6 *Acetophenone 19.6 8.6 3.7 117.4
7 Acrylonitrile 16.4 17.4 6.8 67.1
8 Allyl alcohol 16.2 10.8 16.8 68.4
9 Amyl acetate 15.8 3.3 6.1 148.0
10 Aniline 19.4 5.1 10.2 91.5
11 Anisole 17.8 4.1 6.7 119.1
12 Benzaldehyde 19.4 7.4 5.3 101.5
13 *Benzene 18.4 0.0 2.0 89.4
14 1.3-Benzenediol 18.0 8.4 21.0 87.5
15 Benzoic acid 18.2 6.9 9.8 100.0
16 Benzonitrile 17.4 9.0 3.3 102.6
17 Benzyl alcohol 18.4 6.3 13.7 103.6
18 Benzyl butyl phthalate 19.0 11.2 3.1 306.0
19 Benzyl chloride 18.8 7.1 2.6 115.0
20 Biphenyl 21.4 1.0 2.0 154.1
21 Bromobenzene 20.5 5.5 4.1 105.3
22 Bromochloromethane 17.3 5.7 3.5 65.0
23 Bromoform 21.4 4.1 6.1 87.5
24 1-Bromonaphtalene 20.3 3.1 4.1 140.0
25 Bromotrifluoromethane 9.6 2.4 0.0 97.0
26 Butane 14.1 0.0 0.0 101.4
27 1.3-Butanediol 16.6 10.0 21.5 89.9
28 *l-Butanol 16.0 5.7 15.8 91.5
29 2-Butanol 15.8 5.7 14.5 92.0
30 *Butyl acetate 15.8 3.7 6.3 132.5
31 Sec-butyl acetate 15.0 3.7 7.6 133.6
32 Butyl acrylate 15.6 6.2 4.9 143.8
33 Butylamine 16.2 4.5 8.0 99.0
34 Butyl lactate 15.8 6.5 10.2 149.0
35 Butyraldehyde 14.7 5.3 7.0 88.5
36 Butyric acid 14.9 4.1 10.6 110.0
37 *Gamma butyrolactone 19.0 16.6 7.4 76.8
38 Butyronitrile 15.3 12.4 5.1 87.3
39 Carbon disulfide 20.5 0.0 0.6 60.0
40 *Carbon tetrachloride 17.8 0.0 0.6 97.1
41 *Chlorobenzene 19.0 4.3 2.0 102.1
42 1-Chlorobutane 16.2 5.5 2.0 104.5
43 Chlorodifluoromethane 12.3 6.3 5.7 72.9
44 *Chloroform 17.8 3.1 5.7 80.7
45 3-Chloro- 1-propanol 17.5 5.7 14.7 84.2
46 m-cresol 18.0 5.1 12.9 104.7
47 Cyclohexane 16.8 0.0 0.2 108.7
48 *Cyclohexanol 17.4 4.1 13.5 106.0
49 Cyclohexanone 17.8 6.3 5.1 104.0
50 Cyclohexylamine 17.2 3.1 6.5 113.8
51 Cyclohexylchloride 17.3 5.5 2.0 118.6
52 Cis-decahydronaphthalene 18.8 0.0 0.0 156.9
53 Trans-decahydronaphthalene 18.0 0.0 0.0 156.9
54 Decane 15.7 0.0 0.0 195.9
55 1-Decanol 17.5 2.6 10.0 191.8
56 *Diacetone alcohol 15.8 8.2 10.8 124.2
57 Dibenzyl ether 17.3 3.7 7.3 192.7
58 Dibutyl phthalate 17.8 8.6 4.1 266.0
59 Dibutyl sebacate 13.9 4.5 4.1 339.0
60 Dibutyl stearate 14.5 3.7 3.5 382.0
61 *o-dichlorobenzene 19.2 6.3 3.3 112.8
62 2.2-Dichlorodiethyl ether 18.8 9.0 5.7 117.2
63 Dichlorodifluoromethane 12.3 2.0 0.0 92.3
64 1.1-Dichloroethane 16.5 8.2 0.4 84.8
65 1.1-Dichloroethylene 17.0 6.8 4.5 79.0
66 Di-(2-chloro-isopropyl) ether 19.0 8.2 5.1 146.0
67 Dichloromonofluoromethane 15.8 3.1 5.7 75.4
68 1.2-Dichlorotetrafluoroethane 12.6 1.8 0.0 117.6
69 Di-iso-butyl carbino] 14.9 3.1 10.8 177.8
70 Diethanolamine 17.2 10.8 21.2 95.9
71 Diethylamine 14.9 2.3 6.1 103.2
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CHAPTER 3 5 - - S O L U B I L I T Y P A R A M E T E R S 395
TABLE 3 - - H a n s e n solubility parameters for selected liquids. The solvents in alphabetical order.
Hydrogen Molar
72 2-(Diethylamino)ethanol 14.9 5.8 12.0 133.2
73 Para-diethylbenzene 18.0 0.0 0.6 156.9
74 Diethyl carbonate 16.6 3.1 6.1 121.0
75 *Diethylene glycol 16.6 12.0 20.7 94.9
76 Diethylene glycol butyl ether acetate 16.0 4.1 8.2 208.2
77 Diethylene glycol hexyl ether 16.0 6.0 10.0 204.3
78 Diethylene glycol monobutyl ether 16.0 7.0 10.6 170.6
79 Diethylene glycol monoethyl ether 16.1 9.2 12.2 130.9
80 Diethylene glycol monomethyl ether 16.2 7.8 12.6 118.0
81 Diethylenetriamine 16.7 13.3 14.3 108.0
82 *Diethyl ether 14.5 2.9 5.1 104,8
83 Diethyl ketone 15.8 7.6 4.7, 106.4
84 Diethyl phthalate 17.6 9.6 4.5 198.0
85 Diethyl sulfate 15.7 14.7 7.1 131.5
86 Diethyl sulfide 16.8 3.1 2.0 107,4
87 Di(isobutyl) ketone 16.0 3.7 4.1 177.1
88 Di(2-methoxyethyl) ether 15.7 6.1 6.5 142.0
89 N.N-dimethylacetamide 16.8 11.5 10.2 92.5
90 *Dimethylforrnamide 17.4 13.7 11.3 77.0
91 1.1-Dimethylhydrazine 15.3 5.9 11.0 76.0
92 Dimethyl phthalate 18.6 10.8 4.9 163.0
93 Dimethyl sulfone 19.0 19.4 12.3 75.0
94 *Dimethyl sulfoxide 18.4 16.4 10.2 71.3
95 Dioctyl phthalate 16.6 7.0 3.1 377.0
96 * 1,4-Dioxane 19.0 1.8 7.4 85.7
97 Dipropylamine 15.3 1.4 4.1 136,9
98 *Dipropylene glycol 16.5 10.6 17.7 130.9
99 Dipropylene glycol methyl ether 15.5 5.7 11.2 157.4
100 Dodecane 16.0 0,0 0.0 228.6
101 Eicosane 16.5 0,0 0,0 359.8
102 Epichlorohydrin 19.0 10.2 3,7 79.9
103 Ethanethiol 15.7 6.5 7.1 74.3
104 *Ethanol 15.8 8.8 19.4 58.5
105 *Ethanolamine 17.0 15.5 21.2 59.8
106 *Ethyl acetate 15.8 5.3 7.2 98.5
107 Ethyl acrylate 15.5 7.1 5.5 108.8
108 Ethyl amyl ketone 16.2 4.5 4.1 156.0
109 Ethylbenzene 17.8 0.6 1.4 123.1
110 Ethyl bromide 16,5 8.0 5.1 76.9
111 2-Ethyl- 1-butanol 15.8 4.3 13.5 123.2
112 Ethyl butyl ketone 16.2 5.0 4,1 139.0
113 Ethyl chloride 15,7 6.1 2.9 70,0
114 Ethyl chloroformate 15.5 10.0 6.7 95.6
115 Ethyl cinnamate 18.4 8.2 4.1 166.8
116 Ethylene carbonate 19.4 21.7 5.1 66.0
117 Ethylene cyanohydrin 17.2 18.8 17.6 68.3
118 Ethylenediamine 16.6 8.8 17.0 67.3
119 Ethylene dibromide 19.2 3.5 8.6 87.0
120 *Ethylene dichloride 19.0 7,4 4.1 79.4
121 *Ethylene glycol 17.0 11.0 26.0 55.8
122 Ethylene glycol butyl ether acetate 15.3 4.5 8.8 171.2
123 *Ethylene glycol monobutyl ether 16.0 5.1 12.3 131.6
124 *Ethylene glycol monoethyl ether 16.2 9.2 14.3 97.8
125 Ethylene glycol monoethyl ether acetate 15.9 4.7 10.6 136.1
126 *Ethylene glycol monomethyl ether 16.2 9.2 16.4 79.1
127 Ethylene glycol monomethyl ether acetate 15.9 5.5 11.6 121.6
128 Ethyl formate 15.5 8.4 8.4 80.2
129 2-Ethyl hexanol 15.9 3.3 11.8 156.6
130 Ethyl lactate 16.0 7.6 12.5 115.0
131 *Formamide 17.2 26.2 19.0 39.8
132 Formic acid 14.3 11.9 16.6 37.8
133 Furan 17.8 1.8 5.3 72.5
134 Furfural 18.6 14.9 5.1 83.2
135 Furfuryl alcohol 17.4 7,6 15.1 86.5
136 Glycerol 17.4 12.1 29.3 73.3
137 Heptane 15.3 0.0 0.0 147.4
138 Hexadecane 16.3 0.0 0.0 294.1
139 Hexamethylphosphoramide 18.5 8.6 11.3 175,7
140 *Hexane 14.9 0.0 0.0 131.6
141 Hexylene glycol 15.7 8.4 17.8 123,0
142 Isoamyl acetate 15.3 3,1 7.0 148,8
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TABLE 3 C o n t i n u e d - - H a n s e n solubility parameters for selected liquids. The solvents in alphabetical order.
Hydrogen Molar
143 Isobutyl acetate 15.1 3.7 6.3 133.5
144 Isobutyl alcohol 15.1 5.7 15.9 92.8
145 Isobutyl isobutyrate 15.1 2.9 5.9 163.0
146 Isooctyl alcohol 14.4 7.3 12.9 156.6
147 Isopentane 13.7 O.0 O.0 i 17.4
148 *Isophorone 16.6 8.2 7.4 150.5
149 Isopropyl palmitate 14.3 3.9 3.7 330.0
150 Mesitylene 18.0 0.0 0.6 139.8
151 Mesityl oxide 16.4 6.1 6.1 115.6
152 Methacrylonitrile 15.3 10.8 3.6 83.9
153 *Methanol 15.1 12.3 22.3 40.7
154 o-Methoxyphenol 18.0 8.2 13.3 109.5
155 Methyl acetate 15.5 7.2 7.6 79.7
156 Methyl acrylate 15.3 9.3 5.9 89.7
157 Methylal 15.0 1.8 8.6 169.4
158 Methyl amyl acetate 15.2 3.1 6.8 167.4
159 Methyl butyl ketone 15.3 6.1 4.1 123.6
160 Methyl chloride 15.3 6.1 3.9 55.4
161 Methylcyclohexane 16.0 0.0 1.0 128.3
162 *Methylene dichloride 18.2 6.3 6.1 63.9
163 Methylene diiodide 17.8 3.9 5.5 80.5
164 Methyl ethyl ketone 16.0 9.0 5.1 90.1
165 Methyl isoamyl ketone 16.0 5.7 4.1 142.8
166 Methyl isobutyl carbinol 15.4 3.3 12.3 127.2
167 *Methyl isobutyl ketone 15.3 6.1 4.1 125.8
168 Methyl methacrylate 17.5 5.5 4.3 106.5
169 1-Methylnaphthalene 20.6 0.8 4.7 138.8
170 Methyl oleate 14.5 3.9 3.7 340.0
171 2-Methyl- l-propanol 15.1 5.7 15.9 92.8
172 *Methyl-2-pyrrolidone 18.0 12.3 7.2 96.5
173 Methyl salicylate 16.0 8.0 12.3 129.0
174 Morpholine 18.8 4.9 9.2 87.1
175 Naphtha.high-flash 17.9 0.7 1.8 181.8
176 Naphthalene 19.2 2.0 5.9 111.5
177 *Nitrobenzene 20.0 8.6 4.1 102.7
178 *Nitroethane 16.0 15.5 4.5 71.5
179 *Nitromethane 15.8 l 8.8 5.1 54.3
180 1-Nitropropane 16.6 12.3 5.5 88.4
181 *2-Nitropropane 16.2 12.1 4.1 86.9
182 Nonane 15.7 0.0 0.0 179.7
183 Nonyl phenol 16.5 4.1 9.2 231.0
184 Nonyl phenoxy ethanol 16.7 10.2 8.4 275.0
185 Octane 15.5 0.0 0.0 163.5
186 Octanoic acid 15.1 3.3 8.2 159.0
187 1-Octanol 17.0 3.3 11.9 157.7
188 2-Octanol 16.1 4.9 11.0 159.1
189 Oleic acid 14.3 3.1 5.5 320.0
190 Oleyl alcohol 14.3 2.6 8.0 316.0
191 Pentane 14.5 0.0 0.0 116.2
192 2.4-Pentanedione 17.1 9.0 4.1 103.1
193 1-Pentanol 15.9 4.5 13.9 108.6
194 Perfluoro(dimethylcyclohexane) 12.4 0.0 0.0 217.4
195 Perfluoroheptane 12.0 0.0 0.0 227.3
196 Peiaquoromethylcyclohexane 12.4 0.0 0.0 196.0
197 Phenol 18.0 5.9 14.9 87.5
198 Bis-(m-phenoxyphenyl) ether 19.6 3.1 5.1 373.0
199 1-Propanol ~ 16.0 6.8 17.4 75.2
200 2-Propanol 15.8 6.1 16.4 76.8
201 Propionitrile 15.3 14.3 5.5 70.9
202 Propylamine 16.9 4.9 8.6 83.0
203 Propyl chloride 16.0 7.8 2.0 88.1
204 *Propylene carbonate 20.0 18.0 4.1 85.0
205 *Propylene glycol 16.8 9.4 23.3 73.6
206 Propylene glycol monobutyl ether 15.3 4.5 9.2 132.0
207 Propylene glycol monoethyl ether 15.7 6.5 10.5 115.6
208 Propylene glycol monoisobutyl ether 15. l 4.7 9.8 132.2
209 Propylene glycol monomethyl ether 15.6 6.3 11.6 93.8
210 Propylene glycol monophenyl ether 17.4 5.3 11.5 143.2
211 Propylene glycol monopropyl ether 15.8 7.0 9.2 130.3
212 Pyridine 19.0 8.8 5.9 80.9
213 2-Pyrolidone 19.4 17.4 11.3 76.4
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TABLE 3 Continued--Hansen solubility parameters for selected liquids. The solvents in alphabetical order.
Hydrogen Molar
214 Quinoline 19.4 7.0 7.6 118.0
215 Stearic acid 16.3 3.3 5.5 326.0
216 Styrene 18.6 1.0 4.1 115.6
217 Succinic anhydride 18.6 19.2 16.6 66.8
218 1.1.2.2-Tetrabromoethane 22.6 5.1 8.2 116.8
219 1.1.2.2-Tetrachloroethane 18.8 5.1 9.4 105.2
220 Tetrachloroethylene 19.0 6.5 2.9 101.1
221 Tetraethylorthosilicate 13.9 0.4 0.6 224.0
222 *Tetrahydrofuran 16.8 5.7 8.0 81.7
223 Tetrahydronaphthalene 19.6 2.0 2.9 136.0
224 Tetramethylurea 16.7 8.2 11.0 120.4
225 *Toluene 18.0 1.4 2.0 106.8
226 Tributyl phosphate 16.3 6.3 4.3 345.0
227 Trichlorobiphenyl 19.2 5.3 4.1 187.0
228 1.1.1-Trichloroethane 16.8 4.3 2.0 99.3
229 *Trichloroethylene 18.0 3.1 5.3 90.2
230 Trichlorofluoromethane 15.3 2.0 0.0 92.8
231 1.1.2-Trichlorotrifluoroethane 14.7 1.6 0.0 119.2
232 Tricresyl phosphate 19.0 12.3 4.5 316.0
233 Tridecyl alcohol 14.3 3.1 9.0 242.0
234 Triethanolamine 17.3 22.4 23.3 133.2
235 Triethylamine 17.8 0.4 1.0 138.6
236 Triethyleneglycol 16.0 12.5 18.6 114.0
237 Triethylene glycol monooleyl ether 13.3 3.1 8.4 418.5
238 Triethylphosphate 16.7 11.4 9.2 171.0
239 Trifluoroacetic acid 15.6 9.9 11.6 74.2
240 Trirnethylhenzene 17.8 0.4 1.0 133.6
241 2.2.2.4-Trimethylpentane 14.1 0.0 0.0 166.1
242 2.2.4-Trimethyl- 1.3-pentanediol M.I. butyral 15.1 6.1 9.8 227.4
243 Trimethylphosphate 16.7 15.9 10.2 115.8
244 Water 15.5 16.0 42.3 18.0
245 Xylene 17.6 1.0 3.1 123.3
246 o-xylene 17.8 1.0 3.1 121.2
*Indicates use in author's standard set of test solvents.
phase, still being a t t a c h e d to the polymer. Electrostatic repul- A long list of applications, in coatings a n d elsewhere, was
sion contributes to stability as well. p r o v i d e d as early as 1975 in a review article b y B a r t o n [43].
Surface active agents, w h e t h e r n o n i o n i c or ionic, are also Many a p p l i c a t i o n s are given in Table 6 a n d in the p r e s e n t
to b e f o u n d w h e r e the affinities of the respective parts of their discussion to give a n idea of w h a t c a n b e studied systemati-
molecules dictate their placement. The h y d r o p h i l i c end with cally using this concept. More recent references a n d varied
a high h y d r o g e n b o n d i n g p a r a m e t e r will be in the aqueous a p p l i c a t i o n s can be found in Refs 3, 4, a n d 44.
phase, a n d the h y d r o p h o b i c end will seek o u t an e n v i r o n m e n t B e e r b o w e r [44] has given m a n y of the m o r e theoretical
where energy differences are lowest. a p p l i c a t i o n s for solubility p a r a m e t e r s including correlations
Increases in t e m p e r a t u r e lead to lower h y d r o g e n b o n d i n g of the R e h b i n d e r effect of crushing strength of a l u m i n u m
p a r a m e t e r s , especially. F o r this r e a s o n solvents with high oxide u n d e r various liquids, the w o r k of a d h e s i o n for liquids
h y d r o g e n b o n d i n g p a r a m e t e r s , such as glycols, glycol ethers, on mercury, the Joffe effect of the consequences of i m m e r -
a n d alcohols, b e c o m e b e t t e r solvents for m o s t p o l y m e r s at sion in various liquids on the fracture strength of soda-lime
higher t e m p e r a t u r e s . This can m a r k e d l y affect h o t - r o o m sta- glass, a n d correlations of friction on polyethylene t r e a t e d
bility in water-reducible coatings, for example, since m o r e of with fuming sulfuric acid H2SO4 + SO3 [44].
the solvent will p a r t i t i o n to the p o l y m e r phase, w h i c h swells, Direct a n d practical a p p l i c a t i o n s of solubility p a r a m e t e r s
b e c o m e s m o r e fluid, a n d has altered affinities for stabilizing in coatings have i n c l u d e d their use as an aid in the selection
surface active agents, for example. They m a y dissolve too of solvents a n d solvent b l e n d s for m a n y years. Most solvent
readily in the d i s p e r s e d polymer. Carefully controlled, these suppliers a n d frequent solvent users have c o m p u t e r pro-
t e m p e r a t u r e effects are a n advantage in water-reducible, g r a m s for this purpose, although as n o t e d above, such pro-
oven-cured coatings, leading to higher film integrity. g r a m s are not an absolute necessity. R e f o r m u l a t i o n to meet
A simple a p p r o a c h to m a n y practical p r o b l e m s is to m a k e a e n v i r o n m e n t a l r e q u i r e m e n t s is especially i m p o r t a n t in this
t w o - d i m e n s i o n a l plot of p o l a r versus h y d r o g e n b o n d i n g pa- respect since one can quickly evaluate w h i c h of the alterna-
r a m e t e r s with a circle (or e s t i m a t e d circle) for the p o l y m e r in tives is m o s t likely to m e e t the given requirements. This
question. One can plot the points for potential solvents a n d includes reducing a m o u n t s of volatile organic solvent (VOC)
quickly arrive at a starting c o m p o s i t i o n for an experiment. a n d often involves mixtures.
This can subsequently be a d j u s t e d if necessary. It should also The m a i n thing to r e m e m b e r in solvent selection using
be kept in m i n d t h a t cyclic solvents generally have higher solubility p a r a m e t e r s is that the resultant values for mixtures
n o n p o l a r p a r a m e t e r s t h a n aliphatic solvents. c a n be e s t i m a t e d from volume fraction averages for each
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TABLE 4--Solubility parameters for polymers. TABLE 4 C o n t i n u e d - - S o l u b i l i t y parameters for polymers.

D P H R D P H R
Cellulose acetobutyrate Chlorparaffin
Cellit BP-300" 16.6 12.0 6.7 10.2 Cereclor 70 20.0 8.3 6.8 9.8
Chlorparaffin 40 17.0 7.6 7.9 11.9
Cellulose acetate
Cellidora Aa 18.2 12.4 10.8 7.4 Chlorinated rubber
Pergut S 5 17.4 9.5 3.8 10.0
Ethyl cellulose Allopren R 10 17.4 4.3 3.9 6.1
Ethocel HE 10 ind b 17.9 4.3 3.9 5.9
Ethocel Std 20 ind b 20.1 6.9 5.9 9.9 Chlorinated polypropylene
Parlon P 10" 19.8 6.2 5.3 10.4
Epoxy
Araldite DY 025 14.0 7.4 9.4 13.7 Chlorosulfonated polyethylene
Epikote 828 21.3 14.2 6.1 17.7 Hypalon 20 b 18.1 3.4 4.9 3.6
Epikote 1001 18.1 11.4 9.0 9.1 Hypalon 30 b 18.2 4.7 2.0 5.0
Epikote 1004 17.4 10.5 9.0 7.9
Epikote 1007 21.0 11.1 13.4 11.7 Cyclized rubber
Epikote 1009 18.9 9.6 10.7 7.8
Phenoxy PKHH 23.4 7.2 14.8 14.9 Alpexb 19.9 0.0 0.0 9.4
Epoxy curing agents Nitrocellulose

Versamid 100 23.8 5.3 16.2 16.1 1/2-sec-Nitrocellulose H 23 a 15.1 14.4 8.6 11.2
Versamid 115 20.3 6.6 14.1 9.6
Versamid 125 24.9 3.1 18.7 20.3 Rosin derivatives
Versamid 140 26.9 2.4 18.5 24.0 Cellolyn 102a 21.2 0.9 8.3 15.4
Pentatyn 255 ~ 17.2 9.2 14.0 10.4
Polyurethane Pentalyn 830" 19.6 5.7 10.7 11.4
Desrnophen 651 17.7 10.6 11.6 9.5 Ester Gum 8L~ 19.2 4.6 7.6 10.4
Desmophen 800 19.1 12.2 9.9 8.0
Desmophen 850" 21.1 14.6 12.0 16.2 Polyamide
Desmophen 1100 16.0 13.1 9.2 11.4 Versamid 930" 17.0 -1.9 14.6 7.4
Desmophen 1150 20.6 7.8 11.6 13.1 Versamid 961 18.9 9.6 11.1 6.2
Desmophen 1200 19.4 7.4 6.0 9.8 Versamid 965 20.4 0.4 14.0 12.9
Desmophen 1700 17.9 9.6 5.9 8.2
Desmolac 4200 18.7 9.6 9.9 8.2 Isocyanate
Macrynal SM 510N 19.9 8.1 6.0 9.8 Desmodur L 17.5 11.3 5.9 8.5
Demodur N ~ 17.6 10.0 3.7 9.3
Phenolic resins Suprasec F-5100" 19.7 12.9 12.8 11.4
Super Beckacite 1001~ 22.7 6.4 8.2 19.4
Phenodur 373 U" 19.3 11.4 14.3 12.4 Polyvinylbutyral
Mowithal B 30 H 18.6 12.9 10.3 8.3
Hydrocarbon resins Mowithal B 60 H 20.2 11.2 13.3 11.2
Piccolyte S-I00" 16.1 0.4 2.8 8.4 Butvar B 76 a 18.2 4.3 12.7 10.4
Piccopale 110" 17.2 1.2 3.5 6.4
Piccoumarone 450 La 19.0 5.4 5.6 9.4 Polyacrylate
Lucite 2042" 17.2 9.4 3.9 10.4
Styrene-butadiene elastomer (SBR) Lucite 2044 16.2 6.8 5.7 9.1
Polysar 5630" 17.2 3.3 2.6 6.4 Plexigum MB 319 18.6 10.8 4.1 11.5
Plexigum M 527 18.4 9.4 6.5 10.7
Acrylonitrile-butadiene elastomer PMMAa 18.2 10.3 7.7 8.4
Hycar 1052 a 18.2 8.6 4.1 9.4
Polyvinylacetate
Polybutadiene Mowilith 50" 20.5 11.0 9.4 13.4
Buna H~ls B-10" 17.1 2.2 3.3 6.4
Polystyrene
Polyisoprene Polystyren LG~ 20.8 5.6 4.2 12.4
Cariflex IR 305 a 16.2 1.4 -0.8 9.4
Vinylchloride/copolymers
Polyisobutylene Laroflex MP 45 18.4 8.4 5.8 9.0
Lutonal IC/1203 ~ 14.2 2.5 4.6 12.4 Vilit MB 30 20.0 8.3 6.7 9.4
Lutonal I60 16.9 2.5 4.0 7.2 Vilit MC 31 20.0 8.3 6.7 9.4
Polyvinylbutyl ether 17.4 4.3 8.4 7.4 Vilit MC 39 18.4 7.6 6.7 6.8
Lignin p o w d e r ~ 19.7 14.3 14.7 11.4 Vinylite VAGD 17.1 10.4 6.5 7.5
Modaflow Multiflow 16.1 3.7 7.9 8.9 Vinylite VAGH 16.5 10.9 6.4 7.7
Vinylite VMCA 17.7 11.1 6.9 8.7
Polyvinylchloride Vinylite VMCC 17.6 11.1 6.8 8.8
Vinylite VMCH 17.6 11.1 6.4 8.6
Vipla KR a 17.2 7.4 8.2 3.4 Vinylite VYHH 17.4 10.2 5.9 7.8
Vinylite VYLF 18.1 10.3 4.2 8.3
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T A B L E 4 Continued--Solubilityparameters for polymers. TABLE 5--List of suppliers and trademarks for paint binders and
polymers.
D P H R
Suppliers Trademarks
B i n d e r s in s o l u t i o n
Bayer (D) Cellit, Desmophen, Desmolac,
Alkyds and polyesters Pergut, Cellidora,
Alftalat AC 366 18.6 10.0 5.0 10.4 Desmodur, Baysilon
Alftalat AM 756 23.0 2.2 4.2 16.9 Alkydal
Alftalat AN 896 22.9 15.2 7.6 18.1 Hercules (USA) Piccolyte, Cellolyn, Pentalyn,
Alftalat AN 950 22.6 13.8 8.1 17.1 Ester Gum, Parlon
Alftalat AT 316 20.5 9.3 9.1 12.4 Ciba-Geigy Araldite
Alflalat AT 576 19.2 5.3 6.3 11.9 Shell (D) Epikote, Cariflex
Mkydal F 261 HS 23.6 1.0 7.6 19.0 Union Carbide (USA) Vinylite, Phenoxy
Alkydal F 41 20.6 4.6 5.5 12.6 Hoechst (D) Macrynal, Phenodur, Alpex,
Durofta] T 354 17.3 4.2 7.9 9.3 Mowithal, Alftalat,
Dynapol L 812 22.6 I3.1 5.8 16.8 Mowilith
Dynapol L 850 20.0 6.2 7.0 9.5 Reichhold (CH) Super Beckasite, Uformite
Plexal C-34a 18.1 9.0 4.8 10.4 Polymer Corp. (CAN) Polysar
Soalkyd 1935-EGAX 18.0 11.6 8.5 9.0 Goodrich (USA) Hycar
Vesturit BL 908 18.8 12.0 6.0 11.5 Hills (D) Vilit, Vesturit, Buna Hills
Vesturit BL 915 17.7 13.0 7.6 11.5 BASF (O) Lutonal, Laroflex, Plastopal,
Polystyren
Amino resins Monsanto (USA) Modaflow, Multiflow, Butvar
BE 370 20.7 6.1 12.7 14.8 Montecatini Edison (I) Vipla
Beetle 681 22.2 -0.4 10.1 18.4 ICI (GB) Cereclor, Allopren, Suprasec
Cymel 300~ 19.9 8.3 10.4 14.4 Du Pont (USA) Lucite
Cymel 325 25.5 15.2 9.5 22.2 Hagedom (D) l/2-sec, nitrocellulose H 23
Dynomin MM 9 18.8 14.0 12.3 10.5 R6hm (D) Plexigum
DynominUM 15 19.9 15.8 13.4 11.7 Rohm and Haas (USA) Paraloid
Soamin M 60 15.9 8.1 6.5 10.6 Dynamit Nobel (D) Dynapol
Synresen A 560 22.1 5.0 11.3 15.5 SOAB (S) Soamin
Plastopal H~ 20.3 8.1 14.6 12.4 BIP Chemicals (GB) Beetle
Uformite MX-61 22.7 2.8 5.4 16.2 Dyno Cyanamid (N) Dynomin
Acrylate resins DSM Resins (S) Uracron
Uracron 15 19.2 7.7 5.7 10.6 Reichhold Chemie (CH) Super Beckasite, Uformite
Paraloid P 400 19.2 9.6 9.3 12.2 Wacker (D) Wacker
Paraloid P 410 19.6 9.1 6.8 12.2 Dow Chemical (CH) Ethocel
Paraloid experimental resin QR 954 18.4 9.8 10.0 12.4 Cray Valley Prod. (GB) Versamid
W. Biesterfeld (D) Chlorparaffin
Silicone resins Synres (NL) Synresen
American Cyanamide (USA) Cymel
Baysilon UD 125 19.4 9.9 10.1 6.9 Polyplex (DK) Plexal
Wacker 190 F 16.6 1.9 8.0 8.0 Pennsylvania Industrial Piccopal, Piccoumarone
Chemical Corp. (USA)
A d d i t i o n a l S p e c i a l Data
DEN 438 (Dow epoxy novolak) 20.3 15.4 5.3 15.1
DEN 444 (Dow epoxy novolak) 19.5 11.6 9.3 10.0 probably be aggressive to a chemically resistant coating
Zink silicate (CR)--Chemical resistance 23.5 17.5 16.8 15.6 where very limited data have indicated a single solvent or two
2-Comp epoxy (CR)--Chemical 18.4 9.4 10.1 7.0 are s o m e w h a t aggressive. A nearest n e i g h b o r search involves
resistance
Polyvinylidinefluoride 17.0 12.1 10.2 4.1 calculation of the q u a n t i t y Rs for a whole database, for exam-
Coal tar pitch 18.7 7.5 8.9 5.8 ple, a n d then arranging the p r i n t o u t i n RED n u m b e r order
PA6 polyamide chemical resistance 17.0 3.4 10.6 5.1 with the potentially most aggressive at the top of the list.
PA66 polyamide solubility 17.4 9.8 14.6 5.1 Solvents with RED less t h a n 1.0 are "good" a n d easily recog-
PAll polyamide chemical resistance 17.0 4.4 10.6 5.1
Cellophane swelling 16.1 18.5 14.5 9.3 nized.
EVOH--solubility (ethylenevinyl 20.5 10.5 12.3 7.3 I n m a n y cases a m a r g i n a l solvent is desired, in which case
alcohol) RED n u m b e r s just u n d e r 1.0 will be sought. Marginal solvent
Note: D = dispersion;P = permanent dipoles;H = hydrogenbonding;R = quality will ensure that p o l y m e r adsorbed onto p i g m e n t sur-
interaction radius. faces has little reason to dissolve away from that surface
~Takenfrom Hansen, C. M., "Solubilityin the CoatingsIndustry,"Fi~rgoch
Lack, VoL 17, No. 4, 1971, pp. 69-77. where it is desired as a stabilizing factor i n the product. The
bCalculatedfrom solubilitydata in PolymerHandbook, 2nd ed., John Wiley solvent in this case should have a RED n u m b e r for the pig-
& Sons, Inc., New York, 1975.
m e n t surface greater t h a n 1.0 to aid i n the p l a n n e d affinity
approach to p i g m e n t dispersion stability. A sketch of the opti-
m u m relations is given in Fig. 4, where the m a r g i n a l solvent is
solubility p a r a m e t e r c o m p o n e n t . Solvent quality can be ad-
N u m b e r 1. Solvent 2 would p r o b a b l y be too expensive and, i n
justed by the RED n u m b e r concept or graphically as de-
addition, will probably dissolve the polymer too well. I n spe-
scribed above. cial applications this extended polymer c h a i n configuration is
A c o m p u t e r search for nearest neighbors for a given single desirable, b u t a solid a n c h o r to the p i g m e n t surface is re-
solvent has b e e n used m a n y times to locate alternates. A quired. A good a n c h o r has high affinity for the p i g m e n t sur-
similar application is to predict which other solvents will face a n d m a r g i n a l or n o affinity for the solvent. Solvent 3
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TABLE 6--Examples of the use of the solubility parameter. to this polymer are desired, while still maintaining affinity for
Activity coefficients the other polymer. Miscible blends of two polymers have
Aerosol formulation been found using a solvent mixture composed exclusively of
Biological materials and compatibility nonsolvents. This is demonstrated schematically in Fig. 5,
Chromatography where it can be seen that different percentage blends of Sol-
Coal solvent extraction
Compressed gases vents 1 and 2 will have different relative affinities for the
Cosmetics polymers. No other alternative theory of polymer solution
Cryogenic solvents thermodynamics can duplicate this predictive ability. Poly-
Dispersion mer miscibility is enhanced by larger overlapping solubility
Dyes
Emulsions regions for the polymers as sketched in Fig. 6. Polymers A and
Gas-Liquid solubility B should be compatible, while C will not be. Such a system-
Grease removal atic analysis allows modification of a given polymer to pro-
Membrane permeability and swelling vide more overlap and enhanced compatibility. The
Paint film appearance advantages of a copolymer containing the monomers of A or
Pharmaceutical
Pigments B and C should also be evident. Such a copolymer will essen-
Plasticizers, polymers, resins tially couple the system together.
Plasticization Van Dyk et al. [45] have correlated the inherent viscosity of
Polymer and plasticizer compatibility polymer solutions with the solubility parameter. This is inter-
Printing ink
Reaction rate of radical polymerization esting in that the solubility parameter is a thermodynamic
Resistance of plastics to solvents consideration, while the viscosity is a kinetic phenomena.
Rubber blends Solvents with higher affinities give greater polymer chain ex-
Solid surface characterization--organic and inorganic tension in solution, and the inherent viscosity--the solution
Solid surface modification viscosity divided by the solvent viscosity at polymer concen-
Solvent extraction
Solvent formulation, environmental aspects trations approaching zero--is an expression reflecting poly-
Surface tension mer chain extension in solution. Higher intrinsic viscosities
Urea-water solutions were found for solvents with solubility parameters nearest
Vaporization of plasticizers the polymer solubility parameters.
Viscosity of polymer systems
Water-based polymer systems, coalescents The use of supercritical gases as solvents has become more
common in recent years. Space limitations prevent going into
the details of these developments. It should be noted, how-
ever, that when a gas is compressed its cohesive energy den-
would adsorb onto the pigment surface preferentially, and sity increases. This means that nonpolar gases with their low
pigment dispersion stability will be poor. Pigments have been nonpolar solubility parameters can begin to dissolve given
characterized by long-time suspension studies where some organic materials which otherwise have solubility parame-
solvents will suspend the fines for days, months, or years, ters which are too high. Increasing the nonpolar solubility
while others of similar viscosity yield rapid settling. The parameter of the gas by increasing the pressure causes a
suspending solvents are the "good" ones and can be used to
define a sphere for surface wetting/adsorption.
In other cases better matches between solvent and polymer
solubility parameters are required. This is true when two
polymers are mixed and one of them precipitates. This is
most likely the polymer with larger molecular weight, and it
must be dissolved better. Lower RED numbers with respect
Pigment
~p
~p
~h
FIG. 5-Solubility relations for polymer mix-
~h tures can be quickly evaluated to ensure solu-
FIG. 4-Solubility parameter re- tion stability. Even mixtures of nonsolvents can
lations for optimum pigment be systematically used to regulate solution be-
dispersion stability. havior,
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14
12 3: Dewetting
10
~;p
~p 6
4
I I ! I I I | | ! ! I I ! I I 9
0 2 4 8 8 10 12 14 16
~h
FIG. 7-Schematic diagrams showing surface
energy/contact angle characterizations using
FIG. 6-Schematic representation showing ex- the Hansen solubility parameters (cohesion en-
pected miscibility of Polymers A and B with ergy parameters).
each other but not with Polymer C.
closer match with the corresponding parameter for potential types of chemical protective clothing such as butyl rubber,
solutes. Similar behavior is found for polar gases such as nitrile rubber, plasticized polyvinyl chloride, neoprene, Viton
carbon dioxide. The prevailing pressure and temperature rubber, polyvinyl alcohol, etc. [47]. Figure 8 shows the impor-
conditions determine its cohesive energy density and changes tance of combined use of the RED number and molecular
in pressure or temperature change solubility relations for this volume in correlating 3-h breakthrough times for a flu-
reason. Whereas nonpolar gases are most suitably used for oropolymer chemical protective product [48]. Monomers
relatively nonpolar solutes, carbon dioxide--and in principle with terminal double bonds diffuse more rapidly than com-
other polar gases--are most suitably used in connection with parisons with non-double-bonded molecules of similar size
more polar solutes. The solubility parameters for carbon di- and solubility parameter would have predicted. The smaller
oxide have been reported [46] based on the room temperature cross section at the end of the molecule reminds one of a nail,
solubility of the gas in different liquids (Sd, 8,, ~h equal to 15.3, and the preferred direction and relative rapidity of transport
6.9, 4.1). These parameters resemble those of a higher ketone. become easily understandable.
Pigment wetting/suspension characteristics have been pre- In addition it should be noted that even biological materi-
sented earlier [2,4,10]. Mixtures of nonsuspending solvents als, some of which have interest for coatings applications and
could also be found which, when admixed, provided predict- use, have been assigned Hansen solubility parameters [49].
ably higher affinity and suspension of pigment particles for These include keratin (which relates to skin permeation), fat,
prolonged periods of time. An exceptionally clear demonstra- sucrose, blood serum and zein (which are proteins), urea,
tion of pigment adsorption properties is given in Ref 4 where lignin (wood penetration), and chlorophyll (which closely
a triangular plot of the three partial parameters shows the resembles lignin) [46,49]. The characterization of other bio-
logical materials is also possible, of course.
clearly different adsorption properties of untreated zinc ox-
Even inorganic salts have been characterized by solubility
ide powder and organic phosphate surface-treated zinc oxide
parameters [50]. The practice of dissolving polymers in solu-
powder. This triangular approach to plotting was developed
tions of organic liquids and inorganic salts can thus be ex-
by Teas [41].
plained by the solubility parameter. A solubility parameter
Other surface characterizations have also been given for
correlation of the chemical resistance of an inorganic zinc
surfaces such as coatings and metal substrates [ l 7,18]. These silicate coating is reported in Table 4. Finally it might be
characterizations have been of the type sketched in Fig. 7. noted that Hildebrand presented a chapter on the solubility
Such cohesive energy plots can lead to systematic modifica- parameters of metals [1]. Unfortunately we do not often coat
tions of systems to improve adhesion. It might be added metal, but rather metal oxides, for which no solubility param-
parenthetically that equal information can be obtained from eter work has been reported.
plots of the cosine of the contact angle versus the solubility
parameter as for plots of these same data versus liquid sur-
face tension [17]. The energy information obtained in these CONCLUSION
types of studies, the critical surface tension, corresponds to
the condition of RED equal to 1.0, with a solubility parameter The background and many uses of the solubility parameter
approach, that is, marginal affinity. concept have been described in detail. Tables of solubility
The list of applications has recently been expanded to in- parameters for many liquids and polymers have been pre-
clude correlations of the breakthrough times for common sented. Systematic use of solubility, swelling, or permeation
www.iran-mavad.com

J D, P, H, R = 16.6, 5.4, 4.0, 3.8 BREAKTHROUGH'ro~. "=" "NO="

150 -- FIT = 0 . 9 9 7 FOR 68 < MV < 98
<am 9 9
OSTC
>alto [] 0
OBCN Evaluation uncertain X
NONE 0.~
BCL
MSO [] OCH^ 0 OSTY
MM~'~~ c F I ~ _mE'r
u (oL__ oN'm
100 --
;'...., ~'~ ~
LE ~-v~" ~,~ ~ "E~zz ~o o,c,
BOND ,~c _~ d~ ___x~L "D o~,

"OC''r-- _~ ~cO~ .02"' "?'~
":_'Z~" ~ci .....\
[]
ALN
-
o~r
0
. . . . . .
. ... . . . . - \
:Z
..... ~ , . ~ x . , ~ - - . . ,~,, \ rl~.A
MICO - CBBO'X
ALI., o"~ ",,00~\ O,~c
50 --
\\ \ ^~00.ME
' I ' I I ' I ' I ~'~

0.0 1.0 2.0 3.0 4.0 5.0
RED NUMBER
FIG. 8-Effects of molecular size (molar volume) and affinity (RED number) on the breakthrough time of Challenge 5100 [48].
d a t a for p o l y m e r s allows their c h a r a c t e r i z a t i o n by these s a m e [2] Hildebrand, J. and Scott, R. L., Regular Solutions, Prentice-Hall
cohesive energy p a r a m e t e r s . Surfaces can also be character- Inc., Englewood Cliffs, NJ, 1962.
ized using these s a m e p a r a m e t e r s . This provides d a t a for op- [3] Barton, A. F. M., Handbook of Solubility Parameters and Other
t i m i z i n g solvent selection, i m p r o v i n g compatibility, a n d Cohesion Parameters, CRC Press Inc., Boca Raton, FL, 1983.
[4] Gardon, J. L. and Teas, J. P., "Solubility Parameters," Treatise
e n h a n c i n g p i g m e n t d i s p e r s i o n a n d adhesion. W h e n all of the
on Coatings, Vol. 2, Characterization of Coatings: Physical Tech-
m a t e r i a l s involved in a given p r o d u c t a n d a p p l i c a t i o n can be niques, Part II, R. R. Myers and J. S. Long, Eds., Marcel Dekker,
c h a r a c t e r i z e d with the s a m e energy p a r a m e t e r s , the possibil- New York, 1976, Chapter 8.
ity exists to predict interactions a m o n g them, even in compli- [5] Burrell, H., "Solubility Parameters for Film Formers," Official
c a t e d situations. M e t h o d s for e s t i m a t i n g the three H a n s e n Digest, Vol. 27, No. 369, 1972, pp. 726-758; Burrell, H., "A
solubility p a r a m e t e r s have b e e n given with as m u c h detail as Solvent Formulating Chart," Official Digest, Vol. 29, No. 394,
has b e e n possible to ensure their m o r e u n i f o r m use in the 1957, pp. 1159-1173; Burrell, H., "The Use of the Solubility
future. It has n o t b e e n possible to deal with all the p r i m a r i l y Parameter Concept in the United States," VI Federation
theoretical p r o b l e m s with the solubility p a r a m e t e r concept. d'Associations de Techniciens des Industries des Peintures,
S o m e of these are dealt with in the literature cited, m o s t Vernis, Emaux et Encres d'Imprimerie de l'Europe Continentale,
n o t a b l y in Refs 3, 4, 12, a n d 20. Congress Book, 1962, pp. 21-30.
[6] Blanks, R. F. and Prausnitz, J. M., "Thermodynamics of Poly-
A simple a p p r o a c h is d e s c r i b e d to u n d e r s t a n d affinities in mer Solubility in Polar and Nonpolar Systems," Industrial and
such varied m a t e r i a l s as gases, liquids, polymers, biological Engineering Chemistry, Fundamentals, Vo]. 3, No. 1, 1964, pp.
materials, surfaces, organic a n d inorganic coatings, inor- 1-8.
ganic salts, a n d metals. An a p p e a l is m a d e to the scientific [7] Hansen, C. M., "The Three Dimensional Solubility Parameter--
c o m m u n i t y to e x p a n d r e s e a r c h on this seemingly universal Key to Paint Component Affinities I," Journal of Paint Technol-
approach. ogy, Vol. 39, No. 505, 1967, pp. 104-117.
[8] Hansen, C. M., "The Three Dimensional Solubility Parameter--
Key to Paint Component Affinities II," Journal of Paint Technol-
REFERENCES ogy, Vol. 39, No. 511, 1967, pp. 505-510.
[9] Hansen, C. M. and Skaarup, K., "The Three Dimensional Solu-
[1] Hildebrand, J. and Scott, R. L., The Solubility of Nonelectrolytes, bility Parameter--Key to Paint Component Affinities III,"
3rd ed., Reinhold, New York, 1950. Journal of Paint Technology, Vol. 39, No. 511, 1967, pp. 511-514.
www.iran-mavad.com

[10] Hansen, C. M., "The Three Dimensional Solubility Parameter mers," Journal of Applied Polymer Science, Vol. 32, 1986, pp.
and Solvent Diffusion Coefficient," Danish Technical Press, Co- 3515-3539.
penhagen, 1967 (doctoral dissertation). [31] Hoy, K. L., "Tables of Solubility Parameters," Union Carbide
[I 1] Hansen, C. M. and Beerbower, A., "SolubilityParameters," Kirk- Corp., Research and Development Dept., South Charleston, WV,
Othmer Encyclopedia of Chemical Technology, Supplement Vol- 1985 (1st ed., 1969).
ume, 2nd ed., A. Standen, Ed., Interscience, New York, 1971, pp. [32] Reid, R. C. and Sherwood, T. K., Propertiesof Gases and Liquids,
889-910. McGraw-Hill, New York, 1958 (Lydersen Method, see also Ref
[12] Barton, A. F. M., "Applications of Solubility Parameters and 31).
Other Cohesion Energy Parameters in Polymer Science and [33] McLellan, A. L, Tables of Experimental Dipole Moments, W. H.
Technology," Pure and Applied Chemistry, Vol. 57, No. 7, 1985, Freeman, San Francisco, 1963.
pp. 905-912. [34] "Tables of Physical and Thermodynamic Properties of Pure
[13] S~rensen, P., "Application of the Acid/Base Concept Describing Compounds," American Institute of Chemical Engineers Design
the Interaction between Pigments, Binders, and Solvents," Jour- Institute for Physical Property Research, Project 801, Data Com-
nal of Paint Technology, Vol. 47, No. 602, 1975, pp, 31-39. pilation, R. P. Danner and T. E. Daubert, Project Supervisors,
[14] Van Dyk, J. W,, paper presented at the Fourth Chemical Con- DIPPR Data Compilation Project, Department of Chemical En-
gress of America, New York, 25-30 Aug. 1991. gineering, Pennsylvania State University, University Park, PA.
[15] Anonymous (Note: This was in fact Van Dyk, J. W. but this does [35] Hansen, C. M., "Selection of Chemicals for Permeation Testing
not appear on the bulletin), "Using Dimethyl Sulfoxide (DMSO) Based on New Solubility Parameter Models for Challenge 5100
in Industrial Formulations," Bulletin No, 102, Gaylord Chemical and Challenge 5200," under contract DTCG50-89-P-0333 for the
Corp., Slidell, LA, 1992. U.S. Coast Guard, June 1989, Danish Isotope Centre, Copenha-
[16] Karger, B. L., Snyder, L. R., and Eon, C., "Expanded Solubility gen.
Parameter Treatment for Classification and Use of Chromato- [36] CRC Handbook of Chemistry and Physics, 65th ed., R. C. Weast,
graphic Solvents and Adsorbents," Analytical Chemistry, Vol. 50, Editor-in-Chief, Boca Raton, FL, CRC Press Inc., 1988-1989,
No. 14, 1978, pp. 2126-2136. pp. C-672-C-683,
[17] Hansen, C. M. and Wallstr6m, E., "On the Use of Cohesion [37] Majer, V., "Enthalpy of Vaporization of Organic Compounds,"
Parameters to Characterize Surfaces," Journal of Adhesion, Vol. Handbook of Chemistry and Physics, 72nd ed., D. R. Lide, Edi-
15, 1983, pp. 275-286. tor-in-Chief, Boca Raton, CRC Press Inc., 1991-1992, pp. 6-100-
[18] Hansen, C. M., "Characterization of Surfaces by Spreading Liq- 6-107.
uids," Journal of Paint Technology, Vol. 42, No. 550, 1970, pp. [38] Fishtine, S. H., "Reliable Latent Heats of Vaporization," Indus-
660-664; Hansen, C. M., "Surface Dewetting and Coatings Per-
trial and Engineering Chemistry, Vol. 55, No. 4, 1963, pp. 20-28;
formance,"Journal of Paint Technology, Vol. 44, No. 570, 1972,
also, Vol. 55, No. 5, pp. 55-60 and Vol. 55, No. 6, pp. 47-56.
pp. 57-60.
[39] Saarnak, A., Hansen, C. M., and Wallstr6m, E., "Solubility Pa-
[19] Hansen, C. M. and Pierce, P. E., "Surface Effects in Coatings
rameters, Characterization of Paints and Polymers," report from
Processes," Industrial and Engineering Chemistry, Product Re-
Scandinavian Paint and Printing Ink Research Institute, Janu-
search and Development, Vol. 13, No. 4, 1974, pp. 218-225.
ary 1990.
[20] Gardon, J. L., "Critical Review of Concepts Common to Cohe-
[40] Barton, A. F. M., Handbook of Polymer-Liquid Interaction Pa-
sive Energy Density, Surface Tension, Tensile Strength, Heat of
Mixing, Interracial Tension and Butt Joint Strength," Journal of
rameters and Solubility Parameters, CRC Press, Inc., Boca Raton,
FL, 1990.
Colloid and Interface Science, Vol. 59, No. 3, 1977, pp. 582-596.
[21] Patterson, D., "Role of Free Volume Changes in Polymer Solu- [41] Teas, J. P., "Graphic Analysis of Resin Solubilities," Journal of
tion Thermodynamics," Journal of Polymer Science: Part C, No. Paint Technology, Vol. 40, No. 516, 2968, pp. 19-25.
16, 1966, pp. 3379-3389. [42] Hansen, C.M., "Some Aspects of Acid/Base Interactions"
[22] Flory, P. J., Principles of Polymer Chemistry, Cornell University (Einige Aspekte der S/iure/Base-Wechselwirkung) (in German),
Press, New York, 1953. Farbe und Lack, Vol. 83, No. 7, 1977, pp. 595-598.
[23] van Krevelen, D. W. and Hoftyzer, P. J., Properties of Polymers: [43] Barton, A, F. M., "Solubility Parameters," Chemical Reviews,
Their Estimation and Correlation with Chemical Structure, 2nd Vol. 75, No. 6, 1975, pp. 731-753.
ed., Elsevier, Amsterdam, 1976. [44] Beerbower, A., "Boundary Lubrication--Scientificand Techni-
[24] Beerbower, A., "Environmental Capability of Liquids," Interdis- cal Applications Forecast, AD747336," Office of the Chief of
ciplinary Approach to Liquid Lubricant Technology, NASAPubli- Research and Development, Department of the Army, Washing-
cation SP-318, 1973, pp. 365-431. ton, DC, 1972.
[25] Fedors, R. F., "A Method for Estimating both the Solubility [45] Van Dyk, J. W., Frisch, H. L., and Wu, D. T., "Solubility, Sol-
Parameters and Molar Volumes of Liquids," Polymer Engineer- vency, Solubility Parameters," Industrial and Engineering
ing and Science, Vol. 14, No. 2, 1974, pp. 147-154 and 472. Chemistry Product Research and Development, Vol. 24, No. 3,
[26] Koenhen, D, N. and Smolders, C.A., "The Determination of 1985, pp. 473-478.
Solubility Parameters of Solvents and Polymers by Means of [46] Hansen, C. M., "25 Years with Solubility Parameters," (25
Correlation with Other Physical Quantities," Journal of Applied reed Opl~selighedsparametrene) (in Danish), Dansk Kemi, Vol.
Polymer Science, Vol. 19, 1975, pp. 1163-1179. 73, No. 8, 1992, pp. 18-22.
[27] Anonymous, "Co-Act--A Dynamic Program for Solvent Selec- [47] Hansen, C. M. and Hansen, K. M., "SolubilityParameter Predic-
tion," brochure, Exxon Chemical International, Inc., 1989. tion of the Barrier Properties of Chemical Protective Clothing,"
[28] Dante, M. F., Bittar, A. D., and Caillault, J. J., "Program Calcu- Performance of Protective Clothing: Second Symposium, ASTM
lates Solvent Properties and Solubility Parameters," Modern STP 989, S.Z. Mansdorf, R. Sager, and A. P. Nielsen, Eds.,
Paint and Coatings, Vol. 79; No. 9, 1989, pp. 46-51. American Society for Testing and Materials, Philadelphia, 1988,
[29] Hoy, K. L., "New Values of the Solubility Parameters from Va- pp. 197-208.
por Pressure Data," Journal of Paint Technology, Vol. 42, No. [48] Hansen, C. M., Billing, C. B., and Bentz, A. P., "Selection and
541, 1970, pp. 76-118. Use of Molecular Parameters to Predict Permeation Through
[30] Myers, M. M. and Abu-Isa, I. A., "Elastomer Solvent Interac- Fluoropolymer-Based Protective Clothing Materials," The Per-
tions III-Effects of Methanol Mixtures on Fluorocarbon Elasto- formance of Protective Clothing; Fourth Volume, ASTM STP 1133,
www.iran-mavad.com

J. P. McBriarty and N. W. Henry, Eds., American Society for [50] Hansen, C. M., "The Universality of the Solubility Parameter,"
Testing and Materials, Philadelphia, 1992, pp. 894-907. Industrial and Engineering Chemistry Product Research and De-
[49] Hansen, C. M., "The Affinities of Organic Solvents in Biological velopment, Vol. 8, No. 1, 1969, pp. 2-11.
Systems," Journal of the American Industrial Hygiene Associa-
tion, Vol. 49, No. 6, 1988, pp. 301-308.
www.iran-mavad.com

Part 9: Films for Testing
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MNL17-EB/Jun. 1995
i
Cure: The Process and Its 36

Measurement
by Thomas J. Miranda 1
INTRODUC~ON initiated by complex initiator systems such as those used to

polymerize ethylene or propylene and sometimes referred to
One of the most critical, and often misunderstood proper- as Ziegler-Natta catalysts made from an organometal and an
ties of a coating is cure and its measurement. The optimum inorganic compound like titanium tetrachloride. Cationic ini-
physical and chemical properties of a coating depend largely tiation can be done using Lewis acids such as aluminum
on proper curing conditions. For example, a thermosetting chloride or boron trifluoride and are usually carried out at
acrylic polymer when applied to a panel and dried without low temperatures. Butyl rubber is made by such a process.
curing will be brittle and have poor solvent resistance and low Group transfer is a relatively new type of polymer initiation,
hardness. When properly cured, the film properties will while the anionic processes use organometals (butyl lithium)
change dramatically and the properties which were designed to produce polymers. Block polymers are made by anionic
into the coating become apparent. Similarly, an oil-based processes. Condensation polymers have lower molecular
paint will be soft and tacky and slowly become hard and weight than addition types and are produced by stepwise
scratch resistant as its cure develops. To appreciate the scope addition with elimination of water as a byproduct and require
of the material in this chapter, it may be well to review a few a longer time to synthesize using an endothermic process [4].
film-forming mechanisms, polymer fundamentals, and some
background into the development of tests and what they
Cure Concept and Illustrations
mean.
We can simplistically illustrate the concept by considering
a long chain polymer (thermoplastic) as a wire fence with a
Background and Film Formation number of strands (Fig. I) such as used on a farm. An individ-
ual can pass through the fence by spreading the strands apart,
Polymers
and standing on the fence will cause the strand to sag or
A polymer is a high-molecular-weight interreaction prod- elongate. If, however, we take that fence and lace it with wire
uct of related polyfunctional molecules [1 ]. The term polymer such that a hogwire fence is produced, then we see the
is derived from the Greek poly (many) and met (part). Poly- changes in the physical properties of this (thermoset) fence.
mers are formed from monomers (mono -- one) (met -- part) First, it would be difficult to pass through the fence; second,
by a process of polymerization. Polymers consist of long one can stand on the fence since it is stronger and will not
chains of macromolecules with molecular weights of a few yield as would the single strand fence. If one considers the
thousand up to many millions. For example, ultrahigh-mo- ability to pass through the fence as solvent action, it is easy to
lecular-weight polyethylene may have a molecular weight of 4 visualize how solvent molecules can permeate and dissolve a
to 6 million, while alkyds have molecular weights of a few thermoplastic polymer, but difficult or impossible to dissolve
thousand. The concept of macromolecules was developed by a thermoset polymer. In fact, a thermoset polymer will tend
Herman Staudinger in 1920 [2]. Staudinger's theory was to swell, such as a rubber band in a hydrocarbon solvent. This
supported by the work of Wallace Carothers, who introduced is because the solvent molecules can solvate the linear por-
the concept of functionality and the distinction between ther- tions of the rubber, but are constrained by the sulfur cross-
moplastic and thermosetting polymers [3]. links from totally dissolving the polymer. Another aspect of
There are two types of polymers: addition and condensa- cross-linking is that the molecular weight increases enor-
tion. Addition polymers have high molecular weight and are mously, which explains why solvent resistance increases and
characterized by fast chain reaction syntheses that are exo- certain physical properties such as hardness, scratch resist-
thermic and initiated by free radical, coordination polymer- ance, and toughness are enhanced. The thermoset polymer is
ization, cationic, group transfer, or anionic mechanisms. a three-dimensional network polymer. Cure must not be con-
Free radical-initiated polymerization is initiated by incorpo- fused with dry time such as that measured in oil-containing
ration of a free radical producer such as benzoyl peroxide polymers which dry by interaction with atmospheric oxygen.
which decomposes with heat to form free radicals, which in Here such terms as set-to-touch, print free, time to lint free, and
turn initiate polymerization. Coordination polymerization is time for sand pickup relate to the speed at which solvent
evaporates and not to the ultimate cure or cross-linking of a
Senior Consultant, Consolidated Research, Inc., 16731 Brick Rd., coating system. Cure, therefore, refers to the cross-linking of
Granger, IN 46530. a polymer to produce a three-dimensional network.
407
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THERMOPLASTIC (no c r o s s l i n k i n g ) CURE MECHANISMS

S S S
Coating films can be made by a number of methods. The
principal mechanisms of film formation are represented by
S S S lacquers, emulsions, and thermosetting (via oxidative cross-
linking or by reactive cross-linking) coatings. For a review of
S S film formation, the reader is referred to the Federation of
Societies for Coatings Technology Monograph on Film For-
mation [5].
THERMOSET (crosslinking) Lacquers

s s s Lacquers consist of a thermoplastic polymer which is dis-
solved in a solvent. When the coating is applied, the solvent
I I evaporates and a thermoplastic film is formed. This is the
type of coating used in certain furniture and automotive
S
I S
l S
finishes.
S = solvent molecules Emulsions

= linear polymer Another means for forming a thermoplastic film is film
[ = crosslinked segments
formation from an emulsion. In this case, a polymer, such as
FIG. I-Polymers. a vinyl acetate-acrylic copolymer emulsion (or latex), is cast
onto a substrate and then the water carrier leaves the film by
evaporation. In the latex, water is not a solvent but a dispers-
TYPES OF FILMS ing medium. Microscopically, the polymer molecules look
like tiny ball bearings suspended in water (Fig. 2). Surface
As described above, polymers can be classified as thermo- active agents keep the polymer from settling. As the water
plastic and thermoset in nature when derived from addition evaporates, hydrodynamic pressure causes the small spheres
and condensation polymerization as well as by their physical to crowd closer and closer together until capillary action
response to heat and solvent action. forces the particles to fuse and form a continuous film. If the
polymer is too hard, a poorly adherent film forms. This is why
paint manufacturers recommend that water-based, latex-
Thermoplastic type paints not be applied at low temperatures. At low tem-
peratures, the particles cannot fuse properly, and the paint
A long-chain polymer such as polyethylene is considered
will fail prematurely. To facilitate fusion, small amounts of
thermoplastic since it can be dissolved in certain solvents and
coalescing solvent such as diethylene glycol monobutyl ether
can be repeatedly softened or melted when heated and hard-
(butyl Carbitol TM Union Carbide Corp.) are added. These sol-
ened when cooled.
vents lower the glass transition temperature of the copolymer
and facilitates fusion. These are examples of physical drying
as compared to chemical drying discussed next (see Fig. 2).
Thermoset
On the other hand, a polymer prepared, for example, from
Oxidative Cross-Linking
a phenol-formaldehyde condensate cannot be liquified and
solidified repeatedly after it is formed. These polymers are In oxidative cross-linking, a polymer is prepared from an
termed thermosetting and tend to degrade if heated repeat- unsaturated fatty acid or oil such as castor, tall, soya, linseed,
edly. The reason for this is that they are cross-linked. or tung oil, and a small amount of a siccative (drier) such as
OWOWOWOWOWOWOWOWOWOWOW Latex on surface
W W W W W W W W
0000000000OO000000OOOO Water evaporates
Fused film
O=Polymer particles
W=Water
FIG. 2-Drying of a latex film.
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CHAPTER 36--CURE: THE PROCESS AND ITS M E A S U R E M E N T 409
lead, cobalt, manganese, or zirconium salts, for example, Melamine can be condensed with up to 6 mol of formalde-
naphthenates, octoates, etc., is added. The film is cast by hyde and 6 mol of methanol to form hexamethoxymethyl
brushing, spraying, or other means and allowed to dry. In the melamine (HMMM). The reaction product has the following
first stages, the solvent evaporates, leaving a tacky film. The structure and is often referred to as MF resin:
film can be easily deformed or thumb printed. But, as the film
ages, it slowly becomes less tacky and finally print free and N(CH2OCH3)2
cured. What has happened? The film slowly absorbed oxygen
from the atmosphere and formed hydroperoxides on the car- /A
bon alpha to the double bond. The drier decomposed the N N
hydroperoxide and formed free radicals that initiated cross- t II
(CH3OCH2)2N--C C--N(CH2OCH3)2
links between the chains derived from the fatty acid portion
of the alkyd (which imparts improved properties to the film), N
resulting in a cured or cross-linked film. A simplified reaction Hexamethoxymethyl melamine
scheme is shown in the following [6]:
Hexamethoxymethyl melamine can be reacted to contain
R--CH=CH--CH2--CH~-~-CH--R' 02 )
from one to six methoxymethyl groups. Methanol is used to
R--CH--CH=CH--CH~-~CH--R' cap the hydroxyl group to prevent premature reaction. Other
I alcohols are commonly used, including butanol and isobu-
OOH tanol. In applying a melamine formaldehyde resin, the resin
R--CH--CH=CH--CH~---CH--R' + .OOH usually is reacted with a functional polymer such as a ther-
mosetting acrylic or alkyd polymer containing an acid or
where R is CH3(CH2) 4 and R' is (CH2)TCO2CH 3. hydroxyl group that can react with the MF resin. This can be
depicted in the following manner:
The initial products are converted to polymers according to:
Initiation: RH + 02 ) R" + "OOH 2 Polymer--[- + M--N(CH2OCH3)2 )
1
CH2OH
Propagation R" + 0 2 ) RO0"
Polymer-----[--
RO0" + RH ) ROOH + R"
CH2(~
Termination RO0" + R" ) ROOR
RO0" + ROO" > ROOR + 02 / CH2
M--N + 2CH3OH
R'+R" >R--R \
CH~
Termination by coupling doubles the size of the molecule I
since two fragments are now joined (assuming that the chain CH20
length is about equal). In this way oil-bearing oxidative Polymer I
curing leads to networks having the proper chemical and
physical properties. where M denotes a methoxy-substituted melamine functional
unit. In this illustration, only two of the melamine meth-
oxymethyl functions are shown reacting with the hydroxyl
Reactive Cross-linking groups of an alkyd or other hydroxyl functional polymer.
In this type of cross-linking, a reactive intermediate is Note also the formation of a byproduct, methanol. Formalde-
added to a polymer and a further chemical reaction is initi- hyde can also form as a byproduct.
ated either by heating alone, heating in the presence of a
catalyst, or by some other form of initiation.
Urea
Melamine A scheme similar to that described above for melamine is
Melamine formaldehyde condensates are used to cure also applicable to urea formaldehyde (UF) resins. In this case,
a reactive polymer. Melamine is 1,3,5 triamino-s-triazine urea is reacted with formaldehyde and endcapped with either
and is produced from the condensation of 3 moles of methyl, butyl, or isopropyl alcohols. A fully reacted urea in-
dicyandiamide: termediate would have a structure
NH2
(CHaOCH2)2--N--C --N--(CH2OCH3) 2
II
0
I iL N,N' bishydroxymethylurea
H2N--C C--NH 2
and is capable of reacting with hydroxyl groups to produce a
N
cross-link with the elimination of byproducts as water, alco-
Melamine hol, and formaldehyde.
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Epoxy ings, and high-performance coatings such as for aircraft. In

Epoxy resins are derivatives of cyclic ethers. Aromatic ep- this case the isocyanate is a di- or triisocyanate, which leads
oxy resins are produced from the reaction of epichlorohydrin to cross-linking. Toluene diisocyanate is widely used, hut
and bisphenol A, and the latter is a condensation product of other isocyanates such as 1,4-diphenyl methane diisocyanate,
acetone and phenol. Aliphatic epoxy resins are prepared by isophorone diisocyanate, and trimers of hexamethylene di-
the peroxidation of unsaturated linear or cyclic olefins. A isocyanate are also used. The higher-molecular-weight isocy-
simple epoxy, the diglycidyl ether of bisphenol A, is shown anates are preferred for their lower vapor pressure, thus pro-
below (Z = phenylene group) viding for improved working conditions.
Isocyanates are used to cross-link a variety of polymers
O CH3 O containing hydroxyl or amine functionality. In the case of
/\ i
CH2--CHz--O--Z--C--Z--O--CHz--CH--CH2
/\ amine functionality, a urea cross-link is formed. For example,
an acrylic polymer can be prepared from methytmetha-
[ crylate, butyl acrylate, and hydroxyethyl methacrylate. This
CH3 polymer can be cross-linked through the pendant hydroxyl
These epoxy functional groups can react with active hydro- groups of the hydroxyethyl methacrylate portion by poly-
gen groups such as amines, hydroxyls, and acids. For exam- functional isocyanates:
ple, they can react with acid groups in a thermosetting
Acrylic polymer
acrylic, alkyd, or other polymer and produce a cross-linked I
polymer. It is interesting to note that the reaction product of (CH2)2
the epoxy and acid function produce additional hydroxyl I
O--C~-~O
groups which can be reacted with a melamine formaldehyde
or urea formaldehyde adduct to produce improved proper- t
HN T NH
ties, such as hardness, chemical resistance, or solvent resist- I
ance in the cured films. The reaction of two acrylic polymer O=C--O
chains with an epoxy resin is shown as follows: I
(CH2)2
[ Acrylic polymer
Acrylic polymer
COOH
0 0 Urethane cross-linked acrylic
CH3
/\ i /\
CH2--CH--CH2--O--Z--C--Z--O--CH2--CH--CH2Epoxy resin
T = CH3--C6H 3- (from toluene diisocyanate)
I Urethane cross-linking is also used in polyesters where the
CH3 hydroxyl groups are obtained from polyfunctional alcohols,
COOH such as trimethylolpropane or pentaerythritol. Similarly, ep-
I Acrylic polymer oxy resins can be cross-linked through the hydroxyl groups
formed during epoxy reactions.
l
I
Acrylic polymer Catalyzed Cross-linking
C=O This type of cross-linking is used in phenolic and silicone
I H
O reactions wherein a catalyst is added to facilitate the cross-
O CH3
I I I linking reaction.
CH~ CH--CH2--O--Z--C--Z--O--CH2--CH CH2
Phenolics
t
CH3 OH O Phenolic resins are condensation reaction products of phe-
I nol or substituted phenols and formaldehyde. Two types of
C-~O
I phenolics are obtained depending upon the catalyst and reac-
Acrylic polymer tion conditions. Using an acid in its preparation, a thermo-
where Z represents a phenylene group. plastic, soluble novolac resin is obtained. Under basic condi-
tions, the thermoset product formed is a resole resin which is
Cross-linked acrylic polymer cross-linked at the final stages of the reaction. A phenol-
Isocyanates formaldehyde condensate may have a structure as shown:
The term urethane applies to the reaction product of an OH
hydroxyl group and an isocyanate. For example, an alcohol I
and isocyanate react by rearrangement to produce a urethane
C C
CH3--CH2--OH + R - - N ~ C = O ~R--N--CqO If I
L I HOH2C--C C--CH2OH
H O--CHz--CH3 \//
Alcohol + Isocyanate Urethane C
This reaction is used in applying isocyanates to the produc- CH2OH

tion of insulation and seating foams, reaction injection mold- Phenol-formaldehyde (P--F) condensate
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CHAPTER 36--CURE: THE PROCESS AND ITS M E A S U R E M E N T 411
Alkyd resins can be cross-linked by reaction of the hydroxy- source for initiation. Electron beam (EB) and ultraviolet radi-
methyl function and an hydroxyl group on the alkyd with the ation is used to cure coating films. These processes induce
elimination of water: either free radical or carbonium ions to initiate polymeriza-
tion, which occurs rapidly at ambient conditions.
OH
I
/C\~ HEAT CURE MEASUREMENT
2 + HOH2C--C C--CH2OH
I II I
CH2OH C C It is very important for the user of coatings to know
\// whether a coating is adequately cured. This can be done
C quickly in qualitative testing or in more sophisticated test
methods requiring instrumentation. The rapid methods are
CH2OH
desirable because of time and cost, but in some cases do not
Alk, 'd Phenol-Formaldehyde Condensate really tell the true story. In some cases, even instrumented
f testing only tests a certain range of cross-linking and could
lead to erroneous conclusions. We shall discuss the qualita-
--CH20 H2C--C C--CH2 OH2C-- + 2 H20 tive methods first, then proceed to the more quantitative.
II I What should be borne in mind is that we are attempting to
C C ascertain a molecular process, cross-linking, and its relation-
\//
C ship to coating performance.
I Many thermoplastic coatings "dry" by simple evaporation
ALKYD CH2OH ALKYD of solvent, and though cure was defined above as the cross-
Cross-linked alkyd linking of a polymeric system, such drying of lacquers can be
considered a form of curing even though no cross-linking
Silicones occurs. This is true for nitrocellulose lacquers, cellulose ace-
These useful polymers are prepared from silicon by chlo- tate, and solvent soluble acrylics where no cross-linking takes
rination, then subsequent reaction with alkyl or aryl halides place. To measure cure for such coating, the time for either
to form alkyl/aryl chlorosilanes. Upon hydrolysis, these pro- print-free or tack-free is measured. At some time during evap-
duce silicones. The alkyl silicones, such as dimethyl silicone, oration, the coating goes from tacky, to set-to-touch, to tack-
free. Upon further drying, the coating becomes print-free,
CH3 whereby a thumb print will not be visible on the coating. This
I
[ Si O--]n-- can also be measured by dropping cotton linters onto the
J surface and noting the time after which they do not adhere to
CH3 the coating. Also see ASTM D 2091, which describes a stan-
dard method for print resistance of lacquers.
are low-molecular-weight or cyclic materials used in anti-
These tests also apply to coatings which dry by oxidative
foam applications. The linear forms are specialty elastomers.
cross-linking, for example, alkyds. Here, times are noted for
Blends of methyl and phenyl silicones have higher-tempera-
ture resistance and find use in heat-resistant coatings or poly- solvent evaporation, and the coating is monitored for set-to-
mers. Silicones can be cross-linked when prepared with mul- touch, then print-free.
ti functional silane monomers such as trichloromethyl silane.
Upon hydrolysis, the silicone chains can be cross-linked Solvent Rubs (ASTM D 4752 Test Method for
through siloxane bridges: Measuring MEK Resistance of Ethyl Silicate
(Inorganic) Zinc-Rich Primers by Solvent Rub)
CH3
f A convenient, often-used method for determining cross-
[ Si O--].-- linking involves solvent rubs. A cloth soaked with methyl
I ethyl ketone (MEK) is rubbed vigorously on the film, and then
O
the film is examined after a specific number of rubs. Acetone
I
[ Si O--In- is also used for this test. If the film is removed, softened, or
[ loses gloss, then the film is considered not adequately cross-
CH3 linked. Films which are unaffected are considered cured. For
Cross-linked silicone example, certain acrylic, epoxy, or polyester coatings can
survive this test. The problem with this test is that the individ-
Silicones can also be cross-linked by peroxide initiators. In ual testing the coating is not standardized. One person may
this case a silicone monomer containing a vinyl or allyl group exert much more pressure than another, and this can affect
is copolymerized to provide an active site along the chain. the final result.
When used in a gasket or caulk, a small amount of a peroxide
is added which initiates polymerization and cross-links the
Hardness Measurements
resin system. Silicone reactions are usually catalyzed by 01"-
gano zinc or tin compounds. Another way of obtaining information concerning cross-
Curing can also be accomplished using radiation as a linking is to measure some physical property such as, hard-
www.iran-mavad.com

ness, scratch resistance, or impact resistance. There are a the quality of pencils. Someone suggested scratching a paint
number of tests which provide this information. film, and it was noticed that the different hardnesses of pen-
cils were able to penetrate through the coating. This test was
Knoop and Pfund Hardness (ASTM D 1474 Test later used by coating technologists, and it is widely used in
Methods for Indentation Hardness or Organic the industry today. In this technique a number of pencils with
Coatings) known hardnesses are employed. The pencil is t r i m m e d so
A useful test of cure is to measure the Knoop hardness in that 5 mm of lead is exposed. The lead diameter is 1.8 m m
which a pyramidal diamond indenter is pressed into the film and is sharpened by rubbing it perpendicular to the surface of
to cause indentation. The method is described in ASTM No. 400 carbide abrasive paper. The pencil is held at a 45 ~
D 1474. A weight is applied to the indenter for a specific time, angle to the coating and pushed along the surface to peel
and the length of the indentation line is measured with a away the coating. The pencil which fails to scratch the coat-
microscope. The Knoop hardness number (KHN) is calcu- ing is the value used as pencil hardness. This method is
lated from [8]: simple, the equipment low in cost, and the results can be
quickly obtained. However, values can differ depending upon
KHN = L/Ap = L/lZCp the operator, the method of sharpening the lead, and the
where L = applied load (kg), Ap = projected indentation area variances of lead hardness from different pencil lots and
(mm2), l = length in mm of the long diagonal of the indenta- manufacturers.
tion mark, and Cp is an instrument constant. Because of the
thinness of coating films, this method is more useful in plas- Gardner Impact (ASTM D 2794 Test Method for
tics since it requires almost a 75% indentation into the film Resistance of Organic Coatings to the Effects o f Rapid
and can be influenced by substrate considerations. Deformation (Impact))
The Pfund Hardness Number (PHN) is obtained using a This is a valuable test which measures the impact resist-
hemispherical quartz or sapphire indenter, which is pressed ance of a coating and can be used to correlate with cure. An
into the film. The Pfund Hardness Number is calculated undercured coating may exhibit a lower Gardner Impact
from: value, but as cross-linking density increases, the impact val-
PFN = L/A = 4L/wd2 = 1.27 L/d 2 ues improve. The test consists of placing a coated flat panel
under a weighted spherical ball assembly and then dropping
where the weighted ball onto the panel from different heights. The
L = applied load in kilograms, cylinder in which the ball assembly is mounted is calibrated
A = area of projected indentation in mm 2, and such that an operator can measure the impact directly in inch
d = diameter of the projected indentation in mm. pounds. Impact measurements are done by dropping the ball
directly on the coating surface or on the reverse side. The
Sward (See ASTM D 2134, Sward Rocker, and ASTM results are reported as inch-pounds direct or reverse. Direct
D 4366, Pendulum Damping) impact is less severe than reverse impact. A dimple is formed
Sward hardness depends upon the change in surface prop- in the test panel which can be examined visually or with a
erties and viscoelastic properties of a film. This method, X10 glass to determine the extent of cracking which occurs.
which was discontinued in 1990, is used for automotive fin- An appliance acrylic may have a direct impact of only 10
ishes and consists of a rocker containing two spirit bubble in.-lb, while a polyester urethane powder coating may have a
indicators. The pendulum is rocked, and the number of reverse impact of 160 in.-lb. The value of the Gardner Impact
swings are recorded and a reading taken at the point where test is that the test can be done quickly, it is widely recognized
the swings are equal to half the original value. Several types in the coatings industry, and it gives some correlation with
of pendulum units are used including Sward, Perzoz, and cross-link density in that the optimum physical properties of
Koenig. As cure increases, the Sward number increases. The a coating develop as the molecular weight increases.
value of a Sward test is that a n u m b e r is obtained which can
be compared to other coatings. This test must also be con-
ducted under very clean conditions, as lint and surface imper- Thermal Analysis
fections can interfere. Temperature control is important in Thermal analysis is an important analytical tool for deter-
this test as in other tests involving determining physical prop- mining the response of material to changes in temperatures.
erties of coatings. The problem with this test is that it only This method of analysis can be used to monitor the glass
measures cross-linking density to a point; then cannot detect transition temperature, Tg, of a coating, and this can be re-
over cure since a plot of Sward numbers versus cure tends to lated to the cross-linking density. For example, a ladder of
reach a limiting value. A comparison of values obtained by paint panels cured at various times or temperatures can be
different test methods is shown in Table 1 [9]. Note how the prepared and then studied by thermal analysis to determine
values differ, especially between different brands of pencils the change in Tg as a function of bake schedule. From this, the
and the limiting value of Sward Hardness. optimum cure cycle can be determined to insure a quality
finish.
Pencil (ASTM D 3363 Test Method for Film Hardness Thermal analysis units have several modes for determining
by Pencil Test) Te: differential scanning calorimetry (DSC), thermo-
Pencil hardness is a test which was developed by the manu- mechanical analysis (TMA), and dynamic mechanical analy-
facturers of pencils who tried to develop a means for checking sis (DMA) are useful tools for obtaining quantitative mea-
www.iran-mavad.com

CHAPTER 36--CURE: THE PROCESS AND ITS MEASUREMENT 413
TABLE l mHardness test correlation.

Pencil (Brands)
Panel No. KIlN Sward A B C D E
1 3.09 24 5B 6B 5B 6B 4B
2 4.33 28 4B 6B 6B 6B 4B
3 2.77 24 5B 6B 5B 4B 3B
4 2.61 22 3B 4B 5B 4B 3B
5 5.81 38 2B 2B 2B 2B HB
10 25.7 54 H H H H 2H
12 39.1 40 3H 2H 2H 4H 3H
14 40 8H 9H 7H 7H 9H
sures of cross-linking b y m e a s u r i n g Tg. The glass t r a n s i t i o n Impedance Measurements

t e m p e r a t u r e is a s e c o n d o r d e r t r a n s i t i o n t h a t r e p r e s e n t s a
t e m p e r a t u r e w h e r e segmental m o t i o n occurs along a p o l y m e r Myers [16] s t u d i e d the drying behavior of latex systems
c h a i n backbone, a n d it is a c c o m p a n i e d by a volume change. A using ultrasonic i m p e d a n c e m e a s u r e m e n t s , I n this work, a
c o m p a r a t i v e s t u d y of changes of cross-linking m e a s u r e d b y latex coating was cast on a quartz crystal a n d ultrasonic en-
S w a r d hardness, evaporative rate analysis, a n d DSC s h o w e d ergy was b e a m e d at an 11 ~ angle at the u n d e r s i d e of the
t h a t Tgchanges c a n be followed to high levels of cross-linking, coating a n d reflected to a d e t e c t o r w h i c h m e a s u r e d the atten-
w h e r e a s S w a r d m e a s u r e m e n t s r e a c h e d a limiting value while u a t i o n of the initial b e a m as a b s o r b e d by the drying coatings.
Tg c o n t i n u e d to rise [10]. As w a t e r evaporated, there were changes in i m p e d a n c e t h a t
W i t h DSC, a plot of e n d o t h e r m / e x o t h e r m is m a d e as a could be c o r r e l a t e d to drying.
function of t e m p e r a t u r e at a set rate of t e m p e r a t u r e rise. As
the Tg is reached, there is an a b r u p t change in the e n d o t h e r m
w h i c h a p p e a r s on a plot. Similarly, Tg can be m e a s u r e d using Evaporative Rate Analysis
a plot of c h a n g e in e x p a n s i o n with t e m p e r a t u r e with the TMA
mode. Here a s a m p l e is p l a c e d u n d e r a quartz p r o b e a n d t h e n A novel m e t h o d for studying cure is evaporative rate analy-
heated. As the film expands a plot is o b t a i n e d in w h i c h a sis (ERA) developed by John Anderson [17]. This w o r k was
change in slope occurs. The intersection of the tangents of the carried out to d e t e r m i n e the cleanliness of the surface of
e x p a n s i o n curve yields the Tgvalue. I n the p e n e t r a t i o n m o d e a spacecraft. Anderson r e a s o n e d that if a radioactive C 14 liquid
d e p r e s s i o n occurs indicating the Tg. Plots can be m a d e of Tg w o u l d be p l a c e d on a clean surface, the e v a p o r a t i o n rate
versus b a k e cycle to note the o p t i m u m Tgof a coating. F u r t h e r would be r e t a r d e d due to cleanliness. In fact, however, the
details on t h e r m a l analysis a p p l i c a t i o n s can be f o u n d in the opposite was true.
literature [11 - 13 ]. Nevertheless, this m e t h o d was developed to m e a s u r e de-
gree of cleanliness. If a small a m o u n t of diethyl succinate-C -14
Dynamic Mechanical Analysis is d e p o s i t e d on a surface a n d a controlled sweep of n i t r o g e n is
applied, the rate of e v a p o r a t i o n can be m o n i t o r e d using a
Another w a y of o b t a i n i n g Tg is to use d y n a m i c m e c h a n i c a l Geiger counter. The principle is that on a clean surface there
analysis in which a coating film is fixed to the ends of a tuning is no i n t e r a c t i o n between the solvent a n d the clean substrate,
fork a n d the fork driven over a frequency range a n d at differ- a n d n o r m a l e v a p o r a t i o n occurs. If, however, the surface con-
ent t e m p e r a t u r e s o r at a fixed frequency w i t h varying t e m p e r - tains a c o n t a m i n a n t , then the radioactive liquid will interact
ature to provide a plot of d a m p i n g versus t e m p e r a t u r e . This with the surface c o n t a m i n a n t a n d r e t a r d the rate of evapora-
i n f o r m a t i o n yields Tg as well as m e c h a n i c a l d a m p i n g infor- tion of the r a d i o c a r b o n . Plots c a n be o b t a i n e d relating clean-
m a t i o n a b o u t the film [14].
liness to e v a p o r a t i o n rate.
Anderson a p p l i e d this technique to the cure of organic
Torsion Pendulum [14,15] coatings. H e s h o w e d t h a t in an u n d e r c u r e d surface solvent
A n o t h e r m e t h o d for m e a s u r i n g d y n a m i c m e c h a n i c a l p r o p - r e t e n t i o n increased, leading to longer residence of the ra-
erties of coatings is to s u s p e n d the film with a weight, then d i o c a r b o n on an u n d e r c u r e d surface. This is u n d e r s t a n d a b l e
twist the weight so that it will oscillate as a p e n d u l u m . This is in view of the example given in the beginning of this c h a p t e r
not entirely acceptable since coating films m a y n o t have the of the ability of a solvent to pass t h r o u g h a wire fence anal-
strength to s u p p o r t the weight of the a p p a r a t u s . One way to ogy. By p r e p a r i n g c o a t e d panels having different cure times
o v e r c o m e this is to invert the a p p a r a t u s so that the p e n d u l u m o r t e m p e r a t u r e s , t h e n m e a s u r i n g the ERA of each panel, a
weight is s u s p e n d e d w i t h counterweights. A m o r e practical plot of r e t e n t i o n versus bake is obtained. This m e t h o d was
m e t h o d is to use the t o r s i o n b r a i d p e n d u l u m in w h i c h a a p p l i e d to the m e a s u r e m e n t of cure of a variety of coatings by
fiberglass b r a i d is s a t u r a t e d w i t h a coating a n d the p e n d u l u m m a n y coatings technologists [10,18]. The only p r o b l e m was
oscillated. As the coating cures, changes in oscillation can be t h a t there was no quantitative m e a n s for m e a s u r i n g the rela-
c o r r e l a t e d with d a m p i n g a n d Tg. tionship of ERA to cure until it was s h o w n that DSC of Tg
www.iran-mavad.com

could be correlated to the values obtained using ERA mea- [8] Paul, S., Surface Coatings, John Wiley & Sons, New York, 1985,
s u r e m e n t s [10]. p. 485.
[9] Sato, K., Progress in Organic Coatings, Vol. 8, No. 1, 1980.
[10] Miranda, T. J., Journal of Paint Technology, Vol. 43, No. 553,
REFERENCES 1971, p. 51.
[11] Seymour, R. B. and Carraher, C. E., Jr., Polymer Chemistry, An
[1] D'Alelio, G. F., Fundamental Principles of Polymerization, John Introduction, 3rd ed., Marcel Dekker, New York, 1992, p. 139.
Wiley & Sons, Inc., New York, 1952, pp. 5-22. [12] Stevens, M. P., Polymer Chemistry, An Introduction, 2nd ed.,
[2] Staudinger, H., Uber Polymerization, Vol. 53, 1920, pp. 1073- Oxford University Press, 1990, p. 167.
1085. [13] Miranda, T. J., Mechanical Behavior of Materials, Vol. III, The
[3] Mark, H. and Whitby, G. S., Eds., Collected Papers of Wallace
Society of Materials Science, Japan 1972, p. 392.
Hume Carothers on High Polymeric Substances, Interscience,
New York, 1940.
[14] Lambourne, R., Ed., Paint and Surface Coatings, Ellis Horwood
[4] Paul, S., Surface Coatings, Chapter 1, John Wiley & Sons, New Ltd., 1987, p. 607.
York, 1985. [15] Allcock, H. R. and Lampe, F. W., Contemporary Polymer Chem-
[5] Wicks, Z. W., Jr., Film Formation, Federation Series on Coatings /stry, 2nd ed., Prentice Hall, Englewood Cliffs, NJ, 1990, p. 427.
Technology, Blue Bell, PA, June 1986. [16] Myers, R. R., Journal of Polymer Science, C, Vol. 35, No. 3, 1971.
[6] Paul, S., Surface Coatings, John Wiley & Sons, New York, 1985, [17] Anderson, J. L., Root, D. E., and Green, G., Journal of Paint
pp. 452-453. Technology, Vol. 40, No. 320, 1968.
[7] Brown, W. H. and Miranda, T. J., Official Digest, Vol. 36, No. [18] Rossi, A. G. and Paolini, A., Journal of Paint Technology, Vol. 40,
475, 1964, p. 92. No. 328, 1968.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Film Preparation for Coating 37

Tests
by Robert D. Athey, Jr. 1
THE PERFORMANCEOF A COATINGFILMin a test is likely to be mance criterion. The preparation of the test film should thus
dependent on the physical form of the film. For instance, film correspond to the standard field application of the material,
thickness is an important factor in physical and appearance a s well.
measurements (until the coating gets too thick), so there Another portion of film influence on the test is film thick-
must be some control of the film thickness. Appearance is ness. The presentation by the Technical Committee from
also related to how smooth the film surface is, and care to Toronto in the 1990 National FSCT meeting and Paint Show
make the film appropriately will ensure that the appearance [1] dealt with hardness measurements in films of varying
measurements are germane to the end-use. The substrate thickness. However, the control of film thickness was not as
used as the carrier for the test film, even temporarily, may straightforward as might have been thought. Hardness values
affect the property measurements, as well. turned out to be dependent on film thickness along with other
The primary concern in making films for tests is that the equally important variables [2].
film prepared be homogeneous and consistent with previous Fluid rheology, concentration, and other factors govern the
or future films for the same test. The jargon of the trade calls amount of coating left after the application process. Knowing
the art of making films "casting," but many film formation the process variables associated with a film-casting technique
methods are used to form the film, and each method has its are essential to getting what is needed for the ultimate test
own set of advantages and drawbacks. and results therefrom. Certain other properties of the film
(opacity, permeability, erosion rate by some attacking mode,
etc.) will depend on the thickness of the film. So, understand-
ing thickness control in the casting process is crucial to
T E S T R E Q U I R E M E N T S OF F I L M S obtaining meaningful results in terms of meeting specifica-
tions in reproducibility.
Test requirements come in two classes, appearance and
In instances where fluid or gas permeation resistance or
physical properties. Choice of application method for the film
corrosion barrier properties are to be tested, a "pinhole,"
may affect the appearance in some cases. For instance, the
"holiday," or "mudcrack" in the film is a fatal flaw. The film
"multicolor" paints must be applied by dip or spray tech-
preparation technique must eliminate (as much as possible)
niques for laboratory testing, or the appearance does not give
any such fatal flaw, or the test method should prescribe what
the desired mottle of nearly circular spots. Roller, brush, or
is to be done (for example, replications) in cases where an
even drawdown bar will cause these spots to become streaks.
unseen fatal flaw is detected by the test.
Choice of application method for appearance includes drying
technique, as some films require special drying conditions to
attain their desired special appearance. Examples include
leafing aluminum flake "metallic" look paints, hammertones, FILM C A S T I N G T E C H N I Q U E S
and wrinkle finishes.
Choice of application method driven by physical property Free Films
testing is also necessary. Think carefully of the three kinds of Free films, that is, films not applied permanently to a sub-
stresses (tensile, compression, shear) and recognize that all strate, are used for a wide variety of tests and accordingly
are blended in a hardness or adhesion evaluation by indenter, vary in thickness and size. The most common castings of free
pencil, mandrel bend, or dart impact test on a coating. Recog- films are used for permeation or strength and elongation
nizing these stress combinations can make one aware of film testing. They can also be used for cold flex tests or moisture/
preparation needs. In cases where adhesion is stronger than solvent absorption studies related to permeation. Free film
cohesion of the film, one should be able to distinguish be- thickness can be measured as described in ASTM D 1005:
tween adhesive failure and cohesive failure. Film preparation Test Method for Measurement of Dry-Film Thickness of Or-
should not conflict with these objectives. ganic Coatings Using Micrometers.
The physical properties to be tested in specific ASTM meth- Probably the most common ~ee film castings are laid down
ods have a "significance and use" section in the method to on a "nonstick" surface, such as the silicone-coated papers
ascribe the relation of the test value to some "in use" perfor- (available through Leneta and other suppliers) or TEFLON TM
or polyethylene sheets. Release substrates are described in
~Athey Technologies, P.O. Drawer 7, E1 Cerrito, CA 94530-0007. ASTM D 823: Test Methods for Producing Films of Uniform
415
www.iran-mavad.com

Thickness of Paint, Varnish, and Related Products on Test For thicker films (1 cm or more), a PYREX TM or TEFLON TM
Panels. Lack of release-substrate wetting is the most common coated baking pan can be used with some success. For in-
problem encountered when trying to obtain a continuous stance, about 300 mL of a latex formulation in a 9 by 12 in.
film. Water-borne coatings are especially difficult to for- (23 to 30 cm) Pyrex TM baking dish will yield plenty of thick
mulate for good wetting of these substrates. One trick to use film for testing. Occasionally, there is a "mudcracking" prob-
with such formulations is to prepare the sample at higher lem, but it can be reduced periodically by releasing the edges
than normal solids content, which results in increased viscos- of the film from the vertical sides of the dish with a spatula to
ity, and resistance to beading is improved. An alternative is to allow uninhibited shrinkage. This way usually results in in-
apply several coats until the dried "beaded-up" portions creased size pieces, and 1 infl (6.25 cm 2) is all you need for
merge to form a continuous film. the moisture absorption or solvent swell test. Using this tech-
A vacuum plate makes it easier to hold down the paper or nique, it is possible to obtain large enough pieces for mois-
polymer film for film casting and is an aid to good results. ture vapor transmission tests at application thicknesses that
Figure I is a diagram of the vacuum plate formed from are common for roof coatings.
aluminum. Older versions had eyes at the bottom surface The "mudcracking" problem is serious for any coating. The
through which screws could affix the plate to a table top. If cause is the lack of "wet gel strength" to resist the tensile
this system is to be vacuum supplied from a sink faucet stresses within the shrinking membrane. Strictly speaking,
aspirator, a liquid trap (vacuum side-fitted Erlenmeyer flask) unless the coating cross-links, it is not a gel, but simply a
should be placed in line between the vacuum plate and the high-viscosity fluid or "pseudogel." The problem may be alle-
aspirator. This will ensure that any liquid coming from the viated by assuring that the upper surface does not "skin over"
aspirator will not get to the vacuum plate or coating sub- through controlling the humidity or solvent-vapor environ-
strate. ment over the drying surface.
Grenko [3] suggested several coated paper techniques for The literature describes mercury pool casting [7,8] or tin
obtaining free films, such as decal paper coated on the face foil casting [9] with mercury amalgamation used to remove
side or outdated matte or semimatte photopaper. The decal the tin without stressing the coating film. ASTM D 4708 Prac-
paper could be floated on water and the paper peeled off. tice for Preparation of Free Films of Organic Coatings also
Grenko did not describe the removal of photopapers from the describes the tin foil amalgamation technique. These tech-
film. He also cited Sager [4] for a technique using an embroi- niques are no longer in common use, as the mercury vapor is
dery hoop for holding a nonmoisture proof cellophane. After deemed a health hazard.
the coating film had been applied, one simply poured water Rarely, but occasionally, a free film of a polymer or binder
on the inverted cellophane and the coating film dropped off. material is needed for testing water vapor permeation or
These techniques are likely to be most appropriate for solvent absorption, for instance. Some of these tend to be tacky, and
borne or 100% reactive formulations. Water-borne coatings powder applied to the surface will make them easier to han-
may be inappropriately leached or weakened by the water dle. Although pearl cornstarch is preferred over the powdered
used to loosen and isolate the films. talcs, baby powders and similar talcum powders are often
Grenko [3] also mentioned the use of metal substrates for used.
free film isolation. Brightwell [5] used glass onto which a thin Rotational casting is a means of obtaining nonporous,
silver film had been vacuum deposited. Bayor and Kempf [6] nonmudcracked free films. The standard jar-mill roller (see
used thin aluminum foil that was later dissolved from most of Fig. 2) may be used with a variety of open containers (quart or
the back with hydrochloric acid doped with a minute amount gallon jars, earless paint cans with a 4-in. (10-cm) circle cut
of platinum chloride. The latter dissolved off only enough out of the bottom . . . . ) to centrifugally cast the film with good
aluminum foil to leave a foil "frame" at the edges of the film to thickness control. An alternative device, the Caframo REAX 2
support it and to facilitate handling. This technique with
aluminum foil dissolution in an acidic, aqueous medium pre-
sumes no sensitivity of the coating components to acid or
water.
FIG. 1 - V a c u u m plate---pulling a vacuum

through the side nozzle holds paper or paper- FIG. 2-Lab roller mill--Although this device is most often
board substrates tight for drawdown film used for pebble milling, an empty earless paint can on the
casting. (Courtesy P. N. Gardner Co.) rollers may be used to cast films. (Courtesy of Indco Inc.)
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CHAPTER 37--FILM PREPARATION FOR COATING TESTS 417
rotating mixer [10], may be used to hold the paint can with its als are "notch sensitive," that is, the results of a tensile or
main axis along the rotation axis of the clamp (see Fig. 3). other physical test may be reduced by the presence of a notch,
This rotational casting technique was used successfully in a scratch, or crack in the film [13].
study by the Los Angeles Society for Coating Technology
Technical Committee to obtain tensile and moisture vapor
permeation film samples from acrylic latex compounded with Dry Coatings on Substrates
silane modified talcs [II]. It is derived from an older practice
at the Thiokol Rubber Co. to form films of castable elasto- Test coatings on a substrate are generally applied for a wide
mers in a rolling pipe [12]. variety of appearance and physical property tests. Color and
Equipment for this technique is easy to set up and use. opacity are commonly evaluated on coated paper charts,
Introduce 100 mL of coating into a 1-gal can and let it roll though unsealed paper charts with a porous surface are avail-
overnight. This will result in a film approximately 6 by 18 in. able, as well. Coating on substrates to simulate actual use is
(15 by 46 cm). That is a sufficient amount for 6-in. (15-cm) common so the paint lab has many kinds of steel, aluminum,
tensile bars and 2-in. (5-cm) permeation circles. Close control wood, or other substrates in stock as needed by the customer
of film thickness is achieved by knowing the area of the or the paint company.
cylinder and concentration. From these, the weight of coating Plastic panels are rarer, but can be made available when
needed can be calculated. Films of tacky coatings or pressure- needed. Several companies now offer such products. Plastic
sensitive adhesive formulations can be made by this tech- panels may need special surface preparation techniques to
nique. After the film is formed, the can is placed in a refrigera- assure wetting and adhesion (solvent washes, chemical etchs
tor or freezer to facilitate film removal. with alkali or acid, low-temperature plasma, or corona dis-
To obtain a centrifugally cast powder coating film, a sam- charge or chemical oxidation, etc.). As painting plastics be-
ple of the powder is introduced into the can. Then, a hot air come more and more important for automotive, computer,
gun is held at the outside of the rolling can, and the powder sign, and other industries, the manufacturers will make pan-
coating will melt to coat the inside. Care is needed to elimi- els available to potential paint suppliers.
nate scorching, and practice is needed to determine how Panels of metal are a special case for the preparation of test
close the flame should be to the can to get a good film. Other films for paint. One may have to do a precoating surface
techniques to obtain a film include melting on a Teflon TM preparation on the metal, and consultation with appropriate
sheet on a hot plate or in between Teflon sheets in a heated specifying agencies may be necessary. The Steel Structures
(Carver, PHI . . . . ) press. Painting Council has many grades of hot-rolled steel prepara-
Spraying is occasionally used to make free films (e.g., onto tion techniques that vary from wire brushing through sand
a silicone-coated paper). There is no problem with this tech- blasting to expose "white metal" [14]. Other preparations
nique when it is done by a skilled practitioner. However, films such as phosphatizing, galvanizing, anodizing, etc., are
made with this technique may not give as good permeation unique to specific industries or industry segments and will
test results as from one made by a film from a fluid-flow require lab preparation of panels or freshly treated panels
technique. from the customer or a commercial source. An annual hand-
A note of caution should be added about handling free films book contains descriptions of some of these techniques for
made for physical testing. Any undue stresses may chip or lab usage [15]. Preordered steel panels that are subsequently
crack the film. This is especially important for permeation or stored in special corrosion-inhibitor-treated packaging may
physical property tests. In the case of the latter, some materi- skew exposure tests if they are not rigorously cleaned of
corrosion inhibitor just prior to the coating steps. Cleaning
procedures may require rinsing with hydrocarbon solvent or
acetone and hot-air drying just before paints are applied.
Exposure panels made of metal must also have special edge
protection to ensure that only the coated face has the expo-
sure test applied.
The casting technique on a paper or paperboard substrate
is a skill one learns through apprenticeship. First, the panel
needs to be clean and dust free. For horizontal castings,
which is a way to obtain good flat films, it is necessary to
ensure that the surface is level during casting and drying.
Tape the chart or panel to the level surface so it doesn't curl as
the film loses solvent or dispersing media and tries to shrink.
Unsealed paper charts will curl in a convex manner since any
water in the coating swells the paper fibers, and the substrate
may try to curl the sheet in a concave manner when the film
tries to shrink across the top surface from which evaporation
is taking place. Vacuum plates are available, as noted earlier,
to hold down the paper, foil, or cardboard chart during the
FIG. 3-Caframo "REAX 2"---This device was designed as a film-casting process. The paper board chart should be stored
rotational mixer for fluids, but a gallon paint can will fit in it for in the same humidity environment that will be used in drying/
rotational film casting, as well. (Courtesy of Caframo Ltd.) curing the coating as the wood-pulp fibers are hygroscopic.
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Concrete, plaster, a n d asphalt/gravel test blocks o r panels EQUIPMENT FOR FILM PREPARATION
m a y be p r e p a r e d in the lab o r m a y be p u r c h a s e d . However,
w h e n e v e r possible such blocks should be o b t a i n e d from the D r a w d o w n Bars
c u s t o m e r since paint-lab results m a y n o t c o m p a r e well w i t h
The d r a w d o w n b a r s are the simplest of the film casting
the c u s t o m e r ' s results if details such as porosity, surface
devices to use. One s i m p l y m a k e s a p u d d l e of coating on the
salinity, surface pH, soluble c a l c i u m o r s o d i u m ion content, desired s u b s t r a t e a n d moves the d r a w d o w n b a r over the pud-
etc., are not equivalent. These m a t e r i a l s m a y be hygroscopic dle to m a k e the d e s i r e d wet film thickness. Application of the
a n d will need equilibration in the drying/curing e n v i r o n m e n t film with a d r a w d o w n b a r n o m i n a l l y gives a g o o d c o n t i n u o u s
p r i o r to coating. I n addition, s o m e concrete castings, t h a t is, film, b u t the spacing b e t w e e n the b a r a n d the s u b s t r a t e m a y
tilt-up wall constructions, often have surface residues of f o r m have little to do with the film thickness obtained. S p e e d o f
coatings that h a d been u s e d to a i d release from the forms. pulling the d r a w d o w n b a r over the fluid will affect the film
Surface c h a r a c t e r i z a t i o n for such release aids o r rigorous thickness since fluid rheology influences film thickness. High-
cleaning m a y be needed. There is a n ASTM s t a n d a r d p r a c t i c e molecular-weight p o l y m e r s m a y cause the edges of the film to
for p r e p a r a t i o n of m o r t a r panels for testing paints: ASTM d r a w in a n d increase the wet-film thickness. The f o r m u l a t i o n
M e t h o d of Making a n d P r e p a r i n g Concrete a n d M a s o n r y m a y not wet the d r a w d o w n bar, a n d this a d d s a n o t h e r factor
Panels for Testing Paint Finishes (D 1734). to the control of film thickness. Wetz a n d coworkers [17]
Grenko [3] has d e s c r i b e d press coating of b i t u m e n s on s h o w e d a l m o s t 100% d e p o s i t i o n of the wet film a n d f o u n d a
a l u m i n u m o r felts, with shims p l a c e d in the press to a t t a i n r e l a t i o n s h i p b e t w e e n wet-film a n d dry-film thickness.
a p p r o p r i a t e thickness. His w o r k was b a s e d on earlier w o r k by
Greenfield [16]. Tel = 0.057 + 0.588GS(0~/Or), o r
Tdf = 0.057 + 0.955T~(og#r),
where:
Wet Films for Testing Tar = dry film thickness, mils
There are a variety of reasons one m a y w a n t to have a close Twf = wet film thickness, mils
look at the wet film. S i m p l y w a t c h i n g the drying process m a y Ot = density of liquid
m a k e a n y p r o b l e m s with m o i s t u r e c o n d e n s a t i o n on the film, 0f = density of dry film
G = clearance of d r a w d o w n bar(mils), a n d
p i g m e n t float, etc., apparent. There are test films m a d e to
S = weight fraction of solids in liquid.
assess wet hiding or sag resistance (ASTM D 4400: Test Meth-
ods for Sag Resistance of Paints Using a M u l t i n o t c h Applica- Grenko [3] m a k e s the p o i n t t h a t these relationships are only
tor). G o o d film casting practice, for example, a level surface true for d r a w d o w n blades having substantial flat surface be-
for casting, consistent technique, etc., is a r e q u i r e m e n t for tween the leading edge of the b a r and the trailing edge. The
r e p r o d u c i b i l i t y of results. E q u i p m e n t n e e d e d for special tests B y k - G a r d n e r i n f o r m a t i o n [18] suggests the following expec-
will be included in the following section. tations for varying film thicknesses cast:
TABLE l--Drawdown bars for film casting.

Type Design Details Suppliex~ Reference
"Bird" knife Permanent fixed gap P.N. Gardner [3]
Two-path applicator Bar has two cuts of P.N. Gardner [20]
(Wasag [11]) different depth
machined into top
and bottom
Eight-path applicator Stainless steel P.N. Gardner [20]
square tube with
eight different
depth cuts in each
of top and bottom
edges
Gardner "Microm" Micrometers on P.N. Gardner [20]
applicator (also each side lower or
Hercules-Gardner raise blade of "U"
adjustable [3]) shaped deviced
"Universal" blade Blade forms "U" P.N. Gardner [20]
applicator shape with sides
having slots and
thumb screws to
raise or lower
Dow latex film "U" shaped blade Byk-Gardner [3]
applicator with wider cut for
larger gap so
second cast film
covers first
aThere may be many other suppliers, but only one is cited herein as a space savings technique.
www.iran-mavad.com

15 to 100/xm 50%
100 to 300 txm 60%
300 to 500 txm 80%
over 500/~m 90%
The hand-held drawdown bars are covered in an ASTM speci-

fication: Method E in ASTM D 832, Practice for Rubber
Conditioning for Low-Temperature Testing.
A wide variety of drawdown bars are commercially avail-
able, though your local machine shop can make special or-
ders of any design, if needed. Table 1 lists a few of the
available types of drawdown bars, with commercial sources FIG. 6-Film casting knife--Micrometers adjust the
blade clearance. (Courtesy of Byk-Gardner Inc.)
reports on them. Some rectangular design devices have dif-
fering gap depths on the sides so one may choose the film
thickness needed for casting (see Figs. 4 and 5). Several drawdown bars have gradations of cuts into the
Stainless steel or aluminum are the preferred materials of wet-film thickness controlling surfaces. For instance, the
construction, as corrosion can damage the region of the Erichsen suppliers offer the Kruse Multi Clearance applica-
drawbar controlling thickness of applied film. Good labora- tor, having six to ten adjacent film strips of 10 to 200/zm in
tory practice dictates immediate cleaning of the paint contact thickness for assessment of color yield, opacity . . . . (see Fig.
surfaces after every usage to minimize the threat of corrosion 7) [19]. A similar device, the Leneta TG19 Logicator, is in-
or other damage. A caution on marking the drawdown bars, tended for hiding power and spreading rate measurements. It
as some manufacturers label them not with the gap spacing, is available from P. N. Gardner [20] and has eight "gates"
but a number half the gap spacing since that is the expected ranging from 2.65 to 10.4 rail in depth.
wet film thickness to be obtained. There are motorized film application devices specified in
ASTM D 823, Test Methods for Producing Films of Uniform
Some drawdown bars have film thickness adjustment
Thickness of Paint, Varnish, and Related Products on Test
choices by micrometers or other techniques (see Table 1 and
Panels, as Method C. The Model 509/1 Film Applicator from
Fig. 6). When these are used, the settings should be checked
Erichsen [19] may be fitted with any sort of drawdown bar or
with feeler gages to make certain user wear has not made
blade (see Fig. 8). Speed of the motion of the applicator may
them inaccurate. These also require dismantling and clean-
be preset, so the variation among several samples may be
ing after every use. If oil is used to inhibit corrosion and make
minimized.
the mechanics move smoothly, make sure they are rigorously
Two devices Grenko [3] included with drawdown bars are
cleaned of oil prior to usage.
more like bulk coating devices as they do not require putting
down a puddle of coating before applying the blade. Indeed,
these devices contain the coating and apply it to a stack of
FIG. 4-Applicator frame~step gap appli-

cator-Two film thickness choices are
available with this device. (Courtesy of
Byk-Gardner Inc.)
FIG. 5-Multiple clearance applica-

tor-Eight film thickness choices are FIG. 7-Multiple gap drawdown bar--Six or eight gaps
available on one device. (Courtesy of are machined along the same edge for casting side-by-side
Byk-Gardner Inc.) films for comparison. (Courtesy of Erichsen GMBH & Co.)
www.iran-mavad.com

FIG. 9-Pfund crytometernThe white

style shown is for black/dark paints, while
a similar black style is used for white/light
paints. (Courtesy of Byk-Gardner Inc.)
with a wide space between each set of double slots [21]. Their
slots are 1, 2, 4, 8 and 16 rail in depth (see Fig. 10).
FIG. 8-Electrically driven drawdown device--Four speeds As paint film drip or sag depends on the rheological charac-
may be chosen to control drawdown rate. (Courtesy of Erichsen teristics, the thickness of the coating that first sags may be
GMBH & Co.) related to the gravity-applied shear stress by the outer ele-
ments furthest away from the substrate on that film. Other
rheological factors (high shear viscosity, ca. 10 000 s-1, for
sheets, one sheet at a time as the sheets are pulled out from
underneath the device. One such device is the Parks Film-O- instance) are also important in sag and leveling. Sag test
Graph cylinder. One puts the cylinder on a stack of Leneta devices complying with ASTM D 3730, Guide for Testing
charts or metal panels, fills the cylinder with the coating, and High-Performance Interior Architectural Wall Coatings, and
several federal specifications and the New York leveling test
pulls each sheet from underneath the cylinder. A portion of
the rim edge of the cylinder is milled out to act as the gate to blades are available from P.N. Gardner [20] and Byk-
allow coating at a desired thickness. One may even use it for Gardner [18].
very viscous coatings (even putty) by forcing the fluid through
the tube with a loose-fitting plug from the top and wiping the Wire-Wound R o d s
bottom of the tube over the substrate to be coated.
The second of the devices discussed was the Parks Rapid For very thin films, the wire-wound rods are quite useful
coater. Paper sheets were stacked in the bottom of a box with for quickly and easily applying films. The wire-wound rods
their ends out of a side slot at the bottom. The box was then are simple rods of 12 or 16-in. (30 to 40-cm) length, of I/4, 3/8,
filled with coating fluid, and each sheet was withdrawn indi- or 1/2 in. (0.63, 0.45, or 1.27 cm) diameter, with a sprial wind
vidually. Grenko [3] noted this was not a precision device, but of wire tight about 75 to 80% of the rod. Table 2 shows a
it was adequate for some purposes. selection of wet film thicknesses obtained from the rods with
Grenko [3] also described the flat Parks Film-O-Graph, different wire diameter.
which used a flat plate with spring clips to hold shims along The film laid down with a wire-wound rod is almost exactly
the sides of the sheet of substrate. One poured the coating a tenth the thickness of the wire winding. Strictly speaking, as
onto the substrate between the shims and used a bar such as a the film has the rod depart, there are ridges in the film in the
ruler or other straight edge to doctor off the excess and make direction of travel of the rod. However, these collapse to make
the coating as thick as the shims. Bending of the scraper bar a quite smooth film unless there is rheological inhibition in
by the very slightest amount would make very thin films the formulation or the coating is very fast drying. This tech-
almost impossible, but for thick films (for example, roof coat- nique is quite effective to simulate paper or can coating end
ings), this technique worked well. products. There are industrial production systems that era-
Some applicators are meant only for the wet film tests. Two
especially useful applicators for these are the sag test devices
and the wet hiding test devices. The latter, most frequently
the Pfund Cryptometers (available from Erichsen [19] and
Byk-Gardner [20]), have black or white glass (ceramic) beds
over which a transparent wedged cover levels the coating film
(see Fig. 9). Although these devices are quite hard, care in
cleaning will assure they do not get scratched. They must be
stored carefully, wrapped, and covered.
The sag test film casters essentially drawdown several nar-
row films in gradations of film thickness. Many are simply
slotted U-shaped drawdown bars with variations in slot depth FIG. l O - N e w York paint club leveling
from 1 to 6 mil, 3 to 12 mil, and 14 to 60 mil. However, the test blade--The slotted blades are for as-
New York Paint Club Technical Committee designed a spe- sessment of sag and leveling. (Courtesy
cial "leveling test blade" that had double slots for each depth of Byk-Gardner Inc.)
www.iran-mavad.com

TABLE 2--Selected coating thicknesses from wire wound rods. Spray Outs
Wire Wet Film Thickness S p r a y application, including b y weight on a panel h a n g i n g
Size Diameter (in.) Mils Micrometers on a b a l a n c e in a spray booth, can be done with good preci-
2.5 0.0025 0.25 6.4 sion. Good s p r a y out a p p l i c a t i o n on panels can be done by
3 0.003 0.3 7.6 those skilled in the art. To control the weight a p p l i e d in a
3.5 0.0035 0.35 8.9 s p r a y booth, a triple b e a m b a l a n c e m a y be a t t a c h e d to a b e a m
4 0.004 0.4 10.2
4.5 0.0045 0.45 11.4 5 o r 6 ft. (1.5 o r 1.8 m) above the floor, a n d a hanger-wire
5 0.005 0.5 12.7 panel h o l d e r is h u n g from it as the s p r a y target. A c a r d b o a r d
5.5 0.0055 0.55 14.0 shield over the b a l a n c e will keep off overspray. Tare the bal-
6 0.006 0.6 15.2 ance a n d p r e s e t weight n e e d e d to apply. Take off a few tenths
10 0.01 1.0 25.4 of a g r a m to give a p o i n t e r i n d i c a t o r w a r n i n g w h e n the s p r a y
20 0.02 2.0 50.8
30 0.03 3.0 76.2 has a l m o s t r e a c h e d the desired weight. S p r a y quickly to mini-
40 0.04 4.0 101.6 mize evaporation.
50 0.05 5.0 127.0 There are a u t o m a t e d s p r a y devices. Grenko [3] related the
60 0.06 6.0 152.4 a u t o m a t e d spray device design from Bell Labs [23] to M e t h o d
70 0.07 7.0 177.8
80 0.08 8.0 203.2 A of ASTM D 823. The Bell Labs design has the gun travel
90 0.09 9.0 228.6 over s t a t i o n a r y panels, while an alternative design has the
panels on a moving belt u n d e r a s t a t i o n a r y s p r a y gun, s i m i l a r
to a design r e p o r t e d from Battelle [24]. I n either case, the
ploy w i r e - w o u n d rods to m e t e r coatings onto roll substrates, a m o u n t of coating a p p l i e d to the panel is controlled by the
as well. speed of the moving belt a n d by nonvolatile content of the
s p r a y e d fluid. G r e n k o [3] notes the s a m p l e panels on the
A s i m i l a r device called the "spiral-film applicator" is avail-
moving belt m a y be held to the belt with m a g n e t s or suction
able from E r i c h s e n [19]. It is a w i r e - w o u n d r o d with a perpen-
cups. Erichsen [19], G a r d n e r [20], a n d others offer auto-
dicular h a n d l e (see Fig. 11). It is available to apply film
m a t e d spray a p p l i c a t o r s for lab s a m p l e p r e p a r a t i o n (see Figs.
thicknesses from 10 to 2 0 0 / ~ m in widths of 80, 150, or
12 a n d 13).
220 ram. B y k - G a r d n e r offers a handle that attaches to the
The s p r a y technique is p a r t i c u l a r l y i m p o r t a n t , b u t p r e c a u -
ends of the w i r e - w o u n d r o d for lab film p r e p a r a t i o n as well
tions are necessary to assure evenness of coating on the
[18]. The Accu-Lab TM Lab D r a w d o w n Machine has a r o d substrate. The spray p a t t e r n should extend b e y o n d the edges
h o l d e r a n d s u b s t r a t e h o l d e r to assure precision in l a b o r a t o r y of the substrate w h e n the nozzle is a i m e d at the center of the
m a n u a l film p r e p a r a t i o n [22]. target. The s p r a y p a t t e r n - - b e it flat, fan, o r c i r c u l a r - - h a s less
There are also two-wire rods in w h i c h a second, smaller p a i n t at the edges t h a n at the center. Moving the s p r a y nozzle
wire is w o u n d in the grooves m a d e b y the first w i n d i n g wire. across the target or the target u n d e r the center of the nozzle
These yield h i g h e r a p p l i c a t i o n rates t h a n do the single-wound m a k e s the d e p o s i t i o n m o r e likely to be consistent in thick-
wire rods. There is potentially an advantage to the two-wire ness.
rods sincc they leave a different p a t t e r n in the coating. The
ridges left are larger a n d m a y level faster a n d uniformly.
Dip Coating
Dip coating is p a r t i c u l a r l y i m p o r t a n t in s o m e special cases.
F o r instance, the edge p r o t e c t i o n of c o r r o d i b l e panels in
p r e p a r a t i o n for the a p p l i c a t i o n of a test coating is a c o m m o n
practice. The Golden Gate Society for Coatings Technology
Technical C o m m i t t e e use a red lead vinyl 1/2-in. (1.27-cm) dip
for edge p r o t e c t i o n of their exposure panels quite success-
fully, as a t t a c k c o r r o d e d only the desired exposure surfaces
[25]. The p o i n t is that d i p p i n g assures film thickness w i t h o u t
holidays t h a t o t h e r techniques do not. This is p a r t i c u l a r l y
true for o d d - s h a p e d test specimens such as fragments of a
p r e s s u r i z e d gas cylinder in an u n p u b l i s h e d Mellon Institute
c o r r o s i o n study.
Grenko [3] briefly reviewed two-dip coaters. Bruins [26]
first designed one using a tire p u m p a n d needle valve to
control the rate of panel w i t h d r a w a l from the coating, while
Payne designed an electric m o t o r - d r i v e n device a d o p t e d for
ASTM D 823 M e t h o d B. A c o m m e r c i a l lab device is available
from P. N. G a r d n e r [20], with variable w i t h d r a w a l speeds at 2
FIG. 11-Spiral wire drawdown applicator--The handle to 20 in. (5 to 50 cm) p e r minute. It c a n d i p a p a n e l of up to
shown grips the end of the wire-wound rod for application with 2 lb (0.9 ks) a n d 1 ft 2 (0.3 m) in a r e a (12 by 12 in. (3.65 by
one hand. (Courtesy of Erichsen GMBH & Co.) 3.65 cm).
www.iran-mavad.com

Again, care must be taken while dip coating. Film thickness

control is a battle between wetting surface forces and the
shear forces of drainage through the thickness of the film.
Drip edges on the bottom edge may be avoided to some
degree by having the panel holder inverted to hold the bottom
edge upward for a portion (or intermittent portions) of the
drying period.
Spin Coating
Grenko [3] described the work of Walker and Thompson
[27] attaching a panel to a turntable and rotating for I min at
300 rpm to obtain a 25-/zm varnish film thickness. He also
described the Sward-Gardner [28] relation of film thickness
(F) to viscosity (V, in poise) and nonvolatiles, % N, as
F = O . 4 N + V4 + 3
where spin rate was 290 rpm for 60 s. Their work had a
precision of 5 to 10%, and corrections for time or rpm varia-
tions were offered. Parker and Siddle [29] suggested modify-
ing the method by adjusting viscosity to equivalence for all
fluids to be compared and using volume solids rather than
weight percent nonvolatiles. Plots of film thickness versus
volume percent nonvolatile were straight lines for non-
thixotropic fluids, but curvature existed for thixotropic fluids.
A commercial lab spin coating device is currently available
from Erichsen [19]. There are two versions, one with 600 rpm
speed set, and another adjustable from 50 to 2000 rpm (see
Fig. 14).
FIG. 12-Single setting lab spray applicator,
(Courtesy of Erichsen GMBH & Co.)
O T H E R TIPS ON PRACTICE OF THE ART
Dust is always a problem, especially in formulation labs

that have pigment dusting in the lab and plant. Cover cast
FIG. 13-Programmable lab spray applicator. (Courtesy FIG. 14-Lab spin coating device. (Courtesy of Erichsen
of Erichsen GMBH & Co,) GMBH & Co.)
www.iran-mavad.com

films immediately to keep the dust off. The easiest cover is the [8] Gloor, W. E., "Effect of Heat and Light on Nitrocellulose Films,"
top of a box from a typewriter paper or file folder s h i p m e n t Industrial and Engineering Chemistry, IECHA, Vol. 23, 1931, p.
container. Simply cut out 1/2 in. (or 1 cm) strip from two, 980.
[9] Long, J. S., Egge, W. S., and Wetterau, P. C., "Action of Heat
three, or four sides for free flow of air. Of course, a similar
and Blowing on Linseed and Perilla Oils and Glycerides Derived
cover can be made from this plywood. Keep the cover o n top from Them," Official Digest, Federation of Paint and Varnish
of the lab refrigerator or book shelf so it's always at hand. Clubs, ODFPA, Vol. 19, 1927, p. 30.
Make sure the film is drying u n d e r appropriate tempera- [10] Caframo Lab Products, P.O. Box 70, Wiarton, Ontario, Canada
ture a n d h u m i d i t y conditions. S o m e t h i n g in the f o r m u l a t i o n NOH 2TO (519-534-1080).
m a y respond i n a n adverse m a n n e r to c o n d e n s i n g m o i s t u r e [11] Athey, R. D., Jr. et al., "Latex Coating Formulation Evaluation
that can form droplets o n the surface as evaporating solvent of Organosilane Treated Talcs: A Statistically Designed Study--
rapidly cools the system. I n moisture-cure a n d reactive two- Part II. Experiment Design and Test Results," Journal of Wa-
package urethanes, the c o n d e n s i n g moisture m a y react with terborne Coatings, Vol. 8, No. 2, May 1985, p. 10.
[12] DePugh, C. C., private communication.
the isocyanates to modify degree of cure, which c a n reduce
[13] Takano, M. and Nielsen, L. E., "The Notch Sensitivity of Sensi-
strength, solvent resistance, etc. In systems that do not react tive Materials," Journal of Applied Polymer Science, Vol. 21, 1976,
with the c o n d e n s i n g water, one m a y still get pits, pinholes, or p. 2193.
haziness from the c o n d e n s i n g water droplets o n the surface. [14] Steel Structures Painting Manual, Systems and Specifications,
Paint applicators are learning to pay a t t e n t i o n to h u m i d i t y Vol. 2, Steel Structures Painting Council, 4400 Fifth Ave., Pitts-
variation a n d its effects o n the end p r o d u c t surface. burgh, PA 15213.
[15] Metal Finishing Guidebook and Directory Issue, M. Murphy, Ed.,
Elsevier Publishing, 3 University Plaza, Hackensack, NJ.
[16] Greenfield, S. H., "A Method of Preparing Uniform Films of Bi-
tuminous Materials," ASTM Bulletin, American Society for Test-
CONCLUSION
ing and Materials, No. 193, October 1953, p. 30.
[17] Wetz, J. M,, Golding, B,, and Case, L.C., "Film Thickness
How the film is prepared for testing can have a d r a m a t i c Relationships of Organic Coatings," Official Digest, Federation of
effect o n the test results. The thought p u t into film prepara- Paint and Varnish Production Clubs, ODFPA, Vol. 31, 1959, p.
tion prior to p r e p a r a t i o n a n d the care used in casting can he 419.
crucial factors in o b t a i n i n g m e a n i n g f u l a n d reproducible re- [18] Instruments Catalog '91, Section 8, Byk-Gardner Inc., 2435
sults. Linden Lane, Silver Spring, MD 20910 (301-589-9044).
[19] Erichsen, T. J. Bell, 1340 Home Ave., Akron, OH 44310 (216-
633-3644).
[20] P. N. Gardner Co. Inc., 316 N. E. 1st St., Pompano Beach, FL
33061-6688 (800-762-2478).
REFERENCES
[21] Industry Tech, 188 Scarlet Boulevard, Oldsmar, FL 34677 (813-
855-5054).
[1] Toronto Society for Coatings Technology Technical Committee
[22] New York Paint Club Technical Committee, Official Digest, Vol.
presentation, 1990 National Paint Show Voss/APJ Competition 32, No. 430, 1960, p. 1435.
presentation, available from the Federation of Societies for [23] Arlt, H. G., "Paint Films of Controlled Thickness," Bell Laborato-
Coatings Technology, 492 Norristown Rd., Blue Bell, PA 19422- ries Record, Vol. XIV, 1936, p. 216.
2350. [24] Mueller, E. R., "A Simple Semi-automatic Laboratory Spraying
[2] Athey, R. D., Jr., "Coating Tests--Hardness of the Film," Euro- Device," Products Finishing, PRFIA, Vol. 15, No. 2, 1950, pp. 36,
pean Coatings Journal, Vol. 92, No. 10, December 1992, p. 461. 38.
[3] Grenko, C., "Preparation of Films for Test," ASTM STP 500, [25] Golden Gate Society for Coatings Technology, "Corrosion Inhi-
Paint Testing Manual, G. G. Sward, Ed., American Society for bitive Performance of Some Commercial Water-Reducible Non-
Testing and Materials, Philadelphia, 1972. Toxic Primers," Journal of Coatings Technology, Vol. 53, No. 682,
[4] Sager, T. P., "The Preparation of Thin Films," Industrial and November 1981, p. 29.
Engineering Chemistry, Analytical Edition, IENAA, Vol. 9, 1937, [26] Bruins, P. F., "Production of Uniform Test Films of Shellac and
p. 156. Other Finishes," Industrial and Engineering Chemistry, Analyti-
[5] Brightwell, E.P., "An Optical Method for Measuring Film cal Edition, IENAA, Vol. 9, 1937, p. 376.
Thickness of Paint Films," Official Digest, Federation of Paint and [27] Walker, P. H. and Thompson, J. G., "Some Physical Properties
Varnish Clubs, ODPFA, Vol. 28, 1956, p. 412. of Paints," Proceedings, American Society for Testing and Materi-
[6] Bayor, E. H. and Kempf, L., "Preparing Fragile Paint and Var- als, ASTEA, Vol. 22, Part II, 1922, p. 465.
nish Films," Industrial and Engineering Chemistry, Analytical [28] Sward, G. G. and Gradner, H. A., "Uniform Varnish Films for
Edition, Vol. 9, 1937, p. 49. Exposure Tests," Industrial and Engineering Chemistry, INCHA,
[7] Clarke, G. L. and Tschentke, H. L., "Physicochemical Studies on Vol. 19, 1927, p. 363.
the Mechanism of Drying of Linseed Oil. 1. Changes in Density [29] Parker, R. C. and Siddle, F. J., "The Hardness of Paint, Varnish
of Films," Industrial and Engineering Chemistry, IECHA, Vol. 21, and Lacquer Films," Journal, Oil and Colour Chemists Associa-
1929, p. 621. tion, JOCCA, Vol. 21, 1938, p. 363.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Measurement of Film 38
Thickness
by C. M. Wenzler 1 and J. F. Fletcher I
O N E OF T H E MAJOR R E Q U I R E M E N T S OF PAINT a n d coating testing the i n n e r wheel is referenced to the scale on the o u t e r wheel
is the m e a s u r e m e n t a n d control of film thickness. E n s u r i n g a n d the value noted,
that a specification is achieved is i m p o r t a n t in l a b o r a t o r y Starting from m a x i m u m value avoids the possibility of
tests, p a i n t application, a u t o m a t i c spraying, a n d o t h e r coat- p u s h i n g p a i n t a h e a d of the i n n e r disk, creating an e r r o r
ing a p p l i c a t i o n methods. c o n d i t i o n w h e n the gage indicates a value h i g h e r t h a n the
A n u m b e r of test m e t h o d s are available, a n d the choice is true wet film thickness.
d e p e n d e n t on: (1) the l o c a t i o n - - l a b o r a t o r y o r site; (2) the A n u m b e r of ranges are available.
m a t e r i a l c o a t e d - - m e t a l (ferrous o r nonferrous), wood, plas-
ter, b r i c k a n d plastic; (3) the c o n d i t i o n of the c o a t i n g - - w e t o r
dry; a n d (4) the c o n d i t i o n of the s u r f a c e - - r o u g h or smooth,
flat o r shaped, thick or thin, etc. Pfund Wet Film Gage
As s h o w n in Fig. 2, this gage consists of a convex lens, L,
whose r a d i u s of curvature is 250 m m , at the l o w e r e n d of t u b e
WET FILM THICKNESS T1 t h a t slides in the o u t e r t u b e T2. C o m p r e s s i o n springs, S,
keep the lens out of contact with the p a i n t film until p r e s s u r e
The m e a s u r e m e n t of wet film thickness provides the first is a p p l i e d on tube T1. In m a k i n g a m e a s u r e m e n t , the gage is
o p p o r t u n i t y to check the coating a n d its a p p l i c a t i o n process. p l a c e d on the p a i n t e d surface a n d the lens is p u s h e d slowly
It also offers an a s s e s s m e n t of the s p r e a d i n g rate w h e n a p a i n t t h r o u g h the film until s t o p p e d by the substrate. The p r e s s u r e
is applied. It is very i m p o r t a n t that wet film m e a s u r e m e n t s is released, a n d the d i a m e t e r of the spot of p a i n t t r a n s f e r r e d
are m a d e as soon as the coating is a p p l i e d to avoid e r r o r due to the lens is m e a s u r e d . A 1 to 1 ratio for the thickness a d d e d
to solvent loss d u r i n g the curing process. by the p a i n t d i s p l a c e d b y the lens to the actual thickness has
Reference to the technical d a t a for v o l u m e solids in the been a s s u m e d a n d is a c c o u n t e d for in the e q u a t i o n
coating is r e q u i r e d to establish the wet a n d d r y ratio so that
wet film thickness values can be converted to d r y film equiva- t = D2/16R (1)
lents. I n m o s t cases wet film thickness gages can be cleaned
with solvents a n d reused. where
ASTM Test Methods for M e a s u r e m e n t of W e t Film Thick-
ness of Organic Coatings (D 1212) s t a n d a r d i z e s the I n m o n t D = diameter, m m , of spot, a n d
wet film gage (formally k n o w n as I n t e r c h e m i c a l a n d com- R = r a d i u s of curvature, m m , of the lens.
m o n l y k n o w n as the wet film wheel) a n d the Pfund wet film
gage. These two gages are detailed in the following sections, Table 1 gives film thickness a n d the c o r r e s p o n d i n g spread-
a n d two n o n s t a n d a r d i z e d m e t h o d s are also described. ing rate in square feet p e r gallon for spots from 3 to 38 m m in
diameter.
It has been observed that a substantial p r o p o r t i o n of p a i n t s
Inmont Wet Film Gage (Wet Film Wheel)
do n o t obey the 1 to 1 relationship. The actual thickness,
The I n m o n t wet film gage consists of two concentric o u t e r o b t a i n e d by i n d e p e n d e n t methods, m a y be several times, o r
disks with an inner eccentric disk with a s m a l l e r d i a m e t e r only a fraction of, the thickness calculated b y the equation. A
p o s i t i o n e d b e t w e e n t h e m as s h o w n in Fig. 1. The o u t e r disks small a m o u n t of t h i n n e r a d d e d to a p a i n t m a y increase t h e
are scaled, with the clearance between the i n n e r disk and the d i a m e t e r of the spot on the lens a n d give a c o r r e s p o n d i n g
o u t e r disk from zero to a m a x i m u m value as shown. increase in the calculated thickness. This p h e n o m e n o n has
The gate is used as follows. The disks are p l a c e d with the been a s c r i b e d to the effects of surface tension. Hence, for b e s t
m a x i m u m clearance on the s p e c i m e n of coating a n d rolled results, a correction factor should be established for each
t o w a r d the m i n i m u m clearance in either direction. The p a i n t type of p a i n t b a s e d on the k n o w n thickness of a freshly pre-
will coat the i n n e r disk until the clearance is greater t h a n the p a r e d film m e a s u r e d b y the I n m o n t gage.
wet film thickness. The p o i n t at w h i c h the coating stops on R e p r o d u c i b i l i t y is within a b o u t 2% for films 2 mils ( 5 0 / z m )
thick, decreasing to a b o u t 10% for films 5 mils (125/zm)
1Elcometer Instruments, Ltd., Manchester, England. thick, then b e c o m i n g better as thickness increases.
424
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CHAPTER 3 8 - - M E A S U R E M E N T OF FILM THICKNESS 425
ECCENTRICINNERWHEEL
WETF~M I . . . .
FIG. 1-1nmont gage (Interchemieall wet film wheel(left) and 120 photo(right).
Notch Gages (Wet Film Comb) vent-resistant ABS plastic, should only be used once as the
solvent in the coating may soften the plastic. Plastic combs
Notch gages are formed on the edge of a piece of material
can be tagged and kept as a permanent record of wet film
so that each notch has a different clearance from the refer-
measurement.
ence shoulders to its neighbors (Fig. 3). Many different mate-
Aluminum combs are prone to wear, and the condition of
rials are used, such as stainless steel, aluminum, and plastic the gage should be monitored before use.
in a variety of shapes: square, rectangle, triangle, hexagon, Gages are available in many ranges, from 0.5 rail (2.5/xm)
etc. It should be noted that combs made of aluminum are to 160 mils (4 mm/4000 /xm) (for high-build, low-solvent-
known to wear on rough surfaces. It is a simple low-cost content coatings). The teeth are normally square ended, but
device which is useful when approximate values are satisfac- for thicker coatings pointed teeth are often used.
tory as the notches have discreet values and are not continu- Notch gages are supplied by various coating equipment
ous. The gage is dipped vertically into the film until the suppliers, e.g., Nordson, Elcometer Inc. and are described in
reference shoulders are resting firmly on the substrate. The ASTM Practice for Measurement of Wet Film Thickness of
thickness of the film is between the highest coated notch face Organic Coatings by Notched Gages (D 4414).
and the next highest notch value.
Several different methods of manufacture of these gages
exist from spark-eroded stainless steel precision combs, Needle Micrometer
through punched aluminum sheet, to plastic flow molded This method was used to study the relationship between
combs. The stainless steel combs can be certified with mea- the clearance of a doctor blade and the thickness of the wet
surements of the tooth displacements, which are traceable to film left by the blade [1]. A needle is attached vertically to the
national standards. As the stainless steel is hard wearing, this objective holder of a microscope. The barrel is lowered until
certificate can be valid over a period of up to one year. On the the needle just touches the film that has been spread on a
other hand, plastic combs, although manufactured from sol- plain metal panel. The contact is observed through a horizon-
A r 8
r,
FIG. 2-Pfundgage(left) and photo(right). (Figuretakenfrompreviousedition

of this manual,)
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TABLE 1--Spreading rate by Pfund film gage. then be r e m e a s u r e d after removing the coating with a scraper
Diameter or solvent. The coating thickness is then the difference be-
Thickness
of Spot, tween the two m e a s u r e m e n t s .
mm mm Mils Ft/Gal ASTM Test Method for M e a s u r e m e n t of Dry-Film Thick-
3 0.002 25 0.089 18 088 ness of Organic Coatings (D 1005) details a preferred
4 0.004 00 0.157 10 175 procedure using a dial m i c r o m e t e r m o u n t e d o n a support
5 0.006 25 0.246 6 512 with a clamp to hold the specimen (see Fig. 4). This m e t h o d is
6 0.009 00 0.354 4 522
7 0.012 25 0.482 3 321 r e c o m m e n d e d only for thicknesses over 0.5 mil a n d is accu-
8 0.016 00 0.630 2 543 rate _+0. I mil.
9 0.020 25 0.805 2 009 A hand-held dial gage, the Elcometer Model 126 (Fig. 5),
10 0.025 00 0.985 1 628 m a y be used. I n this case the dial records the difference i n
11 0.030 25 1.19 1 345
12 0.036 00 1.42 1 130 position between the foot that sits o n the surface of the coat-
13 0.042 25 1.66 963 ing a n d the stylus with its ball end, which passes through a
14 0.049 00 1.93 830 hole prepared in the coating to the surface of the substrate.
15 0.056 25 2.21 723 This is particularly useful for site work. However, for best
16 0.064 00 2.52 636
17 0.072 25 2.84 563 accuracy a n d precision, the firmly m o u n t e d dial gage speci-
18 0.081 00 3.19 502 fied in ASTM Method D 1005 is preferred.
19 0.090 25 3.55 450
20 0.100 00 3.94 407
21 0.110 25 4.34 369 Gardner Needle Thickness Gage
22 0.121 00 4.76 336
23 0.132 25 5.20 307 This i n s t r u m e n t is designed to m e a s u r e the thickness of
24 0.144 00 5.67 282 electrically n o n c o n d u c t i n g films o n metal (conducting) sub-
25 0.156 25 6.15 260 strates. It is small e n o u g h to be used i n the field where the
26 0.169 00 6.65 241
27 0.182 25 7.18 223 substrate can be m a d e part of the electric circuit. The needle
28 0.196 00 7.72 207 makes only a m i n u t e p u n c t u r e in the film. I n m a n y instances,
29 0.210 25 8.28 193 particularly in a go no-go determination, the damage is so
30 0.225 00 8.96 180 slight that the method m a y be considered nondestructive for
32 0.256 00 10.08 158
34 0.289 00 11.38 141 m a n y e n d users.
36 0.324 00 12.76 125 The case a l u m i n u m h o u s i n g contains the needle screws for
38 0.361 00 14.21 113 forcing the needle through the film a n d a lamp to signal w h e n
the needle contacts the substrate. For use in the field a n d for
occasional use in the laboratory, the electric circuit com-
tal microscope (Fig. 4). W h e n contact is made, the needle a n d prises the needle, the substrate, a dry cell, the lamp, a n d a
its image reflected by the film just meet. The needle is t h e n cord that connects with the substrate. I n the laboratory, if
lowered into the film until it just touches the metal panel. m a n y m e a s u r e m e n t s are to be made, it is advisable to use a
This contact is noted by the deflection of a galvanometer in step-down t r a n s f o r m e r a n d to c o n n e c t to a 110-V source.
series with the panel, a dry cell, a n d the needle. The thickness The thickness is read o n a dial attached to the screw. One
of the film is calculated from the n u m b e r of t u r n s made by the t u r n of the dial raises or lowers the needle by 2 mils. The dial
focusing screw of the vertical microscope between the two is graduated in steps of 0.05 mil. Range is 0 to 15 mils.
points of contact. The zero setting of the needle is obtained by retracting the
It should be noted that this technique is only applicable to needle within the housing, placing the gage o n a plane metal
m e a s u r e m e n t s m a d e in a laboratory as it is impractical for block, a n d lowering the needle until the lamp signals contact.
work on site. The block is replaced by the specimen, a n d the needle is
lowered u n t i l the lamp again signals contact. The difference
between the two readings is the thickness of the film.
DRY FILM THICKNESS (DESTRUCTIVE
METHODS) Gardner Carboloy Drill Thickness Gage
As there are m a n y circumstances u n d e r which coatings a n d In m a n y instances films are so hard that they successfully
paints are used, n o single m e t h o d of dry film thickness mea- resist p e n e t r a t i o n by the needle p e n e t r o m e t e r described
s u r e m e n t is universal. Some methods are destructive, a n d above. This difficulty has been overcome by substituting a
these are most often used w h e n nondestructive methods are Carboloy drill for the needle. The drill is a needle t e r m i n a t i n g
n o t applicable. The nondestructive methods are limited to in a p y r a m i d having three faces. The drill is secured in a
coatings on metals. chuck that can be rotated a n d advanced independently. The
rotation is controlled by finger action o n a k n o b at the u p p e r
end of the chuck shaft. I n all other respects, the operation is
Micrometers and Dial Gages
the same as that of the needle gage.
W h e n a chip or flake of coating is freed from the surface of This m e t h o d has been standardized by ASTM as Procedure
the coated object, its thickness can be m e a s u r e d directly B in Test Method for M e a s u r e m e n t of Dry Film Thickness of
using a micrometer. Alternatively, the total thickness of the Non-metallic Coatings of Paint, Varnish, Lacquer, a n d Re-
substrate a n d coating can be measured; the substrate can lated Products Applied on a N o n - m a g n e t i c Base (D 1400).
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CHAPTER 3 8 - - M E A S U ~ M E N T OF FILM THICKNESS 427
FIG. 3-Wet film comb 115 and photo.
FIG. 4-Dial micrometer.
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ple, specimens with poor adhesion may be torn off, exposing

the base, even if the chisel does not penetrate the film.
Microscope for F i l m T h i c k n e s s
Classical Method
To use a microscope to assess film thickness, a section is
prepared and the width of the coating is measured using a
graticule in the eyepiece of the microscope. For an approxi-
mate assessment, a flake of the coating can be used, but for
best results from this method the specimen should be pre-
pared as follows.
The specimen is mounted in a block of wax. The face of the
mount is cut or ground to a smooth surface. The prepared
specimen is then inspected under the microscope. ASTM
Method for Microscopic Measurement of Dry Film Thickness
of Coatings on Wood Products (D 2691-88) is based on this
method; however, as paints are often hard and brittle, a
grinding and polishing method is preferred to the blade
method indicated in D 2691.
Brightwell Method [2]

This method does not require removal of a chip and elabo-
rate mounting and preparation. A tiny furrow is made in the
film or a small chip is removed. A prism or ribbon of light is
projected on the selected area at an angle of 45 ~. The distor-
FIG. 5-Elcometer dial gage 126. tion of the beam is examined with a microscope equipped
with a micrometer eyepiece. Apparatus for this is available in
Gardner Gage Stand the Schmaltz optical surface analyzer (Carl Zeiss).
The apparatus is calibrated by measuring known depths
Although the Gardner needle gage and the Carboloy drill milled in a smooth metal block. The ribbon of light is focused
gage may be operated by manually holding the gage against on line A, and the filar micrometer reading is recorded. The
the specimen, using the Gardner gage stand is less tiring and procedure is repeated on line BC. The difference multiplied
more accurate, especially when many measurements are to by the calibration factor equals the thickness of the film.
be made. The stand provides constant known pressure [up to Table 2 compares results by this method with results with a
10 lb (5 kg)] on the specimen and ensures that the needle or micrometer.
drill are always perpendicular to the specimen.
Stopped Method [3]
A cut is made in the film with a sharp knife. The microscope
Gardner Micro-Depth Gage is focused, in turn, on the upper and lower edges of the cut.
The thickness of the film is computed from the vertical ad-
Although in outward appearance this gage resembles the justments of the microscope. If the value is not known, it may
gages described in the last two subsections, only the estab- be found as follows: Put a piece of plate glass on the stage.
lishing of the zero setting is the same. Measurement is not Lower the tube until it just touches the plate. Record the
restricted to nonmetallic films on metal--any type of film on reading of the fine adjustment. Now raise the tube as far as
any type of substrate may be measured, and the film is always possible and again record the fine adjustment. Now raise the
damaged. tube as far as possible and again record the fine adjustment.
In this gage, a chisel replaces the needle of the gage. The
zero setting having been established, the chisel is advanced
by an amount estimated to be less than the thickness of the TABLE 2--Film thickness (mils) by optical surface analyzer and
dial micrometer (Brightwell).
film. The gage is placed on the specimen and drawn toward
the operator through a distance of a few millimetres. If the Surface Analyzer Dial Micrometer
scratch made by the chisel does not penetrate the film, the 0.39 0.4
chisel is advanced by a small increment, and another scratch 0.46 0.5
is made. The procedure is repeated until the substrate is 0.71 0.8
0.98 1.0
reached and exposed. Inspection is best made with the aid of 1.30 1.3
a low-power magnifier. The range is 0 to 40 mils (1000/~m). 1.51 1.4
Repeatability depends on the magnitudes of the increments 2.28 2.1
and the compressibility of the film and substrate. For exam- 3.58 3.5
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CHAPTER 38--MEASU~MENT OF FILM THICKNESS 4 2 9
The distance of the tube from the plate divided by the number
of turns of the adjusting screw gives the value for each turn.
Tooke Inspection Gage (Paint Inspection Gage P.I.G.)

[4]
This gage (shown in Fig. 6) provides for estimating the
thickness of a film from the geometry of a V-groove cut in the
film by a special tool. With the aid of a x 50 illuminated
FIG. 6-Groove in paint film.
magnifier equipped with a reticle in the eyepiece, the oper-
ator measures the lateral distance from the top edge of the cut
and the projection of the intersection of the cut and the sub- TABLE 3--Tooke inspection gage tip specifications.
strate. To make a measurement, a "bench mark" of ink ap- Precision of
plied to the surface of the film serves to make the top edge of Maximum Thickness One
the cut readily visible. A short cut is then made at a right angle Coating Determination Division on
Tip Thickness,mils Represents,mils Reticle Scale, mils
to the bench mark with the selected cutting tip. Film thick-
ness is then obtained by counting the scale divisions as de- 1 50 _+0.25 1.0
scribed previously. x2 20 _+0.13 0.5
x 10 3 -+0.025 0.1
The relationship among the tips is summarized in Table 3.
Saberg Drill
does include the electronic gage based on the magneto-resis-
This method is similar to the Tooke inspection gage
tor probe.
described in the previous subsection; however, a circular drill
is used to penetrate the film. The hole can then be inspected
Magne-Gage [5]
using the x 50 magnifier with graticule, and the width of the
cut from the outer edge to the print where the drill penetrates This instrument (Fig. 7) consists of a small permanent bar
to the substrate is a measure of the coating thickness. For the magnet, 2 mm in diameter, suspended from a horizontal
instrument kit supplied by Elcometer Inc., Rochester Hills, lever arm. The arm is actuated through a spiral spring by
M148309 (Model 195), the calculation of coating thickness is turning a dial. The tip of the magnet is brought into contact
as follows: with the paint film (on iron or steel), and the dial is then
turned until the magnet is detached. The attractive force be-
1. For measurement in mils, multiply graduations by 0.79.
tween the magnet and the film support is indicated on the
2. For measurement in micrometers, multiply graduations by
dial, and the thickness of the nonmagnetic paint film is ob-
20.0.
tained from a calibration curve relating thickness to dial
3. This method is now described in ASTM Test Method for
reading.
Measurement of Dry Film Thickness of Protective Coating
The gage can be used to measure coatings on convex and
Systems by Destructive Means (D 4138).
concave surfaces as well as on flat ones provided the radius of
the curvature is not too small. Unless special calibrations are
made, cylinders should not be less than 1/2 in. (1.27 cm) in
D R Y FILM T H I C K N E S S diameter, spheres not less than 3/4 in. (1.9 cm), and fiat pieces
(NONDESTRUCTIVE METHODS) should be at least 3/4 in. (1.9 cm) square.
Magnets for thicknesses in the following ranges are avail-
Permanent Magnet Thickness Gages able: 0.0 to 0.002, 0.002 to 0.007, and 0.007 to 0.025 in.
Permanent magnet coating thickness gages can be used to ASTM Method for Nondestructive Measurement of Dry
determine the thickness of films applied to magnetic sub- Film Thickness of Nonmagnetic Organic Coatings Applied to
strates such as steel, iron, magnetic stainless steel, etc., pro- a Ferrous Base (D 1186) has standardized the operation on
viding that the coating is nonmagnetic. Materials such as the magne gage.
nickel and cobalt, that are naturally magnetic have to be
treated with care, while paints containing magnetic particles, Hand-HeM Magnetic Gages
such as some ferrous micaceous iron oxide (MIO), can cause These gages are being superseded by electronic gages, and
errors when using magnetic gages. some--such as the Tinsley gage and the chemigage--are no
Simple magnetic coating thickness gages or mechanical longer manufactured. However, many thousands of these
gages use the principle that the attractive force between a types are still in use, so it is appropriate to describe them.
permanent magnet and the magnetic metal substrate is in- The simplest form of these gages contains a magnet sus-
versely proportional to the distance between them. pended from a coil spring housed in a pen-style body manu-
The principal limitations are (1) the film must be suffi- factured from aluminum or plastic. A scale is drawn on the
ciently hard to prevent indentation, and (2) the film must not body and a marker used to indicate the extension of the
be tacky causing the magnet to be held by the surface of the spring on the scale. The reading on the scale when the magnet
coating. lifts off the surface corresponds to the thickness of the coat-
Electronic magnetic coating thickness gages are also avail- ing.
able, but these will be described in a separate section entitled The scale on these instruments is nonlinear, leading to poor
Electromagnetic Thickness Gages; however, this section resolution at the maximum range, usually 20 mils (500/~m),
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FIG. 7-Magne gage (courtesy of American Instrument Co.).
FIG. 8-Elcometer pull off gage 157.
a n d great care m u s t be t a k e n to ensure that they are u s e d

vertically to avoid the influence of gravity on the spring-
m a g n e t c o m b i n a t i o n . S o m e of these types of gages have de-
sign features to o v e r c o m e the gravity effect w h e n the gage is
FIG. 9-Elcometer magnetic coating thickness gage 211.
u s e d horizontally. An example of this type of gage is the
E l c o m e t e r Model 157 (Fig. 8).
A c o m m o n form of the h a n d - h e l d m a g n e t i c gage is s h o w n holding the scale. R o t a t i o n of the ring raises or lowers the
in Fig 9, a n d its principle is illustrated in Fig. 10. A b a l a n c e d magnet.
b e a m w i t h a m a g n e t fitted to one e n d a n d c o u n t e r b a l a n c e d b y The gage is placed o n the surface to b e tested in a n y
a b r a s s weight at the o t h e r is a t t a c h e d at the pivot to a helical o r i e n t a t i o n as the b a l a n c e weight ensures that gravity effects
spring. The o t h e r end of the spring is a t t a c h e d to a ring are neutralized. The ring or scale wheel is p u s h e d f o r w a r d
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CHAPTER 38--MEASUREMENT OF FILM THICKNESS 431
Elcometer (Model I01)

ELCOMETER
The Elcometer is one of the first magnetic thickness gages
111 INSPECTOR
to be commercially available, being patented in 1948. Based
MAGNETIC ATTRACTION
on magnetic permeability, the magnetic flux acts on an arma-
ture suspended in between the two magnetic arms of the unit
(Fig. 11) north and south poles. The turning moment of the
magnetic flux is countered by a helical spring, and the magni-
OUTER CASE
tude of the magnetic flux changes with the distance between
, BALANCEWEIGHT
~'--'J~ \ TENSION SPRING the ends of the magnetic arms (ball feet) and the substrate
! ' ~ --~\ ~ SCALE beneath the coating. A pointer attached to the armature indi-
_..~ "--"-'-'~, ~ BALANCEARM cates the thickness of the coating. Instruments covering
~. ( . . ~ ,....~"k% " \ / MAGNET ranges from 0 to 3 mil (0 to 80/~m) to 0 to 0.75 in. (0 to
-- ,/COATING 18 mm) are available.
Magneto Resistor (Electronic)

! ,! This instrument combines a permanent magnet with a
magneto-resistor in a probe to provide a signal which varies
with the intensity of the magnetic field, which in turn is
influenced by the distance of the magnetic substrate from the
tip of the probe (Fig. 12).
FIG. lO-Magnetic coating thickness gage principle. The scale of the instrument is nonlinear and uses an ana-
logue meter movement to indicate the thickness. In operation
it is necessary to set zero on the uncoated metal and calibrate
to a thickness of known value to obtain the best accuracy.
(anticlockwise rotation) to bring the magnet in contact with These instruments have been superseded by the electro-
the coating and to set the scale to a maximum reading. The magnetic induction types and by digital electronics, but again
ring or scale wheel is then rotated clockwise until the magnet many instruments are in use and the principle embodied in
breaks free, the thickness of the coating being indicated by a the probe is still used for ferrite detection in stainless steel
pointer.
This type of gage is calibrated against plated standards
available from NIST, and accuracy against these standards of
- 5% of reading are achieved. It should be noted that the steel
used to make NIST standards is not always representative of ELCOMETER
engineering steels, and therefore a practical operating accu- FERRITE MEASUREMENT
racy of _+10% is obtained in the field. FERRITECTOR TYPE 1581
ELCOMETER
MAGNETIC RELUCTANCE PRINCIPLE
SCALE
PERMANENT MAGNET
NOgEA#'ggus -- t:.;iil
\ ~;~ ~ j MAGNETIC LINES
SENSING ELEk ,STAINLESS STEEL
OFFORCE
WELD SEAM I:ERRITE

FIG. 11-Elcometer 101 principle. FIG. 12-Magneto resistor principle.
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weld materials. In this application the magnetic properties of The voltage output from the probe can be amplified and
the substrate change with the ferrite content and the gage is calibrated and then used to display a thickness value. Three
calibrated in reverse, that is to say, zero, with the probe away types of electronic coating thickness gages have been devel-
from the influence of the magnetic material (free air) and oped on the basis of this probe technology using analogue,
maximum (Ferrite Number 28) on a 20 mil/thou in. digital, and microprocessor electronics. These types of gages
(500-/~m)-thick coating on a mild steel base. have been standardized by ASTM as Test Method B of
For ferrite measurement, the probe is applied to an D 1186.
uncoated weld.
Analogue Electromagnetic Thickness Gages
The simplest form of instrument uses a nonlinear scale on a
E l e c t r o m a g n e t i c T h i c k n e s s Gages meter movement to display the voltage output from the probe
The electromagnetic induction method for measuring film in thickness terms. The Elcometer Model 145 (Fig. 14) is an
thickness is based on the effect of a magnetic metal substrate example of this type of unit.
on the balance of the alternating magnetic field in the probe In common with most electronic coating thickness gages,
tip, generated in the probe (Fig. 13) by a signal applied to the the instrument must be calibrated by setting the needle to
central coil. zero with the probe on the uncoated magnetic metal sub-
When the probe is away from the influence of the substrate strate and then setting the upper scale point using the calibra-
(free air condition), the net voltage output from the two outer tion control with the probe on a known thickness of coating.
coils tends to zero. As the substrate is brought towards the Two forms of thickness standard are in common use: (1)
tip, the field is increasingly out of balance between the two the plated type, as illustrated by the standards available from
outer coils until, with the uncoated substrate in contact with NIST and other sources, and (2) the measured and
the tip, the net voltage output from the coils tends toward V unmeasured plastic shims available commercially from gage
max. manufacturers. In many applications the plastic shims are
preferred as calibration on the work to be measured reduces
the errors of calibration due to surface finish, curvature, and
ELECTROMAGNETIC substrate composition. More details of this are given later in
ELCOMETER S FIELD
ELECTROMAGNETIC this chapter under EFFECTS OF SURFACE FINISH,
INDUCTION PRINCIPLE i
CURVATURE AND SUBSTRATE COMPOSITION ON
= m l i:!t:! ELECTROMAGNETIC AND EDDY CURRENT MEA-
SUREMENTS.
==ml t tl
DETECTIONCOILS
atoll ili|ll
~i
:!: i:
m]
mum
~ 1 ~ ENERGISECOIL
Digital Electromagnetic Thickness Gages
Advances in electronic components and instruments de-
mlm[:!:|!:|l ~ sign techniques have made it possible to significantly reduce
:i: i: I the size of coating thickness gages while returning and en-
hancing the features users find necessary. The use of digital
electronics means that the voltage output from the probe can
PROBE BALANCED
~l:f :1:l:ir~i" be converted to a numerical value early in the processing of
the signal, thus reducing the effects of instrument tempera-
ture changes and component drift on the accuracy of the
/PROBE TIP result. It is also possible to use a linear scaling, making it
possible to have a fixed resolution over the full range of the
instrument scale although resolutions are often enhanced in
the 0 to 10 rail range (0 to 100/~m when scaled in metric
units). An illustration of this type of instrument is shown in
Fig. 15, but it should be noted that this type of product is
already being superseded by microprocessor-based designs.
The same principles of calibration apply to digital electro-
magnetic coating thickness gages as apply to the analogue
types, and accuracy capabilities of _+5% of readings are
achieved in the field.
Microprocessor Electromagnetic Thickness Gages

The development of microprocessor electronics and their
application to portable coating thickness gages has made it
possible to improve the accuracy and reproducibility of these
instruments as well as allowing developments in range, spe-
I TO FERROUS SUBSTRATE
cial calibration techniques for rough surfaces, memory of
readings, statistical calculation, and printouts.
In a microprocessor design, the characteristic of the probe
FIG. 13-Electromagnetic induction principle. voltage output against coating thickness value is stored in the
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FIG. 14-Analogue electromagnetic thickness gage 145.
FIG. 15-Digital electromagnetic thickness gage 245.
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memory of the instrument for many values over the range of effect that a high-frequency alternating field (3 000 000 Hz or
the probe. The actual voltage output from the probe is digi- 3 MHz) has an electrically conductive surface causing highly
tized and then compared with the stored values. A thickness localized current flow or eddy currents. These currents gener-
value is then calculated from these data and displayed. This is ate their own magnetic impedance of the coil, generating a
achieved in typically 0.3 s. Using this technique, accuracies of high-frequency field. The magnitude of these changes is pro-
_+1% of reading are possible. portional to the distance from the probe coil to the substrate,
As a microprocessor instrument is in effect a dedicated that is, to the thickness of the coating (Fig. 18).
computer, many calculations can be performed on the data, Calibration by adjustment to zero on a piece of metal of the
and features such as correction for temperature changes, same type, shape, and thickness as the samples to be mea-
storage of calibration conditions and corrections to these sured is vital to ensure accuracy. Instruments are available
calibrations, averages, and other statistical values can be in- using analogue, digital, or microprocessor designs, but many
cluded in the instrument's software. microprocessor instruments offer the facility for a dual
Figure 16 illustrates one of the microprocessor-based ferrous (F) electromagnetic induction and nonferrous (N)
electromagnetic thickness gages Model 256, available eddy current principle instrument using the two different
from Elcometer Inc., Rochester Hills, Michigan. This instru- probe designs such as the eddy current instruments illus-
ment is available in three levels of software: (1) basic~ trated in Fig. 19. This type of gage is also described as ASTM
measurements only; (2) statistical--measurement, memory, D 1400.
and statistical calculation; and (3) top--measurement, mem-
ory, statistics, and printout.
Figure 17 illustrates the trends in microprocessor designs
E F F E C T S OF S U R F A C E F I N I S H ,
with the smallest electronic coating thickness gage available,
CURVATURE, AND SUBSTRATE
Model 345, Launched in October 1991, the unit supersedes
COMPOSITION ON ELECTROMAGNETIC
analogue and digital designs at a lower cost.
AND EDDY CURRENT MEASUREMENTS
The accuracy of coating thickness measurements carried

Eddy Current Thickness Gages
out using the methods described in the last two subsections
The eddy current method for measuring film thickness is depends on the technique used in calibrating the instru-
applied to coatings on nonferrous metals. It is based on the ments. The three major influences on the calibration are
FIG. 16-Microprocessor electromagnetic thickness gage 256.
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profile. This is achieved b y using a thin foil 1.0 mil (25 p.m)
over the profile to set the lower c a l i b r a t i o n p o i n t a n d a thicker
foil 5.0 mils (125/zm) o r 10.0 mils (250/zm) to set the u p p e r
value over the profile. The i n s t r u m e n t will t h e n indicate the
thickness over the peaks for the coating b e t w e e n the values of
foil chosen.
This m e t h o d is m o s t a c c u r a t e a n d r e p r o d u c i b l e w h e n 15 to
20 readings are t a k e n on each c a l i b r a t i o n foil to establish a
m e a n value a n d the m e a n value is t h e n reset to the correct
value of the foil. Trials have shown that the m e a n of 15 to 20
readings taken over a n a r e a of coating give a m e a n value
within a few p e r c e n t of the actual value over p e a k s deter-
m i n e d by sectioning.
The m e t h o d does not, however, take into a c c o u n t situa-
tions w h e r e access to the s u b s t r a t e is not possible for
c a l i b r a t i o n purposes. In this case, the m e t h o d d e s c r i b e d in
SSPC PA2 w h e r e a c o r r e c t i o n factor is a p p l i e d to r e a d i n g s
taken using a s m o o t h surface c a l i b r a t i o n in the i n s t r u m e n t is
m o r e a p p r o p r i a t e . I n either case it is i m p o r t a n t to agree w i t h
the m e t h o d before m e a s u r e m e n t s start to avoid discrepancies
in reporting.
Curvature
The shape a n d metal wall thickness can also influence the
a c c u r a c y of the calibration. The degree to w h i c h a p a r t i c u l a r
i n s t r u m e n t is affected d e p e n d s on the design of the probe.
FIG. 17-Smallest microprocessor electromagnetic M a n y m o d e r n i n s t r u m e n t s exceed the limits identified in
thickness gage 345. SSPC PA2 of 1 Nov. 1982.
The effect of shape is m o s t evident w h e n taking readings on
an u n c o a t e d sample. W i t h an i n s t r u m e n t c a l i b r a t e d on a
surface finish, curvature, a n d shape of the substrate c o m p o s i - s m o o t h piece of m e t a l 0.125 in. (3.175 m m ) thick, changes of
tion. m o r e t h a n 0.2 rail ( 5 / z m ) in the r e a d i n g at zero will be seen
on curves with a r a d i u s below 0.12 in. (3 m m ) convex o r
0.96 in. (25 m m ) concave on a typical e l e c t r o m a g n e t i c induc-
Surface Finish tion probe. Values will vary b e t w e e n m a n u f a c t u r e r s a n d f r o m
different p r o b e types.
A variety of surface finishes are to be f o u n d on m e t a l to
w h i c h a protective or decorative coating is to be applied. In This e r r o r can also be e l i m i n a t e d by c a l i b r a t i o n on a shape
closely r e p r e s e n t i n g the s p e c i m e n to be tested. However, it
s o m e cases the coatings u s e d require an a n c h o r p a t t e r n of
profile d e p t h w h i c h forms a p a r t of the specification. C o m p a - should be n o t e d that once below the values of curvature
rators such as the K e a n e - T a t o r Surface Profile C o m p a r a t o r or i n d i c a t e d in the m a n u f a c t u r e r ' s literature, changes in curva-
the I n t e r n a t i o n a l S t a n d a r d s O r g a n i z a t i o n ISO 8503 are u s e d ture have a significant effect on calibration, i.e., the calibra-
to d e t e r m i n e the surface finish after shot o r grit blasting. Also tion on a shape will not be applicable to a n o t h e r shape.
Testex Tape a n d the E l c o m e t e r Surface Profile Gage can be
used to m e a s u r e p e a k to valley heights of profiles. These
Substrate Composition
i n s t r u m e n t s are shown in Fig. 20 along with the p h o t o g r a p h i c
s t a n d a r d s for cleanliness ASTM Pictorial Surface P r e p a r a - In the case of e l e c t r o m a g n e t i c i n d u c t i o n probes, m o s t are
tion S t a n d a r d s for Painting Steel Surfaces D 2200-1989 a n d insensitive to the m a j o r i t y of steel specifications in general
SSPC-VIS1. engineering use. However, w h e n h i g h - c a r b o n steels are
Surface finish also influences c a l i b r a t i o n as the q u a n t i t y of coated, the c a r b o n content sufficiently alters the m a g n e t i c
m e t a l directly b e n e a t h the p r o b e is r e d u c e d by the effects of p r o p e r t i e s of the steel to cause the n o r m a l c a l i b r a t i o n curve
shot a n d grit blasting as the p r o b e tip sits on the highest a p p l i e d within the i n s t r u m e n t s to be in e r r o r with respect to
peaks. This has the effect of increasing the value of thickness linearity. Thus, a n i n s t r u m e n t c a l i b r a t e d at zero a n d say 5
i n d i c a t e d using a gage c a l i b r a t e d on a s m o o t h surface by as mils (125/~m) m a y have an e r r o r at 2 mils (50 ~ m ) of m o r e
m u c h as 1.5 mils (35/~m) at 4 mils (100/~m) coating thick- t h a n 0.2 rail (50 ~m) or 10%. A similar effect can be seen with
ness for the highest values of profile. s o m e cast irons.
It is possible to use a r o u g h surface c a l i b r a t i o n t e c h n i q u e to This e r r o r can be o v e r c o m e b y calibrating as for the r o u g h
eliminate this e r r o r a n d m a k e the i n s t r u m e n t r e a d the correct surface d e s c r i b e d in the section earlier in this c h a p t e r entitled
value of coating thickness over the peaks by using the statisti- Surface Finish. F o r best accuracy, choose a foil just b e l o w
cal p o w e r of the m i c r o p r o c e s s o r type gages to calibrate on the the expected coating thickness value for the lower c a l i b r a t i o n
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FIG. 18-Eddy current principle.
FIG. 19-Microprocessor eddy current gage model 300.

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CHAPTER 38--MEASUREMENT OF FILM THICKNESS 437
FIG. 20-Surface profile instruments (group) with model numbers as brochure.
p o i n t s a n d a value well above the expected coating thickness "zero" with a n a l u m i n u m calibration a n d zero on a b r a s s
value for the u p p e r c a l i b r a t i o n point. component.
W h e n coatings a p p l i e d to n o n f e r r o u s metals are being
m e a s u r e d using eddy c u r r e n t techniques, the c o m p o s i t i o n of
the s u b s t r a t e a n d its effect on electrical conductivity are the S T A T I S T I C S IN FILM T H I C K N E S S
i m p o r t a n t factors with respect to calibration. Materials such MEASUREMENT
as a l u m i n u m a n d c o p p e r have very s i m i l a r characteristics
a n d similar c a l i b r a t i o n values. However, zinc, brass, a n d As m a n y r a n d o m variations c a n be expected in a coating
process, it is a p p r o p r i a t e to classify the thickness of the
o t h e r n o n f e r r o u s metals a n d alloys have different character-
coating using a statistical analysis. In fact, m a n y n a t i o n a l
istics, a n d c a l i b r a t i o n on an u n c o a t e d s a m p l e is essential.
specifications utilize a statistical a p p r o a c h in r e c o g n i t i o n of
Differences of up to 2 mils (50 ~m) c a n be seen b e t w e e n these variations, e.g., SSPC PA2.
The sources of these variations are many, a n d only a few
TABLE 4--X-ray fluorescence can be used for these applications.
examples can be cited h e r e - - o p e r a t o r e r r o r in taking the
m e a s u r e m e n t , recording error, variation due to surface o r
Coating Substrate curvature or composition, local variation in substrate due to
Chromium Steel, copper local heat t r e a t m e n t o r due to f o r m i n g o r working the metal,
Cadmium Steel, copper inclusions in the metal or in the coating, etc.
Copper Steel, zinc, brass The influence of these factors can be greatly r e d u c e d by
Nickel Steel, copper, Kovar, aluminum, Alloy 42,
inconel taking a statistically significant n u m b e r of r e a d i n g s for each
Nickel-phosphorous Steel, copper, Kovar, aluminum, Alloy 42 a r e a of the coating to be tested. This g r o u p of readings can
Zinc Steel, copper, brass then be s u m m a r i z e d using m e a n a n d either s t a n d a r d devia-
Zinc-nickel Steel tion or range to show the average a n d the s p r e a d of r e a d i n g s
Gold Nickel, aluminum, Kovar
Rhodium Nickel, gold a b o u t the average.
Palladium Nickel A statistically significant n u m b e r of readings w o u l d be 20
Silver Steel, copper, Kovar to 50; however, if the process is u n d e r statistical control as
Tin Steel, copper, Kovar, aluminum defined, five readings in each g r o u p o r s u b g r o u p is sufficient.
Titanium nitride Steel Many of the m i c r o p r o c e s s o r - b a s e d coating thickness in-
Ferrous oxide Aluminum, plastic
s t r u m e n t s are capable of calculating a n d r e c o r d i n g m e a n
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values (~), standard deviation (or), and highest and lowest In XRF instruments an X-ray source or tube is used to
values (range) within a batch of readings. produce p h o t o n emissions as they have an energy distribu-
It is important to establish the method of evaluating the tion capable of fluorescing all elements c o m m o n l y used in
information before embarking on an evaluation of a coating plating. The X-ray beam can be accurately illuminated to
system so that the correct disciplines are applied to collecting provide a small focal spot and high-intensity energy suitable
the data and evaluating it for further decisions. for noncontact measurement of complex layers on small
components. The characteristic X-rays emitted by the target
materials are detected using a gas-filled "proportional coun-
ter" in which the passage of the X-ray ionizes the gas and
X-RAY FLUORESCENCE (XRF) produces a pulse of electrical charge proportional to the
energy of the X-ray.
Over recent years, developments in performance and re- The XRF instruments' electronics convert the charge pulse
ductions in cost have pushed X-ray fluorescence to center into a digital signal that can be interpreted as thickness or
stage, particularly for metal-on-metal applications and ever analyzed for composition and produce the measurement in-
smaller parts. Beta-ray backscatter (BBS) techniques had formation by comparison with standards of k n o w n thickness.
been widely used to measure plated coatings; however, limi- XRF instruments have developed with optical alignment sys-
tations in performance--e.g., a m i n i m u m of 20% difference tems and motor-driven sample stages to position the sample
in atomic n u m b e r between the coating and the substrate is and computerized analytical equipment to store calibration
r e q u i r e d - - m e a n that while gold over nickel, copper, or Kovar data to calculate and present data to the user in a suitable
can be measured, nickel over copper or Kovar cannot be mea- format. Table 4 shows some of the applications which can be
sured using BBS techniques. Other disadvantages exist, such successfully measured using XRF.
as limits in the aperture/component geometry, and measure-
ment times have led to the further development of XRF tech-
niques and technology. REFERENCES
[1] New Jersey Zinc Co., "Leaves from a Paint Research Note Book,"
Principle of XRF Measurement [6] No. 1, 1937, p. 33.
[2] Brightwell, E. P., "An Optical Method for Measuring Film Thick-
If sufficient light energy collides with an electron, it is ness of Paint Films," Official Digest, Federation of Paint and Var-
possible for the electron to be driven out of its atomic orbit, a nish Production Clubs, ODFPA, Vol. 28, 1956, p. 412.
process known as the photoelectric effect. An atom with an [3] Stoppel, E. A., "Measurement of Thickness of Varnish Films,"
electron removed from its orbit is unstable, so to restore Proceedings, American Society for Testing and Materials, ASTEA,
equilibrium, an electron from a higher shell must drop into Vol. 23, Part 1, 1923, p. 286.
the vacant orbit. This transition causes an emission of energy [4] Tooke, R., Jr., "A Paint Inspection Gage," Official Digest, Federa-
in the form of a light wave or photon. tion of Societies for Paint Technology, ODFPA, Vol. 35, 1963, pp.
When the inner shell electrons are ejected from an atom, 691-698.
[5] Brenner, A., "Magnetic Method for Measuring the Thickness of
the emitted p h o t o n has high energy, and they fall into the Non-magnetic Coatings on Iron and Steel," Journal of Research,
region of the electromatic spectrum called X-rays. X-rays National Bureau of Standards, JRNBA, Vol. 2, 1938, p. 357.
have characteristic energy levels determined by the element [6] Stebel, M. D. and Silvermann, W. M., "XRF Programmable Plat-
which is emitting and can therefore be used to identify the ing Thickness Measurement Instrumentation," Proceedings of the
elements in a sample. International Coil Winding Association, November 1984.
www.iran-mavad.com

MNL17-EB/Jun. 1995
39
Drying Time
by Thomas J. Sliva 1
THE PROCESS OF DRYING INVOLVESseveral physical and/or ENVIRONMENT

chemical changes, such as solvent evaporation, oxidation,
and polymerization, all of which are time dependent. The When determining drying time, a controlled environment
various stages of drying that occur in organic films may be is essential. Variations in temperature, relative humidity, and
subjective, difficult to measure reproducibly, and are influ- circulation of air and light will have an effect on the drying
enced by many factors such as film thickness, substrate, tem- time of a coating. The typical standard environment used for
perature, humidity, light, and air circulation. Therefore, it is determining the drying time of air dry coatings is a tempera-
essential that most of these variables must be minimized in ture of 73.4 ~ +_ 3.6~ (23 ~ _ 2~ and a relative humidity of 50
order to make drying time determinations more quantitative. +__ 5% under diffuse daylight (about 25 fc).
Relative humidity should be strictly controlled for mois-
ture-cure and two-package urethane coatings since their cure
PREPARATION OF S P E C I M E N S is greatly affected by the existing relative humidity. The effect
of variation in temperature was discussed by Algeo and Jones
Substrate Preparation [1], who observed a difference of 4 h for a particular paint
dried at 73 and 77~ (22.7 and 25~ both at 50% relative
It is essential that the substrate to be used and the applied humidity.
wet film thickness be agreed upon in advance, preferably to All testing should be conducted in a well-ventilated room
conform to the intended use of the coating. Flat glass panels free from direct drafts and dust. Airflow is important in deter-
are typically the substrate of choice. Ground and polished mining drying time. For films that dry by oxidation, the rate
glass plates are more suitable for low-viscosity coatings that of drying is a function of the concentration of oxygen at the
may tend to crawl. All panels must be thoroughly cleaned, interface. Since oxygen can reach the surface only by diffu-
dried, and placed in a horizontal position on a level surface. sion, the rate of drying is a function of the thickness of the
stationary air layer. For films that dry by solvent evaporation,
Application the continuous removal of solvent-laden air hastens drying.
The test coating should be filtered to remove any dirt or

contamination. Test films are typically prepared, in dupli-
cate, using a drawdown or doctor blade adjusted to obtain a TEST M E T H O D S
uniform film thickness. Films should be drawn down at a
uniform rate of application to avoid drag on the coating. It is ASTM D 1640: Test Methods for Drying, Curing,
recommended that all test films should be prepared and or Film Formation o f Organic Coatings at Room
tested by one operator properly skilled in the method to be Temperature
used and that a control (known) coating be run alongside the
test coating. All testing should be done within an area, any Method D 1640 is the most commonly used method to de-
point of which is not less than 1/2 in. (15 mm) from the edge of termine the various stages and rates of film formation in the
the test film. drying of organic coatings normally used under conditions of
Table I can be used as a general guide for film application ambient room temperature. The method describes eight
when nothing more specific is agreed upon between the pur- stages of the drying process:
chaser and seller. The dry film thicknesses shown in Table 1
are suggested. I. Set-To-Touch Time
Other methods of application, such as spraying, dipping, or The test film is lightly touched with the tip of a clean finger,
flood coat, may be used provided the film thickness obtained and the fingertip is immediately placed against a piece of
is consistent with that recommended under actual usage. clean, clear glass to determine when the film does not
Other substrates, such as metal, may be used provided they adhere to the finger or transfer to the glass.
are smooth and flat.
2. Dust-Free Time
1Assistant technical director, DL Laboratories, 116 East 16th St., This test is generally performed by either of two methods
New York, NY 10003. that determine when dust or cotton fibers lightly dropped
439
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440 P A I N T A N D C O A T I N G T E S T I N G M A N U A L
TABLE 1--Recommended film thickness of materials to be tested.

Material Dry Film Thickness, mils
Oil paints 1.8 + 0.2
Enamels 1.0 + 0.1
Drying oils 1.0 _+ 0.1
Water-based paints 1.0 _+ 0.1
Varnishes 0.85 _+ 0.1
I
Lacquers, resins solutions 0.5 _+ 0.1 I I
, !
'J
! I
on the test film can be r e m o v e d by blowing over the test

film.
a. Cotton Fiber Test Method i '
I I
Individual a b s o r b e n t cotton fibers are d r o p p e d from a
height of 1 in. (25 ram). The film is c o n s i d e r e d to be dust
free w h e n the cotton fibers can be lightly b l o w n off the
test film. FIG. 1-Zapon Tack Tester. The base of the tester is
padded and wrapped with aluminum foil. The weight, at
3. Tack-Free Time
right, is set on the base for a definite interval. After the
The test film is c o n s i d e r e d to be tack free when no sticki- weight is removed, the time required for the tester to tip
ness is observed u n d e r m o d e r a t e pressure. This can be over is the measure of tack.
m e a s u r e d by either of two methods:
a. Paper Test Method
The test film is c o n s i d e r e d d r y - h a r d after m a x i m u m down-
A special p a p e r (K-4 Power Cable Paper) [3] is placed on
w a r d t h u m b p r e s s u r e (without twisting) a p p l i e d to the test
the test film u n d e r a weight of 2 psi (13.8 kPa). After 5 s,
film leaves no m a r k w h e n the contacted a r e a is lightly
the weight is r e m o v e d a n d the test film inverted. If the
p o l i s h e d with a soft cloth.
p a p e r d r o p s off within 10 s, the film is c o n s i d e r e d tack-
free. 6. Dry-Through (Dry-To-Handle) Time
A variation of the above m e t h o d is used to test the tack- The test panel is p l a c e d in a h o r i z o n t a l p o s i t i o n at such a
free time of insulating varnishes. The varnish is consid- height t h a n w h e n a t h u m b is p l a c e d on the film, the a r m of
ered tack free w h e n the p a p e r is placed on the test film the o p e r a t o r is in a vertical line from the wrist to the
u n d e r a weight of 1 lb (450 g) for 1 m i n and tested as shoulder. The o p e r a t o r b e a r s d o w n on the film with the
above. t h u m b , exerting m o d e r a t e p r e s s u r e a n d at the s a m e t i m e
b. Tack Tester twisting the t h u m b t h r o u g h an angle of 90 ~. The test film is
This is a m e c h a n i c a l device w h i c h consists of a strip of considered d r y t h r o u g h w h e n the film is not distorted b y
metal 1 in. (25 ram) wide, 3 in. (75 m m ) long, a n d 0.016 b e a r i n g d o w n with m o d e r a t e t h u m b p r e s s u r e a n d twisting
to 0.018 in. (0.41 to 0.46 m m ) in thickness. It is b e n t to 90 ~.
form a base 1 in. (25 m m ) square a n d a vertical length 1 7. Dry-To-Recoat Time
by 2 in. (25 b y 50 ram) angled at 135 ~ The b o t t o m of the
The test film meets this r e q u i r e m e n t w h e n a second coat
base of the tester is covered with a l u m i n u m foil [4] (Fig.
can be a p p l i e d w i t h o u t causing a n y film irregularities, e.g.,
1). A 300-g weight is placed on the center of the base a n d
lifting, wrinkling.
allowed to set for 5 s. The test film is tack free w h e n the
tester tips over i m m e d i a t e l y after the weight is removed. 8. Print-Free Time
Occasionally, tack-free t i m e m a y be longer t h a n dry- The test film meets this r e q u i r e m e n t w h e n i m p r i n t i n g fab-
h a r d or d r y - t h r o u g h t i m e due to the inclusion of external ric u n d e r a p r e s s u r e of 1/2 o r 1 lb/in. 2 (3.5 or 7.0 kPa) shows
plasticizers in the coating.
the coating to be p r i n t free. This p r o c e d u r e is similar to
4. Dry-To-Touch Time ASTM D 2091: Test M e t h o d for Print Resistance of Lac-
The test film is c o n s i d e r e d dry-to-touch w h e n no m a r k is quers.
left w h e n the film is t o u c h e d by a finger. The following
variations are used: An i n d i c a t i o n of the a c c u r a c y of these m e t h o d s is the preci-
sion s t a t e m e n t developed in ASTM D 1640 in w h i c h d u p l i c a t e
a. Drying Oils--The film is c o n s i d e r e d dry-to-touch w h e n
d e t e r m i n a t i o n s within a l a b o r a t o r y should agree within
it does not r u b u p a p p r e c i a b l y w h e n a finger is r u b b e d
__+10% [5].
lightly across the surface.
b. Lacquers (and S e a l e r s ) - - T h e film is c o n s i d e r e d dry-to-
touch w h e n no p r o n o u n c e d m a r k s are left by a finger Federal Test Method Standard 141C, Method
touching the film. Sealers are generally tested on w o o d 4061.2: Drying Time
o r o t h e r p o r o u s substrates.
This m e t h o d is similar to ASTM D 1640. It includes essen-
5. Dry-Hard Time tially the above stages of drying with the exception of dry-to-
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CHAPTER 3 9 - - D R Y I N G TIME 441
touch. However, it includes a test for free-from-after-tack. coating is still mobile. A single coating o r a m u l t i - c o a t sys-
This test is applicable to coatings w h e r e tackiness persists t e m of p a i n t o r varnish is c o n s i d e r e d to be t h r o u g h - d r y
beyond, o r r e a p p e a r s at, the t h r o u g h - d r y stage. It is similar to w h e n a specified gauze a t t a c h e d to a p l u n g e r is placed on
the P a p e r Test Method, discussed earlier in this chapter, the test film u n d e r specified pressm-e (1500 g) for 10 s,
except that a 2.8-kg (6.2-1b) weight is used. after w h i c h time the p l u n g e r h e a d is t u r n e d t h r o u g h an
angle of 90 ~ over a p e r i o d of 2 s a n d r e m o v e d (Fig. 2). If no
d a m a g e or m a r k i n g s are n o t e d on the test panel, the film is
ISO Standard 9117: Paints and Varnishesm
said to have achieved "through-dry state."
Determination o f Through-Dry State and
Through-Dry T i m e - - M e t h o d o f Test 2. Through-Dry Time
This s t a n d a r d describes a m e t h o d for d e t e r m i n i n g u n d e r This is the p e r i o d of t i m e b e t w e e n a p p l i c a t i o n of a coating
s t a n d a r d conditions w h e t h e r a single coat or a m u l t i - c o a t to a p r e p a r e d test p a n e l a n d the time to achieve the
system of p a i n t or related m a t e r i a l has, after a specified "through-dry state" as outlined above.
drying period, r e a c h e d the t h r o u g h - d r y state, i.e., a pass/fail
test. The test p r o c e d u r e m a y also be u s e d to d e t e r m i n e the
t i m e taken to achieve that state. British Standard B.S. 3900: Methods o f Test for
Paints
1. Through-Dry State Parts C-1 t h r n C-4 of British S t a n d a r d B.S. 3900 describe
This state defines the c o n d i t i o n of a film in w h i c h it is d r y drying tests for d e t e r m i n i n g the wet edge time, surface dry-
t h r o u g h o u t its thickness as o p p o s e d to that c o n d i t i o n in ing, hard-drying, a n d f r e e d o m f r o m residual tack tests. Part
w h i c h the surface of the film is dry b u t the b u l k of the C-8 describes a test for d e t e r m i n i n g print-free state or time.
I
| iii
Plunger
~ Ball-joint
..-- Plunger head
~-. Baseplate
Baseplate and plunger assembly
- Plunger
\ Clip
Rod for rotating
IIIIIIIII - plunger head
~L~auze
Rubber disc Double-faced
adhessive tape
Detail showing assembled plunger head

FIG. 2-Through-Dry Tester.
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1. Wet Edge Time (BS3900, C1) The state of a coating or varnish when gauze of a specified
This procedure is used for determining whether the edge of grade, under specified force and after a specified time, does
a film of paint remains "alive" after a specified period of not leave an imprint on the surface of a coating.
drying. Following a touch-up coat over the film after the
specified drying period, the area is evaluated for lack of
film continuity, absence of leveling, or variation in color or
sheen. DIN 53 150: D e t e r m i n a t i o n o f D r y i n g T i m e o f
2. Surface Drying (BS3900, C2) Paints
This procedure is used to determine the time after which a Drying time is determined in this method by the adherence
coating is applied and when approximately 0.5 g of the or nonadherence of sand or paper to the film under various
ballotini (small transparent solid glass spheres) can be loadings. Stage I is determined with sand (0.16 to 0.315 mm)
poured onto the surface of the film from a height of be- or glass beads (ballotini). The sand is allowed to remain on
tween 50 and 150 m m and lightly brushed away without the film for 10 s. The remaining stages are determined using
damaging the surface. disks of typewriter paper (22 mm in diameter and weighing
3. Hard-Drying Time (BS3900, C3) about 60 g/m 2) and various loads ranging from 5 to
A rubber-faced plunger is covered with cotton twill, rough 5000 g/cm 2. Interposed between the load and the test disk is a
side outwards, and then loaded to a toal weight of 1.8 kg soft rubber cushion. The load remains on the disks for 60 s.
(4 lb). The rotating plunger drops into the panel and makes The criteria for the seven stages are as follows:
a three-quarter turn while in contact. The paint film is dry- 1. Sand easily removed with a soft brush.
hard when no damage is observed (Fig. 3). 2. Disk under load of 5 g/cm 2 does not adhere.
4. Freedom from Residual Tack (BS3900, C4) 3. Disk under load of 50 g/cm 2 does not adhere.
4. Disk under load of 500 g/cm 2 does not adhere, but film is
After a specified drying period, a paper-backed gold leaf is
temporarily marred.
placed on the test panel and covered with a microscope
5. Disk under load of 500 g/cm 2 does not adhere, but film is
slide and an 800-g weight. After I0 s, the weight and slide
not marred.
are removed and the panel is held vertically and lightly
6. Disk under load of 5000 g/cm2 does not adhere, but film is
tapped to detach the gold leaf. The surface of the paint film
temporarily marred.
is examined for adhesion of gold leaf.
7. Disk under load of 5000 g/cm 2 does not adhere, hut film is
5. Print-Free (BS3900, C8) not marred.
FIG. 3-Hard-drying time apparatus: Assembly.
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CHAPTER 3 9 - - D R Y I N G TIME 443
FIG. 4-Circular drying time recorder. (Courtesy of Byk-Gardner.)
FIG. 5-Straight line recorder. (Courtesy of Byk-Gardner.)
MECHANICAL DEVICES the drying film. Motor speeds are available to cover drying
times of 1, 6, 12 and 24 h (Fig. 4).
In an attempt to improve the accuracy and reproducibility A transparent template with time increments can be placed
of the drying time test procedure, various mechanical devices over the dried coating at the end of the test. The appropriate
have been developed. The following sections outline these time circle can then be used to determine the dry time.
devices and the procedures used in determining drying char- During the early stages of drying, the coating tends to flow
acteristics. back into the wake of the stylus. When the tendency of the
flow has ceased, the film may be considered set. As the drying
process continues, a skin will form. Visually, this part of the
film formation is seen when the stylus begins to tear the
Circular Drying-Time Recorder
surface of the film. The film may be considered surface dry or
The device consists of a synchronous motor in a metal case dust free when the skin is no longer ruptured by the stylus. It
resting on a rubber-tipped tripod and rotating a vertical shaft. is considered through dry when the stylus rides above the
A pivotal arm assembly is attached to the shaft, operating a film.
vertical stylus with a Teflon sphere that does not stick to the Circular drying time devices have been developed for use
drying film [6]. Under a 12-g load, the stylus scribes an arc in when determining the drying time of bake finishes that cure
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Five-gram brass weights m a y be a d d e d to apply greater

pressure on the needles a n d thus r e c o r d t h r o u g h drying. The
i n s t r u m e n t has also been found useful in evaluating gel t i m e
of m a n y t w o - c o m p o n e n t surface coatings.
I . C . I . D r y i n g T i m e Recorder
This i n s t r u m e n t consists of a m e t a l box p l a t f o r m w h i c h will
a c c o m m o d a t e flat panels, usually m a d e of glass. A gantry
moves between a n d parallel to the long d i m e n s i o n of the flat
panels [8]. This g a n t r y will c a r r y up to three d e t a c h a b l e
devices for each panel. These include a flock dispenser, a s a n d
hopper, a b a n d a g e roller, a n d a ball-pointed needle. These
can be used in any c o m b i n a t i o n to test up to six coatings,
three on each panel.
The different stages in drying w h i c h can be m e a s u r e d , de-
p e n d i n g on the device used, are dust free, surface dry, a n d dry
through.
N O PICK-UP T I M E TRAFFIC P A I N T R O L L E R
This device is d e s c r i b e d in ASTM S t a n d a r d D 711: Test

M e t h o d for No-Pick-Up Time of Traffic Paint.
The a p p a r a t u s consists of a steel cylinder weighing 11 lb,
14 oz (5385 g) with two O-rings [6]. It is rolled along a drying
film of traffic p a i n t w h i c h has b e e n a p p l i e d on a glass plate.
The p a i n t is d r y w h e n no p a i n t adheres to the O-rings (Fig. 6).
REFERENCES
[1] Algeo, W. J. and Jones, P. A., "Factors Influencing the Accurate
FIG. 6-No pick-up time traffic paint roller. (Courtesy of Measurement of Drying Rates of Protective Coatings," Journal of
BykoGardner.) Paint Technology, JPTYA, Vol. 41, 1969, p. 235.
[2] The dust-free tester was designed and built by Technical Subcom-
mittee 37 of the New York Paint and Varnish Production Club
at elevated t e m p e r a t u r e s [up to 500~ (260~ The com- and is described in "Investigation of Methods for Measuring
pactness of the i n s t r u m e n t allows the u s e r to place it in an Drying Time," Official Digest, Federation of Paint and Varnish Pro-
oven at a specified t e m p e r a t u r e . duction Clubs, ODFPA, Vol. 20, November 1948, pp. 836-843.
This paper also includes a study of the Zapon Tack Tester.
[3] Paper meeting this requirement may be obtained from Crocker
Straight Line Drying Time Recorder Technical Papers, Inc., 431 Westminster St., Fitchburg, MA
01420, their Grade R 20-34.
This device consists of multiple needles being d r a w n over
[4] U.S. Patent 2,406,989, 3 Sept. 1946. It is known as the Zapon Tack
m u l t i p l e (up to six) parallel coated glass strips [7]. Its speed
Tester.
can be varied to cover drying p e r i o d s of 6, 12 a n d 24 h (Fig. 5). [5] See Prane, J. W., "A Latin Square Drying Time Study," Paint
It defines the following stages in the drying process: Industry Magazine. August 1961, for a study of precision of drying
1. The first stage is a p e a r - s h a p e d d e p r e s s i o n c o r r e s p o n d i n g time measurements.
[6] Available from Byk-Gardner, Inc, Gardner Laboratory 2435
to the t i m e it takes for the solvent to evaporate.
Linden Lane, Silver Spring, MD 20910 or Paul N. Gardner Co.,
2. The second stage is the cutting of a c o n t i n u o u s track corre- Inc., 316 N. E. First Street, Pompano Beach, FL 33060.
s p o n d i n g to a sol-gel transition. [7] Available from T. J. Bell Inc., 1340 Home Avenue, Akron, Ohio
3. The third stage is an i n t e r r u p t e d t r a c k c o r r e s p o n d i n g to 44310, as well as manufacturers listed in Ref 6.
the surface d r y time. [8] Available from Erickson GMBH & Co., KG, D-5870 Herner, Ger-
4. In the fourth stage, the needle no longer penetrates the many and Paul N. Gardner Co., Inc., 316 N.E. First Street,
film, indicating the final drying time. Pompano Beach, FL 33060.
www.iran-mavad.com

Part 10: Optical Properties
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MNL17-EB/Jun. 1995
ii
Color and Light

by Fred W. Bitlmeyer, Jr. 1 and Harry K. Hammond, 1112
BECAUSE COLOR IS A SIGNIFICANT FACTOR i n t h e a p p e a r a n c e o f International Electrotechnical Commission (IEC). However,

an object, it is an important characteristic of any paint. Ap- this is structured from the viewpoint of illuminating engi-
pearance, of which color is a part, is one quality of a product neering. It is less readily available and a much more costly
that every customer can judge for himself. No matter how document than ASTM E 284.
good the physical properties of a paint, if its color does not
meet the expectation of the customer, the finished product
will be rated as unsatisfactory. LIGHT SOURCES
Color, often thought to be a property of the paint itself,
depends on three objective aspects: (1) the spectral composi- Light is electromagnetic radiation weighted by the re-
tion of the light in which the paint is viewed, (2) the spectral sponse of the normal h u m a n eye. It occupies a small portion
reflectance of the paint, and (3) the spectral response of the of the electromagnetic spectrum between ultraviolet and in-
eye of the observer. The subjective interpretation of the re- frared radiation. Its wavelength range is approximately 380
sponse to these aspects by the brain is also an essential part of to 780 nm (Fig. 1).
color. Describing the color of a paint or other material re-
quires consideration of all of these and not merely the spec-
Natural and Artificial Daylight
tral character of the material. The three objective aspects of
color are considered in sections entitled LIGHT SOURCE, Despite modern dependence on interior illumination, day-
REFLECTION AND TRANSMISSION, and THE EYE. The light is still an important light source since most objects are
sciences involved include chemistry, physics, physiology, and at some time viewed in it. The spectral composition of day-
psychology. These are broad subjects, and only enough dis- light, however, is quite variable, depending upon the hour of
cussion is included to provide a background for understand- day, the season of year, and the amount of cloud cover. One
ing the development of test methods. Readers desiring to way of dealing with this variability is to use standard light
pursue these subjects in detail should consult an appropriate sources and their spectral power distributions when making
text [1-6]. visual or instrumental color measurements and calculations
(see later in this chapter under CIE Standard Sources and
Illuminants).
TERMINOLOGY
Incandescent Sources
To understand this chapter and to make the best use of it,
the reader should be familiar with the terminology of appear- Other light sources must replace daylight when appropri-
ance. The precise definition of terms is becoming increas- ate. For use in homes, incandescent lamplight is generally
ingly important in today's world community. The paint termi- preferred because it imparts a soft, mellow effect similar to
nology standard, ASTM Definitions of Terms Relating to that of candlelight.
Paint, Varnish, Lacquer, and Related Products (D 16), is the
primary source of terms and definitions relating to paint, but Fluorescent Sources
it contains very few appearance terms. The reader should
refer to ASTM Terminology of Appearance (E 284) for terms In stores and offices, fluorescent lamps can provide high
and definitions relating to color and other appearance attrib- levels of illumination with low power consumption and heat
utes. All significant terms used in this section are defined in generation. The most commonly used fluorescent lamp,
ASTM E 284. known as cool white, has a spectral distribution consisting of
An important international source of appearance terms is a relatively smooth curve throughout the visible spectrum.
the International Lighting Vocabulary [7], published jointly by This arises from the fluorescent emission from a phosphor
the International Commission on Illumination (CIE) and the coated on the inside of the lamp tube. The fluorescence is
excited by ultraviolet radiation from mercury vapor inside
the tube. This lamp is, however, deficient in power in the red
~Color consultant, 1294 Garner Avenue, Schenectady, NY 12309-
5746. end of the visible spectrum. Modifications of it, known as
2Consulting scientist, BYK-Gardner, Inc., 2435 Linden Lane, Silver deluxe and super-deluxe versions, have been designed to
Spring, MD 20910. overcome this deficiency. Fluorescent lamps have also been
447
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400 700
Blue Green Red

\ t
\ I
/
\ /
\ /
\ /
\ /
\ /
\ /
k /
Frequency, Hz X /
1024 1020 1016\~ / 1012 10s 104
I I I I I ~/I I I i I I
i
Cosmic !I "1rand X :l OV ! Infrared Ultra-high frequency
rays I rays and radio broadcast
I !
I
I
i
I ! I I I I i
10-4 104 10 8 1012
Wavelength, nm
FIG. 1-Electromagnetic spectrum showing the relatively small portion that the visible
spectrum occupies.
designed with phosphors emitting only in three rather nar- REFLECTION AND TRANSMISSION
row regions of the spectrum. When these three bands are
selected to peak near 450, 530, and 610 nm, light is provided Opaque, Transparent, and Translucent Films
that is especially pleasing to the eye and energy efficient.
When light strikes an object, some of it may be reflected,
The color-balance and color-rendering properties among
some may be absorbed, and if the object is not opaque, some
the various types of commercial fluorescent lamps can be
may be transmitted. The reflected light may be concentrated
vastly different one from another. in a glossy, mirror-like reflection, scattered uniformly in all
directions, or distributed between these two extremes, which
are known as specular reflection and diffuse reflection, re-
spectively. A highly polished metal can reflect as much as 99%
Other Sources of the incident light in the specular direction. A white pow-
Other light sources have been developed for special pur- der, such as barium sulfate, scatters light uniformly in all
poses. They include arc lamps (sodium, mercury, neon, directions, and it, too, can reflect as much as 99% of the
xenon), metal halide lamps, and high-intensity discharge incident light. Specular reflection is related to the visual per-
(HID) lamps. None of these lamps has been adopted as stan- ception of gloss; diffuse reflection is related to the visual
dard for use in color measurement. perception of lightness and, when it is wavelength dependent,
to that of color.
Transmission can also be diffuse or regular, depending on
whether or not light is scattered in passing through a mate-
Color-Matching Booths rial. Specimens that both transmit and reflect light are called
translucent.
Because of the variation in spectral composition of differ- A spectrophotometer is used to provide information on the
ent natural and artificial sources, it is essential that visual spectrally selective character of a material. Figure 2 shows
color matching be done under standardized illumination, typical spectral reflectance curves of some paints. A trained
such as that provided by a color-matching booth. This device colorist can obtain valuable information from such curves,
allows the colorist to compare the colors of specimens under but spectral data alone are unsatisfactory as a means for
controlled and standardized illumination. Carefully manu- color identification.
factured and maintained light booths permit a colorist to Among the ASTM standards on reflectance and transmit-
make a visual match with confidence that the illumination tance measurement [8], the most useful include ASTM Prac-
duplicates that used at another time or place. However, the tice for Obtaining Spectrophotometric Data for Object-Color
spectral power distribution of daylight illumination in color- Evaluation (E 1164), ASTM Test Method for Reflectance Fac-
matching booths is not the same as that of natural daylight. tor and Color by Spectrophotometry Using Hemispherical
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CHAPTER 40--COLOR AND LIGHT 449
100% Infrared radiation, with wavelengths longer than 780 nm,

WHITE
is associated with heat transfer. It is widely used for the
identification and analysis of chemical compounds. The near-
infrared region, with wavelengths from 780 to about
'10 000 nm, is important for camouflage detection. Most
paint pigments do not absorb radiation in this region, but
some inorganic pigments reflect visible light and absorb radi-
ation in the near-infrared.
Fluorescence
PERCENT Some materials have the property of fluorescing when irra-
REFLECTANCE diated by ultraviolet or short-wavelength visible radiation.
They emit radiation at longer wavelengths in the visible range
or even in the near-infrared. The effect of fluorescence is to
increase the apparent reflectance since the eye responds to
the sum of the fluoresced and the reflected energy. This sum
may even exceed the amount of light reflected by an ideal
white material at the wavelengths of maximum fluorescent
emission. Many fluorescent pigments have relatively poor
lightfastness in outdoor applications.
Most modern colorimeters and spectrophotometers are de-
signed to evaluate properly the colors of fluorescent materi-
als, although many do not have light sources adequately
simulating the ultraviolet content of natural daylight. In such
a case the instrument will not produce the same amount of
O~
fluorescence as would daylight.
4OO 700
WAVELENGTH, NANOMETERS Two ASTM standards apply to the measurement of fluores-
FIG. 2-Spectrophotometric curves typical of those mea- cence. ASTM Test Method for Identifying Fluorescence in
sured on paint films. Note the sharp drop in the curve for rutile Object-Color Specimens by Spectrophotometry (E 1247) pro-
titanium dioxide (white) as the violet end of the spectrum is vides two instrumental methods to supplement simple visual
approached. The drop continues in the ultraviolet, where this
examination of the specimen under ultraviolet light to detect
pigment absorbs light strongly. (Based on Ref. 2.)
the presence of fluorescence. ASTM Practice for Color Mea-
surement of Fluorescent Materials (E 991) specifies the in-
Geometry (E 1331), ASTM Test Method for Color and Color- strument geometry required for the measurement and shows
Difference Measurement by Tristimulus (Filter) Colorimetry how to assess the performance of daylight-simulating instru-
(E 1347), ASTM Test Method for Transmittance and Color ment light sources.
by Spectrophotometry Using Hemispherical Geometry
(E 1348), and ASTM Test Method for Reflectance Factor and
Color by Spectrophotometry Using Bidirectional Geometry Retroreflection
(E 1349). 3 Retroreflection is defined in ASTM E 284 as "reflection in
which the reflected rays are preferentially returned in direc-
Ultraviolet a n d I n f r a r e d Spectral Regions tions close to the opposite of the direction of the incident
rays . . . . "It is important in paints and coatings used for signs
Ultraviolet and infrared radiation can have important ef- viewed at night, pavement and pedestrian markings, and
fects on paint. Ultraviolet radiation, with wavelengths shorter other safety devices. The measurement of retroreflection re-
than 380 nm, is the principal stimulus of fluorescence of quires special instrumentation and special test methods for
certain pigments, is an aid to identification and analytical the determination of daytime and nighttime colors of
determination of certain ingredients of paint, and may pro- retroreflecting materials. Among the ASTM standards deal-
mote decomposition of pigments or binders. Colorless pig- ing with this subject are: ASTM Practice for Describing
ments absorbing in the ultraviolet region can impart protec- Retroreflection (E 808), ASTM Practice for Measuring Photo-
tion against such decomposition. Ruffle titanium dioxide metric Characteristics of Retroreflectors (E 809), ASTM
absorbs in the ultraviolet, as its spectral curve shows (see Fig. Practice for Measuring Colorimetric Characteristics of
2). Retroreflectors under Nighttime Conditions (E 811), ASTM
Test Method for Coefficient of Retroreflection of Retro-
3Asnoted in ASTM E 284, in the Discussion under reflectance, "The reflective Sheeting (E810), ASTM Test Method for
term reflectance is often used in a general sense or as an abbreviation Retroreflectance of Horizontal Coatings (D 4061), ASTM
for reflectance factor . . . . " This simplifying convention is used in this Guide to Properties of High Visibility Materials Used to Im-
chapter, as it is in many textbooks. The reader should refer to
ASTM E 284 for the definitions of reflectance, transmittance, and prove Individual Safety (F 923), and ASTM Specification for
radiance, and the corresponding factors. Note that commercial in- Nightime Photometric Performance of Retroreflective Pedes-
struments measure reflectance factor, not reflectance. trian Markings for Visibility Enhancement (E 1501).
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THE EYE Perception

The Visual System Perception is defined as the translation of retinal images by
the observer into meaningful information about the environ-
The human eye functions in a manner similar to a camera. ment. The perception of objects and their colors thus repre-
It has a lens to focus images of objects and an iris to control sents the overall response of the visual system, including both
the amount of light that enters (Fig. 3). A complex light- the eye and the brain. Vision is called a psychophysical phe-
sensitive layer, called the retina, plays a role analogous to that n o m e n o n - p h y s i c a l in the way light reaches the eye, psycho-
of the film in a camera. Neither the structure of the retina nor logical in how the brain interprets the neural signals. The
its function are fully understood. It contains two different psychological factor determines, for example, whether a
types of light receptors that send information along neural given color combination is interpreted as pleasing or
pathways to the visual cortex of the brain. They are called displeasing. The mechanism of seeing is physical; the inter-
rods and cones because of their shapes. The rods are respon- pretation of what is seen is psychological.
sible for black-and-white vision at low light levels; they are Objective color measurement is, however, confined to
not considered further in this section. At usual daylight levels, physical aspects. For example, the perceived color of a speci-
the rods are overwhelmed and do not contribute to vision. men may be changed by changing the color of the area sur-
The cones are responsible for color vision. There are three rounding it. This phenomenon, called simultaneous contrast,
types of cones, each with a different spectral sensitivity. The cannot yet be evaluated instrumentally.
exact spectral response of each type of cone is not known, Another example of a perceptual phenomenon is chromatic
although it is assumed that each cone response function is adaptation, defined as the changes in the visual system's sen-
related to the absorption curve of its pigment. The absorption sitivities due to changes in the spectral quality of the illumi-
curves are broad and overlapping (Fig. 4). They peak in the nating and viewing conditions. These changes tend to com-
short, middle, and long wavelength regions of the visible pensate, for example, for the effect of the change in
spectrum; thus the designations blue, green, and red (sensi- illumination from distinctly bluish daylight to distinctly yel-
tive) cones are sometimes used. lowish incandescent lamplight. The colors of familiar objects
Detailed models of color vision have been proposed [10,11], tend to appear the same (they tend to exhibit color constancy)
but they are presently based on incomplete information. when the observer goes between environments illuminated
What happens to the neural signals from the retina on the by the two kinds of light. Yet the actual colors have all been
way to and in the brain is not well understood, but for most shifted because of the change in spectral composition of the
work related to color and appearance, it does not need to be. incident light.
Temporal
side
stalline
lens
rI Vitreous
/ humor
Blind
Optic
nerve
Cornea"
Nasal side
FIG. 3-Cross-sectional diagram of the eye showing features of most interest for
color vision [9].
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LIGHTNESS
0
L
"~- -1
.>_
rr
(9
(I)
(9
HUE
9>-- "2
2
o} S CHROMA
3 FIG. 5-Arrangement of the hue, lightness, and chroma axes
-3 in the usual cylindrical representation of color space.
\ \ tor among these names is a sense of the amount, in contrast

to the kind, of hue in the color. In this section we use chroma
as the name for this third variable and show it also in Fig. 5.
-4 This quantity is exemplified by the distance between the point
I I I I
400 500 600 7o0 representing the color and the neutral axis.
Wavelength, nm Colored Lights
FIG. 4-Spectral curves showing the relative sensitivities of
When we deal with colored lights instead of objects, two
the three types of cones in the eye, peaking in the short (S),
medium (M), and long (L) wavelength regions (based on Ref 10.) changes need to be made in the above system: Lightness is
replaced by brightness and chroma by saturation. Brightness
in this sense is defined as the attribute by which an area
appears to emit more or less light.
The V a r i a b l e s o f Perceived Color
The fact that the eye perceives color because it has three
Object Colors: Opponent Systems
types of cones with differing spectral sensitivities implies, A widely used alternative to the hue-lightness-chroma sys-
and experience confirms, that perceived color should have tem described above is an opponent-color system that
three variables. Several sets of these variables are of interest mimics the behavior of the neural signals transmitted from
because of their wide use. the retina to the brain. The lightness axis, often labeled L, is
retained, but the hue circle is replaced by two opponent-type
axes at right angles and perpendicular to the lightness axis
Object Colors: Cylindrical Systems (Fig. 6). Commonly they are a redness-greenness and a yel-
Of great interest to the paint colorist are the variables lowness-blueness axis labeled a and b, respectively, as in the
applying to the perception of object colors. Hue is always one figure. Scales of this type are displayed in many color-mea-
of the variables; the Munsell system (see later in this chapter suring systems; examples are given later in this chapter under
under Munsell System) is an example. Hue is defined as the COLOR ORDER SYSTEMS.
attribute of color described by common names such as red,
yellow, green, blue, etc. The hues are commonly arranged in a
Color Constancy a n d M e t a m e r i s m
circle in the order of their appearance in the spectrum, with
the circle closed by the purples, mixtures of the red and blue Color Constancy
at the ends of the visible spectrum (Fig. 5). As previously noted under Perception, color constancy is
A second important variable of object colors is lightness, the general tendency of colors to remain constant in appear-
the attribute by which an object is judged to reflect more or ance when the color of the illumination is changed. Note that
less light. It is often represented graphically by a line through this term refers to what happens to the color of a single
the center of the hue circle and perpendicular to its plane specimen when the illumination is changed.
(also shown in Fig. 5). The upper and lower ends of this line,
often called the neutral or achromatic axis, are white and Metamerism
black, respectively. Of greater concern to the colorist, because it is of industrial
The third variable in this set has several different names, importance and largely under his control, is what happens to
referring to variations among what we can perceive: Chroma, the relationship of two colors when the illumination is
saturation, and colorfulness are examples. The common fac- changed. Suppose, for example, that two colors, matching in
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L = 100 = White this is why the same pigment formulation should be used
when remaking the color. Whenever pigments used for the
/--J ,%., match have different spectral characteristics from those used
in the sample, the resultant color match should be tested for
(Green) -
the absence of metamerism by several observers and under
several different types of illumination, for example, daylight,
incandescent lamp light, and fluorescent lamp light, prefera-
bly using a color-matching booth. If the match is not satisfac-
tory, spectrophotometric analysis of the two formulations
a (Red) should be carried out to determine their spectral differences,
and the new formulation should be adjusted to minimize
these differences. ASTM Practice for Visual Evaluation of
(Blue)
Metamerism (D 4086) specifies procedures for identifying
the presence of metamerism and evaluating it semiquantita-
tively. Means of minimizing metamerism in both visual and
instrumentally aided color matching are described later in
0 = Black this chapter in the section entitled COLOR MATCHING.
FIG. 6-Arrangement of the lightness, redness-
greenness, and yellowness-blueness axes in the
usual opponent-color representation of color space
[I]. C O L O R I M E T R Y A N D T H E CIE S Y S T E M
Colorimetry is defined as the science of color measure-

daylight, are formulated by using different sets of pigments. ment. Its modern development began in 1931, when, in the
The two colors may not match under another type of illumi- interest of standardization and to focus attention on the
nation, such as incandescent lamplight, since the two speci- properties of material objects such as paint films, interna-
mens may exhibit different types and degrees of color con- tional standards and recommendations were established by
stancy. This phenomenon is known as illuminant metam- the International Commission on Illumination (Commission
erism, and the colors are said to be metameric. Illuminant Internationale de l'l~clairage, CIE). These recommendations
metamerism is defined as the property of two specimens [12] define standard lights and observers and a methodology
having different spectral characteristics (resulting in the ex- for combining their properties with those of the objects to
ample from the use of different pigments; see Fig. 7) and describe color and related appearance parameters.
having the same color when viewed under a given source, but
different colors when viewed under a different source. Ob- CIE Standard Sources and Illuminants
server metamerism also exists in which two colors match to
some observers but not to others. Here it is necessary to note two conventions of CIE termi-
Only when colors have identical spectral curves can they be nology [7] reflected in ASTM E 284. A source is defined as a
expected to match under all types of light and to all observers; real emitter of light, whereas an illuminant is defined as a
60
=~ 40
O
e-
C
20
o ...... , I I ,! I
0 0 0 0 0 0 0
0 ~ 0 tO 0 tO C,
Wavelength, nm
FIG. 7-Spectrophotometric curves of two highly metameric paint films. To most
observers, the films match visually and are a dull green color in daylight, but Sample
A shifts color to a strong reddish brown in incandescent lamp light while Sample B
exhibits color constancy for this change of illumination.
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table or figure giving the spectral power distribution of the spond to the use of imaginary primary lights designated X, Y,
corresponding source. and Z. The Standard Observer is defined by the amounts, s
y(4), and 2(4), of these primaries required to match the spec-
Incandescent Source and Illuminant trum colors; these are plotted in Fig. 9. The symbol (X) indi-
In 1931, the CIE defined a tungsten-filament incandescent cates that the quantity depends on the wavelength, 4. The
lamp of 2856 K color temperature (see later in this section quantities ~(4), y(4), and s are known as the color-match-
under Other Features of the CIE System) as Source A. ing functions of the 2931 CIE Standard Observer.
Later, when measurement of spectral power distributions be- The transformation from real primaries to X, Y, and Z was
came easier, the fundamental definition was changed to the made so that the color-matching function ~(4) is equal to the
lamp's spectral power distribution, known as Illuminant A. spectral luminous efficiency function V(4), that is, the effec-
The spectral power distribution of Illuminant A is given in tiveness of radiation to stimulate the perception of light. This
Ref 12, in a CIE/ISO standard [13], and in abbreviated form choice means that the tristimulus value Y of a given color,
in ASTM Practice for Computing the Colors of Objects by called its luminance, contains all the information about the
Using the CIE System (E 308). lightness of the color.
Daylight Source and Illuminants 1964 Supplementary Standard Observer

The CIE also recommended in 1931 standard Source C, The data for the CIE 1931 Standard Observer were ob-
consisting of liquid filters used in combination with Source A, tained with a visual colorimeter in which the field of view
representing north-sky daylight. Later, the fundamental defi- subtended an angle of only 2~ at the eye of the observer. This
nition was changed to that of Illuminant C [12]. was selected to correspond to the size of the fovea, that part of
Source and Illuminant C do not duplicate the ultraviolet the retina containing only cones used in color vision. Later,
content of natural daylight and thus do not provide correct the CIE studied color vision in a 10~ field, with the central 2 ~
daylight color rendition of fluorescent materials. For this rea- portion disregarded. This corresponds to sample sizes more
son, the CIE adopted in 1968 a series of standard illuminants like those used in commerce, but for which the spectral
duplicating the spectral power distributions of various sensitivity of the eye is somewhat different from that for the
phases of natural daylight, called the D series. They are 2~ field. With the newer data, the CIE established the
designated by their correlated color temperatures (see later in 1964 Supplementary Standard Observer [12,15]; see also
this section under Other Features of the CIE System). The ASTM E 308. Where confusion might result, quantities refer-
most important of these daylight illuminants [12,13] is D65, ring to the 1964 Supplementary Standard Observer are given
with a correlated color temperature of 6500 K. The spectral the subscript 10; for example, its color-matching functions
power distributions of Illuminant C and several of the D are :~jo(4), 3~1o(4), and 21o(4).
series are tabulated in ASTM E 308. Unfortunately, very few
real sources, whether for visual or instrumental use, simu-
lated any of the D illuminants satisfactorily. The CIE has Calculation of Tristimulus Values
recommended procedures for assessing the quality of day- The tristimulus values X, I1, and Z of a color can in principle
light simulators [14]. The relative spectral power distribu- be obtained by direct matching, as were the tristimulus val-
tions of CIE Standard Illuminants A, C, and D65 are shown in ues of the spectrum colors defining the standard observers.
Fig. 8. But this is impractical, and one of two other methods is
Fluorescent Illuminants always used. One of these involves the design and use of
tristimulus (filter) colorimeters and is discussed later in this
In 1986, the CIE defined [12], but did not recommend as chapter under Tristimus (Filter) Colorimeters. The other
standard illuminants, a series of twelve spectral power distri- requires knowledge of the spectral reflectance curve of the
butions representative of various types of fluorescent lamps, specimen, obtained by spectrophotometry, and the following
including cool white, lamps simulating daylight well, and procedure.
three-band lamps. These data should be used when calcula- At any wavelength, the contribution to a tristimulus value
tions involving fluorescent lamps are required. is given by the product of the relative spectral power of the
illuminant, S(4), the reflectance of the specimen, R(A), and
CIE Standard Observers one of the color-matching functions of the observer, for ex-
ample, ~(4). These products are summed over the visible
1931 CIE Standard Observer wavelengths, then normalized by multiplication by a normal-
In order to evaluate colors consistently, a standard ob- ization factor k; for example,
server was defined by the CIE in 1931 [12,15] by evaluating
X = k X S(4) R(A):~(A)
the spectral responses of a small group of well-trained indi-
viduals. The spectral responses of the CIE 1931 Standard (and similar equations for Y and Z), where E is the sign for
Observer were determined by means of experiments, like summation over the visible wavelength region. The quantity k
those described later in this chapter under Additive Mixing is chosen to make Y for perfect white equal to 100:
of Lights, in which the observer determined the amounts of
three primary colors (red, green, and blue) required to match k = 100/E S(4)2~(h)
the colors of all wavelengths of the visible spectrum. These The CIE had defined "perfect white" as the perfect reflecting
sets of three values are called tristimulus values. For conve- diffuser, the ideal reflecting surface that neither absorbs or
nience, the data were transformed mathematically to corre- transmits light, but reflects all of it. Most textbooks,
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250
CIE Illunlinmits
200 A
. . . . 065
150
i,.
I
II t'",~... I
.'>_ I l ""~.~.,,.,,...~_.~../
I/ ~ ":
m
o 100
r162 # /
1""4 ....
i I +,..,.~.^~ %
il \
i,
/; / t"
i/
50
.,,.j] /
/
o" I
/ ,
; #
i/ ,,#
0 : ~,'7"- I I I I I I I I
300 350 &00 ~,50 500 550 600 650 700
Wavelentjfh(nm)
FIG. 8-Relative spectral power distributions of CIE standard Illuminants A (in-
candescent lamp light), C (north-sky daylight), and D65 (actual daylight) [6].
ASTM E 308, and Ref 12 provide examples of the use of these Chromaticity Coordinates and Diagram
equations. Because the fundamental process is integration,
An important use of the CIE tristimulus values X, Y, and Z
for which s u m m a t i o n is an approximation, the process is
usually referred to as (tristimulus) integration. is the calculation of coordinates describing the chromaticity
If a large n u m b e r of sets of reflectance data are to be of a color, that is, its hue and chroma, ignoring its luminance
integrated for the same illuminant and observer, it is conve- or lightness. The CIE chromaticity coordinates x, y, and z are
nient to combine quantities such as S()0 g(,~) by multiplying c o m p u t e d from the tristimulus values X, Y, and Z by dividing
them together and normalizing the products so that k -- 1. each of these by the s u m X + Y + Z. Thus x = X/(X + Y + Z),
The resulting tristimulus weighting factors can then be stored etc. Since x + y + z -- 1, only two chromaticity coordinates
and used by multiplying them by whatever function R(X) is need be given; usually they are x and y. These chromaticity
desired. The CIE has not tabulated or r e c o m m e n d e d specific coordinates can be plotted to yield the 1931 CIE x, y chroma-
sets of tristimulus weighting functions, but a substantial ticity diagram, shown in Fig. 10, or the 1964 CIE xl0, Yl0
n u m b e r can be found in ASTM E 308. They m a y be used for diagram for the Supplementary Standard Observer; the two
wavelength intervals of 10 or 20 nm. For closer intervals, are quite similar.
such as 5 or I nm, the tables in E 308, Ref 12, or Refs 13 and Features of the chromaticity diagrams include: (1) the loca-
15 should be used. tions of the spectrum colors around the horseshoe-shaped
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2.00
1.50
"~ 1.00
0,50
0 ~
400 500 600 700
Wavelength, nm
FIG. 9-The color-matching functions of the CIE 1931 standard observer; they are
the tristimulus values of the colors of the spectrum [1].
spectrum locus, from 400 nm (violet) at the lower left to spectrum locus. For purple colors where the line would end at
700 nm (red) at the right; (2) the straight line along which the purple locus, it is extended back through the white point
purples lie joining these two ends of the spectrum locus; and to the spectrum locus, and the wavelength at that point is
(3) the location of whites (illuminant points) near the middle designated as the complementary wavelength of the sample.
of the diagram. As an alternative to the three tristimulus The fractional distance from the white point to the sample
values, colors can be specified by the chromaticity coordi- point relative to the distance to the spectrum or purple locus
nates x and y together with the luminance Y (or their equiva- is called the (excitation) purity of the sample. Dominant
lents in the 1964 system). These can be arranged in a three- wavelength correlates well with the hue of the sample, but
dimensional color space (Fig. 11). purity does not correlate well with any perceived quantity
and is little used today.
Other Features of the CIE System

Blackbody Locus, Color Temperature, and Correlated
Dominant Wavelength, Complementary Wavelength, Color Temperature
and Purity When a metal, such as a lamp filament, is heated, it first
Dominant wavelength is defined as the wavelength along radiates heat in the infrared region, then light with a chroma-
the spectrum locus at the end of a line drawn from the white ticity at the red c o m e r of the diagram. As it gets hotter, the
point (usually Illuminant C) through the sample point to the chromaticity shifts through the oranges and yellows. The line
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0.6
, 1 \
o65.f4. ooK
Z2:~
0
0 0.2 0.4 0.6 0.8
Z
FIG. 10-The CIE 1931 x,y chromaticity diagram showing the various features
described in the text [I].
along which these chromaticities lie for perfect absorbers and mended two more nearly uniform color spaces that, although
emitters of radiation is called the blackbody locus and is not perfect, have been widely used. Here we describe the one
shown in Fig. 10. If the metal did not melt, its color would that is most widely used in the paint and related industries
continue along this locus through white to light blue at infi- and mention briefly the second, more useful when colored
nitely high temperature. The temperature of a perfect lights are considered. The equations for these two spaces,
blackbody can be correlated with its chromaticity and is known by official acronyms CIELAB and CIELUV, are found
called the color temperature of the body. It is measured in in Refs 1 to 6 and 12 and in ASTM E 308.
kelvins, K; the color temperature of Illuminant A is, for exam-
ple, 2856 K. Many light sources, including the phases of day- CIE 1976 L*, a*, b* (CIELAB) Space
light and fluorescent lamps, have chromaticities that are CIELAB is an opponent-type color space, with a lightness
close to, but not on, the blackbody locus. In that case, the axis L*, a redness (positive values)-greenness (negative) axis
color temperature closest to the chromaticity of the source is a*, and a yellowness (positive)-blueness (negative) axis b*, all
used and called its correlated color temperature. An example mutually perpendicular, as illustrated in Fig. 6. The transfor-
is Standard Illuminant D65, with a correlated color tempera- mations from Yto L*, from X and Y to a*, and from Z and Y to
ture of 6500 K. b* are all nonlinear, using cube-root functions.
The equations for these transformations are:
U n i f o r m Color S p a c e s L*= 116 (Y/Y.) 1/3- 16
From almost the beginning of the CIE system, it was recog- a = 500 [(S/Xn) 1/3 - (y/y.)l,3]
nized that distances in the CIE space did not correlate well
b* = 200 [(Y/Yn) 1/3 -- ( Z / Z n ) 1/3]
with visual estimates of the magnitudes of color differences.
Many proposals have been made for deriving quantities that where X,~, Y., and Z. are the tristimulus values of the illumi-
are more uniformly visually spaced. In 1976, the CIE recom- nant or white point, and there are some restrictions on the
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- 100
-80
-60
- Ir,~
-40
0.8
0.6
0.4
Y 0.6
u0
FIG. 11 - A three-dimensional representation of CIE color space with the luminance
(lightness) axis Y rising above the chromaticity diagram [1].
use of the equations for very small values of X, Y, or Z de- COLOR ORDER SYSTEMS
scribed in the references cited above.
Because CIELAB does not have tristimulus values or chro- In this section are discussed briefly the major color order
maticity coordinates as defined for the 1931 and 1964 CIE systems, consisting of physical exemplifications or atlases il-
systems in Chromaticity Coordinates and Diagram, it does lustrating underlying systems. References 16 and 17 provide
not have a chromaticity diagram. useful general coverage.
An alternative set of CIELAB coordinates retains L* but
combines a* and b* to give chroma C* and hue angle h Munsell System
(measured in degrees):
Dating from the early 1900s, the Munsell system is ac-
C* -= (a .2 + b*2) 1/2, h = tan -1 (b*/a*)
cepted by most users as the standard for equal visual spacing.
These correlate well with visual judgments of lightness, It is described in ASTM Test Method for Specifying Color by
chroma, and hue, respectively. Perhaps the widest use of the Munsell System (D 1535). Its color solid is like that of Fig.
CIELAB is in the calculation of color differences (see later in 5 with the sole exception that lightness is called value in the
this chapter under Color Difference Calculations). Munsell system. Munsell Hue is designated by position
around the hue circle in a notation combining letters desig-
nating five major hues (red, yellow, green, blue, purple) and
CIE 1976 L*, u*, v* (CIELUV) Space their pairs (R, YR, Y, GY, G, BG, B, PB, P, RP) with numbers
from 1 to 10. Munsell Value, to which CIE lightness L* is a
The CIELUV space has a chromaticity diagram with coor-
good approximation, runs from zero for black to 10 for white.
dinates u' and v', which are linear transformations ofx and y,
Munsell Chroma, which expresses the degree of departure of
respectively. The linearity is important for the additive mix-
the color from the gray of the same lightness, starts at zero
ing of colored lights (see later in this chapter under Additive and is open-ended. To describe a color in the Munsell system,
Mixing of Lights). For the three-dimensional CIELUV space, the hue, value, and chroma are noted in a prescribed se-
these are combined with the (nonlinear) L* transformation to quence, as for example, 8R 4/10. This designation indicates
give opponent-type axes u* and v*, whose meanings are the that the hue is red (toward yellow-red), the value is 4, and the
same as those of CIELAB a* and b*, respectively. An alterna- chroma is 10.
tive set of hue angle and chroma coordinates, like those in The Munsel[ Book of Color is available in two collections of
CIELAB, and a color-difference equation, much less widely painted color chips. The glossy finish collection contains ap-
used than the CIELAB equation, are also part of this system. proximately 1600 removable chips, the matte collection ap-
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v0 0.2 0.4 0.6 0.8

X
FIG. 12-Lines of constant Munsell Hue and closed curves of constant Munsell
Chroma, at Munsell Value 5 plotted on the ClE 1931 chromaticity diagram [19].
p r o x i m a t e l y 1200 p e r m a n e n t l y m o u n t e d chips. The chips are Universal Color Language

a r r a n g e d on pages of c o n s t a n t Munsell Hue; in any one row The Munselt system a n d the ISCC-NBS system are b o t h
they are perceived as having the s a m e Munsell Value and in parts of a Universal Color Language [20], a six-level system
a n y one c o l u m n as having the s a m e Munsell C h r o m a w h e n for describing color to a n y d e s i r e d degree of accuracy. Level 1
viewed u n d e r daylight i l l u m i n a t i o n on a m e d i u m - g r a y back-
consists of the use of 13 hue a n d neutral names. At this level,
ground. The colors progress from very light at the top to very
the color with Munsell n o t a t i o n 8R 4/10 w o u l d be d e s c r i b e d
d a r k at the b o t t o m a n d from n e u t r a l at the left to high c h r o m a
as orange. I n Level 2, w h i c h has 29 categories, i n t e r m e d i a t e
at the right (or the reverse on facing pages). In 1943, the
hue n a m e s are added. Here the color w o u l d be d e s c r i b e d as
underlying Munsell system was defined in colorimetric t e r m s
r e d d i s h orange. Level 3 is the ISCC-NBS system, a n d Level 4
[18], a n d since 1968 the chips in the glossy editions of the
Munsell Book of Color have b e e n p r o d u c e d to m a t c h these is the Munsell system as used in the Munsell Book of Color;
specifications. Figure 12 shows contours of equal Munsell designations at these levels are given above. Level 5 uses
H u e a n d C h r o m a at Value 5 on the 1931 CIE x, y c h r o m a t i c i t y i n t e r p o l a t e d Munsell notations b a s e d on visual c o m p a r i s o n
diagram. of the color with Munsell Book chips. W i t h practice it is
possible to interpolate accurately to 1/10 value step, 1/4
c h r o m a step, a n d from 1 hue step at c h r o m a / 2 to 1/4 hue step
ISCC-NBS System at c h r o m a n e a r / 1 0 a n d above. Thus, at this level the color
In the 1950s the Inter-Society Color Council (ISCC) a n d the might be designated very a c c u r a t e l y as 8.25 R 4.1/9.75. The
N a t i o n a l B u r e a u of S t a n d a r d s (NBS) developed the ISCC- final stage, Level 6, of the Universal Color L a n g u a g e is b a s e d
NBS M e t h o d of Designating Colors [20] b a s e d on the Munsell on the results of color m e a s u r e m e n t , expressed as CIE chro-
system b u t g r o u p i n g s i m i l a r colors to p r o d u c e a s m a l l e r n u m - m a t i c i t y c o o r d i n a t e s x, y, a n d L u m i n a n c e Y. N o w the color
b e r (267) of categories. These are d e s i g n a t e d by descriptive might be specified with greatest a c c u r a c y as x = 0.527, y =
color names, for example, d a r k r e d d i s h orange for the group 0.343, Y = 12.5.
c o n t a i n i n g 8R 4/10.
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CHAPTER 4 0 - - C O L O R AND LIGHT 459
W
6~e ~ Series with
~C~ a ~ same white
~0~ / ~ caL~ 7 content
e ~ ea .
Full Furl
color color
% ">'<
B
FIG. 13-Two opposing constant-hue pages in the Ostwald system [1].
Ostwald S y s t e m colors. For example, an orange might be said to have 80%

resemblance to red and 20% to yellow; its hue notation would
This system [21], which is not illustrated by any set of
be Y80R. Chromaticness is the resemblance of the color to
samples now commercially available, consists of 24 charts of
the (imaginary) color of the same hue having the maximum
approximately constant hue containing sets of chips having
possible chromatic content. Lightness is not an explicit vari-
nearly constant chroma but different lightnesses. The chips
able in the system; the third resemblance can be to either
are arranged (Fig. 13) on each chart in a triangular array, as
white or black. Scales of resemblances to white, black, and
shown. The most important atlas based on the Ostwald sys-
the aforementioned maximally chromatic color are chosen so
tem in the United States was the Color Harmony Manual,
that these three add to 100%, so only one of the resemblances
available in the 1940s and 1950s [22].
to white or black need be specified. For the notation, resem-
blance to black has been selected, so that the three variables
DIN S y s t e m of the system are blackness, chromaticness, and hue. The
complete NCS notation for the orange sample considered
The DIN Color System is the official German Standard above in the Munse]l system, for example, is approximately
Color System [23]. Its coordinates are hue (for which domi- 3070 YBOR.
nant wavelength is used), saturation (like chroma except rep- In the NCS atlas, pages of constant hue notation contain
resenting difference from black instead of from gray of the chips arranged on a grid in the form of an equilateral triangle,
same lightness), and relative darkness. Contours of constant as shown in Fig. 15. Note that there is a similarity to the
DIN hue and saturation, applicable to all lightness levels, are Ostwald triangle, the difference being that in the Ostwald
shown on the 1931 CIE x, y diagram in Fig. 14. From time to system the corner points are real samples; in the NCS, they
time, atlases of DIN samples have been available in glossy are imaginary elementary colors. The NCS is subsidized by
and matte finish and in transparent films. In the former two, the Swedish government and aggressively marketed, and thus
chips are arranged on pages of constant hue, similar to the is available at lower cost than most other atlases.
Munsel] arrangement.
OSA-UCS System
Natural Color S y s t e m
The Optical Society of American Uniform Color Scales
Developed in the late 1960s and 1970s, the Natural Color system [25,26] was developed by a committee of the OSA
System (NCS) [24] is the national standard color order sys- between 1947 and 1976. Although the committee concluded
tem in Sweden and several other European countries. It is that no perfectly equally visually spaced system can exist be-
based on an entirely different principle from that of the other cause color space itself is not Euclidean, it attempted to
systems discussed, namely the resemblances of colors to six achieve the best possible compromise and is generally
imaginary elementary colors, unique red, yellow, green, and thought to have succeeded. The 558 samples of the OSA atlas
blue, and black and white. The four hues are placed 90 ~apart are arranged in a rhombohedral lattice in which each sample,
on the hue circle. This does not lead to visually equal hue except those at the edges, has twelve nearest neighbors. The
spacing. Two opponent-type axes result, perpendicular to the axes of the color solid are lightness, L (with both positive and
black-white lightness axis. The third variable of the system is negative values around zero at middle gray) and two oppon-
chromaticness. ent axes, j (from the French ]aune for yellow), with positive
In terms of resemblances, hue is defined as the resem- values toward yellow and negative values toward purple-blue,
blance of a color to the two nearest chromatic elementary and g (for greenness), with blue-greens at the positive end and
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0.8
0.,
///,,,
sgo
Y .
! l/l I .,' A _ / _ f / / ' , 2

490~ @ i90tO7110
0.2: ~
0.1 '
~ 0.1 " o , i o 02 0.3 0., 0.5 0.e 0.T

X
FIG. 14-Lines of constant DIN hue and closed curves of constant DIN saturation on
the CIE 1931 chromaticity diagram. The figure applies to all DIN darkness levels
modified from 23].
[16,
pinks at the negative end. One of the features of the lattice is adjacent major axes directed toward reds, yellows, greens,
the existence of many planes of closely related samples, and blues. A typical Colorcurve notation would be L40 R1Y3,
sometimes varying along all three axes, that appear strikingly representing at lightness level 40 the lattice point one step
beautiful. away from neutral toward the reds and three steps toward the
The OSA-UCS system is described in ASTM Practice for yellows. This is an orange only slightly different from the
Specifying Color by Using the Optical Society of America sample discussed above. The Colorcurve atlas contains about
Uniform Color Scales System (E 1360). A portion of the 2200 painted samples.
OSA-UCS lattice illustrating the arrangement of samples is Another feature of the Colorcurve system is that spectral
shown in Fig. 16, and Fig. 17 shows the spacing of samples of reflectances are furnished for the aim points. These can be
the L = 0 plane on the 1964 CIE xl0, Yl0 diagram. additively mixed like tristimulus values to obtain the spectral
curve corresponding to any Colorcurve notation; this can be
the basis for computer colorant formulation (see subsection
Colorcurve System later in this chapter entitled I n s t r u m e n t a l and Computer-
Aided Color Matching) to provide a match with minimum
This new color order system was introduced in the United
States in 1989. It is based on a color space similar to CIE 1964 metamerism to the surrounding Colorcurve samples. ASTM
tristimulus space [27]. Aim points are laid out according to Practice for Specifying and Matching Color Using the
additive mixing (see subsection later in this chapter entitled Colorcurve System (E 1541) describes the system in more
Additive Mixing of Lights) of CIE 1964 tristimulus values detail, including a tabulation of spectral reflectances, tristim-
Xlo, Yl0, Zlo for Illuminant D65, starting from eight specified ulus values, and CIELAB coordinates for the sample aim
CIELAB points. The CIELAB lightness axis L* (designated points.
only as L) is retained, but coordinates along the CIELAB-type
opponent axes are replaced by a simple numbering system
Printed Systems
giving the sample location in terms of the number of lattice For each of the color order systems described above, atlas
steps between it and the neutral axis in the directions of two samples consist of painted chips individually matched to the
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0.6
W '1 !
~ L-O
4
9 ,~o
P~
.//'\~
0.5
eo ./
.',: . /"k.'//"
9 x~,0 / 9 0.4
/ Vx./,,
.,
Ylo /-~.,.....'," ,
,.. o_ ~
9 ~e/"
/~"#
. /
2
4
oJ," ,," ,,: 080 -

0,3- - ~ .r~--~
",'." / ,t --4
0,2
f
(,Jc-, 10 I i I I
0.:' 0.3 0.4 (15 O.S
S Xlo
FIG. 15-Arrangement of colors on a constant-hue
page in the NCS system. They are located according FIG. 17-Section of the CIE 1964 Xlo, Ylo diagram showing the
to their resemblances to ideal white (W), ideal black locations of points on the L = 0 plane of the OSA system
(B), and the imaginary Color C having 100% chroma- (ASTM E 1360, from Ref 3).
ticness [24].
and it is especially difficult to reproduce the samples accu-
+L rately in subsequent printings or editions. Their cost is, how-
ever, relatively low.
I ,,,7 g Single-Number Color Scales
J
0-20
~+j .....
Occasions arise in which the colors of samples vary along a
single direction in color space. In such a case the color can be
described adequately by a single scale value. Three cases are
of interest: whiteness, yellowness, and series ranging from
colorless to highly colored as the concentration of a colored
component increases.
Whiteness Indices
Whiteness scales start at the point corresponding to an
ideal white, which may be the perfect reflecting diffuser (see
subsection earlier in this chapter entitled Calculation of Tri-
stimulus Values) or some other industry standard, often
.g" I~ -I1-1 assigned a whiteness of 100. From this number are sub-
tracted amounts corresponding to departures toward lower
-L
lightness and the addition of chromaticness. For example, in
FIG. 16-Cuboctahedron around the center point of the OSA
ASTM Test Method for Indexes of Whiteness and Yellowness
system showing its three axes, _+L (lightness), +_j(yellowness-
blueness), and _ g(greenness-redness). There are twelve near- of Near-White, Opaque Materials (E 313), the recommended
est neighbors around the center point, with the L,j,g coordi- equation for whiteness index W I can be expressed in terms of
hates shown. The entire OSA space is formed by extending this CIE 1931 tristimulus values for Illuminant C as
figure in all directions [16].
WI = Y- 4(0.847Z - Y)
The first term is the luminance, Y, which approximates per-
specified aim points with a mean accuracy of about one ceived lightness, and the second term is a measure of depar-
CIELAB unit. Many other collections, produced by printing, ture from white toward yellow. The CIE has defined a white-
exist. Of necessity, they all have the characteristic that large ness index [12] as
groups of samples are produced at the same time; it is not
W = Y + 800(x. - x) + 1700(y. - y)
possible to adjust the color of each one individually for clos-
est conformance to the aim point. In many instances average where x and y are the 1931 chromaticity coordinates of the
accuracy is much poorer than that for the painted atlases, sample with lightness Y, and x . and y. are the values for the
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illuminant point. CIE 1964 values can also be used. This ceding paragraph. But there are many factors, such as fa-
equation allows for departures from white in any hue direc- tigue, poor color memory, and subjectivity, as well as the
tion, weighted by the factors shown. In each case the value for perceptual phenomena described earlier under Perception,
the perfect white is 100. that make the eye at least suspect for close color evaluation
work. Therefore the use of the eye as detector has been almost
Yellowness Indices entirely replaced by the use of two types of photoelectric
Indices of departure from achromatic toward yellow are instruments developed since the 1940s for color measure-
formulated similarly to the second term in the ASTM ment.
E 313 WI equation given above. The indices start at zero and
increase as yellowness increases. In ASTM E 313, the yel-
Spectrophotometers
lowness index YI is given by
Spectrophotometers provide detailed information on the
YI = 100 (1 - 0.847Z/Y)
color properties of specimens, in the form of spectral reflec-
A similar equation, given in ASTM Test Method for Yel- tances (or transmittances), required for the calculation of
lowness Index of Plastics (D 1925), includes the effect of CIE tristimulus values and derived color coordinates, as de-
change in tristimulus value X as well as Y and Z scribed earlier under Colorimetry a n d the CIE System and
in ASTM E 308. Spectrophotometers are described here and
YI-- 100[(1.28X- 1.06Z)/Y]
their abridgments in the form of tristimulus (filter) colorime-
This equation is equally applicable to paint films. ters in the next section.
When radiation strikes a sample, it may be reflected, ab-
Scales for Liquids sorbed, or transmitted. Each of these can be measured by
When only a limited range of color is involved, for example, most spectrophotometers. All spectrophotometers consist of
in the testing of the color of oil, clear varnish, lacquer, or a light source, a monochromator, arrangements for illumi-
solvents used in the paint industry, simple methods are used nating and viewing the sample, a photodetector, and an out-
consisting of comparison of the specimen with standard col- put device. In modern instruments, the latter consists of a
ored solutions or glasses ranging from colorless to highly computer that processes the signals from the detector and
colored. A standardized series of these colors is used to pro- provides for the calculation of tristimulus values and a wide
vide a specialized color scale. The color is often a measure of variety of other color-related quantities. Each of these com-
concentration of ingredient. One difficulty in the use of these ponents is described briefly.
special color scales is that the color of the specimen may not
match that of the standard; this can make rating on a single- Light Source
number scale difficult. Nevertheless, their simplicity, low In most cases the exact nature of the light source in a
cost, and adaptability to special situations has resulted in spectrophotometer is of little importance as long as it has
wide use of single-number scales for certain applications. adequate power and stability at all wavelengths in the visible
Among such scales useful to the paint industry are those spectrum. Incandescent lamps or xenon flash tubes are
described in ASTM Test Method for Saybolt Color of Petro- widely used. When fluorescent samples are measured (see
leum Products (Saybolt Chromometer Method) (D 156), earlier under Fluorescence), the source must illuminate the
ASTM Test Methods for Soluble Nitrocellulose Base Solu- sample directly and may be filtered to simulate a standard
tions (D 365), ASTM Test Method for Color of Clear Liquids source, such as CIE daylight D65. Most color measuring
(Platinum-Cobalt Scale) (D 1209), ASTM Test Method for spectrophotometers are designed with these features.
ASTM Color of Petroleum Products (ASTM Color Scale) ASTM E 991 provides more information on the measure-
(D 1500), ASTM Test Method for Color of Transparent Liq- ment of fluorescent samples.
uids (Gardner Color Scale) (D 1544), ASTM Test Method for
Color of Solid Aromatic Hydrocarbons and Related Materials Geometry of Illumination and View
in the Molten State (Platinum Cobalt Scale) (D 1686), and In most spectrophotometers, the geometry of sample illu-
ASTM Test Method for Measurement of Color of Low-Col- mination and viewing follows CIE recommendations [12].
ored Clear Liquids Using the Hunterlab Color Difference Me- Two standard geometries are widely used. In hemispherical
ter (E 450). These and other single-number color scales were geometry, light from the source usually illuminates the white
intercompared [28]. interior of a hollow, approximately spherical cavity called an
integrating sphere, and the diffused light from the sphere
illuminates the sample from all angles in the hemisphere
bounded by its surface. The sample is viewed at an angle near
I N D U S T R I A L COLOR M E A S U R E M E N T
the normal or perpendicular to its surface. If the sample is
Instruments Using the Eye as Detector glossy, the specular or mirror reflection from its surface will
result in a portion of the wall of the integrating sphere also
The eye is the ultimate arbiter in color evaluation because, being viewed. The user is given the option of making this part
of course, it passes the final judgment on the acceptability of of the sphere white, thus including the specular component,
a color. The first color-measuring instruments used the eye as or black, excluding it.
detector, and this practice is still followed when use of a In bidirectional geometry, illuminating and viewing are at
simple color comparator suffices, as in many of the test angles along the normal to the sample surface (designated 0 ~
methods for single-number color scales described in the pre- and 45 ~ from the normal, or the reverse. The use of
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CHAPTER 40--COLOR AND LIGHT 4 6 3
bidirectional geometry with the specimen illuminated by Obtaining Tristimulus Values from Spectral Data
white light is required when fluorescent samples are mea- The first step in utilizing spectral data is the calculation
sured. Hemispherical and bidirectional geometries are de- of CIE tristimulus values, as described earlier under
scribed in ASTM Guide for Selection of Geometric Condi- Calculation of Tristimulus Values. This step is performed
tions for Measurement of Reflection and Transmission automatically as part of the measurement sequence in all
Properties of Materials (E 179) and in ASTM E 1164 as well modern spectrophotometers designed for color measure-
as by the CIE [12]. ment. It is usual that the spectral bandpass of the monochro-
In typical 45/0 or 0/45 geometry, several illuminating or mator and the measurement interval are selected to be the
viewing beams, distributed around the azimuth at 45 ~ to the same. For highest accuracy, the correct set of tristimulus
normal, may be used. When a specimen exhibits direc- weighting factors, corresponding to the instrument band-
tionality, that is, its reflectance changes when it is rotated in pass, selected from among those added to ASTM E 308 in
its own plane, the use of an instrument with multiple beams 1994, must be used in calculating tristimulus values. In addi-
provides data that average over the directionality, giving a tion, the user must select the standard illuminant and the
single number characteristic of the average properties of the standard observer used, and (when hemispherical measuring
specimen. If it is desired to measure the directionality, an geometry is utilized) select the inclusion or exclusion of the
instrument with one illuminating (or viewing) beam, or two specular component in reflectance measurement.
180~ apart in azimuth, should be used and measurements
made at several different specimen orientations. Spectrocolorimeters
For the measurement of specimens exhibiting gonio- Some spectrophotometers are designed so that the mea-
chromatism, in which the reflectance changes when the illu- sured spectral reflectances or transmittances cannot be ac-
minating or viewing angles are changed, the use of special cessed for examination; only the resulting tristimulus values
instruments capable of measuring at different combinations and other color coordinates can be printed out. Such instru-
of these angles is required. Several such multiangle instruments are designated spectrocolorimeters.
ments, known as goniospectrophotometers, are commer-
cially available. To date, no firm recommendations have been Tristimulus (Filter) Colorimeters
made on the number of combinations or the optimum angles
required to characterize such goniochromatic specimens. Among the earliest photoelectric color-measuring instru-
Such specimens of interest in the paint industry include the ments were those in which the source-filter-photodetector
so-called metallic and pearlescent coatings for the automo- combinations duplicate the tristimulus functions of the Stan-
tive industry. dard Observer and a CIE Standard Illuminant, usually Illumi-
nant C [29]. How well their filters are designed and matched
to the spectral characteristics of the source and of the detec-
Monochromator, Detector, and Output tor determines how accurately the instrument performs. To-
The light reflected or transmitted by the specimen is di- day a high degree of accuracy is attained in the resulting
rected to the monochromator, in which a narrow (typically 10 tristimulus values.
to 20 nm) band of wavelengths is selected from the full spec- Because of their ease of operation, good precision, and
trum of the incident light. The monochromators in modern relatively low cost, tristimulus (filter) colorimeters have
instruments usually use holographic diffraction gratings or found wide application for industrial control. They are used
interference filters to isolate the narrow wavelength range. primarily as color-difference meters to evaluate the differ-
Spectral light is received by the detector, usually a silicon ence in color between a production specimen and a standard
photodiode. Detection may be accomplished by an array of of similar spectral character. This last limitation is important
diodes, each positioned permanently to receive light of a for most colorimeters. Because of their design, most colorim-
given wavelength, thus eliminating the need for a spectrum eters provide colorimetric data for only one combination of
scanning device. The electrical signal from the detector is illuminant and observer and therefore cannot detect
usually amplified, digitized, and entered in an interfaced metamerism. When specimens are metameric, a colorimeter
computer. In addition to ASTM E 1164, the following test can give incorrect data on the differences among them. Filter
methods cover the operation of modern spectrophotometers" colorimeters should not be used to evaluate pairs of speci-
ASTM E 1331, E 1348, and E 1349. mens that may be metameric. This limitation should be
clearly understood.
Spectroradiometers The use of colorimeters is described in ASTM E 1347. This
standard replaces ASTM Test Method for Directional Reflec-
Instruments closely related to spectrophotometers but tance Factor, 45-deg 0-deg, of Opaque Specimens by Broad-
made to measure light incident from external sources are Band Filter Reflectometry (E 97) (discontinued in 1992).
known as spectroradiometers. They could be used in the
paint industry when, for example, the specimen must be
sensed remotely after illumination external to the instru- Selection and Calibration o f Instruments
ment. Methods for making such measurements are described The potential user of color-measuring instrumentation
in ASTM Practice for Obtaining Spectroradiometric Data must consider with care the selection of the proper instru-
from Radiant Sources for Colorimetry (E 1341) and ASTM ment(s), depending on his samples and measurement needs.
Practice for Obtaining Colorimetric Data from a Visual Dis- ASTM E 179 and ASTM Practice for Identification of Instru-
play Unit Using Colorimeters (E 1455). mental Methods of Color or Color-Difference Measurement
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of Materials (E 805) address this topic. They should be con- C o m m e r c i a l Instruments

sulted, if possible, before the purchase of a new instrument.
Instrument design changes have been so frequent in recent
The user of any color-measuring instrument must give reg-
years that published information in a manual such as this
ular attention to its calibration. Appropriate calibration stan-
would almost certainly become obsolete by the time the man-
dards, available from instrument manufacturers and, in
uscript is printed. For this reason, detailed information on
some cases, national standardizing laboratories, should be
suppliers and their instrumentation is not included. Such
obtained, maintained in good condition, and used at frequent
intervals in an established routine [30]. A collaborative refer- information, including types of instruments manufactured
ence program [31] is available by means of which a user's and their design features and performance characteristics,
instrument performance can be compared to that obtained can best be found by first consulting buyers' guides [36,37]
for the same samples by the color community as a whole and that are revised annually. Another useful source of informa-
by national standardizing laboratories. tion is the lists of exhibitors at paint shows, such as the
With proper calibration and maintenance, modern color- descriptions published annually in the Journal of Coatings
measuring instruments are capable of a repeatability and Technology. In contacting suppliers of instrumentation, the
reproducibility far greater than the repeatability with which user might request that they send literature, measure samples
the samples themselves can normally be prepared for indus- sent them, or have a representative visit the user to demon-
trial measurement. Thus, special care must be taken to estab- strate the instrument. Another procedure is to negotiate a
lish a highly reproducible method of paint sample prepara- rental-purchase contract. While some suppliers are reluctant
tion and to establish by careful measurement and periodic to negotiate such contracts, the procedure provides users the
verification the uncertainties associated with this step in the opportunity to evaluate the instrument with their own opera-
measurement process. ASTM standards that deal with these tors at their own facilities. Most major manufacturers cur-
matters are E 1164, E 1331, ASTM Practice for Reducing the rently in the field supply both spectrophotometers and color-
Effect of Variability of Color Measurement by Use of Multiple imeters meeting the descriptions given earlier under
Measurements (E 1345), E 1348, and E 1349. See also ASTM Spectrophotometers and Tristimulus (Filter) Colorime-
Practice for Selection of Coating Specimens and Their Prepa- ters.
ration for Appearance Measurements (D 3964) and Standard Several recent trends provide insight into possible future
Guide for the Preparation, Maintenance, and Distribution of developments in color-measuring equipment and its uses.
Physical Product Standards for Color and Geometric Appear- These trends can be classified in three groups: (1) miniaturi-
ance of Coatings (D 5531). zation, (2) multi-angle evaluation, and (3) location and type
The following two subsections apply mainly to spectropho- of use.
tometers. 1. Miniaturization. Many manufacturers now supply portable
spectrophotometers and colorimeters that provide small
Precision size and light weight. Many are battery operated for full
The modern age of computer-interfaced color measuring portability; others may use fiber-optics probes to separate
spectrophotometers began in the mid-1970s. By then it had the measuring head from the remainder of the instrument.
been clearly demonstrated that such instruments could sur- In many, the precision is good, but limitations related to
pass the eye in the precision of color measurement. Repeat- measurement geometry may increase bias. If very small
ability of instrumental color measurement is about 0.1 illuminated and viewed areas are used, there may be an
CIELAB unit of color difference [32] (see later in this chapter advantage in that smaller portions of samples can be mea-
under Color Difference Calculations). The average repro- sured, but averaging of multiple measurements (see
ducibility within a group of similar instruments is about 0.2 ASTM E 1345) may be required to obtain representative
CIELAB units [33]. Note that 0.5 CIELAB unit is approxi- values for nonuniform samples.
2. Multi-Angle Evaluation. Several manufacturers now supply
mately the smallest difference that can be detected visually.
Repeatability and reproducibility values are published in the instruments with multi-angle geometry for the measure-
Precision and Bias section of ASTM E 1164. ment of goniochromatic samples, such as those containing
metal flake or pearlescent pigments. For research in this
field, a goniospectrophotometer is required. For quality
Bias
control, however, use of one angle of illumination with
This quantity, the difference between a measured result for several angles of view may suffice. As noted earlier under
a standard sample and the result when it is measured in a Spectrophotometers, the selection of illuminating and
reference laboratory, is difficult to quantify in the color field viewing angles has not yet been standardized.
where there are no "absolute" values. It is usual to accept the 3. Location and Type of Use. In earlier times, production sam-
results obtained in a national standardizing laboratory as the ples were taken to a quality-control laboratory for evalu-
reference. On this basis, when instruments are selected to ation. This procedure is still desirable in some instances to
minimize differences in measuring geometry and are prop- permit control of such variables as ambient light, tempera-
erly calibrated and used, the average bias for a group of ture and humidity, and atmospheric contamination, but
standard samples can be as low as 0.5 CIELAB unit [34]. In today time is being saved by making measurements on the
addition, the differences between the two sets of measure- production floor. For continuous processes, on-line instru-
ments can be utilized effectively to model and correct the mentation is finding greater use. In addition, color mea-
systematic spectrophotometric errors leading to the bias [35]. surement and computer-aided color matching (see later in
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C H A P T E R 4 0 - - C O L O R AND L I G H T 465
this chapter under Instrumental and Computer-Aided Alternative equations for determining AH* and its sign have
Color Matching) are today finding extensive use at point- been described [41]. The unit of CIELAB color difference is
of-purchase locations such as retail paint stores. two to three times the just perceptible color difference.
In the use of color differences, it is important to examine
the components of the color difference, such as AL*, Aa*, and
Ab*, or AL*, AC*, and AH*, as well as AE* itself. The magni-
COLOR DIFFERENCE EVALUATION FOR tudes and signs of these components can provide valuable
COLOR CONTROL information on remedial action needed to bring a production
batch on shade.
The control of the color of industrial paint products may be The interpretation of measured color differences becomes
aided by use of the results of color measurement, as described more complex when the specimens are goniochromatic and
in the last section. The instruments provide color coordinates measurements are made at several combinations of illumi-
of sample and standard from which accurate measures of nating and viewing angles. The quantitative meaning of color
color difference may be derived. These data can also be used differences as the angles change has not yet been thoroughly
to establish color tolerances. Of course, color differences may studied.
also be judged visually, and several ASTM standards address Since the adoption of the CIELAB equations and their in-
this topic: ASTM Practice for Visual Estimation of Color Dif- clusion in ASTM D 2244, a number of new color-difference
ferences (D 1729), ASTM Test Method for Evaluation of Vi- equations have been developed. One of these, known as the
sual Color Difference With a Gray Scale (D 2616), and ASTM CMC (1 :c) equation [42,43], is a modification of CIELAB that
Guide to the Selection, Evaluation, and Training of Observers has improved uniformity of visual perception of its color
(E 1499). This guide also describes materials and methods differences. It will be included in an "ASTM Guide to the
for the testing and evaluation of the observer's color vision. Selection and Use of Color-Difference Equations" (under de-
velopment).
Color-Difference Calculations Color Tolerances

In the 1931 and 1964 CIE systems, equal distances in differ- A valuable means of recording the experience gained in the
ent parts of color space do not represent equally perceived production of a given color is through the use of color toler-
color differences. Although many proposals for more uni- ances, expressed as numerical limits to AE* and its compo-
form color spaces have been made, an ideally uniform space nents or as color-tolerance charts. Because no color space is
has not been and may not ever be devised. However, modern entirely uniform and industrial color tolerances are often
color-measuring instruments compute sets of color coordi- based on acceptability considerations between buyer and
nates that correlate better with perceived color differences seller, not perceptibility, color differences should be used
than do CIE tristimulus values. only as a guide until enough experience has been accumu-
Among the many modifications of CIE tristimulus values lated for each color to allow specification of a tolerance limit,
that have been proposed for more uniform color spaces,
those proposed by Hunter [29], MacAdam [38-40], and the Tolerance Charts
CIE [12] are preferred for use in the paint industry and are Color-tolerance charts are usually enlarged sections of a
given in ASTM Test Method for Calculation of Color Differ- nearly visually equally spaced diagram, such as the CIELAB
ences from Instrumentally Measured Color Coordinates a*, b* diagram. A color-tolerance chart is set up with the
(D 2244). The most widely used of these is the CIE 1976 coordinates of the standard at the center, and the differences
L*a*b* (CIELAB) space discussed earlier in the subsection Aa* and Ab* of production batches are entered as they are
entitled Uniform Color Spaces. Omitting subscripts ab made (Fig. 18a). The process is described in ASTM Practice
throughout for convenience, the total CIELAB color differ- for Establishing Color and Gloss Tolerance (D 3134). As ex-
ence, AE*, is given by perience is gained, it should be possible to draw a tolerance-
limit curve enclosing most, if not all, of the acceptable
AE* = [(AL*)2 + (Aa*)2 + (Ab*)2] 1'z batches and excluding most, if not all, of the unacceptable
where, for example, AL* = LTRIA L -- LSTANDARD. It is conve- batches. Because no known diagram is perfectly visually uni-
nient to express AE* in terms of differences in the Munsell- form, the tolerance limit figure may not be a circle or an
type coordinates hue, chroma, and lightness, but the hue ellipse and may not be centered on the location of the stan-
angle h defined earlier in the subsection entitled Uniform dard.
Color Spaces does not have the same dimensions and scaling Lightness differences between the standard and batch
as chroma C* and lightness L*. Instead of using h, it is must also be taken into account. This can be done by use of a
necessary to define CIELAB hue difference AH* to combine separate tolerance for AL*, but better practice is to use a
with AC* and AL* second chart (Fig. 18b), in which AL* is plotted against either
Aa* or Ab*, depending on the data. The batch readings should
AH* = [(AE*) 2 - (AC*)2 - (AL*)2]'/2 fall within the tolerance figure on both charts.
Then It must be emphasized that the final criterion for accep-
tance of a color is always its visual appearance, to which
~* = [ ( A H * ) 2 -~ (AC~") 2 -}c (z~kn*)2] I/2 instrumental measurements, color differences, and tolerance
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0
0
0
AL*
2
O
L3y~rld: X Accelml~Match
B Border~e~
O
9 ~Color O
Ab*
I
o
-!
0 8
0
0
-!
II I I , , , ~ Aa*
'
-2 - 0 I
Aa" l 2z ., ,, , 2
(b) ~ Tolerances
FIG. 18-Color tolerance charts plotted in the CIELAB system: (a) chromaticity tolerance figure on a Aa*, Ab* diagram; (b)
lightness tolerance figure on a AL*, Aa* diagram. In this case, a plot of AL* versus Ab* would have served as well. (Based on
ASTM D 3134.)
charts provide only clues. Instrument malfunctions, mis- area of the card, produce white again (Fig. 19). In this area,
calibrations, miscalculations, and operator errors can be re- the reflected lights from the three sources add together. These
vealed only by use of confirming visual observations. three lights are called the additive primaries. By adjusting the
intensities of each of the three lights, a wide range of colors
can be produced.
Indices of Metamerism
The procedure just described can provide an analytical tool
Another important use of color-difference equations is to for color measurement. If an adjacent spot on the white card
quantify indices of metamerism as an aid in reducing this is illuminated by light of an unknown color, it could be
defect between standard and batch. The CIE [12,44] has rec- matched visually, in principle, with the three-light combina-
ommended that indices of metamerism be calculated as the tion by adjusting their intensities. This is the basis for color
color differences between two samples that match under a matching by addition of lights. The additive principle is used
standard illuminant or to a standard observer when mea- to produce the colors in television [45].
sured for a test illuminant or a test observer. For illuminant The analytical device described above is also a simple ver-
metamerism, the standard illuminant is usually daylight, and sion of the visual colorimeter used to generate the tristimulus
the second can be selected by the user. For observer values of the spectrum colors that form the basis for the CIE
metamerism, the standard observer is either the CIE 193l or Standard Observers (see earlier in this chapter under CIE
1964 observer, and a corresponding second "standard de- S t a n d a r d Observers). At each wavelength, the total light
viate" observer is provided [44] based on the range of normal reflected is the sum of the power reflected from each of the
color vision found in the human population. three primary lights. Since tristimulus values are obtained by
adding such sums across the spectrum, they too are produced
by additive mixing. It is not necessary to know the spectral
COLOR MIXING nature of the additive primaries to predict the resulting
colors.
Additive Mixing of Lights
When a white card is illuminated, its apparent color is the
Subtractive Mixing in T r a n s p a r e n t Films
color of the incident light; a red light, for example, makes it
appear red. Three colored lights (red, green, and blue), if Now consider the light falling on a white card after passing
carefully chosen, would, when placed to overlap on the same through a film that contains three transparent colorants, yel-
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CHAPTER 40--COLOR AND LIGHT 4 6 7
result would be black (Fig. 20). These three colorants are

called the subtractive primaries. If varying quantities of them
were combined in subtractive mixing, a wide variety of colors
could be produced. However, these mixture colors cannot be
RED / ~ GREEN predicted from the colors of the primaries alone, as in the
additive mixing described above. One must also know their
YELLOW
spectral character and compute, wavelength by wavelength,
how much light is removed by each primary through absorp-
tion, using the well-known Beer's law relationship. From
what is not absorbed, tristimulus values can be calculated in
the usual way.
MAGENTA A CYAN
Pigment M i x i n g
Most paint films contain, in addition to three colored pig-
ments (one of which may be black), a white pigment used as
an opacifier. The mixing of colors produced in this way is
more complex than simple subtractive mixing in transparent
BLUE
films because of the scattering of light caused by the white
pigment (and by opaque colored pigments as well). Again, it
is necessary to know the spectral character of all the colo-
rants present. The Beer's law calculation of the transparent
case is replaced by the Kubelka-Munk relation: For opaque
FIG. 19-Representation of the additive mixing of colored films, as is usually the case in the paint industry, this is a
lights showing the additive primaries red, green, and blue form- simple equation relating the reflectance R(h) of the film at
ing the mixture colors yellow, cyan, and magenta where the each wavelength to the~ratio of two constants describing what
primaries overlap in pairs and white where all three overlap. happens to the light in the film
K(A)/S(A) = [1 - R(A)]2/2R(A)
low, cyan (blue-green), and magenta (red-purple). This might
be the situation with a free-standing transparent plastic film, where K(A) is the Kubelka-Munk absorption coefficient, and
for example. If the three colorants were ideally chosen, all the S(~t) is the Kubelka-Munk scattering coefficient. Here R(X)
must be expressed as a fraction, not the usual percentage. The
light would be absorbed when all three were present, and the
quantities K(X) and S(X) refer to the mixture of pigments in
the paint film. These are calculated by adding the separate
contributions of each pigment, using its K(X) and S()t)
weighted by its concentration C in the mixture
K(A)MIXTUR E -- C~KI(A) + C2K2(A) + 999
YELLOW CYAN S(X)MIXTURE C l S l ( X ) -b C282()k) -{- 9 . .
GREEN where there are as many terms as there are pigments used.
These equations form the basis for computer color matching
described in the next section.
COLOR MATCHING
RED X BLUE
One of the major objectives of industrial coloring is to
match the color a customer wants. Whether this is done
visually or with the aid of instruments and computers is often
a matter of work load and economics. Therefore we address
both visual and instrumental matching. In either case, a
major objective of color matching in paint systems is the
formulation of a nonmetameric match to a given paint sam-
MAGENTA ple. The difference in spectral character of the samples of
a metameric pair is the property determining their metam-
erism, and achieving a nonmetameric match places several
FIG, 20-Representation of the subtractive color mixing of requirements on the formulation.
transparent colorants showing the subtractive primaries yel- First, the same pigments must be used. This requires iden-
low, cyan, and magenta forming the mixture colors green, blue, tification of the pigments in the sample to be matched. Sec-
and red where the primaries are mixed in pairs and black where ond, the pigments must be used in the same resin system
all three are mixed together. since the spectral properties of pigments can depend upon
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the choice of binder. Finally, the s a m e degree of d i s p e r s i o n tions of m e t a m e r i s m indices a n d p i g m e n t costs allow the
m u s t be achieved since the a b s o r p t i o n a n d scattering p r o p e r - selection of the m o s t suitable results.
ties of p i g m e n t s that d e t e r m i n e their spectral c h a r a c t e r C o m p u t e r color m a t c h i n g has been discussed in a b o o k
change with degree of dispersion. This usually m e a n s that the [49], a n d some textbooks [1,2,5,50,51] provide useful sum-
s a m e m e t h o d of d i s p e r s i o n m u s t be used. maries. The underlying K u b e l k a - M u n k theory, applied to
p a i n t systems, has been the subject of several articles [52-55]
directed to p a i n t colorists. More complex theory a p p e a r s to
Visual Color Matching be n e e d e d only in special cases, such as m a t c h i n g a u t o m o t i v e
The selection of visual color m a t c h e r s should be m a d e with p a i n t s containing metal flake or pearlescent pigments. The
great care, a n d reference should be m a d e to ASTM E 1499 d e v e l o p m e n t of such theories is still in its early stages.
for details of h o w to m a k e the selection, test the color vision
of the candidates, a n d t r a i n t h e m in m a k i n g visual judg-
ments.
REFERENCES
Beyond this there is no substitute for the experience of the
visual color matcher. He or she m u s t learn the skill by prac- [1] Billmeyer, F. W., Jr. and Saltzman, M., Principles of Color Tech-
tice. This should include b e c o m i n g familiar with one of the nology, 2nd ed., Wiley, New York, 1981.
better color o r d e r systems a n d atlases a n d learning h o w to [2] Hunter, R. S. and Harold, R. W., The Measurement of Appear-
use it, coupled with knowledge of the b e h a v i o r of the p a i n t ance, 2nd ed., Wiley, New York, 1987.
system a n d p i g m e n t s available, to predict the colors that [3] Wyszecki, G. and Stiles, W.S., Color Science: Concepts and
result from mixing t h e m u n d e r carefully controlled condi- Methods, Quantitative Data and Formulae, 2nd ed., Wiley, New
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sential. Visual m e t h o d s of recognizing a n d controlling [4] Hunt, R. W. G., Measuring Colour, 2nd ed., Ellis Horwood,
m e t a m e r i s m have been d e s c r i b e d [46,47]. These require no Chichester, England, 1991.
[5] McDonald, R., Ed., Colour Physics for Industry, Society of Dyers
m o r e than knowledge of the b e h a v i o r in mixtures of the
and Colourists, Bradford, England, 1987.
p i g m e n t s used a n d a good color m a t c h i n g b o o t h (see earlier [6] McLaren, K., The Colour Science of Dyes and Pigments, 2nd ed.,
in this c h a p t e r u n d e r Color Matching Booths). Adam Hilger, Bristol, England, 1986.
[7] CIE-IEC International Lighting Vocabulary, Publication CIE No.
17.4, Central Bureau of the CIE, Vienna, 1987.
Instrumental and Computer-Aided Color [8] ASTM Standards on Color and Appearance Measurement, 4th ed.,
Matching ASTM, Philadelphia, 1994.
The i m p o r t a n c e of eliminating m e t a m e r i s m dictates that, [9] Burnham, R. W., Hanes, R. M., and Bartleson, C. J., Color: A
for a color m a t c h i n g aid, the i n s t r u m e n t of choice is clearly Guide to Basic Facts and Concepts, Wiley, New York, 1963.
[10] Boynton, R.M., Human Color Vision, Holt, Rinehart and
the s p e c t r o p h o t o m e t e r . Display of the spectral curves of sam-
Winston, New York, 1979.
pies, and the c o m p u t e r - a i d e d c o l o r - m a t c h i n g o p e r a t i o n s that
[1t] Hurvich, L. M., Color Vision, Sinauer, Sunderland, MA, 1981.
lead to spectral curve shapes m i n i m i z i n g m e t a m e r i s m , can- [12] Colorimetry, 2nd ed., Publication CIE No. 15.2, Central Bureau
not be achieved by the use of o t h e r types of instruments. The of the CIE, Vienna, 1986.
s p e c t r o p h o t o m e t e r can also be used in a simple but powerful [13] ClE Standard on Colorimetric Illuminants, Publication CIE No.
m e t h o d of organic p i g m e n t identification [48] b a s e d on ex- $001 (ISO IS 10526), Central Bureau of the CIE, Vienna, 1986.
t r a c t i o n of the p i g m e n t s into solution followed by spectro- [14] A Method for Assessing the Quality of Daylight Simulators for
p h o t o m e t r y . This can be an i m p o r t a n t aid to selecting the Colorimetry, Publication CIE No. 51, Central Bureau of the CIE,
s a m e p i g m e n t a t i o n for the m a t c h as was used in the stan- Vienna, 1981.
dard. [15] CIE Standard on Colorimetric Observers, Publication CIE No.
M a n y m o d e r n c o l o r - m e a s u r i n g s p e c t r o p h o t o m e t e r s can be $002 (ISO IS 10527), Central Bureau of the CIE, Vienna, 1986.
o b t a i n e d with c o m p u t e r software for color matching. Most of [16] Billmeyer, F. W., Jr., "A Survey of Color Order Systems," Color
Research and Application, Vol. 12, 1987, pp. 173-186.
these systems w o r k very well, b u t it m u s t be e m p h a s i z e d that
[17] Agoston, G. A., Color Theory and Its Application in Art and De-
the i n v e s t m e n t in b u i l d i n g up the d a t a b a s e that is essential sign, 2nd ed., Springer, New York, 1987, Chaps. 8-10.
for their use, a n d in taking all the steps necessary to bring the [18] Newhall, S. M., Nickerson, D., and Judd, D. B., "Final Report of
coloring process u n d e r precise control, is not a small one; the O. S. A. Subcomnqittee on the Spacing of the Munsell
only when large n u m b e r s of colors m u s t be m a t c h e d on a Colors," Journal, Optical Society of America, Vol. 33, 1943, pp.
daily basis can the cost of setting up a n d m a i n t a i n i n g such a 385-418.
system be justified. [19] Judd, D. B., Color in Business, Science and Industry, 1st ed.,
The details of h o w c o m p u t e r color m a t c h i n g works are Wiley, New York, 1952.
b e y o n d the scope of this chapter. In s u m m a r y , most systems [20] Kelly, K. L. and Judd, D. B., "Color: Universal Language and
call for m e a s u r e m e n t of the s a m p l e to put its spectral d a t a Dictionary of Names," NBS Special Publication 440, U.S. Gov-
into the computer. These d a t a are m a t c h e d at each of (usu- ernment Printing Office, Washington, 1976.
ally) 16 wavelengths across the s p e c t r u m by Kubelka-Munk- [21] Jacobson, E., Basic Color." An Interpretation of the Ostwald Sys-
tem, Paul Theobald, Chicago, 1948.
type calculations (see earlier u n d e r Pigment Mixing), using
[22] Granville, W. C., "Color Harmony Manual, a Color Atlas Based
stored values of K(A) and S(h) for the useful p i g m e n t s in the on the Ostwald Color System," Color Research and Application,
p r o d u c t line. The results a r e the p i g m e n t concentrations in Vol. 19, 1994, pp. 77-98.
the formulation. Several f o r m u l a t i o n s arising from m i x i n g [23] Richter, M. and Witt, K., "The Story of the DIN System," Color
different p i g m e n t s are usually produced. Additional calcula- Research and Application, Vol. 11, 1986, pp. 138-145.
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[24] HS.rd, A. and Sivik, L., "NCS--Natural Color System: a Swedish [41] S~ve, R., "New Formula for the Computation of CIE 1976 Hue
Standard for Color Notation," Color Research and Application, Difference," Color Research and Application, Vol. 16, 1991, pp.
Vol. 6, 1981, pp. 129-138. 217-218.
[25] MacAdam, D. L., "Uniform Color Scales," Journal, Optical Soci- [42] McDonald, R., "Industrial Pass/Fail Colour Matching," Journal,
ety of America, Vol. 64, 1974, pp. 1691-1702. Society of Dyers and Colourists, Vol. 96, 1980; Part I, pp.
[26] Nickerson, D., "Uniform Color Scales Samples: A Unique Set," 372-376; Part II, pp. 418-433; Part III, pp. 486-495.
Color Research and Application, Vol. 6, 1981, pp. 7-33. [43] News: "CMC Colour-Difference Formula," Color Research and
[27] Stanziola, R., "The Colorcurve System| '' Color Research and Application, Vol. 9, 1984, p. 250.
Application, Vol. 17, 1992, pp. 263-272. [44] Special Metamerism Index: Change in Observer, Publication CIE
[28] Johnston, R.M., "Colorimetry of Transparent Materials," No. 80, Central Bureau of the CIE, Vienna, 1989.
Journal of Paint Technology, Vol. 43, No. 553, 1971, pp. 42-50. [45] Hunt, R. W. G., The Reproduction of Colour in Photography,
[29] Hunter, R.S., "Photoelectric Tristimulus Colorimetry with Printing and Television, 4th ed., Fountain Press, Tolworth, En-
Three Filters," Journal, Optical Society of America, Vol. 32, 1942, gland, 1988, distributed by Van Nostrand Reinhold, New York.
pp. 509-538. [46] Longley, W. V., "A Visual Approach to Controlling Meta-
[30] Carter, E. C., Billmeyer, F. W., Jr., and Rich, D. C., "Guide to merism," Color Research and Application, Vol. 1, 1976, pp.
Material Standards and Their Use in Color Measurement," ISCC 43-49.
Technical Report 89-1, Inter-Society Color Council, Princeton, [47] Winey, R. K., "Computer Color Matching with the Aid of Visual
NJ, 1989; see also Carter, E. C. and Billmeyer, F, W., Jr., "Mate- Techniques," Color Research and Application, Vol. 3, 1987, pp.
rial Standards and Their Use in Color Measurement," Color 165-167.
Research and Application, Vol. 4, 1979, pp. 96-100. [48] Kumar, R., Billmeyer, F. W., Jr., and Saltzman, M., "Identifica-
[31] Color & Appearance Interlaboratory Testing, Collaborative Test-
tion of Organic Pigments in Paints," Journal of Coatings Technol-
ing Services, Inc., Herndon, VA 22070.
ogy, Vol. 57, No. 720, 1985, pp. 49-54; see also Billmeyer, F. W.,
[32] Billmeyer, F. W., Jr. and Alessi, P. J., "Assessment of Color-mea-
Jr., Saltzman, M., and Kumar, R., "Identification of Organic
suring Instruments," Color Research and Application, Vol. 6,
Pigments by Solution Spectrophotometry," Color Research and
1981, pp. 195-202.
[33] Stanziola, R., Momiroff, B., and Hemmendinger, H., "The Spec- Application, Vol. 7, 1982, pp. 327-337.
tro Sensor--A New Generation Spectrophotometer," Color Re- [49] Kuehni, R. G., Computer Colorant Formulation, D.C. Heath,
search and Application, Vol. 4, 1979, pp. 157-163. Lexington, MA, 1975.
[34] Billmeyer, F. W., Jr. and Hemmendinger, H., "Instrumentation [50] Judd, D. B. and Wyszecki, G., Color in Business, Science, and
for Color Measurement and its Performance," Golden Jubilee of Industry, 3rd ed., Wiley, New York, 1975.
Colour in the C1E, Society of Dyers and Colourists, Bradford, [51] Allen, E., "Colorant Formulation and Shading," Chap. 7 in Color
England, 1981, pp. 98-112. Measurement, F. Grum and C. J. Bartleson, Eds. Academic, New
[35] Berns, R. S. and Petersen, K. H., "Empirical Modeling of Sys- York, 1980, pp. 290-336.
tematic Spectrophotometric Errors," Color Research and Appli- [52] Billmeyer, F. W., Jr. and Abrams, R. L., "Predicting Reflectance
cation, Vol. 13, 1988, pp. 243-256. and Color of Paint Films by Kubelka-MunkAnalysis," Journal of
[36] Optical Industry and Systems Purchasing Directory, Optical Pub- Paint Technology, Vol. 45, No. 579, 1973; Part I, pp. 23-30; Part
fishing Co., Pittsfield, MA, annually. II, pp. 31-38.
[37] Modern Paint and Coatings Paint Red Book, Communications [53] Mudgett, P. S. and Richards, L. W., "Kubelka-Munk Scattering
Channels, Inc., Atlanta, annually. and Absorption Coefficients for Use with Glossy, Opaque Ob-
[38] MacAdam, D. L., "Visual Sensitivities to Color Differences in jects," Journal of Paint Technology, Vol. 45, No. 586, 1973, pp.
Daylight," Journal, Optical Society of America, Vol. 32, 1942, pp. 43-53.
247-274. [54] Phillips, D. G. and Billmeyer, F. W., Jr., "Predicting Reflectance
[39] Chickering, K.D., "Optimization of the MacAdam-Modified and Color of Paint Films by Kubelka-Munk Analysis. IV.
1965 Friele Color-Difference Formula," Journal, Optical Society Kubelka-MunkScattering Coefficient," Journal of Coatings Tech-
of America, Vol. 57, 1967, pp. 537-541. nology, Vol. 48, No. 616, 1976, pp. 30-36.
[40] Chickering, K. D., "FMC Color-Difference Formulas: Clarifica- [55] Rich, D. C., "Computer-Aided Design and Manufacturing of the
tion Concerning Usage," Journal, Optical Society of America, Vol. Color of Decorative and Protective Coatings," Journal of Coat-
61, 1971, pp. 118-122. ings Technology, Vol. 67, No. 840, 1995, pp. 53-60.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Gloss
by Harry K. Hammond 1111 and Gabriele Kigle-Boeckler2
THE APPEARANCEOFANOBJECTor material can be described by Specular Gloss

its color and gloss characteristics. Like color, gloss can be
Specular gloss is defined in ASTM E 284 [3] as the "ratio of
subdivided into several aspects depending on viewing condi-
flux reflected in specular direction to incident flux for a speci-
tions. In 1937, Richard Hunter identified five aspects of gloss
fied angle of incidence and source and receptor angular aper-
[1] and the functions of reflectance by which they could be
tures" (Fig. 4). This aspect of gloss has been measured most
evaluated. Latest studies by K. Lex [2] expanded Hunter's
frequently because it is the one for which an instrument is
gloss terms and divided them into two groups. One group is
most easily constructed. In practice the divergence angles of
based on visual observation with the eye focused on the
source and receptor are precisely specified in ASTM Test
surface of the material (Fig. 1). For the other group, the eye is
Method for Specular Gloss (D 523) [4] as are the directional
focused on the image of the object reflected by the material
angles of incidence and reflection. Tolerances are specified
(Fig. 2). However, experience has shown that no single objec-
for all angles. For simplicity, glossmeter geometries are iden-
tive measurement of gloss will provide perfect correlation
tified by reference to the incidence angles, most frequently
with the integrated subjective appraisal of glossiness that the
20, 60, and 85~. However, the associated source and receptor
eye so quickly renders. For this reason, the gloss evaluation
aperture angles and their tolerances play a vital role in deter-
requirement of an object or material should first be examined
mining the reproducibility of instrument readings.
and the most useful gloss measurement aspects then selected.
Sheen
A S P E C T S OF GLOSS A N D T H E I R Sheen is defined in ASTM E 284 [3] as "the specular gloss at
DEFINITION a large angle of incidence for an otherwise matte specimen."
The usual angle for sheen measurement is 85 ~ from the per-
The simple term "gloss" is defined in an ASTM standard, pendicular to the specimen. This is about the maximum angle
Terminology of Appearance (E 284) [3] as "angular selectivity that can be used without encountering difficulty in position-
of reflectance, involving surface-reflected light, responsible ing the optics to illuminate and view the specimen at near-
for the degree to which reflected highlights or images of grazing angles.
objects may be seen as superimposed on a surface." To indi-
cate specific types of "angular selectivity," such as those in-
volving specular gloss, sheen, or haze and to illustrate the Haze
difference between an evaluation where the focus is on the Haze in coating films is often designated "reflection haze"
surface and one where the focus is on the reflected image, the because in plastics there is encountered a near-forward scat-
complexity of the phenomenon "gloss" is illustrated in Fig. 3. tering in transmission that is designated transmission haze.
By focusing on the reflected image of an object, an observer ASTM E 284 [3] defines haze in reflection as "percent of
obtains information on how distinctly the object is reflected reflected light scattered by a specimen having a glossy surface
by the surface. A reflected light source may appear brilliant or so that its direction deviates more than a specified angle from
diffuse depending on the specular gloss of the surface. The the direction of specular reflection."
outline of a reflected object may appear distinct or blurred
depending on image clarity. A halo surrounding the image of
the reflected object is an indication of haze. Focusing on the Image C l a r i t y
surface of an object provides information on the size, depth,
and shape of surface structures contributing to such things as This aspect of gloss has often been referred to as "distinct-
waviness or directionality of brush marks. ness of image." It is essentially independent of haze or change
in specular gloss. ASTM E 284 [3] defines distinctness-of-
image gloss as "the aspect of gloss characterized by the
~Consulting scientist, BYK-Gardner USA,2435 Linden Lane, Silver
Spring, MD 20910. sharpness of images of objects produced by reflection at a
2Technical marketing manager, gloss, BYK-Gardener USA, 2435 surface." During visual observation, the sharpness of the
Linden Lane, Silver Spring, MD 20910. light-dark edge of a reflected object can be observed. Image
470
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CHAPTER 4 1 - - G L O S S 471
/
m
FIG. 1-Observer focuses on the image of reflected object.
clarity is a critical parameter of glossy surfaces having only has m a n y small indentations that are perceived as a pattern
small amounts of waviness. of both highlighted and non-highlighted areas. This pattern is
interpreted by an observer as a three-dimensional structure
of hills and valleys.
Waviness
One obvious type of waviness is designated "orange peel."
ASTM E 284 [3] defines orange peel as "the appearance of
Directionality
irregularity of a surface resembling the skin of an orange." A ASTM E 284 [3] defines directionality, perceived, as "the
surface m a y be described as exhibiting orange peel when it degree to which the appearance of a surface changes as the
\t....O O0
FIG. 2-Observer focuses on the illuminated surface of object.
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appearance [
I I
! I !
I
focus on surface focus on reflected J

Image
I
I I i
waviness distinctnessof image J

(OOI)
I
=': II I tl II
FIG. 3-Flow chart depicting relationships of various appearance characteristics.
surface is rotated in its own plane, under fixed conditions of VISUAL G L O S S EVALUATION
illumination and viewing." A surface exhibits directionality
when specular gloss measurements are a function of the di- Early investigations of gloss were carried out by observing
rection for which measurements are made. When paint is differences in the characteristics of images reflected in the
applied by brushing in one direction, the brush marks can surfaces of specimens. In 1932, the Detroit Paint and Varnish
cause the surface to have a directional characteristic. Metallic Production Club [5] reported on investigations carried out
materials frequently exhibit directionality when the surface is with their distinctness-of-image gloss comparator. In 1936,
polished in one direction. Hunter [6] reported an investigation where reflected images
of a target pattern were observed.
FIG. 4-Reflected light flux distribution from a semigloss surface is depicted by a broken
curve. Three lines are shown proceeding from the specimen surface. The center one depicts
the specular direction, the image of a ray reflected from a mirror-like surface. The two other
rays represent the range of angles passing through the aperture (AP) to the detector (shown
as a rectangle).
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FIG. 5-"Landolt Rings." Broken rings of bvarious sizes are used to provide a
scale for visual evaluation of the distinctness of surface-reflected images?
Only in comparatively recent times has there been a major light sources. One source consists of a tubular fluorescent
effort to investigate visual scaling of gloss and to endeavor to desk lamp modified by placing a matte-black reflecting mate-
develop correlation between visual and instrumental mea- rial behind the tubes and a coarse wire-mesh screen in front.
surements. O'Donnell did a doctoral thesis on visual gloss The directions of illumination and view can be adjusted to be
scaling at Rensselear Polytechnic Institute, Troy, New York. 20, 60, or 85 ~as desired for comparing specimens having high
Results were first presented, in part, at an ASTM Symposium gloss, intermediate gloss, or sheen. The other light source is a
in 1984 [7] and more fully in a journal article in 1987 [8]. clear-bulb incandescent lamp. Light from the selected source
illuminates the specimens at the chosen angle. The sharpness
of reflected images permits a subjective comparison of the
Development o f a Documentary Standard relative gloss of similar surfaces.
In 1990, ASTM Committee D-1 on Paint and Related Coat-

ings and Materials published ASTM Method for Visual Evalu-
Use o f Landolt Rings
ation of Gloss Differences Between Surfaces of Similar Ap-
pearance (D 4449) [9] for making visual evaluations of gloss Landolt rings have been used by ophthamologists to evalu-
between surfaces of similar appearance. It uses two types of ate visual acuity for nearly a hundred years [10]. The test
www.iran-mavad.com

FIG. 6-Schematic diagram of a gloss meter. Source is on left, detector on right. Lenses are
used to provide beam control. Source aperture is designated AP1, receptor aperture AP2.
consists of locating the gaps in a graduated series of sizes of INSTRUMENTAL MEASUREMENT

incomplete rings whose radial thickness and gap are equal to TECHNIQUES
one fifth the diameter of the ring. For gloss evaluation of
trans-illuminated rings, reflections are viewed on mylar. Specular Gloss Measurement
Rings have different sizes and different gap orientations. An
image-gloss scale is associated with the different sizes of The design of many gloss meters is based on the precise
rings. An image-gloss scale ranging from 10 to 100 in steps of measurement of the specular component of reflected light. A
ten was established for eleven sizes of rings from the largest light source, usually a small filament incandescent lamp, is
to the smallest. The development of the scale is not docu- placed at the focal point of a collimating lens. The axis of the
mented, but it ostensibility took place in the General Motors collimated beam is set to the desired angle of illumination. A
Automotive Division about January 1977. Visual observers receptor lens with an aperture in the focal plane followed by
select the smallest size of ring for which they can call the gap an illumination detector completes the basic optical design
orientation correctly. The numerical size of the rings is used (Fig. 6 and Fig. 7). The size of the receptor aperture and the
as an inverse index of distinctness-of-image gloss (Fig. 5). size of the source image in that aperture are the elements that
ASTM has not published a method for visually evaluating complete the optics and that determine the high, low, and
distinctness-of-image gloss by using Landolt rings, but equip- intermediate gloss scale readings. The specular angle largely
ment for this purpose is available?
determines the magnitude of the reflected light. However, the
tolerances assigned to the source and receptor apertures are
Visual Evaluation of Orange Peel what determine the accuracy and reproducibility of measure-
ments made with instruments having the same angles of
The automotive industry established a physical standard illumination and view.
for orange peel consisting of ten high-gloss panels with vari-
Periodic calibration or verification of instrument perform-
ous degrees of orange peel structure. 4 The panels are visually
ance requires the use of calibrated gloss standards. For per-
ranked from 1 to 10 with Panel Number 1 depicting very
pronounced orange peel and Panel Number 10 illustrating no manence they should be made of glass or ceramic material.
orange peel. The visual observer can use these panels as a ASTM D 523 recommends the use of a primary standard of
supportive tool to evaluate degree of orange peel. polished black glass of known refractive index for which the
Fresnel (specular) reflectance [11] has been computed for
3Apparatus for evaluating distinctness of image using Landolt the angle of incidence of the geometry for which the instru-
rings, available from Paul N. Gardner Co., Pompano Beach, FL. ment is designed. Since about 1990, national standardizing
4Set of orange-peel panels can be obtained from Advanced Coat- laboratories have preferred a primary reference stan-
ings Technology, 273 Industrial Dr., Hillsdale, MI 49242.
www.iran-mavad.com

CHAPTER 41--GLOSS 475
FIG. 7-Photograph of a modern miniature glossmeter. Note size of the hand holding the
instrument?
FIG. 8-Diagram depicting the positions of source and receptor for the three geometries of
ASTM D 523.
SApparatus designated "micro-TRLgloss," available from BYK-

Gardner USA, Silver Spring, MD.
www.iran-mavad.com

476 PAINT AND COATING T E S T I N G M A N U A L
dard made of a wedge of clear quartz. Polished black glass /'--- PHOTOT/JBE I "~
working standards can be calibrated by direct comparison of / I ~o,,or,,,E. ,~Ms,Z,_~ 2
.SOURCE N 7"
their reflectances with that of a quartz wedge. /x,..-.~. ~ VIEW/N(; ,BEAM t / "~'~ ~' BEAM
Experience has shown that a single measurement geome- - - ~
try, such as 60 ~, m a y not provide instrument readings of gloss /I \ "~1~ V- l_ - ~ ,'/ .-,
that correlate well with visual observations when comparing II \ I X ~ ~ z-----~ ,'V , ..." ji,
different gloss levels. This is why ASTM D 523 [4] provides for
II
'/ .NI.,~-~
/ "f'/l'.'}".'.. ~
I ""'~Z,,,.
// / d" ~.. / .-'""'.
9
- "" ~
measurement at three different angles of incidence, namely / .,,;

Z-COLLtCT&Q \ ",'~ I I ,/,
/ , +x f / . .'" \\
Lt,~S \ ",,',,9 ~ / "3 ~- I
20, 60, and 85 ~ (Fig. 8). Each of the three geometries uses the / ..
same source aperture, but a different receptor aperture. The

choice of geometry depends on whether one is: (1) making a
general evaluation of gloss, (2) comparing high-gloss finishes
or (3) evaluating low-gloss specimens for sheen. ASTM D 523
[4] states that the 60 ~ geometry is used for intercomparing
most specimens and for determining when the 20 or 85 ~ ge-
ometry may be more applicable. The 20 ~geometry is advanta-
geous for comparing specimens having 60 ~ gloss values
higher than 70. The 85 ~geometry is used for comparing speci-
mens for sheen or near-grazing shininess. It is most fre-
quently applied when specimens have 60 ~ gloss values lower
than 10.
| |169174
The ASTM d o c u m e n t a r y gloss standard originally pub- @o@@
lished in 1939 contained only the 60 ~ geometry [12]. The
desirability of using an auxiliary geometry of 85 ~ for sheen A/,#PZ. /P'/E.r CO~ T R OZ. (,/NIT R~C~O~DER MN/T
evaluation was recognized shortly afterward. However, the FIG. 9 - S c h e m a t i c diagram of a goniophotometer.
use of another geometry with smaller angles of incidence and
view, such as 20 ~ and a smaller receptor aperture to provide
improved differentiation of high-gloss finishes was not pub-
lished until 1947 [13]. The three geometries, 20, 60, and 85 ~,
were originally published as separate ASTM standards. In
1953, ASTM D 523 was revised to incorporate all three geom-
etries, and it still does.
Meanwhile the Paint Committee of the International Orga-
nization for Standardization, ISO TC-35, was investigating
gloss measurements with various commercial instruments
prior to drafting an international standard. A paper docu-
menting what the committee had been doing was published
in 1976 by the Chairman of the Gloss Task Group, Dr. Ulrich
Zorll [14]. In 1978, the ISO Paint Committee published ISO LAMP-',"s~ 18.1 /
2813, essentially an international version of ASTM D 523
[15]. In keeping with the usual ISO procedure, the standard CONDENSERLENS'~/~
A
was made available in English, French, and German.
Instrument manufacturers report that measurement preci- '~'RECEIVER
~
sion, reproducibility, and data-handling capabilities of gloss SOURCESLIT--*'LENS~~
"~
meters have been improved markedly in recent years. New
instruments have been designed that are smaller, more porta-
SOURCEOBJECT '4"~ ~RECEIVER
ble, and more convenient to use. Data storage and analysis / OBJECTLENS
are frequently included as well as the capability of electroni-
cally transferring data to a personal computer [16,17].
! 1
Goniophotometry
Gonio means angle, and photometer means light; so a
goniophotometer is an instrument for measuring the angular
distribution of reflected or transmitted light. This type of
instrument is used regularly in the research laboratory to SPECULARGLOSS
investigate the distribution of light flux (Fig. 9). A go- RECEIVERWINDOW
niophotometer with appropriate apertures can also be used -L""~/AZERECEIVERWINDOW
to provide gloss data for a wide variety of angles and aper- FIG, 1 0 - S c h e m a t i c diagram of an instrument for reflection
tures. When goniophotometric measurements are desired, haze measurement,
www.iran-mavad.com

.CHAPTER 4 I - - G L O S S 477
SPECIMEN - t
SOURCE OBJECT L E N S - ~ //~

\ "'/I ~
~ 5o SLIT
20 SLIT
-- 'D/I SLIT
Rs SLIT
FIG. 12-Schematic diagram of an instrument for image clar-
ity measurement. 7
each side of the s p e c u l a r r e c e p t o r a p e r t u r e (Fig. 10). ASTM

Test Methods for M e a s u r e m e n t of Gloss of High Gloss Sur-
faces by G o n i o p h o t o m e t r y (E 430) [20] describes two meth-
FIG. 11-Photograph of a haze-and-gloss-measuring in- ods for evaluating reflection haze, one at 20 ~, a n o t h e r at 30 ~.
strument? An i n s t r u m e n t using a 30 ~ angle has been c o m m e r c i a l l y avail-
able for m o r e than.15 y e a r s ] Since a b o u t 1992, a 20 ~ labora-
tory gloss m e t e r has been e q u i p p e d with auxiliary a p e r t u r e s
for haze evaluation, thus p e r m i t t i n g m e a s u r e m e n t of 20 ~
reference should be m a d e to ASTM Practice for Go-
n i o p h o t o m e t r y of Objects a n d Materials (E 167) [18], Analy- specular gloss and haze with the s a m e i n s t r u m e n t (Fig. 11).
sis of g o n i o p h o t o m e t r i c curves was t r e a t e d by Nimeroff [19].
Measurement of Reflection Haze Measurement of Image Clarity

Haze is a gloss p a r a m e t e r that causes a high-gloss surface
A variety of different technologies is c o m m e r c i a l l y avail-
to a p p e a r milky and lighter, thereby losing contrast. W h e n
able to m e a s u r e i m a g e clarity [21-24]. The two m o s t often
visually evaluating the reflected image of a hazy object, one
used principles are: (1) m e a s u r e m e n t of the c o n t r a s t in de-
observes halos a r o u n d distinct reflection outlines caused by
p e n d e n c e of the wavelength of the transferred sinus wave
scattered light. Haze can result from various m a t e r i a l or
(fourier-transformation) resulting in a m o d u l a t i o n transfer
process p a r a m e t e r s such as degree of dispersion, floccu-
lation, i n c o m p a t i b i l i t y of raw m a t e r i a l s (pigment-additive- function o r (2) evaluation of the steepness of the reflection
resin) o r from p o o r a p p l i c a t i o n procedures. Microscopic ir- indicatrix. ASTM E 430 [20] describes the design of a com-
regularities cause small a m o u n t s of reflected light to be scat- mercially available i n s t r u m e n t b a s e d on the evaluation of the
tered adjacent to the direction of specular reflection or to reflection indicatrix (Fig. 12). The i n s t r u m e n t illuminates the
modify the refractive index of the m a t e r i a l just b e n e a t h the s p e c i m e n at a 30 ~ angle a n d m e a s u r e s the light reflected at
surface. 0.3 ~ from the s p e c u l a r angle with an a p e r t u r e of 0.3 ~ width.
Haze is m o s t often associated with high-gloss surfaces An a t t e m p t was m a d e to correlate the surface waviness of
when small a m o u n t s of reflected light are scattered in a coatings with i m a g e clarity m e a s u r e m e n t s [23,25]. However,
region 1 to 4 ~ from the direction of specular reflection. There- different surface profiles provided nearly the s a m e i m a g e
fore, it is useful to place apertures several degrees wide on clarity readings [21].
6Apparatus designated "haze-gloss," available from BYK-Gardner 7Apparatus designated "Dorigon," available from Hunter Associ-
USA, Silver Spring, MD. ates Laboratory, Inc., Reston, VA.
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FIG. 13-Photograph of an orange-peel-measuring instrument?
Profile Amplitude
.................,~--T.~F.-.+
@ I E : Dis,anc.
Light Intensity @ ~} @
--I i
r"-~ (~~ ! r"~
@|
Distance
@@@
FIG. 14-Schematic diagram of the measurement principle for evaluation of orange
peel.
8Apparatus designated "wave-scan," available from BYK-Gardner

USA, Silver Spring, MD.
www.iran-mavad.com

Measurement of Waviness (Orange Peel) [5] The Detroit Club, "Accurate Gloss Measurement by a Practical
Means," Scientific Section Circular, No. 423, National Paint,
The p h e n o m e n a of waviness is most observable on a glossy
Varnish, and Lacquer Association (NAPVA), 1932.
surface, a critical appearance p h e n o m e n a in the automotive
[6] Hunter, R. S., "Gloss Investigations Using Reflected Images of a
industry. Waviness has been evaluated by visual m e a n s a n d
Target Pattern," Journal of Research, National Bureau of Stan-
by use of a profilometer. The correlation between profilom-
dards, JRNBS, Vol. 16, 1936, pp. 359-366.
etry m e a s u r e m e n t s a n d visual perception is satisfactory for
[7] O'Donnell, F. X. D. and Billmeyer, F. W., Jr., "Psychometric
surfaces with similar optical properties. The operation of a
Scaling of Gloss," Review and Evaluation of Appearance: Mea-
profilometer, however, is very time c o n s u m i n g a n d limited to surements and Techniques, ASTM STP 914, American Society for
laboratory use. W h e n the eye of an observer is focused o n a Testing and Materials, Philadelphia, PA, 1986, pp. 14-32.
painted surface, various types of waviness can be identified [8] Billmeyer, F. W., Jr. and O'Donnell, F. X. D., "Visual Gloss
that involve size, structure, a n d shape. Variations in process Scaling and MultidimensionalScaling Analysis of Painted Spec-
or material parameters c a n cause differences in surface struc- imens," Color Research and Application, Vol. 12, No. 6, Decem-
ture. For example, poor flow or levelling properties of a coat- ber 1987, pp. 315-326.
ing will usually cause a long wave structure often called or- [9] ASTM Standard D 4449, Test Method for Visual Evaluation of
ange peel. Changes i n substrate roughness, o n the other Gloss Differences Between Surfaces of Similar Appearance, An-
hand, will exhibit a shortwave structure of higher frequency. nual Book of ASTM Standards, Vol. 06.01, American Society for
Because waviness is often caused o n the p r o d u c t i o n line, it is Testing and Materials, Philadelphia, PA, 1994.
i m p o r t a n t to control it there. [10] Landolt, E., "Nouveaux Opto-types pour la determination de
After considerable research, a n i n s t r u m e n t was produced l'acuite visuelle," Archives d'Ophthalmologie, Vol. 19, 1899, pp.
in 1992 that will provide a n objective evaluation of waviness 465-471.
[26] (Fig. 13). [11] Fresnel, A., "Calcul des Tientes que Polarisation Developpe dan
A diode laser source is used to i l l u m i n a t e the specimen at Lames Cristallesees," Annal Chemie et Physic, Vol. 17, 1821, p.
60 ~. The reflected light intensity is evaluated at the specular 312.
angle. During the m e a s u r e m e n t the i n s t r u m e n t is moved [12] Hunter, R. S. and Judd, D. B., "Development of a Method of
along the surface for a distance of a b o u t 10 cm. The intensity Classifying Paints According to Gloss," ASTM Bulletin, No. 97,
of the reflected light is a m a x i m u m w h e n c o m i n g from a 1939, p. 11.
valley or peak of a n orange peel element. The detector re- [13] Homing, S. C. and Morse, M. P., "The Measurement of Gloss of
ceives less light from the slopes (Fig. 14). The h u m a n eye Paint Panels," Official Digest, Federation of Paint and Varnish
c a n n o t resolve the actual heights of the structural elements of Production Clubs, ODFPA, Vol. 19, 1947, pp. 153-160.
a p a i n t e d surface (2 to 4/xm), b u t the contrast between light [14] Zorll, U., "Progress Towards International Agreement on Gloss
a n d dark areas provides a n i m p r e s s i o n of depth. The contrast Measurement of Paint Films," Journal of the Oil and Color Chem-
of a surface structure can be expressed by use of the statistical ists Association, Vol. 59, 1976, pp. 439-442.
p a r a m e t e r "variance." The final m e a s u r e m e n t results are di- [15] ISO 2813, Paints and Varnishes--Measurement of Specular
vided into a short wave c o m p o n e n t (structure size between Gloss of Non-Metallic Paint Films at 20, 60 and 85, International
0.06 a n d 1 ram) a n d a long wave c o m p o n e n t (structure size Organization for Standardization.
between 1 a n d 10 ram) using a n electronic filtering proce- [16] New Product, "The Micro-Gloss Family," Color Research and
dure. This evaluation reflects the s i m u l a t i o n of the visual Application, Vol. 15, No. 4, August 1990, p. 242.
perception at different distances a n d permits categorizing [17] Paint Red Book, Communication Channels, Inc., 6255 Barfield
structure sizes with their causes. Road, Atlanta, GA 30328.
[18] ASTM Standard E 167, Practice for Goniophotometry of Objects
and Materials, Annual Book of ASTM Standards, Vol. 06.01,
American Society for Testing and Materials, Philadelphia, PA,
1994.
[19] Nimeroff, I., "Analysis of Goniophotometric Reflection Curves,"
REFERENCES Journal of Research, National Bureau of Standards, JRNBA, Vol.
48, No. 5, pp. 441-448; also Journal, Optical Society of America,
[1] Hunter, R. S., "Methods of Determining Gloss," NBS Research JOSA, Vol. 42, 1952, pp. 579-583.
Paper RP 958, Journal of Research, National Bureau of Stan- [20] ASTM Standard E 430, Test Methods for Measurement of Gloss
dards, Vol. 18, No. 77, January 1937, p. 281. of High-Gloss Surfaces by Goniophotometry, Annual Book of
[2] Lex, K., "Die erweiterte Glanzmessung und die Messung von ASTM Standards, Vol. 06.01, American Society for Testing and
Oberflaechenstrukturen," Pruftechnik bei Lackherstellung und Materials, Philadelphia, PA, 1994.
Lackverarbeitung, Vincentz Verlag, Hannover, Germany 1992, [21] Czepluch, W., "Visuelle und messtechnische Oberflae-
pp. 70-74. chencharakterisierung dnrch Glanz," Industrie-Lack, Vol. 58,
[3] ASTM Standard E 284, Terminology of Appearance, Annual No. 4, 1990, pp. 149-153.
Book of ASTM Standards, Vol. 06,01, American Society for Test- [22] International Standard ISO 10 215, Anodized aluminum and its
ing and Materials, Philadelphia, PA, 1994. alloys--Visual method of image clarity of anodic oxidation coat-
[4] ASTM Standard D 523, Test Method for Specular Gloss, Annual ings.
Book of ASTM Standards, Vol. 06.01, American Society for Test- [23] Loof, H., "Goniophotometry with the Zeiss GP 2," Journal of
ing and Materials, Philadelphia, PA, 1994. Paint Technology, Vol. 38, No. 501, 1966, pp. 632-639.
www.iran-mavad.com

[24] Matsuta, M., Kito, K., and Kubota, T., "New Portable Orange mit dem Gonioreflektometer GR-COMP," Farbe und Lack, 1985,
Peel Meter for Paint Coatings," Proceedings, Williamsburg Con- Nr. 1 l, 1979, pp. 920-924.
ference, 8-11 Feb. 1987, pp. 25-28. [26] New Product, "Wave-Scan for the Measurement of Surface
[25] Ladstaedter, E. and Gessner, N., "Die quantitative Erfassung Structure," Color Research & Application, Vol. 18, No. 1, Febru-
yon Reflexionsvermoegen, Verlaufsqualitaet und Glanzschleier ary 1993, p. 69.
www.iran-mavad.com

MNL17-EB/Jun. 1995
42
Hiding Power
by Leonard Schaeffer 1
1. CONCEPTS, RELATIONSHIPS, e. Standard Test Substrates

TERMINOLOGY
An opacity test substrate generally has an ordered pattern
of contrasting colors or shades, usually black and white, al-
a. Opacity
though black and grey and grey and white are also used.
When light enters a paint film, some or all of it is absorbed Juxtaposition of contrasting areas permits both visual obser-
or reflected by the film before reaching the substrate, thereby vation and photometric measurement of film opacity. For
hiding the substrate to a lesser or greater degree. The light photometric measurements only, individual black glass and
that reaches the substrate is partly absorbed by it and partly white glass panels are sometimes employed to take advantage
reflected back in conformance with the substrate's visual pat- of their excellent planarity. Clear plastic can also be used as
tern. Reflection from the substrate eventually emerges from an opacity test substrate by placing it over black-and-white
the film carrying the substrate reflectivity information per- backgrounds. Standard black-and-white opacity test sub-
ceived as visibility or lack thereof and referred to as hiding. strates are defined in paint technology as having CIE-Y reflec-
Opacity m a y he qualitatively defined as the property of a tances of 0.01 (1%) m a x i m u m and 0.80 (80%), respectively. 2
paint film that enables it to prevent the passage of light and White test areas are seldom exactly 80%, but equations are
thereby to hide the substrate on which it has been applied. available for correction of photometric values to that stan-
Note that opacity is a film property, whereas hiding power is a dard (see Eqs 1 and 2).
property of the whole paint. Hiding is a more general term
used frequently to refer to either opacity or hiding power.
L Contrast Ratio
b. Light Absorption The extent to which a paint film obscures or hides the
contrasting features of the test substrate on which it is uni-
If most of the light is absorbed by the film before reaching formly applied is the measure of its opacity. This is expressed
the substrate, the film is dark in color and hides the substrate photometrically as the ratio of the luminous (CIE-Y) reflec-
well, in which case hiding has been produced by light absorp- tance over the darker to that over the lighter area of the
tion. substrate, which is referred to as the contrast ratio (CR). The
Y-reflectance is employed because this CIE parameter is de-
signed to match the sensitivity of the h u m a n eye. The CR and
c. Light Scattering the reflectance are expressed as a percentage or as a decimal
If most of the light entering the film is reflected back and fraction, the latter to be assumed unless otherwise indicated.
reemerges without having reached the substrate, the film is A CR value of unity indicates that too little light has reached
white or light in color and hides the substrate well. The the substrate for the substrate reflectance characteristics to
reflection mechanism of the film involves multiple internal have a measurable effect on the emergent light flux; thus,
refractions and reflections that scatter the light to produce a there is complete absence of contrast, or complete hiding.
net reversal in its direction. Hiding in this case is produced by Lesser CR values define intermediate levels of contrast, or
light scattering. incomplete hiding. The contrast ratio of a given paint film
varies with substrate reflectances and therefore has signifi-
cance only with respect to a known substrate and primarily to
d. Incomplete Hiding a standard black-and-white substrate as defined in 1.e. In
practice, the white area of a commercially available black-
In all cases, the light-absorbing and light-scattering proper- and-white substrate normally deviates somewhat from the
ties of the film act together to produce its opacity. If the film is ideal reflectance of 8 0 % whereas the black area is normally
low in both light-absorption and light-scattering ability, 1% or less, which has no measurable effect on test results and
m u c h of the light reaches the suhstrate. Such a film therefore is therefore treated mathematically as having zero reflec-
hides poorly and is characterized as being low in opacity.
2CIE = Commission Internationale d'Eclairage. Reflectances are
1The Leneta Company, 15 Whitney Road, Mahwah, NJ 07430. measured with specular (mirror) reflection excluded.
481
www.iran-mavad.com

tance. Conventional symbols used in this c o n n e c t i o n are as SR is usually expressed in square feet p e r p o u n d (ft2/lb) o r
follows: square metres p e r k i l o g r a m (m2/kg). SR is inversely related to
W = the reflectance of the white a r e a of the test sub- the film thickness; thus, for a given paint, the lower the SR,
strate, the higher the film thickness a n d film opacity.
R~ = the reflectance of the p a i n t film over a white a r e a of
reflectance W,
j. Spreading Rate and Film Thickness
R0 = the reflectance of the p a i n t film over the black area,
Relationships
C~ = Ro/Rw, the CR of the a p p l i e d p a i n t film,
C0.80 = Ro/Ro.8o, the CR w h e n W = 0.80, a n d Let
C = C0.80, the a b b r e v i a t i o n s o m e t i m e s used in equa- H= s p r e a d i n g rate of the coating (equivalent to SR), 4
tions. T= wet film thickness (equivalent to WFT), 4
In careful hiding p o w e r m e a s u r e m e n t s , if the white s u b s t r a t e D= coating density (prior to loss of volatiles),
reflectance deviates m o r e t h a n 0.01 from the s t a n d a r d value t= d r y film thickness (exclusive of air) s (equivalent to
of 0.80, one of the following c o r r e c t i o n equations 3 is em- DFT),
ployed d d r y film density ( d i s p l a c e m e n t density), 5
N = nonvolatile fraction by weight (equivalent to NVW),
WR0(1 - 0.80R0)
C0.80 = f(Ro, Rw, W) = (1) and
R o ( W - 0.80) + 0.80Rw(1 - WRo) N v = nonvolatile fraction by volume (equivalent to NVV).
(1) U.S. U n i t s
Co.so = f(Cw, Ro, W) - WCw(1 - 0.80R0) (2)
Cw(W - 0.80) + 0.80(1 - WRo) H(flZ/gal) T(mil) = 1604.2 (3)
H (fl2/gal) t (mil) = 1604.2ND + d (4)
g. Visual Observations of Contrast
H(ftZ/lb) T(mil) = 1604.2 + D (lb/gal) (5)
Although i n t e r m e d i a t e levels of c o n t r a s t c a n n o t be directly
H (flZ/lb) x t (mil) = 1604.2N + d(lb/gal) (6)
quantified by visual means, the eye is qualitatively very sensi-
tive to c o n t r a s t variations. It can identify equalities o r n e a r l y (2) M e t r i c U n i t s 6
c o m p l e t e a b s e n c e of c o n t r a s t with c o n s i d e r a b l e precision,
w h i c h is the basis for the original as well as several c u r r e n t H(mZ/L) x T(p~m) = 1000 (7)
hiding p o w e r m e t h o d s to be described. Indeed, such visual H(m2/L) x t (p~m) = 1000ND + d (8)
observations are the b a s i c criteria of w h a t constitutes hiding
a n d h i d i n g power, to w h i c h all i n s t r u m e n t a l hiding m e a s u r e - H(m2/kg) x T(/~m) = 1000 -: D(kg/L) (9)
m e n t s trace t h e i r validity. H(mZ/kg) t (/zm) = 1000N d (kg/L) (10)
(3) U . S . - - M e t r i c Unit C o n v e r s i o n s
h. Film Thickness
n (ft2/gal) = H (mZ/L) 40.746 (11)
This is usually expressed in t h o u s a n d t h s of an inch (mils)
o r in m i c r o m e t e r s (~m). A liquid p a i n t usually contains a H (ft2/lb) = H (m2/kg) 4.8882 (12)
s u b s t a n t i a l q u a n t i t y of volatiles, so that its d r y film thickness T(mil) = T(txm) + 25.4 (13)
(DFT) is substantially less t h a n the original wet film thickness
(WFT). The W F T of a r c h i t e c t u r a l p a i n t s a p p l i e d in the field D (Ib/gal) = D (kg/L) X 8.3454 (14)
are typically in the n e i g h b o r h o o d of 3 to 4 mils (75 to
100/~m). W i t h o t h e r coating types, it m i g h t b e as low as 1 mil (4) D r y V e r s u s W e t F i l m R e l a t i o n s h i p s 7
(25/~m) or as high as 60 mils (1500/zm). W i t h volatile-free ND = N~cl (15)
liquid coatings, the W F T a n d DFT are the s a m e except for a
t = N~T (16)
possible small increase in density d u r i n g curing. W i t h pow-
d e r coatings, for w h i c h film f o r m a t i o n a n d curing are concur- T = td + ND (17)
rent, the t e r m W F T is i n a p p l i c a b l e a n d DFT r e d u n d a n t , so
t h a t it is a p p r o p r i a t e to refer simply to film thickness.
2. D E F I N I T I O N OF H I D I N G P O W E R ( H P )
i. Spreading Rate
Qualitatively, h i d i n g p o w e r is the p r o p e r t y of a p a i n t t h a t is
W h e n p a i n t is applied, w h e t h e r for test p u r p o s e s o r in m a n i f e s t e d as o p a c i t y in its films. Quantitatively, it is the
actual usage, the a r e a covered p e r unit q u a n t i t y of p a i n t is
called the s p r e a d i n g rate (SR) for that p a r t i c u l a r application.
4Note that WFT and SR, when the latter is expressed by volume,
W h e n the q u a n t i t y of coating is expressed volumetrically, as are inverse ways of stating the same information.
is usual with liquid paints, the SR is usually expressed in 5Refers to films containing no air or hypothetically compressed to
square feet p e r gallon (ft2/gal) o r square metres p e r litre exclude air.
(m2/L). W h e n the quantity is expressed gravimetrically, the 6The following metric notations are identities: kg/L = g/mL =
g/cm 3 = g/cc.
7These are applicable to both common and metric units since the
3Derived from Eq 39 by equating to W = 0.80. units all cancel.
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CHAPTER 42--HIDING POWER 483
spreading rate at which the film opacity is just sufficient to b. White Pigments
give complete hiding over the specified standard black-and-
When dispersed in a paint binder, some white pigments
white substrate (see 1.e). The "complete hiding" point is de-
scatter light strongly and thereby contribute to hiding, while
termined visually in some test procedures and photometri-
others scatter very poorly and make little if any contribution.
cally in others.
On that basis white pigments are classified as hiding pigments
or as extenders. White hiding pigments in a paint formulation
a. Visual Hiding P o w e r End-Point are sometimes called "prime pigments" as distinguished from
the nonhiding "extender" types. The latter are also referred to
In the visual determination of hiding power, the operator as "inerts" in view of their apparent passivity with regard to
increases the film thickness gradually and records the both light absorption and scattering. The difference in scat-
amount of paint applied at the supposedly exact point of tering behavior between hiding and extender pigments is a
complete hiding. In practice, instead of perceiving such a function of their refractive indices.
point, a range of uncertainty is reached beyond which, when
hiding seems unquestionably complete, it also seems that the
true end-point has been exceeded. To resolve this dilemma c. Refractive Index
and to obtain repeatable results, the operator chooses an end-
point at which it seems that, only a negligible increase in film Most pigments are crystalline in nature. If a single crystal
thickness is required to completely obscure the contrasting of white pigment were grown sufficiently large, it would be
features of the substrate. This so-called complete hiding end- perceived as shiny and transparent like glass, and objects
point is therefore more accurately described as just short of observed through it would look bent and distorted as when
complete hiding. observed through a glass prism. This is due to the change in
direction, referred to as refraction, that occurs when light
passes between media in which it has different velocities, as
b. Photometric Hiding Power End-Point illustrated in Fig. 1. The relationship between the angles in
Uncertainty as to the end-point also exists when measuring this figure is expressed by Snell's law of refraction
hiding power photometrically. A curve of film thickness ver- n = sin//sin r (18)
sus contrast ratio approaches CR = 1 asymptotically, so in
theory there is no point at which the contrast is completely in which i and r are the angles of incidence and refraction,
obscured. Thus in practice the CR end-point for hiding power respectively, and n is a constant referred to as the refractive
measurements must be less than unity. A CR value of 0.98 is index, which is the ratio of the velocity of light in the incident
generally accepted in paint technology as representing the to that in the refraction medium. If the large pigment crystal
point of photometric complete hiding because it is in fact very postulated previously is pulverized and dispersed in a paint
close to being visually complete, and a higher CR end-point film, each small particle will refract incident light in the same
could not be identified with as much precision. The concept way as described for the large one. Light will also be partially
of 98% as the contrast ratio for complete hiding was origi- reflected at the surface, and both refractions and reflections
nally based on the Weber-Fechner law, which states that will occur within the pigment particle itself. This activity,
differences of 2% in reflectance (with moderate illumination) endlessly repeated with a multitude of pigment particles as
are imperceptible to the h u m a n eye [1]. Actually, this level of illustrated in Fig. 2 (Ref 2, p. 1), results in the scattering of the
contrast, though slight, is definitely visible. original incident light with concomitant film opacity and
paint hiding power. The greater the difference between the
refractive indices of the pigment and the surrounding me-
dium, the greater the amount of light scattering. Refractive
3. T H E R O L E OF P I G M E N T S I N H I D I N G
POWER
a. Binders and Pigments I

A typical paint binder, by itself, forms a transparent and
virtually colorless film that neither absorbs nor scatters light
to any appreciable degree and therefore makes no contribu-
tion to the hiding power of the coating of which it is a part.
This task resides entirely in the pigment constituent of the
paint. Pigments are fine-particle-size, insoluble, and usually
crystalline solids that when dispersed in paint vehicles con- of
tribute to the various properties of the mixture, among which
are the optical properties of color and hiding power. Pig-
ments that absorb light strongly over the entire visible spec-
trum are black; those that are optically selective, absorbing
!
I
\
strongly in parts of the visible spectrum and poorly in other FIG. 1-Bending of a light ray by refrac-
parts, are colored, viz. blue, red, yellow, etc., corresponding tion towards the normal as it enters a me-
to the spectral region of nonabsorption. Those that absorb dium of lower light velocity (higher
poorly over the entire visible spectrum are white. refractive index).
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d. White Hiding P i g m e n t s
A r o u g h i n d i c a t i o n of the relative hiding p o w e r of a white
p i g m e n t can be calculated from its refractive index using the
Fresnell equation of reflectivity (Ref 2, p. 1),
F%- ( n - nm) 2 100 (19)

(n + rim) 2
w h e r e F is the Fresnell reflectivity, n is the refractive index of
the pigment, a n d nm is the refractive index of the m e d i u m in
which it is dispersed. Since the refractive index of a p a i n t
b i n d e r is in general very close to 1.5, Eq 19 can be rewritten as
(n -- 1.5) 2
['~ 100 (20)
(n + 1.5) 2
Tables 1 a n d 2 illustrate the use of this equation a n d the
general principle that the h i g h e r the refractive index of a
p i g m e n t the greater its hiding power. The relative hiding
p o w e r values shown therein indicate the m a g n i t u d e of varia-
tion related to index of refraction. Other factors can also
affect hiding p o w e r substantially, as discussed in Section 9.
FIG. 2-Light-scattering behavior of a pig-
mented film.
e. E x t e n d e r P i g m e n t s
indices are r e p o r t e d in Tables 1 a n d 2 with respect to a
v a c u u m as the m e d i u m of incidence. Values with respect to Pigments in this category have low refractive indices in the
air are practically the same. Since white p i g m e n t s are crystal- n e i g h b o r h o o d of 1.5. In the form of a powder, with the sur-
line in nature, they usually possess different refractive indices r o u n d i n g m e d i u m being air with a refractive index of 1.0, the
along the different crystal axes. Their indices also vary some- difference in the two indices p r o d u c e s substantial light scat-
w h a t with the wavelength of the light, generally being higher tering, so that extender p i g m e n t s look white. But d i s p e r s e d in
at the blue (short wave length) end of the s p e c t r u m t h a n at p a i n t binders, w h i c h like themselves typically have a value of
the red (long wavelength) end. Tables 1 a n d 2 give average a b o u t 1.5, they scatter light very p o o r l y and are virtually
values [1,3]. transparent. This is i n d i c a t e d by the low HP values listed for
t h e m in Table 2 as c o m p a r e d with the white hiding p i g m e n t s
in Table 1. Although extender p i g m e n t s are also referred to as
TABLE 1--Refractive index and relative hiding power of some "inerts," the latter t e r m is s o m e w h a t of a m i s n o m e r . They
white hiding pigments.
have an indirect b u t strong influence on light scattering a n d
Refractive Relative HP, hiding p o w e r t h r o u g h p h e n o m e n a referred to as "crowding"
Pigment Index F%a
and "dry hiding." They also have i m p o r t a n t effects on o t h e r
Titanium dioxide (ruffle) 2.76 8.8 physical p r o p e r t i e s of paints such as consistency a n d gloss.
Titanium dioxide (anatase) 2.55 6.7
Zirconium oxide 2.40 5.3
Zinc sulfide 2.37 5.0
Antimony oxide 2.19 3.5
Zinc oxide 2.02 2.2 f. Colored P i g m e n t s
White lead carbonate 2.01 2.1
White lead sulfate 1.93 1.6 If a p i g m e n t a b s o r b s s o m e wavelengths of light m o r e
Lithopone 1.84 1.0 strongly t h a n others, it reflects b a c k a higher p r o p o r t i o n of
~Calculatedfrom Eq 20. the weakly a b s o r b e d wavelengths a n d is perceived as having
the color of the latter (e.g., red, blue, yellow, etc.). Light
a b s o r p t i o n of this n a t u r e is referred to as "selective." Colored
TABLE 2--Refractive index and relative hiding power of some p i g m e n t s can vary greatly in hiding p o w e r d e p e n d i n g on their
extender pigments.
light a b s o r p t i o n a n d light-scattering abilities. W i t h r e g a r d to
Refractive Relative HP, light scattering, as with white p i g m e n t s this is a function of
Pigment Index F%a
the refractive index or m o r e specifically the difference in re-
Barium sulfate 1.64 0.20 fractive index b e t w e e n the p i g m e n t a n d s u r r o u n d i n g me-
Calcium sulfate 1.59 0.08
Calcium carbonate 1.57 0.05 dium. Refractive indices of colored p i g m e n t s vary widely
Magnesium silicate 1.57 0.05 with wavelength, ranging from 1.3 to 2.7. These variations
Aluminum silicate 1.55 0.03 cause such p h e n o m e n a as bronzing, dichroism, color change
Silica 1.55 0.03 with film thickness, a n d differences in u n d e r t o n e u p o n di-
aCalculated from Eq 20. lution with white p i g m e n t s (Ref 4, p. 22).
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4. EARLY VISUAL H I D I N G P O W E R
METHODS
a. Brushouts
The earliest methods for determining hiding power em-
ployed the practical procedure of brushing the paint uni-
formly onto combination black-and-white test substrates,
increasing the amount of paint in small increments until
reaching the point of essentially complete hiding at which the
amount of visual contrast was considered negligible. The
quantity of paint was determined by weighing the container
and brush in grams before and after painting. The corre-
sponding spreading rate (SR) is the hiding power (HP) by
definition and was calculated from the equation
SR (ft2/gal) =
Test Area (ft2) Paint Density (lb/gal) x 454
(21)
Weight of Paint (g)
For single-pigment paints, the value calculated from Eq 21
can be converted to pigment hiding power using the equation FIG. 3-Gardner contrast hiding power board.
SRpigment (ftZ/lb) - SRpaint (ftZ/ga]) (22)

Pigment Concentration (lb/gal) black to white. After printing, a coat of nitrocellulose lacquer
Variants of these equations provide for the use of metric or other suitable clear sealer was applied. Many of those chart
instead of U.S. units. types became and continue to be commercially available.
b. Early Test Substrates c. Contrast Design and Visual Sensitivity

Originally in the study of hiding power, test surfaces were Kraemer and Schupp [6] evaluated contrast surfaces in a
prepared in individual laboratories by painting black stripes variety of designs prepared on glossy photographic paper.
on white-painted panels. In response to the need for stan- These included the customary checkerboard design, a design
dardized test surfaces, studies were made on oil cloth and of narrow 15-ram-wide bands, another with much broader
linoleum having printed checkerboard-type designs [5]. The bands, and one with dark half circles on a light background.
Gardner Contrast Hiding Power Board was a two-square-foot The results seemed to favor a narrow band design subse-
area glass checkerboard with black and white squares quently employed by the Krebs Pigment Co. in preparing the
painted on the underside of a thin piece of glass (Fig. 3). The diamond stripe grey and white contrast charts illustrated in
first formalized ASTM method used a linoleum checkerboard Fig. 4. The test area of that chart was 1 ftz (0.0929 mE). The
surface in the brushout test procedure described in 4.a. The use of a grey-and-white contrast combination was based on
Gardner glass board was used in the same way. Since the the idea that this is more representative than black and white
"complete hiding" end point in those early methods was de- of the degree of contrast encountered by paints in actual use.
termined when the paint was freshly applied and still wet, the
resultant hiding power value pertained only to the wet hiding
d. Relative Dry Hiding Power--Krebs Method
power of the paint, not to the dry. This was not a problem in
the earliest days of hiding power measurement when typical Although the introduction of paper test charts as replace-
paints contained relatively little volatile constituent and the ments for linoleum or glass made dry hiding power measure-
opacity of the film therefore did not change markedly while ments easier, they were still not easy enough. The problem
drying. But, with the advent of modern paint formulations was that it required the preparation of a considerable number
containing substantial amounts of volatiles, the composition of paint-outs at various spreading rates to obtain one that
and with it the opacity of the dry paint film could be substan- after drying could be identified with confidence as repre-
tially different than that of the initially applied film. The need senting the "complete hiding" end-point. One solution to this
to measure dry hiding power therefore became of paramount problem was to determine comparative or relative dry hiding
importance. As a practical problem in this connection, expen- power. In the Krebs Pigment Co. method, their square-foot
sive linoleum and glass test surfaces had to be cleaned for grey-and-white diamond stripe chart was used for that pur-
reuse after each test, which made it very difficult to use them pose in the following manner: A partial hiding ladder of six to
for the study of dry hiding power. This problem was partly eight brushout standards is made by applying a standard
overcome with the introduction of paper test charts circa paint at spreading rates ranging from 400 to 800 ftE/gal (10 to
1931 that were printed in various designs such as checker- 20 m2/L) and allowing the brushouts to dry. The spreading
board, concentric diamond-shaped bands, spirals, crescents, rates are precontrolled approximately by syringing specified
etc., and with various degrees of contrast such as black-white, volumes of paint onto each chart and then determined accu-
black-grey, grey-white, and a graded series of stripes from rately by weight measurements and calculation as described
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! !
i
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i
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II j I
Ii ! !
i l I
II
504540353025201510 5
B
C Di A
FIG. 5-Diagram of early model of Pfund cryptometer.
causes the line to disappear. The wet film thickness at the

point of complete hiding is determined from the scale reading
at the toe of the wedge and the thickness of the shim at the
heel, from which the HP in ftZ/gal or mZ/L can be calculated
using Eq 3 or Eq 7. Dark-colored paints cannot be measured
using this instrument because of the lack of contrast with the
black glass background. Nelson and Norris of the New Jersey
Zinc Co. used this cryptometer to determine HP of colored
pigments with results as shown in Table 3. The pastes were
prepared by rubbing the colors in No. 0000 lithograph var-
nish. The rubbing was regulated to represent the maximum
development usually obtained in practice. In addition to the
regular black glass instrument, they used one specially made
with white glass for several measurements.
(2) Black and White

FIG. 4-Krebs diamond-stripe hiding power chart. Pfund [8] introduced the black-and-white cryptometer in
1930. It eliminated the well, making cleaning easier, and
worked for use with paints of any color because of the black-
in 4.a. A single test paint panel is likewise prepared at an and-white instead of all-black background. Referring to Fig.
intermediate spreading rate. After drying, that panel is com- 6, the black glass B and the white glass W are fused along line
pared with the standard panels to determine the two that LM. Longitudinal grooves catch the overflow of paint. The
bracket it in contrast. Then by visual interpolation a fairly wedge is moved to the right to make the line disappear, then
precise estimate is made of the spreading rate of the standard to the left to make it reappear. The position of the plate is
paint required to match the contrast of the test paint panel. reversed and the observations repeated. From the mean of all
The relative dry hiding power of the test paint is the percent readings, the hiding is calculated as with the all-black cryp-
ratio of its spreading rate to that of the standard paint at tometer (4.e.(1)). Comparison of results for white paints
equal visual contrast, thus shows that the two cryptometer types (all-black and black-
and-white) yield the same values within experimental error
% Relative Hiding Power SRTestPaint X 100 (23)
(Ref 4, p. 22).
-
SRstd. Paint
(3) Rotary Type

e. P f u n d C r y p t o m e t e r s The rotary cryptometer was a short-lived device designed
to overcome the jerky movement of the top plate of the
(1) All Black regular cryptometer [9]. The wedge of the cryptometers of
Introduced in 1919, this was one of the first laboratory Figs. 5 and 6 was replaced with a circular glass plate mounted
instruments made for determining HP [7]. Referring to Fig. 5, in a metal frame (Fig. 7). The thickness of the film was read
A is a plate of black glass whose upper surface is optically flat; on a scale located on the bottom plate. While the movement
B is a transverse groove 10 mm wide and about 2 mm deep. of the plate was much smoother with this instrument, it was
Beginning at the left edge of the groove is a millimetre scale found that bubbles often obscured the end-point.
etched in the upper surface of Plate A. C is a plate of clear
glass whose lower surface is optically flat. D is a steel shim (4) Assessment of Cryptometers (Ref 4, p. 25)
cemented to C so that a wedge of paint may be formed be- The cryptometer is a simple instrument requiring only
tween the plates. This wedge abruptly becomes "infinitely small quantities of paint, and determinations are quickly
thick" at B, and so long as hiding is not complete, the line of made. However, reading the end-point is difficult, and the
demarcation is visible. Sliding the wedge to the left eventually mean of a number of determinations is therefore advisable.
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CHAPTER 4 2 - - H I D I N G P O W E R 487
TABLE 3--Hiding power (m2/kg) of some colored pigments f. Hallet H i d i m e t e r

measured with a Pfund cryptometer~ (Nelson and Norris).
Along with the Pfund cryptometer, the Hallet hidimeter
Black Glass White Glass
[12] was one of the very early devices for evaluating HP. The
Lampblack ... 105 objective of a regular microscope is replaced by a long tube
Carbon Black ..- 41
fitted with a plain g r o u n d glass objective; the eyepiece is
Chromic oxide 29 -..
Prussian blue 72 ... replaced with a small hole. The principle of the device is the
Chinese blue 106 --. light-diffusing property of g r o u n d glass. If a contrast sub-
Blue toner 51 -.. strate is viewed t h r o u g h a plate of g r o u n d glass, the contrast
Light green 129 ...
b o u n d a r i e s b e c o m e more b l u r r e d as the distance b e t w e e n
Medium green 187 ...
Deep green 188 ... plate a n d substrate increases. If a liquid p a i n t sample is
Light green 101 ..- sandwiched b e t w e e n them, it blurs the b o u n d a r y further, a n d
Medium green 167 ... the distance required to make the b o u n d a r y disappear de-
Deep green 181 ..-
creases. Since that distance is the thickness of the intervening
Light green 62 --.
Medium green 98 ... p a i n t film, it is a m e a s u r e of the hiding power of the paint.
Light green 154 ... This m e a s u r e m e n t is essentially comparative because it can-
Medium green 202 ... not be translated into regular hiding power units.
Deep green 150 ...
Green toner 91 ..-
Green toner dark 130 -..
Chrome yellow 23 27
Hansa yellow 31 34
Lt. chrome orange 44 56 5. E A R L Y P H O T O M E T R I C H I D I N G P O W E R
Med. chrome orange 17 20 METHODS
Dk. chrome orange 29 .-.
Lithol toner 66 -.. a. Pfund P r e c i s i o n Cryptometer
Lithol toner 75 ...
Maroon toner 65 ... I n this device (Fig. 8) a photoelectric cell is used to m e a s u r e
Madder lake 36 ... the reflectance of p a i n t c o n t a i n e d in a wedge-shaped layer
Toluidine toner 137 ...
Light para toner 224 ... [13]. The base plate consists of black-and-white areas B a n d
Deep para toner 160 ... W, whose b o u n d a r y is parallel to the length of the plate
Light para toner 41 ... instead of perpendicular as with the visual cryptometer. The
Deep para toner 35 ... photoelectric device is shifted until a position is f o u n d where
~Multiplyby 4.9 to obtain HP in fta/lb. the reflectance of the p a i n t over the black area is 98% of that
over the white area. The film thickness a n d HP calculations
are the same as with the visual cryptometers described in
Most users c a n repeat their o w n results, b u t agreement section 4.e.
a m o n g different users is n o t satisfactory although it is im- This cryptometer eliminates the uncertainties of the visual
proved by the use of a s t a n d a r d p a i n t [10]. Another m a j o r type, as there is n o sliding of the top plate over the base plate
disadvantage of cryptometers is that they m e a s u r e only wet a n d no need to estimate visually the appearance a n d disap-
HP. One study [11 ] reported that cryptometers were satisfac- pearance of a n indistinct line. However, it retains the disad-
tory with low-opacity b u t not high-opacity paints. Consider- vantage of p e r m i t t i n g only wet hiding m e a s u r e m e n t s a n d has
ation of its advantages a n d disadvantages suggests that the therefore b e e n superseded by other photometric devices a n d
cryptometer is better suited for control work t h a n for specifi- methods that p e r m i t the m e a s u r e m e n t of dry hiding power.
cation requirements. The cryptometers s h o w n in Figs. 5 a n d
6 c o n t i n u e to be commercially available.
b. H a n s t o c k M e t h o d
Hanstock [14] studied the relationship of light transmis-
sion through free p a i n t films to opacity a n d HP o n a black-
and-white substrate. For his t r a n s m i s s i o n work, he employed
a flicker p h o t o m e t e r a n d f o u n d that p a i n t films were perfectly
!
! diffusing a n d that films having the same degree of light trans-
I' L m i s s i o n had approximately equal opacity. He further showed
the correspondence b e t w e e n refractive index, the Fresnel re-
~%\\\ ~\\\"/////////,~,~:~v////////////,,;
1
lationship, a n d HP.
The p r o b l e m with the t r a n s m i s s i o n concept is that m o d e m
r paints have so m u c h opacity it is difficult to m e a s u r e accu-
,,x~\x~ ,:;:.:/"...(///,/~",;,k4/; rately the t r a n s m i s s i o n of films of c o m m e r c i a l thickness.
i
Moreover, HP is concerned in practice with p a i n t in i n t i m a t e
contact with opaque surfaces a n d not as a free film. Conse-
1,4 quently, m e a s u r e m e n t of light t r a n s m i s s i o n t h r o u g h p a i n t
FIG. 6-Pfund black-and-white r films is done today only for very specialized research.
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"1
I I
FIG. 7-Rotary cryptometer.
i f " ....-;,,/K ~"x" \
t ~, i ," i7.) L~ ..z'~'~"'v

W B
',,ii/4.-
,,,
I le , / . -
bY'z
,I;.'.& 9
G
Detail of Plate. i,.j..'i;.L' ................... 1 F
"
W P P~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .r~
. I Wl
FIG. 8-Pfund precision cryptometer. Uses a photoelectric cell instead of the eye to
measure reflectance.
c. Use o f t h e Fell E q u a t i o n This p r o c e d u r e was a d a p t e d b y M a r c h e s e a n d Z i m m e r m a n to

d e t e r m i n e the hiding p o w e r of p a i n t s at a c o n t r a s t ratio of
An e m p i r i c a l relationship b e t w e e n spreading rate (SR) a n d
0.98, a n d the m e t h o d was used for m a n y years by the Tita-
c o n t r a s t ratio (CR) was f o u n d b y Fell a n d r e p o r t e d by S a w y e r
[15] in the following form n i u m Pigment Co. (Ref 4, p. 24). Experience has s h o w n that
r e a s o n a b l y satisfactory results can be o b t a i n e d if the equa-
l o g ( C R x 10) = m SR + b (24) tion 'is used for i n t e r p o l a t i o n b e t w e e n points close to the
w h e r e m a n d b are e x p e r i m e n t a l constants. desired c o n t r a s t ratio. But, as p o i n t e d out by Switzer [16],
Since the g r a p h for this equation is a straight line, it is a e x t r a p o l a t i o n of results can lead to serious errors. He further
simple m a t t e r after d e t e r m i n i n g m a n d b from m e a s u r e m e n t s p o i n t e d out that the Fell equation m e t h o d allows only a single
at two CR levels to find the SR required for any desired CR. estimate of HP from at least two test applications, thus re-
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quiring a considerable effort to obtain an estimate of in- M = the dry film weight,
tralaboratory precision. N = the fractional nonvolatile content of the paint by
weight,
A -- the film area, and
d. New York Paint Club (NYPC) Method
D -= the density of the paint.
This method employed doctor blades to apply films at The CR of each chart is measured and plotted against the
several thicknesses on black-and-white cardboard hiding corresponding WFT. From a smooth curve drawn through
power charts. After the films had dried, reflectance, weight, the points, the CR at the specified WFT is obtained. If this is
and area measurements were made from which contrast ra- equal to or greater than the specified CR, then the require-
tios and corresponding wet film thicknesses were calculated. ment for dry opacity has been met.
CR values (rather than log 10 CR as in the Fell equation) were
plotted against reciprocal film thickness and the HP calcu-
lated from the wet film thickness at 0.98 CR. If the white area
of the chart deviated appreciably from the standard reflec- 6. G E N E R A L H I D I N G P O W E R
tance of 0.80, the contrast ratio was corrected using Eq 1 or METHODOLOGY
Eq 2. The Club reported that most of the effort in this method
was to determine film thicknesses. To minimize that effort a. Film Application
they modified the method by casting films on black and white The objective is to determine the spreading rate at a speci-
glass plates and determined thicknesses with an Inter- fied level of dry film opacity, which is usually full hiding as
chemical wet-film thickness gage in accordance with ASTM perceived visually or corresponding to the contrast ratio: C =
Test Methods for Measurement of Wet Film Thickness of R0/R0,0 = 0.98. The basic experimental procedure is to apply
Organic Coatings (D 1212). Any error in film thickness, of a uniform film on a suitable test substrate, to observe its
course, carries over to the HP value. According to Mitton, the opacity either visually or photometrically, and to determine
revised method sacrifices accuracy and precision for speed its spreading rate. Since it is not possible to apply a film with
[17]. In addition, graphical averaging makes it burdensome precision at a predetermined dry opacity, several such appli-
to estimate the precision with which the HP has been deter- cations need to be made over a range of spreading rates and
mined for the same reason pointed out in 5.c in connection their results plotted graphically or otherwise interpolated to
with the Fell equation method. the desired hiding power end-point. This laborious procedure
is exemplified in the visual methods discussed in 4.a and 4.d
e. Van Eyken-Anderson Method and in the contrast ratio (CR) methods discussed in 5.e and
5.f. The Fell equation and NYPC methods (5.c and 5.d) at-
The method proposed by Van Eyken and Anderson [18] tempt to reduce the workload to only two spreading rate de-
uses CRs and film thicknesses in the same way as the NYPC terminations by plotting SR against CR or log CR and finding
method described in 5.d, except that films of different thick- the hiding power end-point graphically on the basis of per-
nesses are applied in a single operation by using a doctor ceived empirical straight-line relationships. Kubelka-Munk
blade having seven clearances. A die is used to prepare uni- theory (see Section 8) shows how the end-point can be calcu-
form area punch-outs of the paper charts to determine lated with just one spreading rate determination.
spreading rate by the basic weight-area-density-NVW calcu-
lation (see Eq 26). The defects of this method are that the
small areas used for reflectance and weighing make the b. Spreading Rate (or Film Thickness)
achievement of good precision difficult (Ref 4, p. 31), and Determination
there is no provision for correcting CR if the white substrate
reflectance differs from 0.80. In both visual and photometric hiding power methods, the
procedures for observing film opacity are well-defined and
can be performed with dispatch. The experimental task most
f. Federal Test for Dry Opacity demanding on the operator's time and ingenuity is to deter-
This is Method 4121 of U.S. Federal Test Method Standard mine the spreading rate or film thickness of the applied
No. 141. It is a pass-fail test calling for a minimum dry film coating with good precision. Although gages are available to
contrast ratio at a specified WFT. Black-and-white hiding measure wet and dry film thickness directly and quickly, the
power charts are used as the test suhstrate. For routine test- most accurate procedure, by far, is to determine the weight of
ing, the paint may be applied either by brush or doctor blade. applied paint film on a measured test area and then to calcu-
For referee tests, application is by doctor blade only. The late the spreading rate or film thickness as described in 4.a
density and the nonvolatile content of the paint are also and 5.f. The equations in both of those methods contain
required. Several drawdowns are made to bracket the speci- mixed metric and common units. When the units are all met-
fied WFT. The weight of dry paint film is determined for a ric, the equations are simpler. Letting M = dry film weight
measured area on each drawdown and the WFT then calcu- and A = the film area and using the symbolism in 1.j:
lated from the equation
H (m2/L) = A (cm 2),N.D (kg/L) (26)
61 M(g) 10M (g)
WFT (mils) = (25)
A (in. 2) N D (g/mL) 104M (g)
r(/zm) - (27)
where A (cm2)-N.D (kg/L)
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See 1.j.2 for equations interrelating spreading rate, wet film discoloration at high temperatures, but they are used widely
thickness, and dry film thickness. See 1.j.3 for conversions with air-dried coatings for general hiding power observa-
between metric and U.S. units. tions. Black-and-white charts can be used for precision pho-
If the volatiles have a relatively low evaporation rate as with tometric hiding power measurements by taking appropriate
most architectural coatings, the film might be weighed rap- steps to allow for weight variations in the substrate due to
idly before appreciable loss of volatiles, in which case Eqs 26 humidity and inherent random variations in the area weight
and 27 would still apply but with M as the wet film weight and of paper. These steps include the use of unpainted control
N as unity. The disadvantage of this procedure is that it charts and the averaging of multiple test results. Charts with
demands very skillful and speedy manipulation to minimize combinations of gray and black, gray and white, and grada-
loss of volatiles before weighing. For that same reason, it is tions of gray on a white background are used in visual hiding
not applicable at all to coatings containing fast evaporating power tests to obtain what are considered to be more practi-
solvents. cal hiding power measurements.
With powder coatings, for which the spreading rate is nor-
mally expressed on a weight basis, Eq 26 becomes
A (cm2).N
n (m2/kg) - (28) b. Clear Plastic Film
10M (g)
Assuming negligible volatile content, the value of N in this Polyester is the preferred chemical type. Because of heat
equation can be taken as unity. distortion, its use is generally confined to air-dried coatings.
After the film has dried, a square of convenient size is cut and
the area measured. Values of R0 and Rw are read by placing
c. P h o t o m e t r i c M e a s u r e m e n t s the painted plastic film alternately on a black and a white
background with the underside moistened with a suitable
The CIE-Y reflectance is measured because this function liquid (e.g., mineral spirits or dibutyl phthalate) to remove
defines the human eye's quantitative response to the lumi- the air interface and establish good optical contact. The dry
nous character of light across the visual spectrum. This is film weight is determined as the difference in the weight of
valid for chromatic as well as nonchromatic colors, as re- the painted and unpainted substrate by stripping off the paint
ported by Tough [19], who found good correlation in a large film with a strong solvent.
series of colored paints between visual hiding power mea-
surements and contrast ratio values based on CIE-Y measure-
ments with a spectrophotometer. The end-point of 0.98 CR is
effective with colors, although it appears that other end-
c. Glass Panels
points, for example CIELAB color difference: AE = 1.5,
would make some difference in the relative HP of various Individual black and white glass panels are used to take
colored paints [20]. However, the simplicity of the 0.98 end- advantage of the superior levelness of glass for casting of
point and its history of validity and general agreement among uniform films and because the hard, smooth surface permits
various workers make it the best choice regardless of color rapid wet film thickness measurements with an ASTM-type of
(Ref 4, p. 31). CIE-Y measurements can be made with the wet-film thickness gage (5.d). The same information is ob-
green filter of a tri-stimulus colorimeter or with a spectropho- tained less rapidly but with much better precision by scraping
tometer. When properly standardized, results with the two off and weighing a defined area of dry film and calculating as
instrument types should be the same. As a precaution, there described in Section 6.b. In some tests, contrast ratios are
should be coordination between correspondent laboratories calculated on the questionable assumption that separate film
with regard to instrumentation. In all cases, reflectance mea- applications on black and white glass panels are identical in
surements must be made excluding surface reflection, which film thickness.
is implicit for instruments designed with 00/45~geometry and
optional with most other instrument types.
d. Painted Metal Panels

7. C U R R E N T L Y U S E D T E S T S U B S T R A T E S Panels of this type are generally used with coatings that are
applied by spraying and cured by baking. The weight of the
The substrate is generally the major factor affecting the applied film is determined by weighing the panel before the
specific experimental details of a test procedure. It is selected coating is applied and again after drying. The spreading rate
or specified on the basis of its adaptability to the type of or film thickness is then calculated as described in 6.b. If
coating being tested and for its perceived advantages in the desired, the dry film thickness can be determined without
required or preferred test procedure. weighing, though with considerably less precision, by direct
measurement with a magnetic or an eddy current thickness
gage. Black-and-white panels are used for contrast ratio mea-
a. Paperboard Charts
surements or for visual observation of opacity. The use of all-
Substrates of this type are described in 4.d. Their employ- black panels is described by Mitton for measuring the hiding
ment with baking finishes is limited because of distortion and power of baking enamels [21].
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8. KUBELKA-MUNK (K-M) TWO-CONSTANT H = the s p r e a d i n g rate in any stated unit, e.g., mZ/L,
THEORY ftZ/gal, mZ/kg, ftZ/lb, cm2/g.
S = the scattering coefficient, a m e a s u r e of the ability
a. Introduction of the p a i n t to scatter light, expressed in units re-
ciprocal to T or the s a m e as H.
The light t h a t enters a p a i n t film is subjected to scattering
K = the a b s o r p t i o n c o e f f i c i e n t - - a m e a s u r e of the abil-
a n d a b s o r p t i o n as d e s c r i b e d in Section 3, a n d w h a t e v e r is not
ity of the p a i n t to a b s o r b light, expressed in the
a b s o r b e d b y the film or s u b s t r a t e eventually r e e m e r g e s as
s a m e unit(s) as S.
reflected light. In 1931 K u b e l k a a n d M u n k [22] p u b l i s h e d
e = 2.718 2 8 . . . the exponential base for n a t u r a l loga-
equations defining the optical b e h a v i o r of a t r a n s l u c e n t mate-
rithms.
rial in t e r m s of two constants referred to as coefficients of
P = scattering p o w e r - - a m e a s u r e of the ability of a
scattering a n d absorption. Steele [23] in 1935 s h o w e d h o w
film to scatter light. A unitless film c o n s t a n t de-
these equations were a d a p t a b l e to the m e a s u r i n g of p a p e r
fined m a t h e m a t i c a l l y b y the relationships: P = ST
opacity, a n d J u d d et al. [24] in 1937 did the s a m e in connec-
o r P = S/H.
tion with coatings. K u b e l k a [25] in 1948 r e a r r a n g e d the origi-
nal equations into new a n d simplified forms from w h i c h Subscripts
Switzer [26] in 1952 developed equations designed specifi- x indicates an experimentally d e t e r m i n e d value, e.g., Tx, Hx,
cally for the study of hiding p o w e r b y expressing the film Px.
thickness (or SR) as a function of the CR. Using these equa- c indicates a value calculated for a specified c o n t r a s t r a t i o
tions a n d their derivatives, the c o n t r a s t ratio of a coating can C,e.g.,Pc, Hc.
be calculated for any s p r e a d i n g rate (or vice versa)" from m e a - 0.98 indicates a value calculated for C = 0.98, e.g., H0.98,
s u r e m e n t s m a d e at only one a n d its p h o t o m e t r i c hiding T0.98.
p o w e r t h e r e b y d e t e r m i n e d by a single test application. This is H indicates a value p e r t a i n i n g to a s p r e a d i n g rate, e.g., Cn,
in c o n t r a s t with the m o r e l a b o r i o u s p r o c e d u r e of o b t a i n i n g PH, s..
CR values at two o r m o r e s p r e a d i n g rates for i n t e r p o l a t i o n o r T indicates a value p e r t a i n i n g to a film thickness, e.g., C~,
e x t r a p o l a t i o n to the hiding p o w e r end-point. The calculations S T.
a p p e a r f o r m i d a b l e b u t are readily a c c o m p l i s h e d with a suit- a a n d b are simplifying functions of R=, defined by
ably p r o g r a m m e d computer. G r a p h s a n d tables are also
available for this purpose, although not as convenient a n d a = I/2 (1/R~ + R~) (29)
accurate as a computer. The e x p e r i m e n t a l steps are straight- b -= V2 (1/R= - R=) (30)
forward, and, as with m o s t h i d i n g p o w e r methods, the m o s t
difficult a n d t i m e - c o n s u m i n g o p e r a t i o n is to d e t e r m i n e the F r o m these definitions are derived the a d d i t i o n a l relation-
e x p e r i m e n t a l s p r e a d i n g rate (or film thickness) with suffi- ships
cient precision. H o w that is a c c o m p l i s h e d is the essential b = (a z - 1) 1/2 (31)
difference b e t w e e n various K u b e l k a - M u n k - b a s e d methods.
R==a-b=a-(a 2 - 1) ~/2 (32)
Note that R=, a, a n d b are three forms of the s a m e constant,
b. Equation Symbols
so t h a t the d e t e r m i n a t i o n of any one of t h e m is equivalent to
The symbols u s e d here are b a s e d on ASTM Test M e t h o d for d e t e r m i n i n g all three. S o m e t i m e s they are used together in
Hiding Power of Paints by Reflectometry (D 2805-88) as fol- the s a m e equation.
lows: Additional simplifying functions w h i c h can b e expressed in
G = the s u b s t r a t e reflectance e x p o n e n t i a l - l o g a r i t h m i c form, or using h y p e r b o l i c co-
F o r a white s u b s t r a t e G = W. tangents are
F o r a s t a n d a r d white substrate G = W = 0.80. [eZbe+l~
F o r a b l a c k s u b s t r a t e G -- B. U = f(P, R=) -- b ~e2bf _ 1 ] = b coth bP (33)
F o r a s t a n d a r d b l a c k s u b s t r a t e G = B <- 1 -~ 0.
Rc = the reflectance of a film a p p l i e d over a s u b s t r a t e of a n d the converse of Eq 33
reflectance G.
R~ = reflectivity~a p r o p e r t y of the p a i n t - - t h e limiting P = f ( U ' R = ) = ~---bln ( U + b~ = b C ~ (34)
reflectance of the p a i n t film as it is i n c r e a s e d in
thickness. Also defined as the reflectance at com- in w h i c h
plete hiding as evidenced b y R0 = R~ over a black-
In = sign of n a t u r a l logarithms, viz., log ~x = In x,
a n d - w h i t e s u b s t r a t e o f u n i f o r m film thickness.
coth = sign of hyperbolic cotangents, defined b y coth x
C~ = the c o n t r a s t ratio of a film a p p l i e d at u n i f o r m
eZ~+ 1,
thickness over a b l a c k - a n d - w h i t e substrate; thus, - - - and
e 2~ - 1
C~ = Ro/R~,
C0.s0 = the c o n t r a s t ratio over a s t a n d a r d black-and-white c o t h - 1 = sign of inverse hyperbolic cotangents, defined b y
substrate, thus C0.80 = Ro/Ro.so.
C = a b b r e v i a t i o n for C0.s0; the two are used inter-
coth-J x = - In
2 \ x - 11
.t
changeably, thus C = C080 = Ro/Ro.ao. Values of n a t u r a l l o g a r i t h m s a n d hyperbolic functions are
T = the film thickness in any stated unit, e.g.,/zm, mils. available in p u b l i s h e d tables a n d in calculators. Since the
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t a n g e n t function is frequently p r o v i d e d w i t h o u t the m2/kg. These are t r a n s l a t a b l e into film thicknesses a n d U.S.
cotangent, the relationships b e t w e e n the two are stated here units using the conversion equations in 1.j.3. E q u a t i o n s for
as follows the n u m e r i c a l conversion of scattering coefficients expressed
in various units to s t a n d a r d i z e d metric s p r e a d i n g rate units
c o t h x = 1/tanhx, c o t h - 1x = t a n h - 1 1Ix
are given in Table 4.
c. O r i g i n a l K - M E q u a t i o n s
e. G e n e r a l K-M H i d i n g P o w e r M e t h o d
The original equations are as follows:
F o r n o n o p a q u e films The e x p e r i m e n t a l procedure, in brief, is to d e t e r m i n e the
reflectivity R= of the p a i n t a n d R0 a n d Hx of a n o n o p a q u e
G/R~ - i + (1 - GR~)e (l/R| -R~)ST
Ra = f (ST, R~, G) = (35) p a i n t film, from w h i c h the scattering coefficient S of the p a i n t
G - R= + (1/R= - G)e (1/R= - R=)ST is calculated. F r o m R= a n d S is t h e n calculated the s p r e a d i n g
rate I t c at any specified c o n t r a s t ratio C o r vice versa, or m o r e
F o r o p a q u e films
specifically the s p r e a d i n g rate H0.98 w h e n C -- 0.98, w h i c h b y
R= = f(K/S) = I + K/S - (K2S 2 + 2K/S) 1/2 (36) definition is the hiding p o w e r of the paint. The K-M equations
used in these calculations are derived from Eq 38 (the simpli-
w h o s e converse a n d m o r e useful form is
fied form of Eq 35) a n d can be p r o g r a m m e d for quick com-
K/S = f(R=) = (1 - R=)2/2R= (37) p u t e r solutions.
F u n c t i o n a l forms are shown in this discussion along with
(1) D e t e r m i n a t i o n o f Reflectivity R~
the c o r r e s p o n d i n g explicit forms for a clearer p e r c e p t i o n of
the variables. S o m e t i m e s the functional form will be used by A p a i n t film is a p p l i e d u n i f o r m l y over a black-and-white
itself for b o t h brevity a n d clarity. substrate at n o r m a l s p r e a d i n g rate (or film thickness) a n d
E q u a t i o n 35 shows the reflectance of a p a i n t film in t e r m s d r i e d in the m a n n e r usual for the p a r t i c u l a r coating. After
of two basic optical characteristics of the paint: the scattering drying, the reflectance values R o, Rw, a n d W are m e a s u r e d . If
coefficient, S, .and reflectivity, R=, a n d two values t h a t are the c o n t r a s t ratio Cw = Ro/Rw is less t h a n 0.96, the applica-
characteristic of the p a r t i c u l a r application: the reflectance G tion is r e p e a t e d as a second coat or at a s o m e w h a t higher film
of the s u b s t r a t e a n d the thickness T of the film. E q u a t i o n 36 thickness. A p o r o u s film should not be r e c o a t e d n o r a n im-
shows that R~ could be r e p l a c e d by K in Eq 35, b u t R~ is practically high film thickness a p p l i e d in a single coat due to
preferred b e c a u s e the r e s u l t a n t equation forms are m u c h the possible effect on R=. If the original or r e c o a t e d film hides
s i m p l e r a n d also b e c a u s e R= can in s o m e cases be m e a s u r e d completely, then R 0 -- Rw = R=. If not, calculate
directly.
1( R~ (39)
a=f(Ro, P~,W)=~ R~ + -W--Ro
d. S c a t t e r i n g C o e f f i c i e n t a n d S c a t t e r i n g P o w e r
a n d from Eq 32:
The p r o d u c t S T in Eq 35 is a unitless film constant referred R = = a - (a z - 1) 1/2
to b y K u b e l k a [23] a n d J u d d [22] as the scattering p o w e r of
the film a n d s y m b o l i z e d here b y the letter P. Thus, given t h a t The preceding two equations m a y be p r o g r a m m e d sequen-
P = S T a n d e m p l o y i n g simplifying forms of R~ a n d the tially to give
function U of Eq 33, Eq 35 can be r e w r i t t e n in the m u c h
R~ = f(Ro, Rw, W) (40)
a b b r e v i a t e d form
1 -G(a-U) (2) D e t e r m i n a t i o n o f R 0 a n d H x
R c = f(U, R~, G) -- f(P, R~, G) - (38)
a+U-G This requires the a p p l i c a t i o n of a u n i f o r m film at a spread-
ing rate (or film thickness) such that the c o n t r a s t ratio Cw is
Since film thickness T a n d s p r e a d i n g rate H are reciprocally
within the range of 0.96 to 0.985. These limits are established
i n t e r d e p e n d e n t (see Eqs 3 a n d 7), it follows that P = STT --
SH/H, with the scattering coefficient (St o r SH) being ex- b e c a u s e too low a CR requires excessive e x t r a p o l a t i o n to the
p r e s s e d in a unit reciprocal to t h a t of T (e.g., m i l - 1,/~m- 1) o r C = 0.98 end-point, a n d h i g h e r CR values b e c o m e increas-
in the s a m e s p r e a d i n g rate units as H (e.g., ft2/gal, m2/L, ft2/lb, ingly insensitive to s p r e a d i n g rate (or film thickness) varia-
m2/kg, cm2/g). A clarifying c o n c e p t in w h i c h s p r e a d i n g rate tions. If the initial a p p l i c a t i o n is outside that range, the
units are m a n d a t o r y is to c o n s i d e r scattering as a n entity a p p l i c a t i o n is r e p e a t e d at a h i g h e r o r lower film thickness, as
quantifiable in area units, with the scattering coefficient as required.
the a m o u n t of scattering p e r unit q u a n t i t y of coating o r
coating ingredient, a n d scattering p o w e r as the a m o u n t of TABLE 4--Unit conversion equations for scattering coefficients.
scattering p e r unit area of film. S p r e a d i n g rate units have the
further a d v a n t a g e over film thickness a n d reciprocal film S (mZ/L) = S (ft2/gal) + 40.746
" = S (mil 1) X 39.37
thickness of being directly relatable to gravimetric as well as " = S(/~m -1) 1000
volumetric quantities. Thus, for understandability, conve- " = S(mm 1) 1
nience, a n d s t a n d a r d i z a t i o n , it is preferable to use s p r e a d i n g S (mZ/kg) = S (ft2/lb) + 4.888
rate units for scattering coefficients a n d hiding p o w e r a n d " = S (crnZ/g) + 10
S (m2/L) = S (mZ/kg) D (kg/L)
m o r e specifically the m e t r i c s p r e a d i n g rate units m2/L a n d
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The film m a y be applied on a b l a c k - a n d - w h i t e o r an all- P = f(U, R~)

b l a c k substrate. If black-and-white, t h e n the test a p p l i c a t i o n
which are solved sequentially to give
can be the s a m e one used for d e t e r m i n i n g R~ in 8.e.(1). If an
all-black test surface is employed, the i n d i c a t e d c o n t r a s t ratio Pc = f (C, R~) (46)
range is still required, b u t since it can't be m e a s u r e d directly,
(d) The hiding p o w e r H0.98 is then calculated from H c =
it is calculated from
S/P c w h e r e C = 0.98.
Calculation steps (a) t h r o u g h (d) can be c o m b i n e d into a
Co.8o = f(Ro, R~) = R o ( l - 0.80Ro) (41)
R 0 + 0.80 (1 - 2aR0) single c o m p u t e r p r o g r a m to r u n as follows
Having o b t a i n e d a film w i t h i n the specified c o n t r a s t ratio INPUT: R0, Hx, R~, C--OUTPUT: S, H c (47)
range, R0 is r e c o r d e d a n d H , is d e t e r m i n e d by a suitable Note that the s a m e equations a n d p r o g r a m can be u s e d to
method. Various techniques for d e t e r m i n i n g the s p r e a d i n g calculate the s p r e a d i n g rate H C for any value of C, not j u s t for
rate are available, b u t the most precise is a weight-area-den- C = 0.98.
sity-NVW m e t h o d as discussed in Section 6.b, using applica- Carrying the calculation sequence b a c k to Eq 40 for a single
ble Eqs 26 or 27. The d r y film weight M in those equations is test a p p l i c a t i o n on a black-and-white substrate, the com-
usually o b t a i n e d as the difference in the weight of the test b i n e d p r o g r a m w o u l d be
a r e a before a n d after a p p l i c a t i o n of the paint. Sometimes, as
with b l a c k glass, it is o b t a i n e d by removing a k n o w n a r e a of INPUT: Ro, Rw, W, Hx, C--OUTPUT: R~, S, H c (48)
film a n d weighing it directly. Such weighings can be per- with the r e m i n d e r that the c o n t r a s t ratio Cw = Ro/Rw is
f o r m e d on an analytical b a l a n c e with great accuracy. The r e q u i r e d to be in the range 0.96 to 0.985 for these o p e r a t i o n s
density D a n d nonvolatile N of the p a i n t m u s t of course also to provide reliable information.
be d e t e r m i n e d if not already known.
W i t h c o n s i d e r a b l y less precision, the thickness of the dry (4) Contrast Ratio at a Specified Spreading Rate
film can be m e a s u r e d using a caliper or electronic gage on a Although this is not hiding p o w e r as such, it is frequently
metal panel, from w h i c h the s p r e a d i n g rate can be calculated used as an alternative hiding p o w e r criterion. After Step (b) of
using one of the following relationships 8.e.(3), calculate the scattering p o w e r P at the specified
1000 ND s p r e a d i n g rate H from: PH = S/H, then calculate the c o n t r a s t
H (m2/L) - - - (42)
t (/~m)-d ratio CH from Eq 33:
or U~ = f(PH, R~)
1000 N and
H (m2/kg) = (43)
t (/~m).d (kg/L) a + U - 0.80
CH = f(UH, R~) = (49)
where (a + U)[1 - 0.80(a - U)]
N = the nonvolatile fraction by weight (NVW) of the test which together give
paint,
C , = f(Pm R~) (50)
D = the density of a liquid paint,
d = the density of the d r y (or cured) film, and The c o m p u t e r p r o g r a m for this series of calculations w o u l d
t = the thickness of the d r y (or cured) film. therefore be
(3) Calculation o f Ho.9s INPUT: R0, Hx, R~, H - - O U T P U T : S, CH (51)

Having d e t e r m i n e d R~ of the p a i n t a n d Ro a n d H~ of the test Going b a c k to Eq 40, for a single test a p p l i c a t i o n on a black-
film, Ho.9s is o b t a i n e d by the following sequence of calcula- and-white substrate the c o m b i n e d p r o g r a m w o u l d be
tions:
INPUT: Ro, Rw, W, Hx, H - - O U T P U T : R~, S, CH (52)
(a) The scattering p o w e r P~ of the test film is calculated
from A basic defect of this a n d other m e t h o d s that e m p l o y con-
trast ratio as the c r i t e r i o n of HP is that CR values are only
P~ = f(Ro, R~) = bCOth - 1 c o m p a r a t i v e as o p p o s e d to spreading rates, w h i c h have in-
trinsic a n d practical significance.
1 - RoR=
[1-aR~ = ~bln (1
\ bRo ! R--~-o-~j (44) f. Judd Graph
(b) The scattering coefficient S of the p a i n t is calculated Prior to the availability of m o d e r n c o m p u t e r s , K-M equa-
from S = Pfl~. tions were m u c h too complex for a practicable hiding p o w e r
(c) The scattering p o w e r Pc of a p a i n t film at the c o n t r a s t test m e t h o d . J u d d [24] therefore l a b o r i o u s l y w o r k e d out a
ratio C = 0.98 is calculated from general solution to Eq 35 in the form of a g r a p h r e p r o d u c e d in
[( 1 -C12-1] 1/2-1- 1 - C Fig. 9. The g r a p h relates the four variables Ro, Co.8o, R~, a n d P
so that from any two of t h e m the o t h e r two can be deter-
Uo = f(C, R~) = a + 1.60 C] 1.60C (45)
mined. It consists of two families of curves for c o n s t a n t
and Eq 34 values of R~ a n d P, plotted on the c o o r d i n a t e s R 0 and Co.so,
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.95 ARoo= .95

DIAGRAM SHOWING INTERRELATION 15.0
12.0
OF REFLECTANCE Ro P = 10.0
i
9.0 =.90
.90" REFLECTIVITY - Roo CONTRAST RATIO - Co,8o 8.0
AND SCATTERING POWER - P 7.0,
.85- (Constructed from Formula of Kubelka and Munk) 6.0 ,Roo= .85
P=5.0
P=4.0 ,Roo= .80

.80,
3.5
P=3.0. ,Roo= .75

.75'
Ro 2.5A
.70, = .70
P=2.0
.65. ,Roo= .65
1.5 ,Roo= .60

.60
.55J, P =, 1.0
.50.
.60 .65 .70 .75 .80 .85 .90 .95 1.00
CONTRAST RATIO - - Co.8o

FIG. 9-Judd graph derived from Kubelka-Munk Eq 35.
The P curves were referred to in the original J u d d g r a p h as m a y be d e m o n s t r a t e d as follows: S u p p o s e a p o r t i o n of p a i n t

curves of SX (or ST). The p o r t i o n p e r t i n e n t to white paints (R~ for w h i c h R~ -- 0.85 is tinted with a black c o l o r a n t to a n R~
-> 0.75) has been enlarged a n d is shown in Fig. 10. Experi- value of 0.78 a n d the u n t i n t e d a n d tinted paints are a p p l i e d at
mentally, R o, Rw, W, a n d Hx are d e t e r m i n e d as in 8.e. 1 a n d the s a m e thickness such that P -- 5.0. F r o m Fig. 9, o r m o r e
8.e.2 for a film a p p l i e d u n i f o r m l y on a b l a c k - a n d - w h i t e test accurately from Fig. 10, it can be d e t e r m i n e d that the colo-
substrate. If W deviates f r o m 0.80 b y m o r e t h a n 0.01, C0.80 is r a n t a d d i t i o n has increased the c o n t r a s t ratio to 0.965 from
calculated using c o r r e c t i o n Eqs 1 or 2. Px a n d R~ are deter- its original value of 0.945, r e p r e s e n t i n g a c o n s i d e r a b l e in-
m i n e d at the g r a p h p o i n t c o r r e s p o n d i n g to Co.8o a n d R o, a n d crease in visual film opacity. To d e t e r m i n e w h a t this a m o u n t s
the scattering coefficient of the p a i n t calculated from S = to in t e r m s of p h o t o m e t r i c hiding power, the P values of the
PxHx. The value of P0.98 is located at the intersection of the R= u n t i n t e d a n d tinted p a i n t s at the intersection of their R=
curve with the vertical line for C = 0.98. The hiding p o w e r is curves with the vertical line C = 0.98 are f o u n d to be 7.5 a n d
t h e n calculated from//o.98 = S/Po.98. If desired, the s p r e a d i n g 6.0, respectively. Since S is unaffected by tinting, the spread-
rate can be d e t e r m i n e d for c o n t r a s t ratios o t h e r t h a n 0.98 in ing rate change at C = 0.98 is calculated thus
the s a m e way. Conversely, CH m a y be d e t e r m i n e d for a n y
/-/tinted -- Puntinted __ 7 . 5
specified value of H by first calculating: P , = S/H, t h e n - 1.25
finding the d e s i r e d value of C~/ at the intersection of the Huntinted Printed 6.0
curves for the d e t e r m i n e d PH a n d R~. r e p r e s e n t i n g an increase of 25% in hiding p o w e r b y tinting to
The J u d d g r a p h is also useful for depicting the basic optical a lower R~ value. This hiding increase was o b t a i n e d at negli-
p r o p e r t i e s of paints. It shows t h a t p a i n t s with high S values gible m o n e t a r y cost b u t at a sacrifice in p a i n t quality in
are lighter over black b a c k g r o u n d s t h a n p a i n t s of the s a m e r e g a r d to brightness of a p p e a r a n c e . F o r that reason, in evalu-
reflectivity with low S values. Also, if their S values a n d film ating a series of p a i n t s experimentally, a fair c o m p a r i s o n
thicknesses are the same, p a i n t s with high reflectivity are requires t h a t all R~ values be a d j u s t e d by tinting to that of its
p o o r e r in hiding t h a n p a i n t s of low reflectivity. The latter fact lowest reflectivity m e m b e r . E x a m i n a t i o n of the J u d d g r a p h
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CHAPTER 4 2 - - H I D I N G P O W E R 495
.95 o a
=.95 Associated with the Mitton graph is a table of Factor A
values derived from Eq 46: Pc = f (C, R~), in which Factor Ac
= 1604.2/Pr Values of Factor Ar are given in this table for C
= 0.98, 0.95, and 0.93, for all values of R~ from 0.08 to 0.98 (8
to 98%). The C value of most interest for hiding power calcu-
lations is 0.98, representing full photometric hiding as de-
fined in Section 2.b. If desired, Pc is easily calculated from
.90 .~= .90 Factor Ac.
The graph and table are typically used as follows: After
determining R= and R0 experimentally, the index graph is
consulted in order to select the appropriate expanded graph
on which the scattering power Px of the experimental paint
film is to be found. Factor A0.98 is determined from the table
for the measured value of R~. At this point either the film
.85 < = .85 thickness Tx or spreading rate Hx of the test film associated
with Ro is determined. If, as Mitton intended, Tx is deter-
mined in mils, then the scattering coefficient S is calculated
in reciprocal mils from S = Px/Tx, and the hiding power is
calculated from the equation
//0.98 (ft2/gal) = S (mil-1)'30.98

.80 ,o = .80
The preceding simple relationship holds when S is ex-
pressed in reciprocal mils and hiding power in ft2/gal. If the
spreading rate in m2/L is determined instead of the film
thickness, then after determining Px and R=, the scattering
coefficient is calculated as: S (m2/L) = Px.Hx (mE/L) and the
hiding power calculated from
.75 = .75
90 9,5 1(30 o~ S (m2/L).A0.98 _ S (m2/L)
//o.98 (mE/L) --
C O N T R A S T R A T I O - - C0eo 1604.2 P0.98
FIG. 1 0 - J u d d graph derived from Kubelka-Munk Eq 3 5 ~ a
portion of Fig. 9 enlarged. At a later date Mitton commented that graphical and tabu-
lar aids for Kubelka-Munk calculations had become unneces-
sary with the advent of inexpensive programmable cal-
shows that, after adjustment to the same R~ value, films of the culators [28]. Nevertheless, the Mitton graph and table
different paints applied at the contrast ratio C = 0.98 all have continue to be used in a number of important test methods,
the same P0.98 value, and, since H0.98 = S/P0.98, their hiding and both the Judd and Mitton graphs are useful for instruc-
powers will be directly proportional to their scattering coeffi- tional purposes.
cients. Thus the scattering coefficient alone can be an ade-
quate hiding power comparator, without actually tinting the
individual paints, h. Typical Kubelka-Munk Hiding Power Results
Tables 5, 6, and 7 are based on the testing of various
g. Mitton Graph and Table [27] commercial paints and pigments. They are intended to illus-
trate magnitudes of hiding power and scattering coefficient
As with the Judd graph, these provide precalculated solu- values encountered in K-M hiding power measurements. The
tions to K-M equations, but with much greater precision. scattering coefficient values are intended to supplement and
They were designed for the experimental procedure de- clarify, by specific examples, the relationships shown in Table
scribed in 8.e, in which R0 and Hx are determined for a film 4. With regard to pigments (Table 7), it is of course disper-
applied on an all-black test surface, and R~ is determined in a sions that are actually measured and the values for the pig-
separate test application. The test surface of choice is black ments then calculated from their concentrations in the
float glass because the extremely level nature of the surface dispersions. For example
permits the application of very uniform films with a doctor
blade. Mitton also describes the use of all-black metal panels Hpigment(m2/kg) _ (ma/kg) =
Spigrnen t 1
to test spraying/baking-type finishes [21]. The graph is de- Hcoating (m2/L) Scoating(ma/L) Pigment Conc. (kg/L)
rived from Eq 44: P -- f(Ro, R~) and is plotted as a family of
curves at constant R~ on coordinates of scattering power P The values in Table 7 should be considered as comparative
and reflectance Ro. The ordinate is indicated as "ST (Factor because the hiding power of pigments can vary widely de-
B)," which is the same as P, and the abscissa as RB, which is pending on the conditions of measurement (Ref 4, p. 34),
usually and in this case necessarily the same as R0. It consists being effected by PVC, effectiveness of dispersion, the pres-
of a small-scale index graph (Fig. 11) divided into 31 sections, ence of other pigments in the same dispersion, and the nature
each then expanded to a much larger scale on a separate of the vehicle. Even within a specific chemical class it can
sheet. Figure 12 shows one of the expanded sections. vary considerably depending upon the particular method of
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FIG. 11-Mitton graph of Kubelka-Munk Eq 44.
manufacture employed. Nevertheless, it is frequently useful cluded that at practical film thicknesses S is constant within
to determine pigment hiding power values for a comparison experimental error. The writer in his laboratory obtained es-
of their efficiency under specified conditions. sentially constant S values within a wet film thickness range
of 100 to 50 ~m (10 to 20 mZ/L, 400 to 800 ft2/gal) for white
i. Theoretical P r o b l e m s a n d Practical alkyd gloss, latex gloss, and latex flat paints. Moreover, the
Considerations effect of any variation of S with film thickness that might
occur is minimized in experimental practice by casting films
The validity and usefulness of the Kubelka-Munk equations with contrast ratios fairly close to the 0.98 CR hiding end-
in hiding power calculations are predicated on the constancy point, as called for in 8.e.(2). This is not difficult to do.
of the scattering coefficient S over a suitably wide film thick- Refractive indices and resultant scattering coefficients vary
ness range. Judd [24] studied this question in connection with the wavelength of light. Thus the effective scattering
with water-borne paints and vitreous white enamels and con- coefficient of a paint is actually an average for all of the
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FIG. 12-Mitton graph--expansion of Sector 5 in Fig. 11.
encountered wavelengths. With nonchromatic paint films, are made fairly close to the hiding power end-point (C =
the wavelength composition of the light flux remains con- 0.98), so that the Kubelka-Munk extrapolation and thus any
stant and therefore so does the scattering coefficient upon associated error is relatively small.
which constancy the validity of K-M equations is predicated. As discussed by Mitton (Ref 4, p. 27), Kubelka-Munk theory
Chromatic paint films, however, absorb light selectively and has been questioned because it is "phenomenological" rather
therefore change the composition of broad-band illuminants than based on fundamental theoretical considerations, and
with a resultant change in the effective scattering coefficient. the measurements and equations omit needed corrections for
This would in theory appear to disqualify chromatic paints surface reflection that are theoretically substantial. However,
from Kubelka-Munk hiding power calculations. In practice, in experimental practice the errors are generally small de-
however, the equations are used successfully for that purpose spite the theoretical defects. Simpson took note of this in his
(Ref 29; Ref 4, p. 31), which is undoubtedly related to the comment that when uncorrected values of S and K are in-
previously noted fact that the experimental measurements serted back into the uncorrected K-M equations, "it would
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TABLE 5--Air-dried architectural alkyd coatings--hiding power and scattering coefficient data (Ref
29; Ref 4, p. 33).
Gloss Semi-Gloss Flat Gloss Gloss Gloss Gloss
White White White Gray Orange Yellow Green
R~ average 0.8798 0.8679 0.9119 0.5654 0.3910 0.6682 0.6940
P0.gs (unitless) 8.510 8.I58 9.436 3.394 2.150 4.436 4.759
Metric Units
Ho.9s (mZ/L) 7.706 8.330 10.32 19.71 15.48 8.629 13.57
To.98 (~m) 129.8 120.0 96.92 50.74 64.60 115.9 73.7
S (mZ/L) 65.58 67.95 98.39 66.89 33.28 38.28 64.58
S (~m 1) 0.0656 0.0680 0.0984 0.0669 0.0333 0.0383 0.0646
U.S. Units
/-/o.98 (ft2/gal) 314.0 339.4 420.4 803.0 630.8 351.6 552.8
To.9s (mils) 5.109 4.726 3.816 1.998 2.543 4.562 2.902
S (ft2/gal) 2672 2769 4009 2725 1356 1560 2631
S (mil- 1) 1.665 1.726 2.499 1.699 0.8455 0.9723 1.640
NOTE:Valuesare shownhere to four significantfiguresfor illustrativepurposes only.Experimentalprecisionis in no
case to more than three significantfigures.
TABLE 6--Powder coatings--Representative hiding power and K value of a black tinter is d e t e r m i n e d by adding a m e a s u r e d
scattering coefficient data.
ratio to the s t a n d a r d p a i n t sufficient to reduce the reflectivity
White Light Gray Orange to a b o u t 0.40. The K value of the tinted p a i n t is its initial K
R~ 0.8234 0.6860 0.4389 value plus the tinter contribution, thus
P0.gs (unitless) 7.011 4.655 2.449
Metric Units K2=K 1 +XK, (a)
Ho.9s (m2/kg) 18.09 20.22 10.26
Density (kg/L) 1.60 1.66 1.41 from which
To.gs (/zm) 34.55 29.79 69.12
S (m2/kg) 126.8 94.13 25.13 XKt = K2 - K, (b)
U.S. Units
//o.98 (fta/lb) 88.3 98.7 50.1 a n d dividing through (b) by the c o m m o n value of S
Density (lb/gal) 13.35 13.85 11.77
T0,98 (mils) 1.36 1.17 2.72 XKtlS = K2/S - K J S (c)
S (~t2/lb) 619.2 459.5 122.7
in which
NOTE:Derivedfrom test resultsobtainedby ASTMSubcommitteeDO1.51 on
Powder Coatings.
K, = the a b s o r p t i o n coefficient of the tinter,
X = the ratio of tinter to paint,
TABLE 7--White pigments--hiding power and scattering K~ = the initial K value of the paint,
coefficient values~. /s = the K value of the p a i n t after tinting, a n d
Lead Zinc Zinc Anatase Rutile S = the scattering coefficient of the paint.
Carbonate Oxide Sulfide TiOz TiO2
R~ (estimated) 0.91 . . . . . . . . . . . . The ratios K2/S a n d K1/S are calculated from m e a s u r e d
Po.9s (unitless) 9.5 . . . . . . . . . . . . values of R= for the tinted a n d u n t i n t e d paints using Eq 37:
Metric Units K/S = (1 - R=)2/2R~. If the s t a n d a r d paint is a n u n t i n t e d
//o.98 (m2/kg) 3A 4.1 11.9 23.5 30 white with a reflectivity no lower t h a n 0.93, then its absorp-
S (m2/kg) 29 39 113 223 285 tion c o n t r i b u t i o n K 1 is considered negligible c o m p a r e d with
U,S. Units that of the tinter, in which case K1/S is dropped from Eq (c) to
//0.98 (ftE/lb) 15 20 58 115 147 give
S (ft2/lb) 140 190 550 1090 1390
abased on reported hiding power values at a PVC of 28% [30,31]. XKt/S = K J S (d)
The a b s o r p t i o n coefficient K t of the tinter can be calculated

appear that a n approximately correct answer is obtained" from Eqs (c) or (d) since all other terms in these equations are
(Ref 2, p. 111). known.
Having d e t e r m i n e d K,, the S-value of a test p a i n t can be
d e t e r m i n e d using the same tinting procedure a n d equations
j. C a l c u l a t i o n o f H i d i n g P o w e r f r o m T i n t i n g D a t a
as before, b u t this time calculating u n k n o w n S from k n o w n Kt
Initially the S a n d R~ values of a s t a n d a r d white p a i n t are instead of vice versa. With the values S a n d R= of the test p a i n t
d e t e r m i n e d in accordance with the procedure described in having thus been determined, its hiding power H0.9s can be
8.e. The K value of the p a i n t can then be calculated from Eq calculated as in 8.e.(3)(c) a n d (d) w i t h o u t the tedious require-
37: K/S = (1 - R~)2/2R~. m e n t of m e a s u r i n g the spreading rate.
F r o m 8.d, S a n d K can be considered as concentrations of Experimental evidence for the validity of this procedure is
"scattering" a n d "absorption" per u n i t weight or volume, The given by Mitton a n d Jacobsen [32], who, equating the tinting
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U~
!
:5200! /
p-
UJ
0
CL
rr
2800
2400
/e
/
Z
/|
2000
1"
LU
i
1600 CURVE IF PERFECT
"1"
/@ CORRELATION (i.e. 45 ~ CURVE)
/
1200
0r r /
ii
806
j S = 106(TS) - 162
E r = 0.997
(3
40C m std. dev. about regression = 76
Z
U~
UJ /
i t 1 1 t t l,, t t
3 400 800 ~200 ~600 2000 2400 2800 3200 3600
TINTING-STRENGTH VALUES IN UNITS OF cm2/g
FIG. 13-Scattering coefficients determined by tinting and by hiding power tests.
strength of a white pigment with its scattering coefficient, S B / S A = ( K A 2 / S A - K A 1 / S A ) -~- ( K B 2 / S B - K B I / S B ) (c)

measured S (cm2/g) for a number of white pigments by direct
hiding power measurement and by the tinting procedure. As If the comparison paints are both untinted high reflectance
shown in Fig. 13, the correlation between the two methods is whites then, as pointed out in 8.j, the untinted K-values can
very close. If this simplified method is to work, the K value of be considered negligible and Eq (c) becomes
the black tinter must be the same in any paint being tested.
SB/SA = KA2/SA + K~2/SB (d)
Also, the tinter must not change the degree of dispersion of
the white pigment so as to cause a change in its S value. These As stated at the end of 8.f, at the same reflectivity R~, the HP
conditions are not always met, so that it is safest to apply the values of Paints A and B will be in the same ratio as their
method only under favorable circumstances, when interac- scattering coefficients.
tion of tinter and paint are known to be negligible.
k. Determination o f Relative Hiding Power of

Untinted White Paints from Tinting Data
For this purpose there is no need to determine the K value 9. FACTORS A F F E C T I N G W H I T E H I D I N G
of the tinter as in 8.j. An equal ratio of black tinter is added to POWER
Comparison Paints A and B, sufficient to reduce their R~
values to about 0.40. The R~ values of Paints A and B are As shown in Tables 1 and 7, futile titanium dioxide is by far
measured before and after tinting and the four corresponding the most effective of the white hiding pigments in producing
K/S values calculated from Eq 30. Then, as in Eq (c) of 8.j, for light scattering and hiding power, which is true on a cost as
Paint A: well as a weight basis. This fact has effectively eliminated the
use of other white hiding pigments except for special proper-
XKt/S A = KA2/S A - - KA1/S A (a) ties or considerations. The important variables that deter-
for Paint B: mine the scattering and hiding efficiency of a titanium
dioxide pigment in a paint are: (1) its mean crystal and parti-
XK/SB = KBz/S~ - KB,/SB (b) cle size, (2) the state of pigment dispersion, (3) its concentra-
Next, dividing Eq (b) into Eq (a), X and Kt cancel to give tion in the paint film, and (4) film porosity.
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a. Crystal and Particle Size c. Pigment Concentration

By decreasing the particle size of the pigment, the number In Section 3.c it was pointed out that a very large single
of particles and surfaces for light reflection and refraction crystal of a white hiding pigment is actually transparent.
increase, and the light scattering ability of a given quantity of Without undertaking a theoretical analysis, it is to be expec-
pigment will therefore tend to be enhanced. However, if the ted that as the concentration of pigment increases and its
particle size is too small in relation to the wavelength of light, particles become more crowded, they approach the optical
the wave front passes around rather than through it, so there condition of a very large particle with resultant loss of scatter-
is no light scattering, and the dispersion is transparent. Obvi- ing efficiency and hiding power. The "crowding" effect was
ously, there is some intermediate optimum size related to the studied by Stieg [36-38], whose results were used by Mitton
wavelength of light at which maximum scattering efficiency (Ref 4, pp. 34-35) to draw curves of hiding power H09~ versus
is obtained. The wavelength of the visible spectrum ranges PVC for pure futile and anatase titanium dioxide in alkyd
from approximately 0.4 to 0.7 lxm, peaking in luminosity at enamels. These are shown in Fig. 14, in which HP is ex-
0.55/xm. The mean crystal size for maximum opacity ranges pressed in ft2/lb of nonvolatile matter. If the paint is for-
from approximately 0.20 to 0.30 txm depending on both the mulated at 50% nonvolatile by volume, the hiding power
PVC and the fraction of the pigment consisting of single results would be half that shown in the figure, but the shape
crystals. Commercial grades of titanium dioxide developed of the curves would be unchanged. Note the maximums in the
for high-gloss finishes exhibit a single-crystal content of curves at 25 to 30% PVC, above which hiding power actually
about 20% and have a mean crystal size between 0.22 and begins to decrease with increasing concentration of pigment.
0.24 ixm. The adverse effect of lesser crystal size in such When calculated in terms of ft2/lb of pigment, the results
formulations is shown in Table 8 [33]. appear as shown in Fig. 15, clearly indicating the drastic
decrease in TiO2 efficiency due to crowding.
Stieg [36] found empirically that the relationship between
b. Pigment Dispersion TiO 2 hiding power and PVC, as shown in Fig. 15, could be
expressed by the equations
The process of obtaining a satisfactory dispersion involves
the wetting of the pigment by the dispersion medium to futile: H0.98 (ft2/lb) = 370-410 (PVC) '/3 (53)
displace air, breakdown of larger particles by milling, and anatase: H0.98 (ft2/lb) = 290-330 (PVC) T/3 (54)
stabilization after the dispersion has been obtained. With
alkyd media, standard grades of titanium dioxide disperse The PVC values in these equations are decimal fractions.
easily and develop full hiding with very little milling. Thus, Expressed in metric units, the equations become:
the main reason for milling alkyd dispersions is to reduce or rutile: H0.98 (mi/kg) = 75.7 - 83.9 (PVC) 1/3 (55)
eliminate oversize particles that effect the appearance of the
film. With latex paints, milling can have an important effect anatase: H0.98 (m2/kg) = 59.3 - 67.5 (PVC) '/3 (56)
on opacity depending on the grade of pigment employed [33], The question has been studied [36,39] of whether extenders
but the appearance factor is also an important consideration, added to a gloss or semigloss paint film might tend to in-
particularly with semigloss and gloss finishes. crease the spacing of the TiO 2 pigment and thereby its scat-
A major factor affecting the efficiency of TiO 2 in the com- tering efficiency. The physical picture that emerges is of large
pleted formulation is the phenomenon referred to as "floccu- particle-size extenders acting as massive intrusions having no
lation," which is the formation of large particle groups or effect on the original TiO2 spacing, and of fine particle size
"floccules" due to weak forces of cohesion. Floccules are extenders dispersing uniformly so as to increase TiOz spac-
easily broken down but can spontaneously and quickly recur ing, but no differently in this respect than an equal volume of
in the wet paint or drying paint film. Despite their weak binder. Consequently, when binder is replaced by an equal
bonding, floccules have the optical effect of increasing the volume of large particle-size extender, TiO 2 efficiency de-
mean particle size, thereby decreasing the scattering effi- creases, whereas with small particle-size extenders, TiO~ effi-
ciency of the pigment. An auxiliary phenomenon related to ciency has been found to remain essentially the same and in
increased particle size is the preferential scattering of longer no case improved.
wavelengths. Balfour and Hird took advantage of this phe-
nomenon to quantify pigment flocculation by measuring
back-scattered infrared radiation (wavelength 25/.m) from a d. Film Porosity
dried paint film to obtain what they refer to as a "flocculation
The preceding relationships pertain to pigment concentra-
gradient" [34,35].
tions at which there is sufficient binder to wet the pigment
completely and form a continuous phase, which means below
TABLE 8--Scattering coefficient of a 20% PVC TiO2-alkyd paint the critical pigment volume concentration (CPVC). Above the
film versus crystal size of pigment. CPVC, the dried film becomes porous, containing entrapped
Mean air that increases pigment-scattering efficiency by' effectively
Crystal Size, lowering the refractive index of the surrounding medium.
S, ,urn I /*m
The air itself, as particulate matter in contact with the higher
0.76 0.24 refractive index binder, contributes to light scattering. Thus,
0.73 0.20 if the curves of Fig. 14 were extended to a sufficientlv high
0.64 0.16
PVC, the hiding power of the film would begin to rise again
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I000
oO
E3
/
o
O9
900
I Z
tl.I 9 80O
0
ft. rr
g
ILl
LL
3: UJ
60O
tr"
<
:3
o
0r~ 50(1
I I I ! I 1 I I
15 20 25 30 35 40 45 50
PIGMENT VOLUME CONCENTRATION
FIG. 1 4 - H i d i n g power Ho.m (ft2/gal) of solids at various PVC levels.
I- ture of the extender. The Porosity Index is calculated from the

Z
LU equation
_~ 18o
fi- CPVC (1 - PVC)
LL e.I. = 1 - (57)
o 160 PVC (1 - CPVC)
c3 Rutile
z
The low-cost hiding power obtained from porosity is unfortu-
o
n 140 nately accompanied by a deterioration in the quality of the
tr
uJ
Q. film as manifested by poor scrub, soilant, and stain resist-
120 ance. This is due to an insufficiency of binder, resulting in an
W
LL air phase continuum that gives ready capillary access to
LU
rr I00 staining materials.
<
0
O9
[ ao
w 10. M I C R O V O I D S F O R W H I T E H I D I N G
6o
POWER
(,) 40
_z Through the use of encapsulated preformed microvoids, it
has been found possible to obtain some of the hiding power
------
i ,I ,i I
r
i0 ?.0 30 40 50 60 benefit of entrapped air while avoiding or minimizing the
PIGMENT VOLUME CONCENTRATION deleterious effect of film porosity. The microvoids are sup-
FIG. 1 5 - H i d i n g power Ho.gs(ft2/Ib) of pigment at various PVC plied as a water dispersion of hollow beads having a plastic
levels. outer shell and water-filled core. Incorporated into a latex
paint, the water in the core evaporates during the drying of
the film and is replaced by air that functions as light-scatter-
due to the opacification effect of film porosity. Obviously this
ing particulates shielded from staining penetrants by the sur-
is an extremely impractical use of expensive titanium dioxide
rounding plastic shell. Because the microvoids alone are not
with no relation to actual formulation practice. However, able to produce the desired level of opacity in a film of normal
porosity does in practice make a major contribution to hiding thickness, the inclusion of titanium dioxide pigments in the
power in the important interior flat wall paint sector. In paint formulation along with microvoids is essential. One
paints of that type, inexpensive inert white pigments are in- widely used microvoid bead product is referred to as "opaque
cluded in the formulation along with titanium dioxide for the polymer" and employs a shell of thermoplastic polystyrene.
esthetic purpose of producing a flat finish and to contribute Another type is a vesiculated bead in which titanium dioxide
hiding power by means of porosity. Stieg and Ensminger [38] and water-filled "vesicles" are associated in a cross-linked
showed that with paints over the CPVC that contain both polyester/styrene matrix. By using such products to partially
TiO2 and extender, hiding power is in a straight-line relation- replace titanium dioxide pigment, raw material cost savings
ship with the Porosity Index (P.I.), with the slope of the line have been demonstrated with no loss in film integrity or
depending on the percentage of prime pigment and the ha- hiding power [35,40].
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11. F O R M A L H I D I N G P O W E R M E T H O D S tal results but with a slightly different equation sequence as

described in 8.e.(4), thus: P~ = f (Ro, R~), S = PxH~,Pn = S/H,
a. A S T M M e t h o d s C . = f (P., R~). This sequence is summarized in the com-
puter program identified as Eq 51: INPUT: R o, Hx, R~, H--
D 344: Test Method for Relative Dry Hiding Power of
Paints by the Visual Evaluation of Brushouts OUTPUT: S, Cn.
Earlier versions of D 2805 and its predecessor standards
This is essentially the same as the Krebs Method described
included or referenced the Mitton tables and graphs de-
in 4.d, differing only in requiring black-and-white instead of
scribed in 8.g for solving the K-M equations. The method can
grey-and-white charts and in permitting checkerboard or
be adjusted by appropriate experimental modifications to the
other suitable contrast designs as well as the diamond-stripe
pattern. Modern charts are 0.1 m 2 in area (1.076 ft 2) instead measurement of baked enamels on black-painted metal pan-
of 1 ft2 as specified originally. Provision is made for reporting els as discussed in 7.d, or to other types of coatings and test
results in m2/L as well as ft2/gal. substrates.
D 2805: Test Method for Hiding Power of Paints by

Reflectometry
This was adopted in 1969 and is actually a combination of
D 5007: Test Method for Wet-to-Dry Hiding
two earlier methods, D 1738 and D 2614, that differed only in
Change
technique. It conforms with the general Kubelka-Munk
method described in 8.e but is designed specifically for air- This is a rapid visual test designed to measure percent
dried coatings. Originally it provided for the use of either change in hiding power during drying. The paint is drawn
black glass or charts for determining Hx and R 0. In later ver- down on a black-and-white test chart using a special
sions black glass is mandatory. R~ is determined by a sepa- multinotch applicator (Fig. 16) having eight notches with
rate application as described in 8.e.(1). The need for two test clearances in geometric progression ranging from 67 to
applications does not represent a significant extra effort since 264 p~m (2.65 to 10.4 mils). The clearance corresponding to
only the application on black glass requires the time-con- an agreed visual endpoint (see 2.a) is estimated immediately
suming spreading rate determination. The latter is accom- after application and again after drying. The ratio of the two
plished by placing a template of predetermined area on the clearances multiplied by 100 gives the percentage change in
dry film, scraping off and discarding the film outside the
hiding power:
confines of the template, then carefully scraping off the re-
maining film in the defined test area and weighing it on an CLEARANCEwET E N D P O I N T : WFTwETE N D P O I N T =
analytical balance. The spreading rate is then calculated from CLEARANCEDRvENDPOINT WFTDRyENDPOIT
the density and nonvolatile content of the paint using Eq 26.
Having obtained the experimental values: R0, Hx, and R~, the SPREADING RATEDRYENDVOINX
scattering coefficients and hiding power H0.98 of the paint are SPREADING RATEwETENDPOINX
calculated from these values using the Kubelka-Munk se-
quence shown in 8.e.(3) thus: P~ = f (Ro, R~), S = PxH~,Pc = f The equation assumes that, for any one drawdown, the
(C;R~), He = PJS for C = 0.98. These calculation steps can be ratio of clearance to WFT for the several notches does not
carried out individually or combined into the previously de- deviate appreciably. On that basis WFT variations due to
scribed computer program identified as Eq. 47: INPUT: R~, application technique or paint theology would not affect the
R0, H~, C--OUTPUT: S, H~. final test result. This is not a precision test but provides
The method also provides for calculating the contrast ratio significant information of a practical nature with minimal
C , at a specified spreading rate H, using the same experimen- effort.
i'- BB~
~Notchclearances 24 8.56 217 48 2.65 67
are not drawn to scale 28 7.04 179 TmV~.==
FIG. 16-Multi-notch applicator for ASTM D 5007.
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CHAPTER 4 2 - - H I D I N G POWER 503
D 5150: Test Method for Hiding Power of pass, the CR at the specified spreading rate must have a
Architectural Paints Applied By Roller specified minimum value.
This is a visual comparison method designed for use with Method 4122, Contrast Ratio at a Specified Dry Film
interior wall finishes and intended to provide practical infor- Thickness on Black and White Glass Panels
mation from tests performed on a convenient laboratory
An applicator is selected to obtain precisely the desired dry
scale. The test substrate is a large, sealed paper test chart (Fig.
film thickness, the latter being measured with a micrometer
17) with a series of stripes numbered 1 through 6 on a white
to the nearest 0.0001 in. Separate drawdowns are made on
background. The stripes range in shade from very light grey
black and white glass panels. Reflectances RB and Rw are
to black and were selected so that the color difference AE*b measured and the CR calculated. This is a simplistic concept
between each successive stripe and the white surround is in a in view of the undoubted difficulty in obtaining, measuring,
geometric progression from 2 to 64 CIELAB units. The di- and then repeatedly applying a precise predetermined dry
mensions of the test area are 24 by 36 in. = 6 ft 2 (610 by film thickness.
9 1 4 r a m -- 5575 cm2), sufficiently large to simulate practical
application of paints with a roller. The paint is applied at a
specified, controlled spreading rate, and the hiding power is c. ISO (International Standardization
reported as the stripe number of the darkest stripe perceived Organization) Methods
as being completely obscured. The concept of this test is that ISO 2814, Contrast Ratio (CR) at a Nominal
in practical applications the levelness of the paint film and Spreading Rate (SR) of 20 m2/L on Black-and-White
hence its effective opacity is affected by the rheological prop- Charts or Polyester Film
erties of the paint. Thus, in practice paints tend to have lower
A paint film is applied with a 100-p~m clearance applicator
hiding power than indicated by more customary test methods
to give a nominal wet film thickness of 50/~m, corresponding
in which films are applied with maximum uniformity using a
to a spreading rate of 20 m2/L. Black and white substrate
blade-type applicator. Relative practical hiding power among
reflectances are measured and the contrast ratio calculated
paints can be influenced for that same reason.
without a determination of actual spreading rate, Films cast
on a clear polyester are measured, as described in 7.b, by
placing the film alternately on black and white glass. Because
b. U.S. Federal Test Method Std. 141 different paints and application techniques with the same
applicator give films differing significantly in thickness, the
Method 4121, Contrast Ratio at a Specified Spreading method is satisfactory only as a rough guide for paints of the
Rate same type and color evaluated by one operator.
This pass-fail test was previously described in some detail
in 5.f. Paint films are applied on black-and-white charts by ISO 3905, Contrast Ratio (CR) at a Spreading Rate
brush or drawdown, and spreading rates are determined by a (SR) o f Precisely 20 m2/L on Black and White Charts
typical weight-area-density procedure, discussed in 6.b. CR This method, like ISO 2814, is intended to measure the CR
values are plotted at several spreading rates to obtain graphi- at 20 m2/L, but the SR in this case is determined carefully.
cally the CR at a specified spreading rate. For the test paint to Drawdowns are made with three applicators to obtain no-
FIG. 17-Large gray scale chart (6 ft, 2 5575 cm 2) for roller application tests per
ASTM D 5150.
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m i n a l wet film thicknesses of 40, 50, a n d 60 txm c o r r e s p o n d - fore a n d after application, with a specified volume being de-
ing to SRs of 25, 20, a n d 16.67 m2/L. After drying, the CR livered to the c h a r t surface by syringe. W i t h d r a w d o w n s ,
values are m e a s u r e d a n d the SR values d e t e r m i n e d b y a p r e s u m e d l y identical a p p l i c a t i o n s are m a d e on glass a n d
typical weight-area-density m e t h o d as discussed in 6.b. The charts a n d the W F T d e t e r m i n e d on glass by m e a n s of a n
d r y film weight is d e t e r m i n e d as the difference between the I n t e r c h e m i c a l (ASTM D 1212) wet film thickness gage. F o r
p a i n t e d a n d u n p a i n t e d chart, with considerable p r e c a u t i o n s the test p a i n t to pass, the dry p a i n t film is r e q u i r e d to com-
taken, as discussed in 7.a to avoid error due to n o n u n i f o r m pletely obscure the c o n t r a s t p a t t e r n of the chart.
chart weight. A g r a p h of CR versus SR is p r e p a r e d on square-
ruled p a p e r from which the CR at exactly 20 mZ/L is deter-
m i n e d by interpolation. The m e t h o d is restricted to paints Method 14.2, Spreading Rate Determined at Full
with a reflectance value of at least 25%. Weaknesses of this Visual Hiding (for Quick-Drying Coatings)
m e t h o d are: (a) it fails to correct for possible variations in the Successive thin coats are a p p l i e d by spraying onto black-
reflectance of the white substrate, as discussed in 1.f; (b) the a n d - g r a y or black-and-white charts until visual hiding of the
specified SR of 20 mZ/L c o r r e s p o n d s to a wet film thickness of d r y film is complete. The SR is calculated from the difference
only 5 0 / z m (2 mils), at w h i c h thickness irregularities in the in weight of the coated a n d u n c o a t e d chart. This can be
surface of p a p e r test charts can have an a p p r e c i a b l e effect. expressed in m2/kg of dry film or mZ/L of the original liquid
coating.
ISO 3906, Contrast Ratio (CR) at a Spreading Rate
(SR) of Precisely 20 m2/L on Polyester Film
This m e t h o d is essentially the s a m e as ISO 3905, differing Method 14. 7, Contrast Ratio on Black and White Glass
only in the use of polyester film instead of black-and-white Panels at a Given Spreading Rate or Dry Film
charts. Like ISO 3905, the m e t h o d fails to correct for devia- Thickness
tions in the white substrate from the ideal reflectance of 80%. This is m o d e l e d after the NYPC m e t h o d d e s c r i b e d in 5.d.
However, the p r o b l e m of surface irregularity is largely over- W F T is d e t e r m i n e d with an I n t e r c h e m i c a l gage or DFT with a
c o m e due to the s u p e r i o r levelness of the plastic film. Since m i c r o m e t e r . The target film thickness is b r a c k e t e d experi-
true hiding p o w e r is a s p r e a d i n g rate, n e i t h e r this m e t h o d n o r mentally to o b t a i n two points on a CR versus reciprocal film
ISO 3904 o r ISO 3905 m e a s u r e hiding p o w e r as such. thickness g r a p h a n d the CR at the target thickness deter-
ISO 6504, Kubelka-Munk Method for White and Light- m i n e d by interpolation. The experimental CR values are cor-
Colored Paints rected for W -- 0.80 before plotting the graph.
This is in a c c o r d a n c e with the general K-M hiding p o w e r
m e t h o d d e s c r i b e d in 8.e. It calls for an all-black s u b s t r a t e
w h i c h can be glass or polyester film over b l a c k glass. The
Mitton g r a p h a n d table d e s c r i b e d in 8.g are included, w h i c h f. French Standards Association (AFNOR)
makes it very s i m i l a r to early versions of ASTM D 2805. NF-T30-075, Spreading Rate at a Contrast Ratio (CR)
of 0.98
d. British Standards Institute, BSI 3900 Paint films are cast on clear polyester at several thicknesses
a n d CR values d e t e r m i n e d after drying by m e a s u r i n g reflec-
Part D4. Comparison of Contrast Ratio of Paints of the Same
Type and Color--This m e t h o d is technically identical with tances over a black-and-white substrate. Dry films just below
ISO 2814 (11.c). a n d above 0.98 in CR are m e a s u r e d by weight or m i c r o m e t e r
Part D6. Contrast Ratio at 20 m2/L Using Polyester Film-- to o b t a i n e x p e r i m e n t a l s p r e a d i n g rates in mZ/kg or m2/L a n d
This m e t h o d is technically identical with ISO 3906-1980 results i n t e r p o l a t e d to o b t a i n the s p r e a d i n g rate at exactly CR
(11.c). = 0.98. The i n t r o d u c t o r y text points out that this m e t h o d
Part DZ True Hiding Power (SR at C = O.98) by the Kubelka- m e a s u r e s true hiding p o w e r in preference to ISO 3905 a n d
Munk Method--This m e t h o d is technically identical with ISO 3906 (11.c) which simply c o m p a r e CR values at 20 mE/L. It
6504 (11.c) a n d in a c c o r d a n c e with early versions of ASTM also refers to the e x p e r i m e n t a l film thickness not being lim-
D 2805 a n d the general K-M hiding p o w e r m e t h o d d e s c r i b e d ited to 50/~m as in the ISO methods. No provision is m a d e in
in 8.e. this m e t h o d to correct for deviations of the white s u b s t r a t e
from W = 0.80.
e. Canadian General Standards Board, (CGSB) 1-
GP-71 NF-T30-076, Spreading Rate at Complete Visual
Method 14.1, Visual Hiding at a Specified Spreading Hiding
Rate This is referred to as a "simplified" method. Several films
The test substrates are black-and-white o r b l a c k - a n d - g r a y are cast on polyester to o b t a i n one that shows full hiding
c h e c k e r b o a r d charts with an a r e a of 0.1 m 2. The a p p r o p r i a t e w h e n p l a c e d over a black-and-white b a c k g r o u n d . The d r y
chart is specified a c c o r d i n g to a list of CGSB color n u m b e r s , film thickness is m e a s u r e d by difference with a m i c r o m e t e r
with b l a c k - a n d - g r a y being used for lighter colors. The p a i n t is and the hiding p o w e r calculated in m2/L. Potential users
a p p l i e d by b r u s h o r d r a w d o w n . In b r u s h a p p l i c a t i o n the SR is should c o n s i d e r w h e t h e r this method, t h o u g h simple in con-
controlled accurately by weighing c o n t a i n e r a n d b r u s h be- cept, might be excessively b u r d e n s o m e in execution.
www.iran-mavad.com

g. German Standards Institute (DIN) [11] Saxena, K. G. and Chowdhry, K. K., "Determination of Opacity
of Wet Films of Ready-Mixed Paints and Enamels," Paintindia,
DIN 53162, Hiding Power of Air Drying Nonchromatic Vol. 12, No. 1, 1962, p. 103.
Paints [12] Hallet, R. L., "An Instrument for Measuring the Hiding Power of
This is a K u b e l k a - M u n k m e t h o d which is essentially the Paints," Proceedings, American Society for Testing and Materi-
same as ISO 6504, b u t includes auxiliary test procedures for als, Vol. 20, Part II, 1920, p. 426.
m e a s u r i n g paint density a n d nonvolatile content. The Mitton [13] Pfund, A. H., "Hiding Power Measurements in Theory and Prac-
tice," Proceedings, American Society for Testing and Materials,
n o m o g r a p h a n d table (8.g) are employed.
Vol. 30, Part II, 1930, p. 882. Pfund, A. H., "The Photoelectric
Cryptometer," Proceedings, American Society for Testing and
D I N 53164, Relative Scattering P o w e r o f W h i t e (Ti02) Materials, Vol. 31, Part II, 1931, p. 876.
Pigments [14] Hanstock, R. F., "The Opacity of Paints," Journal, Oil and Colour
This m e t h o d measures the K u b e l k a - M u n k scattering coef- Chemists' Association, Vol. 20, 1937, p. 5.
ficient S of a TiO2 p i g m e n t a n d reports its value as a percent- [15] Sawyer, R. H., "Hiding Power and Opacity," Symposium on
age of the scattering coefficient of a reference p i g m e n t Color, ASTM STP 50, American Society for Testing Materials,
m e a s u r e d in the same way. The d e t e r m i n a t i o n of S is based Philadelphia, 1941, p. 22.
on the solution of Eq 44: P = f (R o, R~) using the Mitton [16] Switzer, M. H., "Critical Analysis of the Fell Hiding Power Rela-
tionship," American Paint Journal, Vol. 40, No. 13, 1955, p. 72.
nomograph. The method calls for the test p i g m e n t to be
[17] Mitton, P. B., "A Mathematical Analysis of the Precision in De-
dispersed in a n alkyd or a plasticized polyvinyl chloride vehi-
termining Hiding Power," American Paint Journal, Vol. 30, 1958,
cle. R~ is m e a s u r e d from a thick, full hiding film of the p. 156.
dispersion a n d R0 from a n o n o p a q u e film applied on a black [18] Van Eyken, W.W. and Anderson, F.T., Jr., "An Improved
plastic substrate. The spreading rate H~ of the p i g m e n t is Method of Hiding Power Determination," American Paint Jour-
d e t e r m i n e d in a u n i q u e way, by igniting a k n o w n area of film nal, Vol. 43, No. 31, 1959, p. 78.
on plastic a n d weighing the residue. This m e t h o d is basically [19] Tough, D., "The Use of Contrast Ratio in the Measurement of
the same as DIN 53162 a n d other K-M methods (8.e), with the Hiding Power," Journal, Oil and Colour Chemists' Association,
difference that only relative values are reported. There is no Vol. 39, 1956, p. 169.
attempt to report actual scattering coefficients or to calculate [20] Gall, L., "On the Hiding Power of Colored Pigments in Paints
hiding power in physical units, although this could easily be and Printing Inks," Farbe und Lack, Vol. 72, 1966, p. 1073.
done on the basis of the a c c u m u l a t e d dat~. [21] Mitton, P. B., "Measuring Hiding Power of Baked Coatings on
Metal," Metal Finishing, Vol. 72(G), 1974, p. 44.
[22] Kubelka, P. and Munk, F., "Ein Beitrage zur Optik der
Farbenstriche," Zeitschrift fur Technische Physik, Vol. 12, 1931,
REFERENCES p. 593.
[23] Steele, F. A., "The Optical Characteristics of Paper," Paper Trade
[1] Gardner, H. A. and Sward, G. G., Physical and Chemical Exami- Journal, Vol. 100, No. 12, 1935, p. 37.
nation of Paints, Varnishes, Lacquers and Colors, 9th ed., May [24] Judd, D. B., Harrison, W. N., Hickson, E. F., Eickhoff, A. J.,
1939, p. 10. Shaw, M. B., and Paffenbarger, G. C., "Optical Specification of
[2] Simpson, L. A., "Measuring Opacity, Part I," Paint, Pigments and Light-Scattering Materials," Journal of Research, National Bu-
Coatings Journal, Vol. 179, February 1989. reau of Standards, Vol. 19, p. 287.
[3] Mitton, P.B., Vejnoska, L.W., and Frederick, M., "Hiding [25] Kubelka, P., "New Contributions to the Optics of Intensely Light
Power of White Pigments: Theory and Measurement--I," Offi- Scattering Materials--Part I," Journal, Optical Society of Amer-
cial Digest, Federation of Paint and Varnish Production Clubs, ica, Vol. 38, 1948, p. 448.
Vol. 33, 1961. [26] Switzer, M. H., "Equation for Calculating Hiding Power Index
[4] Mitton, P. B., Paint Testing Manual, ASTM STP 500, Chap. 1.3: and Spreading Rate of Paints," ASTM Bulletin, American Society
Hiding Power, "Physical and Chemical Examination of Paints, for Testing and Materials, No. 181, 1952, p. 75.
Varnishes, Lacquers and Colors," 13th ed., 1972. [27] Mitton, P.B., "Easy, Quantitative Hiding Power Measure-
[5] Gardner, H. A., Sward, G. G., and Levy, S. A., "Hiding Power ments," Journal of Paint Technology, Vol. 42, 1970, p. 159.
and Tinting Strength of Pigments and Paints," Scientific Section [283 Mitton, P. B. to Weaver, J. C., personal communication, 1977.
Circular, National Paint, Varnish, and Lacquer Association, No. [29] Mitton, P. B., Madi, A. J., and Rode, J. W., "Development of a
362, 1930. Test Method for Hiding Power," Journal of Paint Technology,
[6] Kraemer, E. O. and Schupp, O. E., "Determination of Hiding Vol. 39, 1967, p. 536.
Power of White Paints," unpublished paper presented at the [30] Hallett, R. L., "Hiding Power and Tinting Strength of White
Washington, DC meeting of the American Chemical Society, Pigments," Proceedings, American Society for Testing and Mate-
March 1933. rials, Vol. 30, Part II, 1930, p. 895. "Hiding Power of Pigments,"
[7] Pfund, A. H., "Hiding Power of White Pigments and Paints," Proceedings, American Society for Testing and Materials, Vol.
Journal, Franklin Institute, Vol. 188, 1919, p. 675. 26, Part II, 1926, p. 538.
[8] Pfund, A. H., "Hiding Power Measurements in Theory and Ap- [31] Titanium Pigment Company, "The Handbook," 1956.
plication," Proceedings, American Society for Testing Materials, [32] Mitton, P. B. and Jacobsen, E. E., "Reflectometry Method for
Vol. 30, Part II, 1930, p. 878. Measuring Tinting Strength of White Pigments," Official Digest,
[9] Sward, G. G. and Levy, S. A., "An Instrument for Hiding Power Federation of Paint and Varnish Production Clubs, Vol. 34,
Determinations," Scientific Section Circular, National Paint, 1962, p. 704.
Varnish, and Lacquer Association, No. 433, 1933. [33] Simpson, L. A., "Measuring Opacity, Part II," Paint, Pigment &
[10] Brodgen, D., "The Precision of the Pfund Black and White Cryp- Coatings Journal, Vol. 179, March 1984.
tometer," Official Digest, Federation of Paint and Varnish Pro- [34] Balfour, J. G. and Hird, M. S., Journal of the Oil and Color
duction Clubs, Vol. 33, 1961, p. 1297. Chemists Association, Vol. 58, 1975, p. 331.
www.iran-mavad.com

[35] Simpson, L. A., "Measuring Opacity, Part III," Paint, Pigment [38] Stieg, F. B. and Ensminger, R. I., "The Production and Control
and Coatings Journal, Vol. 179, April 1989. of High Dry Hiding," Official Digest, Federation of Paint and
[36] Stieg, F. B., "A New Look at the Hiding Power of Titanium Varnish Production Clubs, Vol. 33, 1961, p. 792.
Pigments," Official Digest, Federation of Paint and Varnish Pro- [39] Stieg, F.B., "The ABCs of White Hiding Power," Journal of
duction Clubs, Vol. 29, 1957, p. 439. Coatings Technology, Vol. 49, 1977.
[37] Stieg, F. B., "The Effect of Extenders on the Hiding Power of [40] Fasano, D. M., Hook, J. W., Hill, W. H., and Equi, R. S., "For-
Titanium Pigments," Official Digest, Federation of Paint and mulating High PVC Paints with Opaque Polymer Additives,"
Varnish Production Clubs, Vol. 31, 1959, p. 52. Resin Review, Vol. 37-2, 1987.
www.iran-mavad.com

MNL17-EB/Jun. 1995
im
Mass Color and Tinting

Strength of Pigments
by Julio I. Aviles 1
DEFINITIONS that m a y contain more than one pigment but are tested and
used as if they contain only a single pigment.
The mass color (MC) of a coating is defined in ASTM Ter- 9 Saturation is "the attribute of a visual sensation that per-
minology Relating to Paint, Varnish, Lacquer, and Related mits a judgment to be made of the proportion of pure
Products (D 16) as: chromatic color in the total sensation." Saturation can also
"the color, when viewed by diffuse reflected light, of a be described in a mathematical m a n n e r as in ASTM E 284.
pigment-vehicle mixture of such thickness as to obscure 9 Scattering is "the process by which light or other electro-
completely the background. Sometimes called over-tone magnetic radiant flux passing through matter is redirected
or mass-tone." over a range of angles."
9 Shade is "a color produced by a dye or pigment mixture
Mass color is produced by the reflected light (R= at infinite
including black dye or pigment."
thickness) of an opaque coating and depends on the pigment
9 Tint is "a color produced by the mixture of white pigment
concentration, degree of dispersion, coating thickness, and
or paint with a chromatic pigment or paint."
the light absorption (K) and scattering (S) of pigments and 9 Tristimulus values are "the amounts of three specified stim-
binders. Mass color is applicable to both chromatic and ach- uli required to m a t c h a color." In the CIE system, these
romatic pigments. stimuli are assigned the symbols )2, Y, and Z.
Other definitions of interest, taken from ASTM Terminol-
ogy of Appearance (E 284), are as follows:
9 Brightness is an "aspect of visual perception whereby an TINTING STRENGTH
area appears to emit more or less light."
9 Chroma is the attribute of color used to indicate the degree Tinting strength is a measure of the effectiveness with
of departure of the color from a gray of the same lightness. which a unit quantity of a colorant changes the color of a
Chromatic is a term meaning "perceived as having a hue; material (ASTM E 284). It m a y be thought of as a pigment's
not white or black." "coloring power." For those colorants that both scatter and
9 CIE 1931 standard colorimetric system is "a system for absorb, the scattering and absorption tinting strengths must
determining the tristimulus values of any spectral power be specified. ASTM D 284 defines scattering tinting strength
distribution using a set of reference color stimuli X, Y, A as "the relative change in the scattering properties of a stan-
and the three CIE color-matching functions s ~()t), ~(~t) dard black material (with no scattering colorant present)
adopted by the CIE in 1931." when a specified a m o u n t of a white or chromatic scattering
9 Colour Index is a listing of colors by n a m e and n u m b e r by colorant is added to it" and absorption tinting strength as the
The Society of Dyers and Colourists, London, 1987. It is relative change in the absorption properties of a standard
available from the American Association of Textile Chem- white material when a specified a m o u n t of an absorbing
ists and Colorists, P.O. Box 12215, Research Triangle Park, colorant, black or chromatic, is added to it."
NC 27709. Pigment concentration is important to coating strength
9 Hue is "the attribute of color perception by means of which and cost, and therefore tinting strength can be an important
a color is judged to be red, orange, yellow, green, blue, relative economic value factor in selecting one paint over
purple, or intermediate between pairs of these, considered another. There is no particular value of tinting strength that
in a close ring." can be stated as desirable unless an end use is stated. In
9 Lightness is "(1) the attribute of color perception by which certain cases a high value is desirable and in others a low
a nonself-luminous body is judged to reflect more or less value is needed to achieve a desired color/strength effect. In a
light." "(2) the attribute by which a perceived color is general sense, tinting strength is determined by dilution of a
judged to be equivalent to one of a series of grays ranging test paint and a reference paint with a standard "mixing white
from black to white." paint" in the case of chromatic paints or a standard "tinting
9 Masstone is a pigment-vehicle mixture that contains a sin- color" in the case of white paints, drawing down the resulting
gle colorant only. This definition includes certain colorants pastes on a suitable substrate, and then instrumentally mea-
suring tristimulus values or visually comparing the speci-
1Senior technical service representative, Kronos Inc., Wyckoffs mens. The latter comparison technique has lower precision
Mill Road, Hightstown, NJ 08520. than the former. Details for the preparation of a standard
507
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mixing white paint are described in ASTM Test Methods for the pigment in an agreed on solvent-free vehicle and then
Relative Lightfastness of Pigments Used in Artists' Paints letting it down with additional vehicle that has been tinted
(D 4303) or a commercial titanium-dioxide white artists' with a lamp black that has been predispersed in a vehicle
paint may be used. It should be understood that the mixing similar in nature to the test vehicle. Refined or low-bodied
white paint must be made with the same vehicle type-- linseed oil should not be used. Both dispersion and let-down
acrylic, alkyd, or oil--as the paint to be tested. are achieved with an automatic, mechanical muller. Tristim-
In color tints, differences in gloss and haze may be mis- ulus values are determined with a colorimeter.
taken for a lighter tint or lower tinting strength than really ASTM Test Method for Relative Tinting Strength of White
exists. In grays, these factors may be interpreted as higher Pigments by Visual Observation (D 332) is a procedure for
white pigment strength than exists. Instruments cannot com- determining the relative tinting strength of white pigments by
pensate for specular gloss or haze differences between a sam- visual evaluation of blue tints. It is only applicable for com-
ple and a standard, and this can result in erroneous tint paring a test pigment with a reference standard. Specified
strengths. It is possible to equalize gloss differences between amounts of white pigment and a blue tinting pigment that
the specimens by top coating with a clear coating. Evaluation conforms to ASTM Specification for Ultramarine Blue Pig-
through the clear coating reveals the true tinting strength ment (D 262) are dispersed together in a refined linseed oil
differences between sample and standard. with an acid number of about 4 using a glass hand muller or
Tinting strength results can also be affected if the lightness, an automatic muller. The pastes are drawn down together on
chroma, and saturation of the sample differ significantly a panel and visually evaluated for tinting strength. A numeri-
from those of the standard, since this involves matching two cal rating of tinting strength is obtained by preparing disper-
color variables, lightness and chroma or lightness and satura- sions with the standard white pigment and more or less of the
tion, by adjusting only the amount of pigment used [1,2]. tinting pigment and comparing them until the lightness of the
test paste is matched. The weight of the tinting pigment is
used to calculate the relative tinting strength.
Chromatic Paints
ASTM Test Method for Determining the Relative Tinting
Strength of Chromatic Paints (D 4838) is a method used for
determining the absorption tinting strength of a chromatic
PIGMENT DISPERSION
(define) test paint relative to that of a paint of the same
Mass color and tinting strength require that the pigments
chemical type. The method is intended for comparison of
be well dispersed in the binder to achieve maximum tinting
paints that contain the same chemical type vehicle (acrylic,
strength. Ideally, it would be desirable to break down pig-
alkyd, or oil) and single-pigment colorants of the same Colour
ment agglomerates to individual particles, i.e., to an ultimate
Index name and number. Knowledge about the amount of
pigment and other components of the paint is not necessary. dispersion state. However, in actual practice this would be
difficult, if not impossible, to achieve. Therefore, pigments
The color measuring instrument can be either a spectro-
under investigation for MC and TS must be processed in the
photometer that provides 1931 CIE tristimulus values X, Y, Z
same manner and receive the same level of mechanical work.
for CIE standard illuminant C, or a tristimulus colorimeter
Mechanical mullers, Fig. 1, which are instruments that have
providing either such tristimulus values or colorimeter read-
ings R, G, B. Other related test methods useful in following two circular, usually ground, glass-grinding surfaces that
ASTM D 4838 are ASTM Test Method for Computing the contain the pigment and vehicle, are used for dispersing the
Colors of Objects by Using the CIE System (E 308) and ASTM two components. (A satisfactory muller is supplied by the
Practice for Obtaining Spectrophotometric Data for Object- Hoover Color Corp., 13 Cordier St., Irvington, NJ 07111.)
Color Evaluation (E 1164). Development of tinting strength is dependent on the force
ASTM Test Method for Color and Strength of Color Pig- applied to the glass plates, the number of revolutions used,
ments with a Mechanical Muller (D 387) is used for compar- and the mass of pigment and of vehicle used. If muller condi-
ing the color and strength of a pigment with a reference tions, pigment, and vehicle have not been agreed on by pur-
standard of the same type. The test method is not to be used chaser and seller, the mandatory dispersing conditions given
with white pigments. The pigments are dispersed in a suitable in the Annex of ASTM D 387 should be used to achieve the
vehicle with a mechanical muller. Opaque drawdowns are maximum level of tinting strength. These conditions include:
made on white paper charts that have a black band and a 9 Determination of the appropriate ratio of color pigment to
surface that is impervious to paint liquids. These are then dispersing vehicle for the standard and test pigments.
compared either visually or instrumentally for color and 9 Determination of appropriate masses of pigment and vehi-
strength differences. cle to use.
9 Preparation of a standard tint by application of 100 lb to
the muller plates, introducing the appropriate mass of pig-
White Paints
ment/vehicle, and mulling the paste for 100 revolutions in
ASTM Test Method for Relative Tinting Strength of White two stages of 50 revolutions each. This is then repeated on
Pigments by Reflectance Measurements (D 2745) is a proce- three more specimens of the standard mixture except the
dure for determining the relative tinting strength of white mulling is carried out for 200, 300, and 400 revolutions in
pigments by reflectance measurements made on black tints. stages of 50 revolutions.
It is only applicable for comparing a test pigment with a 9 Each of the four specimens is compared one to the other for
reference standard. The method is conducted by dispersing tinting strength, and the minimum number of revolutions
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CHAPTER 4 3 - - M A S S COLOR AND TINTING S T R E N G T H OF PIGMENTS 509
Spatula and Hand Muller

G r i n d i n g pigment/vehicle c o m b i n a t i o n s can be d o n e with a
s p a t u l a or a h a n d m u l l e r by r u b b i n g o r mulling the m a t e r i a l s
over a 3 by 12-in. (8 b y 30-cm) strip area on a glass plate, Fig.
2. The r u b b i n g is done by p u s h i n g the m u l l e r u p one side a n d
pulling it d o w n the other side of the strip a r e a so all color
particles receive the s a m e a m o u n t of rubbing. One r u b is one
up a n d d o w n course. Early studies by Ayers [16] i n d i c a t e d
that a m u l l e r gave m o r e reliable results t h a n a spatula a n d
that the r u b b i n g surface m a y vary a great deal w i t h o u t affect-
ing the results. Stutz's [17] results during investigation of the
tinting strength of white p i g m e n t s also f o u n d a m u l l e r supe-
r i o r to a spatula. It was also f o u n d that a weighted or un-
weighted m u l l e r can be used w i t h o u t affecting the results.
AUTOMATIC MULLERS
A u t o m a t i c or m e c h a n i c a l mullers have two circular glass-
grinding surfaces that c o n t a i n the pigment/vehicle paste. The
grinding surfaces are usually c o n s t r u c t e d of g r o u n d glass
with one s t a t i o n a r y a n d weighted to exert a p r e s s u r e of
FIG. 1-Hoover Automatic Muller. Automatic means motor 100 psi (440 N) a n d the o t h e r rotary with r o t a t i o n effected b y
driven. (Courtesy of Hoover Color Corp.) a motor. Because r o t a t i o n is a b o u t the disk centers, paste at
the center can receive less mulling t h a n paste l o c a t e d n e a r the
n e e d e d to develop m a x i m u m or full tinting strength is de- edges. To c o m p e n s a t e for this effect, it has been f o u n d helpful
termined. to s p r e a d the paste in a ring a p p r o x i m a t e l y halfway b e t w e e n
the edge a n d center. The revolutions p e r mulling cycle can be
P a r a m e t e r s to r e c o r d a n d the dispersing conditions for three a d j u s t e d in i n c r e m e n t s of 1 to 999. Mechanical m u l l e r advan-
p i g m e n t s used in an i n t e r l a b o r a t o r y test to d e t e r m i n e the tages include very good d e v e l o p m e n t of tinting strength, pos-
precision of this s t a n d a r d m e t h o d are given in Table 1. sibility to rapidly mull small quantities of materials, a n d effi-
cient processing of a large n u m b e r of samples.
The Annex of ASTM D 387, briefly d e s c r i b e d above, has a
specific way to operate an a u t o m a t i c muller w h e n determin-
PIGMENT-DISPERSION TECHNIQUES ing tinting strength or m a s s color.
It should be kept in m i n d t h a t the techniques d e s c r i b e d in

this c h a p t e r p e r t a i n to p r e p a r i n g specimens for d e t e r m i n a -
Laboratory Miniature Media Mills
tion of tinting strength, m a s s color, etc., and are not m e a n t There are c o m m e r c i a l horizontal or vertical l a b o r a t o r y me-
for p i g m e n t dispersion in general. The general topic of pig- dia mills that can process up to a q u a r t of millbase. F o r small
m e n t d i s p e r s i o n is discussed elsewhere in this m a n u a l as well grinds, a m e d i a mill can be s i m u l a t e d with a l a b o r a t o r y dis-
as in n u m e r o u s references [3-7]. There is a vast a m o u n t of p e n s e r e q u i p p e d with a fiber or Teflon | l%-in, disk, a 200-mL
literature that deals with the surface t r e a t m e n t of organic tall-form beak, a n d media. Equal volumes of millbase to me-
p i g m e n t s to improve ease of dispersibility, a n d interested d i a are used. Grinds m a y b e 60.0 g for c a r b o n b l a c k a n d s o m e
r e a d e r s are e n c o u r a g e d to seek such i n f o r m a t i o n in the clas- organics to 160.0 g for inorganic pigments. The millbase
sic w o r k of Hayes [8] as well as others [9-11 ]. Detail a b o u t the m u s t be p r e p a r e d carefully to eliminate gross a n d oversized
surface t r e a t m e n t of inorganic pigments is also in the litera- agglomerates. Peripheral i m p e l l e r speed should be 2000 ft
ture [12-14]. M u c h of the following i n f o r m a t i o n is a b r i d g e d (610 m) p e r minute, a n d the mixture should be g r o u n d for a
a n d modified from the c h a p t e r with the s a m e title in the set t i m e o r to a set dispersion level such as H e g m a n value
previous edition of this m a n u a l [15]. 7.0 + . Advantages of m e d i a mills include d e v e l o p m e n t of the
TABLE l--Interlaboratory pigment dispersing parameters and specific conditions obtained for
maximum tinting strength (data taken from ASTM D 387).
Pigment Type
Parameter Yellow Iron Oxide BON Red Pthalocyanine Green
Force applied, lb (N) 100 (440) 100 (440) 100 (440)
Total no. revolutions 100 (2 x 50) 200 (4 x 50) 400 (8 x 50)
Mass of color pigment, g 1.0 0.6 0.75
Mass of dispersing vehicle, g 1.7 1.4 1.8
www.iran-mavad.com

FIG. 3-Pall All-Glass Mill. Grooved plug rotates in

female part of stopcock, (Courtesy of Industrial and
Engineering Chemistry.)
shot are a m o n g the m e d i a used to avoid lead c o n t a m i n a t i o n .

The bottle is c h a r g e d with 550 g of grinding media, 2 m L of
FIG. 2-Rubbing pigment and vehicle with glass muller and the liquid colorant, a n d 75 m L of white paint. It is t h e n closed
slab. with a cork, concave on the i n n e r end to m a t c h the glass end
of the bottle, a n d p l a c e d in the h o l d e r of the rotating ma-
highest m a s s color a n d tinting strength, s i m u l a t i o n of actual chine. The bottle is then tilted a n d r o t a t e d slightly by h a n d to
factory grinding conditions, a n d low cost. wet the c o n t a i n e r walls. The mill is t h e n m e c h a n i c a l l y r o t a t e d
until the p a i n t is h o m o g e n o u s in that no streaking of the c o l o r
is seen. The t i m e in seconds for mixing is d e t e r m i n e d .
Laboratory Roller M i l l
Small three-roller mills have been found useful for grinding
small, laboratory-size batches of paint. Rolls of such mills are REFERENCES
a b o u t 4 in. (10.16 cm) in d i a m e t e r a n d 8 in. (20.82 cm) in
length. Batches as small as 5 g have been p r e p a r e d in such [1] Zeller, R. C., "The Meaning of Tint Strength," Color Research
mills. and Application, Vol. 3, 1978, p. 34.
[2] Vernardakis, American Ink Maker, Vol. 62, No. 2, 1984, p. 24.
[3] Varley, D. M. and Bower, H. H., Journal of the Oil and Colour
Pall Glass Mill Chemists Association, Vol. 62, 1979, p. 401.
[4] Patton, T. C., Paint Flow and Pigment Dispersion, 2nd ed., Wiley-
Metal-free, small quantities of p i g m e n t p a s t e have b e e n
Interscience, New York, 1979.
p r e p a r e d with the Pall Glass Mill [18], w h i c h is depicted in [5] Carr, W., Journal of the Oil and Colour Chemists Association, Vol.
Fig. 3. It is a heavy ground-glass s t o p p e r in a heavy glass joint. 61, 1978, p. 397.
The mixed, u n g r o u n d m a t e r i a l s (1 to 8 g) are placed in the [6] Hafner, O., Journal of the Oil and Colour Chemists Association,
joint, a n d the s t o p p e r / p l u n g e r is inserted. The s t o p p e r is Vol. 57, 1974, p. 268.
r o t a t e d with a small m o t o r at a b o u t 150 r/min. In this mill, [7] Parfitt, G. D., Dispersion of Powders in Liquids, 2nd ed., Wiley-
grinding pressure ranges f r o m 20 to 30 psi. The Pall Glass Interscience, New York, 1973.
Mill is said to be an i m p r o v e m e n t over h a n d mulling b e c a u s e [8] Hays, B. G., American Ink Maker, Vol. 62, No. 6, 1984, p. 28.
it saves time a n d b e c a u s e it results in greater d e v e l o p m e n t of [9] Hampton, J. S. and MacMillan, J. F., American Ink Maker, Vol.
63, No. 1, 1985, p. 16.
tinting strength.
[10] Topham, A., Progress in Organic Coatings, Vol. 5, 1977, p. 237.
[11] Merkle, K. and Schafer, H. in Pigment Handbook, Vol. III, T. C.
Patton, Ed., Wiley-Interscience, New York, 1973, pp. 157-167.
PIGMENT CONCENTRATION [12] Linden, H., Rutzen, H., and Wegemund, B., U.S. Patent
4,167,421 (1979).
Paste viscosity has an effect on grinding efficiency, a n d it [13] Hauxwell, F., Stansfield, J. F., and Topham, A., U.S. Patent
d e t e r m i n e s the level of m a s s color a n d tinting strength that is 4,042,413 (1977).
developed. Ayers [16] investigated i r o n oxides, a n d the results [14] Franklin, M. J. B., Goldsbrough, K., Parfitt, G. D., and Peacock,
i n d i c a t e d t h a t color developed faster as p a s t e viscosity in- J., Journal of Paint Technology, Vol. 42, 1970, p. 740.
[15] Mitton, P. B., "Mass Color and Tinting Strength," Chapter 1.4 in
creased. A low-viscosity paste h a d a reflectance of 26% at a
Paint Testing Manual, STP 500, 13th ed., G. G. Sward, Ed., The
wavelength of 700 nm, w h e r e a s high-viscosity paste was American Society for Testing and Materials, Philadelphia, PA,
d a r k e r a n d r e d d e r with a reflectance o f 23%. There is a p o i n t 1972.
above w h i c h viscosity has no effect. [16] Ayers, J. W., "A Discussion of the Accuracy and Utility of Meth-
ods of Test for Mass Tone and Tinting Strength," Proceedings,
American Society for Testing and Materials, Vol. 34, Part II, 1934,
M I X I N G T I M E OF LIQUID C O L O R S p. 497.
[17] Stutz, G. F. A., "Tinting Strength of White Pigments," Proceed-
One of the p r o p e r t i e s of oil o r universal liquid colorants is ings, American Society for Testing and Materials, Vol. 34, Part II,
the ease with w h i c h they c a n be i n c o r p o r a t e d into white 1934, p. 521.
[18] Pall, D. B., "A New All-Glass Mill," Industrial and Engineering
paints. A m e t h o d for testing the speed of i n c o r p o r a t i o n has
Chemistry, Analytical Edition, Vol. 14, 1942, p. 346.
been d e s c r i b e d by Paul a n d D i e h l m a n [19]. This m e t h o d in- [19] Paul, M. R. and Diehlman, G., "Method and Apparatus for De-
volves use of a m e c h a n i c a l rotating bottle that contains a termining the Interval Required to Disperse Oil Colors Through-
white paint, the liquid colorant, a n d a g r i n d i n g media. W h e n out a Paint Medium," Proceedings, American Society for Testing
the test was first developed, No. 11 lead shot was used; how- Materials, Vol. 34, Part II, 1934, p. 490.
ever, t o d a y glass beads, z i r c o n i a grinding media, a n d steel
www.iran-mavad.com

Part 1 I:
Physical and Mechanical Properties
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MNLI7-EB/Jun. 1995
Adhesion
by Gordon L. Nelson 1
ORGANICCOATINGSAREAPPLIEDto a variety of substrate mate- Wa = Y, + Y2 - Y12 (1)

rials (woods, metals, plastics, ceramics) for decorative,
where W,, is the work of adhesion, and Y~ and Y2 are the
protective, and functional applications. In each case, it is
surface tensions of the two phases. The maximum force per
imperative that the coating adheres well to the substrate.
unit area, ~2, to effect this process is the ideal adhesive
Accordingly, adhesion assessments should be an integral part
strength [8]
of coating development. This may seem a straightforward
task, but coating adhesion is, in fact, extremely complex and ~2 = [16/9 (3) 12] (Wc,/Zo) (2)
often poorly understood. The growing use of plastics to re-
where Z0 is the equilibrium separation between the two
place metals and other "traditional" materials renders the
phases, usually about 5 a. The average value W~ for polymers
issue even more complex [1-2].
is typically 50 ergs/cm 2, yielding a theoretical value for o"2 of
The objectives of this chapter are to review briefly salient
15 000 psi (103 mPa). For practical purposes this value is
concepts of the adhesion process and to discuss currently
never attained, primarily due to the fact that perfect intermo-
accepted standard test methods.
lecular contact is most unlikely. In fact, this is at least an
order of magnitude higher than the practical adhesive
strength usually observed. This deviation from ideality has
FUNDAMENTAL CONCEPTS led to the promulgation of several theories of adhesion, none
of which are universally recognized [9]. This is not unexpec-
While the very definition of "adhesion" is of some contro- ted, since most theories deal exclusively with the mechanisms
versy [1], adhesion may be loosely defined as the attraction of bond formation and disregard the fact that bond strength
between dissimilar bodies for one another. ASTM D 907 on is ultimately a function of both the degree of bond formation,
Terminology of Adhesives defines adhesion as "The state in the nature of the bond (chemical and physical), and the
which two surfaces are held together by interracial forces rheological properties of the bonding phases. The strength of
which may consist of valence forces or interlocking action or an adhesive bond is, in fact, a function of all of these factors.
both." In discussing adhesion assessment, one must consider S u m m a ~ paragraphs about basic theories of adhesion follow
the issue from two different aspects: basic adhesion and below.
practical adhesion. Basic adhesion signifies the summation of
all interracial, intermolecular forces, whereas practical adhe-
sion is used to represent the forces or work required to Fracture Theory
disrupt the adhering system [3]. The next section will be The area of interracial bonding between coating and sub-
devoted to theories and concepts of basic adhesion and will of strate will, in most instances, contain voids or defects. The
necessity be brief. The perspective will be from that of a result is deviation between the ideal adhesive strength and
polymeric coating on a plastic substrate [2]. Metal and metal the practical limit.
oxide substrates will be discussed where appropriate. The Good [10] and Williams [11] have applied the theory of
reader is referred to Refs 4- 7 for a more thorough discussion. cohesive fracture to coating fracture. The concept that frac-
ture propagates from the weakest point, a defect, is funda-
mental to fracture mechanics. The strength of a bond, in
BASIC A D H E S I O N terms of the energy required to induce fracture, is described
as a function of the defect size and the energy dissipated by
Work of Adhesion irreversible processes (plastic deformation, light emission,
Bonding between polymeric coatings and substrates may and electric discharge). The general equation given is
be viewed as the union of two contiguous polymer phases, f = k (EF/d) in (3)
one a solid and the other a liquid which solidifies to form a
where f is the fracture stress, k = (4&r)I/2, E the elastic
thin film. The reversible separation of the two phases may be
expressed by the work of adhesion modulus of the material, d the defect length, and F the frac-
ture energy or total work per unit area of fracture surface,
which is dissipated. Accordingly, the fracture energy
lDean, College of Science and Liberal Arts, Florida Institute of
Technology, 150 West University Blvd., Melbourne, FL 32901-6988. f = Wa + W~ (4)
513
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Copyright 91995 by ASTM International www.astm.org

where W~ is the work of adhesion and We is the total work for "rL
the irreversible processes. For all practical purposes W~ is
much greater than Wa, therefore [12-13]
f = Wi (5)
~/~ ~ . DROP
Weak Boundary Layer Theory 9s r ", ///

Proposed by several workers [14-16], the weak boundary
layer theory maintains that true interracial fracture does not
occur, and that fracture usually occurs cohesively in a weak
boundary layer (WBL), which may be near the interface be- 7 LcosO = 7S-TSL
tween coating and substrate. Experimental evidence has per-
FIG. 2-Contact angle.
haps disproved the first point [10], that true interracial failure
can occur, but it has been shown that the second is valid in
some instances [17-18]. This has been validated somewhat by the observation that
Of practical importance to WBL investigations is the locus
adhesive strength is a function of polymer molecular weight,
of fracture, which can occur in one or more of the zones in
structure, and contact time.
Fig. 1. For a strong bond, the boundary layer (layers) must be
Key to this theory is the concept that no clear-cut interra-
rheologically sound and chemically durable. The zone of fail-
cial boundary exists, but rather that an interphase exists
ure may, of course, be studied by SEM, TEM, and FT-IR. In
which consists of polymer chain segments from both contigu-
fact, thin layers of coating have been noted where interfacial
ous phases. The theory has been criticized for giving insuffi-
failure was only thought to occur on visual examination.
cient weight to the contribution of van der Waals attractive
forces. Nevertheless, for the case of solvent-borne organic
Wetting--Contact Theory coatings applied to plastic substrates, this phenomenon is
The wetting-contact theory states that van der Waals at- intuitively appealing.
tractive forces alone provide sufficient coating/substrate Interdiffusion of coating and substrate polymer molecular
bond strength given perfect molecular contact, and that the segments is a function of polymer-polymer compatibility. An
extent of contact and resulting bond strength are functions of interphase forms as a result of the blending of the two phases.
wetting energetics [20-28]. No one denies the importance of Although polymer pairs are generally incompatible, Helfand
wetting in adhesion, i.e., the lower the contact angles, the and others [34-38] have utilized statistical thermodynamics
more the interracial area of contact, which generally yields to predict that interdiffusion also occurs as a result of the
improved adhesion (Fig. 2). tendency for free energy at the interface to minimize. A useful
However, thermodynamic wetting is a necessary but not equation which describes interfacial thickness as a function
sufficient condition for the establishment of coating film ad- of the Flory-Huggins interaction parameter as derived from
hesion. Wetting is a kinetic phenomenon as well. Further- Hansen solubility parameters is [36,38]
more, this model does not consider the effects of weak bound~
ai = 2 (m/x) lj2 (6)
ary layers or the effects of defects or fracture mechanics.
What is the effect of surface contamination on the contact Where a~ is the interracial thickness expressed as the cross
angle? sectional area of a lattice cell, m is a lattice constant directly
proportional to nearest-neighbor contacts, and x is the Flory-
Diffusion Theory Huggins interaction parameter. By this equation, interfacial
Voyutskii and others [29-33] have proposed that coating thickness increases by interdiffusion as the solubility param-
adhesion between high polymers arises from interdiffusion. eter difference between the two phases decreases. Although
experimental verification is scarce, adhesive strength has
been shown to decrease with increasing disparity in the solu-
1 bility parameters of the two phases [39].
A, film 2 It is important to note that diffusion should occur in the
3 latter stage of bond formation, the first stage being wetting to
4 establish contact. Additional support for the theory comes
5 from the observation that adhesive strength between certain
high polymers increases with time [30]. This theory, however,
cannot be applicable to systems involving one or more hard
B, solid solids (metals, glass, or metal oxides).
Chemical Adhesion
The bond strength of covalent bonds is one to two orders of
magnitude greater than van der Waals attractive forces.
There have been numerous applications where interracial
FIG. 1-Weak boundary layer theory. Possi- chemical bonds have been employed to promote adhesion.
ble zones of failure (after Good [19]). Dramatic increases in bond strength have been reported [40].
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CHAPTER 44--ADHESION 5|5
Coupling agents such as chrome complexes [41], silanes on these substrates. It has also been claimed that the reverse
[42], and titanates [43] have been used effectively. Organic is true, however [51-52].
functionalities, including isocyanates, carboxyls, amides,
amines, hydroxyls, and epoxides [43-44], have been reacted
interfacially to enhance adhesion. Combination o f Phenomena
Adhesive strength has been shown to increase with func- The preceding theories interpret adhesion in terms of sin-
tional group concentration as expressed by gle phenomena, each of which undoubtedly plays some role
f = kC~ (7) in interfacial bonding between coating and substrate. One
should be cautioned, however, against exclusive use of a sin-
where fis the adhesive strength, C the functional group con- gle theory to explain the adhesion of a given system. A more
centration, and k and n are positive constants [45]. There, logical approach has been proposed by Allen [53]
however, appears to be an upper limit for functional group
concentration above which adhesion may tend to decrease qJ = a~bA + b~8 + C~c + ... (8)
[46-47]. which suggests that a combination of phenomena is more
realistic, that is, that basic adhesion is the summation of all
interatomic or intermolecular interactions at the interface.
Mechanical Adhesion
One would think that systematic studies could be made to
In mechanical adhesion substrate roughness is thought to assess the contribution of a given variable to the adhesion
provide a mechanical locking of the coating to the substrate. process, with the others being held constant. This would
However, if there is not intimate contact between the coating reveal useful information as to factors critical to coating ad-
and the substrate, then increased roughness should lead to a hesion for a particular system. Unfortunately, being able to
decrease in adhesion by producing uncoated voids. In the accomplish that task is questionable given that adhesion as-
practical application of electroless metals on polymer sub- sessment not only involves factors of basic adhesion but vari-
strates, etchants are used which create deep channels, ination in application of the applied external stress (tensile,
creasing adhesion. Other examples are anchor coats for shear, or peal) and many other factors.
PTFE, adhesion to porous anodic films on aluminum, and hot It can be concluded that adhesion is an interfacial phenom-
melt polyolefin coatings on metals. Mechanical adhesion is enon in which both physical and chemical forces operate
also important for porous substrates such as wood, cloth, and when surfaces develop to form an interface. Adhesive
paper. Since good adhesion can be obtained on smooth sur- strength is a measure of the degree to which the two surfaces
faces such as glass, questions can be raised about the general are attracted. This is a function of wettability, relative surface
validity of the mechanical adhesion mechanism. It should energetics of both phases, and of the kinetics of wetting. For
also be noted that mechanical abrasive treatment of a solid integrity of a bond at the interface between a coating and a
surface may also yield macroradicals and active secondary substrate, one needs to consider the following factors:
chemical products, which if they do not come into contact 1. Thermodynamics and kinetics of the formation of the
with atmospheric oxygen, may interact with components of bond.
the coating. This has been shown for certain adhesives. Active 2. The forces acting near the interface in both the coating and
radicals or functionality would yield adhesion, better de- the substrate.
scribed as mechanico-chemical adhesion than just mechani- 3. The cohesive forces within the coating layer.
cal [7,48-49]. 4. Internal stresses in the coating layer.
5. The behavior of the coating layer under stress.
To understand basic adhesion one must understand the
Electrostatic Adhesion
surface chemistry, surface physics, surface architecture,
In the theory of electrostatic adhesion, when two dissimilar coating polymer chemistry and physics, polymer rheology,
materials are brought into contact, a charge transfer takes coating internal stresses, fracture mechanics, and effects of
place which results in the formation of an electrical double changes in the environment. In fact, it has been noted that
layer, much like a capacitor. Work would then be required to spontaneous loss of adhesion can occur due solely to internal
separate the two charged layers. This is thought to be particu- strain of the coating [54-56].
larly applicable to metal-polymer bonds. Indeed, ionizing
discharge has been shown to affect a copper to acrylic bond
but not copper on salt (NaC1) or glass. This theory would not
Effects o f Substrates
be applicable to two nonpolymer systems [49-50]. Additional Chemistry
The adhesion of organic coatings to metals is at a high level
Acid-Base Adhesion of development in the practical sense. The contribution of
surface energy, chemical functionality, surface irregularities,
In the acid-base adhesion theory, it is said that the strength and contaminants (oxides, adsorbed water, etc.) have been
of the adhesive bonds is increased significantly by acid base identified.
interactions between coating and substrate. Appropriate On the other hand, coating adhesion to plastic suhstrates
modification of surface acidity or basicity of the substrate has presented additional complexities. Polymer surfaces are
should increase adhesion. Modification of surface acidity or often more difficult to wet and bond because of low surface
basicity of inorganic solids can increase mechanical proper- energy, incompatibility, chemical inertness, or the presence
ties (modulus, extension to break, and toughness) of coatings of contaminants (oils, lubricants, plasticizers, etc.), and weak
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boundary layers. Surface modification techniques have been

developed to enhance adhesion. In the absence of surface
preparation, coating adhesion is felt to be a function primar-
ily of van der Waals and/or polar-dipolar attractive forces,
mechanical adhesion (from surface irregularities), and in-
terdiffusion. This latter contribution to adhesion has been
studied using scanning electron microscopy. In Fig. 3 is pre-
sented a scanning electron micrograph of a thermoplastic
acrylic coating applied to modified polyphenylene oxide (a
blend of PPO and polystyrene), an important engineering
thermoplastic. The first coating contains 60% of the recom-
mended amount of solvent. The interface formed is sharp and
well-defined. In this instance, adhesion appears to be due
largely to mechanical and attractive forces. Figure 4 shows
the same substrate and coating, which in this case contains
100% of the recommended amount of solvent. The sharp
interface seen in Fig. 3 is no longer present, an intermediate
zone or interphase having formed in its place. Diffuse inter- FIG. 4 - S E M of diffuse interface.
face formation of this magnitude is undoubtedly unique to
coatings applied to plastics. Bond strength will be a function
of formulation, solvent content, and drying time [2]. All metals (except gold) are known to exist with an oxide
Organic coatings are complex formulations; thus, the poly- film on their surfaces. The volume of oxide formed may be
mer chemistry at the developing coating substrate interface smaller than the metal reacted, and consequently the oxide
will clearly be impacted by the solid surface, whether plastic, film is porous and nonprotective (alkali and alkaline earth
metal, or inorganic, that is, the polymer interface may be metals) or the volume may be larger and therefore protective
somewhat different than the bulk coating (i.e., a boundary (transition metals and aluminum). However, in the latter
layer). Fully developed coatings may also be porous or case, migration of metal cations from the surface leaves
permeable, thus aging and weathering may impact adhesion, vacancies which aggregate to form cavities. Treatment of a
as water, oxygen, and other agents penetrate to the polymer metal before coating to produce a preferred or controlled
coating solid interface [7,57]. Indeed, some coatings that bonding surface is therefore common [7, 57]. From the above
have acceptable adhesion while dry may fail badly when discussion, it is clear that chemical interaction between coat-
tested under high humidity or after immersion in water for ing and solid can occur even when not recognized or antici-
several hours. pated.
It has been shown for polyolefin-metal adhesion that oxida- Finally, change in substrate may impact adhesion. Weath-
tion of the polymer attached to the surface occurs through ering failures such as blistering and scab corrosion are often
action of oxygen absorbed by the metal and the polymer. The regarded as adhesion failures by coatings development chem-
appearance of oxygen-containing groups in the otherwise ists. Delamination of coatings in the absence of substrate
inert polymer should promote an increase in the extent of corrosion can also be produced by weathering. A common
interaction with the metal. Adhesion in this case would also problem involves the interfacial chalking of an epoxy primer
be increased by oxygen donor fillers [7,57]. and a topcoat that has a high UV light transmission. In the
presence of UV light, moisture, and oxygen, the epoxy primer
is degraded at the interface between the primer and topcoat,
leading to delamination of the topcoat from the primer.
Delamination of clear or semitransparent exterior wood
coatings can also occur by UV, water, and oxygen attacking
the wood substrate. Delamination of the intact coating results
when the wood substrate coating interface is destroyed. The
solution to this problem is to add organic and inorganic UV
absorbers to the coating to protect the wood substrate from
degradation.
PRACTICAL A D H E S I O N
Given the complexities of the adhesion process, can adhe-

sion be measured? As Mittal [3] has pointed out, the answer is
both "yes" and "no." It is reasonable to state that at the
present time no test exists which can precisely assess the
actual physical strength of an adhesive bond. But it can also
be said that it is possible to obtain an indication of relative
FIG. 3 - S E M of sharp interface. adhesion performance.
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CHAPTER 4 4 - - A D H E S I O N 517
Practical a d h e s i o n test m e t h o d s are generally of two types: guish b e t w e e n h i g h e r levels of a d h e s i o n for w h i c h m o r e so-
implied a n d direct. I m p l i e d type tests include i n d e n t a t i o n or p h i s t i c a t e d m e t h o d s of m e a s u r e m e n t are required. I n mul-
scribe techniques, r u b testing, a n d wear testing. Criticism of ticoat systems, a d h e s i o n failure m a y occur b e t w e e n coats so
these tests arises when they are used to quantify the strength that the a d h e s i o n of the coating system to the s u b s t r a t e is not
of adhesive bonding. But this, in fact, is not their purpose. An d e t e r m i n e d . In Test M e t h o d A an X-cut 1.5 in. (3.8 cm) long is
i m p l i e d test should be used to assess coating p e r f o r m a n c e m a d e in the film (to the substrate) with a sharp cutting
u n d e r actual service conditions. Direct m e a s u r e m e n t s , on the device. A 1-in. (2.5-cm)-wide pressure sensitive t a p e is ap-
other hand, are i n t e n d e d expressly to m e a s u r e adhesion. Peel, plied over the cut a n d firmly a d h e r e d with a pencil eraser a n d
lap-shear, a n d direct tensile are c o m m o n examples. Meaning- t h e n removed, a n d a d h e s i o n is assessed qualitatively on a 0 to
ful tests of this type are highly sought after, p r i m a r i l y b e c a u s e 5 scale.
the results are expressed b y a single discreet quantity, the In Test M e t h o d B, a lattice p a t t e r n with either six or eleven
force required to fracture the coating/substrate b o n d u n d e r cuts in each direction is m a d e in the film (to the substrate),
p r e s c r i b e d conditions [2]. pressure-sensitive tape is a p p l i e d over the lattice a n d t h e n
removed, a n d a d h e s i o n is evaluated by c o m p a r i s o n with de-
scriptions and illustrations.
Test Methods F o r Test M e t h o d A, the following rating scale is used:
I n practice, a b a t t e r y of tests is used to evaluate a d h e s i o n by 5A No peeling o r removal.
inducing b o n d r u p t u r e by different modes. Criteria d e e m e d 4A Trace peeling o r removal along incisions.
essential for a test to w a r r a n t large-scale a c c e p t a n c e are: use 3A Jagged removal along incisions up to 1/16 in. (1.6 m m )
of a s t r a i g h t f o r w a r d a n d u n a m b i g u o u s procedure, relevance on either side.
to its i n t e n d e d application, reproducibility, a n d quan- 2A Jagged removal along m o s t of incisions up to 1/8 in.
tifiability, including a meaningful rating scale for assessing (3.2 m m ) on either side.
p e r f o r m a n c e . Test m e t h o d s used for coatings on metals are: 1A Removal from m o s t of the a r e a of the X u n d e r the tape.
peel a d h e s i o n or "tape testing," G a r d n e r i m p a c t flexibility 0A Removal b e y o n d the a r e a of the X.
testing, a n d adhesive joint testing including shear (lap joint) F o r Test M e t h o d B, 3/4 in. (1.9 cm) cross-cuts are made.
a n d direct tensile (butt joint) testing. These tests do not, in F o r coatings having a d r y film thickness up to a n d includ-
fact, strictly m e e t the criteria listed, b u t an appealing aspect ing 2.0 mils (50/xm), eleven cuts are spaced 1 m m apart.
of the above tests is that in m o s t cases the equipment/instru- F o r coatings having a dry film thickness b e t w e e n 2 mils (50
m e n t a t i o n is readily available or can be o b t a i n e d at reason- ~xm) a n d 5 mils (125/xm), six cuts are spaced 2 m m apart.
able cost [2]. F o r films thicker t h a n 5 mils (125 /xm), M e t h o d A is used
A wide diversity of test m e t h o d s has been developed over instead of M e t h o d B. F o r Test M e t h o d B, a d h e s i o n is r a t e d
the years. In this c h a p t e r only selected test m e t h o d s devel- according to the following scale (as illustrated in Fig. 5.):
o p e d t h r o u g h the consensus process will be discussed in
5B The edges of the cuts are completely smooth; n o n e of
detail. The r e a d e r should recognize, however, that n u m e r o u s
the squares of the lattice is detached.
test m e t h o d s have been developed w h i c h m e a s u r e aspects of 4B Small flakes of the coating are d e t a c h e d at intersec-
a d h e s i o n [7,58-61] and that there generally is difficulty in tions; less t h a n 5% of the a r e a is affected.
relating these to basic a d h e s i o n p h e n o m e n a .
3B Small flakes of the coating are d e t a c h e d along edges
a n d at intersections of cuts. The a r e a affected is 5 to
The Tape Test 15% of the lattice.
2B The coating has flaked along the edges a n d on parts of
By far the m o s t used test to access coating "adhesion" is the the squares. The a r e a affected is 15 to 35% of the
peel test. In use since the 19308, in its simplest version, a lattice.
piece of adhesive tape is pressed against the p a i n t film. The 1B The coating has flaked along the edges of cuts in large
test consists of observing w h e t h e r the film is peeled off w h e n
ribbons, a n d whole squares have detached. The a r e a
the tape is removed. The m e t h o d can be refined to m e a s u r e affected is 35 to 65% of the lattice.
the force r e q u i r e d for film removal. In o t h e r tests, crosses or a 0B Flaking a n d d e t a c h m e n t worse t h a n G r a d e 1.
cross-hatched p a t t e r n are cut into the coating, a tape applied
a n d removed, a n d the coating r e m o v a l assessed against an Repeatability within one rating unit is generally observed
established rating scale. The currently widely used version for coatings on metals for b o t h methods, with r e p r o d u c i b i l i t y
was p u b l i s h e d in 1974 as ASTM D 3359, S t a n d a r d Test Meth- of 1 to 2 units. The m e t h o d is widely used a n d is viewed as
ods for Measuring Adhesion by Tape Test. Two test m e t h o d s "simple" as well as low in cost.
are covered.
These test m e t h o d s cover p r o c e d u r e s for assessing the ad-
Peel Adhesion Testing on Plastic Substrates
hesion of coating films to metallic substrates only b y applying
a n d removing pressure-sensitive t a p e over cuts m a d e in the ASTM D 3359 has d r a w n fire w h e n used for substrates
film. Method A is p r i m a r i l y i n t e n d e d for use at job sites, while other t h a n metal, such as plastics. The central issues are t h a t
M e t h o d B is m o r e suitable for use in the laboratory. The the test lacks r e p r o d u c i b i l i t y a n d does not relate to its in-
cross-hatch test, M e t h o d B, is not considered suitable for t e n d e d application. Both concerns are well founded. Poor
films thicker t h a n 5 mils (125 /xm). Both test m e t h o d s are r e p r o d u c i b i l i t y is a direct result of several factors intrinsic to
used to establish w h e t h e r or not the a d h e s i o n of a coating to a the m a t e r i a l s e m p l o y e d a n d the p r o c e d u r e itself. More i m p o r -
substrate is at a generally a d e q u a t e level. They do not distin- tantly, in this instance the test is being a p p l i e d b e y o n d its
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518 PAINT A N D COATING T E S T I N G M A N U A L
FLEXIBLE
Surface of cross-cut area from ADHE~~
Classification which flaking has occurred.
(Example for six paralled cuts)
5B None ~llmllullllllmlllll~j ~ 'ADHESIVE
iiilUlUllm
iIIIIIll //f //I///////// 9 "/,/l~f/////////// -
pllllll
4B Illllll / RK~H~AOHERENO
iIIIllll
i!11111
- EXPERIMENTAL
-- I k - . - p.--
3B - "r- ~'- P'--

' f ]o
i ,
-- ~P'I
COMPRESSI o.V
FIG. 6-Peel profile [62].
2B
both. It is worthwhile to note the significant compressive
force which arises from the response of the tape-backing
material to being stretched, which precedes the tensile force.
I & d tql
l e ale I l l Both tensile and compressive forces are involved in tape
1B I 9 r
B4A 1,6,1 testing.
It t a#l
Close scrutiny of the tape test with respect to the nature of
the tape employed and certain aspects of the procedure itself
reveal several factors, each or any combination of which can
OB Greater than 65~, dramatically affect the results of the test as discussed below.
FIG. 5-Classification of adhesion test results. From ASTM The Tape Controversy
D 3359,
Given the withdrawal of the originally specified tape, 3M-
710, ASTM D 3359-91 no longer specifies a specific tape.
intended scope. ASTM D 3359 was designed for relatively Differences in tapes can lead to different results for reasons
ductile coatings applied to metal substrates, not for coatings noted above since small changes in backing stiffness and
(often brittle) applied to soft plastic parts [1]. adhesive rheology cause large changes in the tension area. It
Nevertheless, the tape test enjoys widespread popularity. is also important to note that tapes, like most products, are
The tape test is economical to perform, lends itself to job site manufactured to meet minimum standards. A given lot may
application, and most importantly, after decades of use, peo- surpass these criteria and be suitable for general market
ple feel comfortable with it. Unfortunately, the often unique distribution, but a source of serious and unexpected error for
functional requirements of coatings on plastic substrates tape testing [63]. There was, in fact, a commercially available
dictate that the tape test as written may not be a satisfactory tape test kit which included a tape with adhesion variations of
measure of practical adhesion performance. up to 50% claimed by the manufacturer [6,#]. And, of course,
When a flexible adhesive tape is applied to a rigid coated tapes age on storage. Bond strengths change over time.
substrate surface and then removed, the removal process has While there are tapes available which would appear to de-
been described in terms of the "peel phenomenon," as illus- liver consistent performance, a given tape does not adhere
trated in Fig. 6. equally well to all coatings, t:or example, the peel removal
Peeling begins at the "toothed" leading edge (at the right) force of the tape previously recommended by ASTM (3M-
and proceeds along the coating-adhesive interface. It is rea- 710) was examined with seven coatings. It was found that
sonable to assume that any coating removal is due to a tensile while peel was indeed consistent for a given coating, it varied
force generated along this interface, which would be a func- by 25% between the highest and lowest ratings among coat-
tion of the rheological properties of the backing and adhesive ings. This observation could be the result of several factors,
layer materials and the strength of the bond between the notably coating composition and topology, but the bottom
adhesive layer and the coating surface. Note, however, that in line is that no single tape is likely to be suitable for testing all
actuality this force is distributed over a discreet distance (0 to coatings. It is also useful to note the tape test does not give an
A on Fig. 6), which relates directly to the properties described absolute value for the force required for bond rupture, but
[63], not concentrated at a point (0 on Fig. 6) as in the theoret- serves only as an indicator that some minimum value for
ical case, though tensile force is greatest at the origin for bond strength was met or exceeded [1,2].
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CHAPTER 44--ADHESION 519
Procedural Problems substrate-film interface, this force is taken to be the "force of

adhesion." An obvious limitation is, of course, the strength of
The tape test is operator intensive. By design it was made as
the adhesive bond of the stud to the cured coating. Such
simple as possible to perform and requires a minimum of
methods have been available since the 1930s. Many of these
specialized equipment and materials which must meet cer-
test methods have unfortunately suffered from their own lack
tain specifications. Therefore, the burden of accuracy and
of reproducibility. This is not unexpected since the forces
reproducibility relies largely upon the skill of the operator
involved are not quite as simple as appearance would have it
and his/her ability to perform the test in a consistent manner.
[5,66].
Key steps which directly reflect the importance of operator
It is essential that the force is applied strictly in the direct
skill include the angle and rate of tape removal and the visual
normal to the sample and that no bending moment is active
assessment of the tested sample. It is not unexpected that
across the test area. Deviations from symmetry in the test
different operators might obtain different results [1,2].
arrangement, poor alignment, deviations from homogeneity
Peel Angle and Rate and of thickness of the adhesive (coating), and random varia-
tions in the strength of the bond between film and substrate
The standard requires that the free end of the tape be affect test results [5,66].
removed rapidly at as close to a 180~ angle as possible. But if The stress at locations where the adhesive film is thinner
peel angle and rate vary, the force required to remove the tape will be higher than the average stress and will be transmitted
can change dramatically. Nearly linear increases were ob- to the film under test. Another factor may be peeling during
served in peel force approaching 100% as peel angle was test, which is not easily identified or analyzed.
changed from 135 to 180~, and similar large differences can The adhesive used to bond a stud to the coating has the
be expected in peel force as peel rate varies. These effects are potential to influence the coating film properties by penetra-
related in that they both reflect certain rheological properties tion through the film into microcracks and possibly into the
of the backing and adhesive which are molecular in origin, substrate [66]. Test adhesive flexibility may also be an issue,
but the most useful conclusion is that these phenomena can as well as the flexibility of the substrate, if the sample is
make large contributions and must be minimized to assure unrestrained.
reproducibility [65]. There exist now within ASTM both laboratory and field
versions of direct tension tests for coatings. Test Method for
Visual Assessment
Measuring Adhesion of Organic Coatings to Plastic Sub-
The final step in the test is visual assessment of coating strates by Direct Tensile Testing, ASTM D 5179, while limited
removed from the specimen, and this can be subjective in to organic coatings on plastics, uses a restrained sample and
nature. This assessment can vary among individuals evaluat- commonly available tension test apparatus. The second,
ing the same specimen [65]. Method for Pull-Off Strength of Coatings Using Portable Ad-
Performance in the tape test is based on the amount of hesion-Testers, ASTM D 4541, defines a class of portable pull-
coating removed compared to a relative scale. But it was off adhesion testers for field evaluation of coating adhesion.
found that the exposure of substrate can be due to factors ASTM D 5179 is the successor to numerous attempts to
other than coating adhesion, arising from the requirement develop a reproducible coating tension test and was approved
that the coating he cut (hence the synonym "cross-hatch ad- in 1991. It will be discussed first.
hesion test"). Justification for the cutting step is reasonable;
cutting provides a free edge from which peeling can begin ASTM D 5179
without having to overcome the cohesive strength of the coat- This test covers the laboratory determination of adhesion
ing layer. This might be suitable for coatings applied to metal of organic coatings to plastic substrates by mounting and
substrates, but for coatings applied to plastics, the cutting removing an aluminum stud from the surface of a coating
process can lead to false indications of poor adhesion. This is and measuring the force required to break the coating/sub-
due to the unique interracial zone mentioned earlier. For strate bond with a tensile tester. The test method provides an
coatings on soft plastics, how deep should this cut penetrate? inexpensive test assembly which can be used with most ten-
Is it possible to cut only to the interface? sile test machines. The method is used to compare the pull-off
If microscopic examination of panels is included, in several strength (commonly referred to as adhesion) of coatings to
instances it is clearly evident that coating removal results various plastic substrates, thus allowing for a quantitative
from substrate failure at or below the interface, not from comparison of various coating/substrate combinations.
adhesive failure between coating and substrate. At the same A carefully prepared aluminum stud is bonded directly to a
time, it is also observed that cohesive failure within the coat- coated, cured panel using a cyanoacrylate adhesive. The ad-
ing layer is a frequent occurrence. The latter observation is hesive is allowed to cure for 2 h at room temperature. Adhe-
significant in that the tape test assessment criteria make no sive buildup is removed from around the stud. The specimen
provision for it [1,2]. is then subjected to test on a tensile tester equipped with an
upper coupling adapter and a restraining device (Fig. 7) to
Direct Tensile Testing provide for sample alignment and minimal substrate flexing.
The sample bearing the stud is installed in the restraining
A long-used approach to coating adhesion testing is the device, with only the stud pertruding. The tensile machine
direct tensile test, perhaps "conceptually" the simplest of all crosshead is lowered so the upper coupling adaptor can be
methods for measuring adhesion. A dolly or stud is bonded to attached to the specimen.
the coating film. The normally applied force which is re- When testing thin substrates, a piece of plastic is placed in
quired to remove the film is measured. If failure occurs at the the restraining device behind the specimen to insure a rigid
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A (3/4" diameter hole)
Y//////~
CI
///////~/I
- - T O P PORTION
4"
~PREPARED SAHPLE
| I
UPPERCOUPLING
TOP VIEN
ADAPTOR
BOTTOHPORTION
~~SAHPLE DEVIcERESTRAINING
[
I I
- - PREPARED
SAHPLE
IN DEVICE
(A) (B) (O
FIG. 7-Direct tensile restraining device. From ASTM D 5179.
assembly. The tension test is conducted, and pull strength strengths of two orders of magnitude has been observed (Ta-
recorded. Each specimen is rated according to type of coating ble 1) for diverse coating-plastic combinations.
failure, as follows:
A Adhesive failure of the coating from the substrate. A S T M D 4541
C Cohesive failure in the coating. This test method defines a class of portable adhesion testers
AC Combination of adhesive failure at the coating/sub- for measuring the pufl-off strength of coatings. The method
strate interface and cohesive failure in the coating. covers a procedure and apparatus for evaluating pull-off
S Adhesive failure at the stud. strength by determining either the greatest perpendicular
CS Combination of adhesive failure at the stud and cohe- force (in tension) that a surface area can bear before a plug of
sive failure in the coating. material is detached or whether the surface remains intact at
For multilayer coatings, failure between the layers is noted a prescribed force (pass/fail). Failure will occur along the
and labeled as CM. Five specimens of each coated substrate weakest plane within the system comprised of the test fixture,
are tested one day and five on a second day. If one specimen adhesive, coating system, and substrate and will be exposed
differs significantly from the other four tested at the same by the fracture surface. The method maximizes tensile stress
time, fails because of an uneven (nonplanar) stud, or for as compared to the shear stress applied by other methods
another reason performs unlike the other four, a replacement such as scratch or knife adhesion, and results are not compa-
specimen is tested. The stud and specimen are carefully ex- rable. It is recognized that the pull-off strength reflects both
amined. The adhesive should have been applied uniformly to material and instrumental parameters and therefore provides
the entire stud surface. Coating should have pulled off uni- a relative, not absolute, measure of adhesion. The pull adhe-
formly over the entire stud surface either with adhesive fail- sion testers defined are portable and capable of applying a
ure from the substrate (A) or cohesive failure in the coating concentric load and counter load to a single surface so that
(C). If failure is less than 90% A or C (or CM), if the adhesive coatings in the field can be tested even though only one side is
has failed at the stud, a retest, exercising particular care in the accessible. Measurements are limited by the strength of adhe-
specimen and stud preparation is performed. Pull strength sion bonds between the loading fixture and the specimen
for the ten runs on each coating substrate combination are surface or the cohesive strength of the substrate. The pull-off
averaged and reported. test is performed by securing a "loading fixture" (dolly or
The precision and bias are primarily dependent upon the stud) normal (perpendicular) to the surface of the coating
accuracy of the force measurements, the alignment of the with an adhesive. After the adhesive is cured, the testing
device, and the care exercised in stud and specimen prepara- apparatus is attached to the loading fixture and aligned to
tion and in the care in testing. A ten-laboratory round robin apply tension normal to the test surface. The force applied to
on ten samples gave an average standard deviation of 29% for the loading fixture is then gradually increased (in less than
reproducibility and 22% for repeatability. A range of pull 100 s) and monitored until either a plug of coating material is
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TABLE 1--Representative pull strength for organic coatings on plastics.
Failure Pounds Per
Sample No. Coating Substrate Mode Square Inch~
1 Lacquer Polyester/polycarbonate C 58
2 Lacquer Polycarbonate A 36
3 Lacquer ABS C 82
4 Lacquer Polycarbonate A 37
5 Lacquer ABS C 93
6 Lacquer PVC AC 103
7 Enamel Polycarbonate A 308
8 Urethane ABS A 639
9 Urethane ABS A 476
10 Urethane Metal S 666
11 Enamel Metal 75% A 342
12 Lacquer PPO/Nylon C 226
13 Enamel PPO/Nylon C 226
14 Enamel PPO/Nylon A 242
"To convert to metric, multiply by 6.89 kPa.
NOTE:ABS = acrylonitule-butadiene-styrene
PVC = polyvinylchloride
PPO = polyphenylene ether
d e t a c h e d or a specified value is reached. The n a t u r e of the

failure is assessed as to the percent of adhesive or cohesive
failure, a n d the actual interfaces and layers involved are iden-
tified. The pull-off strength is c o m p u t e d based on the maxi-
m u m indicated load, the i n s t r u m e n t c a l i b r a t i o n data, and the
I I DETACHING
- ' ~ X" ASSEMBLY
original surface a r e a stressed (Fig. 8).
This m e t h o d is general a n d is applicable to any p o r t a b l e
a p p a r a t u s meeting the standard's basic r e q u i r e m e n t s for de-
t e r m i n i n g the pull-off strength of coatings. F o u r a p p a r a t u s
are c o m m o n l y recognized to meet the r e q u i r e m e n t s of the
standard.
It is k n o w n that the rigidity of the substrate affects pull-off
strength results and is not a controllable test variable in field C;~i~~~GGRIP
m e a s u r e m e n t s as defined by this standard. F o r example, steel
substrates of less t h a n 1/8 in. (3.2 m m ) thickness show re-
d u c e d pull-off strength results c o m p a r e d to 1/4-in. (6.4-mm)-
thick panels.
E r r o r s in m e a s u r e m e n t in this test result from a l i g n m e n t of BASE~" ~ ~
Z&,< ' ~ l \\ I ANNULAR RING
the a p p a r a t u s that is not n o r m a l to the surface, p o o r defini- '~ ~ ...~....k.! ~*"
tion of the a r e a stressed due to i m p r o p e r a p p l i c a t i o n of the SYSTEM - - - ' ~ 7 7 ~ ~ ~ ~ SUBSTRATE
adhesive, p o o r l y defined glue lines and boundaries, holidays
FIG. a-Portable adhesion tester. From ASTM D 4541.
in the adhesive caused by voids o r inclusions, i m p r o p e r l y
p r e p a r e d surfaces, a n d sliding or twisting of the fixture dur-
ing the initial adhesive cure. Also, scratched o r scored sam- b u t i o n t h a n B. Test Assembly B shows strong stress peaks at
ples m a y contain stress c o n c e n t r a t i o n s leading to p r e m a t u r e the coating layer periphery. The result is that the Test Assem-
fractures. I n t e r l a b o r a t o r y d a t a have been o b t a i n e d for four
bly B shows 20 to 60% lower breaking strength results t h a n
c o m m e r c i a l test a p p a r a t u s a n d are presented in Table 2.
the s a n d w i c h m e t h o d for several organic coatings on metal
ISO 4624 [67].
F o r Test Assembly B, b r e a k i n g strength values have b e e n
S i m i l a r pull-off test m e t h o d o l o g y has been a p p r o v e d
t h r o u g h the I n t e r n a t i o n a l S t a n d a r d s Organization, a n d the shown to be a function of the d i a m e t e r of test cylinders
p a r a m e t e r s involved have been carefully studied. ISO 4624, (studs) as well as their geometry. On the range of 10 to 28 m m
"Pull-off Test for Adhesion," was a p p r o v e d in 1978. ISO 4624 diameters, a factor of two in breaking strength was seen with
specifies two different tests assemblies (A and B of Fig. 9) a p e a k at a b o u t 14-mm diameter. It was observed that tensile
Test Assembly A (Sandwich Method) consists of a s u b s t r a t e forces only affected the central p a r t of the test area. Even test
p a i n t e d on one o r both sides, with test cylinders (studs) with a cylinders of the s a m e diameter, but different shapes, gave
specified d i a m e t e r b o n d e d coaxially to the coated test surface different results, up to 45% lower, It has been noted that
a n d on the reverse. Test Assembly B consists of a rigid sub- while u n i f o r m tensile stress can only be a p p r o a c h e d , the
strate coated on one side, with one test cylinder (stud) applied length of the test cylinder (stud) should be no less t h a n half its
to that side only. While the latter is the m o r e practical, Test diameter. W h e n this is done, similar results are achieved
Assembly A on stress analysis shows a s m o o t h e r stress distri- regardless of cylinder d i a m e t e r [67].
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TABLE 2--ASTM D 4541 interlaboratory data.

Instrument Patti Elcometer Hate Dyna
Loading Fixture Diameter 13 mm 20 mm 19 mm 50 mm
Paint Sample (mean of 3 results)
A 1160 586 1185 201
B 1099 674 1157 185
C 1033 827 1245 190
D 1678 888 1686 297
number. Comparisons must be made carefully in concert

with an examination of the locus of failure. Practically speak-
ing, while absolute values are only approached, relative val-
ues and studies of the locus of failure are sufficient for most
purposes.
ASTM D 2197
-Y- ' i Used to a lesser extent than the preceding methods is ASTM
D 2197, Test Methods for Adhesion of Organic Coatings by
Test ossembly A Test ossembly B
Scrape Adhesion.
FIG. 9-1S0 4624 test assemblies. This test method covers the determination of the adhesion
of organic coatings such as paint, varnish, and lacquer when
applied to smooth, flat (planar) panel surfaces. The materials
Perhaps it is only coincidence, but it is interesting to note in
under test are applied at uniform thickness to planar panels,
Table 2 for apparatus meeting ASTM D 454l that the loading
usually sheet metal of uniform surface texture. After drying,
fixture diameter and geometry differ significantly and at least
the adhesion is determined by pushing the panels beneath a
partially account for the greater than a factor of 4 variation in
rounded stylus or loop loaded in increasing amounts until the
test results, with the apparatus having a 50-mm loading fix-
coating is removed from the substrate surface.
ture diameter showing the lowest numerical results.
The method is most useful in providing relative ratings for
Substrate thickness (flexibility) has a significant effect
a series of coated panels exhibiting significant differences in
upon results. In a study of steel panels in the range of 2 to 30
adhesion. The balanced-beam, scrape-adhesion tester (Fig.
mm thick, breaking strength increased to a thickness of 15
mm using Test Assembly B. A comparison of results with the 10) consists of a balanced beam to which is secured a plat-
sandwich method for substrates above 15 mm thickness, form for supporting weights and a rod at an angle of 45 ~ that
however, still showed breaking strength values about one holds the scraping loop. The rod is set so that the scraping
third higher for Test Assembly A. These observations can be loop contacts test surfaces directly below the weights. The
explained in terms of differences in stress distribution. Thin- loop is a 1/16-in. (1.6-mm)-diameter rod bent into a "U" shape
ner substrates show increased stress intensity at the periph- with an outside radius of 0.128 _+ 0.002 in. (3.25 _+ 0.05 mm)
ery, which is distinguishable up to 15-mm thickness [67]. hardened to Rockwell HRC 56 to 58 and chromium plated
ISO 4624 specifies that tensile stress shall not be increased and polished.
at a rate greater than 1 MPa/s, so that failure occurs within 90 At least 1/2 in. (1.3 cm) at the end of a test panel is
s of initial stress application. An investigation of the rate of uncoated. The surface of the substrate must be hard enough
tensile stress increase in the range 0.15 to 1.2 MPa/s yielded so that it is undamaged by the scraping loop. The test proce-
indistinguishable results [67]. dure is as follows. A test panel on the sliding platform is
Sample parameters are important. Coating thickness (and placed so that it may be moved away from the operator and
adhesive thickness) is a key factor. The energy stored in a 5- the uncoated portion is toward the main beam support.
rail (125-/~m) coating, by virtue of its internal strain, in- Weights are placed on the weight support using an initial
creases as the coating thickness increases and at a particular amount estimated to be appropriate for the particular coat-
thickness can be sufficient to overcome the work of adhesion ing. The beam is lowered until the loop rests on the uncoated
at the interface (spontaneous peeling). The variation is larg- portion of the specimen and the full load is applied; then the
est at thicknesses below 125/zm (5 mils), which of course is sliding platform is slowly pushed away from the operator 1 to
the area of most practical application. It was also observed 2 s/in. for a distance of at least 3 in. (76 ram). If the coating is
that at the lowest coating thickness for the coatings studied, removed, the testing is continued using successively smaller
cohesive failure occurred in the uppermost parts of the coat- loads (0.5-kg increments) until the coating is not removed. If
ing, leaving a very thin film of coating on the test cylinder the coating is not removed by the initial scrape, the testing is
(stud). With thicker coatings, the fracture propagated deeper continued, using successively larger loads (0.5-kg incre-
into the coating. Through study of the locus of failure, one ments) until the coating is removed or until the maximum
can also study the effects of environmental conditions (aging, load of 10 kg has been applied. A new area of the test surface
solvents, moisture) and of coating resin cure [67]. is used each time a scrape is made. When the critical load has
Clearly, stress distribution changes, as altered by test appa- been approximately located, the test is repeated five times at
ratus and sample parameters, can alter results dramatically. each of the three loadings: above, below, and at the load
Pull-off strength (breaking strength) is therefore a relative determined in the first trial.
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FIG. lO-Balanced-beam scrape adhesion tester.
For each applied load, the number of times the coating was ASTM D 4146 Test Method for Formability of Zinc-Rich
removed or adhered is tabulated. The load where the scrape Primer/Chromate Complex Coating on
results change from mainly adhering to mainly removed, Steel. (This method is a tape test after
ignoring the first 1/2 in. (13 mm) of the scratch if the coating dome-shaped deformation).
was removed, is the adhesion failure end point. ASTM F 518 Practice for Determining the Effective Ad-
hesion of Photoresist to Hard-Surface
Photomask Blanks and Semiconductor
Wafers During Etching.
Other ASTM Standards ASTM F 692 Method for Measuring Adhesion Strength
of Solderable Films to Substrates.
Other ASTM standards which pertain to aspects of adhe-
sion measurements of films and coatings include the follow- Additional tests exist for electrodeposits, and bending, bur-
ing: nishing, and wrapping tests for coatings on wire. Tests for
adhesives have also been applied to coatings as wel]. Use of
ASTM B 533 Standard Test Method for Peel Strength reverse impact tests, lap and butt joint tests, and tensile shear
of Metal-- Electroplated Plastics. tests have been reported [1].
ASTM B 571 Test Methods for Adhesion of Metallic
Coatings. (This method includes bend,
CONCLUSIONS
burnishing, chisel-knife, draw, file, grind-
saw, heat-quench impact, peel, push, and
Basic adhesion is the summation of multiple phenomena.
scribe-grind tests).
Ideal adhesion is probably neither obtainable nor measurable
ASTM C 313 Test Method for Adherence of Porcelain
experimentally. Practical techniques do, however, allow suffi-
Enamel and Ceramic Coatings to Sheet
cient assessment of relative adhesion for most purposes, if
Metal.
used with care and knowledge. Workers need to understand
ASTM C 988 Test Method for Adherence of Porcelain
both basic adhesion concepts and the factors affecting practi-
Enamel Cover Coats Direct-to-Steel. (This
cal adhesion for systems of their interest if they are to make
test method is a drop weight deformation
improvements in real world products.
test).
ASTM D 3281 Standard Test Method for Formability of
Attached Organic Coatings with Impact- REFERENCES
Wedge Bend Apparatus. (This test method
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[3] Mittal, K. L., "Adhesion Measurement: Recent Progress, Un-
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Prepainted Sheet. (This method includes a Mittal, Ed., American Society for Testing and Materials, Phila-
tape pull-off test). delphia, PA, 1978, pp. 7-8.
www.iran-mavad.com

[4] Mittal, K. L., Adhesion Aspects of Polymeric Coatings, Plenum [39] Voyutskii, S. S., Yagnyatinskaya, L., Kaplunova, Y., and
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www.iran-mavad.com

MNL17-EB/Jun. 1995
45
Abrasion Resistance*
by Mark P. Morse 1
T H E P R O B L E M OF R E S I S T A N C E TO ABRASION exists all a r o u n d US: tion to not giving a s m o o t h ride, w o u l d not last long on
on floors, walls, furniture, automobiles, farm i m p l e m e n t s , concrete r o a d s in c o m p a r i s o n to the service life of a g o o d
c o n s t r u c t i o n equipment, military gear, appliances, shoe r u b b e r tire. The ability of a material, such as a r u b b e r tire, to
soles, a n d so on. Because resistance to a b r a s i o n is a basic u n d e r g o elastic d e f o r m a t i o n a n d recover or "to ride with the
factor in the d u r a b i l i t y of a coating, its m e a s u r e m e n t is of blow" is associated with g o o d a b r a s i o n resistance.
practical i m p o r t a n c e to b o t h p r o d u c e r a n d consumer. The energy transferred to an elastic m a t e r i a l by an im-
Abrasion is caused by m e c h a n i c a l actions such as rubbing, p a c t i n g object is largely r e t u r n e d to the object, t h o u g h redi-
scraping, or erosion from w i n d a n d water. It can take two rected, instead of being expended in the d e s t r u c t i o n (separa-
general forms: m a r r i n g or wearing. tion a n d removal of material) of the i m p a c t e d surface. F r o m a
f u n d a m e n t a l viewpoint, this is a consequence of the smaller
deceleration a n d hence smaller force generated, since force is
DEFINITIONS
equal to the p r o d u c t of mass a n d acceleration, w h e n the
i m p a c t is with a m a t e r i a l that will d e f o r m or "give" with the
M a r a b r a s i o n consists of p e r m a n e n t d e f o r m a t i o n s that
i m p a c t i n g object. If the d e f o r m a t i o n caused by the object is
have not r u p t u r e d the surface of a coating. The resistance of a
not elastic, the m a t e r i a l will yield a n d flow, causing d a m a g e .
coating to m a r r i n g is its ability to w i t h s t a n d scuffing actions
Therefore, soft materials with a low tensile strength are not
t h a t t e n d to disfigure or change the a p p e a r a n c e of its surface.
a b r a s i o n resistant.
S o m e examples of potential causes of m a r r i n g of organic
The fact that elastic m a t e r i a l s are often a b r a s i o n resistant
coatings are: (a) sliding an object across the surface of furni-
does not m e a n that h a r d m a t e r i a l s are not a b r a s i o n resistant.
ture; (b) r u b b i n g of a belt buckle, button, zipper, or r o u g h
Theoretically, however, if one is given two m a t e r i a l s of equal
fabric on an a u t o m o b i l e finish; (c) sliding a toy across a wall
tensile strength, the m a t e r i a l of lower m o d u l u s should have
or a refrigerator door, etc.
the best a b r a s i o n resistance. The deceptive factor here is that
W e a r a b r a s i o n is caused by m e c h a n i c a l action that re-
a h a r d m a t e r i a l usually has a m u c h h i g h e r tensile strength
moves m a t e r i a l from the surface of a coating. In m a n y cases,
t h a n a soft material. Thus, w h e n a r u b b e r is c o m p a r e d with
the removal is gradual or progressive due to repetitive me-
steel, materials with orders of m a g n i t u d e difference in tensile
chanical action.
strength are being considered. The fact that r u b b e r is abra-
sion resistant e m p h a s i z e s that the value of a low m o d u l u s of
R E L A T I O N S H I P TO O T H E R PHYSICAL elasticity and a d e q u a t e tensile strength are factors that play a
PROPERTIES role in obtaining good a b r a s i o n resistance.
In theory, a very h a r d m a t e r i a l that has a h a r d n e s s a n d
Abrasion resistance is not a unique o r isolated p r o p e r t y of a cohesive strength a d e q u a t e to completely resist any i m p a c t
m a t e r i a l b u t is r a t h e r related to other physical characteristics force it might e n c o u n t e r w o u l d not be d e p e n d e n t on r u b b e r -
such as hardness, cohesive a n d tensile strength, elasticity, like elasticity to reduce or dissipate i m p a c t stresses. It w o u l d
a n d toughness. Also, from the s t a n d p o i n t of retaining its be m o r e a b r a s i o n resistant t h a n the best elastic b u t w e a k e r
protective or decorative function, the thickness of a coating m a t e r i a l [1].
can be a n i m p o r t a n t factor.
Hardness, Elasticity, and Tensile Strength CORRELATION WITH E N D - U S E

A b r a s i o n resistance is related to hardness, yet the relation- PERFORMANCE
ship is not simple. A first t h o u g h t m i g h t be that the h a r d e r a
coating, the b e t t e r w o u l d be the a b r a s i o n resistance; how- F r o m the discussion above, it is a p p a r e n t that the m e a s u r e -
ever, this is not always true. Steel is m u c h h a r d e r t h a n rub- m e n t of a b r a s i o n resistance involves m e a s u r i n g a complex
ber, for example, b u t steel "tires" on an automobile, in addi- c o m b i n a t i o n of interrelated p r o p e r t i e s a m o n g w h i c h there is
no direct relationship. The task of devising a test m e t h o d o l -
ogy that will correlate with end-use p e r f o r m a n c e is, there-
*This chapter is an abridged and modified version of the chapter
with the same title, written by A. Gene Roberts, found in the previous fore, complex a n d difficult but not impossible to develop. If
edition of this manual. the test m e t h o d subjects the m a t e r i a l u n d e r test to a c o m p o s -
1Consultant, 71 S. Shelburne Road, Springfield, PA 19064. ite of destructive forces similar to those m e t in service, t h e n
525
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the test method will correlate--or predict--the service per- Rubbing (friction) and scraping methods obviously wear
formance of the material in at least a qualitative or relative away the test surface in a different manner than methods in
ranking respect. which abrasive particles are contacted with the surface. One
When accelerated tests are being considered, even tests aspect of the mechanistic difference lies in the angle of con-
that rank materials in the same sequence as actual service tact with the surface. Abrasive particles striking the surface of
tests, a quantitative correspondence with actual service is a coating at nearly normal incidence tend to compress, scar,
seldom expected or obtained. Actual end-use tests, while the and cut into the coating. As a result, minute portions of the
most reliable in providing an indication of a material's proba- coating eventually should be crosscut and displaced. On the
ble long-term durability, suffer from the difficulties of en- other hand, the rubbing and scraping types of abrasion that
suring equivalent usage and measurement, especially when take place at near grazing incidence would tend to undercut
the comparison of different materials is attempted. Because and to shear through very thin layers of the coating in succes-
of such difficulties and because service tests are usually very sive, irregular slices that ultimately wear it away. Different
time consuming, a wide variety of test machines have been devices might incorporate various degrees of these basic pro-
developed to provide an accelerated indication of the abra- cesses, depending on the angle and force of particle attack.
sion resistance of coatings and related materials such as vinyl Apart from the nature of the above mechanisms, it should
flooring, linoleum, and wall coverings. In a comprehensive be apparent that whatever the mechanism, it is not main-
review article by Harper [2], there is a list of no less than 49 tained uniformly in friction methods. Such methods suffer
different abrasion-causing machines. An investigation by the from changes in the abrading conditions as the testing pro-
International Study Committee for Wear Tests of Flooring ceeds, either because of heating of the specimen or clogging
Performance [3], in which seven commercial, organic floor- of the abradant or other.
ing materials were systematically tested on 21 abrasion ma- If an abrasion test using the direct impingement of parti-
chines of 17 different types, indicated that very few of these cles is chosen so the undesirable frictional effects are
machines were capable of providing a reliable comparison of avoided, there may be doubt about whether the method cor-
the abrasion resistance of widely different materials that relates well with a type of service in which the coating is, for
could be correlated with end-use performance. In addition, example, walked upon. Yet, the previously mentioned ASTM
the different machines did not correlate very well with each round robin of abrasion tests carried out with floor coatings
other. clearly established the validity of particle-impingement-type
On the basis of a round robin conducted in 1956 by ASTM tests for evaluating this type of end-use service life.
with six different clear floor coatings evaluated by six differ- Until the mechanism of abrasion is more completely stud-
ent abrasion test methods [4], only two of the methods were ied and understood, industry must continue to rely to a large
found to correlate with actual end-use performance and to extent on experimentation and even intuition when devising
have the reproducibility necessary for acceptance as ASTM abrasion test methods. In addition, properly designed test
standards. These were ASTM Test Method for Abrasion Re- programs must be employed to determine the extent to which
sistance of Organic Coatings by Falling Abrasive (ASTM a given method correlates with actual end-use performance
D 968) and ASTM Test Method for Abrasion Resistance of [1]. A side variety of useful abrasion testing procedures are
Organic Coatings by Air Blast Abrasive (ASTM D 658). The jet described in sections that follow.
abrader, Method 6193 of Federal Test Method Standard No.
141C, which became available after the testing, appears to
correlate well with the two cited ASTM methods and with
LOOSE F O R FALLING A B R A S I V E
various types of end-use performance. In addition, the jet
METHODS
abrader offers greater speed and precision of measurement
[1]. Even today, with other tests also available, these tests are
Falling Abrasive Test
still important and widely used. However, more recent com-
parative testing (see COMPARISON OF WEAR ABRASION This widely used abrasion test method has both ASTM and
TESTERS) indicates ASTM D 658 is superior to ASTM D 968 federal counterparts. Originally developed at Gardner Labo-
and that ASTM Test Method for Abrasion Resistance of Or- ratory [5], the method has been studied and further devel-
ganic Coatings by the Taber Abraser (ASTM D 4060) is supe- oped by others [6]. ASTM D 968 employs an apparatus, Fig.
rior to both of these tests as regards precision and sensitivity 1, that is simple and inexpensive compared with other more
in differentiating between coatings. complicated instruments, and the test results correlate rea-
sonably welt with various types of service [4]. However, the
method is laborious and time consuming since large quan-
M E C H A N I S M OF A B R A S I O N tities of abrasive must be handled due to the slow rate of
abrasion, particularly when the material under test is abra-
The success of the particle impingement types of abrasion sion resistant.
testers in correlating with service performance is perhaps not Over the years a variety of abrasives have been used in the
surprising when one considers the abrading mechanism. basic apparatus. These abrasives include sand, emery, and
Whether or not a particular type of abrasion test correlates various grades of silicon carbide (Carborundum). Sand, al-
with end-use performance depends not only on a similarity of though having the disadvantage of a slow abrasion rate, is
abrading mechanisms in both cases, but also on the extent to readily available and has given reproducible results at low
which that mechanism is maintained during the course of the cost. Therefore, it has been the abrasive of choice in the
abrasion test. It is on the latter factor that many methods fail. standard methods. Only sand and silicon carbide are used in
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CHAPTER 4 5 - - A B R A S I O N R E S I S T A N C E 527
Gloss Reduction Test

Some methods of gloss reduction utilize the impingement
of a definite quantity of abrasive coupled with measurement
of gloss. A modified version of ASTM D 986 was used by
Sward [5] to measure the effect of abrasion on paints, var-
nishes, and lacquers. A large guide tube of 2.5-in. (6.35 cm)
diameter was used to make an abraded area large enough for
gloss determinations. Ottawa sand of 20 to 30 mesh was used
as the abrasive. To distribute the sand uniformly throughout
the cross section of the guide tube, a wire spider web was
inserted just below the outlet tube in the stream of falling
sand.
A B R A S I V E BLAST M E T H O D S
Air Blast Abrasive (Bell Laboratory Abrasiometer)

ASTM D 658 employs a particular size of silicon carbide
abrasive that passes from a hopper through a guide tube and
impinges onto the specimen. The abrasive flow is facilitated
with an air blast [7]. The abrasion rate is markedly greater
than that obtainable with a free-falling abrasive as is used in
ASTM D 968. This device, which was originally known as the
Bell Laboratory abrasiometer, was adopted for use in ASTM
D 658 after the good results obtained in the round robin test
described under CORRELATION WITH END-USE PER-
FORMANCE. The test requires rather cumbersome test
equipment and the need to replace the abrasive after it has
been used five times. In addition, the abrasive must be sieved
after each use to remove any large particles of coating that
may have chipped off during the test. This testing device is
not commercially available; however, details for its construc-
tion are available at ASTM Headquarters in Philadelphia.
A view of that part of the abrasive blast device which con-
tains the abrasive guide tube, nozzle, and specimen stage is
FIG. 1-Falling sand
abraser (courtesy of presented in Fig. 2. The controlled air that enters the nozzle
Paul N. Gardner Co.). has passed through an array of regulating devices: filters,
pressure reduction valve, mercury pressure leg, air equalizing
chamber, flow meter, and manometer. When it is adjusted to
ASTM D 968, which specifies that a natural silica sand graded a standard air pressure, air flow, and abrasive flow, the device
to a particular sieve size and known as Ottawa sand is the is capable of good precision.
standard sand abrasive and a silicon carbide of particular The specimen is mounted at a 45 ~ angle to the nozzle,
sieve size is the other standard abrasive. Abrasion resistance which is lowered to touch the test surface. Then the air flow is
is expressed in terms of the volume of abrasive required to adjusted to the specified pressure, and the stream of abrasive
wear through a unit thickness of the coating with the abrasive is released and allowed to flow until the coating is worn
falling from a specified height through a guide tube. The through to the substrate. The end point is considered to be
substrate is supported at a 45 ~ angle to the vertical. reached when a worn spot about 2 mm in diameter appears
in the center of the wear pattern. The abrasion resistance
(abrasion coefficient) is calculated as the weight in grams of
Pebble Abrasion Wear Test abrasive required per rail of coating.
A device similar to the Bell Laboratory abrasiometer was
This test method was originally developed as an adhesion designed by Koch at Hercules [8]. The main difference be-
test for floor finishes, but it is more properly classified as an tween the two devices is in nozzle design.
abrasion test. The coatings to be investigated are applied to
the walls of a hexagonal iron box; 6 lb (2.72 kg) of flint peb-
Roberts Jet Abrader
bles are placed in the box, and then the box is rotated so that
the pebbles strike the coatings. A rotational speed of 38 rpm With this abrader, which is pictured in Fig. 3 and available
applied for 2 h (1 h in each direction) is sufficient to differen- from Kamaras Instruments, Garrett Park, MD, abrasion re-
tiate most floor coatings. The apparatus for this test is not sistance is evaluated in terms of the time required for a
commercially available. closely controlled jet of fine abrasive to penetrate through the
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coating to the substrate. The first disclosure of bare substrate

is taken as the end point, and it is visually signalled by an
abrupt change in gloss or color. The high speed of the abra-
sive jet particles used in this test results in a rapid abrasion
rate that permits most coatings to be tested in a matter of
seconds.
The jet abrader method avoids the adverse heating, gum-
ming, and abradant-clogging effects associated with the rub-
bing and friction methods. The small scale of operation per-
mits the economical use of continuously fresh abrasive, and it
allows a large number of tests to be made on a single 15.2 by
7.6-cm specimen. This method makes practical the use of a
reference panel for instrument calibration and affords the
opportunity for interlaboratory standardization of instru-
ments and results.
A prototype jet abrader was developed at the National Bu-
reau of Standards (NIST) [9,10]. The abrading conditions are
set from outside the test chamber, and the abrasive flow is
controlled by adjusting the voltage to the vibrator on which
the abrasive storage chamber is mounted. The amplitude of
vibration determines the amount of abrasive that sifts into
the gas (carbon dioxide) stream.
Abrasion resistance is usually expressed in terms of time
per unit thickness (seconds/milL but coatings of the same
thickness may be compared on the basis of total abrasion
time. Abrasion time is proportional to coatings thickness up
to about 6 mils. At greater thickness, the abrasion rate begins
to decrease due to hindrance of abrasive particles in the
abraded pit. Very thick coatings on the order of 100 mils may
be evaluated as small specimens on which weight loss for a
FIG. 2-Abrasion test apparatus (ASTM D 658).
given abrading time is determined. This test procedure is
detailed in Method 6193 of Federal Test Method Standard
No. 141C. Any panel of uniform coating thickness can serve
as a reference panel if it has a convenient abrasion time. A
suitable reference panel can be made by bonding plastic film
of uniform thickness to a rigid substrate by means of a very
thin coat of adhesive.
Gravel Projecting Machine

This machine, which is commonly termed a gravelometer,
is a device designed to evaluate the resistance of automotive
and railway finishes to abrasion by flying gravel and road
ballast. ASTM Test Method for Chip Resistance of Coatings
(ASTM D 3170) has a description of such a device and pro-
vides a procedure for its use. Figure 4 illustrates the interior
components of a device that meets specification given in
ASTM D 3170. A test chamber is provided in which a coated
panel is supported vertically and blasted with a stream of
particular gravel. One pint of this gravel is introduced into an
air stream having a pressure of 70 _+ 2 psi (4.92 +_
0.14 kg/cm 2) over a 10-s period. Tests are usually conducted
in a cold room to simulate winter-like driving conditions. At
the completion of the test, the coated panel is visually rated
for degree of chipping by using a photographic reference
standard provided with D 3170. SAE Method J400 describes
FIG. 3-Roberts Jet abrader (courtesy of Kameras Instru- the test procedure used for evaluating the chip resistance of
ments), automotive coatings.
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CHAPTER 45--ABRASION ~ S I S T A N C E 529
VIBRATING a n d cools it. The a m o u n t of film m a t e r i a l lost during a test is a

GRAVEL m e a s u r e of a b r a s i o n resistance. It is expressed as a "wear
HOPPER ,~. factor" that is the p r o d u c t of the r a d i u s of film r e m a i n i n g on
PLEXIG SS DOOR ,<, /DOOR',,, \
the disk a n d the n u m b e r of revolutions in thousands.
AIR VALVE . ,n
CON'rROL,,a7/,.,,, Z Ii RUB 'ER I1
PANEL E~ ~ t~ LINING I! Wolf Abrasion Method
AIR PRESSURE-- ~ ~ _ - - - - ' ~ HI This early m e t h o d [12] was the f o r e r u n n e r of other m o r e
REGULATOR ~ - ~ (r e l a b o r a t e i n s t r u m e n t s such as the C a m p a n d the T a b e r de-
vices. A leather disk on the end of a rod is moved in a circular
,,,-.--= u .~ m a n n e r on the film being tested. The a b r a s i o n factor is given
as the loss in g r a m s per 100 cm 2 of surface,
,cc ssooo.,
~
FIG. 4-Interior of a gravelometer (courtesy of the Q-Panel
FILTER
Camp Abrasion Tester
F o r this test, the coating is applied to a 10.2 by 10.2-crn
metal panel, a n d the panel is fastened to a h o r i z o n t a l turn-
Company), table that rotates at a speed of 30 r p m b e n e a t h a weighted,
circular, rubber, ink eraser ( E b e r h a r d - F a b e r No. 1071) t h a t
acts as the a b r a d e r [13]. The eraser a b r a d e r is a t t a c h e d to a
METHODS USING ROTATING DISKS side a r m on a lever at an offset angle that causes a 0.64-era-
wide p a t h to be w o r n in the film. A c o u n t e r records the
Bell Laboratory Rotating Disk Abrasion Test n u m b e r of revolutions r e q u i r e d to wear t h r o u g h the film. The
In this method, a circular panel coated with the finish is m a c h i n e is m a d e a u t o m a t i c by placing a c o p p e r trailer be-
r o t a t e d while s u b m e r g e d [11] in a b e d of sand. The a p p a r a t u s h i n d the a b r a d i n g disk. This trailer activates a circuit-break-
ing relay w h e n it contacts the metal panel exposed by w e a r i n g
is illustrated in Fig. 5. A t u r n t a b l e to w h i c h the 4-in.
a w a y of the film. Tests can be checked within 500 revolutions
(I 0.2 c m ) - d i a m e t e r s p e c i m e n is m o u n t e d is c o n t a i n e d within
in a total of 5000 to 8000 revolutions. Most coatings fail
the hopper. Ottawa s a n d of 20 to 30 m e s h is a d d e d to the
within the range of 2000 to 46 000 revolutions. The e r a s e r
h o p p e r until the s p e c i m e n is covered to a d e p t h of 5 in.
a b r a d i n g disks are c h a n g e d after each 5000 revolutions.
(12.7 cm). The disk is t h e n rotated at speeds of 750 to
1000 r p m for several t h o u s a n d revolutions as specified. Dur-
ing the test, the sand is circulated t h r o u g h a device that cleans FDC Wear Test
This test was devised to d e t e r m i n e the resistance of cellu-
lose nitrate furniture lacquers to a b r a s i o n [14]. It m e a s u r e s
the loss of weight w h e n the lacquer film is a b r a d e d by nylon
fabric. The m a c h i n e used, which is s h o w n in Fig. 6, is the
modified c a r p e t a b r a s i o n m a c h i n e of the Wool Industries
Research Association of England. A 10.2 by 10.2-cm lac-
quered glass panel is a t t a c h e d to the plate carrier, with lac-
quered side down. During the test, it rotates at 37 r p m while
in contact with the nylon-covered a b r a d i n g head, w h i c h is
also rotating at the s a m e speed and in the s a m e direction.
However, the centers of the plate and the h e a d are offset,
which results in u n i f o r m a b r a s i o n of the film. After a speci-
fied n u m b e r of revolutions a n d conditioning, the weight loss
is d e t e r m i n e d a n d is taken as the a b r a s i o n resistance of the
specimen.
Schiefer Abrasion Testing Machine

(This m a c h i n e is available from F r a z i e r Precision Instru-
m e n t s Co., Inc., 925 Sweeney Dr., Hagerstown, MD 21940.)
The m a c h i n e was designed for m e a s u r i n g w e a r resistance of
textiles such as rugs a n d fabrics [15-18], b u t it offers a
FIG. 5-Bell Laboratory rotating potentially useful m e a n s for evaluating the w e a r a b r a s i o n of
disk abrasion tester. Specimen ro- organic coatings. It has two unique features: (a) a u n i f o r m
tates while buried in sand. (Cour- a b r a s i o n p a t t e r n a n d (b) i n t e r c h a n g e a b l e steel a n d Carboloy
tesy of Bell Telephone Laborato- a b r a d e n t disks with crosscut a n d rod p a t t e r n s that r e d u c e
ries.) heating a n d clogging (Fig. 7).
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/VEiGHT To conduct a wear abrasion test, the specimen is mounted

on a motor-driven rotating plate where it is abraded uni-
formly in all directions by the motion of the offset rotating
abradent mounted directly above it. Both specimen and
abradent rotate in the same direction with approximately the
Hs FOR I.IIPTINQ same angular velocity, 250 rpm, each about its own axis. The
pLATE CAAi~Ls
axes are spaced I in. (2.54 cm) apart and are parallel. The
abradent is loaded with a standard weight.
PLATE
R.s COUN'I's
Hr METHODS USING ROTATING WHEELS
Taber Abraser
This apparatus, Fig. 8, is widely used for evaluating the
wear abrasion resistance of organic coatings. A procedure for
its use is given in ASTM Test Method for Abrasion Resistance
of Organic Coatings by the Taber Abraser (ASTM D 4060), in
Method 6192 of Federal Test Method Standard No. 141 C, and
in ISO/DIN Methods 3494 and 4584. ASTM D 4060 utilizes a
specimen in the form of a 4-in. (10.2-cm)-diameter disk or a
4-in. (10.2-cm) square mounted on a turntable that is rotated
FIG. 6-FDC wear tester. Nylon fab- at a fixed speed under a weighted abrading wheel. "Calibrase"
ric on rotating head is used to abrade
resilient abrading wheels are designated CS-10 and CS-17
furniture lacquer rotating on offset
axis (courtesy of Furniture Develop- with the latter being the most abrasive. Because of the slow
ment Council, England). hardening of the rubber bonding materials in this type wheel,
a wheel should not be used if it has aged longer than one year.
Before each test and after every 500 cycles (revolutions), the
abrading wheel is resurfaced with an abrasive disk that is
placed on the turntable. A vacuum pickup is used to remove
any loose particles generated during actual tests. Wear abra-
sion resistance is expressed in terms of (a) Wear Index, which
is the weight loss per specified number of revolutions (usually
1000) under a specified load (500 or 1000 g), and/or (b) wear
cycles per mil, which is the number of cycles required to wear
through a 1-mil thickness of coating and is reported as the
number of revolutions per mil. In an ASTM round robin,
Taber abraser tests with a series of organic coatings produced
abrasion resistance values that exhibited a within-laboratory
coefficient of variation of 10% and an interlaboratory coeffi-
FIG. 7-Schiefer abrasion testing machine (courtesy of FIG. 8-Taber Abraser (courtesy of Taber Indus-
Frazier Precision Instrument Company). tries).
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CHAPTER 45--ABRASION RESISTANCE 531
cient of variation of 30%. Another study of the reliability of abrasion. Weights ranging from 55 to 275 g are applied to the
test results was conducted by Hill and Nick in 1966 [19]. tape depending on the nature of the coating under test. Abra-
sion resistance is reported either as the number of cycles
required to produce the onset of visible scuffing or as the
T E S T S B A S E D ON R E C T I L I N E A R M O T I O N number of cycles required to wear through to the substrate.
Straight-Line Reciprocating Machines

C O M P A R I S O N OF W E A R A B R A S I O N
These machines, as shown in Fig. 9, pull a sled or boat back TESTERS
and forth over the surface of a coated panel. The sled surface
can be a brush, a sponge, rubber, or sandpaper. A sled travel ASTM Subcommittee D-01.23 conducted a round robin to
of at least 10 in. (25.4 cm) is provided by the machines, and determine the comparative precision, sensitivity, and corre-
they can provide reciprocating cycles ranging from 35 to 60 lation of four wear abrasion testing procedures, The proce-
per minute. dures were (a) air blast silicon carbide (ASTM D 658), (b)
Both dry and wet surface tests may be performed with falling sand (ASTM D 968), (c) falling silicon carbide (ASTM
these machines. For dry surface tests, wear abrasion resist- D 968), and (d) Taber Abraser (ASTM D 4060). The wear
ance is reported as: (a) number of cycles to reach a certain abrasion resistance of four coatings with significantly differ-
visual end point, (b) degree of abrasion observed after a ent apparent resistances to abrasion were tested with each
specified number of cycles, and (c) number of cycles required device. The results obtained from these tests are recorded in
to abrade through the coating to the substrate. ASTM Report RR D01-1037, which is available at ASTM
Procedures for conducting wet adhesion (scrub resistance) Headquarters.
tests on interior paints are described in ASTM Test Method From the results, it was concluded that the air blast silicon
for Wet Abrasion Resistance of Interior Paints (ASTM carbide test and the cycles per rail Taber abraser test had
D 4213) and in Method 6141 of Federal Test Method Stan- better sensitivity in differentiating coating abrasion resist-
dard 141C. In these test procedures, coating films are applied ances than the other test procedures. The falling sand test, air
to a plastic substrate and allowed to dry. A sponge surface is blast silicon carbide test, and Taber abraser cycles per rail
mounted on the sled. Both the sled and the coating surface test ranked the coatings in the same order as the expected
are wet with a soap solution of specified composition. Wet performance. The falling silicon carbide test reversed the
abrasion resistance is reported as: (a) computed rate of ero- ranking of two of the coatings. The precision exhibited by the
sion of the wet coating film and (b) number of cycles required four test procedures are as given in Table 1.
to wear through the coating film to the substrate or to pro-
duce breaks in the film.
T E S T F O R MAR A B R A S I O N R E S I S T A N C E
RCA Tape Tester (See also above-described Gloss Reduction test.)
This device is available from Norman Tool and Stamping
Co., 15415 Old State Rd., Evansville, IN 47711. It is being Balanced Beam Tester
actively used for evaluating the abrasion resistance of appli-
ance finishes and of coatings on television set controls. It is A useful test for determination of mar resistance involves
reported to have greater sensitivity than the Taber Abraser in the use of a balanced beam scrape tester. ASTM Committee
determining differences in the abrasion resistance of coat- D-01.23 has developed a proposed test procedure using such
ings. The machine abrades a 2 by 2-in. (5.1 by 5.1 cm) coated a tester, which consists of a balanced beam equipped with a
panel surface by passing computer or polyester tape over the loop stylus attached to the end of a rod set at an angle of 45 ~
surface. A fresh tape surface is presented for each cycle of The test is carried out by placing a coated test panel on a
movable platform and a weight on the beam. The stylus is
lowered gently onto the coated surface, and then the platform
is pushed against the stylus at a rate of J/4-in. (6 ram) per
second for a distance of at least 3 in. (75 mm). At the end of
each stroke the stylus is raised off the coated panel and the
TABLE l--Comparison of abrasion resistance test method

precision.
Coefficients of Variation
Within Between
Laboratory Laboratories
Taber Abraser (ASTM D 4060) 4% 16%
Air Blast Silicon Carbide 7% 10%
(ASTM D 658)
FIG. 9-Reciprocating abrasion tester. WA-2168 Model Failing Sand (ASTM D 968) 9% 35%
D12VF! machine with cut-out base, recorder, and several test Falling Silicon Carbide 11% 45%
accessories in foreground. (Courtesy of Paul N. Gardner Co.) (ASTM D 968)
www.iran-mavad.com

panel is moved slightly to the side to provide a new test RAIN OR WATER EROSION
surface. The coating is examined for marring. If none is
visually observed in the initial scrape, successively greater Rain erosion resistance of aircraft coatings has been stud-
weights are added to the beam until marring is apparent. If ied in two types of testing machines [20]--whirling arm and
marring is produced in the initial scrape, testing is continued jet. In the whirling arm tester, specimens having an airfoil
using successively lighter weights until the coating is not contour are fastened to the leading edges of the two arms of a
marred. The weight required to just produce visible marring propeller-like blade that is rotated at angular velocities equiv-
is taken as the mar resistance value. Details about the bal- alent to flying speeds of up to 700 mph. Simultaneously drops
anced beam tester and its operation can be found in ASTM of water fall on the whirling arms. Both the simulated air
D 2197, Test Methods for Adhesion of Organic Coatings by speed and the quantity of "rainfall" can be varied and closely
Scrape Adhesion, ASTM D 2248, Practice for Detergent Re- controlled. In the jet-type tester, a high-pressure jet of water
sistance of Organic Finishes, and MIL-P-7788A. impinges on the specimen. A rotating slotted disk in the path
of the water jet breaks the stream of water into individual
drops to simulate rainfall.
P r i n c e t o n Scratch Tester In both of the above methods, having the water in the form
of individual drops is a basic principle of the test. This is
This apparatus is similar to the balanced beam tester, but
because the erosion that occurs on the leading edges of the
instead of having a moveable specimen table, the beam as-
airfoils on high-speed aircraft flying through rain is often the
sembly itself moves on a V-shaped track with the coated panel
result of cavitation produced by the high-energy impacts of a
remaining immobile. The stylus is held at a 90 ~ angle.
multitude of individual droplets. At very high velocities, the
water droplets, in effect, behave as tiny solid projectiles.
I m p i n g i n g Abrasive M e t h o d
An impinging abrasive method is described in ASTM Test
Method for Mar Resistance of Plastics (ASTM D 673) and in TRAFFIC PAINT TESTS
Method 1093 of Federal Test Method Standard No. 406. Al-
though this test was designed for determining the mar resist- The Dorry tester uses a crushed quartz abrasive that is fed
ance of plastics, it has a potential for determining this prop- onto a grinding plate against which the coating, face down on
erty of organic coatings. its paper base and weighted with 100 g of sand, is abraded.
The test consists of allowing a stream of silicon carbide to The Hickson tester is a heavy duty, permanently mounted
fall on the specimen and then determining the degree of machine in which a motor-driven solid rubber tire is rotated
marring by gloss measurements. The apparatus consists of a against a braked rotating concrete disk on which the test
hopper that dispenses the abrasive through small openings as paint has been applied. The test correlates quite well with the
it rotates at 7 rpm. Abrasive flow is about 225 g per minute. service performance of traffic paints.
The New Jersey Zinc Company (presently Zinc Corporation
of America) tester is a portable machine in which a pair of
Taber Abraser Mar Test rubber-tired wheels revolve in a layer of sand on the test
The Taber Abraser can be used to evaluate the mar resist- platform.
ance of organic coatings. A mild abrading is produced by Another tester, the abradometer, is a large machine that
using wheels covered with paper. Mar resistance is reported utilizes a motor-driven wheel set at a slight shear angle to a
as the number of cycles of rotation required to just produce a large wheel on the rim of which up to 46 specimens are
barely visible scuffing or loss of gloss. mounted. A brake load is applied during the test.
In the Payne abrasion machine, five specimens at a time
oscillate through a 25-mm distance while being abraded with
Coin Mar Test an abrasive wheel.
This test consists of dragging the edge of a coin across the
surface of a coated panel and visually determining the degree
of marring produced. The procedure can be used as a "pass/
MISCELLANEOUS METHODS
fail" test or for comparing the mar resistance of coatings on a
relative basis. Results will vary from laboratory to laboratory
Brief mention is made to several less-well known tests that
due to the particular coin used and the pressure used for
may be of interest. In The Sproul-Evans apparatus [21] the
contact. specimen is rotated in a cylinder containing silicon carbide
powder. A procedure by Wellinger [22] involves using a rod
coated with the test paint and rotated in a container of sand.
Fingernail Test
A sensitive method for measuring the tread wear of automo-
In this test, the back of a fingernail is dragged across the bile tires involving the use of a nonhazardous radioisotope of
surface of a coating and the degree of marring is visually iodine was developed by Outbridge [23]. Conceivably, this
observed. The procedure can be used as a "pass/fail" test or technique could be used to evaluate the abrasion resistance of
for comparing the mar resistance of coatings on a relative coatings. Marks and Conrad [24] developed an abrasion com-
basis. parator apparatus that utilizes high-velocity emery particles
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CHAPTER 45--ABRASION RESISTANCE 533
REFERENCES
[1] Roberts, A. G., Chap. 5.2, "Abrasion Resistance," Paint Testing

Manual, ASTM STP 500, 1972.
[2] Harper, F. C., "The Abrasion Resistance of Flooring Materials: A
Review of Methods of Testing," Wear, WEARA, Vol. 4, 1961, pp.
461-478.
[3] International Study Committee for Wear Tests of Flooring Per-
formance, "Performance of Abrasion Machines for Hoofing Ma-
terials," Wear, WEARA, Vol. 4, 1961, pp. 479-494.
[4] Interim Report, "Abrasion Resistance of Floor Coatings," Group
20 Subcommittee IX on Varnish, ASTM Committee D-l, 1956.
[5] Sward, G. G., "Improved Abrasion Apparatus," Scientific Section
Circular, National Paint, Varnish, and Lacquer Association, No.
581, June 1939.
[6] Hipkins, C. C. and Phair, R. J., "The Falling Sand Abrasion Tes-
ter," ASTM Bulletin, No. 143, December 1946, pp. 18-22.
[7] Arh, H. G., "Paint Films of Controlled Thickness," Bell Laborato-
ries Record, Vol. 14, No. 7, 1936, pp. 216-217.
[8] Koch, W., "Development of an Abrasion Test for Use with Nitro-
cellulose Lacquers," Industrial and Engineering Chemistry,
Analytical Edition, Vol. 2, 1930, p. 407.
[9] Roberts, A. G., Crouse, W. A., and Pizer, R. S., "Abrasion Jet
FIG. IO-PEI abrasion tester. Specimen in chamber on gy- Method for Measuring Abrasion Resistance of Organic Coat-
rating table is abraded by glass or stainless steel sphere in a ings," ASTM Bulletin, No. 208, September 1955, pp. 36-41.
slurry of abrasive particles. (Courtesy of National Bureau of [10] Roberts, A. G., "Improved NBS Abrasion Jet Method for Mea-
Standards.)
suring Abrasion Resistance of Coatings," ASTM Bulletin, No.
294, February 1960, pp. 48-51.
[11 ] Burns, R., "A Wear Test for Finishes," Bell Laboratories Record,
propelled by high-pressure air to evaluate the resistance of Vol. 9, No. 9, 1931, pp. 426-429.
p l a s t i c s - - p a r t i c u l a r l y aircraft g l a z i n g - - t o abrasive particles. [12] Wolf, H., "The Testing of Varnishes, II. Testing of Resistance to
Haze due to abrasion is m e a s u r e d with aid of a light integrat- Abrasion," Farben Zeitung, Vol. 26, 1921, p. 3111.
[13] Camp, A. D., "Chipping and Abrasion Tests for Paint Coatings
ing sphere.
on Metal," Industrial and Engineering Chemistry, Vol. 20, 1928,
Although the PEI abrasion tester was designed a n d devel- pp. 851-852.
oped by the Porcelain E n a m e l Institute to m e a s u r e the abra- [14] Furniture Development Council, London, "A Wear Test for Ni-
sion resistance of porcelain enamels, this tester has also trocellulose Lacquers," Research Note A12, November 1937.
proven to be useful in d e t e r m i n i n g the wet a b r a s i o n resist- [15] Schiefer, H. F., Journal of Research, National Bureau of Stan-
ance of organic coatings. It is specified to be used i n ASTM dards, Vol. 39, RR 1807, 1949, p. 1.
C 448, Test Methods for Abrasion Resistance of Porcelain [16] Schiefer, H. F., Crean, L. E., and Krasny, F. F., "Improved Sin-
gle-Unit Schiefer Abrasion Testing Machine," Journal of
Enamels. The tester, which is pictured in Fig. 10, has a
Research, National Bureau of Standards, Vol. 42, RR 1988, 1949,
gyrating table with positions for n i n e specimens. Abrasive- pp. 481-497.
retaining rings a n d lids are clamped over the specimen to [17] Schiefer, H. F. and Werntz, C. W., Textile Research Journal, Vol.
form individual test chambers. Each c h a m b e r is charged 22, 1952, pp. 1-12.
with glass or stainless steel spheres, a n d a slurry of abrasive [18] ASTM D 4158, Test Method for Abrasion Resistance of Textile
particles is added through a filling aperture located in the lid. Fabrics (Uniform Abrasion Method).
[19] Hill, H. E. and Nick, D. P., "Study of the Reliability of Tuber
The table gyrates at 300 cycles per m i n u t e to cause abrasion
Abrasion Results," Journal Paint Technology, Vol. 38, No. 494,
of the specimens. The a m o u n t of a b r a s i o n is evaluated by March 1966, pp. 123-130.
m e a s u r i n g the loss of gloss or loss of weight in the specimens [20] Grace, J. K. and Frey, G. C., "Laboratory Testing of the Rain-
after a specified time period. Erosion Resistance of Aircraft Finishes," ASTM Bulletin, No.
The Peters abrasion block is based o n a block that has a 168, September 1950, pp. 56-61.
weight of 2 kg and a size a n d c o n t o u r suited to h a n d opera- [21] Evans, W. W., "An Apparatus and Method for Determination of
tion. Three 50 by 80-ram abrasive surfaces are provided. Each Resistance to Abrasion of Rubber Products," Proceedings ASTM,
Vol. 23, Part II, 1923, pp. 517-523.
has a r u b b e r base over which a l u m i n u m oxide abrasive paper
[22] Welinger, K. and Uetz, H., "Abrasion Wear Research on Rub-
is stretched. The block is d r a w n back a n d forth from edge to ber," Rubber Chemistry and Technology, Vol. 34, 1961, pp.
edge across the test surface while water is applied. This is 482-492.
c o n t i n u e d until the coating begins to show wear t h r o u g h to [23] Outbridge, R., Proceedings of Rubber Technology Conference,
the substrate. The n u m b e r of back a n d forth cycles to reach 4th, London, 1962, Preprint No. 21.
[24] Marks, M. E. and Conrad, P., "Resistance of Plastics to Abrasive
this end p o i n t is taken as a m e a s u r e of abrasion resistance.
Particles," Modern Plastics, Vol. 23, March 1946, pp. 165-168.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Dynamic Mechanical and 46

Tensile Properties
by Loren W. Hill I
DYNAMICMECHANICALAND TENSILE PROPERTIES are d e t e r m i n e d a p p l i c a t i o n of force, called "uniaxial extension." In a s h e a r

in all b r a n c h e s of m a t e r i a l s science. There is a large b o d y of test (Fig. 1B), one face of the cube is held s t a t i o n a r y a n d the
p u b l i s h e d s t r u c t u r e / p r o p e r t y i n f o r m a t i o n that can be inte- s a m p l e is p u s h e d sideways by a p p l i c a t i o n of force at the
g r a t e d with coatings r e s e a r c h a n d development. By using opposite face. Note that different symbols (e epsilon o r 3~
s t r u c t u r e / p r o p e r t y information, coatings chemists can design g a m m a ) are used for strain in these two tests. A single s y m b o l
a n d o p t i m i z e c h e m i c a l structures of the b i n d e r c o m p o n e n t s is used for stress (or sigma), b u t subscripts indicate the type of
of coatings. Purposeful a n d enlightened f o r m u l a t i o n with test. In Fig. 1, F is force a n d A, B, a n d C are initial s a m p l e
well-designed c o m p o n e n t s m a k e s it possible to o b t a i n desir- dimensions. The p r o d u c t A B is the initial cross-sectional
able coatings p e r f o r m a n c e in m a n y cases. area.
D e t e r m i n a t i o n of d y n a m i c m e c h a n i c a l a n d tensile p r o p e r - It is evident in Fig. 1 that strain is defined quite differently
ties requires the use of free films. This r e q u i r e m e n t is a in tension a n d shear tests. In a tension test, strain is the
serious l i m i t a t i o n b e c a u s e many, if not most, of the perform- fractional increase in s a m p l e length. In a shear test, strain is
ance p r o p e r t i e s of coatings are influenced by coating-sub- the distance m o v e d by the movable face divided b y s a m p l e
strate interactions. Therefore, tests of coatings intact on their thickness, i.e., the distance between the s t a t i o n a r y a n d mova-
end-use substrates m u s t be thoughtfully coupled with free ble faces. In b o t h tests, stress is force divided by cross-sec-
film d e t e r m i n a t i o n s . The practical utility of basic m e t h o d s tional area, a n d m o d u l u s is stress divided by strain. Since
d e s c r i b e d in this section is greatly e n h a n c e d w h e n results are strain is unitless, stress a n d m o d u l u s have the s a m e units
i n t e r p r e t e d in relation to results of adhesion, abrasion, hard- (force/area). It is evident in Fig. 1A that cross-sectional a r e a
ness, flexibility, toughness, a n d internal stress tests as de- will decrease as AC increases. If the initial cross-sectional
scribed elsewhere in the m a n u a l . a r e a is used to calculate or,, the resulting E is called "engineer-
D y n a m i c m e c h a n i c a l analysis (DMA) a n d stress-strain ing" modulus. If the change in cross-sectional a r e a is incorpo-
analysis (SSA) of tensile p r o p e r t i e s are c o m p l e m e n t a r y meth- r a t e d in the calculation, the resulting E is called "true" m o d u -
ods in several ways. DMA involves very small strains, w h e r e a s lus.
SSA involves the m a x i m u m strain that the s a m p l e can with- The r e l a t i o n s h i p between tensile m o d u l u s a n d s h e a r m o d u -
stand. Since the small strains used in DMA usually do not lus is
exceed the tensile strength or yield strength of the sample, the
E = 2 (1 + v,)G (1)
m e t h o d is nondestructive. This feature facilitates p r o p e r t y
d e t e r m i n a t i o n over a wide t e m p e r a t u r e range on a single w h e r e /, is Poisson's ratio [1,2]. F o r m a t e r i a l s that do n o t
sample, that is, DMA is often used as a t e m p e r a t u r e - s c a n n i n g u n d e r g o change in volume with strain, /, = 0.5, a n d Eq 1
method. In contrast, SSA d a t a are usually o b t a i n e d at a single b e c o m e s E = 3G. Experimentally, /, is very close to 0.5 for
t e m p e r a t u r e , preferably on an i n s t r u m e n t located in a con- r u b b e r y m a t e r i a l s a n d slightly less t h a n 0.5 for m a n y t h e r m o -
trolled t e m p e r a t u r e a n d h u m i d i t y room. Since the s a m p l e is plastic p o l y m e r s [1,2].
b r o k e n in each test, it is very a r d u o u s to c a r r y out SSA over a
wide t e m p e r a t u r e range, a n d SSA is not a m e n a b l e to t e m p e r -
a t u r e scanning. Definitions of Dynamic Properties
In d y n a m i c testing, an oscillating strain is applied, a n d the
DEFINITIONS resulting oscillating stress is measured, or conversely an
oscillating stress is applied, a n d the resulting oscillating
Tensile Versus Shear Tests strain is measured. Definitions a n d m a t h e m a t i c a l t r e a t m e n t s
do n o t d e p e n d on w h i c h of these m o d e s of o p e r a t i o n is used.
Two types of d e f o r m a t i o n of a b l o c k - s h a p e d s a m p l e are Relationships b e t w e e n strain, stress, a n d time are sketched in
depicted in Fig. 1. These d e f o r m a t i o n s are used frequently in Fig. 2 for tensile DMA with a p p l i c a t i o n of strain a n d m e a s u r e -
p r o p e r t y d e t e r m i n a t i o n s b e c a u s e they can be carried out re- m e n t of stress. The m a x i m u m a p p l i e d strain is %. The maxi-
p r o d u c i b l y a n d treated b y simple m a t h e m a t i c s . In a tension m u m resulting stress is at.0. Oscillation is d e p i c t e d as a sine
test (Fig. 1A), the s a m p l e is pulled a p a r t with straight line wave, b u t w h e t h e r o r not the driver of the i n s t r u m e n t in use
actually delivers a sine wave oscillation m a y d e p e n d on the
IMonsanto Co., Springfield, MA 01151. p a r t i c u l a r instrument. The s a m p l e is held u n d e r sufficient
534
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CHAPTER 46--DYNAMIC MECHANICAL AND TENSILE PROPERTIES 535
Tc I
e
I
I
I
e
I
i!
I I
I
11 I '
L.. _ I~ S
L A d
q
A. TENSILE B. SHEAR
E = Tensile Strain 7 = Shear Strain
at = Tensile Stress as = Shear Stress
A C AX
E ....... 7 =
C C
F F
(3" t ---- Os =
AxB AxB
E = Tensile Modulus G = Shear Modulus
O"t Gs
E = G =
E 7
FIG. 1-Deformations of test samples: A. tensile, B. shear. The two types of deformation
have different definitions and different symbols for strain, stress, and modulus.
tension so that it r e m a i n s taut (not slack) even w h e n the

Tensile Storage M o d u l u s = E' - ~,,o cos8
oscillating strain is at a m i n i m u m . E0 (2)
The sine waves for strain a n d stress have the s a m e fre-
quency, b u t for viscoelastic s a m p l e s the waves are out of Tensile Loss M o d u l u s -- E" - ~r''~sin8 (3)
p h a s e by an a m o u n t , 8, called the phase lag. Theoretically and EO
experimentally, ~ is zero for an ideal (Hookean) elastic solid.
E pr
If an ideal (Newtonian) liquid could be tested in this way, Loss Tangent = - - = tan8 (4)
w o u l d be 90 ~ F o r viscoelastic materials, 8 lies between 0 a n d E'
90 ~ a n d the value of ~ is a r a t h e r direct i n d i c a t i o n of visco- The t e r m "storage" is associated with the elastic p a r t of the
elastic c h a r a c t e r [1-4]. r e s p o n s e E' b e c a u s e m e c h a n i c a l energy input to elastic mate-
Definitions of d y n a m i c p r o p e r t i e s d e p e n d on the concept of rials is "stored" in the sense of being completely recoverable.
resolving the stress wave of Fig. 2 into two waves, one that is The t e r m "loss" is associated with the viscous part of the
in p h a s e with strain a n d one that is 90 ~ out of phase with response E" b e c a u s e m e c h a n i c a l energy input to ideal liquids
strain. The in-phase resolved plot represents elastic response, is totally lost t h r o u g h viscous heating. The ratio E"/E' is
a n d the 90 ~ out-of-phase resolved plot represents viscous re- viscous response expressed relative to elastic response. This
sponse. In terms of modulus, the s e p a r a t e d responses result ratio reduces to sin6/cosS, which is tan& Thus, the n a m e "loss
in the following definitions tangent" is a p p r o p r i a t e .
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d In the N e w t o n i a n liquid limit (8 = 90~ 4" is zero b y Eq 9, a n d

I I
, i all of the response is viscous, 4' from Eq 8. F u r t h e r m o r e in
' I
this limit, G' is zero by either Eq 9 or Eq 5, a n d the viscous
response could alternatively be expressed in t e r m s of G" from
Eq 6. Thus, in d y n a m i c shear tests, m o d u l u s a n d viscosity
d e t e r m i n a t i o n s are one a n d the s a m e experiment. Usually
Stress (at) e x p e r i m e n t e r s will choose Eqs 5 a n d 6 w h e n the s a m p l e has a
or lot of elastic c h a r a c t e r and only a little viscous character,
Strain (E) w h e r e a s the logical choice for m a i n l y viscous m a t e r i a l s hav-
ing only a little elastic c h a r a c t e r will be Eqs 8 a n d 9. In
principle, it w o u l d be valid to express tensile DMA results in
t e r m s of d y n a m i c viscosities as well. This is not done very
often, p r o b a b l y b e c a u s e viscosity is strongly associated with
T i m e or Angle shearing experiments, not with tensile experiments. The close
FIG. 2-Applied oscillating strain (~) and resulting oscillat- association of viscosity with shear is the basis for o m i t t i n g
ing stress (~rt) in a dynamic mechanical analysis experiment the w o r d "shear" at the left in Eqs 8 a n d 9.
with tensile deformation. The phase lag (6) and maximum The relationships between m o d u l u s values defined in Fig. 1
values of strain (Co) and stress (~rt,o) are indicated. a n d the d y n a m i c m o d u l u s values are [ 1 - 4 ]
E 2 = E '2 + E "2 (11)
A check of limiting values of a is consistent with assign-
G 2 = G '2 + G "2 (12)
m e n t of elastic a n d viscous responses in Eqs 2 and 3. W h e n 8
= 0 ~ cos8 = 1.0 a n d sin8 = 0. By Eq 3, E" is zero a n d all of Use of complex n u m b e r s a n d quantities such as i =
the response is elastic, i.e., E ' from Eq 2. W h e n 8 = 90 ~ cos8 has been avoided here. If r e a d e r s w o u l d like definitions of
= 0 a n d s i n ~ -- 1.0. N o w E ' is zero b y E q 2 and all of the such quantities as the "complex tensile storage modulus," E*,
response is viscous, i.e., E ' from Eq 3. they should consult Refs 1 - 4 . Complex n o t a t i o n m a y be con-
DMA relationships in Eqs 2 a n d 3 relate directly to charac- venient for m a t h e m a t i c a l derivations, b u t complex m o d u l u s
terization of s a m p l e s that are solid or semi-solid. Other objec- values, with their i m a g i n a r y parts, a d d little or nothing to the
tives of DMA include following viscosity a n d elasticity i n t e r p r e t a t i o n of s t r u c t u r e / p r o p e r t y relationships.
changes as the cure of t h e r m o s e t coatings takes place a n d
d e t e r m i n i n g the melt-flow p r o p e r t i e s of p o w d e r coatings be-
fore the onset of cross-linking. W h e n viscous response is the Definitions of Tensile Properties
m a i n interest, DMA is often carried out in shear.
The t e r m "tensile properties" logically refers to all proper-
The t r e a t m e n t for shear DMA is identical, b u t with selec-
ties that can be d e t e r m i n e d in tests that involve tensile defor-
tion of a p p r o p r i a t e s h e a r symbols from Fig. 1, the definitions
m a t i o n as d e p i c t e d in Fig. 1A. C o m m o n tests t h a t involve
arc
tensile d e f o r m a t i o n include stress-strain tests, creep tests,
a n d stress relaxation tests. Stress-strain tests are used m u c h
S h e a r Storage M o d u l u s = G' - as,0 cos8 (5)
m o r e frequently t h a n the others. Therefore, the t e r m s "tensile
To
properties" a n d "stress-stain properties" are often used inter-
S h e a r Loss M o d u l u s = G" - ~176sin8 (6) changeably. Creep a n d stress-relaxation tests are s o m e t i m e s
To referred to as "transient tests" b e c a u s e responses, either elon-
gation or stress, change with t i m e and are d e t e r m i n e d as a
G"
Loss Tangent = - - = tan8 (7) function of t i m e [5].
G' Terminology, definitions, a n d symbols for stress-strain
Once the e x p e r i m e n t e r s have values of o~,o, T0/and 8 in hand, tests have been taken from a n earlier edition of the P a i n t
it is their choice w h e t h e r to express results in t e r m s of m o d u - T e s t i n g M a n u a l [6] a n d from several ASTM standards:
lus values, Eqs 5 a n d 6, or in t e r m s o f " d y n a m i c viscosity." F o r D 2370 Test M e t h o d for Tensile Properties of Organic
d y n a m i c viscosity, the frequency of oscillation, to in r a d i a n s Coatings
p e r second, is required, b u t this frequency is usually known. D 638M Test M e t h o d for Tensile Properties of Plastics
The frequency is required b e c a u s e viscosity is (shear stress)/ (Metric)
(rate of s h e a r strain). In a d y n a m i c s h e a r test, rate of shear D 882 Test M e t h o d for Tensile Properties of Thin Plas-
strain is the p r o d u c t to x T. Definitions of d y n a m i c viscosity tic Sheeting
are D 412 Test Methods for Vulcanized R u b b e r a n d Ther-
m o p l a s t i c R u b b e r s a n d T h e r m o p l a s t i c Elasto-
D y n a m i c Loss Viscosity = 4' - G" _ trs,0 sin8 (8) mers--Tension
to toT0 D 883 T e r m i n o l o g y Relating to Plastics
In a stress-strain test, the s a m p l e is elongated at c o n s t a n t
D y n a m i c Storage Viscosity = 4" - G' _ ors,0cos8 (9)
to toTo rate. The force, also called "load," required to m a i n t a i n con-
stant rate of elongation is determined. Force is converted to
4'
Loss Tangent = - - = t a n a (10) tensile stress (~rt) b y division by the initial cross-sectional a r e a
4" (A X B in Fig. 1A). Results are p r e s e n t e d as a plot of stress (trt)
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C H A P T E R 4 6 - - D Y N A M I C M E C H A N I C A L AND T E N S I L E P R O P E R T I E S 537
on the vertical axis versus strain (either ~ or 100 E = % /llll//f STRESS RELAXATION EXPERIMENT
elongation) on the horizontal axis. A hypothetical example is
shown in Fig. 3 [5, 6]. The tensile modulus (E) is the slope of E I" : RELAXATION TIME
the initial, linear portion of the plot (see Fig. 3). If the initial
CREEP EXPERIMENT
part of the plot is not linear, several calculations for esti-
mating E have been suggested in ASTM D 638M. Use of the 1" = RETARDATION TIME
slope for E amplifies the simple definition of tensile modulus 17
given in Fig. 1A. Other terms used for tensile modulus include
"elastic modulus," "Young's modulus," and "stiffness." d T =
The first point on the plot of Fig. 3 where the slope is zero is E
called the "yield point." Strain at the yield point is called FIG. 4 - A mechanical model consisting of a spring and a
"elongation at yield" (ey). Stress at the yield point is called dashpot permits definition of relaxation time and retardation
"yield strength" (err). Elongation is continued until the sam- time,
ple breaks. Strain at the break point is called "elongation at
break" (eB). Stress at the break point is called "tensile
divided by the modulus of the spring. Tau has units of time.
strength" (%) as shown in Fig. 3. However, in some cases
Results of the creep experiment for the Maxwell model can be
(not shown) the stress is higher at the yield point than it is at
expressed as
the break point. In such cases, ASTM standards specify that
the "tensile strength" be indicated as the higher value of stress ~(o)
E(t) = e(0) + t (13)
and be designated as "tensile strength at yield." Practice is not q-
uniform with regard to this latter "tensile strength" terminol-

ogy. When stress is first applied, the spring extends instanta-
neously by an a m o u n t ~(0). Then retarded further elongation
Results of transient tests have not frequently been pub-
takes place due to flow in the dashpot. It is evident in Eq 13
lished for coatings. Such tests clarify viscoelastic character
that the retarded elongation is linear with time. The value of r
quite directly. Possibly unexpected field failures of coatings
can be obtained from the product (reciprocal of the slope)
could be avoided in some cases if more attention were given
(intercept) [4,5].
to viscoelasticity. Only the most simple form of retardation
In a tensile stress relaxation experiment, the sample is
and relaxation concepts are treated here.
elongated instantaneously by an a m o u n t ~, and thereafter ~ is
In a tensile creep experiment, the sample is subjected to
held constant. Stress is determined as function of time, tr(t).
constant stress, or,, and elongation is determined as a function
Analysis of the dependence of stress on time yields "relaxa-
of time, e(t). Analysis of dependence of elongation on time
tion time," r. For the Maxwell model, T values are the same
yields "retardation time," T (tau). The simplest mechanical
whether from creep or relaxation. For real materials, experi-
model that permits definition of T is the Maxwell model as
mentation is required to determine whether or not retarda-
shown in Fig. 4. This model consists of a series connection of
tion and relaxation values are equal. Results of the stress
an ideal Hookean spring of modulus, E, and a dashpot that
relaxation experiment for the Maxwell model can be ex-
contains an ideal Newtonian liquid of viscosity, r/. As indi-
pressed as
cated in Fig. 4, ~-is the viscosity of the liquid in the dashpot
or(t) = o(0)e t/T (14)
When the instantaneous elongation is applied, the time zero
response is entirely in the spring. Then the dashpot extends
with time relieving stress on the spring. It is evident from Eq
14 that the value of r can be obtained as the time at which
P OB stress has been reduced to 1/e (0.368) of its initial value.
0u Alternatively, one can obtain the value of -r from the negative
(9
U of the reciprocal of the slope of a plot of In a(t) versus t [4,5].
t-
O To represent mechanical response of viscoelastic poly-
meric materials, it is usually necessary to use more elaborate
(/)
(/~ mechanical models and to replace a single value of r by "a
LU spectrum of relaxation times" [1,2].
IZ
I--
O~
PREPARATION OF FREE FILM SAMPLES

.I Methods for preparation and cure of adherent films are
Ey EB
described elsewhere in the manual and in ASTM Test Meth-
STRAIN ods for Producing Films of Uniform Thickness of Paint, Var-
FIG. 3 - A hypothetical stress-strain curve for a ductile nish, and Related Products on Test Panels (D 823-87). Since
film. Tensile properties are defined: tensile modulus (E), dynamic mechanical and tensile property determinations re-
elongation at yield (ey), elongation at break (eB), yield stress quire free films, ASTM Practice for Preparation of Free Films
(~ry), and tensile strength (~rB). of Organic Coatings (D 4708-87), is also very useful. Details
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concerning thickness measurements, which are required for the dogbone tends to control where failure occurs in tension
calculation of cross-sectional area, are given in ASTM Test tests, but for thin samples this narrowing causes the cross-
Method for Measurement of Dry-Film Thickness of Organic sectional area to be too small for many load measuring cells.
Coatings Using Micrometers (D 1005). The dogbone shape also provides more area for clamping
The most widely used method for free film preparation which facilitates the balance between slip-free clamping and
involves application on release substrates, i.e., low surface avoidance of rupture at the clamp.
energy substrates. Four release substrates are described in There is extensive literature on the notch sensitivity of poly-
ASTM D 4708-87. Low surface energy results in poor adhe- meric materials in stress-strain tests [7]. The challenge in
sion so that the coating can be stripped from the release preparation of high Tg coating samples is to avoid undesired
substrate after it is cured. Surface tension differences be- notches, nicks, or cracks along the edges. Small edge cracks,
tween the coating and release substrate must be carefully which are very difficult to detect even with magnification, can
balanced. If the surface tension of the liquid coating is higher cause premature failure in tension tests. Usually samples are
than the critical surface tension of the release substrate, the die cut, and the sharpness and condition of cutting edges of
coating will crawl inward from the edges to give nonuniform the die affect uniformity of sample edges.
thickness. In extreme cases of crawling, the coating will break
up into unconnected puddles.There are many types of release
paper and many surface treating agents to convert glass or
metal panels into low-energy surfaces. It is worthwhile to try
D E T E R M I N A T I O N OF D Y N A M I C
several release surfaces to find the balance which will avoid
PROPERTIES
crawling but will still permit separation. Tendency to crawl
can be reduced by use of high-viscosity formulations. Viscosi-
Description of Dynamic Mechanical Analysis
ties for draw-down application (see ASTM D 823-87) can be
(DMA)
quite high compared to those required for spray application. One of the reasons for rapidly expanding use of DMA for
The second most widely used method for preparation of coatings and other research is the availability of automated
free films involves amalgamation of tin by mercury. ASTM D and computer-controlled instrumentation. Automated in-
4708-87 describes use of 25-1xm-thick dental tin foil. The foil struments and the suppliers of these instruments are listed in
is smoothed onto glass plates before application of the coat- Table 1 [4]. A common feature of all these instruments is
ing. In our laboratory we have used 7.6 by 15.2-cm (3 by 6-in.) oscillatory deformation, an example of which is shown in Fig.
tin-plated steel panels (Type DT panels, Q-Panel Co.) The tin 2. Variable features include: the type of deformation (tensile,
plate on the panels amalgamates much more quickly than shear, or poorly defined), free versus forced oscillation, fre-
that on tin-plated food can stock. After the coating is cured, quency scan versus temperature scan versus either, sensitiv-
the panel is placed in a wide-mouth quart jar containing ity for thin film analysis, capability of transversing the entire
mercury to a depth of only 0.64 to 1.3 cm (1/4 to 1/2 in.). The range of property behavior (glassy to transition to rubbery)
jar is tightly capped during amalgamation. During a period of during a single temperature scan, breadth and rate of temper-
one and one half to two days, mercury creeps up the panel ature scan, breadth and rate of frequency scan or range and
underneath the coating as tin is amalgamated. After the film number of frequency settings, versatility of sample holding
is completely freed from the substrate, it can be lifted off and devices, ruggedness versus flimsiness, amount of attention
wiped to remove mercury. The amalgamation procedure is required once a run has been started, accuracy and versatility
best carried out in a hood reserved for this purpose. The work of the associated software for control during the run and data
surface of the dedicated hood can consist of a metal grid treatment and plotting after the run. In several cases, newer
mounted 1.3-cm (1/2 in.) above a shallow tray that contains models permit determination of properties at several fre-
sulfur. Other safety precautions include careful attention to
panel handling procedures and disposal procedures, frequent
monitoring of air flow velocities, use of protective gloves, and TABLE 1--Automated DMA instruments.
mercury vapor monitoring devices. Danger of exposure to CSL Rheometer--Carri-Med
mercury vapor has resulted in prohibition of amalgamation Dynamic Mechanical Analyzer, DMA 442--Netzsch
methods in some coatings laboratories. Dynamic Mechanical Analyzer, DMA 7--Perkin-Elmer
Dynamic Mechanical Analyzer, DMA 983--TA Instruments
Thickness is an important consideration in preparation of Dynamic Mechanical Rheological Inst., RPA 2000--Monsanto
samples for dynamic mechanical and tensile property tests. Dynamic Mechanical Thermal Analyser--Polymer Labs
Usually tests are more reproducible if samples are thicker Dynastat/Dynalyzer--Dynastatics/Imass
than normal coatings thicknesses. However, film formation Mechanical Spectrometer; RMS 800, RDS II, RDA--Rheometrics
seldom occurs in exactly the same way for thick films as for Rheolab MC 20--Physica
Rheovibron/Autovibron--Imass
thin ones. Several reasons for dependence of cured film prop- Rheovibron DDV-II-C,Automated--Orientec
erties on thickness have been discussed [5]. In our laboratory, Servo-Hydraulic Machine--Instron
films of 1 mil (25 ~m) and up have been analyzed routinely. It Solids Analyzer, RSA II--Rheometrics
has not been possible to analyze or even handle very thin free Torsional Braid Analyzer--Plastics Analysis Instruments
Torsionautomat--Brabender
films such as beverage can coatings which are approximately Viscoanalyser--Indikon/Metravib
3 to 5 /zm thick. VOR Rheometer--Bohlin
Coatings and thin plastic film samples are usually prepared Weissenberg Rheogoniometer--Carri-Med
as rectangular strips, whereas thicker materials are prepared NOTE:In addition, severalthermo-mechanicalanalysisinstruments havean
as dogbone-shaped samples. The narrowing in the middle of option of oscillatoryloading of the TMAprobe.
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CHAPTER 4 6 - - D Y N A M I C MECHANICAL AND TENSILE PROPERTIES 539
quencies during a single temperature scan. Although it is r e c o m m e n d e d SI unit is Pa. The value of E" (25 ~ is 6.86 x 108
necessary to use a rather low temperature scan rate in multi- dynes/cm 2. Inserting E' and E" (25 ~ values into Eq 11 and
ple frequency runs, the a m o u n t of data obtained is remark- solving for tensile modulus, E, we obtain E = 1.382 101~ In
able. Chances of acquiring an instrument that will actually this case E = E' (25 ~ to a very close approximation, and the
function well in the intended experiments are greatly in- contribution of E" (25 ~ to E is negligible. Hard, tough coat-
creased by asking suppliers about these variable features. ings often have tensile modulus values from SSA ranging
The procedure for carrying out a DMA run on an auto- from 1 101~ to 3 10 l~ dynes/cm 2 [5,7,8], in agreement
mated instrument is rather simple, with details depending on with the DMA value. For a quantitative comparison of E from
the particular instrument. Usually the associated software SSA and E from DMA via Eq 11, the strain rate from SSA
includes a "run" p r o g r a m which prompts the operator to would have to be matched with the oscillating frequency
input sample data (e.g., thickness) and settings for the run from DMA.
such as initial and final temperatures, frequency of oscilla- The viscous response is not always negligible relative to
tion, heating rate, etc. After the input steps, there is usually a elastic response, of course. The E" contribution is highest at
cooling period. The instrument takes over when the preset the temperature of the m a x i m u m in tan delta, 79~ in Fig. 5.
initial temperature is reached. Thereafter nothing is required Note that E' (79 ~ is 1.04 109 dynes/cm 2, a n d E " (79 ~ is 5.15
of the operator until the run is finished. Usually initial and 108 dynes/cm 2. F r o m Eq 11, E = 1.16 109 dynes/cm 2,
final temperatures are selected to span the glassy region, and E > E' (79 ~ for this case. If we actually carried out SSA at
transition region, and rubbery plateau region. For direct ten- 79 ~and a strain rate corresponding to 11 Hz, we would expect
sile DMA, the run program usually contains a tensioning sub- to find E = 1.16 109 dynes/cm 2. During the elongation in
routine, which provides constant static tension sufficient to SSA it would not be evident that a significant fraction of the
avoid slack in the sample in the glassy region and then de- resistance was viscous in nature. However, after the sample
creasing static tension as the sample softens in the transition broke or was released from the grips, retraction would be
region. Modification of the tensioning sub-routine is often delayed (not instantaneous) and part of the deformation
necessary. If tension is too high, films break in the glassy would be permanent.
region or are pulled apart in the transition region. If tension The middle portion of the plots in Fig. 5 represents the
is too low, slack results or the oscillatory stress falls below transition region where E' drops sharply and both E" and
measurable values. Skilled operators soon develop several tan8 go through a maximum. The glass transition tempera-
modified run programs with different tensioning parameters ture, Tg, is usually taken as the temperature of the m a x i m u m
that are suitable for samples of various properties and dimen- in the tan8 plot, 79 ~ in Fig. 5. Some users of DMA prefer to
sions. define the temperature of the m a x i m u m in the E" as Tg, 55 ~ in
Various support materials, such as glass braids and metal Fig. 5. The lower Tg value agrees more closely with that
springs or shims, are used when the sample is a viscous liquid obtained from differential scanning calorimetry, but the
and the objective is to follow cure as the coating formulation higher value can be obtained with better reproducibility be-
is converted to a solid. Use of supports makes it difficult to cause the tan8 peak is sharper than the E" peak. Regardless of
obtain absolute values of E', but relative values are often the data point selected to express Tg, it is important to re-
sufficient for c o m p o n e n t optimization. The position of peaks m e m b e r that Tg depends on rate of testing for viscoelastic
in E" or tan8 plots are usually not shifted when a support is materials.
used. When coating samples do not contain solvents, e.g., The effects of changing rate of testing, i.e., frequency in
powder coatings and 100% active coatings, parallel plate, and DMA, are shown in Table 2. The 11 Hz data of Table 2
cone and plate geometries can be used. correspond to the run depicted in Fig. 5. A ten-fold increase in
In some cases, DMA is treated as an adjunct to frequency results in a 7 to 9 ~ increase in Tg with a slightly
thermomechanical analysis (TMA). The TMA probe is driven stronger dependence on frequency at the higher frequencies.
up and down in an oscillatory m a n n e r as temperature is In a recent review, H a r t m a n n [9] noted that a 7~ Tg change
scanned. General indications of liquid-like character during per decade change in frequency is used as a "rule-of-thumb."
transitions can be obtained, but quantitative DMA data are Results of Table 2 are consistent with this generalization. The
not often obtainable in this manner. height of the tan6 peak is nearly independent of frequency,
but the width increases with increasing frequency. Very simi-
lar dependence of height and width on frequency was ob-
Interpretation of DMA Plots
served for lightly cross-linked epoxy films [9]. Values of E'
DMA plots are shown in Fig. 5 for a clear film prepared (min) increase slightly with increasing frequency (Table 2).
from an acrylic polyol (ACR) and an etherified melamine The structural implications of E' (min) will be discussed in
formaldehyde (MF) cross-linker. Plots are labeled according the next sub-section.
to Eqs 2, 3, and 4. The storage modulus level at the left is Height and width of tan8 peaks reflect structural homoge-
typical of amorphous, unpigmented films in the glassy state. neity and cross-link density. Homogeneous, uncross-linked,
The 25~ data are of interest for comparison with modulus noncrystalline polymeric materials of narrow molecular
values obtained from the slope of stress-strain plots because weight distribution usually have tan8 (max) values greater
SSA is usually carried out at 25~ The value of E' (25 ~ from than one and sometimes greater than two. Such tan8 peaks
the computer printout corresponding to Fig. 5 is 1.38 101~ are very narrow. A broader molecular weight distribution
dynes/cm 2. The same value expressed in other units is 1.38 results in a wider peak and a lower value of tan8 (max).
109 Pa or 2.00 l0 s psi (1 pascal = 1 newton/m 2 -- 10 dynes/ Introduction of cross-links invariably reduces tan8 (max) and
c m 2 = 1.45 10 -4 pounds-force per square inch). The usually increases peak width. For homogeneous cross-linked
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11
STORAGE MODULUS
oo
I--
bJ
-1 ~
/
"8 LOSS T A N G E N T
'7
w I i o o i ! I I 1 i i i i i i ! I ~
o o o o o o o o o o
TENPERATURE (C)
FIG. 5 - D M A plots for a clearcoat prepared from an acrylic polyol (ACR) and an etherified
melamine formaldehyde (MF) resin, ACR/MF 70/30. The film was cured before DMA for
30 min at 120~ with 0.5% para-toluenesulfonic acid. DMA was carried out at 11 Hz. See
Table 2 for dynamic properties.
TABLE 2--Dynamic properties of acrylic/MF clearcoat.

Frequency, TanS, PW,a E', ( m i n ) , Temperature of E'
Hz Tg, ~ max A, ~ dynes/cm2 (rain), ~
3.5 76 0.49 45 3.3 X l0 s 108
11.0 79 0.49 50 3.6 X 108 112
35.0 83 0.52 55 4.2 X 108 116
110.0 88 0.52 59 4.7 x l0 s 121
aPWis peak width at half height.
samples, peak width reflects the broadness of the distribution mains with extended regions of varying composition at the
of lengths of chains between junction points in the network boundaries [4,10]. Diffuse domains have also been created in
[2,3]. For sound and vibration damping, materials with both multiblock uncross-linked polymers, and block design has re-
high and wide tan6 peaks would be desireable, but height and sulted in controlled broadening of tan6 peaks [11].
width cannot be adjusted independently [9]. High peaks tend The relationships between transition width and coating
to be narrow, and wide peaks tend to be low. These observa- end-use performance have been presented for radiation-
tions have resulted in speculation concerning a general com- cured coatings [12], polyol/melamine thermoset coatings
parability of peak areas of the glass transition. Eventually [13,14], gel coats [14], and can coatings [14]. Although the
theoretical treatment of peak areas may prove to be useful for glass transition is emphasized in this section, many polymers
structure/propert3) correlations. are known to have multiple transitions. Low-temperature
Samples that undergo partial phase separation during mo- transitions are observed in DMA as tan6 or E" peaks that are
lecular weight buildup and cross-linking often have very quite small compared to the glass transition peaks. As dis-
broad transitions [4,9,10]. Manson and Sperling [10] have cussed in the section entitled Relationship to Other Me-
described the use of interpenetrating polymer networks to chanical P r o p e r t i e s , good impact resistance is often attrib-
limit and control the extent of phase separation. When Tg uted to transitions that produce low-temperature loss peaks.
values of the separate domains are close to one another, a Interpretation of tan6 peak broadening in terms of
general broadening is observed. When Tg values of the sepa- structural nonuniformity requires considerable restraint he-
rate domains are considerably different, tan6 plot shapes cause in some cases broadening is caused by physical or
provide considerable structural information. Observation of chemical changes that take place during the temperature
two narrow peaks with low tan6 values between them indi- scan. In some cases, DMA has its own uncertainty principle;
cates distinct phase separation with little mixing at domain the structural features that are under study are changing
boundaries. Observation to two broad and indistinct peaks during the determination. Physical changes include loss of
with high tan6 values between them indicates diffuse do- plasticizer or absorbed water and morphological changes
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CHAPTER 4 6 - - D Y N A M I C MECHANICAL AND TENSILE P R O P E R T I E S 541
such as partial crystallization. Chemical changes include ad- 4A 3 + 3B 4 ~ I d e a l N e t w o r k (density = 1.10g/cm 3)

ditional cross-linking of t h e r m o s e t coatings during the scan
The m a s s of the n e t w o r k f o r m e d b y this r e a c t i o n is 10 200 g (3
a n d oxidative or t h e r m a l degradation. In general, if the tem-
x 3000 + 4 x 300), a n d the volume is 10 200/1.10 = 9273
p e r a t u r e of processing the samples is well above the t e m p e r a -
c m 3. This volume of cured film contains 24 tool of chain ends
ture of the tan8 p e a k u n d e r analysis, there is m u c h less
c h a n c e that p r o p e r t i e s are c h a n g i n g d u r i n g the scan. (4 x 3 + 3 x 4 ) c o m i n g into j u n c t i o n points in the network.
By definition, a chain has two ends; therefore, there are 12
tool of elastically effective chains in 9273 c m 3 of ideal net-
Determination of Cross-Link Density w o r k film. F r o m Eq 15, Ve = 12/9273 = 1.29 X 10 -3 mo1/cm 3.
E q u a t i o n 17, a t t r i b u t e d to Scanlon [18,24], formalizes this
F o r u n p i g m e n t e d , cross-linked coating films, the level of
type of calculation
storage modulus, E', in the r u b b e r y plateau region above Tg is
an i n d i c a t i o n of cross-link density. A wide range of variation
has been observed from a p p r o x i m a t e l y 4 x 107 dynes/cm ~ for v~
=3 4 5
-~C3 + 2 C4 + ~C5 + . . . . .
1
~fcf
21.=3
(17)
lightly cross-linked films to a p p r o x i m a t e l y 2 x 109 dynes/cm 2
for very highly cross-linked films. Increases in E' values in the where Cf is the concentration of "f" functional reactant ex-
r u b b e r y p l a t e a u have b e e n a t t r i b u t e d to increases in cross- pressed in unusual units, i.e., moles of reactant per cubic
link density for m a n y types of studies: increasing cure tem- centimeter of final film. Difunctional reactants contribute to
p e r a t u r e a n d cure t i m e [13,16-18], increasing r a d i a t i o n dose v o l u m e b u t do not increase the n u m b e r of moles of chains.
in electron b e a m curing [15], increasing the s t o i c h i o m e t r i c Therefore, there is no C2 t e r m in Eq 17.
b a l a n c e in epoxy films [2,19] a n d in p o l y o l / m e l a m i n e films Ideal n e t w o r k calculations have been carried out for sev-
[13,17,18], increasing the functionality of the cross-linker in eral types of coatings such as polyester p o l y o l / m e l a m i n e films
r a d i a t i o n cure films [20] a n d in p o w d e r coatings [21,22], a n d [17], epoxy/diamine films [19], and p o w d e r coating films
increasing the m o l e c u l a r weight of the m a i n film former in [21,22]. The ue values calculated from r e a c t a n t structures
acrylic clearcoats [23]. agree r e m a r k a b l y well with e x p e r i m e n t a l Ue values from Eq
Quantitative aspects of the relationship between E' in the 16.
r u b b e r y p l a t e a u and cross-link density have recently been Although v~ is useful for n e t w o r k characterization, m o s t
clarified [18]. Cross-link density is defined as coating chemists can m o r e easily visualize a n e t w o r k b a s e d
v~ ~ moles of elastically effective n e t w o r k chains (15) on the value of Mc
p e r cubic c e n t i m e t e r of film
M c = weight of s a m p l e in g r a m s that contains one (18)
Cross-link density can be calculated using Eq 16 m o l e of elastically effective chains
G' E' If chain lengths in the n e t w o r k vary, one can place a b a r over
ve - - (16) M c a n d refer to this quantity as " n u m b e r average m o l e c u l a r
RT 3RT
weight of effective n e t w o r k chains." Based on Eqs 15 a n d 18,
where the storage m o d u l u s values, G' or E', are o b t a i n e d in the relationship b e t w e e n ue a n d Mc is
the r u b b e r y plateau, T is t e m p e r a t u r e in degrees K corre-
s p o n d i n g to the storage m o d u l u s value, a n d R is the gas Mc- p (19)
constant (8.314 x 107 dynes/degrees K 9 mole in the cgs unit v~
system). Inserting the 3.5 Hz d a t a from Table 2 (E' = 3.3 X
w h e r e p is film density in g/cmL F o r the 4A3 + 3B 4 example,
108 dynes/cm 2 a n d T = 108~ = 381~ into Eq 16 gives Ve =
Mc = 1.10/1.29 10 -3 = 853 g/tool. F o r the film of Table 2,
3.47 X 10 -3 moles/cm 3. Since Eq 16 has no c o r r e c t i o n for
the experimental density is 1.12 g/cm 3, and Mc is 1.12/3.47
frequency d e p e n d e n c e of E', a m o r e a c c u r a t e value w o u l d be
10 -3 = 323 g/tool. Of course, a high value of Mc c o r r e s p o n d s to
o b t a i n e d if frequency were r e d u c e d until E ' no longer de-
a loose n e t w o r k a n d a low value to a tight network.
p e n d e d on frequency. E x t r a p o l a t i o n to zero frequency was
used in cross-link density calculations for p o w d e r coatings E q u a t i o n 16 can be c o n s i d e r e d e m p i r i c a l or the result of
[21]. F o r a p o l y u r e t h a n e film of low Tg b u t relatively high kinetic theory of r u b b e r elasticity [20,24-28]. The theory was
cross-link density, E ' plots were identical in the r u b b e r y pla- developed for networks that have very long chains between
teau at 11 a n d 110 Hz [18]; thus, no frequency e x t r a p o l a t i o n j u n c t i o n points. F o r long chains, c o n f o r m a t i o n s can be
was necessary for this case. treated by statistical-mechanics concepts. The chains in net-
E q u a t i o n 16 has b e e n called "the ideal n e t w o r k law" with works of greatest interest for coatings are m u c h too short for
an analogy i m p l i e d to the ideal gas law [18]. In an ideal such treatments. F o r long chains between j u n c t i o n points,
network, all chains are elastically effective. Conversion in the results of the theory are often expressed as [20]
n e t w o r k f o r m i n g reaction is complete, a n d there are no small G
loops or dangling ends. F o r ideal networks f o r m e d by func- re= Vc + Up gRT (20)
tional group reactions of t e r m i n a l l y functional (telechelic)
starting materials, the value of Ve can be calculated directly where ve is s u m of a chemical contribution, vc, a n d a physical
from Eq 15. The calculation requires only a b a l a n c e d chemi- contribution, up. The physical c o n t r i b u t i o n is attributed to
cal equation a n d an e x p e r i m e n t a l d e t e r m i n a t i o n of c u r e d film chain e n t a n g l e m e n t s [28] o r physical constraints [25-27].
density. F o r example, c o n s i d e r a tetrafunctional core- The factor, g, is related to j u n c t i o n p o i n t d i s p l a c e m e n t u n d e r
actant B 4 (M n = 3000) cured by a trifunctional cross-linker stress a n d is r e p o r t e d to d e p e n d on functionality [20,25]. If
A3 (M~ = 300) the r e a d e r chooses to use r u b b e r elasticity theory, Eq 16 is
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obtained from Eq 20 w i t h g = 1.0, G = G', and vp = 0 of results is likely to conclude that rubber is very hard. This
(relative to vc). example illustrates that DMA can be used to understand the
A new theory is needed that results in Eq 16 by consider- results of paint tests more fully.
ation of entropy of conformations of short chains. This ap- Among the many scratch tests that have been devised, the
proach would avoid applying long chain theory to material most widely used is pencil hardness. Although pencil hard-
having short chains. ness results are quite reproducible when carried out by one
skilled in the art, these results sometimes do not correlate
Relationship to Other Mechanical Properties with either penetration or pendulum hardness results. Fur-
thermore, there is no known dynamic property that corre-
Knowledge of dynamic properties is useful for optimizing lates well with pencil hardness. The plowing action involved
the chemicaJ structure of coatings components. When the
in pencil hardness failures may involve large localized defor-
binder is a copolymer, monomer ratios can be altered to
mations. A relation to stress-strain analysis, which involves
control Tg. In thermosets, increasing the functionality of the
cross-linker is expected to cause an increase in cross-link large deformations, is more likely.
density. DMA is a very direct method for determining Flexibility of coatings is often measured by mandrel bend
whether purposeful structural changes have actually had the tests and falling weight impact tests (see a previous chapter in
desired effects. this book). In thermoplastic polymer studies, good flexibility
In addition to general structure/property uses of DMA, and impact resistance are often associated with low tempera-
progress is being made in establishing relationships between ture peaks in E" and tan8 plots [30]. Rubber-toughened epoxy
dynamic properties and the results of paint test methods for coatings clearly show the low temperature peak attributable
hardness, flexibility, impact resistance, and solvent resist- to the rubber phase [31]. Polyester/melamine films have
ance. DMA has some inherent limitations in the establish- much better mandrel bend performance than do acrylic/mel-
ment of these property/property relationships. The oscil- amine films of similar Tg and cross-link density. DMA scans
latory deformation, e.g., e0 in Fig. 2, is very small. If the paint beginning at - 100~ show a weak tan6 peak at - 70~ for the
performance property depends critically on large deforma-
PE/MF films, but no such peak is observed for the ACR/MF
tions, a property/property correlation should not be expected.
films [18]. In some cases [12,13], extreme broadening of the
Results of paint performance tests usually depend to some
peak in the E" plot has been associated with improvements in
extent on interactions between coating and substrate. When
dependence on coating-substrate interactions is dominant, a flexibility of coatings.
free film method such as DMA should not be expected to Pigments often increase the toughness of coatings without
correlate with results of paint tests. broadening the transition or introducing low-temperature
DMA has helped elucidate the causes of reversals in rank loss peaks [15]. The main effect of increasing pigment volume
order of hardness among films when different tests are used content (PVC = 0 to 55%) on DMA plots is to increase E'
[5,29]. As described elsewhere in the manual, hardness is values moderately in the glassy region and strongly in the
determined by penetration, pendulum, and scratch test meth- rubbery plateau [15]. Values of Tg often increase by about 5 to
ods. The most important property for influencing hardness is 10~ at PVC = 0.4 relative to the corresponding clear coat-
Tg. However, even for a series of films that have the same Tg, ings [15].
considerable differences are sometimes observed in hardness Solvent resistance as measured in methyl ethyl ketone dou-
test results. We have observed that penetration hardness de-
ble rub tests is related to E' values in the rubbery plateau, i.e.,
pends more directly on the E ~(25 ~ value than on Tg. Films of
to cross-link density [5,13]. MEK resistance also depends on
the same Tg can have quite different values of E' (25~ Pendu-
lum hardness depends more directly on E" values than on E' the solubility parameter of the coating. Although the double
values. This result is expected because damping of the swings rub test is widely used to determine the degree of cure of
of a pendulum depends on conversion of mechanical energy thermoset coatings, the only ASTM method adopted relates
into heat through viscous effects in the coating. As noted to zinc-rich primers (D 4752-87). Relationships between the
earlier, E" is a measure of viscous response. Films which have number of double rubs and E' (rain) values are quite repro-
nearly the same E' (25 ~ values and the same penetration ducible within a coating type but not from type to type. For
hardness can have quite different E" (25 ~ values and quite example, with acrylic clearcoats, 200 double rubs are ob-
different values of pendulum hardness. The back and forth tained when E' (min) = 2 108 dynes/cm 2 [13]. Films of this
rolling motion of a Sward Rocker is also damped by viscous type having 50 to 100 double rubs typically have E' (min)
effects, and therefore depends strongly on E" values. In this values in the range of 5 107 to 1 to l0 s dynes/cm 2. In
case, there is also a contribution from sliding friction. Usually
contrast, polyester polyol powder coatings, cured with sev-
pendulum hardness is determined at a single temperature,
eral types of cross-linkers, yielded 200 + double rubs despite
but Sato [29] describes studies of damping time as a function
having E' (rain) values as low as 5 107 dynes/cm 2 [22]. The
of temperature. Plots of the reciprocal of damping time ver-
sus temperature have exacdy the same shape as the tan8 plot lack of generality in the relationship of MEK resistance to E'
for the same films. Both glassy and rubbery materials have (min) for various coatings types is believed to result in part
low tan~ values as shown in Fig. 5. If a pendulum hardness from differences in solvent-polymer interactions. There may
test is carried out at room temperature on a material that is in also be a weak dependence of MEK resistance on Tg as well as
its rubbery region at room temperature, a careless interpreter a strong dependence on E' (rain).
www.iran-mavad.com

D E T E R M I N A T I O N OF T E N S I L E ~ooo
PROPERTIES
(/)
Description of Stress-Strain Analysis (SSA)
Instrumentation for SSA is described in detail in the ASTM
f__=
test methods listed in the section of this chapter entitled
Definitions of Tensile Properties. In most cases, specific in- i q) I
struments are not identified, apparently to avoid commercial 1o O(~ 100
implications, but it is generally known than Instron | instru- STRAIN (%) STRAIN (%)
ments (Instron Engineering Corp.) are widely used. For or-
ganic coatings the most suitable test method is usually ASTM
D 2370. However, other tension test methods contain addi-
tional useful information. ASTM D 638M is useful for selec-
tion of metric units and units consistent with SI recommen-
dations. ASTM D 882 has rather extensive data on statistical 2,ooo
treatments for plastic sheeting, but the statistical methods
could be beneficially applied to coatings films. For certain
types of coatings, such as flexible primers or coatings for
plastic substrates, rubbery behavior is expected, and ASTM D
412 provides useful information such as data treatment when 03
a crack moves slowly across the sample as opposed to the I
more usual instantaneous failure mode. Often stress-strain 500
curves do not start out with constant slope as shown in Fig. 3,
but instead have an initial curvature caused by takeup of
STRAIN (%)
FIG. 6-General kinds of stress-strain curves for various
slack. The initial curved portion is called a "toe," and toe types of coatings. Scales indicate order-of-magnitude val-
compensation is described in ASTM D 638M and in ASTM D ues.
882. Some stress-strain curves have no linear (i.e., no
Hookean) region from which to calculate the slope for modu-
lus values. In such instances the "toe corrected" origin and modulus values (initial slope), tensile strengths up to about
another point on the curve are joined by a straight line. The 8000 psi (5.5 x 107 Pa = 5.5 x 108 dynes/cm2), and elonga-
slope of the line is reported as the "secant modulus." The tions below 10%. Ductile materials (6B) usually have lower
elongation percentage at the second point selected is always initial slopes, tensile strengths in the 4000 to 6000 psi range,
reported along with the value of secant modulus. Graphical and elongations of about 100%. The upper plot in 6B corre-
illustrations of secant modulus determinations are given in sponds to yielding with uniform sample deformation be-
ASTM D 638M and in ASTM D 882. Among the various test tween the grips. The lower plot in 6B corresponds to a ductile
methods, D 638M contains the most complete list of defini- sample that necks down at the yield point, and further elon-
tions and symbols. gation ( - 4 0 % to 110% in Fig. 6) occurs with increase in
Determination of "tensile energy to break" is described in length of the necked part of the sample. Elastomeric (rub-
ASTM D 882. The area under the stress-strain curve, e.g., see bery) samples (6C) have much lower initial slopes than brittle
Fig. 3, is divided by sample volume to obtain this quantity, materials, tensile strengths of about 2000 psi, and elonga-
which has also been called "work-to-break" or "toughness" tions of the order of 400 to 500%. The upward curvature near
[5]. Recommended units are megajoules per cubic meter. the end of the lower plot in Part C is attributed to strain-
ASTM D 882 describes how an integrated chart paper area induced crystallization [2].
(distance 2) can be converted to energy/volume by using the Materials represented in 6A and 6B of Fig. 6 have Tg values
ordinate setting (force/distance of chart paper), the abscissa above the test temperature. Therefore, modulus values de-
setting (distance of elongation/distance of chart paper), and pend on secondary interactions of polymer chain segments
the sample dimensions. Now that computers are used to and partial crystallinity, if any exists. The elastomeric mate-
control operation and to treat data for SSA [32], numerical rial (6C) has Tg well below the test temperature. Therefore,
integration is nearly instantaneous, and tensile energy to modulus values depend in part on cross-link density, chain
break is likely to be reported more often. This SSA property entanglements, or both.
may prove to be useful for correlations with paint test results. Stress-strain curves are carried out at a constant rate of
strain and results depend on strain rate selected. In genera], a
higher rate results in higher modulus. The two curves in 6A
Interpretation of Stress-Strain Curves
could represent the same material strained at different rates.
Schematic stress-strain curves for various types of poly- In fact a large increase in strain rate could cause the plots of
meric materials are shown in Fig. 6 [2]. This extremely wide 6B to be converted to the plots of 6A. Dependence on strain
range of property variation is represented in coatings of vari- rate is evidence of viscoelasticity. Strain rate dependence in
ous types. Scales on the graphs give an order-of-magnitude SSA, therefore, has the same origin as dependence on oscil-
indication of property values. Brittle materials (6A) have high latory frequency in DMA (see Table 2).
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A recent study of silicone-epoxy resins cross-linked with

amines of various functionality [32] illustrates the extreme Fief. No. 1 62.0
range of stress-strain properties exhibited by coating films.
Tensile strength ranged from 31 to 4418 psi. Percent elonga-
tion ranged from 7 to 177%. Unfortunately, neither modulus
values nor tensile energy to break were reported. Property
48.2
variations were attributed to differences in degree of entan-
glement and to partial phase separation. In a network-form-
ing thermoset system, it would be impossible to get a tensile 6
strength as low as 31 psi unless incompatibility had pre- :E
vented occurrence of the network-forming reaction. 5 34.5
Examples of all types of behavior shown in Fig. 6 are repre-
sented in a single figure for coatings used on naval aircraft
4
[33] (see Fig. 4, Ref 33). One plot shows results for a polysul-
fide sealant that has a tensile strength of about 250 psi and an
elongation > 130%. Results for a flexible polyurethane primer 3 20.7
are a tensile strength of 3500 psi, a yield strength of 3200 psi,
an elongation at break of 90%, and an elongation at yield of
40%. The plot shows that a polyurethane topcoat yields and
breaks at about the same point: 4000 psi and 22% elongation. 6.9
The plot for an epoxy primer shows brittle behavior (no yield
point), a tensile strength of 2300 psi, and an elongation at
~ 0
break of 7%. The authors [33] report that replacing the epoxy 0 4 8 12 16 20 24 28
primer by the flexible polyurethane primer eliminated the PercentElongation
need for the sealant coat. FIG. 7-Stress-strain curves for UV-cured cycloaliphatic
SSA has been used extensively to characterize cationic UV- epoxide films flexibilized with oligomeric propylene oxide
cured cycloaliphatic epoxy/polyol coatings [34-36]. The triol. Strain rate is 40% per minute. See Table 3 for tensile
mechanism of introduction of polyol is a chain transfer step properties.
[34], which permits use of a wide range of epoxy:polyol ratio
without need for stoichiometric balance. Selection of flexible for Elongation of Attached Organic Coatings with Conical
polyols with this wide formulating latitude permits prepara- Mandrel Apparatus (D 522-88) describes how to calculate
tion of cross-linked films with an extremely wide range of percent elongation from the crack length in a conical man-
mechanical properties. Numerous stress-strain curves have
drel bend test. Comparison of elongation of adherent coat-
been presented for this type of system with oligomeric pro-
ings by the conical mandrel method and elongation of the
pylene oxide polyols [35] and with oligomeric caprolactone
same coating as a free film from SSA would certainly be of
polyols [36]. Examples of stress-strain curves for a cycloali-
interest, but such comparisons were not found in the litera-
phatic diepoxide (CYRACURE | UVR-6110, Union Carbide)
ture.
and a propylene oxide triol (MW = 702) are shown in Fig. 7
The logic of associating yield behavior in SSA with post
[35]. The corresponding tensile properties are given in Table
formability of coil coated metal was noted in 1977 [37]. In
3. Films from Compositions 1 through 4 all give brittle failure
1987, Koleske [35,36] confirmed that compositions that ex-
(compare Fig. 6A) and only moderate changes in tensile prop-
hibited a yield point performed well in the demanding post-
erties (Table 3) despite a large change in composition. At
Composition 5 (70/30 epoxy:polyol, see Table 3) a yield point forming operations carried out on beverage can ends.
is first noted, and thereafter very large property changes Evans and Fogel [38] provided convincing evidence that
occur despite relatively small changes in composition. Com- gloss retention during abrasion of floor coatings is related to
positions in the 4 to 6 range (see Table 3) are reported to give the area under stress-strain curves. This area, divided by
excellent post forrnability, as required for coatings on bever- sample volume, is called "work-to-break" or "toughness" as
age can ends, while maintaining adequate hardness and sol- noted in the subsection of this chapter entitled Definitions of
vent resistance [34-36]. Tensile Properties. The authors provide a clear example of
the need to match strain rates when attempting to correlate
SSA results with paint test results.
Relationship to Other Mechanical Properties Failure of attempts to correlate pencil hardness with pene-
Stress-strain analysis (SSA) is used in a general way to tration hardness, e.g., Tukon Hardness, probably result be-
assess suitability of a binder for various coating end uses. cause the former has a strong requirement for toughness,
Most coating chemists associate modulus with coating hard- whereas the latter is more dependent on the modulus value
ness and percentage elongation at break with coating flexibil- at room temperature (see chapter subsection entitled
ity. Quantitative correlations of these properties are not pub- Relationship to Other Mechanical Properties).
lished very often, however. The lack of published correlations DMA is much more generally applicable to determination
may result from the fact, noted above, that paint tests of of cross-link density (see chapter subsection entitled
adherent coatings depend on coating-substrate interactions, Determination of Cross-Link Density) than is SSA. If the Tg
whereas SSA is carried out on free films. ASTM Test Method of a coating binder is well below the temperature at which
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TABLE 3--Tensile propertiesa of UV-cured cycloaliphatic epoxide films flexibilized with oligomeric propylene
oxide triol.
C~176176162 Tensile Tensile
Film Epoxide, Triol, Modulus,d Strength, Elongation,
N o. b wt% wt% psi psi %
1 90.0 10.0 3.88 x 10s 9.5 x 10 3 6.6
2 85.0 15.0 3.72 X 10s 8.9 X 10 3 6.6
3 80.0 20.0 3.33 10s 8.4 x 10 3 7.4
4 75.0 25.0 2.95 x 10s 7.0 X 10 3 8.1
5 70.0 30.0 2.05 x 105 4.3 x 103 16.2
6 66.7 33.3 1.48 105 3.7 103 24.3
7 63.4 36.6 0.70 10s 2.5 x 103 54.0
8 60.0 40.0 0.26 X 105 2.0 x 103 88.4
~Strain rate, 40% per minute.
bKeyedto the plots in Fig. 7.
CWeight% of polymericbinder. (Filmsalso contain 2.9 wt% photoinitiator and 0.5 wt% flow agent.)
a1% secant modulus. (The modulus range expressed in pascals is 2.68 109,No. 1. to 1.79 l0s, No. 8.)
SSA is carried out, t h e n the m o d u l u s from the initial slope of REFERENCES

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ization of Some Reactive Polyester Powder Coatings Systems," Coatings Technology, D. Brezinski and T, J. Miranda, Eds., Fed-
Verfkroniek, Vol. 62, 1989, p. 238. eration of Societies for Coatings Technology, Philadelphia,
[22] Higginbottom, H. P., Bowers, G. R., Grande, J. S., and Hill, L. 1991.
W., "Structure/Property Studies of MF-eured Powder Coatings," [35] Koleske, J. V., "Mechanical Properties of Cationic Ultraviolet
Progress in Organic Coatings, Vol. 20, 1992, p. 301. Light-Cured Cycloaliphatic Epoxide Systems," Proceedings,
[23] Oshikubo, T., Yoshida, T., and Tanaka, S., "Studies on Acrylic Radcure Europe '87, 4-7 May 1987, Munich, W. Germany.
Resins and Melamine Formaldehyde Resins for High Solids [36] Koleske, J. V., "Copolymerization and Properties of Cationic,
Coatings," Proceedings, Tenth International Conference in Or- Ultraviolet Light-Cured Cycloaliphatic Epoxide Systems,"
ganic Coatings Science and Technology, 9-13 July 1984, Athens,
Proceedings, RadTech '88--N. America, 24-28 April 1988, New
Greece, p. 317.
Orleans, p. 353.
[24] Scanlon, J., "The Effect of Flaws on the Elastic Properties of
Vulcanizates," Journal of Polymer Science, Vol. 43, 1960, p. 501. [37] Hill, L. W., "Stress Analysis: A Tool for Understanding Coating
[25] Flory, P. J., "Molecular Theory of Rubber Elasticity," Polymer Performance," Progress in Organic Coatings, Vol. 5, 1977, p. 277.
Journal, Vol. 17, No. 1, 1985, p. 1. [38] Evans, R. M. and Fogel, J., "Comparison of Tensile and Morpho-
[26] Flory, P. J. and Erman, B., "Theory of Elasticity of Polymer logical Properties with Abrasion Resistance of Urethane Films,"
Networks," Macromolecules, Vol. 15, 1982, p. 800. Journal of Coatings Technology, Vol. 49, No. 634, 1977, p. 50.
[27] Erman, B. and Flory, P. J., "Relationships Between Stress, [39] Hergenrother, W. L., "Determination of the Molecular Weight
Strain and Molecular Constitution of Polymer Networks. Com- Between Cross-links of Elastomeric Stocks by Tensile Retrac-
parison of Theory and Experiments," Macromolecules, Vol. 15, tion Measurements. II Polyurethanes," Journal of Applied Poly-
1982, p. 806. mer Science, Vol. 32, 1986, p. 3683.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Flexibility and Toughness*

by Mark P. Morse I
DEFINITIONS Coatings, as the polymers from which they are prepared,

are viscoelastic in nature, that is, they behave both as viscous
To PERFORM PROPERLYIN USE, a coating must possess the liquids and as elastic solids. The coatings have elastic recov-
proper amount of flexibility and toughness to withstand ery and yet will flow with time when placed under a stress. In
cracking when subjected to stresses produced by shrinking or general, viscoelastic behavior and mechanical properties are
swelling, forming, mechanical abuse, and weathering. Flexi- markedly affected when a coating enters the glass transition,
bility is the ability of a material to be bent or flexed without softening point, or other relaxation. To be certain that the
cracking or undergoing other failure. Toughness is the properties of a coating will fulfill the needs of its intended use,
strength and resilience of a material; it is the material's ability the viscoelastic behavior of the coating should be measured,
to withstand great strain imposed in a short time period controlled, and designed to meet the particular end use.
without tearing, breaking, or rupture. The softening point of a coating can be used as an index of
flexibility. The softening point is between the temperature
INTERPRETATION where the coating changes from being hard and glassy and
the temperature where it is leathery or rubbery. For example,
if a coating has a softening temperature region near the
The flexibility of a coating applied to a substrate depends
temperature of the forming operation, the coating is less
not only on its distensibility, but also on the coating thickness
susceptible to failure by cracking or a similar mechanism
and on the adhesion between coating and substrate. Good
than if the softening region was above the forming tempera-
adhesion tends to give better apparent flexibility than does
ture. Measurement of energy storage (related to elasticity)
poor adhesion. The toughness of a coating is dependent on its
and energy loss (related to viscous losses) as a function of
hardness, stiffness, resiliency, distensibility, and the exis- temperature is a means of predicting impact resistance.
tence of an energy dissipation mechanism that operates at Impact resistance of a paint film can be considered as en-
temperatures far below room temperature and is discernable ergy dissipation by vibration or rotation of various molecular
by dynamic mechanical measurements made over a broad segments so that at no time will sufficient energy be focused
temperature or frequency range. to cause fracture. Since the impact tests performed on paint
Generally, the bend and impact tests used to evaluate flexi- films often produce deformations beyond the elastic limit of
bility and toughness are much more severe than actual ser- the films, flow within the films must take place or fracture will
vice conditions. This is because the tests are usually per- occur [3].
formed on relatively fresh, unaged coating films. Since To obtain good impact resistance, the paint film must con-
coating films tend to lose flexibility during use due to volatil- sist of a polymer that has a sufficiently high molecular weight
ization of free plasticizing components and chemical changes to have strong intermolecular entanglement (and therefore,
such as degradation, cross-linking, and the like, these severe high tensile strength), but sufficiently low viscosity (by choice
tests that exceed normal expectations are useful in predicting of proper molecular constituents and limiting molecular
long-term serviceability [1]. weight) that flow and accompanying energy dissipation will
take place.
BASIC P R O P E R T I E S A F F E C T I N G COATING Polymer viscosity increases as molecular weight increases
PERFORMANCE so that polymers with very high molecular weights will have
greater flexibility than those polymers with intermediate or
Both flexibility and toughness depend on very basic proper- low molecular weights. At the same time, molecular weights
ties: the viscoelastic behavior of the coating and its physical below the critical molecular weight for entanglement lead to
transitions and relaxations. The following is a discussion of very low tensile strengths and the mechanical behavior ob-
these properties taken from a paper by Skrovanek and Schoff served is brittleness. It has been found that modulus is the
[2]. dominant factor in the relationship between the tensile prop-
erties of a coating and its impact resistance [4].
In addition to dynamic mechanical behavior, the relaxation
*This chpater is an abridged and modified version of the chapter
entitled "Flexibility," written by G a r m o n d G. Schurr, found in the behavior as measured by dissipation or damping of coatings
previous edition of this manual. has been determined by application of dynamic electrical
fConsultant, 71 S. Shelburne Rd., Springfield, PA 19064. tests [5]. In a dielectric relaxation test, a periodic electrical
54"/
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potential is a p p l i e d to the s a m p l e coating situated b e t w e e n a coatings have a definite second o r d e r t r a n s i t i o n t e m p e r a t u r e

p a i r of electrodes. The dielectric c o n s t a n t a n d dissipation fac- k n o w n as the glass t r a n s i t i o n t e m p e r a t u r e , Tg. Coatings at a
t o r are m e a s u r e d as a function of frequency a n d t e m p e r a t u r e . t e m p e r a t u r e b e l o w Tg are h a r d a n d brittle with p o o r flexibility
a n d i m p a c t resistance unless there is a n o t h e r relaxation at
low t e m p e r a t u r e s as exists in p o l y c a r b o n a t e s that have a high
TECHNIQUES FOR MEASURING BASIC Tg of a b o u t 160~ (at 1 Hz) a n d yet have excellent i m p a c t
VISCOELASTIC PROPERTIES resistance b e c a u s e of a relaxation that occurs at a b o u t - 90~
(at 1 Hz). If coatings do not have this type loss m e c h a n i s m , at
Thermal Mechanical Analyzer (TMA) t e m p e r a t u r e s just above Tg they are flexible, a n d at t e m p e r a -
tures substantially above Tg they t e n d to develop viscous
This i n s t r u m e n t employs t r a n s d u c e r s to sense the p o s i t i o n r a t h e r t h a n elastic properties. There is a t e n d e n c y for all
of a vertical r o d that rests on the surface of a coating sample. t h e r m o p l a s t i c coatings to have identical flexibility p r o p e r t i e s
The i n s t r u m e n t is usually e q u i p p e d with a furnace a n d pro- if these p r o p e r t i e s are m e a s u r e d at the s a m e t e m p e r a t u r e
g r a m p l a n n e r so that beating, cooling, a n d isothermal tem- relative to Tg, for example, at 10~ above Tg [1,6].
p e r a t u r e o p e r a t i o n s can be employed. Flexibility a n d toughness m e a s u r e m e n t s are usually m a d e
W i t h its use, softening points a n d glass transitions can be at a t e m p e r a t u r e of 25 +_ I~ after the coatings are equili-
d e t e r m i n e d from plots of coating i n d e n t a t i o n as a function of b r a t e d at that t e m p e r a t u r e . However, there are m a n y in-
t e m p e r a t u r e . Also, changes in stresses within a coating at a stances w h e n test are p e r f o r m e d at lower t e m p e r a t u r e s as
c o n s t a n t t e m p e r a t u r e (creep) can be d e t e r m i n e d from plots m i g h t be e n c o u n t e r e d in cold climates.
of i n d e n t a t i o n versus time [2].
Strain Rate
Dynamic Mechanical Thermal Analyzer (DMTA)
Strain rate is the rate at w h i c h a coating s p e c i m e n is elon-
This i n s t r u m e n t p r o d u c e s vibrations in a coating film over
gated a n d is usually expressed in p e r c e n t per minute,
a wide frequency range a n d / o r t e m p e r a t u r e range. It can scan
in./in./min o r cm/cm/min. This is the rate of extension relative
a wide range of s a m p l e t e m p e r a t u r e s at different rates. The
to s p e c i m e n size. That is, if a s p e c i m e n 10 c m long is elon-
resulting d e f o r m a t i o n s from the sinusoidally applied stresses
gated at rate of 1 cm/min, it is the s a m e as a s p e c i m e n 1 c m
are analyzed to c o m p u t e values related to energy storage a n d
long being elongated at a rate of O. 1 c m / m i n (1 m m / m i n ) . In
energy loss [2].
b o t h cases, the strain rate is 10% p e r minute.
Strain rate has a great influence on the flexibility a n d
toughness of a coating. In general, the effect of increasing the
EXTERNAL FACTORS AFFECTING strain rate is similar to decreasing the coating t e m p e r a t u r e ,
FLEXIBILITY AND TOUGHNESS that is, as the strain rate is increased, flexibility a n d tough-
ness decrease.
Flexibility a n d toughness are not c o n s t a n t characteristics There can be critical strain rates where flexibility has s h a r p
of a specific coating. A n u m b e r of external factors affect these changes w h i c h are very similar to the effects p r o d u c e d at the
properties. glass transition t e m p e r a t u r e [7]. This m e a n s that the strain
rate used in a test m u s t be closely controlled. In s o m e tests,
Humidity such as b e n d test, this is difficult to do. This also m e a n s that
tests p e r f o r m e d at a low strain rate (cupping test) are likely to
W a t e r is a g o o d plasticizer for a l m o s t all p a i n t films. A p r o d u c e different flexibility ratings t h a n those p r o d u c e d by a
change in relative h u m i d i t y of as little as 2% can be detected high strain rate (conical m a n d r e l test) [1, 7].
in flexibility m e a s u r e m e n t s . S o m e p a i n t films, such as those
b a s e d on latexes, i m b i b e m o i s t u r e very rapidly, whereas
others r e a c h e q u i l i b r i u m with the a t m o s p h e r e very slowly. It
FLEXIBILITY AND TOUGHNESS
is imperative that tests be c o n d u c t e d in an a t m o s p h e r e of
MEASUREMENTS
controlled relative h u m i d i t y a n d that the s p e c i m e n s are con-
d i t i o n e d in that a t m o s p h e r e for a d a y or m o r e before the tests
Mandrel Bend Tests
are p e r f o r m e d . Generally, flexibility a n d toughness tests are
c a r r i e d out at a relative h u m i d i t y of 50 _+ 5%. The 10% Both conical a n d cylindrical m a n d r e l s are often used for
tolerance is needed b e c a u s e of the difficulty in m o r e accu- evaluating the flexibility of coatings. Even t h o u g h it is diffi-
rately controlling relative h u m i d i t y in m o s t laboratories. If cult to control the strain rate in these m a n u a l l y o p e r a t e d
the e n v i r o n m e n t c a n n o t be controlled at this r e c o m m e n d e d tests, they can provide very useful flexibility ratings.
level, then the relative h u m i d i t y should be m e a s u r e d a n d
r e p o r t e d along with the m e c h a n i c a l properties. Conical Mandrel Tests
A conical m a n d r e l test consists of m a n u a l l y b e n d i n g a
coated metal panel over a cone. As described in ASTM Test
Temperature
M e t h o d for E l o n g a t i o n of Attached Organic Coatings with
The flexibility a n d toughness of coatings are d e p e n d e n t on Conical M a n d r e l A p p a r a t u s (D 522), a conical m a n d r e l tester
t e m p e r a t u r e . This is p a r t i c u l a r l y true of t h e r m o p l a s t i c coat- consists of a metal cone, a rotating panel b e n d i n g arm, a n d
ings, b u t it also is a factor for t h e r m o s e t coatings. These panel clamps. These items are all m o u n t e d on a m e t a l base as
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CHAPTER 4 7 - - F L E X I B I L I T Y AND TOUGHNESS 549
FIG. 1-Bending a specimen over a conical mandrel (courtesy of Gardner Laboratory) [I].
illustrated in Fig. 1. The cone is smooth steel 8 in. (203 mm)

in length with a diameter of 1/8 in. (3 mm) at one end and a
diameter of 1.5 in. (38 mm) at the other end.
When a coating is applied on a V32-in. (0.8 mm)-thick cold-
rolled steel panel, as specified in ASTM D 522, a bend over the
mandrel produces an elongation of 3% at the large end of the
cone and of 30% at the small end of the cone. The coated
panel is bent 135 ~ around the cone in approximately 1 s to
obtain a crack resistance rating under simulated abuse condi-
tions. In some instances, longer bend times have been found
to be useful. For example, if the percent elongation of the
coating at the point of cracking is to be determined, the
method specifies a bend time of 15 s.
Since variations in temperature and humidity can affect
mandrel bend tests, it is imperative that the coated panels be
conditioned at a standard temperature and relative humidity
before performing the test, which is conducted under the
same conditions.
The crack resistance value of a coating is obtained by mea-
suring the distance from the furthest end of the crack to the
small end of the mandrel. This distance is converted to cone
diameter by means of a plot given in ASTM D 522. The man-
drel diameter at which cracking occurs is taken as the crack
resistance value.
If the elongation of the coating at the onset of cracking is to FIG. 2-Bending a specimen over a cylindrical man-
be reported, a bend time of 15 s is used and the diameter at drel (courtesy of Gardner Laboratory) [ 1].
which the onset of cracking occurred is converted to percent
elongation from a plot given in ASTM Test Methods for Man- (25 mm), 3/4-in. (19 mm), 1/2-in. (12.7 mm), 3/s-in. (9.5 mm),
drel Bend Test of Attached Organic Coatings (D 522). 1/4-in. (6.4 mm), and 1/8-in. (3.2 mm) diameters. Examples of
cylindrical mandrel testers are given in Figs. 2 and 3.
Cylindrical Mandrel Bend Tests The panel should be bent over a mandrel with the uncoated
When executing cylindrical mandrel flexibility tests, a side of the panel in contact with the mandrel surface. The
coated panel is bent manually over one or more cylindrical panel should be bent approximately 180 ~around the mandrel
rods or surfaces of different diameters. ASTM D 522 states at a uniform velocity in a time of i s. If cracking has not
that the testing device should include mandrels with I-in. occurred, the procedure is repeated using successively
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where t is the thickness of the coated panel a n d r is the radius

of the mandrel. Actually, observed elongations are greater
t h a n values calculated from the above expression a n d vary
with different types of metal substrates. Table 1 contains
i n f o r m a t i o n about the influence of panel thickness a n d type
metal on percent elongation of a coating.
Crack resistance of a coating is d e p e n d e n t o n its thickness,
that is, the thicker the film, the lower the crack resistance.
Values of crack resistance obtained by the m a n d r e l b e n d tests
should be corrected for film thickness w h e n c o m p a r i s o n s are
made between different coatings. ASTM D 522 contains cor-
rections to be added to elongation values o b t a i n e d with coat-
ings having thickness greater t h a n 1 rail (0.03 m m ) w h e n
applied to 1/8-in. (0.8-mm)-thick steel panels (Table 1).
Conical m a n d r e l b e n d test procedures similar to those
given in ASTM D 522 are found in ISO Method 6860 a n d BS
3900. Cylindrical m a n d r e l b e n d test procedures similar to
those given in ASTM D 522 are found in ISO 1519, DIN 35
152, and BS 3900 E l .
T-Bend Tests
FIG. 3 - A n illustration of a cylindrical mandrel test apparatus. T-bend tests are a m e a n s of evaluating the flexibility of
coated strip metal that is to be formed during a fabrication
process (Fig. 4). Multiple 180 ~ bends of the coated metal are
smaller and smaller diameter m a n d r e l s until cracking is ap- made, a n d the a m o u n t of cracking produced at each b e n d is
parent. The cracking-resistance value of a coated panel is the visually determined. Ratings are classified as 0T, 1T, 2T, 3T,
m i n i m u m diameter at which cracking does not appear. a n d so on. The 0T ( p r o n o u n c e d zero T) b e n d consists of
This testing procedure can be applied as a "pass~fail" test by m a k i n g a 180 ~ b e n d with the p a i n t o n the outside of the b e n d
d e t e r m i n i n g whether cracking is produced by b e n d i n g over a a n d pressing the b e n d flat so there is no space between the
specified m a n d r e l diameter. metal surfaces. This operation is repeated successively to
A table for converting m a n d r e l diameter to percent elonga- produce a 1T ( p r o n o u n c e d one T), 2T, 3T, etc. b e n d s (Fig. 5).
tion is given in ASTM D 522. The relationship between diam- These successive bends result in two, three, etc. thickness o f
eter of a m a n d r e l and the elongation of a coating has b e e n the metal a r o u n d the first bend. It should be a p p a r e n t that the
derived by Schuh a n d Theuerer [8] to be: greater the n u m b e r of thicknesses a r o u n d which the coated
metal is bent, the less severe the test. The DiAcro Brake F o r m
Percent Elongation = lO0(t/(2r + t)) (1) m a c h i n e is suitable for this test.
TABLE 1--Factors affecting elongation measurements of coated panels by mandrel bend tests.
Mandrel Diameter, in.
Panel Thickness I 3/4 J/2 3/8 1/4 I/8
CORRECTIONSTOBE ADDEDFORTHICKNESSOFPANELSUBSTRATE
1/64in. Correction, % 1.5 2.0 3.0 4.0 5.9 11.1
1/32 in. Correction, % 3.0 4.0 5.0 7.7 11.1 20.0
1/18in. Correction, % 5.9 7.7 11.1 14.3 20.0 33.3

Metal Type 1 3/4 1/2 3/8 1/4 1/8
CORRECTIONSTOBE ADDEDFORTYPEOFMETALPANELSUBSTRATE
3/4 hard brass Correction, % 3.4 4.6 6.9 9.6 14.2 29.1
Annealed brass Correction, % 3.6 4.9 7.5 10.3 15.9 33.5
Cold-rolled steel Correction, % 3.3 4.4 6.7 9.0 13.8 28.0

Metal Type 1 3/4 1/2 3/8 1/4 1/8
CORRECTIONSFORFILMTHICKNESSTOBE ADDEDPERMIL OFCOATING

3/4 hard brass Correction, % 0.21 0.26 0.38 0.50 0.73 1.38
Annealed brass Correction, % 0.21 0.26 0.38 0.50 0.74 1.43
Cold-rolled steel Correction, % 0.21 0.26 0.38 0.50 0.73 1.37
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SPECIMEN
DINGDIE
FIG. 4-T-Bend test using a die around which the specimen is

bent (ASTM D 4145: Test Method for Coating Flexibility of
Prepainted Sheet).
iNSERTTHISENDINV I S E ~ \ ~ 1/2in. TO3/4 in.
/// I
2 in. MINIMUM A
fl WIDTH
COATEDSURFACE ~ / 0T BEND
(.,
/COATED SURFACE/ 1TBEND

FIG. 6-Erichsen Cupping Tester (early model),
SCOATED 9 Cupping Tests

URFACE. / 2TBEND
9
A relatively slow rate of forming test can be conducted with

a cupping tester that pushes a punch into the unpainted side
of a coated panel until the increasing deformation produces
cracks in the coating. Test procedures are given in ISO TC 35,
3TBEND BS 3900 E4, NFT 30-019, SIS 18 41 77, DIN 50 101, and DIN
50 102. There are six models of Erichsen Cupping Testers;
they provide different test conditions to simulate different
FIG. 5-T-Bend test in which the coated specimen is bent forming operations. Two of these models are shown in Figs. 6
around itself (ASTM D 4145: Test Method for Coating Flexibility and 7. BYK-Gardner Cupping Testers are a]so suitable for
of Prepainted Sheet).
conducting these test procedures (Fig. 8). The BYK-Gardner
devices use a spherical punch and provide a range of cupping
Test results are reported as passing the smallest T-bend on speeds. The maximum cupping depth is approximately
which cracks are observed. In some cases, cracking can be 18 m m (0.7 in.). The cupping action is stopped when crack-
detected by removal of a pressure-sensitive tape placed on the ing in the coating is visually detected. The depth of cupping at
bend edges and observing the degree of removed coating that point is indicated on a digital display and is considered to
particles. ASTM Test Method for Coating Flexibility of be the flexibility rating. The cupping tester can be equipped
Prepainted Sheet (D 4145) describes this test procedure. with a stereo microscope for observing the onset of cracking.
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FIG. 8-BYK-Gardner Cupping Tester.
Forming Tests
In many industrial operations, metal is coated flat and then
formed into various shapes by drawing the coated metal. This
can be simulated directly or by elongating a coated metal
sheet. A testing machine that has provided useful formability
evaluations is the Erichsen Stamping Testing Machine (Fig.
7). It provides deformations in a few seconds by application
of high pressure to a stamping tool. The stamped coated
metal is examined for cracking as a "pass/fail" test.
Any tension testing instrument capable of rapidly elon-
gating a metal strip can be used for determining drawability.
A coated metal strip would be elongated at a high rate of
strain until cracking occurs. The elongation would be mea-
sured with an extensiometer [1]. Drawability would be re-
ported as the percent elongation obtained just before crack-
ing is observed. Since elongation is rate dependent, the rate of
elongation used should be reported.
ASTM Test Method for Formability of Attached Organic
Coatings with Impact-Wedge Bend Apparatus (D 3281) de-
scribes a procedure for determining the formability of coated
metal strips using an impact wedge bend apparatus termed
the Coverall Bend Tester (Fig. 9). At the start of the test, the
coated panel is bent 170 to 180 ~ over a 1/s-in. (3.2 mm) cylin-
drical mandrel attached to an impact platform. The platform
is adjusted to provide a taper of 0 to 1/s-in. This allows the
platform to create a wedge that provides stress angles be-
tween 170 and 180~ The end of the coated panel with the 180~
stress angle is defined as having 0T bend. The height of the
impacter is adjusted until the load to produce a 0T bend is
determined. The distance of the cracking produced in the
coating by the impact is measured from the edge of the most
severe bend outward to the edge of the least severe bend. The
amount of film removed from the coating is indicative of its
lack of formability.
ASTM Test Method for Formability of Zinc-Rich Primer/
Chromate Complex Coatings on Steel (D 4146) also provides
a procedure for determining the formability of coated strip
metal. An outline of a testing machine that can produce a
9
sufficiently high pressure for pressing a l%-in. (41-mm)-

FIG. 7-Erichsen machine for testing stamping lacquers diameter indenter ball into the coated metal is provided. The
(early model). (Figure from previous edition of this manual.)
rate of forming can be adjusted over a range of 0.2 to
1.0 in./min (4.8 to 25 mm/min). A dial gage monitors the
movement of the indenting ball. Adhesive tape is applied over
the dome formed in the metal, and the tape is rapidly re-
moved. The amount of coating removed is given a rating by
comparing it with a set of photographic standards.
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cover a range of 0.5 to 60% elongation. See Federal Test

Method Standard 141C, Method 6226.
ASTM Test Method for Impact Resistance of Pipeline Coat-
ings (Falling Weight Test) (G 14) describes a test procedure
for determining the impact resistance of pipe coatings. A
fixed weight of 3.0 lb (1.36 kg) and having a s/8-in, nose diam-
eter is dropped through a guide tube onto a coated pipe
specimen. The height of the weight is adjusted until the mini-
mum height at which cracking appears is attained. A pin hold
detector is used to determine the presence of cracks in the
impacted pipe. An equation is given for calculating the im-
pact resistance from the weight and its height of drop re-
quired to just produce cracking.
A different type of impact tester was developed and is being
used at the Bell Laboratories of AT&T (Fig. 11). A coated
panel is subjected to repeated glancing blows by a case-hard-
ened steel ball at the end of a short arm that is pivoted to
another arm connected to a rotating shaft. During the test,
the coated panel is mounted on a platform that moves so that
FIG. 9-Coverail bend test, After specimen is bent over a 1/e-in. successive blows do not strike the same spot. The energy level
mandrel, the bent portion is shaped into a wedge when a more of the blows may be held constant, as in a "pass/fail" test, or it
severe test is needed (ASTM D 3281: Test Method for Formabil-
ity of Attached Organic Coatings with impact-Wedge Bend Ap-
paratus).
Impact Resistance Tests

The most commonly used impact testers drop a weight
onto an indenter resting on the surface of a coated panel that
is resting on a platform (Fig. 10). A die in an opening in the
platform allows the panel to be pushed down by the indenter
to form a dimple in the panel. The weight is dropped through
a guiding tube whose height is marked in increments.
There are a number of possible combinations of weights,
indenter sizes, die sizes, and weight heights that can be used
in performing impact tests. The tests can be performed by
impacting either the coating directly (coating facing upward)
or indirectly (coating facing downward).
Cracking observed on or around the impact-produced
dimple is considered failure, and the force to produce the
cracking is given in inch-pounds (killigrams-meters), that is,
weight times height. The test can be performed either to de-
termine the inch-pounds required to produce cracking or to
determine whether a coating passes or fails at a specified
inch-pound value. ASTM Test Method for Resistance of Or-
ganic Coatings to the Effects of Rapid Deformation (Impact)
(D 2794) describes such a test procedure and offers three
procedures for determining the degree of cracking produced
in an impact deformation: (a) visual inspection with a magni-
fier, (b) visual inspection after application of an acidified
copper sulfate solution, and (c) use of a pin hole detector.
The General Electric Impact Flexibility Tool is used for
simultaneously making several indentations of different
sizes. From these indentations, conclusions can be made re-
garding crack resistance and the amount of draw that a
coating applied to sheet metal can tolerate. This tester con-
sists of a steel cylinder that has knobs (segments of spheres)
of different radii machined on each end. The cylinder is
dropped onto a coated panel that is supported coating side
down by a rubber pad. The height of drop is adjusted so that
the boundary of the cylinder is just discernible. This proce-
dure assures that each knob is used to its limit. Eight knobs FIG. 10-Gardner impact tester, a falling weight impact tester.
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visually r a t e d for cracking. In s o m e cases, an exposure of 2 h

in a n oven at 150~ (65~ is i n t r o d u c e d into the above cycle
conditions.
A r a p i d cold crack t e s t that has been developed is b a s e d on
the use of cooled air entering a transparent, i n s u l a t e d box.
Cold air t h a t has b e e n cooled at a r a p i d controlled rate is
i n t r o d u c e d into the box, a n d the coatings are observed for
cracking. The coatings are then r a t e d by d e t e r m i n i n g the
t e m p e r a t u r e decrease from r o o m t e m p e r a t u r e that is re-
quired to p r o d u c e visual cracks in the coatings [4].
Effects of Aging and Weathering

The u l t i m a t e m e a s u r e of satisfactory flexibility a n d tough-
ness of a coating a p p l i e d to a s u b s t r a t e is p e r f o r m a n c e u n d e r
service conditions. Most flexibility a n d toughness tests are
p e r f o r m e d on relatively fresh-coated panels, that is, tests are
FIG. 11-Bell Laboratories impact tester and specimen. Ball usually p e r f o r m e d after the panels have been c o n d i t i o n e d in a
on end of the rotating arm repeatedly strikes specimen, which specified a t m o s p h e r e for a specified p e r i o d b e t w e e n 24 h a n d
is moving from left to right (courtesy of Bell Laboratories) [1]. seven days. The results o b t a i n e d are applicable to service
conditions if these are c o n c e r n e d with post f o r m i n g o r service
i n d o o r s w i t h o u t a d e g r a d i n g a t m o s p h e r e , since m o s t coatings
c a n be a d j u s t e d by c h a n g i n g the speed of the rotating shaft to
do not c h a n g e a p p r e c i a b l y in their physical service p r o p e r t i e s
d e t e r m i n e the onset of cracking. If the h a m m e r energy level
u n d e r such conditions. However, if the service c o n d i t i o n s in-
r e q u i r e d to d e s t r o y the coating is desired, a t r a n s p a r e n t , cali-
clude exposure to weathering, this factor can cause apprecia-
b r a t e d scale of shaft speed in revolutions is s u p e r i m p o s e d
ble changes to o c c u r in the coatings properties.
over the i m p a c t pattern. This tester is not c o m m e r c i a l l y avail-
The effects of moisture, t e m p e r a t u r e changes, a n d expo-
able.
sure to sunlight (ultraviolet wave lengths) e n c o u n t e r e d in
There are a n u m b e r of o t h e r i m p a c t testers t h a t have been
o u t d o o r exposure generally reduce the flexibility a n d tough-
developed over the years a n d u s e d to s o m e extent. These
ness of organic coatings. Therefore, it often is desirable to
include the P a r l i n - d u P o n t Tester, C a m p I m p a c t Test, H a r t
c o n d u c t tests for flexibility a n d toughness after p e r i o d s of
I m p a c t Tester, Ball Punch, General Electric Ball Drop, a n d
w e a t h e r i n g to d e t e r m i n e h o w a coating will p e r f o r m u n d e r
Navy Falling Ball test. None of these testers are c o m m e r c i a l l y
actual w e a t h e r conditions [1].
available.
Cold Crack Resistance Tests REFERENCES

Tests in w h i c h coatings on substrates are cycled t h r o u g h [1] Schurr, G. G., "Flexibility,"Paint Testing Manual, ASTM STP 500,
elevated t e m p e r a t u r e , low t e m p e r a t u r e , a n d r o o m t e m p e r a - 13th ed., H. A. Gardner and G. G. Sward, Eds., American Society
ture e n v i r o n m e n t s are called cold c r a c k tests. They have b e e n for Testing and Materials, Philadelphia, 1972, pp. 333-337.
used in the coatings i n d u s t r y for m a n y years as an i n d i c a t i o n [2] Skrovanek, D. J. and Schoff, C. K., "Mechanical Analysis of Or-
of the ability of a coating to resist cracking in service a n d ganic Coatings," Progress in Organic Coatings, Vol. 16, 1988, pp.
135-163.
therefore are c o n s i d e r e d to be tests of coating flexibility.
[3] Moore, R. J., "Molecular Basis for Impact Resistance of Epoxy
ASTM Test M e t h o d for T e m p e r a t u r e - C h a n g e Resistance of Paint Films," Journal of Paint Technology, VoL 43, No. 554, March
Clear Nitrocellulose L a c q u e r Films Applied to W o o d (D 1211) 1971, pp. 39-46.
is a n e x a m p l e of such a cold c r a c k test. It describes a proce- [4] Morse, M. P., "Physical Properties of Paint Films Relating to
d u r e for testing l a c q u e r coatings a p p l i e d on wood. The testing Service," presented at Gordon Research Conferences, Organic
cycles consists of 1 h at 120~ (49~ 1 h at - 5 ~ ( - 2 1 ~ Coatings Section, 15-19 Aug. 1955.
a n d 1/2 h at r o o m t e m p e r a t u r e . Results are r e p o r t e d as the [5] Varadarajan, K., "Review of Dielectric and Dynamic Mechanical
n u m b e r of cycles r e q u i r e d to p r o d u c e visible cracking in the Relaxation Techniques for the Characterization of Organic Coat-
coating. ings," Journal of Coatings Technology, Vol. 55, No. 704, Septem-
Automotive coatings are subjected to cold crack cycle tests. ber 1983, pp. 95-104.
[6] Tordella, J. P., "Mechanical Properties of Amorphous Polymers,"
A typical test for exterior coatings on m e t a l panels consists of
Official Digest, Vol. 37, 1965, p. 349.
(1) equilibration at r o o m t e m p e r a t u r e , (2) exposure in a hu- [7] Supnik, R. H., "Rate Sensitivity: Its Measurement and Signifi-
m i d i t y c a b i n e t at 100~ (38~ a n d 100% relative h u m i d i t y for cance," Materials Research Standards, Vol. 2, 1962, p. 498.
20 h, a n d (3) exposure in a freezer at - 22~ ( - 30~ for 4 h. [8] Schuh, A. E. and Theuerer, H. C., "Measurement of Distensibility
After r e m o v a l from the freezer, the coated panels are allowed of Organic Finishes," Industrial and Engineering Chemistry, Vol.
to s t a n d at r o o m t e m p e r a t u r e for 2 h. Then the coatings are 9, 1937, p. 9.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Hardness
by Paul R. Gudvin, Jr. 1
P H Y S I C A L C O N C E P T S OF H A R D N E S S sion of opinions by those present concerning their under-

TESTING standings of concepts that were connoted by hardness as
applied to organiccoating films.
HARDNESS IS A TERM HAVING a d i f f e r e n t m e a n i n g to d i f f e r e n t The consensus was that the subject of hardness is very
people. It is resistance to penetration to a metallurgist, resist- complex. Several of the characteristics of an organic film are
ance to wear to a lubrication engineer, a measure of flow simultaneously judgmentally weighed in order of relative im-
stress to a design engineer, resistance to scratching to a min- portance to obtain the usual expression of hardness judg-
eralogist, and resistance to cutting to a machinist. While ment. The same physical characteristics of films were em-
these actions appear to differ greatly in character, they are all ployed, and the weighing importance of the various
related to the plastic flow stress of the material, i.e., Young's characteristics chosen is not carried out in the same manner;
Modulus, Y [1]. K. Sato wrote an overview paper on the choices are operator dependent and are based on experience
hardness of coating films [2] which merits mentioning and with results in practical use of the material.
reviewing. At the time of this first meeting in 1947, the purpose of the
Hardness is not a fundamental property of materials but a group was to (1) study the subject of hardness and attempt to
composite one dependent on the elastic moduli, elastic limit, define some of the physical properties or attributes of an
the hardening produced by "working" a metal, etc. Empirical organic coating which affect hardness, (2) limit the study to
relationships are used to determine other properties from the the development of procedures for measuring the attributes
easily measured hardness, but all such schemes are of doubt- of film hardness, and (3) further evaluate limitations to
fill or limited validity. smooth films of organic coatings as they are normally applied
Hardness testing can be a very useful tool for studying on a substrate. Switzer [4] conducted a survey to determine
modern materials, but it is plagued by well-known experi- which methods were being used by the coatings industry to
mental difficulties. Reasons for the unusual behavior of hard- measure hardness. They found that some form of scratching
ness data at very low loads are explored by Monte Carlo or abrasion was used 84% of the time, pendulum or damping
simulation, which will be discussed later. These simulations hardness (also referred to as entropy hardness) 56% of the
bear remarkable resemblance to the results of actual hard- time, and indentation hardness 20% of the time. The percent-
ness experiments. The limit of hardness as load or indenta- ages total more than 100% because some companies sur-
tion depth tends to zero, which is shown to depend on experi- veyed use more than one procedure to evaluate hardness. In
mental error rather than upon intrinsic material properties. 1991, ASTM Task Group D01.23.14 conducted a similar sur-
The large scatter of hardness data at very low loads is ensured vey. The study showed pencil hardness to be the most com-
by the accepted definition of hardness. A new definition of monly used test method with the Sward-type rocker method
hardness is suggested which eliminates much of this scatter the next most widely used [5]. The m o d e m trend in industries
and possesses a limit as indentation depth approaches zero. as a whole has been towards an increasing use of indentation
Some simple calculations are used to show the utility of this methods.
new approach to hardness testing.
Over the years, many methods and devices have been em-
Scratch Hardness
ployed to measure the hardness of organic finishes. P. C.
Wheeler, chairman of a technical committee within the Dal- Scratch hardness is the oldest form of hardness measure-
las Paint and Varnish Production Club, as it was called then, ment and was probably first developed by mineralogists.
reported [3] the results of a survey of findings concerning Back in 1822, F. Mohs [6] evaluated comparative scratch
how coating hardness is measured. Following this survey, the hardness of many materials. Assuming the liquid state to be
first meeting of what is now called ASTM Task Group equivalent to "zero" hardness, he arranged solid materials
DO1.23.14, Hardness, Mar and Abrasion Resistance, was held into ten hardness groups, rating them as follows: talc, 1;
in June 1947. The Hardness Group of Subcommittee XVIII, gypsum, 2; calcite, 3; fluorite, 4; apatite, 5; orthoclase, 6;
as they were called at the time, of Committee D-1 was orga- quartz, 7; topaz, 8; corundum, 9; diamond, 10. As the system
nized in Atlantic City to provide an opportunity for expres- was set up, any material of a given Mohs hardness number
could scratch any other material with a lower Mohs hardness,
~President, P. R. Gu6vin Associates, P.O. Box 811, Westerville, OH and about 99% of all known materials have hardness ranging
43086-0811. from Mohs 1 to 9. However, the Mohs scale, though conve-
555
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nient to apply, is essentially qualitative in nature. The wide Hardness of Plastic Materials. Their published [14] statement
variety of hardness test procedures that have been used may said:
be described by the following sections. This method fills a need for a test to determine the rela-
As user demands for improved resistance to scratch and tive resistance of a plastic surface to defacement by a
hardness increased for applications such as automotive fin- sharp abrasive particle as occurs in tableware, optical
elements, and similar applications.
ishes, high-performance coatings were developed and be-
came more widely used. As the primary objective was to When the Bierbaum Microcharacter Hardness Tester wasn't
improve the surface hardness rather than resistance to defor- useful any more for ASTM purposes, it was withdrawn in
1964.
mation of the coating, scratch resistance tests were examined
[7]. The coatings industry developed, adapted, or adopted Clemen Scratch Hardness Tester--The current instrument,
various instruments and test methods, which are described shown in Fig. 1, is marketed by Erichsen GMBH & Co. This
below. device is available in two versions: hand-operated and motor
driven. Both determine the scratch resistance of protective
Bierbaum Microcharacter--This instrument, designed by surface coatings, such as paint and lacquer finishes, plastic
C. H. Bierbaum [8-12], has a polished prismatic diamond coatings, etc. It consists of a sliding test panel carrier
cube (diamond pyramid) held in an elastic support as a mounted on a base frame. A scratching tool is fixed at the end
scratching tool. It is a rather elaborate device consisting of a and a sliding weight in the middle of a counterpoised lever
microscope, stage, and diamond tool on a balanced arm. The that is supported by two pillars. Operated by means of a
sharp point is the corner of a cube, one edge of which acts as a dropping and lifting mechanism, the scratching stylus or
leading edge, being inclined to the horizontal surface of the needle is moved along the test surface during the working
specimen at 35.25 ~. The lubricated specimen is slowly moved stroke, but is lifted for the return traverse.
under the point, and the standard load is 3 g. The scratch
The weight-loaded blade or ball-shaped carbide tool is ap-
width w in micrometre is measured under a microscope
plied with a defined force (0 to 20 N) to the specimen, which
according to recommendations made by the inventor, and
is moved with constant speed. The scratch hardness is mea-
several readings are averaged to give:
sured by the force necessary to cut through the coating to the
104 substrate. It is operated manually or uses a motorized drive.
Bierbaum Microhardness - (1)
w2 Suitable scratching tools are: the Clemen scratching stylus, a
chisel-shaped tool with a tungsten carbide edge, or a scratch-
Bierbaum scratch hardness is the ratio of the load on the ing needle according to Danske Elv~erkers Forening (DEF)
diamond, in kilograms, to the square of the scratch width (w), 1053, Method 14, which is an inexpensive, ball-shaped, hard-
in millimetres. It was marketed in the United States by the ened-steel tool easily replaced when worn.
AmeriCan Optical Company primarily for testing the hard-
ness of metals. It had been used on plastics [13] but never Dantuma Scratch Tester--This device was developed in
gained general acceptance for use on organic finishes. 1940 by H. Dantuma in the physical laboratory of Sikkens
In 1958, ASTM Committee D-20 on Plastics adopted D (now Akzo-Sikkens) [15,16]. It employs a novel means of
1526-58T, Tentative Method of Test for Bierbaum Scratch increasing the load during travel of the scratching tool across
FIG. 1-Clemen Scratch Hardness Tester. (Courtesy of Erichsen GMBH & Co.)
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CHAPTER 48--HARDNESS 559
pearance. It has three tungsten carbide hemispheres or ball

~~ "% !. ".... ~
points 0.5 mm (Opel), 0.75 mm (Bosch), and 1.0 m m (to
.
relate to International Standardization Organization [ISO]

1518) in diameter that are spring loaded. Holding the instru-
ment upright and placing its point on the test surface, one
draws a 5 to 10-ram-long line at a rate of approximately 10
mm/s. The stylus should produce a scratch that is just visible.
By locking the slider each time, one can control the applied
pressure, which is marked in newtons. Thus, one can gradu-
ally approach the correct setting. Three scales are engraved
into the pencil for the three pressure ranges: 1.0 to 3 N
(accuracy 0.1 N), 2.0 to 10 N (accuracy 0.5 N), and 3.0 to 20 N
(accuracy 1.0 N). The hardness is defined as the minimum
load or force, in g, on the ball point, that leaves a mark in the
surface just visible to the unaided eye [I8].
FIG. 2-Dantuma Scratch Tester. (Figure from previous edi-
tion of this manual.) Graham-Linton Hardness Tester--This device, illustrated in
Fig. 5, might also be considered an adhesion tester. As shown
the film. Referring to Fig. 2, as Arm B, with Tool G resting on in the figure, it is essentially a small, circular blade upon
Panel H, is lowered, Arm A follows. The scratching tool which pressure is exerted by a coil spring. A scale, graduated
travels from H to L, a distance of 5 cm. The load varies from 0 in 100-g increments from 0 to 2000 g, indicates the load on
to 5000 g. Operation may be by hand crank or motor. Four the blade.
types of hardened-steel scratching tools are provided: a ball 1
Hoffman Scratch Tester--The Hoffman Tester is one of the
rnm in diameter, a simulated finger nail, and two wedges. The
"old line" instruments in the paint industry and comes as
Dantuma Scratch Tester was never produced for distribution.
close as any instrument to date of being "the paint chemist's
du Pont Scratch Testing Machine--This type of instrument educated knife." Figure 6 shows the original instrument that
was once used at the du Pont lacquer plant at Parlin, New was developed and patented [19]. There is a low carriage with
Jersey, for determining the hardness of lacquers and their a weighted level on one end. The scratching tool is a sharp-
resistance to scratching. It was one of the first to electrically edged, hardened-steel cylinder with its axis at an angle of 45 ~
signal the end point of the test. It is shown in Fig. 3. to the plane of the film. This cylinder is attached to the lever
The device consists of a wooden base on which is mounted: arm, and the load is varied by varying the position of the
(1) a fulcrum holding a graduated level equipped with weight on the lever. This instrument has been used for adhe-
weights and a needle point, (2) a transformer, (3) a 6-V lamp, sion and mar resistance tests. A General Electric Company
and (4) a metal plate. These parts are connected in series, the test method [20] and a federal test method [21] specify how
transformer being used to step down ordinary light voltage to the instrument is to be used. Figure 7 shows the refined in-
that of the small lamp. The metal panel, coated with lacquer, strurnent. The edge of the hardened-steel tool is positioned at
is placed coated side up on the metal plate under the needle. 45 ~ with respect to the test surface and can be loaded at any
The weight is adjusted, and the panel is drawn along the plate value between 0 and 250 g or 0 and 2500 g. The Hoffman
Tester, when used in the lower range of up to 250 g loading,
in the direction of the long axis of the instrument. This
operation is repeated, each time using an increased weight, has been used for determining scratch resistance of a surface
coating. It has had its greatest application, however, in the
until the needle penetrates the film. When this happens, the
high range, up to 2500 g, for cutting completely through the
electric circuit is closed, and the lamp lights.
coating to the support surface for measuring such properties
Erichsen Hardness Tester--The Erichsen Company [17] such as degree of cure and adhesion.
markets a pocket-size hardness tester, Model 318, shown in In use, the desired loading is set on the cutter dial, and the
Fig. 4, that somewhat resembles a mechanical pencil in ap- lower edge of the instrument is held against the test surface to
FIG, 3-du Pont Scratch Testing Machine.
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FIG. 6-Original Hoffman Scratch Tester.
FIG. 4-Erichsen Model 318 Hardness Tester. (Cour-

tesy of Erichsen GMBH & Co.)
FIG. 7-Current Hoffman Scratch Tester. (Courtesy of The

Paul N. Gardner Company, Inc.)
Inspector's Dur-O-Test Pocket Size Hardness Tester--The

Inspector's Dur-O-Test Pocket Size Hardness Tester, shown
in Fig. 8, is a simple pocket instrument used to evaluate the
vulnerability (scratch hardness) of surfaces such as coatings,
varnishes, plastic coverings, etc. Especially valuable for quick
"on line" tests in plants, paint shops, building sites, etc., it
determines the force required to scratch or scar a surface
with a defined spherical tool. It consists of an engraving
needle with spherical tip of tungsten-carbide of 0.75-ram
(0.03-in.) diameter. The spring tension of the tip can be al-
tered and set with a fixing device. The instrument has three
interchangeable springs. The limitation is an inability to test
elastic coatings.
In the operation, the scratch needle extends slightly out of
the jacket. A line is drawn on the surface to be tested in 1 s
while maintaining sufficient pressure to keep the needle
against the rod stop. If the tension is high, the surface will be
FIG. 5-Graham-Linton Hardness Tester. clearly marked. If low, there will be no mark. The correct
tension will result in a barely visible mark.
Laurie-Baily Hardness Tester--This apparatus [22], shown
ensure uniform contact. While held in this position, the inin Fig. 9, was among the first to be developed for films and
strument is drawn in a direction away from the cutter. The was invented by A. P. Laurie and F. G. Baily of Heriot-Watt
nature of the mark left by the cutter, if any, is observed, and College, Edinburgh. The apparatus consists essentially of a
the test may then be repeated at a different cutter loading. hardened, blunt steel point upon which pressure is exerted by
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by hand, the speed recommended by Parker and Siddle being

30 cm/min. Appreciably greater speeds give inconsistent re-
sults.
Pencil Hardness Tester--Rating the hardness of an organic
finish according to the hardness of a lead (graphite) pencil
that will just scratch it was described by Wilkinson [23].
Gardner [24] studied the method using pencils sharpened to
different shapes: sharp cones, rounded cones, and chisels. He
found the principal source of error lay in the character of the
point because it was difficult to reproduce points. Other
sources of error were the pressure on the pencil and the angle
at which the pencil was held while it was moved over the
organic finish. Gardner built a device to hold eight pencils at
one time at an angle of 45 ~ to the panel, but found that it was
impossible to align all pencils uniformly. Modern production
has overcome this problem, and several companies offer a
pencil hardness gage composed of eight mechanical drawing
lead holders (pencils) permanently mounted in a circular
FIG. 8-Inspector's Dur-O-Test Pocket Size Hardness Tester. array on a plastic cylinder. A small metal tube through the
(Courtesy of The Paul N. Gardner Company, Inc.) center of the cylinder provides storage for spare leads and a
guide for positioning pencils for a test.
ASTM Test Method for Film Hardness Test (D 3363) is
practical for laboratory use, for use on a production line, or in
the field to assess quantitatively the rigidity or firmness (elas-
tic modulus) of organic coatings applied to rigid substrates
such as metal or plastic. Hardness values may define require-
ments for particular coating applications or may be used to
evaluate state of cure or aging of a coating.
In this test, pencil leads of increasing hardness values are
forced against a coated surface in a precisely defined manner
until one lead mars (marks) the surface. Surface hardness is
defined by the hardest pencil grade which fails to mar the
organic coating surface.
Today, pencils are available in about 14 different grades of
hardness, ranging from the softest, 6B, to the hardest, 6H,
although hardnesses greater than 6H have been available.
Pencil leads are blends of graphite, clay, and binders. They
range in hardness from softest to hardest as follows: 6B, 5B,
4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, and 6H. Over the
years certain features of the method have been standardized.
They are:
1. The lead is "squared" against fine abrasive paper (as op-
posed to a sharp, fine point).
2. The pencil is held at an angle of 45 ~to the surface of the test
panel.
Variations in the method have occurred with respect to
FIG. 9-Laurie-Bailey Hardness Tester. how the test is actually carried out. Smith [25] made a study
in 1956 and used the following method:
1. Strip the wood from the lead for a distance of approxi-
a vertical coil spring. The spring tension is controlled by an mately 1/4in. (6 ram) using care not to nick the lead. Square
adjusting screw and can vary from 0 to 2000 g. The finish to the exposed lead by a gentle rotary motion against No. 400
be tested is placed under the point and slowly moved horizon- carbide abrasive paper.
tally by hand as the pressure is increased until a scratch is 2. Hold the pencil in a writing position, that is, at approxi-
made. Then the scale readings are recorded. mately 45 ~and push forward against the film. Use pressure
short of breaking the lead. By turning the pencil after a
Parker-Siddle Scratch Tester--This tester is a very simple test, a new edge is available for use, and three or four trials
form of the Schopper type in which the toad on a needle is may be made with one dressing of the lead.
increased as the scratch is made. The point of the needle is a 3. Clean the marks with a soap or "artgum" eraser. Any
hemisphere 0.2 mm in diameter. The panel carrier is moved marring of the surface, visible at an oblique angle in strong
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light, indicates that the pencil is h a r d e r t h a n the film. The that c a n n o t be r e m o v e d by r u b b i n g with a soft r u b b e r
h a r d n e s s is expressed as the grade of the next softer pencil. eraser.
In developing this m e t h o d , S m i t h d e t e r m i n e d the pencil In 1972, ASTM Task G r o u p D01.53.02 Cure reviewed the
h a r d n e s s of 14 different organic finishes that varied widely in results of the H o u s t o n Society for Paint Technology a n d un-
d e r t o o k p r e p a r a t i o n of a pencil h a r d n e s s test m e t h o d . By
hardness. Five different b r a n d s o f pencils were used, a n d the
1973, r o u n d - r o b i n testing had been completed, a n d D 3363
results are shown in Table 1. The results i n d i c a t e d that there
received final approval on 25 Oct. 1974.
were variations in h a r d n e s s between different b r a n d s of pen-
cils a n d that it was necessary to use only one b r a n d to o b t a i n Rondeau Scratch Tester--This device, shown in Fig. 1O, was
reproducibility. developed a n d p a t e n t e d [27] by H e r b e r t F. Rondeau, also
S m i t h also c o m p a r e d the K n o o p h a r d n e s s a n d S w a r d belongs to the type where the load on the scratching tool
r o c k e r h a r d n e s s versus pencil h a r d n e s s of the 14 organic a u t o m a t i c a l l y increases as the test is being m a d e . The tool,
finishes. These results, also in Table 1, showed that pencil p a r a b o l i c in shape, is m o u n t e d on the free end of a cantilever
hardness r a t e d the various organic finishes in the s a m e o r d e r spring, one end being moveable in a slot in the frame. At the
of h a r d n e s s as the two other m o r e e l a b o r a t e methods. This is start of a test, the tool rests on the test surface u n d e r zero
interesting because, according to Smith, three widely differ- load. The finish end of the slot is 0.100 in. (2.5 m m ) n e a r e r to
ent m e c h a n i s m s were involved. They are: the test surface t h a n it is at the start. At the finish end, the
l o a d is the rated value of the spring. At i n t e r m e d i a t e dis-
S w a r d r o c k e r = d e f o r m a t i o n within the elastic limit.
tances, the load is p r o p o r t i o n a l to the distance. Three springs
K n o o p h a r d n e s s = d e f o r m a t i o n beyond the elastic limit.
are provided, giving loads of 300, 600, a n d 1200 g at the finish
Pencil = d e f o r m a t i o n b e y o n d the elastic limit
end.
a n d tearing a w a y of material.
Smith's w o r k p r o v i d e d a b r o a d f o u n d a t i o n for the pencil Scheppard-Schmitt Scratch Dynamometer--The principle
h a r d n e s s test, a n d m a n y features of his m e t h o d are used of this device was e m p l o y e d by E a s t m a n Kodak's S. E. Schep-
today. It was the exact m a n n e r in which the pencil was ap- p a r d a n d J. J. S c h m i t t [28] in the d e v e l o p m e n t of a n e w
plied to the test that was never adopted. scratch hardness instrument. The scratching tool is a hard-
Those test m e t h o d s which have been a d o p t e d and are used ened steel, 45 ~ tetrahedron.
a l m o s t universally were outlined by the H o u s t o n Society for M e a s u r e m e n t of scratch resistance is expressed as the
Coatings Technology [26] in 1966. The H o u s t o n Society de- threshold load p r o d u c i n g a scratch o r by a curve expressing
scribed two b a s i c methods, which were: the relation between the load a n d size (width) of the scratch.
1. The Disbonding Method in which the pencil, at an angle of
45 ~ is p u s h e d into the organic finish. The organic finish is Schopper Hardness Tester--This device [29], shown in Fig.
considered to have failed w h e n a pencil removes chips, 11, was one of the first to provide for a u t o m a t i c a l l y increasing
flakes, scales, or shears the finish from the substrate with- the load on the scratching tool while the scratch is being
out breaking the lead of the pencil. This m e t h o d has also made. Arms extending u p w a r d from the panel c a r r i e r end in
been an a d h e s i o n test. slots above the b e a m carrying the scratching tool. A roller
2. The Indentation Method consists of using the pencil as an resting on the b e a m is guided by the slots. As the panel carrier
i n d e n t a t i o n i n s t r u m e n t by d r a w i n g the p o i n t (at an angle is d r a w n along, the roller travels with it, t h e r e b y increasing
of 45 ~ across the film to p r o d u c e a c o n t i n u o u s indentation. the load on the scratching tool. Provision is m a d e for auto-
The H o u s t o n Society developed a special carriage to hold matically lifting the load from the s p e c i m e n at the end of each
the pencil a n d apply a l o a d of 200 g to it while the carriage trip a n d also for a sidewise d i s p l a c e m e n t of the s p e c i m e n to
was being d r a w n across the test panel. The organic finish is provide a new p a t h for r e p e a t tests. The i n t e r p r e t a t i o n of
considered to have failed w h e n the pencil leaves an inden- results is the s a m e as with other types of scratching devices,
tation in the film (visible u n d e r a 15 magnifying glass) that is, according to the c h a r a c t e r of the m a r k u n d e r a partic-
T A B L E 1--Hardness test correlation (Smith).

Panel Knoop Sward Pencil Pencil Pencil Pencil Pencil
No. Hardness Hardness Brand A Brand B Brand C Brand D Brand E
1 3.09 24 5B 6B 5B 6B 4B
2 4.33 28 4B 6B 6B 6B 4B
3 2.77 24 5B 6B 5B 4B 4B
4 2.61 22 3B 4B 5B 4B 3B
5 5.81 38 2B 2B 2B 2B 3B
6 9.23 50 HB F HB HB HB
7 11.2 25 HB F HB HB H
8 21.1 58 F H H H 2H
9 17.4 54 F F F H 2H
10 25.7 54 H H H H 2H
11 21.0 60 2H 2H 2H 4H 3H
12 39.1 40 3H 2H 3H 4H 4H
13 34.9 30 6H 5H 5H 5H 6H
14 ... 40 8H 9H 7H 7H 9H
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AT START OF TEST under controlled conditions that enable quantitative evalu-

AT END OF TRAVEL J ation of the ability of coatings to withstand repeated horizon-
INGREASING STYLUS /
-,; " ~ l .~'-- 4 FORGE -- tal and vertical abrasions. There are three scratching tools: a
1-mm cutting carbide sphere, a Clemen designed scratch
cutting tool, and a VW designed scratch cutting tool; two
'~:':':::!-V~,': suP~T A2-.2~'~ speeds: 35 and 1 mm/s, and two load ranges: 0 to 20 and 0 to
\~,,,~, \,,, oa~:_ i x\\\~\ xx\\\\x\~, \\',,,,x\\\\\\\\x\\,, \\xk\\\~~, ,xx\ 90 N.
.u ,oRT | '.ULL YLUS
XGURS,O..,O0 .. \ The test is performed by selecting a load which is applied to
TEST SURFAGE ZERO FORGE
AT STARTIN6 the cutter and can remain either constant in value or auto-
POSITION
matically increased at a linear rate. The weighted cutter is
FIG. 10-Rondeau Scratch Tester. brought into contact with the coated surface at a constant
speed, and it penetrates the coating when a critical force is
attained. The force required to be applied to the tool to pene-
trate the coating and just touch the substrate is the measure
at the scratch hardness. Testing using the automatically in-
creased force shortens the test and quickly evaluates the
scratch resistance at the coating.
Simmons Scratch Tester--This coating hardness measur-
ing instrument [31] is another tester of the increasing load
type and is suitable only for films on metal. When the stylus
breaks through the film, a relay stops the machine. Hardness
is reported as the weight necessary to penetrate the film.
Steel Wool Scratch Tester--The Panelgraphic Rotary Steel
Wool Scratch Tester (Fig. 13) is constructed so scratch resis-
tance may be measured using loads of 13 and 24 lb/in. 2 (0.9
and 1.7 kg/cm 2) on the steel wool pad attached to a square
FIG. 11-Schopper Hardness Tester. (Photo from previous testing foot of 1.25 in. 2 (8.065 cm2). The 0000 steel wool on
edition of this manual.) the testing foot is then rotated for five revolutions, after which
the sample is visually inspected for scratches in the coating
and rated. The test then may be repeated in other locations to
ular load or tool, or the load at which a particular tool makes
determine uniformity of the coating. This instrument is being
a mark.
removed from production and will not be available for pur-
Sheen Scratch Tester--This instrument determines the chase.
scratch resistance (i.e., scratch hardness) of paint coatings While this test may be acceptable for materials that are
and is designed to meet the requirements of the British Stan- homogeneous or essentially homogeneous, when attempting
dards (BS) Method of Test for Paints (BS3900: Part E2). Its to measure the scratch resistance of relatively thin coatings,
usefulness, however, extends beyond the rigid limits for oper- other complicating factors arise. The measured scratch re-
ating conditions set by this authority as the test provides data sistance of the coating is dependent upon factors indepen-
outside the specification. Performance is related to many fac- dent of the coating itself, including the coating thickness and
tors that include the hardness of the coating with other the substrate over which the coating is applied. Stated an-
physical properties such as adhesion, lubricity, resilience, other way, scratch resistance is not an intrinsic property of a
etc., as well as the influence of coating thickness and curing coating, and it may mean different things depending on how
conditions. It is a quantitative indication of the extent to the property is measured. When attempting to measure only
which serious damage is resisted when a loaded needle is the resistance of a material to surface scratching, the concept
raked across a relatively smooth, flat surface. of "mar resistance" comes into play.
The instrument is shown in Fig. 12. The needle arm is
counterpoised and rigid to prevent whip or chatter at the ball Teledyne Taber Shear~Scratch Tester--Shear and scratch
point. Weights totaling 2000 g and providing increments of tests are significant because rigorous controls are exercised
100 g from 100 g are supplied and additional weights are over these parameters affecting materials' resistance to shear
available. A total load of 6 kg can be used for very hard and scratch. The unique Model 502 Teledyne Taber Shear/
coatings. A 2000-g weight (or two) is useful for baked coat- Scratch Tester [32] features three cutting tools: the S-20
ings. The l-ram tungsten carbide-tipped needles are held in a tungsten carbide tool for shear testing and 139-55 and 139-58
chuck and can readily be removed for inspection and replace- diamond tools for scratch testing. The instrument is shown in
ment. Fig. 14. A tool is fixed to the underside of a beam pivoted on
ball bearings. Riders provide for adjusting the load on the
Sikkens Scratch Hardness Tester--Sikkens Scratch Hard- tool between 0 and 1000 g.
ness Tester, Model 601, is marketed by Erichsen Company The test films for this tester are prepared on panels contain-
[30] and conforms to ISO 1518, BS 3900:E2 and Stichting ing a hole in the middle for locating on a turntable. In making
Nederlands Normalisatie-Instituut (NEN) 5336. This device a test, the panel is rotated counterclockwise. Three tools are
simulates a scratching or scouring action and creates stresses provided: "thumb-nail" contour shear tool (S-20) lapped to a
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FIG. 12-Sheen Scratch Tester. (Courtesy of The Paul N. Gardner Company, Inc.)
FIG. 13-Steel Wool Scratch Tester. FIG. 14-Teledyne Taber Shear/Scratch Tester. (Courtesy of
Courtesy of The Paul N. Gardner Com- The Paul N. Gardner Company, Inc.)
pany, Inc.)
simple and quick method for testing the surface hardness of

25-mm radius with a 30 ~ clearance, a diamond cut to the coatings with regard to stresses inflicted by scratching with
shape (diamond pyramid) of a corner of a cube, and a dia- sharp edges or other rough surfaces. The speed of measuring
mond cut to the shape of a cone.
even permits testing during the production, e.g., coil coating.
Wolff-Wilborn Scratch-Hardness Tester--This test appa- The test instrument, Model 291, enables the test to be carried
ratus, shown in Fig. 15, is another pencil method that belongs out in accordance with Wolff-Wilborn and ensures that the
to the group of scratch-hardness testing instruments that is a specified force and angle remain constant throughout. This
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V. (DIN 53 153) [33]. Like its n a m e implies, it is a universal

h a r d n e s s tester.
Indentation Hardness
M i c r o h a r d n e s s testing has proved to be very p o p u l a r in
m a n y industries b e c a u s e of its simplicity a n d nondestructive
nature. It has b e e n p a r t i c u l a r l y successful for quality control
w o r k w h e r e it can be used as an i n d i c a t o r of surface durabil-
ity and, in s o m e cases, of strength. Static i n d e n t a t i o n hard-
ness tests are "nondestructive" physical tests that e m p l o y
either a ball, cone, or p y r a m i d t h a t is forced into a surface.
The load p e r unit a r e a of i m p r e s s i o n is t a k e n as the m e a s u r e
of hardness. The testers use indentors classified by the follow-
ing names: Brinell, Rockwell, Vickers, a n d Knoop. A sketch of
these indenters is s h o w n in Fig. 17.
The h a r d n e s s of a m a t e r i a l can be defined as a m e a s u r e of
its resistance to indentation. Basically, a n i n d e n t a t i o n hard-
ness test can be classified into two categories [34]:
FIG, 15-Wolff-Wilborn Scratch Hardness Tester. (Cour-
1. Those b a s e d on a m e a s u r e of the residual d e f o r m a t i o n
tesy of Erichsen GMBH & Co.)
after the i n d e n t e r was removed.
2. Those b a s e d on the l o a d - i n d e n t a t i o n characteristics.
i n s t r u m e n t is specified in MIL C 27227, w h i c h has b e e n dis- I n d e n t i o n h a r d n e s s values have been r e p o r t e d in a n u m b e r
c o n t i n u e d as a specification. of different ways, such as: d e p t h of the indentation, the w i d t h
In the test, pencils of various grades of h a r d n e s s are moved of the indent, the l o a d necessary to p r o d u c e a specific d e p t h
over the p a i n t e d surface at an angle of 45 ~ to the h o r i z o n t a l o r length of indent, the l o a d divided by the projected, p l a n a r
a r e a of indent, etc. The l o a d divided by the projected, p l a n a r
with a 7.5-N (735-dyne) force. The softest pencil h a r d n e s s
a r e a of indent is really an expression of p r e s s u r e a n d has
that p r o d u c e s injury to the film is the Wolff-Wilborn h a r d n e s s
b e c o m e the widely accepted m e t h o d of r e p o r t i n g i n d e n t a t i o n
of the coating.
hardness.
Consider the force on an a n n u l u s of r a d i u s x a n d the w i d t h
Universal Hardness and Adhesion Test Instrument--This dS. The load L is d i s t r i b u t e d over the c o n t a c t a r e a as a pres-
Erichsen Model 413 h a r d n e s s tester, s h o w n in Fig. 16, will sure P. The a r e a of the a n n u l u s lying on the curved surface of
allow a n o p e r a t o r to d e t e r m i n e Clemen S c r a t c h Hardness, the i n d e n t a t i o n is 2wxdS, a n d the force on it is P2wxdS a n d
Micro S c r a t c h H a r d n e s s ( m a r resistance), a n d the Buchholz can be resolved into two c o m p o n e n t vectors, dH a n d dV. By
I n d e n t a t i o n H a r d n e s s test Deutsches Institut ftir N o r m u n g e. conditions of symmetry, the h o r i z o n t a l c o m p o n e n t dH is an-
FIG. 16-Universal Hardness and Adhesion Test Instrument. (Courtesy of Erichsen

GMBH & Co.)
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E n g l a n d in 1925 by R. S m i t h a n d G. S a n d l a n d [36]. Its early

a c c e p t a n c e by i n d u s t r y was limited to the largest l a b o r a t o -
ries, a n d its use was chiefly for research purposes.
I n d e n t a t i o n h a r d n e s s testing using the Brinell a n d
Scleroscope m e t h o d s grew in i m p o r t a n c e , a n d d u r i n g W o r l d
W a r I practically all h a r d n e s s testing was d o n e o n either one
or the o t h e r of these instruments. During this time, Stanley P.
Rockwell, a metallurgist in a large ball-bearing m a n u f a c t u r -
ing plant, was p a r t i c u l a r l y c o n c e r n e d with h a r d n e s s control
of ball races. As a result, he invented the tester w h i c h has
b e c o m e k n o w n as the Rockwell H a r d n e s s Tester.
The i n d e n t a t i o n h a r d n e s s of a m a t e r i a l is related to its
modulus. The t h e o r y of the i n d e n t a t i o n h a r d n e s s of an elastic
m a t e r i a l test has b e e n derived for a spherical indenter.
Young's m o d u l u s E is related to the indenting force F, the
r a d i u s of the i n d e n t e r r, a n d the d e p t h of i n d e n t a t i o n h. If the
FIG. 17-Hardness indenters' geometries and indentation m o d u l u s of the i n d e n t e r is m u c h greater t h a n the m o d u l u s of
shapes. (Courtesy of Wilson Instruments, Inc.) the test surface, the r e l a t i o n s h i p is
E = (3/4)(1 - vZ)r - 1/2h -2/3F (4)
nihilated by an equal a n d opposite dH on the opposite side of
the annulus. The vertical c o m p o n e n t dV is therefore P2zrxdS w h e r e v is Poisson's ratio (lateral c o n t r a c t i o n versus longitu-
and dinal extension). In the case of viscoelastic materials, a simi-
lar relationship holds, b u t the variation with i n d e n t e r r a d i u s
d2 a n d p e n e t r a t i o n are s o m e w h a t modified. M e r c u r i o [37] has
L = P-n--- (2)
4 discussed the relationship of Tukon h a r d n e s s to modulus.
The theory of i n d e n t a t i o n h a r d n e s s tests on h o m o g e n e o u s
4L L
P - - (3) m a t e r i a l s has received m u c h interest in the last few decades.
7rd2 Ap
D. T a b o r has b e e n w o r k i n g intensely in this area. In his recent
where P is the m e a n pressure a n d Ap is the projected, p l a n a r p a p e r [38] he said
a r e a of indent. Therefore, the m e a n pressure on the surface of The hardness of a solid is usually u n d e r s t o o d to m e a n its
the i n d e n t e r is equal to the ratio of the load L to Ap. resistance to local d e f o r m a t i o n . The simplest m e t h o d of
The i n d e n t a t i o n hardness tests are p e r f o r m e d by pressing quantifying it is to press a h a r d i n d e n t e r of specific geom-
an i n d e n t e r of p r e s c r i b e d g e o m e t r y against the test surface. etry into the body, divide the load by the a r e a of the
The load is controlled at s o m e c o n s t a n t value, a n d the dura- i n d e n t i o n formed, a n d express the a n s w e r in units of
k i l o g r a m s p e r square millimeters o r pascals (1 kg m m -2
tion of the i n d e n t a t i o n process is usually specified for a visco-
10 7 Pa) . . . . F o r elastic solids such as rubber, the
elastic material. The size of the i n d e n t a t i o n m a y be m e a s u r e d i n d e n t a t i o n p r e s s u r e is a direct m e a s u r e of the elastic
with a m i c r o s c o p e after the removal of the load. An alternate p r o p e r t i e s of the material.
p r o c e d u r e is to m e a s u r e the d e p t h of i n d e n t a t i o n after a given
time interval. The latter p r o c e d u r e is preferred for viscoelas- A n o t h e r example of this type study is that of Lebouvier et al.
tic bodies. The h a r d n e s s n u m b e r is generally calculated by [39].
dividing the l o a d by the area of the indentation. The h a r d n e s s W. W. W a l k e r [40] evaluated the K n o o p h a r d n e s s of three
values o b t a i n e d are i n d e p e n d e n t of the s p e c i m e n thickness if organic coatings using a Model LR Tukon M i c r o h a r d n e s s
the i n d e n t a t i o n d e p t h is less t h a n one tenth the s a m p l e thick- Tester in a c c o r d a n c e with ASTM Test Methods for Indenta-
ness. tion H a r d n e s s of Organic Coatings (D 1474) except he cali-
Since coating films are very thin, the i n d e n t a t i o n a p p a r a t u s b r a t e d the i n s t r u m e n t at 100 g l o a d a n d ran the tests at 200 g
m u s t be capable of m e a s u r i n g precisely very small indenta- load. In addition, he tested the pencil hardness of the s a m e
tions. Because it is difficult to set the zero position, a small coatings in a c c o r d a n c e with ASTM Test M e t h o d D 3363.
p r e l o a d m a y be applied before the a p p l i c a t i o n of the m a i n C o m p a r a t i v e d a t a are shown in Table 2.
load. A n u m b e r of different instruments, d e s c r i b e d later, have W. W. W a l k e r c o n c l u d e d that a useful correlation existed
been devised for m a k i n g i n d e n t a t i o n hardness m e a s u r e m e n t s between the 200-g K n o o p i n d e n t a t i o n h a r d n e s s a n d pencil
on organic coatings.
The beginning of the twentieth century m a r k e d a milestone TABLE 2--Comparison of pencil and Knoop hardness of selected
in the history of h a r d n e s s testing. In t 900, Dr. J. Brinell, chief coatings.
engineer at Fagersta I r o n Works in Sweden, p r e s e n t e d a pa- Lead Paint
p e r to the Swedish Society of Technologists in w h i c h he Pencil Hardness, Hardness,
described his ball test. In the s a m e year, he showed his Paint Lead No. KI-IN KHN Difference
hardness tester at the Paris Exposition. Following the Brinell Epoxy powder 5H 51.5 30.2 21.3
innovation was the d e v e l o p m e n t of the scleroscope (1906) Polyurethane 3H 45.3 22.7 22.6
[35]. The 136 ~ d i a m o n d p y r a m i d hardness indenter, com- Solvent Epoxy H 31.7 8.9 22.8
Metal Panel . . . . . . 195 _+ 1 ...
m o n l y referred to as the Vickers indenter, was i n t r o d u c e d in
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HARDNESS 565
hardness of thick paint films but that further work needs to be To achieve this, two separate head assemblies were re-
done. quired. Basically the rheometer consists of a specimen stage
Krautkrgmer Branson conducted a similar test using their or platform, indenter-LVDT transducer head assembly,
MicroDur Portable Hardness Tester fitted with a Vickers in- weights, transducer amplifier indicator, and a 10-in. (25.4
denter. The preliminary results, shown in Fig. 18, represent cm) strip chart recorder. In normal use, the specimen or test
an evaluation of eight organic coatings. The results are prom- panel is clamped on the platform, and the instrument is
ising. However, additional work is needed. zeroed in with the indent or tip just touching the specimen.
This is done by using the knurled rings on the heads and the
Bell Telephone Laboratories Indenting Rheometer--The BTL platform ring (the rings on the sensitive head have 80 threads
Indenting Rheometer, shown in Fig. 19, was designed and per inch or 80 threads/25.4 mm) to obtain a coarse adjust-
developed by Eugene M. Corcoran of the Bell Telephone Lab- ment follow by a fine adjustment on the transducer amplifier-
oratories specifically for use as an indenting rheometer, sen- indicator. A load (weight) is applied to the weight tray (by
sitive enough for use with organic coatings but with sufficient means of an overhead pulley), and the depth of indentation is
load-deflection capacity to make it useful for relatively thick recorded as a function of time. After a specified period of
materials such as molded plastics and casting resins. time, the load is removed and the recovery is recorded.
Vicker8 Hardness
800
700 - 9 = ' ~
600 L-. . . . . . . . . . . . ~ - ~ ....
500 ......................................................................................................................................................
400 .........................................................................................................................................................................................
300 .........................................................................................................................................................................
200 I I L I J , i i
2H 2H 2H H H H H H
Pencil Hardness
FIG. 18-Comparison of Vickers hardness versus pencil hardness.
FIG. 19-Bell Telephone Laboratories Indenting Rheometer.
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Brinell Indentation Hardness Tester--In 1900, J. A. Brinell

p u b l i s h e d the results of his tests that involved pressing steel
balls into m a t e r i a l s [41]. The Brinell test is b a s e d on the
following f o r m u l a
P
H - (5)
1rD (D - X/-D
~ - d2
2
The r e l a t i o n s h i p b e t w e e n the h a r d n e s s H a n d the d i a m e t e r of

the d e p r e s s i o n d has b e e n w o r k e d out on a form for a given
size steel ball whose d i a m e t e r is D.
Buchholz Indention Hardness Tester--This device, s h o w n

in Fig. 20, is m a d e by the E r i c h s e n C o m p a n y [42] a n d has
b e e n s t a n d a r d i z e d in G e r m a n y [33]. It is a simple, p o r t a b l e
i n s t r u m e n t and, like the Knoop, m e a s u r e s the length of the
recovered i n d e n t i m p r e s s i o n after the toad has b e e n removed.
In fact, the resultant impression, t h o u g h m u c h larger, is quite
similar in a p p e a r a n c e to the K n o o p impression. FIG. 20-Buchholz Indention Hardness Tester. (Courtesy of
A d i a g r a m of the Buchholz I n d e n t i o n H a r d n e s s Tester in Erichsen GMBH & Co.)
use is shown in Fig. 21. Basically a weighted (500-g) wheel,
with an included angle of 60 ~ from center to each edge (total
angle of 120~ is p l a c e d on a c o a t e d test panel. The test panel
is m a r k e d "5" in the diagram, a n d the coating is m a r k e d "4."
The wheel is removed, a n d the length of the i m p r e s s i o n m a d e
b y the indenter, m a r k e d "3" in the diagram, that r e m a i n s is
m e a s u r e d by m e a n s of a small, 20 microscope, m a r k e d "2"
in the diagram, a n d an a t t a c h e d light source, m a r k e d "1" in
the diagram. To facilitate m e a s u r e m e n t , the i m p r e s s i o n is il-
l u m i n a t e d from the side, t h e r e b y creating a s h a d o w in that
side of the impression. The i m p r e s s i o n m a y be m e a s u r e d to
within 0.05 m m ( c o m p a r e d to 0.001 m m for the Knoop).
CDIC Hardness Penetrometer--Still a n o t h e r variation ap-

plied to artists' colors is the CDIC (the old Cincinnati-Dayton-
I n d i a n a p o l i s - C o l u m b u s Paint a n d Varnish P r o d u c t i o n Club) FIG. 21-Buchholz Indention Hardness Tester
H a r d n e s s P e n e t r o m e t e r [43]. A d i a g r a m of it is s h o w n in Fig. in use. (Courtesy of Erichsen GMBH & Co.)
22. By this device, a 1/2-in. chisel is caused to p e n e t r a t e the
film that has been a p p l i e d to metal. Chisel a n d m e t a l are
Using a F i s c h e r s c o p e | H100V M i c r o h a r d n e s s Tester, W.
wired in series with an electric bulb, w h i c h lights up w h e n the
W. Weiler developed a dynamic, nondestructive test m e t h o d
chisel contacts the panel. The i n s t r u m e n t was never c o m m e r -
to m e a s u r e the m i c r o h a r d n e s s of surface layers, coatings, a n d
cialized.
h o m o g e n e o u s m a t e r i a l s in the ultra-low l o a d range of 0.025
Fischerscope | Microhardness Tester2--The F i s c h e r s c o p e |
to 1 N [44]. The m e t h o d was b a s e d on using a conventional
H100V, shown in Fig. 23, is a d y n a m i c m i c r o h a r d n e s s tester
Vickers i n d e n t e r c o u p l e d to a d i s p l a c e m e n t m e a s u r i n g de-
w h i c h can be used on a variety of materials, including coat-
vice.
ings, to m e a s u r e h a r d n e s s u n d e r load. It works with very
small test loads up to 256 mN. D e t e r m i n a t i o n of h a r d n e s s General Electric Indention Tester3--This device, developed
b a s e d on the plastic and elastic d e f o r m a t i o n of a m a t e r i a l is b y C. Dantsizen, consists of a dial m i c r o m e t e r , the foot of
the direct result of m e a s u r e m e n t s u n d e r load. H a r d n e s s m e a - w h i c h t e r m i n a t e s in a metal sphere 0.20 in. (5 m m ) in d i a m e -
s u r e m e n t is expressed in N / m m 2, c o r r e s p o n d i n g to the quo- ter, a n d with m e a n s for applying a load. The d e p t h of indenta-
tient of l o a d P over area of i m p r e s s i o n A (whereby A can be tion is r e a d on the dial. The General Electric I n d e n t i o n Tester
derived directly from the d e p t h of indentation). This defini- was not widely used within the General Electric Co. n o r did it
tion of h a r d n e s s is physically meaningful b y providing a mea- gain i n d u s t r y acceptance.
s u r e m e n t of hardness to an u n c e r t a i n t y of _+ 1%. This ICI Pneumatic Microindenter--This c o m m e r c i a l l y avail-
requires exact m e a s u r e m e n t of l o a d a n d i n d e n t a t i o n depth, able device, 4 shown in Fig. 24, was developed b y M o n k a n d
w h i c h is possible with a F i s c h e r s c o p e | H100V M i c r o h a r d -
ness Tester.
3Christian Dantsizen, personal communication to G. C. Sward,
1938.
2Available from Fischer Technology, Inc., 750 Marshall Phelps Rd., 4Available from Research Equipment (London), Ltd., 64 Wel-
Windsor, CT 06095. lington Road, Hampton Hill, Middlesex, England.
www.iran-mavad.com

CHAPTER 4 8 - - H A R D N E S S 567
the apparatus and went further than Gardner et al. [46] in the
R interpretation and meaning of the curves. Included in the

data were curves showing how an alkyd finish changed prop-
erties as a function of temperature and accelerated weather-
ing.
Knoop Indenter--At the National Bureau of Standards
(now known as the National Institute of Standards and Tech-
nology), Frederick Knoop and his associates [47] developed a
diamond-based pyramid indentation tool as an improvement
over the Vickers indenter. This indenter gave well-defined
indentations and reproducibility of results when testing glass
o a J and crystals of the Mohs scale, and dental plastics and
enamels.
C.,SEL--H ; , The Knoop indenter, illustrated in Fig. 25, is a pyramidal
30 ~ BEVEL-'-- diamond with included longitudinal angles of 172~ 30' and an
EO included traverse angle of 130~ 0'. It produces a diamond-
shaped (rhomb) indentation having long and short diagonals
of an approximate ratio of 7 to 1. The depth of indentation is
._t about 1/30th of its length. In essence, the Knoop indenter is a
shallow double wedge. The Knoop indenter is subsequently
mounted in a machine which applies a load, without impact,
at a constant rate and has a microscope equipped with a filar
eyepiece for measuring the size of the indentation within
_ 1%. Although the Knoop indentation hardness method was
FIG. 2 2 - C D I C H a r d n e s s P e n e t r o m e t e r . developed originally for measuring the hardness of metals,
shortly thereafter Lysaght [48] suggested its use for organic
coatings. Gusman [49] reported on its use for organic coat-
Wright [45], As the name implies, it is a pneumatic type (air ings. The instrument was specified in ASTM D 1474, adopted
pressure) instrument that measures and records the depth of in 1957.
indentation or penetration of a ball-ended needle under the In its use for organic coatings, a load of 25 g is applied for
application of a constant load and the recovery subsequent to 18 s, after which time the indenter is removed from the coat-
removal of the load. The needles have steel or sapphire ends ing, and the length of the long diagonal of the impression
and vary from 0.0025 to 0.063 in. (1.6 mm) in radius. A remaining in the coating is measured as quickly as possible.
preload of 0.1 g must be applied. A 5-in. (12.7-cm), pneu- This dimension is then used to obtain the Knoop Hardness
matically operated, strip-chart recorder provides curves of Number (KHN), Which is the ratio of the load, in kg/mm 2, to
the indentation and recovery thereof. An indenter movement the projected planar area.
of 6 /xm causes a full-scale deflection on the recorder. A
calibration knob is divided into 0.5-/xm divisions, thereby L L (6)
KHN-
giving an accuracy of about 0.2/xm (0.008 rail). Ap ICp
However, the chart can be read to within 0.1 /xm (0.004 where
mil). The specimen stage or table is a Frigister unit which can L = load in kilograms applied to the indenter,
raise or lower the specimen temperature. Disadvantages are Ap -- projected area of indention in m m 2,
that it is not a sturdy instrument and must be handled with l = measured length of the long diagonal of the indenta-
some care. The panel or specimen must be small enough to fit tion in ram, and
on the rather small Frigister stage. Also, the use of relatively Cp = indentor constant relating l t o Ap, usually 7.028
sharp indenters (referred to by the authors as needles) means 10-10.
that, in many cases, the organic coating will be cut or pene- Most writers refer to I and Ap as the unrecovered length and
trated, yielding spurious results. area, but as we shall see later, this is not true. Elastic recovery
The load limit appears to be less than 100 g, and the design of the indentation impression takes place the instant the
does not appear to be conducive to the use of commercially indentor is removed, and substantial viscoelastic recovery
made Knoop or Vickers pyramid indenters. Finally, results takes place before a measurement can be made.
obtained using the Frigister to heat or cool the specimen can The real difference between the P fund and Knoop methods
be misleading. If the indenter is at room temperature, then is that with the Pfund, the hardness measurement is made
the specimen temperature where the indenter contacts will when the indenter is under load, while with the Knoop the
not be the same as the temperature of the Frigister. However, measurement is made of the indentation impression remain-
the I e I pneumatic microindentation apparatus was still the ing after both the load and indenter have been removed. This
first commercially available instrument that appears to have remaining Knoop impression is smaller than the original
the sensitivity necessary to be seriously considered as an made while under the loaded indentor because all of the
indenting rheometer suitable for use with organic coatings. elastic and substantially all of the viscoelastic (creep) recov-
Monk and Wright gave some results obtained from the use of ery occur in the indentation impression once the load is
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removed. This will be explained and actually shown in the quite coincidentally, the numerical results can be quite simi-
subsection on theory. lar. This similarity in numerical results (PHN ~ KHN) with
Therefore, the operation of the Pfund and Knoop methods organic coatings probably could never have been achieved
rests on two entirely different principles. Each measurement deliberately. How fortunate for the paint industry that the
represents a completely and substantially different point on a equivalence exists.
viscoelastic creep-creep recovery curve for any given material Of the two test methods, the Modified Pfund and the Tukon
or organic coating (see Fig. 26). Yet, the amazing part is that, gage with the Knoop indenter, the former is a dynamic hard-
FIG, 23-Fischerscope | H100V Microhardness Tester. (Courtesy Fischer Technol-

ogy, Inc.)
FIG. 24-1CI Pneumatic Microindenter. (Courtesy Research Equipment (London), Ltd.)
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~ RATIOOF Fig. 27, consists of a counterbalanced brass beam containing

DIAGONALS the Indenter C. Illuminating light is reflected into the in-
denter by the clear Glass G and reflected back up to the
172~30' INCLUDEDANGLES 130~ 7.11 TO 1 Microscope 0, where the planar diameter of indent is mea-
FIG, 25-Diagram of Knoop Diamond Indenter. sured by means of a filar eyepiece (shown in the upper right
hand corner of Fig. 27). The results are expressed as the load
on the indentor, in grams, necessary to achieve a specified
ness test and the latter is a static hardness test. Those in the diameter of indent. Table 3 shows typical results at an indent
automotive industry know how difficult it can be to obtain of 3 divisions (each division is approximately 0.1 ram). Addi-
repeatable Knoop hardness numbers on metallic finishes. tional data can be found in the work by Pfund, and Schuh and
Secondly, with some types of finishes, the ends of the long Theuerer [51,52].
diagonal of the Knoop impression recover, yielding rounded In making a hardness determination, instead of attempting
ends. In others, the organic finish sometimes recovers in such to find the exact load necessary to produce the specified
a manner as to partially close the indent near the ends of the diameter of indent, it was preferable to apply loads producing
long diagonal. However, the main reason for this preference diameters both greater and less than the value sought and
is that the Pfund measures the indent under load. That is then interpolate to the specified diameter. However, this
when the coating is resisting the indentation.
method is not precise because the relationship between load
Pfund Hardness Tester--After numerous, unsuccessful at- and diameter is not linear. Although this method of always
tempts to grade the hardness of varnishes by means of the achieving the same indent results in geometrically similar
scratch test in which graded pencils, crystals, etc. were used, indents in all cases, this theoretical consideration of geomet-
A. H. P fund, an associate professor of physics from Johns rically similar indents is significant only when the material
Hopkins University, Baltimore, MD, modified the Brinell In- being measured is thick enough for the hardness measure-
dention Test [50]. In this method the measurements are made ment to be uninfluenced by the thickness of the material.
on the organic coating while the loaded indentor is in contact Such is not the case here. The theoretical consideration of
with the coating. At first a 1/16-in.-diameter steel ball was geometrically similar indents will be discussed in the subsec-
forced under load into the varnish, and the diameter of the tion on theory.
resultant circular impression was measured under the micro- As this method was rather tedious and time consuming, the
scope. This was soon changed to a quartz cylinder terminat- instrument and method were modified in the early 1950s by
ing in a hemisphere 1/4-in. (6 ram) in diameter. The results are the Bell Telephone Laboratories. The modified Pfund and test
expressed as the load on the indentor, in grams, necessary to method were incorporated into ASTM D 1474 [53]. The Modi-
achieve a specified diameter of indent. The device, shown in fied Pfund device is shown in Fig. 28. The instrument devel-
--[ S
: E.EO
= Y=)I +Y2
S S S -t/k1
. . . . i-e J
S
)'2 =
st)
LOAD
L LOAD
YU= f ( ~ l
TIME
t
APPLIED REMOVED
FIG. 26-Creep and creep recovery curves of viscoelastic material.
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C)
,L
M2
V, /
Ai W
FIG. 27-Diagram of Pfund Hardness Indenter.
oped at the Bell Telephone L a b o r a t o r i e s a n d initially a d o p t e d

by the ASTM as M e t h o d D 1474 is shown in Fig. 29.
The i n d e n t e r is a t r a n s p a r e n t , colorless synthetic quartz o r
s a p p h i r e h e m i s p h e r e whose spherical r a d i u s is 0.125-in. (1/4-
in.) (6 m m ) d i a m e t e r with a m a x i m u m spherical eccentricity
of 0.002 in. (0.05 ram). The i n d e n t e r is m o u n t e d in a h o l d e r
weighing 1000 g so that the i n d e n t e r is always u n d e r a l o a d of
1000 g w h e n m a k i n g m e a s u r e m e n t s . Hence, we see that in
this m e t h o d the l o a d is kept c o n s t a n t a n d the resultant diame-
ter of i n d e n t is recorded. This is exactly opposite to the
original Pfund m e t h o d .
In operation, the test panel is b r o u g h t into contact with the
l o a d e d indenter, a n d after 60 s (while still u n d e r load) the
d i a m e t e r of the circular i m p r e s s i o n is m e a s u r e d by m e a n s of
a filar m i c r o m e t e r m o u n t e d in the eyepiece of the micro-
scope. E a c h filar division r e p r e s e n t s 0.1 m m , a n d the diame-
ter of the i m p r e s s i o n is converted into a Pfund h a r d n e s s
n u m b e r (PHN), expressed in k g / m m 2 units, as follows
L L 1.27
PHN - - - - - - - (7)
A 'rrd 2 d2
FIG. 28-BTL designed modified Pfund Hardness Gage.
TABLE 3--Pfund hardness.

Thickness, Hardness at where
Coating" rail Three Divisions L = l o a d in k i l o g r a m s (1 kg) a p p l i e d to the indenter,
A 0.7 730 A = p l a n a r or p r o j e c t e d a r e a of i n d e n t i o n in square milli-
1.3 380 meters, a n d
3.0 47 d = d i a m e t e r of the i n d e n t a t i o n in millimeters.
B 0.6 435 Therefore, the PHN is the load, in kilograms, divided by the
1.I 130 p l a n a r o r projected a r e a of indentation.
3.5 <5 The p l a n a r or p r o j e c t e d area of i n d e n t deserves s o m e expla-
C 0.5 188 n a t i o n a n d was covered in detail in the introduction. Figure
1.0 35 30 illustrates w h a t is m e a n t by this for the case of a spherical
1.8 <5 i n d e n t o r where the h a r d n e s s m e a s u r e m e n t is m a d e while the
h e m i s p h e r e is u n d e r l o a d a n d in contact with the coating.
H 0.6 875
1.1 720 Initially the h a r d n e s s o r PHN was r e p o r t e d as 10d. The rea-
3.1 370 son for changing it to the l o a d divided b y the p l a n a r a r e a of
"A = 10-gal e s t e r - g u m v a r n i s h , B = e s t e r - g u m v a r n i s h a t 25 gal, C = e s t e r -
i n d e n t a t i o n was to m a k e the r e p o r t e d PHN results have the
g u m v a r n i s h at 40 gal, H = l a c q u e r e n a m e l . s a m e units of m e a s u r e m e n t as the K n o o p h a r d n e s s n u m b e r
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HARDNESS 571
where the cone had an included angle of 120~ and the tangen-
tial spherical tip of 0.40 mm in diameter.
Wilson| | Hardness TesterS--Vincent E. Lysaght of
Wilson Mechanical Instrument Co. took the work of the late
Frederick Knoop and applied the technique to the testing of
nonmetallic materials ranging from plastics to diamonds [48]
using their Tukon Hardness Tester.
The Wilson| | Microhardness Tester offers a variety
of possibilities as a tool in research and development, materi-
als testing, and quality control program. Some coating manu-
facturers use the Sward Hardness Tester to get approximate
hardness values but rely on this tester to qualify a coating. It
can be fitted with either a Vickers or a Knoop indenter. A
comparison of these two indenters is shown in Fig. 31. A
Knoop indenter is typically used to measure the hardness of
coatings, whereas the Vickers indenter is used for hardness
testing of harder materials such as metals.
This instrument, with the precision of x-y stage, makes it
possible to locate indentions with great accuracy. The instru-
ment has undergone many refinements such as having a
computer controlled X-Y Auto Traversing Stage System and a
software program for running statistical process analyses.
One of their latest instruments is shown in Fig. 32.
Wallace Microhardness Tester H-76--The Wallace Mi-
croindention Tester [55], like the Wilson| | Hardness
Tester, can also employ a Vickers diamond pyramid indentor
FIG. 29-Commercial modified Pfund Hardness Gage. and uses a capacitive form of measurement to determine the
depth of indention under load. Figure 33 shows the Wallace
tester. This instrument measures the depth of penetration of
/ an indentor into a material under a known load, the depth of

penetration being a function of that indicated on a dial gage.
Basically, the instrument consists of an indentor, sup-
ported by leaf springs, attached to a parallel plate capacitor
~
which forms one half of a capacitance balance circuit. When
R S P H E R I C A L INDENTER
no load is applied, the indentor "floats" in a "null" position,
electronically balanced by the second half of the capacitance
balance circuit. This "null point" (i.e., the point of electrical
ANAR OR PROJECTED AREA A= 7 r r 2
balance) is indicated by a zero reading on the center zero
meter located in the base of the instrument.
The test panel is supported on a table that is raised or
lowered by means of an accurately made wedge. The dial
micrometer gage follows and indicates the lateral movement
of the wedge which is, in turn, converted to vertical move-
ment of the table. Primary loads of usually less than 1 g and
secondary loads between 1 and 300 g are placed on the weight
platform, which, in turn, is attached to the indenter.
In operation, the instrument is first set to a zero position,
D= DIAMETER OF INDENT
and a test panel is placed on the specimen table or stage. The
FIG. 30-Planar area of contact of the Pfund Indenter. panel is raised to the indenter. The primary load is applied to
the indentor, and the system is once again zeroed. The secon-
(KHN) also in ASTM Method D 1474. Surprisingly, the PHN dary load is applied for the predetermined time during which
and KHN values come very close numerically. the panel is raised to maintain the indenter in its zeroed
position. At the end of the predetermined time, the reading on
Rockwell Hardness Tester--Indentation hardness tests have the gage is taken and the corresponding depth of indentation
been used as a means of checking the uniformity of the is obtained by dividing the gage reading by the wedge ratio
mechanical properties of metals since the 19th Century. The (20 to 1 or 40 to 1). The Wallace Microhardness Tester was
Rockwell Hardness Tester began as a hard steel conical in-
denter having a hemispherical tip of 0.50 mm in diameter. It 5Available from Wilson Instruments, 6 Emma Street, Bingham,
was first used by Hugueny (1865) during his patent studies of NY 13905.
6Available from H. W. Wallace & Co., Ltd., St. James Road,
hardness [54]. The machine was improved when Wilson in Croydon, England and Testing Machines, Inc., 400 Bayview Avenue,
1926 produced his polished spheroconical diamond indenter Amityville, N.Y. 11701.
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FIG. 31-Comparison between a Knoop and Vickers Indenter. (Courtesy Wilson Instruments, Inc.)
FIG. 33-Wallace Microhardness Tester H-7. (Courtesy of H.

W. Wallace & Co., Ltd.)
FIG. 32-Wilson| | Hardness Tester. (Courtesy Wil-

Indentation Hardness Miscellaneous
son Instruments, Inc.) Imprint Resistance--Organic coatings for chairs, desks,
a n d o t h e r furniture often a p p e a r hard, b u t when subjected to
used in a cooperative investigation by the M a n c h e s t e r Sec- c o n t i n u o u s p r e s s u r e they m a y creep, yield, or flow e n o u g h to
tion of the Oil and Colour Chemists' Association [56] a n d is be p e r m a n e n t l y a n d seriously d a m a g e d . Print resistance is a
c o m m e r c i a l l y available. According to Fink-Jensen [57], it is m e a s u r e of this p h e n o m e n o n . The p r i n t resistance of an or-
possible to o b t a i n an accuracy of 0.3 to 0.5/xm or a b o u t 0.01 ganic coating should be related to its glass transition temper-
to 0.02 mil. ature, Tg. Andrew Mercurio discussed this viscoelastic
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CHAPTER 4 8 - - H A R D N E S S 573
behavior of polymers at length in his article [37]. Expressed

mathematically
P
AV (8)
B-
V
F/A
E - (9)
,X//l
F/A
G - (10)
0
where B is the bulk modulus expressed in terms of the applied
pressure, P, the initial volume, V, and the decrease in volume,
AV. In tension, we obtain Young's modulus, E, given in terms
of the applied force, F, per unit of original cross-sectional
area, A, the original length, I, and the change in length, Al. The
shear modulus, G, is also expressed in terms of the applied
force per unit original cross-sectional area and the angle of
deformation, O. In each case the numerator is termed the
stress and the denominator is defined as the strain. Only two
of these moduli represent independent properties of the iso-
tropic material in question since the moduli are related
through the Poisson ratio, v. FIG. 34-Twisting cork hardness tester.
E = 2(1 + v)G (11)

is employed for coating hardness testing in France and Eu-
E
B - (12) rope. The specific apparatus employed in these methods is
3 (1 - 2v)
different, but, in principle, the tests are the same. These tests
This simple, basic method was adopted by the Federal Gov- are described below.
ernment (Federal Test Method Standard No. 141, Method The pendulum hardness tests are closely related to the
6211, Print Test). However, in 1980, the federal government Sward Rocker Hardness Test. The hardness pendulum rests
canceled this test method in favor of an ASTM test method (D on the test surface and pivots on two hardened steel balls. The
2091: Test Method for Print Resistance of Lacquers). Another time required for the pendulum to decay from some initial
ASTM test method is Test Method D 1640: Test Methods for amplitude to some final amplitude is a measure of the hard-
Drying, Curing, or Film Formation of Organic Coatings at ness of the coating film.
Room Temperature. Print resistance may be evaluated by the The theory of the pendulum or rocker hardness testing was
load required to make an impression within a given time, the derived by Persoz [59]. Pierce et al. [60] made a detailed
time required under a given load, or by comparing the im- experimental investigation of the Sward Rocker Hardness
print under identical loads and duration of test. The tempera- Test. The observed mechanics of the Sward Rocker were
ture may also be varied. This test is sometimes used as a found to be in complete agreement with the Persoz analysis.
drying time test. The Sward hardness of a coating was found to be influenced
Twisting Cork Tester--This device [58], shown in Fig. 34, by temperature, humidity, film thickness, substrate hardness,
was an attempt to simulate a thumb being pressed on a film and air pressure. Coefficient of rolling friction values were
and then twisted. It consists of a cork at the lower end of a recovered from the values of Sward hardness and the physi-
vertical rod upon which may be placed varying weights. By cal parameters of the rocker. The coefficients of rolling fric-
means of an arm in the rod, the cork can be turned or twisted tion are related to the shear modulus and loss tangent of the
through any desired angle. coating. The analysis shows that if the physical parameters of
The average reader may consider that perhaps this device different rockers or hardness pendulums are known, it is
belongs in the section on drying time. However, it was devel- possible to relate the hardness values obtained on different
oped for measuring the hardness of oils and oil mixtures, instruments.
which can be soft enough to defy the use of more conven- Pendulum or damping is the least understood hardness test
tional methods. method. A pendulum supported on the specimen by a ball or
cylinder was applied to hardness testing by Le Rolland [61]
and can be used to measure strain hardenability. Similarly,
Pendulum-Rocker (Damping) Hardness
the Herbert Pendulum Tester [62] employed the strain-
A few pendulum hardness tests are in use by the coating hardenability principle to measure hardness. The Herbert
industry. The Sward Rocker Hardness Test is widely used in Pendulum Tester consists of a 4-kg arched casting which is
the United States; The K6nig Pendulum Test is commonly supported on the horizontal plane surface of the specimen by
used in Germany and Europe; and the Persoz Pendulum Test a 1-mm-diameter ball. The ball can be either hard steel or
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d i a m o n d . In a p e n d u l u m h a r d n e s s test, an inverted com- p e n d u l u m to d i m i n i s h from the initial to the final value. It is

p o u n d p e n d u l u m is s u p p o r t e d on a h a r d steel ball w h i c h rests d e s c r i b e d in the ISO R e c o m m e n d a t i o n 1522 as follows:
on the m e t a l u n d e r examination. The h a r d n e s s is m e a s u r e d The p e n d u l u m rests on two stainless steel balls, 5 _+
b y the d a m p i n g p r o d u c e d as the p e n d u l u m swings from side 0.005 m m diameter, of h a r d n e s s HRC 63 _ 3, 30 _+ 0.2
to side. W h e n a p p l i e d to p o l i s h e d plate glass, the p e n d u l u m m m apart, a n d is c o u n t e r p o i s e d (to adjust the n a t u r a l
oscillates so that ten single swings requires 100 s. If the device frequency of oscillation) b y m e a n s of a weight sliding on
a vertical r o d a t t a c h e d to a cross bar. The p e r i o d of
is t h e n p l a c e d o n a s p e c i m e n of lead, the time h a r d n e s s (for
oscillation should b e 1.4 +_ 0.2 s o n a polished plate glass
ten swings) is only 2 to 4 s, and o t h e r metals give i n t e r m e d i a t e panel; the time for d a m p i n g from a 6 ~ d i s p l a c e m e n t to a
values. This device does not a p p l y to m e a s u r i n g coating h a r d - 3 ~ displacement, on the s a m e substrate, should be 250 _+
ness, b u t those d e s c r i b e d b e l o w use this p e n d u l u m principle. 10 s. The total weight of the p e n d u l u m should be 200 _
KOnig Pendulum--The K6nig p e n d u l u m h a r d n e s s tester 0.2 g.
[63] is currently m a n u f a c t u r e d in E n g l a n d by Sheen, Ltd. a n d
Persoz Pendulum--Persoz designed the p e n d u l u m h a r d -
in G e r m a n y by Erichsen G M B H & Co. The one shown in Fig.
ness tester [59] shown in Fig. 35. It is m a n u f a c t u r e d in Ger-
35 is m a n u f a c t u r e d b y Sheen, Ltd. It uses the d a m p i n g p r o p -
m a n y by Erichsen GMBH & Co. It was a result of Persoz's
erties of organic surfaces (e.g., paints, coatings, plastic mate-
m a t h e m a t i c a l analysis a n d e x p e r i m e n t a l studies. It is w r i t t e n
rials, films of all kinds, a n d p a p e r ) to d e t e r m i n e the hardness.
up in the ISO R e c o m m e n d a t i o n 1522 as follows:
The m e a s u r e m e n t s are so sensitive that the drying process of
The p e n d u l u m rests on two stainless steel balls, 8 _+
layers of p a i n t c a n b e followed from the start of the drying to
0.005 m m diameter, of h a r d n e s s HRC 59 _+ 1, 50 -+ 1 m m
c o m p l e t e hardening. It has b e e n s t a n d a r d i z e d in the United apart. A c o u n t e r p o i s e is not provided. The p e r i o d of oscil-
States a n d G e r m a n y . It is in a c c o r d a n c e with ASTM D 4366: lation should be 1 -+ 0.001 s on a polished plate glass
Test M e t h o d for H a r d n e s s of Organic Coatings b y P e n d u l u m panel a n d the t i m e for d a m p i n g from a 12 ~ d i s p l a c e m e n t
D a m p i n g Tests, DIN 53 157, ISO 1522, Association Suisse de to a 4 ~ d i s p l a c e m e n t on the s a m e s u b s t r a t e s h o u l d be at
N o r m a l i s a t i o n (SNV) 37 112, a n d N a t i o n a l F e d e r a t i o n of Tex- least 420 s. The total weight of the p e n d u l u m s h o u l d be
tiles (NFT) 30 016 for p e n d u l u m h a r d n e s s test instruments. 500 _+ 0.1 g, a n d its center of gravity at rest s h o u l d be 60
In its operation, the oscillations of a s t a n d a r d p e n d u l u m _+ 0.1 m m b e l o w the p l a n e of the fulcrum, the p o i n t e r tip
being 400 + 0.2 m m b e l o w the plane of the fulcrum.
s u p p o r t e d on the test surface by balls are d a m p e n e d m o r e
strongly on softer surfaces. The degree of d a m p e n i n g is mea- The Persoz p e n d u l u m is p r o n e to skidding on surfaces
sured b y the time in seconds taken for the a m p l i t u d e of the having a low coefficient of friction. However, c o m p a r e d to the
K6nig p e n d u l u m , the Persoz p e n d u l u m is p a r t i c u l a r l y useful
with relatively soft organic coatings. This is a result of longer
d a m p i n g time of the Persoz p e n d u l u m (about two times t h a t
of the K6nig), w h i c h m a k e s it m o r e sensitive to small differ-
ences b e t w e e n soft organic finishes where the d a m p i n g times
are relatively short. The Persoz p e n d u l u m h a s b e e n s t a n d a r d -
ized: United States, ASTM D 4366; France, NTF 30 016.
A c o m p a r i s o n of similarities a n d differences b e t w e e n the
K6nig a n d the Persoz p e n d u l u m h a r d n e s s i n s t r u m e n t s is
shown in Table 4. BYK-Gardner, Inc. d i s t r i b u t e d a g r a p h
w h i c h c o m p a r e s K6nig h a r d n e s s values with Persoz h a r d n e s s
values. This g r a p h is shown in Fig. 36. The source of the d a t a
is r e p u t e d to be from Volkswagen Co.
Rolling Ball Hardness Tester--Dr. H o w a r d Moore devised a
rolling ball tester at the Navy Yard L a b o r a t o r i e s in Philadel-
phia. A d e s c r i p t i o n of it a p p e a r s in the l l t h edition of
Gardner~Sward Physical and Chemical Examination of Paints,
Varnishes, Lacquers, and Colors, 1950. The device was used to
evaluate the drying times of coatings a n d m e a s u r e d the t i m e
r e q u i r e d for a small steel ball to roll a fixed distance over the
coating. Using this principle, a n e w i n s t r u m e n t for testing
h a r d n e s s p r o p e r t i e s using the rolling ball concept. It is s h o w n
in Fig. 37 a n d is m a r k e t e d by the Paul N. G a r d n e r Co. u n d e r
the n a m e G a r d c o Rolling Ball H a r d n e s s Tester. The instru-
m e n t utilizes a 1.5-in. (38 m m ) d i a m e t e r steel ball confined in
a r a c e w a y a b o u t 6 in. (15 cm) long, all m o u n t e d on a p l a t f o r m
w h i c h m a y be accurately tilted by an electrical solenoid.
M o u n t e d at each end of the r a c e w a y is an electrical sensor for
detecting the presence of the ball. The r a c e w a y a s s e m b l y tilts
to an equal a n d opposite incline whenever the ball is detected
at the low end of the raceway. An electrically a c t u a t e d t i m e r is
FIG. 35-K6nig/Persoz Pendulum Hardness Tester. c o n n e c t e d to register the n u m b e r of seconds r e q u i r e d for the
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HARDNESS 575
TABLE 4--Comparison of K6nig and Persoz hardness testers.

K6nig Persoz
Weight 200 +_ 0.2 g 500 +_ 0.1 g
Ball diameter 5 mm/0.2 in. 8 ram/0.3 in.
Deflection:
Start 6~ 12~
End 3~ 4~
Period of oscillation (1 oscillation) 1.4 s 1s
Damping time on glass 250 _+ 10 s 420 +_ 10 s
400-
T 380-
360-
340-
320-
300-
,.> 280-
r
260-
o 2401
220
2oo1
~ 18o1
16o
14o.
120- FIG. 37-Rolling Ball Hardness Tester. (Courtesy of The
i00- Paul N. Gardner Company, Inc.)
80-
60-
40-
20- ./ .o-
;0 I I I I I I i
50 70 90 iiO 130 150 170
HARDNESS IN KOENIG SECONDS ~-
FIG. 36-Comparison of K6nig hardness values versus

Persoz hardness values.
ball to complete a set n u m b e r of complete cycles of the ball in

the raceway. Specimens u p to 12 in. 2 (77.4 cm 2) a n d up to 1/2
in. (12.7 ram) thick are accommodated, a n d the new tester
should find application i n evaluating coated sheet metal, wo-
ven products, coated wood, floor coverings, paper, a n d lea-
ther.
Sward Rocker Hardness Tester--George Gilbert Sward was

FIG. 38-George Sward's Original Rocker Hardness
awarded a patent [64] for his coating hardness tester that was
Tester. (From the patent.)
developed w h e n he was associated with the National Paint,
Varnish, a n d Lacquer Association [65]. This is s h o w n in Fig.
The Rocker operates o n the same principle as does the
38. It is perhaps the best k n o w n a n d most widely studied Swinging Beam a n d other p e n d u l u m s . However, it is
i n s t r u m e n t for m e a s u r i n g the hardness of organic coatings. self-contained a n d requires no separate scale. Some
ASTM Committee D-20 o n Plastics wrote a standard using the models also have their o w n circular level. It consists of
Sward hardness tester, D 2134. Committee D-20 t u r n e d over two flat, 4-in. chromium-plated, b r o n z e rings, spaced 1
the responsibility of D 2134 to Committee D-1 i n 1991. They in. (25.4 ram) apart. Amplitudes of oscillations are indi-
are in the process of rewriting D 2134 a n d will be developing cated by two tube-style levels i n the lower half. The level
at the left is for m a r k i n g the start of a test; the one o n the
data for the Precision a n d Bias statement since m a n y coat-
right for m a r k i n g the end.
ings companies use the i n s t r u m e n t o n a daily basis.
As to its operation a n d use, the following is from the 12th At the present time, Sward-type rocker hardness instru-
edition of this m a n u a l [66]: m e n t s are m a n u f a c t u r e d i n G e r m a n y by Erichsen as the
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Sward-Zeidler Rocker Hardness Tester and in England by

Sheen Ltd. A picture of the Sheen instrument is shown in Fig.
39.
To make a test, fasten the panel to a leveling table and
adjust to a level position. Place the Rocker on the panel and
set it in motion so that the bubble in the left hand tube travels
slightly beyond the mark on the tube. Start to count swings
when the bubble just fails to travel beyond the mark. Begin
with zero. Stop the count when the bubble in the right hand
tube fails to travel beyond its mark. The number of swings
multiplied by 2 is the Rocker value. Alternately, the sum of
the two successive determinations may be used.
To calibrate the Rocker, adjust the angle of the left hand
tube to about 22.5 ~ with the horizontal and that of the right
hand tube to about 16~ Place the Rocker on a level sheet of
polished plate glass and proceed as directed above. When in
correct adjustment, the Rocker swings 50 times in 60 + 0.5 s.
If 50 swings are not obtained, minor adjustments may be FIG. 39-Sward-Type Rocker Hardness
made by means of the weight on the vertical screw. Lowering Tester by Sheen, Ltd. (Courtesy of The Paul
the weight increases the number of, and at the same time, N. Gardner Company, Inc.)
accelerates the speed of the swings. Major adjustments may
be made by changing the angles of the tubes. Changing the nation of why ASTM Subcommittee D01.23 and Task Group
angle of the right tube has a greater effect than an equal DO1.23.14 had difficulty with the data became apparent. They
change in that of the left tube. may have overlooked the information (Table 5) that two out
By widening the angle between the two tubes, the number of three Sward rockers were outside the proposed mass speci-
of swings can be increased to one hundred or more, thus fication, 100 __ 10 g, proposed for D 2134, Test Method for
increasing the sensitivity, However, at wide amplitudes, the Determining the Hardness of Organic Coatings with a Sward-
swings become somewhat more violent and too much should Type Hardness Rocker.
not be attempted in this direction. The rockers should be Baker, Elleman, and McKelvie used the equations from
wiped off frequently with soft paper or a clean cloth. Solvent Parker and Siddle and Persoz to derive the following formula
should be used, if needed. to calculate the number of Sward rocker rocks (N)
In using the Rocker or the pendulums, it is essential that
the film support be firm. Any movement absorbs energy and tb 1 (% + ~) ~fMga__ (13)
N - - -- log--.
lowers apparent hardness. Thin panels may bend; warped 2Tr 2Try (0, + ~) V I
panels may rock. To eliminate this source of error, H. F.
where
Payne designed a holder, called the Cyanamid Holder. It is
essentially a small screwpress. It eliminates slight curvatures a = distance of center of gravity from instantaneous cen-
and holds panels firmly. It takes panels up to 6 in. (15 cm) in ter,
width. 0 -- angle between the vertical and the plane containing
Films on heavy gage metal with a plane surface or films on the instantaneous center of rotation and the mass
plate glass or other rigid material may be supported on lumps center,
of stiff putty or molding clay. 00 = initial amplitude of the rocker, and
Another aid to proper use of the Rocker is a shield to e~ = amplitude of the rocker after N rocks.
protect it from air currents. One such shield is shown in Fig. Mathematical analysis of pendulums, balls, and rockers,
40. have been made by B. Persoz [59], Baker et al. [70], D. G.
Moore [67] studied the reproducibility of Sward rocker Flom [71], and P. E. Pierce et al. [60]. Persoz developed the
hardness measurements and found that a single measure- relatively heavy (500-g) pendulum shown in Fig. 35. Baker et
ment came within one unit of the average seven out of ten al. found that heavy rockers with a high moment of inertia
times. A deviation of more than two units appeared no more appeared to give the best results. Flom investigated the rela-
than 8 out of 100 times. Boscoe [68] explored the influence of tion of rolling friction to the dynamic shear modulus for
atmospheric pressure and compared Sward rocker hardness polymers and emphasized the importance of elastic hystere-
with that obtained using other methods. He found that the sis losses in rolling friction (not to mention the viscous damp-
greatest differences were due to differences between individ- ing effect). They demonstrated that, for the case of a rigid
ual Sward rockers. This was also observed by Nielson [69], sphere rolling on a viscoelastic surface, the following rela-
and Baker et al. [70] did a study on variations in results due to tionship existed
subjective differences in observers making the measure- p~ = Ktan8 (W/Ga2) 1/3 (14)
ments. Pierce et al. [60] also studied various factors which
influence the value of Sward hardness such as temperature, where
humidity, film thickness, substrate, and air pressure. ~, -- coefficient of roiling friction,
On analysis of the papers by Baker, Elleman, and McKelvie tan8 = dynamic loss tangent,
[70] and Pierce, Holsworth, and Boerio [60], a possible expla- G = shear modulus,
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Fig. 40-Sward Rocker with shield for protection from draft.
TABLE 5--Comparison of Sward rockers. of vinyl acetate copolymer coatings working i n a range of film
Rocker Number thickness from 1.2 to 125 mils. At constant film thickness he
Dimension 1 2 3 found the following relation between the hardness, N, a n d the
elastic modulus, E
Value of a (cm) 0.896 0.400 1.175
Moment of inertia I about 2085 1616 1829 E ~- K N 3 (18)
center of gravity (cm.g 2)
Period, T (s) 1.093 2.10 0.95 If we assume that E is very nearly the same as G, although it is
Mass, M (g) 114.2 87.4 105.4 well k n o w n that E ~ 3 G or less b u t not unity, substituting
Radius, r (cm) 5.075 5.075 5.075
Value of 0o 44~ 42~ 43~ into Eq 18 a n d r e a r r a n g i n g gives
Value of 0,, 27~ 27~ 27~ G 1/3 = N K ' (19)
which, according to Pierce et al., is the same as Eq 17 if we

a = sphere radius, assume that tan8 for the series of films studied is approxi-
W = load, a n d mately the same. Cass went further in his analysis and arrived
g = a constant. at the final equation
For the Sward rocker, a a n d W are c o n s t a n t a n d Eq 14 E = KtN3/t 3 (20)
becomes
where
tx = K ' G l/3tan~ (15) E = elastic modulus,
Pierce et al. showed, a m o n g other things, that the coefficient Kt = c o n s t a n t for varying thickness,
of rolling friction was inversely proportional to the Sward N = Sward rocker hardness n u m b e r , a n d
rocker hardness n u m b e r , N. This can be expressed as t = film thickness.
However, by examining Cass' data we are able to go one step
Ix oc 1 / N (16)
further, because the data show
Substituting this in Eq 16 a n d r e a r r a n g i n g gives
K t = 39t TM (21)
G 1/3 = N I C tan6 (17)
hence
In a plot of Sward rocker hardness against G~/3//tan8 I0-4,
E = 39N 3t0"54 (22)
a linear relationship was f o u n d for hardness up to a b o u t 60;
b u t for harder films, the plot curved a n d asymptotically ap- showing, as was stated earlier, that the Sward rocker hard-
proached a value of 100. This indicated that the Sward rocker ness is related to, or is a m e a s u r e of, the m o d u l u s (stiffness) of
was optimized for the range of hardness below 50, which a material as a f u n c t i o n of its thickness. However, this is true
corresponds to the range of hardness most frequently en- only within certain l i m i t a t i o n s - - t h e film m u s t be thick
countered with organic coatings. R. A. Cass [ 7 I ] compared e n o u g h a n d the substrate hard enough so that only the film
the Sward rocker hardness with the (tensile) elastic m o d u l u s properties are being measured.
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Pierce et al. found hardness to increase as film thickness K~nig Hardness in seconds
decreased to less than a few mils (their data were very lim-
ited). They also showed that softer substrates yielded lower
hardness values for identical coatings, which simply means
that the organic coatings were not thick enough for the mea-
150
sured hardness to be uninfluenced by the substrate. It is also
obvious that the hardness value measured using a Sward
rocker can be influenced by a "skin effect," or hard outer
surface, while the bulk of the film is relatively soft.
Uses of the Sward Rocker--It is redundant to state that the
Sward rocker is known and used all over the world. Canadian 100
Government Specification Board standardized it in Method
116.2, Hardness, in Canadian Government Specifications 1-
GP-71, Methods of Testing Paints and Pigments. We have
seen that it can measure the coefficient of rolling friction and,
within certain limits, measure the dynamic mechanical prop-
/
erties such as shear modulus or compliance of materials.
50
In addition to these it has been specified in ASTM Method
D 2134. Softening may be encountered when a plasticized
material comes into contact with an organic coating. How-
ever with regard to softening by plasticizers, it has been ob-
served in the author's laboratory that, in some instances, the
indentation hardness of the coating is unaffected, while the
0 i i I I I I I I I
Sward rocker hardness decreases. This is due to an almost 20 30 40 50 60 70 80
2 10
invisible film of plasticizer that has exuded out onto the
surface of the coating, thereby acting to dampen the oscilla- S w a r d H a r d n e s s in s e c o n d s
tions of the rocker. FIG. 41-Comparison of K6nig hardness values with Sward
BYK-Gardner, Inc. has distributed a graph which com- Rocker hardness values.
pares K6nig hardness values with Sward Rocker hardness
values and Persoz hardness values with Sward Rocker hard-
ness values. These graphs are shown in Fig. 41 and Fig. 42.
Persoz Hardness in seconds

Rebound Hardness Testing
The rebound hardness test measures the mechanical prop- 320
erties of a material during very short time intervals. The test,
which uses very simple apparatus, is performed by dropping 280
an elastic steel ball from an initial height h0 onto a fiat test
surface. The rebound height hi of the ball is measured. The
impact resilience or hardness of the sample is the ratio of the 240
rebound height to the initial height. The impact process
occurs over a very short time interval (10 _3 to 10 -4 s) [72].
The resilience R is related to the loss tangent of the material 200
J
[73:75].
R = hJho = exp ( - wtanS) (23) 160
This loss tangent applies to a very fast impact process.
The results depend on geometric factors such as the thick- 120
ness of the plate and the radius of the ball [75], as well as on
the coating thickness and hardness of the substrate. Hard
substrates, such as window glass, give good test results. The 80
test has been used in a number of investigations of coatings
[46, 76]. A more elaborate form of the rebound apparatus has 40
been developed by Raphael and Armeniades [77]. Their ADL
Rebound Tester has provision for temperature control and
can operate from liquid-nitrogen temperatures to several 0 I t t I I I I I
hundred degrees centigrade. 2 10 20 3o 40 50 60 7o

ADL Ball Rebound Apparatus--The ADL Ball Rebound S w a r d H a r d n e s s in s e c o n d s
Hardness Test Apparatus, developed by Arthur D. Little, FIG. 42-Comparison of Persoz hardness values with Sward
Inc.'s M. Gordon and B. Grievenson [78] consists essentially Rocker hardness values.
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of a penetrometer and a brass block containing a heating 1. Single scratches made with a needle or other sharp instru-
element enclosed in a glass dome that can be subjected to a ment.
vacuum. The brass block can be heated from 0 to 300~ at 2. A large number of scratches made by abrasive particles
rates of up to 30~ per minute. The specimen block can be falling or impinging on the specimen.
cooled very quickly by sucking a stream of cold CO2 gas 3. A large number of fine scratches made by an abrasive
through a side arm straight upon the specimen disk. The medium being rubbed against the specimen, called scuff-
polymer film to be tested is mounted on the brass block, ing.
which has a circular perforation through which the ball hits In No. 2 and No. 3, the results are similar in that there is a
the specimen disk. The mounted specimen is placed inside loss of gloss or a haze produced on the surface of the speci-
the glass dome, which can be evacuated or filled with an inert men being tested. Also, the abrasive medium in No. 3 may not
gas. The test ball (1/8 in. steel ball bearing) is released electro- be an abrasive per se, but can be a type of fabric.
magnetically from the top of the dome. The rebound height is Regarding single scratches made with a needle or other
measured against an illuminated scale at the back of the sharp instrument, two schools of thought have existed as to
dome. The rate of testing (i.e., the interval between successive exactly what constitutes a mar. One school of thought consid-
ball rebounds) may be adjusted from 3 to I0 s per test. A ers the end point to be any marring, whether a depression or a
similar apparatus was used by Jenckel and Klein [79] investi- scratch. The other school considers a mar to have occurred
gation of the relationship between ball rebound energy ab- only if, within the scratch depression itself, skin rupture of
sorption and temperature in polymers. the organic finish has occurred as evidenced by light scatter-
ing. This skin rupture is gaining wider acceptance, because it
Shore Scleroscope--Shore scleroscopes, developed by
can be quantified or measured and given a number. Also, the
Shore [35], have been manufactured since 1907 as the pio-
skin rupture mechanism, as evidenced by light scattering, is
neer American standard for testing the hardness of metals
identical to that encountered in No. 2 and No. 3.
and other materials. They consist of a calibrated glass tube
Finally, there is another type of mar that has not been
with a diamond-tipped metal "impactor" located inside. The
mentioned yet, because it does not fit into the definition
hardness is measured by the height that the impactor
expressed at the beginning of this section on mar resistance.
rebounds. This instrument is available in various models
This is the streaking or marking mar wherein the organic
depending upon the application. They are used to determine
coating itself is not necessarily physically damaged, but it has
the hardness of thick elastomers, but results are greatly influ-
been marked or streaked by a transfer of material to the
enced by the substrate when thin polymers are tested. The
coating. The most common example of this occurs when a
American Bowling Congress (ABC) specifies a Scleroscope
coin, such as a nickel, is rubbed across the coating. If the
hardness for coatings used on bowling pins. However, the
metal is transferred to (streaks) the coating, the coating is
hardness of the thin clear coating is insignificant when com-
said to be marred. This same mechanism occurs when a
pared to the plastic substrate and maple wood core.
fingernail is used. The acceptance or use of this type of
marring or mar resistance seems to be losing ground to the
scratching types, and, at the risk of being redundant, a test for
P H Y S I C A L C O N C E P T S OF M A R it has been never quantified or standardized.
RESISTANCE TESTING General Motors Corp.'s Engineering Standards Group
wrote, in 1988, GM9150P, Resistance to Marring or Scuffing.
The mar resistance of an organic coating is its ability to In the test method a Bronzette Gem paper clip, No. 1, is
withstand scratching, scuffing, and/or denting actions, which allowed to traverse a coated panel with a weight of 750 g
tend to disfigure or mar (change) the surface appearance of applied to it. The coated specimen is pulled towards the
the coating. Mar resistance, as defined above, is a resistance operator at a speed of approximately 37 mm/s. The coated
of the surface of the coating to permanent deformation, as a specimen is then rotated 90 ~ counterclockwise. This is then
consequence of the application of dynamic mechanical repeated until the four directions are completed. The panel is
forces. In this sense it is distinguished from print resistance, then examined for marring or scuffing. A satisfactory coat-
pressure mottling, and block resistance, in which the applied ings shows no marring or scuffing. An unsatisfactory coatings
mechanical forces are static. Some examples of potential shows marring or scuffing. Rejected specimens are rein-
marring of organic coatings are: sliding an ash tray or other spected after a minimum of 15 rain to be certain that the mar-
object across a desk or other item of furniture, rubbing one's ring is not superficial and does not disappear upon standing.
belt buckle, zipper, or buttons along the organic coating on Ford Motor Co.'s Quality Laboratory and Chemical Engi-
an automobile as it is being washed, a child sliding a toy or neering Group wrote, in 1973, BN 8-4, Resistance to Scuffing.
other object along a wall, refrigerator door, etc., and a woman In the test method, a Taber abraser is used to determine the
dragging a wash basket full of wet clothes off the top of a resistance to scuffing of materials such as painted substrates,
washer or dryer. vinyl, genuine leather, and luggage compartment mats. A
When we refer to the scratching associated with marring, special scuffing head is used.
we are really referring to relatively fine surface scratches.
This distinguishes the type of scratch encountered in mar
Single Scratch Methods
testing from that encountered when attempting to evaluate
hardness or adhesion by means of various types of scratch BTL Balanced Beam Mar Tester--This method [80] was
tests. There are, in general, three different ways in which developed in 1945 by R. J. Phair of the Bell Telephone Labo-
materials are scratched when being tested for mar resistance: ratories (BTL). The apparatus is shown in ASTM Method D
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2197: Test Methods for Adhesion of Organic Coatings by tering. A m a r or b r e a k d o w n point is distinguished from de-
Scrape Adhesion [53]. I n m a r testing, the r o u n d e d tool is pressions in the coating by holding the m a r r e d specimen
replaced by a c h r o m i u m - p l a t e d p h o n o g r a p h needle. The ap- nearly at eye level in flat lighting, so that no highlight reflec-
paratus consists of a balanced b e a m to which is secured a tions are visible. The least weight required to make a line that
platform for supporting weights, a rod at a n angle of 45 ~ shows a distinct light scattering or whitish reflection in the
which holds the scratching needle, and a sliding or movable depression made by the needle is the m a r resistance value of
table on which to support a n d move the specimen. Initial the organic finish. Care m u s t be taken to avoid reflections
a d j u s t m e n t s are performed to ensure that the apparatus is from the wall of depressions in the finish which are not cut
level a n d that the end of the needle is directly in line with the through.
weight support rod. Years ago w h e n telephone sets were made of metal, it was
The procedure differs from that employed in adhesion test- found that the baked black enamel used on the metal base of
ing in that the panel is d r a w n toward rather t h a n away from the desk type telephone would get through the n u m e r o u s as-
the operator. A 50-g m i n i m u m load with 50-g i n c r e m e n t sembly operations in a n u n m a r r e d condition if the value of
creases is used. The end p o i n t is reached w h e n the u p p e r m a r resistance was 200 g or better. Materials having m a r
surface of the paint film has been ruptured. A b r e a k d o w n resistance levels of less t h a n 200 g would not necessarily
point is distinguished from depressions in the finish by hold- suffer damage to a degree sufficient to expose the base metal,
ing the m a r r e d specimen nearly at eye level in flat lighting so but were rejected in m a n y cases on the basis of unsatisfactory
that no highlight reflections are visible. The least weight re- appearance.
quired to make a line which shows a distinct whitish reflec- ASTM Task Group D01.23.14 Hardness, Abrasion a n d Mar
tion from the subsurface of the finish, b u t not from the base, Resistance r a n a p r e l i m i n a r y r o u n d - r o b i n test seeking a can-
is the m a r value. Care is taken to avoid reflections from the didate apparatus a r o u n d which they could write a test
side walls of depressions in the finish which are not cut method. The results of the r o u n d - r o b i n tests are shown in
through.
Table 6.
The m a r p o i n t can also be observed by inspecting the
As a result of their findings, they wrote D 5178: Test Method
marks u n d e r a microscope of 80 to 100 power. The deepest
for Mar Resistance of Organic Coatings [53] using the equip-
section of a depression will scatter the light where m a r r i n g
m e n t R. Phair originally designed for adhesion testing. Sev-
has occurred if it is i l l u m i n a t e d along its length a n d at a n
eral operators have expressed a lack of interest in this test
angle of a b o u t 20 ~ from the plane of the specimen. The ap-
method as the end p o i n t is difficult to recognize. Also a m a r k
pearance of a depression m a r k without m a r r i n g is illustrated.
judged to be a m a r m a y disappear overnight.
Mar values of 200 g or more are usually indicative of suffi-
cient resistance to withstand the scarring actions e n c o u n - Princeton Scratch Tester--This apparatus is somewhat sim-
tered in n o r m a l assembly of telephone apparatus. ilar to the balanced b e a m tester, b u t instead of having a
In m a k i n g a determination, the specimen is placed on the movable specimen table, the b e a m assembly itself moves on a
movable table with a starting load of 50 g on the weight V-shaped track, the specimen r e m a i n i n g immobile. Also, the
platform. The needle is lowered slowly onto the specimen, needle is held at a n angle of 90 ~ to the surface of t h e speci-
with the end of the apparatus nearest the needle being di-
men.
rectly in front of the operator. The movable table is pulled
toward the operator with a slow, steady motion, at a rate of 1 Hoffman Scratch Tester--This device, described in the sec-
to 11/2 in. (25 to 38 mm)/s, for a distance of at least 3 in. (76 tion on hardness in this m a n u a l , has also been used to
mm). At the end of each stroke the needle is raised off the determine m a r resistance. However, its use as a m a r tester
specimen, a n d the specimen is moved slightly to the side. This has never gained wide acceptance. The scratches obtained
procedure is repeated with a 50 g increase in load each time are usually quite large a n d often go down to the substrate.
until the surface of the organic coating has been disrupted or
ruptured. Rondeau Scratch Tester--The same criteria that apply to
Mar resistance is expressed as the load in grams required to the H o f f m a n scratch tester just m e n t i o n e d also apply to the
r u p t u r e the surface of the coating as evidenced by light scat- R o n d e a u Scratch Tester.
TABLE 6--ASTM Task Group D01.23.14 on hardness, abrasion and mar resistance. Results of round-robin tests on mar.
Scrape
Adhesion
Eraser Coin Erichsen (Balanced RCA Tape
Sample/ Hardness (Pencil) (Rubs) (Mar) (Swing) Beam)b Abrader
Collaborator 1 2 3 4 1 4 1 4 5 2 3 4
No. 1 Zero F/H F F H 4 F P P 58 6 4 9 cycles
No. 2 Medium H/2H F H H 5 H P P 67 10 8 7 cycles
No. 3 Hi resis H/2H F 2H 2H 5 2H P P 62 >10.5 12 15 cycles
No. 4 Urethane H/2H F 2H 2H 4 HB P P 68 10.5 10 14 cycles
Orange lacquer H/2H F 2H H 5 Slight "Fair P 90 10.0 12 55 cycles
No. 188 HB/H HB 2H B 3 Slight aFair P 47 10.5 10 10 cycles
~Cointest (nickel)scratched the film but did not mar (metal marking) the surface.
bGrams, weight.
www.iran-mavad.com

Impinging Abrasive Method Scuffing Methods

Falling abrasive particles are used as the principle in ASTM Taber Abraser Mar Test--Use of the Taber Abraser for a m a r
D 673: Test for M a r Resistance of Plastics [81]. This principle test for polyester resins was studied by Sherr a n d Martin [86]
was also a d o p t e d as M e t h o d 1093: M a r Resistance, of F e d e r a l employing ASTM D 1044: Resistance of T r a n s p a r e n t Plastics
Test M e t h o d S t a n d a r d No. 406. However, on 4 Jan. 1982, the to Surface Abrasion [81]. They m e a s u r e d the increase in haze
F e d e r a l G o v e r n m e n t canceled this test m e t h o d a n d r e p l a c e d (transmission) of a b r a d e d t r a n s p a r e n t plastics after 100 a n d
it with ASTM Test M e t h o d D 673. As i n d i c a t e d by the titles, 200 cycles/revolutions of the specimens. J. M. Carter 7 from
the test was designed for b u t n o t limited to plastics. Therefore U.S. Plywood Corp. modified this ASTM m e t h o d so that it
it can be used for testing m a r resistance of organic coatings. could be used to m e a s u r e the m a r resistance of organic coat-
It was developed by B o o r in 1942 [82] a n d a d o p t e d as tenta- ings on o p a q u e substrates. His m e t h o d consisted of observing
tive by the ASTM in the s a m e year. The test consists of for the first visually p e r c e p t i b l e mar, w e a r track, or change in
allowing a m e a s u r e d s t r e a m of No. 80 c a r b o r u n d u m particles gloss. The n u m b e r of cycles required to cause such a change
to fall onto the specimen. Then, the degree of m a r r i n g or m a r is expressed as the m a r resistance of the coating. This m e t h o d
resistance is evaluated by m e a n s of gloss m e a s u r e m e n t s in was used in s o m e p r e l i m i n a r y r o u n d - r o b i n w o r k in the mid-
a c c o r d a n c e with ASTM D 1003: Test M e t h o d for Haze a n d 1960s.
L u m i n o u s T r a n s m i t t a n c e of T r a n s p a r e n t Plastics [81]. It The following p r o c e d u r e was a d o p t e d for a second r o u n d -
should be n o t e d that, according to the U.S. Naval O r d n a n c e r o b i n test:
L a b o r a t o r y [83], the m e t h o d is useful for b o t h r e s e a r c h a n d Mar resistance is expressed as the n u m b e r of a b r a s i o n
d e v e l o p m e n t a n d design criteria. A similar test was developed cycles r e q u i r e d to p r o d u c e a visually p e r c e p t i b l e mar,
by the British in 1942 [84]. Instead of m e a s u r i n g the loss of w e a r track, or change in gloss. The p a i r of CS-10F Cal-
gloss, the change in light t r a n s m i s s i o n t h r o u g h the s p e c i m e n ibrase wheels to be used shall be m o u n t e d on their re-
was measured. Of course this restricted one to the use of spective flange holders, taking care not to h a n d l e t h e m b y
t r a n s p a r e n t materials. Incidentally, it a p p e a r s that G. G. their abrasive surfaces. The 1000 g loads shall be fixed to
each side. The ST-11 stone shall be m o u n t e d fine side up
S w a r d first suggested the loss of gloss of a surface by a
or the ST-11 disk shall b e m o u n t e d abrasive side u p on
definite a m o u n t of falling abrasive [85]. the t u r n t a b l e a n d the wheels shall be refaced for 25 cy-
The a p p a r a t u s consists of a hopper, motor, tube, s u p p o r t cles, b r u s h i n g the residue from the stone during the
assembly, s p e c i m e n holder, a n d the optical e q u i p m e n t re- process. Adjust the suction p i c k u p to just clear the sur-
quired to m e a s u r e the gloss a n d loss thereof. Uniform distri- face of the track. The abrasive wheels shall be refaced
b u t i o n of abrasive is o b t a i n e d b y r o t a t i o n of the conical after each test. C A U T I O N - - D o not t o u c h the surface of
h o p p e r at 7 r p m as abrasive flows t h r o u g h holes 0.070 in. ( 1.8 the wheels after they are refaced. The s p e c i m e n shall be
m m ) in diameter. The abrasive flow rate is a b o u t 225 g/min. m o u n t e d on the s p e c i m e n h o l d e r or t u r n t a b l e with the
coating side up. Adjust the suction p i c k u p to just clear
Usually, several a b r a s i o n tests with increasing a m o u n t s of the surface of the track. The Calibrase wheels and 1000 g
abrasive are m a d e , that is, 200, 400, 800, 1200, a n d 1600 g. loads shall be m o u n t e d as above. After each cycle or
A special light p r o j e c t o r a n d glossmeter are u s e d to mea- revolution of the specimen, stop the t u r n t a b l e a n d ob-
sure the gloss of the specimens. The following equation is serve for the first perceptible sign of w e a r t r a c k starting
used for calculating the percentage of gloss. to show. Observe by looking at an angle of 45 ~ incident to
the s p e c i m e n with a light source in a line with a n d at
gloss, p e r c e n t = 10011 - I2 (24) right angles to the incident angle. A r e a d i n g shall n o t be
11 c o n s i d e r e d valid unless the m a r includes at least 75 per-
cent of the possible circumference of the w e a r t r a c k a n d
where as wide as the w i d t h of the Calibrase wheels.
I1 = photoelectric cell r e a d i n g at the specular angle (45~ In 1992, Task G r o u p D01.23.14 Hardness, M a r a n d Abra-
and sion Resistance initiated r o u n d - r o b i n w o r k using a test
I2 = photoelectric cell r e a d i n g at the 60 ~ angle (15 ~ off m e t h o d developed by E. I. du Pont Co. for a u t o m o t i v e fin-
specular).
ishes. The s a m e Taber a b r a s e r used in Test M e t h o d D 673 is
The percentage gloss of the a b r a d e d or m a r r e d spots is employed, b u t changes of gloss r a t h e r t h a n t r a n s m i t t e d haze
plotted against the respective a m o u n t s of abrasive used to are being measured.
o b t a i n a characteristic curve for each different material.
Since such curves for different m a t e r i a l s are often f o u n d to Erichsen Scar-Resistance Tester--This i n s t r u m e n t [87],
change slope irregularly, they m a y cross each other, a n d the shown in Fig. 43, is in frequent use t h r o u g h o u t the world to
rating of a series of different m a t e r i a l s using a given a m o u n t m e a s u r e coating surface damage. This device was designed to
of abrasive m a y not b e representative of their relation at replace the t r a d i t i o n a l fingernail m a r test. It contains a scar-
o t h e r a m o u n t s of abrasive. One w a y to arrive at an overall ring tool in the form of a disc m o u n t e d on a screw a n d u n d e r
p e r f o r m a n c e is to average the percentage of gloss at the pressure from a helical spring. The spring applies a force
various a m o u n t s of abrasive or the area u n d e r each curve. w h i c h is a d j u s t a b l e of 0 to 20 N. The i n s t r u m e n t is p l a c e d
In 1988, C o m m i t t e e D-20 stated in the Precision a n d Bias onto the surface so that it rests on the two guide wheels a n d
section of Test M e t h o d D 673: "a m e a n i n g f u l p r e c i s i o n state- the m a r k i n g wheel, w h i c h is locked t h e n presses onto the
m e n t c a n n o t be developed at this t i m e b e c a u s e of the small surface with the preset force from the spring. The scar resist-
n u m b e r of l a b o r a t o r i e s presently k n o w n to be using this test
method." 7private communication between J. M. Carter and E. M. Corcoran.
www.iran-mavad.com

Miscellaneous Methods
Belt Buckle Test--At least as late as 1969, one of the m a j o r
automotive companies used a belt buckle as one m e t h o d of
evaluating the m a r resistance of the organic coatings on their
automobiles. However, the exact method is not k n o w n to this
writer.
Coefficient-of-Friction Mar Test--One of the leading m a n u -
facturers of m a r resistance additives for organic coatings
uses a sort of coefficient-of-friction test to evaluate m a r resist-
ance. This test consists of w r a p p i n g a 500-g weight i n cheese-
cloth, placing the weight at one end of a test panel a n d slowly
l i k i n g the weighted end of the panel. The angle at which the
weight slips off is taken as a n indication of the coefficient of
friction. The lower the angle, the better the m a r resistance.
Coin Mar Test--A leading m a n u f a c t u r e r of organic coating
resins uses a nickel (five-cent piece) to evaluate the m a r resist-
ance of p i g m e n t e d organic coatings. The m a n n e r or method
that is used makes it a streaking or m a r k i n g type of m a r test.
The test consists of dragging a nickel over a pigmented coat-
ing a n d seeing how m u c h metal is transferred to the coating,
as manifested by the size a n d color of the streak.
Fingernail Mar Test--Another leading m a n u f a c t u r e r of m a r
resistance additives for organic coatings uses a fingernail to
evaluate m a r resistance. To make a test the back of a finger-
nail is dragged along the surface of the coating. If the coating
is marked, it is considered to be marred. This is also a streak-
ing or m a r k i n g type of m a r test. Others have used the edge of
a fingernail in a similar m a n n e r .
FIG. 43-Scar-Resistance Tester. (Courtesy of Erichsen

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www.iran-mavad.com

CHAPTER 48--HARNESS 583
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No. 510, August 1936, pp. 223-224. Rebound Tester," American Chemical Society, Organic Coatings
[66] Gardner, H. A. and Sward, G. G., Physical and Chemical Exami- and Plastics Chemistry Division, Preprints, Vol. 23, No. 2, 1963,
nation of Paints, Varnishes, Lacquers, and Colors, 12th ed., pp. 273-280.
Gardner Laboratory, Inc., Bethesda, MD, 1962, p. 138. [78] Gordon, M. and Grieveson, B. M., "Rebound of Relaxation
[67] Moore, D. T., "Precision of the Sward Hardness Rocker," Paint, Sprectra and Principle of Constant Isoelastic Curing Rates,"
Oil and Chemical, Vol. 113, No. 21, 1950, p. 41. Journal of Polymer Science, Vol. 29, 1958, pp. 9-35.
[79] Klein, E. and Jenckel, E., "Dependence of the Modulus of Elas-
[68] Boscoe, P. J., "The Calibration of the Sward Rocker," Official
ticity of High Polymers on the Temperature," Z. Naturforsch.,
Digest, Federation of Paint and Varnish Production Clubs, Vol.
Vol. 7a, 1952, pp. 800-807.
26, 1954, pp. 1030-1038.
[80] Phair, R. J., "Scratch Adhesion and Mar Testing of Organic
[69] Nielsen, H. K. R., "Some Comments on the Hardness Determi-
Finishes," Bell Laboratories Record, Vol. 23, August 1945, pp.
nations with the Sward Hardness Rocker," Comptes Rendus,
284-286.
1953, pp. 188-193.
[81] ASTM Annual Book of Standards, Vol. 08.01.
[70] Baker, D. J., Elleman, A. J., and McKelvie, A. N., "A Theoretical [82] Boor, L., "Mar Resistance of Plastics," Modern Plastics, Vol. 20,
and Statistical Study of Sward Hardness Determinations of September 1942, pp. 79-83.
Paint Films," Official Digest, Federation of Paint and Varnish [83] Barnett, F. R. and Prosen, S. P., "Validity of Mechanical Tests for
Production Clubs, Vol. 22, 1950, pp. 1048-1065. Glass Reinforced Plastics," Materials Protection, Vol. 3, June
[71] Cass, R. A., "The Sward Rocker for Measuring the Modulus of 1964, pp. 32-40.
Elasticity of Paint Films," Journal of Paint Technology, Vol. 38, [84] Starkie, D., "The Hardness and Scratch Resistance of Plastics--
1966, pp. 281-284. A New Method of Test," Journal, Society of Glass Technology,
[72] Tillett, J. P. A., "Fracture of Glass by Spherical Indenters," Vol. 26, 1942, pp. 130-144.
Proceedings of the Physical Society (London), Vol. B69, 1956, pp. [85] Sward, G. G., "Improved Abrasion Apparatus," Scientific Section
47-54. Circular, National Paint, Varnish, and Lacquer Association, No.
[73] Staverman, A. J. and Schwarzl, F., Die Physik der Hoch- 581, June 1939.
polymeren, Vol. IV, H. A. Stuart, Ed. (in English), Springer, [86] Sherr, A. E. and Martin, F. G., "Mar Resistance as Measured by
Berlin, 1956, Chaps. 1 and 2. the Taber Abraser," American Chemical Society, Organic Coat-
[74] Marvin, R. S., "Measurement of Dynamic Properties of Rubber," ings and Plastics Chemistry Division, Preprints, Vol. 24, No. 2,
Industrial and Engineering Chemistry, Vol. 44, 1952, pp. 696- 1964, pp. 174-179.
702. [87] Erichsen Technical Information Leaflet 435E, Group 14.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Stress Phenomena in Organic

Coatings
by Dan Y. Perera ~
INTEREST IN THE STRESS PHENOMENA in organic coatings is 9 = strain, a n d

relatively new. The i m p o r t a n c e of u n d e r s t a n d i n g a n d mea- v = Poisson's ratio.
suring this stress b e c a m e evident as facts a c c u m u l a t e d a b o u t Stresses are especially d a m a g i n g at edges [14] w h e r e they
its role in coating d e g r a d a t i o n [1-10]. This is also s u p p o r t e d c a n n o t cancel each o t h e r o r in the m i d d l e of the plate if
by the fact t h a t m a n y coatings used t o d a y (e.g., thermosets) defects or heterogeneities are present.
are m o r e susceptible to developing high stresses t h a n tradi-
tional ones (e.g., alkyd paints). It is now quite clear that stress
can affect coating a d h e s i o n and/or c o h e s i o n a n d p r o v o k e Film F o r m a t i o n
d e l a m i n a t i o n and/or cracking.
Since the d e v e l o p m e n t of stress is involved in practically all During film f o r m a t i o n a n d regardless of the m e c h a n i s m
stages of coating life (film formation, exposure to various involved (evaporation of solvent, coalescence, c h e m i c a l reac-
climatic conditions), its m e a s u r e m e n t is essential for a b e t t e r tion, o r their c o m b i n a t i o n ) , in almost all cases the coating
u n d e r s t a n d i n g of coating behavior. tends to contract. If this c o n t r a c t i o n is p r e v e n t e d by coating
In addition, the m e a s u r e m e n t of stress can be used to a d h e s i o n to its substrate a n d / o r the m o b i l i t y of m a c r o m o l e c -
evaluate other i m p o r t a n t characteristics of a coating, such as ular segments is hindered, a tensile stress will develop in the
the glass t r a n s i t i o n t e m p e r a t u r e (Tg) a n d the critical p i g m e n t coating.
volume c o n c e n t r a t i o n (CPVC). I n the literature a certain confusion reigns a b o u t the
d e n o m i n a t i o n of the stress arising during film formation.
F o r example, for solvent-based coatings a n a u t h o r m a y use
these terms: cure stresses, solvent removal stresses, residual
O R I G I N S OF S T R E S S IN ORGANIC
stresses, shrinkage stresses, internal stresses. F o r simplifica-
COATINGS
tion, I suggest referring to the stress arising d u r i n g film for-
m a t i o n as internal stress (St).
Stresses originate in organic coatings as a result of their
a d h e s i o n to the substrate. G o o d a d h e s i o n is, on the one hand, If a liquid p a i n t is a p p l i e d on a substrate [8] a n d the devel-
i n d i s p e n s a b l e for a d e q u a t e s u b s t r a t e protection, b u t on the o p m e n t of stress is m e a s u r e d as a function of time, a n u m b e r
other h a n d prevents the n o r m a l m o v e m e n t of a coating. of stages can be observed (Fig. 1).
The three m a i n causes w h i c h provoke stress in an organic In Stage 0, the coating is still liquid a n d is m o b i l e e n o u g h to
coating are [11]: p e r m i t volume contraction, a n d consequently no stress devel-
ops,
1. Film formation.
I n Stage 1, the film starts to form, the volume c o n t r a c t i o n is
2. Variation in t e m p e r a t u r e .
restricted a n d stress develops.
3. Variation in relative h u m i d i t y (RH).
In Stage 2, a n u m b e r of processes can occur. Depending on
The stresses i n d u c e d by film formation, v a r i a t i o n in tem- the coating composition, the evolution of stress can include
perature, a n d variation in RH are known, respectively, as various c o m b i n a t i o n s of increasing, decreasing, a n d station-
internal, thermal, a n d hygroscopic. The latter two stresses are a r y stress levels. If no d a m a g e occurs to the film (cracks,
also referred to as h y g r o t h e r m a l (sur). microfissures, loss of adhesion), a decrease in stress results
It is i m p o r t a n t to realize that, due to the coating a d h e s i o n from r e l a x a t i o n processes w h i c h occur from the m o m e n t the
to its substrate, stress exerts its action m a i n l y in a plane stress develops b u t only b e c o m e evident at this stage. It also
parallel to the substrate [6, I2,13]. Therefore, one can write follows that the m e a s u r e d stress values are a result of two
E9 opposite processes, one tending to develop stresses in the
s - (1)
1--u coating (in this case due to the v o l u m e shrinkage) a n d the
other tending to decrease t h e m (due to stress relaxation).
where E x a m p l e s of stress d e v e l o p m e n t as a function of t i m e for
S = stress, latex coatings [15] above a n d below the CPVC are shown in
E = elastic modulus, Fig. 2.
It is i m p o r t a n t to a d d that stress starts to develop in a
~Head of Department, Coatings Research Institute (CoRI), Ave. P. coating w h e n its Tg is at least equal to the e x p e r i m e n t a l
Holoffe, B-1342 Limelette, Belgium. t e m p e r a t u r e [6]. F o r solvent-based coatings (Fig. 3), this is
585
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Despite the limitations of Eq 2, which assumes that the

S strain is isotropic and linear, Eqs 2 and 3 enable one not only
to better understand the factors affecting the S F but eventu-
2
ally to calculate it approximately.
Variation of Temperature
When coated substrates are exposed to variations in tem-
perature, dimensional changes are induced. If the thermal
expansion coefficients of the coating (a~) and the suhstrate
(as~) are different, which is usually the case, a thermal stress
(S r ) will develop in the coating [2, 7,11,19,20].
__0___/ TIME
FIG. 1-Schematic description of stress (S) dependence
Since the thermal strain, er is given by
er ~ (aFt _ asr) AT
the combination of Eqs 1 and 4 gives
(4)
on time.
s~ = s 2 I
E
-- V
(~ - ~)c/r (5)
also confirmed by the fact that stress appears when Phase 2 of

the evaporation kinetics (the diffusion process) starts [16]. At
Determination of Tg
this point in the evaporation, referred to as solidification, the
solvent volume fractions are equal to the solvent concentra- A schematic description of the stress dependence on tem-
tion necessary to bring the Tg of the coating to a temperature perature [18] is represented in Fig. 4.
equal or higher than the experimental one [6,17]. Such a dependence indicates the possibility of determining
If Eq 1 is extended to accommodate the specific effect of the Tg of a coating from the stress measurement. This is due
to the fact that E, ars, and v (see Eqs 1 and 5) also show a
internal strain, ee [6], then
profound change at Tg.
E F ~ V s -- V t - - AV (2) Below temperature a the coating is in the glassy region, and
3Vs 3Vs above temperature b the coating is in the rubbery region.
The linear dependence of S on temperature in the glassy
where region greatly facilitates the measurement of Tg. This linear-
Vs = volume of coating at solidification, and ity is due to the fact that in this region 17,, a r, and u are
V t = volume of coating at time t after solidification. practically independent of temperature.
Three examples of the stress dependence on temperature
One can write [18] that and Tg determination by thermal stress measurements [18]
are shown in Fig. 5.
sF = E 1 dV (3)
1-v 3V s When the stress magnitude in the rubbery region is small
(e.g., elastomers, coatings with a low degree of cross-linking),
S a. c. e.
b.
I >,,
TIME
FIG. 2-Schematic description of stress (S) dependence on time for latex coatings
[15]: (a) and (b) PVC < CPVC; (c) and (d) PVC > CPVC; (e) PVC < CPVC in the
presence of a poor coalescent; (f) PVC > CPVC in the presence of a poor coalescent.
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CHAPTER 49--STRESS PHENOMENA IN ORGANIC COATINGS 587
vs Since in accordance with the molecular theory of rubber

elasticity in its simplified form [22,23]
E,. = 3veRTr (6)
I
and
Sr 2Er r (7)
giving
Er Sr
I ve . . . . (8)
3R T~ 6R Trr
where R, S,, Er, and Tr are, respectively, the gas constant, the
stress, the elastic modulus, and the temperature at the begin-
ning of the rubbery region. If Sr is measured and e~ is known
or determined from separate measurements (e.g., by
thermomechanical analysis, TMA), ve can be calculated.
Others have used the evaluation of Tg by stress measure-
ments to investigate the effect of a pretreatment on certain
pigments [24], the state of cure of baking enamels [21], and
the modification of epoxy coatings [19a,25].
TIME
FIG. 3-Schematic representation of the de- Variation of Relative Humidity
pendence of V s / V E and stress (S) on time [16].
V s = volume of solvent present in the film; Vr = Dimensional changes induced by absorption and desorp-
volume of the dry film. tion of water as a result of variation in RH is another cause of
stress development in a coating [11,26,27]. As in the case of
temperature, if a mismatch between the expansion coeffi-
cients of the coating and the substrate exists, a hygroscopic
stress (S H) will arise in the coating.
[',
I Since the hygroscopic strain g~ is given by
one can write that

eH_ ~(ct~ - asH) A RH (9)
S H = fRH2 E (a~ - aH)dRH (10)

JRHI I -- V
where ~ and ~ are, respectively, the hygroscopic expansion

coefficients of the coating and the substrate.
Some examples of the S H dependence on RH is given in Fig.
6.
INTERDEPENDENCE OF STRESSES
While in previous subchapters the various stresses (S F, S r,

S~) were discussed separately, in practice they can act to-
T~-%--
gether in such a way that the total stress (S,ot) is small or, as in
many cases, very important [11]
T
FIG. 4-Schematic re ~resentation of de- S,ot = S r +-- S T + S H (11)
pendences of S, E, ~ r and v on temperature The positive and negative signs are arbitrarily chosen. The
(D US]. positive sign denotes a coating tendency to contract (tensile
stress) and the negative sign a coating tendency to expand
the Tg can be determined with fair accuracy just by carrying (compressive stress). S e is practically always positive.
out a few measurements in the glassy region and then extrap- Equation 11 indicates the existance of two climatic condi-
olating the straight line to S T = O. tions which might provoke a high stress in a coating:
For coatings with a significant stress in the rubbery region 1. Low temperatures and RH's induce high tensile stresses
(e.g., highly cross-linked thermosets), the measurement of (e.g., a dry, cold winter).
stress in this region might provide a way to approximately 2. High temperatures and RH's induce high compressive
determine the cross-link density, Ve [21]. stresses (e.g., a humid, warm summer).
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10" S
2 3
1 ~ k " ~'"~
6 lb 2'o 3'0 4'o 5'o 6 lb 2'o 3'0 6 1'0 2b 3'o 4'o 5'o 6'0 -fo T
FIG. 5-Stress (S, MPa) dependenceon temperature (T, ~ for three coatings at RH = 0%
[an epoxy (1), a polyurethane (2), and an epoxy/melamine system (3)] [18].
According to Eq 11 a n d d e p e n d i n g on the type of coating

a n d the way it was cured, a n u m b e r of situations can arise.
F o r example, for a t h e r m o s e t t i n g coating cured at a high S
t e m p e r a t u r e (i.e., at T > Tg, RH = 0%) a n d then exposed to
different RH's, since S e ~ 0, the Sto t is given b y 10-
Stot m S T - SH (12)
8-
In Fig. 6, for one coating, the stress is positive regardless of
RH, m e a n i n g that S T is always higher t h a n S"; b u t cases
w h e r e negative stress values are o b t a i n e d are not rare. 6
It could be d e m o n s t r a t e d [11] that the s a m e coating condi-
tioned in an identical e n v i r o n m e n t b u t with different previ- 4 2 1
ous histories can develop different values of stress. Thus, a
coating c u r e d u n d e r i s o t h e r m a l and c o n s t a n t RH conditions
(e.g., 21~ a n d 50%) will develop a total stress given by
Stot = S e - S " (13)
Now, if the c o a t e d s u b s t r a t e is first h e a t e d at T > Tg for
"gQ~
I
sufficient t i m e to enable a m a x i m u m stress relaxation a n d
t h e n b r o u g h t b a c k to the initial conditions (i.e., 21~ a n d 50%
RH)
Stot = S r - S H (14) I
100
The results o b t a i n e d [ 1 1 ] show that in certain cases (e.g., FIG. 6-Stress (S, MPa) dependence on
for a n epoxy coating), the Stot can be very different [Sr (Eq relative humidity (RH, %) for a polyester
13) = 5 MPa; Sto t (Eq 14) = 0.4 MPa]. powder coating (1); an epoxy (2); a poly-
Interesting cases are those where the Tg of a coating is urethane (3); and a latex coating (4) [27].
close to or below the e x p e r i m e n t a l t e m p e r a t u r e once they are
i m m e r s e d in w a t e r or exposed to a high RH [28]. Under such
conditions S r or S r can relax a n d therefore S t o t = S H.
after the i m m e d i a t e w i t h d r a w a l of the coated substrate f r o m
Such a situation is illustrated schematically in Fig. 7 a n d
w a t e r (Curve 3 in Fig. 7), in c o m p a r i s o n with the initial stress
for a p a r t i c u l a r epoxy coating in Fig. 8.
(Sto ~ = S ~ - S " or Stot = S r - S ~I) are due to the high
Once a coated s u b s t r a t e is i m m e r s e d in w a t e r one can
observe first the d e v e l o p m e n t of a hygroscopic compressive hygroscopic tensile stress (S,o, = S ~ ) .
stress followed by its decrease. The time necessary to r e a c h The above findings are i m p o r t a n t not only for u n d e r s t a n d -
zero stress is m a i n l y d e p e n d e n t on the type of coating. The ing the m e c h a n i s m of the stress d e v e l o p m e n t in organic coat-
w i t h d r a w a l of the coated substrate from w a t e r provokes first ings b u t also for practical reasons such as choosing the
the d e v e l o p m e n t of a relatively high tensile hygroscopic stress experimental conditions of n a t u r a l o r accelerated w e a t h e r i n g
followed by its decrease. The decrease in stress (Curves 2 a n d tests, i.e., the m a g n i t u d e of stress developed in a coating
4 in Fig. 7) is due to relaxation processes facilitated by the low m i g h t d e p e n d as m u c h on n a t u r a l climatic conditions as on
Tg of the coating. The m u c h higher stress values a t t a i n e d the type a n d o r d e r of cycle selected in the laboratory.
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CHAPTER 4 9 - - S T R E S S P H E N O M E N A IN ORGANIC COATINGS 589
HeO
(I)
TINE
0
I
I
I
t
I
I
FIG. 7-Schematic description of the stress (S) dependence on time at two experi-
mental conditions (water and 50% RH). X = the initial stress [28].
4-%
3'
2' 0 C 0 ~_
1:
0-
J
27d I 76d
H20 50
(1) I (X)
--2'
1 I TIIE (d)
0 20 40 60 80 100
FIG. 8-Epoxy coating. Stress (S, MPa) dependence on time (d, day) at two experimental
conditions (water and 50% RH); ~ = initial stress [28].
STRESS MEASUREMENT Therefore, efforts were m a d e to directly d e t e r m i n e the

stress arising in a coating. Among the m e t h o d s one can find in
E q u a t i o n s 1, 3, 5, and 10 show that, if one knows the values the literature are: optical [29-32], strain gages [19a,33,34],
of E, e, a n d ~, of a coating, then in principle the various brittle l a c q u e r m a t e r i a l s [35], X-ray diffraction [36], a n d can-
stresses can be calculated. However, except for relatively tilever (beam) [2,4, 8,11, 26, 37-43 ].
simple cases, this is difficult b e c a u s e the above coating char- The cantilever (beam) m e t h o d a p p e a r s to be the m o s t
acteristics can be time, t e m p e r a t u r e , a n d relative h u m i d i t y widely used a n d is suitable for d e t e r m i n i n g the stress in a n
dependent. organic coating. This m e t h o d m a k e s use of the fact t h a t for a
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strate deflection, its measurement should be made at a dis-

tance higher than 80 m m from the clamping point [8].
Variation (2) is m u c h simpler to analyze and can be designed
to eliminate the effect of weight loss on the coated substrate
deflection by choosing the right distance between the two
FIG. 9-Schematic description of the knife edges [43].
vertically fixed at one end cantilever Each variation has its advantages, but if correctly used they
(beam) method [67]. should give identical results. For example (1) is more suited
to evaluating stress in water [28] and (2) to determine the
effect of temperature [2,11].
Among the techniques used to measure the deflection of
coated substrates, one can mention: capacitive transducers
[42,43], laser [44], travelling microscope [4, 8,26], automatic
micrometer [11].
A commercial apparatus, the CoRI stressmeter (Fig. 11), is
based on Variation (2) and the mathematical analysis de-
scribed in Ref 43. This apparatus is almost completely auto-
matic and enables one to measure the stress from about - 5
to 100~ under a variety of RH's.
FIG. 10-Schematic description of the freely supported beam A n u m b e r of mathematical equations are proposed in the
method [67]. literature to calculate the stress, but in the author's opinion
those proposed by Corcoran [40] are the closest to the real
coating under stress, applied on a substrate, the coated sub- situation (e.g., considers the fact the stress develops in two
strate will deflect in the direction which relieves the stress. directions)
Since the deflection can be measured and the elastic proper- S = dEst3 dE(t + c)
+ - - (15)
ties of the substrate are k n o w n from separate determinations, 312c(t + c)(1 - Vs) 12(1 - v)
the stress can be calculated.
S -- 4d'Est3 + 4d'E(t + c) (16)
Two variations of the cantilever (beam) method are de-
3Fc(t + c)(1 - Vs) 12(1 - v)
scribed in the literature: a one-sided coated substrate either
(1) fixed vertically at one end [4,8,26,37] (Fig. 9) or (2) freely where
supported on two knife edges [2,11,41,43] (Fig. 10). d = deflection of the substrate (Fig. 9),
The stress analysis of (1) is more complicated and shows d' = deflection in the middle of substrate (Fig. 10),
that to eliminate the effect of clamping on the coated sub- E s = elastic modulus of the substrate,
FIG. 11-CoRI stressmeter apparatus (Courtesy of Braive Instruments, Liege, Belgium).
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CHAPTER 4 9 - - S T R E S S P H E N O M E N A I N ORGANIC COATINGS 591
Vs =
Poisson's ratio of the substrate, EFFECT OF COATING COMPONENTS
t =
thickness of the substrate,
c =
thickness of the coating, Since E, E, and v (Eqs 1, 3, 5, and 10) are known to be
/(Eq 15) =
length of the coated substrate between the affected by the coating components, one should expect the
point at which it is clamped and the point at same to hold for stress development. This section will briefly
which the deflection is measured (Fig. 9), and review the influence of pigmentation, solvents, and binder.
l(Eq 16) = distance between the two knife edges (Fig. 10).
Equations 15 and 16 assume, among other things, good Pigmentation
adhesion between the coating and the substrate, isotropic It has been shown that pigmentation, both the pigment
elastic properties of the coating and the substrate, the elastic volume concentration (PVC) and the type of filler (i.e., pig-
limit of the substrate is not exceeded, and the stress is con- ments and extenders), affects the development of internal
stant throughout the coating thickness. stress [7,41,45-50]. To illustrate this, examples are presented
The second term in Eqs 15 and 16, which contains a num- in Figs. 12 to 17.
ber of coating properties difficult to determine, can be Figures 12 and 13 show, respectively, the stress depen-
neglected if Es "> E and t -> c. dence on time for a thermoplastic binder in solution and a
latex, filled with a titanium dioxide (TiO2). Some PVCs are
Most commonly, stainless steel or cold laminated steel
above the CPVC, and some are below the CPVC.
[4,8,11,26,42,43] shims are used. Other substrates such as
The different stages occurring during the film formation,
aluminum can also be used.
discussed previously, can be recognized. In Stage 1 stress
The elastic modulus, Es, of each shim can be determined increases relatively rapidly. For latex coatings, this stage cor-
prior to use with the CoRI stressmeter by applying Eq 17 responds to the transition phase of the evaporation kinetics
p/3 when the greatest part of the coalescence occurs. In Stage 2
Es - (17) (which corresponds to Phase 2 of evaporation kinetics), de-
4d't3b
pending on the PVC and the type of filler, the stress can
where decrease or first decrease and then increase. For PVC <
P = weight placed in the middle of the substrate, CPVC, this decrease is mostly due to the relaxation process,
b = width of the substrate, and but for PVC > CPVC is mostly due to relief processes such as
d', l, t = as in Eq 16. filler/binder dislocations and/or formation of microfissures.
It is important to add that, although it is not difficult to Determination o f the CPVC

make the measurements, nevertheless great care is necessary. The plot of the maximum internal stress (Sin) as a function
One should always use the correct substrate thickness, ade- of PVC enables one to determine the CPVC of a coating. Some
quately condition it, and precisely calibrate the apparatus. examples are presented in Figs. 14 and 15.
J
t3: S
"IJ ....o..---o
l&_
I ~ ~,s5 _
so
I z ~ r'" I I
1 3 5 7 5 25 105 5
FIG. 1 2 - S t r e s s (S, MPa) as a function of time [hour (h) and day (d)] for a polyisobutyl
methacrylate filled with Ti02. The numbers in the figure indicate the different PVCs (%) investi-
gated [48]. CPVC = 51%.
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1.1t S
0"91
0.7
0.1]~ HOUR
I" I I I I l l I I I I I I ' l I l I I I I I I l l I r
1 3 5 7 1 5 9 13 17 21 25 29 33
FIG. 1 3 - S t r e s s (S, MPa) as a function of time for a latex (vinyl acetate/vinyl versatate copolymer filled with
TiO~) [50]: 45% (O); 5 0 % ([]); 55% (X); 60(A). C P V C = 52%.
These figures, as well as o t h e r results p r e s e n t e d in Refs 48

a n d 49, clearly indicate that S m is a function of PVC. S m ~s]SB
increases with PVC up to a certain PVC a n d then decreases.
This PVC c o r r e s p o n d s to the CPVC, indicating the possibility
of accurately d e t e r m i n i n g this characteristic [51,52] from
XI
II
stress m e a s u r e m e n t s , a n d agrees well with the CPVCs calcu- t3
lated or d e t e r m i n e d by o t h e r m e t h o d s (density, various me-
chanical properties).
The d e p e n d e n c e of S m on PVC can be u n d e r s t o o d if one
considers Eq 1 a n d the w a y E, e, a n d v are affected by the
It
PVC.
F o r PVC < CPVC, E increases with increasing PVC b e c a u s e
the E of an inorganic filler is in general higher t h a n that of an 9
organic b i n d e r [53]. F o r PVC > CPVC, E decreases as a result
of the increasing film d i s c o n t i n u i t y [22, 54]. Since in general
a n d v are d e c r e a s e d (or are little affected) by the PVC, it
follows that the increase of S m with PVC is m a i n l y due to the
effect of PVC on E.
A
Figures 14 a n d 15 also show that the m a g n i t u d e of Srn is
d e p e n d e n t on the type of filler. There are fillers w h i c h induce
a higher stress (e.g., TiO z, r e d iron oxide) t h a n others (e.g.,
CaCO 3, talc). This is due to the filler/binder interaction (rein-
forcing effect), w h i c h is d e t e r m i n e d by the n a t u r e and, in 3
particular, by the surface area a n d the acid/base c h a r a c t e r of
the b i n d e r [55].
E x a m p l e s of S m = f(PVC) for coatings containing a mix-
ture of fillers are p r e s e n t e d in Figs. 16 a n d 17. PVC
An e x a m i n a t i o n of the results o b t a i n e d with b i n a r y a n d
t e r n a r y filler coating systems indicates that the stress S m t can t0 20 30 40 50 60 70
be calculated b y m e a n s of an additive rule FIG. 1 4 - M a x i m u m internal stress (Sm, MPa)
as a function of PVC (%) for a solvent-based
x=i thermoplastic binder filled with a TiO2 (X), a red
Smt = n l S m l + rlzSm2 + ... + rliSrrl i = ~ n~Smx (18) iron oxide (O), a yellow iron oxide (A), and a
x=l
talc (G) [48].
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CHAPTER 4 9 - - S T R E S S P H E N O M E N A I N ORGANIC COATINGS 593
7Sm
Sm
_
!
I I
3,2-
: o / ,',
3-
i 5 ./
2.4--
1.6-
.?.-
28-
OA-
The presence of solvents in a coating can affect the magni-

tude and especially the rate of development of internal stress.
This is illustrated in Fig. 19.
For thermoplastic binders in solution, the slower the evap-
FIG. 15-Sm (MPa) as a function of PVC (%)
for a styrene acrylic copolymer filled with a oration of a solvent from a coating, the slower the develop-
Ti02 (Q), a calcium carbonate (X), and talc ment of internal stress and vice versa. One should note that
(9 [49]. the coating cast from fast-evaporating solvents (Curve 1, Fig.
19) produces slightly higher stress values than those cast
from more slowly evaporating ones (Curves 3 and 4, Fig. 19).
The results obtained were explained by using Eq I, the
where principle of plasticizing effectiveness of solvents and the
nl, n2, n~ = volume fraction of different fillers pres- stress relaxation favored by the presence in the coating of the
ent in the mixtures, and slower evaporating solvent [16].
Srnl, Srn2, Srni = maximum stress of different single filler For coatings containing a mixture of solvents (Fig. 20),
systems at a given A below or equal to I both the development rate and the stress magnitude are
(A -- reduced PVC, PVC/CPVC). mainly determined by the presence in the film of the less
In the literature one can atso find simplified methods to volatile solvent(s).
determine the CPVC of latex coatings based on the same The situation may be different if the film formation is a
principle. They simply compare the force [56] or the result of solvent evaporation and cross-linking processes
deflection induced by the internal stress for flexible plastic (e.g., epoxy and polyurethane coatings). Under such circum-
stances the coating containing faster evaporating solvents
substrates [57] (Fig. 18) coated with paints of different PVCs.
can develop smaller stress values [58]. For such coatings, the
These methods can be useful, but one has to be aware that
volume of solvent present in the film after most of the cross-
they are valid only if both the thickness of the various paints
linking has occurred (Eq 2) and which determines the magni-
and the time necessary to reach the maximum stress are the
tude of eF will increase the slower the solvent evaporates. If
same. the stress relaxation process is negligible, it follows that for
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cizing effectiveness [17, 60], the molar volume, and the steric
3,6" hindrance of solvents. The Plasticizing effectiveness affects
the internal stress magnitude, while the molecular dimen-
Sm sions affect the evaporation kinetics and consequently the
rate of the stress development.
3.2-
Binder
2.8 To understand the role of the binder, the essential compo-
I nent of an organic coating on stress development, one can
I consider once again the general Eq 1 (see also Eqs 3, 5, and
2.4- 10) and/or the Tg of a coating with respect to the experimen-
I
tal temperature.
I Equation 1 indicates that the stress is directly affected by
2. I I the magnitude of E, e, and u of the binder. The smaller the
I II values of E, e, and v, the smaller the magnitude of stress.
With respect to the Tg, it should be remembered that the
binders having their Tg below or close to the film formation
1.6 Il temperature (T) develop a negligible internal stress, while
I I those having their Tg > T develop an important one. This is
due to the fact that at T > Tg~ the mobility of the binder
1.2- molecular segments is high and the stress arising during film
formation can partially or totally relax. Moreover, it can be
shown that for a thermoplastic binder in solution having a Tg
0.8 > T, the lower the Tg of the binder, the less will be the solvent
in the film after its formation (see Eqs 2 and 3) and therefore
the smaller the internal strain and stress in the dry coating
[16].
0.4 In brief, any change occurring in the molecular structure of
a binder (e.g., crosslinking, crystallinity, molecular weight,
steric hindrance) might induce a change in E, E, v, and Tg and
thus affect stress development.
10 30 50 70
FIG. 17-Sm (MPa) as a function of
PVC (%) for a latex binder containing a
TiO2 (O), calcium carbonate (X), and STRESS VERSUS ADHESION AND
their mixture: TiO2 (n = 0.4)/CaCl 3 (n = COHESION
0.6) (17) [49].
It is accepted that the stress arising in a coating can reduce
the adhesion and cohesion, two crucial properties of an or-
such coating systems the faster the solvent evaporates the
ganic coating for obtaining durable coatings [1-10,61-65].
smaller the internal stress.
The way the stress affects adhesion is described in detail in
The influence of solvents on internal stress is also evident
Refs 61 and 62. It is shown that the application of an energy
for latex coatings where certain solvents, for example the
balance analysis [66] leads to the factor /3 acting against
coalescents, play an important role in the film formation
adhesion
process [1,5,50,59].
Examples of how the level and the type of coalescent affect Ee 2
/3 = cU,.~--c - (19)
internal stress are presented in Figs. 21 and 22, respectively. 1-v
Figure 21 shows that: (1) the coalescent level affects the
where Ur is the recoverable strain energy.
time necessary to reach the maximum stress, and (2) for each
Because it is the energy that expresses the effect of e, tensile
formulation, there is an optimal coalescent level to obtain a
or compressive strains are identical in their effect [61].
tight continuous coating developing the lowest internal To accommodate the effect of stress [18,27,67], Eqs 1 and
stress. 19 are combined
In Fig. 22, the results obtained with three solvents used in
latex coatings are given. One can see that the type of solvent /3 ~ cSE (20)
influences both the value and the development rate of the Equation 20 indicates that adhesion is directly affected by
internal stress. c, S, and 9 and the larger their values the higher the tendency
As in the case of thermoplastic coatings, the influence of of the coating to detach from its substrate. Thus, if a high
solvents on internal stress development in latex coatings was stress arises in a coating, in order to prevent its detachment,
explained [15,50,59] by taking into consideration the plasti- it should be applied in a thinner layer.
www.iran-mavad.com

CHAPTER 4 9 - - S T R E S S PHENOMENA IN ORGANIC COATINGS 595
FIG. 18-Determination of the CPVC by comparing the curvature of painted plastic substrates [57].
4-5
2-
1-
TIME
' 2'0 ' ,~ ' ~o ' do ' 16o ' do ' ~ ' '
FIG. 19-Stress (S, MPa) as a function of time (day) in a thermoplastic varnish cast
from methyl ethyl ketone and ethyl acetate (1); toluene (2); xylene (3); methyl isobutyl
ketone and isobutyl acetate (4--), at 52% RH and 21~ [.16"].
3.2-
~o ~ ~ ~o
2.4- O~
A0 A
~ e
1.6-
0.8- 0
TIN(
J 2'o ' ~ ' 6'0' ~o ' ~o' 1~o' !~o' 1~o' ~o'26o
FIG. 20-Stress (S, MPa) as a function of time (day) for a thermoplastic varnish
cast from toluene (X); isobutyl acetate (9 and their mixtures [1/1 (W/W) (0) and 113
(W/W) (A)] [16].
www.iran-mavad.com

2.o-_S
1.6-
1.2-
0.8-
percent Texanol by weight of binder solids [501. 71+'~
1.4
1.
0.6
1 3 5 7 10
FIG. 22-Stress (S, MPa) as a function of time (h, hour; d, day) for a styrene acrylic
latex paint containing Texanol (9 Dalpad A (X); Dalpad A + propylene glycol (0)
[501.
Since stress develops in most organic coatings, the product out applying any external force. This is due to the fact that at
c S e should also be considered in adhesion tests performed in a particular film thickness a spontaneous detachment should
laboratories. The corrected mathematical equations for pull occur [61]. Unfortunately, this method can only be used for
off and peeling at 90 ~ are given by Eqs 21 and 22 [61,67], badly adherent coatings. For all other coatings, extremely
respectively high film thicknesses, difficult to apply and cure, would be
necessary.
(21) If the adhesion forces exceed the cohesive strength of a
coating and the stress developed is high, damage will prefer-
F entially occur in the coating (cracking, fissuring) rather than
- ~- "1, - cSE (22) at the coating/substrate interface. The verification of this
b
principle can be realized by determining the stress and the
where ultimate properties of a coating. Since most of organic coat-
o- = stress applied to pull the coating from the substrate, ings are viscoelastic, it is essential that these properties be
K = bulk modulus of the coating, evaluated under the conditions (strain rate, temperature, RH)
3' = interracial work of adhesion, corresponding to the stress development in the coating. The
F = force applied to peel the coating, and presence of stress concentrations (e.g., existence of het-
b = width of the coating. erogeneities) in the coating and of a fatigue process are fac-
Equations 20, 21, and 22 also indicate the possibility of tors decreasing the overall stress at which the coating will
determining the adhesion of a coating (i.e., the factor y) with- crack.
www.iran-mavad.com

sis
CHAPTER 4 9 - - S T R E S S PHENOMENA IN ORGANIC COATINGS 597
16-
s. RH = 5%
4
9 Initial
9 168h 3
12
9 552 h
x 1008 h 2~ 60 ~ 5% RH
-I
4
-2
-3
21 ~ 90% RH
0 , -4
0 20 40 60 80
FIG, 23-Stress (S, MPa) as a function of tem-
perature (T, ~ for a primer/clearcoat system 0 400 800 1200
after different periods of weathering [9].
tauv
Screen
FIG, 25-Stress ($, MPa) as a function of
time of weathering (tour, hour) for a primer/
12 ciearcoat system at two climatic conditions
[g].
T=21 ~
~. Initial W E A T H E R I N G AND S T R E S S
9 168h DEVELOPMENT
8 9 552 h
x 1008 h In most cases when organic coatings are exposed to weath-
ering (accelerated or natural), they undergo chemical and
physical modifications which are expressed in the change of
Tg, E, a, v, and cross-link density. Under such circumstances
4 and according to Eqs 1, 3, 5, and 10, one can also expect to see
changes in stress development.
Confirmation of this and the role played by stress in the
coating deterioration is given in Ref 9.
In this study a clearcoat/basecoat system exposed in a QUV
apparatus to alternating dry and wet cycles cracked after
0
about 1000 h.
By measuring the stress as a function of temperature and
RH, it has been shown that weathering provoked: (1) an
increase of Tg, which in turn induced higher tensile stresses
(Fig. 23), and (2) an increase of coating sensitivity to mois-
-4 ture, which induced higher compressive stresses (Fig. 24).
I 1 I i I i i I I 'l The representation of the stress as a function of time of
0 20 40 60 80 I O0 weathering for two experimental conditions similar to those
present in the accelerating apparatus (Fig. 25) indicates that
RH
FIG. 24-Stress (S, MPa) as a function of RH
every time the experimental conditions changed (every 4 h)
(%) for a primer/clearcoat system after different the coating ~was exposed to an increasing stress.
periods of weathering [9]. The processes thought to lead to fissuring of the clearcoat
are described in Fig. 26.
Briefly, the chemical degradations induced by UV, water,
and oxygen, which decrease the coating cohesion, combined
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Weathering Chemical Degradation Physical Effects
Light/Oxygen/Water
1 1 1 - Breaking of bonds - Weight loss (volatilisation, Embdttlement
material rinsed by water) +
Formation of new Stress development
Clearcoat crosslinks - Increase of Tr [
- Formation of hydro- - Water absorption Cracking

phUic groups
Basecoat =-_.---
FIG. 2 6 - S c h e m a t i c representation of processes causing crack formation in a clearcoat [9].
w i t h t h e fatigue p r o c e s s at steadily i n c r e a s i n g h y g r o t h e r m a l [20] Geldermanns, P., Goldsmith, C., and Bedetti, F., Proceedings,
stress levels are t h e c a u s e s of t h e c o a t i n g d e g r a d a t i o n . First International Technical Conference on Polyamides, Ellen-
ville, NY, November 1982, Society of Plastic Engineers.
[21] Perera, D.Y.: (a) Proceedings, XIXth FATIPEC Congress,
Aachen, Vol. I, 1988, p. 1; and (b) Material Priifung, Vol. 31,
1989, p. 57.
REFERENCES [22] Zosel, A., Progress in Organic Coatings, Vol. 8, 1980, p. 47.
[23] Hill, L. W. and Kozlowski, K., Journal of Coatings Technology,
[I] K6ning, W., Proceedings, VIth FATIPEC Congress, Wiesbaden, Vol. 59, No. 751, 1987, p. 63.
Germany, 1962, p. 424. [24] Yamabe, H. and Funke, W., Farbe Und Lack, Vol. 96, No. 7, 1990,
[2] Dannenberg, H., Society of Plastic Engineering Journal, Vol. 21, p. 497.
1965, p. 669.
[25] Shimbo, M., Ochi, M., Inamura, T., and Inoue, M., Journal of
[3] Prosser, J. L., Modern Paint and Coatings, July I977, p. 47.
Materials Science, Vol. 20, 1985, p. 2965.
[4] Saarnak, A., Nilsson, E., and Kornum, L. O., Journal of the Oil
[26] Nilsson, E., Fdrg och Lack, Vol. 2, 1975, p. 318; Vol. 23, 1977, p.
and Colour Chemists" Association, Vo]. 59, 1976, p. 427.
179; Vol. 23, 1977, p. 199.
[5] Hamburg, H. R. and Morgans, W. M., Hess's Paint Film Defects:
[27] Perera, D.Y. and Vanden Eynde, D., Proceedings, XVIth
Their Causes and Cure, 3rd ed., Chapman and Hall, London,
FATIPEC Congress, Liege, Belgium, Vol. 1, 1982, p. 129.
1979.
[28] Perera, D.Y. and Vanden Eynde, D., Proceedings, XXth
[6] Croll, S. G., Journal of Applied Polymer Science, Vol. 23, 1979, p.
FATIPEC Congress, Nice, 1990, p. 125.
847.
[29] De Waard, R., Stock, Ch. R., and Alefrey, T. Jr., ASTM Bulletin,
[7] Sato, K., Progress in Organic Coatings, Vol. 8, No. 2, 1980, p. 143.
TP56, 1952, p. 53.
[8] Perera, D. Y. and Vanden Eynde, D., Journal of Coatings Tech-
nology, Vol. 53, No. 677, 1981, p. 39. [30] Zubov, P. J., Lepilkina, L. A., Gilman, T. P., and Leites, A. Z.,
[9] Oosterbroek, M., Lammers, R. J., van der Ven, L. G. T., and Colloi'd Journal, Vol. 23, 1961, p. 23.
Perera, D. Y., Journal of Coatings Technology, Vol. 63, No. 797, [31] Imamura, H., Mokuzai Gakkaishi, Vol. 16, 1970, p. 168; Vol. 19,
1991, p. 55. 1973, pp. 89 and 393; Vol. 22, 1976, pp. 325 and 331.
[10] Kamarchik, P., Jr. and Jurezak, E. A., Proceedings of Radtech, [32] Theocaris, P. S. and Paipetis, S. A., Journal of Strain Analysis,
Edinburgh, Scotland, Great Britain, 1991. Vol. 8, 1973, p. 286.
[11] Perera, D. Y. and Vanden Eynde, D., Journal of Coatings Tech- [33] Shimbo, M., Ochi, M., and Shigeto, Y., Journal of Applied Poly-
nology, Vol. 59, No. 748, 1987, p. 55. mer Science, Vol. 26, 1981, p. 2265.
[12] Crackin, F. L. and Bersch, C. F., Society of Plastic Engineers [34] Association Belge pour l'Etude, l'Essai et l'Emploi des Mat6riaux
Journal, Vol. 15, 1959, p. 791. (ABEM), "Cours d'initiation ~tl'analyse des contraintes," Bruxel-
[13] Bierwagen, G. P., Journal of Coatings Technology, Vol. 51, No. les, 1973.
658, 1979, p. 117. [35] Kanno, A. and Murato, Y., Proceedings, 15th Japanese Congress
[14] Bauer, C. L., Farris, R. J., and Vratsanos, M. S., Journal of Coat- on Materials Research, Japan, 1972, p. 177.
ings Technology, Vol. 60, No. 760, 1988, p. 51. [36] Nakamura, K., Nishino, T., and Airu, X., Proceedings, XXth
[15] Perera, D. Y. and Vanden Eynde, D., Journal of Coatings Tech- Congress AFTPV, Nice, France, 1991, p. 73.
nology, Vol. 56, No. 716, 1984, p. 111. [37] Sanzharovskii, A. T., Vysokomolekularnie Soedinenia, Vol. 2, No.
[16] Perera, D.Y. and Vanden Eynde, D., Journal of Coatings 11, 1960, pp. I698-1702, 1703-1708, 1709-1714.
Technology, Vol. 55, No. 699, 1983, p. 37. [38] Gusman, S., Paint Technology, January 1963, p. 17.
[17] Hansen, Ch. M., Industrial and Engineering Chemistry Research, [39] Simpson, W. and Boyle, D. A., Journal of the Oil and Colour
Vol. 9, 1970, p. 282. Chemists' Association, Vol. 46, 1963, p. 331.
[18] Perera, D. Y., Proceedings, XVlth International Conference in [40] Corcoran, E. M., Journal of Paint Technology, Vol. 41, No. 538,
Organic Coatings Science and Technology, Athens, Greece, 1969, p. 635.
1990, p. 309. [41] Aronson, P. D., Journal of the Oil and Colour Chemists' Associa-
[19] Shimbo, M., Ochi, M., and Arai, K., Journal of Coatings Technol- tion, Vol. 57, 1974, p. 66.
ogy: (a) Vol. 56, No. 713, 1984, p. 45, and (b) Vol. 57, No. 728, [42] Crolt, S. G., Journal of Coatings Technology: (a)Vol. 50, No. 638,
1985, p. 93. 1978, p. 33; (b) Vo]. 51, No. 659, 1979, p. 49.
www.iran-mavad.com

CHAPTER 49--STRESS PHENOMENA IN ORGANIC COATINGS 599
[43] Croll, S. G., Journal of the Oil and Colour Chemists' Association, [57] D6rr, H. and Holzinger, F., "Le dioxyde de titane KRONOS
Vol. 63, 1980, p. 271. darts les peintures-6mulsion, '~ Kronos International, Inc.,
[44] O'Brien, R. N. and Michalik, W., Journal of Coatings Technology, Leverkusen, Germany, 1990.
Vol. 58, No. 735, 1986, p. 25. [58] Croll, S. G., (a) Journal of the Oil and CoIour Chemists' Associa-
[45] Kris, G. J. and Sanzharovskii, A. T., Lakokrasochnye MateriaIy i tion, Vol. 63, 1980, p. 230, and (b)Journal of Coatings Technol-
Primenenie, Vol. 3, 1970, p. 27. ogy, Vol. 53, No. 672, 1981, p. 85.
[46] Haagen, H., Farbe und Lack, Vol. 85, No. 2, 1979, p. 94. [59] Perera, D.Y. and Vanden Eynde, D., Journal of Coatings
[47] Croll, S. G., Polymer, Vol. 20, No. 11, 1979, p. 14. Technology, Vol. 56, No. 718, 1984, p. 69.
[48] Perera, D. Y. and Vanden Eynde, D., Journal of Coatings Tech- [60] Hansen, Ch. M., Official Digest, Vol. 37, No. 480, 1965, p. 57.
nology, Vol. 53, No. 678, 1981, p. 40. [61] Croll, S. G., Journal of Coatings Technology, Vol. 52, No. 665,
[49] Perera, D. Y. and Vanden Eynde, D., Journal of Coatings Tech- 1980, p. 35.
nology, Vol. 56, No. 717, 1984, p. 47. [62] Croll, S. G., Journal of the Oil and Colour Chemists' Association,
[50] Perera, D.Y. and Vanden Eynde, D., Journal of the Oil and Vol. 63, 1980, p. 200.
Colour Chemists' Association, Vol. 11, 1985, p. 275. [63] Pierce, P. E. and Schoff, C. K., "Coating Film Defects," Federa-
[51] Bierwagen, G. P., Journal ofiPaint Technology, Vol. 44, No. 574, tion of Societies for Coatings Technology, Philadelphia, PA,
1972, p. 45. 1988.
[52] Bierwagen, G. P. and Mallinger, R. G., Journal of Coatings Tech- [64] Schmid, E.V., Polymers Paint Colour Journal, VoL 180, No.
nology, Vol. 54, No. 690, 1982, p. 73. 4258, 1990, p. 212.
[53] Sato, K., Progress in Organic Coatings, Vol. 4, 1976, p. 271. [65] Farris, R. 3., Maden, M. A., and Goldfarb, J., Proceedings, The
[54] Bierwagen, G. P. and Hay, T. K., Progress in Organic Coatings, Adhesion Society, 14th Annual Meeting, Clearwater, FL, 1991,
Vol. 3, 1975, p. 281. p. 138.
[55] Toussaint, A. and D'Hont, L., Journal of the Oil and Colour [66] Kendall, K., Journal of Physics D: Applied Physics, Vol. 4, 1971, p.
Chemists' Association, Vol. 64, 1981, p. 302. 1186; Vol. 6, 1973, p. 1782.
[56] Helmen, T. and Strauch, D., Farbe und Lack, Vol. 96, No. 10, [67] Perera, D. Y., Proceedings, XVIlth FATIPEC Congress, Lugano,
1990, p. 769. Switzerland, Vol. 1, 1984, p. 13.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Slip Resistance
by Paul R. Gudvin, Jr. 1
AN OVERVIEW OF THIS SUBJECT as it relates to the coating tional Safety a n d Health f u n d e d a project that dealt with
i n d u s t r y was p u b l i s h e d in 1978 [1]. This c h a p t e r is an expan- slipperiness a n d safety of workers engaged in structural steel
sion a n d u p d a t e of that paper. Although a m a j o r i t y of the erection [11].
i n s t r u m e n t s a n d test m e t h o d s for slip resistance were devel-
o p e d in ASTM c o m m i t t e e s with responsibilities o t h e r t h a n
for paint, they all can be used to m e a s u r e the slip resistance of Definitions
paints a n d coatings.
The following are useful, specific definitions that have b e e n
Specific s t a n d a r d s for slip resistance and its testing m a i n l y
developed by ASTM C o m m i t t e e D-21 on Polishes a n d f o u n d
refer to flooring a n d o t h e r p e d e s t r i a n w a l k w a y areas. At this
in ASTM Test M e t h o d for Static Coefficient of F r i c t i o n of
t i m e there are no coefficient of friction (COF) s t a n d a r d s in
Polish-Coated F l o o r Surfaces as M e a s u r e d by the J a m e s Ma-
the coating industry. One industry, the floor polish industry,
chine (D 2047) [12].
established a COF value of less t h a n 0.5 as a slippery surface
a n d a value of greater t h a n 0.5 as a not slippery surface [2]. Coefficient of Friction--The ratio of the h o r i z o n t a l
c o m p o n e n t of force r e q u i r e d to overcome friction, to the
OSHA has p r o p o s e d that the COF for working surfaces, such
vertical c o m p o n e n t of the object weight or n o r m a l force
as walkways a n d a r o u n d machinery, in a p l a n t be not less a p p l i e d t h r o u g h the object, which tends to cause the
t h a n 0.5 [3]. The U.S. D e p a r t m e n t of Justice has p r o p o s e d a friction.
m i n i m u m COF of 0.6 for level walking surfaces and of 0.8 for Dynamic Coefficient of Friction--The ratio of the hori-
r a m p s for its Americans with Disabilities Act [4]. If these zontal c o m p o n e n t of force required to cause a b o d y to
p r o p o s a l s b e c o m e law, p a i n t e d walking surfaces m u s t meet slide at a relatively constant velocity to the vertical com-
or exceed these standards. p o n e n t of the weight of the object or force a p p l i e d to it.
The relatively constant velocity used to cause the b o d y to
slide over the surface is to be not less t h a n 0.125 ft/s n o r
ASTM ACTIVITY m o r e t h a n 0.5 ft/s (38 to 152 mm/s). The vertical c o m p o -
nent shall result in a contact pressure of not less t h a n
M a n y studies of COF m e a s u r e m e n t by various ASTM com- 1 psi (6.9 kPa) n o r m o r e t h a n 13 psi (90 kPa) applied
u n i f o r m l y over the area in m u t u a l contact.
mittees o c c u r r e d over the p a s t 20 years. F o r the most part,
these studies have been divided into specific c o m m i t t e e s with Friction--The resistance developed b e t w e e n the physi-
a task group of C o m m i t t e e F-13 on Safety a n d Traction for cal contacting surface of two bodies when there is move-
m e n t or t e n d e n c y for m o v e m e n t of one b o d y relative to
F o o t w e a r u n d e r t a k i n g the task to i m p r o v e c o m m u n i c a t i o n s
a n o t h e r parallel to the plane of contact.
between the various groups studying COF a n d thus prevent
d u p l i c a t i o n of effort. Slip Resistance--That p r o p e r t y of a floor surface that is
designed to prevent slipping. A surface having a static
Task G r o u p D01.23.15 on Slip Resistance is involved with
coefficient of friction of 0.5 o r greater as m e a s u r e d in
m e a s u r e m e n t of p a i n t and coatings COF. The group has de- a c c o r d a n c e with ASTM D 2047 is considered to be a slip-
veloped a test m e t h o d that describes a slip-angle test a p p a r a - resistant surface.
tus a n d a horizontal-pull slip m e t e r that functions u n d e r wet Static Coefficient of Friction--The ratio of the horizon-
a n d d r y conditions a n d t h a t can be used to m e a s u r e b o t h tal c o m p o n e n t of force a p p l i e d to a b o d y that just over-
static a n d d y n a m i c COF. comes the friction or resistance to slipping to the vertical
Other areas of activity dealing with the COF include ce- c o m p o n e n t of the weight of the object or force a p p l i e d to
r a m i c s [5], plastics [6], polishes [7], skid resistance [8], a n d it. The vertical c o m p o n e n t shall result in a contact pres-
footwear [9]. A study b y the Consumers' Union [10] i n d i c a t e d sure of not less t h a n 1 psi (6.9 kPa) n o r m o r e t h a n 13 psi
a need for good m e a s u r e m e n t of slipperiness. Evidence in (90 kPa) applied u n i f o r m l y over the area in m u t u a l con-
1976 i n d i c a t e d that available i n s t r u m e n t a t i o n was inade- tact.
quate a n d that results o b t a i n e d with it d i d not correlate with In a general sense, slipperiness can be defined as the ten-
practical observations. The N a t i o n a l Institute of Occupa- dency or liability to cause s o m e t h i n g to slide s u d d e n l y or
involuntarily. In m a n y cases, an organic p o l y m e r surface (i.e.,
~Consultant, P. R. GuOvin Associates, P.O. Box 811, Westerville, a coating) is involved. In terms of the flooring m a r k e t area,
OH 43086-0811. for which these definitions were written, the flooring surface
600
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CHAPTER 50--SLIP RESISTANCE 601
could be an alkyd e n a m e l on a p o r c h or deck, a vinyl- or t h a t actually c a r r y the n o r m a l l o a d W b e t w e e n the two sur-

p o l y u r e t h a n e - c o a t e d athletic g y m n a s i u m floor, a waxed vi- faces, the following relation also exists
n y l - c o m p o s i t i o n floor tile, an epoxy-coated concrete factor
W = p,~.A
floor, a n d so on. Slipperiness can be c o n s i d e r e d as being
m a d e up of two factors, skid resistance a n d slip resistance. w h e r e Pm is defined as the flow pressure of the softer m a t e r i a l
Skid can be defined as an act of sliding w i t h o u t r o t a t i o n a n d in the vicinity of these local areas of true contact. W h e n A is
slip as a slide t h a t occurs suddenly o r involuntarily. e l i m i n a t e d b e t w e e n these equations, the friction coefficient is
obtained
ix -- F / W = s/p,~
C O N C E P T OF T H E C O E F F I C I E N T OF
FRICTION F r i c t i o n is the universal force b e t w e e n surfaces t h a t op-
poses sliding motion. W h e n surfaces of bodies are in contact,
Slip is a w o r d that has m a n y m e a n i n g s [13,14]. In certain the interactive force at the surface m a y have c o m p o n e n t s
areas of the coating industry, slip is c o n s i d e r e d to be the b o t h p e r p e n d i c u l a r a n d tangential to the surface. The perpen-
ability of an object to move in a relatively free or dicular c o m p o n e n t is called the " n o r m a l force," a n d the tan-
u n e n c u m b e r e d b u t controlled m a n n e r w h e n one sheet of gential force is called the "friction force." W h e n there is
metal passes over a n o t h e r sheet as in a coating-line feeding relative sliding b e t w e e n the bodies, the frictional force always
operation, w h e n it moves along a conveyor system in coating, acts in the opposite direction of this motion.
printing, fabrication, or p a c k a g i n g operations, and the like. Most dry surfaces behave a p p r o x i m a t e l y a n d within limits
The coating m u s t have p r o p e r "slip" or "lubricity" to allow the according to Coulomb's frictional law. C o u l o m b f o u n d that
coated object to pass t h r o u g h the coating system to a further just before motion, the friction b e t w e e n two surfaces is
fabrication or p a c k a g i n g section of the line. In fact, slip is slightly greater t h a n w h e n the surfaces are in steady m o t i o n
very i m p o r t a n t to fabrication operations w h e r e i n the c o a t e d relative to each other, that the frictional force is p r o p o r t i o n a l
object is in contact with a tooling system as in fabrication of to the n o r m a l force pressing the surfaces together, and t h a t
bottle caps, or with other m e t a l surfaces in b e n d i n g opera- this force is i n d e p e n d e n t of both the contact a r e a and, except
tions, etc. Yet, o t h e r coatings such as floor coatings are de- at the start, the speed of relative m o t i o n of the bodies. The
signed to decrease this ability to move easily u n d e r an applied constant ratio of the tangential force to the n o r m a l force is
force. In either case, the frictional resistance b e t w e e n objects k n o w n as the "coefficient of friction" (COF) a n d d e p e n d s on
is being modified a n d controlled with such control being at- the n a t u r e of the two surfaces. To initiate sliding against
t a i n e d b y the inherent p r o p e r t i e s of the m a t e r i a l s used for the friction, it is necessary to a p p l y a tangential force at least as
coating or use of additives in the coating. It is i m p o r t a n t to great as the COF a n d the n o r m a l force before the onset of
u n d e r s t a n d that at times low friction is desired a n d that at m o t i o n take place. The a p p l i e d tangential force is resisted by
other times r e a s o n a b l y high friction is desired. the equal a n d opposite force of static friction, a n d the force
Friction is the p r o p e r t y t h a t d e t e r m i n e s the degree of slip r e q u i r e d to overcome static friction is usually greater t h a n
or resistance to slip t h a t exists. Both static a n d d y n a m i c o r the force n e e d e d to sustain u n i f o r m sliding motion.
kinetic friction are i m p o r t a n t p r o p e r t i e s of coatings. Static
friction is the a m o u n t of friction b e t w e e n two surfaces at the
precise instant w h e n one c o m m e n c e s to move over the other.
D y n a m i c friction is the friction b e t w e e n two surfaces w h e n D E T E R M I N A T I O N OF T H E C O E F F I C I E N T
they are moving p a s t one a n o t h e r w i t h o u t interruption. The OF FRICTION
coefficient of static friction is usually equal to or greater t h a n
t h a t of d y n a m i c friction [15]. The coefficient of friction, ix, is a Three types of i n s t r u m e n t s are used to m e a s u r e the COF,
m e a s u r e of slip with a high coefficient of friction denoting a n d these are illustrated in Fig. 1 [17]. These are drag-type
p o o r slip a n d a low coefficient of friction denoting g o o d slip meters that are b a s e d on fx = F/W, p e n d u l u m - t y p e m e t e r s
[16]. This p a r a m e t e r is the ratio of the force F (frictional that m e a s u r e the energy loss of the p e n d u l u m as an indirect
force) r e q u i r e d to move one surface over a n o t h e r surface to i n d i c a t i o n of the d y n a m i c friction, a n d articulated-strut de-
the total force W pressing the two surfaces together vices that are b a s e d on the direct a n d f u n d a m e n t a l principle
of the resolution of forces that take place w h e n an object
ix = F/W slides d o w n an incline as described below. The angle at which
A c u r r e n t theory of the m e c h a n i s m of dry friction describes a flat or plane surface m u s t be inclined for a solid object to
the force of friction arising from the s h e a r strength of m i n u t e slide with a steady speed d o w n the incline is the "angle of
interaction areas or areas of true c o n t a c t b e t w e e n the con- friction." The tangent of this angle is the COF b e t w e e n the
tacting surfaces. These i n t e r a c t i o n areas are d i s t r i b u t e d in a solid block of m a t e r i a l a n d the inclined plane
m o r e or less r a n d o m m a n n e r over the total a p p a r e n t contact
/x = tan4~
area. This can be expressed b y the following relation for the
friction force The principle involved in this equation is used in the slip-
angle a p p a r a t u s d e s c r i b e d in ASTM Test Methods for Mea-
F = s.A
suring Static F r i c t i o n of Coatings Surfaces (D 4518) [18]. The
where s is the average s h e a r strength of the interaction areas, state of the art of slip-resistance studies t h r o u g h 1975 has
a n d A is a r e a of actual contact. Since it is the interaction areas b e e n s u m m a r i z e d by B r u n g r a b e r [19].
www.iran-mavad.com

a. DRAG TYPE METER
~ l:Ol~lM*=ilal
FLOORSURFACE
I
b. ARTICULATED STRUT
DEVICE
INITIAL ' ~ S I T I O N AT
POSITION
FLOORSURFACE / i
C. PENDULUM
DEVICE
f
\\
i
q FLOORSURFACE /
FIG. 1-Schematics of different friction measurement devices (courtesy of the Na-

tional Institute of Standards and Technology).
S E N S O R MATERIALS The sensor material may be composed of the same com-

pound as the test compound or different. In most ASTM
It is obvious that two surfaces are required for COF mea- studies of flooring, leather is used as the primary sensor
surements of any surface, and the sensor material, or surface material. It is commonly used in the manufacture of shoes,
against which the specified compound is tested, should be and, probably more important, it has the lowest COF of any
defined and specified. It is essential to obtaining meaningful, shoe-sole material. Although the rationale for its selection is
reproducible results that the sensor material be selected
not well documented, leather conforming to Federal Specifi-
to represent use conditions and be well defined. Properties
cation KK-L-165C is specified as the sensor material. Where a
such as uniformity (surface character including flatness,
nonleather sensor material is to be used, rubber conforming
roughness, chemical composition, resilience, and shear mod-
ulus), permanence in that chemical and physical characteris- to ASTM Test Method for Rubber Property--Abrasion Resis-
tics should not change with time, and availability in a usable tance (NBS Abrader) (D 1630) [20] is used. Neoprene has
form that does not require excessive preparation should all be been used in certain round-robin studies. In other instances,
considered when selecting a sensor. Both sensor material and three leathers with three levels of oil content, two Kraton |
test material should be reported when the coefficient of fric- thermoplastic elastomers, and l 5 different rubbers were used
tion is given. to generate statistical data [21] for ASTM Test Method for
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CHAPTER 50--SLIP RESISTANCE 603
Static Slip Resistance of F o o t w e a r Sole, Heel, or Related METHODS FOR DETERMINING

Materials by H o r i z o n t a l Pull S l i p m e t e r (HPS) (F 609) [22]. C O E F F I C I E N T OF FRICTION
The test m e t h o d s a n d e q u i p m e n t d e s c r i b e d b e l o w were

developed for flooring materials. However, they can be ap-
plied to testing the slip resistance a n d COF of p a i n t a n d
LUBRICANTS coatings on various substrates against themselves as well as
against a variety of substrates.
In those instances w h e r e slip is to be i n c r e a s e d (friction ASTM Test M e t h o d for Determining the Static Coefficient
decreased), a variety of slip agents or lubricants are available. of Friction of Ceramic Tile a n d Other Like Surfaces by the
These include m i c r o n i z e d polyethylene p o w d e r s a n d sili- H o r i z o n t a l D y n a m o m e t e r Pull-Meter M e t h o d (C 1028-84)
cones. See Table 1 for m o r e slip agents. M a n y slip agents also [26] utilizes a pull m e t e r - a n d - h e e l a s s e m b l y to m e a s u r e the
function as a b r a s i o n - r e s i s t a n c e a n d m a r - r e d u c t i o n agents. In COF of tile a n d like materials. The test m e t h o d specifies a
certain instances, they can be u s e d as a n t i b l o c k agents. Lubri- s t a n d a r d c e r a m i c tile with an average COF b e t w e e n 0.45 a n d
cants are often used in the plastics processing industry where 0.55 and a neolite sensor material. Currently c o n s i d e r a t i o n is
they function as melt viscosity reducers, flow agents to im- being given in an ASTM s u b c o m m i t t e e to modifying this
prove flow onto metal surfaces, and, at times, costabilizers. device for i m p r o v e d r e p r o d u c i b i l i t y o r discontinuing the
Factors t h a t s h o u l d be c o n s i d e r e d in selecting a l u b r i c a n t method.
include melting point, polarity, a n d solubility. Of course, the ASTM Test M e t h o d for Static a n d Kinetic Coefficients of
l u b r i c a n t should not interfere with a d h e s i o n or any cross- Friction of Plastic F i l m a n d Sheeting (D 1894) [27] is con-
linking m e c h a n i s m that is used. C o m m o n l u b r i c a n t families c e r n e d with d e t e r m i n a t i o n of static a n d d y n a m i c COFs. The
as well as selected specific lubricants are listed in Table 1. test m e t h o d specifies only the force-measuring i n s t r u m e n t
Polyethylene a n d polytetrafluoroethylene are available in a since the test m e t h o d uses a plastic film o r sheet sliding over
p o w d e r o r m i c r o n i z e d form in a variety of particle sizes [23], itself. One c o m p a n y that m a n u f a c t u r e s slip-resistance coat-
a n d silicones are available as f o r m u l a t e d p r o d u c t s designed ings i n t e n d e d for c o m p l i a n c e with OSHA a n d ADA require-
for use in the coating i n d u s t r y [24,25]. The m i c r o n i z e d poly- m e n t s specifies this test m e t h o d for d e t e r m i n a t i o n of p r o d u c t
mers are i n c o m p a t i b l e a n d act as a filler that rises to the COF.
coating surface where they function as tiny "ball bearings" ASTM Test M e t h o d for Static Coefficient o f F r i c t i o n of
Polish-Coated F l o o r Surfaces as M e a s u r e d by the J a m e s Ma-
that decrease friction a n d often i m p r o v e a b r a s i o n a n d m a r
chine (D 2047) [12] is the only slip-resistance test m e t h o d
resistance.
recognized b y the floor-polish industry. Unfortunately, its use
is limited to the l a b o r a t o r y since it is n o t portable. Sensor
TABLE 1--Lubricants. m a t e r i a l s of leather a n d r u b b e r are specified.
M e t h o d A of ASTM Test Methods for Measuring Static
Esters
F r i c t i o n of Coating Surfaces (D 4518) [18] involves a plat-
Wax esters form containing a sled that is slowly raised until the angle of
Fatty alcohol esters m o v e m e n t is reached. M e t h o d B involves a horizontal-pull
Fatty esters tester. S o m e l a b o r a t o r i e s have modified their I n s t r o n tensile
Glycerol esters
testers to p e r f o r m similar operations. This a p p r o a c h has the
Fatty Acid Amides advantage of providing a graphic r e c o r d of the forces in-
volved.
Alkanolamides Other ASTM m e t h o d s for m e a s u r i n g friction include ASTM
Monoamides Test Method of Measuring Surface Frictional Properties Us-
Bisamides
ing the British P e n d u l u m Tester (E 303) [28], ASTM Con-
Metallic Compounds s u m e r Safety Specification for Slip-Resistant Bathing Facili-
Aluminum stearate
Barium stearate
Calcium stearate TABLE 2--Canadian government standards for coefficient of
Molybdenum sulfide friction.
Zinc stearate
Static COF Sliding COF
Waxes and Other Hydrocarbons Dry Wet Oily Dry Wet Oily
Fluoropolymers For leather with:
Micronized polyethylene
Micronized polytetrafluoroethylene Epoxy coating 0.75 0.75 -.. 0.50 0.50 --.
Montan waxes Polyurethane coating 0.85 0.85 -.. 0.50 0.50 .--
Oxidized polyethylene waxes
Paraffins, low melting For rubber with:
Polyethylene waxes
Epoxy coating 1.00 0.90 0.70 0,80 0.80 0.40
Silicones Polyurethane coating 1.00 0.85 1.00 0.85 0.85 0.70
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TABLE 3--Devices for measuring the coefficient of friction.

Device Manufacturer Comment Reference
DRAG-TYPEFRICTIONMEASURINGDEVICES
Dynamometer Pull Meter Chatillion Inc. Tests are being discontinued by
ASTM C21.06
Gardco Washability Wear Paul N. Gardner Co. Inc. Instrument is being evaluated at [27]
Friction Tester, Model D several companies
12VF
Coefficient of Friction Tester, Paul N. Gardner Co. Inc. Meets ASTM D-1894-78 [27]
Model FM-1055 and -1055F requirements. Model F has a
force transducer for strip chart
readout.
Instrumentors Slip/Peel Tester Instrumentors, Inc., Designed to meet ASTM D 1894

Model SP-101B Cleveland, OH;
available from IMASS,
Accord, MA
Floor Friction Tester, Model 80 Technical Products Co. Portable device
TMI Slip & Friction Tester, Test Machine Inc., Flat bed plate laboratory
Models 32-06 Amity, NY horizontal pull slipmeter
TOPAKA| Horizontal Slip Pioneer Eclipse Co. Described in ASTM D-21 Proposal [7]
Tester P 128
Universal Slip-Resistance William English Ltd. Device has been removed from [29-32]
Tester market
Whiteley Model HPS III Slip Whiteley Industries, Inc. Can be used to test in accordance
Master with ASTM F 609
DYNAMICPENDULUM-TYPESKIDRESISTANCETESTER
British Portable Skid Road Research ASTM E 303 utilizes this device [28]
Resistance Tester Laboratory,
Crowthorne,
Berkshire, England
Sigler Coefficient of Friction Frazier Precision Specified in Federal Test Method [33-34]
Machine Instrument Co., Standard No. 501a
Hagerstown, MD
Tortus Floor Friction Tester Ceramic Research, Very good for microinvestigations [35-38]
Penkhall Stake-on- of floor surfaces
Trout, England
ARTICULATEDSTRUTTESTERS
Ergodyne Slip-Resistance William English Ltd., Small and lightweight in nature
Tester Alva, FL
James Machine AIDE, Inc., Racine, WI Used in ASTM D 2047. Considered [12,39]
to be a comparison standard
testing device.
NBS/Brungraber Slip Tester, Slip-Test Inc., Mark I useful on dry surfaces and [5,32,40-41]
Model Mark I and Model Lewisburg, PA Mark II useful on wet surfaces
Mark II
Model 9505 Mobility/Lubricity Altek Co., Torrington, Used to measure slip resistance
Tester CT such as beverage exterior can
coatings
ties (F 462) [22], ASTM Test M e t h o d for Static Coefficient of F ew slip-resistance standards exist in m o s t industries, in-
Friction of Shoe Sole and Heel Materials as Measured by the cluding the coating industry, even though there are m a n y
J a m e s M ach i n e (F 489) [22], and ASTM Test M e t h o d for painted surfaces in pedestrian walkways. The United States
Static Slip Resistance of Footwear, Sole, Heel, or Related Navy has two specifications--MIL-D-23003A Military Speci-
Materials by Horizontal Pull S li p m e te r (HPS) (F 609) [22]. fication-Deck Covering Co m p o u n d , Nonslip, Rollable and
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CHAPTER 50--SLIP ~ S I S T A N C E 605
MIL-D-24483A Military Specification-Deck Covering, Spray- REFERENCES

On, N o n s l i p - - t h a t specify COF values. Both specifications
use h o r i z o n t a l slip testers. [1] Guevin, P. R., "Review of Skid and Slip Resistance Standards
The C a n a d i a n G o v e r n m e n t Specification B o a r d a d o p t e d Relatable to Coatings," Journal of Coatings Technology, Vol. 50,
two s t a n d a r d s for deck coatings based on the above U.S. Navy No. 643, August 1978, pp. 33-38.
[2] Federal Register, Vol. 24, (Tuesday, 17 March 1955), pp. 1513-
specifications. One involves nonslip epoxy coatings, I-GP-
1524.
192, and the o t h e r nonslip involves p o l y u r e t h a n e coatings, 1- [3] Federal Register, Vol. 55, No. 69 (Tuesday, 10 April 1990), pp.
GP-200. The COF specifications for these materials are given 13360-13441.
in Table 2. This i n f o r m a t i o n points out s o m e i m p o r t a n t as- [4] Federal Register, Vol. 56, No. 14 (Tuesday, 22 Jan. 1991), pp.
pects of slip resistance m e a s u r e m e n t s . First, value differ- 2296-2395.
ences in slipperiness of various shoe-sole m a t e r i a l s u n d e r [5] Ceramic Engineering and Science Proceedings, Vol. 13, Nos. 1-2,
different conditions are used. Second, it points out the impor- 1992, pp. 1-91.
tance of specifying the n a t u r e of the shoe-sole material. Over- [6] ASTM Research Report D20-1131, 9 Sept. 1986.
[7] Annual Book of ASTM Standards, Vol. 15.04 (1984, 1985, 1986).
all, leather has lower COFs t h a n rubber.
[8] "Walkway Surfaces: Measurement of Slip Resistance," Walkway
Surfaces: Measurement of Slip Resistance, ASTM STP 649, C.
Anderson and J. Senne, Eds., ASTM, Philadelphia, 1978.
[9] "Slips, Stumbles, and Falls: Pedestrian Footwear and Surfaces,"
Slips, Stumbles, and Falls: Pedestrian Footwear and Surfaces,
ASTM STP 1103, B. E. Gray, Ed., ASTM, Philadelphia, 1990.
TEST D E V I C E S F O R M E A S U R I N G T H E COF [10] Consumer Reports, Vol. 42, No. 7, July 1976, pp. 417-419.
[11] Stanevich, R., "Correlation of Subjective Slipperiness Judg-
As m e n t i o n e d earlier, there are three types of devices used ments with Quantitative COF Measurements for Structural
to m e a s u r e the COF, n a m e l y drag, p e n d u l u m , and articulated Steel," CDC Contract No. 200-86-2929, NIOSH, Morgantown,
strut-based devices, The drag-type meters can be subdivided WV, 31 Oct. 1987.
into two classes: (1) horizontal-pull slip meters that are porta- [12] Book of ASTM Standards, Vol. 15.04.
ble, inexpensive, a n d u s e d directly on a floor or o t h e r surface [13] Paint~Coatings Dictionary, S. LeSota, Ed., Federation of Socie-
u n d e r test a n d (2) b e n c h - t o p slip meters that are used p r i m a r - ties for Coatings Technology, Philadelphia, 1978.
[14] Additives for Plastics, Vol. 1, R.B. Seymour, Ed., Academic
ily in the laboratory. Both of the devices in these subclasses
Press, New York, 1978.
are s o m e t i m e s referred to as "fish scale-type testers." The [15] Cramp, A. P. and Masters, L.W., "Preliminary Study of the
devices are simple, m o t o r i z e d p o w e r units with force-mea- Slipperiness of Flooring," National Bureau of Standards, NBSIR
suring devices such as d y n a m o m e t e r s . One such device, de- 74-613 (July 1974).
veloped at an i n s u r a n c e c o m p a n y [42], has been used by an [16] Burwell, J. T. and Rabinowicz, E., "The Nature of the Coefficient
ASTM s u b c o m m i t t e e in a r o u n d - r o b i n study [21] to evaluate of Friction," Journal of Applied Physics, Vol. 24, 1953, pp.
w a l k w a y slipperiness [43]. Use of such devices has b e e n vali- 136-139.
d a t e d in a n o t h e r study [44]. General results from s o m e ASTM [17] Adler, S. C. and Pierman, B. C., "A History of Walkway Slip-
Resistance Research at the National Bureau of Standards," NBS
m e m b e r s indicates that p e n d u l u m - t y p e devices are not appli-
Special Publication 565, National Bureau of Standards, Wash-
cable for further c o n s i d e r a t i o n in the m e a s u r e m e n t of the ington, DC, December 1979.
COF. [18] Annual Book of ASTM Standards, Vol. 06.01.
P e n d u l u m - t y p e COF devices [12, 33-34] consist of a p e n d u - [19] Brungraber, R. J., "An Overview of Floor Slip-Resistance Re-
l u m that is faced with a certain shoe-sole or heel material. search With Annotated Bibliography," Report NBSTN 895, Na-
The p e n d u l u m can be adjusted to sweep a p a t h across a tional Bureau of Standards, Washington, DC, January 1976.
flooring surface so that the contact pressure between the [20] Annual Book of ASTM Standards, Vol. 09.01.
[21] ASTM Research Report F13-I001, 27 July 1979.
facing a n d the floor follows a p r e d e t e r m i n e d , t i m e - d e p e n d e n t
[22] Annual Book of ASTM Standards, Vol. 15.07.
pattern. The p e n d u l u m ' s resultant loss of energy is p u r p o r t e d [23] "Innovation in Powder Technology," Technical Data Brochure,
to be a m e a s u r e of the d y n a m i c friction. Shamrock Chemicals Corporation, Newark, NJ.
Articulated-strut meters [12,39-41] involve a p p l i c a t i o n of a [24] "Byk-Mallinckrodt Paint-Additives," Technical Data Notebook,
known, constant vertical force to a shoe that is faced with a Byk-Mallinckrodt USA, Inc., Wallingford, CT.
p a r t i c u l a r sole o r heel m a t e r i a l along with a p p l i c a t i o n of an [25] "Dow Coming | Additives," Technical Data Brochure 24-391
increasing lateral (forward) force until slip occurs. The ratio E-93, Dow Coming Corporation, Midland, MI.
of the lateral force at slip to the k n o w n vertical force is the [26] Annual Book of ASTM Standards, Vol. 15.02.
[27] Annual Book of ASTM Standards, Vol. 08.02.
static COF. The vertical force is a p p l i e d to the top so t h a t the [28] Annual Book of ASTM Standards, Vol. 04.03.
article tested is only subjected to a vertical load. As the test [29] English, W., "Horizontal Pull Slipmeter," U.S. Patent 4,895,015
progresses, the articulated strut is slowly inclined so the test (1990).
article continues to be u n d e r a constant vertical l o a d a n d in [30] English, W., "Improved Tribometry on Walking Surfaces," Slips,
a d d i t i o n u n d e r an increasing h o r i z o n t a l or tangential l o a d Stumbles, and Falls: Pedestrian Footwear and Surfaces, ASTM
until slip occurs. The tangent of the angle that the articulated STP 1103, B. E. Gray, Ed., ASTM, Philadelphia, 1990, pp. 73-81.
strut m a k e s with respect to the vertical at the instant of slip is [31] English, W., "Improved Static Coefficient of Traction Meter,"
Ceramic Engineering & Science Proceedings, Vol. 13, Nos. 1-2,
taken to be the ratio of the horizontal a n d vertical c o m p o - 1992, pp. 22-28.
nents of the force a p p l i e d to the show a n d thus is the COF. [32] Kohr, R. L., "A Comparative Analysis of the Slipperiness of
Devices of the three types are s u m m a r i z e d in Table 3. Floor Cleaning Chemicals Using Three Slip Meters," Ceramic
www.iran-mavad.com

Engineering and Science Proceedings, Vol. 13, Nos. 1-2, 1992, pp. [38] Andres, R. O. and Chaffin, D. B., "Ergonomic Analysis of Slip-
14-21. Resistance Measurement Devices," Ergonomics, Vol. 28, No. 7,
[33] Sigler, P. A., Geib, M. N., and Boone, T. H., "Measurement of 1985, pp. 1065-1080.
Slipperiness of Walkway Surfaces," Research Report, 1897, Na- [39] James, S. V., "What is a Safe Floor Finish?" Soap and Sanitary
tional Bureau of Standards, Washington, DC, Journal of Re- Chemicals, Vol. 20, October 1944, pp. 111-115.
[40] Brungraber, R. J., "Portable Tester for Measuring the Static
search, Vol. 40, 1948, pp. 339-346.
Coefficient of Friction between a Floor Surface or the Like and a
[34] Jablonsky, R. D., "Standardization of Test Methods for Mea- Shoe Sole or Heel Material or the Like," U.S. Patent 3,975,940
surement of Floor Slipperiness," Walking Surfaces: Measurement (1976).
of Slip Resistance, ASTM STP 649, C. Anderson and J. Senne, [41] Brungraber, R. J., "Portable Tester for Measuring Slip Resis-
Eds., ASTM, Philadelphia, 1978. tance," U.S. Patent 4,759,209 (1988).
[35] Harrison, R. and Malkin, F., "A Small Mobile Apparatus for [42] Irvine, C.H., "A New Slipmeter for Evaluating Walkway
Measuring the Coefficient of Friction of Floors," Journal of Phys- Slipperiness," Materials Research & Standards, Vol. 7, No. 12,
ics D: Applied Physics, Vol. 13, 1980, pp. L77-L79. December 1967, pp. 535-542.
[36] Brough, R., Malkin, F., and Harrison, R., "Measurement of the [43] Irvine, C. H., "Evaluation of Some Factors Affecting Measure-
Coefficient of Friction of Floors," Journal of Physics D: Applied ment of Slip Resistance of Shoe Sole Materials on Floor Sur-
faces," Journal of Testing and Materials, Vol. 4, No. 2, March
Physics, Vol. 12, 1979, pp. 517-528.
1976, pp. 133-138.
[37] Proctor, T. D. and Coleman, V., "Slipping, Tripping and Falling [44] Irvine, C. H., "Evaluation of the Effect of Contact-Time When
Accidents in Great Britain--Present and Future," Journal of Oc- Measuring Floor Slip Resistance," Journal of Testing and Evalu-
cupational Accidents, Vol. 9, 1988, pp. 269-285. ation, Vol. 14, No. 1, January 1986, p. 19-22.
www.iran-mavad.com

Part 12: Environmental Resistance
www.iran-mavad.com

MNL17-EB/Jun. 1995
Prevention of Metal Corrosion 51

with Protective Overlayers
by William H. Smyrl I
THE PREVENTION OF CORROSION BY SURFACE PROCESSING enjoys In the discussion that follows, aspects of corrosion that
significant economic leverage, and, as evidence, one may cite involve thermodynamics and kinetics will be developed as a
the widespread use of coatings, films, and inhibitors for met- basis for the description of the specific nature of corrosion of
als and semiconductors in many service environments. All metals under protective films and overlayers. Some emphasis
engineering metals used in modern technological societies will be given to protection of thin metal films and microstruc-
are unstable with respect to corrosion, and the result is a loss tures that are particularly sensitive to corrosion and whose
of properties. Natural oxide films provide protection against successful protection provides a basis for advancing protec-
continued attack for some metals, and alloying extends the tion technology in general.
life of other metals by developing highly stable passive films.
Where metals may not be protected by oxide films, other
modification methods have been developed to reduce corro- CORROSION IN AQUEOUS SOLUTIONS
sive attack. In reality, the improvement of corrosion resist-
ance of metals by modification of the surface has been prac- The driving force for a reaction is the change in Gibbs free
ticed since the invention of metal tools. Some of the earliest energy, AG, for reactants to products. Mathematically, this
techniques to prevent corrosion involved coating with may be expressed by
greases or natural oils. More modern methods were devel-
oped in the 19th and 20th centuries and include multiple
coatings, zinc galvanizing, electroplating of other pure met- Aa=EC- EC
products reactants
als, and vacuum physical vapor deposition of mostly pure
metal coatings by electron beam and sputtering techniques. The summation signs are used as a general notation to indi-
The metal coatings are better barriers than organic films be- cate that all reactants and products are included in the calcu-
cause of the lower permeability of the former to moisture, lation. From the nature of the free energy function, this calcu-
oxygen, and ions. Inhibitors or conversion coatings and lation applies to initial (reactants) and final (product) states
primers for paints are cheaper than metal coatings and are and is independent of intervening states. The reaction may be
used widely by paint manufacturers even though they remain investigated under controlled reversible conditions such as in
highly proprietary in nature. an electrochemical cell or under irreversible conditions such
The use of organic coatings to protect metal surfaces is as in corrosion, and the same total free energy change (AG)
practiced widely. Much of the use is for atmospheric expo- will be appropriate. A quite general predictive capability may
sure of motor vehicles as well as for structural units such as be applied to specific corrosion reactions since all the avail-
bridges and buildings. The successful implementation of ex- able thermodynamic data may be used for corrosion calcula-
isting technologies has greatly reduced the effects of corro- tions directly. This enables the position of final equilibrium of
sion of automobiles, for example, in the past decade in re- the corrosion system to be established. The thermodynamic
sponse to consumer demand. Despite many recent advances, calculations have the limitation that no information concern-
coating technologists and scientists acknowledge that much ing the rate of the reaction is provided, only what the final
is unknown and that new processes and understanding are state will be for the process.
the keys for further progress [1]. Defects in the metal sub- The value of AG for reactions of elements to form a com-
strate and in the overlayers are among the primary concerns pound, all in their standard states at a particular tempera-
because they are the source of localized corrosion phenom- ture, is the standard free energy of formation of the com-
ena. Defects may occur on length scales from atomic-level pound, AG~r. Here, the subscript T denotes the temperature.
lattice vacancies to arrays of defects at grain boundaries (for Description of the detailed calculations are beyond the scope
crystalline materials) or to random pores or cracks (for exam- of this discussion, but several excellent textbooks are avail-
ple, in noncrystalline films). Avoiding such defects by proper able [2,3].
quality control is a major concern in coatings science and The most extensive tabulations of thermochemical data for
technology. chemical compounds in their standard state at 25~ are in a
series of National Bureau of Standards publications [4].
~Professor, Corrosion Research Center, Department of Chemical These are NBS Technical Notes 270-3, 270-4, and 270-5,
Engineering and Materials Science, University of Minnesota, Minne- which supersede the older NBS Circular 500 for the elements
apolis, MN 55455. they cover. These tabulations also update the older data of
609
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610 PAINT A N D COATING T E S T I N G M A N U A L
L a t i m e r [5]. The b o o k by L a t i m e r [5] r e m a i n s a valuable As a s u m m a r y , the general c o r r o s i o n of metallic m a t e r i a l s

reference b e c a u s e of the d e s c r i p t i o n of techniques to e s t i m a t e in aqueous solutions is well understood. The a n o d i c or oxida-
t h e r m o d y n a m i c quantities w h e r e reliable d a t a are sparse. tion r e a c t i o n of the metal is s u p e r i m p o s e d on a c a t h o d i c
Lewis a n d Randall [3] t a b u l a t e d t h e r m o d y n a m i c data, in- reaction, a n d the two are b a l a n c e d locally on a h o m o g e n e o u s
cluding d a t a for aqueous solutions of a n u m b e r of electrolytic surface. The rate of the reaction is a function of b o t h the rate
solutions that are valuable for c o r r o s i o n calculations. There of m e t a l dissolution a n d the rate of the cathodic (reduction)
is overlap b e t w e e n this t a b u l a t i o n a n d the JANAF t h e r m o - reaction. E a c h r e a c t i o n m a y be influenced in general b y the
c h e m i c a l tables [6], b u t the latter also tabulate the s t a n d a r d c o m p o s i t i o n of the solution, especially the pH a n d the elec-
enthalpy a n d free energy of f o r m a t i o n of chemical com- trolyte anion, a n d by the n a t u r e of the (oxide) films, if any,
p o u n d s at several t e m p e r a t u r e s along with - (G O - I~298)/T. w h i c h m a y be f o r m e d at the metal/electrolyte interface. If
Oxide a n d hydroxide solubility are strongly influenced by several oxidizing species are present in the solution, each
the p H of the a q u e o u s phase. P o u r b a i x recognized this a n d m a y act in parallel so that the total rate of metal dissolution is
s u m m a r i z e d the t h e r m o d y n a m i c stability of m e t a l - a q u e o u s increased. F o r example, m o s t metals will react directly to
systems by the use of p o t e n t i a l - p H diagrams. The t h e r m o d y - displace h y d r o g e n from w a t e r a n d to p r o d u c e an oxide of the
n a m i c d a t a t a b u l a t i o n s a l r e a d y quoted [3-6] should be uti- metal or s o m e o t h e r c o r r o s i o n process. The a d d i t i o n of oxy-
gen will increase the rate of c o r r o s i o n of the metal, usually in
lized for detailed calculations, however.
direct p r o p o r t i o n to the c o n c e n t r a t i o n of the oxygen added.
Usually w h e n studying corrosion, one is n o t c o n c e r n e d
The specific details will vary with each metal to reflect the
with the conditions for t h e r m o d y n a m i c stability, b u t r a t h e r
t h e r m o d y n a m i c , kinetic, a n d m a s s transfer driving forces
with the rate of attack a n d h o w it m a y be altered in basically
that are acting [7].
unstable conditions b e c a u s e only a limited n u m b e r of sys-
H e t e r o g e n e o u s surfaces are c o m m o n l y observed in corro-
tems have absolute or thermodynamic stability. As a practical
sion situations a n d are of the three general classes: (1) the
m a t t e r it is necessary to accept s o m e rate of c o r r o s i o n a n d / o r
inclusion of foreign metal i m p u r i t i e s on the metal surface, (2)
to control or mitigate the rate of attack. Thus kinetic stability
the n o n u n i f o r m coverage of the surface by a film, either an
is always relative a n d subject to i n t e r r u p t i o n if control is not oxide film o r a n artificial coating in a q u e o u s solutions, a n d
maintained. Controlling the rate of d e g r a d a t i o n m a y be ac- (3) n o n u n i f o r m conditions in the electrolyte environment. All
complished, for example, by the use of cathodic or a n o d i c these are of great i m p o r t a n c e b e c a u s e localized, or nonuni-
protection, the use of inhibitors, the m a i n t e n a n c e of protec- form, corrosion of metals m a y be caused by any of the three.
tive surface films, or buffering the c o m p o s i t i o n of an other- A form of galvanic corrosion a n d pitting c o r r o s i o n is caused
wise aggressive solution. All these techniques are used widely by the first type of heterogeneity, while crevice a n d pitting
to extend the life of metallic structures with continuing im- c o r r o s i o n are p r o d u c e d by b o t h (2) a n d (3).
provement. Restrictions of geometry, e.g., in crevices a n d corners, pre-
Corrosion reactions are electrochemical in nature. The ki- vent mixing of solutions everywhere, a n d local b u i l d u p of
netics of the c o r r o s i o n reactions are t h e n related to the ki- r e a c t i o n p r o d u c t s o r the e x h a u s t i o n of an oxidant m a y occur.
netics of the electrochemical reactions that occur during the The local kinetics will be relatively i n d e p e n d e n t of t h a t in
c o r r o s i o n process. The reactions involve not one b u t at least o t h e r regions except t h a t there m a y be coupling t h r o u g h the
two electron transfer reactions, and the reactions are not in electric field a n d electrical c u r r e n t m a y flow b e t w e e n a local-
series but are in parallel. Coupling of parallel o r s i m u l t a n e o u s ized c o r r o s i o n site a n d the s u r r o u n d i n g surface. This m a y
reactions is a f u n d a m e n t a l feature of the c o r r o s i o n process. lead to n o n u n i f o r m corrosion, p a r t i c u l a r l y where the b u i l d u p
E a c h of the s i m u l t a n e o u s reactions m a y consist of multiple of p r o d u c t s increases the aggressiveness of the local solution.
steps, respectively, as described above, b u t the simultaneous, In this case, c o r r o s i o n will be m o s t severe, not where the
i n d e p e n d e n t reactions are coupled electrically. The indepen- c o n c e n t r a t i o n or flux of the bulk solution o x i d a n t is highest
dent reactions occur on the s a m e surface at the s a m e time, b u t where it is lowest. Crevice c o r r o s i o n is c o n s i d e r e d to be
b u t also at the s a m e potential. The reactions m a y be c o u p l e d an e x a m p l e of this type of attack, a n d the aggressive solution
chemically as well, e.g., t h r o u g h p H effects, but this is not within a crevice or pit is one w h i c h is m o r e acidic t h a n the
essential. The specific relation that defines the coupling of external solution.
s i m u l t a n e o u s c o r r o s i o n reactions on an isolated metal sur- Anodic dissolution, plus hydrolysis of the p r o d u c t m e t a l
face is ion, causes an increase of h y d r o g e n ion concentration. On the
o t h e r hand, r e d u c t i o n of either h y d r o g e n ions o r dissolved
oxygen reduces the h y d r o g e n ion concentration. If the net
EIo=- E c o r r o s i o n r e a c t i o n plus hydrolysis w o u l d lead to a n increase
anodic cathodic
of h y d r o g e n ion concentration, the process m a y occur inde-
There will then be zero net c u r r e n t to the c o r r o d i n g metal p e n d e n t l y of any o t h e r process a n d w o u l d accelerate with
electrode. The relationship is w r i t t e n in terms of currents (Ia time to s o m e steady state w h e r e diffusion out of the occluded
a n d Ic) r a t h e r t h a n c u r r e n t densities for r e a s o n s w h i c h will be region w o u l d limit the buildup. If the c o r r o s i o n r e a c t i o n plus
discussed. The potential at w h i c h the b a l a n c e is satisfied is hydrolysis leads to no net change in H + concentration, a n
the m i x e d or corrosion potential. It is d e t e r m i n e d by the rates acid solution in a crevice o r pit could only be c r e a t e d b y
of the s i m u l t a n e o u s reactions a n d is not defined by the state s e p a r a t i o n of the a n o d i c a n d cathodic regions. Concentrating
of the system in a t h e r m o d y n a m i c sense. The corrosion po- the c a t h o d i c r e a c t i o n on the o u t e r surface w o u l d occur natu-
tential always lies b e t w e e n the e q u i l i b r i u m potentials of the rally if dissolved oxygen, for example, were the p r i m a r y b u l k
a n o d i c a n d c a t h o d i c processes, respectively. oxidant. Coupling this with a net anodic r e a c t i o n (plus hy-
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CHAPTER 5 1 - - P R E V E N T I O N OF METAL CORROSION 611
drolysis) in the inner region for an overall current balance simulated atmosphere or aqueous conditions. Electrochemi-
would lead to a steady state crevice or pit. cal methods have been used extensively in such tests to ana-
For separation to occur as described above, a quite general lyze and monitor the corrosion behavior of metals.
condition imposed on the corrosion kinetics must be obeyed. Several weather factors are known to influence outdoor
The outside surface must support a cathodic reaction, and it corrosion [10-13]. Precipitation, ambient and dew-point
must be supported at a potential that is positive of the poten- temperatures, atmospheric pollutants, wind direction and
tial of the anodic reaction in the crevice. The direction of wind velocity, and solar radiation can be considered as
current flow through the solution establishes this criterion. A weather factors in outdoor and/or urban corrosion tests.
qualitative laboratory test may be used to identify metal Among these factors, moisture or relative humidity, tempera-
solution combinations that could cause localized attack by ture, and pollutants such as sulfur dioxide and chlorides are
the mechanism described above. The test involves the corro- the most important variables.
sion kinetics on the metal of interest. Cathodic currents must Relative humidity is known to be the most important factor
be observed on the metal in the exterior solution at potentials in determining the atmospheric corrosion rate. It has been
that are positive of the anodic region for the crevice condi- reported that rapid acceleration of corrosion occurs beyond a
tions or the separated reactions will not support increased certain value of relative humidity, defined as the critical hu-
anodic dissolution in the isolated region. This is a very defini- midity [14-15]. The period in which the relative humidity
tive test, and very few metal-environment combinations exceeds the critical humidity is called the time-of-wetness,
match the criterion. and this factor is quite significant in determining atmo-
Ohmic drop restricts the penetration of current into a spheric corrosion rate of metals [16]. In addition, in the pres-
small-gap, occluded region [8]. This causes the anodic reac- ence of a pollutant such as sulfur dioxide, the critical humid-
tion to be distributed over a relatively small region, which ity at which corrosion is enhanced to a significant extent will
concentrates the attack. At greater depths in the gap, the decrease with increasing pollutant concentration [17-I8].
metal is isolated from the external surface reactions. It has been reported that comparatively large aggregates of
Newman [9] calculated the limited depth to which a reaction water are present on oxyhydroxide surfaces at humidities
may penetrate inside a circular geometry, in this case a ca- below 40% [19]. Even on clean metal surfaces obtained under
thodic protection reaction. The reaction is concentrated near ultrahigh vacuum or reducing conditions, significant quan-
the opening. tities of water are adsorbed on air-formed films when exposed
Composition gradients are considered to be important for to the environments containing only oxygen and water vapor
pitting and differential aeration corrosion as well. For pitting for more than a microsecond [13]. As a result, monolayers of
corrosion, similar conditions to those for crevice corrosion adsorbed water may provide the medium for electrochemical
are considered important. Pits may be initiated in ways that microcells that may drive a heterogeneous corrosion process.
are different from crevice corrosion, e.g., at foreign metal Water may also exist in the form of complex mixtures with
inclusions. However, the propagation of pits depends largely oxides, hydroxides, and mixed oxyhydroxides [19-20].
on a locally aggressive solution. Stirring to eliminate concen- The corrosion rate of metals is accelerated by the presence
tration effects will stop the growth of pits. Differential of air pollutants such as sulfur dioxide, nitrite, nitrate, hydro-
aeration could also drive corrosion at locally variable rates gen sulfide, chloride, and some kinds of salts [10,15]. These
under an electrolyte film of nonuniform thickness. The diffu- species may derive from gas-borne particles or from reac-
sion-limited flux of oxygen through the film would be directly tions at the surface. Reaction with adsorbed water mono-
proportional to the film thickness. If the local corrosion rate layers yield electrolyte films that facilitate further corrosion
is limited by the oxygen flux, the attack will be most severe at processes. Among these pollutants, sulfur dioxide, chlorine
low film thicknesses. For active/passive metals, increase of gases, sulfur gases, and ozone are important species that
the oxygen flux may exceed the peak current for active disso- promote corrosion in the presence of water.
lution and cause the metal to adopt the passive state. In this The corrosion-accelerating effect of sulfur dioxide with hu-
case, then, thin films of electrolyte will reduce the corrosion midity has been reported by many investigators [I0,13,15].
rate. Vernon [15] suggested that sulfur dioxide may change the pH
in electrolyte films present on metal surfaces and enhance the
corrosion rate. Rice et al. [13] also suggested that sulfur diox-
A T M O S P H E R I C C O R R O S I O N OF M E T A L S ide is readily soluble in water to form sulfurous acid; these
local acidic regions accelerate oxide formation, and the cor-
Most atmospheric corrosion tests have been conducted in rosion rate is also enhanced by other electrochemical effects.
environments such as indoor atmosphere, outdoor atmo- It has been reported that wetting of the metal surface is
sphere, and laboratory tests under simulated conditions. In- promoted in the presence of ammonia, and the water droplets
door corrosion studies have been performed for the electron- contain higher concentrations of sulfates than for the same
ics, computer, and communication industries for the concentration of sulfur dioxide with no ammonia [10,22].
development of more durable materials with desirable struc- The effect of chlorine gas or chloride on atmospheric corro-
tural, magnetic, and electrical properties. On the other hand, sion has been reported [10,13]. In aqueous electrochemical
outdoor studies aimed at understanding corrosion behavior corrosion studies, the chloride ions usually enhance pitting
are highly dependent on atmospheric weather factors, espe- corrosion of many metals and also degrade the oxide sur-
cially in marine and urban areas. The latter studies have been faces. Rice et al. [13] reported that chlorine gases reduce the
performed in the automobile, marine, and aircraft industries. surface pH and yield hygroscopic corrosion products that
Laboratory tests attempt to use accelerated methods under influence the amount of adsorbed water. A direct relationship
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between the amount of chlorides in corrosion products and were used to study the effects of pollutants, relative humidity,
atmospheric corrosion rates was reported by Sereda [10]. and so on. They used the electrolytic cells such as two- and
The effect of ozone gas on copper and silver corrosion has three-electrode cells for studies of the corrosion kinetics and
been known to be significant, while cobalt, nickel, and iron for the measurement of corrosion currents. The polarization
are insensitive to ozone [13]. It has been reported that ozone resistance method was used to determine atmospheric corro-
may enhance the corrosion rate of metals sensitive to H2S. sion kinetics under thin electrolytic layers. Mazza et al. [40]
The atmospheric corrosion rate can be measured either in have used a galvanic cell that consisted of a sandwich formed
field tests in different atmospheres or with accelerated tests of bronze covered by its artificial corrosion products on
in the laboratory. The field tests require long exposure times which a high-porosity gold film was applied. They monitored
and yield complicated data that prevent detailed analysis. the corrosion current with a zero resistance ammeter and
Accelerated tests are performed under simulated atmo- obtained instantaneous and continuous information on the
spheric conditions, and they are the easiest way to acquire corrosion rate of the bronze. Tosto and Bruco [41] used gal-
more information with various setup conditions. However, it vanic cells of copper-steel to obtain the relation between the
may not be possible to simulate practical service conditions. corrosion content and relative humidity. They found that the
There are several methods to monitor and control the cor- corrosion current depended on relative humidity (RH).
rosion rates by means of either field or laboratory tests. The As a rapid electrochemical method for monitoring atmo-
conventional method is the weight loss determination, which spheric corrosion, measurements of electrode po*ential using
requires long-term exposure unless a continuous method is a suitable reference electrode have been developed by several
used that involves the quartz crystal microbalance [23-24]. investigators [42-43]. Although the method gives no absolute
Another method is the electrical resistance method and mea- data on corrosion rates, it is a fast and easy method for on-site
surement using electrochemical cells. Electrical resistance investigations. Thin film methods to measure corrosion rates
methods use the changes in the electric resistance of thin were discussed by Howard [44]. Pourbaix and his coworkers
wires or foils to monitor failure, but they cannot be used for [42, 45] developed an accelerated electrochemical wet and dry
determination of the instantaneous corrosion behavior method that was designed to use alternate immersion cycles
[25-27]. in an electrolyte bath. The electrode potential was monitored
Electrochemical methods have been developed to take ad- when the steel electrode was in the wet part of the cycle. They
vantage of the electrochemical basis for atmospheric corro- concluded that their method was selective and yielded repro-
sion [28-29]. Corrosion currents can be monitored electro- ducible data.
chemically, and the instantaneous value of current can be Electrochemical cells designed to simulate thin electrolytic
detected. One way to monitor atmospheric corrosion with an films formed during atmospheric corrosion have been devel-
electrochemical method is to design a cell that will work oped by several investigators [46-47]. Fishman and Crowe
under thin electrolyte layers (less than 500 ~xm) with consid- [47] have studied the thin film of electrolyte with a potentio-
eration of the effects of corrosion products and dilute pollu- static polarization technique. The corrosion current in-
tants [30]. creased with an increase of relative humidity. They con-
Electrochemical methods for monitoring atmospheric cor- cluded that the resultant corrosion rates were consistent with
rosion have been well reviewed by Mansfeld [30-31]. Most of those reported from long-term weight loss measurements.
the studies have been aimed at macroscopic measurement of Fiaud [46] created a thin electrolytic film (80-/xm thickness)
time-of-wetness that is associated with electrochemical cor- using the device similar to one developed in the field of thin
rosion [10,12,16,17]. Galvanic cells with electrodes of differ- layer electrochemistry [48]. Platinum and nickel were used as
ent metals have been commonly used [16, 32]. Sereda [10] has electrodes and sodium sulfate (Na2SO4) solution was used as
developed galvanic cells of platinum-iron and platinum-zinc the electrolyte with change of pH by addition of sulfur diox-
couples to determine the time-of-wetness. Time-of-wetness ide (H2SO4). SO2 gas was introduced into the electrolyte
was arbitrarily defined as the interval during which the exter- through a membrane. They observed the depolarization ef-
nal potential exceeded 0.2 V. This figure was the period dur- fect of SO2, oxidation of SO2, and reduction of SO 2 with use of
ing which the relative humidity was greater than 85% [12,16]. cyclic voltammetry and linear polarization techniques.
Tomashov [33] has used sandwich-type galvanic cells of iron-
copper, iron-zinc, iron-aluminum, and copper-aluminum.
They concluded that the method was suitable for fast deter- C O R R O S I O N OF T H I N METAL FILMS A N D
mination of the corrosivity of the atmosphere and that the MICROSTRUCTURES
direct measurement of corrosion rate for testing metals was
possible. Corrosion of a metal occurs by the same fundamental
Several investigators [17,34-36] have used galvanic cells reactions whether it is used in a large structure like an auto-
consisting of steel-copper and electrolytic cells consisting of mobile, a bridge, or a heat exchanger, or in a small structure
individual metals (steel, zinc, or copper) to which an external characteristic of magnetic, optical, or microelectronic de-
potential was applied. They concluded that the cell current vices, or under a protective layer [49]. The uniqueness of each
gave qualitative agreement with the weight-loss data. Re- application is tied up in the definition of the environment to
cently, extensive studies have been performed by Mansfeld which the metal is exposed or which develops with time, as
and his coworkers [30-31,37-39]. They used galvanic cells well as the definition of a characteristic size of the corroding
and electrolytic cells which consisted of two electrodes and material. Since the time to failure of a material (i.e., its life-
three electrodes. Galvanic cells such as copper-steel, copper- time) is normally inversely proportional to the corrosion rate
zinc, steel-zinc, steel-aluminum, and aluminum-zinc couples and directly proportional to the thickness of the corroding
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CHAPTER 5 I - - P R E V E N T I O N OF METAL C O R R O S I O N 613
material (its characteristic size), small dimensions are more duce corrosion that is the result of the natural instability of
susceptible to corrosion failure and loss of properties. For the metal in an aggressive environment. Rarely are the thin
example (see Fig. 1), a 50-nm cobalt magnetic film may be film metals stable in the environment, so techniques must be
corroded completely in about 38 h at a corrosion rate of found to stabilize the structures and extend the lifetimes.
1 /~A/cm2. The desired lifetime is about five years, so a protec- In the other example of Fig. 1, aluminum interconnects in
tive film (e.g., diamond-like carbon) must be used to moder- microelectronic devices have characteristic widths of 1 ~m
ate the rate of attack. The protective layer must be thin to or smaller. Ionic conduction along adsorbed water layers at
read or write to the cobalt film with the magnetic head, and the silicon dioxide (SiO2) surface can lead to electrochemical
defects in the protective layer will lead to localized corrosion corrosion and "breaks" in the A1 conductor. If the corrosion
attac. Wear and friction are mechanical processes that result rate were I/~A/cm2, the lifetime of the A1 interconnects would
from the relative movement of the disk and head. The head is be about 48 days, rather than the 10 to 20-year lifetime de-
designed to fly very close to the disk to take advantage of the sired. A protective layer is required for this application as
magnetic properties [50], but it comes to rest on the disk well.
surface when the system is idle. Humidity and other factors The corrosion phenomena of thin films chosen for mag-
affect wear and friction, and layers or films may be added to netic, optical, or electrical applications have unique charac-
lubricate the magnetic film. Of more interest here, however, teristics, but they are often similar to those observed for bulk
are the chemical effects that cause corrosion. Accelerated materials [35, 50, 56]. Thin films have bulk metallurgical prop-
tests have been used to determine disk reliability [51], tests erties in thicknesses larger than 1 to 3 nm and have the same
that measure the affects of wear, friction, atmospheric con- chemical reactions as well. Both observations lead to the
taminants, humidity, oxygen diffusion, and galvanic corro- general conclusion that both bulk metals and films 30 nm or
sion. Also described by Antler and Dunbar et al. [51] is the thicker will have similar corrosion behavior. On the other
comparison between field test experience and laboratory- hand, thin film materials have small grain size and are pre-
simulated corrosion test results. Earlier results on microelec- pared for magnetic disk applications in "tracked" or grooved
tronics failures are reviewed by Schnable et al. [52], geometries. The small grain size causes films to have more
Comizzoli et al. [53], Wood [54], and Stojadinovic et al. [55]. homogeneous properties, with fewer inclusions and smaller
Whatever the mode, the result is a loss of information at the chemical segregation effects than ordinary bulk materials.
site of degradation and the loss of properties. Better prepara- The tracks have sharp edges and dimensions to generate
tion and processing, or better design, may reduce flaws and unique morphologies in the films. The homogeneous proper-
defects that cause mechanical failure, but they may not re- ties would make the films less susceptible to corrosion, but
the defects generated at edges could be sites for enhanced
attack. The dimensions and geometry of the tracks may lead
THIN FILM MATERIALS to nonuniform chemical composition in the recesses, which
would produce localized corrosion effects as well. Atmo-
spheric corrosion has been studied under simulated condi-
CONTINUOUS FILM MAGNETIC MEDIA METAL CONDUCTOR LINES tions for thin magnetic films [35], and, as in other cases, it
CONTINUOUS FILM OPTICAL MEDIA METAL CONTACTS
was found that the affect of humidity and atmospheric pollu-
tants was synergistic. The level of humidity may influence the
IMULTIPLELAYERSANDWICHARRAYS I J PARALLELLINES- SPOTS J condensation of thin moisture films on surfaces, which will
facilitate transport across surfaces and may cause the accu-
mulation of water in microscopic domains. In the latter, the
5oo ~, DL- CARBON ~I' concentrations of dissolved contaminants may approach sat-
COBALTALLOY 500 ,~ Fq FI uration conditions. The contamination may come from dust
CVD - SiO 2 or inclusions of other layers [49]. The conditions are difficult
Ni P F to simulate in the laboratory because of the lack of knowledge
of local conditions in the microscopic regions that are rele-
AI vant to the problem. In addition, it has been difficult to make
in situ measurements for conditions that simulate atmo-
spheric-corrosion measurements, which would give a direct
TYPICAL DIMENSIONS TYPICAL DIMENSIONS indication of the processes responsible for corrosive attack.
50 nm (500~,) THICKNESS 1 grn Several standard tests have been developed to assess atmo-
spheric corrosion damage [ASTM Test Method for Assessing
Galvanic Corrosion Caused by the Atmosphere (G 104-89);
EXAMPLE: Feo,74Tb0,26FOR MAGNETO-OPTIC STORAGE ASTM Practice for Conducting Atmospheric Corrosion Tests
MEDIA - HIGH DENSITY MEMORY DEVICES.
on Metals (G 50-76 (1990)); ASTM Practice for Rating of
MAGNETIC PROPERTIES ARE DE6RADED BY Electroplated Panels Subjected to Atmospheric Exposure
OXIDATION DURING LOCAL HEATING (2200 "C) (B 537-70 (1992)] without addressing the mechanism of the
BY LASER DURING DATA STORAGE. attack.
FIG. 1-Thin film materials for magnetic, optical, metal con- The second topic relates to protective layers and en-
ductor lines and microelect~onic contacts make them highly capsulants. Pore-free conventional protective layers over
susceptible to have small dimensions are highly susceptible to magnetic films are too thick to be compatible with the mag-
corrosion. netic properties of thin film disk materials. In addition, poly-
www.iran-mavad.com

mer films can change the adhesion properties of the surface

and interfere with the operation of the magnetic head. Highly
resistive but electroactive overlayers could lead to galvanic
attack of the substrate through holes in the thin film. Sput-
tered diamond-like carbon films [51,57-60] could fall into
this category (see Fig. 1).
A protective layer plated or sputtered over an active metal
may have pores and defects that will permit the corrosive
medium to contact the active substrate metal and thereby
promote galvanic corrosion. The holes or defects may be
present on a heterogeneous surface in the geometry of either
regular arrays or random arrays. The mathematical modeling
of galvanic behavior in plating corrosion systems has been
discussed by Smyrl and Newman [21], where earlier work
was also reviewed. They determined the current and potential
distributions of galvanic corrosion system, which consisted
of anodic disks in a cathodic plane as shown in Fig. 2. They
solved the Laplace equation for potential with nonlinear
(Butler-Volmer) boundary conditions with the use of finite
difference method. The numerical modeling of galvanic cor-
rosion in which the geometry consists of various array forms
has been performed by Morris and Smyrl [61-63] in this
laboratory. Either regular or random arrays of disks in the
cathodic plane were used for the simulation of a heterogene-
ous surface. Most treatments of the regular array use the
symmetry element derived from symmetrical geometry of the FIG. 2-Multilayer "sandwich" arrays may have
system. For mathematical simplicity, a particular hexagonal underlayers exposed through holes or holidays in
symmetry element can be approximated by a circular geome- the overlayer, and galvanic interactions may en-
hance the corrosion rate in such systems.
try, thus eliminating any angular dependence. For random
arrays, the arrays simulated using a Voroni tessellation of the
plane into random polygons as shown in Fig. 3 were used for where they join, and more remote areas of each are relatively
the disk-cathodic plane geometry. The Voroni tessellation has unaffected by the galvanic coupling. It has recently been
proven to be useful for modelling the transport and mechani- found that the active perimeter measure of the interactions is
cal properties of disordered or composite media. The geomet- more relevant than the area ratio, and the former may be
rical properties of the Voroni tessellation and algorithms for used to correlate the behavior of several geometries [61-63].
generating the tessellation have been described by Winterfeld The nonuniform current distribution is also obtained if
[64]. The model established by Morris and Smyrl included the cathodic surrounding plane is highly resistive but
the Laplace equation for potential distribution with nonlin- electroactive. For example, resistive sputtered carbon films
ear boundary conditions, and it was solved by a finite element would cause the cathodic galvanic current to flow only to
method. The potential distribution of the system was ob- areas at the periphery of holes and defects [65], and the total
tained from numerical simulation of a regular array of disks area would not be important in determining the galvanic
over a cathodic plane. The disks were of alternating sizes current. However, smaller holes would increase the galvanic
(disks with two different diameters) distributed on the sur- current at a constant area ratio because the active perimeter
rounding plane. The models for the tertiary current distribu- would increase.
tion, which includes both potential distribution and mass In summary, investigations in bulk solution provide a basis
conservation with use of a geometry of the random array, are on which to begin to analyze atmospheric corrosion behav-
in progress in our laboratory. ior. As the electrolyte phase decreases in thickness, ohmic
Since the total anodic current must be equal to the total and diffusion effects become more dominant and galvanic
cathodic current, the area ratio between anodic and cathodic
components of the total area is an important parameter in
galvanic corrosion. If the currents to each area were uniform,
the area ratio is the only parameter that would affect the
galvanic interaction for a particular combination of metals.
On the other hand, Smyrl and Newman [2I] found that ohmic
effects in the electrolyte may cause a nonuniform galvanic OR
current distribution on the component areas, and this leads
to the conclusion that under such conditions some parts of
the cathodic area are not important in determining the total
galvanic current. The effect is even more pronounced under FIG. 3-Simulations of galvanic interactions in multilayer
circumstances where the electrolyte phase is very thin, that is, arrays have been carried out with regular patterns or with (more
galvanic current from cathode to anode flows only near realistic) Voronoi tessellation representations.
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CHAPTER 51--PREVENTION OF METAL CORROSION 615
coupling is strongly affected. The more remote areas will planted surfaces, for example, delamination by buckling is
show the behavior expected for uniform exposure to an ag- practically unknown. Effective porosity in the treated layer
gressive environment. Effects of local composition and local could exist due to shadowing of the surface from the beam by
physical geometry then will become more dominant. Behav- contaminating particles. The problem has not been observed,
ior in the local areas would be expected to be very similar to but the exact reason is not known. With the exception of ion
the behavior in bulk electrolyte at the same composition implantation [67], only a few studies on corrosion have been
conditions. Further general comparisons must be developed done on films deposited using energetic deposition methods.
as further research is conducted. Ion-beam-assisted deposition coatings are adherent and
more ductile than bulk materials due to the microcrystalline
or amorphous structures. The adhesion is better for the films
COATINGS AND OVERLAYERS FOR deposited by energetic beam techniques as compared to films
CORROSION CONTROL derived from physical vapor deposition. More details may be
found in the cited report [66] or in the original literature.
In the past 15 to 20 years, an explosion of interest in surface Polymeric materials are widely used as protective coatings
modification techniques has mostly involved the deposition because they are transport barriers which limit access of
of thin films, the application of coatings, and the formation of reactive species (i.e., water, oxygen, ions) to the substrate
surface alloys. The development of many of the techniques surface. Leidheiser and Granata [68] have discussed the roles
has been driven by the need for the semiconductor electron- that each of these species may play in degradation processes
ics industry to create improved processing procedures. As a on metal surfaces, and, in particular, the role of ion transport
spin off of the advancing technology, other fields, such as through bulk films and "ion channels" in films. Several tech-
corrosion protection, have benefited from the new processes. niques are discussed in this paper for characterizing ion
A recent panel report [66] has summarized the general sur- transport: d-c measurements, electrochemical impedance
face modification techniques that are used. The techniques analysis, under-the-coating sensing, and radio tracer mea-
are divided into three broad categories: surements. Characteristic d-c resistances of 1011 ohm.cm 2 are
9 Low-energy inorganic coating techniques. For the most observed for films without continuous aqueous pathways
part these are mature technologies that have been used for through the coating, as first described by Asbeck and Van Loo
many years. [69]. The resistance drops to the order of 108 ohm-cm 2 if
9 Polymer coatings include traditional paints, thermo- continuous aqueous pathways exist where such pathways
plastics, poly(vinyl chloride)s, epoxies, urethanes, and have high rates of transport. It is also clear that films and
poly(methylmethacrylate). coatings are heterogeneous and the aqueous pathways are
9 Techniques involving the use of energetic ions. The tech- surrounded by regions of lower transport rates. The resist-
niques have developed rapidly in the last 10 to 15 years; ance of films may also decrease with time as the ion channels
several have neither reached maturity nor found use for or pathways equilibrate with an external aqueous environ-
corrosion protection. Only those designated as low cost and ment.
scalable for widespread use are viable for corrosion protec- For films with high resistance and no ion channels, the
tion, except in critical applications. In addition, most tech- impedance of the film is dominated by its geometric capaci-
niques that require vacuum processing are too costly for tance. For films of lower resistance, the low-frequency imped-
most applications. ance is dominated by the sum of the resistance of the film and
Inorganic sol-gel films are formed from a sol through con- the resistance of the electrolyte. If corrosion proceeds under
tinuous stages of increasing concentration of a solid precur- the coating because of ingress of the aqueous environment,
sor. Typically, the sol is a solution of polymeric species or a the low-frequency impedance decreases in value. It has been
suspension of"oligomers" including particles in the colloidal- argued that there is a strong correlation between the sites for
size range. During deposition through states of increasing corrosion under the film and the intersection of the ion chan-
solids concentration, the sol might gel, but the gel state is nels with the underlying surface, but it has been difficult to
often a fleeting transient that quickly empties of liquid. Nev- confirm the correlation with direct observations.
ertheless, the structures formed during this stage have vary- The nature of the easy pathways for transport appears to be
ing amounts of porosity and influence the structure of the related to several factors. One of the factors is the presence of
final film. This processing offers good control of composition pigment and filler particles, which could facilitate the forma-
and homogeneity at low temperatures. It is not directional tion of aqueous pathways adjacent to the pigment or filler and
nor equipment intensive. Complex shapes of arbitrary size would be influenced by the interaction of the particles with
can be coated with good uniformity. The cost of high-purity the polymer matrix [68]. The channels could also form by
liquid precursors may be high, but for thin-film applications coalescence of voids or pores in the polymer matrix, and this
the materials cost would be acceptable. would be influenced by the formation processes of the films.
Films deposited using energetic deposition techniques are Aggregation of solvent in the film could be influenced by the
dense, highly adherent, have few pinholes, and can be laid prior history of the film, by the presence of impurities, and by
down at low temperatures. They are attractive for corrosion retained solvent.
protection. Ion-beam-assisted deposition and ion implanta- The presence of channels has been demonstrated to be a
tion have the best adhesion properties, while RF sputtering function of the glass transition temperature (Tg) of films as
has the best throwing power. Three important factors affect- well. That is, below T~, the polymer will be brittle unless a
ing the performance of films are porosity, adhesion, and secondary, low-temperature relaxation exists, and this will
stress. Although there are compressive stresses, in ion-im- favor the formation of microcracks and defects. Above Tg, the
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film will be m o r e flexible a n d less susceptible to f o r m a t i o n of SUMMARY

fracture channels. A r m s t r o n g et al. [70] have investigated the
influence of Tg on ion t r a n s p o r t a n d p e r m e a b i l i t y in chlori- The a t m o s p h e r i c c o r r o s i o n of metals is one of the m o s t
n a t e d r u b b e r films. i m p o r t a n t single p r o b l e m s facing c o r r o s i o n science a n d tech-
Pigment a n d filler particles can have a beneficial influence nology. F r o m small n a n o s t r u c t u r e s to large buildings a n d
b e c a u s e of the r e d u c e d t r a n s p o r t of water, oxygen, a n d ions. bridges, coating techniques are being developed to m o d e r a t e
The effect will d e p e n d on the p i g m e n t volume fraction, the the rate of d e g r a d a t i o n with s o m e success. The use of low-
c h e m i c a l composition, the geometry, a n d the d i s p e r s i o n as cost coatings continues to increase as the coatings are m a d e
noted by Burns a n d Bradley [71]. E q u i l i b r i u m w a t e r u p t a k e m o r e i m p e r m e a b l e a n d m o r e a d h e r e n t to the p r o t e c t e d sub-
m a y cause plasticization a n d subsequent d e p r e s s i o n of Tg, as strate. Higher-cost films applied b y high-energy m e t h o d s are
finding wider use in critical a p p l i c a t i o n s w h e r e conventional
well as swelling, w h i c h counteracts the effects of r e d u c e d
coatings are inadequate. In all systems w h e r e p r o t e c t i o n is
t r a n s p o r t rate c a u s e d by the solid particles [72]. Pigments
necessary, the early detection of c o r r o s i o n is desirable in
that have oxidizing c h a r a c t e r can induce passivation of the
o r d e r to p l a n r e p l a c e m e n t a n d m a i n t e n a n c e m e a s u r e s a n d to
underlying metal, as observed for c h r o m a t e o r v a n a d a t e addi-
avoid c a t a s t r o p h i c failures. Detection of the presence of cor-
tives [73]. Other p i g m e n t s m a y inhibit the cathodic r e a c t i o n
r o s i o n can be a c c o m p l i s h e d in two ways: detection of the
a n d thus suppress c o r r o s i o n as well [74].
agent that causes c o r r o s i o n or detection of the results of the
De-adhesion of organic coatings is responsible for en- c o r r o s i o n process either on the m a t e r i a l of interest or on a
h a n c e d c o r r o s i o n rates on one h a n d a n d is the result of s p e c i m e n of the material. Sensors a n d m o n i t o r s are receiving
c o r r o s i o n on the o t h e r hand. Leidheiser [75] has discussed greater attention in accelerated life testing of materials, a n d
de-adhesion processes which include: loss of a d h e s i o n w h e n eventually they will be developed m o r e widely for o p e r a t i n g
wet, cathodic delamination, c a t h o d i c blistering, swelling of systems or in p o r t a b l e m o n i t o r i n g systems. The savings to
the polymer, gas blistering b y corrosion, o s m o t i c blistering, i n d u s t r y a n d the public at large w o u l d be in the billions of
t h e r m a l cycling, a n d anodic u n d e r m i n i n g . W i t h few excep- dollars if the onset of failure processes could be detected
tions, the loss of a d h e s i o n processes requires that reactive p r i o r to their c u l m i n a t i o n in a c a t a s t r o p h i c event [79].
species such as water, oxygen, a n d ions p e n e t r a t e t h r o u g h the
coating. Bonds of the coating with the surface of a steel sub-
strate m a y be a t t a c k e d b y high p H conditions, which are the
result of c o r r o s i o n reactions o r i m p o s e d c a t h o d i c p r o t e c t i o n REFERENCES
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"New Radio Frequency Technique for Deposition of Hard Car-
Anti-Corrosive Pigment Containing Vanadate/Phosphate," Ad-
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1985, p. 610.
Scantlebury and M. Kendig, Eds., The Electrochemical Society,
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Pennington, 1989.
Bulino, D.A., "Summary Abstract: Characterization of Ion-
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Beam Deposited Diamond-like Carbon Coating on Semiconduc-
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p. 2327. sives on Mild Steel," Advances in Corrosion Protection by Organic
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[62] Morris, R. G. and Smyrl, W. H., "Current and Potential Distri- Organic Films by the Kelvin Probe Method," Berichte
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www.iran-mavad.com

MNL17-EB/Jun. 1995
Natural Weathering
by Lon S. Hicks I and Michael J. Crewdson 2
NATURALWEATHERINGDESCRIBESTHE PROCESSof exposing ma- testing was "real world," with results being returned from
terials to the effects of the outdoor environment. Deteriora- product surveys and consumer complaints.
tion caused by the atmosphere occurs to all materials placed The idea for exposure fences and racks to expose paint
in an outdoor environment. Natural weathering tests are an specimens moved the testing to the research and develop-
extremely important part of the process of determining the ment stage and away from the after market survey. Research
aging characteristics of a material. Weathering tests are used into improved coatings were made on specimens before the
to improve the durability of exposed materials. product went to market, thus reducing the possibility for
All materials exposed to the elements deteriorate; the rate failures in the marketplace.
and extent of deterioration is dependent upon the material In the early 1920s certain climates were noticed to be more
and the severity of the exposure conditions. Weathering tests severe on exposed materials than others. At the same time,
provide the means to improve the resistance of a material to Florida experienced a land boom with increased develop-
those factors. ment; as the number of consumer items increases, it became
Paint is currently the single most important material tested apparent that life expectancy for these products was much
for its weathering-resistance properties. Paint is used as a less in the "Sunshine State" than in the Northern Temperate
decorative item, but equally as important, paint is used as a Zone. Prior to this time, natural weathering tests were con-
protective layer. Painted products are found in many varied ducted mostly in the Northeast and Midwest, where the ma-
environments with equally varied effects upon exposed sur- jority of the large paint companies were situated, but the
faces. Weathering tests offer an initial view of the expected discovery of the faster weathering led several of these manu-
performance of the paint to the environment. facturers (along with car companies) to set up their own
Natural weathering tests are not, however, simply a case of exposure stations in South Florida.
setting specimens out in the sun and watching what happens; Also at this time, several independent weathering stations
a meaningful test involves a more thorough understanding. A were founded (see Fig. 1) to provide this important service to
number of important factors must be carefully considered all companies. The cooperation between independent test
when planning and conducting a weathering test: the cause stations and paint manufacturing companies over the last 60
and effect relationship between the weather and the material, years has led to a g~eater understanding of the cause and
the subtle differences in exposure techniques, and the report- effect relationship betkveen the weather and material and also
ing and inspection methods employed. To achieve the most
to refining and improving techniques used to conduct weath-
reliable test result, these fundamentals must be appreciated.
ering tests.
Early weathering tests were almost always at a 45 ~ angle
HISTORICAL facing south as this was considered the optimum position
(see Fig. 2). The fact that most exposure stations in the early
The origins of natural weathering testing of paints goes years were all in the Northern United States made this even
back as far as early caveman drawings in the Ice Age. We do more so. As the focus of outdoor weathering shifted to Flor-
not know if these cave dwellers painted on the outside walls, ida, realization set in concerning the importance of the angle
for if they did, the elements would have long since eroded of exposure and other variables affecting the outcome.
away the evidence. Inside, where conditions are less severe,
the paintings have survived tens of thousands of years.
The modern paint era was the catalyst for current weather-
ing tests. Consumer awareness of deterioration propelled the F A C T O R S OF I N F L U E N C E
search for more durable products. At the same time, paint
manufacturing companies became cognizant of the fact that The major influencing factors in the atmosphere involved
durable products sell better; thus they have increased their
in the process of weathering are:
efforts to improve paint durability. At this time, the only
1. Sunlight.
2. Temperature.
~Vice president and technical director, respectively, Sub-Tropical
Testing Service, 8290 S.W. 120th St., Miami, FL 33156. 3. Moisture
2General manager/technical director, Q-Lab, 13131 SW 122nd 4. Pollution
Ave., Miami, FL 33186. 5. Biodeterioration.
619
www.iran-mavad.com

FIG. 1-Aerial view of exposure site.
FIG. 2-Overview of exposure racks.
Paint will degrade w h e n exposed to the elements in the atmo- d e g r a d a t i o n produced. Any test m e t h o d e m p l o y e d to examine
sphere due to the action of these influencing factors, w h i c h w e a t h e r i n g m u s t be designed so t h a t the exposure c o n d i t i o n
cause the basic structure to b r e a k down. These factors inter- is as s i m i l a r as possible to that of the i n t e n d e d end use of the
act synergistically to p r o d u c e the d e t e r i o r a t i o n of the mate- material. This is the only way a c c u r a t e p r e d i c t i o n s m a y be
rial we see as a w e a t h e r i n g effect. m a d e concerning the expected life of the material.
The relative p r o p o r t i o n of each of these factors is i m p o r - An o u t d o o r w e a t h e r i n g test is c o n d u c t e d using the n a t u r a l
tant in d e t e r m i n i n g h o w the overall d e g r a d a t i o n process will elements in an u n c o n t r o l l e d environment. Test fixtures a n d
occur. W h e n the factors of influence are changed, so is the m o u n t i n g techniques can be chosen to create a s i m i l a r expo-
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CHAPTER 52--NATURAL WEATHERING 621
sure position as the end use. These techniques include chang- Range Wavelengths, nm
ing angle and orientation, backing type, and the use of speci-
UVC less than 280
ally designed frames to produce a specific microclimate. UVB 280-320
The material under test is itself a major factor in the test. UVA 320-400
The simultaneous exposure of a reference specimen with a
known long-term weathering history will ensure that the test-
There is no UVC at the Earth's surface as wavelengths
ing is realistic. If the expected results are given by the refer-
below 295 to 300 nm are filtered out by the atmosphere [1].
ence specimen, there is a greater degree of confidence that the The percent composition of the UV regions is shown in Fig. 6.
influencing parameters will produce the correct type of Generally, the shorter the UV wavelength, the more damag-
changes in the specimen, which is exposed simultaneously. ing its effect on materials. The UVA and the shorter wave-
length UVB are responsible for most photodegradation.
Therefore the range of sunlight that comprises the smallest
percentage of the solar spectrum is the primary cause for
Sunlight material degradation. This becomes clear when we consider
The effect of exposure to sunlight is the fundamental cause the quantum theory, which describes light as discrete pack-
of the weathering deterioration of most materials. The pri- ages of energy called photons. The lower the wavelength, the
mary component of paint weathering is photodegradation. greater the energy contained in these packets (Fig. 7).
Photodegradation occurs as a result of light energy break-
Spectral Power Distribution ing a chemical bond in the exposed material, causing a deteri-
The wavelength distribution of sunlight that reaches the oration of the physical structure [2]. As the wavelengths be-
Earth's surface is important because of the relative effect on come shorter, the energy of each individual packet becomes
the material caused by each wavelength region. greater, allowing that photon to break progressively stronger
Sunlight can be divided into three major regions: ultravio- molecular bonds. Thus, chemical structures able to with-
let (UV), visible, and infrared (IR). Each region has its own stand irradiation at 350 nm may not be able to endure radi-
distinct wavelength range [1] (see Fig. 3).
1. Ultraviolet--wavelengths less than 400 nm. TABLE 1--Relative proportion of sunlight wavelength ranges.
2. Visible--wavelengths between 400 to 700 nm. Wavelength, Irradiance,
3. Infrared--wavelengths above 700 nm. Range nm W m 2 Percent
The relative proportion of each of these wavelength regions UVC <280 0

is shown in Table 1 and described in Fig. 4. The visible region UV UVB 280-320 5
UVA 320-400 63 6.1
constitutes the largest portion of the overall solar energy;
however, it is the UV portion of the sun's energy that is the Visible 400-800 580 51.8
most destructive element. The ultraviolet can itself he divided
into three distinct wavelength ranges [1]; only the UVA and Infrared 800-3000 472 42.1
the UVB reach the Earth's surface (Fig. 5). Total 280-3000 1120 100.0
SUNLIGHT SPECTRUM
TOTAL HEMISPHERICAL
1.8
1.6
r 1.4
Y
~ 1.2
~ 0.8
z 0.6
0.4
0.2
0
/
300
i I l l l l l
400 500 600

i
700
I l l I
8OO
WAVELENGTH nm
FIG. 3-Solar power distribution, Miami, Florida (solar noon, 26 ~ tilt).
www.iran-mavad.com

ation at 320 nm. As the energy level in the p h o t o n s increases,

SOLAR SPECTRUM however, there is a r e d u c t i o n in quantity available. The ultra-
WAVELENGTH RANGE PERCENT violet wavelengths in sunlight c o n t a i n these high-energy pho-
tons. So while the UV m a k e s up only 6% of the total energy, it
300-400 (6.1%) is t h a t small p e r c e n t a g e that causes the d a m a g e to occur.
The first law of p h o t o c h e m i s t r y states that only light that is
a b s o r b e d can cause damage. Thus, if the a b s o r b a n c e of darn-
aging UV energy c a n b e prevented or otherwise reduced,
d e t e r i o r a t i o n will be slowed. This p r e m i s e forms the basis for
800-3000 (42.1%) m u c h of the r e s e a r c h in p a i n t formulation.
The visible p o r t i o n of the solar s p e c t r u m is r e s p o n s i b l e for
a limited a m o u n t of physical d e g r a d a t i o n [3] a n d only in a
few m a t e r i a l s that are susceptible. S o m e dyes a n d p i g m e n t s
400-800 (51.8%)
are sensitive to wavelengths in the lower regions of the visible
spectrum. This manifests as color changes in m o s t m a t e r i a l s
b u t w i t h o u t changes to o t h e r physical properties. P r i n t e d m a -
FIG. 4-Percent composition of sunlight. terials, paper, a n d dyes are affected by the visible wave-
lengths.
The infrared region causes heat b u i l d u p to o c c u r on ra-
d i a t e d specimens, b u t has not otherwise been associated with
causing significant d e t e r i o r a t i o n to occur. The IR is a factor
SUNLIGHT SPECTRUM in the d e t e r i o r a t i o n b e c a u s e a b s o r p t i o n of these wavelengths
TOTAL ULTRAVIOLET causes s p e c i m e n t e m p e r a t u r e to rise, w h i c h in t u r n leads to
1.4 a n increase in the rate of p h o t o d e g r a d a t i o n .
1.2 Radiant Exposure

E x p o s u r e to solar r a d i a t i o n causes d e t e r i o r a t i o n to occur,
a n d the m o r e energy a b s o r b e d d u r i n g exposure, the greater
0.8 the deterioration. The intensity a n d total dosage of solar
energy affect the rate and extent. Daily intensity levels are
0.6
d e t e r m i n e d by the season, latitude, a n d a t m o s p h e r i c condi-
0.4 tions of the location [4]. A typical day showing total a n d
1
z_ ultraviolet r a d i a t i o n is shown in Fig. 8.
0.2 R a d i a n t energy is m o n i t o r e d a n d r e c o r d e d using r a d i o m e -
ters. These i n s t r u m e n t s collect i n c o m i n g solar r a d i a t i o n from
0 ..........
300 310 320 330 340 350 360 370 380 390 400 a 180 ~ solid angle, which is identical to the energy collected
b y the exposed specimens. F o r m o r e accurate m e a s u r e m e n t
WAVELENGTH nm of the a m o u n t of r a d i a n t energy the p a i n t s p e c i m e n is receiv-
FIG. 5-Ultraviolet spectral power distribution (solar noon, 26 ~ ing, the i n s t r u m e n t is tilted at the s a m e angle as the exposure
tilt).
rack.
The integrated total of solar r a d i a t i o n will be the dosage of
solar energy o n the sample. This total will be affected m o s t l y
b y a t m o s p h e r i c conditions such as cloudiness: a clear d a y can
yield as m u c h as 30 MJ m -2 ( a p p r o x i m a t e l y 700 langleys)
SOLAR SPECTRUM solar energy, w h e r e a s a heavily cloudy a n d overcast d a y m a y
WAVELENGTH RANGE P E R C E N T be b a r e l y above zero.
100-
90 Seasonal Variations
I- 80 On an a n n u a l basis, the dosage of solar energy will change
Z 70 due to the altitude of the sun a n d the distance b e t w e e n the
LU sun a n d the E a r t h [5]. This b e c o m e s m o r e a p p a r e n t w h e n the
O 60 VISIBLE
rr 50 angle of the fixed exposure r a c k is taken into account. S o l a r
w r a d i a n t exposure increases w h e n the specimens are posi-
o_ 40
t i o n e d at an angle n o r m a l to the incident radiation. There-
30
fore, in the s u m m e r m o n t h s in Florida, a 5 ~ tilt angle will
20
receive m o r e energy t h a n a 45 ~ tilt angle. In the w i n t e r
10 UVC months, however, w h e n the sun achieves a m u c h lower ze-
0
<280 280-320 320-400 400-800 800-3000 nith, the 45 ~ angle receives the m o s t energy [6] (Fig. 9). This
W A V E L E N G T H R A N G E nm seasonal difference in r a d i a n t energy levels can be seen in Fig.
10.
I ImU PERCENTI
Over the c o m p l e t e solar cycle of twelve m o n t h s , a fixed
FIG. 6-Percent composition of UV, visible, and infrared. exposure at the s a m e angle as the latitude of the exposure site
www.iran-mavad.com

CHAPTER 5 2 - - N A T U R A L W E A T H E R I N G 623
WAVELENGTH ENERGY
RELATIVE ENERGY PER PHOTON
Z
I
600 If
W
z 500 i
I
UII
400
v 300 ~
>-
20O
LU
z
IIlII 100
0 i ! i ! I
2O0 300 400 500 600 700 800

W A V E L E N G T H nm
I --B-E = hNaC/r]
FIG. 7-Energy per photon at each wavelength in sunlight.
SOLAR ENERGY
DALLY INTENSITY
1200
1000
04
E
800
>..
I.- 600
co
z
uJ 400
I-
z
i
200
0
6 7 8 9 10 11 12 1 2 3 4 5 6 7 8
T I M E O F DAY
TOTAL TUV (xlO)[

FIG. 8-Daily intensity levels of sunlight, Miami, Florida: Total and ultraviolet, 26~
tilt angle. (TUV is shown by the lower line.)
will receive the most radiation, as shown in Table 2. Variable energy as a means of timing exposures will further help to
angle exposures where the tilt angle of the rack is changed even out the seasonal differences in the weathering effect
seasonably to follow the zenith of the sun can be used to produced. The radiant energy for one year for Miami and
increase the radiant exposure by up to 10% depending on Arizona for each of the commonly used exposure angles is
location and local climate variability. Short-term exposures, shown in Table 2.
those less than one year, will be affected by seasonal differ-
ences in solar energy due to angle of exposure. This impor-
tant factor must be considered when equating exposure inter-
Temperature
vals. Timing exposures by amount of radiant exposure will The temperature of a material on exposure is a primary
reduce some of these inequities. The use of total ultraviolet factor whose influence must be understood in order to relate
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tion, though, that once the breakdown mechanism has been

initiated, an increase in thermal load will accelerate the rate
of change. A general rule of thumb that has been accepted
,u. I NOV.-MAR. recently is that an increase of 20~ in the temperature of an

exposed specimen results in a doubling of the deterioration
rate.
Many chemical reactions have a threshold activation en-
ergy, i.e., the temperature level at which a sequence of events
will be initiated. Therefore, as thermal input increases,
higher threshold levels are surpassed and new mechanisms
are initiated. This may cause a change in the overall deterio-
ration produced if the new pathway is significantly different
from that at the lower temperature.
It is therefore necessary to conduct the weathering test at
the correct temperature. The comparison being made here is
SOUTH IL
that of the actual end use exposure condition to that found in
the test method. By having the temperature too low, the rate
of change is slowed and deterioration will not be as severe.
ANGLE AT Conversely, if the temperature is too high, the rate may pro-
S O L A R NOON ceed too quickly and the effect will be more severe.
FIG. 9-Angle subtended by sunlight on exposed panel, Paint specimens on exposure derive their temperature
from two sources: the ambient air and the radiated infrared
from sunlight. The intensity of the sunlight will determine
the cause and effect relationship of weathering. For most how much higher the temperature of an exposed specimen
materials, the moderate high temperatures found in service will be above ambient. Wind speed will assist in reducing the
do not cause deterioration per se. However, when the temper- temperatures slightly [7]. The average specimen temperature
ature rises in conjunction with solar radiation, the rate and will show the same seasonal range as that for air temperature
type of deterioration can vary greatly. (Fig. 11), but will be determined on any given day by the level
In a normal first-order chemical reaction, raising the tem- of solar irradiance (Fig. 12).
perature of the environment by 10~ leads to a doubling of The angle of exposure, paint color, and season also contrib-
the speed of that forward reaction. However, because mate- ute to determine the actual temperature at any given time.
rial degradation is not a simple one-step chemical reaction, Thus the specimens are generally hotter during the day than
weathering deterioration does not proceed twice as fast when at night, in the summer than in the winter, and on a sunny
the temperature is raised by 10~ There is a definite indica- day rather than on a cloudy one. On any given day, the tem-
SOLAR RADIANT ENERGY

MIAMI, FLORIDA
7001 _ ~
600
400
300
200
J/,N F~S M/,R ACR UkY JdN J6L AU'GSEPT OCT NOV D~;C
MONTHS
I
I'-'~'- 45 DEGREES I 5 DEGREES ~ 26 DEGREES J
D
FIG. 10-Seasonal variations in solar energy measured at different fixed angles of

exposure.
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TABLE 2--Solar radiant energy, average 1990-1991. perature of a n exposed p a i n t sample will follow closely the
Solar Radiation, MJ m 2, irradiance level of the sun. The temperature of the exposed
Angleof Exposure material can be m a n i p u l a t e d even in an o u t d o o r exposure
Month 45~ 5~ 26~ VA~ test; these techniques are discussed later in "Accelerated Nat-
January ural Weathering."
Florida 556.79 420.48 514.34 556.79

Arizona 612.50 425.49 Moisture
February Water is a p r i m a r y factor affecting the deterioration of

exposed materials. I n c o n j u n c t i o n with solar radiation a n d
Florida 587,50 483.37 618.09 587.50 high temperatures, the moisture content in a n d s u r r o u n d i n g
Arizona 607.94 476.40 a n exposed sample is very i m p o r t a n t in d e t e r m i n i n g the
March weathering response of that material [8]. The presence of
water falls into two categories:
Florida 601.51 569.90 661.61 661.61 1. Gaseous.
Arizona 631.54 601.35 2. Aqueous.
April
Relative Humidity
Florida 545.76 573.12 623.35 573.35 The gaseous phase is that which describes the moisture
Arizona 724.23 784.77 c o n t e n t of the air. The a m o u n t of water vapor contained in
May the a m b i e n t air is the absolute humidity. W a r m air is able to
hold more water i n the vapor phase t h a n cold air. The rela-
Florida 468.30 600.77 577.21 600.77 tionship between the actual moisture c o n t e n t of air a n d the
Arizona 735.51 897.85 m a x i m u m c o n t e n t at any particular t e m p e r a t u r e is the rela-
June tive humidity. W h e n the air is fully saturated, the relative
h u m i d i t y is 100%.
Florida 441.17 589.38 529.25 589.38 Any material placed on exposure will endeavor to m a i n t a i n
Arizona 648.94 856.13 a moisture c o n t e n t e q u i l i b r i u m with its s u r r o u n d i n g s [9].
July Physical stresses are created as the material loses or gains
water c o n t e n t in order to equilibrate, as can be seen in Fig.
Florida 434.21 566.95 531.66 566.95 13. The greater the range of h u m i d i t y in the enveloping atmo-
Arizona 649.66 830.43 sphere, the greater the overall stress on the material. Because
moisture is a m a j o r factor in the synergistic effect of weather
August
o n exposed materials, a higher moisture c o n t e n t will contrib-
Florida 475.86 572.30 557.65 572.30 ute to increased degradation more t h a n will lower moisture
Arizona 684.23 774.86 levels. A relative h u m i d i t y value of 70% is considered the
critical threshold for corrosion [10]. This indicates that a
September
constant cycling of h u m i d i t y levels at high values increases
Florida 475.00 502.78 526.62 526.62 the rate of deterioration.
Arizona 658.02 647.56
Rainfall
October The effective source of visible surface moisture has two
Florida 545.50 500.14 561.06 545.60 origins, a n d they each have a different effect on the exposed
Arizona 712.30 596.29 material. The distinction between the two types m u s t be
clearly understood.
November Rain is a n external source of water that is applied to the
Florida material via the surface layers. As most rainfall is of short
522.87 425.90 509.88 522.87
Arizona 669.54 471.38 duration, this effect is primarily at the surface a n d does not
play a direct role in the deterioration of the bulk of the
December material.
Rainfall has the greatest influence at the surface a n d is
Florida 524.10 394.72 492.33 524.10
Arizona 601.06 400.22 responsible for washing away surface layers d u r i n g periods
of heavy rain. For example, rain assists in increasing the rate
Total
at which a specimen m a y chalk, b u t m a y also help to remove
Florida 6178.55 6199.76 6703.02 6827.51 surface attachments such as dirt a n d mildew.
Arizona 7935.44 7762.70 Rainfall will cause a t h e r m a l shock on exposed specimens,
NOTE:VA = variableangle, which can be severe in certain circumstances. W h e n the rain
occurs at a time when the material is heated from r a d i a n t
exposure, the cooling effect causes a rapid drop in the tem-
perature of the specimen. This thermal shock can cause me-
chanical stress as the specimen contracts. I n the s u m m e r in
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TEMPERATURE
MIAMI 1990
'~
~
~
I, .,,~,,,J,
'
~^k,J
vy
A A, .i t
uJ
._1
0
or)
'~1 V
v[ ~.... I I!
,o t0 mluu imUUl imi

-
JAN FEB MAR APR MAY JUN JUL AUG SEPT OCT NOV DEC
MONTHS
[~BLACK PANEL(C) AMBIENT(C) [

FIG. l 1-Daily maximum black panel versus ambient temperature. (Lower line
equals ambient temperature.)
RADIANT ENERGY AND TEMPERATURE

MIAMI 1990
80
70
-~ 50
C~
u~ 4O
20
MONTHS
[--BLACK BOX IC~ SOLARENERGYMJ / m,'[

FIG. 12-Daily maximum black box temperature versus daily solar radiant energy.
(Upper line equals black box temperature,)
Florida, the temperature of a black panel can drop from 70 to much deeper levels within the material. Condensation mois-
25~ in about 2 rain. ture has high levels of dissolved oxygen, which accentuates
photodegradation by taking part in the chemical reaction.
Condensation The total amount of time a sample is wet is an extremely
Condensation arises when the sample temperature drops important factor in the determination of the degree and rate
below the dew point temperature of the surrounding air. This of degradation. Prolonged exposure to surface condensation
causes water vapor in the air to condense on the material. The will allow the absorption or permeation of a relatively high
physical and chemical responses of the material caused by level of water and oxygen, and as the day progresses a strong
condensation have a far greater effect on the material than pressure will be exerted by the atmosphere for water desorp-
rainfall. The condensation effect can also be apparent at tion. The longer the intervals of wetting and drying, the
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will show the additional effect of the pollution on overall

MOISTURE EQUILIBRIUM weathering.
+ MATERIAL V E R S U S ATMOSPHERE Although pollutants may directly affect the paint indepen-
dently of other weathering factors, most often the changes do
not occur until the other influences are present. Changes in
"z paints on exposure in industrial areas, which are seen in a

relatively short time but which do not show changes in rural
areas, are a clear indicator of the effect of the pollution.
Solar energy can act to change the chemical structure of
0 /k J/' Ix,// the emitted waste product; for example, atmospheric SO2 in
water does not become sulfuric acid until radiated. The sulfu-
1.1,1
>
v V V'v" v ric acid then causes a color change due to reaction with the
pigment.
._1
iii
Large-scale pollution such as the effect of acid rain is felt
, , , , , , , , , , , , , , , , , , , , , 0 , , , , , i , 1 , , , , , , , , , i , , ,
2 3 4 5 6 7 8 throughout most of the northeastern United States, with the

TIME SCALE (DAYS) greatest effect in Pennsylvania, New Jersey, and New York.
Acid rain resistance can be included as part of the routine
I "-~'= MATERIAL ATMOSPHERE l testing procedure by exposure at known polluted sites. The
FIG. 13-Ambient versus sample moisture cycling. effect is known and is widespread.
Local pollution problems such as the smog in Los Angeles
create a problem for the testing industry. Because the chemi-
deeper into the material will be the cycling effect. Water cal effect of each emission is different, the weathering result
absorption and desorption rates are also a function of the of a single material may vary from city to city depending
diffusion coefficient of the material. The faster the rate of upon the industrial base.
cycling, the more the effect remains at the surface and the
less penetration is made into the bulk of the material.
The photochemical degradation mechanism is also accen- Biodeterioration
tuated by the presence of moisture. Rates of deterioration are The phenomenon of material degradation due to attack by
greatest when the solar radiation is present in conjunction biological organisms can take many forms. The most com-
with high moisture levels. It follows, therefore, that surface mon form of biodeterioration of specimens exposed outdoors
breakdown effects such as chalking will occur due to rainfall, in Florida is mildew. The organisms that constitute mildew
condensation, and sunlight interaction, whereas bulk sub- are fungi, which are individually microscopic but can be seen
strate deterioration such as cracking is due in large part to the with the unaided eye when grouped in colonies or having
synergistic effects of humidity, condensation, and tempera- threaded structures called hypha. The spores of the fungi
ture, causing mechanical stress and release of strain in the attach to the surface of the material, using the constituent
paint film. As surface layers break down, more of the interior chemicals at the surface as a food source. All fungi are char-
bulk of the material is exposed as a new surface layer. acterized by their inability to synthesize their own foods from
The role of moisture in exposed material breakdown is very carbon dioxide and water. They must therefore utilize an
important, but it is also important to know the source of the external supply of carbohydrate as their energy source. The
moisture. The different physical (and chemical) effects pro- exact chemical nature of that source will vary for each fungal
duced will differ with each source. A climate such as Miami's species, but the more opportunistic species can use the paint
(Fig. 14), with a range of high humidity and a high percentage directly.
of total wet time (approximately 50%), will allow moisture to As the mildew grows, surface conditions are altered. Break-
play a full part in the weathering process [11]. down products are formed that can act as a food source for a
second fungal species, which will find the surface of the paint
a favorable place to live. This succession of different orga-
Pollution
nisms constitutes the microecology of the painted material's
Atmospheric pollution is a significant, but lesser part of the surface [12]. The complicated natural order that occurs in
overall weathering effect. Industrial emissions consisting of mildew attack on exposed products makes it very difficult to
compounds that mix with water to form acid rain cause ascertain which species is causing the most damage.
chemical reactions to occur on exposed materials. The severe Real-time exposure testing outdoors in conditions favor-
long-term effect of pollution on even durable materials can be able to growth is the only way to truly test the mildew-
seen by the effect on ancient monuments and statues, which resistance properties of any product. Single culture testing of
have withstood centuries of exposure only to succumb in mildewcides and mildewstats are useful as a preliminary test
recent years to atmospheric contaminants. Short-term expo- o n l y .
sure to pollution can be just as severe if the material is The subtropical region of Florida is used extensively for the
susceptible. evaluation of fungus growth. The warm, wet climate pro-
Pollution is a powerful influence on paint durability, but its motes rapid growth on unprotected materials, with visible
effect is difficult to control and monitor. Analysis of the hyphae present in just a few days. A number of different
atmosphere will reveal the constituents of the pollution, and exposure methods are employed to study mildew growth, the
comparison to exposure in a clean pollution-free atmosphere most common being a vertical north orientation. This gives a
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MOISTURE LEVELS
MIAMI 1990
_ _ . , ., I
.0 ,, 'v'
w
.J
< 60
O 50
G0
40
30
20
10
0
MONTHS
I RELATIVE HUMIDITY % 1 TOTAL WET TIME (HR)

FIG. 14-Daily maximum humidity and total wet time.
shaded, damp location without the natural mildewstatic ef- cause the exposure consists of all of the major environmental
fect of solar UV radiation. A vertical south position is also parameters in high quantity except pollution.
used to study mildew growth as part of the total deterioration Each climate type has its own distinct characteristic pat-
mechanism. Exposure under a roof overhang is commonly tern, which derives from the range of influencing parameters
used (Fig. 15), and a tropical forest exposure is the most at that location. These can be measured and examined to
rigorous example of natural exposure conditions. determine the relative importance of each. Several important
Mildew organisms thrive in the damp conditions found in climatological types used in weathering are described below.
subtropical-type climates, and growth is greatest during the
summer months when rainfall and ambient relative humidi-
ties are at their highest level and temperatures are 20 to 30~ Climatological Types
Growth is slowed when average daily humidity drops signifi- Subtropical
cantly below 70%; however, during the winter, steady growth
The subtropical climate of southern Florida is recognized
will still occur on northern exposures and in tropical forests,
worldwide as the primary benchmark testing location. It is
where moisture levels are higher and temperatures are in the
the climate to which all other locations are inevitably com-
optimum range.
pared. It is no accident that this area is as important as it is,
Algae as a biodeterioration factor is different from mildew.
for it is the only true subtropical region within the United
Algae is a green plant and able to synthesize food from sun-
States. Due to the historical considerations discussed earlier,
light, carbon dioxide, and water. Its attachment to paint sur-
Florida is accepted worldwide as the standard in natural
faces is not an actively attacking one as' is the case with
weathering. The great majority of materials will fail faster in
mildew. The paint film is merely supplying a substrate for the
Florida than anywhere else because the climate contains all
algae. By its presence on the surface, however, algae affects
of the major influencing parameters except pollution and in
the microclimate and resulting deterioration may occur.
relatively high amounts (Fig. 16). The factors act together
synergistically, each one increasing the effect of the other.
The high temperatures and humidity complement the pho-
CLIMATOLOGY todegradation from solar radiation. The sun's energy is more
potent as there is a greater relative proportion of UV to total
Natural weather exposure testing of paints and coatings is energy. The time of total wetness is close to 50% of the total
conducted at many different sites, each with its own distinct time, thereby ensuring a constant cycle of wetting and drying.
set of influencing factors. It is the combination of the weath-
ering factors that causes the deterioration particular to that Desert
location. The desert of the Southwest United States (especially the
As indicated earlier, paint exposure testing facilities are Phoenix area) has also come to be regarded as a primary
located in many areas, but the subtropical area of Florida is weathering testing site. Exposure conditions in the desert are
regarded by the United States and by much of the rest of the very different than in Florida. The desert is widely used be-
world as the primary benchmark testing climate. This is because the climate consists of clear skies and prolonged un-
www.iran-mavad.com

CHAPTER 5 2 - - N A T U R A L WEATHERING 629
be examined during natural exposure testing in southern

Florida.
Temperate with Pollution

Exposure in an industrial environment will indicate
whether a paint is susceptible to atmospheric pollution.
There are many sources of pollution emission into the atmo-
sphere, and the method of administration to the paint is
usually by washout during rainfall. In the United States the
geographic area most affected by acid rain is the Northeast,
with the next most severe area covering most of the rest of the
East and the Midwest [13]. It is no coincidence that this is the
industrial heart of the country.
The U.S. paint industry has long used Louisville, Kentucky
as a typical temperate industrial exposure (Fig. 19). As a large
paint manufacturing center, this area has become accepted
as a location for exposure to acid rain. The temperature
continental climate can be as severe as Florida, but only for a
short period during the summer when the temperatures are
high, humidity increases, and sunlight levels are similar to
the subtropics.
Rainfall pH values below 4.5 have been recorded in some
areas of Pennsylvania and New Jersey, as shown in Fig. 20.
Paints and other exposed materials used in this area must be
made to withstand this acid rain effect. This can be tested in
Florida by artificially adding the acidic solution to the out-
door exposure test; however, outdoor exposures should be
conducted in the actual polluted environment to best deter-
mine resistance.
Marine
Marine Atmosphere--Exposure to a marine atmosphere
adds the corrosive influence of salt spray. Predominant test
FIG. 15-Vertical exposure under roof. sites are located on the coasts of Florida, New Jersey, North
Carolina, Texas, and California. The salt aerosols in the atmo-
sphere settle on the exposed panel and work to enhance
interrupted solar radiation. High temperatures are produced
rusting. The closer to the surf, the greater the percentage of
on exposed materials, and there is a higher absolute dosage of
salt in the atmosphere. A marine atmosphere test combines
solar UV than in Florida (Fig. 17).
the natural weathering of the site's climate with the addi-
For most materials, however, especially paints, the greater tional natural corrosivity of the sea salt.
solar UV does not produce faster deterioration than in Flor- Marine Immersion--Exposure in seawater is used to test
ida. This is due to the lack of moisture in the exposure. antifouling paints and rust-protective agents. Two exposure
Without moisture cycling, the effect of temperature and UV is possibilities exist: floating immersion and fixed exposure. The
much reduced. There is also no biodeterioration and no cor- floating rack positions the panels either completely or par-
rosion associated with desert exposure. tially immersed; the level remains the same through each tide
cycle. The fixed exposure in the tidal zone causes the panels to
Extreme Cold be alternately submerged and dry.
At the opposite end of the exposure scale from the desert is
exposure testing in extreme cold weather. Low temperatures Climate Affects Exposure
are accompanied typically by lower sunlight. International Weathering deterioration is a function of the material's
Falls, Minnesota is used as an exposure site for cold weather reaction to the influencing parameters. The two primary test-
testing because this area frequently records the lowest tem- ing locations are both located in hot, sunny climates that
perature in the continental United States (Fig. 18). Cold produce accelerated deterioration compared to most of the
weather exposure is used to test for specific failure types: cold rest of the United States. If different climates produce differ-
cracking and freeze thaw deterioration. As the temperature ent exposure results, there is a possibility that exposure to
passes through the freeze threshold, any water on the surface only one set of conditions will not reveal the deterioration
or in the bulk of the material forms into ice crystals. As the that may occur in another set [14].
water freezes, its volume increases by approximately 10%, Paint deterioration is determined by a number of mecha-
which is enough to create a substantial physical force on the nisms, each with its own threshold level for initiation. There
paint film. This is the one environmental factor that cannot is a level for each of the influencing factors at which the paint
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MIAMI, FLORIDA
CLIMATE RANGE
100
90
80
70
60
50
40
30 ~= -" ~ ~ ' ~ ' - B ' ~ ~ ~.
+8.7 -- - ~ - - - t = - ~ . ~ _ . . . ~ _
20
10
0 I i I i i i I i i ! i i
MONTHS
-"='-Avg Temp (c) --e-Percent Sun ~ Rainfall (in)

FIG. 16-Climate summary, subtropical (Miami, Florida).
PHOENIX, ARIZONA
CLIMATE RANGE
100
90
80
70
60
50
40
30
+22.2
20
i0
0] illl
J N F B MAR APR MAY JUN J L AUG SEPT O T N V D C

MONTHS
I - = = - A v g Temp (C) * Percent Sun ~ Rainfall (in) [
FIG. 17-Climate summary, desert (Phoenix, Arizona).
will become susceptible. When the factors interact, the over- Other climates are missing one of the factors or are reduced
all influence is a complicated matrix that is constantly chang- in effectiveness due to the winter season.
ing.
Degradation is the result of the material's response to its
environment. When the environment changes, so do the Instrumentation
changes that occur in the material. This does not always The atmospheric data required for weathering testing go
manifest as a slower or faster response, but also perhaps as a above and beyond that given by the National Weather Ser-
different one. Generally, however, it is practical to consider vice. The factors affecting material durability must be moni-
Florida as the most severe climate because it has all the tored to understand the cause and effect relationship between
influencing parameters in high abundance all year round. paint and the atmosphere. An exposure station weather re-
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INTERNATIONAL FALLS, MINNESOTA

CLIMATE RANGE
lOO
90
80 31
70
60
50
40
30
20
10
0 ,
-10
-20 I i I !
JAN FEB MAR APR MAY JUN JUL AUG SEPT OCT
. . . . . . NbV O C
MONTHS
I ,'-~- Avg Temp (C) '~ Percent Sun ~ Rainfall (in) ,I
FIG. 18-Climate summary, extreme cold (International Falls, Minnesota).
LOUISVILLE, KENTUCKY
CLIMATE RANGE
100
90
80
70 +35
60
50
40
30
20
10
0 -I- I I I i i i 9
JAN FEB M,~R APR MAY JUN JUL AUG SEPT OCT NOV DEC
MONTHS
I --=-Avg Temp (C) ; Percent Sun ~ Rainfall (in) I

FIG. 19-Climate summary, temperate (Louisville, Kentucky).
port comprises information relevant to the exposed speci- which is sensitive in the range of 300 to 3000 nm. The ultravi-
men. olet is measured using a sensor that is sensitive in the range of
The major additional items reported are the solar energy, 300 to 400 nm. The widely used Eppley Total UV Radiometer
black panel (or specimen) temperature, and total time of (TUVR) (Fig. 22) has a sensing range of 295 to 385 nm. These
wetness. These are the most relevant atmospheric measure- "total" sensors collect incoming radiation from all angles,
ments concerning material exposure. Table 3 lists several having a 180 ~ sensitive diffusion cover. This is termed hemi-
parameters and equipment used to collect the information. spherical radiation. Total radiation measurements include
As discussed earlier, for weathering requirements, the total both the direct beam from the sun and the diffuse energy
solar radiation is measured using a pyranometer, such as the from the atmosphere [15]. Direct beam radiation, excluding
Eppley Precision Spectral Pyranometer (PSP) (Fig. 21), the diffuse sky, is measured with a pyrheliometer such as the
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97.co / /
,~.. 9 6,3,$ /
4.'
FIG. 21-Precision spectral pyranometer (PSP).
FIG. 20-Precipitation pH in northeastern United States.
TABLE 3--Weathering instruments and sensors.

Measured Parameter Equipment Used
Solar Energy
Total hemispherical Pyranometer (hemispherical) PSP
Total ultraviolet UV Radiometer (hemispherical) TUVR
Normal incidence Pyrheliometer (6 ~ solid angle) NIP
Temperature
Ambient Thermometer
Black panel Black panel sensor RTD probe
White panel White panel sensor RTD probe
Sample temperature Thermocouple attached to panel
Moisture
Rainfall amount Rain gage
Rainfall duration Heated wetness sensor (impedance)
Total wet time TOW sensor (impedance)
Relative humidity Psychrometer or hygrograph
Wet bulb temperature Thermometer (in wick)
Miscellaneous
Wind speed Anemometer and wind vane
Salt aerosols Wet candle
Sea water temperature Floating thermometer
Air quality EPA measurements
NOTE: All sensors should be connected to continuously monitoring and
recording devices, e.g., computer-controlleddata acquisition system. FIG. 22-Total ultraviolet radiometer (TUVR).
Eppley N o r m a l I n ci d e n c e P y r a n o m e t e r (NIP). This has a 6 ~ The intensity of the r ad i at i o n is integrated with respect to
solid angle field of view and m e a s u r e s f r o m 300 to 3000 nm. time, thus allowing the a m o u n t of radiant exposure to be
To w o r k COlTectly, it must be m o u n t e d on a solar tracking calculated. Values for r ad i an t exposure are given in
device. megajoules per square m et r e (MJ m-2). This is the r e c o m -
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m e n d e d SI unit; an older t e r m used for these values is the

langley, w h i c h is 1 calorie p e r square centimetre (1 cal cm-2).
To directly convert langleys to megajoules, m u l t i p l y the lang-
ley a m o u n t by 0.041 84. This accounts for b o t h the conver-
sion from calories to joules a n d the change in unit area.
Black panel t e m p e r a t u r e is a m e a s u r e m e n t widely used in
w e a t h e r i n g exposures, b o t h n a t u r a l and accelerated. It is the
surface t e m p e r a t u r e of a b l a c k - p a i n t e d metal panel (Fig. 23)
a n d is used to o b t a i n a reference t e m p e r a t u r e for a p a i n t
panel exposed to a r a d i a n t energy source. E x p o s e d m a t e r i a l s
a b s o r b infrared energy from a light source, w h i c h causes
their t e m p e r a t u r e to rise above that of the a m b i e n t air tem-
perature. A b l a c k panel m e a s u r e m e n t is the expected maxi-
m u m t e m p e r a t u r e a colored panel might achieve w h e n ex-
p o s e d to a p a r t i c u l a r energy source since b l a c k a b s o r b s all
light energy. This t e m p e r a t u r e value is thus an i n d i c a t i o n of
the actual exposure t e m p e r a t u r e , which is m o r e relevant t h a n
air t e m p e r a t u r e . The black panel t e m p e r a t u r e will follow the
light intensity o u t p u t level of the sun.
Total t i m e of wetness is the a c c u m u l a t e d t i m e an exposed
p a i n t panel has visible surface m o i s t u r e [16]. The two sources
for this are rainfall and condensation. Surface m o i s t u r e can
be m e a s u r e d b y using a sensing e l e m e n t that requires w a t e r
to complete an electrical circuit, thus o p e r a t i n g a r e c o r d i n g
device. This will r e c o r d the a c c u m u l a t e d time for b o t h
rainfall a n d condensation; the time for rainfall can be re-
moved to o b t a i n the time due to c o n d e n s a t i o n only. The
sensor is described in m o r e detail in ASTM Practice for Mea-
s u r e m e n t of Time-of-Wetness on Surfaces E x p o s e d to Wet-
ting Conditions as in A t m o s p h e r i c Corrosion Testing (G 84).
A rainfall d u r a t i o n sensor (Fig. 24) m e a s u r e s only the
wetness time due to precipitation. The sensor is essentially
FIG, 23-Black panel thermometer. the s a m e as for total wetness m e a s u r e m e n t except that a
c o n s t a n t heating e l e m e n t is i n c o r p o r a t e d so that any surface
m o i s t u r e will evaporate quickly, switching off the sensor very
shortly after the rainfall has stopped. Keeping the t e m p e r a -
FIG. 24-Rainfall duration sensor.
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ture of the sensor above the d e w p o i n t will also prevent con-

d e n s a t i o n from forming.
In a d d i t i o n to the specialized i n s t r u m e n t s detailed above,
m a n y m o r e recognizable p a r a m e t e r s m u s t be m e a s u r e d . Am-
bient t e m p e r a t u r e a n d relative h u m i d i t y can yield general
i n f o r m a t i o n c o n c e r n i n g the climate at the test site a n d the
c o n d i t i o n of the a t m o s p h e r e s u r r o u n d i n g the exposed speci-
men. These m e a s u r e m e n t s are m a d e following W o r l d Meteo-
rological O r g a n i z a t i o n (WMO) practices with m e r c u r y ther-
m o m e t e r s , psychrometers, o r - - m o r e c o m m o n l y - - r e c o r d i n g
h y g r o t h e r m o g r a p h s in a W M O shelter (Fig. 25). W i n d speed
is a factor in the cooling of p a i n t panels a n d is m e a s u r e d with
an a n e m o m e t e r . A r a i n gage (Fig. 26) collects rainfall to deter-
m i n e the a m o u n t of precipitation. The rate of rainfall can be
important; 25 m m in 30 m i n can be quite different from the
effect of 5 m m in 2 h.
M1 of these d a t a can be collected a n d displayed in such a
m a n n e r as to c h a r a c t e r i z e a w e a t h e r i n g climate. If the influ-
encing p a r a m e t e r s are c o m p a r e d , it is possible to convey the
severity of the w e a t h e r with respect to the exposed m a t e r i a l s
(Fig. 27).
FIG. 26-Rain gage.
EXPOSURE TYPES
Exposure Frames
The m o s t c o m m o n type of exposure frame in use t o d a y is
the a l u m i n u m rack designed for open (unbacked) exposures
(Fig. 28). This type of rack a n d associated h a r d w a r e should be
constructed with n o n c o r r o d i b l e m a t e r i a l to prevent any con-
tact c o r r o s i o n effect with a specimen. Typical racks consist of
a r e c t a n g u l a r frame, adjustable hinged flaps with vinyl strips,
a n d a c l a m p i n g device to keep specimens securely fastened
(Fig. 29). This type of exposure frame is very versatile in that
it can be tilted to any specified angle or direction a n d can be
adjusted to a c c o m m o d a t e different-size specimens. S o m e ad-
vantages in using this type of frame are: (1) any size s p e c i m e n
can easily be m o u n t e d and removed, and (2) the hinged flap
with vinyl strip can be adjusted to protect the top p o r t i o n of
the s p e c i m e n so that any changes in a p p e a r a n c e resulting
from w e a t h e r i n g can be detected.
A n o t h e r type of exposure frame is k n o w n as the "black box"
(Fig. 30). This insulated exposure is used m a i n l y for recreat-
ing the conditions found on the flat surfaces of an a u t o m o -
bile. It consists of an a l u m i n u m box p a i n t e d black a n d open
on top. Panels to be tested are p l a c e d over the open t o p side. If
FIG. 2 5 - W M O instrument house. there are insufficient panels to cover the open area, black
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MIAMI CLIMATIC DATA

JULY 1990
50
40
LU
,_J
30
r
20
10
0
2 3 4 5 6 7 8 9 10 11 12 13 14 1516171819202122 232425262728 293031
DAYS
I --I-- BLACK PANEL (C) -'t-SOLAR RADIATIONl ~ WET TIME (HR) -1

FIG. 27-Morlthly weather summary, Miami, Florida.
FIG. 28-Exposure rack with panels.
metal "dummy" panels must be used to completely cover the this type of frame is commonly referred to as "backed expo-
top side to maintain a high temperature during the daytime. sure.
A third type of exposure frame in use but to a lesser degree
is the solid wood rack. Like the black box, this frame also Exposure Angles
elevates sample temperature, but not to the degree of a black The choice of exposure angle that a paint manufacturer
box. Generally, 3/4-in. (19-mm) untreated plywood is used uses for outdoor weathering is a critical decision. The angle
when constructing this type of rack. Depending on the condi- of the specimens on exposure have a definite impact on the
tion to be simulated, the plywood can be left unpainted or amount and type of degradation that can be generated. The
painted black to further increase sample temperature. Using exposure angle will affect the amount of solar radiation de-
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FIG. 2 9 - C l o s e u p of panels on exposure.
FIG. 3 0 - B l a c k box at 5 ~ south.
posited on the sample, the a m o u n t of time the sample re-

TABLE 4--Panel exposure temperatures.
ma i n s wet from rainfall or dew, and the t e m p e r a t u r e of the
sample (Table 4). To generate meaningful test results, it is Temperature, C
i m p o r t a n t to expose specimens at an angle similar to end use. Maximum Minimum
The basic angles of exposure that are used m o s t c o m m o n l y Exposure Type White Black White Black
are as follows: Open back, 45 ~ 45 60 20 18
Solid back, 45 ~ 50 70 19 17
1.45 Degrees South--Specimens are exposed at an angle of Open back, 5~ 48 67 20 18
45 ~ f r o m horizontal a n d facing the e q u a t o r (see Fig. 28). Solid back, 5~ 52 73 19 17
This is the m o s t c o m m o n angle used for architectural Black box, 5~ 55 76 17 15
Ambient air (32) (20)
house paints and industrial coatings. This angle is also
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CHAPTER 5 2 - - N A T U R A L WEATHERING 637
FIG. 3 1 - P a n e l s on e x p o s u r e at 5 ~.
used as a c o m p r o m i s e w h e n end use p o s i t i o n is u n k n o w n

or variable.
2.5 Degrees South--Specimens are exposed at an angle of 5 ~
from horizontal a n d facing the e q u a t o r (Fig. 31). This
angle is p r e f e r r e d over horizontal to avoid w a t e r p o n d i n g
on the sample. W h e n exposing in a s u b t r o p i c a l environ-
ment, the 5 ~ angle will increase the yearly a m o u n t of solar
radiation, especially during the summer, a n d also the total
time of wetness w h e n c o m p a r e d to 45 ~ south. This angle is
also used for black box testing and for a u t o m o t i v e finishes.
3.90-Degree Racks--Specimens are exposed at a right angle
to the g r o u n d (Fig. 32). E x p o s u r e racks can be facing n o r t h
or south d e p e n d i n g on the end use of the coating. Gener-
ally, w h e n testing for m i l d e w resistance, architectural
paints are exposed vertically (90 ~) n o r t h to m a x i m i z e mois-
ture retention.
4. Station Latitude--Exposure frames are tilted so that the
specimens are exposed at an angle from horizontal equal to
the geographic latitude of the exposure station. F o r the two
b e n c h m a r k w e a t h e r i n g locations, Miami, F l o r i d a is at 26 ~
latitude a n d Phoenix, Arizona is at 34 ~ latitude.
5. Variable Angle--The angle of exposure of the specimens is
c h a n g e d on a seasonal basis to ensure m a x i m u m solar
r a d i a n t exposure. F o r the Miami, F l o r i d a w e a t h e r i n g loca-
tion, the schedule calls for 5 ~ exposure in the s u m m e r , 45 ~
exposure in the winter, a n d 26 ~ in the m o n t h s of the equi-
nox (see Table 5 for angle schedule).
Orientation
S t a n d a r d exposure is for the s p e c i m e n to face the equator.
In the N o r t h e r n H e m i s p h e r e this m e a n s t h a t south is the
p r e d o m i n a n t direction for the exposure of specimens. This is
the m o s t severe direction as it enables the sun to shine di-
rectly on the specimens for a greater p o r t i o n of the day.
FIG. 3 2 - W o o d siding panels on e x p o s u r e at 90 ~ Exposures in any other direction would only be used if any
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TABLE 5--Variable angle schedule per ASTM E 782. the changes is to provide either a m o r e realistic exposure o r
Month Tilt Angle to p r o d u c e faster d e t e r i o r a t i o n w i t h o u t the loss of a n y agree-
m e n t in test results c o m p a r e d to the actual end use environ-
March Latitude angle
April-August Latitude angle - 20 ~ m e n t [14].
September Latitude angle O u t d o o r exposure in M i a m i can be considered an acceler-
October-February Latitude angle + 20 ~ a t e d test in its own right if the i n t e n d e d c o m p a r i s o n is to
NOTE: Latitude angle = tilt angle equal to the latitude at the exposure exposure in a t e m p e r a t e o r n o r t h e r n climate. All the neces-
location. sary p a r a m e t e r s are p r e s e n t in greater a m o u n t s . The corol-
lary is simple: increase the severity of the influencing p a r a m e -
ters a n d the rate o r degree of d e t e r i o r a t i o n will increase.
o t h e r factor of influence was c o n c e n t r a t e d so heavily in a
A s t r a i g h t f o r w a r d o u t d o o r test involves p o s i t i o n i n g the
different direction that it took p r e c e d e n c e over the solar
s a m p l e on a frame w h e r e the elements of the w e a t h e r can
influence. This m a y be the case w h e r e m a r i n e a t m o s p h e r e
w o r k t o g e t h e r to p r o d u c e the deterioration. To accelerate the
exposures are used a n d the s a m p l e faces the shoreline r a t h e r
overall w e a t h e r i n g process, one or m o r e of the influencing
t h a n south.
The m a j o r exception to the south exposures is found with p a r a m e t e r s can be increased. The p a r a m e t e r s that can be
the testing of p a i n t s for residential use. Paint applied to i n c r e a s e d are t e m p e r a t u r e , wetness, and solar radiation, a n d
w o o d e n sidings is extremely susceptible to the effect of there are several s t a n d a r d test m e t h o d s designed to do just
m i l d e w attack, especially on the s h a d e d side of the house, that.
w h i c h is p r e d o m i n a t e l y m o r e conducive to fungus growth. A
vertical (90 ~) n o r t h exposure is c o m m o n for p a i n t e d w o o d e n
sidings. However, at times, equal m i l d e w g r o w t h on replicate
specimens has been observed by the a u t h o r on vertical (90 ~ Black Box
south exposures.
The first p a r a m e t e r n o r m a l l y modified w h e n there is a need
for acceleration is the test for s p e c i m e n t e m p e r a t u r e b e c a u s e
Mounting it is the easiest to control. There will be an increase in the rate
There are several different m e t h o d s for m o u n t i n g speci- of the f o r w a r d d e g r a d a t i o n r e a c t i o n as the t h e r m a l l o a d is
m e n s onto a test frame. The type of backing chosen d e p e n d s increased.
m o r e or less on the m a t e r i a l being tested a n d the end use The simplest w a y to increase the t e m p e r a t u r e is to p o s i t i o n
application. Generally, since m o s t paints are applied to a the s p e c i m e n on a solid backing of d a r k color with a high
wood, a l u m i n u m , or steel substrate, m o u n t i n g of specimens insulation factor (R). This m e t h o d is widely used for residen-
is done on an o p e n - b a c k e d rack. However, if a s o m e w h a t tial sidings, roofing materials, a n d others. A c o m p a r i s o n of
accelerated test is necessary or a s p e c i m e n m u s t be tested to a the t e m p e r a t u r e s of black a n d white panels on various expo-
p a r t i c u l a r standard, then m o u n t i n g specimens in a black box sure frames on one s u m m e r day in F l o r i d a is shown in Table
m i g h t be necessary. A different m o u n t i n g technique w o u l d 4.
apply to residential siding material. In this case, m o u n t i n g The black box exposure is used to test a u t o m o t i v e finishes,
against a w o o d e n backing w o u l d m o r e closely simulate end a n d its specific p u r p o s e is to increase the t e m p e r a t u r e of the
use conditions. test panels to the s a m e as the nearly h o r i z o n t a l surfaces of a
A n o t h e r i m p o r t a n t criterion that can have an effect on the car. This test m e t h o d is d e s c r i b e d in ASTM Practice for Con-
o u t c o m e of an exposure test is the location a n d s u r r o u n d i n g ducting Accelerated O u t d o o r E x p o s u r e Tests of Coatings
obstructions in the i m m e d i a t e a r e a of the test site. In accor- (D 4141). C o m m i t t e e DO 1.27 on Accelerated Testing of Paints
dance with ASTM Practice for A t m o s p h e r i c E n v i r o n m e n t a l has c o n d u c t e d several studies r e g a r d i n g the black box [17],
E x p o s u r e Testing of N o n m e t a l l i c Materials (G 7), the test w h i c h was originally developed by General Motors. The box
r a c k is to be p l a c e d in a l o c a t i o n so that no s h a d o w from a is m a d e of a l u m i n u m , p a i n t e d black, with the p a i n t panels
n e i g h b o r i n g o b s t r u c t i o n shall fall on a n y s p e c i m e n w h e n the forming the top surface. The black box exposure also serves
sun's angle of elevation is greater t h a n 20 ~. Also according to
to lower the panel t e m p e r a t u r e overnight b e l o w that of the
ASTM G 7, the a r e a b e n e a t h a n d in the vicinity of the weath-
s u r r o u n d i n g air, creating a longer c o n d e n s a t i o n period.
ering racks should be c h a r a c t e r i z e d by low reflectance a n d by
The conditions as they affect the p a i n t panels are a good
g r o u n d cover typical of that climatological area. In desert
s i m u l a t i o n of the actual end use condition, so this test m a y be
areas this will be gravel, w h e r e a s in m o s t t e m p e r a t e areas the
considered by s o m e n o t as an accelerated test b u t as one that
g r o u n d cover will be low-cut grass.
is realistic of the end use for that climate. If the definition of
an accelerated o u t d o o r test is one w h e r e the influencing
ACCELERATED NATURAL WEATHERING conditions are altered over the o p e n - b a c k e d direct weather-
ing test, the Black Box Test is indeed a n accelerated test.
The possibility of deriving an accelerated test from o u t d o o r A further acceleration is i n t r o d u c e d using the H e a t e d Black
exposure seems like a m i s n o m e r . There are, however, m a n y Box Test. This is a black box i n c o r p o r a t i n g heating elements
test m e t h o d s that a i m to do just that. The basic idea is very inside the air space. The air t e m p e r a t u r e inside the box is
simple: to artificially increase the severity of the o u t d o o r m a i n t a i n e d at an artificially high level even w h e n there is no
exposure to b o o s t d e g r a d a t i o n rates. The s e c o n d a r y a i m of incident solar energy.
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Salt Spray The day-time spray is normally of very short duration, in-
tended as a harsh thermal and moisture shock to the paint
In Florida, corrosion tests are accentuated by spraying with
surface. The nighttime spray cycles are of longer duration,
salt water in the Scab Test. This uses the natural effects of the
intended to soak the paint thoroughly in a simulation of the
weather to break down the coating, then increases the corro-
overnight condensation effect. This occurs naturally very
sion at a scribe mark.
rarely in the desert of Arizona.
The paint panels are exposed to direct weathering at either
Both of these accelerated outdoor tests recognize the im-
45 or 5~ and are sprayed at regular intervals (normally twice
portance that wetness plays in deterioration. One important
weekly) with a 5% sodium chloride solution (Fig. 33). The
note here is that the timing of the water application is vital to
spray is scheduled for times when the paint panel will be dry,
produce the correct type of failure.
thus maximizing the absorption effect.
This test has proven to be an excellent method for deter-
mining the corrosion resistance of automotive coatings. The Follow the Sun
advantage is that the results are very similar to the results of
actual car corrosion determined from field studies. The si- Increasing the level of solar radiation for an outdoor test
multaneous effect of sunlight and saltwater produces an over- can be done in two ways. The exposure frame can be designed
all deterioration effect rather than a single failure mode as is to track the sun across the sky so that the specimens remain
usually given by salt fog tests such as ASTM Test Method of at normal incidence, which will yield greater radiant expo-
Salt Spray (Fog) Testing (B 117). sure. The limit for this test method is that the intensity level
cannot exceed 1 Sun. A simpler method simply adjusts the tilt
angle of the rack in response to the height of the sun in the
Spray Rack sky. This "variable angle" exposure uses the schedule outlined
The stresses due to moisture vapor content into and out of in ASTM Practice for Exposure of Cover Materials for Solar
the specimen are important for the overall breakdown of Collectors to Natural Weathering Under Conditions Simu-
most materials. Moisture vapor acts as a catalyst in the pho- lating Operational Mode (E 782), which is summarized in
tochemical breakdown process. In Arizona's desert environ- Table 5 and is based on the latitude of the exposure. The
ment with high temperature and solar radiation, exposure effect is to increase the solar radiation dosages up to 10%
tests are accelerated using the spray rack, which wets the over the fixed latitude angle rack.
specimens on a regular basis during the day and overnight.
The result produces an effect similar to Florida exposure,
Fresnel Reflector Concentration
plus a slight speedup in the deterioration rate. This rate of
increase has been seen as ranging from one to two times the An equatorial mount using an array of mirrors to reflect
rate for direct weathering in Florida. sunlight back onto an exposure frame will greatly increase
The exposure is conducted as a solid-backed direct weath- the incident solar enegy (Fig. 34). This is the Fresnel Reflector
ering, with the specimens sprayed daily on a regular basis Concentrated Sunlight device, as specified in ASTM Practice
during the night and/or day with distilled or deionized water. for Performing Accelerated Outdoor Weathering of Nonme-
FIG. 33-Salt spray testing (Scab Test) in Florida.
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FIG. 34-Fresnel reflector concentration device.
tallic Materials Using Concentrated Natural Sunlight (G 90) efficient. As a result, the m a c h i n e is n o r m a l l y e m p l o y e d in the
a n d w h e n used for testing coatings p e r ASTM D 4141. This desert, where clear skies a n d strong sunlight are f o u n d
type of exposure is m o r e closely related to that p r o d u c e d by a l m o s t every day. It w o u l d be incorrect, however, to say that
a n o t h e r accelerated device, the xenon arc, t h a n to o u t d o o r this device will not w o r k correctly out of the desert environ-
test methods. The c o n c e n t r a t i o n is a factor of one for each ment; the time for a c c u m u l a t i o n of energy, however, w o u l d
m i r r o r (less the efficiency of the reflector, w h i c h is a b o u t be greater.
80%), so in effect the solar i r r a d i a n c e on the s p e c i m e n is The test d u r a t i o n for the Fresnel Concentration is deter-
a b o u t eight times the n o r m a l incidence tracking frame. The m i n e d by solar r a d i a n t exposure, n o r m a l l y the total ultravio-
high intensity of the light exposure causes the s a m p l e t e m p e r - let. As the energy levels at the target b o a r d are too high for
ature to rise also; if a w a t e r s p r a y cycle is added, all weather- direct m e a s u r e m e n t s on a p e r m a n e n t basis, the dosage m u s t
ing factors are increased. be calculated from direct m e a s u r e m e n t s using a c o r r e c t i o n
The high intensity of the solar energy on the p a i n t causes factor for the reflectance of the mirrors. The m i r r o r m a t e r i a l
d e t e r i o r a t i o n rates of 4 to 16 times the rate for non- is chosen for its flat reflectance properties, t h e r e b y reflecting
accelerated exposure. There is no direct relation b e t w e e n all wavelengths equally. If the reflectance value of the m i r r o r
a m o u n t of r a d i a n t exposure a n d extent of d e g r a d a t i o n w h e n m a t e r i a l is m o n i t o r e d closely, it is possible to m a k e a c c u r a t e
the i r r a d i a n c e level is altered. Caution m u s t therefore be used calculation of the intensity level at the s p e c i m e n position.
w h e n quoting acceleration a n d correlation factors from test- W h e n the i r r a d i a n c e is integrated, dosage levels for the
ing on this machine. W i t h the sun as the energy source, m o s t Fresnel C o n c e n t r a t i o n Device are eight times greater t h a n
of the p r o b l e m of m a t c h i n g light sources is removed. This can n o r m a l incidence. One y e a r of r a d i a n t exposure from a fixed
o c c u r when using s o m e l a b o r a t o r y - a c c e l e r a t e d w e a t h e r i n g rack can be r e a c h e d in a b o u t six weeks exposure on this
devices. device.
The paint panels are m o u n t e d on a target b o a r d that is The c o m m o n t h r e a d to all o u t d o o r accelerated (or acceler-
p o s i t i o n e d upside d o w n on the b o t t o m of the air tunnel. The ated outdoor) tests is that one or m o r e factors have been
m i r r o r s are a r r a n g e d in a Fresnel array, whose focal p o i n t is increased to speed up the rate of the deterioration. This is
the target board. The panels are cooled by forced air from the usually i n t e n d e d to give the test a m o r e realistic c o m p a r i s o n
air tunnel, w h i c h is directed across the front a n d b a c k of the to an i n t e n d e d end-use environment. The exception to this
w o u l d be tests that increase solar intensity above naturally
panel. A set of nozzles is p o s i t i o n e d so that w a t e r s p r a y m a y
found levels.
be d i r e c t e d onto the face of the panels.
The device works o p t i m a l l y w h e n there is u n o b s t r u c t e d
direct b e a m r a d i a t i o n as the m a c h i n e is designed to follow
INSPECTION AND REPORTING
the sun a n d reflects only the i n c o m i n g energy from a small
solid angle. It is important, therefore, for the m a c h i n e to be
Visual
aligned with the sun at all times during the day. Clouds will
d i s r u p t the o p t i m u m condition, a n d overcast days will pre- I n t e r i m inspections of a m a t e r i a l to c h a r t the d e g r a d a t i o n
vent the Fresnel C o n c e n t r a t o r from o p e r a t i n g at its m o s t progression t h r o u g h o u t a n exposure p e r i o d will p r o d u c e ira-
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CHAPTER 52--NATURAL WEATHERING 6 4 1
p o r t a n t i n f o r m a t i o n on the rate at w h i c h a s a m p l e degrades TABLE 6--List of surface appearance standards.

a n d at w h a t t i m e interval certain p r o p e r t i e s b e c o m e notice- Property ASTM Method
able. To a c c o m p l i s h this, visual or i n s t r u m e n t a l techniques
Color change (v) ASTM D 1729
are used to assess the severity of degradation. Chalking
W h e n visual inspections are p e r f o r m e d at p e r i o d i c inter- Manual ASTM D 4214
vals, a n u m b e r of variables are i n t r o d u c e d t h a t m a k e it diffi- Tape ASTM D 4214, TNO
cult to get consistent a n d r e p e a t a b l e assessments. To mini- Dirt retention (p)
Mildew growth (p) ASTM D 3274
mize these variables, inspection p r o c e d u r e s m u s t be Checking (p) ASTM D 660
standardized. W h e n viewing specimens for color change or Cracking (p) ASTM D 661
for w e a t h e r i n g effects, it is very i m p o r t a n t to use the s a m e Flaking (p) ASTM D 772
light source a n d viewing conditions. F o r this reason, eval- Blistering (p) ASTM D 714
Surface rust (p) ASTM D 610
uations are c o n d u c t e d a c c o r d i n g to ASTM Practice for Vi- Scribe rust (p) ASTM D 1654
sual Evaluation of Color Differences of Opaque Materials Erosion (p) ASTM D 662
(D 1729). In this test m e t h o d , spectral qualities are outlined Color (i) ASTM D 2244
for different light sources, w h i c h are to b e used for various Gloss (i) ASTM D 523
evaluations. A viewing b o o t h will allow the m o s t consistent D of I (i) ASTM E 413
readings over an extended p e r i o d of t i m e as o p p o s e d t o exam- NOTE:( v ) = visual; (i) = instrumental; (p) = pictorial.
ining changes outdoors where daylight is not always the
same.
reporting. More c o m p l e t e descriptions of these effects can be
Reporting Scales found in o t h e r chapters of this manual.
W h e n evaluating the ability of a coating to w i t h s t a n d
w e a t h e r i n g effects, the changes over a p e r i o d of t i m e m u s t be
charted. To do this with consistency, r e p o r t i n g scales are
e m p l o y e d to r e c o r d the a m o u n t of change. In m a n y instances Nondestructive
it is not practical for the p e r s o n m o s t interested in the dura-
bility of a coating to see h o w a p a r t i c u l a r coating p e r f o r m s Nondestructive testing is a i m e d at inspection w i t h o u t the
over a p e r i o d of time. This is quite often the case as s p e c i m e n s d i s t u r b a n c e of the integrity of the specimen. This will, by the
are exposed in a different c o u n t r y or region of the United above definition, include mostly all the visual evaluations a n d
States in o r d e r to achieve answers in a s h o r t e r p e r i o d of time. all the i n s t r u m e n t a l l y assisted optical m e a s u r e m e n t s . True
This m a k e s it necessary to leave the inspection process up to nondestructive testing, however, is a i m e d at investigating de-
a n o t h e r individual. A p r o b l e m is the fact that no two people fects that c a n n o t be seen easily with the eyes or surface
perceive a degree of change in exactly the s a m e way. In o r d e r s c a n n i n g equipment.
to m i n i m i z e this p r o b l e m , certain p r o c e d u r e s are followed so Nondestructive tests aim to d e t e r m i n e physical changes in
that all interested parties will "'see" the defect(s) the same the structure of a m a t e r i a l that c a n n o t be d e t e r m i n e d vi-
way. This is done by using generally accepted e x a m i n a t i o n sually. It is particularly useful in seeing changes at the molec-
p r o c e d u r e s a n d the use of p h o t o g r a p h i c reference standards. ular level, in the b u l k p a r t of the material, or in underlying
The A m e r i c a n Society for Testing a n d Materials (ASTM), layers.
the F e d e r a t i o n of Societies for Coatings Technology (FSCT), Many of the c o m m o n physical tests e m p l o y e d to assist in
a n d the I n t e r n a t i o n a l S t a n d a r d s Organization (ISO) each evaluating the effect of w e a t h e r i n g are in fact "destructive,"
have e x a m i n a t i o n p r o c e d u r e s similar in quantitative descrip- The p a i n t s a m p l e is d i s t u r b e d during the m e a s u r e m e n t pro-
tions. The m a i n difference lies in the quantitative a n d qualita- cess, as in testing a d h e s i o n or chalking. W h e n a destructive
tive n u m b e r i n g scales used. FSCT uses a scale from 10 to 0, test is used, several disadvantages are evident: the s p e c i m e n
with 10 being "perfect" o r "absent of failures." ISO uses a c a n n o t continue exposure b e c a u s e the place w h e r e the test
scale from 0 to 10, with 0 representing a n " u n c h a n g e d " condi- was c o n d u c t e d will affect the continuity, a n d a p e r m a n e n t
tion. I n d e p e n d e n t test labs in the United States use the
r e c o r d of the c o n d i t i o n at that time is lost. These p r o b l e m s
ASTM/FSCT scale in their ratings unless i n s t r u c t e d otherwise
can be overcome by using a large n u m b e r of replicates so t h a t
by their client. It should be n o t e d that "perfect" is not a
there will be enough virgin m a t e r i a l for testing.
p r e f e r r e d term, a n d the testing labs will use the t e r m "as
W h e n the s a m e s a m p l e can be studied t h r o u g h o u t the test,
received."
it m a y be easier to get a m u c h clearer picture of the sequence
Failure Modes of events of the p r o g r e s s i o n of failure m e c h a n i s m . This is
Evaluating a n d recording type a n d degree of failure m o d e s especially true at the earliest sign of changes in the material.
in a p a r t i c u l a r coating is not a difficult task if visual inspec- If it is possible to d e t e r m i n e the changes that o c c u r at the
tions are p e r f o r m e d properly. Although m o s t ratings are sub- m o l e c u l a r level during the initial stages of d e t e r i o r a t i o n a n d
jective in t e r m s of degree of failure, an experienced a n d well- follow the p r o g r e s s i o n t h r o u g h to failure, it is possible to
t r a i n e d i n s p e c t o r consistent in his or h e r ratings is able to develop m o d e l s which will assist in p r e d i c t i n g long-term du-
p o r t r a y a good image of any d e g r a d a t i o n present. In o r d e r to rability from s h o r t - t e r m testing.
do this, all relevant s t a n d a r d s including the FSCT pictorial The range of m e t h o d s i n c l u d e d in nondestructive testing is
s t a n d a r d s m u s t be used w h e n applicable. Table 6 lists the varied, a n d Table 7 lists those which have b e e n d e m o n s t r a t e d
m o r e c o m m o n l y u s e d evaluation s t a n d a r d s for p a i n t failure to have an a p p l i c a t i o n in weathering.
www.iran-mavad.com

TABLE 7--List of nondestructive testing methods. REFERENCES

Property ASTMMethod
[1] Luckiesh, M., Artificial Sunlight, D. Van Nostrand Co., Inc., New
Electromagnetic ASTM D 1186 York, 1930.
Strain gage ...~
Infrared thermography ...a [2] Searle, N.D., "Weathering," Encyclopedia of Polymer Science
Electron microscopy ...a and Engineering, Wiley, New York, 1989.
X-ray radiography ...a [3] Mathew, W. R., "Predicting the Effects of Weathering on Color,"
Ultrasonic holography ...a Plastics Engineering, May 1986.
Video imaging systems ...~ [4] Bennett, I., "Monthly Maps of Mean Daily Insolance for the
aStandard for applicationto coatings being developed. United States," Solar Energy, Vol. IX, No. 3, July-September
1965.
[5] Juriaanse, A. and Zahradnik, B., "Natural Weathering of Poly-
TABLE 8--List of physical testing standards. propylene: Counteracting the Influence of Season and Exposure
Property ASTMMethod Orientation," Proceedings, ANTEC, 1986.
[6] Auld, W. E., natural weathering engineering drawings, personal
Impact ASTM D 2704 copy, 1961.
Elasticity
Elongation ASTM D 522 [7] Fischer, R.M., Murray, W. P., and Ketola, W. D., "Thermal
Bend ASTM D 522 Variability in Outdoor Exposure Tests," Progress in Organic
Hardness ASTM D 3363 Chemistry, Fall, 1990.
Adhesion ASTM D 3359 [8] Kreese, P., "Influence of Inert Pigments on the Anti-Corrosive
Abrasion ASTM D 4060 Properties of Paint Films," Polymers Paint and Colour Journal,
Mar 1978.
Chip resistance ASTM D 3170
[9] Lindberg, B., "Moisture and Painted Wood," Journal of the Oil
and Colour Chemists Association, June 1986.
[10] Evans, U. R., The Corrosion and Oxidation of Metals: Scientific
Principles and Practical Application, Arnold Publishing, London,
1960.
Mechanical Properties [11] Crewdson, M. J., "Corrosion Test Methods: A Further Review,"
National Coil Coaters Association Proceedings, April 1986.
There is a m a j o r distinction that m u s t be made between [12] O'Neill, T.B., "Succession and Interrelationships of Micro-
surface appearance changes in a material a n d intrinsic physi- organisms on Painted Surfaces," Journal of Paint and Coatings
cal properties. Changes can occur on the surface without Technology, Vol. 58, No. 734, 1986.
affecting the bulk of the material. [13] Likens, G. E., "Acid Precipitation," Chemical and Engineering
A m a j o r portion of a complete weathering p r o g r a m is the News, November 1976.
m e a s u r e m e n t of the physical changes produced during expo- [14] Crewdson, M.J., "The Present Status of Weathering in the
sure. A result of UV degradation a n d associated failure modes United States," Proceedings, Suga International Weathering
can have a direct impact on the relationship between stress Symposium, October 1988.
a n d strain of a coating and the elastic a n d inelastic reaction [15] Zerlaut, G. A., "Solar Radiation Measurements: Calibration and
Standardization Efforts," Advances in Solar Energy, American
w h e n force is applied. To have a better u n d e r s t a n d i n g of the
Solar Energy Society, 1982, pp. 43-66.
true performance of a weathered specimen, it is necessary to
[16] Sereda et al., "Measurement of the Time of Wetness by Moisture
perform tests to determine certain mechanical properties. Sensors and their Calibration," Atmospheric Corrosion of Metals,
Table 8 lists the more c o m m o n l y performed m e c h a n i c a l tests ASTM STP 767, 1982.
o n weathered p a i n t panels. A more complete description of [17] Morse, M. P. in Permanence of Organic Materials, ASTM STP
their relevance is given in other chapters of this m a n u a l . 781, ASTM, Philadelphia, 1982.
www.iran-mavad.com

MNLI7-EB/Jun. 1995
53
Accelerated Weatherin9
by Valerie D. Sherbondy I
PAINTS AND COATINGS ARE USED both to protect substrates and example, weathering factors are different for various parts of
to provide an aesthetically pleasing appearance. In an out- the world and for different countries. Some locations receive
door environment, both of these functions can be affected by more sunlight and heat, while others are cloudy and cool.
weathering. The four major factors involved in weathering There are also seasonal variations. Even for long-term test-
are sunlight, moisture, oxygen, and heat. Light, especially in ing, the data for a specimen placed outside during January
the ultraviolet (UV) region, may lead to discoloration, prema- would not necessarily concur with data for a duplicate speci-
ture loss of gloss, scaling, embrittlement, and chalking. Mois- men placed outside in July because of initial exposure effects.
ture may cause blistering, flaking, mildew, and early 10ss of Even if the same location and time of year are used, the
adhesion. Heat may cause embrittlement, cracking, peeling, natural weathering factors change from year to year. In con-
and checking. Oxygen in the atmosphere promotes oxidation trast to natural weathering, data produced under controlled
of the surface of the coating, which may eventually lead to laboratory conditions can be used as comparative data, as-
oxidation of internal layers, causing embrittlement, soften- suming the same equipment, equally aged lamps, etc., even if
ing, cracking, or crazing. These elements contribute individu- testing was conducted during different times of the year or
ally as well as in combination to cause coating failures. over several years.
Naturally occurring and man-made chemicals in the envi- In addition to reproducibility, a great advantage of acceler-
ronment also contribute to coating degradation and could be ated weathering is that the results are available more quickly
considered a fifth element of weathering. However, the type than with natural weathering, which is a phenomenon that
and levels of chemicals can vary dramatically, even over short may take years. The time saved on testing can translate into
distances. Therefore, they cannot be considered as universal cost savings when developing new products or when
in character as the four factors mentioned previously. Per- choosing a new coating system for buildings, tanks, or equip-
haps as a consequence of this, and also partly due to tradi- ment where historic data about coating performance are not
tion, chemical resistance testing is usually considered to be available.
separate from artificial weathering. Therefore, this chapter Even though there are many advantages to accelerated
will consider only those devices that incorporate an ultravio- weathering, it is important to recognize that these data
let light source. Although the effects of chemicals cannot be should be used for comparative purposes only since at this
ignored, they are discussed elsewhere in the manual. time a direct correlation to natural weathering has not been
Accelerated or artificial weathering involves the use of lab- proven for any weathering device currently being used. One
oratory equipment to simulate the degradation that occurs reason a correlation has not been developed is because data
during actual outdoor exposure [1-3]. Accelerated weather- obtained through artificial weathering have been produced
ing is the term most often applied to artificial weathering by subjecting the sample to unnatural conditions, and the
because the elements of light, heat, and moisture are either results may or may not duplicate those found during natural
longer in duration or more intense than the actual time and weathering. If similar failure modes are experienced in an
conditions encountered in outdoor exposure. This causes the accelerated weathering device and at an outdoor test site, a
coating to weather or degrade more rapidly, in a time sense, direct correlation may be developed for that product. The
than when placed in a natural environment. However, in an calculated correlation would be valid only for the tested ma-
attempt to accelerate the effects of natural weathering, the terial under the stated, specific conditions, and the actual
laboratory conditions may be overly aggressive and thus field conditions usually differ from the conditions found in a
cause results that are not attained during natural weathering. test fence area.
Artificial weathering devices should be designed to produce It should be noted that not all results obtained by acceler-
test conditions that are controllable and reproducible, so that ated weathering devices are reproducible [3]. Studies have
data are reproducible on a day-to-day basis and comparable concluded that even though the settings may be the same, the
on a laboratory-to-laboratory basis. This differs from outdoor maintenance of the device--including light source, filters,
or natural weathering where there are no controls over envi- and gauges--affect the exposure levels and thus the results of
ronmental factors. Due to this variability of conditions, the the testing. The cleaning and disposal of light filters is often
results of natural weathering often are not reproducible. For subjective and a major source of variation that changes the
amount of light at critical wavelengths. The intensity of the
~Assistant laboratory director, KTA-Tator, Inc., 115 Technology light is also dependent on the changing of, rotation of, and
Drive, Pittsburgh, PA 15275. power supplied to the light source. These factors may speed
643
www.iran-mavad.com

up or slow down the degradation process due to changes in and the UV-C region is 200 to 280 nm. Although the UV-C is
both temperature and UV light exposure. Since this is known the most damaging region, these wavelengths are filtered out
to occur, testing specifications are sometimes written to in- by the atmosphere. Therefore, if light sources produced out-
clude a standard material with the test specimens or to input in this region, they would cause abnormal degradation
clude an actual measurement of the light during the testing. and their use should be avoided when performing accelerated
This measurement is discussed later in this chapter. weathering unless there is a possibility of UV-C exposure.
Even if the light source was not changing with time, each Both the UV-A and the UV-B regions cause degradation of
device has areas of more intense exposure. For this reason, coatings. The energy of the shorter wavelengths present in the
most devices have recommended manual rotation proce- UV-B region, - 9 1 to 102 kcal/mol (3.8 to 4.3 J/tool), cause
dures for the exposed specimens. These procedures should be more severe and rapid degradation of coatings than the wave-
performed at regularly spaced intervals to decrease the ef- lengths in the UV-A region. In the UV-B region, the energy
fects of uneven exposure. These effects would be greater on levels are high enough to break carbon-nitrogen, carbon-car-
short-term tests, where the specimens would not be moved bon, nitrogen-hydrogen, carbon-oxygen, and carbon-hydro-
through the different stages. gen bonds in the polymeric portion of the coating. In the
Aside from the conditions of the device, the conditions UV-A region, the longer wavelengths do not have sufficient
surrounding the device also affect performance. Most devices energy, - 7 1 to 91 kcal/mol (3.0 to 3.8 J/tool), to break certain
require a ventilated area to maintain ambient conditions so bonds, namely carbon-hydrogen. Thus, it is apparent that
temperature changes within the device can be maintained or UV-A radiation differs from UV-B radiation in both wave-
obtained. For example, a relatively high ambient temperature length and severity of damage.
may reduce the amount of condensation on some devices, The breaking of chemical bonds first leads to a degradation
while high amounts of ventilation may slow the temperature of the coating surface layers and is manifested by chalking,
recovery after a water spray in other devices. It should be fading, and loss of gloss. Once the outer layers of polymer are
noted that ambient conditions are not specified by ASTM lost, pigments are exposed. Without the protective polymeric
standards, although the manufacturers recommend general binder, the pigments can fade and erode, causing a change in
guidelines. Ambient conditions will vary between laborato- color and/or appearance.
ries, adding an unknown variable that may affect the results. Light has been simulated in accelerated weathering devices
by mercury arcs, open and enclosed carbon arcs, fluorescent
lamps, and reflection of collected sunlight. However, as the
E L E M E N T S OF W E A T H E R I N G results produced by accelerated testing were compared to the
results obtained from natural weathering, the light sources
There are many component factors that contribute to the were modified to attempt to achieve similar results. Depend-
weathering of a coating. The general components are light, ing on the exact coating type and the service environment,
moisture, heat, and oxygen, which are always present in vari- several different specifications have been developed that indi-
ous amounts. This section concentrates on these general cate which light source should be used. Most of these test
components and on how they are simulated and intensified. specifications require the use of open or "sunshine" carbon
arcs, xenon arcs, and fluorescent lamps. These light sources
were chosen since they were found to more closely simulate
L i g h t [4] the degrading ultraviolet light range of sunlight or to rapidly
Sunlight is composed of light from the visible, ultraviolet, produce dramatic changes in the coating.
and infrared regions of the electromagnetic spectrum (Fig. 1).
The damaging region of sunlight has been determined to be Enclosed Carbon Arc
the ultraviolet light (UV) region, especially the shorter wave- Originally, these lamps were used to test the light fastness
lengths ranging down to 295 nm. The portion of sunlight in of textiles. They were then combined with a water spray to be
the UV region is relatively small, only 5 to 7%, due to the an industry-wide artificial testing device. Although mercury
filtering effects of the atmosphere. The UV region has been and carbon arcs have been in use for over 75 years, when they
divided into three domains: UV-A, UV-B, and UV-C. The UV-A were used to test paint, it was discovered that they produce
region is 315 to 400 nm, the UV-B region is 280 to 315 nm, light that accelerates chalking and fading more than crack-
The Electromagnetic Spectrum

X-rays and gamma rays
~i - Ultraviolet Visible LI_
Infrared Microwave and radio
I I
Schuman
t
Ultraviolet .= n-
Infrared
,3 6
I I I I I i I I I I
0 100 200 300 400 500 600 700 800 900 1000
Wavelength--Nanometers (nm)
FIG. 1-The electromagnetic spectrum.
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CHAPTER 53--ACCELERATED WEATHERING 645
ing. The c a r b o n arc consists of neutral solid a n d cored c a r b o n CXW Sunshine Carbon Arc with Cortex D Filters vs.
electrodes. The flame p o r t i o n of the l a m p is enclosed in a Miami "Average Optimum" Global Radiation
borosilicate globe. The globe creates a semisealed atmo- 2.00
sphere that sustains the arc a n d filters out UV light b e l o w
275 nm. The l a m p s p r o d u c e two large spectral peaks t h a t Carbon
1.80 -
center n e a r 350 a n d 380 nm, b u t they deliver essentially no
emission b e l o w 340 nm, w h e r e the light is m o r e severe in its
d e g r a d a t i o n capabilities a n d m o r e d a m a g i n g to p o l y m e r i c N 1.20-
m a t e r i a l s (Fig. 2). I n addition, even the light in the visible

region, 400 to 800 nm, was also low c o m p a r e d to sunlight, W
o .80 - -
Z
m e a n i n g that any visible color change due to the change of <
the p i g m e n t w o u l d require a lengthy exposure. As a result, the
rr
Y
i n d u s t r y d e m a n d e d a light source that p r o v i d e d a b e t t e r sim- tr .40 - -
ulation of n a t u r a l sunlight, especially since m o r e d u r a b l e ma-
terials were being developed.
0.00 I I I I I I I
300 375 450 525 600 675 750
Open-Flame Carbon Arc W A V E L E N G T H - nanometres
I n response to i n d u s t r y d e m a n d s , the o p e n flame c a r b o n FIG. 3 - S p e c t r u m of light produced by a sunshine carbon arc.

Used with permission of the Atlas Electric Devices Co.
arc or sunshine c a r b o n arc was developed. This d e s c e n d e n t of
the c a r b o n arc p r o d u c e d a s p e c t r u m closer to that of sunlight.
The l a m p operates in a free flow of air instead of in a globe. Xenon Arc
The l a m p is c o m p o s e d of c o p p e r - c o a t e d electrodes a n d a The a d o p t i o n of the xenon arc l a m p for accelerated weath-
central core of rare earth. The l a m p is s u r r o u n d e d by a stain- ering devices was the next i m p r o v e m e n t in artificial weather-
less-steel filter frame that also acts as an air duct. The f r a m e ing equipment. The xenon l a m p consists of a b u r n e r tube a n d
holds flat, optical, heat-resistant, borosilicate glass panels a light filter system. There are two types of xenon arc lamps.
that filter p o r t i o n s of the lower wavelength light from the One type of xenon arc l a m p is cooled by w a t e r circulated
spectrum. The s p e c t r u m p r o d u c e d by this light source is t h r o u g h the l a m p housing. The cooling w a t e r also filters out
m o r e similar to that of sunlight in the region b e t w e e n 310 a n d the long-wavelength infrared light. The o t h e r type of xenon
370 n m (Fig. 3). However, there was still a spectral i m b a l a n c e l a m p is air cooled. Both l a m p types p r o d u c e a s p e c t r u m
due to a large b a n d b e t w e e n 370 a n d 450 nm, b u t the region closer to sunlight w h e n filtered a n d set at the correct ir-
b e t w e e n 450 a n d 800 n m was m u c h closer to n a t u r a l sunlight r a d i a n c e setting. There are several filters a n d c o m b i n a t i o n s of
t h a n the enclosed c a r b o n arc l a m p s h o w n in Fig. 3. The filters that can be used. The three c o m m o n filter c o m b i n a -
disadvantage of this light source is the emission b e t w e e n 260 tions used for artificial w e a t h e r i n g of p a i n t are quartz/boro-
a n d 310 nm, which includes a p o r t i o n of the u n d e s i r a b l e silicate, borosilicate/borosilicate, a n d quartz/quartz. The first
UV-C region. Although this light source was an i m p r o v e m e n t , c o m b i n a t i o n allows the UV region to extend d o w n to 270 n m
the i n d u s t r y requested the spectral d i s t r i b u t i o n of the light be (Fig. 4). The borosilicate/borosilicate c o m b i n a t i o n has a cut-
even closer to that of sunlight. off at 280 nm, w h i c h makes the s p e c t r u m closer to t h a t of
CDMC Enclosed Carbon Arc vs. Xenon Arc With Borosilicate Inner/Boro Outer vs.
Miami "Average Optimum" Global Radiation Miami "Average Optimum" Global Radiation
2.00 2.00
X e n o n .35 / 340 n
Enclosed C a r b o n 1.80 -- . J
1.80 - -
%
= 1.20 -- '~ 1 . 2 0 -
W W
o
z
.80- ~ .80 --
<
~ ,
< <
.40-- ~ .40 -
0.00 I I I I I I o.0o I I I I I I I
300 375 450 525 600 675 750 300 375 450 525 600 675 750
WAVELENGTH - nanometres WAVELENGTH - nanometres

FIG. 2 - S p e c t r u m o f light produced by an enclosed carbon FIG. 4 - S p e c t r u m of light produced by a xenon arc. Used with
arc. Used with permission of the Atlas Electric Devices Co. permission of the Atlas Electric Devices Co.
www.iran-mavad.com

natural sunlight, which cuts off at 295 nm. The quartz/quartz

combination produces a spectrum that extends to below 1.2
250 nm, i.e., into the undesirable UV-C region, and although
used to test coatings, it is the least popular of the three filter 1.0
combinations 9 E
r-
Since the xenon arc source decays as the lamp ages, the 0.8
irradiance of the light source should be monitored and can be E
controlled by adjusting the lamp wattage. Most new devices 0.6

have a monitoring system to compensate for the decay. The 0
t-
most c o m m o n settings are 0.35 or 0.55 W/m 2at 340 nm. Both 0.4
settings produce a spectrum with approximately the same ~5
cutoff wavelength (determined by the filter). The settings are I--
09
both within the range of natural sunlight. The 0.55 W/m 2
setting is closer to s u m m e r sunlight, while the 0.35 W/m z 0.0 I
setting is closer to winter sunlight. If the wattage settings are 260 280 300 320 340 360 380 400
varied, the degradation rate will change.
Wavelength (nm)
Fluorescent UV Lamps [5,6]
UVA-340 Compared to Summer Sunlight
The most recent development in light sources is the fluores-
FIG, 6-UV-A 340 lamps versus summer sunlight. Used
cent UV lamp. These lamps were not developed to simulate with permission of the Q-panel Co.
the entire spectral range of natural sunlight. Rather, they
simulate only the damaging UV region found in sunlight.
Currently there are three types of fluorescent UV bulbs. The because of the rate at which degradation takes place. Since
FS-40 and UVB-313 produce light with a m a x i m u m output at the cutoff of the UVA-340 lamp is higher, the degradation
313 n m (Fig. 5)9 The UVB-313 has a higher intensity and thus process takes a longer period of time than with the UVB-313
a greater weathering acceleration rate than the FS-40, The lamp, but may more closely match the degradation seen in
UVB-313 also has a higher, more stable output than the the field. Both lamps are c o m m o n l y used in the paint indus-
FS-40. Both of these lamps have outputs down to 275 nm, try, and the choice of UVA or UVB lamp depends on the need
which is below the cutoff of natural sunlight. The third type for either speed or accuracy 9
of fluorescent lamp is the UVA-340 lamp that produces a
spectrum very similar to that of natural sunlight (Fig. 6). The Lamp Stability
spectrum is made up of wavelengths in the UV-A region with Once a light source has been selected, it is assumed that
a small a m o u n t of the UV-B region wavelengths. The cutoff several tests run over a period of months or years can be used
matches that of natural sunlight. Although the results pro- to evaluate the relative performance of the paints 9 However,
duced by the UVA-340 lamp are closer to that of sunlight, the this assumption is not always true. The xenon-arc source is
UVB lamp is the most widely used fluorescent light source currently the only device that always is sold with the ir-
radiance measurement as an operating parameter and not
just as an option. Even with this control, the output of the
1.2 light source m a y vary depending on the care and mainte-
nance of the device9 The devices should be cleaned and
1.0 changed as r e c o m m e n d e d to ensure the most reproducible
and even spectral distribution and irradiance. The newer de-
~- 0.8 UVB-313 ~ j vices have the option of monitoring and adjusting the light
output for all of the different light sources. In the future,
these settings m a y become a required part of the report for
0.6
the testing results.
0
t- There are several monitoring instruments available to mea-
0.4 sure the light output including pyranometers, radiometers,
"0
t~ spectroradiometer, and light-sensitive materials 9 However,
-- 0.2 each of these devices m a y be used to measure different char-
J acteristics of light9 Two different-colored light sources could
0.0 .-<,. I I I I produce the same response if a pyranometer is used to mea-
260 280 300 320 340 360 380 400 sure the light. These devices measure the a m o u n t of radiant
power regardless of the spectral distribution. Even when fil-
Wavelength (nrn) tered to restrict the wavelength of light being measured, it
was found that the response was not sufficiently sensitive for
UV-B Lamps Compared to Summer Sunlight
the UV range.
U V B - 3 1 3 a n d FS-40 Radiometers have been modified with filters to select areas
FIG. 5-UV-B lamps versus summer sunlight, Used with per- of the spectral distribution 9 These are classified as wide band,
mission of the Q-panel Co. broad band, or narrow band. The wide-band instruments
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CHAPTER 53--ACCELERATED W E A T H E R I N G 647
measure the light output over a range of several hundred The theory behind cyclic moisture exposure is based on the
nanometers. Broad-band instruments function over a range permeation of the test liquid into the coating, which may
of 20 to 100 nm, while narrow-band instruments measure cause certain coatings to swell. During the drying cycle, re-
less than 20 nm. The most commercially successful radiome- verse permeation or evaporation will occur, causing the coat-
ter measured the total ultraviolet light using a wide-band UV ing to shrink, resulting in cyclic stressing of the system. The
filter. However, when these devices were used to measure process by which degradation takes place and how fast it will
natural sunlight in comparison to the light sources, it was occur is influenced by the permeability of the coating and the
found that sensitivity to shorter wavelength UV was less than contact time required to initiate water penetration. The rate
its peak sensitivity to visible light, which could be affected by of water and chemical degradation is increased by increased
temperature changes. temperature and ultraviolet light.
The currently used radiometer, developed for exterior Moisture can be simulated by water spray, condensation,
monitoring, has a narrow band filter and a thermoelectrically fog, or immersion. Depending on the device used, degrada-
cooled detector. This is suited for long-term use and is easily tion acceleration is possible by increasing the number of wet/
operated in the field by relatively inexperienced personnel. dry cycles or increasing the time of exposure. Since acceler-
For internal use and for the most accurate measurements, ated weathering devices run around the clock (and day after
spectroradiometers are available. These would not withstand day for that matter), it is possible to cycle the specimen
external use and normally require operation by skilled per- through several wet and dry periods and still meet or exceed
sonnel. the 8 h of average wetness found in natural weathering. An-
In contrast to actual light measurements, there are indus- other way to accelerate the damage caused by moisture is to
tries, other than the paint industry, that rely on the use of increase the time period of exposure to moisture. Prolonged
light-sensitive reference materials. The reference material is exposure may degrade coating just as much as the stresses
placed on the cabinet at the same time as the test samples and caused by wet/dry cycling.
monitored, usually for color changes, to evaluate the effec-
tiveness of the light source. These materials must be inher-
ently unstable to achieve the desired result. This instability
Temperature
should be considered when choosing a reference material. The third factor of weathering is heat or temperature. The
The reaction of some materials may vary widely, and the degradation of coatings occurs more rapidly at elevated tem-
sensitivity is often a result of the total environment, so all of peratures, and temperature variation can lead to expansion
the other factors of exposure must remain constant. One of and contraction stresses in the coating. These stresses may be
the major problems with using this technique in the paint magnified by the expansion and contraction of the substrate
industry is the short life of these materials relative to the itself, which can lead to cracking, peeling, checking, or loss of
more durable paint systems. adhesion. Temperature can also accelerate the effects of
Even with all of the variability of light sources, proper care other weathering factors such as light and moisture. In accel-
of the instrument can yield consistent results between labora- erated weathering, cyclic testing at only slightly elevated tem-
tories. Most of these instruments have been run for many peratures can produce accelerated results. The temperature
years with less monitoring and fewer quality-control proce- chosen for testing should be within the expected temperature
dures than are in use today, and the data have been accept- range of the service environment. Drastic increases in tem-
able over many years. This is due to the fact that most compa- perature are not necessary to produce noticeable effects and
nies understand that the test results can only be used relative in fact should be avoided. Testing at excessive temperatures
to other test results and to that end often include several can either cause premature or unreasonable failures or even
competitive materials in the test protocol. enhanced performance that would not be realized under ac-
tual use conditions. High temperatures may cause the coat-
ing to bake or cure excessively and cause it to become brittle
Moisture with decreased impact resistance, or it may become more
resistant to the environment than would occur if it were only
Another important characteristic of weathering is mois- air dried under ambient conditions. To prevent these occur-
ture. Moisture is commonly overlooked as a significant factor rences, temperatures near those of actual or expected expo-
of paint degradation because it is a common belief that struc- sure should be used. The temperature should be monitored so
tures are only wet when it rains, when they are splashed, and the data have meaning relative to other test results.
when they are immersed in fluids. Actual time-of-wetness
studies have shown that samples placed outside in several
different locations in the United States and Canada were wet Oxygen
approximately 30% of the time [7]. This averages to approxi- Changing the degree of oxygen exposure of specimens by
mately 8 h per day. The water in a natural environment is introduction of ozone or pure oxygen is possible with a few
caused by dew or condensation, rain, or melting snow or ice. testing devices, but this modification technique is not com-
The water may be absorbed or pass through the coating. If the monly practiced. Oxygen exposure is usually inadvertently
liquid passes through and interacts or reacts with a water- changed in artificial weathering devices. The condensation,
soluble material, an osmotic cell may be formed. If it passes fog, immersion, or water spray used to create moisture can
through the coating and reacts with the substrate, for exam- introduce oxygen to the test environment and the surface of
ple wood, the interracial bond between coating and substrate the panels. Even in natural weathering, oxidation of a coating
may be destroyed or weakened. surface usually occurs in the presence of moisture.
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Oxidation involves b r e a k i n g b o n d s within a cured coating.

E i t h e r p r i m a r y or s e c o n d a r y b o n d s m a y be affected by oxida-
tion. Since the oxidation process is different for different
chemical types (acrylic, epoxide, vinyl, etc.) of coatings, the
results of oxidation can range from e m b r i t t l e m e n t to soften-
ing along with crazing, cracking, o r discoloration. Oxidation
usually begins as a surface p h e n o m e n o n that breaks d o w n
the o u t e r p o l y m e r i c b i n d e r layers. W a t e r can then pass
t h r o u g h the film to the i n n e r layers a n d cause further break-
d o w n (often at an accelerated pace) of b i n d e r a n d additives.
Other Factors
Although light, heat, moisture, a n d oxygen play i m p o r t a n t
roles in the d e t e r i o r a t i o n process, it should be r e c o g n i z e d
t h a t there are o t h e r factors that affect coating stability.
W e a t h e r resistance is d e p e n d e n t on the curing or drying
process, the s u b s t r a t e being painted, a n d a p p l i c a t i o n meth-
ods. These conditions c a n n o t be fully s i m u l a t e d u n d e r con-
trolled l a b o r a t o r y conditions since, as with n a t u r a l weather-
ing, these conditions are s e l d o m the same.
In actual service, most coatings experience e n v i r o n m e n t a l
factors that often continually change, are not reproducible, or
are unforeseeable at the t i m e of application. E x a m p l e s are
acid r a i n or o t h e r transient e n v i r o n m e n t a l pollutants. Chemi- FIG. 7-Xenon arc weathering device used with permis-
cal exposure, p a r t i c u l a r l y in the vicinity of chemical plants or sion of A.E.D. Co.
o t h e r heavy industrial environments, can also c o n t r i b u t e to
degradation. Testing for c h e m i c a l resistance is discussed
or s p e c i m e n r a c k rotates at 1.0 r p m for b o t h the c a r b o n arc
elsewhere in the manual.
a n d water-cooled xenon arc, a n d at 2.0, 3.7, or 5.2 r p m for the
air-cooled xenon arc to ensure u n i f o r m r a d i a t i o n on all sam-
ples. W a t e r is sprayed onto the specimens as a fine mist.
ACCELERATED WEATHERING DEVICES Exposure to light a n d to darkness is alternated, a n d the w a t e r
s p r a y is intermittent. A blower in the base of the a p p a r a t u s
Carbon Arc and X e n o n Arc provides a flow of air t h r o u g h the c h a m b e r a n d over the
Carbon arc a n d xenon arc l a m p devices are u s e d to expose specimens. The airflow controls the t e m p e r a t u r e of the sam-
specimens to UV radiation, elevated t e m p e r a t u r e , a n d w a t e r ples a n d removes c a r b o n c o m b u s t i o n products. The speci-
spray. C a r b o n arc a p p a r a t u s principles a n d o p e r a t i n g proce- m e n s are m o u n t e d vertically on racks above a n d below the
dures are given in ASTM Practice for Operating Light-Expo- center line of the r a d i a t i o n source. During testing, specimens
sure A p p a r a t u s (Carbon Arc Type) With a n d W i t h o u t W a t e r should be exposed equally from the u p p e r a n d lower racks.
for Exposure of N o n m e t a l l i c Materials (G 23), a n d the test The light source for these devices should be chosen b y the
conditions for p a i n t a n d coatings are outlined in Practice for c h e m i c a l n a t u r e of the m a t e r i a l to be tested since the spectra
Conducting Tests on Paint a n d Related Coatings a n d Materi- of the various light sources are different a n d p r o d u c e differ-
als using Filtered O p e n - F r a m e Carbon-Arc Light a n d W a t e r ent w e a t h e r i n g results. F o r b o t h the c a r b o n arc- a n d the
Exposure A p p a r a t u s (D 822). The basic principles a n d oper- xenon arc-based devices, it is very i m p o r t a n t to m o n i t o r the
ating p r o c e d u r e s for xenon arc devices are f o u n d in ASTM levels of i r r a d i a n c e at a selected wavelength if the d a t a are to
Practice for Operating Light-Exposure A p p a r a t u s (Xenon- be used for c o m p a r i s o n purposes. This is r e q u i r e d b e c a u s e
Arc Type) W i t h a n d W i t h o u t W a t e r for Exposure of N o n m e - there is a progressive decrease in r a d i a t i o n intensity as the
tallic Materials (G 26).
l a m p ages. This can be o v e r c o m e b y progressively increasing
There are several devices m a n u f a c t u r e d b y several c o m p a -
the l a m p wattage, t h e r e b y m i n i m i z i n g the changes in inten-
nies that use either c a r b o n arc o r xenon arc light sources. The
sity, a n d b y m o n i t o r i n g the r a d i a t i o n o u t p u t as described in
basic a p p a r a t u s is outfitted with one or two c a r b o n arcs o r a
ASTM G 26. The n e w e r devices m o n i t o r a n d a u t o m a t i c a l l y
single xenon arc (Fig. 7). The s p e c i m e n r a c k varies in d i a m e -
ter with the d i a m e t e r d e p e n d e n t on the n u m b e r or type of adjust the wattage to keep the intensity constant.
l a m p s used since different r a c k sizes are used to a c c o m m o - Both c a r b o n arc a n d xenon arc p r o c e d u r e s include four test
date the change in i r r a d i a n c e from the different light sources. methods:
S a m p l e s should be m o u n t e d on the r a c k at a distance such 1. Continuous exposure to light a n d i n t e r m i t t e n t exposure to
t h a t the location of each s a m p l e assures that incident ir- w a t e r spray.
r a d i a n c e does n o t vary b y m o r e t h a n 5% from the average. 2. Alternate exposure to light a n d darkness a n d i n t e r m i t t e n t
The units usually have a u t o m a t i c t e m p e r a t u r e controls a n d exposure to w a t e r spray.
m a y or m a y not have a u t o m a t i c h u m i d i t y control. The d r u m 3. Continuous exposure to light w i t h o u t w a t e r spray.
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4. Alternate exposure to light and darkness Without water exterior of the specimen rack is exposed to room tempera-
spray. ture, and the ifiside is exposed to heat and humidity produced
A typical cycle used for evaluating coatings with these devices by the lights and a heated water bath. The condensation is
is 102 rain of light at 145 _ 5~ (63 +_ 3~ and 18 min of caused by the temperature differential that exists between the
light and water spray at 60 to 63 +__2.5~ (15.5 to 17 +_ 1.5~ front and back of the mounted specimens. The exposure can
be varied by changing the temperature, the length of the lighL
and/or the condensation segments of the cycle. A few models
Fluorescent UV/Condensation are also available with a spray option. The spray option can
With fluorescent UV bulb devices as described in ASTM be used to simulate thermal shock or erosion by water.
Practice for Operating Light- and Water-Exposure Apparatus The samples are mounted in brackets, which form the
(Fluorescent UV-Condensation Type) for Exposure of Non- cabinet wall. The panels are stationary and set at an angle so
metallic Materials (G 53), specimens are cycled between ex- condensate can run off the test surface and be replaced by
posure to UV light and condensation in a heated environment fresh condensate in a continuous manner. Vents along the
(Fig. 8). bottom of the chamber permit an exchange of ambient air
The light source for the QUV [8] and UV-CON [9] is com- and water vapor to prevent oxygen depletion of the conden-
posed of eight fluorescent lamps that produce light in the sate. The specimens are placed approximately 50 m m from
ultraviolet range. The light source may be any of the UV the lamps. Both the lamps and the panels should be manually
fluorescent bulbs produced. The particular bulb used will rotated at specified intervals to ensure even UV exposure. To
determine the nature and speed of results acquired. The maintain consistent irradiance, the fluorescent lamps are
FIG. 8-Fluorescent bulb/cyclic condensation. Used with permission of the Q-panel

Co,
www.iran-mavad.com

rotated after a specified number of hours with two of the The wet-dry cycles can be varied from 1 to 10 h. Since the
eight being replaced. By rotating the lamps and replacing cabinet is not outfitted with a light source, it is necessary to
only 25% of the light source at any one time, an almost manually move the panels from the Prohesion Cabinet to a
constant level of exposure is ensured. fluorescent UV/condensation device to incorporate the ele-
Various test cycles can be selected. If no conditions are ment of light into the test.
specified, ASTM G 53 suggests 4 h of UV light at 60~ and 4 h
of dark condensation at 50~ Test temperatures of 50, 60,
and 70~ are widely used. UV Light-Cyclic Immersion
A proposed ASTM method entitled "Standard Practice for
Conducting Cyclic Immersion/Atmospheric Exposure Tests"
Fluorescent UV-Salt Fog is currently being developed. Its intended use is for the cyclic
The Mebon Prohesion Cabinet [10] was originally devel- testing of specimens, either manually or automatically,
oped as an alternative to the standard salt fog cabinet, ASTM through an atmospheric environment and an immersion en-
Test Method of Salt Spray (Fog) Testing (B 117) for conduct- vironment. The atmospheric environment may consist of
ing corrosion resistance studies (Fig. 9). Recently it has been light, heat, air, and/or chemical gases or fumes. The immer-
suggested for use as an accelerated weathering device when sion portion of the cycle varies and is dependent on the con-
used in conjunction with a fluorescent UV condensation destruction material used to make the individual devices. In
vice [11]. addition, the liquid may be heated, cooled, oxygenated,
The Prohesion Cabinet introduces a spray or fog by means and/or filtered.
of an external reservoir and a peristaltic pump operating at a Cyclic exposure alternates wetting and drying of the sam-
flow rate of from 0.5 to 1.5 mL/h. Although a variety of solu- ples in combination with UV light. The immersion portion of
tions can be used, one consisting of 0.4% ammonium sulfate the cycle allows permeation of the test liquid into the coating.
and 0.05% sodium chloride (Harrison's solution) is recom- This imbibing of the test liquid may cause swelling of certain
mended for corrosion studies. A series of experiments with coatings and substrates that would not occur during a salt fog
this device indicated that, at least for corrosion rate studies, or condensation cycle. During the drying cycle, reverse per-
this solution provided more realistic results than the warm, meation or evaporation may occur, causing the coating to
5% sodium chloride solution used in salt fog cabinets shrink and cause cyclic stressing/straining of the system.
[12-14]. The conclusion that these test results were more Reactions during the immersion portion of the cycle are
realistic was based on an analysis of the corrosion products. influenced by the permeability of the coating and require
This analysis revealed that the amount of sulfur and chlorine time to initiate. The rate of water/chemical degradation is
salts on panels exposed to the particular salt solution was increased by increased temperature. However, long, hot ex-
similar to the amount and type found on the panels that had posures may cause abnormal degradation. The atmospheric
been corroded at an outdoor location. exposure after immersion may cause concentration of salts
The fog, introduced at ambient temperature, is eliminated and chemicals on the surface, further increasing the rate of
by forcing air through the device at 23 to 55~ Not only does degradation. Care should be taken to select exposure media
this assist in drying the panels, it also replenishes the oxygen. that approximate those expected during intended service.
FIG. 9-Mebon prohesion cabinet. Used with permission from Q-panel.
www.iran-mavad.com

The proposed standard currently lists four different devices are set at an angle to produce a shoreline effect during the
that meet the requirements. Description of three of the de- immersion cycle. The drying cycle is accomplished through
vices follows. heat generated during the UV cycle and evaporation.
The first device, the Envirotest [15], is commonly con- Various test conditions can be used, but the default cycle is
structed of stainless steel, but a model constructed of polyeth- 6 h at UV light exposure at 60~ 2 min of water spray, 6 h of
ylene is available (Fig. 10). The chamber contains a center condensation at 50~ and a maximum level of ponding water
axle with spokes for sample mounting. The lower half of the covering half of each sample. The UV light source may be any
test chamber contains the immersion solution. Four fluores- of the fluorescent bulbs and should depend on the material
cent bulbs with a heating element are contained in the upper being tested. The spray is limited to water at this time.
half of the chamber. The type fluorescent bulb, UVB-313, The third device is the Sunchex apparatus [17] is con-
UVA-340, or FS-40, should be chosen by the nature of the structed of corrosion-resistant material and is suitably sized
specimens to be tested. The distance of the samples from the for tabletop operation. An air-cooled xenon arc lamp and a
light source can be varied slightly by moving the sample horizontal specimen tray are housed in the device. When in
mounts, but they should remain constant during the testing test operation, specimens are alternatively exposed to UV
period. light, water, immersion, and heat.
The chamber is fitted with ports in both the atmospheric The immersion cycle is produced by a continuous water
and immersion sections. The ports are used for exhausting, flow over the specimen for a variable amount of time. The
draining, and/or recycling liquids or gasses. These ports also water depth has a maximum of 0.75 in. (1.9 cm). The dry
allow the immersion solution to be heated, cooled, filtered, cycle is accomplished by pumping the water from the speci-
and/or oxygenated during the test without disturbing the cy- men tray. The UV light exposure is provided by the 1500-W
cle. The immersion solution may be deionized, fresh, or salt lamp that is mounted approximately 21 cm above the speci-
water, acid solutions, or alkali solutions. men tray. Uniform radiation distribution over the samples is
The device allows use of a variety of UV light/immersion achieved by the use of parabolic reflectors, glass optical fil-
cycles and immersion solutions. However, a default cycle is ters, and reflective materials on the chamber walls.
rotation at a speed of 20 rpm, a rotation distance of 420 ~ a Various test conditions can be used. The light cycle is
pause of 4 h, a temperature of 140~ and an immersion variable from 1 to 999 min, and the immersion and dark
solution of tap water. periods can be varied between 1 and 99 min. A default cycle
The second device, the QUV/HO [16], is constructed of for paint test has not been developed since this device is
corrosion-resistant materials and encloses eight fluorescent currently being used in the plastic, rubber, and textile indus-
UV lamps, a heated water pan, specimen drawers, and provi- tries.
sions for deionized water spray. The samples are alternately
exposed to UV light, water spray, condensation, and immer-
sion. Fresnel Reflector
The immersion cycle is produced by water spray collected There are three methods for accelerating natural weather
in the specimen drawers. The depth of immersion is con- exposure: black box, heated black box, and fresnel reflector.
trolled by the time duration of the water spray and by These are described in ASTM Practice for Conducting Accel-
plugging overflow holes to a desired depth. The specimens erated Outdoor Exposure Tests of Coatings (D 4141). The
FIG. lO-Cyclic immersion/fluorescent bulb. Used with permission of KTA-Tator,

Inc.
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first two m e t h o d s accelerate the w e a t h e r i n g by increasing the

t e m p e r a t u r e of the exposed surface and are discussed in the
n a t u r a l w e a t h e r i n g section. The fresnel reflector is the only
m e t h o d that collects a n d intensifies n a t u r a l sunlight to accel-
1000
]
I
E
SPECTRAL REFLECTANCE
J
OF MIRRORS _ O
85 Z
o~
90 LU~
erate weathering. The basic principles for this m e t h o d are 600

found in ASTM Practice for Performing Accelerated O u t d o o r 400 LL
kU
W e a t h e r i n g of N o n m e t a l l i c Materials Using Concentrated "~
E UV IRRADIANCE rr
N a t u r a l Sunlight (G 90). It is p e r f o r m e d in the desert region c9 200 AT TARG ET rr
<
of Arizona using Sun-10, FRECKLE, EMMA, EMMAQUA, or ~, .J
o t h e r similar devices that involve the use of a m i r r o r a r r a y

[6,18]. A m o r e detailed d e s c r i p t i o n of this device is p r e s e n t e d 9 100
34 ~ S GLOBAL
AIR MASS 1.35 /~ IJJ
O_
u)
in the c h a p t e r that deals with n a t u r a l weathering. -~
The c o n c e n t r a t i o n of sunlight is achieved by collecting m" 60
sunlight on ten m i r r o r s a n d focusing the reflected light onto zO 40
DIRECT BEAM
the specimen. The a s s e m b l y is designed to actually follow the -<
a AIR MASS 1.35
t r a c k of the sun as it moves t h r o u g h the sky. The device is ~ 20
e q u i p p e d with a b l o w e r to regulate the surface t e m p e r a t u r e __
of the specimen. The m a x i m u m surface t e m p e r a t u r e that can >
be r e a c h e d is limited to no m o r e t h a n 10~ above the maxi- D 10
m u m t e m p e r a t u r e n o r m a l l y achieved by n a t u r a l weathering. 5
The test m a y be p e r f o r m e d with o r w i t h o u t w a t e r spray. The
w a t e r spray is provided by a n oscillating nozzle assembly, 4
w h i c h supplies deionized w a t e r as a fine, dense mist. The
w a t e r is s p r a y e d on the s a m p l e s for set cycle times. A corn- 2
m e n cycle is 8 m i n of w a t e r spray p e r hour. Exact cycles are
given in ASTM G 90.
Since this m e t h o d uses n a t u r a l sunlight, the s p e c t r u m pro- 300 320 340 360 380 400
d u c e d follows that of n a t u r a l sunlight b u t at a higher inten- W A V E L E N G T H , nm
sity level (Fig. 11). The testing can be p e r f o r m e d for specific FIG. 11-Spectrum of light produced by fresnel-reflectot test-
levels of solar exposure o r for specific time periods. The ing devices.
q u a n t i t y of light is m e a s u r e d b y a r a d i o m e t e r , a n d it is ex-
p r e s s e d as total solar r a d i a n t exposure. The preferred m e t h o d
is b a s e d on solar exposure since this accounts for the n a t u r a l REFERENCES
seasonal variations of sunlight. This allows, for example,
results o b t a i n e d in J a n u a r y to be directly c o m p a r e d to those [1] Kampf, G., Sommer, K., and Zirngiebel, E., "Studies in Acceler-
ated Weathering. Part I. Determination of the Activation Spec-
o b t a i n e d in July.
trum of Photodegradation in Polymers," Progress in Organic
Coatings, Vol. 19, 1991, pp. 69-67.
[2] Sommer, A., Zirngieble, E., Kahl, L., and Schonfelder, M.,
Ultrafast Weathering "Studies in Accelerated Weathering. Part II. Ultrafast Weather-
In contrast to all of the above methods, this technique of ing--A New Method for Evaluating the Weather Resistance of
ultrafast w e a t h e r i n g does n o t wait for visual changes to occur Polymers," Progress in Organic Coatings, Vol. 19, 1991, pp.
on the surface. At the present time, this m e t h o d is still being 79-87.
evaluated to d e t e r m i n e if there is any correlation b e t w e e n the [3] Fischer, R.M., Ketola, W.D., and Morrey, W.P., "Inherent
i n f o r m a t i o n g a t h e r e d using electron spin r e s o n a n c e (ESR) Variability in Accelerated Weathering Devices," Progress in Or-
s p e c t r o s c o p y to m o n i t o r radical f o r m a t i o n a n d n a t u r a l ganic Coatings, Vol. 19, 1991, pp. 165-179.
[4] Brennan, P. J. and Fedor, C., "Sunlight, UV and Accelerated
w e a t h e r i n g results [2]. The t h e o r y b e h i n d ultrafast weather-
Weathering," SPEAutomotive RETEC, 1987, Technical Bulletin
ing is b a s e d on the a s s u m p t i o n that the radicals w h i c h form
L-822, The Q-Panel Company, 2600 First Street, Cleveland, OH
within the first several hours of the test will reveal the relative
44145.
stability of the coating. F o r this testing, the process of radical
[5] Grossman, G., "Correlation of Weathering," Journal Coatings
f o r m a t i o n is i n d u c e d by ultraviolet r a d i a t i o n greater t h a n
Technology, Vol. 49, No. 633, 1977, pp. 78-82.
t h a t of sunlight. The light is filtered to remove u n w a n t e d [6] Fischer, R., "Accelerated Test with Fluorescent UV-Condensa-
s h o r t e r wavelengths a n d also focused on the s a m p l e using a tion," SAE Technical Paper, No. 84/1022, 1984.
cooled mirror. The s a m p l e is placed b e t w e e n the poles of a [7] Grossman, D. M., "Know Your Enemy: The Weather," Journal
m a g n e t in the microwave r e s o n a t o r of the spectrometer. The Vinyl Technology, Vol. 3, No. 1, 1981, pp. 12-19 (also available as
radical f o r m a t i o n is plotted as a function of light-exposure a reprint from the Q-Panel Company).
time. E a c h p a i n t will p r o d u c e a characteristic curve. If a [8] ASTM has found suitable devices available from Atlas Electric
correlation is f o u n d to exist, the curves of different paints are Devices Co., 4114 Ravenswood Ave., Chicago, IL 60613 and
then to be c o m p a r e d to d e t e r m i n e w h i c h exhibits the best UV from Quartzlampen GmbH, 6450 Hanau/Main, Germany (do-
light stability. This testing could be c o m p l e t e d over several mestic distributor is Batson Machinery, Inc., P.O. Box 3978,
hours instead of days, months, or years. Greenville, SC 28608).
www.iran-mavad.com

[9] ASTM has found suitable devices available from Q-Panel Co., [16] ASTM has found suitable devices available from the Q-Panel
26200 First Street, Cleveland, OH 44145 and from Arias Electric Co., 26200 First Street, Cleveland, OH 44145.
Devices Co. [17] ASTM has found suitable devices available from Suga Test in-
[10] Licensed by Mebon Limited, Nottinghamshire, England to struments Co., Ltd., 4-14 Shinjuku 5-chome, Shinjuku, Tokyo,
Q-Panel Co., 26200 First Street, Cleveland, OH 44145. 160, Japan.
[11 ] Skerry, B. S. and Simpson, G. H., "Combined Corrosion/Weath- [18] ASTM has found suitable devices available and used by DSET
ering Accelerated Testing of Coatings for Corrosion Control," Laboratories, Inc., Box 1850 Black Canyon Stage 1, Phoenix, AZ
Paper No. 412, Proceedings, Corrosion '91 symposium, The 85029 and at Sub-Tropical Testing Service, 8290 S.W. 120th
NACE Annual Conference and Corrosion Show, 1991, NACE, Street, P.O. Box 560876, Miami, FL 33156.
Houston, TX.
[12] Cremer, N. D., "Prohesion Compared to Salt Spray and Out-
doors Cyclic Methods of Accelerated Corrosion Testing," presen-
tation at Federation of Societies for Coatings Technology, 1989 BIBLIOGRAPHY
Annual Paint Show, reprinted by the Q-Panel Company.
[13] Harrison, J. B. and Tickle, T. C. K., Journal of Oil and Colour Hamburg, H. R. and Morgans, W. M., Hess's Paint Film Defects and
Chemists' Association, Vol. 45, 1962, pp. 571-575. Their Causes and Cure, 3d ed., Capman and Hall, London, 1979.
[14] Harrison, J. B., Journal of Oil and Colour Chemists' Association, Reich, L. and Stivala, S., Elements of Polymer Degradation, McGraw-
Vol. 62, 1979, pp. 18-25. Hill, New York, 1971.
[15] ASTM has found suitable devices available from KTA-Tator, Slusser, J., Kinmonth, R., and Leber, R., Atlas Sun Spots, Vol. 18,
Inc., 115 Technology Drive, Pittsburgh, PA 15275. Issue 39, 1988.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Biological Deterioration of
Paint Films
by David L. Campbell 1
D E S C R I P T I O N OF T H E P R O B L E M
Water-borne liquid paints can experience viscosity loss, pu-

trefaction, gas formation, color change, and pH drift as a
result of the degradation of some or all of the organic constit-
uents [1]. This deterioration can be caused by bacteria or
fungi-releasing enzymes in the paint or by enzymes which
have been introduced into the paint through contaminated
raw materials or equipment. Viscosity loss in water-borne
paints can also be caused by the presence of oxidants/re-
ductants in raw materials [2,3].
Micro- and macroorganisms can destroy both the decora-
tive and protective properties of paint films. Algal and fungal
growth can cause discoloration of water- and solvent-borne
paint films and ultimately destroy their integrity (Figs. 1 and
2). The susceptibility of paint films to attack by microorgan-
isms is determined in part by the chemical nature of the
nonvolatile binder, the choice of pigmentation, and the pig-
ment volume concentration. To a much greater degree, how-
ever, the susceptibility or resistance of a paint film to biologi-
cal attack is determined by the presence and concentration of
antimicrobial agents.
M I C R O O R G A N I S M S ASSOCIATED WITH
PAINT
Microorganisms associated with paint and paint films have

been well established. These organisms include bacteria,
fungi, and terrestrial algae.
The bacteria genera Pseudornonas, Aerobacter, Enterobac- FIG. 1-Fungus discoloration of paint films. Appearance of
ter, Flavobacterium, and Bacillus are frequently isolated from house one year after painting shows rapid fungal discolora-
spoiled paints [4,5]. Of these, the Bacillus are unique in that, tion of paint inadequately protected against microorganisms,
under conditions of stress such as heat, cold, or dehydration,
some are able to form spores which are resistant to high
fungi have been popularly labeled the trees and fruit of fungi.
temperatures and dry environments and more resistant to
In reality, they represent the two different growth forms in
bactericides. Opperman and Goll [6, 7] found anaerobic bac-
the life cycle of fungi. The mycelial structures are observed
teria in contaminated water-borne paints and raw materials.
The aerobic culture methods commonly used would not de- when the fungi are actively growing and reproducing. Spore
tect the presence of these bacteria, which are capable of clusters are found when conditions for growth and reproduc-
utilizing organic paint components as nutrients. tion are less favorable. Spores are more resistant to environ-
Fungi are present on the surface of paint films in two mental changes and antimicrobial agents than are the
forms. They may be present as thread-like structures techni- mycelial forms. Spores and spore clusters are frequently diffi-
cally referred to as mycelia or as clusters of spherical, usually cult to differentiate from soil or soot particles. Examination
black-colored, spores. These two different appearances of with a magnifying lens or microscope is frequently necessary
for positive identification by even the skilled microbiologist.
IProject manager, Technical Center, Rust-Oleum Corporation, Photomicrographs of the two different forms of fungal
8105 Fergusson Drive, P.O. Box 70, Pleasant Prairie, W153158-0769. growth are shown in Figs. 3 and 4.
654
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CHAPTER 5 4 - - D E T E R I O R A T I O N OF PAINT FILMS 655
FIG. 2-Fungus disfigurement of paint films. Appearance of house three years

after painting. Chalking of the paint has physically removed fungus from vertically
exposed areas, but, in absence of chalking under the eaves, fungus growth has
continued and showed an inadequately preserved paint.
cated the consistent presence of bacteria within the paint film

and at the paint-wood interface. Flavobacterium marinum
was by far the predominant bacterium isolated. Despite the
differences in the chemical nature of latex emulsion binders,
Drescher [I0] isolated essentially the same microorganisms
from latex emulsion paint films exposed at the same location.
The microflora of interior paint films in breweries, dairies,
canneries, and other food-processing plants were reported by
Krumperman [11] and included many fungi rarely found on
exterior paint films (Fig. 5). Prominent among these are As-
pergiUus sp. and Penicillium sp. Found to a lesser extent were
Cladosporium sp. and Aureobasidium pullulans. His investi-
gations again indicated the frequent occurrence of the bacil-
lus Flavobacterium marinum.
FIG. 3-Spores of fungus on a paint film. Magnifica-

tion x 150.
Numerous fungi are found on and within paint films, al-

though a few predominate. Goll and Coffey [8] were the first
to observe and report the wide-spread growth of
Aureobasidium pullulans. In isolation studies of oil and alkyd
paint films at six wide-spread geographical locations,
Rothwell [9] confirmed the predominance of Aureobasidium
puUulans but noted the close resemblance of, and predomi-
nance in certain geographical areas of Cladosporium species
(sp.). Other fungi frequently isolated include Ahernaria FIG. 4-Mycelia of fungus on a paint film. Mag-
dianthicola and Phoma pigmentivora. The same studies indi- nification x 75.
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FIG. 6-Test fence exposure of paints. Specimens are placed

5 ~ off vertical and are offset so that runoff from higher speci-
mens does not contaminate specimens below, This arrange-
ment allows different paint to be applied to each panel.
Accumulation (D 3274). Photographic reference standards

for rating the disfigurement of paint films are illustrated in
this method.
The composition of fungi and algae permits the use of
chemical identification. The ASTM Guide for Determining
the Presence of and Removing Microbial (Fungal or Algal)
Growth on Paint and Related Coatings (D 4610) contains
FIG. 5-Fungus disfigurement of paint films. Appearance of procedures for chemical, visual, and subculture determina-
ceiling in a food processing plant only six months after paint- tion of fungi and algae. The chemical procedure uses 5%
ing. The high humidity and the nutrients supplied by food aqueous sodium hypochlorite solution applied to the disfig-
processing create an environment especially favorable to ured area of the film with bleaching as an indication of algae
growth of fungi.
or fungi. The test has its limitations and thus should be
interpreted with some degree of caution. Insect eggs or fecal
Algae, which contain chlorophyll, manufacture their own material will bleach since both are composed of protein. The
organic carbon from atmospheric CO 2 and light energy in test should be limited to white or light-colored paint since on
photosynthesis. The nuisance growth of terrestrial algae on deeper-colored paint films the bleaching of fungal or algal
painted surfaces has been described by Skinner [12] and growth may be insignificant compared to that of the paint.
Drisko et al. [13]. The Cyanobacteria (blue-green algae) Os- Moreover, a heavy chalk face interferes with the test, and
cillotoria sp. and Scytonema sp. predominate in tropical con- areas discolored by metal may give false results. ASTM
ditions. Algae may be filamentous or unicellular organisms D 4610 therefore contains the visual and subculture proce-
and vary in color from green to brown to black. The green dures which can be used for confirmation of the chemical test
alga Protococcus sp. (Pleurococcus) is prevalent in the tem- results. A subculture may be made by applying a prepared
perate climates (Fig. 6). petri dish containing a raised convex surface of nutrient agar
culture medium directly to the surface to be sampled and
exerting moderate pressure. Replace the cover and incubate
D E T E R M I N I N G T H E P R E S E N C E OF for 72 h at 98~ (36.7~ Examine the agar surface visually in
FUNGAL OR ALGAL G R O W T H ON PAINT accordance with ASTM D 3274. The culture medium must
FILMS contain the nutrients necessary for growth of algae or fungi.
When doubt exists as to whether the defacement is due to

algae, fungi, or dirt, the surface can be examined using mag- ANTIMICROBIAL A G E N T S
nification of 10 to 100 to distinguish among fungal, algal,
or dirt disfigurement as described in the ASTM Test Method Chemical agents used to control or prevent the deteriorat-
for Evaluating Degree of Surface Disfigurement of Paint ing effect of microorganisms are referred to as microbistats if
Films by Microbial (Fungal or Algal) Growth or Soil and Dirt they do not kill microorganisms but prevent their reproduc-
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C H A P T E R 5 4 - - D E T E R I O R A T I O N OF P A I N T F I L M S 657
tion and as microbicides if they kill microorganisms. Most of TABLE 2--Microorganism cultures used for test methods.
the microbistats and microbicides used in paint films effec- Test Microorganism ATCCNumber
tively control fungi, algae, and bacteria by interfering with
ASTM D 2574 Pseudomonas aeruginosa 10145
their metabolic functions. Method 627 la Aspergillusoryzae 10196
Table 1 lists more frequently employed antimicrobial Nuodex Aureobasidium pullulans 9348
agents used in paints as bactericides, algicides, or fungicides Hutchinson Aspergillus flavus 9643
as r e c o m m e n d e d by the manufacturers. AspergiUus niger 9642
PeniciUium funiculosum 9644
ASTM D 3273 Aureobasidium pullulans 9348
Aspergillus niger 9642
Penicillium citrinum 9849
DETERMINING MICROBIOLOGICAL aFederal Test Method Standard 141.
R E S I S T A N C E OF P A I N T S
The microbial resistance of paints and paint films is an employ synthetic growth media. These are summarized in
important characteristic of such paints, and considerable at- Table 3.
The more c o m m o n l y employed tests include the following.
tention has been given to developing laboratory and field tests
that will predict the resistance of paints to biodeterioration.
Some of the tests require the use of pure culture microorgan-
Bacterial R e s i s t a n c e o f Liquid Paints
isms. Those employed are listed in Table 2 and m a y be ob-
tained from: American Type Cultures Collection, 12301 Resistance of emulsion paints in the container to attack by
Parklawn Drive, Rockville, Maryland 20852. Many tests bacteria can be determined in accordance with the ASTM
Test Method for Resistance of Emulsion Paints in the Con-
tainer to Attack by Microorganisms (D 2574). This test pre-
TABLE 1--Antimicrobial agents used in paints and paint films. dicts the package stability of water-thinned latex emulsion
ALGICIDES paints as related to bacterial growth in the paint and degrada-
diiodomethyl-p-tolylsulfone tion of organic constituents.
2-methylthio-4-tert.-butylamino-6-cyclopropylamino-s-triazine
The test consists of two parts. The paint under test is first
FUNGICIDES cultured on tryptone glucose agar to determine if living bacte-
diiodomethyl-p-tolylsulfone ria are present. A negative result indicates the absence of
barium rnetaborate
2 -n-octyl-4-isothiazolin-3 -one bacteria but not necessarily resistance to attack. To deter-
potassium dimethyldithiocarbamate mine if the test paint can withstand bacterial attack, a speci-
methylene bis(thiocyanate) men of "spoiled" paint containing Pseudomonas aeruginosa is
2-(thiocyanomethylthio) benzothiazole introduced into the test paint, and the latter is incubated at
2-(4-thiazolyl)benzimidazole
N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide r o o m temperature for a period of six weeks. At intervals of 24,
zinc dimethyldithiocarbamate 48, and 72 h and at one-week intervals for the remainder of
zinc 2-mercaptobenzothiazole the test period, the inoculated test paint is streaked on
3-iodo-2-propynyl butyl carbamate tryptone glucose extract agar slants. The test paint is reported
tetrachloroisophthalonitrile to be resistant to bacterial attack if no living organisms can be
N-(trichloromethylthio)phthalimide
tributyltin benzoate recovered through six weeks of incubation. Conversely, the
tribntyl tin salicylate paint is reported to be "not resistant to bacterial attack" if
tributyltin oxide living bacteria are recovered at any time during the incu-
zinc oxide bation period. The principal difference between the ASTM
BACTERICIDES test and previously employed tests of this type is the use of
tributyltin oxide "spoiled" paint as an inoculum, rather than aqueous suspen-
tributyltin benzoate sions of bacteria removed from laboratory growth medium.
barium metaborate
potassium dimethyldithiocarbamate By employing paint containing P. aeruginosa, already
p-chloro-m-cresol adapted to a paint environment, the shock of a drastic envi-
alkylamine hydrochlorides ronmental change is eliminated. Repeated inoculations m a y
6-acetoxy-2,4-dimethyl- 1,3-dioxane be necessary to obtain a "spoiled" paint for use as an inocu-
tetrahydro-3,5 -dimethyl-2H- 1,3,5,-thiadiazine-2-thione
2 (hydroxymethyl)amino ethanol lure, but once prepared, it can be maintained indefinitely.
1,2-dibromo-2,4,-dicyanobutane
1-(3-chloroallyl)-3,5,7-triaza- 1-azoniaadamantane chloride
hexahydro- 1,3,5-triethyl-5-triazine Measuring the Fungal R e s i s t a n c e of Paint Films
2-(hydroxymethyl)amino-2-methyl-1-propanol
4-(2-nitrobutyl)morpholine The inability to duplicate the use environments of exterior
3,4,4-trimethyloxazolidine and interior paint films has made it difficult to develop suit-
4,4-dimethyloxazolidine
5-chloro-2-methyl-4-isothiazolin-3-one able accelerated tests for the evaluation of their funsal resist-
2-methyl-4-isothiazolin-3-one ance. Most laboratory tests have been based on the widely
1,2-benzisothiazolin-3 -one used agar plate method or modifications of it. Simply de-
1,3-bis(hydroxymethyl)-5,5 -dimethylhydantoin scidbed, the agar plate test consists of placing a painted sub-
hydroxymethyl-5,5-dimethylhydantoin
strate on a bed of agar, inoculating the system with the test
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TABLE 3--Formulae of growth media for bacteria and fungi.

Tryptone Federal
Glucose Test
Extract Method Malt
Ingredient Agar~ 6271 Agar~ Hutchinson Zabel
NaNO3 -.. 3.0 g . . . . . . . . .
NH4NO3 . . . . . . . . . 1.5 g ...
NH4SO4 . . . . . . . . . . . . 1.47 g
KCI ..- 0.25 g ... 0.5 g ...
MgSO4. . . . 0.5 g ... 0.5 g 0.5 g
7H20
KH2PO4 . . . . . . . . . . . . 10.0 g
K2HPO4 .-. 1.0 g ... 1.0 g 0.5 g
Agar 15.0 g 15.0 g 15.0 g 15.0 g 15.0 g
Glucose 1.0 g . . . . . . . . . 10.0 g
Sucrose -.. 30.0 g . . . . . . . . .
Malt . . . . . . 30.0 g . . . . . .
extract
Tryptone 5.0 g . . . . . . . . . . . .
Beef extract 3.0 g . . . . . . . . . . . .
H20 to 1000 mL 1000 mL 1000 mL 1000 mL 1000 mL
make
aPrepared Tryptone-GlucoseExtract Agar and Malt Agar may be obtained from Difco Laboratories, Inc.,
Detroit, Michigan,and Baltimore BiologicalLaboratories, Inc., Baltimore, Maryland.
organism, a n d observing growth during a prescribed incu- Nuodex Method

b a t i o n period. I n order to improve the accuracy of the mildew test as
required by the exterior p a i n t Federal Specification TT-P-19,
Federal Test Method Standard 141
Nuodex laboratories modified the test as follows: Aure-
Method 6271 (Mildew Resistance) is the agar plate test obasidium pullulans replaced Aspergillus oryzae because it is
most frequently referred to in specifications for paints uti- the fungus most frequently isolated from exterior house
lized by agencies of the U.S. Government. This m e t h o d em- paints. Malt-extract agar replaced the sucrose-mineral salts
ploys sucrose, m i n e r a l salts, agar m e d i u m , and, in accord- agar because, in it, A. puUulans exhibits growth forms typi-
ance with Federal specifications TT-P-19 (Paint, Acrylic cally observed o n exterior paints rather t h a n yeast-like forms
Emulsion: Exterior), Aspergillus oryzae is the inoculating or- that it exhibits w h e n grown o n the sucrose-mineral salts agar.
ganism. The agar m e d i u m is prepared according to the recipe
s h o w n in Table 3. The pH of the m e d i u m may be adjusted to Hutchinson Method
5.5 to 6.5 with 0.1 N hydrochloric acid (HC1) or s o d i u m hy-
The H u t c h i n s o n Method [14] is similar to the Federal
droxide (NaOH). The m e d i u m is sterilized in a n autoclave for
Method 6271, b u t employs glass string rather t h a n filter paper
15 m i n at 15 lb/in. 2 (1.034 x 105 Pa) a n d 121~ Approxi-
as the p a i n t substrate, a liquid broth culture m e d i a contain-
mately 30 mL is poured into each sterile petri dish a n d al-
lowed to harden. ing no c a r b o n source a n d a mixed s u s p e n s i o n of AspergiUus
The i n o c u l u m is prepared by adding 10 mL of sterile water
niger, AspergiUus flavus, a n d PeniciUium funiculosum.
c o n t a i n i n g 0.005% nontoxic wetting agent such as Tween-80
to a t u b e d subculture of A. oryzae. The mixture of spores a n d ASTM Test Method for Resistance to Growth o f Mold
mycelia are removed by gently stroking the agar surface with
on the Surface o f Interior Coatings in an
a sterile camel's hair brush. The aqueous s u s p e n s i o n is re-
Environmental Chamber (D 3273)
moved a n d diluted with sterile water to 100 mL. This test is used to evaluate the resistance of interior p a i n t
The test p a i n t is b r u s h e d o n each side of a sheet of films to fungus attack a n d reportedly provides m o r e accurate
W h a t m a n filter paper No. 3.0, or equivalent, a n d allowed to results by virtue of removing the artificial aspects of the
dry for 24 h. Squares of the p a i n t e d filter paper, 1.25 in. previously described laboratory method. Test paints are ap-
(3.18 cm) o n the side, a n d with guide lines of waterproof ink plied to either white pine or gypsum b o a r d panels m e a s u r i n g
1/8 in. (0.32 cm) from each edge, are centrally placed o n the 3 in. (7.0 cm) by 4 in. (10.2 cm) by 0.5 in. (1.3 cm). Two
agar surface of each dish. Using a sterile pipet, 1.0 to 1.5 m L coats of p a i n t are applied to both sides a n d all edges of the
of the diluted spore-mycelial i n o c u l u m is distributed over the panels at a spreading rate of 450 ft/gal (11.1 m/L) per coat.
painted surface a n d s u r r o u n d i n g agar surface. Duplicate The specimens are then conditioned at 75~ (24~ a n d 50%
plates should be prepared. The inoculated agar plates are relative h u m i d i t y for four days after application of the last
i n c u b a t e d for seven days at 28 to 30~ a n d 90% relative coat before being placed in the test chamber. The c h a m b e r
humidity. At the end of the i n c u b a t i o n period, the specimens m a y be any cabinet capable of m a i n t a i n i n g a relative h u m i d -
are examined visually at 1 a n d approximately x 18 magnifi- ity of 95 to 100% a n d a t e m p e r a t u r e of 90~ (32~ a n d l a r g e
cation. Fungal growth on the agar surface or o n the edges of e n o u g h to a c c o m m o d a t e specimens, a water bath, a n d a soil
the painted filter paper is ignored, a n d such specimens are bed that serves as a n i n o c u l u m source. The soil bed is con-
considered to pass the test if free of growth w i t h i n the guide- structed of a stainless steel or plastic tray with a m o n e l m e s h
lines. b o t t o m (16 mesh). The soil employed is a good quality, green-
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CHAPTER 54--DETERIORATION OF PAINT FILMS 6 5 9
house grade potting soil containing 25% peat moss. The pH of Sterilization and Specimen Assembly
the soil is maintained between 5.5 and 7.6. The soil is inocu- The chambers are autoclaved for 40 rain at 121~ stored at
lated with spore and mycelium suspensions of Aure- room temperature for 24 h and cooled, then reautoclaved for
obasidium puUulans, Aspergillus niger, and Penicillium sp. 15 rain at 121~ After chamber cooling, the painted strips are
prepared from 10 to 14-day-old agar slants. At least 14 days inserted aseptically. The strips are positioned with the
should be allowed for the fungi to sporulate prior to begin- painted surface up at about a 15~ angle from:the vertical and
ning any tests. center inserted until the bottom of the painted zone is about
Panels can be placed in the cabinet at any angle desired. 0.5 cm above the vermiculite surface.
Inoculation of the paints is accomplished naturally by air-
borne spores. To maintain a continuous inoculation, a small Inoculation and Incubation
fan (1/250 HP operating at 300 rpm) is mounted on a wall of Spore suspensions of A. puUulans (ATCC strain 16624) are
the cabinet just above the level of the soil bed and directed prepared by growing the fungus for 14 days at 28~ on malt
over the surface of the soil. By virtue of the mesh tray bottom extract agar (25 g of malt extract and 15 g of agar per liter)
just above the water bath, the soil remains moist to ensure plates. Discs (5 m m in diameter) of mycelium are cut from
maximum growth of the fungi. The test panels are rated for the pigmented margin of the colony and transferred individu-
fungal growth over a four-week period. When operating prop- ally into tubes containing 10 mL of sterile distilled water. The
erly, unpainted wood panels or paints containing no antimi- tubes are then agitated vigorously for 5 s on a vortex stirrer,
crobial agent should develop a 4 to 6 mold growth rating forming a uniform suspension of spores and mycelial frag-
within two to three weeks. The advantage of the environmen- ments.
tal chamber method is its close duplication of use conditions. The spore suspension is then aseptically pippetted on the
top (5 mL amounts per strip) of the painted zone on the
Zabel Test specimens and distributed so it runs uniformly down the
The Zabel Test [15] was developed to overcome the diffi- painted surface, The spore suspensions should be used within
culty in achieving the growth of Auseobasidium pullulans in 1 h of preparation, The stain chambers are then incubated at
the ASTM environmental chamber. The procedure involves 28~ for 30 days. Darkness is maintained except lighting for
five major steps: (1) the preparation and treatment of par- occasional observation.
tially painted wood specimens; (2) the preparation of stain
chambers; (3) sterilization of the specimens and assembly in Disfigurement Evaluation
the stain chambers; (4) inoculation of the painted wood and Blue stain development in the wood and fungus growth on
incubation; and (5) disfigurement evaluation. the paint are observed and recorded weekly.
Specimen Preparation and Treatment Field Exposure Tests

Because of the many different angles of exposure and de-
Flat strips of veneer (7.5 cm long, 3.0 cm wide, and 0.5 cm
gree of protection of paint films on houses, buildings, and
thick) are cut from the sapwood of southern yellow pine. The
industrial plants, the only absolutely accurate field exposure
strips are heat sterilized for 20 rain at 121~ cooled, and then
test to measure the fungal and/or algal resistance of paint
painted by brushing one heavy coat on the upper half of one
films is the application of the paint on these structures. This is
surface. After the paint has set and hardened (two to three
not economically feasible, and thus it has been the practice to
days), the strips are soaked in distilled water for 15 rain,
apply and expose paints on panels affixed to test racks, pro-
placed individually in Petri plates supported on small glass
viding various angles of exposures (Figs. 6, 7, and 8). See
rods (or placed individually in large glass tubes and cotton
ASTM Practice for Determining by Exterior Exposure Tests
stoppered) and surface sterilized by steaming for 15 rain in
Susceptibility of Paint Films to Microbiological Attack
an autoclave at 100 to 101 ~ The painted specimens are then (D 3456).
ready for introduction to the stain chambers.
To ensure accurate measurements of fungal or algal resist-
ance, at least duplicate test panels should be mounted so that
Stain Chambers painted surfaces are exposed both totally to sun and rain and
The stain chambers are screw cap 16-oz French square protected from exposure as occurs on the underside of panels
bottles. These are vertically positioned, and 20 g of vermicu- exposed at a 45 ~ angle. Paints exposed to the atmosphere
lite are added. should be examined regularly during the period in which the
The agar medium is prepared according to the formula paint shows no chalking, since chalking of paint films fre-
shown in Table 3. A micronutrient solution is prepared as quently physically removes fungus growth from the surface.
follows: Fe(NO3)3.gH20, 723.5 rag; ZnSO4.7H20, 439.8 mg;
and MnSO4.4H20, 203.0 mg; dissolved in 600 mL of double
Insect-Resistant Paints
distilled water, cleared of precipitate with H2SO4 (CP grade),
and made to a final volume of I L. The micronutrient solution While insects do not pose a deteriorative threat to paints or
is added to the nutrient media in amounts of 2 mL per liter. paint films, their attachment to paints following application
The micronutrient-enriched nutrient media is then poured and prior to the hardening of the paint film presents a serious
into the vermiculite-containing stain chambers (100 mL per decorative problem in many geographical areas. Thus, insect-
chamber). A small square of filter paper is placed on the resistant paints are requested continuously, and tests mea-
surface to minimize vermiculite displacement during the suring this property are needed. The best-known test for mea-
pouring, then removed. suring insect resistance of paints is that devised by Westgate
www.iran-mavad.com

FIG. 7-Test fence exposure of paints. Overhanging eave

duplicates house construction and allows evaluation of fungus FIG. 8-Test fence exposure of paints. Specimens are placed
resistance in both protected and unprotected areas. Because at an angle of 45 ~ to accelerate weathering comparable to that
the overlapping siding permits runoff, only one paint system on roofs, window sills, and other similarly oriented areas.
should be used in any vertical area. Compare with Fig. 6. Because of early chalking of paint so exposed, such arrange-
ments are not suitable for evaluation of fungus resistance.
However, the underside of 45 ~ exposure provides excellent
and Bolton [16]. The essential feature of this laboratory
conditions for evaluating fungus resistance in protected envi-
method is a lethal chamber from a hiding power sheet,
ronments.
111/2 in. (28.6 cm) by 171/2 in. (44.5 cm). The treated paint is
applied at a definite spreading rate by means by a doctor
blade. The amount, in milligrams, of insecticide per square may be obtained in the pupal stage from biological supply
foot of dry film equals houses. The flies are transferred most easily from the rearing
cage to the lethal chamber by allowing them to fly upwards
45.4 WNI/A
toward a light. The rearing cage is placed on its back. On the
where door is placed a sheet of pressed wood containing a hole in
W = weight, pounds, per gallon of paint, which the capped test roll is inserted. A light is arranged
N = percentage of nonvolatile matter, above the test roll. The sliding glass door is now pulled out,
I = percentage of active ingredient in the nonvolatile and the flies stream upward into the test roll. The lower end of
portion of the paint, and the roll is closed with a second Petri dish after the specimen
A = area, square feet per gallon of paint. Convert to of flies (50 to 100) has been transferred. The flies may be kept
square meters per liter by multiplying by a factor of
under observation during the entire period of contact, which
0.025.
may be terminated within 30 s by blowing the flies into a
The sheet bearing the dried film is rolled up to the diameter
recovery cage supplied with food. After 24 h have elapsed, the
of a Petri dish and fastened in place with tape. This tube,
dead and living flies are counted, and the percentage mortal-
when capped on both ends with Petri dishes, forms a lethal
chamber that may be handled, observed, and stored with ity is calculated.
ease. It may also be taken apart and given a variety of treat- The method has been used to study many of the variables
ments between tests. that influence the action of insecticides in paints. Although
The test insects, for example, the common housefly Musca some insecticide-treated paints show pronounced and pro-
domestica, may be reared from eggs in the laboratory or they longed lethal action, the same results may be obtained with
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CHAPTER 5 4 - - D E T E R I O R A T I O N OF PAINT FILMS 661
sprays w h i c h deposit residues on the paints at a m u c h l o w er [8] Goll, M. and Coffey, G., "Mildew on Painted Surfaces," Paint, Oil
rate of application. and Chemical Review, POCRA, Vol. 111, No. 14, 1948.
[9] Rothwell, F. M., "Microbiology of Paint Films, IL Isolation and
Identification of Microflora on Exterior Oil Paints," Official Di-
gest, Federation of Paint and Varnish Production Clubs, ODFPA,
REFERENCES Vol. 30, 1958, p. 368.
[10] Drescher, R. F., "Microbiology of Paint Films, IV. Isolation and
[1] Howard, P.H., Saxema, J., and Durkin, P. R., "Review and Identification of Microflora on Exterior Emulsion Paints," Amer-
Evaluation of Available Techniques for Determining Persistance ican Paint Journal, APJOA, Vol. 42, No. 38, 1958, pp. 80-102.
and Routes of Degradation of Chemical Substances in the Envi- [11] Krumperman, P. H., "Microbiology of Paint Films, V. Micro-
ronment," EPA Report No. 560/5-75-006, 1975, p. 474. organisms Found on the Interior Paint Films of Food Processing
[2] Winters, H. and Goll, M., "Nonenzymatic Oxidative Degradation Plants," American Paint Journal, APJOA, Vol. 42, No. 38, 1958, p.
of Hydroxyethyl Cellulose Thickened Latex Paints," Journal of 72.
Coatings Technology, Vol. 48, No. 622, November 1976, pp. [12] Skinner, C. E., "The Role of Algae in the Deterioration of Deco-
80-85. rative and Marine Paints," Paint Research Association, Ted-
[3] Winters, H., "Viscosity Loss in Cellulosic Ether-Thickened Latex dington, Middlesex, England.
Paints Caused by Oxidant/Reductant Impurities," Journal of [13] Drisko, R. W. and Crilly, J. B., "Control of Algae Growth on
Coatings Technology, Vol. 52, No. 664, May 1980, pp. 71-76. Paints at Tropical Locations," Journal of Paint Technology, Vol.
[4] Winters, H., "Synthesis of Extracellular Cellulases in Aqueous 46, No. 595, August 1974, pp. 48-55.
Emulsion Coatings by Pseudomonads," Journal of Paint Tech- [14] Hutchinson, W. G., "The Use of Glass String as a Carbon-Free
nology, Vol. 44, No. 575, December 1972, pp. 39-46. Substrate for the Rapid Evaluation of Fungus Resistant Paints,"
[5] Buono, F., Stewart, W. J., and Freifeld, M., "Evaluation of Latex Report 5687, Office of Scientific Research and Development, 31
Paint Preservatives," Journal of Paint Technology, Vol. 45, No. Oct. 1945.
577, February 1973, pp. 43-53. [15] Zabel, R.A. and Homer, W. E., "An Accelerated Laboratory
[6] Opperman, R. A. and GoU, M., "Presence and Effects of Anaero- Procedure for Growing Aureobasidium pullulans on Fresh Latex
bic Bacteria in Water-Based Paint. I," Journal of Coatings Tech- Paint Films," Journal of Coatings Technology, Vol. 53, No. 675,
nology, Vol. 56, No. 712, May 1984, pp. 51-54. April 1981, pp. 33-37.
[7] Opperman, R. A., "Presence and Effects of Anaerobic Bacteria [16] Westgate, M.W. and Bolton, A. N,, Jr., "Testing Insecticidal
in Water-Based Paints. II," Journal of Coatings Technology, Vol, Paints," Scientific Section Circular, National Paint, Varnish and
57, No. 730, November 1985, pp. 33-38. Lacquer Association, No. 715, 1946.
www.iran-mavad.com

MNLI7-EB/Jun. 1995
Chemical Resistance
by Alan H. Brandau 1
THE ABILITYOF A COATINGTO RESIST chemical deterioration or Other materials can also be used as specified by customer
staining is an essential element in its evaluation. What fol- or seller. The procedure utilizes open and watch glass covered
lows is a review of established test procedures with various spot tests with the reagent at ambient temperature as well as
levels of complexity and equipment sophistication that pro- immersion tests in the reagent.
vide a standardized tool for evaluating potential flaws such as
discoloration, softening, swelling, adhesion loss, gloss reduc-
tion, etc. These tests provide a c o m m o n ground for crucial Staining in the Transportation Industry
c o m m u n i c a t i o n of performance properties between the man- ASTM D 1308, mentioned above, is supplemented by
ufacturer and end user of a coating. Since these tests are to be ASTM D 1540, Test Method for Effect of Chemical Agents on
representative of actual exposure conditions, it is vital that Organic Finishes Used in the Transportation Industry. Mate-
the tests approximate, as closely as possible, genuine condi- rials or chemicals suggested as reagents include:
tions in the field [1].
9 Glycol-based antifreeze up to 100%
9 Acid, alkali, and salt solutions
9 Soap and synthetic detergent solutions
STAINING 9 Lubricating oils and greases
9 Polish abrasives, creams, and waxes
Staining tests provide a thorough method of determining 9 Road oils and tars
the ability of a coating to resist staining from household 9 Rubber, elastomers, plastics, tapes
chemicals, chemical reagents, and other materials c o m m o n 9 Gasoline
in today's environment. The tests generally expose the coat- 9 Water
ing surface to a spot of the reagent on the coating surface or 9 Hydraulic fluids
by immersion of a coated test panel in the reagent for a 9 Alcohol windshield washing solutions
specified period with timed check points. As with ASTM D 1308, discoloration, change in gloss, blis-
tering, softening, swelling, loss of adhesion, or other phenom-
ena are examined after testing. With some reagents, exposure
Staining from Household Chemicals to sunlight or UV light for a specified time is required. Ele-
Test Method for Effect of Household Chemicals on Clear vated temperature is also used to more closely simulate sur-
and Pigmented Organic Finishes, ASTM D 1308, encompas- face conditions in hot, sunny climates. Gasoline resistance
ses the evaluation of discoloration, change in gloss, blister- tests combine dripping of fuel at ten drops per minute at a 20 ~
ing, softening, swelling, loss of adhesion, or other phenom- angle with a UV lamp trained on the surface at a 90 ~ angle.
ena resulting from a variety of household chemicals. Adequate ventilation and safe handling of the dispensing and
Materials or chemicals suggested as reagents include: collecting vessels are essential to safety when working with
9 Distilled water, hot and cold gasoline. The staining potential of solid materials requires
9 Ethyl alcohol, 50% by volume close contact and heat exposure before evaluation.
9 Vinegar, 3% acetic acid
9 Alkali solution
9 Acid solution
Staining Resistance of Furniture Finishes
9 Soap and detergent solutions Staining resistance of furniture finishes is covered as part
9 Lighter fluid of ASTM D 2571 (Test Methods for Heat-Shrinkable Tubing
9 Fruit cut for Electrical Use), 11.0, Resistance to Oils, Greases, Cosmet-
9 Oils and fats ics, and Other Household Chemicals. This procedure is con-
9 Condiments cerned with materials such as cosmetics, alcohol, boiling
9 Beverages water, and coffee.
9 Lubricating oils and greases Boiling water and hot coffee, prepared by various methods,
are poured on a horizontal panel surface and allowed to dry,
IVice president, Marketing, Consolidated Research, Inc., 200 E. and the surface is examined for graying, spotting, softening,
Evergreen Ave., Mount Prospect, IL 60056. staining or other film deterioration. Cosmetics are applied to
662
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CHAPTER 5 5 - - C H E M I C A L R E S I S T A N C E 663
the coating surface and placed in a 50~ oven overnight and

examined for discoloration or film failure. Fifty percent alco-
hol or 100 proof vodka is trapped on the coating surface with
a watch glass for at least 6 h, allowed to evaporate, and then
observed for whitening or spotting that cannot be removed
with light polishing with a dry cotton pad.
SOLVENT/FUEL RESISTANCE
ASTM D 2792, Test Method for Solvent and Fuel Resist-

ance of Traffic Paint, relates a method of evaluating the resist-
ance of a coating to solvent and fuel that causes blistering,
wrinkling, loss of adhesion, and loss of hardness. The coating
is applied to tin panels and air dried for 90 h. Half the panel is FIG. 1-Battelle chemical resistance
immersed in the test liquid, and the vessel is covered for a cell, (Courtesy of Battelle Memorial Insti-
period of 4 to 18 h as may be specified by the customer. The tute.)
panels are then removed and examined for defects. The pan-
els are allowed to dry for another 24 h and reexamined for
film defects and softening as compared to the unimmersed
portion of the control panel.
If subtle differences between coatings are important such
as comparative research and development efforts, then the
panels can be examined more often without drying at inter-
vals such as 1, 2, 4, 6, 24, and 48 h.
Battelle Chemical Resistance Cell

Several advantages over other immersion methods are
claimed for this cell [2], which was developed in the course of
research sponsored by Steel Shipping Container Institute,
Inc. at Battelle Memorial Institute:
9 Panels may be flat or indented
s Edge effects area voided
9 Simultaneous testing in liquid and vapor FIG. 2-Bratt conductivity cell. (Courtesy of S. G. Wil-
9 Wider range of temperature son.)
The cell consists of a Pyrex glass tube, open at both ends,
held horizontally between coated test panels (Fig. 1). A conve- Gearhart-Ball Solvent Resistance
nient glass tube size is 2 in. (5.08 cm) in diameter and 3 in.
(0.762 cm) in length with the ends ground flat. Gaskets are Gearhart-Ball [4] solvent resistance tests utilize free coat-
used between tube and panels to give a liquid-tight seal. The ing films. The cup test employs fastening the free film over the
frame has screw adjustments for tightening the assembly. A top of a beaker or dish (Fig. 3). Approximately 20 mL of
sponge rubber pad behind one panel evens the pressure. A
glass ring is used to surround the dimple when an indented
panel is under test. The cell is filled through a hole in the
middle of the tube. In use, the cell is half filled and stoppered
tightly.
Bratt Conductivity Cell for Chemical Resistance

This cell [3], shown in Fig. 2, was designed to use conduc-
tivity of a film during chemical resistance tests as a measure
of its chemical resistance. The cell proper is a 2-oz vial from
which the bottom has been removed, in effect becoming a
short piece of glass tubing. The cell is formed by the base
plate and an additional plate with a hole that fits over the top
of the vial and rests on the shoulder.
During a test, a potential of 15 V is applied to the cell. The
metal substrate serves as the positive electrode. The external
resistance is selected to produce a voltage drop of about 14 V FIG. 3-Cup test for solvent resistance.
across the cell. (Courtesy of F. M. Ball.)
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/ \
_ _~__;_~_: IZ ~ - - ~ -
,,, L,..,,.J ,,,

l
I 3-' 2
=t~J
->~,
5" 9
t
t I
t "~[ Fl --.Iii/ ) ~ i Wood
~, Cork
Stopper
I/4"Dowel
Pins
I by 6" Test
Tube
I-Liter Chemically-
Resistont Gloss
Beaker
t 300 ml of Na OH
Solution to this Level
&
l
FIG. 4-Distensibility test for solvent resistance. FIG. 5-Apparatus for alkali resistance test.
(Courtesy of F. M. Ball.) A = specimen clamp; B =
tensile specimen strip; C = alligator clip and weight; D
= one inch distance marking. provides a quick relative test without having to wait for expo-
sure results. The MEK resistance of some two-component
solvent is poured over the film, and the length of time re- ethyl silicate zinc-rich primers has been shown to correlate
quired to puncture the film is noted. This test would be con- well with the cure of the primer as determined by diffuse
sidered a crude screening test. More precise data can be reflectance infrared spectroscopy.2
derived from the distensibility test where a tensile strength
strip (see ASTM D 2370.8) is clamped with either a tensile
tester jaw or an alligator clip on the upper end, and the ACID R E S I S T A N C E
bottom end is clamped with an alligator clip with a 12-g
weight and immersed in a clear beaker containing the solvent Acid resistance is determined by exposing a coated panel to
reagent (Fig. 4). The beaker is immediately marked with the freshly prepared mortar as well as a hydrochloric acid solu-
initial length, and the time required to elongate the strip one tion and is fully described in ASTM D 3260, Test Method for
inch is recorded. Resistance to Acid and Mortar of Factory-Applied Clear Coat-
ings on Extruded Aluminum Products. The acid resistance
test is performed by first sealing the edges of a specially
Solvent Rub Resistance
coated panel with a paraffin and beeswax mixture and then
Although solvent resistance can be evaluated using ASTM
D 1308, many use or adapt a solvent rubbing technique'with a
gauze cloth soaked in a solvent (MEK is common) and rub-
bing with the thumb back and forth in 2-in. (5.08-cm) strokes.
This procedure, ASTM D 4752, Test Method for Measuring
MEK Resistance of Ethyl Silicate (Inorganic) Zinc-Rich
Primers by Solvent Rub, is imprecise because the person's
strength and the size of the thumb is variable. Nevertheless, it
2Starr, T. L., Henton, L. E., Lewis, W. S., and Rideout, F. A.,

"Improved Field Reliability of High Performance Coatings Systems:
Phase II--Develop Procedures and Criteria in Critical Performance FIG. 6 - Q panel is
Areas," available from Steel Structures Painting Council, 4400 Fifth scored with an "x" to ex-
Ave., Pittsburgh, PA 15213. pose bare substrate.
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CHAPTER 55--CHEMICAL RESISTANCE 665
II] ~=::1
.'-'I:
+o T+r
1
2O
- ;' ",'~, )..+t 12A
I +16
ao
li- +-" 6
0--Angle of lid, 90 to 125 deg.

l--Thermometer and thermostat for controlling heater in base.
2--Automatic water levelling device.
3--Hurnidifying tower.
4--Automatic temperature regulator for controlling heater.
5--Immersion heater, nonrusting.
6---Air inlet, multiple openings.
7--Air tube to spray nozzle.
8--Strip heater in base.
9--Hinged top, hydraulically operated, or counterbalanced.
10---Brackets for rods supporting specimens, or test table.
1 l--Internal reservoir.
12--Spray nozzle above reservoir, suitably designed, located, and bamed.
12A--Spray nozzle housed in dispersion tower located preferably in center of cabinet.
13--Water seal.
14--Combination drain and exhaust+ Exhaust at opposite side of test space from spray nozzle, but
preferably in combination with drain, waste trap, and forced draft waste pipe.
16--Complete separation between forced draft waste pipe and combination drain and exhaust to avoid
undesirable suction or back pressure.
17--Forced draft waste pipe.
18--Automatic levelling device for reservoir.
19--Waste trap.
20---Air space or water jacket.
21--Test table or rack, well below roof area.
FIG. 7 - D i a g r a m of s a l t - s p r a y (fog) c a b i n e t .
immersing the panel in a 10 vol% solution of 31.6% solution coated surface and covering with a small watch glass, or just
of HC1 at ambient temperature for 6 h, followed by rinsing, leaving the material on the surface uncovered. The coating is
drying, and examination for blistering, peeling, lifting, craz- then checked for staining after a period of time or at 1, 2, 4, 6,
ing, flaking, or discoloration. Mortar resistance is performed 24, and 48-h intervals.
by applying a fresh mortar patty, prepared to a specified For detergent resistance of appliance finishes, a solution of
formula, to both sides of the specially coated panel and then a specified detergent containing a high percentage of sodium
placing in a high relative humidity cabinet for seven days. phosphate is applied and the temperature maintained at
The mortar is then carefully removed and the panel wiped off
165~ (73.8~ for the duration of exposure, usually 250 to
with a damp cloth followed by examination as with the acid
500 h. The test panel is submerged at least six inches into the
test.
solution. This is a more severe test than a spot test, but it is
more representative of actual service conditions. Examina-
tion is done after rinsing and blotting the panel and looking
ALKALI A N D D E T E R G E N T R E S I S T A N C E for any manifestation of coating failure.
ASTM D 1647, Test Method for Resistance of Dried Films
ASTM D 1308, Test Method for Effect of Household Chemi-
of Varnishes to Water and Alkali, describes an alkali resist-
cals on Clear and Pigmented Organic Finishes, is also recom-
ance immersion test using coated test tubes. The use of test
mended for evaluating alkali and detergent resistance. It is a
simple common sense technique that can be used for many tubes coated by dipping into the coating prevents the reagent
materials or chemicals that can stain or discolor a coating. from creeping under the edge of a flow-on film. As many as 20
The choice of testing materials should be related to the coat- tubes are prepared for this test, allowing examination after 1
ings end use. As previously mentioned, ASTM D 1308 de- to 8, 16, and 24 h (Fig. 5). The exposed specimens are rinsed
scribes techniques for either immersing the coated substrate with water and allowed to dry for 30 min before examining
in the reagent, putting a small amount of the material on the for whitening, blistering, or removal of the film.
www.iran-mavad.com

WATER A N D M O I S T U R E R E S I S T A N C E time. The metal panels are exposed to the settling fog of an
atomized neutral (pH 6.5 to 7.2) sodium chloride solution
There are a n u m b e r of types of chambers such as moisture consisting of 5 parts by weight sodium chloride and 95 parts
chambers, salt fog cabinets, and other accelerated weather- distilled or deionized water. The sample is then periodically
ing equipment that tests coating moisture resistance as well checked to see if the rusted exposed metal has propagated
as other resistance criteria. This type c h a m b e r is useful for under the coating causing coating failure. As with water re-
spot checking accelerated long-term environmental durabil- sistance, the results are compared to a standard or a specifi-
ity. But to be practical, all that is needed to test moisture or cation.
water resistance is to partially immerse a coated sample in a A typical salt spray cabinet as shown in Fig. 7 incorporates
glass beaker containing water. The water is maintained at a basic chamber, an air saturator tower, a salt solution reser-
100~ (37.7~ for an extended period of time, and the panels voir, atomizing nozzles, specimen supports, a heater, and
are periodically checked for discoloration, whitening, or blis- controls for maintaining specified temperature. Such cham-
tering of the film. The test results are compared to a specifica- bers are available commercially from several suppliers. The
tion or a standard sample run concurrently. The procedure testing procedure, ASTM B 117, Test Method of Salt Spray
for this test is ASTM D 870, Standard Practice for Testing (Fog) Testing, describes this method in more detail.
Water Resistance of Coatings Using Water Immersion.
REFERENCES
SALT FOG T E S T
[1] Lambourne, R., Ed., "Paint and Surface Coatings: Theory and
Salt fog resistance is important for marine, automobile, Practice," John Wiley and Sons, New York, 1987, pp. 664-671.
and aircraft coatings and any other exterior coating exposed [2] Nowacki, L. J., "Protective Linings for Steel Shipping Con-
tainers," Corrosion, CORRA, Vol. 14, 1958, p. 100.
to salt spray by being near the ocean or exposed to salted road
[3] Hough, R. W., Chairman, "The Bratt Conductivity Cell for Mea-
conditions. The severe corrosion caused by salt is well suring Chemical Resistance," Official Digest, Federation of Paint
known. The test requires a salt fog cabinet and coated panels. and Varnish Production Clubs, ODFPA, Vol. 31, 1959, p. 1460.
The coating is scored to the bare substrate with a X shape [4] Gearhart, W. M. and Ball, F. M., "Half-Second Cellulose Acetate-
(Fig. 6). The edges are sealed with a weather-proof tape, and Butyrate: IV," Official Digest, Federation of Societies for Coatings
the panel is placed in the cabinet for a specified period of Technology, Vol. 31, 1959, p. 1460.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Testing Coatings for Heat

Resistance and Flame
Retardance
by Wayne Ellis 1
HEAT RESISTANCE degradation including rust formation, blistering, loss of ad-

hesion, dulling, and ~chalking.
WHEN ORGANICCOATINGSare exposed to elevated tempera-
tures, the initial effect is usually softening, followed by hard-
ASTM M e t h o d D 1211
ening, embrittlement, and degradation. The rate of response
and the extent of degradation depend on coating composi- Another test method involving temperature exposure is
tion, temperature, and length of exposure. There is a distinc- ASTM Test Method for Temperature-Change Resistance of
tion in the terminology used to define the resistance of coat- Clear Nitrocellulose Lacquer Films Applied to Wood (D
ings to such changes. Below 400~ (200~ the property is 1211). A common failure of clear films applied to wood is
called "thermal resistance," while above that temperature the cracking or checking that may occur over a period of time,
property is identified as "heat resistance." Both thermal and either with the grain or at an angle to the grain. This "cold
heat resistance relate not to occasional heating, but to resist- check" test is designed to accelerate the occurrence of checks
ance to change from exposure to a constant heat influence or cracks by cycling at the temperatures of exposure. In this
over months or years. Special organic coatings can be for- procedure, which constitutes a single cycle, lacquer-coated
mulated to provide thermal resistance, such as those de- wood panels are first subjected to a temperature of 120 5~
signed to protect steel surfaces exposed to elevated tempera- (48.9 + 2.8~ for 1 h, followed by exposure at - 5 - 2~
ture during service life. The upper temperature limit for most ( - 21 l~ for 1 h, and then a return to room temperature
organic coatings is in the range of 400~ (200~ In general, for 30 min. The number of cycles used is a decision by the
inorganic coatings exhibit better heat resistance than organic testing agency.
coatings. A special group of products are thermal protection
coatings, including ablative coatings to protect space vehicles
during atmospheric re-entry and intumescent coatings that FLAME RETARDANCE
protect wood or other cellulosic surfaces exposed to fire.
Evaluation of heat resistance is carried out on coated speci- Terminology
mens exposed to selected temperatures representative of ser-
vice conditions and later subjected to other exposure condi- The technical terminology relating to flame retardance
tions to determine susceptibility to loss of protective func- must be understood. The general concept concerned is
tion. burning characteristics. (With one exception [1], these stan-
dard definitions are found in ASTM Terminology of Fire
Standards (E 176). Several interrelated terms are:
ASTM M e t h o d D 2 4 8 5 9 fire performance test--A procedure that measures the re-
sponse of a material, product, or assembly to heat or flame
Typical of this kind of testing is ASTM Test Methods for under controlled conditions. A fire performance test allows
Evaluating Coatings for High-Temperature Service (D 2485). the quantitative description of one or more fire perform-
This method provides an accelerated means of determining ance characteristics for the specific fire and other parame-
performance when coatings are exposed to high tempera- ters of the test.
tures. In Method A, for interior service coatings, coated steel 9 fire resistance--The property of a material or an assemblage
panels are heated for 24 h in a muffle furnace at a selected to withstand fire or to provide protection from it.
temperature. One panel is plunged immediately into water 9 fire retardancy--In paint, this is the ability of a paint to
for thermal shock, while another is cooled and then subjected retard the spread of flame over a coated suhstrate, usually
to a bend test. In Method B, for exterior service coatings, at the sacrifice of the paint film.
coated steel panels are heated in a muffle furnace at increas- 9 fire-retardant coating--A fluid-applied surface covering on a
ing steps of temperature from 400 to 800~ (205 to 425~ combustible material that delays ignition and combustion
One panel is subjected to salt spray for 24 h, while another is of the material when the coating is exposed to fire.
exposed outdoors for twelve months. When test exposures are o flame resistance--The ability to withstand flame im-
completedelhe panels are examined and evaluated for film pingement or give protection from it.
9 flame-retardant coating--A fluid-applied surface covering
~Deceased, formerly of Harleysville, PA. on a combustible material which delays ignition and re-
667
www.iran-mavad.com

duces flame spread when the covering is exposed to flame Tests for Combustibility
impingement.
A S T M Method E 136
9 flame-spread index--A n u m b e r or classification indicating a
comparative measure derived from observations made dur- ASTM Test Method for Behavior of Materials in a Vertical
ing the progress of the boundary of a zone of flame under Tube Furnace at 750~ (E 136) is a small-scale method de-
defined test conditions. signed to identify materials that do not aid combustion or
9 surface flame spread--The propagation of a flame away add appreciable heat to an ambient fire. This method is not
from the source of ignition across the surface of a liquid or intended to apply to laminated or coated materials; however,
a solid. it is useful in evaluating material believed not to be combusti-
ble.
Figure 1 shows a cross section of the vertical tube furnace.
The specimen, nominally 1.5 in. (38 mm) wide by 1.5 in. (38
mm) thick in cross section with thermocouples attached, is
Rationale for Test Selection inserted in a furnace controlled at 1382 + 10~ (750 +_ 5.5~
and held there until temperatures at the specimen thermo-
Note the conceptual difference in the definitions between
couples are at furnace temperature. The standard contains an
fire-retardant and flame-retardant coating. Testing coatings
instructive commentary section describing the rationale for
for burning characteristics may be carried out to compare the
the test, its limitations, and usefulness of the test results. This
response to flame exposure of different specimens or to evalu-
test method presently does not contain a precision and bias
ate the performance under fire conditions. In the former
statement.
mode, small-scale testing is appropriate. But, while small-
scale testing may be useful in preliminary evaluations in the A S T M Method D 2863
latter mode, large-scale testing is essential if test results are to ASTM Test Method for Measuring the Minimum Oxygen
be used as a measure of performance in fires in buildings or Concentration to Support Candle-like Combustion of Plastics
other structures. Small-scale tests are categorized as flame- (Oxygen Index) (D 2863) is a small-scale method that mea-
test standards. Large-scale tests are categorized as fire-test- sures the minimum concentration of oxygen in a flowing mix-
response standards. Only the latter are appropriate in fire risk ture of oxygen and nitrogen that will just support flaming
assessments. The scale of test is indicated in each of the combustion. Figure 2 shows the typical equipment layout.
following test method descriptions. Film or thin-sheet test specimens are nominally 2.0 in (52
T H E R M O C O U P L E LEADS T3AND T,
(THERMOCOUPLE T= PLACED AT
I t~P.ATI~hl r T 1=r IMITIAI
THERMOCOUPL
(204ram DOWN)
TERMINALS FOR 5(
NICHROME WIRE
~ES
~,L
ER
HIGH TE
INSULA1 l CYLINDER
YLINDER
:~COVER
SPACING AND SU
(3) FOR INNER C~t
METAL RING
Inch-Pound Equivalents
mm 76 102 152 254 273 6.4 cm 2 1.29
in, 3 4 6 10 10-V4 1 in.2 No, 16 Awg
FIG. 1 - C r o s s section of furnace assembly.
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CHAPTER 5 6 - - T E S T I N G COATINGS FOR H E A T R E SISTA N C E 669
GLASS COLUMN (MINIMUM DIMENSION 450 MM H x 75 MM ID)
METAL SHROU A~
(OPENING DIAM. = 50 MM)
GLASS COLUMN
SECTION A - A
OPTIONAL DEVICE FOR
RESTRICTING COLUMN
OPENING (SEE NOTE 3)
E NOTE 5)
1. BurningSpecimen 6. Glass Beads in a Bed 11. PressureGage

2. Clampwith Rod Support 7. Brass Base 12. PrecisionPressureRegulator
3. Igniter 8. Tee 13. Filter
4. Wire Screen 9. Cut-Off Valve 14. NeedleValve
5. Ring Stand 10, Orificein Holder 15. Rotameter
FIG. 2-Typical equipment layout.
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mm) wide and 5.5 in. (140 mm) long. The minimum oxygen The method is useful in laboratory comparison of intu-
concentration is measured under equilibrium conditions of mescent paint formulations, but large-scale testing by
candle-like burning. The equilibrium is established by the Method E 84 is desirable for correlation with real fire condi-
relation between the heat generated from the combustion of tions. Precision: Table 2 indicates the repeatability of this
the specimen and the heat lost to the surroundings as mea- method. The standard deviation shown relates to the maxi-
sured by one or the other of two arbitrary criteria, namely, a mum difference that would be expected between duplicate
time of burning or a length of specimen burned. This point is specimens. The degree of repeatability is dependent on the
approached from both sides of the critical oxygen concentra- level of flame-spread ratings.
tion to establish the oxygen index.
While this method is useful for comparing resistance to A S T M Method E 162
combustion of organic materials, correlation with burning ASTM Test Method for Surface Flammability of Materials
characteristics under actual use conditions is not implied. Using a Radiant Heat Energy Source (E 162) is a small-scale
Precision: In a testing program in which 18 laboratories procedure, intended for research and development purposes,
checked the same five materials, the standard deviation was for measuring the surface spread of flame under exposure to
0.4 for materials with an oxygen index below 21% and 0.7 to a radiant heat source. Figure 4 shows details of the test equip-
1.4 for materials with an oxygen index above 21%. Table 1 ment. The specimen, which is representative of the material
contains results from another test series. Bias: There are no or assembly being evaluated, has dimensions of 6 by 18 in.
recognized standards on which to base an estimate of bias. (150 by 460 mm) by the sheet thickness. It is placed at a
A S T M Method D 1360 downward angle of 30~ from the vertical, facing a gas-fired
porous refractory heat-radiating surface, 12 by 18 in. (300 by
ASTM Test Method for Fire Retardancy of Paints (Cabinet 460 mm), operating at 1238~ (670~ The rate at which
Method) D 1360 is a small-scale test method. This procedure flames travel along the surface depends on the physical and
measures the relative fire-retardant properties of coatings by thermal properties of the specimen. The orientation of the
determining the weight loss and char index of coated wood specimen is such that ignition is forced near its upper edge
panels exposed to flaming ethyl alcohol. It is useful for com- and the flame front progresses downward. The time of arrival
paring the burning behavior of coating materials under speci- of the flame front at each of 3-in. (76-mm) marks on the
fied conditions; however, the test results do not always corre- specimen holder is recorded, and observations are made for
late with large-scale spread-of-flame tests, such as ASTM Test
flashing, dripping, and any other behavior characteristics
Method for Surface Burning Characteristics of Building Ma-
that appear to be of interest. The maximum temperature rise
terials (E 84). D 1360 is a measure of combustibility, through
as indicated by thermocouples in the stack is recorded. The
weight loss, rather than a measure of flame-spread index
test is completed when the flame front has progressed to the
value. The precision of this method is yet to be determined.
15-in. (380-mm) mark or after an exposure of 15 rain, which-
ever occurs first, provided the maximum temperature of the
Tests for Flame Spread stack thermocouples is reached.
A flame-spread index, I~, is calculated as the product of the
A S T M Method D 3806
flame-spread factor, Fs, and the heat evolution factor, Q. F~ is
ASTM Test Method for Small-Scale Evaluation of Fire- calculated from a plot of
Retardant Paints (2-ft Tunnel Method) (D 3806) determines
the protection afforded to a substrate by a coating by evaluat- I s = FsQ
ing the flame spread over the coated surface when the speci- with vertical distance as a function of flame-arrival time at
men is ignited under controlled conditions in a small tunnel. each horizontal mark. The Q factor is calculated from the
Figure 3 shows the layout of the 2-ft (610 mm) tunnel appara- equation Q ~ CT//3, where C is an arbitrary constant, T is the
tus. The test panels are wood, 1/4 by 37/8 by 237/8 in. (6 by 100 observed maximum stack-thermocouple temperature differ-
by 605 mm). The tunnel apparatus is calibrated with a zero- ence between the temperature-time curve for the specimen
flame-spread panel and with another reference panel coated and that for a similar curve of a calibration specimen, and/3 is
with a paint rated for flame spread "by the method of ASTM E the mean stack thermocouple rise for unit heat input of a
84. A standard gas flame is applied to the lower end of the calibration burner. The flame-spread indices determined by
inclined test panel, and the progress of the flame front up-
this method may be compared with those determined in
ward is observed, measured, and recorded at 15-s intervals. ASTM Method E 84, although correlation is not necessarily
The test results establish a basis for comparing surface-burn-
obtained. A precision and bias statement for this method is
ing characteristics of different coatings without specific con-
being developed by ASTM Committee E-5 on Fire Standards.
sideration of all the end-use parameters that might affect
surface-burning characteristics under actual fire conditions.
A S T M Method E 84
ASTM Test Method for Surface Burning Characteristics of
TABLE I--Precision results.
Building Materials (E 84) is also called the 25-ft (7.6-m)
Laboratory-To-Laboratory Within Laboratory tunnel test, or the Steiner tunnel test, or the NFPA 255 test. A
Type Standard Deviation Standard Deviation
large-scale test, E 84 is applicable to exposed finishes on
B 0.5 to 1,1 Below 0,2 ceilings or walls. The test is conducted with the material in a
C 0.4 to 1.5 0.1 to 0.3 (est.) horizontal position with the exposed surface facing down-
D 0.5 to 1.4 Below 0.6
ward. The purpose of the test is to determine the relative
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CHAPTER 5 6 - - T E S T I N G COATINGS FOR H E A T R E S I S T A N C E 671
Materials of Construction and Equipment List

Description
Item No Item Description Item No Item
A Base Plate 1/2 x 10 x 24 Steel plate F Glare Shield 1/le x 21/= x 22 Metal sheeting
B Framework 1/g x 1 x Angle iron throughout G ignition Transformer 115 V, 60 Hz, 5000 V, 20 A secondary
C Side and Front Panels 1/4Transite cut to specifications H Spark Switch Push button type
D Side Glass 1/s x 2 x 24 Polished Vycor Cut as I Ceramic Insulator
ShOWn
E Burner Artificial Gas Model J Spark Wire 1Ae OD Nichrome
Gas Control Valve 1/a Orifice, 1" Pipe size, outlet 3 oz/in 2 K Thermocouple Megopak Type J, totally shielded
(not shown)
Gage, Gas (not shown) 0-30 oz/in 2 Dial Recording Potentiometer 115 V, 60 Hz, 0-300~ Type J concl
Note: All Dimensions Expressed in Inches Unless Otherwise Noted.
\liil~r,,. M,,,e,"'- M- IT
/"1 K J"lJ,,ft" 3. 73;,8 II v / It ";'1

-"d - k - 2 1/4 TO 115 V. A,-. ~ TO 3 oz./in 2 ~ 2 4 101/2 =J
SECTION A ~ A FRONT VIEW SIDE VIEW REAR VIEW

METRIC EQUIVALENTS
in. mm in. mm
%e 1.6 3 76
3/a2 2.4 4 102
l/a 3.2 7 178
1/4 6.4 7`% 187
i/= 12.7 10 254
1 25.4 101/2 267
11/z 38 18-% 480
21/4 57 22 560
2z/4 70 24 610
FIG. 3 - F l a m e tunnel.
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TABLE 2~Repeatability. ~ record smoke emission. Figure 5 shows details of the test
Flame-Spread Ratings StandardDeviation Coefficientof Variation furnace and the specimen placement.
The specimen is exposed to the standard flame conditions
0 to 25 1.2 9.6
25 to 75 3.1 6.2 for 10 rain or less if the specimen is completely consumed in
75 to 135 3.65 3.5 the fire area and no further progressive burning is evident and
0 to 135 2.85 4.6 if the photoelectric cell reading has returned to the baseline.
aThisinformationwas derivedfromJournalofPaint Technology,Vol.39, No. The flame-spread index (FSI) is determined by calculation
511, 1967,p. 495. from the plotted time-distance curve in relationship to the
area under a similar curve for the reference material, select
grade red oak. Arbitrarily, red oak is assigned a flame-spread
burning behavior of the specimen by observing flame spread. index of 100 and the inorganic reinforced-cement board an
The test exposes a nominal 24-ft (7.32-m)-long by 20-in. (508- FSI rating of zero. The precision and bias of this method has
mm)-wide specimen to a controlled air flow and flaming fire yet to be determined.
exposure adjusted to spread the flame along the entire length Several studies have been conducted to examine the rela-
of a reference material (select-grade red oak) in 5.5 min. A tionship of the flame-spread index (FSI) test results obtained
photoelectric cell is placed at the vent end to detect and for materials with their behavior in large-scale fire-growth
|I
Location of Thermo- k..--~9 -~--j_

- ~ .
couples (8) in Stock

(Parallel Connected)
45" E
..... 4 ......
0.040 in. Sheet Steel Stock ..... -t ....... f

Stop for Centerinl
0.050 by 20~ by36 in. ~ - I 4
Specimen Holder
Sheet Steel Mounting Over Panel
Plote--~
13 by 19in. Radiant ~--~

Panel 12by 18in.fl Reducing
Radiating Surface
J ,--/ ;tar
)e Topped
For Gas
~4b from
-~ in. Diom Stainless Steel an( afar
Traverse R o d s ~ ( 2 ) ~ l
2 by2 rte Valve
Steel $
Filter f
2.8;n. Water ~ ~ ~ i Rodi
F .........
Metric Equivalents
in. mm in. mm
0.040 1.0 6 152
1/2 12.7 9v2 241
rye 16.0 18 457
7/a 22.2 19a/8 492
13/, 44 3/4 by 3/, 19.2 by 19.2
2 51 1'/2 by 1'/, 38 by 32
21/2 64 12 by 18 305 by 457
2.8 71 13 by 19 330 by 483
4 102 2 by 2 by 1/8 51 by51 by3.2
43/s 111 0.050 by 201/4 by 36 13 by 514 by 914
43/, 121
100 ft~/min = 47.21 L/s
FIG. 4-Details of construction of test equipment.
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CHAPTER 56--TESTING COATINGS FOR HEAT RESISTANCE 673
DRAFT VENTS FOR GAS

G~I I r.F' FIRE END REMOVABLE EOUIDISTANTLY ANALYSI S --------~
CONN-E-CTION~'~ TOP LID SPACED WINDOWS (OPTIONAL) I
\ 'A' 82 's' 82 \ ~, ~ :~ ~. / '~',-.I
INTAJ~JE S H U ~ R ~- "l~" ' ' ~ ,, I - I* E'-'-CT'~...,,.:_~LL
lI
,'I- . . . . -r-% . . . . ~ . . . . --. . . . . . . . . . . . -.BE-4 I 2 ~ -- 0
OPENINC " t I if- -- /
~RAIR II'A'~ I~'B'~ U If I &.-'-II '~, ~,G,,T
I '"
IGNITING FIRE F~ERSU R E ~ N T S SECTION
INSULATED
17 '/~" * ~," SHEET ~ T A L
:~'-"~z__~. ~'rE: FORSE~ION
6-B SEE FIG. 2
G PIPE
+_ 1 / 2 " DAMPER
SECTION A-A SECTION C-C

Inch-Pound Units Sl Uldts
12 1/2 in. 305 ~'12.7 mm
173/4 I/4 in. 451 6.3 mm
54 5 in. 1371 127 turn
25 ft 7.62 m
REMOVABLE I/4"INCRC~IC REINFORCED zZP-CONo6 o'mEa

~LIQUID SEAL TOP L I D "~ CFJ'gENTBOARD~ 1 -- STRUCTURALHATERIAL5
2" HINERALCOMPOSITIONINSULA
DOUBLEP A N ~
OBSERVATION
WINDOWs
OUTSIDE P " BY 4 1 / 2 ~ BY
/X2 FIRE BRICK
i~ TElCP. 2 6 0 0 ~
OPTION: CASTABLE ~ / SECTION B-B

REFRACTORY OR FIRE
8RICK
Inch-Pound Units Sl Units Inch-Pound Units Sl Units
1 .
Ifl. 6.3 mm 20 in. 508 mm
2 in. 51 mm 9 by 41/2 by 21/2 in. 230 by 115 by 65 mm
1 9
4 _+ ~m. 102 1200"F 649~
I 1.
7~ _+~, ,n. 191 13 mm 2600~ 1427~
12 + ~ in. 305 + 13 mm
FIG. 5 - ( t o p ) T e s t f u r n a c e , s h o w i n g s o m e critical d i m e n s i o n s ( n o t a c o n s t r u c t i o n d r a w i n g ) ; ( b o t t o m ) t e s t
f u r n a c e s h o w i n g s o m e critical d i m e n s i o n s ( S e c t i o n " B - B " is n o t a c o n s t r u c t i o n d r a w i n g ) .
www.iran-mavad.com

affles
~ d p p o r t Rod
in.I
FIG. 6-Corner construction.
e x p e r i m e n t s a n d with the fire-test response of o t h e r labora- after 20 m i n o r s o o n e r if the flame b e c o m e s uncontrollable.

tory methods. Reports of o t h e r c o m p a r i s o n s with large-scale Precision: Tables 3 a n d 4 are b a s e d on a r o u n d r o b i n involving
e x p e r i m e n t s can be found in the references to this chapter. five m a t e r i a l s tested by five laboratories. Bias: There are no
C o m p a r i s o n s have also been m a d e b e t w e e n Test Methods E recognized s t a n d a r d s by w h i c h to estimate bias of this test
84, E 162, a n d D 3894 [1]. method.
ASTM Method D 3894

Full-Scale Compartment Fire Tests
ASTM Test M e t h o d for Evaluation of Fire Response of
Rigid Cellular Plastics Using a Small Corner Configuration (D ASTM Method E 603
3894) is i n t e n d e d for evaluation of cellular plastics; however, At p r e s e n t there is no ASTM s t a n d a r d test m e t h o d for
this large-scale test is useful for c h a r a c t e r i z a t i o n of the b u r n - c o n d u c t i n g full-scale r o o m fire tests, although there is consid-
ing b e h a v i o r of coatings a p p l i e d to representative substrates. erable e x p e r i m e n t a l activity. ASTM Guide for R o o m Fire Ex-
It simulates configurations of two a d j a c e n t walls o r two adja- p e r i m e n t s (E 603) describes full-scale c o m p a r t m e n t fire ex-
cent walls a n d ceiling. It is useful in p r e d i c t i n g p e r f o r m a n c e p e r i m e n t s designed to evaluate the fire characteristics of
of such m a t e r i a l s in a F a c t o r y M u t u a l L a b o r a t o r i e s full-scale materials, products, o r systems u n d e r actual fire conditions.
c o r n e r wall test. 2 Figure 6 shows the c o r n e r c o n s t r u c t i o n of E 603 is i n t e n d e d as a guide for design of e x p e r i m e n t s a n d for
the D 3894 setup. The test configuration provides a critical the i n t e r p r e t a t i o n of the results. The guide m a y be used to
surface g e o m e t r y affording a c o m b i n e d h e a t flux that in- establish l a b o r a t o r y conditions that simulate a given set of
cludes the conductive, convective, a n d radiative responses of fire c o n d i t i o n s as realistically as possible.
a n y specific b u r n i n g material.
The s p e c i m e n consists of a corner, s u p p o r t e d b y an outside
frame, m a d e from panels each m e a s u r i n g 610 by 1220 by T TABLE 3--Precision for maximum flame spread for
polyisocyanurate cellular plastic, glass-fiber-filled, 1-in. thick,
m m (2 by 4 ft by T in.), T being the thickness of the test panel, covered with aluminum foil.
a n d a ceiling section of s i m i l a r c o m p o s i t i o n m e a s u r i n g 1220
Values Expressed as Percent of
by 1220 by T m m (4 by 4 ft b y T in.). A s t a n d a r d b u r n e r is used the Average
for ignition. Visual observations are made, a n d a r e c o r d of Average,
in. l.*ra VRb lrc IR d
flame-travel distance from the test c o r n e r j u n c t i o n o u t w a r d
on the h o r i z o n t a l p l a n e is m a d e at the start of the test a n d at Walls and ceiling 34 5 13 14 37
Walls only 27 21 32 59 91
least every 15 s for the test duration. The test is t e r m i n a t e d
~vr is the within-laboratory coefficient of variation of the average.
bur is the between-laboratories coefficientof variation of the average.
2For details contact Factory Mutual Research Corp., P.O. Box clr = 2.83 v~.
09102, Norwood, MA 02062. dlR = 2.83 Vn.
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CHAPTER 5 6 - - T E S T I N G COATINGS FOR H E A T R E SISTA N C E 675
TABLE 4--Precision for time to maximum flame travel. structural units t h a t constitute p e r m a n e n t a n d integral parts
Values Expressed as Percent of of a finished building.
Average, the Average E 119 is the p r i n c i p a l m e t h o d for evaluating structural
min uf vR b lrc ll~d integrity of b u i l d i n g assemblies u n d e r actual fire conditions.
Walls and Ceiling: It is the m e t h o d d e s i g n a t e d in b u i l d i n g codes a n d fire codes to
Material: 4 0.46 12 26 34 74 rate structural integrity in fire exposure. The test exposes a
5 0.56 26 35 74 99 full-scale s p e c i m e n within a s t a n d a r d furnace to a s t a n d a r d
3 1.02 26 58 74 164 fire that is controlled to achieve specified t e m p e r a t u r e s
1 4.76 18 19 51 54 t h r o u g h o u t a p r e s c r i b e d t i m e period. The test m e a s u r e s h e a t
2 8.51 8 12 23 34 t r a n s m i s s i o n a n d m e a s u r e m e n t of load-carrying ability of the
Walls Only:
s p e c i m e n d u r i n g the test exposure. Figure 7 is the time-tem-
Material: 4 1.34 12 49 34 139
5 2.28 91 95 257 269 p e r a t u r e relationship used in controlling the test. Precision
3 6.88 10 50 28 141 a n d bias of the m e t h o d are not stated. M e t h o d E 119 has b e e n
1 7.39 15 28 42 79 in wide a n d c o n t i n u o u s use since 1917 for fire rating b u i l d i n g
2 9.14 12 15 34 42 assemblies. It has wide acceptance.
Materials:
There are no s t a n d a r d test m e t h o d s for ablative coatings.
4 = Rigid polyurethane cellular plastic, 25.4 mm (I in.), w/FR
> 25 FS. NASA SP 5014 [2] describes the general topic. Thermogravi-
5 = Rigid polyurethane cellular plastic, 25.4 mm (1 in.), 2 pcf. m e t r i c analysis is useful in u n d e r s t a n d i n g the effect of high
3 = Rigid isocyanurate cellular plastic, 25:4 mm (1 in.), 2 pcf. t e m p e r a t u r e on inorganic as well as organic coatings.
1 = Plywood, 1/2 in. AD.
2 = Same as in Table 3. ASTM Method E 1131
ovr is the within-laboratory coefficient of variation of the average. ASTM Test M e t h o d for C o m p o s i t i o n a l Analysis by Thermo-
byR is the between-laboratories coefficient of variation of the average.
Cl,. = 2.83 ur. gravimetry (E 1131) provides a general t e c h n i q u e i n c o r p o r a t -
d l R = 2.83 v R . ing t h e r m o g r a v i m e t r y to d e t e r m i n e a m o u n t s of volatile mat-
ter, c o m b u s t i b l e material, a n d ash content of c o m p o u n d s . It
is applicable, using either an inert or a reactive gas environ-
Analysis of d a t a from r o o m fire experiments can serve two
ment, to solids a n d liquids in the t e m p e r a t u r e range f r o m
purposes: (1) to relate the severity of the r o o m fire e x p e r i m e n t
r o o m t e m p e r a t u r e to 1830~ (1000~ The test m e t h o d is an
to the l a b o r a t o r y - m e a s u r e d fire properties, which establishes
e m p i r i c a l technique using t h e r m o g r a v i m e t r y in w h i c h the
e m p i r i c a l relationships that validate the strengths a n d the
m a s s of a substance, h e a t e d at a controlled rate in an a p p r o -
weaknesses of the various fire test m e t h o d s n o w being used o r
priate environment, is r e c o r d e d as a function of t i m e or
p r o p o s e d to control the m a t e r i a l s to be used in the rooms;
temperature.
a n d (2) to evaluate m a t e r i a l s a n d p r o d u c t s for acceptability,
p a r t i c u l a r l y those m a t e r i a l s for w h i c h t h e r e are no a d e q u a t e
m a t e r i a l p r o p e r t y tests. This s t a n d a r d contains a detailed Historical M e t h o d s
rationale for full-scale c o m p a r t m e n t fire tests. It should be
The heat a n d fire test m e t h o d s d e s c r i b e d are those m o s t
consulted in detail.
used t o d a y in c h a r a c t e r i z i n g coatings. Historically, a variety
of o t h e r bench-scale screening tests have b e e n used, b u t they
are no longer in vogue as they do not relate to actual service
Testing Intumescent, Fire-Retardant, and Ablative
Coatings
24 O0
These special-purpose coatings are i n t e n d e d to protect sub- ~J
strates from d a m a g e by fire exposure. I n t u m e s c e n t coatings f "1200
IIIIBJ
are designed for cellulosic substrates, as fire-retardant coat-
ings for structural steel substrates, a n d as ablative coatings
for the exterior of re-entry space vehicles. See the reference
!BHH (0
section for m o r e specific references. ~=z60G //

- Boo
I n t u m e s c e n t coatings a p p l i e d to w o o d panels are tested for
flame-spread index by ASTM E 84. Evaluation of fire-retar- s
d a n t coatings for the p r o t e c t i o n of structural steel is con- -600
P
d u c t e d a c c o r d i n g to ASTM E 119.
E BO0 -400
ASTM Method E 119
ASTM M e t h o d for Fire Tests of Building Construction a n d 400 200
Materials (E 119) is a large-scale fire e n d u r a n c e test applica-
ble to assemblies of m a s o n r y units a n d to c o m p o s i t e as- 0
00 2 4 6
semblies of structural m a t e r i a l s for buildings, including load-
bearing walls a n d o t h e r walls, partitions, columns, girders, Time~, h
beams, slabs, a n d c o m p o s i t e b e a m a n d slab assemblies for FIG. 7-Time-temperature relationship used
floors a n d roofs. It is also applicable to o t h e r assemblies a n d for test control.
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conditions. Details of the following historical tests m a y be [2] Plunkett, J. D., "NASA Contributions to the Technology of Inor-
f o u n d in ASTM STP 500 [3]: Schulz fire-retardant tester, NJZ ganic Coatings," NASA SP-5014, 1964.
box test, stick a n d wick test, vertical m a t c h test, crib test, fire- [3] Van Heuckeroth, A. W., "Fire Retardance and Heat Resistance,"
tube test, SS-A-118 acoustical tile test, Schlyter test, a n d the Chap. 6.3, Paint Testing Manual, 13th ed., American Society for
8-ft t u n n e l test. Testing and Materials, Philadelphia,1972, pp. 355-365.
[4] Babrauskas, V. and Williamson, R. B., "Historical Basis of Fire
Resistance Testing," Fire Technology, Vol. 14, Nos. 3 and 4, 1978,
Recommendations for Further Reading pp. 184-198, 304-316.
[5] Magee, R. S. and McAlevy, R. F., III, "The Mechanism of Flame
Additional b a c k g r o u n d material can be f o u n d i n Refs 4-7. Spread," Journal of Fire and Flammability, Vol. 2, 1971, pp. 271-
297.
[6] Shorter, G. W., Ed., Fire Test Performance, ASTM STP 464, p.
REFERENCES 1070.
[7] Williamson, R. B. and Baron, F. M., "A Corner Test to Simulate
[1] McGuire, J. H., "The Spread of Fire in Corridors," Fire Technol- Residential Fires," Journal of Fire and Flammability, Vol. 4, April
ogy, Vol. 4, No. 2, May 1968, pp. 103-108. 1973, pp. 91-105.
www.iran-mavad.com

MNL17-EB/Jun. 1995
Water-Resistance Testing of
Coatings
by Wayne Ellis*
OTHER CHAPTERS IN THIS MANUALcover the influence of w a t e r hand, is evaluated on free films.) W a t e r resistance m a y be
on the f o r m u l a t i o n a n d d u r a b i l i t y of organic coatings. Recent evaluated as p a r t of o t h e r test regimes, such as exposure
ASTM p u b l i c a t i o n s a b o u t the m o i s t u r e effects in b u i l d i n g testing, w a t e r repellency, corrosion, c h e m i c a l resistance, salt-
m a t e r i a l s are listed in the B i b l i o g r a p h y at the end of this fog resistance, a n d cycling tests such as humidity-cycling a n d
chapter. These p u b l i c a t i o n s describe m o i s t u r e p r o b l e m s a n d light-and-water-exposure testing.
solutions involving coatings a n d their uses. Although this
c h a p t e r is i n t e n d e d to describe only the p r i n c i p a l testing a n d
evaluation of w a t e r resistance, s o m e general r e m a r k s m a y be TRADITIONAL TEST METHODS
helpful in u n d e r s t a n d i n g the test conditions.
Spot tests a n d i m m e r s i o n tests of coatings a p p l i e d to sub-
strates t r a d i t i o n a l l y have b e e n used as "quick a n d dirty" tech-
niques to c o m p a r e specimens. Criteria for evaluation include
E F F E C T S O N C O A T I N G S OF E X P O S U R E TO
softening, blistering, solvation, color change, loss of adhe-
WATER AND WATER VAPOR
sion, a n d rusting o r o t h e r d e t e r i o r a t i o n of the substrate.
These observations should lead to further a n d m o r e c o m p r e -
The a d h e s i o n of coatings to substrates is strongly influ-
hensive testing related to i n t e n d e d conditions of p r o d u c t use.
enced b y the a b s o r p t i o n of w a t e r a n d b y the p e r m e a b i l i t y of
Such testing m a y include exposure to controlled condensa-
the coating to w a t e r vapor. The m e c h a n i s m of this influence
proceeds as follows: 1 tion, 100% relative humidity, or w a t e r fog to evaluate mois-
ture blistering resistance. Even m o r e intensive testing m a y
1. A b s o r p t i o n of w a t e r molecules in the coating film. involve w a s h a b i l i t y a n d scrub resistance.
2. Inclusion of w a t e r in the interface b e t w e e n film a n d sub-
strate.
3. Blister formation.
4. Corrosion/erosion of the substrate.
SPECIMEN PREPARATION
5. Flaking o r peeling of the film.
Careful p r e p a r a t i o n of coated specimens is essential to as-
Although there is no fixed relationship b e t w e e n w a t e r absorp- sure a p r o p e r a n d meaningful relationship to field exposure
tion a n d w a t e r v a p o r permeability, generally the h i g h e r the a n d to avoid false test results. The s u b s t r a t e c o m p o s i t i o n a n d
w a t e r a b s o r p t i o n the m o r e p e r m e a b l e the film is to w a t e r surface p r e p a r a t i o n , s p e c i m e n p r e p a r a t i o n , a n d the n u m b e r
vapor. N o r m a l l y the p e r m e a b i l i t y m e a s u r e m e n t s are m a d e on of specimens should be agreed u p o n b e t w e e n involved parties
freshly a p p l i e d films. It should be n o t e d t h a t with progressive p r i o r to testing. Applicable m e t h o d s for the p r e p a r a t i o n of
aging a n d weathering, films b e c o m e m o r e cross-linked, a n d test panels are given in ASTM Methods D 609, 3 D 1734, 4 a n d
in the case of water-sensitive binders, the water-soluble addi- Practices D 1730. 5 Test Methods D 8236 cover a p p l i c a t i o n
tives are w a s h e d out b y exposure to r a i n a n d dew. Hence such techniques for the p r o d u c t i o n of u n i f o r m films.
films will show decreasing p e r m e a b i l i t y with time.
Water resistance is defined b y ASTM as " m e a s u r e d ability to
r e t a r d b o t h p e n e t r a t i o n a n d wetting by w a t e r in liquid form". 2 IMMERSION TESTING
Nearly always it is a r e q u i r e d p r o p e r t y for coatings. W a t e r
resistance generally is m e a s u r e d on specimens of coatings ASTM Practice for Testing W a t e r Resistance of Coatings
a p p l i e d to n o m i n a l l y i m p e r m e a b l e substrates such as metal, Using W a t e r I m m e r s i o n (D 870) describes basic principles
wood, o r masonry. (Water v a p o r permeability, on the other
aD 609, Practice for Preparation of Cold-Rolled Steel Panels for
*Wayne Ellis is deceased. He was a former Chairman of the Board Testing Paint, Varnish, Conversion Coatings, and Related Coating
of ASTM and served as a standards consultant and First Chairman of Products.
the Board of the Building Environment and Thermal Envelope Coun- 4D 1734, Method of Making and Preparing Concrete and Masonry
cil. Panels for Testing Paint Finishes.
~Eric V. Schmid, Exterior Durability of Organic Coatings, Redhill, 5D 1730, Practices for Preparation of Aluminum and Aluminum-
Surrey: FMJ International Publications, 1988. Alloy Surfaces for Painting,
2ASTM D 996, Terminology of Packaging and Distribution Envi- 6D 823, Test Methods for Producing Films of Uniform Thickness of
ronment. Paint, Varnish, and Related Products on Test Panels.
677
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~:~12 " ~
0--Angle of lid, 90 to 125 ~

l~Thermometer and thermostat for controlling heater (Item No. 8) in base
2--Automatic water levelling device
3~Humidifying tOWer
C--Automatic temperature regulator for corztrolling heater (Item No. 5)
5--Immersion heater, nonrusting
6.--Air inlet, multiple openings
7--Air tube to spray nozzle
8~Strip heater in ba.se
9--Hinged top, hydraulically operated, or counterbalanced
10--Brackets for rods supporting specimens, or test table
11 ~lnternal reservoir
12--Spray nozzle alcove reservoir, suitably designed, located, and baffled
12AmSprey nozzle housed in dispersion tower located preferably in center of cabinet
13--Water seal
14---Combination drain and exhaust. Exhaust at opposite side of test space from spray nozzle (Item 12), but preferably in coml0ination with drain, waste trap, anti forced
draft waste pipe (Items 16, 17, and 19).
1 6 ~ o m p l e t e separation between forced draft waste pipe (Item 17) and combination drain and exhaust (Items 14 and 19) to avoid undesirable suction or back pressure.
17--Forced draft waste pipe
18~Automatir levelling device for reservoir
19--Waste trap
20~Air space or water jacket
21--Test table or rack, well below roof area
FIG. l - T y p i c a l salt s p r a y c a b i n e t (Fig. X1.1 of A S T M B 117).
and operating procedures for testing water resistance of coat- (Fig. l), a water reservoir, a supply of suitably conditioned
ings by the partial or complete immersion of coated speci- compressed air, one or more atomizing nozzles, specimen
mens in distilled or demineralized water at ambient or ele- supports, provision for heating the chamber, and necessary
vated temperatures. Coated specimens are partly or wholly means of control. Coated specimens are placed in an enclosed
immersed in water in a container that is resistant to corro- chamber where a water fog surrounds them. The tempera-
sion. The exposure conditions are varied by selecting the ture of the chamber is usually maintained at 100~ (38~
temperature of the water and the duration of the test. The exposure condition is varied by selecting the duration of
Failure may be caused by a number of factors, including a the test.
deficiency in the coating itself, contamination of the sub- Failure in water fog tests may be caused by a number of
strate, or inadequate surface preparation. Any effects such as factors, including a deficiency in the coating itself, contami-
color change, blistering, loss of adhesion, softening, or em- nation of the substrate, or inadequate surface preparation.
brittlement are observed and reported. These test results Any effects such as softening (measured by pencil hardness),
typically are a pass or fail determination, but the degree of color change, gloss change, blisters, loss of adhesion, embrit-
failure also may be measured. tlement, and rusting or corrosion of substrate are observed
and reported.
WATER FOG T E S T I N G
ASTM Practice for Testing Water Resistance of Coatings 100% RELATIVE H U M I D I T Y T E S T I N G

Using Water Fog Apparatus (D 1735) covers the basic princi-
ples and operating procedures for testing water resistance of Practice for Testing Water Resistance of Coatings in 100%
coatings in an apparatus similar to that used for salt spray Relative Humidity (D 2247) covers the basic principles and
testing. 7 The apparatus required consists of a fog chamber operating procedures for testing water resistance of coatings
by exposing coated specimens in an atmosphere maintained
7ASTM B 117, Test Method of Salt Spray (Fog) Testing. at 100% relative humidity so that condensation forms on the
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CHAPTER 5 7 - - W A T E R - R E S I S T A N C E TESTING OF COATINGS 679
io,'~
I
I
I
Ii I sJ i k
I
IS I
I /11
I
0---Angle of lid, 90 to 125 ~
l--Hinged top, hydraulically operated, or counterbalanced
2--Water seal
3---Constant-level water tank unheated with overflow outlet and equalizer connection
C--Heater water tank for supplying heat and humidity to cabinet
5--Immersion heater
6--Watertemperature limit control
7--Thermostatic controller for room temperature. Pdmaw limit control for immersion heater (5)
8--Wator line
9--Insulation if necessary (see A1.3)
I 0--Temperature recorder (optional)
11 --Drain
FIG. 2 - H u m i d i t y cabinet (Fig. A1.1 of A S T M D 2247),
specimens. The apparatus (Fig. 2) consists of a test chamber,

a heated water tank, and suitable controls. Heated water
m
vapor is generated at the bottom of the chamber, causing

saturation of the air immediately above the water tank. As the
saturated mixture rises, it cools below the dew point tempera-
ture, causing condensation on the specimens suspended
above. Condensation is uncontrolled. (For testing at 100%
RH with controlled condensation, see ASTM D 4585, de-
scribed below.)
Effects of exposure at 100% relative humidity may be color
change, blistering, loss of adhesion, softening, or embrittle- FIG. 3 - C o n t r o l l e d condensation apparatus
ment. Any such effects are observed and reported. They may (Fig. 1 of A S T M D 4585).
be caused by a number of factors including a deficiency in the
coating itself, contamination of the substrate, or inadequate air. The temperature and amount of condensate forming on
surface preparation. the specimens are controlled by the test temperature and
room temperature.
CONTROLLED CONDENSATION TESTING The specimens are inclined so that the condensate runs off
the test surface by gravity and is replaced by fresh condensate
Practice for Testing Water Resistance of Coatings Using in a continuous process during the condensate cycle. Expo-
Controlled Condensation (D 4585) differs from D 2247 in that sure conditions are varied by selecting the temperature of the
the coated specimens are mounted with the uncoated face test, the duration of the test, and periodic drying of the
exposed to room temperature air. The apparatus (Figs. 3 and specimens. Failure may be caused by a number of factors
4) consists of a test chamber in which the specimens form the including a deficiency in the coating itself, contamination of
roof of a chamber that is fitted with suitable water supply and the substrate, or inadequate surface preparation. Any effects
controls. such as color change, blistering, loss of adhesion, softening,
Water vapor is generated by heating a pan of water at the or embrittlement are observed and reported.
bottom of the test chamber. The specimens form the roof or
walls of the test chamber so that the back sides of the speci- CYCLE TESTING
mens are exposed to the cooling effects of room temperature
air. The resulting heat transfer causes water vapor to con- Test Method for Finishes on Primed Metallic Substrates for
dense on the coated specimens as liquid water saturated with Humidity-Thermal Cycle Cracking (D 2246) covers an accel-
www.iran-mavad.com

which one or m o r e cracks is visible. Evaluation before a n d

after exposure m a y be done for checking (D 6608), for crack-
ing (D 6619), for erosion (D 6621~ a n d s o m e t i m e s for w a t e r
b e a d i n g (D 292111).
ASTM Test M e t h o d for H u m i d - D r y Cycling for Coatings on
W o o d a n d W o o d Products (D 3459) is a p r o c e d u r e for evalu-
ation of coatings designed for use on interior w o o d and w o o d
p r o d u c t s by exposure alternately to low a n d high h u m i d i t y at
an elevated t e m p e r a t u r e . Test panels having a m i n i m u m a r e a
of 12 by 12 in. (300 b y 300 ram) are exposed in 48-h cycles in
exposure c h a m b e r s m a i n t a i n e d at 97 _+ 2% relative h u m i d i t y
a n d 122 ___ 3.5~ (50 -+ 2~ the o t h e r c h a m b e r m a i n t a i n e d at
50 _+ 5% relative h u m i d i t y a n d 73.5 _ 3.5~ (23 _ 2~ At
each change of conditions during cycling, the panels are
inspected u n d e r strong light for possible d a m a g e or change,
w h i c h m a y be in the base m a t e r i a l o r in the coating.
Testing for the effect of w a t e r exposure c o m b i n e d with
o t h e r exposures is not d e s c r i b e d in this chapter. Such testing
includes light-and-water exposure a p p a r a t u s using carbon-
arc ultraviolet, 12 Xenon-arc/3 a n d fluorescent U V . 14
FIG. 4-Apparatus and cross section (Fig. 2 of ASTM D
4585).
e r a t e d m e a n s for d e t e r m i n i n g the t e n d e n c y of an organic BIBLIOGRAPHY

coating to fail by cracking w h e n exposed to h u m i d i t y - t h e r m a l
cycling. It is evaluated by alternate exposure of p r e p a r e d Lieff, M. and Trechsel, H. R., Eds,, Moisture Migration in Buildings,
s p e c i m e n s in a c a b i n e t m a i n t a i n e d at 100~ (38~ a n d 100% ASTM STP 779, 1982.
Schwartz, T. A., Ed., Water in Exterior Building Walls: Problems and
relative h u m i d i t y (with c o n t i n u o u s c o n d e n s a t i o n on the spec-
Solutions, ASTM STP 1107, 1991.
imens), then in a cold box at - 10~ ( - 23~ allowing only a Trechsel, H. R. and Bomberg, M., Eds., Water Vapor Transmission
m a x i m u m of 30 s for transfer. S p e c i m e n s are r a t e d (using a Through Building Walls and Systems: Mechanisms and Measure-
grid overlay) by counting the n u m b e r of grid squares w i t h i n ment, ASTM STP 1039, 1989.
8D 660, Method for Evaluating Degree of Checking of Exterior

Paints.
9D 661, Method for Evaluating Degree of Cracking of Exterior
Paints.
1~ 662, Method for Evaluating Erosion of Exterior Paints.
HD 2921, Method for Qualitative Tests for the Presence of Water
Repellents and Preservatives in Wood Products.
12ASTM D 5031, Practice for Testing Paints, Varnishes, Laquers,
and Related Products Using Enclosed Carbon-Arc Light and Water
Exposure Apparatus.
~3ASTM G 26, Practice for Operating Light-Exposure Apparatus
(Xenon-Arc Type) With and Without Water for Exposure of Nonme-
tallic Materials.
14ASTM D 4587, Practice for Conducting Tests on Paints and
Related Coatings and Materials Using a Fluorescent UV-Condensa-
tion Light- and Water-Exposure Apparatus.
www.iran-mavad.com

Part 13: Specific Product Testing
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MNL17-EB/Jun. 1995
Aerospace and Aircraft

Coatings
by Charles R. Hegedus, 1 Stephen J. Spadafora, 2 David F. Pulley, 2
Anthony T. Eng, 2 and Donald J. Hirst 2
ORGANICCOATINGSARE PRIMARILYapplied to aircraft for envi- system. Therefore, selection of appropriate test and evalu-
ronmental protection and appearance. Reference 1 con- ation procedures is an essential component for determining
dudes, "The rate controlling parameter for the corrosion of acceptable coatings for aircraft application.
aircraft alloys, excluding the mechanical damage factor, is
the degradation time of the protective coating system." This
dearly indicates the importance of the coating system's dura- VISCOSITY
bility and its ability to control corrosion and erosion. Relative
to appearance, commercial aircraft benefit from the aesthetic The viscosity of aircraft coating components, component
characteristics of the coating system, while military aircraft mixtures, and raw materials is valuable to the formulator,
rely on camouflage properties to minimize enemy detection manufacturer, and applicator for assessment of rheological
and tracking during mission operations. characteristics. These characteristics affect paint application
To meet operational requirements, aircraft coating systems properties such as atomization, leveling, sagging, and
traditionally consist of a primer and a topcoat. Primers in- brushability.
hibit corrosion of the substrate and enhance adhesion of
subsequent topcoats, while topcoats are applied for appear- Cup Methods (Cup Viscometers)
ance and to enhance overall durability of the coating system.
Self-priming topcoats, which perform as both primer and In aircraft coating specifications and at application sites,
topcoat in a single coating, have recently been introduced Zahn and Ford cup viscometers are used for admixed paints
[2,3]. In addition, specialty coatings are strategically applied because they are inexpensive, easy to use and maintain, and
to perform various functions such as protection against rain produce practical quantitative data. Although the stand-
erosion, chafing, immersion in fuel, and high temperature. mounted, standard Ford cup is more accurate due to its
References 4 through 6 provide more detail on the formula- stability, deeper capillary orifice, and larger volume, the dip-
tion and properties of aircraft coatings. type Zahn cup is preferred since it is easiest to use and
A number of factors affect the performance of aircraft coat- maintain. Zahn and Ford viscometers are described in ASTM
ings, including the substrate material, the aircraft's opera- Test Method for Viscosity by Dip-Type Viscosity Cups
tional environment, and flight conditions. Aircraft structures (D 4212) and ASTM Test Method for Viscosity of Paints,
and skins are manufactured from numerous metallic alloys Varnishes, and Lacquers by Ford Viscosity Cups (D 1200),
and polymeric composites with a variety of pre-paint treat- respectively.
ments, thus complicating the adhesion and corrosion inhibi-
tion characteristics of the coating system. Environmental Brookfield and Stormer Methods
conditions also can vary dramatically (arctic, tropical, ma-
fine, industrial, desert, etc.). Skin temperatures during flight Brookfield and Stormer viscometers are rotation-type vis-
can range from - 5 4 to 177~ ( - 6 5 to 350~ while ground cometers described in ASTM Test Method for Rheological
conditions may be relatively benign or highly corrosive. Air- Properties of Non-Newtonian Materials by Rotational
craft type and mission also play important roles in coating (Brookfield) Viscometer (D 2196) and ASTM Test Method for
Consistency of Paints Using the Stormer Viscometer (D 562),
system performance. A commuter aircraft that hops from
respectively. The Brookfield viscometer, which measures ab-
island to island in the tropics sees frequent pressurization
and depressurization along with high temperature, humidity, solute viscosities in centipoises (cP) using a rotating spindle,
and salt water. In contrast, a military tactical aircraft may fly is particularly effective in determining viscosities of non-
far fewer hours but will experience extreme structural loads Newtonian fluids due to its ability to measure shear stress
during flight conditions. These flight conditions place envi- (that is, torque of rotating spindle) at various speeds and
ronmental and mechanical stresses on the aircraft coating shear rates. Since the cup viscometers described above offer
relative simplicity and ease of use, the Brookfield viscometer
is not used at application sites. However, it is frequently used
~Lead Applications Chemist, Air Products and Chemicals, 7201 as a research tool to characterize the viscosities of polymeric
Hamilton Blvd.. Allentown, PA 18195-1501.
2Chemical Engineers, Materials Engineer, and Materials Engineer- resin materials and dispersions.
ing Technician, respectively, Naval Air Warfare Center, Aircraft Divi- The Stormer or Krebs-Stormer viscometer uses a rotating
sion, Warminster, PA 18974-0591. paddle to measure relative viscosity expressed in Krebs units.
683
www.iran-mavad.com

It is designed to provide controlled, uniform, and relative this is determined by subtracting the volatile fraction of the
data based on a paddle-stirring motion. This type of viscome- coating from the total to determine the nonvolatile content.
ter is rarely used in the laboratory or required in current The method specified in ASTM Test Method for Volatile Con-
specifications due to the ease of use and maintenance of cup tent of Coatings (D 2369) is used. A method that provides a
methods and to the accuracy of the Brookfield method. volumetric assessment is ASTM Test Method for Volume
Nonvolatile Matter in Clear or Pigmented Coatings (D 2697).
DENSITY
Pigment Concentration
Wet coating density measurements provide a check on the Three methods are available to determine the pigment
theoretical density value and on the uniformity of the manu- weight concentration within a coating: ASTM Test Method
factured product. Determination of density by any conve- for Determination of Pigment Content of Solvent-Type Paints
nient or suitable method in this Manual is acceptable; how- by High Speed Centrifuging (D 2698); ASTM Practice
ever, a weight-per-gallon cup is normally used due to the ease for Separation of Vehicle from Solvent-Reducible Paints
of use of this instrument. (D 2372); and Federal Standard 141 Method 4021, Pigment
Content (Ordinary Centrifuge). These methods use the fact
that pigment particles, generally being more dense than the
F I N E N E S S OF G R I N D A N D COARSE vehicle, will settle under centrifugal force. One distinction
PARTICLES between these methods is the variation in rinsing solvent(s)
used to separate the polymer from the pigment. Although
Fineness of grind and presence of coarse particles are de- each method utilizes a different solvent blend, it is common
termined to assess the quality and uniformity of the pigment to deviate from the specified method by using solvents which
dispersion and coating finish. In order to produce a high gloss are appropriate for the specific paint under analysis. All three
coating of good appearance, a paint should be free of coarse methods result in a quantitative determination of pigment
particles. However, the extremely low gloss requirements of weight concentration in the paint; however, the latter two
some aircraft camouflage paints require relatively large parti- methods lend themselves to chemical analysis of the pigment
cle sizes. Fineness of grind is determined by ASTM Test sample after this determination.
Method for Fineness of Dispersion of Pigment-Vehicle Sys-
tems (D 1210), commonly referred to as the Hegman scale.
The coarse particle content is determined by the weight re- Volatile Concentration
tained on a 325-mesh sieve as specified in ASTM Test Meth- ASTM D 2369 is a standard experimental method to deter-
ods for Coarse Particles in Pigments, Pastes, and Paints mine the total volatile content of a coating. In contrast, ASTM
(D 185). Practice for Volatile Organic Compound (VOC) Content of
Paints and Related Coatings (D 3960), offers a method of
calculating the VOC using the nonvolatile content, the water
S O L I D S A N D VOLATILE C O N C E N T R A T I O N / content (if any), and the density of the coating. These latter
CONTENT values are predetermined using referenced ASTM methods,
and they are subsequently used in the calculations to deter-
General mine VOC of the paint. It should be noted that in solvent-
Several analysis techniques are used to determine the total borne coatings the VOC is the volatile content; however,
solids, pigment concentration, and volatile concentration of water-borne coatings obviously have a nonorganic volatile
aircraft coatings. This information can be used as a check on component which must he taken into account when perform-
the coating composition when compared to the theoretical ing these calculations. The VOC is typically recorded in units
value as determined from the formulation. It can also be used of grams of organic volatiles per liter of paint with pounds per
to determine the quality of an as-received product and its gallon used as an alternate.
potential surface coverage per volume of paint. In addition,
restrictions on the volatile organic compounds (VOC) content
Chemical Analysis
of coatings increase the importance of determining the vola-
tile concentration, and methods to determine this value are A variety of methods are used to analyze the chemical com-
continuously being developed and refined. The following position of aircraft coatings and their components. The spe-
methods are currently used to determine these compositional cific technique which is selected is determined by the mate-
properties for aircraft coatings. rial being analyzed and the level of quantitative or qualitative
data required. Some of the more common techniques to
analyze polymer and solvent systems are gas chromatogra-
Total Solids Content
phy, infrared and ultraviolet spectroscopy, and nuclear mag-
The total solids content of a coating, often referred to as its netic resonance (NMR). Atomic absorption and X-ray spec-
nonvolatile content, is a measure of the combined polymer troscopy are common techniques for determining the
and pigment content in a paint. It is typically represented as chemistry of inorganic pigments. Table 1 provides some of
the weight fraction or percentage of these "solid" components the common ASTM methods used to analyze aircraft coat-
relative to the as-received "wet" coating. For aircraft coatings, ings.
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CHAPTER 5 8 - - A E R O S P A C E AND AIRCRAFT COATINGS 685
TABLE 1--Analytical methods for aircraft paint components. used to evaluate specific aspects of the material at that time,
Compound ASTMMethod such as FTMS 141 method 3011.2, Condition in Container,
method 3021.1, Skinning, or method 4208, Evaluating De-
Ketones D 2804: Test Method for Purity of
Methyl Ethyl Ketone by Gas gree of Settling of Paint. In most cases, it is essential that: (1)
Chromatography the paint be free from skinning, (2) the pigment has not
Isocyanate D 3432: Test Method for Unreacted reagglomerated or formed a compacted cake at the bottom of
Toluene Diisocyanates in the container and it can be easily redispersed to form a
Urethane Prepolymers and consistent mixture, and (3) the applied coating has properties
Coating Solutions by Gas
Chromatography similar to when it was manufactured.
Water D 4017: Test Method for Water in
Paints and Paint Material by Karl
Fischer Method Accelerated Conditions
Lead, Cadmium, and D 3335: Test Method for Low
Cobalt Concentrations of Lead, To speed the evaluation of a coating's behavior under stor-
Cadmium, and Cobalt in Paint by age conditions, methods have been devised to accelerate this
Atomic Absorption Spectroscopy behavior by subjecting the coating to extreme conditions.
Chromium D 3718: Test Method for Low
Concentrations of Chromium in One common example is specified in FTMS 141 method
Paint by Atomic Absorption 3019.1, Storage Stability at Thermal Extremes, which sub-
Spectroscopy jects the coating to 49~ (120~ or - 12~ (10~ for 168 h,
depending on the type of storage suspected. Methods involv-
ing cyclic exposure to high and low temperatures have also
Because of growing concerns over potentially toxic materi- been used. With the development of high-performance water-
als, restrictions are being placed on the lead and chromium borne coatings for aerospace applications, one major con-
content of many aircraft paints. These restrictions are in cern is the freeze-thaw stability of these coatings. ASTM Test
direct conflict with corrosion control requirements since Method for Freeze-Thaw Resistance of Water-Borne Paints
chromate salts, such as strontium chromate, barium chro- (D 2243) is used to evaluate coating consistency and perform-
mate, and zinc chromate, have been shown to be excellent ance after 17 h at - 18~ (0~
corrosion inhibitors for many metals. Therefore, many speci- Another technique for predicting storage stability of coat-
fications require analysis for these pigments to ensure either ings is by evaluating the settling properties of pigments under
their presence or their absence. Specific methods to deter- accelerated conditions. Aircraft coating specifications rarely
mine lead and chromate content are listed in Table 1. contain this type of evaluation; however, centrifugation is
often used as a research tool to evaluate the tendency of
various pigments to settle and compact in specific vehicles.
S T O R A G E STABILITY The centrifugal force and the duration are selected on a case
by case basis to ascertain differences between systems.
General
The effects of long-term storage on aircraft coating per-
formance are a major concern. Long durations of time and FLASH POINT
extreme temperatures can have drastic effects on the chemi-
cal and physical nature of paints, causing them to have differ- General
ent properties than when they were originally manufactured. The flash point of a coating is the minimum fluid tempera-
Since many aircraft manufacturing, rework, and mainte- ture at which the solvent vapors are ignited by a spark or
nance activities have paint storage facilities which have only flame. It can be predicted roughly as the weighted average of
moderate environmental controls, determining the effects of the individual flash points for each of the solvents in a coating
these conditions is necessary. Of primary importance are formulation. The closed-cup technique is generally preferred
chemical stability and pigment dispersion. These properties since container breakage during shipment and storage often
are assessed in the laboratory following long-term and accel- leads to flammable vapors being trapped in a confined space.
erated storage conditions. Naturally, these flash points tend to be lower than the corre-
sponding open-cup values.
Long-Term Evaluation
Pensky-Martens
Methods typically used for determination of stability of
aircraft coatings are specified in ASTM Test Method for Pack- The Pensky-Martens test is a closed-cup method that can be
age Stability of Paint (D 1849), and Federal Test Method conducted on an admixed coating or on one of the separate
Standard (FTMS) 141 method 3022.1, Storage Stability components in the liquid (uncured) state. The material may
(Filled Container). In these methods, the packaged coating is be refrigerated to bring it to a temperature below the expec-
allowed to sit undisturbed at ambient conditions for an ap- ted flash point. It is then placed in a closed metal cup, heated
propriate period of time. (One year is typical for aircraft slowly while stirring, and periodically exposed to a pilot flame
coatings.) At that time, the coating is reevaluated to compare through a shutter mechanism. A thermometer immersed in
its physical and optical properties with those originally found the fluid measures the coating temperature. The flash point is
for the as-manufactured material. Other methods may be the minimum temperature at which the solvent vapors ignite,
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yielding a large flame that propagates over the surface of the drying times of paint films. As many as eight stages of the
fluid. The procedure is covered in ASTM Test Methods for paint drying process are recognized by coatings authorities.
Flash Point by Pensky-Martens Closed Tester (D 93), Method Determination of a particular set of drying properties is im-
A for clear coatings and Method B for pigmented coatings. portant for aerospace coatings due to the strict time and
processing constraints placed on production and mainte-
nance painting facilities. No particular drying time parame-
Setaflash
ters are universal throughout the aircraft industry. Each
The Setaflash test uses an enclosed apparatus with auto- paint facility has acceptable limits for these drying properties
matic controls to determine the flash point. It is easier to depending on their function, schedule, and climatic condi-
operate than the Pensky-Martens tester and utilizes an elec- tions. For example, set-to-touch time may be more important
tric heater for efficient heat transfer and greater accuracy. to a small parts shop where components are handled shortly
ASTM Test Methods for Flash Point of Liquids by Setaflash- after painting. In contrast, dry-hard times may be paramount
Closed-Cup Apparatus (D 3278), Method B describes the test at a production facility for painting entire aircraft that must
procedure. be flown shortly after painting.
Tag Set-to-Touch
The Tag tester is similar to Pensky-Martens, except that the A film is set-to-touch when it clings weakly to the finger
cup is placed in a bath containing a mixture of water and under gentle pressure but none of the film transfers to the
ethylene glycol. Only coatings with no suspended solids (such finger. This property indicates that the painted piece can be
as, fillers) can be evaluated. ASTM Test Method for Flash handled gently, but excessive contact will diminish the qual-
Point by Tag Closed Tester (D 56) is the applicable test ity of the coating. This property may be considered important
method. to shops painting small aircraft components which must be
moved from the application area.
POT LIFE Tack-Free

Pot life is the length of time in which the flow properties Basically, tack is the tenacity of the film to cling to foreign
(such as, viscosity) of catalyzed paints will not change within objects. This component of drying is not considered of major
an acceptable range for application. Acceptable coating con- importance in production painting; however, it may be used
ditions can vary from no change up to gellation. Pot life to ascertain the overall drying characteristics of a coating.
requirements in the aerospace industry tend to be controlled
by production limitations. Since a normal production work
Dry-to-Recoat
shift is 8 h, many paints have been required to have a pot life
spanning this period. More recently, restrictions on the vola- This stage of drying is considered to be the most important
tile organic content compounds (VOC) of paints have re- for painting of aircraft because it is one of the major factors
sulted in high solids coatings which tend to inherently pos- controlling the production rate. Dry-to-recoat is the time at
sess higher viscosity and shorter pot life (2 to 6 h). Pot life of which a second coat, or specified overcoat (such as, topcoat),
aircraft coatings is usually determined by measuring viscos- can be applied without developing irregularities in the coat-
ity as a function of time after mixing the paint for application. ing system, such as lifting, blistering, or loss of adhesion. If
Substantial increases in viscosity are an indication that the overcoated prior to the recoat time, these defects can be
pot life is nearly expended. caused by a number of factors, one of which is the trapping of
It should be noted that the issue of pot life can be cir- solvent in the original coat.
cumvented via the use of plural-component spray equipment,
which is becoming more common in the production painting
Dry-Hard
of aircraft. This equipment stores the various components of
a multi-component paint separately and then mixes those The most common technique is to squeeze or pinch the
components at the desired ratio immediately before or at the coated surface with the thumb and forefinger with maximum
spray gun. This equipment not only negates pot life as a factor pressure. The dry-hard time is when this procedure can be
but also minimizes the amount of catalyzed multi-compo- performed without leaving a permanent mark on the coating
nent paint that is wasted due to unused material. The only surface. This drying stage is also important in production
drawback is that this equipment is most effectively and effi- painting of aircraft since painting is usually the last stage of
ciently used when large volumes of paint (5 gal or more) are maintenance and the aircraft can be flown after the coating is
used as opposed to small quantities (1 gal or less), which are dry-hard.
typical of touchup maintenance operations.
FILM THICKNESS
DRYING TIME
Aircraft coatings are developed and manufactured to be
ASTM Test Method for Drying, Curing, or Film Formation applied within acceptable thickness limits. Coatings which
of Organic Coatings at Room Temperature (D 1640) defines are applied outside of these limits will not exhibit their opti-
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CHAPTER 5 8 - - A E R O S P A C E AND AIRCRAFT COATINGS 687
mum performance properties. For example, thin coatings tant. In addition, color change is often used to assess the
may not have the required tensile and shear strength, making effects of environmental exposure (weathering, immersion in
them susceptible to cracking and chipping, especially around fluids, etc.) on aircraft coatings. Means of characterizing
fastener heads and at panel seams. In contrast, coatings aircraft coating colors range from qualitative visual assess-
which are too thick may lack flexibility and can exhibit exces- ment to quantitative measurements with instruments, the lat-
sive internal stresses. Another important consideration is the ter providing the obvious advantage of consistent, numerical
excessive weight that coatings add to an aircraft, causing results. For the latter, ASTM Test Method for Calculation of
additional fuel consumption. Therefore, coating thickness is Color Differences from Instrumentally Measured Color Coor-
diligently controlled and measurements are performed in dinates (D 2244) is followed, resulting in a color description
both the wet and dry states. in either the XYZ or Lab color coordinates. Color differences,
Wet coating films are checked for thickness during aircraft as qualified by a delta E value, are determined by using these
application processes using various wet film thickness gages color coordinates as described elsewhere in this manual to
according to ASTM Test Method for Measurement of Wet determine delta E.
Film Thickness of Organic Coatings (D 1212). A tooth gage is One additional note must be made with respect to color
commonly used in the aerospace industry since it is simple to measurement of aircraft coatings. Colorimeters and spectro-
use, inexpensive, and can be used to obtain good approxima-
photometers can both be used to quantitatively measure
tions of dry film thickness. These approximations are made
color. Colorimeters use a specified light source with defined
by multiplying the wet film thickness by the coating volume
radiation wavelengths and intensities, typically resulting in a
percent solids.
direct output of XYZ and/or Lab color coordinates. Spectro-
The thickness of cured aircraft coatings can be determined
photometers measure light reflected from the coating surface
either destructively or nondestructively. Destructive methods
over an entire wavelength region. (In the case of color charac-
involve the chipping or cutting of dry films from a substrate
terization, this is the visible region of the spectrum.) Of the
and subsequent measurement of the coating thickness with a
gage. This approach is typically not taken for aircraft coatings two, colorimeters are less expensive and easier to use. How-
since the coating-substrate bond must be destroyed. Nonde- ever, colorimeters do not account for metamerism. Meta-
structive techniques include micrometer, eddy current, mag- merism is a phenomenon that occurs when an object appears
netic induction, and a magneto-resistor/thermistor system. to be different colors under different light sources. This effect
These are the most desirable methods of dry film thickness is observed with some coatings for military aircraft, which
determination used in the aerospace industry, both in the use unconventional pigments to obtain camouflage proper-
field and in the laboratory due to their accuracy and ease of ties. In order to confirm that two colors are the same, their
use. One problem encountered is that aircraft are constructed total reflectance over the entire visible spectrum must match.
of a number of types of materials. Therefore, the method used These data are obtained using a spectrophotometer. In addi-
to determine coating thickness may depend on the substrate tion, spectrophotometers are frequently used for military air-
material, especially if a nondestructive method is used. craft coatings to determine their reflectance characteristics
outside of the visible region, most commonly the infrared and
ultraviolet regions.
OPTICAL PROPERTIES
General
Opacity (Contrast Ratio)
The appearance of an applied coating is determined by a
number of optical properties (color, gloss, opacity, etc.). In Opacity or hiding power is the ability of a coating to mask
the commercial aerospace industry, where public opinion is a the underlying substrate. Opacity of aircraft coatings is
consideration, these optical properties can strongly affect the usually quantified by its contrast ratio according to ASTM
initial impression of the aircraft and are considered to be Test Method for Hiding Power of Paints by Reflectometry
important with respect to customer recognition. The optical (D 2805). In this method, the coating is applied over white
properties of coating systems for military aircraft affect the and black substrates. (Contrast ratio or Leneta charts are
detectability of these aircraft and thus effect their sur- typically used.) A colorimeter is used to measure the coating's
vivability in potentially threatening scenarios. In both the luminous reflectance (Y) on the black and white surfaces.
commercial and military sectors, optical properties are speci- Contrast ratio is then determined by:
fied with strict tolerances and are closely monitored with
Contrast ratio = Y(hlack)/Y(white)
instrumentation as well as with the naked eye.
Contrast ratio is a function of coating dry film thickness.
The method must define the coating thickness at which the
Color contrast ratio is determined; 2.0 mils is common for aircraft
The colors used on commercial aircraft tend to be strong topcoats. Applying a coating to a precise thickness is difficult
and vibrant for recognition and attraction. The colors of mili- and may require several attempts. An alternative approach is
tary aircraft coatings are empirically selected in order to to determine the contrast ratio at several coating thicknesses
achieve either theater-specific (desert, forest, arctic, etc.) or and subsequently fit the data to a quadratic equation. This
multi-theater (world-wide) camouflage paint scheme require- equation can then be used to determine the contrast ratio at
ments. In either case, paint color is considered to be impor- the desired coating thickness.
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Reflectance and Gloss scribe lines create a matrix of 100 squares. Adhesive tape is
firmly applied over the scribe area and is subsequently re-
Incident light which is reflected from a surface has two
moved with a quick upward motion. Coating adhesion is then
components, specular and diffuse. Specular reflectance or
characterized using standard ratings for the amount of coat-
gloss represents light that has been reflected off a surface
ing removed according to the ASTM method.
when the angle of incidence equals the angle of viewing.
As mentioned above, the coated specimens can be sub-
Diffuse reflectance is light reflected in all directions other
jected to a specific environment prior to testing adhesion
than specular. Specular reflectance data are usually obtained
characteristics. This practice is most commonly performed
via glossmeters whereas diffuse reflectance data are obtained
with the tape tests. A typical exposure for aerospace coatings
by the use of goniophotometers.
is a 24-h immersion in water at 21~ (70~ More severe
Gloss of aircraft coatings is measured by instruments that
exposures are becoming common as coating technology ad-
have been standardized to either 60 ~ or 85 ~ incident angles
vances. One example is immersion in water at 65~ (150~
according to ASTM Test Method for Specular Gloss (D 523).
for seven days. Immediately upon removal from the water,
Commercial aircraft coatings have high gloss and are usually
the coating is scribed and tested.
characterized at 60 ~. In contrast, many military aircraft are
painted with low gloss coatings for camouflage purposes. In
addition to gloss analysis at 60 ~, military coatings are also Scrape Adhesion Test
analyzed at 85 ~ in order to minimize glare at grazing angles.
The scrape adhesion test is described in ASTM Test Method
Directional reflectance represents the optical data that are
for Adhesion of Organic Coatings by Scrape Adhesion
obtained from analyzing reflected diffuse light. This type of
(D 2197). Scrape adhesion is used to characterize the adhe-
data are normally obtained via goniophotometric equipment.
sive and shear strength properties at the primer-substrate
Several methods describe procedures for these measure-
interface. The instrument used for this test is the Gardner
ments, including ASTM Test Method for Directional Reflec-
Labs Scrape Adhesion Test Apparatus (Model SG- 1605). The
tance Factor, 45 deg, 0 deg, of Opaque Specimens by Broad-
specimen for this test has an area which is uncoated with the
Band Filter Reflectometry (E 1347) and Practice for Go-
substrate exposed. The test is performed by guiding a
niophotometry of Objects and Materials (E 167). The use of
weighted stylus at a 45 ~ angle to the specimen along the
diffuse reflectance of aircraft coatings is typically limited to
exposed substrate into the coating system. The scrape adhe-
those for tactical military functions which require camou-
sion value is recorded as the heaviest weight used without
flage properties.
shearing the coating from the substrate. Typical scrape adhe-
sion values for aerospace primers fall into the 3 to 5-kS range.
The scrape adhesion test is also used to determine the
ADHESION
intercoat adhesion between a topcoat and a primer. When
testing this property, a specimen with a section of primer
General
exposed is used and the stylus is guided across the primer
For aircraft coatings to provide maximum protection into the topcoat. Typical scrape adhesion values for aero-
against degradation, they must firmly adhere to their sub- space topcoats also fall into the range of 3 to 5 ks. This test
strate. Because of the complex nature of adhesion, various can also be performed after exposure to severe environmental
techniques have been devised to determine the adhesive char- conditions.
acteristics of coatings. Since a coating's adhesion to its sub-
strate can be significantly affected by environmental condi-
Peel and Tensile Tests
tions, these tests are often performed after exposure to
accelerated conditions such as immersion in water at ele- Peel test methods are rarely used for aircraft coatings. In-
vated temperature. Common adhesion tests used to evaluate stead, a modified version of an adhesive peel test is occasion-
aircraft coatings are tape and scrape tests. Other techniques, ally used. In this test, two thin metal strips are bonded to-
such as mechanical peel, tensile, and shear tests, are used less gether using the coating as the adhesive. One end of the
frequently. specimen is left unbonded, and the metal strips at this end are
separated to form a "T." They are subsequently pulled apart in
a tensile machine, and the force needed to pull the two strips
Tape Tests
apart is recorded as the adhesive peel strength of the coating.
Adhesion tape tests are described in ASTM Test Methods The type of failure (adhesive or cohesive) is also recorded. An
for Measuring Adhesion by Tape Test (D 3359). These are the adhesive failure indicates that the coating strength exceeds
easiest and most versatile of the adhesion tests because they that of the coating-substrate adhesive strength.
can be conducted in both laboratory and field environments. The most common tensile adhesion test used on aerospace
Tape tests are performed by cutting through the applied coat- coatings is a tensile pull-off test, also referred to as a button
ing, into the substrate. A variety of scribe patterns can be test. In this test, a flat head paten is bonded to the surface of
used. One common pattern (described in the "A" method of the coating with an adhesive. A tensile force is then applied to
D 3359), which is used to evaluate aircraft coatings, is two the paten perpendicular to the coating surface until the paten
scribes forming an "X." An alternative pattern (described in is removed. The location at which the paten is removed from
the "B" method of D 3359), is formed by scribing eleven par- the surface must be carefully examined. In many cases, the
allel lines through the coating, followed by a second set of adhesive which bonds the paten to the coating will fail or the
eleven lines which are perpendicular to the first set. These coating may fail cohesively. In these cases, it can only be
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CHAPTER 58--AEROSPACE AND AIRCRAFT COATINGS 689
stated that the adhesive strength of the coating exceeds the heights. The weight of the impact cylinder and the highest
tensile strength recorded. Only if the coating fails adhesively height that causes no cracking or disbondment of the coating
is the recorded tensile strength that of the coating-substrate are used to calculate an impact strength, usually in inch-
adhesion. pounds. This test can be performed directly on the coated
side of the panel or, like the GE impact test, on the reverse,
uncoated side.
FLEXIBILITY
General Tensile (Elongation) and Fatigue Tests

Flexibility is an important property for aerospace coatings,
For aerospace coatings, free films of the coating generally 5
particularly at low temperatures ( - 51~ which is common
mils thick or greater are prepared and tested for tensile char-
for aircraft cruising at high altitudes. Cracking of coatings at
acteristics. Epoxy primers have relatively high tensile
skin joints and around fastener heads can lead to corrosion of
strengths (>2500 psi) but very poor elongations (<10%),
exposed areas. Corrosion inhibiting epoxy primers used on
whereas flexible primers can have elongations exceeding
aircraft tend to be brittle and exhibit poor flexibility, whereas
100%. It should be noted that the rate of deformation has a
the urethane topcoats are generally more flexible, especially
significant effect on mechanical properties, including tensile,
at low temperatures. Sealant materials and elastomeric
and this must be clearly specified as part of the testing proce-
primers occasionally are used to improve the overall flexibil-
ity of the paint system. dure. For this reason, elongations obtained from impact tests
cannot usually be directly correlated with those from tension
tests.
Mandrel Bend Fatigue tests are not usually performed to study coating
performance. However, fatigue testing of coated specimens
The flexibility of high-performance coatings is commonly
with fasteners has been performed to study cracking of air-
characterized by the mandrel bend test method outlined in
craft paints around fastener heads. In these studies, increased
ASTM Test Methods for Mandrel Bend Test of Attached Or-
flexibility of the coating generally leads to less cracking and
ganic Coatings (D 522). This test is normally conducted at
better overall performance. Isolated studies [8] have been
low temperatures such as - 51~ and is performed by bend-
reported in which coatings were used as a variable in fatigue
ing a painted specimen 180~ around mandrels of various
diameters with the coating aligned away from the mandrel. testing of metal test fixtures. In these studies, a series of
After allowing the specimen to return to room temperature, specimens were exposed to a corrosive environment to in-
the coating is examined for cracking along the bend. The duce corrosion fatigue. In these cases, flexibility and corro-
smallest (most severe) mandrel diameter which the coating sion inhibition are essential characteristics of the coating.
can withstand without cracking is recorded. One standard
military specification requirement for this test on low gloss
coatings is a 2-in. mandrel bend while more flexible coatings
can withstand mandrel bends of 88 to 88 in. at low tempera- WEAR RESISTANCE
tures without cracking.
General
Impact Tests Aircraft coating systems can experience wear due to a num-
The most universal test for measuring impact flexibility of ber of causes and mechanisms. The most obvious of these is
aerospace coatings is Method 6226 (G.E. Impact) of Federal abrasion at leading edges of wings, antennas, and radomes
Test Method Standard 14 lB. The test apparatus consists of a caused by impingement of rain, sleet, dirt, and other debris.
solid steel cylinder weighing 1.69 kg (3.7 lb) which has spher- Since these leading edges are critical to flight dynamics, spe-
ical knobs protruding from the end. These knobs are designed cial wear-resistant coatings are often applied to these areas to
such that the coating system is subjected to elongations of protect the underlying substrate from damage. Another form
0.5, 1, 2, 5, 10, 20, 40, and 60%. The impact is accomplished of wear can be caused from the movement of adjacent parts
by allowing the steel cylinder to fall freely from a height of such as flaps and stabilizers. In addition, internal parts such
1.05 m (42 in.) through a hollow cylinder guide, striking the as bearings may be coated to prevent excessive wear. Since all
reverse uncoated side of the specimen. The imprints formed of these types of wear cause different mechanisms of coating
from the knobs are examined, and the impact elongation is degradation, a number of varying tests are performed to
recorded as the highest deformation without cracking of the simulate in-service conditions. For example, coatings which
coating. A standard requirement for this test on aircraft top protect against rain erosion do not usually protect well
coats is 20% elongation. against erosion from sand. Specifications for aircraft coat-
Another commonly used test is the Gardner impact test ings (other than those for rain erosion) typically do not con-
specified in ASTM Test Method for Resistance of Organic tain wear tests; however, development and selection of new
Coatings to the Effects of Rapid Deformation (Impact) aerospace coatings often require that characterization of
(D 2794). This test is performed in a similar fashion to the wear properties be performed. Therefore, careful evaluation
G.E. impact test described above; however, the weighted of wear mechanisms and selection of suitable evaluation
cylinder has a rounded end and is dropped from various methods is essential for these types of coatings.
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Rain Erosion Shore Hardness

There are a number of facilities throughout the United The Shore hardness test (ASTM Test Method for Rubber
States which have built equipment to evaluate rain erosion. Property-Durometer Hardness (D 2240)) is inappropriate for
Some of these facilities are discussed in Refs 9 and 10. In thin coatings (thickness <6.4 mm or 0.25 in.). However, for
general, coatings are applied to a small specimen which is thicker coatings such as sealants, ablative, and intumescent
subsequently secured to a test fixture arm. The test is per- materials it can be used to evaluate hardness, cure, and
formed by spinning this arm in a chamber with falling water environmental effects.
droplets that impinge upon the coated surface. Parameters of
the test include:
Arco Microknife
1. Substrate material, thickness, and geometry.
2. Coating type and thickness. Although the microknife test was originally designed to
3. Water droplet size and falling rate. evaluate adhesive strength of coatings, it has been used to
4. Testing arm speed (specimen-water droplet impact). determine hardness. This can be performed by placing a spec-
Although attempts to correlate data from various test rigs ified weight on the diamond stylus and determining the num-
have been unsuccessful at obtaining quantitative relation- ber of scratch cycles required to cut through the coating. It
ships, trends in coating performance have been observed. can also be performed by determining the weight needed to
These trends generally agree with rain erosion performance get through the coating with a specified number of cycles.
on aircraft.
Mar Resistance
Air Blast Mar resistance is not usually considered a critical property
for aircraft coatings. One method is the balance beam test
Techniques that are used to evaluate erosion from sand,
that uses the scrape adhesion apparatus described in ASTM
dirt, and other foreign debris typically involve an air blast to
Test Methods for Adhesion of Organic Coatings by Scrape
impinge particles on to the coating surface. A common
method is ASTM Test Method for Abrasion Resistance of Adhesion (D 2197). The method determines the weight re-
quired to mar a coating surface with a stylus.
Organic Coatings by Air Blast Abrasive (D 658). This method
uses 75-/~m silicon carbide particles flowing at a rate of 45
g/rain with an air supply pressure of 13 kPa. The method is
often modified to evaluate effects of other particles and air
CORROSION INHIBITION
pressures. The results can be reported as the weight of debris
necessary to abrade a unit film thickness or as the weight loss
Salt Spray
of coating per weight of abrasive used. Corrosion resistance is an important property for aero-
space coatings, and numerous tests have been developed to
evaluate the corrosion preventive properties of coatings,
Taber Abraser ranging from simple exposure studies to sophisticated elec-
ASTM Test Method for Abrasion Resistance of Organic trochemical analysis.
Coatings by the Taber Abraser (D 4060) is a frequently used Salt spray tests are commonly used as accelerated corro-
test throughout the coatings industry because it is well de- sion resistance tests for coatings. The two primary methods
fined and relatively easy to perform. As such, it is often used used for aircraft coating systems are the 5% NaC1 neutral salt
for aircraft coatings to assess their wear characteristics. Care spray test covered by ASTM Test Method of Salt Spray (Fog)
must be taken in interpreting Taber abraser results since Testing (B 117) and the acidified SO2/salt spray test covered
reproducibility of data from lab to lab is not consistent. by ASTM Practice for Modified Salt Spray (Fog) Testing
(G 85). Specimens coated with an aircraft finishing system
are usually scribed with an "X" through the coating into the
HARDNESS AND MAR RESISTANCE substrate and then exposed for various times (usually 1000 to
3000 h for ASTM B 117 and 48 to 1000 h for ASTM G 85).
Pencil Hardness Exposure periods for coatings vary for different substrate
materials and can be selected either as a specified duration or
The most frequently used test for hardness of aircraft coat- as the point where significant differences in finishing system
ings is the pencil hardness test, ASTM Test Method for Film performance are observed. After exposure, the panels are
Hardness by Pencil Test (D 3363). Briefly stated, it is per- inspected for corrosion in the scribe area and blistering or
formed by guiding pencils of various hardness across a coat- uplifting of the coating across the specimen. Subsequently,
ing surface to determine the hardest pencil that will not the coatings can be carefully removed from the surface with-
scratch or mar the coating. The test is used on aircraft coat- out disturbing the underlying substrate by using a chemical
ings for several reasons, including: stripper, and the specimen surface can be examined for evi-
1. To assess coating cure and cure rate. dence of corrosion.
2. To evaluate the coating's ultimate hardness. Standard aircraft epoxy primer/polyurethane topcoat sys-
3. To evaluate damage caused by weathering and operational tems perform well on aluminum substrates in the neutral
fluids (such as, by comparing coating hardness before and test, normally exhibiting no significant corrosion products in
after exposure). the scribe or any blistering of the coating after 1000 h. These
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materials may last up to 3000 h without any evidence of cial adhesion. References 12 and 13 provide detailed descrip-
corrosion. The SO2/salt spray environment simulates stack tions of EIS and its application for analyzing organic coating/
gases such as those found in industrial areas and on diesel- metal substrate systems. EIS measurements can be made
powered aircraft carriers. It is an extremely aggressive envi- using equipment like EG&G Princeton Applied Research
ronment, and aircraft systems exposed to this environment Corp. (PARC) Model M388 Impedance System. Test cells
tend to fail at much shorter times than in the neutral test. A consist of a glass o-ring joint clamped onto a coated metal
system exhibiting no significant corrosion products or blis- specimen [12]. Electrolytes used for specimen exposure can
tering after 500 h is normally considered acceptable in this range from distilled water to neutral or low pH salt solutions.
acidified environment. For an EIS experiment, the test cell described above is filled
Because numerous materials are used in the construction with the selected electrolyte solution. A reference electrode
of aircraft, the contact of dissimilar materials is common. (such as, Calomel) and a counter electrode (such as, platinum
When this occurs, the potential for galvanic corrosion is high or graphite) are immersed in the cell with the metal substrate
if the two dissimilar materials are not insulated from each serving as the working electrode. The EIS cell is allowed to
other. In many cases, organic coatings are applied to provide reach equilibrium as indicated by its open circuit potential or
this insulation. Therefore, it is becoming common to assess steady-state rest potential. Small excitation amplitudes, usu-
the ability of aircraft coatings to inhibit galvanic corrosion by ally in the 5 to 10-mV range, are introduced to the system, and
painting and exposing specimens containing dissimilar mate- the response signal is measured. These data can be correlated
rials. One example is a graphite-epoxy composite coupled to to an electrical circuit consisting of resistors and capacitors.
aluminum. The information from this electrical circuit is a model depict-
ing the electrochemical reactions occurring in the coating-
substrate system. Because of the detailed quantitative infor-
Immersion Studies
mation that is obtained from EIS analysis, it's use as a tool to
Total immersion corrosion tests can be severe depending research high-performance aircraft coatings is growing. In
on the immersion solution, duration, and exposure tempera- many cases, attempts are made to correlate EIS data with
ture. Again, blistering or uplifting of the coating or corrosion results from other corrosion studies such as salt spray. This
of the underlying substrate constitutes failure in this test. approach provides a detailed assessment of coating integrity,
Although this type of evaluation is not typically performed on durability, and corrosion inhibition.
aircraft paints, coatings requiring a high degree of im-
permeability, like those used in or around aircraft bilge areas,
galley, lavatories, and other areas where water can be en- WEATHERING AND ENVIRONMENTAL
trapped, would be evaluated with this type of test. EXPOSURE
Filiform Corrosion Outdoor Exposure

Filiform corrosion occurs on painted aluminum, steel, and Outdoor exposure tests are normally conducted over pe-
magnesium in a high-humidity and elevated temperature riods of one year or more. In an effort to produce timely
environment containing oxygen and chloride ions. Filiform results, these tests are not frequently performed on aircraft
initiates at points where the coating ruptures (commonly coatings. However, one common specification for an aero-
around fastener patterns or panel seams) and propagates as space topcoat, MIL-C-83286, does require a one year expo-
filaments under the coating. If unchecked, damage of the sure of coated panels on an outdoor test rack in Florida. It is
coating system can allow other corrosion mechanisms such specified that the panels must be at a 45 ~ angle and facing
as stress corrosion cracking, exfoliation, and crevice corro- south. After this exposure period, the coating is evaluated for
sion to ensue. Typical filiform corrosion tests involve expos- changes in color, gloss, and flexibility.
ing coated specimens to hydrogen chloride vapors and then The U.S. Navy has instituted a program to evaluate the
placing them into a high-humidity (85 to 95% RH) and ele- exterior durability of coatings in its operational environment
vated temperature (85 to 140~ environment for a specified by placing exposure racks on aircraft carriers and other ships.
duration such as 1000 h. It should be noted that this type of Results of these exposures have resulted in identification of
corrosion is prominent on pure aluminum. For this reason, successful aircraft coatings. Details of this effort are provided
the test is performed on aluminum clad specimens in lieu of in Ref 14.
aluminum alloy.
Accelerated Weathering
Electrochemical Analysis
The components of outdoor natural weathering which have
Reference 11 provides a thorough review of electrochemi- the most significant effects on coatings and other materials
cal methods used to evaluate the performance of corrosion are ultraviolet radiation and water (humidity, condensation,
protective coatings. Of these methods, electrochemical im- rain, etc.). It has been proposed that these conditions can be
pedance spectroscopy (EIS) is one of the most promising simulated and that the resulting effects can be accelerated by
techniques because it provides both qualitative and quantita- subjecting coatings and other materials to high-intensity light
tive information about the corrosion resistance properties of (including ultraviolet wavelengths) and water.
the coatings and the substrates to which they are applied. In The most common accelerated weathering methods used
addition, EIS can give insight on the nature of their interfa- for aircraft coatings are the xenon-arc Weatherometer and
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the QUV accelerated weathering tester. The former method is variable. Following exposure, the specimen is usually evalu-
described in ASTM Practice for Operating Light-Exposure ated for degradation of the coating (discoloration, softening,
Apparatus (Xenon-Arc Type) with and Without Water for Ex- blistering, etc.) and substrate (corrosion).
posure of Nonmetallic Materials (G 26). Again, there are a
number of test variables which have significant effects on
Water Resistance
coating performance, and various laboratories have adopted
slightly different procedures and parameters. Since there are Resistance to water is usually performed by total immer-
no precise correlations between natural weathering and any sion. The severity of the exposure can range from 24 h at
of the accelerated methods for aircraft coatings, it is espe- ambient temperatures to seven days at 65~ (150~ Since
cially important that the test variables are well defined. One water can play a significant role in coating disbondment [15],
common approach that is used in military and federal specifi- adhesion tests are frequently performed immediately upon
cations (MIL-C-85285, Coating, Polyurethane, High Solids removal of the coated specimen from water immersion.
and TT-P-2756, Polyurethane Coating: Self-Priming Topcoat, Another technique is to measure the water absorption (up-
Low VOC) follows ASTM G 26, Type BF as a guideline. The take) of a coating as a function of immersion time. This is
exposure is performed in a 6000-W, xenon arc weatherometer performed by simply weighing the coated panel (or free film)
with a continuous cycle consisting of 102 min of high-inten- as a function of immersion time. Water up-take values for
sity light only and 18 min of light and water spray. The high-performance aircraft coatings can range up to 20%.
conditions in the chamber are as follows: A third technique to characterize the effects of water on a
1. Black body temperature 60~ (140~ coating is to determine its water vapor transmission rate
2. Relative humidity 50% (WVTR). WVTR is a measure of the rate at which water will
3. Intensity of the arc wavelength 0.55 W per m 2 permeate through a coating. ASTM Test Method for Water
at 340 nm Vapor Transmission of Organic Coating Films (D 1653) de-
The exposure period is 500 h, and the coating is subsequently scribes two methods to determine WVTR. In Method "A," a
evaluated for changes in gloss, color, and flexibility. free film of the coating is sealed to the open mouth of a cup
The second common method for accelerated weathering is containing distilled water. In Method "B," the free film is
described in ASTM Practice for Operating Light- and Water- sealed to a cup containing desiccant. These fixtures are ex-
Exposure Apparatus (Fluorescent UV-Condensation Type) posed to controlled environments (temperature and humid-
for Exposure of Nonmetallic Materials (G 53). In this case, ity), and they are weighed periodically to determine the rate
specimens are subjected to periods of ultraviolet light and of water vapor diffusion through the coating. Aircraft coat-
condensation, respectively. During the condensation period, ings must exhibit low WVTRs to maintain their adhesion and
the coating surface is exposed to 100% relative humidity at corrosion inhibition.
elevated temperature, while the back side of the specimen is
exposed to cooler air, thus producing water condensate on
Organic Solvent Resistance
the coating. Exposure parameters include UV intensity, dura-
tion of exposure to each condition, and temperature of the Resistance to organic solvents is usually performed by rub-
chamber and condensate. bing a coated panel with a cloth dampened with a specified
solvent. Since toluene and methyl ethyl ketone (MEK) are
both harsh and have been frequently used in the aerospace
Humidity
industry, they are common solvents. After rubbing the sur-
Since high temperature and humidity can cause coating face, the coating is inspected for color change, dissolution, or
disbondment and substrate corrosion, extreme humidity ex- any abnormality which may have been caused by the solvent.
posure is often performed on aircraft coatings to evaluate The cloth can also be inspected for residue which may be
their resistance to such environments. Again, exposure pa- apparent by a color change.
rameters vary and must be clearly specified for reproducibil-
ity and interpretation of results. ASTM Practice for Testing
Hydraulic Fluids and Engine Oils
Water Resistance of Coatings in 100% Relative Humidity
(D 2247) is usually followed. The chamber conditions are Hydraulic fluids and engine oils are frequently used at ele-
49~ (120~ and 100% relative humidity with constant con- vated temperatures, and therefore their attack on aircraft
densation on the coated panels. A typical exposure period can coatings can be accelerated and more severe. Table 2 de-
range from 30 to 90 days. scribes typical immersion tests using these fluids.
FLUID RESISTANCE HEAT RESISTANCE
Aircraft coatings are frequently subjected to aggressive op- Aerodynamic heating can produce skin temperatures of
erational and environmental fluids. Several examples are hy- 121~ (250~ in level flight and 176~ (350~ during high-
draulic fluids, engine oils, fuel, deicing solutions, and speed maneuvers. Painted components adjacent to engines
cleaners. In order to assess the resistance of aircraft coatings and exhaust tracks may experience unusually high tempera-
to these fluids, a number of exposure tests are performed. The tures. This heat may exceed the maximum service tempera-
exposure can range from a simple wiping action to long-term ture of some organic coatings, which may cause darkening,
immersion. The temperature of the exposure is also a critical embrittlement, and/or premature aging. The heat resistance
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C H A P T E R 5 8 - - A E R O S P A C E AND A I R C R A F T C O A T I N G S 693
TABLE 2--Aircraft operational fluid immersion tests. be adequately performed, strippability tests are conducted in
Material Duration Temperature the laboratory as part of the coating evaluation procedure.
One common testing procedure is accomplished by applying
Lubricating oil (MIL-L-23699) 12l~ (250~
Hours: 24 / a chemical paint stripper, such as MIL-R-81294, onto the
Hydraulic fluid (MIL-H-83282) 66~ (150~ surface of a coated specimen. After a specified period of time
Hours: 24 (usually 1 h), the panel is abraded with a stiff bristle brush
Fire-resistant hydraulic fluid 21~ (70~ and rinsed with water to remove loosened paint. Usually, 90%
Days: 7
Jet fuel (JP-4, JP-5) removal of the coating from the substrate is considered ac-
2 l~ (70~
Days: 7 ceptable.
of a coating is determined by subjecting a coated panel to a CLEANABILITY

constant temperature for a specific period of time. For exam-
ple, specification MIL-C-85285B requires that a polyurethane Low-gloss aircraft coatings, such as those used in camou-
topcoat withstand exposure to a 121~ (250~ oven for 1 h flage schemes on military aircraft, become dirtier and are
without a significant color change (maximum delta E value of more difficult to clean and restore than high-gloss coatings.
1.0). This is primarily due to the increased surface roughness of
low-gloss coatings, which entraps carbonaceous and oily
soils as discussed in References 17 and 18.
Thermal Fatigue
The cleanability or the ease at which dirt and soil can be
Thermal fatigue refers to the resistance of a coating to removed from a coating surface can be quantified by consis-
stresses induced by rapid temperature changes. Often called tently soiling a coating and using a standard cleaner and
thermal shock, this simulates the effect of take-off from hot cleaning motion in attempts to remove this soil. Measuring
(and sometimes humid) ground temperatures to the cold at- the color difference of the coating prior to soiling and subse-
mosphere at high altitudes and then back again. The MIL-C- quent to cleaning provides an indication of the coatings
81945B intumescent coating used on weapons must with- cleanability. The following is a detailed procedure for the
stand 60~ (140~ 95% relative humidity for 24 h followed evaluation of the cleanability of aircraft coatings. The soil in
by -40~ (-40~ for 24 h. The coating is then cycled be- this procedure was generated using a hydraulic fluid. This
tween the two chambers for 28 days. Cracks extending deep soil is representative of that found on operational aircraft.
into the coating indicate failure in this test. Method 503.1 of Other soils can be derived from greases and lubricating oils.
MIL-STD-810 provides further guidance.
Thermal C o n d u c t i v i t y APPARATUS REQUIRED
Stored weapons (bombs, missiles, etc.), including those 1. Test panels 7.62 by 15.24 by 0.05 cm (3 by 6 by 0.02 in.) of
used on military aircraft, must be protected from accidental 2024 T3 aluminum alloy chromate conversion coated
fuel fires. This is accomplished with exterior, insulating coat- with materials conforming to military specification MIL-
ings on those weapons that delay ordnance reactions and C-81706 to produce a coating meeting MIL-C-5541.
provide fire fighters sufficient time to extinguish the fire. The 2. One-liter, wide-mouth, glass jars.
efficiency of these coatings is measured by a unique test, 3. Balance, accurate to 0.1 g.
originally developed by NASA [16]. It uses a small furnace 4. High shear mixer.
burning JP-4 or JP-5 aviation fuel to produce a constant heat- 5. Hog bristle brush (Gardner WG-2000-B).
flux of 10 btu/ft2-s at a flame temperature of approximately 6. Acid brushes.
1800~ (982~ A coated panel is mounted to an open port 7. Rubber roller, 2270 g (5 lb).
above the furnace, and the temperature of the uncoated back- 8. Forced draft oven capable of 105~ (221~
side is recorded as a function of time. The thermal efficiency 9. Wear tester (Gardner Heavy Duty Wear Tester).
is calculated from these data. It is expressed as the number of 10. Template for positioning and holding test panels on the
seconds/mil of coating thickness for the backside tempera- wear tester.
ture to reach either 500~ (260~ or 1000~ (537~ (Most 11. Cellulose sponge backed with nylon web (Scotch Brite
explosives and propellants react between these two tempera- 63).
tures.) Specification MIL-C-81945B requires that intu-
mescent coatings have a minimum thermal efficiency of 2
s/rail to 500~ (260~ P R E P A R A T I O N OF SOIL
1. Place 50 g of carbon black (such as Raven 1040 manufac-

STRIPPABILITY tured by Columbian Chemical Company) in 500 g of hy-
draulic fluid meeting military specification MIL-C-83282.
Aircraft are periodically returned to depot maintenance 2. Homogenize the carbon black and hydraulic fluid mixture
facilities for inspection and overhaul. At this time, the air- using a high shear mixer for 15 min. Prior to application of
craft's exterior coating system is removed by chemical and/or the soil to the specimen, thoroughly stir or shake the mix-
mechanical means. In order to insure that this procedure can ture to obtain a thorough dispersion.
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P R E P A R A T I O N OF T H E CONTROL a n d clean for an a d d i t i o n a l 5 cycles. Rinse the test panel

FORMULA CLEANER u n d e r a flowing s t r e a m of tap w a t e r at r o o m t e m p e r a t u r e
for 2 rain a n d allow to fully dry.
1. Any desired aircraft cleaned can be used. However, the 3. Measure the L, a, a n d b values on the s a m c o l o r i m e t e r used
following is a control f o r m u l a t i o n m e e t i n g a c o m m o n air- p r i o r to the cleaning p r o c e d u r e a n d r e c o r d t h e m as Lf, af,
craft cleaner (MIL-C-85570, Type II) as listed in P a r a g r a p h a n d bf, respectively.
4.6.13.1 of the specification. 4. Calculate the change in color due to soiling a n d cleaning
2. Mix the first five ingredients listed below, then neutralize according to the following equation
the mixture to a p H of 8.0 with acetic acid. Mix the last two
DELTA E = [ ( L f - Li) 2 d- (af - ai) 2 + ( b f - bi)2] 0"5
ingredients t o g e t h e r a n d t h e n a d d that to the initial mix-
ture. 5. A m i n i m u m of three replicates should be tested for each
Igepal CO-630 (1) 10.0 parts b y weight coating at each condition.
M o n a m i d 150 CW (2) 5.0
Dipropylene glycol methyl e t h e r 10.0
Deionized w a t e r 71.5 REFERENCES
Benzotriazole 0.5
H o s t a c o r 2098 (3) 2.0 [1] Miller, R. N., Predictive Corrosion Modeling Phase I/Task II Sum-
Morphaline 1.0 mary Report, Air Force Wright Aeronautical Laboratories Report
(1) GAF Corporation, o r equivalent. AFWAL-TR-87-4069, Wright-Patterson Air Force Base, OH, Au-
(2) M o n a Industries Inc., o r equivalent. gust 1987.
(3) A m e r i c a n H o e c h s t Corp., or equivalent. [2] Hegedus, C. R., Eng, A. T., and Hirst, D. J., Program Summary:
Unicoat Development, Laboratory Characterization, and Field
Evaluation, Naval Air Development Center, Warminster, PA,
March 1990.
P R E P A R A T I O N OF T E S T P A N E L S [3] Hegedus, C. R., A Combination Primer/Topcoat for Aluminum,
Society of Manufacturing Engineers, Finishing '87 Conference
1. To the c h r o m a t e conversion coated a l u m i n u m s p e c i m e n s Paper FC87-625, September 1987.
described, a p p l y a suitable p r i m e r for the desired topcoat. [4] Chattopadhyay, A. K. and Zentner, M. R., Aerospace and Air-
One such m a t e r i a l is epoxy p r i m e r c o n f o r m i n g to MIL-P- craft Coatings, Federation of Societies for Coatings Technology,
23377 Type I or II to a thickness of 15.2 to 2 2 . 9 / z m (0.6 to Philadelphia, PA, May 1990.
0.9 rail). Allow to dry for 1 h at a m b i e n t conditions. Apply [5] Lewin, J. B., "Aircraft Finishes," Treatise on Coatings Volume 4,
the desired t o p c o a t to the i n t e n d e d thickness. Allow the Formulation Part/, R. R. Meyers and S. J. Long, Eds., Marcel
coating to cure u n d e r the a p p r o p r i a t e conditions. Dekker, 1975, pp. 1-84.
[6] Hegedus, C. R., Pulley, D. F., Spadafora, S. J., Eng, A. T., and
2. After allowing the desired cure t i m e a n d conditions, use a
Hirst, D. J., "A Review of Organic Coating Technology for U.S.
bristle acid b r u s h to coat the p a i n t e d surface of a test panel
Naval Aircraft," Journal of Coatings Technology, Vol. 61, No. 778,
with the soil d e s c r i b e d in the "Preparation of Soil" section. 1989, p. 31.
Remove excess soil by covering the test panel surface with [7] Nicodemus, F. E., Richmond, J. C., Hisia, J. J., Ginsberg, I. W.,
tissue a n d exerting p r e s s u r e b y rolling the tissue with the and Limperis, T., Geometrical Considerations and Nomenclature
roller. R e p e a t this blotting three times using fresh tissue for Reflectance, National Institute for Science and Technology,
each time. B r u s h the soiled surface ten times in one direc- Washington, DC, NBS Monograph 160, October 1977.
tion only, parallel to the long d i m e n s i o n of the test panel, [8] Wanhill, R. J. H., DeLuccia, J. J., and Russo, M. T., The Fatigue
using the bog bristle brush. Bake the test p a n e l at 105~ in Aircraft Corrosion Testing (FACT) Programme, North Atlan-
(221~ for 60 min. tic Treaty Organization (NATO), Advisory Group for Aerospace
3. Measure the L, a, a n d b tristimulus values on a suitable Research and Development (AGARD), Report No. 713, p. 68,
c o l o r i m e t e r a n d r e c o r d the values as Li, ai, a n d b i, respec- February 1989.
[9] Stander, A. O., Summary Report of Rain-Erosion Phenomena,
tively.
Naval Air Engineering Center, Report No. NAEC-AML-2547,
Philadelphia, PA, December 1966.
[10] Military Standard MIL-STD-810, Environmental Test Methods
CLEANING P R O C E D U R E and Engineering Guidelines.
[11] Leidheiser, H. Jr., "Electrochemical Methods for Appraising
1. Dilute the control cleaner b y one p a r t cleaner with nine Corrosion Protective Coatings," Journal of Coatings Technology,
parts distilled w a t e r (by volume). Vol. 63, No. 802, 1991, p. 20.
2. Clean the test p a n e l w i t h i n 4 h using the w e a r tester as [12] Princeton Applied Research Corp., Electrochemical Instru-
follows. Cut the sponge with a n y texture "ribs" r u n n i n g ments Group, Application Note: AC-2, Evaluation of Organic
p e r p e n d i c u l a r to the cleaning stroke. W h e n the dry sponge Coatings by Electrochemical Impedance Measurements, Prince-
is a t t a c h e d to the cleaning h e a d on the w e a r tester, the ton, N J, not dated.
[13] Scully, J.R., Electrochemical Impedance Spectroscopy for
c o m b i n e d weight shall be between 1350 a n d 1400 g. Place
Evaluation of Coating Deterioration and Underfilm Corrosion--
the soiled test panel in the t e m p l a t e at an angle 45 ~ to the A State-of-the-Art Review, Report No. DTNSRDC/SME-86/006,
cleaning stroke. S a t u r a t e the sponge a n d cover the test David W. Taylor Naval Ship Research and Development Center,
panel with the diluted cleaner. After 55 to 65 s, clean the Annapolis, MD, September 1986.
test panel using 5 cycles (10 strokes) of the w e a r tester, [14] Agarwala, V. S., "Corrosion Monitoring of Shipboard Environ-
then i m m e d i a t e l y t u r n the test panel 90 ~ in the t e m p l a t e ments," Degradation of Metals in the Atmosphere, STP 965, S. W.
www.iran-mavad.com

Dean and T. S. Lee, Eds., American Society for Testing and [17] Hegedus, C. R. and Hirst, D. J., Metal Finishing, Vol. 86, No. 7,
Materials, Philadelphia, PA, 1986, pp. 354-365. 1988, p. 39.
[15] Spadafora, S. J., "Synergistic Soiling, Cleaning and Weathering [18] Hirst, D. J. and Hegedus, C. R., "Water Disbondment Character-
Effects on Aircraft Polyurethane Topcoats," Journal of the Oil ization of Polymer Coating/Metal Substrate Systems," Metal Fin-
and Color Chemists' Association, Vol. 71, No. 9, 1988, p. 276. ishing, Vol. 87, No. 1, 1989, p. 37.
[16] Fish, R., "Soil Retention of Aircraft Topcoats," NASA Ames Re-
search Center, Technical Brief 70-10450, Moffett Field, CA, May
1970.
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MNL17-EB/Jun. 1995
59
Architectural Coatings
by Harry E. Ashton ~
INTRODUCTION 3. End use--service location (interior, exterior), end user (in-

dustrial, painter, home), specific substrate (wood, metal,
Definition and Scope masonry), type of object (transportation, bridge, house),
particular exposure (marine, below-grade), etc.
THIS CHAPTERIS CONCERNEDwith the selection and use of 4. Method of cure--air-dry, bake, cold-cure, radiation-cure,
procedures for testing organic finishes intended for use on etc.
interior surfaces, exterior surfaces, or both interior and exte-
rior surfaces. Coatings comprise more than "paints" since the At times the terminology used in the coating industry can
latter are only one kind of coating as defined in ASTM Termi- seem confusing to a tyro in the field. For example, an alumi-
nology Relating to Paint, Varnish, Lacquer, and Related num finish may be used for application to aluminum objects
Products (D 16): or it may contain aluminum pigment and be used on various
objects. Although an automotive coating is intended for ap-
"coating--a liquid, liquefiable or mastic composition plication to automobiles, an architectural coating is not simi-
that is converted to a solid protective, decorative, or
functional adherent film after application as a thin larly intended for architects. Rather, an architectural coating
layer." is for the type of structure customarily designed by architects
in contrast to those designed by civil engineers. Another des-
"paint, n, specific--a classification sometimes employed
to distinguish pigmented drying oil coatings ("paints") ignation intended to reduce this potential confusion is "trade
from synthetic enamels and lacquers." sales coatings" that are coatings marketed through retail-
trade stores, in contrast to "industrial sales coatings" that are
Definitions used by the Federation of Societies for Coating
usually marketed directly to the end user.
Technology (FSCT) [1] for these terms are:
The definition for architectural coating given in the two
"Coating (1) Generic term for paints, lacquers, enamels, ASTM standards, D 5146 and D 5324, referred to below, com-
printing inks, etc. (2) A liquid, liquefiable or mastic combines the definition from ASTM D 16 with that in the FSCT's
position which is converted to a solid protective, decora-
Paint/Coatings Dictionary [1] as follows:
tive, or functional adherent film after application as a
thin layer." "Organic coatings intended for on-site application to in-
terior or exterior surfaces of residential, commercial, in-
"Paint (2) Noun. Any pigmented liquid, liquefiable, or
stitutional, or industrial buildings, in contrast to indus-
mastic composition designed for application to a sub-
trial coatings. They are protective and decorative finishes
strate in a thin layer which is converted to an opaque
applied at ambient temperatures. Often called Trade
solid film after application. Used for protection, decora-
tion or identification, or to serve some functional pur- Sales Coatings."
pose such as the filling or concealing of surface irregular- As with many types of coatings, the titles of the two ASTM
ities, the modification of light and heat radiation guides reflect the two main composition categories--water-
characteristics, etc." borne and solvent-borne. These categories indicate the type
Hence, clear varnishes and lacquers are familiar types of of volatile material used, both in manufacturing and in appli-
coatings that are not, strictly speaking, paints. As one com- cation, to reduce the film-forming ingredients to a suitable
pany has proudly, if not grammatically, referred to their application viscosity.
products, "Plain Paint It Ain't."
Since there are many different types of coatings, it is useful
to classify them into groups. This can he done in several ways Scope
as for example according to:
The intended uses and generic gloss range for conventional
1. Appearance--clear, high gloss, metallic, pigmented, red,
types of architectural coatings are as follows:
stain, textured, etc.
2. Composition--alkyd, latex, oil, solvent-borne, zinc-rich, 1. Interior finishes, low-gloss.
etc. 2. Interior finishes, semigloss and full-gloss.
3. Exterior house and trim coatings, low semigloss to moder-
ISenior research officer (retired), Building Materials Section, Insti- ate gloss.
tute for Research in Construction, National Research Council, Ot- 4. Exterior and/or interior floor finishes, gloss varies with the
tawa, Ontario, K1A 0R6 Canada. particular type of finish.
696
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CHAPTER 59--ARCHITECTURAL COATINGS 697
Each of these finishes is intended for application by brushing, required. These conditions include porosity, presence of
rolling, spraying, or other means to the substrates appropri- grease, dirt, mold, water-soluble or oily contaminants, and
ate to its end use, which may include wood, plaster, masonry, chalking or flaking of previous coatings. The smoothness of
wallboard, steel, previously painted surfaces, and other archi- the substrate affects the spreading rate, texture, and final
tectural suhstrates. appearance of the coating. Building defects arising from poor
One type of architectural interior coating differing from construction or deterioration in service or direct contact of
the generally accepted commercial types is called "high per- the substrate with the ground can result in persistent expo-
formance architectural coating (HIPAC)." Such coatings are sure of the coating to interior or exterior moisture with resul-
extra-durable systems applied as continuous films that cure tant failure by blistering, flaking, or peeling. Similar failures
to hard, tough finishes that are resistant to abrasion, staining, can occur where painted lumber is adjacent to damp ma-
chemicals, detergents, and mildew growth. Coatings of this sonry surfaces. Weathering of wood before painting probably
type usually are two-component epoxides or urethanes, or are will adversely affect the performance of exterior coatings.
moisture-cure urethanes. Other polymer types are not ex- However, some degree of weathering of masonry surfaces
cluded from this high-performance area if they can be for- may have a beneficial effect on performance by passivating
mulated into coatings that meet purchaser performance re- the surface and changing the alkalinity.
quirements. As with many conventional coatings, these high-
performance coatings are formulated at gloss levels that
range from very high to satin (low semigloss). Exterior Coatings
The durability and appearance of these coatings can be
ASTM GUIDES TO TESTING affected by short- and long-term environmental conditions.
ARCHITECTURAL COATINGS Surface dampness during application and drying can ad-
versely affect the adhesion of solvent-borne coatings but not
The ASTM guides listed below provide systematic compila- of water-borne coatings. However, low temperatures during
tions of relevant properties, the related test methods, and, the drying stage can prevent water-dispersed (latex) coatings
where possible, typical values, for the guidance of users. from forming cohesive films. Of course, no water-borne coat-
ing can be applied at temperatures below the freezing point of
ASTM D 3730: Guide for Testing High-Performance Inte-
water. A sunny service environment can be expected to en-
rior Architectural Wall Coatings
courage chalking and other forms of film deterioration. In
ASTM D 5146: Guide for Testing Solvent-Borne Architec-
contrast, a shady location, such as on the north side of a
tural Coatings
structure or nearby trees and shrubs, can protect the film
ASTM D 5324: Guide for Testing Water-Borne Architec-
from sunlight but it can promote mildew growth. Orientation
tural Coatings
of the coating toward sun or shade varies on different parts of
a building, e.g., fascia boards and porches.
CONDITIONS AFFECTING T H E USE OF
ORGANIC COATINGS
Interior Coatings
Substrate Types The porosity, smoothness, and color of the surfaces are
important factors for both new and repaint jobs. On new
Substrates may be wood products, masonry, bare plaster,
construction, low temperatures must be avoided when apply-
metal, wallboard, and even plastic. The nature of the sub-
strate can affect the application and appearance properties of ing water-borne finishes, and painting is preferably done at
a coating, such as uniformity and gloss, and is an important normal room temperature. If drying temperatures are too
factor in determining the type of coating to use. Specific ex- low, long drying times are needed and this can result in
amples of this are: significant dust and dirt accumulation on the film. If drying
temperatures are too high, the film will dry too rapidly and
1. A primer-sealer may be required for porous substrates,
side-by-side application areas may appear different because
such as unpainted drywall, new wood, plaster, or porous
they did not flow into each other. High relative humidity is
masonry.
also to be avoided when applying both solvent- and water-
2. Finishes intended only for interior service do not require
borne coatings. Primer coats should be allowed adequate
resistance to weather factors.
time to dry before applying the next coat.
3. Low-gloss wall finishes do not need the abrasion resistance
required of floor coatings.
Other factors of importance are the quality of the substrate,
General
which with wood products relates to grain, knots, and com-
positional structure, and with masonry and plaster products It should be recognized that proper surface preparation
relates to the degree of porosity and alkalinity. and correct application techniques are as important as the
inherent properties of a coating in contributing to adequate
Substrate Conditions performance. This is especially true for high-performance
coatings. After selecting the best material for a given service,
The condition of the surface is important in determining it is essential that the manufacturer's instructions be fol-
the type of coating and surface preparation that might be lowed.
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S E L E C T I O N OF T E S T S the weight by 100 results in g/mL or by 10 yields lb/Imperial

gallon. The density of water at the test temperature is used for
Service Location precise work or to establish a correction factor if the device is
worn, damaged, or dirty from poor cleaning in a way that
Because coatings on different surfaces, e.g., ceiling, floor,
effectively changes the internal volume of the cup. Typical
wall, and in different service environments, e.g., exterior or
coating densities are in the range of 10 to 12.5 lb/U.S, gallon
interior, are subjected to a variety of conditions, specialized
(1.2 to 1.5 kg/L) for water-borne paints. Solvent-borne coat-
coatings have been developed. The test methods discussed in
ings are in the 8 to 10 lb/U.S, gallon (0.9 to 1.2 kg/L) range due
this chapter cover practically all of the properties of architec-
to the lower density of the solvents used instead of water.
tural coatings. Not all of the tests are needed with any one
Instructions for carrying out the test are given in ASTM Test
coating type or location. Coatings intended for exterior use
Method for Density of Paint, Varnish, Lacquer, and Related
only or for both exterior and interior uses require certain
Products (D 1475). Other devices and methods for measuring
properties not relevant to those intended for interior use only.
density are presented elsewhere in the manual.
Property selection and methods of testing for these properties
must be governed by experience and the requirements in each
individual case and, preferably, by agreement between pur- Coarse Particles
chaser and seller.
To form uniform films with good appearance, liquid coat-
ings must be free of coarse particles and foreign matter. In
V a l u e Judgments general the glossier the film, the more detrimental such parti-
cles are to appearance. These particles are far larger than
The purchaser should first determine the properties re-
those determined in the fineness of dispersion method de-
quired of a coating and then select only the test methods
scribed below. They normally occur as a defect in the produc-
appropriate for those properties. After test selection the pur-
tion process that permits introduction of clumps of dry pig-
chaser should decide which properties are most important
ment or foreign matter such as pieces of shipping bags and
and establish specification requirements accordingly. Since
the like. The content of objectionable material is determined
coating properties frequently tend to oppose each other, such
with ASTM Test Methods for Coarse Particles in Pigments,
as low sheen versus good cleansability or good sag resistance
Pastes, and Paints (D 185) by straining the diluted coating
versus good leveling, some properties may need to be less
through a 325-mesh (45-/~m) screen and weighing the
emphasized if others are to be accentuated. This balance of
amount retained. A typical maximum requirement is 0.5% by
properties must be considered when selecting the tests and
weight. Objects such as pigment lumps, polymer seeds, etc.
establishing the requirements. No attempt is made herein or
with a generally spherical shape are retained on such a
in the ASTM standard guides listed above to indicate relative
screen. Linear objects like fiber strings can flow through this
importance of the various tests. Also, the referenced stan-
screen and may require other removal methods, such as cen-
dards do not recommend specific test values because proper-
trifuging. Screens are inexpensive and readily available, and
ties considered very important by one purchaser may be less
results obtained with them are easy to comprehend. Devices
so to another.
such as centrifuges are more expensive and more time con-
suming than screens, but they often yield more accurate
results than the latter.
P R O P E R T I E S OF LIQUID COATINGS
Density Fineness o f Dispersion

While density, measured in pounds per gallon or kilograms Generally, the more finely a pigment is dispersed, the more
per liter (-=g/mL), has no relation to the quality of a coating, it efficiently it is being utilized. Also, if pigment agglomerates
can be used by the purchaser to ensure product uniformity exceed the thickness of the dry film, it will be impossible to
from batch to batch. In production control, density provides obtain a coating of the desired degree of smoothness. One
a simple check against the formula weight since any signifi- method for measuring the degree of dispersion, commonly
cant deviation indicates an incorrectly made or mixed coat- referred to as "fineness of grind," is to draw the liquid coating
ing, including the presence of entrapped air. Density is gener- down a calibrated tapered groove varying in depth from 4 to
ally measured with a pycnometer, a container of precisely zero mils (100 to zero/zm), which is equivalent to zero to 8
known or measurable volume with a capillary cover through Hegman units. The depth at which continuous groupings of
which surplus liquid is expelled as the test temperature, nor- particles or agglomerates protrude through the surface of the
mally 77~ (25~ is approached. Laboratory pycnometers wet film is taken as the fineness of dispersion value. Good
are typically made of glass and have a narrow neck to reduce dispersion is indicated by high readings in Hegman units or
evaporation of volatile fluids. low readings in mils or micrometres. Lower gloss finishes do
The coating industry uses a special type of pycnometer not generally require a fine dispersion, so they might have a
called a "weight-per-gallon" (mass per unit volume) cup. It is dispersion value of 2.5 mils (65/zm or 3 Hegman units).
a plastic or metal wide-mouth cylinder, a shape convenient Some interior flat latex paints have finenesses as low as 3.5
for handling viscous coatings and polymers. Weight-per- mils (90/~m or 1 Hegman unit). Most interior semigloss and
gallon cups are usually made to hold 83.454 mL so that the gloss enamels have a fineness value of about 1.5 to 0.3 mils
weight in grams required to fill the cup divided by 10 is the (40 to 7/zm or 5 to 7.5 Hegman units), although some full
density in lb/U.S, gallon, or to hold 100 mL so that dividing gloss coatings might be near zero in depth, equivalent to 8
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Hegman units or as fine as can be measured by this method. Volatile Organic Compound (VOC)
Information about conducting the test appears in ASTM Test
Volatile organic compounds evaporate into the atmosphere
Method for Fineness of Dispersion of Pigment-Vehicle Sys- when coatings dry and/or cure, and they are believed to con-
tems (D 1210). tribute significantly to air pollution. The chief offenders in
this regard are solvent-borne coatings, although water-borne
coatings certainly contain some amounts of VOC. In addi-
Flash Point tion, many types of coatings that cure by chemical reaction,
This is almost exclusively a concern with solvent-borne in contrast to those that dry solely by evaporation of organic
coatings. The organic solvents used in these coatings have solvent or water, generate volatile molecules such as formal-
characteristic temperatures at which their vapors support dehyde and related compounds. Both types of materials react
combustion. This temperature is known as the flash point with each other and atmospheric oxygen in the presence of
and is often used for hazard classification in shipping by sunlight (i.e., photochemical reaction) to produce in the
lower atmosphere the actual pollutants, one of which is
common carrier. It is also used to determine conditions of
ozone. Some of the VOCs have also been related to the de-
storage to meet fire regulations and the U.S. Occupational
struction of ozone in the upper atmosphere. Organic vo]atiles
Safety and Health Act (OSHA). There are several accepted that are considered to have negligible photochemical activity
ways for measuring flash point that give somewhat different have, at least to the time of writing, not been included in the
results. For pigmented and/or viscous materials that require calculation of the VOC of a coating for regulatory purposes.
stirring to obtain consistent results, ASTM Test Methods for Such exempt solvents are very few and within a relatively
Flash Point by Pensky-Martens Closed Tester (D 93, Method short time there may be none at all. California and its local
B) is specified. The small specimen size used with ASTM Test agencies have been particularly active in specifying and en-
Methods for Flash Point of Liquids by Setaflash-Closed Cup forcing limits on the amount of VOC in coatings. Examples of
Apparatus (D 3278) eliminates the need for stirring. Since such restrictions are maxima of 350 g/L for "clear wood fin-
solvents do not require stirring, they are generally tested with ishes" and 400 g/L for quick-drying enamels. Since other
ASTM Test Method for Flash Point by Tag Closed Tester states have established their own limits, a national rule on
(D 56). VOC in architectural and industrial coatings is at present
Manufacturers of coatings do not always determine the being developed between representatives of the paint indus-
flash points of their products, but classify them on the basis try and the U.S. Environmental Protection Agency (EPA).
of the solvents they contain. Since this routine does not detect ASTM Practice for Determining Volatile Organic Compound
(VOC) Content of Paints and Related Coatings (D 3960),
inadvertent contamination, large-volume purchases are
U.S.A. EPA approved, and the recent manual by Brezinski [2]
sometimes tested for flash point, in some cases after thinning
discuss applicable ASTM test methods, provide equations for
at the job site. Further details about this technique can be calculating the VOC content in different ways, and provide
found elsewhere in this manual. other information valuable in this area.
Odor D i l u t i o n Stability
Some solvent combinations produce undesirable odors, This property is of concern primarily with solvent-borne
particularly when painting indoors with inadequate ventila- coatings because of the wide differences in solubility charac-
tion and at elevated temperatures. Although interior solvent- teristics of the binders and the solvent power of the various
borne coatings usually contain low-odor or odorless mineral solvents and thinners employed. It is, therefore, desirable to
spirits, they should nevertheless be evaluated for odor. Latex establish that a coating and the specified thinner are compat-
or other water-borne coatings, which contain relatively little ible and the reduced material is stable. Hence the suggested
if any organic solvent, may contain other ingredients such as diluent should, without excessive stirring or shaking, be read-
ammonia, residual monomer, etc., that might also be objec- ily incorporated into the coating in the recommended
tionable in a confined space. Hence both solvent- and water- proportions or to a specified viscosity. Method 4203 in FTMS
No. 141 requires that the mixture be allowed to stand for 4 h
borne coatings should be tested to establish whether the odor
and then be observed for curdling, flocculation, precipitation,
is irritating or merely unpleasant.
or separation into layers. If there is doubt about the stability,
Although not specifically designed for liquid coatings,
some of the material is then flowed onto a glass panel where
ASTM Test Method for Odor of Volatile Solvents and Diluents any incompatibility is more evident.
(D 1296) could be a suitable basis for the evaluation. This
method is a comparative procedure for observing character-
istic and residual odors of volatile organic solvents and is not Penetration (Absorption)
designed to determine subtle odor differences or odor inten- This term refers to the tendency of the nonvolatile vehicle
sity, There are hazards associated with the test, and the Haz- or binder in a coating to penetrate and be absorbed by porous
ards section of the method should be read and heeded when surfaces. Good resistance to absorption (hold-out) is desir-
the test is used. ASTM D 1296 has been approved as a re- able with interior primers and undercoats because it enables
placement for Method 4401 of U.S. Federal Test Methods them to seal such surfaces, thus promoting uniformity in
Standard (FTMS) No. 141 by the U.S. Department of Defense. both gloss and color of subsequent finish coats. Conversely, a
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high level of penetration is desirable with exterior coatings (same operator, different times) as well as poor reproducibil-
because it promotes adhesion on substrates that are unity (different operators).
treated and have layers of rust or degraded, chalky paint. In In ASTM Test Method for Color Development in Tinted
general, the binders in solvent-borne architectural coatings Latex Paints (D 5326), a portion of the semi-dry film is sub-
tend to penetrate chalk and rust very well owing to their lower jected to closely controlled brushing for development of a
molecular weight in comparison to that of latex binders. strong shear force. Although the method is written for testing
Since the latter penetrate very poorly, exterior latex paints are a tinted paint, the basic procedure can be followed for rating
sometimes modified with alkyd or oleoresinous binders to how well different colorants perform in the same tint base or
bind the chalk layer to the old coating. vice versa.
Method 4421 of FTMS 141 is a roughly quantitative
method for measuring absorption that employs filter paper as
a reproducible porous surface. In the test, a friction-top lid Coating Rheology
for a half-pint can is completely filled with paint and covered This term refers to the viscometric characteristics of liquid
with a standard grade filter paper. After 3 h, vehicle migra- coatings. Simple liquids that maintain a constant viscosity at
tion is observed as a spreading circular stain in the paper, and varying shear conditions are said to be Newtonian. Most
the mean distance from the rim of the cover is reported as the architectural coatings are non-Newtonian in character and
degree of absorption or penetration. Blotting paper may also have a higher viscosity at low shear rates than at high shear
be used for this test. Method 6261 of FTMS 141 is a more rates and vice versa. Systems of this type require the applica-
practical procedure than Method 4421, involving application tion of a minimum force to flow and when this force, the
of the material to an imperfectly primed porous surface and, "yield value," is exceeded, the phenomenon is called plastic
after drying, observation for variations in gloss and/or color. flow. Paints that exhibit plastic flow are called Bingham liq-
In the U.S. Federal Specification for Interior Flat Latex Base uids.
Paint (TT-P-29) the test paint is applied with an applicator In the coating industry, thixotropy is a favorable form of
b l a d e to a half-sealed penetration chart, and the above-de- non-Newtonian flow in which a liquid decreases in viscosity
scribed differences between the sealed and unsealed areas are when subjected to a shearing force and then recovers when
measured instrumentally. undisturbed for some time. It is possible for a material to
exhibit both plastic flow and thixotropy. These flow charac-
teristics are directly related to practical application proper-
Color Compatibility ties. High viscosity at low shear rates results in poor leveling
A colorant sometimes fails to disperse completely and yield and good sag resistance. Low viscosity at moderate shear
the desired color in a white or tint base owing to poor com- rates leads to good leveling but poor sag resistance. High
patibility that can be related to the colorant (color develop- viscosity at high shear rates, such as occur during brush
ment), the base (color acceptance), or both. If colorants are application, results in brush drag or poor brushability. Con-
not adequately compatible with bases, lighter or nonuniform sequently, a balance between the different properties must be
shades are produced. Although the problem is generally re- sought.
lated to poor dispersability of the colorant, especially those The different instrumental test methods used for coatings
designed for use with both solvent- and water-reducible coat- are described below. Empirical methods for evaluating vari-
ings, the white pigment in the base may not have been ade- ous application characteristics are described in a later sec-
quately dispersed or may have subsequently flocculated. In tion. The topics of rheology, viscometry, and related charac-
that case, if the shear applied to disperse the colorant also teristics are dealt with on a theoretical, mathematical basis
disperses the white pigment, the color will be lighter and less elsewhere in the manual.
colorful (i.e., less saturated) than expected. When both the
colorant and the white are poorly dispersed, the color change Consistency (Low-Shear Viscosity)
due to shear stress will be some combination of the two Consistency is a general term that describes the perceived
effects. thickness or "body" of liquids and is related to application
Poor color compatibility can be a problem both in the and flow. While it is related to viscosity, consistency does not
production and use of organic coatings. In the factory it distinguish between different viscosity types and does not
causes a loss of monetary value and unpredictable tinting determine the quality of a coating. It is used mainly to ensure
results. In application it results in nonuniform color of the product uniformity and should, therefore, fall within a stated
final film due to the variation in shear forces with different range for satisfactory reproduction of a specific formula. The
modes of application. This is commonly evaluated by apply- most common device for measuring the consistency of archi-
ing the coating with an applicator blade and subjecting a tectural coatings is the Krebs modification of the Stormer
small area of the drawdown to high shear by finger rubbing Viscometer in which a small off-set T-shaped paddle is
the partially dried film. Since rubbing simulates the high immersed to standard depth in the test fluid and rotated at
shear involved with some application methods, a variation 200 r/min for instruments with a stroboscopic timer and 200
between the unrubbed and rubbed areas indicates that the _+ 20 for those without the timer. Weights are varied to obtain
product will probably exhibit the same defect in the field. The the specified shear rate with the greater the load, the higher
color difference can be measured photometrically to obtain the consistency that may be expressed in grams/200 r/rain or
numerical values that are more useful than visual evaluations Kxebs Units (KU). Although the consistency of most architec-
for establishing limits for control work. Unfortunately, the tural coatings is about 150 to 300 g/100 revolutions (72 to 95
finger-rub method has been found to have poor repeatability KU), a much wider range is possible because of the great
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variation that can occur in the rheological properties of these Heat Stability--Exposure to high temperatures can be used
materials. Two paints of the same consistency may have quite as an accelerated test to predict stability of a packaged coat-
different theological properties during application. Consis- ing when stored at normal temperatures or to test for the heat
tency is determined in accordance with ASTM Test Method stability when a material frequently encounters such condi-
for Consistency of Paints Using the Stormer Viscometer tions in service. Although indications of long-term package
(O 562). stability can usually be obtained in several days or weeks at
an elevated temperature such at 125~ (50~ or 140~ (60~
Rheological Properties of Non-Newtonian Materials
occasionally the results of such accelerated tests do not agree
The two methods covered in this subsection are particu- with those at prolonged normal storage conditions. In ASTM
larly suited for coatings that display thixotropic characteris- Test Method for Package Stability of Paint (D 1849), the
tics. However, they measure viscosity under different shear changes in consistency and certain other properties of the
rates. In ASTM Test Method for High-Shear Viscosity Using accelerated aged material are compared to those occurring in
the ICI Cone/Plate Viscometer (D 4287), there is only one a control kept at normal temperatures for a longer period.
very high rate that is similar to that occurring during brush When testing for heat stability, as such, changes in viscosity,
application so that the measured viscosity is related to brush flow, gloss, pH, foam resistance, color uniformity, and wet
drag, spreading rate, and film build. ASTM Test Method for adhesion are usually checked.
Rheological Properties of Non-Newtonian Materials by Rota- Settling--Modern coatings are generally resistant to
tional (Brookfield) Viscometer (D 2196) employs a rotational marked or hard settling, but at times they do exhibit separa-
viscometer to measure viscosity at several shear rates to de- tion and soft settling. The degree of pigment suspension in a
termine the amount of shear thinning and the viscosity shelf-aged specimen and the ease of remixing it to a homoge-
change at low shear rates. The results can be used to evaluate neous condition suitable for the intended use are determined
sag resistance and leveling ability. in accordance with ASTM Test Method for Evaluating Degree
Sag Resistance of Settling of Paint (D 869).
Some coatings sag and form curtains before the film sets.
Resistance to this type of flow is an important property, par-
ticularly for semigloss and gloss finishes, because of the resul- APPLICATION PROPERTIES
tam unsightly film appearance. Sag resistance is determined
in accordance with ASTM Test Methods for Sag Resistance of Application or working properties of a coating are gener-
Paints Using a Multinotch Applicator (D 4400). In this test, a ally compared to a standard or described by requirements in
presheared coating is applied to a test chart with a drawdown the product specification. Working properties are determined
applicator that contains a number of different-sized notches in accordance with Method 4541 of FTMS 141.
to form stripes of the coating. The chart is then hung verti-
cally with the drawdown stripes in a horizontal position. The Brush Application
coating chart is allowed to dry and then examined for sagging
characteristics. Brushed films should be smooth and free of seeds and
when applied to vertical surfaces they should show no sag-
Leveling Properties ging, color streaking, or excessive brush marks. Brush drag
Leveling is an important property when smooth, uniform should not be excessive, although some degree of drag may be
surfaces are to be produced because it affects hiding and desirable for adequate film thickness application. Wall fin-
appearance. Brush marks and imperfections are much more ishes are tested on vertical surfaces and floor coatings on
conspicuous in semigloss and gloss finishes than they are in horizontal surfaces, although evaluation of the latter on verti-
low-gloss materials. ASTM Test Method for Leveling of Paints cal surfaces may be necessary to determine performance on
by Drawdown Method (D 4062) is the most recently devel- stair risers, railings, posts, etc. Brushing properties are deter-
oped method for evaluating this property. In it, a series of mined in accordance with Method 2141 of FTMS 141. Even
ridges is produced by applying the film using a serrated rod. though the test is subjective, someone experienced in the art
After drying, the ridges are compared under a strong oblique can produce quite consistent results, particularly in the evalu-
light to a numbered series of plastic levelness standards. The ation of drag qualities.
results have been shown to correlate well with brush applica-
tions. Brush Drag
As the brush drag (resistance encountered when applying a
Package Stability
coating by brush) increases, any natural tendency of the
Since paints normally are not used immediately after man- painter to spread the material too far is reduced. All other
ufacture, they must remain stable in the can for some reason- factors being constant, increased brush drag results in
able time. At normal temperatures most architectural greater film thickness with consequent improvements in hid-
coatings can be stored for over a year with little change in ing and film durability. Conversely, increasing brush drag too
properties. However, exposure in uninsulated warehouses or much can cause difficulties in easily and uniformly spreading
during shipping to high temperatures in summer or, for the coating. This can lead to excessive sagging, prolonged
water-dispersed coatings, to low temperatures in winter may drying time and, in highly pigmented materials, possibly
cause unacceptable changes in the products. Another unsatis- "mud-cracking" due to excessive thickness. The determina-
factory condition that may occur during storage is excessive tion of the relative brush drag of a series of coatings applied
settling. by brush by the same operator is described in ASTM Test
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Method for Comparison of the Brush Drag of Latex Paints Color

(D 4958). When testing a group of coatings, they must all be
The appearance of color is greatly influenced by several
of the same type--all water-borne or solvent-borne. It has
factors. A color next to a yellow wall looks different than the
been established that the subjective ratings thus obtained
same color next to a blue wall. The visual appearance of a
correlate well with high-shear viscosities obtained instru-
colored object illuminated by incandescent light, fluorescent
mentally using ASTM D 4287 (see above), provided the mate-
light, and natural light differs because the spectral composi-
rials differ in viscosity by at least 0.3 P (0.03 Pa.s).
tion of the different incident light sources varies. Gloss also
affects color appearance. The same color in a low-gloss finish
Roller Application usually appears to differ when in a high-gloss coating even
though instrumentally the colors may be identical. A more
Both wall and floor coatings are frequently applied by theoretical discussion of optical characteristics of coatings
roller. This type of application tends to produce some stipple appears elsewhere in the manual.
pattern. The evaluation of a material's characteristics when
applied by roller is covered by Method 2112 of FTMS 141.
Since foaming often occurs when water-borne coatings are Color Differences by Visual Comparison
roller applied, the amount of foam produced and the number
Visual comparison of colors is fast and often acceptable
of craters that remain after the bubbles have broken should
even though numerical values are not obtained. ASTM Prac-
be determined during the test.
tice for Visual Evaluation of Color Differences of Opaque
Roller Spatter--Some coatings spatter more than others
Materials (D 1729) covers the spectral, photometric, and geo-
when applied by roller. The degree to which a material spat-
metric characteristics of light source, illuminating and view-
ters when roller applied can be determined by the density of
ing conditions, sizes of specimens, and general procedures to
the spatter. In ASTM Test Method for Measurement of Paint
be used in the visual evaluation of color differences of opaque
Spatter Resistance to Roller Application (D 4707) a specially
materials relative to their standards.
designed notched spool is rolled through a film of the test
material that has been applied to a plastic panel. Any spatter
generated falls on a catch paper and after drying is rated Color Differences Using Instrumental
against photographic standards. This procedure eliminates Measurements
the influence of the roller cover, thus determining the spat-
tering characteristics of the material alone. The difference in color between a product and its standard
can be measured by instrument. Generally the tolerance is
agreed on by the purchaser and seller and may also be re-
Spray Application quired if a product specification is involved. Color measuring
instruments provide numerical values that can be compared
Architectural coatings are some times applied by spray. to subsequent measurements. ASTM Test Method for Calcu-
Both air and airless spray are used on commercial work. lation of Color Differences from Instrumentally Measured
Spray application properties are determined in accordance Color Coordinates (D 2244) describes calculation of the small
with Method 2131 of FTMS 141. Manual application is very color differences observable in daylight illumination between
subjective and should be performed only by an individual nonfluorescent, nonmetameric, opaque surfaces such as
skilled in the art of using spray equipment. coated specimens. If metamerism is suspected, visual evalu-
ation should be used to verify the results.
Touch-Up Uniformity
After a paint has dried, areas where less material was ap- Directional Reflectance
plied sometimes become noticeable. If the paint has suitable This property is a measure of the appearance of lightness of
touch-up properties, additional material can be applied to a coating. It is usually assigned a value in specifications for
these areas only, instead of refinishing the complete object-- white and pastel shades with a typical range of 76 to 86% for
wall, side of building, etc. The color, gloss, and leveling of the white finishes. In ASTM Test Method for Color and Color
touched-up areas and the previously coated area should be Difference Measurement by Tristimulis (Filter) Colorimetry
uniform. Differences in these properties are often caused by (E 1347), the directions of illumination and viewing are spec-
short wet-edge time, poor leveling on recoat, and pigment ified so the effect of gloss on the reflectance determination is
orientation or flotation during and after application. Touch- eliminated.
up properties are determined in accordance with ASTM Test
Method for Evaluation of Gloss or Sheen Uniformity
(D 3928). Gloss
Gloss is a measure of the capability of a coating surface to
reflect light in a mirror-like (specular) manner, i.e., light
APPEARANCE OF THE DRY FILM strikes the surface and is reflected at the equal but opposite
angle. In ASTM Test Method for Specular Gloss (D 523), the
Specimens for evaluating appearance properties should numerical gloss units are the ratio of light reflected by a
conform to ASTM Practice for Selection of Coating Speci- specimen to that reflected by the standard black glass that is
mens for Appearance Measurements (D 3964). assigned a gloss value of 100. The gloss of some coatings
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varies greatly with the angle of incidence, so that a complete strate the hiding obtainable when the coatings are applied by
description of their gloss would require measurements to be experienced workers.
made over a wide range of angles. In practice, the gloss of
architectural finishes is adequately characterized by mea-
surements at 60 or 85~ (or both) from a line perpendicular P R O P E R T I E S OF T H E D R Y F I L M
(normal) to the surface. The 85 ~ angle is a very low angle of
illumination (a "grazing" angle of 5~ and viewing the surface Interior and Exterior Coatings
and gloss at this angle is called "sheen." Attempts to standard-
ize the levels of gloss associated with various descriptive gloss Abrasion Resistance
terms have not been very successful since the gloss scale is This characteristic is a measure of the ability of a dried film
continuous with no distinct boundaries. Hence, there is con- to withstand wear from foot traffic and marring from objects
siderable overlap among the gloss classifications in common rolled or pulled across the surface. Dry abrasion resistance is
usage. determined in accordance with ASTM Test Method for Abra-
sion Resistance of Organic Coatings by Air Blast Abrasive
Gloss, 60 ~ (D 658), ASTM Test Method for Abrasion Resistance of Or-
Semigloss enamels are particularly sensitive to poor ganic Coatings by Falling Abrasive (D 968), and ASTM Test
enamel hold-out of primers and undercoats. Low or uneven Method for Abrasion Resistance of Organic Coatings by the
gloss readings are indicative of this defect. Oil and alkyd Taber Abraser (D 4060). In these methods, dry abrasive is
house paints typically have values of 30 to 70 while trim applied to a coated panel using a jet blast (D 658) or the force
enamels have values of 70 to 90 for 60 ~ gloss. Floor enamels of gravity (D 968) when the abrasives are free flowing. In the
generally have a high (90 + ) gloss reading when first applied, case of the Taber test, a weighted wheel that has abrasive
but this decreases with time and traffic. Interior semigloss embedded in a resilient rubber matrix is used. Because of the
enamels after drying 48 h are usually in the range of 40 to 70, poor reproducibility of abrasion methods, testing should be
but measurements taken shortly after drying should be re- restricted to only one laboratory when numerical abrasion
peated after one week because the gloss can decrease signifi- resistance values are to be used. Interlaboratory agreement is
cantly in the first few days of drying. improved significantly when rankings are used in place of
numerical values.
Sheen, 85 ~ Gloss
Adhesion
Although low-gloss paints with good uniformity of appear-
ance at low viewing angles often have little sheen and those The ability of a film to resist removal from a substrate is
with good cleansability usually have moderate sheen, this is certainly an important coating property. It is evaluated by
not always the case so that sheen should not be used as a many different procedures, almost all of which are not com-
measure of other paint properties. ASTM D 523 is useful for pletely satisfactory because the removal force is not applied
characterizing the low-angle appearance of low-gloss coat- at the coating-substrate interface but at the coating surface.
ings when the 85 ~geometry is employed. Most flat wall paints Consequently, when the adhesive bond between coating and
have a sheen of about 1 to 10 whereas velvets or eggshells substrate is greater than the cohesive strength of the coating,
range from 15 to 35. failure occurs within the film, so that adhesion, per se, is not
measured. When muhicoat systems are involved, the failure
can also be between coats. Nevertheless, the tests are used to
Hiding Power estimate whether the adhesion is adequate for the intended
service.
An in-depth discussion of this appearance property can be The test most commonly used with coatings is ASTM Test
found elsewhere in the manual, so this section only briefly Methods for Measuring Adhesion by Tape Test (D 3359). In
reviews the commonly used test methods. ASTM Test Method it, a simple procedure for use in the field comprises cutting an
for Hiding Power of Paints by Reflectometry (D 2805) is pre- X in the film, applying pressure-sensitive tape over the cut,
cise and gives an absolute rather than a comparative result. removing the tape, and qualitatively assessing adhesion on a
The coating is applied with a blade-type applicator to mini- zero to five scale. The more quantitative procedure involves
mize the effects of flow and leveling. Film thickness is pre- making a six- or eleven-cut lattice in the film. After applying
cisely measured and film opacity is instrumentally deter- and removing the tape, coating removal is evaluated by com-
mined. ASTM Test Method for Relative Hiding Power of parison with a scale that is related to the estimated area of
Paints by Visual Evaluation of Brushouts (D 344) is a more removal. If a tool that makes all cuts in one direction is
practical test in which paint is applied with a brush on a available, the test can be made in the field. However, when
checkerboard chart, wet-film thickness is approximately con- individual cuts are made using a metal cutting guide, the test
trolled by spreading rate, and hiding power is visually evalu- is practical only for laboratory use. Since the cuts~ must be
ated by comparison with a standard paint. However, results made through the coating to the substrate, the latter must be
are affected by the flow and leveling of the paint. ASTM Test sufficiently hard to resist the cutting tool. Consequently, the
Method for Hiding Power of Architectural Paints Applied by test is not applicable on soft substrates such as wood, plastic,
Roller (D 5150) is designed to simulate application with the or wallboard [3].
common tools. Although other tools may be used, the method Another laboratory method that requires a relatively hard
describes use of a roller to coat a 6-ft2 (0.56-m 2) chart printed substrate is ASTM Test Method for Adhesion of Organic
with a series of gray stripes. The test is intended to demon- Coatings by Scrape Adhesion (D 2197). In this method,
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coated test panels are pushed beneath a rounded metal loop staining materials such as mustard. The test may be run as
that is loaded with increasing weight until the coating is covered or uncovered drops applied to horizontal plane sur-
removed. The advantage of this procedure is that the results faces or by immersing panels in the relevant fluids.
are numerical. Its limitation is that coatings with very good
adhesion, such as coil-coated substrates, require loads of up
Interior Finishes
to 10 kg. Thus, it is difficult to push panels under the loaded
loop without causing it to skip along the coating surface. Block Resistance
ASTM Test Method for Pull-Off Strength of Coatings Using This is an important property for interior semigloss and
Portable Adhesion Testers (D 4541) also provides numerical gloss finishes since it governs the resistance of dried coating
results. The procedure comprises adhering a metal stud to the surfaces to sticking together when stacked or placed in con-
coating surface with an adhesive, curing the latter, attaching tact with each other. An interior finish often comes in contact
the test apparatus to the stud, and applying a perpendicular with itself, especially on doors, windows, and drawers where
force that is increased until either the coating is detached, a it sometimes adheres to itself. Such blocking is dependent on
specified value is reached, or the adhesive fails. While the the hardness of the coating and the applied pressure, temper-
hardness of the substrate is not a factor, its cohesive strength ature, humidity, and time while the surfaces are in contact.
is important. As a result, failure can occur within the sub- ASTM Test Method for Blocking Resistance of Architectural
strate, the coating, or the adhesive, or at the stud-adhesive Paints (D 4946) covers an accelerated blocking-resistance
interface, the adhesive-coating interface, or even the coating- procedure especially developed for this type coating.
substrate interface. As indicated by the title, the testers are
designed for use in the field. They can, however, be used in Print Resistance
the laboratory unless the adhesive bond strength is very high. The ability of a coating to resist printing is important be-
In this case, a tensile testing apparatus and high-strength cause its appearance is adversely affected if the surface tex-
adhesive are required. ture is modified by contact with another surface, particularly
one with a pattern. Interior gloss and semigloss systems ap-
Wet Adhesion plied to window sills and other horizontal surfaces are often
It is essential that a finish tightly adhere to a given substrate loaded with flower pots and similar objects that tend to leave
or primer under the wet conditions of washing or scrubbing. a permanent impression from the applied pressure. The ten-
The wet adhesion procedure described in Method 6301 of dency for a film to "print" is often a function of the hardness
FTMS 141 is essentially an earlier version of Method A of of the coating and the applied pressure, humidity, and time
ASTM D 3359. In it, two parallel cuts are made 1 in. (25 mm) while the surfaces are in contact. In ASTM Test Method for
apart instead of the X-cut. Then masking tape, which changes Print Resistance of Architectural Paints (D 2064), the resist-
markedly in adhesiveness with time, is pressed against the ance is evaluated by placing a piece of four-ply cheesecloth on
coating surface with a roller instead of semitransparent tape a coated glass slide, and a 500-g weight on a rubber stopper
being rubbed with a pencil eraser. In this method, the water are added to create pressure. The test is accelerated by
immersion prior to testing is described in detail instead of placing the assembly in an oven at 140~ (60~ for an hour.
being referred to in a Note. After cooling, the film is subjectively rated for the degree of
imprinting.
Flexibility
Elongation is a measure of a coating's flexibility. Most Film Porosity
semigloss and full gloss coatings can be bent over a i/s-in. The more porous a coating, the worse are its cleansability
(3.2-mm) mandrel without affecting the film. However, inte- and enamel holdout. In ASTM Test Method for Porosity of
rior flat and eggshell water-borne finishes usually pass at Paint Films (D 3258), a special, colored penetrating medium
1/4 in. (6.4 mm), while solvent-borne coatings of the same is applied to the coating and the change in reflectance indi-
category may pass only a 1A-in. (12.7-mm) bend. Flexibility of cates the degree of porosity.
interior coatings is usually evaluated using one of the man-
drel procedures in ASTM Test Methods for Mandrel Bend Washability and Cleansability
Test of Attached Organic Coatings (D 522). However, mea- The capability of satisfactorily removing marks without
suring elongation directly with a tensile testing machine as damaging the film is essential for good performance of inte-
described in ASTM Test Method for Tensile Properties of rior finishes. A coating may be washable, that is, unaffected
Organic Coatings (D 2370) is a much more discriminating by the detergent solution, but may not have good cleansabil-
way of estimating the flexibility retention of exterior coatings ity. Washability is evaluated by determining the resistance of
[4]. the film to wet erosion either by visual assessment or mea-
sured film loss. Cleansability is evaluated by applying one or
Resistance to Household Chemicals more stains and soils and determining how readily they are
An important property of some finishes is their ability to removed. Frequently the difference between the two terms,
resist discoloration, spotting, softening, blistering, or re- "cleansability" and "washability," is not clearly understood so
moval when subjected to household chemicals or strong that there is confusion as to what is really being tested [5].
cleaners. In ASTM Test Method for Effect of Household For example, the title of ASTM D 3450 is Test Method for
Chemicals on Clear and Pigmented Organic Finishes Washability [sic] Properties of Interior Architectural Coat-
(D 1308), the resistance may be evaluated with household ings, while the method's Scope states that it is designed for
items ranging from cold water, to detergent solutions, to determining "ease of removal of soilant." In general, the pre-
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cision of b o t h types of test is p o o r b e c a u s e several properties, a d h e r e well to chalky surfaces a n d thus do not require modi-
such as hardness, w a t e r a n d detergent resistance, cohesion, fication. At the t i m e of writing, there are no ASTM test meth-
a n d adhesion, are involved, a n d the end-point, except for the ods for a d h e s i o n to chalky surfaces, although w o r k t o w a r d
wet a b r a s i o n m e t h o d , is r a t h e r indefinite. d e v e l o p m e n t of such a test is proceeding. The i n d u s t r y gener-
ally uses a pressure-sensitive tape to test for this property.
Washability The t a p e is pressed firmly onto the dried latex film (fresh films
This p a r a m e t e r is also referred to as "resistance to scrub- do n o t a d h e r e as well as aged, d r i e d films) a n d t h e n r e m o v e d
bing" or "resistance to wet abrasion." ASTM Test M e t h o d for r a p i d l y b y pulling b a c k on itself. M e t h o d 6301 of FSTM 141
Scrub Resistance of I n t e r i o r Latex Flat Wall Paints (D 2486) describes a similar m e t h o d b u t it includes w a t e r exposure.
was developed for interior latex flat wall p a i n t s b u t can be
a p p l i e d to coatings of a l m o s t any type, In the test, the coating Dirt Pickup
is applied to a b l a c k plastic panel that, during s c r u b b i n g with Low-gloss exterior latex paints generally have good resist-
a nylon b r u s h a n d abrasive cleaning agent, is raised b y a ance to dirt pickup, b u t gloss or semigloss latex paints m a y be
n a r r o w shim to c o n c e n t r a t e the test area. The n u m b e r of m o r e subject to this type of disfigurement. Exterior exposure,
b a c k - a n d - f o r t h strokes (cycles) r e q u i r e d to remove the film p a r t i c u l a r l y u n d e r a n overhang (soffit), should indicate in a
over the shim is d e t e r m i n e d . I n t e r i o r latex low-gloss finishes relatively short time (about one year) a paint's t e n d e n c y to
can vary in scrub resistance from less t h a n 100 to m o r e t h a n collect dirt w h e n evaluated in a c c o r d a n c e with ASTM Test
1000 cycles. M e t h o d for Quantifying Dirt Collection on Coated Exterior
ASTM Test M e t h o d for W e t A b r a s i o n Resistance of I n t e r i o r Panels (D 3719).
Paints (D 4213) is similar except that a sponge is used in
place of the bristle b r u s h a n d the shim is not used. In the F u m e Resistance
original method, the loss p e r 100 cycles to erode the film S o m e p a i n t s u n d e r g o a change in a p p e a r a n c e , usually
a l m o s t to exposure of the b l a c k substrate was calculated on color, w h e n subjected to air containing certain sulfur com-
the basis of either weight or volume. In the c u r r e n t m e t h o d pounds, notably h y d r o g e n sulfide a n d sulfur dioxide. This
weight was eliminated, even t h o u g h it is easier to determine, type of a t m o s p h e r e m a y be present n e a r industrial o r o t h e r
b e c a u s e volume characteristics, such as p i g m e n t v o l u m e con- p o l l u t e d areas a n d can cause a p a i n t to yellow or d a r k e n in as
tent, usually have a m o r e direct relation to p e r f o r m a n c e , little t i m e as overnight. At the t i m e of writing, no ASTM or
w h i c h in this case is scrub resistance or washability. federal test m e t h o d s are available for evaluating this color
change, but one p r o c e d u r e used by the i n d u s t r y is as follows:
Cleansability
Apply a sufficient n u m b e r of coats of the p a i n t to two glass
The older of the m e t h o d s for this type m e a s u r e m e n t , ASTM plates to hide completely the glass surface a n d allow to d r y
D 3450, is s i m i l a r to the w e t - a b r a s i o n method, ASTM D 4213, for 6 h. Then expose one plate in a moist a t m o s p h e r e of
except a sponge is used with either the n o n a b r a s i v e o r abra- h y d r o g e n sulfide for 18 h. C o m p a r e the color of the exposed
sive cleaning agent to r e m o v e a c a r b o n black-oil stain. The film with that of the unexposed one. The color difference
ability to r e m o v e the stain is expressed as the ratio (in relative should not exceed that w h i c h exists b e t w e e n two plates
percent) of the reflectance of the cleaned a r e a to that of the coated with a p a i n t m a d e with t i t a n i u m dioxide pigment,
a r e a before a p p l i c a t i o n of the stain. In ASTM Test M e t h o d for lead-free zinc oxide, r a w o r refined linseed oil, and sufficient
Practical W a s h a b i l i t y [sic] of Organic Coatings (D 4828), nu- cobalt a d d e d for drying purposes, and similarly treated.
m e r o u s staining a n d soiling agents found in service, a n d com-
mercial abrasive or n o n a b r a s i v e cleansers, as well as the
s t a n d a r d i z e d cleaning agents, can be used. In the revised edi- REFERENCES
tion, the film m a y be cleansed m a n u a l l y o r mechanically, b u t
only the latter is suitable for i n t e r l a b o r a t o r y testing. [1] Paint~Coatings Dictionary, Stanley LeSota, ed., Federation of So-
cieties for Coating Technology, Blue Bell, PA 19422, 1978.
Exterior Coatings [2] Brezinski, J.J., Manual on Determination of Volatile Organic
Compounds in Paints, Inks, and Related Coating Products, ASTM
Adhesion to Chalky Surfaces MNL 4, 2d ed., ASTM, Philadelphia, PA 19103, 1993.
[3] For more information about the tape test, see Commentary in the
Latex p a i n t s generally have little ability to p e n e t r a t e pow-
Appendix to ASTM D 3359.
dery substrates. Consequently, a d h e s i o n to previous coatings [4] Ashton, H. E., "Flexibility and its Retention in Clear Coatings
that have chalked is p o o r unless the latex p a i n t has been Exposed to Weathering," Journal of Coatings Technology, Vol. 51,
modified to p e n e t r a t e a n d b i n d the chalk layer to the old No. 653, June 1979, p. 41.
coating. However, certain latexes do exist that are designed to [5] Feinherg, H., American Paint Journal, March 31, 1980, p. 45.
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MNL17-EB/Jun. 1995
60
Artists' Paints
by Benjamin Gavett 1
As COATINGS,ARTISTS'PAINTSARE DECORATIVEIN NATUREand through experience and education, must be aware of the par-
are usually intended to endure for decades or centuries under ticular limitations inherent with each type of paint. When
conditions of indoor storage and display. Relative to other new applications are explored, as is often the case with art, it
coatings, they are highly loaded, most often with a single becomes necessary to select and perform tests which will
pigment. Thickness of application ranges from transparent provide confidence that the finished artwork will have the
washes to thick, textural builds. Typical tools used include desired physical integrity.
the airbrush, paintbrush, and palette knife, but paints are The tests described in this section have been found to be
also often applied by other means, such as rags, sponges, or useful to quantitatively and qualitatively describe various
with the hands. They are often modified at the time of appli- characteristics of artists' paints. Acceptability of quality is
cation to change sheen, texture, color, flow, or other charac- determined between buyer and seller. In practice, it is largely
teristics. The substrate used is usually paper or a cotton or dependent upon what is considered characteristic of the par-
linen duck stretched over an open frame, but may be almost ticular paint type. Many of these test methods are ASTM
anything else, including solid or compressed wood panels, standards that the reader should consult for further details. It
paperboard, metal, synthetic fabric, glass, figurines, clothing, is important to note that there are ASTM standard specifica-
or walls. tions for several types of artists' paints, including acrylic
Artists' paints are categorized according to their vehicle or emulsion, watercolor, oil, resin-oil, and alkyd. These repre-
binder. Most common are oil (alkali-refined linseed oil), sent the current consensus, between producers, consumers,
acrylic (acrylic emulsion), and water color (gum arabic). Var- and other interested parties, of minimally acceptable per-
iations of these include cold-pressed linseed oil, other drying formance characteristics and other criteria. Most of the fol-
oils of vegetable origin, and acrylic emulsion copolymers. lowing test methods were not developed for artist paints in
Other natural and syntheticmaterials of historic significance particular. Due to the wide spectrum of types of artists' paints
or which are in more limited current use are acrylic solution, and potential uses, this listing does not include all test meth-
polyvinyl acetate, casein, egg, wax, and various gums. ods that may be relevant. Those included are of varying im-
Although almost any paint will .be used by an artist, those portance and applicability. They are in alphabetical order,
formulated for such use are expected, above all else, to be as grouped loosely into several categories: Shelf Stability, Work-
permanent as possible: However, paint is only one element in ing Properties, Film Properties, and Safety and Compliance.
the process of manipulating materials to transform vision
and ideas into art. Stability of the finished work is a function
Shelf Stability
not only of the paint used, but also of application technique,
substrate, age, storage, handling, and ambient environmental It is common for art materials to languish for years on store
conditions. shelves prior to being purchased. Once purchased, a con-
tainer is typically opened and closed many times during a life
cycle which may take months or years. Stability is evaluated
TESTING OF ARTISTS' PAINTS to help ensure endurance of the product through foreseeable
conditions of storage and use.
Testing of artists' paints is done to ensure quality and
consistency in their manufacture and to establish perform- Appearance
ance parameters such as flexibility, durability, or adhesion to The appearance of the undisturbed paint in the container
various substrates. Some performance criteria, such as light- creates an impression of quality, regardless of the ease of
fastness, are similar among different types of paints. Others restoring it to a homogenous condition. Evaluations for ap-
can be quite different, such as flexibility and drying time ofoil pearance in the retail container are most accurate when
paints versus acrylics. It is up to the manufacturer to perform based on true conditions of storage and use. However, this is
tests necessary to ensure that the paints are of a quality not practical when developing new products. Potential failure
consistent with or exceeding that which is expected and his- may be more quickly realized by placing samples in a labora-
torically true for the type of paint being produced. The artist, tory oven at moderately elevated temperature. As the differ-
ence between normal and test temperature increases, accu-
IAssistant technical director, Golden Artist Colors, Inc., Bell Road, racy in predicting potential problems may decrease because
New Berlin, NY 13411. higher temperatures may exaggerate changes. In a study of
706
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CHAPTER 60--ARTISTS' PAINTS 7 0 7
latex paints published in the Journal of Coatings Technology uated. For example, solvents may migrate through the walls
[1], the authors concluded that an oven temperature of ap- of plastic containers, causing them to become drawn inward.
proximately 50~ most accurately predicted shelf life per- Real time evaluations are best, but potential failure can be
formance. Items to note regarding appearance may include accelerated by increasing temperature or solvent load.
skinning, surface cracking, or separation. Parameters of ac-
ceptability will vary depending upon expectations of the cus- Seeding
tomer for the particular type of paint. Paint ingredient incompatibilities may result in the forma-
tion of agglomerates. This can be readily observed by pre-
Color Change paring drawdowns of the paint, as described in ASTM Prac-
Sometimes the color of a paint film produced from a con- tice for Preparing Drawdowns of Artists' Paste Paint (D 4941)
tainer of paint changes during storage, for example, as can and examining the dried paint film. ASTM Test Methods for
happen when a pigment is not compatible with the pH of the Coarse Particles in Pigments, Pastes, and Paints (D 185) may
formulation. This may be determined by preparing a fresh also be used.
batch of the paint to be tested and immediately preparing a
drawdown from it. Subsequent drawdowns at the same thick- Settling
ness may be periodically prepared from the same batch after In low-viscosity formulations, it is common for pigments to
the paint has aged in the container. The subsequent exhibit some settling. Ideally this would not happen, but if it
drawdowns are compared against the original. The results does, it is important that the pigments are easily remixed.
obtained from this test may be accelerated by using a labora- Settling that occurs over time may be evaluated according to
tory oven. ASTM Test Method for Evaluating Degree of Settling of Paint
(D 869).
Consistency
During storage and use, it is desirable that the paints main- Spoilage~Putrefaction
tain their intended texture and body. Evaluations are based It is necessary to protect against microbial contamination
on visual observation and workability with typical applica- from raw materials and packaging or that may be introduced
tion tools. Items to note include mealiness, tackiness, elonga- during manufacturing. Also, since artists' paints are typically
tion, and break, as well as other body characteristics. Conclu- opened, used, and reclosed many times, it is important that
sions may be drawn by comparing batches of the same they be formulated to resist microbial growth from contami-
formula, made at different times, which have been stored and nation occurring subsequent to purchase by the consumer.
otherwise treated similarly. It is useful to evaluate both full ANSI Z356.5, American National Standard for Art and Craft
and partially empty containers. Materials-Paints and Inks, Section 4.2, describes a test
method for evaluating the effectiveness of preservatives used
Flocculation in paint formulations. Paints to be tested are inoculated with
To determine if the pigment is fully dispersed or has re- pieces of bread which have been covered with a sugar solu-
mained dispersed over time, a tint of the color is prepared tion and allowed to mold. After two weeks, the paints are
with a compatible white. A drawdown is made and the excess inspected for decomposition.
paint is recovered and set aside until the drawdown is dry.
Next, a small amount of the original wet mixture is placed on Viscosity Changes
top of the dried paint film. This paint is then rubbed under Paint stability is quickly and quantitatively evaluated by
pressure in a circular motion (a gloved thumb is suitable) in monitoring viscosity. Viscometer type and method have not
an effort to cause further dispersion of the pigment. If it has been standardized for artists' paints. If needed, a method may
become more fully dispersed, the rubbed paint will appear as be agreed upon between buyer and seller. For most purposes,
a stronger tint against the original drawdown. it is sufficient to ensure consistency of test conditions and
equipment when doing periodic rechecks. Accelerated aging
Freeze-Thaw Stability with the use of a laboratory oven is usually predictable of
Shipping and storage often expose artists' paints to extreme real-time viscosity stability of water-based paints.
temperature fluctuations. Water-based paints can be quickly
ruined if not formulated for protection from freezing. ASTM
Specification for Artists' Acrylic Emulsion Paints (D 5098), in
Working Properties
Section 6.10 of the ASTM Book of Standards, describes the Many attributes of importance to the consumer of artists'
procedure used for testing acrylic paints. The same proce- paints are difficult to measure and report with repeatability.
dure is used for watercolors. To meet the requirements of the This subjectivity is often coupled with varying preferences
standard, the paints must pass five freeze-thaw cycles while among users. An ideal paint for one artist may be lacking in
retaining proper consistency. certain qualities for the next. It is not as important to stan-
dardize these characteristics as it is to determine them and
Package Integrity transfer this knowledge to the buyer.
The expected life and use of the package containing the
paints should be considered when designing appropriate Brushing Characteristics
tests. Consider, for example, how the container will be ship- Paints are brushed out on standard substrates by experi-
ped or how many times a tube will be flexed. Potential inter- enced technicians and rated as being smooth, sticky, tacky, or
actions between the paint and packaging should also be eval- fluid, as described in Section 6.6 of Commercial Standard
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(CS98) for Artists' Oil Paints [2]. This was the original quality Paints (D 4838) may be followed to arrive at instrumentally
standard for artists' paints and was the base from which the derived determinations of tinting strength relative to that of a
subsequent ASTM artists' paint quality standards were devel- standard or reference paint. Simple comparisons between
oped. It is also common to describe artists' paints for their paints can be made by using a white paint of standard compo-
tendency to flow and level or hold brush strokes and peaks. sition and strength to prepare tints, which are then drawn
down along side of each other. The tints are most accurately
Color Variation prepared using a weight-based ratio of the standard white to
If constancy of color is desired, it may be determined by the test color. A ratio based on volume, using syringes, may
placing samples next to each other on a test card and drawing be useful if an accurate balance is not available or if it other-
them down together using a thin film applicator. Compari- wise suits the purpose of the user.
sons of masstone, undertone, and tint are useful. For quanti-
fication and reporting, spectrophotometric measurements Viscosity
and C.I.E. L*a*b* color difference may be obtained according Artists' paints are available in a wide range of viscosities,
to the practices described in ASTM Test Method for Calcula- from pourable ink-like to heavy impasto. Oil paints are typi-
tion of Color Differences from Instrumentally Measured cally expected to maintain definition of the brush stroke,
Color Coordinates (D 2244). provide sharp peaks, and retain their shape as they emerge
from the tube. Water-based vehicles are highly manipulative,
Drying Time and the desired viscosity is dependent on the intentions of the
ASTM D 5098, for acrylics, and ASTM Specification for user and manufacturer. Viscosity, thixotropy, and dilatancy
Artists' Oil, Resin-Oil, and Alkyd Paints (D 4302), specify dry- may be determined with the equipment and techniques de-
ing time requirements. Dust-free drying time of these and scribed in ASTM Test Methods for Rheological Properties of
other types of paints are determined by following the proce- Non-Newtonian Materials by Rotational (Brookfield) Vis-
dures described in ASTM Test Methods for Drying, Curing, or cometer (D 2196).
Film Formation of Organic Coatings at Room Temperature
(D 1640). Film Properties
Fineness of Dispersion Adhesion
Finely dispersed pigments are important for smooth brush- Intercoat and substrate bonding of artists' paints are ex-
ing, realizing tinting strength potential, and maximizing en- tremely important. They become especially critical to evalu-
capsulation of pigment within the binder. ASTM Test Method ate when determining surface preparation techniques for
for Fineness of Dispersion of Pigment-Vehicle Systems new or unusual substrates or when considering multi-media
(D 1210) may be followed to measure this characteristic. applications. There are many types of adhesion testing appa-
ratuses, but a useful and inexpensive test involves cutting the
Odor paint films and attempting to lift them with pressure-sensi-
Evaluation of odor may be important in determining po- tive tape. This is described in ASTM Test Methods for Mea-
tential consumer acceptance of artists' paints. The different suring Adhesion by Tape Test (D 3359).
vehicles have characteristic odors and what is objectionable
to some may not be to others. Formula variations may be Bleeding
rated, based on the acceptability of their odor, by a panel of Artists' paintings are typically created in a manner that
intended users. results in overlapped or layered films. The tendency for color
of an underlying dry paint film to migrate through to subse-
Opacity quendy applied paint is an occasional but usually unwelcome
Opacity is not standardized for artists' paints. It is expected occurrence resulting from the pigment exhibiting some solu-
to vary depending on the pigment and vehicle used. The artist bility in the vehicle. The tendency for bleeding may be deter-
benefits if opacity ratings are reported on the container or in mined by applying an opaque white overstripe onto a smooth,
manufacturers' literature. This characteristic is typically eval- dried paint film. The white is extended off the paint film and
uated by applying a drawdown over a test panel that has onto the uncoated portion of the test support. Discoloration
adjoining areas of black and white. A scale is then established due to bleeding will be readily apparent. This test is described
and colors are assigned values relating to a range from highly as Test Method B of ASTM Test Methods for Bleeding of
transparent to fully opaque. Pigments (D 279).
Tinting Strength Block Resistance

The potency of a color is indicative of its value to the user, Artists' paintings are not typically produced, used, or stored
particularly when blending with white (absorption tinting in a manner which will cause them to come into contact with
strength). Depending on chemical composition, pigments are and stick to other surfaces. However, there are times when
expected to vary accordingly in strength. Identically pig- this does occur, such as in production situations or when
mented paints may exhibit differences due to degree of pro- there is inadequate storage space. If block resistance is im-
cessing or loading. It would not be appropriate to critically portant to the user, the paint in question should be evaluated
compare paints of different vehicles because of differences in because many artists' paints exhibit inherently poor block
the loads they will tolerate. ASTM Standard Test Method for resistance. A case-specific test should be designed to simulate
Determining the Relative Tinting Strength of Chromatic worst case scenarios of pressure, temperature, and humidity
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CHAPTER 60--ARTISTS' PAINTS 7 0 9
fluctuations. Anticipated drying and storage times should Lightfastness

also be considered in the test design. ASTM Test Methods for Lightfastness of Pigments Used in
Artists' Paints (D 4303) describes three methods used to de-
Chemical Resistance termine resistance to fading of acrylic, watercolor, alkyd, and
Resistance to the various liquids which a painting may be resin-oil artists' paints. Included are conditions of exterior
expected to come into contact with is an important character- exposure under glass, artificial daylight fluorescent lamps,
istic. These include varnish vehicles, solvents used in varnish and xenon-arc apparatus. Prior to exposure, samples to be
removal, and cleaning solutions that may be used on the tested are tinted with white until they reach 35 to 45% reflec-
paint film. Chemicals to be tested with a particular paint vary tance at their wavelength of maximum absorption, between
depending on the type of paint and what is expected of it. A 420 and 620 nm. With each method, exposure is continued
procedure for designing appropriate tests may be based upon until specimens have been exposed to a total radiant dose of
the Spot and Immersion Tests described in ASTM Test 1260 MJ/m 2. To meet the ASTM standard specifications for
Method for Effect of Household Chemicals on Clear and use in artists' paints, the pigments must be tested under at
Pigmented Organic Finishes (D 1308). least two of the three methods and exhibit a mean color
change of less than eight color difference units (CIE 1976
Flexibility L*a*b* color difference equation). These test methods are
Paints applied to flexible supports, such as stretched cotton designed to predict performance of artists' paints displayed in
or linen canvas, may be susceptible to potentially destructive typical household or museum environments. Results may not
forces. The different types of artists' paints vary in the degree be indicative of performance if the intended use is more
they will flex without failure. Although there are no estab- rigorous, such as in exterior mural applications.
lished standards, they have different thresholds of expecta- The most recently developed ASTM practices for determin-
tion and, therefore, acceptability. ing the lightfastness of artists' materials uses a method of
During storage or shipping, paintings are often rolled up. exposing samples indoors to sunlight filtered through win-
ASTM Test Methods for Mandrel Bend Test of Attached Or- dow glass while simultaneously exposing a series of eight ISO
ganic Coatings (D 522) describes equipment and methods for Blue Wool Reference materials to control the duration of
determining and rating flexibility. Relevancy is increased by exposure. One half of each specimen and control is shielded
testing the coatings over the intended substrate and primer. from exposure during the test. This test takes longer to run,
Combined with the use of accelerated aging techniques, the but it is relatively inexpensive. It is intended for artists' mate-
mandrel test will help predict natural embritflement of the rials which are not specifically covered by other ASTM stan-
paint film. dard test methods. For details, see ASTM Standard Practice
Paintings must also endure expansion and contraction of for the Visual Determination of the Lightfastness of Art Mate-
the fabric due to changes in environmental humidity and rials by the User (D 5398) and ASTM Standard Practice for
temperature. Sometimes these conditions become extreme, the Visual Determination of the Lightfastness of Art Materials
as when a painting is shipped during freezing weather. Fail- by Art Technologists (D 5383).
ure will occur more quickly if the individual components of
the painting have greater relative differences in their moduli
of elasticity. Use of a temperature and humidity-controlled Yellowing
environmental chamber programmed to expose paintings to While traditional paint vehicles may be expected to yellow
repeated cycles of extreme conditions will accelerate the fail- to some degree, this may be considered a serious flaw if en-
ure that might be observed over time under normal condi- countered in the newer generation of synthetic media. To
tions. determine the relative potential for yellowing of a vehicle, a
Another force of concern is mechanical impact against the standard titanium dioxide white pigment may be formulated
film that may occur during handling. For example, when a into the test vehicle and into one of known stability. They are
painting is mounted on an open-back stretcher, fingers may then exposed to the accelerated methods described in ASTM
inadvertently press into it as it is being carried. The risk of D 4303 and amount of yellowing determined with ASTM
damage increases as temperature decreases and the glass Practice for Visual Evaluation of Color Differences of Opaque
transition temperature is approached. The rate at which ex- Materials (D 1729) or Test Method D 2244. It is also useful to
ternal forces are applied also influences susceptibility to dam- subject films of the unpigmented vehicles to the same tests.
age.
Gloss
Some manufacturers of artists' paints will add inert flatting Safety and Compliance
agents to control the gloss values of the various colors so that
they are similar within a line. Others will allow a color's gloss
Flash Point
to be dictated by the characteristics of the colorant, i.e., toler- Solvent-based paints may require flash point determina-
able load and particle size. Gloss values for artists' paints tion for label warnings and to determine applicability of
have not been standardized. It is a matter of preference and shipping regulations. The prescribed test method can vary
manufacturing philosophy. When required, gloss may be depending on the authority. ASTM Test Methods for Flash
specified between the buyer and seller, with measuring pa- Point of Liquids by Setaflash-Closed-Cup Apparatus (D 3278)
rameters identified. is usually applicable.
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Toxicological Evaluation and furniture application are examples. ASTM Practice for
The Federal Hazardous Substances Act (FHSA) requires all Calculating Formulation Physical Constants for Paints and
art materials to be evaluated by a board-certified toxicologist Coatings (D 5201) provides equations to calculate the theo-
for potential to cause acute and chronic health effects. This retical VOC content of paints, based on the formula and
law was incorporated into the FHSA with the Labeling of exclusive of water and exempt solvents.
Hazardous Art Materials Act (LHAMA), the basis of which is
ASTM Practice for Labeling Art Materials for Chronic Health
Hazards (D 4236). A wide assortment of test methods provide REFERENCES
the information required for the toxicological assessment.
These are not specified by the Standard Practice or LHAMA, [1] Yates, T. P., Boyer, M., Braunshausen, R., Drucker, T. R., Green-
but include all which are embodied in the field of toxicology wald, J., Marek, E. F., Foote, F., Olholt, G., Stromberg, D., and
as well as compositional analysis of the paints and their Scimecca, F. S., "Oven vs Shelf Stability of Latex Paints," Journal
constituents. For example, test procedures described in EN- of Coatings Technology, Vol. 59, No. 745, February 1987.
71-3:1988, Safety of Toys, are used to determine solubility of [2] Mayer, R., The Artist's Handbook of Materials and Techniques, 4th
ed., 1981, The Viking Press, New York, pp. 651-665.
metals present in paint, under conditions intended to simu-
late 4 h in the human alimentary tract. In vitro techniques are
also used for determining potential eye and skin irritation.
BIBLIOGRAPHY
The toxicologist determines any testing that may be required
to supplement the information that exists for the raw materi-
The following books provide additional reading on the sub-
als in a product. Appropriate precautionary label information
jects of artists' materials, their uses, history, and characteris-
is then assigned. The toxicologist must supply the criteria
used in making these determinations to the Consumer Prod- tics. These books also contain extensive reference sections.
uct Safety Commission, the enforcement agency of the Fed- Feller, R., Ed., Artists" Pigments, Vol. 1, 1986, Cambridge University
eral Hazardous Substances Act. Press, Cambridge, England.
Gottsegen, M., The Painter's Handbook, 1993, Watson-Guptill Publi-
Volatile Organic C o m p o u n d s (VOC) cations, New York.
Artists' paints are sometimes applied to substrates that are Mayer, R., The Artist's Handbook of Materials and Techniques, 1981,
covered by VOC regulations. Architectural, sign-painting, The Viking Press, New York.
www.iran-mavad.com

MNL17-EB/Jun. 1995
61
Automotive Product Tests
by Rose A. Ryntz I
EACH OF THE MAJORAUTOMOTIVECOMPANIESrequires a specific v i r o n m e n t a l regulations, i.e., the Clean Air Act of 1990, will
protocol of testing to be p e r f o r m e d on a p p r o p r i a t e substrates severely limit o r e l i m i n a t e the use of such cleaners in the
in o r d e r to grant approval of a p a r t i c u l a r p a i n t or coating. The future.
specification testing is rigorous a n d often takes up to two W a t e r b o r n e cleaners are either acidic or basic in nature.
years to complete. This section a t t e m p t s to provide the r e a d e r T o d a y m o s t cleaners are acidic so t h a t residue r e m a i n i n g as a
with a general guideline of the r e q u i r e d test m e t h o d s utilized possible c o n t a m i n a n t on the surface does not interfere with
b y the big three a u t o m o t i v e c o m p a n i e s (GM, Ford, a n d t o p c o a t cure.
Chrysler) a n d w h e r e a p p l i c a b l e relates to testing r e q u i r e d by W a t e r b o r n e surface cleaners are often a p p l i e d to substrates
a J a p a n e s e counterpart, Toyota, in gaining m a t e r i a l s a n d in a three-to-nine-zone process. E a c h zone consists of a spe-
processes approval. cific cleaning or conditioning step. P r e t r e a t m e n t or surface
cleaning systems are often limited by space c o n s i d e r a t i o n s
a n d are designed functionally to a d o p t as n e a r state-of-the-art
AUTOMOTIVE PRODUCT IDENTIFICATION as possible. Required zones or stages consist of surface
cleaner followed b y a w a t e r rinse a n d ending with a d e i o n i z e d
The approval process at the a u t o m o t i v e m a n u f a c t u r e r s is w a t e r rinse. Additional stages can be a d d e d to a c c o m p l i s h
subdivided into specific categories b a s e d on the s u b s t r a t e to several cleaning processes, conditioners, a n d w a t e r rinses.
be coated, i.e., flexible o r rigid, and the coating type tested, Additional rinsing stages provide m o r e security in r e m o v a l of
i.e., cleaner, primer, topcoat. The o u t d o o r d u r a b i l i t y of the trace c o n t a m i n a n t s , w h i c h could lead to t o p c o a t a d h e s i o n
coating is also a consideration, being designated as a problems.
w e a t h e r a b l e [good resistance to ultraviolet (UV) d e g r a d a t i o n ] After surface cleaning, the substrate is c o a t e d a n d tested to
or a n o n w e a t h e r a b l e (poor resistance to UV d e g r a d a t i o n ) t o p c o a t specifications. I n o r d e r to be qualified as an a p p r o p r i -
quality. ate cleaner, the t o p c o a t should c o n f o r m to all d e s i g n a t e d
testing requirements.
Surface Cleaners and Pretreatments
Surface cleaners are generally defined as w a t e r b o r n e or Primer (Nonweatherable)
solventborne m a t e r i a l s that p r e t r e a t a substrate p r i o r to the
coating process to ensure o p t i m a l wetting of the surface. The Electrodeposited Primer
p r e t r e a t m e n t t h e n renders the s u b s t r a t e m o r e paintable. Ex- Anodic electrodeposition was first i n t r o d u c e d in the 1960s
ceptions to either the w a t e r b o r n e or solventborne m a t e r i a l a n d was subsequently r e p l a c e d b y the cathodic process in the
class do exist, for example, in the p r e t r e a t m e n t processes 1970s. A p p r o x i m a t e l y 75% of all cars m a n u f a c t u r e d in the
utilized on t h e r m o p l a s t i c polyolefins. In these instances, the w o r l d are p r i m e d using this process.
surface p r e p a r a t i o n consists of exposure to plasma, corona, Following p r e t r e a t m e n t , metal parts are i m m e r s e d in the
o r benzophenone/UV r a d i a t i o n to r e n d e r the suhstrate electrocoat dip tank. The p a i n t itself is 75 to 95% water. Upon
paintable. a p p l i c a t i o n of an electrical potential, i.e., voltage, a p a i n t film
The surface cleaner generally acts to remove greases, oils, possessing 85 to 100% solids is d e p o s i t e d u p o n the parts.
a n d d r a w i n g c o m p o u n d s f r o m the s u b s t r a t e to prevent p a i n t Once deposited, the p a i n t film acts as a resistor, increasing
a d h e s i o n loss w h e n coated. I n the case of the plasma, corona, the resistivity as the film thickness increases. This accounts
or benzophenone/UV r a d i a t i o n exposure of a substrate, the for the fact that as one a r e a of a p a r t is coated, uncoated, or
surface is oxidized to p r o m o t e p a i n t adhesion. relatively less coated, areas d r a w increased current, resulting
Most solventborne cleaners are b a s e d on either m e t h y l e n e in a very u n i f o r m coating regardless of the substrate s h a p e o r
chloride or trichloroethylene due to t h e i r s u p e r i o r solvency complexity.
p o w e r for greases a n d oil. At times, i s o p r o p a n o l a n d n a p h t h a The electrocoat technology, often consisting of an a m i n o
are used on solvent-sensitive plastics such as p o l y c a r b o n a t e extended epoxy resin cross-linked with a blocked isocyanate,
to prevent d e g r a d a t i o n of the substrate. However, recent en- provides c o r r o s i o n p r o t e c t i o n over cold-rolled steel for u p to
400 to 500 h in a salt fog cabinet. N o r m a l film builds of the
1Technical specialist, Plastic Trim and Products Division, Ford d r i e d electrocoat film range from 0.8 to 1.5 mils. The elec-
Motor Co., 24300 Glendale Ave., Detroit, MI 48239. t r o c o a t technology is referred to as n o r m a l build, low build,
711
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high build, o r high b u i l d a n d a half, d e p e n d i n g on the film mils. Flexible, weatherable, n o n c o n d u c t i v e p r i m e r s are only
thickness achieved. utilized over "Class A" plastics.
Conductive Primer Conductive Primer

A conductive primer, as the n a m e implies, provides an Weatherable, conductive p r i m e r s can be utilized over flex-
electrical charge to the surface of a plastic to r e n d e r it ible or rigid substrates to provide a p a r t w h i c h can be electri-
p a i n t a b l e b y electrostatic methods. Transfer efficiency of cally grounded. The r e q u i r e m e n t s for conductivity are m u c h
t o p c o a t s is thus improved. the s a m e as those d e s c r i b e d above for n o n w e a t h e r a b l e con-
The conductivity in the d r i e d p a i n t film is achieved m o s t ductive p r i m e r s with conductive p i g m e n t s utilized to provide
often t h r o u g h the use of a conductive c a r b o n b l a c k pigment. resistance.
The p i g m e n t - t g - b i n d e r ratio of the conductive p r i m e r is ad- W e a t h e r a b l e conductive p r i m e r s are often utilized in rub-
j u s t e d to o b t a i n a dry film conductivity of at least 140 strip areas, i.e., the black strip on a b u m p e r or fascia, to
R a n s b e r g units ( m e a s u r e d on a R a n s b e r g meter), <1000 1), provide a two-tone a p p e a r a n c e . Accent colors are applied
at a thickness of 0.8 to 1.2 mils. a d j a c e n t to the conductive p r i m e r to provide aesthetically
As m e n t i o n e d above, the conductive p r i m e r is utilized only pleasing parts.
on plastics since m e t a l is c a p a b l e of holding a potential. Con- W e a t h e r a b i l i t y r e q u i r e m e n t s are m u c h the s a m e as those
ductive p r i m e r s are utilized over b o t h rigid a n d flexible plas- d e s c r i b e d later for m o n o c o a t technology. The c h e m i s t r y uti-
tics. T h r o u g h modifications in the c h e m i s t r y of the primer, lized to achieve the w e a t h e r a b l e n a t u r e of the p r i m e r is the
flexibility requirements, i.e., over flexible plastics, can be s a m e as that d e s c r i b e d above for w e a t h e r a b l e primers.
achieved.
N o n w e a t h e r a b l e primers, as the n a m e implies, are not
Topcoats
ultraviolet resistant. They m u s t be topcoated. The p r i m e r can
be of a o n e - c o m p o n e n t or t w o - c o m p o n e n t nature, d e p e n d i n g Interior Topcoat
u p o n the process capability. The c h e m i s t r y of the o n e - c o m p o - An interior t o p c o a t is utilized to provide a protective a n d
n e n t p r i m e r s for rigid substrates is often c o m p r i s e d of an decorative surface suitable for use on interior parts m a d e of
epoxy ester o r alkyd cross-linked with a melamine, while steel, a l u m i n u m , zinc-based die castings, plastics, pulp pre-
flexible n o n w e a t h e r a b l e o n e - c o m p o n e n t p r i m e r s consist of a form m o l d e d board, or o t h e r substrates. The t o p c o a t often
polyester resin cross-linked with a melamine. Two-compo- provides a p a r t i c u l a r feel, i.e., "soft leather feel," o r a desired
nent primers, on the o t h e r hand, are b a s e d u p o n the s a m e gloss, i.e., less t h a n 6/60 ~ gloss meter, to stop blinding reflec-
basic b i n d e r chemistries cross-linked with a r o m a t i c isocya- tions.
nates in the n o n w e a t h e r a b l e class. The c h e m i s t r y of the interior t o p c o a t varies d e p e n d i n g on
the curing process utilized, i.e., air-dry, low-temperature, or
Nonconductive Primer
h i g h - t e m p e r a t u r e cure. Acrylic a n d u r e t h a n e technology have
A n o n c o n d u c t i v e p r i m e r is not c a p a b l e of holding an elec- been the m a j o r chemistries utilized. On h a r d - t o - c o a t sub-
trical potential a n d is utilized to provide a "Class A" surface. A strates, a p r i m e r is often utilized to gain adhesion.
"Class A" surface is a surface which, w h e n topcoated, will W e a t h e r a b i l i t y a n d "fogging" are two i m p o r t a n t test speci-
provide the s a m e a p p e a r a n c e characteristics (gloss a n d dis- fications to which the t o p c o a t m u s t abide. "Fogging," de-
tinctness of image) as a t o p c o a t e d m e t a l part. The noncon- scribed later, refers to the m i g r a t i o n of plasticizers in the
ductive p r i m e r can be utilized over metal or plastic parts to coated substrate. This is of p a r t i c u l a r concern on i n s t r u m e n t
provide filling characteristics to p o r o u s o r m a r r e d surfaces. panels a n d d a s h b o a r d s since embrittleness of the substrate
The c h e m i s t r y of a nonconductive, n o n w e a t h e r a b l e p r i m e r and/or w i n d s h i e l d c o n t a m i n a t i o n will occur.
is often the s a m e as that e m p l o y e d in the conductive primer.
F i l m thicknesses range from 0.8 to 1.2 mils. Very often, the Exterior Topcoats
n o n c o n d u c t i v e p r i m e r is utilized over only rigid substrates, Monocoat--A m o n o c o a t technology, as the n a m e implies,
i.e., m e t a l a n d rigid plastics. The p r i m e r can be "color keyed" is a final single coat w h i c h provides color, gloss, DOI (dis-
to the t o p c o a t color (i.e., red if a r e d t o p c o a t is to be applied) tinctness of image), a n d durability. It is a p p l i e d to a total d r y
so that a b e r r a t i o n s in the t o p c o a t (i.e., chips, scratches) will film thickness of b e t w e e n 1.5 a n d 2.5 mils d e p e n d i n g u p o n
not be as noticeable. color a n d hiding requirements. It should be satisfactory for
use over specified primers, sealers, or o t h e r enamels, as in
Primer (Weatherable) r e p a i r or two-toning operations. Paints specified u n d e r this
s t a n d a r d can contain acrylic resin, u r e t h a n e resin, alkyd
Primer~Surfacer resin, etc. as the m a i n b i n d e r w h i c h is subsequently cross-
W e a t h e r a b l e p r i m e r s are utilized to provide a UV d u r a b l e linked with a m e l a m i n e resin [referred to as a o n e - c o m p o n e n t
finish over mostly flexible plastics. The p r i m e r is often color (1K) paint] or an isocyanate resin [referred to as a two-com-
c o o r d i n a t e d to the t o p c o a t color to provide an aesthetically p o n e n t (2K) paint]. Necessary p i g m e n t s a n d additives are
pleasing accent color. One could also refer to w e a t h e r a b l e b l e n d e d a n d included to achieve final color match. Paints
p r i m e r s as m o n o c o a t topcoats. shall not contain toxic substances such as chrome, c a d m i u m ,
Primers in this class are m o s t l y flexible acrylic or polyester- etc. u n d e r the Toyota specification.
b a s e d resins cross-linked with m e l a m i n e (one-component) o r The c h e m i s t r y of the m o n o c o a t is modified as n e e d e d to
an aliphatic isocyanate (two-component). They m u s t m e e t reflect its use over flexible or rigid substrates. The corre-
the s a m e flexibility r e q u i r e m e n t s as t o p c o a t s at 1.2 to 1.5 s p o n d i n g cure r e q u i r e m e n t s are m a t c h e d with the s u b s t r a t e
www.iran-mavad.com

CHAPTER 61--AUTOMOTIVE PRODUCT TESTS 713
to be coated so as not to exceed the heat distortion tempera- Gray: L* 65.61

ture of the plastic parts. a* - 1.55
Basecoat/Clearcoat--The specifications for a basecoat/ b* 9.84
clearcoat are much the same as those required of an exterior (utilizing 10~ Standard Observer and Illuminant D65).
monocoat in that they require color match to a standard, a PFUND Crytometer Hiding Power--The hiding power in
particular gloss and DOI, and a minimum durability. The Chrysler Material Standard MS-PP 1-1 covering paint require-
basecoat, containing the necessary pigments and additives to ments and performance over plastics is determined with a
match a particular color standard, is applied to a dry film Pfund crytometer, utilizing the 0.09-ram (0.0035-in.) wedge
thickness of 0.3 to 1.2 mils depending on color. It should be (unless otherwise specified). The hiding power is specified in
satisfactory for use over specified primers, sealers, or other the material standard covering the individual coating.
enamels, as in repair or two-toning operations. Paints speci-
fied under this standard can contain acrylic resin, urethane Odor
resin, alkyd resin, etc. as the main binder which is subse- The material's odor is reviewed in reference to current pro-
quently cross-linked with a melamine resin (1 K) or an isocya- duction materials. Any significant differences must be evalu-
nate resin (2K). Paints shall not contain toxic substrates such ated in laboratory and production trials. Odor testing is per-
as chrome, cadmium, etc. under the Toyota specification. formed at an approved laboratory.
The clearcoat is applied over either a wet (not fully cured)
basecoat (referred to as a wet-on-wet application) or a dry Flammability
(cured) basecoat (referred to as a bake-on-bake application) Although not a requirement for the supplier, a flash point
to provide required gloss, DOI, and "wet look" depth to the of below 27~ necessitates the user to classify paint as a
cured finish. The clearcoat is applied to a dry film thickness of potential fire hazard. Plant security must assure that proper
1.8 to 2.0 mils. It can contain acrylic resin, urethane resin, fire precautions are provided.
alkyd resin, etc. as the main binder which is subsequently Smoke Characteristics--General Motors requires that a
cross-linked with a melamine resin (1K) or an isocyanate material's tendency to smoke during processing be reviewed
resin (2K). Necessary ultraviolet absorbers and hindered in comparison to current production materials. Any signifi-
amine light stabilizers are added to the clearcoat formulation cant differences must be evaluated in laboratory and produc-
to provide the required exterior durability. tion trials.
As in the monocoat technology, the chemistries of the
basecoat/clearcoat are modified to reflect their use over flex- Ultraviolet (UV) Transmission
ible or rigid substrates. Cure requirements are also designed For exterior topcoats, General Motors and Ford require
to reflect the heat distortion temperatures of plastic sub- that a coating be opaque to UV transmission to the under-
strates. lying primer layer or substrate at a film thickness 20% less
than the minimum of the recommended film build range. The
coating shall have been baked at the maximum of the accept-
REQUIREMENTS able cure range on its bake time and temperature process
control chart. Opacity is defined as no transmission between
Material Requirements wavelengths of 290 to 350 nm.
Hiding (ASTM D 2805) Solvent Emissions
ASTM Test Method for Hiding Power of Paints by Reflec- All topcoat materials must meet specific plant solvent emis-
tometry (D 2805) covers the determination, without refer- sions restrictions at spray viscosities which yield acceptable
ence to a material paint standard, of the hiding power of applied appearance. Chrysler specifies that the material shall
paints with Y tristimulus values greater than about 15%. It comply with all the requirements of the Clean Air Act ( u s e
uses the Kubelka-Munk equations to calculate the hiding 1857, as amended) and any applicable federal, state, or local
power from reflectance results obtained by broad-band filter statute pertaining to the establishment and maintenance of
reflectometry. It is utilized by General Motors for all automo- the National Ambient Air Quality Standards as administered
tive exterior topcoat materials. by the Environmental Protection Agency (EPA) or any autho-
Dry Hiding (Ford Laboratory Test Method BI 1-4)--A rized state or local governmental unit. The material shall
basecoat is required to provide complete visual hiding at comply with all of the requirements of the Water Pollution
specified film thicknesses (18 to 23/xm unless specified for Control Act (PL 92-500, as amended) and shall be formulated
special colors) over a black and gray straight-line hiding to eliminate, as far as possible, constituents that would be
chart. classified as hazardous under the Resource Conservation and
1. Black and Gray Straight-Line Hiding Chart Recovery Act (40CFR 260-265, as amended). The material
Hiding chart is 50 by 280 mm, consisting of a black stripe shall contain no benzene, chlorinated, or other toxic com-
of 25 by 280 mm and a gray stripe 25 by 280 mm in a side-by- pounds.
side configuration. Percent Solids by Weight--The weight solids of a material
are determined according to ASTM Test Methods for Volatile
2. CIE L*a*b* Hiding Chart Values
Content of Coatings (D 2369B).
Black: L* 25.74 Percent Solids by Volume--The volume solids of a material
a* -0.13 is determined according to ASTM Test Method for Volume
b* -0.11 Nonvolatile Matter in Clear or Pigmented Coatings (D 2697).
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Volatile Organic Compounds (VOC)--The volatile organic C 70_+4 H 10+_3

compounds (VOC) of a material is determined according to D 62 _+ 3 J 6 max
ASTM Practice for Volatile Organic Compound (VOC) Con- E 50+_3
tent of Paints and Related Coatings (D 3960).
The gloss of exterior topcoats is measured on a Hunter
Density--The density of a material is determined according specular glossmeter at 20 ~ and should be a minimum of 90
to ASTM Test Method for Density of Paint, Varnish, Lacquer,
with no more than 4 units decrease in gloss after rebake.
and Related Products (D 1475).
Distinctness o f Image (DOI)
Viscosity The material shall be subjected to a DORIGON (distinct-
1. Newtonian Viscosity ness of reflected image goniometer) and shall he within speci-
For Newtonian materials, the viscosity is measured accord- fied materials standard values.
ing to ASTM Test Method for Viscosity by Dip-Type Viscosity
Cups (D 4212) with a dip-tank viscosity cup. Appearance
2. Non-Newtonian Viscosity The topcoat shall be smooth and uniform, free of sags,
For non-Newtonian materials, the viscosity is determined craters, pinholes, seediness, abnormal roughness, or exces-
according to ASTM Test Method for Rheological Properties sive metallic mottling. It shall have reasonable tolerance for
of Non-Newtonian Materials by Rotational (Brookfield) Vis- ordinary cleaning and exhibit excellent polishing characteris-
cometer (D 2196) with a rotational (Brookfield) viscometer. tics.
3. Viscosity Stability
The stability of a material to settling or change in viscosity Film Thickness
is usually conducted at package viscosity (as shipped). Tests A material's film thickness shall be determined according
are run after standing for 90 days at room temperature and as to ASTM Test Method for Nondestructive Measurement of
a function of accelerated heat aging (oven stability). The ma- Dry Film Thickness of Nonmagnetic Coatings Applied to a
terial after aging must be free of settling which cannot be Ferrous Base (D 1186).
dispersed by normal agitation and must not increase in vis-
cosity by a percentage of its original viscosity. Hardness
The material shall have sufficient hardness to resist
Throwpower
marring through normal handling.
The throwpower, in reference to cationic electrodeposition Micro Hardness--The microhardness of materials applied
coatings, is the degree to which an electrodeposited film coats over rigid substrates shall be determined on a TUKON hard-
interior or recessed areas. Specific requirements are depen- ness tester according to ASTM Test Methods for Indentation
dent upon voltage, resin type, and auxiliary electrode type Hardness of Organic Coatings (D 1474A).
and will vary by production plant. Taber Wear Resistance--There shall be no material removal
greater than the approved reference panels when tested ac-
pH
cording to ASTM Test Method for Abrasion Resistance of
The pH of waterborne materials shall be determined ac- Organic Coatings by the Taber Abraser (D 4060-81).
cording to ASTM Test Method for pH of Aqueous Solutions
with the Glass Electrode (E 70) and for electrocoat baths Adequacy o f Cure
according to ASTM Test Method for Measurement of Appar-
ent pH of Electrocoat Baths (D 4584). Upon subjection to solvent exposure by (methyl ethyl ke-
tone or xylene) double rubs with a cloth, there shall be no
Resistivity~Conductivity transfer of the material's color nor dulling or softening of a
The resistivity of a material shall be determined according clearcoat.
to ASTM Test Methods for Electrical Conductivity and Resis-
tivity of Water (D 1125). Adhesion
Initial Adhesion--The film shall adhere tightly and not
flake, crack, or powder from the substrate. When scribed with
Performance Requirements
a crosscut (X-scribe) or crosshatch, the coating should main-
Color tain a minimum of 99% adhesion after taping the area.
The material shall match the appropriate master color Moisture Resistance--After exposure to 100% relative hu-
standard after all the baking cycles for the particular color. midity [ASTM Practice for Testing Water Resistance of Coat-
ings in 100% Relative Humidity (D 2247)], the coating should
Gloss maintain 99% adhesion when tested as above.
The gloss of an interior coating is measured on a Hunter
specular glossmeter at 60~ and shall be specified by means of Gravelometer
a letter suffix to the color number assigned by styling as The chip resistance of a coating is determined according to
follows: SAE J400 and ASTM Test Method for Chip Resistance of
A 92min F 35 _+ 3 Coatings (D 3170). The chipping shall not exceed a predeter-
B 80_+4 G 20_+3 mined ranking.
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CHAPTER 61--AUTOMOTIVE PRODUCT TESTS 715
Toughness dent upon coating type and use (i.e., interior or exterior).
Dime Scrape--The material shall not flake, peel, or lose Limits for exposure length are se t by the manufacturer.
adhesion upon subjection to scribing with a dime. This test Weatherometer--Accelerated exposure is run with a carbon
shall be performed only on rigid substrates. arc or a xenon arc for a specified interval dependent upon
Knife Scrape--The material shall not flake, peel, or lose coating type and use. Limits for exposure length are set by the
adhesion upon subjection to scraping with a knife. This test manufacturer.
shall be performed on flexible substrates only. Fadeometer--Interior coatings are run for a specified time
period (usually 100 h) on a Fadeometer and shall not exhibit
Fluid Resistance any discoloration, dulling, or adhesion loss.
When subjected to the specified fluids by the methods and
times specified in the applicable standards, the coating shall Fixed Glass Bonding
show no loss of adhesion, blistering, softening, swelling, or Any coating intended for use in glass bonding areas must
discoloration: be qualified to the requirements for a new topcoat material
9 xylene intended as the bond surface. The coating is measured for its
9 synthetic gasoline adhesive and/or cohesive strength to structural adhesives in a
9 synthetic gasohol lap shear test.
9 naphtha
9 recommended cure check solvent Corrosion Resistance
9 tap water There shall be no blistering or more than 3-ram rust
9 acid rain mixture creepage or loss of adhesion from a line scribed through to
Immersion Test--The material shall show no loss of adhe- bare steel when exposed to salt spray resistance according to
sion, blistering, softening, swelling, or discoloration when ASTM Test Method of Salt Spray (Fog) Testing (B 117) condi-
subjected to immersion testing in the specified fluids accord- tions for a specified time interval.
ing to ASTM Test Method for Effect of Household Chemicals
on Clear and Pigmented Organic Finishes (D 1308). Permeability
Cold Checking Resistance For porous plastic substrates, i.e., SMC (sheet molding
compound), certain manufacturers are requiring that coating
The material shall withstand a minimum of 10 to 15 cycles materials be tested to solvent penetration resistance stan-
of exposure to heat, humidity, and freezing conditions (at dards. General Motors, in particular, has developed a "fluo-
specified times and intervals) with no resultant cracking,
rescent dye microscopy" test to limit the amount of solvent
crazing, or adhesion loss.
permeation into SMC from conductive primers.
Crock Resistance
The material shall not transfer any color onto a cloth when Process Requirements
exposed to the dry crock method set out in the SAE J861
Basic property feasibility must be established as part of
method.
material qualification with each automotive manufacturer.
Flexibility Boundary conditions for key process control parameters
must be established as to their effects on film build, appear-
Coatings intended for use on flexible or semirigid sub-
ance, and durability.
strates shall exhibit no cracking or induced substrate failure
when subjected to bending over mandrels of various diame-
ters at predetermined temperatures.
Viscosity
Viscosity versus temperature charts at various shear rates
Water Resistance must be furnished.
The material shall not blister, dull, wrinkle, or peel when
subjected to controlled condensation according to ASTM Color Feasibility
Practice for Testing the Water Resistance of Coatings Using A statistically designed experiment matrix must be run on a
Controlled Condensation (D 4585) m e t h o d a n d X-scribed. minimum of colors per standard procedure.
Weatherability
Transfer Efficiency
Test panels for Florida durability (facing 5~ south from
Initial comparisons will be made with current approved
horizontal) and accelerated weathering durability are pre-
materials under controlled laboratory conditions to establish
pared in accordance with manufacturer's recommendations
relative transfer efficiency.
for film thickness and bake. The coating shall meet customer
goals for useful life as measured by gloss retention and gen-
eral appearance guidelines (color, adhesion, etc.). Bake Latitude
QUV Exposure--Accelerated exposure is run according to A chart depicting acceptable, unacceptable, and marginal
SAE J2020 or ASTM Practice for Operating Light- and Water- conditions for cure based on appearance, durability, and
Exposure Apparatus (Fluorescent UV-Condensation Type) glass bonding (if applicable) characteristics of the coating
for Exposure of Nonmetallic Minerals (G-53) methods depen- must be furnished.
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Circulation Stability BIBLIOGRAPHY

The supplier must establish that coating performance will
not be degraded under typical, normal production use. Flow ASTM, Annual Book of ASTM Standards, Section 6 Paints, Related
velocity required to maintain suspension or redisperse settled Coatings, and Aromatics, vol. 6.01, 1990.
pigment must be provided prior to loading a circulation sys- Chrysler Motors Corporation Engineering Standard, Material Stan-
tem. dards MS-PP14-1, MS-PPI-1, MS-PD48-1.
Ford Motor Company Engineering Material Specifications ESB-
Crater Resistance M33J100-A, ESB-M6J106-C, ESB-M2J218-A1, ESB-M2J218-A2,
Compatibility with plant-specific materials must be verified ESB-M33J3-A1, ESB-M33J3-A2, ESB-M33J3-A3, ESB-M2J222-A.
with all materials. Typical materials with which the coating General Motors Corporation Engineering Standards GM4349M,
must be compatible include sealers, primers, underbody GM4365M, GM4367M.
deadeners, plastic substrates, competitive coatings, etc. Toyota Motor Corporation Engineering Standard TS H3111G.
The sensitivity of a coating to crater from common in-plant
contaminants (i.e., equipment oils, personal hand lotions,
etc.) must also be established.
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MNL17-EB/Jun. 1995
62
Can Coatings
by Martin B. Price 1
THE CONTAINERINDUSTRY IS A MAJOR USER of p a i n t s a n d coat- TABLE l--United States production of beer and beverage cans.
ings. The r e p o r t e d n u m b e r of cans u s e d in the United States (Millions of cans)
p e r y e a r is a b o u t 130 billion. The m a j o r i t y of these are coated 1991 1990 % Change
individually, m o s t with different coatings on each side. These
coatings provide c o r r o s i o n resistance, c o m p l i a n c e with strict Beer Cans
Aluminum 38 428 38 751 - 0.08
food safety and taste requirements, a n d p r e s e n t attractive Steel 400 400 0.0
long lasting identification characteristics to each container. Total 38 828 39 151 -0.08
The processes r e q u i r e d for the efficient a n d e c o n o m i c a l l y Soft Drink Cans
acceptable m a n u f a c t u r e of two- a n d three-piece cans a n d can Aluminum 52 955 49 235 7.6
Steel 2 855 4 090 -30.2
ends involve c o m p l e x engineering. Unique coatings charac- Total 55 810 53 325 4.7
teristics are r e q u i r e d to c o n f o r m with these complex m e c h a n - All Beverage Cans
ical systems. A m a j o r i t y of the tests currently in use to ensure Aluminum 91 383 87 986 3.9
t h a t all the r e q u i r e m e n t s are m e t are discussed. A brief de- Steel 3 255 4 490 27.5
Total 94 638 92 476 2.3
scription of the processes for can p r o d u c t i o n is included.
decorative exteriors. Phenolic a n d a m i n o b a s e d m a t e r i a l s are

D E S C R I P T I O N OF T H E CAN I N D U S T R Y often used as cross-linking agents. W a t e r - b a s e d spray coat-
ings (often epoxy-acrylic based) are c o m m o n l y u s e d as inte-
The Can Coating Industry r i o r coatings for two-piece can bodies.
Recent modifications in coatings p r o d u c t s u s e d for this
The v o l u m e of coatings c o n s u m e d by coating cans for food
i n d u s t r y have b e e n developed largely in r e s p o n s e to federal
a n d beverage in the United States places the c o n t a i n e r indus-
a n d state p o l l u t i o n a b a t e m e n t requirements, to a n ever in-
try a m o n g the highest users of finishes for all industries. A
creasing need for i m p r o v e d a n d accelerated p r o d u c t i o n in
total of 130 billion cans were s h i p p e d in the United States in
this highly competitive field, a n d to the d e v e l o p m e n t a n d
199 i, m o s t of w h i c h were c o a t e d with decorative a n d protec-
i m p l e m e n t a t i o n of a variety of i m p r o v e d can m a n u f a c t u r i n g
tive coatings. Over 40 million gallons of coating were used
techniques. A significant level of p r o d u c t d e v e l o p m e n t effort
with an e s t i m a t e d sales value of 350 million dollars. The
continues in this field to define new a n d i m p r o v e d products.
United States is b y far the largest u s e r of cans a n d coatings
The qualifications a n d r e q u i r e d testing p r o c e d u r e s for
for cans. Europe, w h i c h currently uses a b o u t 21 billion cans,
coatings for two-piece a n d three-piece containers can vary to
is expected to double its usage d u r i n g the 1990s as this f o r m
some degree. A d e s c r i p t i o n of can p r o d u c t i o n processes for
of p a c k a g i n g b e c o m e s m o r e acceptable as a r e p l a c e m e n t for
these two m a j o r can types will be presented.
glass containers.
I n a d d i t i o n to being one of the largest c o n s u m e r s of coat-
ings, the m e t a l c o n t a i n e r industry, b e c a u s e of the variety of
coatings r e q u i r e d to satisfy its needs, is also one of the m o s t Can Production Processes
technically sophisticated. The type a n d quality of p r o d u c t s Two-Piece Can Production (Fig. I)
identified with this i n d u s t r y are largely influenced by the
unique characteristics of the can m a n u f a c t u r i n g processes. About 70% of the total U.S. p r o d u c t i o n or 95 billion cans
Therefore, can coating f o r m u l a t i o n s are b a s e d on a variety of u s e d in the b e e r a n d beverage p o r t i o n of the c a n n i n g i n d u s t r y
resins, a m o n g which are epoxy, poly(vinyl chloride), acrylic, are c o n s t r u c t e d with a l u m i n u m a n d c o m p r i s e w h a t are com-
polyester, o r alkyd, oleoresinous, a n d phenolics. Coatings m o n l y called two-piece cans. This can type is m a n u f a c t u r e d
b a s e d on epoxies are often chosen for p r i m e r s a n d for can b y press p u n c h i n g cups from sheets or coils of a l u m i n u m or
ends, poly(vinyl chloride) for can ends, oleoresinous a n d phe- steel. The cups are t h e n forced t h r o u g h a series of rings to
nolics for can interiors, acrylic, polyester a n d alkyd resins for iron out a n d form a full-length can a n d to form the b o t t o m
dome. The p r o d u c t at this stage is a c o n t a i n e r with sides a n d
a b o t t o m representing one of the two pieces of a two-piece
~Consultant, Consolidated Research, Inc., consultant, AKZO Nobel
Coatings Inc., 2205 Stannye Drive, Louisville, KY 40222. can. The lid, secured a n d sealed after filling, is the second
2Figures are reproduced with permission. piece.
717
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FIG. 1-Two-piece can production process.
These c o n t a i n e r s require exterior inks a n d coatings for Although b e e r is n o t strongly acidic in nature, a m a j o r con-
d e c o r a t i o n a n d identification. I n c r e a s e d m a n u f a c t u r i n g cern exists r e g a r d i n g taste-alteration potential due to c o n t a c t
speed a n d s m o o t h m o v e m e n t on the p r o d u c t i o n lines re- of the b e e r with m e t a l c o n t a i n e r walls. W h e n a protective
quires the p r o p e r lubricity in the coating. The c o n t a i n e r s also coating is used, it c a n n o t alter the taste of the p a c k a g e d
require a high degree of a b r a s i o n resistance to m a i n t a i n aes- product. It is therefore necessary for b e e r containers, for
thetics a n d prevent can failure. Cans r u b b i n g against each example, to have a coating with a low level of extractables.
o t h e r during m o v e m e n t in any of m a n y p r o d u c t i o n process Coatings suitable for c o n t a i n e r use (a) m u s t b e FDA com-
steps a n d shipping can cause scratches. These are often unac- pliant, (b) m u s t pass subjective taste tests to ensure no contri-
ceptable for aesthetic r e a s o n s and, in extreme cases, can b u t i o n to the flavor of the product, a n d (c) m u s t also m e e t
result in the actual r u p t u r e of the increasingly t h i n n e r stock d e m a n d i n g flexibility requirements. Both the i n t e r i o r a n d
from w h i c h cans are m a n u f a c t u r e d . It is interesting to note exterior coatings m u s t pass m o s t ~f these tests for the can
that cans are frequently so thin t h a t sealing after filling w i t h a p r o d u c t i o n to be acceptable. F o r a m a j o r i t y of cases, after the
c a r b o n a t e d beverage is r e q u i r e d to give the c o n t a i n e r ade- can is p a c k e d a n d sealed, it is subjected to a t h e r m a l treat-
quate rigidity. In addition, a level of flexibility m u s t be inher- m e n t to c o m p l e t e the processing of the contents. M a n y of the
ent in the coating so that the severe crimping, w h i c h is critical c o m m e r c i a l b e e r p r o d u c t s require p a s t e u r i z a t i o n that is nor-
to securing the lid onto the container, can be a c c o m p l i s h e d really carried out at 150 to 180~ (65.5 ~ to 82.2~ Higher
w i t h o u t coating failure o r d e l a m i n a t i o n . t e m p e r a t u r e exposures are r e q u i r e d for processing o t h e r food
Coatings are usually a p p l i e d to the i n t e r i o r of these cans b y p r o d u c t s in m a n y p a c k a g i n g operations. Coatings on the
spray techniques. R a p i d a p p l i c a t i o n is o b t a i n e d b y s h o r t c r i m p e d edges of the can that m a y have survived the actual
b u r s t s of airless s p r a y f r o m a lance p o s i t i o n e d o p p o s i t e the c r i m p i n g p r o c e d u r e m u s t retain adhesion, clarity, color, a n d
center of the o p e n end of horizontally held cans. This proce- a b r a s i o n resistance after these t h e r m a l treatments.
dure is used with m o s t food a n d d r i n k containers. If the
i n t e n d e d can content is acidic, as is the case with m a n y soft Three-Piece Can Production (Fig. 2)
drinks, u n c o a t e d cans can erode. Thus a coating m u s t be I n a typical m a n u f a c t u r i n g process for the three-piece can,
a p p l i e d w h i c h presents an a d e q u a t e b a r r i e r to this erosion. a large m e t a l coil is s h e a r e d into sheets. An "inside" coating is
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CHAPTER 62--CAN COATINGS 7 1 9
FIG. 2-Three-piece can production process.
placed on these sheets usually by roll-coater application and of the main coating, including FDA compliance, and cause no
the coating is cured. When exterior coating is required, the detectable alteration to the taste of the contained product.
"exterior" of the can is coated with the decoration defined by
the customer. This decoration is often overcoated with a clear Preparation of Can Ends
coating and the sheets are cured for a second time. On low- Ends are stamped from sheets that are already coated on
rust potential metal, when paper is the chosen labeling tech- the side to be in contact with the packaged product. With
nique defined by the customer, or when ultraviolet-cured some metals the side destined to become the exterior will also
coatings are employed, this second stoving operation may not require the application of a coating to impart corrosion re-
be required. (The ultraviolet cure process will be discussed sistance. Can-end coatings must have the required flexibility
later.) The coated sheets that are stacked and shipped to the to withstand the crimping necessary to secure the end to the
fabricating plant must easily slide over one another during top or bottom of the container. As with the two-piece can, the
subsequent processing steps. The coated surface is often coating including the crimped sections must maintain integ-
tested to evaluate the nonbinding characteristic of the sheets rity through the elevated temperature food processing steps.
during stacking.
In the fabricating plant, the coated body sheets are slit into Ultraviolet Cured Coatings
individual body blanks; usually about 35 body blanks are About 4 to 5% of can coating in the United States involves
obtained from each sheet. These blanks are coiled into a the use of ultraviolet curing. This process has several distinct
cylinder shape and flanged to permit the formation of a seam advantages over more traditional oven-bake systems. Among
that is then welded, soldered, or cemented. A coating is re- these are the virtual elimination of solvents and related vola-
quired to cover this seam since the initially applied coating is tile organic compound pollutants, improved production effi-
usually destroyed or deformed during the seaming process. A ciency, and low-cost plant installation. At this writing, indus-
coating, either liquid or powder, is applied to this seam and trial production using ultraviolet cure mainly involves
cured or fused. This coating must have all the requirements external clear coatings.
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The process involves the application of a photosensitive Viscosity Stability--The coating can be evaluated for long-
coating to the substrate, followed by a brief exposure to a term stability by placing a sample in an oven at 120~ (48.8~
selected ultraviolet wavelength at a defined intensity. The for an extended time period. Forty days is a typical test
coating is hardened virtually instantaneously. In the two- period. The change in viscosity can be evaluated every seven
piece can manufacturing process the individual cans are days using the technique employed to rate initial viscosity. In
printed, often with ultraviolet light-curable inks, coated with addition, settling, agglomeration, or other changes in appear-
a clear coating, and then exposed to ultraviolet light. The ance can be noted.
extremely fast cure permits the process to proceed rapidly to Density--Density can be measured by using a Gardner TM
the next stage in the can production process which may be "Weight per Gallon" cup [ASTM Test Methods for Indenta-
application of a water-dilutable or solvent-based interior tion Hardness of Organic Coatings (D 1474)]. The process
coating. As the latter coating requires an oven bake, the ultra- involves equilibrating the product to 25~ and pouring it into
violet-cured coating is oven baked as well. Only one oven pass a cleaned cup up to the fill mark, taking care to prevent
is required. foaming. The cap is pressed onto the cup and the overflow
The ultraviolet cure technique has also been used in the carefully wiped from the outside of the cup. The cup is then
preparation of three-piece cans. Sheets, often printed with an weighed on an analytical balance and pounds/gal calculated
ultraviolet-curable ink, are oven coated with an ultraviolet by multiplying the number of grams of paint in the cup by 0.1.
light-curable overprint coating. After radiation curing, a dry- Volatile Organic Compounds (VOC)--The determination of
to-touch condition required for efficient production often de- the VOC of a coating requires an analytical balance and an
velops within a fraction of a second, permitting the sheet to oven controllable at 110 _+ 5~ [ASTM Test Methods for
be flipped to the reverse side. A coating which will eventually Volatile Content of Coatings (D 2369)]. The specimen is
be the "inside" coating of the can is then applied and the placed in an aluminum dish and after dilution with solvent is
entire sheet is cured by a standard oven process. This tech- baked for 60 min and the percent weight loss of the sample
nique is also used for the coating of the exterior of sheets that determined. This is the percent volatile content.
are to be used for calends. Again the economic advantage of The volatile organic compound content (VOC) is deter-
only one oven pass is realized. The importance of inclusion of mined according to Federal Reference Method 24, using the
some measure of the speed of cure in the quality control of weight % volatile content, the density of the liquid coating,
these ultraviolet curable coatings is obvious. and the weight percent water content, using the equations
Ultraviolet coatings have been developed which meet the shown in ASTM Practice for Volatile Organic Compound
requirements of adhesion, flexibility, slip, gloss, abrasion re- (VOC) Content of Paints and Related Coatings (D 3960).
sistance, and food process stability for exterior use. At this Fineness of Grind--This test is used for the determination
stage of their development, these coatings have not been ade- of the fineness of dispersion of pigments in a pigmented
quately evaluated to assure compliance with FDA regulations coating. A Hegman Grind Gauge with a double-wedge steel
and therefore are not available for use on interior food con- scraper placed on a flat, nonskid surface is used (ASTM
tact surfaces. D 1260). A sample of coating is applied at the deep end of the
groove of the gauge surface so it slightly overflows the total
groove. The scraper is then drawn down over the entire length
Testing of Can Coatings of the gauge with sufficient pressure to clean the sides of the
gauge. A reading should be made at this point without delay.
Tests Conducted on Liquid Paint The reading consists of a visual observation made by viewing
Viscosity--As discussed in the previous section, speed of the side of the gauge perpendicularly to the drawn coating:
production is a critical aspect of an economically successful the point where the sample shows a definite speckled pattern
can production plant. The speed of application of paint re- is read from the numbers on the side of the gauge. The quality
quired for the satisfactory coating of two-piece can bodies or of the dispersion is a measure of the effectiveness of the
of three-piece can sheets places unique requirements on the grinding operation in dispersing of pigments for pigmented
flow characteristics of the paint. To ensure complete cover- coatings or of additives, such as wax, for clear samples.
age with the standard thin layer of paint, outstanding flow Flash Point--The flash point of a coating is the minimum
must be assured. The usual means for the determination of temperature at which vapor given off by the coating will
viscosity is with the use of the Brookfield Viscosimeter ignite when exposed to a spark or flame. The Department of
[ASTM Test Method for Rheological Properties of Non-New- Transportation standards for shipment places a minimum
tonian Materials by Rotational (Brookfield) Viscometer flash point requirement for these coatings. A method to deter-
(D 2196)]. mine what is referred to as a closed-cup rating flash point
Alternate means of determining viscosity include the use of uses a Seta Flash apparatus [ASTM Test Methods for Flash
the Ford Cup or the Zahn Cup, ASTM Test Method for Viscos- Point of Liquids by Setaflash-Closed-Cup Apparatus
ity of Paints, Varnishes, and Lacquers by Ford Viscosity Cup (D 3278)]. For an open flash point, a Tag open-cup method is
(D 1200) and ASTM Test Methods for Measurement of Wet often used [ASTM Test Method for Flash Point by Tag Closed
Film Thickness of Organic Coatings (D 212), respectively. Tester (D 56)]. In both methods the substance under test is
These procedures relate flow to the length of time required heated at a controlled rate (for example, 2~ and a flame
for a test liquid to flow through a calibrated orifice at the is passed over the surface. The flash point is defined as the
bottom tapered end of a cup. The Ford technique is generally temperature at which definite ignition is observed.
considered more accurate, though less convenient than the Cure Speed--A variety of methods have been devised for the
Zahn. determination of this difficult to determine and even difficult
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CHAPTER 62--CAN COATINGS 721
to define characteristic of a thermoset coating. One practical several locations on the surface of the specimen. The reported
definition of cure adequacy is the development of sufficient reading is the average of the several readings taken.
hardness in the coating that allows the can manufacturing A StrandGauge TM is often employed in the metal decorator
process to advance to the next stage without marring the industry because of the ease of determining the thickness of
coating. The customer and the coating supplier frequently very thin coatings characteristic of this industry. The equip-
agree on an empirical test to satisfy cure speed requirements. ment is available from the Strand Electronics Ltd., Castro
A simple technique may involve the use of cotton balls. Valley, California.
Nonadherence of fine fiber wads to a surface is often rated as Film Continuity--An important characteristic of a high-
adequate cure because it relates to the ability to permit the quality film placed on the interior surface of a can is freedom
continuation of production. Frequently, a higher degree of from coating voids, meaning the absence of areas where
cross-linking is required, especially for the development of pinholes or discontinuities exist. Can corrosion and contami-
resistance properties encountered by the coating at a later nation of the can contents at these voids could cause taste or
stage of its use. Rubbing a cured surface with a cloth moist- color degradation. One of the accepted methods for evaluat-
ened with a strong solvent is a method frequently employed. ing a surface for these imperfections is an Enamel Rater Test
The determination of hardness using the pencil hardness test (Fig. 3).
described later is a means of assigning a numerical rating to When using a WACO TM Enamel Rater for this test, a con-
the relative degree of cure. tainer to be evaluated is filled with a conductive aqueous
solution and placed on a platform. Electrical contact is made
Tests Conducted on Cured Surfaces on a cleaned area of the can exterior. An electrode is placed in
Hardness--The hardness of a coated panel can be deter- the center of the can contents, and the amount of current
mined with the use of a series of pencils that have lead of flowing through the system is measured. The current flow will
various, known hardness, that is, lead with the following be impeded by the protective coating on the can interior.
increasing hardness: 5B, 4B, 3B, 2B, B, HB, 2H, 3H, 4H, and Flaws or breaks in the coating are areas which will permit
5H. For more details refer to ASTM Test Method for Film current flow. The customers and suppliers usually agree on a
Hardness by Pencil Test--D 3363 06.01. maximum acceptable value.
Film Thickness--An electric film thickness gauge can be An alternative test technique for determining film voids is
used to determine film thickness [ASTM Test Method for the copper sulfate solution immersion test. In this test a sheet
Nondestructive Measurement of Dry Film Thickness of of coated metal is immersed in a solution of acidified copper
Nonmagnetic Coatings Applied to a Ferrous Base (D 1186)]. sulfate for 2 to 4 min. After removal, a careful visual or
The device is calibrated with standard sheets of known film magnifying glass examination of the coated metal will reveal
thickness placed on an uncoated surface of a similar sub- copper-plated areas where inadequate coating protection
strate test section. After standardization, the head of the permitted the copper to plate out onto the metal surface. The
gauge is placed on the coated sample and coating thickness is presence of flaws in the coating is an unacceptable condition
reported usually in mils. The film surface is often measured at for most commercial products.
FIG. 3 - W A C O TM Enamel Rater test device for film voids.
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Mobility/Lubricity--This i m p o r t a n t characteristic of a resistance. In this test, c o a t e d panels are r o t a t e d u n d e r se-

coating can be m e a s u r e d using an AltekTM Mobility/Lubricity lected weighted abrasive wheels. The value is often r e p o r t e d
Tester (Fig. 4). as weight loss in milligrams/cycle x 1000. A n o t h e r specific
The can or flat s a m p l e is m o u n t e d on the unit, and a test test requires the use of a Gavarti TM Gv Cat Test Unit (Fig. 5).
sequence is initiated by sliding a weight across the sample. This device involves the m o u n t i n g of a limited n u m b e r of
The coefficient of friction is d e t e r m i n e d a n d is indicated di- s p e c i m e n s a n d can evaluate c o a t e d metal a b r a s i o n resistance
rectly on an electronic analog meter. rapidly. The device vibrates the cans or coated strips at a rate
Stability to Food Processing and Pasteurization Condi- a n d d u r a t i o n w h i c h can be controlled, e m u l a t i n g the a b r a -
tions-Many foods are p a c k e d into containers in an sion received d u r i n g t r a n s p o r t a t i o n . The cans are visually ex-
u n c o o k e d state. Cans are sealed a n d the entire can is pro- a m i n e d after the allotted t i m e of exposure a n d r a t e d accord-
cessed at an elevated t e m p e r a t u r e for the p e r i o d r e q u i r e d to ing to individual o r c u s t o m e r defined standards.
c o m p l e t e the food processing. A characteristic test p e r i o d is Pack Testing--A r e q u i r e m e n t for p a c k a g i n g of m a n y food
1 h at 250~ (121~ in an autoclave. D e t e r m i n a t i o n of the p r o d u c t s is that no u n d e s i r a b l e effects on the a p p e a r a n c e of
ability of a coating to w i t h s t a n d this t r e a t m e n t is often m a d e the c o n t a i n e r or to the taste or color of the contents occur
by careful e x a m i n a t i o n of a section of coated substrate w h i c h w h e n the p r o d u c t is stored on a shelf for three years or more.
has been m a n d r e l b e n t (ASTM D'1737). The section so An accelerated test to evaluate this characteristic involves the
treated is then p e r m i t t e d to cool a n d next exposed to 100% actual p a c k a g i n g of the substance in question in a test can.
humidity, at 100~ (37.7~ for 16 to 24 h. After cooling, The can is sealed a n d exposed to the food processing condi-
visual e x a m i n a t i o n of the surface for discoloration, for film tions previously described, after w h i c h the p r o d u c t is aged at
rupture, a n d for adhesion, especially in those areas w h e r e an elevated t e m p e r a t u r e for an extended p e r i o d of time. Typi-
film extension has occurred, presents a useful appraisal of the cal conditions are 120~ (48.8~ with a generally a c c e p t e d
ability of the coating to w i t h s t a n d food processing condi- estimate that one m o n t h exposure at this t e m p e r a t u r e relates
tions. to one y e a r of r o o m t e m p e r a t u r e exposure. The coating p r o d -
A less severe test is available for the p a s t e u r i z a t i o n process. uct can be periodically e x a m i n e d b y initiating several con-
This is r e q u i r e d for some foods a n d for some b e e r packaging. tainers at zero t i m e a n d w i t h d r a w i n g t h e m selectively at one-
The t e m p e r a t u r e for this process is 150 to 180~ (65.5 ~ to m o n t h intervals. This test is useful for new p r o d u c t evalu-
82.2~ for 3 h, S i m i l a r visual e x a m i n a t i o n of the surface of ation. A three-year actual test is usually r e q u i r e d by m o s t
the coated steel o r a l u m i n u m s u b s t r a t e is c o n d u c t e d for dis- c u s t o m e r s before they will accept a new p r o d u c t o r a signifi-
c o l o r a t i o n o r blushing, a d h e s i o n loss, or film failure. cant c o m p o s i t i o n a l change in a coating formulation. At the
Abrasion Testing--A critical characteristic of an acceptable end of the test period, evaluations include can a p p e a r a n c e ,
exterior film is its ability to protect cans from m a r r i n g a n d food taste, a n d v a c u u m testing. The latter is a c c o m p l i s h e d b y
scratching the d e c o r a t i o n a n d identification. As m e n t i o n e d piercing the c o n t a i n e r with a device such as a h a n d held
earlier in the Can P r o d u c t i o n p o r t i o n of this discussion, occa- v a c u u m unit w h i c h pierces the can a n d seals a gauge a r o u n d
sionally a b r a s i o n resulting from cans r u b b i n g against each the puncture. This gauge d e t e r m i n e s the p r e s s u r e before c a n
o t h e r especially d u r i n g s h i p m e n t can be severe e n o u g h to opening. Chemical r e a c t i o n of the food p r o d u c t with coating
actually cause r u p t u r e of the metal. or exposed walls can result in a p r e s s u r e change.
Several tests are e m p l o y e d to m e a s u r e the coatings ability Adhesion Test--This test is similar to one used t h r o u g h o u t
to resist abrasion. A simple technique involves r u b b i n g the the coatings industry. It involves pressing Scotch B r a n d
coated surface with a s t a n d a r d pencil eraser, counting the Tape TM to the surface a n d e x a m i n i n g the surface a n d the
n u m b e r of rubs or d o u b l e r u b s r e q u i r e d to r e m o v e the coat- adhesive side of the tape after removal. The surface of the
ing a n d reveal the u n c o a t e d surface. coated substrate is often scored with a r a z o r in an X p a t t e r n
A c o m m e r c i a l device called a TABER ABRADER TES- o r a cross h a t c h p a t t e r n before the tape is a p p l i e d [ASTM Test
TER TM [ASTM Test M e t h o d for A b r a s i o n Resistance of Or- Methods for Measuring Adhesion by Tape Test (D 3359-83)].
ganic Coatings b y the Taber Abraser (D 4060)] is in c o m m o n Flexibility--A test k n o w n as the T-Bend test is c o m m o n
use in the i n d u s t r y for a p r e l i m i n a r y evaluation of a b r a s i o n t h r o u g h o u t the metal coating i n d u s t r y [ASTM Test M e t h o d
for Coating Flexibility of P r e p a i n t e d Sheet (D 4145)]. The test
evaluates the flexibility characteristics of a p a i n t on a sub-
strate by d e f o r m a t i o n of the substrate a n d s u b s e q u e n t evalu-
ation of the a d h e r e d coating. A 0-T b e n d is a b e n d in a section
of metal t u r n e d b a c k on itself after a 180 ~ bend. The b e n d
e x a m i n a t i o n can be visual, microscopic, or it can use Scotch
B r a n d TM t a p e o r copper-sulfate exposure. This is usually de-
p e n d e n t on the customer's stated requirements.
A second 180 ~ b e n d a r o u n d the b e n d a l r e a d y m a d e repre-
sents a lesser level of flexure. A coating that satisfactorily
passes e x a m i n a t i o n on this surface, a n d that has a l r e a d y
failed the 0-T test, will be considered a 1-T flexibility coating.
A third b e n d represents 2-T, etc.
A n o t h e r m e t h o d of evaluating the flexibility of the coating
involves the use of an i m p a c t testing device [ASTM Test
FIG. 4-Altek TM Mobility/Lubricity Tester, M e t h o d for Resistance of Organic Coatings to the Effects of
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CHAPTER 62--CAN COATINGS 723
FIG. 5-Gavarti TM abrasion test unit.
Rapid Deformation (Impact) (D 2794)]. In this test flexibility deviations in gloss level will be observed at varying thick-
is evaluated by dropping a large bullet-shaped weight from a nesses.
measured height down a cylindrical guide tube onto the Color Measurement--The customer will assign an accept-
uncoated surface of a test sheet. The test is referred to as a able level of deviation of the final color of the sheets or the
reverse impact test. Microscopic examination of the im- cans based on a defined standard. Spectrophotometric analy-
pacted area is employed for evidence of cracking in the coat- ses using L A B ranges are reported [ASTM Test Method for
ing. The coating can be tested to the point of metal failure, a Calculation of Color Differences from Instrumentally Mea-
factor which depends on the thickness and strength of the sured Color Coordinates (D 2244)1.
substrate used. Blocking Resistance--Frequently, sheets of coated product
A test more specific to the can industry involves use of the are stacked and stored before being carried to the next station
Erichsen Lacquer Testing Instrument. With this device a cup for processing. Such storage can often occur after an oven
is actually formed from a section of coated metal and the operation, which means that the sheets are stacked at an
corners of the formed cup are examined for signs of inade-
elevated temperature. As sheets are fed to a pile, the pressure
quate flexibility (T. J. Bell, Inc., 1340 Home Ave, Akron, Ohio
imposed on the lower members of the stack can become con-
or A. M. Erichsen, GMBH 587 Hemer, Sundwig, Germany).
siderable, and the sheets must resist adhering to each other.
Extraction Testing--Concentrations levels of coating com-
Efficient and rapid movement of these sheets individually for
ponents capable of being extracted by the container contents
subsequent processing is essential to achieve an economical
must be below a defined limit. The Food and Drug Adminis-
container production rate. Simple tests to evaluate the ability
tration has established a series of limits and has defined
certain liquids to be used for testing based on the planned of coatings to resist this sticking phenomenon are commonly
contents of the container. They are described in detail in the developed that are acceptable to both the customer and the
Code of Federal Regulations, No. 21, Section 175.300. An supplier.
extraction technique is also described in detail in this govern- In one such test a series of coated sheets or panels are
ment publication. stacked face to back. Pressure, usually supplied via a properly
Gloss Measurement--The specular gloss of a coated sample placed weighted block of metal, is imposed on the top sheet
is measured using a 60 ~ gloss meter [ASTM Test Method for or panel of the stack. The stack which can be stored at
Specular Gloss (D 523)]. The meter should be equilibrated controlled temperature for defined periods of time is exam-
and calibrated against standard panels. The meter is placed ined after cooling for ease of separation. The weighted block
over the panel to be tested, several readings are taken at of metal is often of such a physical dimension that the resist-
different spots on the panel, and an average of these readings ance to sticking of the coated panels can be determined con-
is recorded. Care must be taken to control film thickness as veniently (usually reported in pounds/square inch).
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REFERENCES [4] Fiedler, J., "Cans Try New Coats," Industrial Finishing, November
1982.
[1] Lamboune, R., Paint and Surface Coatings; Theory and Practice, [5] Code of Federal Regulations No. 21, Section 175.300, U.S. Gov-
ernment Printing Office, 1988.
John Wiley and Sons, New York, 1987, p. 523.
[6] The Canmaker, Vol. 5, December 199I, p. 28.
[2] The Canmaker, Vol. 5, March 1992, p. 10.
[7] The Canmaker, Vol. 5, December 1991, p. 7.
[3] Chemical Week, 5 Aug. 1992, pp. 22-26. [8] "Guide to Tinplate," International Tin Research Institute Publica-
tion 622, Lamport Gilbert Printers, Reading, England, 1981.
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MNL17-EB/Jun. 1995
ii
Masonry
by Frances Gale 1 and T h o m a s Sliva 2
As WITH MOST OTHER MATERIALS, masonry substrates are Unit Masonry (C 270) includes information about composi-
painted for one or both of two basic reasons: to change tions and properties of different types of mortar and their
appearance or to improve performance in the relevant service uses for new construction and tuck pointing or replacement
environment. Imparting or changing color and increasing of deteriorated mortar.
surface brightness are two important parts of the decorative
function. In some cases coatings are applied to improve the
appearance of the masonry substrate by masking defects or Porosity
repair work. Although, in general, masonry materials do not A physical property that all masonry substrates share is
need protection, per se, coatings can reduce attack in highly porosity. Their interior structures are systems of fine, inter-
acidic atmospheres or salt water immersions. In most cases connected pores. With some materials the pores are ex-
coatings help the masonry to protect the interior of the struc- tremely small. However, because of this inherent porosity, all
ture from penetration of moisture. masonry is somewhat permeable to water. Hence, moisture
Masonry substrates to which paints are applied include can enter them in several ways including through poorly
stone, brick, tile, and concrete and other cement-based mate- designed or faulty flashing, vapor barriers, etc. The presence
rials. As with other substrates, the ideal coating for masonry of excessive amounts of moisture can adversely affect paint
should be economical but must also resist soiling, retain ap-
adhesion and thus performance.
pearance, and be easy to maintain. A coating should function
effectively for a time appropriate to where it is used. Thus an
exterior masonry coating should be able to withstand weath- Absorption Testing
ering without losing adhesion to the underlying surface.
This chapter discusses characteristics of masonry sub- The sorption of water by a masonry material is an impor-
strates that should be considered when selecting paints for tant factor affecting the performance of the coating as well as
application to those surfaces. Information is also provided the substrates. This is because moisture is a necessary condi-
about laboratory and field tests that are appropriate for evalu- tion for most processes of deterioration. Water absorption by
ating the performance of paints. masonry substrates can be determined by laboratory testing.
ASTM Method of Sampling and Testing Brick and Structural
Clay Tile (C 67) contains methods for testing brick and struc-
PROPERTIES OF MASONRY SUBSTRATES tural clay tile to determine physical properties such as ab-
sorption and saturation coefficient. Absorption is measured
Definitions by submersing a representative whole tile or half brick in
water for a 5-h or 24-h period. Percent absorption is deter-
Materials referred to as unit masonry include natural mined by comparing the difference between the saturated
stone, brick, tile, and concrete block. Unit masonry is used in
and dry weights to the dry weight.
conjunction with mortar or caulk. Standard terms relating to The test procedure for absorption by concrete masonry
natural building stones are defined in ASTM Definitions of units described in ASTM Standard Methods of Sampling and
Terms Relating to Natural Building Stones (C 119). Defini-
Testing Concrete Masonry Units (C 140) is similar to that
tions for terms relating to structural clay products are con-
described in ASTM C 67. Three full-size units are used for
tained in ASTM Definitions of Terms Relating to Structural
testing absorption. ASTM Test Methods for Absorption and
CIay Products (C 43). In addition to unit masonry, paints are
Bulk Specific Gravity of Natural Building Stone (C 97) pro-
also applied to monolithic concrete. Standard terminology
vides a standard test method for this type of stone. The test
relating to concrete and concrete aggregates is provided in
procedure is also similar to that described in ASTM C 67
ASTM Definitions of Terms Relating to Concrete and Con-
except the immersion period is 48 h. ASTM Test Method for
crete Aggregates (C 125). ASTM Specification for Mortar for
Specific Gravity, Absorption, and Voids in Hardened Con-
crete (C 642) contains test methods for measuring absorption
~Training coordinator, National Center for Preservation Technol- and voids in cured concrete. Absorption is calculated after a
ogy and Training, National Park Service, NSU Box 5682,
Natchitoches, LA 71497. 48-h immersion and after immersion in boiling water. A
2Assistant technical director, DL Laboratories, 116 E. 16th St., method for determining the volume of permeable pore space
New York, NY 10003. (voids) is also provided.
725
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Efflorescence Surface Finish

When water-soluble salts are present within the masonry Masonry materials display a wide range of surface finishes.
substrate, efflorescence can be an unwanted result. Efflores- Adhesion of coatings to glazed tile and brick, polished stone,
cence is defined as a crystalline deposit of water soluble salts and highly troweled concrete is problematic because the very
on the surface of the masonry material. If migration under a smooth surfaces do not develop a mechanical key. Very po-
painted surface occurs under a painted surface, crystalliza- rous surfaces such as concrete block and natural stone such
tion of the dissolved salts at the coating masonry interface as travertine present a different sort of problem. Thin paint
can push the coating off the substrate. Even if the solution films do not easily cover their rough or irregular surfaces so
passes through the coating and the salts deposit on the sur- that high-build coatings are generally used. Primers or fillers
face, they are unsightly, and recurring efflorescence can be a are sometimes required.
symptom of deterioration taking place with the substrate. If
the salts are deposited below the interface (cryptoflo-
rescence), crystallization pressures within the masonry can COATINGS
lead to eventual disintegration of the masonry material.
The source of soluble salts that results in efflorescence or Both types of water-borne and organic solvent-borne coat-
cryptoflorescence can be the masonry unit itself or compo- ings have been applied to masonry substrates. A brief discus-
nents of the mortar. Secondary sources include contami- sion and examples of each type are provided below. Methods
nated groundwater and residues of chemicals used in clean- for determining physical and chemical properties of paints
ing masonry walls. A test for efflorescence of individual for masonry substrates appear elsewhere in this manual and
masonry units is contained in ASTM C 67. Full-size bricks are in U.S. Federal Test Method Standard No. 141C. The titles of
partially immersed in distilled water for seven days. After federal specifications that specifically refer to application on
oven drying for 24 h, the specimens are inspected for efflores- masonry substrates are listed in this chapter.
cence.
A test for assessing resistance to efflorescence is described
in NBS Technical Note 883 Waterproofing Materials for Ma- Water-Reducible Coatings
sonry. For this test one side of a brick specimen is left Water-borne or -reducible coatings are or form dispersions
uncoated. The brick is placed with the uncoated surface face of the pigment, extender, binder, and additive components in
down in a sodium sulfate solution for seven days. After dry- water. A distinctive feature of latex coatings is that the binder
ing, the coated surfaces are inspected for efflorescence. is also dispersed. Consequently, most of the resulting films
are porous or less compact than corresponding solvent-borne
coatings and so are more permeable to water vapor. This
characteristic is important as most masonry substrates con-
tain moisture at the time the paint is applied. Water vapor
Surface pH permeability is also a factor subsequent to application as it is
The pH of masonry substrates is variable, normally de- virtually impossible to completely prevent access of water to
pending on the chemical composition of the material. Some masonry walls. Transport of this water to the exterior surface,
materials such as brick, tile, and many natural stones have a caused by thermal gradients in the winter, or to below-grade
neutral or slightly acidic pH. Others, including cement-con- interior surfaces, caused by hydrostatic pressure, forces im-
taining materials such as concrete and calcareous stones permeable coatings off the surface.
(e.g., limestone and marble) are naturally alkaline. Mortar Of the water-reducible coatings, portland cement powder
used with neutral or acidic masonry units can sometimes paints have the longest service record. Cement paints form
impart alkalinity to the wall surface. If the pH of the substrate hard, flat, porous films that readily permit passage of water
is high, paints that are sensitive to alkalies should be avoided vapor. Cement paints help to seal and fill porous masonry
surfaces. In addition to portland cement, they can contain
as the alkalinity saponifies them.
specific additives for controlling application, setting time,
Surface alkalinity is not the only cause of coating failure.
water repellency, and color. Federal Specification A-A-1555
Subsequent migration to the surface of construction water,
Water Paint, Powder covers cementitious type paints for pro-
condensed interior water vapor through barrier defects, and
tection, decoration, and waterpi~oofing of interior and exte-
capillary water from contact with the earth ("rising damp")
rior masonry, concrete, and plaster surfaces. The correspond-
can all result in the presence of alkalies and soluble salts. ing Canadian specification was withdrawn when interior
A method for measuring surface pH is described in the latex paints were developed. Although once widely used, ce-
ASTM Test Standard Method for pH of Chemically Cleaned ment paints have been largely replaced by latex paints.
or Etched Concrete Surfaces (D 4262). Although ASTM Other federal specifications for water-reducible paints for
D 4262 is intended for determining whether residual chemi- masonry materials are TT-P-19D Paint, Latex (Acrylic Emul-
cals have been removed following chemical cleaning or etch- sion, Exterior Masonry), and TT-P-55B Paint, Polyvinyl Ace-
ing, the procedure for measuring surface pH of the concrete tate Emulsion (for Exterior Masonry Surfaces), and TT-P-
surface is described. A strip of pH test paper is placed on the 96D Paint Latex Base for Exterior Surfaces.
wet concrete surface and compared with the color chart to Block fillers are sometimes required to fill voids or holes in
determine pH. masonry substrates. TT-F-1098D is a federal specification for
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CHAPTER 63--MASONRY 7 2 7
ready-mixed styrene butadiene copolymer resin filler for cin- crete (D 4259) contains information on instructions for
der and concrete block and stucco. abrading concrete. Procedures described are mechanical
abrading, abrasive blast cleaning, and water blast cleaning.
ASTM Practice for Acid Etching Concrete (D 4260) describes
Solvent-Borne Coatings some of the normal practice for this technique. In brief, the
These materials consist of pigments dispersed in solutions etching solution is applied to the pre-wet concrete surface,
of resins and additives in organic solvents. Unless and after bubbling begins to subside, the surface is flushed
overpigmented, they form smooth, continuous films that are with water. In both practices, a roughened, textured surface
effective moisture barriers where water intrusion must be is the desired result.
prevented. Solvent-borne paints must be applied to dry sur-
faces as excessive moisture may interfere with development Surface pH After Cleaning
of adhesion and, with some coatings, cause blushing. They
are, however, more tolerant than water-borne coatings to Following completion of chemical cleaning or acid etching,
application at temperatures near the freezing point of water. the pH of the masonry surface should be tested to confirm
Solvent-reducible coatings are of both the thermosetting that residual chemicals have been removed. This procedure is
and thermoplastic type. The former type cures by oxidative important because chemicals not removed by water rinsing
polymerization (oil-modified, air-drying alkyds, and ure- may adversely affect the performance and adhesion of paints
thanes), by chemical reaction of multi-components just prior applied to the treated surface. ASTM D 4262 contains a test
to and/or after application (e.g., epoxies and urethanes), and method for pH of chemically cleaned or etched concrete sur-
by heat just after application (baking alkyd, acrylic and ure- faces. In this method, the pH of the water rinses is taken
thane enamel). Thermoplastic coatings form films solely by initially and the end of the final rinse cycle.
solvent evaporation and include acrylic, vinyl, rubber-deriva-
tive, and cellulose-derivative resins and are by definition (al-
Moisture
though not always so called) lacquers. Federal specifications
for solvent-borne coatings are TT-P-24D Paint, Oil, Concrete As stated in the subsection entitled Solvent-Borne Coat-
and Masonry, TT-P-95C Paint, Rubber, for Swimming Pools ings, moisture in the masonry substrate may be detrimental
and Other Concrete Masonry Surfaces. to those coatings that cannot tolerate moisture at or near the
surface during application. Consideration of this factor is
particularly relevant following cleaning procedures that in-
APPLICATION volve water (e.g., steam cleaning and chemical cleaning).
ASTM Test Method for Indicating Moisture in Concrete by
As with any substrate, masonry surfaces must be free of the Plastic Sheet Method (D 4263) contains a test method to
dirt, oil, grease, mildew, efflorescence, and other contami- establish whether sufficient moisture can migrate to the sur-
nants before being coated. It is generally thought that newly face to cause problems. In this method a plastic sheet is taped
constructed masonry walls should age six months before to the concrete surface and allowed to remain in place for a
painting, but latex finishes are frequently applied much minimum of 16 h. Following its removal, the underside is
sooner. Obviously, on older surfaces, any needed repair work visually inspected for the presence of moisture.
should be completed prior to painting. Primers are some- The methods of sampling and testing concrete masonry
times recommended for previously painted surfaces and units contained in ASTM C 140 include a procedure for mea-
should always be used when specified by the coating manu- suring the as-sampled moisture content. As mentioned in the
facturer. TT-P-00620C is a federal specification for condi- sections entitled "Water-Reducible Coatings" and "Solvent-
tioner for heavily chalked previous coatings. Borne Coatings" above, excessive moisture in masonry may
cause coatings either not to develop initial adhesion or be
subsequently forced off the surface. Annex A4 of ASTM
Surface Preparation
Method for Preconstruction and Construction Evaluation of
As with any surface, adequate preparation of masonry sub- Mortars for Plain and Reinforced Unit Masonry (C 780) pro-
strates is essential for obtaining good adhesion of the vides a test method for determining water content of mortar
material to be applied. With some surfaces, a simple dusting sampled at the construction site.
is all that is required; with others more rigorous cleaning is
advisable. ASTM Practice for Surface Cleaning Concrete Unit
Masonry for Coating (D 4261) and ASTM Practice for Prepa- PERFORMANCE TESTS
ratory Surface Cleaning of Architectural Sandstone (D 5107)
describe procedures for cleaning with broom, vacuum, air Field and laboratory testing are useful for evaluating char-
blast, water, detergent water, and steam. ASTM D 5107 also acteristics thought to be essential to good performance of
covers a procedure for chemical cleaning. coatings, hence to predict their performance on masonry
If optimum bond of the coating to the masonry substrate is substrates.
desired, alteration of the surface profile may be necessary.
For concrete that will be exposed to service conditions such
Alkali Resistance
as continuous or intermittent immersion, temperature cy-
cling or mechanical loading, abrading, or acid etching the Federal Specification A-A-1555 contains a proce-
surface is recommended. ASTM Practice for Abrading Con- dure for evaluating the alkali resistance of cement powder
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coated panel is soaked for 14 days in a sodium hydroxide Artificial Weathering Tests
solution with the painted side 1/2 in. above the surface. Fed-
Coated masonry specimens can also be exposed to simu-
eral Specification TT-P-19D for latex coatings applied to
lated weathering conditions in the laboratory. It should be
wood and masonry also contains a procedure for evaluating
recognized, however, that the more accelerated the test con-
alkali resistance.
ditions the less reliable the results.
Federal Specification A-A-1555 contains a test procedure
Water Vapor Permeability for artificially weathering specimens. Concrete panels
painted with cementitious paint are evaluated for checking,
Permeability to water vapor is an important characteristic cracking, and loss of adhesion after 500 h of artificial weath-
to consider when selecting masonry coatings. The parent ering.
standard for determining water vapor permeability is ASTM Although there are no ASTM methods for artificially weath-
Standard Test Methods for Water Vapor Transmission of Ma- ering coated masonry specimens, three standard practices
terials (E 96). Although E 96 is intended for water vapor describe operating conditions for this testing. These are
transmission of materials such as paper, plastic, plaster prod- ASTM Standard Practice for Operating Light- and Water-
ucts, etc., the method has been used to evaluate the perme- Exposure Apparatus (Carbon Arc Type) for Testing Paint and
ability of paints to be applied to masonry materials. In fact, Related Coatings and Materials (D 822), Recommended
Federal Specification TT-C-555b references ASTM E 96 for Practice for Operating Light- and Water-Exposure Apparatus
determining water vapor permeability. (Unfiltered Open-Flame Carbon-Arc Type) for Testing Paint,
Procedures described in E 96 that are used for evaluating Varnish, Lacquer, and Related Products Using the Dew Cycle
masonry coatings are the desiccant (dry-cup) method and the
(D 3361), and Standard Practice for Conducting Tests on
water (wet-cup) method. Two variations are service condi-
Paint and Related Coatings and Materials Using a Fluores-
tions with one side wetted and service conditions with low
cent UV-Condensation Light- and Water-Exposure Apparatus
humidity on one side and high on the other. With the desic-
(D 4587). Equipment used in these practices simulates dete-
cant method, coated specimens are placed in test dishes filled
rioration caused by sunlight and water as rain or dew. Be-
with desiccant; with the water method, they contain water.
cause the natural environment varies with respect to time,
The dish assemblies are placed in chambers where tempera-
geography, and topography, it may be expected that the ef-
ture and relative humidity are precisely controlled. The rate
fects of natural exposure will vary accordingly.
of water vapor movement through the specimens is measured
as a weight gain or loss versus time.
ASTM Test Method for Water Vapor Permeability of Or-
ganic Coating Films (D 1653) contains similar test methods Resistance to Wind Driven Rain
for measuring water vapor permeability. The original version
(1959), specifically for the coatings industry, attempted to ASTM Test Method for Water Permeance of Masonry
cover the entire relative humidity range in one step. It was (E 514) contains a procedure for measuring water penetra-
revised in 1985 to include the wet and dry cup methods from tion and leakage through masonry to evaluate resistance to
E 96. D 1653 still, however, maintains two conditions with the effects of wind-driven rain. Representative materials and
large relative humidity ranges--the dry cup exposed to 90% workmanship are used to construct test walls that are ex-
relative humidity at 100~ (38~ and the wet cup to near 50% posed to water at a rate of 138 L per square meter (3.4 gal per
relative humidity at 73~ (23~ To ensure precise results, square foot) per hour for at least a 4-h period.
specimens must be smooth, continuous films of uniform Federal Specification A-A-1555 contains a test procedure
thickness. for wind-driven rain resistance of patio blocks painted with
cementitious paint. Test panels are placed in a transparent
plastic testing box and sprayed with 60 to 70 gal (228 to
Field Testing 266 L) of water per hour. Specimens are inspected at the end
Some performance tests rely on exposing coated masonry of 8 h for the presence of water.
test specimens to actual conditions in the field. ASTM Prac-
tice for Atmospheric Environmental Exposure Testing of
Nonmetallic Materials (G 7) covers procedures for exposing Other Tests
nonmetallic materials to natural weather. Practice G 7 is in-
tended to facilitate collection of uniform results of exposure Federal Specification TT-C-555B Coating, Textured for Ex-
testing by indicating the variables that should be considered terior and Exterior Masonry Surfaces contains several proce-
and specified. Factors determining degradation due to weath- dures for testing paints to be applied to masonry substrates,
ering include climate, time of year, presence of industrial including evaluating color, flexibility, impact resistance,
atmosphere, etc. The specifics of weathering, however, can be moisture resistance, accelerated weathering, resistance to
accelerated by changing the angle of exposure. ASTM Prac- wind-driven rain, and moisture vapor permeability.
tice for Conducting Accelerated Outdoor Exposure Tests of Federal Specification TT-P-19D is intended to evaluate per-
Coatings (D 4141) includes methods for speeding up natural formance of paints applied to exterior wood and masonry
weathering. The greatest increase occurs when mirrors that substrates. Concrete test panels, prepared in accordance with
concentrate solar radiation on the specimens also follow the Federal Test Method Standard No. 141, are used for some of
sun. the test procedures.
www.iran-mavad.com

CHAPTER 63--MASONRY 729
Specimens C 780 Method for Preconstruction and Construction Evalu-

ation of Mortars for Plain and Reinforced Unit Ma-
Obviously, the use of standardized specimens of the ma-
sonry
sonry substrate is essential to obtaining reliable data in any D 822 Standard Practice for Operating Light- and Water-
testing protocol. ASTM Test Method of Making and Curing Exposure Apparatus (Carbon Arc Type) for Testing
Concrete Test Specimens in the Laboratory (C 192) describes Paint and Related Coatings and Materials
the practice for making and curing concrete specimens using D 1653 Test Method for Water Vapor Permeability of Or-
precisely controlled materials and conditions. ASTM Test ganic Coating Films
Methods of Making and Curing Concrete Test Specimens in D 1734 Method of Making and Preparing Concrete and Ma-
the Field (C 31) contains procedures for making and curing sonry Panels for Testing Paint Finishes
specimens using concrete delivered to the job site. D 3361 Recommended Practice for Operating Light- and
ASTM Method of Making and Preparing Concrete and Ma- Water-Exposure Apparatus (Unfiltered Open-Flame
sonry Panels for Testing Paint Finishes (D 1734) contains Carbon-Arc Type) for Testing Paint, Varnish, Lac-
instructions for making and preparing concrete panels for quer, and Related Products Using the Dew Cycle
testing coatings designed for portland cement concrete. Pan- D 4141 Practice for Conducting Accelerated Outdoor Expo-
els are molded to fit the artificial weathering apparatus de- sure Tests of Coatings
scribed in Artificial Weathering Tests. The method also D 4259 Practice for Abrading Concrete
describes how to mold panels for use on outdoor exposure D 4262 Test Standard Method for pH of Chemically Cleaned
testing racks. or Etched Concrete Surfaces
Method 2051 of Federal Test Method Standard No. 141, D 4263 Test Method for Indicating Moisture in Concrete by
Preparation of Concrete Panels, contains the procedure and the Plastic Sheet Method
materials required to make concrete and masonry panels for D 4587 Standard Practice for Conducting Tests on Paint and
testing paints. Three procedures are described for panels with Related Coatings and Materials Using a Fluorescent
different materials and surface finishes. UV-Condensation Light- and Water-Exposure Appa-
ratus
D 5107 Practice for Preparatory Surface Cleaning of Archi-
SELECTION tectural Sandstone
E 96 Standard Test Methods for Water Vapor Transmis-
There are a number of factors to consider when selecting sion of Materials
paint for a masonry substrate. These include the materials E 514 Test Method for Water Permeance of Masonry
and type of structure to which the paint will be applied as well G7 Recommended Practice for Atmospheric Environ-
as the desired appearance. As with any application, it is mental Exposure Testing of Nonmetallic Materials
important to determine the service conditions under which
the masonry paint must perform. Awareness of these factors
should enable selection of a product that will perform effec-
tively on masonry.
Federal Standards and Test Methods
Federal Test Method Standard No. 141C Paint, Varnish,
Lacquer and Related Materials: Methods of Inspection,
REFERENCED STANDARDS Sampling and Testing
No. 141C, Method 2051, Preparation of Concrete Panels
ASTM Standards 12.7.7.3. Federal Specifications
C31 Practices for Making and Curing Concrete Test Speci- A-A-1555 Water Paint, Powder (Cementitious, White and
mens in the Field Colors)
C 43 Definitions of Terms Relating to Structural Clay
TT-C-555B, Coating, Textured (For Interior and Exterior Ma-
Products
sonry Surfaces)
C 67 Method of Sampling and Testing Brick and Struc-
tural Clay Tile TT-F-1098D Filler, Block, Solvent Thinned, for Porous Sur-
C 97 Test Methods for Absorption and Bulk Specific Grav- faces
ity of Natural Building Stone TT-P-19D Paint, Latex (Acrylic Emulsion, Exterior Wood and
C 119 Definitions of Terms Relating to Natural Building Masonry)
Stones
TT-P-24D Paint, Oil, Concrete and Masonry, Exterior, Egg-
C 125 Definitions of Terms Relating to Concrete and Con-
crete Aggregates shell Finish, Ready-mixed
C 140 Methods of Sampling and Testing Concrete Masonry TT-P-55B Paint, Polyvinyl Acetate Emulsion, Exterior
Units TT-P-95C Paint, Rubber: For Swimming Pools and Other
C 192 Method of Making and Curing Concrete Test Speci- Concrete and Masonry Surfaces
mens in the Laboratory
C 270 Specification for Mortar for Unit Masonry TT-P-96D Paint, Latex Base, For Exterior Surfaces
C 642 Test Method for Specific Gravity, Absorption, and TT-P-97D Paint, Paint, Styrene Butadiene Solvent Type,
Voids in Hardened Concrete White (For Exterior Masonry)
www.iran-mavad.com

SELECTED BIBLIOGRAPHY Kapsanis, K. A., "Coating Concrete: A Review of Regulations, Techni-

cal Activities, and Resources," Journal of Protective Coatings and
Ashton, H. E., "Co~ttings for Masonry Surfaces," Canadian Building Linings, August 1991, pp. 58-65.
Maslow, P., Chemical Materials for Construction, New York, McGraw
Digest, Vol. 131, 1970.
Hill, 1982.
BIA Technical Notes 7F, "Moisture Resistance of Brick Masonry
Morgans, W. M., Outlines of Paint Technology, 1990.
Maintenance," Brick Institute of America, Reston, VA, 1986. NCMA-TEK 10A, "Decorative Waterproofing of Concrete Masonry
BIA Technical Notes 6, "Painting Brick Masonry," Brick Institute of Walls," National Concrete Masonry Association, Herndon, VA,
America, Reston, VA, 1985. 1981.
Boxall, J. and von Fraunhofer, J. A., Paint Formulation, Industrial NCMA-TEK 44, "Maintenance of Concrete Masonry Walls," National
Press, New York, 1981. Concrete Masonry Association, Herndon, VA, 1972.
British Board of Agrement, The Assessment of Masonry Coatings, NCMA-TEK 55, "Waterproof Coatings for Concrete Masonry," Na-
Method of Assessment and Testing No. 33, 1986. tional Concrete Masonry Association, Herndon, VA, 1973.
Clark, E. J. et al., Waterproofing Materials for Masonry, NBS Techni- Panarese, W. C., Kosmatka, S. H., and Randall, F. A., Jr., Concrete
cal Note 883, Government Printing Office, Washington, 1975. Masonry Handbook, Portland Cement Association, Skokie, IL,
1991.
www.iran-mavad.com

MNL17-EB/Jun. 1995
64
Pipeline Coatings
by Loren B. OdelP and AI Siegmund 2
AMERICA IS THE MOST INDUSTRIALIZED NATION o n e a r t h . T o r u n Asphalt enamels and asphalt mastic 7%
this nation, huge quantities of energy are required. Sources of Polyethylene, extruded and bonded 17%
energy vary, ranging from nuclear power to the burning of Coal tar enamels 14%
coal. The most common source of energy used today is based Thin film powder coatings (FBE) 32%
on "fossil fuels," which include oil and natural gas. In many Tape products 30%
instances, great distances are covered between the source of This distribution can vary from year to year.
the fuel and its consumption. The predominant method of
fuel transportation is through carbon-steel pipelines.
Pipelines are not restricted by size, product carried, or WHY USE COATINGS
construction material. This section addresses the most com-
mon type, pipelines made of carbon-steel pipe carrying natu- Corrosion control of steel pipelines is a complicated pro-
ral gas or petroleum products. cess involving several different techniques. Internal corrosion
Thousands of miles of pipeline crisscross the United States. control may be accomplished with the use of coatings and/or
The main goal is to deliver a source of energy to the end user. inhibitors; external corrosion may be minimized using coat-
Most pipelines are buried and are therefore not visible. They ings in conjunction with cathodic protection. In all phases of
may be located under streets, near school yards, and near corrosion control, it is recognized that coatings provide an
peoples' homes. Most have been in service for many years and economical, effective method of control.
may be in need of maintenance and/or replacement. In many cases it is necessary and/or advisable to use a
-Building a major pipeline is a costly, time-consuming combination of coatings with other methods of protection.
project. First, an abundant source of fuel must be located and Careful selection of the coating material in combination with
combined with an end user. State and federal permits must proper application can result in years of trouble-free service.
be obtained, rights-of-way purchased, and financing ob- Coatings provide the widest range of protective properties,
tained. For these and other reasons, pipelines must be long- ranging from excellent mechanical properties to elevated
term commitments. To protect this investment and to pro- temperature resistance. On a per-square-foot basis, coatings
vide safe operations, every possible means of protection must have proven to be the most economical corrosion control
be utilized over the service life. The most economical means system for steel pipelines. This protection is recognized by
of protection has proven to be a combination of coatings and the Department of Transportation (DOT). It is a DOT require-
cathodic protection. This section focuses on the role of coat- ment that all new steel pipelines involved in interstate trans-
ings, their design, choice, and use. portation must receive external corrosion protection in the
form of bonded coatings.
MARKET EXTERNAL COATINGS

The U.S. Department of Commerce estimates that loss of Coal Tar E n a m e l s
steel due to corrosion cost $50 billion a year in the United
States alone. The market for pipeline corrosion coating prod- Coal tar enamels are especially suitable for coating steel
ucts can be estimated in square feet coated, or dollars of pipe. Generally hot applied, either in the yard or in the field,
product. In 1990 this estimate for coatings grew to 300 000 ft2 they are virtually unaffected by long periods of water immer-
(27 870 m 2) with an estimated value of $350 000 000. sion, soil stress, punctures, or bacteria while providing a
Theke are five basic groups of coatings used for pipeline relatively high electrical resistance. These materials work
corrosion control. They are shown below in their dollar-value best in the temperature range of 30 to 180~ (1.1 to 82~
market breakdown: Enamels are degraded by ultraviolet light and therefore
should be wrapped with kraft paper when exposed. Coal tar
enamels are frequently reinforced with a fiberglass mat or
~FAIC, Technical Consultant, Coatings, 416 Crestwood Drive,
Houston, TX 77007 (deceased 4-9-92). embedded with a felt mat as a means of protection. These
ZCoatings Technical Services Manager, ICO, Inc., 9400 Bamboo, products provide years of service and were the first com-
Houston, TX 77041. monly used external protective coatings.
731
www.iran-mavad.com

Coal Tar Mastic Tape and Wrap Systems

Coal tar mastic is heavily filled with clays, silica, fiber glass, Tape-coating systems are usually cold-applied materials
etc., which yields a highly viscous material that is cold ap- consisting of three layers; a primer, a corrosion-resistant
plied to thicknesses of 1/2 to 5/8 in. (1.27 to 1.6 cm). This interlayer, followed by a wrap in the form of a tape for
product can also be field applied as a hot extrusion seamless mechanical protection. These systems are extremely popular
coating. A wide range of pipe diameters can be coated for for repair of existing pipelines by the over-the-ditch method
buried pipeline service. of application. Each of the three layers provides special prop-
erties. The primer is frequently rubber based and modified
with stress corrosion cracking inhibitors to provide good
adhesion. The interlayer is olefin based to resist corrosion,
Coal Tar Epoxides while the outer layer is reinforced to resist mechanical dam-
Coal tar epoxides are two-component materials that re- age and provide maximum moisture resistance.
quire mixing just prior to application. Coal tar plays two A similar system is based on petroleum waxes. This system
important roles in this type of coating: (1) cost reduction, (2) uses a wax-based primer, frequently combined with corro-
improved water resistance. The two components are de- sion inhibitors, followed by an external felt or tape wrap for
signed to air cure, providing a harder film than neat coal tar coating protection.
products. Excellent adhesion is provided by the epoxy com-
ponent if optimum cure is achieved.
Polyethylene
This system is generally an extruded film that encapsulates
the pipe using a mastic, two-part epoxy, FBE, or rubber-
Coal Tar Urethane based primer for adhesion. The polyethylene offers excellent
As with epoxides, coal tar is used primarily as a cost re- moisture resistance and mechanical properties. Since poly-
ducer. In this case, the base components are polyots and ethylene is an extruded product, its application to pipe is
polyfunctional isocyanates, which can also be two-compo- limited to plant environments.
nent spray applied to yield very rapid cure speeds. This re-
duces out-of-service time for the pipelines.
Coal tar products have the advantages of lower cost, excel- INTERNAL PROTECTION SYSTEMS
lent water resistance, wide range of application ability, and
long proven service lives. They can be plant applied or over- It is generally believed that coatings are applied to the
the-ditch applied. They comprise the largest group of coat- internal surfaces of pipelines to improve product flow. As
ings used for the repair and maintenance of existing pipe- flow enhancers, they can provide increased flow rates of from
lines. 5 to 15%. These coatings do, however, provide corrosion
Coal tar products have limitations in protection where ca- protection; and as products carried in the pipeline become
thodic protection is combined with coatings. Temperature more corrosive in nature, the importance of the coatings as
service is limited to 150~ (66~ corrosion barriers are realized. Active lines where acid gases
are involved require the use of coatings as corrosion barriers.
The three systems in common use today consist of two-
component epoxy polyamide/amine systems that are ambient
Fusion Bond Epoxides (FBE) cured, fusion bond systems that are baked, and in situ sys-
Fusion bond epoxy coatings are one of the newest technolo- tems that are field-applied, air-dried systems based on epoxy
gies viable for external protection of steel pipelines. These or urethane chemistry.
materials are heat-activated, chemically cured coating sys-
tems. They are 100% solid products applied in the form of
"powder coatings." Powder coatings are applied directly to APPLICATION TECHNIQUES
preheated pipe, where they melt, fuse, and cure into a contin-
uous film. To improve application efficiency, electrostatic All of the above-mentioned coatings can be plant applied. A
spray equipment is usually employed. The chemistry is such limited few are suitable for field application, although there
that cure often occurs through the residual heat in the pipe. are several good reasons for plant application. The first and
This yields very rapid application parameters. Characteristics foremost is surface preparation of the steel surface to be
of the cured coating include excellent mechanical and physi- coated. Cleaning techniques ranging from abrasive blasting
cal properties. These products are also highly resistant to to mechanical cleaning can be mechanized and automated,
undercreep from cathodic protection, thereby providing resulting in a controlled surface ready for acceptance of the
long-term corrosion resistance. coating system.
FBE products have one of the highest initial costs of the This is closely followed by application technique. Automa-
external coatings and require a greater degree of surface tion can result in a more uniform application of the chosen
preparation than other coatings to achieve maximum protec- coating product, resulting in film thickness control and regu-
tion. They are usually plant-applied materials, although inter- lation of the bake cycle for heat-cured products. Coatings that
nal and external girth welds may be coated and cured in the require heat to achieve chemical reaction can most economi-
field using portable induction heating devices for cure. cally be achieved in a plant environment.
www.iran-mavad.com

CHAPTER 6 4 - - O D E L L AND SIEGMUND ON PIPELINE COATINGS 733
There are o u t s t a n d i n g coating systems t h a t are field ap- TABLE I--Pipeline coating specifications.
plied, Many are used to r e p a i r existing c o a t e d lines o r to coat Affiliation Number Title
lines that previously h a d n o t e m p l o y e d coating systems. The
API RP 5L2 Recommended Practice for Internal
m o s t p o p u l a r technique is a n over-the-ditch system t h a t em- Coating of Line Pipe for Non-
ploys b o t h cleaning a n d coating e q u i p m e n t that travels along Corrosive Gas Transmission Service
the pipe w i t h o u t removing the pipe from service. New a n d API RP 5L7 Recommended Practice for Unprimed
better m e t h o d s of surface p r e p a r a t i o n that use abrasive blast- Internal Fusion Bonded Epoxy
Coating of Line Pipe
ing a n d / o r high-pressure w a t e r blast are used either in con-
NACE RP T-10D Application, Performance and Quality
j u n c t i o n with m e c h a n i c a l cleaning or in place of it. This (Draft) Control of Plant Applied
technique results in cleaner surfaces for coating application. Fusion-Bonded Epoxy External Pipe
Coating c o m p o s i t i o n s continue to change, i m p r o v i n g their Coatings
p e r f o r m a n c e a n d taking advantage of new p o l y m e r s to im- AWWA ANSI/AWWAC210 Liquid Epoxy Systems for the
Interior and Exterior of Steel Water
prove c o r r o s i o n protection. Pipelines
AWWA ANSI/AWWAC214 Tape Coating Systems for the
Exterior of Steel Water Pipelines
AWWA ANSI/AWWAC215 Extruded Polyolefin Coatings for the
~QUALITY CONTROL Exterior of Steel Water Pipelines
AWWA ANSI/AWWAC203 Coal-Tar Protective Coatings and
Success is related to quality control, a n d the a p p l i c a t i o n of Linings for Steel Water Pipelines-
protective coatings to pipelines is no exception. The very best Enamel and Tape-Hot-Applied
coating available can be r u i n e d by p o o r a p p l i c a t i o n o r by AWWA ANSI/AWWAC217 Cold-Applied Petrolatum Tape and
Petroleum Wax Tape Coatings for the
a p p l i c a t i o n to a dirty surface (Tables 1, 2, 3). Exterior of Steel Water Pipelines
A c o m p r e h e n s i v e quality p r o g r a m covers all phases of a
pipeline project, including steel surface quality, coating qual-
ity, a n d p r o p e r a p p l i c a t i o n of the product. The j o b does not
e n d there, for i m p r o p e r installation of a pipeline with a g o o d
coating j o b can result in d a m a g e that m i g h t lead to p r e m a - TABLE 2--ASTM tests for coal tar and related products--a
partial listing.
ture failure.
The e n f o r c e m e n t of a quality p r o g r a m is m o s t easily ac- Number Title
c o m p l i s h e d in a p l a n t environment. Field a p p l i c a t i o n is de- D4 Bitumen Content, Test for
p e n d e n t u p o n t e r r a i n a n d w e a t h e r conditions that can D5 Penetration of Bituminous Materials
h a m p e r r e q u i r e d processes a n d procedures. A quality pro- D36 Softening Point of Bitumen (Ring and Ball)
g r a m t h a t includes a representative f r o m each step of the D71 Density of Solid Pitch and Asphalt
D 2415 Ash in Coal Tars and Pitches
o p e r a t i o n with full responsibility for their p o r t i o n of the D 3143 Flash Point of Cutback Asphalt with Tag
process is vital. A clear set of specifications, outlined a n d Open-Cup
discussed with all parties in advance of the project, will by- G 17 Penetration Resistance of Pipeline Coatings
pass m a n y problems. C o m m u n i c a t i o n s b e t w e e n all represen- (Blunt Rod)
tatives will result in a h i g h e r quality job, resulting in longer
service at a lower cost.
TABLE 3--ASTM tests for corrosion and deterioration on pipeline

PRODUCT DESIGN/FUTURE CONCERNS coatings.
Number Title
There are several sets of specifications that pipeline coat-
D 1002 Adhesion to Steel (shear)
ings m u s t meet in o r d e r to gain wide acceptance. The Ameri- D 1044 Abrasion Resistance (Tabor)
can P e t r o l e u m Institute (API), National Association of Corro- D 2370 Tensile Strength/Elongation
sion E n g i n e e r s (NACE), a n d A m e r i c a n W a t e r W o r k s D695 Compressive Strength
Association (AWWA) have specifications o r r e c o m m e n d e d D 257 Volume Resistivity
practices that guide in the d e v e l o p m e n t a n d use of corrosion- G6 Abrasion Resistance of Pipeline Coatings
resistant coatings. Most specifications are p a r t of individual G8 Cathodic Disbonding of Pipeline Coatings
c o m p a n y p u r c h a s i n g contracts. These c o m p a n y specifica- G9 Water Penetration Into Pipeline Coatings
tions frequently c o n t a i n test p a r a m e t e r s that m u s t be m e t G 10 Bendability of Pipeline Coatings
with c o r r e s p o n d i n g references to ASTM, API, NACE, a n d G 11 Effects of Outdoor Weathering on Pipeline
Coatings
o t h e r methods.
New p r o d u c t s are n e e d e d that take into a c c o u n t the ever G 12 Nondestructive Measurement of Film
changing e n v i r o n m e n t a l regulations. Coatings that provide Thickness of Pipeline Coatings
e n h a n c e d p e r f o r m a n c e at elevated t e m p e r a t u r e s are re- G 13 Impact Resistance of Pipeline Coatings
(Limestone Drop)
quired. New systems b a s e d u p o n a c o m b i n a t i o n of the above G 14 Impact Resistance of Pipeline Coatings
technologies are trying to find their place in the market. (Falling Weight)
Quality p r o g r a m s b a s e d u p o n ISO/ANSI guidelines are set- G 19 Disbonding Characteristics of Pipeline
ting the s t a n d a r d s for future coating projects. The o p p o r t u n i - Coatings by Direct Soil Burial
ties are never ending. G 20 Chemical Resistance of Pipeline Coatings
www.iran-mavad.com

BIBLIOGRAPHY "Coating Work Increases As Pipeline Construction Plans Move

Forward," Pipeline Digest, April 1991.
Aaboe S. and Grutter A., "A High-Performance Thermal Insulation Logue, O. T., "Safety and Pheumoconioses: Abrasive Blasting and
Coating for Subsea Pipelines," Pipeline Digest, April 1991. Protective Respiratory Equipment," Materials Performance, Sep-
Banach, J. L., "Evaluating Design and Cost of Pipe Line Coatings," tember 1991.
Pipe Line Industry, April 1988. Pfaff, T. A. and Fogh, K., "Requirements For External Pipeline
Chapman, G. "New Technology Used On Major Pipeline Rehabilita-
Refurbishing Coatings," Pipeline Digest, May 1990.
tion Program," Pipeline Digest, November 1988.
Clark, J. R., "Innovations In Rehabilitation," Pipeline Digest, Novem- Taylor, S. A. and Chapman, G., "Cleaning Pipelines Using High-
ber 1989. Pressure Water Jets," Materials Performance, September 1991.
Coates, A. C., "Pipeline Recoating--A Cover Up Story," Pipeline Di- Werner, D. P. et al., "Survey Results on Pipeline Coatings Selection
gest, April 1991. and Use," Materials Performance, November 1992.
www.iran-mavad.com

MNL17-EB/Jun. 1995
i
Sealants
by Saul SpindeP
SEALANTSAREPRODUCTSINSTALLEDinto an opening to prevent thereby dries slowly, though the caulk usually sets up to be-
the intrusion of air, water, dust, heat, cold, and other materi- come paintable within a 24 to 48-h period. Oil-based caulking
als such as gases, e.g., radon. The sealant is installed into the compounds are easy to apply, easy to tool, and are available
opening by gun or knife. It is then expected to function even in a range of qualities. Generally, oil-based caulks exhibit
though the space it occupies is stressed because of move- movement of about 5%. Oil-based caulking compounds are
ment, thereby placing significant strain upon the adhesive used primarily by do-it-yourselfers.
forces that bond the sealant to the substrate to which it is
attached. The sealant is also expected to function regardless
of whether it is applied to a horizontal opening or a vertical Butyl Sealants
one or whether it is applied to a building facade subject to
Butyl sealants are based on polyisobutylene or polybntene,
rapid expansion and contraction or to a plaza or deck where
fillers such as talc and/or calcium carbonate and additives
it is subject to puncture by spiked heels.
such as adhesion promoters, antioxidants, and thixotropes.
The opening, or gap, into which a sealant is installed is
Butyl sealants dry by solvent release.
usually called a joint. The sides of the joint may be made of
Butyl sealants can be formulated to move at about +_71/2 to
similar or dissimilar materials, generally varying in width
+_121/2%. They are widely used in mobile home applications.
from 0.250 to 2.00 in. (0.64 to 5.08 cm) with the depth of the
In addition, another class of butyl sealants which are pre-
joint usually about one half the width. When required, pre-
pared without volatile solvents are extensively used as the
formed joint fillers made of materials such as open or closed
primary seal in dual-sealed insulated glass because of their
cell rubber or polyurethane foam are installed to control the
very low moisture vapor permeation properties.
joint depth. Primers are sometimes used to improve adhe-
sion.
The typical building materials that sealants are used with
Acrylic Solvent Release Sealants
are glass, steel, concrete, mortar, granite, marble, aluminum,
or wood. When the sealant is installed into the joint, the These sealants are similar to butyl sealants; however, they
surfaces the sealant contacts must be clean, dry, sound, and are based on polymethylacrylate polymers (or polyethyl or
free of contaminants or loose particles to provide an opportu- polybutyl polymers), resulting in medium-high molecular
nity for the sealant to perform as intended. weight products that, when formulated with colorants,
Caulk or sealant compounds are based on oils, latex poly- thixotropes, and additives, are used as sealants.
mers, butyl, acrylic and blocked styrene solvent-release poly- Acrylic solvent-release sealants exhibit movement similar
mers, and polysulfide, polyurethane, and silicone elastomers. to butyl sealants, namely up to +-121/2%. Acrylic solvent-
The oil-based products exhibit relatively little movement ca- release sealants are versatile in that they adhere to a wide
pability, generally 5% or less, and thus they are traditionally variety of surfaces and, in addition, exhibit excellent resist-
installed in relatively static joints. Acrylic latex polymers can ance to sunlight. Two prime disadvantages of acrylic solvent-
be formulated to possess significant movement, as much as release sealants are: (1) they often require heating in the
+25%, whereas the solvent-release butyl, acrylic, and cartridge when applied at cool temperatures, and (2) they can
blocked styrene sealants can move about +_10%. The elasto- emit acrylic monomer, which is somewhat odiferous and
merics exhibit significant movement, with silicones moving may be toxic in enclosed areas.
as much as 150% (+ 100%, - 50%).
POLYMERS USED IN SEALANTS Block Copolymer Sealant

Elastomeric block copolymer sealants, usually based on
Oil-Based Caulks
either styrene, styrene-butadiene, or isoprene, are another
Oil-based caulks are generally composed of drying oils, class of solvent-release sealants. These polymers exhibit ex-
mineral fillers, thixotropes, and driers. The oil oxidizes and cellent resistance to ultraviolet light, are effective as clear
sealants, generally adhere to a wide variety of substrates, and
~President, D/L Laboratories, 116 East 16 Street, New York, NY are readily paintable. The sealants can be formulated to move
10003. about _ 121/2%.
735
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Polyurethane Sealants Silicone sealants can be formulated to move as much as

150% and are used in many applications, especially where
Polyurethane sealants are available as single or multi-com-
long-term durability is required. Silicone sealants are the
ponent products. The one-component sealant is derived from
primary polymers used in structural glazing.
an in situ reaction of an isocyanate with a hydroxyl compo-
nent. These components cure by the reaction of the isocya-
nate (NCO) with atmospheric moisture, forming a polyurea. Acrylic Latex Sealants
The sealants contain fillers, thixotropes, additives, and adhe-
Acrylic latex sealants are essentially formulated from rela-
sion promoters.
tively high molecular weight acrylic polymers prepared by
Two-component polyurethane sealants are usually based
emulsion polymerization in an aqueous media and include
on an isocyanate-terminated polyether reacted with a hy-
fillers, surfactants, additives, and thixotropes. Acrylic latex
droxyl-terminated polymer. As with other sealants, two-com-
sealants dry by evaporation to form easily applied, highly
ponent polyurethane sealants are combined with fillers, ad-
weatherable products that exhibit good adhesion.
hesion promoters, and other additives and stabilizers.
These acrylic sealants can be formulated to move as much
Polyurethane sealants exhibit good movement capabilities,
as 25%; however, they should not be applied at low temper-
easily exhibiting movement. They generally adhere
atures and are not recommended for use in continuous damp
well to a variety of surfaces and are widely used in commer-
or wet environments.
cial applications, especially where abrasion resistance, i.e.,
traffic applications, is a prerequisite.
TEST PROCEDURES
Polysulfide Sealants
The following is a brief summary of the test methods and
Polysulfide sealants are sold as both one-component and procedures used to evaluate sealants. Where appropriate, ref-
two-component materials. Two-component sealants are for- erence is made to specific specifications and/or procedures
mulated with polysulfide polymers, hiding and color pig- where these tests are covered.
ments, clays, and mineral thixotropes. The second, or reac-
tive component, consists of a curing agent (e.g., lead
peroxide), adhesion promoters, fillers, and stabilizers. Both Extrusion Rate and Application Life
components are mixed just prior to use. This test is performed to measure the extrudability of single
The one-component polysulfide sealants are formulated
and multi-component sealants. Single-component sealants
with ingredients similar to the two-component material ex-
are extruded through a cartridge of known volume and prede-
cept that the cure chemistry is different. One-component termined orifice at 50 psi air pressure. The time to empty the
polysulfides cure by reaction with atmospheric oxygen and cartridge is recorded. Multi-component systems are mixed
moisture and are generally relatively slow to attain full cure. and allowed to stand for 3 h before being extruded in order to
Polysulfide sealants can be formulated to move at 25% develop information on their application properties after
and are used on a wide variety of surfaces. Polysulfides are
mixing.
used widely in insulated glass applications.
Rheological Properties (Flow and Sag)

Silicone Sealants
This test is employed to determine the horizontal or verti-
Silicone sealants are primarily used as one-component cal flow properties of the sealant under conditions of extreme
products usually referred to as RTV (room temperature vul- variations in temperature. Stainless steel channels, open
canizing) materials. They are polysiloxane prepolymers ended for testing vertical (non sag) sealants and close ended
which react with atmospheric moisture and ultimately cure for testing horizontal (self leveling or pourable) sealants, are
to form an elastomer. Silicone sealants are cured generally by filled with the sealant and exposed at an elevated temperature
one of three mechanisms, namely: (122~ 50~ and at a low temperature (40~ 4.4~ Sag
1. Acetoxy cure--A reaction between methyltriacetoxy silane (vertical displacement) is measured, and horizontal deforma-
with polydimethylsiloxane to form an acetoxy-terminated tion is noted.
polymer "intermediate." This material is then reacted with
atmospheric moisture in order to cure. Acetic acid is liber-
Hardness
ated during cure, and its odor can readily be noted.
2. Neutral cure--These sealants are the result of a reaction This test is used to measure the indentation hardness of a
between polydimethylsiloxane with methyltrimethoxy- cured sealant using a Shore A Durometer. If a sealant is too
silane to form the "intermediate." This "intermediate" then hard, it may be indicative of future problems that can result
reacts with atmospheric moisture in order to cure. Alcohol in a loss of resiliency, thereby resulting in either cohesive
is generally liberated during the cure process. breaks or adhesive loss.
3. Amine cure--In this cure mechanism, methyltricyclohexy-
laminosilane is reacted with the polydimethylsiloxane to
Effects of Heat Aging
form an "intermediate" which cures when reacted with
atmospheric moisture. Cyclohexylamine, a heavy musty- Exposure to the atmosphere may cause loss of volatile
odored material, is released during cure. components after cure, resulting in shrinkage, hardening, or
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CHAPTER 65--SEALANTS 737
cracking, which may affect the durability of the sealant. This sealant is applied to the substrate, cured, and immersed in
test can be used to predict premature failure. Sealant speci- water for seven days. After the immersion period, the 180 ~
mens are cured, then heat aged for 21 days at 158~ (70~ peel strength of the sealant is measured and the amount of
and evaluated for volatility (weight loss), cracking, and hard- adhesive loss to the substrate is determined. An additional set
ness. of specimens is prepared, exposed to UV radiation to simu-
late sunlight, and then evaluated for the effect of the actinic
radiation on the interface of the sealant-to-glass bond by once
Tack-Free Time
again measuring peel strength and adhesion properties of the
This is the time required for the surface of a sealant to sealant.
attain a tack-free state. This time may be indicative of the
time interval required for the sealant to resist damage from
light surface contact, job-site or airborne dirt pickup, or im- Effects of Accelerated Weathering
pinging rainfall. This procedure is used to evaluate the effects of exposure to
ultraviolet radiation and water spray to simulate weathering
Staining of Porous Substrates on the sealant. After exposure, the sealant is evaluated for
surface cracking. Specimens are then bent over a 0.5-in.
This test method is useful to determine possible staining by (1.27-cm)-diameter rod under cold ( - 15~ - 26~ tempera-
the sealant on porous substrates. The sealant is applied to ture to evaluate low-temperature flexibility and brittleness.
standard-size joint specimens made of porous materials such The following section lists specifications and standards for
as white marble or granite. The specimens are com- sealants, including their sources.
pressed and clamped and then stored for 28 days at various
conditions including room temperature, elevated tempera-
ture, and ultraviolet-fluorescent weathering. Upon comple-
SEALANT SPECIFICATIONS
tion of the exposures, the specimens are evaluated for
changes in surface appearance and depth of any stain.
Federal Specifications
TT-S-00227E Sealing Compound Elastomeric Type, Multi-
Adhesion and Cohesion Under Cyclic Movement component (For Caulking, Sealing, and Glaz-
(Durability)
ing Building and Other Structures).
The primary intent of an elastomeric sealant is to fill joints TT-S-00230C Sealing Compound Elastomeric Type, Single
in buildings and other structures and thereby render them Component (For Caulking, Sealing and Glaz-
impervious to the elements. These joints are considered ac- ing Building and Other Structures).
tive, meaning that they will expand and contract with temper- TT-S-01543A Sealing Compound, Silicone Rubber Base
ature. (For Caulking, Sealing, and Glazing in Build-
This test method is designed to evaluate the ability of the ings and Other Structures).
sealant to withstand expansion and contraction with temper- TT-C-598B Caulking Compound, Oil, and Resin Base
ature change and not develop any loss of adhesion to the Type (For Masonry and Other Structures).
substrate or any cohesive cracks. When adhesion loss to the TT-S-001657 Sealing Compound, Single Component-Butyl
substrate or cohesive cracks within the sealant develop, water Rubber Based, Solvent Release Type (For
can penetrate, thereby resulting in damage to the structure. Buildings and Other Types of Construction).
Joints are prepared using two similar substrates. The seal-
ant is extruded between the joints (substrates), cured, and
ASTM Standards
then immersed in water for seven days. The specimens are
then hand flexed and evaluated for adhesion loss. If no adhe- ASTM C 570 Specification for Oil- and Resin-Base Caulk-
sion loss is noted, the specimens are compressed and sub- ing Compound for Building Construction.
jected to elevated temperature (158~ 70~ for seven days to ASTM C 669 Specification for Glazing Compounds for
determine whether any heat set or deformation occurs. These Back Bedding and Face Glazing of Metal
test joints are then subjected to ten cycles of compression at Sash.
elevated temperature (158~ 70~ and expansion at low tem- ASTM C 834 Specification for Latex Sealing Compounds.
perature ( - 15~ - 26~ to simulate joint movement during ASTM C 836 Specification for High Solids Content, Cold
extreme temperature changes. (Buildings contract when Liquid-Applied Elastomeric Waterproofing
cold, thereby opening up or expanding the joints, On the Membrane for Use With Separate Wearing
other hand, buildings expand when hot, thereby closing or Course.
compressing the joints.) On completion of this cycling, the ASTM C 920 Specification for Elastomeric Joint Sealants.
specimens are examined for the presence of any adhesive ASTM C 957 Specification for High-So|ids Content, Cold
bond loss or cohesive breaks. Liquid-Applied Elastomeric Waterproofing
Membrane with Integral Wearing Surface.
Adhesion-in-Peel ASTM C 1085 Specification for Butyl Rubber-Based Solvent
Release Sealants.
This test is used to evaluate the adhesive characteristics of a ASTM C 1184 Specification for Structural Silicone Seal-
sealant and its ability to maintain a bond to a substrate. The ants.
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OTHER SEALANT STANDARDS C 765 Test Method for Low-Temperature Flexibility of

Preformed Tape Sealants
Insulating Glass C 766 Test Method for Adhesion after Impact of Pre-
formed Tape Sealants
ASTM E 774 Standard Specification for Sealed Insulating
Glass Units. C 771 Test Method for Weight Loss After Heat Aging of
Preformed Sealant Tapes
Highway/Bridges C 772 Test Method for Oil Migration or Plasticizer Bleed-
Out of Preformed Sealing Tapes
SS-S-20OE Sealing Compounds, Two Component, Elasto- C 782 Test Method for Softness of Preformed Sealing
meric, Polymer Type, Jet Fuel Resistant, Cold Tapes
Applied.
C 792 Test Method for Effects of Heat Aging of Weight
(American Association of State Highway and Transportation Loss, Cracking, and Chalking of Elastomeric Seal-
Officials [AASHTO]) ants
C 793 Test Method for Effects of Accelerated Weathering
on Elastomeric Joint Sealants
C 794 Test Method of Adhesion-in-Peel of Elastomeric
LIST OF ASTM C-24 STANDARDS Joint Sealants
C 797 Practices and Terminology for Use of Oil- and
C 510 Test Method for Staining and Color Change of Resin-Based Putty and Glazing Compounds
Single- or Multi-Component Joint Sealants C 834 Specification for Latex Sealing Compounds
C 570 Specification for Oil- and Resin-Base Caulking Specification of High Solids Content, Cold Liquid-
C 836
Compound for Building Construction Applied Elastomeric Waterproofing Membrane for
C 603 Test Method for Extrusion Rate and Application
Use with Separate Wearing Course
Life of Elastomeric Sealants
C 879 Method of Testing Release Papers Used with Pre-
C 639 Test Method for Rheological (Flow) Properties of
formed Tape Sealants
Elastomeric Sealants
C 661 Test Method for Indentation Hardness of Elasto- C 898 Guide for Use of High Solids Content, Cold Liq-
meric-Type Sealants by Means of a Durometer uid-Applied Elastomeric Waterproofing Membrane
C 669 Specification for Glazing Compounds for Back with Separate Wearing Course
Bedding and Face Glazing of Metal Sash C 906 Test Method for T-Peel Strength of Hot Applied
C 679 Test Method for Tack-Free Time of Elastomeric Sealants.
Sealants C 907 Test Method for Tensile Adhesive Strength of Pre-
C 681 Test Method for Volatility of Oil- and Resin-Based, formed Tape Sealants by Disk Method
Knife-Grade, Channel Glazing Compounds C 908 Test Method for Yield Strength of Performance
C 711 Test Method for Low-Temperature Flexibility and Tape Sealants
Tenacity of One-Part, Elastomeric, Solvent-Release C 910 Test Method for Bond and Cohesion of One-Part
Type Sealants Elastomeric Solvent Release-Type Sealants
C 712 Test Method for Bubbling of One-Part, Elasto- C 919 Practice for Use of Sealants in Acoustical Applica-
meric Solvent-Release Type Sealants tions
C 713 Test Method for Slump of an Oil-Base Knife-Grade C 920 Specification for Elastomeric Joint Sealants
Channel Glazing Compound C 957 Specification for High-Solids Content, Cold Liquid-
C 717 Terminology of Building Seals and Sealants Applied Elastomeric Waterproofing Membrane
C 718 Test Method for UV-Cold Box Exposure of One- With Integral Wearing Surface
part, Elastomeric, Solvent-Release Type Sealants C 961 Test Method for Lap Shear Strength for Hot-Ap-
C 719 Test Method for Adhesion and Cohesion of Elasto- plied Sealants
meric Joint Sealants Under Cyclic Movement C 972 Test for Compression-Recovery of Preformed Seal-
C 731 Test Method for Extrudability, After Package Ag- ing Tapes
ing, of Latex Sealing Compounds C 981 Guide for Design of Built-Up Bituminous Mem-
C 732 Test Method for Aging Effects of Artificial Weath- brane Waterproofing System for Building Decks
ering on Latex Sealing Compounds C 1016 Test Method for Determination of Water
C 733 Test Method for Volume Shrinkage of Latex Absorption by Sealant Back-Up (Joint Filler) Mate-
Sealing Compounds rial
C 734 Test Method for Low-Temperature Flexibility of C 1021 Practice for Laboratories Engaged in the Testing
Latex Sealing Compounds After Artificial Weather- of Building Sealants
ing C 1083 Test Method for Water Absorption of Cellular
C 736 Test Method for Extension-Recovery and Adhesion Elastomeric Gaskets and Sealing Materials
of Latex Sealing Compound C 1085 Specification for Butyl Rubber-Based Solvent Re-
C 741 Test Method for Accelerated Aging of Wood Sash lease Sealants
Face Glazing Compound C 1087 Test Method for Determining Compatibility of Liq-
C 742 Test Method for Degree of Set for Wood Sash uid-Applied Sealants with Accessories used in
Glazing Compound Structural Glazing Systems
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CHAPTER 6 5 - - S E A L A N T S 739
C 1135 Test Method for Determining Tensile Adhesion CAN/CGSB-19.20-M87--Cold-Applied Sealing Compound,
Properties of Structural Sealants Aviation Fuel-Resistant
C 1183 Test Method for Extrusion Rate of Elastomeric CAN/CGSB-19.21-M87--Sealing and Bedding Compound
Sealants Acoustical
C 1184 Specification for Structural Silicone Sealants
CAN/CGSB-19.22-M89--Mildew-Resistant Sealing Com-
C 1193 Guide for Use of Joint Sealants
pound for Tubs and Tiles
C 1216 Test Method for Adhesion and Cohesion of One-
Part Elastomeric Solvent Release Sealants CANICGSB- 19.24-M90--Multicomponent Chemical-Curing
C 1241 Test Method for Volume Shrinkage of Latex Seal- Sealing Compound
ants During Cure CAN/CGSB-19.28-91--Glossary of Terms Related to Seal-
C 1246 Standard Test Method for Effects of Heat Aging ants
on Weight Loss, Cracking, and Chalking of Elasto-
meric Sealants after Cure
C 1247 Standard Test Method for Durability of Sealants
Exposed to Continuous Immersion in Liquids AAMA S T A N D A R D S
C 1248 Test Method for Staining of Porous Substrates by
Joint Sealants 801.1 Voluntary Specifications for Adhesive Type Sealant
C 1249 Test Method for Secondary Seal for Sealed Insu- for Joints of Applied or Integral Fin
lating Glass Units for Structural Sealant Glazing 802.3 Voluntary Specifications for Ductile Back Bedding

Paint and Coating Testing Manual (IRAN)

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Paint and Coating Testing Manual (IRAN)

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MNL17-EB/Jun.

Ashton, Harry E., 696 Gale, Frances, 725 Pellowe, Don, 53

B Hacker, Larry R., 741 R

Ferguson, Russell L., 223

Joseph V. Koleske, Editor

ASTM Manual Series: MNL 17

1916 Race Street, Philadelphia, PA 19103

Printed in Ann Arbor, MI

ASTM WOULDLIKE TO EXPRESS its gratitude to the authors of the previous 13

AT A JANUARY1967 MEETINGOF ASTM COMMITTEED-1 held in Washington, DC, ASTM

A Wolf abrasion method, 529 automotive products, 714

A S T M C 5 3 9 69,71 A S T M C 1034, 69 ASTM D 332, 170, 508

ASTM D 816, 362 ASTM D 1217, 147 ASTMD 1614, 152

ASTM D 2240, 97 nonvolatile content, 756 b i t u m i n o u s coatings, 20

ASTM G 19, 733 Barrier coatings, 238-239 Blue pigments, 197-198

Cobalt blue pigments, 214-215 violets, 210 Contrast ratio, 481-482

Curing agents, epoxy resins, 74-75 Diethylenetriamine, 85-86 Driers, 30-35

E cover coat, 70 colored organic pigments, 207-208

Isocyanates coalescence and adhesion, electron Liquid phase, stationary, gas

Asbeck-Van Loo method, 254-255 stratospheric protection, 11 electrical resistance, 316-317

resistance, architectural coatings, 701 ISO standards, 739 Slumping, 353

color, 148-149 Spectrophotometers, 687 versus adhesion and cohesion, 594,

amino resins, 64 coatings and, 841-842 rhamsan gum, 277

Total solids, traffic marking materials, TT-P-55B, 726, 729 characteristics, 99

electron beam excited X-ray X-ray scattering, particle-size Z

Chapter 1--Regulation of Volatile Organic Compound

PART 2: NATURALLY OCCURRING MATERIALS

Chapter 2--Bituminous Coatings 15

Chapter 3mCellulose Esters 23

Chapter 4~Drying Oils 26

Chapter 5~Driers and Metallic Soaps 30

PART 3: SYNTHETIC MATERIALS

Chapter 6~Acrylic Polymers as Coatings Binders 39

Chapter 7--Alkyd and Polyesters 53

Chapter 8--Amino Resins (Reaction Products of Melamine,

Chapter 9mCeramic Coatings 68

Chapter 10mEpoxy Resins in Coatings 74

Chapter 13~Polyurethane Coatings 89

Chapter 14~Silicone Coatings 95

Chapter 15mVinyl Resins for Coatings 99

Chapter 16--Miscellaneous Materials and Coatings 108

Chapter 17~Plasticizers 115

Chapter 18--Solvents 125

Chapter 19--White Pigments 159

Chapter 20mBlack Pigments 179

Chapter 21mColored Organic Pigments 190

Chapter 22~Inorganic Colored Pigments 209

Chapter 23~Ceramic Pigments 214

Chapter 24mExtender Pigments 2t7

Chapter 25--Metallic Pigments 223

Chapter 26--Pearlescent Pigments 229

Chapter 27--Inorganic Anti-Corrosive Pigments 238

Chapter 28mOil Absorption of Pigments 252

Chapter 29~Bactericides, Fungicides, and Algicides 261

Chapter 30~Thickeners and Rheology Modifiers 268

PART 8: PHYSICAL CHARACTERISTICS OF LIQUID PAINTS

Chapter 31ADensity and Specific Gravity 289

Chapter 32nParticle-Size Measurements 305

Chapter 33ARheology and Viscometry 333

Chapter 34nSurface Energetics 369

Chapter 35~Solubility Parameters 383

PART 9: FILMS FOR TESTING

Chapter 36--Cure: The Process and Its Measurement 407

Chapter 37--Film Preparation for Coating Tests 415