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NANOCOATINGS,

VOLUME I

NANOCOATINGS,
VOLUME I
APPLICATIONS AND STABILITY

DR. KAL RENGANATHAN SHARMA

Nanocoatings, Volume I: Applications and Stability


Copyright Momentum Press, LLC, 2017.
All rights reserved. No part of this publication may be reproduced, stored
in a retrieval system, or transmitted in any form or by any means
electronic, mechanical, photocopy, recording, or any otherexcept for
brief quotations, not to exceed 250 words, without the prior permission of
the publisher.
First published in 2017 by
Momentum Press, LLC
222 East 46th Street, New York, NY 10017
www.momentumpress.net
ISBN-13: 978-1-60650-813-8 (print)
ISBN-13: 978-1-60650-814-5 (e-book)
Momentum Press Nanotechnology Collection
Cover and interior design by S4Carlisle Publishing Service Private Ltd.
Chennai, India
10 9 8 7 6 5 4 3 2 1
Printed in the United States of America

DEDICATION

This book is dedicated to my eldest son Chi. R. Hari Subrahmanyan


Sharma (alias Ramkishan) who turns 15 this August 13, 2016.

ABSTRACT
Global market sizes for nanocoatings and coatings are expected to be
$14.3 billion and $123 billion, respectively by the year 2019. Coatings can
be classified according to their applications or method of preparation or
type of property imparted to the product. They can be either solvent based
or water based. They may comprise polymers or inorganic materials.
Nanocoatings with thickness less than 100 nm can offer superior performance properties compared with conventional coatings. Nanotuff was one
of the first commercial nanocoating. It contained nano-sized particles suspended in an epoxy matrix. Coatings can have specific purposes such as
corrosion resistance, antiabrasive resistance, scratch resistance, chemically
resistance, stain resistance to the objects they are applied on. This book
contains some new theory in the areas of solubility parameter estimates
using isentropic volume expansivity, compressibility, and surface tension
effects during coating flows. Volume I contains separate chapters on introduction, applications, and stability. Volume II contains chapters on
methods, solvents, drying and inks, and properties. Patents from leading
companies such as Xerox, IBM, Intel, BASF, PPG, Boeing, Valspar,
Toyota, Goodyear, Gaze Nanotech, Bell Hellicopter, Procter and Gamble,
and General Electric on nanocoatings are discussed in the book.

VOLUME I: APPLICATIONS AND STABILITY


Corrosion-resistant coating was applied on the Sydney harbor bridge in
Australia. Shellac was used as hot varnish in India in the year 2000 BC.
References to coating in The Wall Street Journal and other leading newspapers in the early part of the 20th century are discussed. These include
references to weld coating of copper on steel substrate, ban of use of castor oils and other named materials in coatings, O-I acquisition of American Coatings, AR coating developed by Blodgett, spray pistol for molten

viii ABSTRACT

metal, development of pore-free metallic coat for oil and gas industry.
Examples in the later part of the 20th century include aluminum coatings,
corrosion-resistant recoat on transnational pipeline, PPG acquisition of
Orica, nonstick coating from water-based polymer coatings, laminate furniture coatings, intelligent coatings on seeds, constructive interference
phenomena and iridescence of butterfly, BASF expansion of its offerings
of binders, architectural coatings, depolymerization principles used for
recycling, and science of shampoo. Nanocoating with 30-nm thickness
was developed to be used in fighting furniture fires. The coating is made
of sulfur-based polymer, polyvinyl sulfonic acid, and a carbohydrate polymer, chitosan found in crustacean shells.
Applications span several industries: (i) aerospace; (ii) biomedical;
(iii) structural; (iv) electronic materials; (v) energy, technology, and environmental; (vi) automotive; (vii) surveillance; and (viii) food industry.
Protective coatings are applied to chopper blades in order to offer UV
resistance and barrier to oil seepage. Electrochromic particles can be used
to tint windows in aeroplanes and luxury cars. Time to switch for opaque
to transparent can be reduced. Multilayer packages can be made in
the food industry with a metallic inner layer for blocking light from
transmitting, a barrier layer made from PET/PP and a glue layer. Viscosity
gradient number and surface tension number are introduced to better characterize coating flows in addition to Reynolds number, Prandtl number,
capillary number, and Marangoni number. Sharpness and longevity of
blades are increased by use of carbon nanocoatings. GMR thin ifilm read
heads have seven layers with a interleaving nano-oxide layer. The photoresist layer used in immersion lithography is found to dissolve into the
immersion liquid. In order to delay the dissolution of the photoresist layer
a miscible blend of terpolymers-containing fluorine with different compositions are applied as a top coat to the photoresist. Parylene coatings can
be used in order to provide barriers to moisture and electric charge. Impact-resistant cable coating comprises of semiconductor layer, insulation
layer, semiconducting outer layer over the central conductor. EB-PVD
methods are used to apply corrosion-resistant coatings made of materials
such as chromium on turbine blades made of superalloys of nickel and
cobalt. Magnesium oxychloride sorrel cement coatings can be used to control and delay the spread of flames in naval warheads. Mathematical model was developed for estimation of the time taken for the transient temperature of the naval warhead to reach alarm temperatures; the naval warhead
cannot be made of materials with relaxation time greater than R2/15.33nr;
the temperature in the naval warhead will undergo subcritical damped

ABSTRACT ix

oscillations in time. Graphene with sheet morphology can be used in order


to increase the light-to-electricity conversion efficiency to 14.6%. Silver
nanomaterials can be used as nanocoatings in order to minimize damages
from growth of microorganisms. CCVD methods are used. Principles
from photodynamic therapy, fullerene chemistry, nanostructuring, X-rays,
computers, pharmacokinetics, and robotics are applied in developing a
strategy for nanorobot, treatment of Alzheimers disease. Thin polymer
film can be laminated and glued to curved glass substrates. Toyota has
obtained a patent in order to prepare magnetic coreshellshell nanoparticles within a magnetic field.
Some of these shapes such as trigonal bipyramid, tetrahedron, cube,
anamantanoid, double square, dodecahedron (Figure 3.1), truncated tetrahedron, cuboctahedron found during morphological characterization of
materials can be explained using self-assembly principles. The effects of
surface tension of the liquid and air can give rise to what is called Marangoni effect. Surface tension can be used to explain the formation of
soap bubbles, capillary rise of fluid in tubes, breakup of drops into a jet of
water in the faucet. Thermocapillary stress can arise in a fluid subjected to
a vertical temperature gradient. Surface tension gradient can arise from a
density gradient. This can induce flow in multilayer coating flows and
instability. The flow field around a stationary underformed bubble in a
vertical temperature gradient was derived. An exact solution at small Marongoni numbers for thermocapillary migration of droplets. The Buckingham and Pi method can be used in order to obtain the dimensionless
groups needed to completely characterize a system in which motion of
bubble or drop is caused by thermocapillary stress which in turn is caused
by a vertical temperature gradient. One set of six dimensionless groups
found significant are Marangoni number, Reynolds number, Prandtl
number, capillary number, viscosity variation with temperature number,
and thermal viscous number. The BuckinghamPi method is used to obtain the dimensionless groups needed in order to completely characterize
the multilayer coating flow system. The significant dimensionless groups
were found to be Reynolds number, layer thickness ratios, 1 and 2, viscosity gradient number, microscale viscous number, stoles and thermocapillary number, and surface tension gradient number.
Some concerns that can arise during coating applications are discussed. The concerns discussed are blistering and peeling, island formation, foaming, blooming, blushing, chalking, substrate surface type,
cracking, tackiness, wrinkling, monolayer stability, bridging, brush narks,
can corrosion, and pinholes.

x ABSTRACT

KEYWORDS
Propertiesanti-abrasive, anti-reflection, chemical resistant, coating types,
corrosion resistant, flame retardant, markets, scope, scratch resistant, selfassembly, silver and anti-microbial coatings, stain resistant, wear resistant,
weatharability, thermal-barrier coatings
Applicationsaluminium coatings, barrier, cable coatings, clay-coat,
core-shell-shell morphology nanoparticles, depolymerisation, diffusion of
moisture, electrochromic window, furniture coatings, GMR thin film
heads, graphene in solar cells, green coating, immersion lithography, intellicoat, laminated and glued structures, multi-layered film in packaging,
nanorobot, non-stick polymer coating, parylene coatings, plating, protective nanocoating, recycling, sebum coating, shaving blade coatings, surveillance, thin film interference, trough coating, weld coating
Stabilityblistering, blooming, blushing, bridging, brush marks, can corrosion, chalking, cheesy film, coating flows, cracking, density gradient,
foaming, island formation, marangoni effects, microscale viscous number,
monolayer stability, peeling, pinholes, substrate surfaces, surface tension
gradient number, tackiness, thermocapillary stress, thin film flow down an
inclined plabe, wrinkling
Historycave and rock paintings, glazed pottery

CONTENTS
LIST OF FIGURES

XV

1.0 INTRODUCTION TO NANOCOATINGS

1.1

Markets

1.2

Earliest Reference to Coatings

1.3

Coatings in Early 20th Century

1.4

Coatings in Later 20th Century

1.4.1

Aluminum Coatings

1.4.2

Peeling in Corrosion Coating of Transnational


Pipeline

1.4.3

Molten Metal Trough Coating

1.4.4

PPG Acquires Orica Coating

1.4.5

Water-Based Polymer Coating for Nonstick


Applications

1.4.6

Furniture Coatings

1.4.7

Thick Chocolate Coatings

1.4.8

Intelligent Coatings on Seeds

10

1.4.9

Thin Film Interference

10

1.4.10 Architectural Coatings

13

1.4.11 Depolymerization and Recycling

14

1.4.12 Sebum Coating Removal using Shampoo

15

1.5

Scope for Nanocoatings

17

1.6

Coating Types

19

1.7

Summary

20

1.8

References

23

xii CONTENTS

2.0 APPLICATIONS
2.1

Aerospace Applications
2.1.1

2.2

2.3

27

2.1.2

Green Coating

27

2.1.3

Electrochromic Window

28

Food Industry

30

2.2.1

Packaging Using Metalized Polymer Film

30

2.2.2

Shaving Blade CoatingsLitigation Losses

33

Electronic Materials

34

2.3.1

Hard rives in Desktop Computers

34

2.3.2

Polymer Blend as Top Coat in Immersion


Lithography

35

Vaccum Plasma Polymerization


and Printed Circuit Board Components

37

Cable Coatings

38

2.3.4

2.5

2.6

26

Protective Coatings on Aircraft Fuselage


and Propellers

2.3.3

2.4

25

Energy, Technology, and Environmental

38

2.4.1

Thermal-Barrier Coatings

38

2.4.2

Graphene-Based Solar Cells

42

Biomedical

44

2.5.1

Antimicrobial Coatings

44

2.5.2

Nanorobot Drug Delivery

46

AUTOMOTIVE

47

2.6.1 Optical MaterialsLaminated and


Glued Structures

47

2.6.2 Magnetic MaterialsCoreShellShell


Morphology

48

2.7

Surveillance

49

2.8

Summary

49

2.9

References

53

CONTENTS xiii

3.0 STABILITY

57

3.1

Underlying ScienceSelf-Assembly

57

3.2

Coating Flows

59

3.3

Thermocapillary Stress Arising from Vertical


Temperature Gradient

63

3.4

Flow of Film Down an Inclined Plane

70

3.5

Thermocapillary StressDensity Gradient

71

3.5.1

Viscosity Gradient Number

75

3.5.2

Microscale Viscous Number

75

3.5.3

Stokes and Thermocapillary Number

75

3.6

Marangoni Effects

75

3.7

Blistering and Peeling

76

3.8

Island Formation

76

3.9

Foaming

78

3.10

Blooming

80

3.11

Blistering

80

3.12

Blushing

81

3.13

Chalking

82

3.14

Substrate Surfaces

83

3.15

Cracking

86

3.16

Tackiness

86

3.17

Wrinkling

87

3.18

Issues in Monolayer Stability

88

3.19

Bridging

90

3.20

Brush Marks

91

3.21

Can Corrosion

91

3.22

Cheesy Film

91

3.23

Pinholes

91

3.24

Summary

91

3.25

References

98

ABOUT THE AUTHOR

101

INDEX

103

LIST OF FIGURES

Figure 1.1.

Constructive and destructive interference during


reflections from smooth and rough surfaces

11

Figure 1.2.

Newtons six colors

12

Figure 2.1.

Cross-sectional view of multilayer composite film


used in food packaging

33

Figure 2.2.

Unitwise operations during nanocoating process

33

Figure 2.3.

Seven layers of giant magneto resistive thin film


heads

35

Cross-sectional view of cable with alternate conducting and insulating properties

39

Sixty-five nanometer thick TiO2 layer coating on


graphene silicon solar cell

43

Figure 3.1.

Dodecahedron nanoscale architecture

59

Figure 3.2.

Film falling down a vertical wall

59

Figure 3.3.

Multilayer coating flow down an inclined plane

70

Figure 2.4.
Figure 2.5.

CHAPTER 1.0

INTRODUCTION TO
NANOCOATINGS
CHAPTER OBJECTIVES

Scope of Nanocoatings
Markets
Emergence
Miniaturization
Color and Pigmentation
Properties
Marangoni Effect
$14.3 Billion Market for
Nanocoating
$125 Billion Market for
Coatings
Shellac
Corrosion Resistance
Antiabrasive Resistance
Scratch Resistance
Stain Resistance
Chemical Resistance
Weld Coats
Castor Oils
Pore-Free Metallic Coat
Spray Coat
Aluminum Coatings
Stickability

Thicker Coating
Constructive Interference
Iridiscense of Butterflies
Drying
Synthesis and Processing
Nanocoating Types
Nanocoating Applications
Enamels, Lacquers, Glaze,
Varnish, Toner Thinner,
Thickener
Solvents
Monomer Reclaimation
Micelles and Shampoo
AR Nanocoatings
Lanmuir and Blodgett
Intellicoat
Explosion
Laminate Coatings
Nonstick Coatings
Architectural Coatings
Weatherability
Atomization
Nanotuff

2 NANOCOATINGS, VOLUME I

Furniture Fire-Retardant
Coating
Coating Types

IssuesCracking,
Crazing, Peel Strength,
Epitaxial Stability

1.1 MARKETS
Coatings are different from enamels and glaze. Enamels are applied to
metal surfaces. Glaze is applied to the surface of a ceramic material in
order to seal a permeable clay body and provide for decoration and protection. Enamels are usually applied to metal surfaces. They vitrify readily
during firing. Example of clay product is CaO.Al2O3.2SiO2. Special colors
used in glazes and enamels are (i) zirconium silicate for white glaze,
(ii) cobalt oxide for blue glaze, (iii) chromium oxide for green glaze,
(iv) lead oxide for yellow color, and (v) selenium and cadmium sulfide for
red glaze. Pigments that impart yellow and orange color are iron oxides,
chromates of lead and zinc and cadmium sulfide. The demand for antifouling coatings in shipping vessels was 71,000 tons in the year 2014.
According to MarketsandMarkets, the global nanocoatings market is
expected to reach $14.3 billion by the year 2019 [1]. The CAGR, compound annual growth rate, expected over the 2014 to 2019 year period is
24.68%. The global coating industry market size is estimated at $123 billion. The year 2019 is the sesquicentennial of M. K. Gandhi, the father of
the nation of India. He obtained the independence for India on August 15,
1947. One of the accomplishments of M. K. Gandhi was Champaran and
indigo, the purple dyeproducing cash crop. He obtained concessions
from the authorities for his peasants through nonviolent means.
Demand for high performance coatings grew by 5% per year. The
coatings industry growth rate is less than 2.5% per year. The nanocoating
market types discussed in this report are classified into antifragment, antimicrobial, easy to clean and antifouling and self-cleaning. The global
antifouling coating market is expected to reach $2.43 billion by the year
2022, according to report by Grand View Research Inc. The durability of
hulls and underwater surfaces of marine vessels are increased using antifouling coatings. Marine vessels include passenger ships, cargoes, yachts,
and drilling rigs.
Nanocoatings applications discussed are in the health care, food and
packaging, marine, water treatment, electronics, construction, automotive,

INTRODUCTION TO NANOCOATINGS 3

energy industries, and others. The leading paint maker PPG markets paints
and coatings in aerospace, architectural, automotive, packaging, and marine industries. They also make industrial coatings and specialty coatings
and materials. They offer more than 1,000 types of coatings. Problems
encountered during coating applications such as crazing and surface
cracking are discussed in Chapter 3.0.
North American paint makers shipped 5 billion gallons worth $80 billion of their products in the year 2002. The global market share was split
as $23.9 billion/1.4 billion gallons of paint from this country, United
States, and $14.8 billion/1.1 billion gallons of paint by Asian producers,
and $10.6 billion/0.9 billion gallons of paint from Africa, Middle East,
and South America [2]. Per the Internet website www.drbeasleys.com, the
field called surface engineering was a $17 billion market in the United
Kingdom. Half of the markets were in the areas of automotive coatings.
Coating in addition to external appearance can have specific purposes. For
example, they can be made to be wear resistant or they can be made to be
corrosion resistant. Antiabrasive nanocoatings were discussed in Sharma
[3]. Scratch resistant, chemically resistant, stain resistant coatings are
nanotechnology-enabled solutions offered to the customer. Self-assembly
principles are used in order to obtain surface attachment within seconds.
The cure times used to be longer in earlier technologies. Architectural
glass, museum glass, shower doors in modern houses, touch screens, dinnerware, and industrial porcelainware are objects where coatings have
added value to the applied product.
Coatings are used on the structural steel used to build bridges, asphalt
and tar and additives on the roads and highways, cladding in high rises,
internal and external masonry in skyscrapers, refurbished constructions,
roofing materials, furniture, curtain walls, window frames and flooring in
high rises, and architectural detailing. One of the examples of application
of bridge coatings is the Sydney harbor bridge project in Australia. It is
the sixth longest arch bridge in the world that spans 503 m in length. According to Akzo Nobel, Netherlands, this bridge is one of the worlds most
recognizable landmarks. They supplied the corrosion-resistant coating
system. The coating system comprises of interzinc epoxy primer, higher
solids intermediate coat, and polyurethane topcoat. The coating was aesthetically pleasing and more environmentally friendly. The bridge was built
over 8.5 years and used 52,800 tons of steel. This included 39,000 tons
of supporting arch that made this construction the largest steel arch
bridge in the world. The RTA, Roads and Traffic Authority, New South

4 NANOCOATINGS, VOLUME I

Wales, Australia, around the time after the 2000 millennium fireworks
near the bridge, decided to upgrade the coating on the bridge. The coating
system used before contained two coats of alkyd primer followed by two
coats of metallic chlorinated rubber, MIO. The corrosion resistance of this
system was not adequate. RTA awarded the tender to AkzoNobel International after taking into account the unit cost of the coating fluid, technical
assistance and service provided, quality, and reliability. AkzoNobel provided to maintenance coatings to the Queen Elizabeth II rail bridge in
Newcastle upon Tyne that supports a metroline that completes around
40 million passenger journeys each year.
The source of corrosion of the highways can be the deicing salts that
are usually added during the winter months. Both the steel and reinforced
concrete structures are found to undergo corrosion. Throgs Neck Bridge
was coated using AkzoNobels corrosion-resistance coating. Coatings can
be used in medicine in transportation sector and advanced materials.

1.2 EARLIEST REFERENCE TO COATINGS


From the days of the Egyptian, Mesopotomian, Indus, and Chinese civilizations, paints and coatings have been known. The cave and rock paintings confirmed by archeologists from the Indus Valley Civilization was
around 5500 BC. Glazed pottery, clothes, ornaments, and other artifacts
through the stone age, bronze age, and iron ages have been found with
coatings. Shellac was used as hot varnish in India around 2000 BC.
Shellac has been alluded to in the famous ithihas, the Mahabharata. The
flammable palace was constructed using shellac given to the five Pandava
heroes to stay. When the Kaurava emperor and his evil advisors set the
palace to flames the Pandavas escaped using a underground passage. The
palace was supposed to have been built using shellac, jute, and butter
ghee. Shellac is a natural-occurring material. It is a mixture of esters, polyesters, and polyhydroxy acids. The resinous secretion of the tree insects
found in Indian Subcontinent is separated into aleuritic acid and shellolic
acid. The genome of the insect Laccifer lacca kerr has been obtained using PCR, polymerase chain reactions, and sequencing. Where these insects
are found and how the components of interest are separated are salient
considerations. Shellac is extracted from tree insects and refined into usable fractions. Ethyl alcohol can be the solvent for shellac. The word lac
beetle is used for the tree insect. The word lac means 100,000.

INTRODUCTION TO NANOCOATINGS 5

1.3 COATINGS IN EARLY 20TH CENTURY


In [4] , it is mentioned that French metallurgist J. Ferrcol found a method
to weld a thick coating of soft copper onto the steel substrate. Initial attempts to coat copper on steel was not successful. The metallurgist
achieved success by cleaning the steel billet 6 inches in diameter and
36 inches long prior to welding the copper onto steel. The thickness of the
coating can be increased or controlled as desired in the commercial application. The coated billet can be reheated, and 3/8 inch wires can be drawn
from them. Drawing mills are used to redraw the wire into various sizes.
The copper coating in the drawn wires is the same as was the copper coating on the billet. This is one advantage of weld coats compared with coats
made from self-assembly. The drawn wires can have higher tensile
strength and durability. Wire nails can be used in boats. Carriage and automobile springs without rust can be made using this methodology.
The War Protection Board issued an order that proscribes the use of
certain coating materials and colors for coating two gallon or larger steel
containers [5]The materials banned for use were tung, orticica, perilla/dehydrated castor oils, alkyd, phenolic, vinyl, urea or melamine resin,
cellulose esters, or ethers. The use of critical oils and resins was expected
to be reduced by 1 million pounds per year as a result of these provisions.
Only black-colored coatings were allowed with exceptions of small areas
for marking purposes.
American Coating Mills Inc. was acquired by Owens Illinois Glass
Co [6]. The directors of both companies had approved the acquisition and
shareholders of American Coating Mills were going to vote on the plan on
February 24, 1927. Clay-coated folding cartons and carton board with
plants were produced by American Coating Mills. This largest producer of
clay-coated cartons employed 700 people and boasted a sales volume in
excess of $6 million. The President of American Coating, R. L. Snideman,
was going to serve as Vice President and Board Member of OwensIllinois. The acquisition was to increase its overall packaging service to its
customers. Owens-Illinois, Toledo, OH, had revenue of $7.4 billion in the
year 2011. It is a leader in container glass products and plastic packaging
products. The companys name has been changed to O-I in 2005. O-I has
been included and excluded in the list of S & P 500 companies. They
partner with Nippon Electric Glass to make glass television screens. They
have had litigations for their asbestos-containing insulation for pipes in the
early 1950s.

6 NANOCOATINGS, VOLUME I

A thick coating of 25.2 m is applied on girders, tanks, and machinery using a spray pistol [7] according to the news item Unique Device for
Coating Iron and Steel with a Non-Corrosive Substance. The inventor
M. U. Schoop developed a device that can be used to spray molten metal.
The hot particles are allowed to move with great speed and were observed
to penetrate the pores of the object that the material is coated on. Reducing
gas is present during the spray and oxidation at the junction of the metals
is not allowed. The supply of spray material is in the form of wire reels.
The gases employed are seen to stream out at high speed and are ignited
on emergence from the pistol. The metal wire gets pulverized at the arc.
The pistol weighs 3.5 pounds and consists of aluminum casing with a
handle, a wire-feed mechanism, a turbine actuating the feed wire mechanism, and nozzles for gas, air, and wire. The wire is fed into the reducing
flame at a certain constant speed. The constant speed is determined such
that the melting rate equals the feed rate. As the wire melts it is found to
scatter by a violent air blast. The coating is applied by bombardment of
small metal particles.
AR nanocoatings were discussed as early as 1938. Coating with
102.8 nm thickness was applied to both sides of glass by an associate of
Nobel Laureate Irving Langmuir of General Electric. The associate was
Katherine B. Blodgett. She used this nanocoating to make glass form
being visible [8] Pure glass is found to transmit 92% of light. Ninety nine
percent of light was transmitted after Ms. K. B. Blodgett coated the glass.
The coated pane could only be viewed using the edges per the news clip
Woman Scientist Discovers Coating to Make Glass Invisible. Clocks,
dial faces and showcase glasses, and window panes cease to be visible.
Light is not reflected from any angle. This can be used in eyeglasses to
keep wearers to be bothered by light reflection or stray beams from side or
behind. Camera lens with 8% less reflection can be prepared. Some cameras with three to four of these lenses can be used to achieve a 25% to
35% light transmission. The chemical formula of the coating is not yet
made public, and the process was not on the market for commercial sale.
Mr. R. Rimbach has worked on the development and promotion of a
new process for coating steel with a pore-free metallic coat, which has successfully demonstrated its resistance to sever corrosion conditions in Texas
oil fields [9] . He was appointed as technical adviser to R. C. Enos, president of Standard Steel Spring Co., Coraopolis, PA. This new coating was
supposed to be used in order to obtain new markets for steel where corrosion precluded its use. Example applications are barrels, tanks, tubings, and
wires. Mr. Rimbachs previous position held was director, Research,

INTRODUCTION TO NANOCOATINGS 7

Standard Steel Car Co. Standard Steel Spring had signed recently a contract with Youngstown Sheet & Tube Co., in order to use its new plating
process where nickel was used. This new process was expected to be efficacious in resisting salt water corrosion, according to tests made back then.

1.4 COATINGS IN LATER 20TH CENTURY


1.4.1 ALUMINUM COATINGS
U.S. Steel Corp., Pittsburgh, PA, developed a new vapor-coating process
[10] for coating light gage, flat rolled steel with aluminum coatings. The
continuous high-speed mill at Fairless Works north of Philadelphia was
considered a major advance in can making and packaging industries. Research scientists at the Monroeville, PA, heated aluminum in a crucible
using an electron beam to a temperature when the metal vaporized. This
was followed by deposition of the vapor as a thin later on a moving steel
strip. The steel strip was in motion rapidly. Process was carried out under
vacuum. The purpose of the vacuum conditions attributed was to prevent
aluminum from oxidizing. Aluminum coating on steel was intended to
compete with tin-coated steel. Electrolyte process was used in order to
make the tinplate. The competitiveness of the aluminum coating compared
with the tin coating depended on the price of tin.
1.4.2 PEELING IN CORROSION COATING OF TRANSNATIONAL
PIPELINE
Corrosion coating of a 800-mile transnational pipeline from Alaska
became controversial [11]. The initial coating was found to be inadequate.
The pipeline had to be recoated. Second wrapping of tape was given. 3M,
Minnesota Mining and Manufacturing, and another company Surfcote
Inc., responsible for the initial coating of Scotchkote, were sued by
Alyeska. The value of the pipeline in 1977 U.S. dollars was $7.7 billion.
Scotchkote was an epoxy coating. Hot oil in the pipeline increased the
corrosion processes. More peeling and debonding of the pipe coating were
seen. The temperatures can get up to 140F. The epoxy resin is sprayed on
a heated pipe and a green film is formed. The Scotchkote can withstand
higher temperatures of up to 200F. These pipelines are large such as
4 feet in diameter and are buried. Adverse reports of debonding of coating

8 NANOCOATINGS, VOLUME I

have come from the customers. The green coating was found to soak up
moisture.
1.4.3 MOLTEN METAL TROUGH COATING
A coating was suspected in a blast [12]. Men were killed when material
was tested by Bethlehem steel. The experimental metal-coating material
that can be used at high-temperature operations was used in a blast furnace.
The explosion occurred at the Bethlehems Sparrows Paint plant where
molten metal is poured into 6-foot wide troughs and then carried to the
railroad cars at the bottom of the structure. The mud-like coating material
is mixed with water and then used to coat the troughs. The purpose of the
coating is to protect the troughs from the searing heat of the molten metal.
One worker near the incident observed steam emanate during the application of the coating. Without much outlet the pressure of the steam had increased. They lamented that the coating used before was powder coatings.
Maryland OSHA, Occupational Safety and Health Administration, officials
investigated the incident in detail. One official said that after the previous
explosion, holes were drilled in the metal troughs in order to provide ventilation and let the steam out. F. R. Peterson and H. Biggs were killed after
receiving multiple injuries from flying metal. N. Price was in critical condition after suffering from a head injury, lacerations, and fractures.
1.4.4 PPG ACQUIRES ORICA COATING
PPG Industries Inc. purchased Orica coating business at Orica, Melbourne, Australia [13]. The acquisition cost was $150 million then. Automotive and industrial coatings were made by Orica in New Zealand and
Australia. PPGs main products in coatings back then were automotive,
industrial, and architectural coatings. Orica retained its architectural and
powder coating business and sold its automotive, refinish, automotive
original equipment, coil, packaging, and production coatings.
1.4.5 WATER-BASED POLYMER COATING FOR NONSTICK
APPLICATIONS
A superslick solution was suggested [14]. Dow chemical Co. team led by
D. L. Schmidt had reported a de novo water-based polymer coating that can
be painted on and baked at temperatures slightly above the boiling point of

INTRODUCTION TO NANOCOATINGS 9

water in the May third edition of the journal Nature. A hard, clear coating
can be used in order to repel adhesives without wetting or being attacked by
solvents. Beading up and sliding of the coating material is not desirable. The
soap-resembling coating formulation until the cure stage was greeted with
cheer by the U.S. Naval Research Laboratory officials. They found the coated surface superior to Teflon and is nonporous. R. F. Brady Jr. called the
coating the best nonstick surface ever made outside the laboratory. He
substantiated his observation with numbers. The stickability measured in
mJ/m2 for the new nonstick coating was 11 to 16 compared with 18 for Teflon, 40 for plastic, and 80 for copper and steel. He fully expected the formulation to be used in self-stick labels, prosthetic devices, bearings and valves,
skillets and utensils, stain-resistant fabrics, and barnacle repellent coatings
on hulls of ships. He wanted more testing done. Teflon is the nickname of
PTFE, polytetrafluoroethylene. This was invented in 1939 by R. Plunkett of
the E. I. du Pont Nemours Corp., Wilmington, DE. PTFE was first used as
slippery bearings that do not need oil. They were used to make nonstick
cooking pans in the kitchens from 1960 [15].
1.4.6 FURNITURE COATINGS
Some polymer coating formulations can be found in [16]. Translucent
polymers are used in side display panels of interaction tower, made according to the furniture designer R. Holbrook for people who spend majority of the day doing computer work. Each polymer panel comes with a
halogen light used to provide the illumination. A wrist rest is molded
directly onto the work surface. Bolon flooring is made of sisal, a natural
fiber that can be woven into carpets. Bolon comes in 50 different weaves.
Solid borders can be provided with a pattern or stripe. The price was $25
to $35 a yard. Parqwood can be used in order to provide the floor with a
wood-like veneer. It is a double-sided laminate coating. The coating can
be used in order to make the floor water repellent. This coating will save
waxing and refinishing costs. Manufactured in Italy, parqwood is made
available in 10 different veneers with maple, oak, and alderwood. The cost
was $4 to $7 per square feet.
1.4.7 THICK CHOCOLATE COATINGS
Thicker coatings won the contest [17]. Thick chocolate coatings on vanilla
ice cream seen in Doverbar was selected by the panel over the chocolate

10 NANOCOATINGS, VOLUME I

ice cream bars prepared by Haagen Dazs, Ben & Jerrys, Eskimo Pie,
Klondlike, Good Humor, and Store Brand. The panelists praised the
creamy, rich ice cream, a thick chocolate coating with bold flavor and a
taste that is not so sweet. The dark chocolate coating was selected compared with a bar with a milk-chocolate coat. The ingredients of the coating
contain an emulsifier, semi-sweet chocolate, and coconut oil. Soy lecithin,
milk fat, cocoa butter, chocolate, sugar, and chocolate processed with alkali
are present in the semi-sweet chocolate.
1.4.8 INTELLIGENT COATINGS ON SEEDS
Polymer coating technology in order to insulate corn and soybean seeds
from the cold soil conditions was announced [18]. Midwest farmers can
plant their seeds earlier. Intellicoat polymer can be used in order to prevent
water or ice from entering the seeds when soil temperatures are low enough
to cause damage. When the soil temperatures exceed 55F the structure of
overcoat changes in order to permit surrounding moisture to penetrate the
seed allowing for germination. Synergistic acquisitions of agro seed companies were attempted by Landec. Canola, sugar beets, sweet corn, and cotton
seeds can also be coated using the temperature-sensitive polymers.
1.4.9 THIN FILM INTERFERENCE
Coatings that can be found during the iridescence of butterfly, soap bubbles, and sea shells was touched upon in [19]. According to the MerriamWebster dictionary, iridescence is defined as a lustrous rainbow-like play
of color caused by differential refraction of light waves that tends to
change with changes in angle of view. The word iris comes from the
Greek goddess of rainbow.
The iridescence of butterfly wings and soap bubbles can be explained
using optical interference principles. Vibrating blue color of wings of butterfly can be seen from low-flying airplane windows. Why does Japanese
beetles wings colors change from gold to green? The blue glow of neon
tetra in a tropical fish tank, pearly pinks and blues of an abalone shell,
deep purple of a ravens back, red of a ruby throated hummingbird, rainbow of an oil slick can be explained using light interference principles.
The nature of the reflecting surface is important. The surfaces can be
smooth or rough. Optical paths from the smooth surface and corrugated
surfaces can lead up for different changes in light color patterns in the eye.

INTRODUCTION TO NANOCOATINGS 11

Light travels as waves. The incident light rays get refracted and
reflected from the surfaces of the butterfly wings. When two rays get
superposed, during constructive interference they become stronger and the
color is striking. The amplitude of the resulting wave is greater than the
amplitude of the reflected rays. When the resulting amplitude is smaller,
destructive interference is said to occur. Destructive interference can lead
to cancellation of color as seen from Figure 1.1. The smoothness of the
surface the rays get reflected from is a salient consideration. When the
surface is rough the light rays may diffract. Diffraction is associated with
bending of light waves or sound waves as the case may be. Sound from
the class rooms heard by the principal as he walks past classrooms is an
example of sound diffraction. The HuygensFresnel principle states that
light wave incident on two slits will spread out and exhibit a pattern. This
pattern is called diffraction pattern.

Figure 1.1 Constructive and destructive interference during reflections from


smooth and rough surfaces

Sir Isaac Newtons colors are shown in Figure 1.2. Orange is the seventh color. Each color light has a different wavelength and frequency. The
speed of light can be calculated by multiplying the wavelength with the
frequency. Violet has the shortest wavelength and red has the longest
wavelength. When an object appears a certain color it is due to the absorption of all colors but the one the eyes see. Objects that are found to
iridesce tend to quell some colors and intensify some colors and the eye
sees the result of optical transformations.
Newton observed that the cause of the colors of peacock feathers was
more than shear pigmentation. It can be because of interaction of light waves
and interference. The arrival of the SEM, scanning electron microscope, and

12 NANOCOATINGS, VOLUME I

Figure 1.2 Newtons six colors

better understanding of the wave nature of light took several years after
the discourses of Sir Isaac Newton. Helen Giradella, a biologist at the
State University of New York at Albany, has studied butterfly colors and
moth scales using scanning microscopy and other characterization tools.
The light patterns seen from iridescence are physical colors. They can be
distinguished from colors from pigmented or painted surface. The colors
from pigmented surfaces are from chemicals. In the case of butterfly, yellow and rusts of the monarch come from chemicals. Ghiradellas SEM
image of the wing of butterfly reveals that it is covered with overlapping
rows of scales. The scale thickness falls in the micron range. Ridges, lamellar, microribs, and other microstructural features of the wings of butterflies can be seen as a result of what is called in introduction to physical
science class as [20] thin film interference. Incident light rays penetrate
layered materials and get reflected from each layer. The thickness of the
layers plays a significant role in reflection of light. The light colors that
get reflected, intensified, or canceled depends on the surface smoothness
and layer thicknesses. In X-ray diffraction analysis the 14 Bravais lattice
structures are identified using reinforced light waves. Microribs were
found perpendicular to the lamellae stacks. This is called rococo architecture. Other microstructures found were rolled-up layers seen in bristle
scales of Astraptes azul butterfly. The distance between the rolled-up layers is approximately one-quarter the wave length of green light (100 nm).
This is a plausible reason for iridescent green seen from this butterfly.
Honeycomb-like diffraction lattice structure was seen in the butterflies
from Peru. The intercavity distance of the insect is 260 nm. This leads up
for green color seen from these butterflies. Bristle morphology is analogous to quarter wave interference mirrors used in solid-state lasers.
Constructive and destructive interference optical transmission can be the
causative factor in dimmer of light seen from astraptes.

INTRODUCTION TO NANOCOATINGS 13

Cells from the human dermis after lysis form a protective coating.
Butterfly epidermal cells also form a coating upon cell death. According
to H. Ghiradella scales are highly structures, scale formation is a virtuoso exercise in biological pattern formation at the cellular level. The
scales change during the metamorphosis from caterpillar into a butterfly.
Carbohydrate based polymer such as chitin is secreted from epidermal
cells as a covering. Upon lysis the cuticle buckles and curls. This is caused
by the forces of contraction. The final morphology is after the mechanical
transformations including some fracture: metallic green of tiger beetles,
multicolored sheens of pigeon feathers, polished brass look of scarab beetles, luster of June beetles, and iridescence of blue fruit flies, Elaeocarpus
angustifolius.
Danainae is a tropical butterfly subfamily. The pupa stage of this butterfly looked like lima bean-shaped polished gold hanging from the undersides of leaves. Their optical properties were examined by two German
researchers. The exterior had a shining golden luster but for a few spots of
pigments. The pupa surface was found to comprise of 520 alternating layers of chitin-based cuticle and water with the distances between succeeding layers changes continuously. This makes them broadband interference
reflectors. Color changes come about as the surface dries out. Prof. G. W.
Kattawar of Texas A & M University, College Station, TX, explained the
polished brass look of scarab beetle species.
1.4.10 ARCHITECTURAL COATINGS
BASF expanding its range of binders for wood coatings [21]. They
launched a series of new products and applications of outdoor wood coatings and window coatings in the acrylic dispersions segment. Coatings
with superior weatherability and blocking resistance were introduced.
These were cost efficient and formulated using conventional rheology
modifiers. They defoam well. Polymer dispersions were used in order to
apply architectural coatings. They presented at a conference about wood
coatings at Stessa, Italy, new binders and formulations for wood paints,
wood stains and industrial window coatings and other exterior structures
such as doors, patios. The polymer dispersions are water based and environmentally friendly. One of their products was an extremely fine-sized,
self-crosslinking, pure acrylate dispersion for decorative, quality industrial
coatings for windows and doors. These dispersions had better water resistance and blocking resistance and better durability. Binder used was
wet and transparent leading to better clarity. Binder added protects

14 NANOCOATINGS, VOLUME I

pigmented decorative coatings used on wooden claddings in European


Union. These coatings were more crack resistant. Binder acts as an elastifying component. Another coating formulation was a binder for primers
and impregnations. These primers can be used for grain enhancement and
improved adhesion induced by easy penetration of the very fine and colloidal stable dispersion particles into the wood. These primers were made
to be compatible with fungicides. Another brand was high-gloss paint and
can be used for wood coatings. These can be used for improved weatherability. These water-based coatings systems can be used as an alternate to
solvent-based architectural coatings. The high-gloss paint can be used in
order to form a tack-free film at room temperature. It is easy to apply and
has a long open time. Haze-free, high-gloss surfaces can be prepared using
these glossy paints. Nanostructured coatings are used for wood coatings
with higher dirt and blocking resistance with higher water vapor permeability. In 2009 the industrial, topcoat, window nanocoatings with better
weatherability were introduced into the market. Binders used in architectural coatings can be used in order to ensure gloss, mechanical stability,
and adhesion of the paint to the surface. Faade coatings, outdoor plasters,
water-based polymer dispersions, solvent-free formulations are made by
BASF. Polymers used in the formulation are styrene, butadiene, and acrylates. Plasters, finished systems, roof coatings, and ceramic tile adhesives
can be made from the coating formulations.
1.4.11 DEPOLYMERIZATION AND RECYCLING
Depolymerization phenomena [22] was found to be relevant in the story on
polyester trash recycling in [23]. The warehouse of Vacuum Depositing
Inc., had piles of plastic films, polyester pieces from electronic waste. The
pile was 25 feet high and weighed 80,000 pounds. The solution offered to
the landfill crisis by E. I. du Pont is to reclaim the monomer from the polymer waste. In the waste tires reclaimation project [24] it was found that is
not cost effective to pyrolyze waste tires. Butadiene monomer recovery
would be a more cost-effective solution. du Pont technologists trucked the
film scraps from Louisville, KY, to a plant in Cape Fear, NC. There they
chopped the scrap and heated the vat containing the scrap to a said temperature and applied pressure. The result was a mixture of the chemical ingredients that went into the manufacture of polyester. Appropriate separations
method can be used and the monomers recovered from the soupy mixture.
Depolymerization and unzipping is discussed in detail in Sharma [22].

INTRODUCTION TO NANOCOATINGS 15

These costs ought to factor into the total life cycle use cost of plastics and
polyesters. Nine percent of this country United States landfills are plastic
scrap. According to EPA it may take decades for the plastic to degrade.
Biodegradable plastic may be considered here. Traditional recycling methods include grinding the plastic and mixing them with concrete as filler
material. Used soda bottles are melted and used as polyester fabric. Depolymerization methods can lead to monomer as fresh and pure as obtained
from the oil barrel. Eastman Kodak was a pioneer in using depolymerization for recycling scrap X-ray films in 1962. Kodak manager saved $5 million a year by regeneration of 100 million pounds of dimethyl terephthalate
from polyester. New plant for recycling by depolymerization can run the
investors $50 million. A retrofit plant from existing one would cost several
million dollars. Sometimes the ventures for recycling using depolymerization have gone out of business. For example, the German giant Hoechst
AG spent $7 million in a retrofit plant at Wilmington, NC, that can be used
for polyester regeneration. The reason for the project not becoming profitable is the $0.40 per pound cost of soda bottles. They had to change the use
of the plant to another recycling project. Depolymerization recycling uses
distillation. The materials used in the inks and coatings are recovered. Dirtier material can be handled. Petrelec is a 1996 launch of du Pont used for
regeneration of 700 million pounds of polyester film. By the year 1998 the
capacity of the plant was expected to be approximately 100 million pounds
per year. Twenty to 25% of the cost of chemicals used in the polyester
business is expected to be recovered. The management at du Pont can now
pitch polyester as the greenest of polymer. Conventional recycling methods result in a lime-green 7Up soda bottle. Depolymerization recycling can
be used to make a clear polyester product. Nylon regeneration is being developed at the reputed BASF and du Pont. Polyol has been recovered from
polyurethane used in foam cushion is furniture and automobile seats by
BASF AG. The profitability is not clear.
1.4.12 SEBUM COATING REMOVAL USING SHAMPOO
The science and marketing of shampoo was discussed in [25]. A hair is a
shaft made out of dead proteins and keratin fibers. Shampoos found in the
supermarket shelves have labels that claim that they contain mango, papaya, apple pectin, wheat germ, or Swiss vanilla can be found. Shampoo
comes from the word champo in Hindi that means to massage or knead.
Shampoos are used to clean hair and avoid dandruff. Shampoos do not

16 NANOCOATINGS, VOLUME I

resuscitate, enliven, or revive hair. The cleaning process includes the removal of sebum. Sebum is a thin layer of oily material found on the skin.
It is produced by the sebaceous glands in the skin. Sebum can be found as
coating on the hair. Sebum also acts as a magnet for dirt and residue from
hair treatment products. Shampoos contain surfactants. They are found to
be responsible in the cleaning action and lathering found during application of shampoo. Surfactant are larger molecules with one end hydrophilic
and other end hydrophobic. The hydrophobic end is found to get attached
to the oily layer of sebum while the hydrophilic end remains anchored in
water. Surfactant action results in the formation of micelles. Micelles are
clusters of 40 to 100 molecules. The hydrophobic ends of molecules that
make up the micelle are found to face the center of the micelle and the
hydrophilic ends are found to stick out in surrounding water. The oil drops
removed from the hair would be attracted to the center of the micelle. This
has resulted in separation of the oil droplets without agglomeration and
redeposition. Surfactants tend to decrease the surface tension of water.
The wettability of the surface is increased. Lather foam is a dispersion of
gas in a liquid. It contains swarms of air bubbles. Lowering the surface
tension of the solution can lead to more bubbles. Cleaning without lathering can be found in home-made shampoos. Marketing personnel like the
lather generating shampoo. The first commonly used surfactant was soap.
The first few shampoos were made from water, soap, and sodium carbonate by British hairdressers. These shampoos were effective when water
with low mineral content is used. When water contained appreciable
amounts of magnesium and calcium the soap was found to form an insoluble precipitate deposited on the hair, ruining the customers hair. Early
part of the 20th century saw the advent of SLS, sodium lauryl sulfate.
Lauryl alcohol was isolated from coconut fat or palm kernel oil was used
to prepare SLS. SLS is an anionic surfactant because its hydrophilic end is
negatively charged. It was found to be an effective cleaner, and found to
foam well and no precipitate was formed. Sebum coating on hair also offered protection to the hair from drying out. Use of SLS can lead to dry
hair, fly-away hair and can be a skin and eye irritant. SLS is sparingly
soluble in water. Ammonium lauryl sulfate, SLES, sodium laureth sulfate,
are more soluble in water. Cationic surfactants can be used as hair conditioners. Thickeners such as xanthium gum, preservatives such as parabens,
emulsifiers such as glycol distearate, color additives and foam boosters
such as cocamide monoethanolamine are added to the shampoo formulation. Pantheol added to the formulation are expected to diffuse into the
hair shaft and bind to the proteins, strengthening their structure. Elastin

INTRODUCTION TO NANOCOATINGS 17

and collagen are added to the shampoo formulation for the purpose of
binding to the hairs surface in order to enhance thickness.

1.5 SCOPE FOR NANOCOATINGS


Nanocoatings can be applied by atomization or spraying. Atomization is
used in order to make an aerosol mist in air or gaseous atmosphere.
Ultrafine droplets are made from the liquid having uniform diameter. The
spray can be polydisperse. The average size of the fine droplets is considered crucial to application to different surfaces such as metals, glass, textiles, plastics, and minerals. Nanocoatings can be used in sanitation,
implants, antifingerprint coating on visual display units, self-cleaning
faade, and paint protection for cars. They can be made to be antimicrobial.
Nanos is a French word and means dwarf. Technolgia means a systematic treatment of an art or craft. One nanometer is one billionth of a
meter (109 m). The covalent radius of helium is 28 pm. One thousand
picometer makes one nanometer. Graphene is the thinnest material created
and can be made in single layers in copper foil [26]. Nanocoatings with
thickness less than 100 nm can offer superior performance properties
compared with conventional coatings. One of the first commercial applications of nanocoating was Nanotuff. Triton systems developed this
product on a 5-year contract from Navy [3]. The application was advanced
abrasion-resistant and chemical-resistant coating for transparent substrates.
Coatings can be used on automotive parts and accessories such as rigid and flexible exterior trim systems, steel and aluminum wheels, body
panels, bumper and break systems, hitches, shocks, axles, coil springs,
under hood/body parts, and sway bars. They can be used to coat metal
roofing, metal building panel, column covers, garage and entry doors,
rainware, gutters, siding, fascia, trim, HVAC, lighting fixtures, storefronts,
curtain walls, windows, louvers. Coatings can be used on different surfaces
and substrates. Commercial truck cab, commercial buses, school buses,
trailers, industrial railcars, agricultural equipment, and construction
machinery and railcars are coated with different colored coatings. PPG
Industries Inc., Pittsburgh, PA, a big player in coatings, makes coatings
for mobile phones, laptops, desktop computers and peripherals, GPS
systems, and beauty products. Coatings can be applied to household appliances such as washing machines, dryers, refrigerators, freezers, dishwashers, ovens, ranges, and microwaves. Sales orders for coatings come from

18 NANOCOATINGS, VOLUME I

makers of sports equipment such as golf balls, fitness equipment, bicycles,


motorcycles and outboard motors, and recreational vehicles. Coating has
been supplied to office furniture, transformers, tool storage, wires, fastners, and radiators.
Nano-sized particles suspended in an epoxy matrix was used in the
coating mix. These coatings can be considered as nanocomposite coatings.
This coating was found to be four times more durable than conventional
coatings. Surfaces treated with nanotuff were found to be free from
crazing, cracking, shatter upon impact. Some flame retardancy was incorporated into the product. Nanoceramic coatings with higher toughness
compared with conventional coatings were developed in the 1990s.
Department of Defense, DoD, encouraged partnerships among academia,
industry, and pentagon in order to evaluate nanocoatings for use in the
seas. R&D 100 awards were given out. DoD estimated a reduction of
$20 million in maintenance costs upon use of nanocoatings in air valves.
Wear-resistant coatings can be applied to personal cars and heavy industrial
machinery.
Alternates for Cd, cadmium, plating is solicited by DoD with the sole
purpose of protection of aircraft components from corrosion. Side-by-side
evaluations of whether the coatings are absolutely essential and whether
the same set of properties can be met using a steel of a different alloy
composition are needed. Reports from operating experience of aircrafts
were used to realize that often times, the real issue for maintenance is service failure attributable to stress corrosion cracking. Questek came up
with a steel grade made up of nanophase precipitated hardened material
equal to 300 M that can be used to address the concerns of service failure.
Concerns about cadmium corrosion are also allayed. Nanocoatings can
offer an alternate to this critical technology. Reduction in cost and time to
market of an order of magnitude can be realized.
Nanocoating with 30-nm thickness was developed to be used in
fighting furniture fires. This coating is better for the environment compared with the flame retardants used currently in order to protect cushions
used in furniture. The coating is made of sulfur-based polymer and a carbohydrate polymer found in crustacean shells. The polyurethane used to
make foams used as furniture cushions are flammable. Fire safety guidelines require use of flame-retardant chemicals. These chemicals have been
shown to act as endocrine disrupters or lead to neurological problems.
The European Union, Canada, and United States have begun to scrutinize
the use of these chemicals. Researchers at Texas A & M University have
developed formulations that do not affect the stiffness of the foam and

INTRODUCTION TO NANOCOATINGS 19

have reduced toxicity. The coating is made of PVS, polyvinyl sulfonic


acid, and chitosan. Chitosan is a long carbohydrate molecule derived from
the shells of shrimp and other crustaceans. Coating prepared by dipping
foam in aqueous forms of the two polymers. Positive charges are possessed by chitosan, and negative charges are possessed by PVS. The two
polymers become entangled by attraction of unlike charges and the coating is created [3]. Weight increase of the foam is 5.5% without alteration
of stiffness of the foam. Tests confirmed that it would take three times as
much conventional flame-retardant material in order to achieve the same
effect. As PVS burns, SO2, sulfur dioxide vapors are generated that makes
a gas blanket on the foam surface, thereby, cutting of oxygen and enabling
the starvation of the fire. Another research group at NIST, National Institute of Standards and Technology, develop clay-based nanocoatings that
can be used to make materials fire proof.
Some of the critical issues in preparation of nanocoatings are as follows [3]:
(i) Process for making optical flakes that are precursors to inks that
are used in currencies
(ii) Functionalization of nanoparticles in the polymer coating
(iii) Particulation for hard, lubricious razor blade coatings
(iv) Materials and methods for barrier, clear and sacrificial coats
(v) Meet necessary qualifications, such as aerospace vehicles

1.6 COATING TYPES


Coatings can be classified according to their applications or method of
preparation or type of property imparted to the product. They can be either
solvent based or water based. They may comprise of polymers or inorganic materials. Aqueous paint composition has been patented by PPG [27].
Paints can be used in order to coat a spectrum of different surfaces. The
purposes of coating the surfaces can be for preserving and protecting the
desired objects and used in decoration and for minimizing damage of ballistic impact. Prototypical paint compositions comprises of a solvent, pigment, and a binder. Decorative paints may be either solvent bases or water
based.
Robotic delivery of paint can result in coating with smaller thickness.
Nanofilm Surface Science, Creative Solutions, Valley View, OH have
commercial coating products that range in thickness from 20 nm to few

20 NANOCOATINGS, VOLUME I

microns. The nanocoatings and surface treatments are durable are optically
clear. Niche properties are added to the surface of glass, ceramics, metals,
and plastic. Surface attachments and bonds are formed during the finishing application.
Coatings can be made that are hydrophobic or water repellant. Dirt
repellant and antigrafitti coatings are also in vogue. Naval vessels are
made corrosion resistant by spraying the paint formulation. The paint formulation should have adequate shelf live and pot life. Thin layers are
formed in the substrate. Physical drying, corrosion protection, mechanical
resistance, heat, and stress resistant to welding and cutting operations are
important considerations. Overcoat compatibility is an added issue. Safety
issues such as health hazards from release of noxious fumes from welding
operations are paramount in design of coating formulation. Volatile solvents may fill the air and exceed OSHA acceptable levels.
Titanium dioxide, TiO2, can be nanoparticulated and used to make
photocatalytic self-cleaning coatings. The coating thickness can be down
to 10 to 20 nm on surfaces. They impart color. These are commercially
available in Japanese and European markets. Applications include selfcleaning glass under sunlight, concrete in construction, water purification.
When used in skyscrapers they help reduce maintenance costs. Titania
powders have photocatalytic properties. Ultraviolet, UV, light-activated
nanocoatings can also be used. Coatings can be made to have fogresistant, biocidal properties. Coatings are applied to glass used in increasing amounts in construction this time and age. This allows for use as solar
coatings, architectural coatings. They can be used for packaging of food
articles.

1.7 SUMMARY
Enamels are applied to metallic surfaces and glaze to ceramic surfaces.
They are clay products. They can come in different colors such as white,
blue, green, yellow, and red glazes. Global market sizes for nanocoatings
and coatings are expected to be $14.3 billion and $123 billion, respectively, by the year 2019. The year 2019 is the sesquicentennial of M. K. Gandhi. North American paint makers shipped five billion gallons worth
$80 billion of their products in the year 2002. Coatings can have specific
purposes such as corrosion resistance, antiabrasive resistance, scratch
resistance, chemically resistance, stain resistance to the objects they are
applied on. Akzo Nobel, Netherlands, had supplied corrosion-resistant

INTRODUCTION TO NANOCOATINGS 21

coating to the Sydney harbor bridge in Australia. The coating system


comprises of interzinc epoxy primer, higher solids intermediate coat, and
polyurethane topcoat. Both steel and reinforced concrete structures are
found to undergo corrosion from the deicing salts that are added in the
winter months and other sources. Coatings were known to the four river
valley civilizations around 5500 BC. Shellac was used as a hot varnish in
India in the year around 2000 BC. Shellac is a mixture of esters, polyesters, and polyhydroxy acids.
In 1908 a French metallurgist found a method to weld a thick coating
of soft copper onto the steel substrate. In 1942 the war protection board
has banned the use of castor oils, urea, and some other substances in coatings. American Coating Mills Inc. was acquired by Owens-Illinois glass
co. in 1947. AR nanocoatings was known as early as 1916. Langmuirs
assistant K. B. Blodgett applied 102.8 nm thick coating on both sides of a
glass slide. M. U. Schoop in the year 1916 developed a pistol that was
used to spray molten metal and form 25.2 m coatings on girders, tanks,
and machinery. Mr. R. Rimbach has worked on the development and promotion of a new process for coating steel with a pore-free metallic coat
which has successfully demonstrated its resistance to sever corrosion conditions in Texas oil fields in 1939.
U.S. Steel Corp., Pittsburgh, PA, developed a new vapor-coating process for coating light gage, flat-rolled steel with aluminum coatings in
1994. A 800-mile transnational pipeline had to be recoated. 3M, the vendor responsible for application of the corrosion coating, was sued by
Alveska. Adverse reports of debonding of epoxy coating have come from
the customers. A coating was implicated in a blast at a Bethlehems Sparrows paint plant. Steam that had formed from hot molten metal and built
pressure had caused the explosion. PPG has acquired Orica coatings
in 1998. They later acquired AkzoNobel (see Volume I, Chapter 3.0).
Water-based polymer coatings can be made with nonstick property. The
stickability measured in mJ/m2 for the new nonstick coating was 11 to 16
compared with 18 for Teflon. Parqwood are laminate coatings can be
applied to provide a wooden veneer to the floor. Traslucent polymers can
be used as furniture coatings and can be used with computers for people
who do computer work all day. Dark chocolate makes better thicker coatings compared with milk-chocolate coat. Intelligent coatings can be made
from temperature-sensitive polymers. These are applied to different seeds.
In cold temperatures ice is prevented from entry into the seeds. At higher
temperatures water is allowed to diffuse into the seeds. The iridescence of
butterfly wings, soap bubbles can be explained using optical interference

22 NANOCOATINGS, VOLUME I

principles. When two rays get superposed, during constructive interference they become stronger and the color is striking. Ridges, lamellar, microribs, and other microstructural features of the wings of butterflies can
be seen as a result of thin film interference [5]. The distance between
rolled-up layers seen under scanning electron microscope was 100 nm.
Rocco architecture, honeycomb lattice structure, was confirmed by study
of morphology of different butterflies. The pupa surface was found
to comprise of 520 alternating layers of chitin-based cuticle and water
with the distances between succeeding layers changes continuously. This
makes them broadband interference reflectors. Color changes come about
as the surface dries out. In the year 2008, BASF announced its expansion
of its range of binders used for wood coatings. Water-based dispersions
were used to make architectural coatings. In 2009 the industrial, topcoat,
window nanocoatings with better weatherability were introduced into the
market. Binders used in architectural coatings can be used in order to ensure gloss, mechanical stability, and adhesion of the paint to the surface.
Monomers can be reclaimed from plastic waste by better understanding of
depolymerization. This may be a more cost-effective solution compared
with pyrolysis. Depolymerization and unzipping is discussed in detail in
Sharma [4]. Eastman Kodak was a pioneer in using depolymerization for
recycling scrap X-ray films in 1962. Kodak manager saved $5 million a
year by regeneration of 100 million pounds of dimethyl terephthalate from
polyester. New plant for recycling by depolymerization can run the investors $50 million. Petrelec is a 1996 launch of du Pont used for regeneration of 700 million pounds of polyester film. By the year 1998 the capacity
of the plant was expected to be 100 million pounds per year. Sebum can
be found as coating on the hair. It is a thin layer of oily material. The oil
drops removed from the hair would be attracted to the center of the
micelle. Surfactant action is seen to result in formation of micelles. Micelles are clusters of 40 to 100 molecules. Shampoo action can be used to
remove dirt and condition hair.
Atomization is used in order to make an aerosol mist in air or gaseous
atmosphere. The covalent radius of helium is 28 pm. Nanocoatings with
thickness less than 100 nm can offer superior performance properties
compared with conventional coatings. One of the first commercial applications of nanocoating was Nanotuff. Triton systems developed this product on a 5-year contract from Navy [2]. Nano-sized particles suspended in
an epoxy matrix was used in the coating mix. These coatings can be considered as nanocomposite coatings. PPG Industries Inc., Pittsburgh, PA, a
big player in coatings, makes coatings for mobile phones, laptops, desktop

INTRODUCTION TO NANOCOATINGS 23

computers and peripherals, GPS systems, and beauty products. Coatings


can be applied to household appliances such as washing machines, dryers,
refrigerators, freezers, dishwashers, ovens, ranges, and microwaves. Sideby-side evaluations of whether the coatings are absolutely essential and
whether the same set of properties can be met using a steel of a different
alloy composition are needed. Nanocoating with 30-nm thickness was
developed to be used in fighting furniture fires. The coating is made of
sulfur-based polymer, polyvinyl sulfonic acid and a carbohydrate polymer,
chitosan found in crustacean shells. The polyurethane used to make foams
used as furniture cushions are flammable. Some of the critical issues faced
in preparing nanocoatings include making the precursour inks used in
Critical issues in preparation of nanocoatings are process to make precursor to inks used in currencies, functionalization of nanoparticles in the
coatings, particulation in lubricious coatings, materials for barrier and
clear coats and meet specifications for aerospace vehicles.
Coatings can be classified according to their applications or method
of preparation or type of property imparted to the product. They can be
either solvent based or water based. They may comprise of polymers or
inorganic materials. Aqueous paint composition has been patented by PPG
[5]. Paints can be used in order to coat a spectrum of different surfaces.
Robotic delivery of paint can result in coating with smaller thickness.
Coatings can be made that are hydrophobic or water repellant. Titanium
dioxide, TiO2, can be nanoparticulated and used to make photocatalytic
self-cleaning coatings. The coating thickness can be down to 10 to 20 nm
on surfaces. They impart color. These are commercially available in Japanese and European markets. Applications include self-cleaning glass
under sunlight, concrete in construction, water purification. When used in
skyscrapers they help reduce maintenance costs.

1.8 REFERENCES
[1]
[2]
[3]

[4]

http://www.marketsandmarkets.com/Market-Reports/nanocoatings-market
-118016795.html
M. F. Ali, B. M. E. Ali, and J. G. Speight, Handbook of Industrial Chemistry, McGraw-Hill Professional, New York, NY, 2005.
K. R. Sharma, On Process Considerations for Nano-Structured Coatings, in
Anti-Abrasive Coatings: Current and Future Applications, M.
Aliofkhazraei (Editor), Woodhead Publishing, Cambridge, United Kingdom,
2014. ISBN-13: 978-0857092113. ISBN-10: 0857092111.
Washington Post 10-28-1908, Coating Steel with Copper

24 NANOCOATINGS, VOLUME I
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]

[21]
[22]
[23]
[24]
[24]

[25]
[26]
[27]

Wall Street Journal 06-02-1942, To Ban Steel Container Coating Material


Wall Street Journal 02-10-1947, Owens-Illinois Glass Co. to Acquire
American Coating.
Washington Post 03-26-1916.
Washington Post 12-27-1938.
Wall Street Journal 06-03-1939, Standard Steel Spring Co. Developing Metal Coating
Wall Street Journal, 11-30-1994.
LA Times, 06-07-1977.
Sun, Baltimore, Maryland, 02-25-1984.
The Wall Street Journal, 08-27-1998.
The Washington Post, 03-07-1994, Chemistry: Nonstick Coat has Staying
Power.
Washington Post, 04-22-1998.
The Wall Street Journal, 07-24-1998, Home Office.
The Christian Science Monitor, 02-20-1997, Creamy DoveBar Wins by a
Lick.
The Wall Street Journal, 08-22-1997.
Washington Post, 06-14-1995, How Nature Stages Her Most Colorful Light
Show.
K. R. Sharma, PHYS 101: Introduction to Physical Science, Course Power
Point Slides and Notes, Texas Southern University, Houston, TX, Spring,
2014.
M2 PressWire, 08-19-2008.
K. R. Sharma, Polymer Thermodynamics: Blends, Copolymers and Reversible Polymerization, CRC Press, Boca Raton, FL, 2012.
The Wall Street Journal, 111-6-1997, Polyester Trash Is Pure Plastic after
an Unzip.
Washington Post, 12-09-1998, Secrets of Shampoo
K. R. Sharma, Imprvement of Devulcanization Yield during Reclamation
of Waste Tires, The Global Journal of Researches in Engineering, Vol.
13, (2013), 1.
Secrets of Shampoo: (Washington Post, 12-09-1998) goes over
K. R. Sharma, Graphene Nanomaterials, McGraw-Hill Professional, New
York, NY, 2009.
M. Plehiers, S. van Loon, J. Courtin, et al., Paint Composition, US Patent
8,129,028, PPG Corporation, Uithoorn, NL, 2012.

INDEX
A
Adhesion, of coating, 37
Aerospace applications, of
nanocoatings
electrochromic window, 2829
green coating, 2728
protective coatings on aircraft
fuselage and propellers, 27
AkzoNobel International, 4
Aluminum coatings, 7
American Coating Mills Inc., 5
Ammonium lauryl sulfate, 16
Antiabrasive nanocoatings, 3
Antimicrobial coatings, 4446
Antireflection nanocoatings, 6
Aquaguard coating, 76
Architectural coatings, 8, 1314
Atomization, 17
Automotive applications, of
nanocoatings
magnetic materials, coreshell
shell morphology, 4849
optical materials, laminated and
glued structures, 4748
Automotive coatings, 3, 8
B
Bilayer graphene, 44
Biomedical applications, of
nanocoatings
antimicrobial coatings, 4446
nanorobot drug delivery, 4647

Blistering, 76, 8081


Blocking resistance, 13
Blodgett, K. B., 6
Blooming, 80
Blushing, 81
Bolon flooring, 9
Bond number, 63
Bridging, 9091
Brush marks, 91
BuckinghamPi method, 74
Butadiene, 14
Butterfly wings, iridescence of, 10
C
Cable coatings, 38
Calcium aluminate cement, 41
Can corrosion, 91
Capillary number, 31, 63, 68
Cartons, clay-coated, 5
Castor oils, 5
Chalking, 8283
Cheesy film, 91
Chemically resistant coatings, 3
Chemical vapour deposition
(CVD), 43
Chitin, 13
Chocolate coatings, 910
Chorinated polypropylene, 79
Chromium blade overcoat, over
carbon coatings, 34
Clay-coated cartons, 5
Clay products, 2

104 INDEX

Coatings. See Nanocoatings


Coextrusion, 31
Color and pigmentation. See
Interference
Columnar structures, 39
Composite coatings, 77
Constructive interference, 11
Copper, 9
Coreshellshell morphology,
4849
Corrosion coatings, of
transnational pipeline, 78
Corrosion-resistance, 34
Covalent coupling, 84
Cracking, 86
susceptibility, 77
Critical thickness, of coating, 4142
D
Damped wave heat conduction, 41
Danainae, 13
Dark chocolate coating, 10
Density gradient, 7175
Dental coatings, 77
Depolymerization, 1415
Desktop computers, 34
Destructive interference, 11
Dewetting, 87
Diffraction, 11
Diffusion, of moisture and oxygen,
3031
Dimethyl terephthalate, 15
Dirtier, 14
Doxil liposomes, 46
Drag coefficient, 69
Dust-prevention coating, 47
E
Elaeocarpus angustifolius, 13
Elastin, 1617
Electrochromic window, 2829
Electronic materials, as
nanocoatings

cable coatings, 38
hard drives in desktop
computers, 34
polymer blend as top coat in
immersion lithography, 3537
vacuum plasma polymerization
and printed circuit board
components, 3738
Electrophoretic deposition, 77
Electrostatic spray coating (ESC),
77
Enamels, 2
Enos, R. C., 6
Eotvos number, 68
Epitaxial strength, 50
Epoxy coating, 7
Ethylenepropylene elastomer, 79
Ethylene vinylacetate, 79
Explosion, molten metal and, 8
F
FeCO particles, 48
Flame assembly, 32
Foaming, 7879
Food industry, nanocoatings in
packaging using metalized
polymer film, 3033
shaving blade coatings, 3334
Furniture coatings, 9
G
Giant magneto resistive thin film,
34
layers of, 3435
Giradella, Helen, 12
Glass, 83
smoothness of, 8485
Glaze, 2
Glued structures, 4748
Graphene sheet, 17
based solar cells, 4244
production of, 4344
Green coating, 2728

INDEX 105

H
Hard drives, in desktop computers,
34
Heat transport simulations, 78
Heat treatment, bloom and, 80
Helmholtz free energy, 62
Holbrook, R., 9
Hot-melt adhesive film, 47
Hydrophobhic coatings, 82
Hydroxyapatite, 7677
I
Ideal surface, to nanocoatings, 83
Immersion lithography, 3537
Impact-resistant coating, 38
Industrial coatings, 8
Intellicoat polymer, 10
Intelligent coatings, on seeds, 10
Interfacial layer, 48
Interference, 1013
Intermediate coat, 3
Iridescence, definition of, 10
Island formation, 7678
L
Laminate coating, 9
Laminated and glued structures,
4748
Lauryl alcohol, 16
Layer thickness ratio, 74
Lighter coatings, 28
Light transmission, 2829
Litigation losses, 3334
Longitudinal stretching, 32
Lotus-effect coatings, 4748,
8283
M
Magnesium oxychloride sorrel
cement coatings, 4041
Magnetic materials, as
nanocoating, 4748
Manganese bismuth alloy, 48

Marangoni effects, 61, 7576


Marangoni number, 31
Metal-coating, 8
Metalized polymer film, 3033
Metallic nanolayer, 31, 50
Metalligand interactions, 58
Methyl methacrylate, 81
Microscale viscous number, 75
Miniaturization, 35
Molten metal, trough coatings, 8
Monolayer
graphene, 44
stability, issues in, 8890
Morton number, 68
Mud-like coating material, 8
Multifunctional packaging, 4445,
59
Multilayered films, 30
Multilayer graphene, 44
N
Nanocoatings. See also specific
coatings
aluminum coatings, 7
applications, 23
in aerospace, 2630
automotive, 4749
biomedical, 4447
electronic materials, 3438
energy, technology, and
environmental, 3844
in food industry, 3034
surveillance, 49
architectural coatings, 1314
corrosion coatings, of
transnational pipeline, 78
depolymerization and recycling,
1415
earliest reference to, 4
in early 20th century, 57
furniture coatings, 9
intelligent coatings on seeds, 10
in later 20th century, 717

106 INDEX

Nanocoatings (Continued)
markets, 24
molten metal trough coatings, 8
PPG acquires Orica coatings, 8
scope for, 1719
sebum coating removal using
shampoo, 1517
stability
blistering, 8081
blistering and peeling defects
in, 76
blooming, 80
blushing, 81
bridging, 9091
brush marks, 91
can corrosion, 91
chalking, 8283
cheesy film, 91
cracking, 86
flow of film down inclined
plane, 7071
flows, 5963
foaming, 7879
island formation, 7678
Marangoni effects, 7576
monolayer stability, issues in,
8890
pinholes, 91
self-assembly, 5759
substrate surfaces, 8386
tackiness, 8687
thermocapillary stress arising
from vertical temperature
gradient, 6370
thermocapillary stress, density
gradient, 7175
wrinkling, 8788
thick chocolate coatings, 910
thin film interference, 1013
types, 1920
water-based polymer coatings,
89
Nanocomposite coatings, 18, 27

Nano conformal coatings, 37


Nanofood, 45
Nanomagnetism, 48
Nanorobot drug delivery, 4647
Nanosilver, 45
NanoSpray combustion process,
4546
Nanotuff, 17, 18
Natural fiber, 9
Newton, Isaac, 1112
Nippon Electric Glass, 5
Nitrocellulose, 83
Nobel Laureate Irving Langmuir
of General Electric, 6
Nylon, 15, 83
O
Occupational Safety and Health
Administration (OSHA), 8
Oil, 27
Opacity, 28
Optical materials, as nanocoating,
4748
Optical transformations, 11
Orica coatings, 8
Oriented polypropylene, 3031
Osmosis, 8081
Osmotic blistering, 81
Owens-Illinois, 5
Ozone, 27
P
Packaging, using metalized
polymer film, 3033
Pantheol, 16
Parqwood, 9
Parylene coatings, 37
Patent infringement, 34
Peacock feathers, iridescence of,
1112
Peeling defects, 76
Petrelec, 14
Photocatalysis, 82

INDEX 107

Pinholes, 91
Planar structures, 39
Plasma parameters, 37
Plastics, 9
Polycrystalline graphene, 44
Polyester fabric, 14
Polyethylene terepthalate, 3031, 45
Polymer blend, as nanocoating,
3537
Polymer coating, 10
water based, 89
Polymer dispersions, 13
Polymer panel, 9
Polyol, 15
Polypropylene, chlorinated, 79
Polytetrafluoroethylene (PTFE).
See Teflon
Polyurethane topcoat, 3
Pore-free metallic coat, 6
PPG Industries Inc., 8
Prandtl number, 31, 68
Printed circuit board components,
3738
Protective coatings, 13
on aircraft fuselage and
propellers, 27
p-xylene, 37
Q
Queen Elizabeth II rail bridge, 4
R
Recycling, 1415
Reynolds number, 31, 68, 74
Richards, J., 49
Rimbach R., 6
Robotic delivery, of paint, 19
Rococo architecture, 12
Rust formation, 81
S
Scotchkote, 7
Scratch resistance, 3

Sebum coating, removal using


shampoo, 1517
Seeds, intelligent coatings on, 10
Self-assembly
principles, 3
underlying nanocoatings, 5759
Self-stick labels, 9
Shampoo, coating and, 1517
Shaving blade coatings, 3334
Sheeting, 82
Shellac, 4
Silica, 48, 84
Silicate shell formation, 49
Silver nanocoatings, 44
SLES, 16
Soap bubbles, iridescence of, 10
Sodium lauryl sulfate (SLS), 16
Solar cells, graphene-based, 4244
Solgel methods, 77
Solvent based coating, 19
Southwest Heart, 28
Specific surface area (SSA), 39
Spraying, 17
Stability, of nanocoatings
blistering, 8081
blistering and peeling defects in,
76
blooming, 80
blushing, 81
bridging, 9091
brush marks, 91
can corrosion, 91
chalking, 8283
cheesy film, 91
cracking, 86
flow of film down inclined
plane, 7071
flows, 5963
foaming, 7879
island formation, 7678
Marangoni effects, 7576
monolayer stability, issues in,
8890

108 INDEX

Stability, (Continued)
pinholes, 91
self-assembly, 5759
substrate surfaces, 8386
tackiness, 8687
thermocapillary stress arising
from vertical temperature
gradient, 6370
thermocapillary stress, density
gradient, 7175
wrinkling, 8788
Stain resistant coatings, 3
Stang, P. J., 5758
Steel, 9
Stickability, 9
Stickiness, 8687
Stokes and thermocapillary
number, 75
Stokes number, 63
Substrate surfaces, 8386
Superparamagnetic nanparticles,
48
Superslick solution, 8
Surface engineering, 3
Surface roughness, 79, 8485
Surface tension, 61, 63
gradient number, 31, 75
Surfactants, 1617
Surveillance coatings, 49
Sydney harbor bridge project, 3
T
Tackiness, 8687
Teflon, 9
Temperature-sensitive
polymers, 10
Terpolymers, 35
Thermal and viscous number,
68
Thermal-barrier coatings (TBC),
3842
Thermocapillary stress, 61

arising from vertical temperature


gradient, 6370
density gradient, 7175
Thick chocolate coatings, 910
Thin film breakage, 78
Thin film interference, 1013
3-aminopropyl trimethoxysilane, 84
Titanium dioxide coating, 19, 43
Translucent polymers, 9
Transmission electron microscope
(TEM), 61
Transverse stretching, 32
2-ethylhexyl acrylate, 81
U
Ultraviolet radiation reflective
particles, 27
Unit operations, during coating,
3233
Utility cost, 3031
V
Vacuum chamber utility costs,
3031
Vacuum plasma polymerization,
3738
Viscosity gradient number, 31, 68,
75
W
War Protection Board, 5
Water-based coatings, 19
foaming, 7879
polymer, 89
Water rolling, 82
Weatherability, 13
Weber number, 68
Weld coats, 5
Wrinkling, 8788
Z
Zinc oxide, 77

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