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ADMIN:
I.W

PVC TECHNOLOGY
Fourth Edition

PVC
TECHNOLOGY
Fourth Edition
W. V. TITOW
M. Phil., Ph.D., C.Chem., F.R.S.C., F.P.R.I., C. Text., A. T.!.
Formerly of the Yarsley Research Laboratories Ltd,
Ashtead, Surrey, England

ELSEVIER APPLIED SCIENCE PUBLISHERS

LONDON and NEW YORK

ELSEVIER APPLIED SCIENCE PUBLISHERS LTD

Ripple Road, Barking, Essex, England
Sole Distributor in the USA and Canada
ELSEVIER SCIENCE PUBLISHING CO., INC.
52 Vanderbilt Avenue, New York, NY 10017, USA

First edition
Second edition
Reprinted
Third edition
Fourth edition
Reprinted

1962
1966
1967
1971
1984
1986

British Library Cataloguing in Publication Data

PVC technology. -4th ed.
1. Polyvinyl chloride
I. Titow, W. V.
668.4'236
TP1180.V48

ISBN-13: 978-94-010-8976-0
e-ISBN-13: 978-94-009-5614-8
DOl: 10.1007/978-94-009-5614-8
WITH 171 TABLES AND 230 ILLUSTRATIONS

ELSEVIER APPLIED SCIENCE PUBLISHERS LTD 1984

Softcover reprint of the hardcover 1st edition 1984

Special regulations for readers in the USA

This publicatiQ1l .has been registered with the Copyright Clearance
Center Inc, (G;~c), Salem, Massachusetts. Information can be obtained
from the CCC 'about conditions under which photocopies of parts of this
publiCatio~ may be made in the USA. All other copyright questions,
including photocopying outside of the USA, should be referred to the
publisher.
The selection and presentation of material and the opinions expressed
in this publication are the sole responsibility of the authors concerned
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, photocopying, recording, or otherwise,
without the prior written permission of the publisher.

Preface to the Fourth Edition

This book continues the tradition of the first two editions of the late
W. S. Penn's original PVC Technology, and the extensively revised
third (1971) edition prepared by myself and B. J. Lanham.
In the present edition the original general format, and the arrangement of chapters, have been largely preserved, but virtually nothing
now remains of Penn's own text: a part of the contents is based on
material from the 1971 TitowlLanham version (revised, updated and
mainly rewritten): the rest is new, including, inter alia, several chapters
specially contributed by experts from the plastics industry in the UK
and Europe. The section listing international (ISO) and national (BS,
ASTM and DIN) standards relevant to PVC, which was first introduced (as Appendix 1) in the 1971 edition, proved a popular feature: it
has now been brought up to date and considerably extended. Two
further appendices provide, respectively, comprehensive unit conversion" tables (with additional information on some of the most frequently
encountered units, and the SI units), and a list of many properties of
interest in PVC materials, with definitions, typical numerical values,
and references~to relevant standard test methods.
For various reasons, work on this edition involved more than the
usual quota of problems: I am truly grateful to the Publisher's Managing Editor, Mr G. B. Olley, for his understanding, patience, unfailing
courtesy and friendly encouragement. I am also most appreciative of
the helpful attitude of all other members of the Publisher's staff who
were concerned with the various aspects of processing the manuscript
and bringing the book out.
If my own contribution to the book has any merit, then I would like
to dedicate it-respectfully and affectionately-to all my friends of the
Yarsley Laboratories with whom I was priviledged to share many
happy years, participating in the worthwhile work of a good team.
W.V.T.
v

Acknowledgements

I am much indebted to Messrs W. B. Duncker, F. J. Olivier and D. J.

Sieberhagen of Vynide Ltd for their most helpful comments on the
draft of Chapter 18 and for the trouble they took-individually and
severally-to provide the drawing for Fig. 18.3, data for Table 18.1,
and a few items of information on certain practical aspects of calendering. I am also grateful to Mr J. M. Hofmeyr of Union Carbide for the
information he kindly supplied on the Ucar range of copolymer resins,
and for his permission to use it in Chapter 24.
It is a pleasure to record my thanks to Mr R. Coates of AECII
Chlor-Alkali and Plastics Ltd for a most useful discussion of the scripts
of Chapters 2 and 3, for items of information I have used in Tables 2.5
and 2.6, and for arranging his Company's permission-which I very
much appreciate-to reproduce from their technical literature the
contents of Tables 3.4-3.7.
For the illustrations contained in the Plates my thanks are due to the
companies and/or individuals identified in each caption, who kindly
provided the original photographs.
A small number of graphs and drawings, and one table (Table 14.1),
are straight reproductions from other publications: the copyright holders' and authors' permissions to use these items-which are mentioned in each individual case-are much appreciated.
A few definitions and sets of numerical data have been directly
quoted (with sources clearly identified) from ISO, British and ASTM
Standards. Such material from ISO specifications is reproduced by
permission of the British Standards Institution granted on behalf of the
International Organisation for Standardisation. The extracts from Britvii

viii

Acknowledgements

ish Standards are reproduced by permission of the British Standards

Institution, 2 Park Street, London W1A 2BS, from whom complete
copies of the standards concerned can be obtained. The material from
ASTM Standards is copyright the American Society for Testing and
Materials, 1916 Race Street, Philadelphia, PA 19103, and is reprinted
with permission.
I am particularly grateful to Mrs Rene Chizlett-whose invaluable
secretarial contribution to the previous edition was greatly missed with
the present one-for timely help with last-minute verification of several
items of information on suppliers of commercial PVC materials.
Mrs Connie von Gernet typed most of the manuscript-it is a
pleasure to acknowledge her professional assistance. I am also most
appreciative of Mrs Micky Kruger's secretarial help with two of the
chapters and urgent correspondence.
No aid on the technical side could be more important than the
support and patience of my wife, Margaret Ley-Titow, during the long
period, not lacking in stress, when the book was being put together.
For all she has done she has my truly appreciative thanks.
W.V.T.

Contents

Preface

Acknowledgements

vii

List of Contributing Authors

xxix

Chapter 1
Introduction-W. V. TITOW . . . . . . . . . . . . .
1.1 PVC: General Terminology and Relevant Definitions
1.2 Early History and Development of PVC . . . . .
1.3 General Statistics
1.4 Outline of the PVC Sector of the Plastics Industry
1.5 Vinyl CWoride Polymers and Copolymers . . . .
1.5.1 PVC Homopolymers: chemical structure; morphology
1.5.2 Vinyl CWoride Copolymers . . . . . . .
1.5.3 'External' Modification of PVC by Other Polym-

1
1
4
10
12
13
13
19

1.5.4 Properties of PVC Compositions

1.6 CWorinated Polyvinyl Chloride (CPVC)
1.7 Material and Test Standards
References . . . . . . . . . . . . . . .

21
24
24
29
30

Chapter 2
Commercial PVC Polymers-W. V. TITOW

37

ers

ix

Contents

2.1 Introduction-Production and Main Types

.
2.2 Polymer Characteristics Cardinal to Behaviour in Processing and/or Service Performance
.
2.2.1 Composition
. . . . . . . . . . . . . .
2.2.2 Molecular Weight (Viscosity Number and K
Value)
.
2.2.3 Polymer Particle Characteristics: particle size and
size distribution; particle shape and morphology .
2.2.4 Purity
. . . . . . . . . . . . . . . .
2.3 Characterisation and Designation of Commercial PVC
Polymers
.
2.4 Examples of Basic Properties of Commercial Polymers as
Used for Some Major Applications . .
2.5 Commercial Sources of PVC Polymers
References. . . . . . . . . . . . . . . .
Chapter 3
Commercial PVC Compounds-W. V. TITOW
3.1 Introduction
.
3.2 Commercial Sources of PVC Compounds
3.3 Types and Applications of Commercial PVC Compounds
.
3.4 Properties and Designation of Commercial PVC Compounds
.
3.4.1 Designation
.
3.4.2 Properties Used in Characterisation of PVC Compounds
'
.
3.4.3 Some Typical Properties of Commercial PVC
Compounds
References
Chapter 4
Elementary Principles of PVC Formnlation-W. V. TITOW
4.1 Introduction . . . . . . . . . . . . . . . . . . .
4.2 The Components, and Basic Types, of a PVC Formulation
.
4.3 Formulation Costing-Basic Points . . . . . . . . . .
4.4 Main General Considerations in the Selection of Principal
Formulation Components . . . . . . . . . . . . . .

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85

Contents

4.4.1 Nature and Characteristics of Individual Components of a Formulation: PVC polymer; heat
stabilisers; plasticisers; lubricants; polymeric modifiers; fillers; colourants
4.4.2 Interactions and Mutual Effects of Formulation
Components: compatibility effects; synergism;
other mutual effects
4.4.3 Side Effects of Formulation Components: 'secondary functionality' effects; undesirable sideeffects
4.5 Some Special End-use Requirements
4.5.1 Food-contact Applications
4.5.2 Resistance to Weathering
4.5.3 Electrical Insulation
4.6 Examples of Basic Formulations
4.6.1 Film and Sheeting
4.6.2 Calendered Plasticised Vinyl/Asbestos Flooring
4.6.3
4.6.4
4.6.5
4.6.6
4.6.7
4.6.8
4.6.9

(Tile~

Pipe and Tubing

Cable Covering and Insulation
Gramophone Records
Blow-moulded Bottles
Injection Mouldings
Extruded Profile
Paste Formulations

Chapter 5
Theoretical Aspects of PlasticisatiOD'--D. L. BUSZARD

5.1
5.2
5.3
5.4
5.5
5.6

General Introduction . . . . . . . . .
Definition of Plasticisers and Plasticisation
Chemical Nature of Plasticisers
Theories of Plasticisation
Stages of Plasticiser Interaction with PVC Polymer
Requirements for PVC Plasticisers
5.6.1 Compatibility and Miscibility: the IL value; solubility parameter 8; clear point temperature;
Flory-Huggins interaction parameter x; Ap/Po
ratio; loop or roll compatibility tests; maximum
torque temperature

xi

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109
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111
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113
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xii

Contents

5.6.2 Effectivity of Plasticisers

5.6.3 Permanence of Plasticisers
5.7 General Relationships between the Structure of Plasticisers and their Behaviour in PVC
5.8 Ageing of Plasticised PVC
5.9 Antiplasticisation
References . . . . . . . . .

132
134
136
138
142
143

Chapter 6
Commercial Plasticisers-D. L. BUSZARD
6.1 Introduction . . . . . . . . . . . .
6.2 Classification of Commercially Available Plasticisers
6.3 Group Characteristics of Major Plasticiser Gasses
6.4 Synonyms and Abbreviations
6.5 Group 1 Plasticisers-Phthalates .
6.5.1 Lower Phthalates . . . .
6.5.2 General-purpose Phthalates
6.5.3 Linear Phthalates
6.5.4 Higher Phthalates
6.5.5 Miscellaneous Phthalates
6.6 Group 2 Plasticisers-Phosphates
6.6.1 Triaryl Phosphates . . .
6.6.2 Trialkyl Phosphates
6.6.3 Mixed Alkyl Aryl Phosphates
6.6.4 Halogenated Alkyl Phosphates
6.7 Group 3 Plasticisers-Trimellitates .
6.8 Group 4 Plasticisers-Aliphatic Diesters
6.9 Group 5 Plasticisers-Polymeric Plasticisers
6.10 Group 6 Plasticisers-Miscellaneous Plasticisers
6.10.1 Epoxy Plasticisers
6.10.2 Chlorinated Paraffins
6.10.3 Monoesters . . . .
6.10.4 Glycol Esters
6.10.5 Hydrocarbon Extenders
6.10.6 Other Miscellaneous Plasticisers
6.11 Storage and Handling of Plasticisers
6.12 Plasticiser Manufacturers
References . . . . . . . . . . . . . .

147
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148
152
152
153
153
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158
159
159
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163
163
163
165
170
170
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173
174
174
175
180
180

Conren~

Chapter 7
Properties of Plasticised PVC-D. L. BUSZARD
7.1 Introduction . . . . . . . . . . . . . .
7.2 Formulation of a Plasticised PVC Compound
7.2.1 The 'Desirability Function'
7.2.2 Computer-assisted Formulating
7.3 Softness and Tensile Properties
.....
7.3.1 Effect of Plasticiser
7.3.2 Compounding at Equal Efficiency
7.4 Low-temperature Properties
7.5 Permanence Properties
7.5.1 Extraction Resistance
7.5.2 Migration Resistance
7.5.3 Volatile Loss
7.5.4 Automotive Fogging
7.5.5 High-humidity Compatibility
7.6 Flame-retardant Properties
7.7 Electrical Properties
7.8 Weathering and Light Stability . . .
7.9 Resistance to Microbiological Attack
7.10 Resistance to Insect and Rodent Attack
7.11 Stain Resistance . . . . . . . . . .
7.12 Toxicity and Health Aspects of Plasticisers
7.12.1 Plasticisers for Food-contact Application
7.12.2 Health and Safety
References . . . . . . . . . . . . . . . . . . .
Chapter 8
FiDers in PVC-I. D. HOUNSHAM and W. V. TITOW

8.1 Introduction . . . . . . . . . . . . . . .
8.2 Mineral Fillers . . . . . . . . . . . . . .
8.2.1 Silicates and Silicas: asbestos; talc; clay
8.2.2 Alkaline-earth Metal Sulphates
8.2.3 Calcium Carbonates
8.3 Calcium Carbonate Fillers-Nature, Properties and Applications . . . . . . . . . . . . . . . . . . . . .
8.3.1 General Types: whiting; ground limestone, marble
and calcite; ground dolomite; precipitated calcium
carbonates

xili

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192
195
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xiv

Contents

8.3.2 Surface Treatments: stearate treatments; organotitanate treatments; proprietary and miscellaneous treatments
8.3.3 Filler Properties and Selection Criteria: maximum
particle size; particle size distribution and mean
particle size; colour (dry brightness); refractive
index; oil (or plasticiser) absorption; dispersion
characteristics; cost.
8.3.4 Applications, and Effects of Filler Loading: flooring; plasticised compounds; rigid PVC
8.4 Functional Fillers
8.4.1 Reinforcing Fillers: asbestos (chrysotile) fibres; inorganic microfibres; glass fibres; carbon fibres;
glass spheres; fine-particle calcium carbonate
8.4.2 Flame-retardant and Smoke-suppressant Fillers
8.4.3 Miscellaneous Functional Fillers: carbon black;
metal powders; wood flour; starch; synthetic
silicas
8.5 Some Filler Suppliers and Trade Names
References . . . . . . . . . . . . . . .

225

228
232
240
240
247
248
251
253

Chapter 9

Stabilisers: General Aspeds-W. V. TITOW

9.1 Introduction . . . . . . . .
9.2 Degradation of PVC Polymer
9.2.1 Thermal Degradation
9.2.2 Photochemical Degradation
9.3 Ideal Requirements for a Stabiliser, and General Factors
Affecting Stabiliser Selection
9.4 Heat Stabilisers
9.4.1 Lead Compounds
9.4.2 Organotin Stabilisers: chemical nature and types;
characteristics and applications
9.4.3 Compounds of Other Metals: metal compounds
with stabilising effects in PVC; composite metal
stabilisers
9.4.4 Organic (Miscellaneous) Stabilisers: esters of
aminocrotonic acid; urea derivatives; epoxy compounds; organic phosphites; miscellaneous organic
co-stabilisers

255
255
256
256
260
261
263
265
270
275

286

Conren~

9.5 Antioxidants and UV Absorbers

9.5.1 Antioxidants
9.5.2 UV Absorbers
9.6 Main Modes of Stabiliser Action
9.6.1 Lead Stabilisers . . . .
9.6.2 Organotin Stabilisers . .
9.6.3 Other Metal-based Stabilisers
9.6.4 Organic Stabilisers, Antioxidants, UV Stabilisers
9.7 Some General Features and Common Faults of Stabilised
Compositions . . . . .
9.7.1 Plate-out . . . . . . . . . . . .
9.7.2 Sulphide Staining
9.8 Testing and Evaluation of Stabiliser Effects
9.8.1 Concept of Stability in Processing, Service and
Tests
9.8.2 Heat Stability Testing
9.8.3 Light Stability Testing
9.9 Detection and Analysis of Stabilisers
References . . . . . . . . . . . . . .
Chapter 10
Commercial Stabillser Practice-P. S. COFFIN

10.1
10.2
10.3
10.4

Introduction
Choosing a Commercial Stabiliser . . .
The Importance of a Well-balanced Lubricant System
One-pack Systems and the Physical Form of Stabiliser
Products . . . . . . . . . . . . . . . . . . . . .
10.5 Hygiene and Environmental Considerations . . . . .
10.6 UK Stabiliser Manufacturers-Product Ranges and Applications
10.6.1 Associated Lead Manufacturers Ltd
10.6.2 Ciba-Geigy Ltd . . . . . . . . .
.....
10.6.3 Durham Chemicals Ltd
10.6.4 Diamond Shamrock Polymer Additives Division
10.6.5 Victor Wolf Ltd
References . . . . . . . . . . . . . . . . . . . . . "

xv

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294
299
299
300
302
304
305
305
308
311
311
315
328
330
330
335
335
337
339
340
341
342
342
346
348
351
356
356

Chapter 11
Some MisceUaneous Components of PVC Formulations-W.

V. TITOW . . .
11.1 Lubricants . . . . . . . . . . . . . . . . . . . .

359
359

xvi

Contents

11.1.1 Functions, Nature and Effects

11.1.2 Interaction and Co-action of Lubricants with
Other
PVC
Formulation
Components:
lubricant/stabiliser effects; mutual effects of
lubricants and plasticisers; effects of polymeric
modifiers; effects of fillers and pigments
11.1.3 Assessment of Lubricant Effects
11.1.4 Sources of Information on Lubricants and their
Commercial Suppliers
11.2 Polymeric Modifiers
11.2.1 Processing Aids
11.2.2 Impact Modifiers: impact resistance-its nature,
significance and measurement; the impact resistance of PVC; the nature, effects and applications of polymeric impact modifiers for PVC
11.3 Colourants
11.3.1 General Nature and Functioning
11.3.2 General Classification
11.3.3 Forms in which Colourants are Available
11.3.4 Choice of Colourant-Main Considerations:
general appearance and colour requirements;
processability and stability in processing; stability and permanence in service; health and
safety considerations
11.3.5 Some Commercial Pigments
11.4 Antistatic Agents
11.4.1 Static Electricity Charges on PVC: Phenomena
and Tests
11.4.2 Nature and Use of Antistatic Agents
11.5 Flame and Smoke Retardants
11.5.1 General Mechanism of Burning of Polymers and
Plastics
11.5.2 Flame Retardance and Smoke Suppression in
PVC Compositions
References

359

364
367
370
371
372

375
401
401
403
405

407
410
419
420
422
424
424
427
435

Chapter 12
MisceUaneous Properties of Special Interest in PVC Materials
and Products-W. V. TITOW

12.1 Introduction

439
439

CQnren~

12.2 Low-temperature Properties

12.2.1 Cold Flex Temperature (Clash and Berg)
12.2.2 Cold Bend Temperature
12.2.3 Low Temperature Extensibility of Flexible PVC
Sheet
12.3 Heat Resistance . . . . . . . . . . . .
12.4 Permeability
12.5 Environmental Stress Cracking and Crazing
12.6 Weathering Resistance . . . . . . . . .
12.7 Resistance to Biological Attack . . . . .
12.7.1 Microbiological Attack (Biodegradation)
12.7.2 Insect and Animal Depredations: attack by termites; attack by rodents
12.8 Chemical Resistance . . . . . .
12.9 Health Hazards . . . . . . . .
12.9.1 Vinyl Chloride Monomer
12.9.2 PVC Compounds and their Regular Constituents
12.9.3 PVC Decomposition Products
12.9.4 Peripheral Hazards
12.10 Burning Behaviour
References . . . . . . . . . .

xvli

439
442
442
442
443
452
466
469
483
483
486
487
495
496
498
499
500
501
509

Chapter 13
Industrial Compounding Technology of Rigid and Plasticised

PVC-W. HENSCHEL and P. FRANZ

13.1 Introduction
13.2 Raw Materials. . . . . . . . .
13.2.1 PVC Polymer and Fillers
13.2.2 Plasticisers
13.2.3 Other Additives . . . .
13.3 Upstream Equipment (Silo Storage to Weighing)
13.3.1 Silo Storage of PVC Polymer and Fillers: silo
sizes; materials of silo construction; raw material intake (silo filling); raw material discharge;
dust removal system . . . . . . . . . . . .
13.3.2 Conveying of PVC Polymer and Fillers:
pneumatic conveying . . . . . . . . . . . .
13.3.3 Storage of Plasticisers: tank sizes; suitable con-

513
513
514
514
519
519
519

519
525

xviii

Contents

struction materials; plasticiser delivery; pointers

on pipe laying
13.3.4 Storage of Additives. . . . . . . . . . .
13.3.5 Metering and Weighing: fundamentals of metering and weighing technology; control and
monitoring equipment . . . . . . . .
13.4 Mixing . . . . . . . . . . . . . . . . . . . . . .
13.4.1 Blending of Bulk Materials in Overall Solid
Phase: introduction; theoretical aspects of mixing, with special reference to dry blending of
PVC compositions; mixers for plastics processing; tank-type or intensive mixer . . . . . .
13.4.2 Melt Compounding: compounding and pelletising; compounding of PVC for feeding calenders; extrusion of film, sheet and board; recycling
13.4.3 Preparation of PVC Pastes: silo storage; metering; pasting-up and dispersion; filtering; degassing; ageing; colouring
13.4.4 Machinery: screw-type machines; machine
drives; control and instrumentation; interlocks;
materials of construction; machines for the production of pastes
13.5 Pellet Cooling and Storage . . . . . . . . . . . . .
13.5.1 Pellet Cooling: nature and outline of the operation; pellet cooler systems
13.5.2 Pellet Mixing and Storage: pellet mixer designs;
handling of PVC pellets
Chapter 14
Extrusion of PVC-General Aspeds--B. J. LANHAM and W.
V. TITOW . . . .
14.1 Introduction
14.2 The Extruder . . . . . . . . . . . . . . . . . . .
14.2.1 Main Components and Their Functions, with
Special Reference to Extrusion of PVC: the
screw; the barrel; the head and die assembly;
heating and cooling; the hopper . . . . . . .
14.2.2 Some General Points Relevant to Extrusion of
PVC: machine outputs and energy efficiency in

530
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Contents

modem extrusion practice; some features of,

and aids to, modem extrusion; use of computers; some material aspects; some features and
common faults of extruded products . . . . .
14.3 PVC Material Flow, Homogenisation and Gelation (Fusion) in the Extrusion Process
14.4 Single-screw Extruders . . .
14.5 Twin-screw Extruders . . .
14.6 Some Commercial Machines
14.7 Ancillary Equipment
14.8 Extrusion of Plasticised PVC
14.8.1 Normal (Relatively Slow) Extrusion
14.8.2 High-speed Extrusion
.
14.8.3 Examples of Industrial Extrusion of Plasticised
PVC: PVC coating of wire and cable; production of pPVC hose with braid reinforcement
References
Chapter 15
Injection Moulding of PVC-The late L. W. TURNER
15.1 Introduction
.
15.2 Melt Properties of Particular Significance, Melt Behaviour in Relation to Moulding Conditions, and Moulding Compounds . . . . . . . . . . . . . . . .
15.2.1 Moulding compounds
.
15.3 Effect of Processing Factors upon Product Properties
15.3.1 Quenching Stresses
.
15.3.2 Orientation and Related Features
.
15.4 The Moulding Process: Available Equipment; Process
Control; Some Features of uPVC Moulding
15.4.1 Rate of Injection and Injection Pressure
15.4.2 Working Surfaces
.
15.4.3 Interaction of PVC with Acetal Polymers and
Copolymers
15.5 Materials and Applications
15.6 Trouble-shooting . . . .
15.6.1 Machine Selection
15.6.2 Processing Features Specific to PVC
15.6.3 General Considerations.
References . . . . . . . . . . . . . . . . . .

xix

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710
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713
714
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723
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728
728
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735
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xx

Contents

Chapter 16
Sheet 'Thermoforming and Related Techniques for PVC-The
late L. W. TURNER
16.1 Introduction
16.2 Materials Used . . . . .
16.3 Vacuum Forming of Sheet
16.3.1 Principal Methods: negative forming; plugassisted forming; drape forming; bubble forming; snap-back forming
16.3.2 Details of Methods
....
16.3.3 The Moulds
16.3.4 Finishing . . . . . .
16.4 Matched-mould and Related Methods
16.5 Tolerances in Dimensions and Dimensional Stability of
Formed Parts . . . . . . . . . . . . .
16.6 Equipment Suppliers
16.7 Materials Assessment and Design Aspects
16.7.1 Effect on Quality of Draw Ratio and Temperature . . . . . . . . . . .
16.7.2 Thermoformability of CPVC
References . . . . . . . . . . . . . . .
Chapter 17
Blow Moulding of PVC-W. V. TITOW . . . . . . . . . .
17.1 Basic Features and Historical Development of Blow
Moulding
17.2 Blow-moulding Processes and Their Application to
PVC
17.2.1 General Characterisation and Main Features of
Processes and Systems: main characteristics of
extrusion; injection, and dip blow moulding; the
role and effects of stretching in stretch-blow
moulding; processing and equipment arrangements; cooling methods
17.2.2 Industrial Blow Moulding of PVC: some process
and equipment considerations; extrusion blowmoulding equipment; injection blow-moulding
equipment; dip blow-moulding equipment;
sources of information on blow-moulding

743
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751
753
754
755
756
757
757
759
761
761

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765

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Contents

equipment . . . . . . . .
17.3 PVC Compositions for Blow Moulding
17.3.1 The Processing Aspect . . .
17.3.2 The End-use Aspect . . . .
17.3.3 PVC Bottle Formulations: PVC polymer; stabiliser system; impact modifiers; lubrication; other
additives . .
17.4 PVC Blow Mouldings
17.4.1 Applications
17.4.2 Properties and Tests
References . . . . . . . . . . .

xxi

784
789
789
792
793
795
795
797
800

Chapter 18
Calendering of PVC-W. V. TITOW

18.1 Introduction
18.2 The Calender . . . . . . . .
18.3 The Calendering Operation: General Features and Their
Effects on the Structure and Properties of Calendered
Sheet
18.4 Calender Lines . . . . . . . . . . . . . . . . . .
18.4.1 General-purpose Line: pre-calender (compounding and feed) section; calendering; the
post-calender train
18.4.2 Special Lines and Arrangements: calendered
flooring lines; lamination on or at the calander
18.5 The Formulation Aspect . . . . . . . . . . .
18.6 Some Faults and Defects of Calendered Sheeting
18.6.1 Simple Dimensional Faults
18.6.2 Structural Defects . . . . . . .
18.6.3 Faults Manifested in Appearance
18.7 Further Processing of Calendered Sheet
18.7.1 Press Finishing
18.7.2 Press Lamination
18.7.3 Surface Treatments: printing; coating; embossing . . . . . . . . . . . . . . . . .
18.7.4 Continuous Lamination
18.8 Properties and Applications of Calendered Materials
References . . . . . . . . . . . . . . . . . . . . .

803
803
804
808
809
809
828
830
833
833
834
835
837
837
837
838
839
840
847

xxii

Contents

Chapter 19

Rigid PVC: Main Products-Production, Properties and

Applications-B. J. LANHAM and W. V. TITOW
19.1 Introduction
19.2 Some Material Properties of uPVC
19.3 uPVC Pipes
19.3.1 Types of uPVC Pipe . . .
19.3.2 Production of uPVC Pipe: equipment and process; some formulation aspects . . . .
19.3.3 Pipe Properties and Their Determination
19.3.4 Some Special Pipe Products .
19.4 uPVC Profiles
19.4.1 Main Types and Applications
19.4.2 Production . . . . . . .
19.4.3 Some Formulation Aspects
19.4.4 Testing and Specifications
19.5 uPVC Sheet and Film
19.5.1 Terminology . . . . .
19.5.2 Production . . . . . .
19.5.3 Applications and Properties
19.6 Gramophone Records . . . . .
19.7 Injection-Moulded uPVC Articles
References . . . . . . . . . . . . .

849
849
856
866
867
869
878
879
883
883
884
886
889
890
890
891
893
896
897
898

Chapter 20

PVC Sheet and its Fabrication-W. V. TITOW

20.1 Introduction
20.2 Unsupported PVC Sheet Materials
20.3 Main Fabrication Techniques Applicable to PVC Sheet
Materials and Parts
20.3.1 Welding: hot-gas welding; extrusion welding;
high-frequency welding; heated-tool welding
20.3.2 Bonding: solvent bonding; adhesive bonding
20.3.3 Machining
20.3.4 Conversion and Manipulation of PVC Film and
Sheeting for Packaging . . . . . . . . . . ,
20.3.5 Surface Decoration, Marking, and Other Surface Processing of PVC Materials and Products:
surface decoration; surface marking; surface

901
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904
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910
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930
932

Contents

processing
References
Chapter 21
PVC Pastes: Properties and Formolation-W. V. TITOW
21.1 Introduction
21.2 PVC Pastes: Rheological Properties and Theory . .
....
21.2.1 Viscosity of a Simple Suspension
21.2.2 Main Compositional Factors Influencing the
Apparent Viscosity of PVC Pastes . . . .
21.2.3 Expressions for the Apparent Viscosity of
Pastes . . . . . . . . . . . . . . . . . .
21.2.4 Variation of Paste Viscosity with Rate of Shear,
or with Time at Constant Shear Rate
21.2.5 Gelation and Fusion of PVC Pastes . . . .
21.2.6 The Measurement of Viscosity of PVC Pastes
21.3 Paste Components and Formulation . . . . . . . .
21.3.1 The Polymer: paste polymers; extender polymers
21.3.2 Plasticisers
21.3.3 Stabilisers
21.3.4 Fillers
21.3.5 Thickening Agents (for Thixotropic Plastisols
and Plastigels)
21.3.6 Miscellaneous Paste Components: viscosity depressants; diluents; other minor additives .
21.4 Pastes for Rigid Products: Organosols and Rigisols .
21.4.1 Organosols
21.4.2 Rigisols
References

xxiii

932
936

939
939
940
941
942
943
945
951
960
962
%2
965
969
970
973
975
975
975
976
978

Chapter 22
Preparation, Processing and Applications of Pastes-W. V.

TITOW . . . . . . . .
22.1 Introduction
22.1.1 Preparation . . . . .
22.1.2 Conversion to Products
22.2 Applications
22.2.1 Rotational Casting . .

981
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982
986
986

xxiv

Contents

22.2.2 Slush Moulding

22.2.3 Paste Casting
22.2.4 Dip Coating and Moulding: hot-dip coating;
hot-dip moulding; cold-dip coating
22.2.5 Spray Coating
22.2.6 Coating of Sheet Materials (Fabrics and Paper):
paste coating (spreading) by doctor knife; paste
coating by roller; direct-coating process; transfer (reverse) coating process; promotion of
adhesion between coating and substrate; surface decoration and finishing of PVC paste
coatings; testing of coated materials
22.2.7 Miscellaneous Paste Processing Methods of
Minor Significance: low-pressure injection
moulding; compression moulding; extrusion
References

Chapter 23
PVC Latices-Revised and edited by W. V. TITOW
23.1 Introduction
23.2 Types of PVC Latices
23.2.1 Homopolymer Latices
23.2.2 Unplasticised Copolymer Latices
23.2.3 Plasticised Copolymer Latices .
23.3 Some Properties of Polymeric Products from PVC
Latices
23.3.1 Mechanical Properties
23.3.2 Toxicity Considerations
23.4 Compounding
23.4.1 Latex Property Modifiers: latex stability; wetting agents; thickeners; antifoaming agents; pH
modifiers and buffers
. . . . . . . .
23.4.2 Polymer Property Modifiers: heat stabilisers;
plasticisers; fillers; pigments
23.5 Anti-blocking Techniques
23.6 Applications
23.6.1 Textile Applications: as bonding agents in nonwoven fabrics; for coating or impregnation of
fabrics . . . . . . . . . . . . . . . . . .

988
991
992
996

998
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Contents

xxv

23.6.2 Paper Treatments . .

23.6.3 Leather Finishes
23.6.4 Adhesive Applications
References

1042
1044
1044
1045

Chapter 24

PVC Solutions and their AppUcations--W. V. TITOW

24.1 Introduction
24.2 Components of PVC Solutions
24.2.1 The PVC Polymer: homopolymers; copolymers;
terpolymers
24.2.2 Solvents and Diluents
24.2.3 Other Solution Constituents
24.3 Preparation of PVC Solutions, and Solution Compositions for Particular Applications
24.4 Applications
24.5 Adhesion of Solution-applied Coatings to Substrates
References . . . . . . . . . . . . . . . . . . . . .

1047
1047
1048
1048
1049
1054
1057
1060
1063
1065

Chapter 25

CeUuIar PVC Materials and Products-W. V. TITOW

25.1 Introduction
25.2 Production Methods and Processes
25.2.1 Foams: dispersed-gas blowing: 'chemical' blowing; gas entrainment (mechanical frothing); insitu gas evolution and cross-linking; solvent
(monomer) blowing
25.2.2 Other Cellular PVC Materials: the 'lost filler'
method; sintering of powder
25.3 Formulation and Process Factors in Foam Production
25.3.1 Effects of Formulation and Processing Variables
on Foam Properties . . . . . . . . . . . .
25.3.2 Chemical Blowing Agents-Nature and Operation . . . . . . . . . . . . . . . . . . .
25.4 Some Surface Treatments-Embossing and Lacquer
Coating of Flexible Cellular Sheet Materials
25.4.1 Mechankal Embossing . . . . . . . . .
25.4.2 Chemical Emboss . . . . . . . . . . .
25.4.3 Emboss Effects by Screen Printing of Paste

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1080
1080
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1092
1093
1094

xxvi

Contents

25.4.4 Lacquer Coating

25.5 Examples of Basic Formulations
25.6 Evaluation and Testing
References . . . . . . . . . . . .
Chapter 26
Applications of PVC-W. V. TITOW . . . . . . . . . . .
26.1 Main Applications of Primary PVC Products . . . . .
26.1.1 Pipes and Tubing: rigid (uPVC) pipes; flexible
tubing . . . . . . . . . . . . . . . . . .
26.1.2 Extruded Profiles and Channels . . . . . . .
26.1.3 Unsupported Sheeting and Film: rigid sheet;
flexible sheet; foil and film
. . . .
26.1.4 Foam: rigid foam; flexible foam . . . . .
26.2 Composite Products (Coated, Laminated, or Filled)
26.2.1 Coated Fabrics
26.2.2 Conveyor Belting
26.2.3 Sheet-type PVC Interior Wall-coverings
26.2.4 PVC Coatings and Coverings on Metal Substrates: wire and cable insulation and coverings;
PVC/metal sheet laminates;
26.2.5 Laminates of PVC with Non-metallic Materials:
sandwich panels; PVC/polystyrene sheet laminate; PVC/polyacetallaminated sheeting.
26.2.6 Unsupported PVC Flooring and Floor Tiles
26.3 PVC Fibres and Fibre Products . . . .
26.4 Miscellaneous Products and Applications
26.4.1 Gramophone Records
26.4.2 Blown Bottles and Containers
26.4.3 Footwear . . . . . . . . .
26.4.4 Battery Separators . . . . .
26.4.5 Powder-coated Products and Mouldings Produced by Powder-coating Methods
26.4.6 Medical Applications
26.4.7 Applications in Motor Cars . . . . . . . . .
26.4.8 Tubular-frame Furniture and Related Applications
26.5 Some Special, Unusual, or Minor Products and Applications
References . . . . . . . . . . . . . . . . . . . . . . .

1094
1095
1095
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1103
1104
1104
1106
1107
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1111
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1112
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1115
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1117
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1117
1118
1118
1118
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1122
1125

Contents

xxvii

Appendix 1

Standards Relevant to PVC Materials and Products-Compiled

by N. HERBERT and W. V. TITOW
1. Plastics Terminology, Properties and Testing: General
1.1 Terminology: general; common names and abbreviations; equivalent terms in various languages . . . .
1.2 General Test Conditions and Methods: conditioning
and testing conditions; some general test methods .
2. Vinyl Polymers and Copolymers
. . . . . . . .
2.1 General (Designation, Coding, Characterisation
Tests) . . . . .
2.2 Viscosity
. . . . . . . . . .
2.3 Chlorine Content
. . . . . . . . . .
2.4 Vinyl Acetate Content in VCNA Copolymers
2.5 Ash and/or Sulphated Ash Content .
2.6 Volatile Matter (including Water)
2.7 Impurities and Foreign Matter
2.8 Bulk Density
2.9 Particle Size . . . .
2.10 Bromine Number
2.11 pH of Aqueous Extract
2.12 Miscellaneous Properties Relevant to Processing
2.13 Methanol Extract
2.14 VCM Content
3. Vinyl Compounds
3.1 General (Designation, Coding, Characterisation
Tests): rigid compounds; flexible compounds, pastes;
miscellaneous
3.2 Properties and Tests: bulk density and pourability;
water absorption; temperature effects; mechanical
properties; miscellaneous properties and analysis
4. Plasticisers
4.1 Bulk Properties . . . . . . . . . . . . . . . .
4.2 Properties in Association with PVC (Compatibility,
Volatility, Migration)
4.3 Effects on PVC .
5. PVC Sheeting and Films
5.1 Rigid
5.2 Flexible
5.3 Sheet and Film Fabrication and Products

1127
1131
1131
1134
1135
1135
1136
1137
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1138
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xxviii

Contents

6. PVC Pipes, Tubing, and Pipe Fittings

6.1 Rigid Pipes and Fittings, Including Pressure Pipes
6.2 Flexible Tubing
6.3 Miscellaneous Standards R~evant to Pipes
7. PVC-coated Materials and Products
7.1 Coated Fabrics, including Conveyor and Transmission Belting .
7.2 Other Coated Materials and Products
8. Cellular Vinyls
8.1 Rigid Cellular Materials
8.2 Flexible Cellular Materials
8.3 Miscellaneous Standards: definition and classification; physical properties-general; thermal properties-general; flammability and burning; chemical
resistance and permeability; insulation materials:
cushioning materials, sandwich structures
9. PVC Wire and Cable Insulation, Cable Sheathing and
Jacketing
10. PVC Flooring
11. Various Product Standards and Tests
11.1 Colour Bleeding and Staining
11.2 Miscellaneous

1150
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1157
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1158
1160
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1162

1163
1165
1167
1167
1167
1167

Appendix 2
Quantities and Units: The SI System: Unit Conversion
Tables--Compiled by W. V. TITOW
1169
Appendix 3
Some Material Properties of PVC
Componnds-Compiled by W. V. TITOW
Index 1
General

Products

and
1185

. , . . . . . . . . . . . . . . . . . . . . . . 1199

Index 2
Material and Product Trade Names . . . . . . . . . . . . 1223
Index 3
Named Equipment and Processes . . . . . . . . . . . . .

1231

List of Contributing Authors

W. V. Trrow

Formerly Manager (Special Projects),

Laboratories Ltd, Ashtead, Surrey, England

Yarsley

Research

D. L. BUSZARD
Market Development and Technical Service, Plastics Chemicals,
Ciba-Geigy Industrial Chemicals, Tenax Road, Trafford Park,
Manchester, MI71WT, England

P. S. COFFIN
General Manager-Technical, Roeol Ltd, Rocol House, Swillington, Leeds, LS26 2BS, England
P.

FRANZ

Manager of Process R&D Department, Buss Ltd, CH-4133

Pratteln, Switzerland
W.

HENSCHEL

Manager of the Design and Construction Department, Buss Ltd,

CH-4133 Pratteln, Switzerland

Miss N.

HERBERT

Head, Standards Information Centre, South African Bureau of

Standards, Private Bag X191, Pretoria 0001, Republic of
South Africa
xxix

xxx

List of Contributing Authors

I. D. HOUNSHAM
Sales Manager, PVC Division, Croxton and Garry Ltd, Curtis
Road, Dorking, Surrey, RH4 lXA, England

B. J. LANHAM
European Marketing Manager, LNP Plastics Nederland BV., PO
Box 13, Ottergeerde 24, Raamsdonksveer, The Netherlands
The late L. W. TuRNER
Formerly Senior Research Associate, Yarsley Technical Centre Ltd,
Redhill, Surrey, England

CHAPTER 1

Introduction
W. V.

TITOW

1.1 PVC: GENERAL TERMINOLOGY AND RELEVANT

DEFINITIONS
The letters 'PVC' stand for 'polyvinyl chloride'. Thus the abbreviation,
like the full name, should-strictly speaking-specifically denote a
homopolymer of vinyl chloride. However, both terms-and in
particular the abbreviation-have acquired a different, wider meaning
in common usage: to the processor and user, as well as the
technologist, 'PVC' is any material or product made of a PVC
composition, i.e. of an intimate mixture of a vinyl chloride polymer or
copolymer with various additives, some of which (e.g. plasticisers in a
flexible PVC composition) may be present in very substantial,
occasionally predominant, proportion. It is usual to refer to the
polymer constituent of such compositions as PVC resin or PVC
polymer. The terms 'compound' and 'formulation' are also sometimes
used as if they were synonymous with 'composition', although the
purist may claim, with some justification, that 'formulation' is the
make-up of a composition (e.g. as recorded on paper), and that the
word 'compound' should be reserved for those PVC compositions
which are produced by melt compounding (in contradistinction to, say,
dry blends or plastisols-see Chapters 13 and 21, respectively).
Some of the additives which the formulator includes in a PVC
composition are heat stabilisers, necessary in all cases to counteract the
inherent thermal instability of PVC resins (especially at the high
processing temperatures); others also function as aids in processing
(e.g. certain polymeric modifiers, lubricants), whilst still others (e.g.
1

W. V. Titow

plasticisers, fillers) modify the material properties to provide the wide

applicational versatility that makes PVC so important among the major
thermoplastics. In terms of the extent of their effect on the material
properties of PVC, plasticisers are the most important group of
additives. PVC compositions incorporating plasticisers (and the
materials and products made from such compositions) are known as
plasticised PVC (sometimes abbreviated to pPVC*); flexible PVC and
soft pvc contain plasticisers in quantities high enough to impart these
properties to the material. PVC compositions and products which do
not incorporate plasticisers are commonly called unplasticised PVC
(uPVC*) or sometimes rigid PVC, although the latter term properly
extends also to PVC materials which may contain some plasticisers but
in a proportion not sufficient to lower the modulus appreciably.
Plasticised materials whose plasticiser contents-whilst generally
low-do reduce the modulus (and usually the strength and hardness) in
comparison with uPVC (but only to values still higher than those
normal for flexible or soft PVC) are sometimes referred to as
semi-rigid PVc.
The term 'vinyl' is also used, as an adjective or noun, in the place of
'PVC' (e.g. in such expressions as 'processing of vinyls', 'vinyl
composition', 'vinyl material', 'vinyl upholstery', 'vinyl foam'), especially-and most commonly-where the material concerned is a
flexible or soft PVC. This terminology is quite common, and thus
sanctioned by usage, but it is worth bearing in mind that it tallies
neither with standard definitions in the PVC field nor with systematic
chemical nomenclature. Thus the current international standard
definition of vinyl resin (ISO 472-1979(E is a resin made by
polymerisation of monomers containing the vinyl group, and hence
includes, for example, polystyrene (which is polyvinylbenzene),
polyvinyl acetate, polyvinyl alcohol, polyvinyl fluoride and polyvinyl
pyrrolidone, along with polyvinyl chloride and all the other polymers
of compounds whose main structural component is the vinyl grouping
CH z = CH-. Whilst the definition is sound and properly based on the
relevant chemical structure, no polymer technologist would refer to,
say, expanded polystyrene as 'vinyl foam': in the common parlance of

* These designations (with a space after the first, lower case letter) are
prescribed by two international standards: ISO 2898/1 and ISO 1163/1 (but
current revision proposals include changes from u PVC and p PVC to PVC-U
and PVC-P). The letters iPVC are sometimes used to designate a high-impact
compound.

introduction

the plastics industry the term 'vinyl' is firmly associated with PVC, in
the way just mentioned.
A few other relevant standard definitions may be noted in passing.
Vinyl chloride plastic: 'A plastic based on polymers of vinyl chloride
or copolymers of vinyl chloride with other monomers, the vinyl chloride
being in the greatest amount by mass'. (ISO 472-1979).
Rigid PVC compounds: 'Rigid plastic compounds composed of
poly(vinyl chloride), chlorinated poly(vinyl chloride), or vinyl chloride
copolymers, and the necessary compounding ingredients. The resin
portion of copolymer compounds shall contain at least 80 percent vinyl
chloride. The compounding ingredients may consist of lubricants,
stabilizers, non-poly(vinyl chloride) resin modifiers, and pigments,
essential for processing, property control and colouring.' (ASTM
D 1784-81).
Unplasticised compounds of polymers of vinyl chloride: 'Compounds
based on homopolymers of vinyl chloride, or copolymers with at least
50% of vinyl chloride, or chlorinated poly(vinyl chloride), or mixtures
of such polymers with each other or with other polymers, the principal
ingredient being a polymer of vinyl chloride. These compounds may
also contain fillers, colorants, and such small quantities of other
ingredients as are necessary to facilitate fabrication, such as stabilizers
and lubricants.' (ISO 1163/1-1980(E)).
Non-rigid vinyl chloride polymer and copolymer moulding and
extrusion compounds: Compounds based on '... nonrigid vinyl
chloride polymer and copolymer classes in which the resin portion of
the composition contains at least 90% vinyl chloride. The remaining
10% may include one or more monomers copolymerized with vinyl
chloride or consist of other resins mechanically blended with polyvinyl
chloride or copolymers thereof. These nonrigid vinyl compounds are
defined by a hardness range and include the necessary stabilizers,
plasticizers, fillers, dyes, and pigments to meet the designated
requirements'. (ASTM D 2287-81).
Flexible PVC compounds: 'Compounds ... manufactured from polyvinyl chloride or from a copolymer of vinyl chloride of which the major
constituent is vinyl chloride, or from both. Such materials shall be

W. V. Titow

suitably compounded with plasticisers and other ingredients.' (BS

2571: 1963).
Plasticised compounds of polymers of vinyl chloride* (pPVC):
'Compounds based on homopolymers of vinyl chloride or copolymers
with at least 50% of vinyl chloride, or chlorinated poly(vinyl chloride),
or mixtures of such polymers with each other or with other polymers,
the principal ingredient of the mixtures being a polymer of vinyl
chloride. These compounds contain plasticizers and may also contain
fillers, colorants, and small quantities of other ingredients such as
stabilizers and lubricants'. (ISO 2898/1-1980(E)).

For the sake of convenience, abbreviations (letter symbols) are used

for some polymers and copolymers in many places in this book. Such
abbreviations are generally in line with the recommendations of the
relevant international standard (ISO 1043-1978). However, in a few
cases where those recommendations are at variance with common
general usage, or in order to avoid inconsistency, the ISO standard has
not been followed. Two notable examples are the author's preference
for EVA (over 'EN AC' recommended by the ISO standard) as an
abbreviation for ethylene/vinyl acetate copolymer, and VCNA for
vinyl chloride/vinyl acetate copolymer. The EVA symbol is very widely
used (and indeed also recommended by another English-language
standard-ASTM D 1600-83), whilst-given its use-IVA' for vinyl
acetate is then more consistent than 'VAC' (the abbreviation favoured
by all standards), and should be acceptable especially in contexts
where there is no chance of confusion with vinyl alcohol (which is in
any case usually designated by 'VAL'). It may also be noted that 'A'
for acetate is recognised, though not preferred, by ISO 1043-1978.

1.2 EARLY HISTORY AND DEVELOPMENT OF PVC

Although Regnault l - 3 prepared some vinyl and/or vinylidene monomers in 1838, and observed the conversion of the latter to a white
powder when exposed to sunlight in sealed tubes,2 it is Baumann's
polymerisation of vinyl chloride (as well as bromide) in 18724 that is
often regarded as the earliest documented preparation of PVC
homopolymer: this was certainly among the 'white, solid masses
* NB called simply 'plasticised vinyl compounds' in an earlier version of this
definition (ISO/DIS 2898, International Draft Standard, 1972).

Introduction

unaffected by solvents and acids' obtained in that work. The polymer

was found to be stable on heating up to Boac, but to decompose
rapidly with evolution of acid vapour at higher temperatures. 5 Early
manifestations, or at least precursors, of budding practical interest in
PVC came in 1912, in the form of British and German patents6 to
Ostromislensky (for the production of 'rubber-like masses' from vinyl
halides), and in the work in Germany by F. Klatte considered by some
to have laid the foundation for the technical production of PVC: 3
Klatte took out a German patent for the production of PVC fibres,3
and Ostromislensky went on to obtain patent cover for 'polyvinyl
halides' (in the USA in 1929). 2 In the meantime (c. 1928) patents were
also being granted for vinyl chloride/acetate copolymers; in the USA to
Du Pont and the Carbide and Carbon Chemicals Corporation, and in
Germany to I. G. Farbenindustrie (now BASF).3,7 The first production
of the copolymers in America (by the Carbide and Carbon Chemicals
Corp.) falls in the period 1928-1930: soon after (1931) B. F. Goodrich
introduced their own 'non-rigid vinyl chloride plastics'. 2 In Germany,
1931 saw the first technical-scale production of vinyl chloride polymer
and copolymers, and the first preparation (by Hubert and Schonburg)
of chlorinated PVC fibres (followed by the first technical production of
both the CPVC polymer and the 'Pe-Ce' fibres from it in 19343).
Industrial development (with emphasis eventually shifting from the
vinyl chloride/acetate copolymer to the homopolymer) thereafter
proceeded in both countries, with full commercial production achieved in
the late 1930s. Whilst some development work was taking place in the
UK in the same period, PVC was first produced there on a commercial
scale in 1942-1943 (by ICI and the Distillers Company).
It is thus comparatively recently that PVC became a commercial
plastics material. The early interest in copolymers (in particular
polyvinyl chloride/acetate) was associated with their use as the first
practical solution to the problem of thermal decomposition in
processing: whilst the general thermal stability of the copolymers is
somewhat poorer than that of the homopolymers they can be
processed at significantly lower temperatures, at which they are
reasonably stable. The effects in this respect of the co-monomer units
in the polymer molecules-sometimes referred to as 'internal plasticisation'-are now well understood.
Effective 'external' plasticisation of PVC homopolymer by the
incorporation of plasticisers first came around 1930, with the finding by
several workers5 ,8 that compounding with dibutyl phthalate (DBP) and
certain other esters would convert the intractable polymer to a material

W. V. Titow

of lower softening point; this could be processed satisfactorily at lower

melt temperatures and was-in the solid state at room temperaturerelatively soft and similar to rubber in some respects. Thus,
chronologically, external plasticisation came after 'internal' plasticisation by copolymerisation, although it is now the main route to the
formulation of flexible and most semi-rigid PVC materials. Among
early suggestions of substances for use as plasticisers, now of only
historical interest, were tung oil9 and alkyd resins. 1o It was also realised
at about the same time (the early 19305) that certain additives, e.g.
alkaline-earth metal soaps,11 would act as heat stabilisers. The main
present-day applications in which vinyl chloride/acetate copolymers are
more suitable than plasticised homopolymer compositions are gramophone records and floor coverings. It is interesting to note that the
first of these applications was originally disclosed in the early 1930s,8,12
i.e. around the time when other less practicable and now long defunct
proposals were also current, e.g. moulded PVC dentures,13 and an
adhesive, consisting of a mixture of PVC with rubber and a cellulose
derivative, for sticking patches on worn places in clothing!14
It was World War II that first brought PVC into its own. It was soon
realised that plasticised PVC was an effective replacement for rubber
in some important applications, notably cable insulation and sheathing.
Thus PVC helped to relieve the acute rubber shortage, and at the same
time established itself as a material in its own right. From then on it
continued growing rapidly in importance, to attain the dominant
position which its properties and versatility secure for it today in so
many applications.
The early processing of PVC, in the pre-war period and to some
extent during the war, was largely carried out by methods and on
machinery originally developed for rubber or celluloid. The processes
involved were mixing, calendering, compression moulding, and
extrusion (including wire coating).
The paddle-type (Gardner) pre-mixers were in use at an early
period, but between about 1942 and 1945 open-mill mixing was widely
practised. The use of internal mixers was also adopted when it was
found that PVC compounds could be readily mixed in them. The open
mills and other machines had to be run at temperatures higher than
those appropriate for rubber: as they were normally steam-heated
steam pressures had to be increased at the risk of grease melting
extensively and draining away from bearings. Electrical heating,
particularly for extruders, was a logical development, but one which
proposals were also current, e.g. moulded PVC dentures,13 and an
adhesive, consisting of a mixture of PVC with rubber and a cellulose

1 Introduction

was fully utilised only slowly. The need to modify the rubber extruders
employed for the early production work soon became plain, and
modifications were made, e.g. to enable the material to be fed-in in
granular form, and to provide higher processing temperatures (by
electrical heating). A special ram extruder was employed in Germany
for a time to produce rigid pipe from a PVC billet. 15
Thanks to the work of Kaufman the early history of PVC polymers,
compounds, and processing is well recorded and documented. 15 ,16 The
development of modern PVC-processing equipment and of the many
specialised processes which form such an important part of present-day
PVC technology has paralleled the remarkable expansion of the
production of PVC and the scope and number of its applications.
The 1970s brought two unforeseen events of major significance both
in their initial impact and their lasting effects upon the PVC
industry-the oil crisis of 1973/74 (with its aftermath of continuing oil
price rises), and the finding that vinyl chloride monomer (VCM) is a
carcinogen.
The oil crisis-after first causing a serious temporary shortage of the
oil-derived principal feedstocks for VCM production (ethylene and
acetylene-see also Chapter 2), and hence of PVC polymers (ct. the
drop, c. 1974, of the curves of Fig. 1.1)-resulted in large, and
continuing, increases in polymer prices. These are the outcome of
higher costs of both the feedstocks and the energy (also largely
oil-supplied) used to process them into monomers and thence into
polymers. It may be noted that one of the developments prompted by
this situation has been a refocusing of interest on coal-based raw
materials and processes, with special reference to the acetylene route
to the production of VCM:
HC:=CH + HCI ~ CHr-CHCl

(1)

Albeit normally more energy-intensive than the ethylene route

(generally favoured with oil feedstocks also because of the higher cost
of acetylene from that source) it can be made completely independent
of petrochemicals by producing the acetylene from coke and quicklime
via calcium carbide:
3C + CaO~

Ca~

+ CO

(2)

(coke)

Ca~

+ 2H20~ HC:=CH + Ca(OH)2

(3)

=:

E
c
o

"c;l

"t:

+'

01

g3

tI

CIl

1964

Fig. 1.1

,----I

1972

/',/

/'

,/

1976

"

,...

./

/'

/"

"",.

/.~

1984

__ x

/'/'

/'

---

/'

/'

/'/'

/'

-- -- --

/"

1980

~,.-----Japan

/"

,,'/

/'

,/

Consumption of PVC polymers in the principal consuming areas.

1968

-----

--~/x--'-~

W~st~rn
Europ~

./

./

/'

:0:::::

00

1 Introduction

The chlorine and hydrogen needed for the HCI used in reaction (1) can
be produced by electrolysis of brine (with caustic soda as a saleable
by-product). Some industrial plants manufacturing VCM and PVC
polymer by this process have been in operation for many years (e.g.
the AECI 'Coalplex' plant at Sasolburg, RSA).
The discovery, in the early 1970s, that exposure to VCM could cause
certain forms of cancer, coupled with the realisation that VCM
concentrations in factory atmospheres and its residual contents in PVC
polymers were comparatively high, had repercussions on PVC polymer
production in several countries. It also caused a serious decline
(especially in the USA and Japan) in the use of uPVC films for food
packaging, and blow-moulded bottles for beverages and oils. The legal
action for 285 million dollars brought in the USA against Borden
Chemical and Goodyear Tire and Rubber Co. (two PVC polymer
producers) by some supermarkets, in respect of 'damage to health' by
PVC film used to wrap meat,17 is an example of the extremes of feeling
in some quarters. Soft PVC was comparatively less affected, as the
dilution effect of large amounts of plasticiser and greater loss in
processing reduced the VCM concentration in the compounds to
relatively low proportions. The considerable effort expended on
investigating and remedying the situation, together with relevant
regulations brought out in the major industrial countries, led to a vast
reduction of VCM contents in both the factory air and PVC polymers
produced by virtually all main manufacturers. The 'clean-up' brought
the content levels down to values now regarded as acceptable on the
basis of data obtained in extensive studies. The subject is discussed in
more detail in Chapter 12 (Section 12.9.1), and also mentioned in
Chapters 2 and 7.
A third topic-albeit of comparatively lesser importance in the PVC
context than the oil crisis and the VCM problem-which has been
receiving increasing attention in recent times is the disposal of plastics
waste and re-usable material. Concern with preservation of resources
and conservation of the environment provides the main incentive in
these two related areas. Dealing with PVC waste involves special
considerations. Selective reclamation, i.e. separation from waste
mixtures with other plastics (which operation is not a straightforward
proposition in itself), and subsequent re-processing are complicated by
the wide variety of PVC formulations, and the increased susceptibility
to heat degradation in re-processing: the main factors in the latter are
the 'heat history' already acquired and the possible presence of

10

W. V. Titow

polymer already partly degraded in the course of past heat treatments

and/or service. Re-processing PVC-containing plastics waste without
separation will normally entail dealing with mixtures in which large
proportions of polyolefins (mainly polyethylene) are present: in view of
the poor compatability of polyolefins with PVC this is not a particularly
attractive practical proposition either with respect to processing or the
resulting product.
Disposal of PVC waste also has its special problems, since the
polymer is not biodegradable, whilst incineration produces irritant,
corrosive and toxic products (see Chapter 12, Section 12.9.3).
Claims are made from time to time of successful reclamation of PVC
from mixed plastics scrap and waste (e.g. by the 'Mesco' process
developed in Japan by Mitsui 18) but the scale of commercial recovery
is still relatively small, and the practical limitations of all existing
methods are recognised. 18 ,19 The re-use of material from discarded
PVC bottles is sometimes cited as a case where a certain measure of
success has been achieved. In France such bottles have been processed
for some time (on a limited scale) by Societe Dorlyl, to produce
reclaimed PVC compounds said to be suitable for the production of
certain grades of sewage and drainage pipes, and telephone cable
sheathing. * The use of granulated PVC bottles as road-surfacing
material in the USA has also been reportedt (as indeed has that of
ground glass bottles!).
Normal recirculation, in the same process, of the clean PVC scrap
generated (e.g. edge trim in calendering-see Chapter 18) is widely
practised, in particular with pPVC for non-critical applications.
General pPVC scrap, both own and from external sources, is also
converted by some processors into such products as cheap garden hose
or core composition for cables (see Chapter 13, Section 13.4.2(d.

1.3 GENERAL STATISTICS

Today the amount of PVC produced worldwide represents about 30%
of the total production of thermoplastics: this is second only to the
production of all polyolefins (i.e. low and high density polyethylene
and polypropylene together). The consumption of PVC in the principal
* Eur. Plast. News, (February 1979), 6(2), 3.
t J. Burbidge, Chapter 8, p. 130, of the general source given in Ref. 5.

1 Introduction

11

consuming areas (where most of the production also takes place) is

illustrated in Fig. 1.1. A breakdown, by main use, of PVC
consumption in 1970 and 1976 is given in Table 1.1 for Western
Europe and the USA.
Production and consumption statistics for PVC (as well as other
plastics) are published each year in the January issue of Modern
Plastics International: some relevant information will also be found in
the current issue of the Modern Plastics Encyclopedia. Data,

TABLE 1.1
Consumption of PVC Polymers, by Main Outlet, in Western Europe (Including UK) and the USA in 1970 and 1976
Western Europe
(1000 metric tonnes)

Outlet

1970
Film and sheet (rigid and
flexible)
Calendered
Extruded
Flooring
Calendered
Coated

}
}

430
(21'5%)

1976

}
}

USA
(1000 metric tonnes)

1970

1976

}
}

605
(191%)

259} 341
82 (24,8%)

195
(61%)

113} 147
34 (10'7%)

550
(27'5%)
230
(115%)

785
(24'7%)
335
(10'6%)

215
(15'7%)
186
(13-5%)

682
(31'9%)
150
(7'0%)

Records

40
(2,0%)

78
(2'4%)

64
(4'8%)

68
(32%)

Blow-moulded bottles

110
(5'5%)

235
(7-4%)

32
(23%)

35
(16%)

20
(10%)
235
(11'8%)

82
(2'6%)
505
(159%)

39
(2'8%)
23
(17%)

104
(4'9%)
177
(8'3%)

Misc. coatings (other than

flooring)

134
(6'7%)

265
(8'3%)

187
(13'6%)

190
(8'9%)

Others (including plastisol

products other than
coatings)

72
(3-6%)

90
(2'9%)

138
(10,1%)

283
(13-2%)

2000
(1000%)

3175
(100,0%)

1372
(100'0%)

2139
(100,0%)

uPVC pipe, conduit and

fittings
Wire and cable covering

Misc. injection mouldings

Misc. extruded products
(including rigid profiles
and cladding, flexible
tubing and profiles)

Total

178
(8'9%)

200 305
105 (14,2%)
75
70

145
(6'8%)

12

W. V. Titow

predominantly for the UK and Europe, usually appear in the January

issue of European Plastics News.

1.4 OUTLINE OF THE PVC SECTOR OF THE

PLASTICS INDUSTRY
Companies operating in the PVC sector of the plastics industry
generally fall into one of four main categories, which are as follows:
(i)
(ii)
(iii)
(iv)

polymer producers;
compounders;
processors;
companies selling finished goods consisting of or containing
PVC.

Polymer importers have not been included in this sequence because

they do not normally engage in technical activities. They are however,
with the producers, members of the more general category of polymer
suppliers.
Some companies fall within more than one of the categories listed:
for example, the polymer producers all produce compounds; some also
produce semi-finished goods. It should be appreciated at this early
stage that the number of polymer producers in any country is very
small when compared with the large numbers of companies in the
other categories. Category (iv) above will contain many companies for
which PVC is but a small part of their interests. Nevertheless, such
companies, e.g. the automobile producers, can use very large
quantities of PVC and are very important to the industry.
The principal processes used to convert the PVC to finished and
semi-finished goods are extrusion, calendering, injection moulding and
spread coating. Although some companies are concerned with more
than one of these processes, most tend to specialise in one process. In
some cases the processed PVC is marketed directly by the processor
(e.g. unplasticised PVC pipes), whilst in other areas the processor
passes on the PVC in semi-finished form to another company which
employs the material in its products, e.g. vinyl automobile upholstery.
In addition to the material producers, converters and users, there
are many companies which specialise in the supply of additives for use
in PVC compounds, e.g. plasticisers, stabilisers, lubricants, fillers, etc.
It is relevant to point out that the value of the total market for some of
these materials exceeds that of many other plastics materials.

Introduction

13

Also worthy of mention-since without them there would be no

PVC industry-are the machinery manufacturers. Many companies
have specialised in equipment for PVC processing, and through their
development work on plant and equipment new applications for PVC
have been made possible.

1.5 VINYL CHLORIDE POLYMERS AND COPOLYMERS

1.5.1 PVC Homopolymers

(a) Chemical Structure

The basic repeat unit of the PVC polymer chain is
HI HI ]

-C-C-

h tl

where i is the degree of polymerisation, i.e. the number of repeat units

in the molecular chain. The units are linked virtually exclusively
'head-to-tail', i.e. -CHz-CHCI-CHz-CHCI-.
In commercial PVC polymers the average values of i range between
about 500 and 1500; this corresponds to a theoretical molecular weight
range of about 31000-94000.

Note: In practice a given amount of linear, thermoplastic polymer

(i.e. a test specimen, processing batch, etc.) will consist of
chain molecules made up of the same basic repeat units, but
differing in size (chain length). A single chain (polymer
molecule) consisting of i repeat units is said to have a degree
of polymerisation of i. The molecular weight of such an
individual chain (neglecting any small difference due to end
groups) may be designated M i , and the species may be
referred to as an 'i-mer' or'ith species'. Since, at least in the
ideal case, M i is the sum of the weights of all the repeat units
in the chain, its value will be different for molecular chains
differing in the value of i. The scatter of Mi values (the
molecular weight distribution) in a given amount (i.e. sample,
batch, etc.) of polymer may be wide or narrow but, as the
chains are not all identical, a single molecular weight figure
quoted for the whole amount can only be an average value.

14

W. V. Titow

Depending on the method of determination, this value will in

practice normally be a number-average molecular weight
(M o ) , weight-average molecular weight (Mw ) , or viseosityaverage molecular weight (Mv ).20 For the same batch of
polymer these values are numerically in the sequence
M w > Mv > Mo, with M v usually closer to Mw than to Mo. In
the ideal, theoretical case of all chains being of identical
length (the same value of i) M o = M w
Solution viscosity measurement is comparatively straightforward (especially with polymers soluble in convenient
solvents) and the data it yields can be used to calculate either
M v or-more commonly with PVC in industrial practicesuch related quantities as specific viscosity, * viscosity number, t logarithmic viscosity number or K value (ct. also
Chapter 2, Table 2.1).
The relationships between these various quantities (valid
only when the relevant viscosities are determined under the
same, standard conditions) are as follows:

,*

Specific viscosity (viscosity increment):

(Tf - Tfo)/Tfo

Viscosity number (formerly known as 'reduced viscosity'

or'RV'): (Tf - Tfo)ITfoc
Logarithmic viscosity number II (formerly known as
'inherent viscosity' or 'logarithmic reduced viscosity', Le.
'IV' or 'RV'): [In (TfITfo)]le
where Tf is the viscosity of a dilute polymer solution (or its
time of flow in standard conditions); Tfo is the viscosity of the
solvent alone (or its time of flow in standard conditions); c is
the concentration of the polymer, in g per ml of solution; and
TfITfo is the viscosity ratio (formerly known as 'relative
viscosity').
* Still sometimes determined by the (now superseded) Method B of ASTM D
1243-58T.
t Method of ISO 174-1974.
:j: Method of ASTM D 1243-66 (reapproved 1972).
For PVC normally the Fikentscher K value-ct. DIN 53 726-1983. (see also
Chapter 2, Note in Section 2.2.2, and Table 2.1).
II Not to be confused with the 'limiting viscosity number' (formerly known as
'intrinsic viscosity'): Iimc-+o [(fl- flo)/f/o C] or limc-+o [(In fl/flo)/c).

15

1 Introduction

The Fikentscher K values corresponding to a range of

viscosity ratios of dilute solutions (0005 g ml- 1 ) of PVC
polymer in cyclohexanone at 25C are listed in DIN 537261983.
Most commercial PVC polymers have Fikentscher K values within
the range 50-80, equivalent to about 50000-500 000 M w , and 3000090 000 MD. The relationship is illustrated in Fig. 1.2. Polymers of much
higher molecular weight have also been made. Like those of other
thermoplastics, the properties of PVC polymer are influenced by both
the molecular weight and molecular weight distribution: the ratio
100000

5'8

90000

80000

70000

r{ 60000

5-2

I~

'"

.J

50

5-0+-100000
40000

30000

48

--50000
20000
46

Fig. 1.2 Relationship between the molecular weight (weight-average and

number-average) and the K value of PVC polymers (the Fikentscher K value
determined at 25C on 0005 g ml- 1 polymer solution in cyclohexanone--d.
Chapter 2, Table 2.1 and Note in Section 2.2.2).

w. v.

16

Titow

Mw/M n (known as the 'dispersion of distribution') is a function of the

extent of the latter (i.e. the width of the distribution curve, although it
is not influenced by its shape). The evaluation of the molecular weight
of vinyl chloride homo- and copolymers by gel-permeation chromatography was reviewed recently by Janca and Kolinsky?!
The polymerisation temperature influences the molecular weight,
and hence the dilute-solution viscosity, of PVC polymers (higher
molecular weights obtained at low temperatures). This factor was
examined by Ravey and Waterman 22 for the polymerisation temperature range 0-70C. Intensive heating may be necessary to ensure
complete dissolution of PVC polymers produced at sub-zero temperatures, for solution viscosity measurement and determination of M w by
light scattering and gel-permeation chromatography.23
The structure of PVC polymer molecules deviates in practice from
the theoretical ideal of linear chains of -CHz-CHCl- units
terminating in -CHz-CHzCl and -CHCl-CH3 groups. The main
differences are listed below:
CHAIN BRANCHING

The chains of commercial PVC polymers are branched. Estimates of

the extent of branching, based on determinations by various
techniques,24,25 range from 05 to 20 branches per 1000 carbon atoms,
and include the suggestion that 5 out of every 1000 carbons are
methyl-branched whilst up to 2 per 1000 carry side-chains of more than
5 carbon atoms. Z6 The two most probable structures for a branch
junction are believed to be Z5
~CH2-CHCI-CH-CHa-CH2-CHCl~

and
~CH2-CHCI-CH2-TH-CH2-CHCl~

where the side-chain R is -CHz-CHCI~, or -CH3 .

The presence in PVC polymers of branch junctions involving the

1 Introduction

17

existence of a tertiary chlorine

~CHz-CCl-CHz-eHCI~

I
CHz
I
CHCI

has been the subject of much speculation,25 * as their formation (by

appropriate radical transfer to polymer in the course of polymerisation) is a valid theoretical possibility, whilst-if present-they would
constitute important sites for initiation of thermal or photo degradation
of the polymer (owing to the relative ease with which the tertiary CI
can be split off-see discussion in Chapter 9). However, no direct
evidence of the presence of tertiary CI, or of any functional
relationship between the number of chain branches and thermal
stability, could be found in a number of studies concerned with these
subjects. 25 ,27-30
END-GROUPS

A large variety of end-groups is encountered in commercial PVC

polymers. Some are acquired by reactions, in the course of
polymerisation, with fragments of initiators, emulsifying or suspending
agents, or other 'external' compounds present (to which chain transfer
can occur). Others are formed in terminating reactions (chain transfer
to monomer or polymer, disproportionation, coupling) involving the
monomer and/or any of the species generated during polymerisation.
Examples of the end-groups originating in the former way are
~CH2-0C-C6H5; ~CH2-o-S02-0R; and ~CH20H (where R
is an alkyl radical): those formed in the 'internal' terminating reactions
are ~CHCI-CH=CH2 (an allyl-chloride type of structure in which
the CI atom is activated by the unsaturated linkage at the 3,4-position
relative to it31 ); ~CH CHCI; ~CCl=CH2; ~CH2-CHCI2;
~CHCI-CH2Cl; and ~CHr-CH2Cl.
* cf. also, for example, the discussion by L. I. Nass of the thermal stability of
PVC, in the Encyclopedia of pvc (see General Bibliography section at the end
of this chapter).

18

w.

V. Titow

OTHER STRUCTURAL PEATURES

The results of several studies32 ,33 confirm the presence of double

bonds, distributed randomly in the polymer chain: ordinary PVC
polymers may contain up to 15 such bonds per 1000 carbon atoms. 25
Some evidence has also been obtained of the presence of oxygen: 25
apart from oxygen-containing end-groups (see above) some oxygen
could be incorporated in the chain during polymerisation, or acquired
through oxidation of the polymer; however, the resulting chemical
groupings have not been identified.

(b) Morphology
Commercial PVC polymers may be regarded as essentially
amorphous,34 although crystalline material contents of about 2-10%
have been reported on the basis of determinations by X-ray diffraction
methods, thermal analysis (DTA, DSC, TMA) , and density
measurements. 35-37 The crystallinity is associated with the stereoregular (syndiotactic) polymer fraction. 38-40
The glass transition temperatures (Tg ) of commercial homopolymers
lie in the range 80-84C (as determined by DTA, DSC and TMA).34,35
Annealing above the Tg increases crystallinity and also the crystalline
melting temperature (as given by the endothermic peak on DTA
curves).35,37 The density of the crystalline fraction has been reported as
1530 kg m-3 (1,530 g cm-3) and that of totally amorphous (quenched)
polymer as 1337kgm- 3 (1337gcm- 3).35
As would be expected, annealing below the Tg has no effect on
crystallinity: however it can increase the density-this has been
attributed to a reduction of the free volume in the polymer without
ordering of its fine structure. 35 Apparently the kind of short-range
non-crystalline ('domain') order which can develop in some essentially
glassy, but partly crystallisable polymers (bisphenol-A polycarbonate,
polyethylene terephthalate)41-44 on heating below the Tg , does not
arise in PVc.
Relatively highly crystalline PVC polymers (up to about 45%
crystallinity) with high syndiotactic material content, have also been
prepared (by polymerisation at low temperatures or in certain
solvents).24,36,38,45,46 The preparation of fibres and film from such
polymers has been reported47 as well as that of plasticised compounds
(with about 50 phr DOp).38,47 The melting points of the crystalline
polymers can be as high as 265_273C24 ,46 (cf. commercial PVC
polymer-about 210C in the absence of decomposition). The

introduction

19

above-mentioned plasticised compounds of crystalline PVC had a

higher modulus and hardness, and lower tensile creep at room
temperature than a similar compound of ordinary commercial PVC
polymer (but lower tensile strength and extension at break): below
-25C the modulus and hardness were lower (i.e. the flexibility greater)
than those of the normal PVC.38
Molecular orientation of the PVC polymer, and the associated
structural anisotropy, can be an important factor in the morphology
(and the properties) of PVC products (especially uPVC). Thus in PVC
mouldings the skin-and-core effects (a well-known, common feature
also of other polymer mouldings) can involve, inter alia, a considerable
degree of orientation in the skin. 48 Biaxial orientation of the polymer
in PVC bottles, films and thermoformed articles increases impact
resistance (ct., for example, Chapter 17) and reduces permeability (ct.
Chapter 12, Section 12.4). The tensile strength and retraction on
heating of extruded products is strongly influenced by longitudinal
molecular orientation imparted by stretching in production (ct., for
example, Chapter 12, Section 12.3), whilst the high degree of
orientation produced in PVC fibres by the drawing process in
manufacture is responsible for their very high tensile strength in
comparison with other PVC products (cf. Appendix 3). The fracture
and yield behaviour of PVC polymers and uPVC compositions is
strongly influenced by the extent and nature of molecular orientation.
Useful investigational work in these areas has been reported by several
authors.49.50--52
1.5.2 Vinyl Chloride Copolymers

Some of these are long-established commercial materials. Others,

more recent, have also become of more than academic interest. The
oldest, and still most widely used, are vinyl chloride/vinyl acetate
copolymers (VCNA).
In most of the vinyl chloride copolymers of commercial interest the
co-monomer units are in a minor proportion (and randomly distributed) in the polymer chain, i.e. most are internal, random
copolymers, with the VC units predominating. Copolymers with
vinylidene chloride (VCNDC) are a notable partial exception here, in
that whilst those used in certain PVC compositions (e.g. some
calendering compounds) for ease of heat-processing contain relatively
small amounts of VDC co-monomer, in others (e.g. those for making

20

W. V. Titow

self-supporting, low-permeability films, or barrier layers in composite

films) it is the VC co-monomer which is the minor constituent (usually
10-15%). Another exception is constituted by acrylic and (some)
modacrylic fibres: by definition,53 the former must contain not less
than 85% of acrylonitrile units in the chain (i.e. only up to 15% of a
co-monomer, which may be VC), and the latter between 85% and
35%-although the material of Dynel (Union Carbide), a well-known
modacrylic fibre, was in fact a 60/40 copolymer of vinyl chloride and
acrylonitrile (see also Table 1.2).
Some PVC graft copolymers are also noteworthy, e.g. those with
ethylene/vinyl acetate copolymers (EVA),62,67 polyolefins,62,68 butadiene/acrylic ester copolymers,62 and acrylic ester polymers. Graft
copolymers of the first three kinds were the subjects of early patents
by, respectively, Bayer and Dynamit Nobel, Montecatini, and
Pechiney-Saint-Gobain. 47 VClEVA graft copolymers are used (typically in blends with PVC homopolymer) in uPVC compositions for
outdoor service, notably in window frames, where good weatherability
and impact resistance at low temperature are required;3 VC/acrylate
grafts are also employed for this application (see Chapter 19, Section
19.4.3). Some graft copolymers with sufficiently high polyvinyl chloride
contents (e.g. VC/EVA with 50-70% EVA) can act as plasticisers for
PVC homopolymer, or as processing aids. The graft copolymers are, as
a rule, more expensive than main-chain copolymers.
As has been mentioned in Section 1.2, the chief effects of the
presence of a significant proportion of a co-monomer in the vinyl
chloride polymer chain are normally similar to (but, in general, more
permanent than) those of plasticising a homopolymer with 'external'
plasticisers: the processing temperature is reduced (albeit the heat
stability also decreases) as is the Tg (and hence the softening
temperature and temperature of deflection under load); the hardness
also usually decreases, and the extensibility increases.

Note: A partial exception to the general trend, which is of some

practical significance, may be noted: some copolymers of vinyl
chloride with N-substituted maleinimide derivatives 3,69 have
Tg values and Vicat softening points significantly higher than
those of vinyl chloride homopolymer: ct., e.g., Hostalit LP
HT 5060 (Hoechst)-a copolymer containing 5% of Ncyclohexylmaleinimide. 69
Copolymers are normally more readily soluble than homopolymers
(see Chapter 12, Section 12.8, and Chapter 24): when used as surface

1 Introduction

21

coatings they adhere better to many substrates (the adhesion may be

further improved by the incorporation of a suitable third co-monomer
in the chain-see Chapter 24).
Broadly speaking, the morphology of most copolymers is similar to
that of PVC homopolymer, except that the reduced regularity of the
chain is an extra hindrance to crystallisation. This occurs also in
VDCNC copolymers where VC is the minor component: the chain
structure of PVDC is favourable to crystallisation and the crystallinity
of the homopolymer is normally high;4o.56 the structural regularity and
hence ease of crystallisation is progressively reduced as the VC unit
content of the polymer chain is increased, until at VC contents;?; 30%
the copolymer becomes non-crystalline. It is for this reason that
VDCNC copolymer films for barrier applications contain only about
10-15% VC. This content level represents a reasonable combination of
easement of processing (the highly crystalline PVDC homopolymer
requires high temperatures) and retention of much of the excellent
barrier effect of the homopolymer associated with its crystallinity
(crystalline regions in polymers are normally impenetrable to diffusant
molecules).
1.5.3 'External' Modification of PVC by Other Polymers

PVC polymers can be modified 'externally' by blending with other

polymers or copolymers (including vinyl chloride copolymers-see
Section 1.5.2 above). On the industrial scale this is widely practised in
uPVC compositions, to improve the melt processability, and/or the
toughness (impact resistance at normal and low temperatures) as well
as-in some cases-the resistance to heat distortion, of the finished
product. The polymeric additives incorporated for these purposes are
known as processing aids and impact modifiers: they are discussed in
Chapter 11.
Those of the polymeric additives which are chlorinated (but not vinyl
chloride) polymers-e.g. chlorinated polyethylene (see Chapter 11)as well as copolymers of vinyl chloride (e.g. VCNA, VCNDC, or the
VC graft copolymers mentioned in Section 1.5.2 above) can have
particularly high compatibility with PVC resins: they can sometimes be
blended in such large proportions that the composition becomes a
plasticised PVC (with high permanence of properties, because the
plasticiser is a high polymer-see Chapter 11, Section 11.2). This can
also be done with some chlorine-free polymeric additives, e.g. nitrile
rubbers (see Chapter 11).

Vinyl chloride/ethylene

Vinyl chloride/propylene (VC/P)

Vinyl chloride/acrylorutrile (VClAN)

Vinyl chloride/vinylidene chloride

(VClVDC)

Similar to vinyl chloride/propylene copolymers-S

2. Extruded films (packaging)-S

3. Viscosity-reducing porymer in pastes-S
4. Solution applications (esp. barrier
coatingsr-SL
5. Latex applications (esp. paper and textile
finishing)-E
6. Fibres, e.g. Saran" (National Plastics Products
Co.)
Fibres (vinyl chloride is the comonomer in some
acrylic or modacrylic fibres, e.g. DyneF (Union
Carbide Chemicals Co.)
Extruded films (packaging); injection
mouldings-S

Refs 57 and 58--polymer production, structure and properties;

Ref. 59-polymer composition
and density; Ref. ~ackaging
film
Ref. 61

Commercially available from Air

Products and Chemicals Ltd,
USA (Airco 400 series)
Developed by Union Carbide
Chemicals Co.

Refs 40 and 53

Refs 40 and 47-general nature and

preparation of the copolymers;
Ref. 55-packal;\ing films; Ref.
56-general revIew (with 92
references)

Literature on this copolymer is extensive-see, e.g., relevant titles

in the General Bibliography section at the end of this chapter

Literature/References

Chapter 26

6. Chapter 26

5. Chapter23

2. Chapters 19 and 26
3. Chapters 21 and 22
4. Chapters 12, 24 and 26

4. Mentioned, inter alia, in Refs

53 and 54
1. Chapters 2, 3, and 18

2. Chapters 24 and 26. The copolymers used for these applications sometimes contain a
third co-monomer
3. Chapters 23 and 26

2. Coatings (solution applications)-SL

3. Adhesives, finishing agents (paper and

textiles)-E
4. Fibres, e.g. Vinyon H H (American Viscose
Corp.)
1. U nplasticised calendered sheets; mouldings-S

1. Chapters 2, 3 and 26

1. Unplasticised mouldinss (including gramophone

records) and sheeting (including sheets for thermoforming and PVC ftooring)-S

Vinyl chloride/vinyl
acetate (VCNA)

Relevant chapters/Remarks

Main applications (with indication of the usual

method ofproduction of copolymer for use in
the applicationa)

Copolymer

TABLE 1.2
Vinyl Chloride Copolymers

<t

::;j

:00:::

Surface coatings-E; SL

Vinyl chloride/vinyl
isobutyl ether
Vinyl chloride/acrylic
ester

2. e.g. PliovicAO (Goodyear. }

USA)

3. Chapter 23

Key: S = suspension polymerisation; E = emulsion polymerisation; SL = solution polymerisation,

Also the generic name for vinylidene chloride copolymer fibres containing at least 80% by weight of vinylidene chloride.
C Production suspended in 1975.

Vinyl ChlOride/fumariC} 1. Extruded products; injection mouldings-8

ester
Vinyl chloride/maleic
2. Low-temperature fusion pastes
ester
Vinyl chloride/itaconic
ester

2. Film and bottles (uPVC) with good transparency, heat weldabihty and impact strength-S
3. Adhesives, finishing agents, coatings-E

1. Window-frame compositions-8

Calendered sheet-S

Vinyl chloride/vinyl
cetyl ether

2. Polr.mers and/or compounds

avaIlable from various sources
in the USA and Europe (e.g.
Pantasote Inc., USA-Pantaprene L; Hiils, West Germany-Vestolit HIS 587;
Wacker-Chemie, West Germany--VinnoIVl\;BIP,
UK-Beetle PVC).
Heat after-treatment required for
good adhesion. In melt processing processability and
thermal stability (of both melt
and products) increase with
increasing TFCE content
Available from the Allied
Chemical Co., USA, and
some Japanese sources
Developed by BASF, West Germany
1. e.g. Vinnoll\ (Wacker
Chemie)-Chapter 19

2. Surface coatings; finishing agents (for paper and

textiles)-E

Mainly surface coatings-E

1. Graft copolymers

I. Extrusion (profiles, esp. window frames),

injection moulding-S

Vinyl
chloride/triftuorochloroethylene

Vinyl chloride/EVA

Refs 40, 47, 61

Refs 47,65,66

BASF technical literature

Allied Chemical Trade literature

Ref. 64

Refs 3, 47 and 62-polymer preparation, structure and propertIes;

Refs 3 and 63-applications

v.>

;:s

~.

f2-

;;-

'-

24

w.

V. Titow

Blends have also been prepared of PVC polymer with a copolymer

of vinyl chloride and an unsaturated dimethacrylate compound
(DMA), in which the latter component could be cross-linked (via the
double bonds in the DMA) to provide a PVC material of improved
strength and stability, and better processability when vacuum-formed
as a sheet. 7o A further refinement of this concept (and a PVC alloy
with an unusual structure) is represented by a blend of PVC polymer
with a butadiene/acrylonitrile copolymer in which both components are
cross-linked to form two separate but intimately interpenetrating networks. Depending on the cross-link density the properties of the
material can range from those of a tough elastomer to those of a soft
plastic. 71
Improved ease of processing and higher temperatures of deflection
under load are claimed for blends of PVC with styrene/maleic
anhydride copolymers (d. for example, Bourland and Wambach in
Plastics Engineering, 1983, 39(5), 23-7). Some versions of the blends
are available as commercial injection-moulding compounds (e.g. from
the Arco Chemical Co., USA).
1.5.4 Properties of PVC Compositions
To make their processing possible, and to achieve the required
performance in service, PVC polymers are compounded with various
additives to make up the compositions which are the substance of the
PVC materials and products of industry and commerce. The properties
of these compositions form one of the major topics dealt with in this
book: almost every chapter features one or more of their aspects,
including their durability, their individual and relative importance in
particular contexts and applications, their measurement, the ways in
which they are influenced by formulation and processing, and others.
Many numerical values of properties characteristic of various compositions and products are quoted in Appendix 3, as well as throughout the
text.
1.6 CHLORINATED POLYVINYL CHLORIDE (CPVC)
This is an old-established material, first produced commercially in the
mid-1930s in Germany by chlorination of PVC polymer in solution (in
a chlorinated hydrocarbon solvent-typically tetrachloroethane or

1 Introduction

25

chloroform) at elevated temperatures (50 to about 100C). CPVC

made by this process is more soluble in solvents than the parent PVc.
The early commercial materials-e.g. Igelit PC (I. G. Farbenindustrie)
and Rhenoflex (Dynamit Nobel)-were used in solution-applied
surface coatings and adhesives. CPVC fibres were also spun from
solvent solutions. These applications still continue to some extent.
Around 1960 the dispersion chlorination process came into use. In
the originally patented version of this4o ,47 PVC polymer in aqueous
dispersion is treated with a large excess of chlorine at relatively low
temperatures (up to 60C) in the presence of a swelling agent (a
chlorinated hydrocarbon, e.g. chloroform) under UV light. The early
commercial polymers produced in this way are exemplified by Trovidur
HT (Dynamit Nobel) and Geon HT (Goodrich). Dispersionchlorinated CPVC polymers are less soluble than those produced by
the solution process and their thermal stability is better.
In both processes chlorination takes place mainly at the -CHzgroups of the PVC polymer chain (Le. the 1: 2 chlorinated configuration, -CHCI-CHCI-, is preferentially formed) so that the resulting
chain structure becomes virtually that of a copolymer of vinyl chloride
with 1: 2 dichloroethylene* a) in Fig. 1.3), rather than that of a vinyl
chloride/vinylidene chloride copolymer b) in Fig. 1.3) which would
be given by preferential 1: 1 chlorination. t The large preponderance of
the 1: 2 chlorination is shown by the IR spectra of CPVC. It is also
evidenced by the products of thermal decomposition: those generated
-CHCl-CHCl-CHz-CHCl-CHCl-CHCl-CHCl-CHCl(a) Vinyl chloride/1:2 dichloroethylene copolymer or a chlorinated PVC
-CHz-CClz-CHz-CHCl-CHz-CClz-CHz-CClz(b) Vinyl chloride/vinylidene chloride copolymer
-CHCl-CHCl-CHCl-CHCl-CHCl-CHCl-CHCl-CHCl(c) Homopolymer of 1: 2 dichloroethylene
Fig. 1.3 Simplified representation of polymer segment structures.

* Production by direct polymerisation of the monomers impracticable,

although some brittle, low molecular weight products have been obtained in
attempts to prepare the homopolymer. 40
t In the dispersion process tendency to 1: 1 chlorination can be increased at
high temperatures if the chlorine concentration is allowed to fall. 4o

26

W. V. Titow

by CPVC contain virtually none of the aromatic hydrocarbons

produced by the pyrolysis of both PVC homopolymer (see Chapter 12,
Section 12.9.3) and VCIVDC copolymers. 4o Complete chlorination
would give a polymer very similar to the symmetrical polydichloroethylene* c) in Fig. 1.3); however, the degree of chlorination of
commercial CPVC polymers is considerably lower than this (see Table
1.3). The density and Tg (and hence the Vicat softening point) increase
with the chlorine content.
TABLE 1.3
Some Properties of Commercial CPVC and PVC Polymers, and FuUy Chlorinated PVC
CPVC
polymer
Chlorine content (weight %)
Density (gcm- 3)

Tgeq

Maximum service temperature

(for commercial compounds) eq
Continuous exposurec
Intermittent exposure c

PVC
Fully chlorinated
homopolymer PVC polymer

6567
152-159b
99-123

568
140
80-84

90

65
80

110

732"
170
175

"Theoretical figure for polymer of 1 :2 dichloroethylene.

b Density of commercial compounds: 147-162. This coincides almost exactly with the
range specified for CPVC pipes and fittings in ISO 3514-1976.
C In non-aggressive environments.

Since the same kind of site (the -CH2- group) is preferentially

chlorinated in the chains of CPVC polymers prepared by either
process, and the total chlorine content ranges are essentially the same,
other structural factors must be responsible for the differences in
solubility and thermal stability between the products of the two
processes. The balance of evidence from investigations carried out
since early times47 indicates that these differences are associated with
the way in which the chlorine atoms substituted into the -CH2groups are distributed within the polymer chain: the distribution does
vary according to the method of preparation in a manner suggesting
* Production by direct polymerisation of the monomer impracticable,
although some brittle, low molecular weight products have been obtained in
attempts to prepare the homopolymer. 40

1 Introduction

27

that the variation is due to different accessibility of the polymer chains

to the chlorine in the two processes. Solution chlorination has been
reported47 to result in a uniform, random, 'statistical' distribution of
the chlorine among the -CHz- groups of the molecular chain, such
as would be expected if all the chains (and all segments within an
individual chain) were equally accessible to the reagent. The
chlorination produced by the dispersior process is believed47 to be
hetrogeneous, in two senses: the chlorine contents of different
molecular chains are not the same, and each individual chain contains
irregularly alternating blocks of polyvinyl chloride and 1: 2 dichloroethylene polymer structures. It has also been found 47 that CPVC
produced by the dispersion process from PVC polymer of high
steroregularity (high syndiotactic material content) has a higher Vicat
softening point than one similarly produced from polymer of low
stereoregularity, whilst there is no corresponding difference between
analogous solution-chlorinated materials.
Chlorination of PVC polymers reduces the forces of attraction
between the molecular chains, as evidenced, for example, by the
comparatively greater ease and extent of stretching of CPVC films
above the Tg . 72 The essentially amorphous morphology of CPVC
polymers is probably a factor in this effect, as even the small amount of
crystalline material present in commercial PVC polymers would have a
constraining effect (with the crystallites acting as quasi cross-links) at
temperatures up to the crystalline melting point. In comparison with
uPVC, the effect of stretching (especially biaxial stretching) of CPVC
sheet upon some of its properties (increases in Young's modulus and
yield stress) is greater, although the permeability to COz of CPVC
sheet was found to increase with biaxial orientation, in contrast with
the reverse effect observed with uPVC: 72 as pointed out by the
investigators, the increase in permeability on biaxial stretching is
characteristic of essentially amorphous polymers which do not
crystallise under tension. 72 ,73 However, the increase in the impact
strength of the CPVC sheet, which was also achieved by biaxial
stretching in the above investigation, was claimed to be greater than
that attainable-in the absence of molecular orientation-through
incorporation of impact modifiers.
Commercial CPVC compounds are formulated on the same general
lines as uPVC compounds (see Chapter 4). However their processing is
influenced by the fact that the melt viscosity of the polymer increases
sharply with the chlorine content. 74 The compounds are used mainly

28

W. V. Titow

for the production of pipes and pipe fittings for hot-water installations
(including, increasingly, domestic central heating systems), where the
general similarity of properties to uPVC (including, inter alia,
suitability for jointing by solvent welding) combined with the greatly
increased temperature resistance in service, are particularly advantageous. Other applications include pipes and fittings for potable water
(CPVC is approved for this purpose by several professional and
regulatory bodies 75), pipework and associated products (fittings,
valves, tanks) for chemical plant (the general chemical resistance of
CPVC is comparable with that of uPVC) , extruded profiles, sheets
(including co-extruded CPVClpPVC sheets), some electrical appliances, and constructional applications.
Some examples of commercial CPVC compounds are: the Lucalor
range (Rhone-Poulenc, France), which includes Lucalor RB 1266
specially developed, and recently evaluated, for central heating
systems; the Dekadur compounds (Deutsche Kapillar Plastik, West
Germany) and the CPVC compounds in the Geon range (B. F.
Goodrich, USA). Some of the properties of three Geon compounds
are listed, by way of example, in Table 1.4.
TABLE 1.4
Some Properties of 'Geon' CPVC Compounds

(Based on manufacturer's published data)

Property

Tensile strength (lbf in- 2 )

(ASTMD 1708)
Flexural strength (lbf in- 2)
(ASTMD790)
Flexural modulus (lbf in- 2)
(ASTMD790)
Izod (notched) impact
strength (ft lbf in -1)
Deflection temperature
under load eC): at
264lbf in- 2
(ASTMD648)
Specific gravity
(ASTMD792)

Geon 88933
(high temperature
extrusion and
injection moulding)

Geon 88934
Geon 88935
(extrusion of (profile co-extrusion
pipes and
with pPVC-high
profiles)
ductility compound)

8200

8400

7300

14500

15600

13600

387000

395000

396000

23

20

32

100

102

82

152

157

147

1 Introduction

29

It may be noted in passing that its higher chlorine content reduces

the flammability of CPVC in comparison with uPVC.

1.7 MATERIAL AND TEST STANDARDS

The properties of PVC materials and products, as well as methods of
their characterisation and testing, are the collective subject of a very
large number of standard specifications. Whilst some companies
(particularly polymer manufacturers) and big user organisations (e.g.
government and military procurement departments, motor car manufacturers) operate their own in some cases, the standards of by far the
greatest importance to the PVC technologist and user in the Western
World are those of the following four groups:
(i)

Standards developed by the appropriate technical committees

of the International Organisation for Standardization and
published by that organisation (ISO standards). The ISO
committees dealing with plastics are TC 61: Plastics and TC 138:

Plastic Pipes, Fittings and Valves for the Transport of Fluids.

(ii) Standards of the British Standards Institution (BS standards).
(iii) Standards of the American Society for Testing and Materials
(ASTM standards)
(iv) Standards of the German Institute for Standards (DIN
Deutsches Institut fUr Normung: DIN standards).

Most other countries also issue their own national standard specifications.
Those standards from the four main sources which relate directly to
PVC are listed (by number and title) in Appendix 1. The list is divided
into sections, grouping the standards by subject and also largely
according to their relevance to the chapters dealing with particular
topics in this book. * In addition, many 'plastics' standards not
specifically or primarily directed to PVC, but nevertheless relevant to
particular aspects of PVC materials, products or technology, are
mentioned in the introduction to Appendix 1, in Appendix 3, and in
various appropriate places in the book.
The numerous references to standard specifications throughout this
* For example, Section 4 of Appendix 1 lists standards dealing with various
aspects of plasticisers, and is thus directly relevant to Chapters 5-7.

30

W. V. Titow

book, and the listings in Appendices 1 and 3, contain in almost every

individual case not just the specification number, but also a year of
issue, since this can serve as a useful point of reference. Most of the
years of issue so quoted should be current at the time of going to press,
but it will be appreciated that international and national standards are
being periodically amended and revised, with consecutive issues
appearing under newer dates. Entirely new standards are also being
brought out. The introduction to Appendix 1 provides guidance on
keeping up to date with proposed, new, and revised standards.
The excellent book by Ives et ai. 76 served for a long time as a
valuable source of information on standard tests for plastics (including
PVC). An updated version, produced by an editorial team, is now
available in a new edition. 77

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63. Edser, M. H. and Bulezuik, B. W. (1974). Polym. Paint Col. J., (4th
December), 1051-6.
64. Ulbricht, J. and Rassler, K. (1976). Plaste u. Kaut., 23(7),487-90.
65. Albert, W. (1963). Kunststoffe, 53(2), 86-93.
66. Bohn, L. (1963). Kunststoffe, 53(2), 93-9.
67. Edser, M. H. and Bulezuik, B. W. (1974). Loc. cit., (18th December),
1090-4.
68. Pegoraro, M., Szilagyi, L., Locati, G., Ballabio, A., Severini, F. and
Natta, G. (1968). Chimica e Ind., 50(10), 1075-81.
69. Kiihne, G., Andrascheck, H. J. and Huber, H. (1973). Kunststoffe, 63(3),
139-42.
70. Sasaki, I. and Ide, F. (1975). Polym. Lett., J. Polym. Sci., 13(7), 427-32.
71. Sperling, L. H., Thomas, D. A., Lorenz, J. E. and Nagel, E. J. (1975). J.
Appl. Polym. Sci., 19(8), 2225-33.
72. De Vries, A. J. and Bonnebat, C. (1976). Polym. Engng. Sci., 16(2),
93-100.
73. Hopfenberg, H. B. and Stannett, V. (1973). In The Physics of Glassy
Polymers, (Ed. R N. Haward), Applied Science Publishers, London,
Chapter 9.
74. Arnold, G. H. (1970). Plast. Polym., 38(133),21-6.
75. Anon. (1979). Plast. Technol., 25(9), 31.
76. Ives, G. c., Mead, J. A. and Riley, M. M. (1971). Handbook of Plastics
Test Methods, Iliffe Books, London.

Introduction

33

77. Brown, R. P. (Ed.) (1981) Handbook of Plastics Test Methods. 2nd Edn,
George Godwin Ltd. and the PRI, London.

GENERAL BIBLIOGRAPHY ON PVC

SPE Vinyl Professional Activity Group (1964). A Guide to the Literature and
Patents Concerning Polyvinyl Chloride Technology, SPE, Stamford, Conn.,
USA.
Sarvetnik, H. A. (1969). Polyvinyl Chloride, Van Nostrand, New York.
Canton, M. J. R. (1970). 'Vinyl Polymers (Chloride)', in Kirk-Othmer
Encyclopedia of Chemical Technology, Vol. 21, 2nd Edn, John Wiley, New
York, pp. 369-412.
Dux, J. P. (1971). 'Vinyl Chloride Polymers', in Encyclopedia of Polymer
Science and Technology, Vol. 14, (Eds H. F. Mark and N. G. Gaylord),
Wiley-Interscience, New York, pp. 305-483.
Matthews, G. (1971). Vinyl Chloride and Vinyl Acetate Polymers, Plastics
Institute Monograph, IIiffe Books, London.
Sedlacek, B. (Ed.) (1971). Polyvinyl Chloride: Its Formation and Properties,
Proceedings of IUPAC Symposium, Prague 1970. Butterworths, London.
Sarvetnik, H. A. (Ed.) (1972). Plastisols and Organosols. Van Nostrand, New
York.
Brydson, J. A. (1975). Plastics Materials, 3rd Edn, Newnes-Butterworths
London, Chapter 12.
Yescombe, E. R. (1976). Plastics and Rubber: World Sources of Information,
Applied Science Publishers, London, pp. 151, 177-80,359.
Nass, L. I. (Ed.) (1978). Encyclopedia of PVC, Marcel Dekker, New York.
Burgess, R. H. (Ed.) (1981). Manufacture and Processing of PVC, Applied
Science Publishers, London.
Owen, E. D. (Ed.) (1984). Degradation and Stabilisation of PVC, Elsevier
Applied Science Publishers, London.

..,;; 't

Fig. 1.4(A)

~I

nn:,
11'

I,

wave

',,:;mml,,!T .1: . , I 'I: ;.1 fT:, IHF.!"ill'''

[A]

I'l~

I
!

"

"
.Itla:.

number, em- 1

r~"

Ii, liI::~~ I:HiI,

length, lim

Infra red spectra of commercial PVC resin (Corvic D60/11-ICI Ltd).

illlEtmmnnmuI:H~:

~H ,I",,'

wave

:to

t.

"...
.'1: I

I,

c;;:

:::;j

:<:::

w
-""

Fig. 1.4(B)

It

..

':i

wave

number. cm-'

Ltd.).

Infra red spectra of plasticised PVC (100 parts Corvic D60111, 60 parts DOP-Bisoflex 81-BP Chemicals

[8]

wave length. lim

V1

:::
!:l
Q'
::

Q..

::

CHAPTER 2

Commercial PVC Polymers

W. V. TITaw

2.1 INTRODUCTION-PRODUCTION AND MAIN TYPES

Commercial PVC polymers are the products of polymerisation (in
some cases also copolymerisation) of vinyl chloride (monochloroethene; chloroethylene) CH2=CHCI.
The monomer itself is commonly produced by the two reaction
routes outlined schematically in Fig. 2.1. The ethylene route via
dichloroethane, which is the most widely utilised, is normally operated
in the form of the so-called balanced process. This combines the
chlorination and oxychlorination of ethylene to dichloroethane,
followed by the latter's pyrolytic dehydrochlorination to vinyl chloride.
Ethylene route (Balanced Process)
O/catalyst
/

\.

' " high temperature

CH2 =CH2

02/catalyst + HO

CH2 Cl-CH2 Cl

...,
,,,

I'

pyro YSIS

~ CH2 =CHCl + HC}

,,

~------------------------------------------------~

Acetylene route
CHa:CH + HC}

(excess)

catalyst
So-250"C

~ CH2=CHCl

Fig. 2.1 Main reaction routes in industrial production of vinyl chloride.

37

38

W. V. Titow

Dichloroethane produced by direct catalytic chlorination of ethylene,

in either vapour or liquid phase, is purified and pyrolysed directly to
vinyl chloride, HCI being formed as a by-product. This is re-used in the
process to make more dichloroethane by oxychlorination of some of
the feed ethylene through joint reaction with oxygen (supplied directly,
or as air):
2CHz=CHz + 4HCI + Oz ~ 2CHzCI-CHzCI + 2HzO
The balanced process embodiment of the ethylene route, long
favoured in the USA, has provided the basis of industrial production of
vinyl chloride in most of the major plants set up since the mid-1960s, in
which petroleum-derived ethylene is used. This feed is cheaper than
acetylene; the process affords the greatest economy when run on a
large scale at or near the full capacity of the plant.
The acetylene route, already mentioned in Chapter 1 (Section 1.2),
was of prime industrial importance until the early 1960s, and especially
favoured in Europe. Although in comparison with the ethylene route it
offers the advantages of lower plant cost and effective operation on a
smaller scale, it is more energy-intensive, and acetylene from
petroleum is more expensive than ethylene. However, as acetylene can
also be readily obtained from coal (see Chapter 1, Section 1.2), this
route remains relevant where raw materials can be derived from that
source and-for reasons just mentioned-where relatively small-scale
operation is required.
Vinyl chloride, often designated by the letters VCM (vinyl chloride
monomer), is a colourless gas at room temperature and normal
pressure (boiling point, -139q, with explosive limits of about
4-20% by volume in air,! For industrial processing it is normally kept
as a liquid under pressure. It has anaesthetic properties and an odour
resembling that of chloroethane. Because of its carcinogenic effects
discovered in the 1970s (see Chapter 1, Section 1.2, and Chapter 12,
Section 12.9.1) VCM is regarded as a health hazard and precautions
must be observed in its handling and processing to prevent direct body
contact and to keep the concentration in the factory air within the
permitted maximum limits laid down by the relevant national
authorities. Maximum content values for VCM in PVC polymers are
similarly laid down, as are limits for amounts extractable from PVC
products. These aspects are discussed in Section 12.9.1 of Chapter 12.
The polymerisation techniques used to produce PVC polymers are,
in order of commercial importance, suspension polymerisation (about

2 Commercial PVC Polymers

39

80% of total commercial polymer production), emulsion polymerisation (about 10-15 %), bulk polymerisation, also called mass
polymerisation (about 10%), and solution polymerisation.
The commercial application of the solution process is almost entirely
confined to the manufacture of copolymers for use in surface coatings
(see Chapter 24), centered on one major American producer (Union
Carbide). The amount produced probably represents less than 3% of
the total PVC polymer sold in the USA. Polymerisation is carried out
in a liquid which may either be a solvent for both the monomer(s) and
the polymer, or only for the monomer(s) so that the forming polymer
precipitates out of the system ('precipitation polymerisation'). This can
also happen in initially homogeneous systems above a certain degree of
conversion. Initiators and selected chain-transfer agents are included in
a typical solution polymerisation system. The resulting polymers can be
of high purity, and the method affords good control over molecular
weight.
In a typical suspension polymerisation process a suspension of
monomer dropiets (about 50-150.um) in water is formed by vigorous
agitation in a pressure vessel (autoclave), and the monomer of the
droplets, which contains a monomer-soluble free-radical initiator, is
polymerised at a slightly elevated temperature, under the autogenous
VCM vapour pressure corresponding to the reaction temperature (up
to 15 MPa at 80C). Protective colloids are included in the aqueous
phase to stabilise the suspension throughout, and also buffers to
counteract development of acidity. When 80-90% of the monomer has
been converted to polymer the reaction is stopped by venting-off
excess monomer from the reactor. The resulting slurry of polymer in
water is freed from the remaining monomer by further evaporation,
either in the autoclave itself or in a separate vessel. This process is
known as stripping: to secure effective high degree of removal of
residual VCM, stripping is assisted and completed by steam 'sparging'.
Different variants, both batch-wise and continuous, of this operation
exist, all essentially involving scrubbing the slurry with steam at an
elevated temperature. Continuous, counterflow scrubbing in an
efficient column can reduce the VCM content of the polymer to below
1 ppm. The stripped slurry is centrifuged to remove free water, and the
resulting wet polymer 'cake' is dried by hot air.
Note: In the so-called microsuspension polymerisation the general
composition and physical state of the system are more akin to

40

w. v.

Titow

those characteristic of emulsion polymerisation, in that an

emulsifying agent is used and the size of the monomer
droplets is comparable with that typical for emulsion systems.
Thus, although a monomer-soluble initiator is employed as in
regular suspension polymerisation-and therefore initiation
takes place inside the droplets-the processing is essentially as
in emulsion polymerisation.
The bulk polymerisation system comprises only the monomer and a
free-radical initiator (typically an acyl peroxide or peroxycarbonate).
Polymerisation is carried out under pressure (to keep the VCM liquid)
and normally at 40-70C. The process has two distinct stages: first
polymer grains form in, and separate from, the liquid VCM phase
(unlike some other polymers polyvinyl chloride is insoluble in its
monomer), giving rise to a heterogeneous system. This stage is carried
out under strong agitation to ensure uniformity and correct morphology of the grains. At a relatively low degree of conversion (about
8-12%) much of the VCM liquid is absorbed onto the porous polymer
grains, and the viscosity, initially low in the essentially liquid system,
becomes too high for effective stirring, whereas the grains develop
enough strength to withstand transfer to a second-stage reactor. Here,
the further polymerisation, and growth of the polymer grains, proceeds
to completion in what becomes essentially a solid (powder) phase.
Additional monomer and initiator required for the second stage are
introduced during the transfer. At about 20% conversion the material
has the appearance and consistency of damp powder, and that of a dry
powder (with all the monomer absorbed into the grains) at about 40%
conversion. Agitation, particularly important in the second stage, is
provided by agitators of special design. Polymerisation is terminated at
a predetermined level of conversion (usually about 80%) by ventingoff unreacted VCM. Residual monomer is stripped from the polymer
by de-gassing (in the reactor or a separate vessel) assisted by
introduction of steam or an inert gas to act as carrier. The bulk
polymerisation process was developed and perfected by the French
company Pechiney-Saint Gobain: subsequently in consequence of
mergers and take-overs it became the property of Rhone-Poulenc
Industries, which is now part of the nationalised French chemical
industry conglomerate. 2
In emulsion polymerisation the system consists of the monomer and
water containing emulsifier(s) and a water-soluble initiator. In
batch-wise operation polymerisation is carried out in an autoclave

2 Commercial PVC Polymers

41

designed for operation at the VCM vapour pressure generated at the

reaction temperature (typically 40-60 oq, say up to about 1 MPa. In
the presence of the emulsifier(s), agitation of the charge in the
autoclave disperses the monomer into very fine droplets (down to
about OI,um). The initiator (commonly potassium or ammonium
persulphate alone or with a reducing agent, or a more complex redox
system-e.g. HzOz/FeSO,Jascorbic acid) produces free radicals in the
aqueous phase, where initiation takes place, at the boundary with the
monomer phase. The degree of conversion is normally about 90%, the
reaction being terminated by venting-off excess monomer. The final
stripping of VCM from polymer produced by the emulsion process is
similar in principle to that practised with suspension polymer, although
it can be more difficult in practice: some spraying methods have been
claimed to be particularly effective. 3 Continuous emulsion polymerisation processes are also operated by a few companies (notably in
Germany). Indeed this type of process was among the earliest
industrial PVC resin production processes to be developed.
In principle, subject to suitability of co-monomer reactivities, all the
four types of polymerisation process mentioned may be used for the
production of vinyl chloride copolymers. In the case of bulk
polymerisation it is also necessary that the copolymers should be
insoluble in their monomers. In practice, the most important
commercial copolymer-vinyl chloride/acetate-is normally produced
by suspension polymerisation (which is cheaper and easier than the
emulsion process) for melt processing, and by the solution process
(where it is also sometimes modified by a third comonomer) for
surface-coating applications (see Chapter 24). Of the other copolymers
of commercial significance for melt processing, those with ethylene,
propylene and vinylidene chloride are all made by the suspension
process.
Graft copolymers of VClEVA are also produced for outdoor
applications (e.g. in window-frame profiles-see Chapter 1, Section
1.5.2 and Chapter 19, Section 19.4.3).
2.2 POLYMER CHARACTERISTICS CARDINAL TO
DEHAVIOUR IN PROCESSING AND/OR
SERVICE PERFORMANCE
The features defining the principal differences among PVC polymers
and primarily responsible for their service properties and/or processa-

w. V. Titow

42

bility are:
1. chemical composition (i.e. whether homopolymer or copolymer,
and-in copolymers-the chemical nature and proportion of
comonomer(s) present);
2. molecular weight (average and distribution);
3. particle characteristics (size and size distribution, morphology).
The nature and amounts of extraneous impurities and adventitious
functional groups in the polymer chains are also significant in some
contexts.

2.2.1 Composition

In the commercial sense the most important copolymers of vinyl

chloride are those with vinyl acetate. The incorporation of this
co-monomer into the polymer chains reduces the melt viscosity (and
hence eases melt processing) and improves solubility (a desirable
feature in some solution applications), but the softening point, heat
stability, and toughness are also reduced. For copolymers of
comparable molecular weights these effects increase with increasing
proportion of the vinyl acetate component. This proportion is in the
range of 10-16% in copolymers for both melt and solution processing,
although in solution polymers modified with a third component the
vinyl acetate content may be as low as 2% (cf. Chapter 24, Table 24.1).
Of the three main melt processing outlets for YCNA copolymers
(which are mentioned also in other chapters), flooring (where ease of
melt flow, and ability to accept large amounts of fillers are important)
and gramophone records (again requiring good flow, and faithful
reproduction of moulding surface detail) call for polymer of high vinyl
acetate content (typically about 15%) and low molecular weight (K
value typically about 50). On the other hand for packaging films and
foils, where easy melt flow must be combined with good melt elasticity,
and good mechanical properties are required in the product, a typical
choice would be copolymer of about 60 K value containing about 10%
vinyl acetate.
In commercial copolymers of vinyl chloride with ethylene and
propylene (see Chapter 1, Table 1.2), the presence of the olefin
component affects the melt viscosity in the same way as that of the
vinyl acetate in YCNA copolymers. However, there is comparatively
very little adverse effect on heat stability and strength properties.

2 Commercial PVC Polymers

43

Nevertheless, the use of these copolymers is very limited, mainly

because they are considerably more expensive than VCNA copolymers.
Incorporation of the required proportion of a co-monomer into the
polymer is achieved by adjusting the monomer contents of the reaction
mixture in accordance with the relevant parameters (respective
reactivity ratios, resonance and polarity factors 4 ), and suitably
controlling the polymerisation conditions.
2.2.2 Molecular Weight (Viscosity Number and K Value)
The average molecular weight of a PVC polymer is usually designated
by the 'viscosity number' or the' K value'. Both are calculated from the
results of determination of the viscosity of a dilute solution of the
polymer. Although the methods of determination are all based on the
same principle some differ in certain respects (e.g. solvent used,
solution concentration), and different standards are employed in
different countries despite the existence of international standards
(ISO 174 and ISO 1628-see Appendix 1, Section 2.2).
The values obtained by the methods in widest use are given in Table
2.1, together with certain other molecular weight indices which are
sometimes determined.
Note: Viscosity number (formerly known as 'reduced viscosity') is
given by the expression:

(11 - 11o)/11oC equivalent to

(t - to)/toc

where: 11 = viscosity of the polymer solution; 110 = viscosity of

the pure solvent; t = average flow time of the polymer
solution in specified conditions; to = average flow time of the
pure solvent in the same conditions; and c = solution
concentration (g polymer per ml of solution).
The concept of K value was first introduced by H. Fikentscher* as an
index of the molecular weight of cellulosic polymers: it is dependent on
the nature of the solvent, but little influenced by the concentration (in
dilute solutions) and the temperature of determination.
For PVC the Fikentscher K value is related to the viscosity ratio 11/110
(formerly known as 'relative viscosity') by an expression of the type

* Cellulosechemie, (1932) 13, 58.

'0

~~'-'

042
044
047
049
052
055
057
060
062
065
067
070
073
075
078

:::.: ..... "1

.::1

50
52
54
57
59
61
64
67
70
73
77
80
83
87
90

~~oS
I\,)
I\,)

~V):::E

::

... Q""l

';> ........ ~

""-<l

0lY)
U <".1,-...
::1

" 00
f-..,
0
.~~

Uo":S
V) ::

cs .......

.S~ . . . .

. . . . <;

:: 0\ ."

E""-~
:::t K lY)

I\,)

...

~.?<".1

0155
0165
0175
0185
0195
0206
0217
0228
0239
025
0264
0275
0285
03
031

1216
1227
1237
1247
1258
1269
1280
1292
1304
1316
1329
1342
1355
1369
1383

~~$ ~~ ~

I\,)

.......

"g Oo~~
~ oS '0 ~ ~

I\,) V)

'<:j

;>Q

.::1 ........ ~ ~:S

]-9

8<".1'"

'r;; ~

I\,)

'be:;

f-..,

45
46
47
48
49
50
51
52
53
54
55
56

44

42
43

tl
.....

::.::

;>

~"I
~

47
49
51
52
53
54
55
57
58
59
60
61

::.::c

;>

.2!~
"1-9

I\,)

~~
....... "I

::

I\,)

lY)

... <;

c~

453
462
471
484
493
501
513
524
536
547
561
572
582
595
605

: .:

I\,)

~.'::1
.2!~::
"101\,)
~"ti~

. :: ~
~"Iu

.,,0'"

eo:: '.

~I\,)Q

~"I""""

E:~'"

.... 0

~~

'0

-,-...

""

49
50
51
52
53
54
55
565
575
585
595
605
615
625
635

~~
::.:: 'i:!

I\,)

I\,)
::
"l

.2!..(:)

~I\,)

c ~

;>0.,

::

;>0.,

u":::~

;>

""~
.::1 U

8-9

025
026
027
028
029
031
032
034
035
037
038
040
042
044
045

~~ ~

1\,)~<".1

008
009
010
0105
011
0115
0120
0125
013
014
0145
015
0155
016
017

~ ........ ~

1\,)~lY)

~ E:~ ~E:~

u":::~

;>

::1U'

CS~
U 0

~::

eol\,)

<".1
::
0

--

.-0"1 '-0"1~

001\,)
::
0

."

275
310
350
380
415
450
495
525
560
600
640
680
720
760
800

~{j

1~

:u .....

........

::~
.g~
.g~

...

100000

70000

54000

40000

~~

.~~

~u

~~

;>

:u

I\,)

~~
"I

I\,)

45500

40000

36000

30000

26000

20000

:::t 0

<;E:

E:~

.......

"I ...
"I
I\,) :::t
..(:)u

~ ~

...

~.~

I\,)~

TABLE 2.1
Some Indices of Molecular Weight of PVC Polymers
(Based in part on table compiled by Matthews and Pearson of leI, first reproduced, with permission, in the previous
editionS)

:-:::

.j:o.
.j:o.

080
083
085
088
091
092
095
098
101
103
106
108
111
113
116
118
121
123
126
128
130
133
135
138

032
033
034
036
037
038
039
040
041
043
044
045
046
047
049
050
051
053
054
056
057
058
06
061

1397
1412
1427
1443
1458
1474
1491
1508
1525
1543
1562
1581
160
162
164
1661
1682
1704
1726
1749
1772
1796
1821
1847
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80

62
63
64
65
66
67
68
69
70
705
71
72
73
74
617
629
641
649
661
671
682
692
702
715
724
733
743
749
758
767
775
783
791
799
807
815
822
830

645
66
675
68
69
70
71
72
73
74
75
76
77
78

047
049
051
053
055
057
059
061
063
065
067
069
071
073
075
077
079
081
083
085
087
089
090
093
0175
018
019
0195
020
0205
021
022
0225
023
0235
024
025
0255
026
027
0275
028
029
0295
030
031
0315
032

840
885
930
975
1025
1070
1120
1175
1230
1300
1350
1420
1490
1570
1650
1720
1810
1900
1980
2070
2170
2260
2360
2460
73000

80000
82000

90000
91500

340000

480000

70000

64000

60000

55000

260000

200000

140000

50000

Zl

'"

<:>

(j

~
~

["

'"....

3
3

The correct current term is logarithmic viscosity number (cf. Chapter 1, Section 1.5.1).
This method involves measurement of the viscosity of 02 g/100 ml solution of PVC polymer in cyclohexanone at 30e.
cThis is the viscosity ratio less unity (TJITJo) -1: see Chapter 1, Section 1.5.1, and Section 2.2.2 herein.
d In this method specific viscosity is calculated from the results of determination on a dilute solution of PVC polymer in
nitrobenzene (04g/100 mI). ASTM D 1243-58T and its subsequent (1966) edition have been superseded by ASTM
D 1243-79, the version currently in force. This gives only one method, whereby the viscosity of 02 g/100 ml solution of ...
PVC polymer in cyclohexanone is determined at 30C, and the logarithmic viscosity number calculated from the results. Vl

94
98
102
105
109
113
117
121
125
130
134
138
142
145
149
153
157
161
165
169
173
177
181
185

w.

46

V. Titow

(see DIN 53726):

75

K
+
) _ cK (
In (..,.,1""'0 - 1000 1.5 cK + 1000

1)

The main parameter determining the molecular weight (K value) of

PVC polymer in all the main polymerisation processes is temperature
(in bulk polymerisation the temperature in the second stage).
Increasing the temperature reduces the molecular weight of the
polymer formed. In emulsion and solution polymerisation addition of
chain-transfer agents can also play a part. In some solution systems
chain transfer to the solvent may limit the maximum molecular weight
obtainable in particular conditions.

2.2.3 Polymer Particle Characteristics

(a) Particle Size and Size Distribution
The particle size ranges characteristic for the main polymerisation
processes are indicated in Table 2.2 together with the parameters
which govern the particle size in each process. Further discussions of
polymer particle sizes and structures, and of their role in processing,
will be found in Chapters 14 (Section 14.3) and 21 (Sections 21.2.2 and
21.3.1).
(b) Particle Shape and Morphology
The grains of a typical suspension polymer have a substantial degree of
sphericity. Under sufficient magnification in reflected light they exhibit
the characteristic puckered surface. Viewed in transmitted light
(especially with the grain partly transparentised, e.g. by plasticiser
absorption) a particle is seen to be surrounded by a dense skin
enclosing a porous interior made up of clusters of small primary
particles, of the order of 11-lm in size, and the associated interstitial
voids.
Bulk polymer grains are similar in general overall shape and
uniformity to those of suspension polymer, although they usually have
a characteristic 'flat sided' appearance and a sample will usually
contain some fines. Their internal structure is also closely similar, but
they have no outer skin, so that their internal pores are more directly
accessible.
The particles of emulsion-produced polymer (spray-dried powder)
are somewhat irregular aggregates of highly spherical primary particles

Depend on
particle
size
distribution

Speed of agitation (finer particles at

higher speeds) in conjunction with choice
of suspension stabiliser (protective
colloid)
Agitator tip speed in the first (prepolymeriser) stage-lower mean particle
sizes at higher speeds
Type and concentration of emulsifier (for a
given emulsifier primary particle size
decreases with concentration); addition of
pre-formed 'seed' latex; grain size affected
by drying and grinding operationsb

Process factors controlling or

affecting grain size

b The grains are aggregates of spherical primary particles (typically about 0'1-2 f-lm in size) which are the originarIatex
particles. The aggregate grains are formed during drying. Their size may be modified by any subsequent grinding.

Grains made up of clusters of primary particles (microgranules). Typical microgranule size of the order of about 1 f-lm.

2-70

100-150

80-200

Bulk polymerisation

Emulsion polymerisation

120-160

50-250

Suspension polymerisation

Means

Typical polymer grain size (JDn)

Range

Process

TABLE 2.2
Polymer Grain Sizes Typical of the Main Polymerisation Processes, and the Relevant Process Factors

:ti

'"<::l

;0

l)

""

'"

'"

48

w.

V. Titow

of about 1!J.m size. It may be noted here that commercial polymers

produced by the emulsion process are of two general types. One,
usually called simply 'emulsion polymer' is intended for use in some
calendering and extrusion formulations (where the rapid fusion rate it
offers is beneficial), and in the production of battery separators by
sintering into porous sheets (see Chapter 25, Section 25.2.2). The
other type is commonly referred to as 'paste polymer' since it is used in
PVC pastes. It is important that the particle size and size distribution
of each type should be appropriate to the application. With pastes
these characteristics strongly influence paste rheology (ct. Chapter 21,
Section 21.3.1).
Within the gross, overall morphological characteristics, many
different variants of the fine structure are possible. A good account of
these has been published by Allsopp. 6 It is these variations that make
individual polymer grades suitable for particular formulations and
processing methods.
Among the basic, general morphological features, particle porosity
(amount, distribution and configuration) is of special importance to
ease of processing, including rapidity and extent of absorption of such
additives as plasticisers and lubricants. Indeed plasticiser absorption is
the basis of one of the important standard polymer characterisation
tests (see below). It may be noted in passing that veNA copolymers,
which are not usually employed in plasticised formulations and which
are easier to process than the homopolymers, are normally made with
denser, low-porosity grain structure. In suspension polymerisation
particle porosity is a function mainly of the choice of suspension
stabiliser (protective colloid) and of the polymerisation temperature:
effective protective colloids promote the formation of denser particles
with relatively high packing density; particle density also increases with
polymerisation temperature. In bulk polymerisation particle porosity
decreases with increasing temperature of the first (pre-polymerisation)
stage of the process, and with increasing degree of conversion in the
second stage (which also increases the bulk density).

2.2.4 Purity
Whilst it is not of quite such fundamental universal significance as the
characteristics mentioned in Sections 2.2.1-2.2.3, polymer purity is
important in many applications. In the normal contexts it is a matter of
the absence (or presence in acceptably low amounts) of extraneous

2 Commercial PVC Polymers

49

contaminants, processing residues (e.g. residual protective colloids,

emulsifiers, etc., on the polymer particles), and 'fish-eyes'. * In the
most general sense, the presence of adventitious functional groups in
the polymer chains may also be included under this heading.
External impurities brought by the polymer into PVC compositions
and products can impair the heat and light stability, strength properties
(by acting as stress-concentrating points), appearance (e. g. in clear
products freedom from fish-eyes is essential), and electrical properties
(important, for example, in cable compounds). Adventitious functional
groups in the polymer can also adversely affect heat stability,
weathering resistance, and electrical properties. These aspects are
considered at several places in this book-see, inter alia, Chapter 1,
Section 1.5.1; Chapter 4, Section 4.4.1(a)); Chapter 9, Sections 9.2.1
and 9.2.2; Chapter 11, Section 11.2.2(a)); Chapter 14, Section
14.2.2(e)); and Chapter 18, Section 18.6.3.
2.3

CHARACTERISATION AND DESIGNATION OF

COMMERCIAL PVC POLYMERS

Certain polymer properties are commonly determined, and their values

quoted, for the purposes of characterisation, quality control, and
technical specifications. Designation systems for the various commercial polymer grades normally include code indications of at least some
of these properties, as well as indication of the applicational purpose,
i.e. whether 'general-purpose' resin (for melt processing) or paste
resin. Some principles and systems for the characterisation and
designation of PVC polymers are laid down in certain standard
specifications (see Appendix 1, Section 2.1). The polymer properties
included in the systems of two major standards organisations-ISO
and ASTM-are listed in Table 2.3. A third standard system (that
contained in DIN 7746 and 7747) is in substantial technical agreement
with the ISO specification. Test standards relevant to these systems are
* Specks of hard polymer which persist in the finished product; called fish-eyes
because of their characteristic appearance in transparent compositions. In
opaque ones can show up as surface 'nibs'. For standard definition see Chapter
4, Section 4.4.1(a. Fish-eyes can originate in the course of polymer
production, but they may also be formed in melt processing as a consequence
of non-uniform fusion (which, in plasticised compositions, may be associated
with non-uniformity of plasticiser distribution): too wide a particle size range
of the polymer can be a factor in such non-uniformity.

W. V. Titow

50

TABLE 2.3
PVC Polymer Properties-Standard Characterisation Tests
Test methodsa

Property
ISO

Dilute solution viscosity

Apparent (bulk) densitl

ISO 174 (Viscosity

number)
ISO 60 ~determined in
gcm- )

ASTM

D 1243 (Inherent viscosity)

D 1895 (test also
gives bulk factor
and pourability)

ISO 1068 (determined in

g cm- 3)
Particle size and size distri- ISO 1624 (Sieve analysis of D 1921 (Sieve analywet slurry)
sis: general
bution C
methods standard)

Compacted bulk density

and

Powder mix time

Flowability (dry flow)b
Plasticiser absorption at
room temperature
Hot plasticiser absorption
Chlorine content (virtually
never determined on
commercial polymers)
Porosity

D 1705 (Sieve analysis of wet PVC

powder slurry)
D 2396
ISO 6168 (Time of flow
D 1755 (Time of flow
through standard funnel)
through standard
funnel)
ISO 4608 (phr of DOP
D 1755 (phr ofDOP
sorbed in test condisorbed in test contions)
ditions)
ISO 4574 (phr min- 1 of
DOP sorbed in test conditions)
a
ISO 1158 (determined as
% by weight)
D 2873 ~ determined
in cm g-l by Hg
intrusion)

Volatile matter
pH of aqueous extract

ISO 1269
ISO 1264

Thermal stability
Vinyl acetate contentd (of
copolymers)

ISO/R 182
ISO 1159 (hydrolysis of
the acetate groups, and
back-titration)

D 1755 (determination of electrical

conductivity)
a

Designation requirements for comonomer (vinyl acetate and others)

content stated in
D 1755, but no test
method given.

51

2 Commercial PVC Polymers

TABLE 2.3-contd.

Property

Test methods
ISO

Specific gravity (of copolymers)

Ash and sulphated ash
Preparation of a paste
Apparent viscosity of
a paste
'Fish-eyes'
}
VCMcontent

ASTM
D792

ISO 1270
ISO 4612
ISO 4575 (Severs rheometer)
ISO 2555 (rotating viscometer)
Mentioned in ISO 1060/2
but no ISO methods yet
available

Those shown in this table are the ones specifically listed, respectively, in

ISO 1060/2, and ASTM D 1755 (homopolymers) and D 2474 (copolymers).

The following ASTM methods are available but not covered by the above two
ASTM standards: chlorine content-ASTM D 1303: volatile matter-ASTM
D 3030; heat stability-ASTM D 793 and D 2115.
b Influenced by polymer particle shape, structure and size distribution.
Bulk density and compacted bulk density relate to the production rate in melt
compounding, and in extrusion of rigid products (profile, pipe) from powder
blends (higher rates at high bulk densities). Bulk and compacted bulk densities
of PVC resins were shown by Ravey and Waterman 7 to correlate linearly with
one another, and hyperbolically with the resin specific surface.
Results of dry flow tests in conjunction with those for plasticiser absorption
are particularly significant as a guide to hopper feeding characteristics of
plasticised dry blends (ct. ASTM D 1755-81, Subsection 16.2).
C Jointly with particle structure, particle size and size distribution affect the bulk
density and packing characteristics of polymer powders and powder compounds,
as well as dry flow in tests and in the course of conveying, metering, feeding and
processing. The presence of substantial proportions of fine particles can impair
dry flow and uniformity of absorption of liquid additives (plasticisers, some
stabilisers) in powder blending and processing, and uniformity of fusion in melt
processing. Rheological properties of PVC pastes are strongly influenced by
polymer particle size and size distribution (cf. Chapter 21, Sections 21.2.2,
21.2.4 and 21.3.1).
d Some manufacturers use IR spectrophotometry, involving comparison with
specially prepared reference spectra. A rapid IR method for the analysis of a
number of copolymers of vinyl chloride has been described by Grisenthwaite. 8

W. V. Titow

52

given in Section 2 of Appendix 1. Whilst the standard characterisation

and designation systems are widely recognised, the test schemes and/or
individual tests used by some polymer producers and consumers differ
occasionally from the standards. By way of an example, the properties
normally evaluated by two manufacturers of Corvic PVC polymers are
listed, with an indication of the tests employed, in Table 2.4.
TABLE 2.4
Tests Used for Routine Characterisation of AECI 'Corvic' PVC Polymers
Property and units

Test method

Relevant leI test

Apparent (bulk) density

(g ml- I or g I-I)

ISO 60

ISO 60

Packing density (g I-lor

gml- I)

Own compaction test

Own compaction test

K value

DIN 53 726

Viscosity number determination to ISO 174:

K value calculated
from standard solution
viscosity data
obtained"

Particle size distribution

Coulter counter: results

related, on the basis of
preestablished correlations, to
those obtainable by the
method of ASTM D 1705

Wet sieving on BS mesh

sieves

Particle porosityb (phr

(of plasticiser
absorbed

ISO 4608 (plasticiser absorption

at room temperature)

Volatile content, moisture (%)

Weight loss after 05 h at 135C

for homopolymers; 1 h for
copolymers

Flowability

ISO 6186

Volume resistivity (Q m
or Qcm)

BS 2782: 1970 Method 202A

(on standard plasticised compound incorporating the
polymer)

Heat stability

Heating tests on compounds

made up in accordance with
intended application. Stability
assessed in terms of yellowness index (reflection or
transmission mode)

"Some definitions of standard terms relating to viscosity are given in ISO/R 1628
(currently under revision).
3
b Sometimes also determined (in cm g-I) by the mercury intrusion method of ASTM
D2873.

53

2 Commercial PVC Polymers

The two main standard polymer designation systems (ISO and

ASTMJ are both based on the principle of indicating the selected
polymer characteristics by appropriate code references to groups of
data-ealled 'data blocks' in the ISO system. However, the systems
differ in that the 'blocks' are not identical in coding, arrangement, and
content. Details of the systems are given in ISO 1060/1 (for
homopolymers and copolymers) and ASTM D 1755 (for homopolymers)
and D 2474 (for copolymers).
The following are examples of designation according to the ISO
system, in which the information belonging to a 'block' is separated
from that of the next 'block' by a comma (two commas after the third
'block' if the optional fourth block is also included).
Homopolymer for melt processing:
ISO 1060-PVC-S

G, 121-57

~ill
~

homcpolymer
suspension-produced
general purpose
(i.e. not for paste)
viscosity number - - - - - - - '
bulk density of O' 56 g rnI- 1
Copolymer for melt processing:
ISO 1060-VCNAC

88-S,

G, 080-75,

17

vinyl chloride/acetate
88% vinyl chloride-derived
suspension-produced
general purpose
viscosity number (80)
bulk density 075 grnl- 1 - - - - - - - - - - - - '
particle size limits (by reference
to numbered 'classes'-here classes 1 and 7)
plasticiser absorption by particles
(X indicates that the value is not specifically designated)

Applications

Apparent densiti
(ISO 60) (g 1- )
Mean particle size
(AECI method) (,urn)
Particle porosity
(plasticiser absorption, ISO 4608) (phr)
Volatile content (AECI
method) (%)

K value (DIN 53 726)

Type

Polymer
properties

530-560

470-520
110-160
24-31
<05

550-580

110-160

16-22

<05

<05

17-24

110-160

60-65

Suspension

66-75

Suspension

Suspension

Rigid, calendered
sheeting (for
packaging)

65-68

Flexible tubing
and cable
compounds

Rigid pipe

<02

110-160

650-750

Copolymer
(suspension)
47-51

VelVA
copolymer
(for flooring)

<05

10-50

350-450

Emulsion (paste
grade)
65-80

Paste polymer

TABLE 2.5
Typical Basic Property Value Ranges of 'Corvic' (AECI) PVC Polymer Grades Recommended for Some Major
Applications

Vl

:0::::
::;j

""'"

2 Commercial PVC Polymers

55

2.4 EXAMPLES OF BASIC PROPERTIES OF

COMMERCIAL POLYMERS AS USED FOR
SOME MAJOR APPLICATIONS
In Table 2.5 some typical property values are illustrated by reference
to one commercial polymer range (Corvic-AECI).
Further illustrations will be found in Table 19.2 of Chapter 19, and
also in various formulations cited, and comments made, in other
chapters.
2.5 COMMERCIAL SOURCES OF PVC POLYMERS
Some large manufacturers of PVC polymers produce in more than one
country, or make their technical know-how and backing available
(under licence or other arrangements) to local producers in other
countries. It is also not unusual for one producer to supply bulk
quantities of monomer to another. In some countries, imported
polymers account for a significant proportion of the PVC resin market.
Some major PVC polymer producers are listed in Table 2.6.
In the early 1980s economic factors brought about considerable
reorganisation of the PVC sector of the plastics industry, especially in
the UK and Continental Europe. Some PVC producers of long
standing ceased operations, and many of their product ranges have
been discontinued.
Instances which may be cited by way of example include the
following. In Europe, the take-over by ICI of Lonza, and extensive
nationalisation in the French chemical industry, resulting in the
concentration of PVC polymer production in the hands of two
companies (Elf Aquitaine and Entreprise Miniere et Chimique)
although manufacture continues through subsidiaries which were
formerly independent producers (see Tables 2.6 and 2.7). In the UK,
the number of manufacturers has been reduced from 4 to 2 between
1980 and 1983: the ones currently operating are ICI, who absorbed
PVC polymer production activities of BP Chemicals Ltd (in exchange
for their own polyethylene production operation), and the Norwegian
company Norsk Hydro, who took over Vinatex Ltd, and the PVC
polymer manufacturing operation of British Industrial Plastics Ltd.
Some polymer trade names no longer current (in some cases as a
result of the recent changes just mentioned) will continue to be of

TABLE 2.6

Some Major PVC Polymer Manufacturers

Manufacturer
AECI
Air Products and Chemicals
Inc.
ATO Chimieu
BASF

Country

Trade name

South Africa

Corvic

USA
France
West Germany

B. F. Goodrich
Borden Chemical
Chemische Werke Hiils
Chemopetrol
Chisso Corp.
Conoco Chemicals Co.
Denki Kagaku
Dutch State Mines
Electro Chern.
EVCC
Hoechst
ICI
Kanegafuchi Chemical
Industry
Mitsui Toatsu Chemicals
Inc.
Montedison

USA
USA
West Germany
Czechoslovakia
Japan
USA
Japan
Netherlands
Israel
Holland
West Germany
UK

Airco
Lacqvyl
Vinoflex, Vinidur,
Lutofan
Geon
Borden
Vestolit
Neralit
Nipolit
Conoco
Denkavinyl
Varlan
Epivyl
Various names
Hostalit
Corvic

Japan

Kaneka

Japan
Italy

Norsk Hydro
Produits Chimiques
Ugine Kuhlmann u
Rhone-Poulenc Ind. u
Shell
Shinetsu Chemical Industry
Co.
Shintech Inc.
Singapore Polymer Corp.
Societe Artesienne du
Vinyle b
Solvay et Cie.
Stauffer Chemical Co.
Tenneco Chemicals Co.
Union Carbide Corp.
Wacker Chemie

Norway and UK

Vinychlon
Sicron, Vipla,
Viplavil (copolymer)
Norvinyl

France
France
Netherlands

Ekavyl
Lucovyl
Carina

Japan
USA
Singapore

Shinetsu
Shintech
SPC

France
Belgium
USA
USA
USA
West Germany

Artevyl
Solvic
SCC
Tenneco
Bakelite
Vinnol

Subsidiary of Elf Aquitaine.

Subsidiary of Entreprise Miniere et Chimique.
C European Vinyls Corporation: joint venture between ICI (UK) and Enichem
(Italy).

57

2 Commercial PVC Polymers

TABLE 2.7
Some Commercial Polymer Trade Names, Past and Present
Trade
name

Manufacturer

Beetle
Breon
Dacovin
Ekaryl
Etinox
Exon
FPC
Halvic
Irvinil
Kohinor
Lonzavyl

British Industrial Plastics Ltd

B.P. Chemicals International Ltd
Diamond Shamrock Corp.
Plastimer SA
Aiscondel SA
Firestone Plastics Co.
Firestone Plastics Co.
Halvic AG
Great American Chemical Corp.
Pantasote Co.
Lonza

Marvinol
Mirvyl
Pekevic
Pevikon
Plaskon
Pliovic
Quirvyl
Ravinil
Reynosal
Ricon
Ruco
Scon
Trovipor
Vixir
Vygen

Uniroyal Inc.
Rio Rodano SA
Neste Oy
Kema Nord
Allied Chemical Co.
Goodyear Tire & Rubber Co.
Rumianca SpA
ANIC SpA
Reynolds Chemical Co.
Rico Chemical Corp.
Hooker Chemicals
Vinatex Ltd.
Dynamit Nobel
Societa Italiana Resine SpA
General Tire & Rubber Co.

Country

UK
UK
USA
France
Spain
USA
USA
Austria
USA
USA
Switzerland,
West Germany
USA
Spain
Finland
Sweden
USA
USA
Italy
Italy
USA
USA
USA
UK
West Germany
Italy
USA

interest, either purely historically or as quality technical products

featured in many practical formulations and important studies. For this
reason a number of such names has been included in Table 2.7.

REFERENCES
1. Hardie, D. W. F. (1964). In Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 5, 2nd Edn, John Wiley, New York, pp. 171 ff.
2. Anon. (1982). Plast. Rubb. Wkly, (964), 20th November, p. 1.
3. British Patent 1553829, ICI; US Patent 4158092, Hoechst.

58

W. V. Titow

4. Burgess, R. H. (1982). Manufacture and Processing of pvc. Applied

Science Publishers, London, pp. 84-6.
5. W. V. Titow and B. J. Lanham (Eds), (1971). PVC Technology, 3rd Edn,
Applied Science Publishers, London, pp. 19-22.
6. Allsopp, M. W. (1982). Chapter 7 of Ref. 4 above.
7. Ravey, M. and Waterman, J. A. (1974). J. Appl. Polym. Sci., 18, 2927-33.
8. Grisenthwaite, R. J. (1962). Plastics, 27 (January) 117-9.

CHAPTER 3

Commercial PVC Compounds

W. V.

TITOW

3.1 INTRODUCTION
There are two general ways in which a user of PVC compounds, i.e.
the processor who converts them into products, can acquire the
compositions he needs. He can do his own compounding, or he can
buy compounds from a commercial producer, either as stock lines, or
specially compounded to his requirements. In-house compounding by
the processor has traditionally involved own compound manufacture as
a separate operation: in the case of solid compositions (as distinct from
pastes) this normally includes conventional batch-wise production of
powder pre-mixes and dry blends. Industrial compounding technology
of solid compounds and pastes is discussed in detail in Chapter 13. A
paper by Adams 1 provides a useful summary of the advantages of
in-house compounding of solid PVC compositions. Recently equipment has been coming into use which makes possible continuous
preparation of powder compounds at the extruder, so that such
compounding can, in effect, be integrated into the extrusion line.
Several advantages, both technical and economic, are claimed for this
kind of arrangement, including suitability for small-scale operations
with relatively low outputs2 (see also Chapter 19, Section 19.3).
However, many small and medium-sized extrusion operators who do
not wish to, or cannot, invest in such equipment, as well as other
processors in these size categories, use purchased compounds: this
brings the benefits of the commercial compounder's special equipment
and expertise without own capital and staff commitments. Even large
processors who are equipped to produce their own compounds usually
59

60

W. V. Titow

have short runs on compositions which they find it more economical to

buy-in. They may also occasionally need to supplement their own
internal compound supply for regularly produced large-volume lines.
The use of externally purchased masterbatches is also quite common.
3.2 COMMERCIAL SOURCES OF PVC COMPOUNDS
The producers of commercial PVC compounds fall into two main
groups: polymer manufacturers who also produce compounds (usually
mainly solid, 'general-purpose' compositions, not pastes), and independent compounders. The latter group includes some processors with
spare compounding capacity, who produce compounds to order and for
general sale.
In addition, imported compounds are available in most countries
(normally ones produced by big foreign polymer producers and
marketed by their local subsidiaries or agents).
Many polymer manufacturers are listed in Chapter 2. In almost any
given country the independent compounders are more numerous. By
way of an example, in the UK-where there are now only two polymer
producers (see Chapter 2)-the following independent compounders
are currently operating:
B & T Polymers Ltd;
Crown Decorative Products Ltd;
S. Dugdale, Son & Co. Ltd;
W. R. Grace Ltd;
P. W. Hall Compounding Ltd;
Industrial Polymers (UK) Ltd;
Phoenix Rubber Ltd;
Plascoat Systems;
Polycol (PVC) Ltd;
Soltak Plastics Ltd;
Wollaston Vulcanising Co. Ltd.
If not readily available from other sources, information on
compounders can often be obtained from manufacturers of compounding equipment widely used in industry, e.g. Buss AG (whose UK
associate Buss-Hamilton Ltd produce a useful compounding manual),

3 Commercial PVC Compounds

61

Werner and Pfleiderer, Pappenmeier, and others (see also Chapter 13,
Section 13.4.4).

3.3 TYPES AND APPLICATIONS OF COMMERCIAL

PVC COMPOUNDS
The compounds are available in all the physical forms in which PVC
compositions are processed, viz. powder compounds (dry blends,
powder coating compositions), melt-compounded pellets (both rigid
and plasticised compositions), and pastes (supplied by many independent compounders).
.
Commercial compounds offered for applications where certain
property standards are desirable or obligatory, are normally formulated to meet the relevant standard specifications, national or ISO.
Some typical examples are compositions for electrical cable and wire
coverings, rigid electrical conduit and junction boxes, pipes and pipe
fittings for various applications. Most compounders will also produce
compositions to meet special customer requirements, which may
include suitability for processing on particular equipment, special
processing characteristics, and conformity with stated property specifications.
A general outline of the main available types of commercial PVC
compounds is given in Table 3.1. Tables 3.4-3.7 provide further
illustrations of the types, and the variety of grades available within
each type for various particular purposes and applications. Where
relevant, the variations may include such features (some illustrated in
the tables) as availability in clear or opaque grades (e.g. in the case of
flexible compositions for extrusion and injection moulding; blowmoulding compounds), coloured or natural grades, and-e.g. for
flexible extrusion and moulding compounds (including those for
profiles, electric cable and wire covering, moulded parts)-grades
giving different types of surface finish (glossy or matt).
Extrusion and injection-moulding compounds are available formulated for cellular products (cf., for example, Tables 3.4 and 3.7, and
also Chapters 15, 19 and 25). Other special grades include compositions for applications involving contact with food, beverages (e.g. milk,
beer, fruit squashes) and potable water; and compositions resistant to
chemicals and particular environments (e.g. for hoses resistant to fuels

TABLE 3.1
Commercial PVC Compounds: General Outline of Types
General type

Extrusion compounds

Nature of composition

Rigid

Flexible

Injection-moulding
compounds

Rigid

Flexible

Blow-moulding
compounds

Rigid
Flexible

Masterbatches

Rigid and flexible

Powder coating
compoundsb

Mainly flexible

Pastes

Common applicational types

Pipe (various kinds)

Rainwater goods (down pipe;
guttering)
Electrical conduit
Profiles (including window
frames)
Sheeting
General purpose
Electrical wire and cable
coverings (various kinds)
Covering for:
chain-link fencing wire
clothes lines
Hose
Profiles
Seals and gaskets
General purpose
Pipe fittings
Electrical junction boxes
Industrial mouldings
General purpose
Footwear
Grommets, gaskets, bushes
Toys
General purpose
Bottles, jars, other containers
Sachets (for toiletries, etc.)
Colour
Filler
Wire coating (fencing)
Dishwasher baskets
Weather and wear resistant
(railings, outdoor furniture)
General purpose
Fabric and paper coating
Dip-coating and moulding
Rotational casting and
slush moulding
Casting
Spraying

Various grades available within each type. See also Tables 3.3-3.7, and relevant
information on the processing and applications of PVC compositions in other chapters.
b Primers required for application of the coating compounds to metal surfaces are
normally available from the compound suppliers.

3 Commercial PVC Compounds

63

and oils; wire and cable covering resistant to seawater), to sulphur

staining, to marring by contact with various materials, to high
temperature and weathering. Some examples are given in Tables
3.5-3.7.
Hot-melt compounds (in the UK originally supplied by Vinatex Ltd*
under the trade name Vinamold3 ) are a special kind of composition,
designed for the production of flexible moulds for the casting of
concrete, plaster, castable resins (e.g. polyester), and GRP. The
softening points of such compounds are, typically, within the range
13G-170C. Thus, whilst moulds with cavities faithfully replicating the
prototype of the object to be cast can be conveniently prepared by
pour-coating with the molten compound, the resulting mould, once set
by cooling, can withstand temperatures up to about 80C without
serious distortion.
Commercial PVC compounds are sold under many trade names.
Several polymer manufacturers who also market compounds use the
same name (with different letter and/or number coding) for both types
of product-e.g. Geon, Conoco, Sicron, Hostalit (see Table 2.6 in
Chapter 2). Some, like Conoco and Ethyl (with an appropriate code)
are also simply the manufacturers' names (cf. Conoco Chemicals Co.;
Ethyl Corp.). Many of the compound trade names are quite free from
such connections-e.g. Welvic (ICI, UK and AECI, RSA), Lucalor
(Rhone-Poulenc, France), Polydon (Industrial Polymers (UK) Ltd),
Vyflex (Plascoat Systems, UK).

3.4 PROPERTIES AND DESIGNATION OF

COMMERCIAL PVC COMPOUNDS
3.4.1 Designation

As in the case of PVC polymers, there are standard designation

systems and characterisation tests laid down in ISO, ASTM, and DIN
specifications viz:
for unplasticised compounds: ISO 1163/1 (Designation);
ASTMD 1784;
DIN 7748
* Taken over by Norsk Hydro-see Chapter 2.

64

W. V. Titow

for plasticised compounds:

ISO 2898 Parts 1 and 2;

ASTM D 2287;
DIN 7749 Parts 1 and 2

All these specifications are listed, with dates and titles, in Section
3.1(a) and (b) of Appendix 1 (ISO 1163/1 and 2898/1 are currently
under revision). The DIN designation systems and test are similar to,
but not identical with, the corresponding ISO ones.
The designation systems are based on principles similar to those used
for PVC polymers, as illustrated by the following examples. The
examples also indicate what properties are used for the purposes of
designation.
ISO

DESIGNATIONS

uPVC DE 080 226: unplasticised compound; D = dry blend; E =

general extrusion; 080 = Vicat softening temperature of 80 2C;
2 = 'class 2' Charpy notched impact strength-i.e. 5-20 kJ m- 2 ;
2 = 'class 2' modulus of elasticity in tension-i.e. 2000-2500 MPa;
6 = 'class 6' density-i.e. 135-140 g cm- 3 .
pPVC GM A84 (XX4): plasticised compound; G = pellets (granules); M = injection moulding; A84 = Shore A hardness of 84 3;
X = 'class X' torsional stiffness-i.e. not designated; X = 'class X'
tensile stress at 100% elongation-i.e. not designated; 4 = 'class 4'
density-i.e. 125-130 g cm- 3 .

DIN

DESIGNATION OF AN UNPLASTICISED COMPOUND

DIN 7748-PVC-U, BGT, 074-30-28: U = unplasticised; B = blow

moulding; G = pellets (granules); T = high clarity; 074 = 'code 74'
Vicat softening temperature-i.e. softening temperature 73-75C;
30 = 'code 30' notched impact strength-i.e. over 20 kJ m- 2 ; 28
= 'code 28' modulus of elasticity-Leo 2500-3000 N mm- 2 .

ASTM

DESIGNATION OF A PLASTICISED COMPOUND (ELECTRICAL GRADE)

Type PVC-54 6 1 5 E2 X: 5 = 'cell 5' Durometer A hardness-i.e.

75-84; 4 = 'cell 4' specific gravity-i.e. 130-134; 6 = 'cell 6' tensile
strength-i.e. 172 MPa minimum; 1 = 'cell l' volatile loss at 105C-

Commercial PVC Compounds

65

i.e. 1% maximum; 5 = 'cell 5' brittleness temperature-i.e. -20C

maximum; E2 = 'cell 2' volume resistivity at 50C-i.e. 10 12 ohm em
minimum; X = average extent and time of burning, respectively,
<25 mm and <lOs.
3.4.2

Properties Used in Characterisation of PVC Compounds

The properties widely standardised for characterisation of PVC

compounds are shown in Table 3.2.
Many companies use more, or fewer, tests than those referred to in
the table, and different test methods in some cases, depending on the
nature and intended application of the particular compound. For
example, a basic characterisation scheme may comprise the following
tests:
Property
Apparent (bulk) density
Dry flow
Volatile content

Test methods
e.g. ISO 60
}
Powder blends
e.g. ISO 6186
e.g. as in Table 2.4

Melt flow

rheometry (e.g. the

Macklow-Smith plastometer,'
or that of ASTM D 3364--cf.
Chapter 15, Section 15.2)

Tensile strength and

elongation at break

ISO, BS, ASTM, or DIN

method, as appropriate

Impact resistance

ISO, BS, ASTM, or DIN

method, as appropriate

Density, relative density

or specific volume

ISO, BS, ASTM, or DIN

method, as appropriate

Volume resistivity

ISO, BS, ASTM, or DIN

method, as appropriate

Durometer hardness, or
BS softness

ISO, BS, ASTM, or DIN

method, as appropriate

Powder
blends
or
meltcompounded
pellets

Cable
compounds

A. Macklow-Smith Ltd, Camberley, Surrey, England.

3.4.3

Some Typical Properties of Commercial PVC Compounds

Examples are given in Tables 3.3-3.7, in general terms, and also by

reference to one manufacturer's range of PVC compounds.

Chemical resistance

ISO 178 (MPa)

ISO/R 1183 (g cm -3)

Modulus of elasticity in tension

Density
Tensile strength
Deflection temperature under load
Flammability

*
*
*

ISO 306, Method B eC)

ISO 179 (Charpy, notched)
(kJ m- 2)

ISO [[63/1

ASTM D 638 (MPa or lbf in -2)

ASTM D 648 (OC or OF)
ASTM D 635 (average extent
of burning-mm and average
time of burning-s)
ASTM D 543

ASTM D 256, Method A

(Izod) (J m- 1 of notch
or ft lbf in -1 of notch)
ASTM D 638 (MPa or lbf in- 2 )

*"

ASTMD1784

*
*
*
*

:::1
0DIN 53 457 (N mm- 2 )

~
:<:::

DIN 7748

DIN 53 460 ("C)

DIN 53 453 (Charpy, notched)
(kJ m- 2 )

Test specifications and property units prescribed in:

Vicat softening temperature

Impact strength

Property

TABLE 3.2
Section A: Standard Tests Used in Characterisation of Unplasticised PVC Compounds

ISO 176, Method B(%)

ISO 177 (mg)
ISO 175 (%)

*
*
*

ASTM D 746, Procedure A ("C)

ASTM D 1203, Method A (%)
ASTM D 257 (Q cm)
ASTMD635
(extent of burning-mm;
burning time--s)

*
*

ASTM D 792, Method A (g cm- 3)

ASTMD2240
ASTM D 412 (MPa or Ibf in- 2 )

ASTM D 2287

DIN 7749 Part

*
*
*

*
*
*
*
*

DIN 53 455 (N mm -2)

*
*

DIN 53 479 (g cm- 3 )

DIN 53505

Test specifications and property units prescribed in:

]b

An asterisk indicates determination of this property not prescribed.

Numerous methods listed in DIN 7749 Part 2 (which corresponds to, but does not coincide with, ISO 2898/2), but not all are commonly used
with commercial PVC compounds.

*
*

Plasticiser loss
Plasticiser migration
Resistance to chemicals

ISO 458 ("C)

IEC Publication 93 (Q cm)

Methods under study

ISO/R 1183 (g cm -3)

ISO 868
ISO 527 (MPa)
ISO 527 (%)
ISO 527 (MPa)

ISO 2898/2

Density or specific gravity

Durometer (Shore) hardness
Tensile strength at break
Elongation at break
Tensile stress at 100% elongation
Torsional siffness as a function
of temperature
Brittleness temperature
Volatile loss at 105C
Volume resistivity
Flammability

Property

Section B: Standard Tests Used in Characterisation of Plasticised PVC Compounds

a-

;::
;::

~0

'1;l
~
~

i'"

~
~

v"

Density (g cm- 3 )
Tensile strength (MPa)
Compressive strength (MPa)
Flexural strength (MPa)
Young's modulus (MPa)
Coefficient of linear thermal
expansion (per 0c)
Specific heat
(cal g-l C- 1 )
(kJ kg- 1 C- 1 )
Thermal conductivity
(Wm- 1 C- 1 )
Softening temperature
(BS 2782) (0C)

141
41
59
83
2800

78

76

Highimpact
pipe

about 025
about 1

133
134
38
41
48
66
55
93
76
79
3400
2400
2400
about 5 x 10- 5

144
48

Highimpact
for close
tolerance
extrusion

137
55
66
90
3400

Pressure
pipe
fittings

3400

72

139
41
66

General
purpose

2800

72

134
41
55

Highimpact

Injection moulding compounds

78

79

73

78

77

73

77

14 X 10- 6 14 X 10- 6 13 X 10- 6 18 X 10- 6 14x 10- 6 14 x 10- 6 14 X 10- 6

93
3400

66

138
45

Electrical Easy-flow General

(thin-wall purpose
conduit
and
extrusions)
general
purpose

16 x 10- 6 16 X 10- 6

137
52
66
93
3400

Pressure
pipe

Extrusion compounds

TABLE 3.3
Section A: Properties GeneraUy D1ustrative of Some Commercial Rigid PVC Compounds

;'!;

:::l

0\
00

Rotational casting and slush moulding

Dipping; fabric coating
Spraying or dipping
Flame resistant composition for casting
or spread-coating
Rotational casting, slush moulding,
dipping or spraying (semi-rigid products)

Application type

115
115
119
127
125

10-20
90-150
10-20
350-500
20-40

Phthalate
Phthalate
Phthalate
Phosphate
Adipate

Density at
25C
(gcm- 3 )

Viscosity
at 25C
(P)

Main
plasticiser
type

Paste properties

Shore A hardness
(ASTM D 2240)

42-44
47-49
72-74
56--58
96--98

Cold-bend
temp. (0C)
(BS 2782: 1970)

-55
-55
-35
-25
-25

Product properties

Section B: Examples of Some General Types of PVC Paste Represented Among Commercial Stock Lines

t}

;::
;:,

.g

.:

3
3
'";:::

"'"
~

42

46

21

21

19
40

146
83

149
82

147
79

Glossy
finish

48

19

46

22

147
79

Good melt flow;

glossy surface
finish
142
76

Good mould
filling
characteristics

Pressure pipe
fittings

Rigid microcellular
profiles for
building
applications
Development
grade

*0

General
purpose

RI7IU43

MPR/7JI70

RI71U67

Injection-moulding grades

Asterisk indicates property values strongly dependent on the density of the extruded cellular product.
Property dependent on the processing history of the product: the figures quoted are conservative values.

Relative density at 23C

Softening temperature
(5 kg Vicat-BS 2782) CCC)
Tensile modulus at 1%
strain b (GPa)
Tensile strength at yield b
(MPa)

Easy processing, Satin (matt)

good melt
surface
flow
finish

Characteristics

R8/M936

General purpose profiles

Profiles and
conduit

R8/JI25

Applications

R71J168

Extrusion grades

TABLE 3.4
Section A: 'Welvic (AECI) uPVC Dry Blend and PeDet Compounds for Extrusion and Injection Moulding
(Data reproduced, with permission, from the technical literature of AECI Chlor-Alkali and Plastics Ltd)

::;j

:0:::

Cl

--_._----~

115
45
6 x 10- 5
14 X 10- 4
5 x 10 14
1 x 1012

C- 1
J m m- 2 S-l C- 1
Qcm
Q

BS 4618
AECI
BS2782
BS2782

Typical value

Rockwell R scale

Hardness
Limiting oxygen index
Coefficient of linear
thermal expansion
Thermal conductivity at 23C
Volume resistivity
Surface resistivity

Units

ASTM D 785
ASTM D 2863

Test method

Property

Section B: Some Representative Values of Other Properties of 'Welvic' (AECI) uPVC

-..l

!}

;:s

l::

~C

r3

"l:I

.,'"
".:

;?!
;?!

""
~

W. V. Titow

72

TABLE 3.5
'Welvic' (AECI) PVC Compoonds for Electric
(Table reproduced, with permission, from the technical
ApplicatkJn

Grade

Use

seclor

C%urs:" Specifica/ion
Softness Hardness Relative
(BSS No.) (Shore A) density
N-Narura/
C-C%urs
CL-Clear

BS2782

Hard dielectric
66 kV cable dielectric
G.P.
High speed, thin wire
insulation
G.P.
G2lU65
GD2lU15 Fast extrusion, filled
G.P.
G3/U6
Cabtyre sheathing,
G3/U87
filled
G4lU7
G.P.
GD2IJI48 Flame retardant
Hame
insulation
retardant
and sheathing
Insulation DI/U21
or
DIIJI91
sheathing GI/U4
GDlIJ034

High tern
perature
insulation
or
sheathing

HIIJ180
H21J2oo
H21J263
H4lU85

Telephones G4lU31
N5/U16
Clear in
sulation

X21J364

JO/1365
X4IJ366

Welding
cable
sheathing Y3/J331
Development

grades

G2IJ301
G2IJ302
H21J246
Y5/J357

105'C rating dielectric

105'C rating dielectric
9O'C rating sheathing
(instrument wiring)
105'C rating sheathing
(appliance wiring)
Telephone headset
wiring and
grommets
Retractable telephone
wire sheathing
aear ripcord and
domestic wiring
Clear ripcord and
domestic wiring
Clear ripcord and
domestic wiring

Petrol/oil resistant
Low HCI emission
sheathing
Low HCI emission
bedding
Crosslinkable hightemperature
dielectric
Trailing cable
sheathing

Tensile properties
Tensile
Tear E/ongastrength strength lion at
(MPa) (Nmm- J) break
(%)
BS2782 BS6746 BS2782

N+C SABS 150-1970

N+C
N+C SABS 150-1970

10
10
9

97
97
97

134
l-41
133

212
209
23-4

104
115
116

240
200
260

N+C
N+C SABS 150-1970
N+C SABS 150-1970
N+C SABS 150-1970

14
20
20
30

94
90
90
83

134
134
148
130

192
205
152
186

99
104
82
72

230

N+C SABS 150-1970

N+C SABS 150-1970

35
40

80

145
128

IH
172

45
63

350
280
330
300

350

N+C SABS 150-1970

21

90

147

178

94

220

N+C US Underwriters
N+C US Underwriters

9
20

97
90

139
135

220
208

122
75

220
280

N+C US Underwriters

18

92

139

190

90

230

N+C US Underwriters

44

74

129

124

63

260

55

N+C SABS 150-1970

45

74

126

186

N+C

54

69

121

117

340

350

CL

24

87

130

232

100

210

CL

35

80

128

211

79

230

CL

45

74

127

186

59

250

N+C

36

79

129

N+C CES) test

20

90

156

N+C CES) test

20

90

159

N+C SABS 150-1970

48

72

125

140

330

N+C

All values are typical results measured in ACE)'s Plastics Technical Service Laboratory.
" C%ur: Standard colours are Natural lOS and Black 901. Non-standard colours are available 00 request. Masterbatches are also available for
colouring purposes:
MBIDIOOI
MBIDIOO9
MBID1201
MBIDI302
MBID/404
MBID/451

White
Cream
Yellow
Orange
Red
Pink'

MBID/501
MBID/509
MBID/601
MBID/606
MBID/607
MBlDn03

Golden Brown
Dark Brownt
Dark Greeot
Green
Turquoise
Blue

MBIDI803 Violet
MBID1901 Black
MBID1957 Grey
' Brighter than BS 6746 C Colour
t Darker than BS 6746 C Colour

73

3 Commercial PVC Compounds

Cable and Wire App6cations

literature of AECI Chlor-Alkali and Plastics Ltd)
Retention of tensile
properties :ter
ageing ( )

Loss in
Hot
defor.
mass on
ageing
mation
(mgcm- 2 ) (%)

Tensile
.strength

Elonga

97
94
97

98
92
94

04
08
04

97
96
92
99

85
100
90
100

98
97

Limiting
n

fIJ:x

ASTM

Cold bend
temperature
('C)

te~eratu,e

'C)

Volume
resistivity
at2lfC
(Oem)

BS2782

BS2782

BS2782

Cold flex

(%)

Surface
finish

Recommended
extrusion
temperatures
('C)

tion at

break
SABS
SABS
1501970 1501970

BS6746

BS6746 D28631976

40

3 x 1014 Glossy
6 x 1014 Satin
4 x 1014 Glossy

-30

29
39

-40
-25

10
15
8

10
06
06
07

39
50
44
68

-50

-40

5
-10
-12
-9

23 x 1014
13 x 1014
12 x 1014
4 x 1013

Glossy
Glossy
Satin
Glossy

145/150115511601165
145/150115511601165
145/1501155/1601165
1401145/1501155/160

100
100

10
07

70

-32
-45

-10
-15

2 x 1013 Satin
28 x 1013 Glossy

140/145/1501155/160
135/1401145/150/155

98

94

06

36

-30

-5

2 x 1014 Satin

94
100

99
96

02
055

39
38

-35

-40

15
-5

1-4 x 1014 Glossy

3 x 1014 Glossy

155/160/165/1701175
145/1501155/160/165

96

90

07

42

-35

-I

8 x 1014 Glossy

145/150/155/1601165

6 x 1013

Glossy

1401145/150/155/160

35 x 1013 Glossy

135/1401145/1501155

90

100

06

100

100

12

70

-40

-30

33

28

25

-45

-22

-40

-20

-50
87

90

053

-40

-35

44

1501155/1601165/170
1501155/16011651170
1501155/1601165/170

145/1501155/16011651170

28

x 1010

Glossy

130/135/1401145/150

20

x 1013

Glossy

1401145/1501155/160/165

x 1012

91

108

055

50

-40

-2

45

Glossy

140/145/1501155/160

93

100

059

65

-45

-8

12 x 1012 Glossy

135/140/145/1501155

Glossy

1401145/150/155/160

29

Satin

135/1401145/1501155

28

Satin

135/140114511501155

70

33 x lO" Glossy

145/1501155/160/165

74

W. V. Titow

TABLE 3.6
'Welvic' (AECI) PVC Compounds
(Table reproduced, with permission, from the technical
Apptication sector

Use o

Grade

Colours: b
N=Natural
C= Colours
B= Black

Specifications

Softness Hardness
(BSSNo.) (ShoreA)

BS2782

Relative
density

BS2782

Crystal-non-toxic

EX31U49 Food

Clear

37

78

123

G. P. extrusionopaque

GIIU4
G2JU65

Profiles
Profiles
Profiles
Profiles
Garden and mining hosing
Garden and mining hosing
Profiles
Profiles and waterstop
Profiles

N+C
N+C
N+C
N+C
N+C
N+C
N+C
N+C
N+C

9
20
30
35
35
35

97
90
83

133
134
130
1-45
126
135
128
1-41
126

Profiles
Profiles
Profiles
Profies

Clear
Clear
Clear
Clear

G.P. extrusioncrystal

G31U6
G31U87
G31J194
G31J196
G41U7
G41U88
G61U9
X2JJ364

X31J365
X41J366

X6IJ346

SABS645

40
46

80
80

80
77
73

60

66

24
35
45
63

87

74
64

130
128
127
126

N+C

99

167

20

90

131

99

137
131
130

80

Rawlplug extrusion

GO/J088

Rawlplugs

Antistatic extrusion

N2JU46

Antistatic hosing

Outdoor weathering

WO/U54
WllUl
W2JU2

Profiles and fencing wire

Profiles and fencing wire
Profiles and fencing wire

N+C
N+C
N+C

5
10
21

97
89

Y3/J331

Y31J182

Fuel hosing
Fuel hosing

Clear
N+C

35
36

79

80

127
129

Oil/grease resislant

Y6IU56

Seals and gaskets

N+C

60

66

145

Low temperature

Y51J165

Refrigeration
Gaskets

N+C
N+C

56

68

131

Clear

42

75

PetroUoil resistant

Development grades EXSlJ265 Irradiationsterilisable

WX4IJ362 Garden and mining

hosing outer

Clear

SABS645
and 1086

122

sheathing
All values are typical results measured in ACEI's Plastics Technical Laboratory.
a When specific contact with a foodslUff is involved. the advice of ACE]'s Plastics Technical Service Laboratory should

be

sought. The approval of the finished article is the fabricator's responsibility.

b Colours: Standard colours are Natural 108 and Black 901 except with Y3/J331 where the standard natural is OA21.
Non-standard colours are available on request. Masterbatches are also available for colouring purposes.

75

3 Commercial PVC Compounds

for Flexible Extrusions

literature of AECI Chlor-Alkali and Plastics Ltd)
Tensile properties
Tensile
strength
(MPa)

Tear
strength
(Nmm- t )

8S2782

8S6746

Elongation
at break
(%)

8S2782

Loss in
mass
on age;nj

(mgcm- )

Hot
deformation
(%)

8S6746

8S6746

300

184

45
73

260
350
330
300
290

04
06
07
10
14

17-2
124
131

63
73
53

350
310
400

07
09
09

232
211
106
145

100
79
59
33

210
230
250
350

053
055
059
09

234
205
186
131
161

116
101

72

39
50

68
77

64
70
76

84

44
50
65
88

Cold
bend

('C)

Cold
flex
temperature
('C)

8S2782

8S2782

temperature

Recommended
extrusion
temperatures
('C)

-45

-7

Glossy

1351140114511501155

-25
-40
-40
-32
-50

8
-10
-9
-10
-15

Glossy

-45
-35
-45

-15
-30
-34

Satin

Glossy

1501155116011651170
145/1501155/1601165
140114511501155/160
1401145115011551160
1401145/1501155/160
140/145/150/155/160
135/140114511501155
135/140114511501155
12511301135/140/145

-35
-40
-45
-45

8
-2
-8
-20

Glossy
Glossy
Glossy
Glossy

1401145/1501155/160
140/145115011551160
1351140/145/150/155
120112511301135/140

170

103

Surface
finish

Satin

Glossy

Satin

Glossy
Glossy
Glossy

Satin

1601165/1701175/180

Satin

145/150115511601165

207
227
207

132
117
105

260
260
320

04
04
05

32
38
40

-30
-30
-35

10
5
-5

Glossy
Glossy
Glossy

160116511701175/180
150/155116011651170
145/1501155/1601165

184

77

300

15

61

-50

-10

Glossy
Glossy

140/145/1501155/160
140/145/150/1551160

Satin

120/125/130/1351140

Satin

125/13011351140/145

Glossy

135/140114511501155

108

-30

350

110
37

230

10

20%

78

-40

-18

63
70
80
87

90
95

Il/Jl09
I2IJl01
131J102
151J104
15/1341
I6IJl05
1611329
17/Jl06
191J130
1811293
19/U109
191J108

B&C
B&C&Cl
B&C&Cl
B&C&Cl
B&C
B&C&CI
B&C&Cl
B&C&CI
B&C
B&C&O
B&C&O
B&C&CI

Heel filler blocks

Translucentgeneral purpose Heel filler blocks
Heel filler blocks, top pieces
and thin unit soles
Unit soles and general curpose
Soling ~rade for footba I boots
Unit so es and general put{'OSO
Football boot soling requinng
good low-temperature properties
Unit soles and general purpose
PVC/nitrile rubber blend for
industrial and minin" footwear
Gumboots and sports ootwear;
also general pur.::.:
Legging section 0 gum boots
and general purpose
Gumboots and slippers;
also general purpose
35
50
53
60

13

65

17/J220

B only

OpaqueA cheap soling compound,

cheaper footwear also general purpose

25

50
60
70
75
80

15/U75
I6IJl23
171J162
171M965
I8IJl63

52

53

54

57

64
61

80
71
69
66

95
86

63

71
66
61
59
57

121

118

119

117

120
121

125
124
122
123

131
126

138

126
127
134
123
133

Colours
Relative
Recommended Softness Hardness
B=Black
grade
density
(BSS No.) (Shore A)
C= Colours
(Natural at 23"'C)
C/=Clear
B&C
B&C
B&C
B&C
B&C

ParticularsQ

OpaqueThin soling for ladies shoes

general purpose Unit soles and general purpose
General pU!JlOSe soling
Superior solmg
General-purpose soling

General type

99

93

103

98

n5
130

157
149
130
145

157
180

107

13-l
149
no
105
100

Tensile
strength
(MPa)

240

410

230

380

280
245

290
295
290
260

260
250

315

340

330

360

400
360

Elongation
at break
(%)

-40

-50

-36

-35

-35
-35

-35

-25

-29

-25

-25
-24

-8
-15
-20
-20

-25

-30
-35
-35

-3
-5

-27

-10
-20
-25
-25
-30

-15
-20

-30

-24
-25
-35
-34
-35

1
1
1
1
1

Cold
Cold
Loss of
bend
flex
mass at
temperature temperature l()(f'C
(%)
("CJ
("CJ

TABLE 3.7
'Welvic' (AECI) PVC Compounds for Flexible Injection Moulding and Footwear
(Table reproduced, with permission, from the technical literature of AECI Chlor-Alkali and Plastics Ltd)

PVClElvaloy blend for joggers

PVClElvaloy blend for the
legging section of gumboots
PVClElvaloy blend for joggers

required

~~e~~l~! ::~~t~~~f i~umboots

Conducting compound formulated

for use on Mauseriet soling
machines. Meets BS 5451: 1971.
Softer version of N3/134O
PVC/nitrile rubber blend for

~~~SeBSaf~~~~t~~s.

Chunky footwear and generalpurpose applications

Ladies footwear and generalpurpose applications
Mens footwear and slippers
and general-purpose applications
Microcellular versIOn of
191J130 for lightweight
industrial footwear
Electrical socket boxes and
general purpose
Conducting compound formulated
for explosive components and

17/J367
17/1336
1811368
19/1356

B&C
B&C

N4IJ354

B only

B&C
B&C

N31J34O

MI8I1353

B&C

B only

MI8IJ278

B&C

1211351

MI61J270

B&C

B&C

MI4IJ274

B&C
40

80
95

70
73

40

32

20

80

80

54

77

57
52

61
60

77

82

90

57

57

69

l'24(0'7)b

121
1-17

1-17
1-16

128

130

134

1'20(07)

1'20(07)

123(07)

95
90

55
35

57

60

200

375
220

330

310

135

150

350

-35
-40

-33

-35

-35

-25
-29

-25
-25

-10

-...l
-...l

All values are typical results measured in AECI"s Plastics Technical Service Laboratory. Test methods according to BS 2782: 1970.
Q Where specific contact with a foodstuff is involved, the advice of AECI's Plastics Technical Service Laboratory should be sought. The approval of the finished article is the fabricator's
Iesponsibility.
Properties quoted for microcellular compounds are approximate values. Densities in parenthesis are minimum blown values using suitable equipment.

Development
grades

Microcellular

78

w.

V. Titow

REFERENCES
1. Adams, H. J. (1976). 34th ANTEC SPE Proceedings, pp. 330-2.
2. Weber, M. (1983). Plastics and Rubber International, 8(5),32-4.
3. Titow, W. V. and Lanham, B. J. (Eds), (1971). PVC Technology, 3rd Edn
Applied Science Publishers, London, pp. 62-3.

CHAPTER 4

Elementary Principles of pvc Formulation

W. V.

TITOW

4.1 INTRODUCTION
As has been mentioned in Chapter 1, PVC resins-whether homopolymers or copolymers-must be modified by the incorporation of
appropriate additives for satisfactory processing and end-use performance. The necessary modifications are more varied and extensive than
those practised with any other polymer of major industrial importance,
but so also is the applicational versatility of PVC in the form of the
resulting materials.
In this chapter the terms 'composition' and 'compound' are used
generically for the material which results when PVC resin is combined
with the necessary additives, and the operations involved in making a
composition are collectively called 'compounding'.
Note: Compounding may consist of, or include as one of its stages,
mixing and/or melt-compounding. The former term applies
either to the blending together of the constituents to produce a
solid composition in the form of a free-flowing powder or
powder agglomerate (either of these may be referred to as
'pre-blend' or 'dry blend', depending on the context), or to
their mixing to form a liquid composition, i.e. a paste, latex,
or solution. Melt-compounding is the operation (commonly
carried out on a mixed pre-blend) whereby the constituents of
a composition are intimately combined with the resin in the
melt, under heat and shear: the resulting compound is
normally pelletised (granulated).
79

w.

80

V. Titow

A composition is processed by the appropriate method to make a

PVC product (e.g. sheet, film, pipe, injection-moulded component,
blow-moulded container, coating on a fabric, etc.): some of the
products may be used to fabricate secondary products by further
processing (e.g. mouldings thermoformed from sheet, wall coverings
made by laminating calendered films). A general outline of this
sequence may be schematically represented as in Fig. 4.1.
The material (and thus, of course, the formulation) of a product is
that of the composition used to make it, but in the product the material
will have had a more extensive 'heat history', having undergone at
least one processing operation after the original compounding. The
basic, general principles of formulating a PVC composition (Le.
deciding on the nature and proportions of its constituents) are
relatively straightforward: however, successful practice calls for a great
deal of specialist knowledge and experience.
A formulator normally designs a composition in response to a stated
need for a product, Le. he starts with the knowledge of the nature and
intended end-use of the product into which the composition will be
processed (these factors will also determine the process to be used): in
the light of this knowledge three main considerations will govern his
choice of the formulation's components and their proportions, viz.

1------ --------,
Compounding

: Physical forms:

JSolid: (a) Fr(l(l-flowlng powd(lr or

r---..L---,

Composition
L..-_.,....----J--

powd(lr agglom(lrat(l
(pr(lbl(lnd; dry bl(lndJ
:
(b) P(lII(lts; granulat(l
I Liquid: (a) Past(l
I
(b) Lat(lx
I
(c) Solution
1-

------1

Proc(lssing

IProd"~

:
1
I

I
I

Furth(lr proc(lsslng

t.I

IS(lcondary product 1

----------J

Fig. 4.1 Stages in the manufacture of PVC products-general outline.

4 Elementary Principles of pvc Formulation

81

Processing requirements: To meet these the composition must

be in the right form (e.g. pellets for most injection mouldings,
paste for spread-coating of a fabric), have the necessary heat
stability under the processing conditions, and other properties
appropriate for the particular process (e.g. the right melt
rheology for injection moulding or extrusion, right viscosity
characteristics in a paste for spread-coating, correct lubricity in
a calendering compound to prevent 'plate-out').
(ii) Service requirements: These will be dictated by the end-use, and
will normally include stability to the service environment.
(iii) Material and process cost economy: Save in certain special cases
(e.g. some military applications) this is always an important
consideration, influencing the design of a formulation.

(i)

4.2 THE COMPONENTS, AND BASIC TYPES, OF A

PVC FORMULATION

As already mentioned in Chapter 1, PVC materials and products fall

into two broad categories: rigid (uPVC) and plasticised (pPVC).
Materials of the latter group with low plasticiser content (up to about
30 phr) are often referred to as 'semi-rigid': the softest pPVC materials
may contain over 100 phr of plasticiser(s).
With the partial exception (not important in the context of the
present discussion) of certain liquid compositions (some solutions and
lattices-see Chapters 23 and 24), virtually all PVC compositions
undergo heat treatment-and most experience 'internal' (frictional)
heat generated by mechanical shearing-in the course of processing
(including the initial compounding). Many end-uses also involve
exposure to heat (albeit usually at temperatures somewhat lower than
those encountered in processing) either as a normal condition of
service (e.g. for flexible PVC insulation on electric wire, or rigid PVC
products exposed to direct sunlight outdoors, as with, say, guttering,
cladding or window frames), or as an occasional hazard. For all these
reasons, the PVC polymers-which are inherently prone to heat
degradation (see Chapters 1, 9, and 12)-have to be protected by the
incorporation of heat stabilisers. Thus the PVC resin itself and a heat
stabiliser are two essential components of virtually every PVC
formulation.
A simple, basic formulation for a solid uPVC composition will also

82

W. V. Titow

normally contain a processing aid (a polymeric additive, to improve

fusion characteristics and melt flow), an impact modifier (also a
polymeric additive, to impart toughness to the relatively brittle PVC
resin), and a lubricant to counteract sticking to hot equipment surfaces
in processing ('external' lubrication) and/or to reduce the frictional
effects within the melt ('internal' lubrication): more than one lubricant
is often used to discharge these functions. Similarly, more than one
processing aid and/or impact modifier may be incorporated for best
results in a particular composition, but-on the other hand-a single
additive may serve in both capacities in some cases (e.g. chlorinated
polyethylene in certain formulations-see Chapter 11).
In a basic formulation for a pPVC composition the plasticiser (or
plasticiser system, if more than one plasticiser is used) is the essential
component in addition to the PVC resin and heat stabiliser. Apart
from its effects on the finished material properties (imparting softness,
flexibility, extensibility, toughness) it plays an important role in heat
processing, combining the functions of processing aid with lubricant
action (particularly internal lubrication; although some plasticisersand especially extenders-can provide external lubrication, it is not
unusual to include lubricants with good 'external' effect in pPVC
formulations) .
In addition to the basic constituents most PVC formulations contain
other components incorporated mainly to impart properties required in
the PVC product for particular end-uses. The most widely used of
these additives are colourants and fillers. The colourants include
pigments (which impart opacity as well as colour to the PVC material)
and dyes (colourants fully soluble in the composition and thus suitable
for transparent materials). Fillers are often included to cheapen the
cost of PVC compositions, although even when this is the primary
purpose the attendant effects on some properties may also be useful,
e.g. reduced shrinkage, increased hardness and stiffness, which are
often brought about by the presence of a substantial proportion of
finer. Some fillers have a purely functional role-e.g. glass fibres and
fine-particle calcium carbonate act as reinforcements in uPVC
compositions. The uses and effects of fillers are discussed in Chapter 8.
Other formulation components with specific end-use functions in the
PVC material are the following:
Antioxidants and UV absorbers: Used to improve the resistance of
PVC products (especially those for outdoor use) to photochemical
degradation and weathering generally (see Chapters 11 and 12).

Elementary Principles of pvc Formulation

83

Antistatic agents: Incorporated to counteract the build-up of

electrostatic charges (with the consequent risk of sparks in some cases,
and the nuisance of dust pick-up) on the surface of PVC productse.g. pPVC conveyor belts, or uPVC mouldings.
Flame retardants: Included, especially in some flexible PVC
materials, to reduce their flammability (enhanced by the presence of
substantial amounts of many plasticisers). uPVC is among the least
flammable plastics materials (see Chapters 7, 8, 11 and 12).
Smoke suppressants: Incorporated to reduce the amount of smoke
generated by burning PVC materials (some additives in this category
also cut down the evolution of HCI in burning)-see Chapters 8, 11
and 12.
Biostats: Included in PVC compositions (especially some flexible
materials) to counteract attack by micro-organisms (bacteria and
fungi)-see Chapters 7 and 12.
Odour control agents: Such additives are used in some formulations
to impart a smell (e.g. leather-like odour to PVC handbags or
upholstery) or to mask odour of another formulation component.
According to their function in a particular composition they may be
referred to as 'reodorants' or 'deodorants'.

Two kinds of functional components included in certain formulations

to act in the processing rather than the service stage are blowing agents
(which, in the production of PVC foam, create the cellular structure by
evolution of gases at the processing temperature) and surface active
agents used to facilitate the mechanical whipping-in of air into PVC
pastes, and to control the resulting bubble formation, in the
air-entrainment method of PVC foam production-see Chapters 11
and 25.

4.3 FORMULATION COSTING-BASIC POINTS

It is usual to express the formulation of a composition on the basis of
100 parts by weight of the PVC resin, using the abbreviation 'phr'
(parts per hundred of resin) for the content of each of the other
components present. For costing purposes the volume cost is usually

w. V. Titow

84

required, and for this the volume content of each component of the
formulation is worked out from the weight content and density values.
These points are illustrated by the following example of a simple
plasticised compound (an extrusion compound of BS softness about
20):
Component

Parts by weight
(g)

Density
(gem- J )

Parts by volume
(em3)

1000
500
70
10
1580

140
099
381
093

7143
5050
184
108
12485

PVC polymer
Plasticiser
Stabiliser
Lubricant

Since, by definition, density = weight/volume, the parts by volume are

obtained by dividing the parts by weight by the density in each case.
Similarly, the density of the compound is given by 158/12485 = 1266
gcm- 3 .
The density of a PVC composition is important for costing purposes
since, although it is convenient to formulate it on a weight basis, the
composition will ultimately be used (and sold) on a volume basis, as a
given weight will produce a certain number of mouldings or a certain
volume of extrudate (e.g. a certain length of pipe of given dimensions).
Thus the volume cost is of direct interest, as is the fact that, in a
comparison of two formulations, it may be higher for the one cheaper
on a weight basis. For example, consider two compounds, A and B, of
which B is 10% more expensive on a weight basis but has lower
density:
Weight eost
perg
per kg
Compound A
Compound B

135
1-10

n
1-1n

OOOln

OOOlln

Volume cost
(perem3)
135 x OOOln = 000135n
110 x OOOlln = 0001 21n

Thus, in this general example, because of the density difference, the

compound which is 10% more expensive on a weight basis is cheaper
in roughly the same proportion on a volume basis.

4 Elementary Principles of pvc Formulation

85

The simple extrusion compound cited at the beginning of this section

may be costed as illustrated below (the component prices used in the
illustration are roughly in line with those applicable to tonne-lot
purchases in the first half of 1980 in the UK).
Formulation
component

PVC polymer
Plasticiser
Stabiliser
Lubricant

Weight
proportion
(kg)

Cost per kg

100
500
70
10
1580

040
050
040
025

C
Cost in formulation

()

(A

x B)

()

40
25
28
025
6805

The weight cost of this compound will therefore be

6805/158 = 04307 per kg,
and the volume cost (given the density as 1266 g cm- 3-see above)
1266 x 00004307 = 0000545 26 per cm3.

4.4 MAIN GENERAL CONSIDERATIONS IN THE

SELECflON OF PRINCIPAL FORMULATION
COMPONENTS

Each component of a particular PVC formulation (i.e. the PVC resin,

stabiliser, plasticiser, etc.) is selected from a large group of available
materials of its type. The choice is made-in the light of the
requirements mentioned in Section 4.1-on the basis of the known
characteristics of the individual candidate materials within the group,
in conjunction with certain other relevant considerations (including the
mutual compatability, interactions, and side effects of the formulation
components when compounded into a composition). The purpose of
this section is to give a general indication of the main factors concerned
in the choice: a comprehensive discussion of the complex subject of the
properties and effects of PVC formulation components would be far
beyond its scope. Further relevant information will be found in various

86

w. v.

Titow

parts of this book (especially Chapters 2, 3, 6 to 12, and 21 to 25). A

useful summary of some important considerations has been provided
by K. Regan in the Buss-Hamilton Compounding Manual. *

4.4.1 Nature and Characteristics of Individual Components of a

Formulation
(a) PVC Polymer
MOLECULAR WEIGHT

In general, the higher the molecular weight of the polymer (and hence
its K value and viscosity number-see Chapters 1 and 2) the better
many mechanical properties of the composition but the more difficult
its processing (because the ease of fusion and melt flow decreases with
increasing molecular weight). The choice of the molecular weight
grade (K value) of a commercial polymer to be used in a particular
formulation is normally a compromise between what is the most
desirable for processing on one hand and service properties on the
other. The processing considerations become less critical with
adequately plasticised compositions, so that polymers of higher K
value can be used in those-typically 65 to 71 t (ICI range 60-65, Fig.
4.2), as against 54 to 65t (ICI range 50-60) in uPVC (with the lowest
molecular weight polymers used in those rigid compositions where the
easiest melt flow is required, e.g. in some injection-moulding and
bottle-blowing compounds). The molecular weight distribution of the
polymer also affects physical properties and processing: it is normally
maintained within certain limits in a given commercial polymer grade.
KIND (PROCESS TYPE)

Except for the special case of formulating PVC solutions for surface
coatings, for which polymer produced by the solution process will
normally be used (see Chapters 2 and 24), the choice will be between
suspension polymers, mass (bulk) polymers or emulsion polymers (i.e.
PVC resins produced by those three polymerisation processes-see
Chapter 2). For PVC paste compositions emulsion polymers are used

* Edited and published by Buss-Hamilton Ltd, Cheadle Hulme, Stockport,

England.
t K values from viscosity determinations on 05 g per 100 ml (polymer/cyclohexanone) solutions. Corresponding ISO viscosity number ranges are, respectively, about 105-125 and 70-105-see Table 2.1 in Chapter 2.

4 Elementary Principles of pvc Formulation

87

80

70

50

60

70

80

K value (059 resin In 100ml cyclohexanone)

Fig. 4.2 The relationship between ICI K value and K value determined by
viscosity measurement on a solution of 05 g PVC resin in 100 ml cyclohexanone (ct. Chapter 1, Fig. 1.2, and Chapter 2, Table 2.1)

because of their particle size and structure characteristics, although

suspension resins are sometimes added as 'extender' ('filler') polymers
to modify the viscosity of pastes: the use of PVC polymers in pastes is
discussed in Chapter 21. Solid compositions (sometimes referred to as
'general purpose' compounds in contradistinction to pastes) for
injection moulding, extrusion, or calendering are commonly formulated with suspension or mass polymers, although mixtures of one of
these with an emulsion resin, or even emulsion resins alone, are
occasionally used in Europe in some uPVC compositions for better
melt flow.
Note: Emulsion resins are not used in electrical insulation compositions, because the residues of additives from the polymerisation process (especially emulsifying agents) which they contain
lower electrical resistivity.

Suspension and mass polymers are, broadly speaking, roughly

88

W. V. Titow

equivalent from the point of view of the final material properties,

although a mass polymer may contain fewer impurities than an
otherwise comparable suspension polymer and hence give compounds
of better clarity (see 'quality' below). The differences between the two
types of polymer are more strongly manifested in processing. Mass
polymers tend to have higher bulk densities than suspension polymers
(for comparable polymer molecular weight and particle porosity), with
greater uniformity of particle porosity and shape (and hence more
uniform and rapid plasticiser absorption), as well as greater ease of
gelation (i.e. ease and completeness of fusion in heat processing) which
is of particular interest in the production of large mouldings. All these
characteristics can offer processing advantages in certain circumstances
and processes, but the fact should not be overlooked that-whilst the
optimum conditions for a suspension and a mass polymer may be
different in a particular process-if they are properly optimised in each
individual case either polymer can be processed satisfactorily.
CHEMICAL NATURE

The PVC resin on which a formulation is based may be a

homopolymer, or a copolymer, or sometimes a mixture of both. The
general differences between the two, their main respective applications
and uses, and the copolymers of the greatest practical interest, have all
been mentioned in Chapters 1 and 2. In broad summary it may be said
that homopolymers have better thermal stability and impart better
physical properties to the composition, whilst copolymers make for
easier melt processing at relatively lower temperatures, and improve
extensibility and filler acceptance in some compositions: copolymers
are also normally used in PVC-based solution formulations for surface
coatings-see Chapter 24. The melt-processing advantages of copolymers versus homopolymers, like those of lower versus higher
molecular weight polymers (see above), are more important in rigid
formulations, as in adequately plasticised compositions the fusion and
melt flow characteristics are primarily governed by the plasticiser.
Vinyl chloride/acetate copolymers form the basis of uPVC compounds
for gramophone records and certain types of sheeting; they are also
used in flooring compositions. In Europe they are sometimes included
with a homopolymer to improve the ease of processing of some rigid
formulations. Vinyl chloride/vinylidene chloride copolymers are employed, alone or in admixture to homopolymer, in some specialised
calendering compounds (for uPVC sheeting), and as viscosity-

4 Elementary Principles of pvc Formulation

89

reducing extender polymer in some paste formulations (see Chapter

21).
QUALITY

It is clearly desirable that the PVC resin used in any formulation

should be of reasonable quality, and the standard grades supplied by
the manufacturers are, generally speaking, reliable and acceptable in
this respect for most purposes. However, some applications call for
particularly high quality (and special high-grade resins are available)
whilst in certain cases a lower than standard quality may be acceptable
in the formulation. Apart from the molecular weight spread (which
should be within appropriate limits for the given nominal K value of
the polymer grade) the factors making up quality in the present context
are: polymer particle size and size distribution (with special reference
to coarse particle content); colour; 'fish-eye' content; and level of
particulate contamination ('speck count').

Note: ISO 472-1979 defines 'fish-eye' as 'a small globular mass which
has not blended completely into the surrounding material and
is particularly evident in a transparent or translucent material'. In PVC polymer fish-eyes (also called gels) are hard,
particulate specks of polymer which are not dispersed in
processing and thus remain as discrete inhomogeneities in the
finished product. A standard method of determining the
number and size of fish-eyes in general-purpose PVC resins is
given in ASTMD3596-77 (see also ASTMD3351-74: Gel
count of plastic film).
Low-grade polymer can be used, in admixture with a standard grade
or even alone, in formulations for the cheaper kinds of injectionmoulding compositions, usually fairly heavily filled, used for the
production of cheap moulded footwear (sandals, slipper soles) and
toys. High-grade polymer is necessary for such uPVC products as
transparent ('clear') packaging film and bottles, and in plasticised
compositions for clear medical products (e.g. containers and tubing for
saline drip sets), clear, flexible hose and packaging film (e.g.
'clingwrap') .
(b) Heat Stabilisers
Whilst the main mechanisms involved in the complex process of
thermal degradation of PVC and its counteraction by stabilisers are

90

W. V. Titow

understood in general terms, the stabilisation of PVC formulations is

still largely a practical art, relying on the specialist interpretation and
application, in the specific context of a particular composition, of
information and principles stemming mainly from practical experience.
For this reason, and also because a great variety of stabilisers is
available (many of which are not single chemicals but compositions
specially developed for particular types of formulations and end-uses)
even a skilled formulator will normally seek the advice of a reputable
supplier when formulating a composition of which he has no previous
experience. The proportion of stabiliser(s) in a PVC formulation will
vary-in broad, general terms between about 05 and 8 phrdepending on the nature and purpose of the composition, the nature of
the stabiliser itself, and the processing (including the kind of
compounding to be undergone--e.g. completeness of dispersion
achievable with modern compounding machinery reduces stabiliser
requirement). Heat stabilisers and their effects are discussed in some
detail in Chapters 9 and 10; only the most basic, general points are
mentioned here.
There is no rigid, standard classification of stabilisers, but-for the
purposes of a brief general discussion-they may conveniently be
considered under the following headings.
LEAD COMPOUNDS

Several lead salts and some lead 'soaps' (notably lead stearates) are
widely used as stabilisers in PVC (the soaps partly for their lubricant
properties). Lead compounds are the oldest general-purpose stabilisers, comparatively cheap, and capable of imparting good long-term
stability. They have always dominated the electrical insulation
applications of pPVC compounds, because lead chloride, formed when
a lead stabiliser reacts with HCl (a principal decomposition product of
PVC-see Chapter 9), is insoluble and non-ionisable, so that the
electrical resistivity remains unimpaired as the stabiliser discharges its
function. In uPVC compositions lead stabilisers are used in many
formulations for extruded cladding and profiles: dibasic lead phosphite is of particular interest for opaque products for outdoor use, as it
imparts very good light stability. In Europe lead stabilisers are also
used in uPVC pipes, although in the USA tin stabilisers (see below)
are favoured for this area of application. The main limitations and
disadvantages of lead stabilisers as a group are toxicity (hazards in
processing, as distinct from potential risks in compounds, are reduced

4 Elementary Principles of pvc Formulation

91

to some extent by various means-see Chapter 9), opacity (or at least

translucency) imparted to PVC compositions, and susceptibility to
staining (through the formation of black lead sulphide) in contact with
sulphur-containing materials (e.g. 'cross-staining' with certain rubbers)
and atmospheres.
BARIUM/CADMIUM AND BARIUM/CADMIUM/ZINC SYSTEMS

The former type of stabiliser system may consist of barium and

cadmium soaps (e.g. laurates, stearates, or myristates) mixed or
co-precipitated, or a liquid salt combination (e.g. barium and cadmium
phenates). The zinc-containing systems incorporate in addition an
organic salt of that met.al (often zinc octoate). Both types of system are
extensively used-and can be considered by the formulator-for a
variety of applications in both flexible and rigid PVC compositions: for
example, most of the flexible calendered film and sheeting compounds
are formulated with these stabilisers, as are many paste products (e.g.
coatings, rotational mouldings), as well as numerous flexible and rigid
extrusion compositions (including, e.g. wire-coating compounds,
profiles), and injection-moulding compounds (e.g. for footwear). Both
types of stabiliser system are quite widely used in conjunction with
synergistic co-stabilisers-an organic phosphite and/or an epoxy
compound (often an epoxidised oil) which enhance the main stabilising
action and improve the weathering resistance of the composition. The
epoxy compound also has a plasticising action, which may be
significant in some rigid formulations, e.g. bottle compounds. Some
proprietary BalCd and BalCd/Zn stabilisers include the synergistic
co-stabilisers as part of the system. Both types of basic system offer
good heat stability and colour control, and good light stability (when
the co-stabilisers are incorporated). Clear compounds can be formulated with the liquid BalCd systems; the soap-based and zinccontaining systems have an opacifying effect and are thus more suited
to translucent or opaque compositions. Although effective and
versatile, the systems are not without their limitations: the presence of
cadmium makes them susceptible to sulphide-staining (through the
formation of yellow cadmium disulphide on contact with sulphur
compounds) although this is counteracted by the presence of zinc in
those of the systems which contain it: 'plate-out' can occur in the
processing of compositions stabilised with these systems (i.e. the
formulation of sticky deposits on the working surfaces of processing
equipment-see Chapter 9); cadmium-containing systems are not

92

W. V. Titow

suitable for food-contact applications and other end-uses (e.g. medical

equipment) where potential toxicity is a problem-other combined
metal salt systems (usually in conjunction with epoxy compounds) are
used in such cases (see below).
TIN STABILISERS

These are organotin compounds, comprising methyl, butyl, octyl and

lauryl tin derivatives, and including also the relatively recent 'estertins'
(see Chapter 9); some contain mercaptan or thio groups (and hence
are usually referred to as 'tin mercaptides' or 'thiotins'), and others
sulphur-free groups derived from carboxylic acids (the tin 'carboxylates'). The tin compounds (and, within this group, especially the
thiotins) are the most effective heat stabilisers for PVC, both flexible
and rigid, imparting a high degree of initial and long-term stability, and
outstanding clarity to transparent compounds (particularly important
in, for example, packaging film and bottles). Their limitations are:
relatively high cost, comparatively poor light stability of thiotinstabilised compounds, and toxicity, although a few tin stabilisers are
permitted for food-contact uses (see Chapter 9). The thiotins can also
impart odour to PVC compositions and cause sulphide cross-staining
with heavy-metal stabilisers or pigments.
Note: Some antimony mercaptide stabilisers are also available.

Whilst generally similar in their action (and limitations) to the

tin stabilisers, they can be more economical in some
formulations, but also make compositions somewhat more
prone to sulphide cross-staining, and less stable to photodegradation. The use of calcium stearate in conjunction with
antimony mercaptide stabilisers increases heat stability
through a strong synergistic effect.
NON-TOXIC STABILISERS

These must be used in products for food-contact and medical

applications, e.g. flexible and rigid PVC packaging films, PVC bottles,
flexible PVC medical tubing, and hose used in food processing. The
relevant regulations and directives (and-in cases of doubt-the official
bodies concerned) should always be consulted when formulating
non-toxic compositions, as the requirements and restrictions applicable
can differ with the application, and from country to country. As has
been mentioned, some tin stabilisers are permitted (with limitations, in

4 Elementary Principles of pvc Formulation

93

some countries, on the percentage present in the formulation, and the

amount extractable) for food-contact uses (see Chapter 9). Systems
consisting of combinations of organic salts of calcium and magnesium,
calcium and zinc, or calcium, magnesium and zinc, may also be used,
commonly in conjunction with an epoxy compound (which here
improves heat as well as light stability, and provides some plasticisation) and-where appropriate-also permitted antioxidants. Some
esters of aminocrotonic acid are permitted food-contact stabilisers in
several countries.

Note: Calcium stearate, regarded for some purposes as a non-toxic

stabiliser, is used in certain compositions (e.g. pastes for
dip-coating applications) which are not primarily intended for
non-toxic end-uses.
NON-METALLIC (ORGANIC) STABILISERS

The materials which may be grouped under this heading are the
already mentioned epoxy compounds and organic phosphites, most
commonly used as auxiliary, synergistic stabilisers with some metal
stabiliser systems. The epoxy compounds are very often epoxidised oils
(e.g. epoxidised soyabean oil), but epoxidised esters and some epoxy
resins can also be used (see also Chapter 9).

(c) Plasticisers
As has been mentioned, plasticisers convert the hard, inherently brittle
PVC resin into compositions of varying degrees of softness and
flexibility, processable into a variety of products with divers properties
and uses (determined to a large extent by the nature and amount of
plasticiser(s) present). Plasticisers and their effects in PVC are
discussed in several chapters of this book (in particular Chapters 5 to
7): because these chapters cover the subject thoroughly, and because
of its complexity and extent, only the most basic, general pointers are
given in the present section.
The proportion of plasticiser in a pPVC composition is always fairly
substantial, and may be very high in very soft materials. For this
reason cost considerations are particularly important in plasticiser
selection. In the absence of special processing and/or service
requirements which may dictate the choice (see below) the formulator
will normally consider first a relatively inexpensive, general-purpose
plasticiser. In most cases this will be a phthalate, very often dioctyl

94

W. V. Titow

phthalate (DOP) which offers good all-round compound properties.

Several phthalates (including DOP) are primary plasticisers, that is
they are highly compatible with PVC resins (in proportions of 100 phr
and over). The cost of phthalate-plasticised formulations (and some
containing other plasticisers) can often be reduced by replacing part of
the main plasticiser by an extender: This is frequently a chlorinated
hydrocarbon which, additionally, has a flame-retardant effect-a useful
feature because substantial plasticisation with phthalates increases the
flammability of PVC compositions (cf. Chapters 11 and 12). Triaryl
phosphate plasticisers (which also act as flame retardants) are the
second most important group of common, primary plasticisers;
however, a triaryl phosphate will rarely be used as the sole plasticiser,
since the low-temperature properties (cold flex, toughness) of its
compounds with PVC resins are comparatively poor. This may be
corrected by the inclusion of a phthalate plasticiser (in adequate
proportion) or-where a stronger effect is required-of an aliphatic
diester plasticiser which imparts particularly good low-temperature
properties. In general, when more than one plasticiser is used, the
properties of the PVC composition will represent a combination of
those normally conferred by each individual plasticiser when present
alone. This is an important feature of plasticiser action, widely utilised
in formulating PVC compositions.
Even within the phthalate group (the largest both in terms of
number of members and usage volume) some plasticisers are
particularly associated with the special properties they promote in the
compound. For example, butyl benzyl phthalate (BBP) is one of the
best solvating, quickest fusing, plasticisers for PVC (and thus promotes
rapid and easy processing of its compositions); it also imparts
particularly good stain resistance to PVC films and surfaces. Ditridecyl
phthalate has a particularly low volatility (for a phthalate) and hence a
high degree of permanence in compounds (useful, for example, in
high-temperature cable coverings). For particularly high levels of
certain properties, beyond what is available even with the best among
general-purpose plasticisers, recourse must be had to other, special
plasticiser types. Selected representatives of these types (all more
expensive, as a rule, than general-purpose plasticisers) are used in
PVC compositions where the particular property or group of properties
they contribute is of special importance. Such special uses are
indicated, in a general way, in the outline summary of plasticiser
effects in Table 4.1. Table 6.1 in Chapter 6 provides a guide to the

Elementary Principles of pvc Formulation

95

main advantages and limitations of major types of plasticiser relevant

to their usage.

(d) Lubricants
The functions of lubricants in PVC compositions are:
(i) to reduce the friction at, and adhesion to, working surfaces
when the composition is being processed (external lubrication);
and/or
(ii) to lower the inter-particle and inter-molecular friction in
processing (internal lubrication); this reduces the effective melt
viscosity and heat build-up.
Some lubricants discharge only, or mainly, one of these two
functions and are, accordingly, referred to as internal or external
lubricants; others act in both ways. The main factor determining the
type of lubricant action is the lubricant's compatibility with PVC: a
true external lubricant is poorly compatible, and a good internal
lubricant highly compatible with the resin. Chemical compounds used
as lubricants include paraffins, paraffin oils, polyethylene waxes, fatty
acids, fatty acid amides and esters, fatty alcohols, and metal soaps.
Lubricants must be used in uPVC compositions (for both internal and
external effects: two or even more lubricants are often combined, up to
a total content of about 3 phr) , and are beneficial in many plasticised
compositions (in amounts within the range O 2-1' 5 phr) mainly for
external lubrication, as much of the internal function is discharged by
the plasticiser. The nature and amount of lubricant(s) used in a
formulation depend critically and in a complex way on several factors,
viz. the other components (see below), the processing to be undergone
by the composition (the correct choice is particularly important in
many calendering compositions), and any subsequent treatments (e.g.
films to be printed must have no exuded external lubricant on the
surface). Possible interaction or co-action with other constituents of
the formulation, especially the stabiliser(s), is a most important
consideration in the choice of lubricant(s) and the amount(s) to be
used. For example, some stabilisers have a lubricant action, and/or
benefit from synergistic co-action with certain lubricants, whilst some
lubricants also exert a stabilising effect; more lubricant may be
necessary in compositions highly loaded with fine-particle fillers
(because of absorption effects), but relatively less if the filler is
surface-coated with a stearate (see Chapter 8); the degree of

Important features of behaviour of plasticiser

in composition:
(a) High compatability with PVC resin
(i.e. suitability for use in high proportions in a composition)
(b) Permanence (low volatility, resistance
to extraction and migration in compositions)

Price economy

Characteristics required

Very soft, flexible products, including

paste mouldings and coatings
Shower curtains, upholstery; gaskets

Polymeric plasticisers;
for some purposes:
trimellitates,
high molecular weight
phthalates,
solid blending resins (e.g.
chlorinated PE, EVA
copolymers, nitrile rubber)

Wide range of cheaper-grade compositions for various purposes

Examples of application

Many phthalates, triaryl phosphates

Selected phthalates, extenders

Typically relevant plasticiser type(s)

TABLE 4.1
Some General Features of Plasticiser Usage

o~

:::J

:<:::

Aliphatic diesters and extenders

BBP, DBP, triaryl phosphates,
polymeric plasticisers

BBP,DBP,
triaryl phosphates,
phthalates

End-use properties imparted to compositions:

(a) Good colour
Phthalates
(b) Good chemical resistance
Polymeric plasticisers
(c) Good low-temperature properties
Aliphatic diesters (sebacates,
adipates, AGS esters)
(d) Electrical properties
high resistivity
Triaryl phosphates
low resistivity
Sebacates
(e) Food-contact applications
Individual plasticisers (high purity
grade) as permitted by relevant
authorities
(f) Mechanical properties
high tensile strength
Triaryl phosphates
high extensibility
Sebacates

(b) Effect on viscosity of pastes:

low viscosity
high viscosity

Processing properties:
(a) Ease of solvation, fusion, and gelation

Packaging films

Clear compositions
Protective clothing
Tarpaulins, flexible tubing for use in
cold conditions

Foamed coatings

5'
;::s

i:>

I::

~
~

.5;,

(")

?-

is

W. V. Titow

98

compatibility of a lubricant with the processing aid and/or impact

modifier in a uPVC composition will affect the choice of type and
proportion of the lubricant. Suppliers provide lubricant systems,
including 'single-pack' stabiliserllubricant combinations, for most types
of PVC compositions, and even a highly skilled formulator can benefit
from their advice.
Lubricants and their uses are discussed in more detail in Chapter 11,
Section 11.1.
(e) Polymeric Modifiers
The polymeric additives used in PVC compositions fall into two broad
functional groups: processing aids and impact modifiers.
PROCESSING AIDS

The polymers used in this capacity improve the melt-processing

characteristics of PVC compositions (rapidity of homogenisation and
fusion) and the properties of the melt (melt strength, cohesion and
elongation are increased; in many cases the melt modulus is reduced),
but they also usually increase the melt viscosity (which is already high
in uPVC compositions): some can also have an external lubricant effect
(lubricating processing aids). At their usual levels of incorporation
(1-6 phr) processing aids do not significantly affect the end-use
properties of the composition.
The processing aids in commercial use may be broadly grouped
under the following headings:
(i) acrylic polymers (acrylates and methacrylates);
(ii) styrene copolymers (with acrylonitrile or certain methacrylates).
Both these general groups contain many proprietary products with
varying applicability in different types of composition. The recommendations of a reputable supplier should, therefore, always be
considered. Poly-a-methylstyrene and some ABS terpolymers are also
used as processing aids (the former can, inter alia, actually reduce the
melt viscosity of a uPVC composition).
IMPACT MODIFIERS

The main function of these additives is to improve the toughness

(resistance to impact at room and low temperatures) of uPVC
compositions, in which they are usually incorporated in proportions of
5 to about 15 phr (the use and effects of impact modifiers are discussed

4 Elementary Principles of pvc Formulation

99

in more detail in Chapter 11, Section 11.2). In most cases there is also
some processing-aid action, but this may be significant only at
processing temperatures higher than those at which regular processing
aids exert their effect. Some types of impact modifier (e.g. (iv), (v),
and certain kinds of (vii) below) are highly compatible with PVC and
may be incorporated in high proportions, to act as plasticisers (see
Chapter 11, Section 11.2). Commercially available impact modifiers
are polymers of the following types:
(i)
(ii)
(iii)
(iv)

acrylonitrile/butadiene/styrene terpolymers (ABS);

methacrylate/butadiene/styrene terpolymers (MBS);
modified acrylic polymers;
ethylene/vinyl acetate copolymers (EVA) and graft copolymers
of vinyl chloride and EVA (EVAIVC);
(v) nitrile rubber (butadiene/acrylonitrile copolymers);
(vi) polyurethane elastomers;
(vii) chlorinated polyethylene (various degrees of chlorination).

While the impact modifiers find their main application in uPVC

compositions (although some, as just mentioned, may be used-in
large proportions-to act as plasticisers), some (notably certain ABS
types) may be incorporated in semi-rigid and even flexible compounds,
not primarily to contribute to toughness, but to improve melt strength
in processing, emboss retention and thermoforming properties of sheet
(where they can also reduce post-forming shrinkage).
In some types of composition very high proportions of a polymeric
modifier are included. Thus up to about 100 phr of particular
processing aids, or modified ABS or MBS impact-modifier systems,
may sometimes be used to improve the heat distortion properties of
the material (the heat deflection temperature under load at 182 MPa
may be raised by about 15C in comparison with that of an unmodified
lkt otherwise similar uPVC composition). Some flexible compositions
may actually contain more of an ABS polymer than PVC resin, so that
the latter may be regarded as a modifier for the former (see Chapter
11, Section 11.2).

(f) Fillers
The use of fillers in PVC is discussed in some detail in Chapter 8, and
referred to in other parts of the book in connection with various filled
compositions and products. Only the most basic points relevant to the
role and application of fillers in PVC formulations are briefly

100

W. V. Titow

TABLE 4.2

Effect of Particulate FiBer Content on Tensile Strength (Ibfin- z) of pPVC

Filler

Precipitated
whiting
Hard clay
Carbon black
Omya BSH

Parts by weight
30
40

10

20

1700
1700
1700
1700

1420
1780
1900
1615

1350
1710
1920
1590

1200
1450
1550
1580

920
1200
1750
1370

50

60

750
890

510
1110

1250

1070

mentioned here. In many compositions a filler is included principally to

reduce material cost: in such 'extender' applications the filler is
nowadays normally some form of particulate calcium carbonate. When
present in a substantial amount this filler will-as will virtually all
mineral fillers in plastics generally-affect some physical properties of
the PVC composition: the common effects are reduced tensile strength
(see Table 4.2), elongation at break, moulding shrinkage and thermal
expansion coefficient, and increased hardness. A particularly important
point concerning the general effects of mineral fillers in plastics
compositions, including PVC, is that even at loadings which in many
cases do not bring about substantial changes in other properties, the
density of the composition may increase significantly; it will also
continue rising with further increases in filler content. Since the
compositions are sold on a weight basis (whilst ultimately used, in the
form of products, on a volume basis-see Section 4.3 above), the
overall material cost saving may drop progressively (in some cases
quite rapidly) with increased filler loading.
Note: e.g., if a given volume of product (say a moulding) weighs

1 kg when produced from a compound of density 11 gcm- 3 ,

the weight of compound of density 14 g cm -3 needed to
produce it will be 14/11 = 127 kg (to the second decimal
place).

Typical applications of calcium carbonate in plasticised PVC include

its use in electrical cable coverings (insulation and sheathing), moulded
footwear (especially the cheaper qualities), moulding compounds for
toys, some grades of sheeting and fabric coatings (in the latter two
applications plasticiser exudation can be reduced, and some improvement in weathering promoted, by the presence of the filler). In

4 Elementary Principles of pvc Formulation

101

unplasticised PVC products calcium carbonate fillers are used at

relatively lower loadings in most cases. The biggest outlets are in rigid
pipes and profiles, and in flooring.
Over the years, calcium carbonate fillers have largely displaced clay
fillers in most applications primarily because of the cost advantages
they offer in virtually every case. Clays are still used, however, in
certain special electrical insulation compounds, where-at loadings of
about 5-15 phr-they benefit the insulation properties. Their generally
low pigmentation effect (due to a refractive index closely approaching
that of many PVC compositions) can also be an advantage in some
cases. Some effects of an electrical grade of clay filler on the properties
of a PVC composition are shown in Table 4.3.
TABLE 4.3
Some effects of a Clay Finer in a pPVC Composition

Filler
Composition a
content
and
properties

Resin
Di-2-ethyl hexyl phthalate
Tribasic lead sulphate
Paraffin wax
Filler: M 501 b

M501 (phr)
Nil
5
15
10
2500 2500 2500 2500
T~nsile strength
(lbfin- 2)
Modulus 100%
extension (lbf in -2) 1500 1700 1800 1900
Elongation at break
(%)
300 280 270 250
Tear strength (lb in-I) 1200 1300 1400 1400
32
38
32
30
BS softness No.
Volume resistivity,
conditioned x 1014
(23C, 65% RH)
11
03
13
15
Volume resistivity
(Qcm x 1014 ,
24 h immersion)
02
3
7
6
Volume resistivity at
60C x 1012
06
50
90 110
a Compounding

100
50

7
1
As stated

} Parts by
weight

20
2400

30
40
50
2500 2400 2500

2000

2200 2300 2400

230
1400
29

170 170 120

1400 1500 1500
28
26
23

13

12

100

90

70

60

and testing was carried out according to the procedure laid

down in BS 2571: 1955.
b Calcined clay for electrical applications: English China Clays International
Ltd.

102

W. V. Titow

In so far as a generalisation can be made, it is useful to remember

that with particulate fillers the larger the particle size the greater the
reduction of surface gloss of the composition, the higher the water
absorption and the tendency to 'stress whitening' (see Chapter 8).
However, the finer the filler the greater the plasticiser demand and the
tendency to absorb lubricants except where t.he particles are effectively
surface-coated (see Chapters 8 and 11).
(g) C%urants
A colourant must be able to discharge its function-Leo to impart the
desired colour, in adequate strength, to the PVC-when present in a
relatively low proportion (normally up to a few phr at most). The
colourants used in PVC may be broadly divided into pigments and
dyes. The pigments are fine-particle materials, intimately dispersiblebut not soluble-in the PVC composition: for this reason they have an
opacifying effect and are resistant to migration (with the partial
exception, in some circumstances, of certain lake pigments and organic
pigments appreciably soluble in plasticisers-see below). Dyes are
colourants soluble (Le. dispersible on a molecular level) in PVC
compositions: they are thus non-opacifying (and hence suitable for
transparent compounds) but, in general, rather prone to migration.
From the standpoint of their chemical nature, dyes are organic
compounds, whilst the pigments fall into three main groups: inorganic
compounds (mainly metal oxides), lakes (dyestuffs precipated onto
inorganic compounds, which act as bases or carriers in this combination), and organic compounds. In addition carbon black may be
regarded as forming a 'group' on its own; metal powders (usually
aluminium) are also occasionally used to impart a metallic colour
effect. The chemical composition, classification and properties of
colourants are discussed in Chapter 11, Section 11.3.
Colourants of the inorganic pigment group are the most widely and
commonly used in PVC: many of these combine good all-round
resistance and high colour value with relatively moderate cost. Inter
alia the group includes titanium dioxide ('Titanium White'), the
pigment universally employed for white compositions, and also
frequently incorporated to enhance the colour in coloured PVC
materials.
Completeness of colourant dispersion is of paramount importance
for optimum colour effect in a PVC composition, whilst ease of
handling and dispersibility of the colourant in compounding are equally

4 Elementary Principles of pvc Formulation

103

important from the point of view of operational efficiency and

economy. Colourants are available in forms particularly suited to these
requirements, viz. as premixed concentrates, or as integral components
of multicomponent 'single-pack' additive systems in which they are
intimately interdispersed with other additives, for direct, joint addition
in the course of compounding a particular type of PVC composition
(See Section 4.4.2 below). A colour concentrate may be a masterbatch
(in which a high proportion of colourant is dispersed in PVC
composition of the same kind as that to be coloured), or a colour paste
in plasticiser(s) suitable for colouring solid plasticised compositions or
pastes, or a concentrated dispersion of colourant in a carrier other than
a plasticiser, compatible with (or useful in) the PVC composition to be
coloured (e.g. a fatty acid, which may serve as lubricant). The
compounding of colourants into PVC, including the preparation of
colour concentrates, is discussed in Chapter 13, Sections 13.4.1(c),
13.4.2(a) and 13.4.3.
It is self-evident that the colourant(s) chosen for a particular
formulation must be suitable for (stable in) the conditions of
processing and ultimate service. The chemical stability of the
colourant, and its colour fastness, to heat and to any potentially
aggressive constituents of the service environment are of particular
importance. Mutual compatibility with, and stability to, the other
components of the formulation (at room as well as elevated
temperatures) is an equally important consideration: in some circumstances inorganic pigments (notably iron and zinc compounds) may
promote degradation of the PVC resin-this can happen in the
presence of an acid (even trace quantities remaining in the pigment
itself as residues from the manufacturing process). The dyestuff
components of some lakes, as well as some organic pigments, may be
sufficiently soluble in plasticisers for migration or blooming to occur in
some plasticised compositions. Colourant manufacturers are, as a rule,
very technically minded and their advice on specific formulation
problems is both readily available and worth having.

4.4.2 Interactions and Mutual Effects of Formulation Components

Most PVC compositions are complex, multicomponent systems. In
addition to the interactions involved in the components' exercising
their primary functions in accordance with the formulation (i.e.
plasticisation of the PVC resin by the plasticiser(s) and its stabilisation

104

W. V. Titow

by the stabiliser(s); lubrication of the composition by the lubricant(s);

etc.), the components can also interact in certain other ways. This
section gives a brief, general indication of the kinds of such secondary
interactions which the formulator should take into account: more
detailed discussion of some of their aspects will be found in other
chapters.
(a) Compatibility Effects
As has been mentioned, it is a cardinal general requirement that the
components of a formulation should be compatible with one another in
both processing and service conditions.
Possible effects of one component on the mutual compatibility of
some of the others should also be borne in mind. For example, the
compatibility of an external lubricant with the PVC resin (which should
be relatively limited, for the lubricant to exercise its function properly)
may be increased by the presence of plasticisers or certain polymeric
modifiers: more external lubricant will then be required in the
particular formulation than in a comparable one where the effect does
not arise (cf. Chapter 11, Section 11.1.2). Similarly, the presence in the
composition of an appreciable quantity of fine-particle filler (or
pigment) able to absorb plasticisers or lubricants may necessitate the
inclusion of these additives in proportions higher than would otherwise
be required, whilst the use of a surface-coated grade of the same filler
(with absorptivity reduced by the coating) would obviate the need for
such compensatory increase (cf. Chapter 8, Section 8.3.3., and Chapter
11, Section 11.1.2).
(b) Synergism
The action of some stabilisers can be synergistically enhanced by
certain other stabilisers or lubricants. Examples are: the effect of
organic phosphite and epoxy co-stabilisers on the heat stability and
resistance to weathering of PVC stabilised with certain stabilisers
(especially BalCd-see Section 4.4.1(b) above, and Chapters 9 and
10), and the synergism of glycerol ester lubricants with sulphurcontaining tin stabilisers, or that of calcium stearate lubricant with
antimony mercaptide stabilisers (see Chapter 11, Section 11.1.2(a)).
(c) Other Mutual Effects
Noteworthy examples are: the activating effect of some stabilisers on
blowing agents in the production of cellular PVC materials (see

4 Elementary Principles of pvc Formulation

105

Chapter 25, Section 25.3), and discoloration which may result through
interaction of some lead stabilisers with impurities in lubricants of the
glycerol ester type (cf. Chapter 11, Section 11.1.2(a)), or through the
interaction of sulphur-containing tin stabilisers with lead-containing
pigments (due to formation of coloured sulphides).
4.4.3 Side Effects of Formulation Components

Some constituents of a PVC composition can, in addition to the

function for which they are incorporated, also exert effects which are
the primary functions of other constituents; undesirable side effects
may also arise. The following examples illustrate some of the effects in
each category.
(a) 'Secondary Functionality' Effects
Such effects are illustrated and exemplified by the following:

(i)

(ii)
(iii)
(iv)
(v)

(vi)
(vii)

Stabilising action of some lubricants and lubricant action of

certain stabilisers (both permitting the use of the other
component in proportions lower than would otherwise be
necessary-see Section 4.4.1(d) above and Chapter 11, Section
11.1.2(a)).
Flow-promoting action (Le. processing-aid effect) of some
polymeric impact modifiers (see Section 4.4.1(e) above and
Chapter 11, Section 11.2).
Internal lubrication by plasticisers, and their impact-modifying
effects.
External-lubricant effect of some plasticisers and extenders (see
Chapter 11, Section 11.1.2).
Flame-retardant effect of phosphate plasticisers and chlorinated compounds used as plasticiser extenders (d. Section
4.4.1(c) above; Chapter 7, Section 7.6; Chapter 11, Section
11.5; and Chapter 12, Section 12.10).
Stabilising action of epoxy plasticisers (cf. Section 4.4.1(b)
above; Chapter 6, Section 6.10.1; and Chapter 9, Section 9.6)
Light-stabilising effect of carbon black, the universal black
pigment in many plastics compositions, including some PVC
materials (see e.g. Chapter 8, Section 8.4.3 or Chapter 11,
Section 11.3).

106

w.

V. Titow

(b) Undesirable Side-effects

Examples of such effects include:
(i)

(ii)

(iii)
(vi)
(vii)

Opacification effects of fillers, many impact modifiers and other

formulation components, which must be considered when
formulating clear compositions.
Susceptibility to 'sulphide staining' (through formation of
coloured sulphides) associated with the presence of stabilisers
which are heavy-metal compounds (especially lead and cadmium-see, for example, Section 4.4.1(b) above, and Chapter
9).
Detrimental effect of emulsion PVC polymer on the electrical
resistance of compositions based on this type of polymer (cf.
Section 4.4.1(a) above and Chapter 2).
Lowering of heat stability of PVC compositions by most
antistatic agents (ct. Chapter 11, Section 11.4).
Tendency to 'stress whitening' promoted by the presence of
some fillers (see Chapter 8, Section 8.3.3) and polymeric
modifiers (see Chapter 11, Section 11.2).

4.5 SOME SPECIAL END-USE REQUIREMENTS

Some end-use requirements may be described as special in that they
dictate, or preclude, the incorporation of certain components in a PVC
formulation. This kind of requirement may be illustrated by the
following examples.

4.5.1 Food-contact Applications (e.g. food-packaging films; bottles)

Non-toxicity of all formulation components is a prime requirement in
such applications. Stabiliser choice will in practice be limited to
selected di-n-octyl tin stabilisers (especially where the highest clarity is
a requirement) and stabiliser systems comprising compounds of
calcium, zinc and magnesium. Plasticisers, and all other components,
should be checked with current lists of permitted materials published

by organisations concerned with the health and safety aspects of

4 Elementary Principles of pvc Formulation

107

plastics products (ct. Chapter 7, Section 7.12 and Chapter 12, Section
12.9), or-in cases of doubt-directly with such organisations.
4.5.2 Resistance to Weathering
This is of paramount importance in such PVC products as rainwater
goods, window frames, cladding, fencing, films for reservoir or
swimming-pool lining, tarpaulins and the like. Particular heat stabiliser
systems, normally incorporating synergistic co-stabilisers of the epoxy
type with chelators, are highly relevant here (see Section 4.4.1(b)
above; Chapter 9; and Chapter 12, Section 12.6), and-among lead
stabilisers-dibasic lead phosphite (see Chapter 9). Ultra violet
absorbers are also widely used in weathering-resistant formulations.
Polymeric modifiers in rigid products (e.g. rain guttering and
down-pipes, window frames) should be of the type which detracts least
from good weatherability, such as VClEVA copolymers or selected
acrylic modifiers (alternatively the PVC resin used may be a VClEVA
graft copolymer-see Chapters 1 and 2).
4.5.3 Electrical Insulation
The use of emulsion PVC polymer is precluded in this application (see
Section 4.4.3(b)(iii) above, and Chapters 1 and 2) because of the
deleterious effect of the trace impurities it contains upon electrical
resistivity (and hence insulation value). Lead stabilisers are the first
choice (for the stabilisation of all but transparent compositions)
because they are electrically non-conductive. For insulation and cable
covering resistant to high temperature selected plasticisers must be
used (ct. Chapter 7, Section 7.5.3 and Chapter 12, Section 12.3).

4.6 EXAMPLES OF BASIC FORMULATIONS

The following examples illustrate something of the principal features of
basic outline formulations for some PVC products of the main groups
listed in Table 1.1, Chapter 1.

108

W. V. Titow

4.6.1 Film and Sheeting

(i) Calendered clear uPVC: food packaging grade:
PVC polymer (S* or Mt, K value 60)
Stabiliser: a di-n-octyl tin (e.g. Irgastab 17 MOLCiba-Geigy)
Lubricants:
Internal: fatty alcohol type (e.g. Irgawax 365Ciba-Geigy)
Internal/external: fatty acid ester type (e.g.
Irgawax 370)

100
11-15 phr
12-20phr
02-05 phr

If an impact modifier is included it should be of the MBS type (and

fully compatible with the lubricant system) to maintain transparency.
For maximum clarity the polymer should be of high-purity, fish-eye free
grade.
(ii) Calendered clear or pigmented uPVC with good stability to light:
technical grade:

PVC polymer (M or S, K value 60)

Stabiliser: a dibutyl tin maleate chosen for both
good heat and light stability (e.g.
Irgastab 1'9)
UV absorber: (light stabiliser, e.g. Tinuvin 320Ciba-Geigy)
Lubricants:
Internal: fatty alcohol type
Internal/external: fatty acid ester type

100
l'5-2'Ophr
02-03phr
10-12 phr
02-04phr

If titanium dioxide pigment is included its presence may further

improve stability to light.
(iii) Extruded (blown) clear uPVC film: non-toxic grade:

PVC polymer (M or S, K value 57-60)

Stabiliser: a di-n-octyltin (e.g. Irgastab 17 MO)
Lubricants:
Internal: a glycerol monoester (e.g. Irgawax 361)
Internal/external: fatty acid ester type (e.g.
Irgawax 370)
* Suspension type. t Mass type.

100
11-15 phr
05-08 phr
05-0'8 phr

4 Elementary Principles of pvc Formulation

Processing aid: an acrylic polymer (e.g. Aeryloid

K-120N-Rohm and Haas)

109

08-20 phr

(iv) Calendered, clear pPVC with good stability to light: generalpurpose and horticultural applications:
PVC polymer (S or M, K value 69-72)
Stabiliser: BalCd liquid (e.g. Irgastab BC 26)
Co-stabilisers: epoxidised soyabean oil
an organic phosphite (chelator)
Plasticisers: DOP
triaryl phosphate
UVabsorber: (light stabiliser, e.g. Tinuvin P)
External lubricant: stearic acid

100
13-16 phr
5 phr
04-0'5 phr
55 phr
10 phr
02-03 phr
02-04 phr

(v) Extruded (blown) filled pPVC film: industrial grade:

PVC polymer (S or M, K value 68-71)
Stabiliser: a BalCd soap complex (e.g. Irgastab
BC 247)
Co-stabiliser: an organic phosphite (e.g. Irgastab
CH301)
Plasticiser: DOP
Plasticiser extender: chlorinated paraffin
(50-52% CI)
Filler: whiting (a coated grade)

100
0,9-1,8 phr
0'3-0'6phr
42phr
13phr
40phr

The barium/cadmium soap stabiliser has some external lubricant action

in this composition, so additional external lubrication may not be
necessary. Otherwise about 03 phr of stearic acid may be added. It is
good practice to use a chelating co-stabiliser with solid Ba/Cd
stabilisers (in the respective proportions of 1 to 3) to improve the
initial colour and light stability of the composition.
4.6.2 Calendered Plasticised Vinyl/Asbestos Flooring (Tiles)

Vinyl chloride/acetate copolymer (K value 55,

13-15% VA)
Stabiliser: a CalZn complex powder (e.g. Irgastab

100
2'0-4'Ophr

CZ45M)

Co-stabiliser: epoxidised soyabean oil

Plasticiser: DOP
External lubricant: stearic acid

60-8Ophr
15 phr
10-2Ophr

110

w.

V. Titow

Pigment: titanium dioxide

Fillers: asbestos (chrysotile)
whiting

10-15 phr
100phr
160phr

Special grades of solid calcium/zinc complex stabilisers are produced by

most manufacturers for vinyl/asbestos flooring compositions. These
stabilisers combine good compatibility with VCNA copolymer and
asbestos, with very good heat stabilisation (even when a substantial
proportion of scrap is added to the compound) and freedom from
sulphide staining of the flooring in contact with rubber objects in
service. They have no appreciable lubricating action; an external
lubricant should, therefore, be included in the formulation; stearic acid
is particularly useful since, in addition to its lubricant effect it can also
enhance stabilisation. The amount required will normally increase with
increasing calcium carbonate filler loading (as well as when substantial
amounts of pigment are incorporated): 01 phr stearic acid per 8 phr
filler may be taken as a general guideline (but with surface-coated filler
grades the effect of the presence of the coating should be taken into
account-see Chapter 11, Section 11.1.2).

4.6.3 Pipe and Tubing

(i) Rigid pipe:

PVC polymer (S or M, K value 66)

Stabiliser: a thiotin complex
Lubricants:
Internal: glycerol monoester of a fatty acid (e.g.
a mono-oleate, Loxiol Glo-Henkel)
External: ester wax (e.g. Irgawax 360)

100
2phr
12 phr
06phr

Pigment, colourant and calcium carbonate filler (a precipitated, coated

grade) may be included.
(ii) Clear, ftexibile tubing (non-toxic-for medical use):
PVC polymer (S or M, K value 65-70)
100
Stabiliser: Ca/Zn type
15-20 phr
Co-stabiliser: epoxidised soyabean oil
2 phr
Plasticisers: DOP
10 phr
high molecular weight polyester (e.g.
37 phr
Reoplex 43O-Ciba-Geigy)
Lubricant: a glycerol monoester (e.g. Loxiol GIO)
00-06 phr

4 Elementary Principles of pvc Formulation

111

4.6.4 Cable Covering and Insulation

(i) General-purpose cable sheathing:

PVC polymer (S or M, K value 68)

Stabiliser: basic lead carbonate
Plasticiser: DIOP
Plasticiser extender: chlorinated paraffin (5052% CI)
External lubricant: dibasic lead stearate
Filler: whiting (a coated grade)

100
5phr
52phr
32phr
05-10phr
40phr

(ii) High-temperature cable compound:

PVC polymer (S or M, K value 68)

Stabiliser: dibasic lead phthalate
Plasticiser: tri-Linevol 79 trimellitate (e.g. Reomol
LTM-eiba-Geigy)
External lubricant: calcium stearate
Flame retardant: antimony trioxide

100
7phr
70phr
1phr
6phr

In this composition calcium stearate contributes to heat stabilisation

whilst acting as lubricant. Di-tridecyl phthalate (DTDP) may be used
as plasticiser instead of the more expensive trimellitate for all but the
most severe conditions (but the efficiency of the latter is better, so that
a lower proportion is required, and trimellitate-plasticised compositions retain their properties better after heating at high temperatures).
An antioxidant is desirable, especially if the compound is to be used in
thin sections. Reomol LTM already contains 02% of an effective
antioxidant (Irganox 1010).
(iii) General-purpose insulation:
PVC polymer (S or M, K value 68)
Stabiliser: basic lead carbonate
Plasticiser: DIOP
Plasticiser extender: chlorinated paraffin (5052% CI)
External lubricant (with stabilising action):
calcium stearate
Filler: whiting (a coated grade)

100
7phr
30phr
30phr
13 phr
70phr

W. V. Titow

112

4.6.5

Gramophone Records

Vinyl chloride/acetate copolymer (K value 47-S0,

lS% VA)
Stabiliser: tetrabasic lead fumarate
Lubricant: a compound or system with mainly
external action
Pigment: carbon black

100
1S-17phr
02-03 phr
10-1S phr

A copolymer resin is used for ease of processing, with low K value for
the best surface-detail reproduction (associated with ease of flow). The
carbon black should be of a sufficiently fine and readily dispersible
grade to meet this important requirement. An antistatic agent is
usually incorporated in the composition: this should be selected inter
alia for minimum effect on thermal stability.
4.6.6 Blow-moulded Bottles
(i) For mineral water:

PVC polymer (S or M, K value S8)

Stabilisers: zinc octoate
calcium stearate
Co-stabilisers: distearyl pentaerythritol diphosphite
epoxidised soyabean oil
Impact modifier: MBS type
Processing aid: acrylic type

100
0IS-020 phr
OOS-OlO phr
04-0S phr
30 phr
100 phr
OS-10 phr

All additives in a formulation for this purpos~ must be of special purity

grade (as well as permitted for food contact) because mineral water
picks up taints easily. For the same reason the use of permitted
organotin stabilisers is not recommended. The epoxy co-stabiliser has
some plasticising action. If the lubricating effect of the calcium stearate
is not sufficient in a particular moulding process lubricant(s), best
suited to the conditions, should be incorporated.
(ii) General purpose, clear:
PVC polymer (S or M, K value 54-58)

Stabiliser: liquid thiotin

Impact modifier: MBS type

100
14-16phr
10-12 phr

4 Elementary Principles of pvc Formulation

Processing aid: acrylic type

Lubricant (internal/external): fatty acid ester type

113

1-2 phr
10-15phr

4.6.7 Injection Mouldings

(i) uPVC pipe fitting:
PVC polymer (S or M, K value 55-60)
Stabiliser: a solid dialkyl tin mercaptide (e.g.

100
l'0-2'Ophr

Irgastab 1'270)
Impact modifier: ABS type
Processing aid: acrylic type
Lubricants:
Internal/external: calcium stearate
fatty acid ester type
External: polyethylene wax
Pigment: titanium dioxide
Colourant: phthalocyanine type

8-lOphr
15-25 phr
08-10 phr
O5-10 phr
005-01 phr
3 phr
002-003 phr

In rigid injection-moulding formulations for components which may be

stressed in service it is advisable to keep liquid additives to a minimum,
as they can lower heat distortion temperature.

(ii) Clear, plasticised compound:

PVC polymer (S or M, K value 65-67)
Stabiliser: liquid Ba/Cd/Zn (e.g. Irgastab BC 206)
Co-stabiliser: epoxidised soyabean oil
External lubricant: liquid, non-polar type (e.g.

Irgawax 360)

100
1,5-25 phr
5phr
03-05 phr

The lubricant used should be chosen, inter alia, for its suitability in a
clear formulation.

(iii) Oil-resistant soling compound:

PVC polymer (S, K value 66-70)
Stabiliser: solid Ba/Cd
Co-stabiliser: epoxidised soyabean oil
Plasticiser: DIOP
Polymeric modifier: nitrile rubber

100
4phr
5phr
80phr
33phr

114

w.

V. Titow

4.6.8 Extruded Profile

(i) High-impact uPVC:
PVC polymer (S or M, K value 60)
Stabilisers: tribasic lead sulphate
dibasic lead stearate
Lubricants (internal/external): fatty acid ester
type
calcium stearate
Impact modifier: ABS type
Processing aid: acrylic type

100
6phr
1 phr
l'9-2'Ophr
0'4-0'8phr
6-10 phr
18-22phr

(ii) Flexible composition:

PVC polymer (S or M, K value 68-70)
Stabiliser: a BalCd soap complex (e.g. Irgastab
BC 247)
Co-stabiliser: an organic phosphite (e.g. decyl
diphenyl phosphite, Irgastab CH 301)
epoxidised soyabean oil
Plasticiser: DOP
External lubricant: stearic acid

100
12-15 phr
04-05 phr
5 phr
47 phr
0'1-04 phr

This is a non-transparent composition which may be pigmented. The

BalCd stabiliser provides some lubrication, reinforced as necessary by
the stearic acid.

4.6.9 Paste Formulations

(i) Cold-dipping paste:
PVC polymer (E, * K value 69-72)
Stabiliser: basic lead carbonate
Plasticisers: DOP
DOS

100
2phr
65 phr
17phr

(ii) Conveyor belting:

PVC polymer (E, K value 69-72)
Stabiliser: tribasic lead sulphate

* Emulsion type.

100
20-30phr

Elementary Principles of pvc Formulation

Plasticiser: triaryl phosphate

Plasticiser extender: chlorinated paraffin (45% CI)
Flame retardant: antimony trioxide
Antistatic agent: e.g. Lankrostat LA3 (Lankro
Chemicals)

115

40phr
35phr
5 phr
lOphr

(iii) Composite coating for upholstery fabric:

Base coat
PVC polymer (E, K value 70)
Stabiliser: liquid Ca/Zn (e.g. Irgastab CZ 57)
Co-stabiliser: epoxidised soyabean oil
Plasticiser: Dap
Filler: whiting
Intermediate (expanded) coat
PVC polymer (E, K value 68-70)
Stabiliser/activator: liquid, zinc-containing (e.g.
Irgastab ABC 2)
Co-stabiliser: epoxidised soyabean oil
Plasticisers: Dap
BBP
Blowing agent: azodicarbonamide (paste, 1: 1
in Dap)
Filler: fine ground whiting

100
15-30 phr
50 phr
85phr
20phr

100
15-25 phr
6'0-8'Ophr
45phr
30phr
25-45 phr
5phr

The zinc-based stabiliser is selected to act also as an activator ('kicker')

for the blowing agent in this foaming composition. The BBP (butyl
benzyl phthalate) is a highly solvating plasticiser, widely used in PVC
foam formulations for rapid, uniform fusion of the composition.
Top coat
PVC polymer (E, K value 70-72)
Stabiliser: liquid BalCd/Zn complex (e.g. Irgastab
BC206)
Co-stabiliser: epoxidised soyabean oil
Plasticiser: DDP
Pigment: titanium dioxide
Filler: whiting
Colourant: as required

100
15-25 phr
50 phr
52phr
0'0-3'Ophr
00-100 phr

The stabiliser is one suitable for clear PVC to enable the formulation
to be used for unpigmented, unfilled compositions.

CHAPTER 5

Theoretical Aspects ofPlasticisation

D. L.

BUSZARD

5.1 GENERAL INTRODUCTION

This is the first of three chapters covering various aspects of plasticisers

and plasticisation. It concentrates on the more theoretical aspects of
the requirements for a PVC plasticiser, theories of plasticiser action
and the major effects of PVC-plasticiser interaction on physical
properties. The more practical commercial aspects and the performance orientated properties are dealt with in later chapters.
5.2

DEFINITION OF PLASTICISERS AND

PLASTICISATION

In September 1951, the Council of the International Union of Pure and

Applied Chemistry (IUPAC) adopted the following definition:
A plasticiser or softener is a substance or material
incorporated in a material (usually a plastic or elastomer) to
increase its flexibility, workability or distensibility. A plasticiser may reduce the melt viscosity, lower the temperature of
the second-order transition or lower the elastic modulus of
the melt.
This may appear to be an unnecessarily elaborate definition, but it
highlights the many functions a plasticiser can have in any given
polymer-plasticiser system. Thus for surface coatings and thin films, a
plasticiser may be defined more specifically as a compound which gives
117

118

D. L. Buszard

flexibility, impact resistance, handle, feel, etc. In rubber, plasticisers

reduce stiffness, permit easier processing and may improve flexibility at
lower temperatures. In thermosetting polymers and certain rigid
thermoplastics, they assist processing and ease of moulding. In PVC,
plasticisers convert the rigid, intractable resins into workable compounds which can exhibit a wide range of properties, depending on the
type and concentration of plasticisers used.
The properties required of plasticisers, or the plasticised PVC
products, generally include compatibility with the resins, non-volatility,
non-flammability, good heat and light stability, good low-temperature
performance and non-toxicity. To some extent these requirements may
conflict, and no single plasticiser can satisfy them all completely. For
this reason plasticiser mixtures are used. In practice, the choice of
plasticiser or even plasticiser mixture will usually involve some form of
compromise.
Plasticisers may be divided into two groups-primary and secondary-with the rather arbitrary division between them depending
mainly on their compatibility with the resins. Primary plasticisers are
highly compatible with PVC polymers up to at least 150 phr. Secondary
plasticisers are less compatible, and are generally used in mixtures with
a primary plasticiser in order to confer some special balance of
properties. The extenders form a branch of this group; they have a
very limited compatibility, but may be included in plasticised
compositions as a part-replacement for other plasticisers to reduce
cost.
At this stage it would be useful to distinguish between 'internal' and
'external' plasticisation of PVc. The above remarks and the sections
ahead apply to externally plasticised PVC, i.e. the resin compounded
with the plasticiser. However, as mentioned in Chapter 1, it is possible
to plasticise internally by copolymerising other monomers into the
chain in order to produce a less uniform, and hence less cohesive,
structure. Chain flexibility may increase, as in copolymers with
vinylidene chloride, vinyl acetate, propylene or alkyl vinyl ethers, thus
giving properties resembling externally plasticised PVC. The principal
technological advantage of internally plasticised systems is a reduction
in the processing temperature of the polymer, and the main functional
benefit is that such systems cannot suffer loss of plasticiser. However,
resins plasticised internally by copolymerisation are generally inferior
to externally plasticised systems in strength and low-temperature
properties.

Theoretical Aspects of Plasticisation

119

5.3 CHEMICAL NATURE OF PLASTICISERS

PVC plasticisers are mainly organic esters with high boiling points.
About two-thirds of the plasticisers in general use are diesters of
phthalic anhydride with CCC lO alcohols. Cs alcohols offer the best
balance of properties for general-purpose plasticisers. The other classes
of more specialised plasticisers are triaryl phosphates, alkyl esters of
dibasic alkyl acids, alkyl trimellitate esters, high molecular weight
polyesters and epoxies. The majority of the extender plasticisers in
common use are chlorinated paraffins or hydrocarbons. Table 5.1 gives
a breakdown of the consumption of plasticisers for PVC as calculated
from information gathered by the British Plastics Federation.!
The expressions 'monomeric plasticiser' and 'polymeric plasticiser'
are commonly and widely used. Although their meaning is well
understood in the art, and rarely causes confusion, it should be
remembered that neither term is strictly accurate.
Monomeric plasticisers are not monomers in the accepted sense of
polymerisable compounds. The word monomeric was originally, and in
this context incorrectly, used as the opposite of polymeric to
distinguish between high molecular weight plasticisers, many of which
were indeed polymers, and compounds of considerably lower molecular weight. The latter might perhaps be better described as simple ester
plasticisers or low molecular weight plasticisers, since in most cases
their molecular weights lie between 300 and 500.
The term polymeric plasticiser is less of a misnomer in that
plasticisers produced by polymerisation (e.g. the polyesters with
TABLE 5.1

Types and Relative Proportions of Plasticisers Used in the

UK in 1981

Plasticiser class

Phthalates
Phosphates
Aliphatic dibasic acid esters
Trimellitates
Polymerics
Epoxies
Chlorinated paraffins
Hydrocarbons
Others

% by weight
740

50
20
05

19

50

95
19

02

120

D. L. Buszard

molecular weights up to 8000) are certainly included under

heading. However, the name is not confined to polyesters, but is
extended to other high molecular weight plasticisers which are
polymers--e.g. high molecular weight complex esters with
polymeric repeat units, or epoxidised oils.

this
also
not
no

5.4 mEORIES OF PLASTICISATION

Two major theories have been proposed to account for the effects of
plasticisation. In the Lubricity Theory, advanced initially by
Kirkpatrick2 and others,3,4 the plasticiser was considered to act as a
lubricant for the sliding contact of the polymer chains, thus facilitating
deformation by reducing intermolecular friction.
An alternative theory was developed through the work of
Doolittle,5,6 and has become known as the Gel Theory. This suggests
that the resistance to deformation of amorphous polymers is due to the
formation of a loose, three-dimensional honeycomb structure, with the
cross-links originating from active centres along the polymer chains.
These active centre cross-links continually break down and re-form in
what has been termed an aggregation-disaggregation equilibrium. In a
plasticised system, while the polymer molecules are continually making
and breaking their contacts with each other, the plasticiser molecules
are also attaching themselves to active centres. The combined effect is
such that, under a given set of conditions, a proportion of active
centres will be solvated or masked by the plasticiser molecules and
hence will be eliminated as potential cross-linking points in the
polymer chain. The second equilibrium has been termed the
solvation-desolvation equilibrium, and it operates simultaneously with
the aggregation-disaggregation equilibrium.
It has been suggested that, in the case of PVC, these active centres
are the dipoles in the polymer chain. The mechanism of dipole
attraction has been discussed in a review by Leuchs. 7 He suggested two
types of plasticiser action-hinge and screen (Fig. 5.1). The hinge type
plasticisers are typified by the readily polarisable aromatic compounds,
and the screen types by polar, aliphatic esters.
An alternative, and in the light of more recent work, more plausible
proposal for active centres in PVC is that the cross-links are actually
areas of ordered structure or crystallites in the polymer. 8,9 This was
extended by Walter,lO who investigated the crystallisation of PVC in

5 Theoretical Aspects of Plasticisation

121

+-

+Scr~~n typ~

Hing~ typ~

Fig. 5.1 Plasticiser mechanisms (after Leuchs7).

the presence of plasticiser, including studies comparing the crystallite

network structure to that of vulcanised rubber.
Observations by Dotyll and Hengstenberg 12 showed that in dilute
solutions with most solvents PVC forms aggregates involving an
average of 11-20 repeat units of the polymer chainY More recent
work on PVC-plasticiser gels 14 ,15 also shows the aggregation of PVC
molecules and demonstrates that the viscoelastic properties exhibited
by such gels are more consistent with semi-permanent crystallite
bonding than with the more labile bonding originating from polar
interaction. Examination of the plasticisation and solvent swelling
properties of a more crystalline syndiotactic PVC 16 ,17 again points to the
importance of crystallinity in determining the physical properties of
plasticised PVC.
However, further work has shown the existence of other morphological features in plasticised PVC, which exhibit structural regularities
unrelated to the crystallinity but which are dependent, at least in part,
on processing conditions. 18-21
It would thus appear likely that the mechanism of plasticiser-PVC
interaction is complex and dependent upon interaction at a number of
levels. These may include energy and entropy factors resulting from
the redistribution of polymer chains, an atomic level interaction of
dipoles and interaction within crystallite, or possibly larger, structures.
The above outline of plasticisation mechanisms has of necessity been

122

D. L. Buszard

very brief. For more detailed reviews of the theories the reader is
referred to several textbooks which cover the subject in much greater
depth,6,22,23 or to an extensive review of relevant literature, prepared
by Stafford for the RAPRA PVC-plasticiser Group.24,25
5.5

STAGES OF PLASTICISER INTERACTION WITH

PVC POLYMER

From the time a plasticiser first comes into contact with a PVC
polymer until the production of the final fused product-and possibly
even for some time after this-a complex series of interactions occurs.
Since the precise processing conditions and heat history of a PVC
plastisol are easier to control, the majority of the initial work
concentrated on the liquid-solid transition. Stich studies demonstrated
that increasing temperature led to an initial lowering of viscosity,
followed by a rapid rise. 26 ,27 Alter26 described the vertical region of the
viscosity/temperature curve as the gel region. Newton and Cronin27
refer to the attainment of 1000 P as the setting temperature.
McKenna28 devised a temperature gradient bar, and, by casting and
stripping of PVC films, determined gelation temperatures. Greenhoe 29
continued work on the temperature gradient bar and was able to define
six transition points between liquid plastisol and the fully fused
product. These were, with increasing temperature, the fluid point
(where the plastisol becomes dry and putty-like), dry point (where it
changes to a dry, crumbly solid), gel point (where physical strength
begins), haze point (where clarity increases), elastomeric point (where
tensile strength and elongation to break develop), and fusion point
(where optimum tensile strengh is attained).
Wheeler and Clifton30 used the concept of the temperature gradient
bar to develop the Geigy Gel Block, and Critchley et ai. 31 published
an extensive comparison of the gelation properties of different
plasticisers determined with this apparatus.
Although for practical reasons it is easier to follow PVC-plasticiser
interaction in plastisols, similar studies have been carried out on melt
blends, using a Brabender Plasti-Corder,32 and on dry blending. 33 ,34
Van Veersen and Dijkers34 compared published data from different
sources,35-39 and demonstrated that different methods involving
different processing techniques still show a comparable trend for the
solvation process of PVC when mixed with plasticisers (Table 5.2).

Diethyl phthalate
Dibutyl phthalate
Dihexyl phthalate
Dioctyl phthalate
Diisodecyl phthalate

Plasticiser

92
97

127
138

56
60

80
86

88
86
104
118
132

eC)

eC)

72

Solid/gel
transition
temperature3?
(0C)

Solvation
point 36

Dry point 35

65
75
75
80
85

Maximum
swelling
temperature 38
eC)

Comparison of Plasticiser Absorption of PVC by Different Methods

TABLE 5.2

58
62
84
84
94

Relative
melting
temperature39
(0C)

N
W

......

S"
;:.

1:;'

"l::l

~::to

"'"f;;

i:l

'"
"~
::to

<:;)

...'"

;;l

u,

124

D. L. Buszard

Sears, Darby and Touchette40 ,41 summarised the stages of plasticisation as follows:
(i) Irreversible uptake of plasticiser into the porous resin.
(ii) Absorption of the plasticiser, during which the total resinplasticiser volume may decrease although the resin particles
swell slowly on the outside.
(iii) Diffusion of the plasticiser within the particles with little or no
volume change, but involving high activation energies. At this
stage the plasticiser is probably present as clusters of molecules
between bundles of polymer segments or molecules.
(iv) The final stage of plasticisation when the plasticiser molecules
penetrate the bundles of polymer molecules so that they are no
longer rigidly held together but behave as a polymer in its
rubbery rather than glassy state.
In some processes these four steps may not be clearly defined and may
overlap. With the usual plasticisers for PVC, of moderate molecular
weight, plasticisation can only proceed through the first two steps at
room temperature. Steps (iii) and (iv) have high activation energies
thus requiring a threshold temperature to be reached.
5.6 REQUIREMENTS FOR PVC PLASTICISERS
It is obviously of great importance for the plastics industry to be able

to select 'good' plasticisers. There is no standardised definition, but the

term is usually concerned with the following general requirements:
(i) compatibility and ease of mixing;
(ii) effectivity in imparting a desirable property or properties
(usually softness or flexibility) to the plasticised polymer;
(iii) permanence.
Unfortunately, some properties of a plasticiser helpful in one aspect
may actually be detrimental in another. For example, a high rate of
diffusion will increase efficiency and rate of gelation but make for
poorer permanence. A good plasticiser is therefore one which fulfils
simultaneously all three principal requirements to the degree necessary
for a particular application. In practice, the choice is generally a
compromise governed by the processing technique to be used, the end
application of the plasticised material and economic factors. Neverthe-

5 Theoretical Aspects of Plasticisation

125

less, it is obviously desirable to be able to assess and compare the

merits of plasticisers in relation to the above three criteria. The subject
has been discussed in detail by Jones et al. 42 and in some aspects by
Boyer,43 Immergut and Mark22 and Van Veersen and Meulenberg.37,44
The following methods of assessing the plasticising characteristics of
plasticisers and/or their correlation with their more fundamental
properties are considered worthy of interest.

5.6.1 Compatibility and Miscibility

There are several theoretical techniques, as well as a number of more
practical technological tests, by which likely plasticisers may be
assessed for their compatibility with PVc.
(a) The J1. Value
This is a numerical index of the degree of interaction (or mixing)
between polymer and plasticiser, and can be determined from the
swelling equilibria of lightly cross-linked polymer film immersed in
plasticiser. J1. is calculated from the equation
2

/-LV2 =

-In (1- V2) -

P2 VIV~

V2 - - - -

Me

where Me is the average molecular weight of the polymer segment

between cross-links, P2 is the density of the polymer, V2 is the volume
fraction of the polymer and VI is the molar volume of the solvent. The
method has been developed by Gee45 and was successfully applied by
Doty and Zable 46 to the evaluation of the miscibility of dialkyl
phthalate plasticisers with PVc. Plasticisers with Jl values below 055
are highly miscible and those above are partly miscible or immiscible
(Fig. 5.2).
(b) Solubility Parameter ()
The Hildebrand solubility parameter () is related directly to a
compound's cohesive energy density, and is a constant for any given
compound. It can be shown 47 ,48 that, given certain not unduly
restrictive conditions, the miscibility of a solvent and solute (or PVC
polymer and plasticiser) will in general be greater the smaller the
difference between their solubility parameters. These values are
therefore a guide to compatibility and miscibility.49

126

D. L. Buszard

+',5

+1

0+..........;........-.__

~ I
o~

~ I

-IO'C----,,:OO,;:_

200

500
Molcculor Wclqhl

Fig. 5.2 Doty!J. value versus molecular weight. 1, Diethyl phthalate; 2,

dibutyl phthalate; 3, dihexyl phthalate; 4, dioctyl phthalate; 5, dilauryl
phthalate.

Solubility parameters can be calculated from the structural formula

and density of the compound involved48 ,sQ-s2 or determined experimentally. Table 5.3 lists the solubility parameters of some common
plasticisers, calculated by the method of Small. so
The solubility parameter is generally a useful guide to the probable
compatibility of plasticisers with a particular polymer, providing a
number of factors are taken into consideration:
(i)

the degree of hydrogen bonding power, and whether the

polymer is a proton donor or acceptor;
(ii) the degree of crystallinity of the polymer;
(iii) possible steric effects in the polymer.
The importance of the last, which is often disregarded, is highlighted

127

5 Theoretical Aspects of Plasticisation

TABLE 5.3

Solubility Parameters of Common Plasticisers

Plasticiser

Molecular
weight

Solubility
parameter
t> (call/2 mrl/2)

194
278
278
362
390
390
418

105
94

Dimethyl phthalate
Dibutyl phthalate
Diisobutyl phthalate
Dihexyl phthalate
Dioctyl phthalate
Diisooctyl phthalate
Dinonyl phthalate
Diisodecyl phthalate
Benzyl butyl phthalate
Tritolyl phosphate
Trixylyl phosphate
Dioctyl sebacate
Ceredor S52 (ICI)

92

90
885
885
85
85

446

312
326
410
426

99

98
975
84
93
97

Polyvinyl chloridea
a Solubility

parameter given for PVC for comparison.

by the plasticising effect of pure isomers of TXP, all of which have the
same calculated solubility parameter53 of 975 but widely differing
compatibility and plasticising effects (Table 5.4).
The solubility parameter of the chlorinated paraffin, Ceredor 552,
suggests that it should be much more compatible than is found in
practice.
TABLE 5.4

Compatibility and Plasticising Effect of Isomers of TXP

Xylenol isomer

Melting point of
TXpeC)

2:6
2:5
3:4
2:3

137

2:4

Liquid at room
temperature

3:5

78
71

58
40

Plasticising effect
Stiffest composition
Most incompatible
Not compatible
Borderline compatibility
Compatible
Compatible

D. L. Buszard

128

(c) Clear Point Temperature

This has been variously termed clear point, solid-gel transition,
fusion point, solution temperature and apparent melting temperature,
but basically it is the temperature at which a mixture of PVC
and plasticiser becomes clear or undergoes an apparent phase
change. 36-38,54-56 It gives an indication of the compatibility and solvent
power of a plasticiser, both of which are greater the lower the clear
point temperature. Test techniques vary considerably-from the use of
fairly concentrated suspensions to the use of 4% suspens\ons, as
described by Van Veersen and Meulenberg,37 or 5% suspensions, as in
the German Standard57 and even virtually single particles in excess
plasticiser. 56 ,58
Although there is variation in the values published, no doubt
because of the wide differences in experimental technique and
variations in polymer and plasticiser samples, the relative ordering of
plasticisers is fairly consistent.
Typical clear point values for common plasticisers are shown in
Table 5.5.
(d) Flory-Huggins Interaction Parameter X
It has been shown that the Flory theory of melting in the presence of a
diluent could be applied to PVC-plasticiser interaction,56,59 and that
the X values correlated well with observed compatibilities.
Anagnostopoulos et al. 56,59 correlated the values of X with the clear
point, using the equation
-

Tm

0'002226+0'3151(1- X)/V i )

(1)

where Vi is the molar volume of the plastidser at the clear point

temperature, T m'
Plasticisers with X values of O55 or above are generally regarded as
incompatible, values between 055 and 03 show moderate to poor
compatibility, and values below 03 good compatibility. It is interesting
to note that arranging plasticisers by X values gives a different order
from that suggested by other methods, for example solubility
parameter, and that particularly in the case of Ceredor S52, the X value
bears more relation to the observed compatibility (Table 5.6).
Unfortunately, the molar volume of the plasticiser at the clear point
temperature is not a readily determinable factor. Bigg58 proposed that

5 Theoretical Aspects of Plasticisation

129

TABLE 5.5

Clear Point Temperatures of Commercial Plasticisers

Plasticiser

Clear point
temperature
(0C)

Dioctyl phthalate
Diisooctyl phthalate
Di-Linevol 79 phthalate
Diisodecyl phthalate
Ditridecyl phthalate
Benzyl butyl phthalate
Low temperature Dioctyl adipate
Diisodecyl adipate
plasticisers
Dioctyl azelate
Dioctyl sebacate
Tritolyl phosphate
Phosphates
Trixylyl phosphate
Re%s 50 (Ciba-Geigy)
Santiciser 148 (Monsanto)
Trioctyl phosphate
Trioctyl trimellitate
Trimellitates
Reomol LTM (Ciba-Geigy)
Morflex 525 (Pfizer)
Crestapol538 (Scott Bader)
Polymerics
Diolpate 150 (Briggs & Townsend)
Diolpate 171
Palamoll 644 (BASF)
Plastolein 9503 (Unilever-Emery)
Plastolein 9506
PLastoLein 9765
ReopLex 430 (Ciba-Geigy)
Reoplex GL
ReopLex 903
ULtramoll I (Bayer)
ULtramoll II

Phthalates

117
116
114

139

150

102
138

156
154
151

98
101
100
98

118

142
132
147

138
164
137
155

141
144
151
163

123

153
155
165

since liTm is proportional to (1 - X)1V1 in eqn 1, VI could be replaced

by the molecular weight, MW, of the plasticiser to give an interaction
parameter, lX, as defined in eqn 2
a = (1- X)

MW

The values of

lX

103

(2)

are also shown in Table 5.6. These correlate

D. L. Buszard

130

TABLE 5.6
Flory-Huggins Interaction Parameters (X)

Plasticiser

Xb

053

062
052
048
032

Dioetyl sebaeate
Ceredor S52 (ICI)
Dioetyl adipate
Trioetyl trimellitate
Benzyl butyl phthalate
Mesamoll (Bayer)
Dioetyl phthalate
Dibutyl phthalate
Oetyl diphenyl phosphate

O 28
010
-003
-005
-035

017

007
005
004
-002

lYe

08
10
14
12
26
25
24
34
33

Calculated by Anagnostopoulos. 56 ,59

58
b Calculated by Bigg.
58
C Calculated by Bigg
from eqn 2.
Q

reasonably well with the Flory-Huggins X values calculated by both

Anagnostopoulos56 ,59 and Bigg,58 as well as with observed compatibilities of plasticisers. Bigg60 also demonstrated that the interaction
parameter, a, related well to the viscosity ageing characteristics of
PVC plastisols.
(e) AplPo Ratio
This was deivsed by Van Veersen and Meulenberg37 ,44,61 as a very
simplistic way of representing the polar-non-polar balance of a
plasticiser by a single figure. It is calculated by dividing the number of
C atoms in a plasticiser molecule by the number of ester groups
present. Aromatic C atoms are not counted.
For example, dioctyl azelate has two chains containing 8 C atoms
and one chain with 7 C atoms-the dibasic acid. The AplPo ratio is
therefore

(2x8)+7 = 11.5
2
Similarly, the dioctyl phthalates have an AplPo ratio of 8 since aromatic
C atoms are ignored.
The AplPo ratio of a wide range of plasticisers correlates well with a
number of properties, including melting point, specific gravity,
modulus, water absorption, etc. (see also Section 5.7).

131

Theoretical Aspects of Plasticisation

TABLE 5.7

Plasticiser
Dimethyl phthalate
Diethyl phthalate
Dibutyl phthalate
Dibutyl succinate
Dihexyl phthalate
Dibutyl adipate
Dioctyl adipate
Dibutyl sebacate
Trioctyl phosphate
Dihexyl azelate
Dioctyl adipate
Diisodecyl phthalate
Dioctyl azelate
Dioctyl sebacate
Ditridecyl phthalate

SGTT

eC)
93
88
86
96
104
98

1
2

121
127

8
95
10

118
117

137

139
142

150
151

4
5

6
8
8

10
115

12
13

The AplPo ratio also correlates well with the clear point temperature,
termed Solid-Gel Transition Temperature (SGTT) by Van Veersen
and Meulenberg37 (Table 5.7). In the same paper they also show clear
relationships with the data of Anagnostopoulos et al., 56 Darby and
Graham,36 Wiirstlin and Klein,62 Jasse,63 and Doty and Zable. 46
(f) Loop or Roll Compatibility Tests
These are extremely simple but very useful tests for assessing the
compatibilities of plasticisers or plasticiser mixtures in a given PVC
formulation. A number of test method variations exist, with differing
degrees of severity, but the general principle is as follows.
A test strip is moulded from the compound and rolled into a fairly
tight roll,37 or bent into a loop of fixed dimensions,64 and stored under
controlled conditions. Compatibility is judged on the amount of
plasticiser exuding out of the compound, when the tension is released,
from the inner surfaces of the PVC sample. The assessment is normally
visual, and although therefore subjective, a considerable degree of
accuracy can be achieved. It is well worthwhile carrying out such a
test-which takes at most 24 h-on any formulation in which
incompatibility can be a problem.

132

D. L. Buszard

(g) Maximum Torque Temperature

This is a method of assessing the interaction between plasticisers and
PVC by means of relative fusion temperature in a Brabender
Plastograph. It has been described by Touchette et at. 39 and by
McKinney32 (see also Section 5.5).
Generally, either time to maximum torque at a fixed temperature or
temperature of maximum torque (with an increasing. chamber
temperature of, for example, 2C min-I) are taken as an indication of
fusion rate or relative interaction. This appears to relate reasonably
well to other methods of assessing interaction.
However, the temperature of maximum torque cannot be taken as
an indication that fusion is complete, as has been suggested by
McKinney,32 since samples of PVC removed from the chamber after
the peak has occurred may still be incompletely gelled or fused, as
shown by an acetone disintegration test. 65 An extensive, regularly
updated bibliography of papers relating to this test method is available
from Brabender. 66

5.6.2 Effectivity of Plasticisers

In fundamental studies, the extent to which the glass temperature (Tg )
of the polymer is lowered by the introduction of a given amount of
plasticiser is frequently used as a criterion of effectivity, since the effect
can be related to the magnitude and mode of changes in polymer chain
mobility.22 Changes in certain dynamic mechanical properties (modulus and damping) are also used. 22 ,41
In the technological context, plasticiser effectivity is usually
expressed and compared in terms of the amount of plasticiser required
to achieve a stated value of some selected property, generally of direct
practical interest. Comparisons have been made on the basis of
elongation, torsional modulus, resilience, 100% tensile modulus, and
hardness. Jones et at. 42 calculated composite or average effective
quantity values for several plasticisers from room temperature
flexibility, 100% modulus, hardness, and tensile creep determinations.
The results are given in Table 5.8.
Many plasticiser manufacturers now include performance data on
their products not only at equal plasticiser content, but also at equal
efficiency as judged by hardness or 100% modulus. Alternatively, an
efficiency factor may be given for a plasticiser, again judged by

Theoretical Aspects of Plasticisation

133

TABLE 5.8
Effectivity Quantities for Common Plasticisers

Plasticiser
Tritolyl phosphate 40/42 ORD
(ORD = ordinary)
Tritolyl phosphate 40/42 LOC
(LOC = low ortho content)
Tritolyl phosphate 52/53 LOC
Tritolyl phosphate HOC
(HOC = high ortho content)
Tritolyl phosphate (tri ortho)
Tritolyl phosphate (tri meta)
Tritolyl phosphate (tri para)
Trixylenyl phosphate
Dibutyl phthalate
Diisobutyl phthalate
Diheptyl phthalate
Dioctyl phthalate
Diisooctyl phthalate
Dicapryl phthalate
Dinonyl phthalate
Dibutyl sebacate
Diisobutyl sebacate
Dioctyl sebacate
Dicyclohexyl sebacate
Paraplex G25 (Rohm & Haas)

Paraplex G50

Average effectivity quantity

350
358
353
363
372
344
381
366
277
297
349
340
353
353
375
275
289
337
332
392
387

hardness or modulus and perhaps related to the performance of a

common plasticiser such as dioctyl phthalate (DOP). Table 5.9 has
been extracted from the technical literature of Albright and Wilson.
It may be thought that a good effectivity is an important property for
a plasticiser and in many cases this is so. However, on occasion the
converse is true. For example, if the plasticiser is appreciably cheaper
than the PVC resin, the lower its effectivity the more will be required
to reach a given modulus or hardness and hence the compound cost
will be lower. In plastisol formulations lower plastisol viscosities and
usually better ageing characteristics may be obtained by using larger
quantities of less efficient plasticiser. (Dinonyl phthalate is particularly
useful in this type of formulation.)

D. L. Buszard

134

TABLE 5.9
Efficiency" of Common Plasticisers Relative to DOP

Plasticiser
Epoxidised soyabean oil
Tricresyl phosphate
Trixylyl phosphate
Dibutyl phthalate
Diisobutyl phthalate
Dioctyl phthalate
Diisooctyl phthalate
Di- Alphanol 79 phthalate
Dinonyl phthalate
Diisodecyl phthalate
Ditridecyl phthalate
Diisooctyl adipate
Diisooctyl azelate
Dibutyl sebacate

Relative efficiency
106
1-13
120
086
100
100
102

094
110
106
118

084
089

072

a The

efficiency factor of a plasticiser is the number of parts

by weight of that plasticiser per 100 parts by weight of PVC
required to give a compound with a modulus, at 100%
elongation at 23C, of 1100 lbf in -2 (76 MN m -2) divided
by 62,8, the corresponding value for dioctyl phthalate
(DOP).

Many of the methods of determining the various aspects of

plasticiser efficiency mentioned above are basic test methods embodied
in national and international standards and specifications, and are
listed in Appendix 1, Section 4.
5.6.3 Pennanence of Plasticisers
It is obviously desirable that once the plasticiser is compounded with
the PVC resin it should be permanently retained. Its loss would not
only cause changes in the properties of the system, but may also have
undesirable external side-effects. For example, plasticised PVC floor
tiles bedded with a bitumen adhesive may blister or lift as a result of
migration of plasticiser from the tile into the adhesive. Permanence is
therefore a necessary property of a good plasticiser.
In practice there are three specific modes of loss of plasticiser from a

5 Theoretical Aspects of Plasticisation

135

plasticised composition. These are:

Volatilisation-in which plasticiser is lost at a surface into air.
Extraction-in which plasticiser is lost at a surface into a liquid.
Migration-in which plasticiser is lost by transference between two
surfaces in intimate contact.
Practical examples of applications for plasticised PVC where these
modes of loss are important are, respectively, high temperature cable,
PVC tubing and refrigerator gaskets.
A fourth mode of loss which is rarely encountered in practical
circumstances is exudation under pressure. 67 However, it is the critical
stage of this phenomenon which is utilised in the loop and roll
compatibility tests (see Section 5.6.1(f)).
It has been suggested by Reed 68 that for a plasticiser to be
satisfactory in general use it should have a boiling point of at least
225C at 4 torr, so that no appreciable volatility losses occur under
room temperature conditions.
Studies of the factors affecting loss by volatility of the plasticiser
from PVC compositions have shown that it is proportional to surface
area,68 sample thickness,68 time,69,7o and increasing air flow 71 ,n (see
also Chapter 12, Section 12.3).
Losses by extraction are generally more complex. In a simple case,
where the extractant, for example a 5% soap solution, merely removes
plasticiser from the surface, the process is controlled by the solid phase
diffusion of plasticiser through the PVC compound. 70 However, a
number of extractants such as petrol, alcohol, etc., are absorbed and
swell the PVC matrix, thus increasing rates of diffusion.
Plasticiser migration is a diffusion process in which the plasticiser
from one material with a high concentration diffuses into another with
a lower concentration. A considerable amount of work has been
carried out by Knappe 73-75 on diffusion and migration from PVC to
other substrates.
It can also be shown that the penetration of many plasticisers
through PVC (which is closely associated with miscibility and solvent
power) varies directly with the bulk density. In Fig. 5.3(a) and (b) the
'apparent' diffusion coefficients (D*) of some plasticisers, determined
by Knappe,73 have been plotted against the viscosity of the same
plasticisers determined at the appropriate temperatures. 76 The linear
relationship is clearly evident.

D. L. Buszard

136

(a)
f------"'.

......
E1""'-

"

''9

(1 )

10

......0

""
I

.,

-10

10

OOA
OBP
EI OOS

"

OOP
x TTP
o ONP

E1'\

\
"\

(2)

".

X\

'{
0

10

20

30

40

50

60

70

Viscosily (c S)

Fig. 5.3 Variation of diffusion of plasticisers in PVC with their bulk viscosity.
(a) At 40C; (b) at 80C. Initial weight concentration ratios: plot 1, 30: 50 wt%;
plot 2, 10:30wt%.

5.7 GENERAL RELATIONSHIPS BETWEEN THE

STRUCTURE OF PLASTICISERS AND
THEIR HEHAVIOUR IN PVC
Several workers have drawn attention to interesting and wide-ranging
regularities which may be considered to amount to significant

137

Theoretical Aspects of Plasticisation

(b)

I
-7
10

..
..........
e

...........

---

(11 .......

--

r---..

I!

..~ r--.-.

~ ~21

,
,

.11>

-. 0

10
10 I
3

Fig.5.3-contd.

9
ViscositJ (cS I

correlations between the structure of plasticisers and their plasticising

properties. 37 ,44,77,78 The following generalisations may be made after
observing the effect of shape-determining features on the performance
of plasticisers:
Influence
Feature
Molecular weight
Increasing molecular weight reduces migration, softening efficiency and volatility.
Polarity
Incorporating extra polar groups
such as ether groups in diesters,
substituting halogens into the benzene ring of phthalates, or substituting aryl groups for alkyl ones,
reduces
softening
efficiency
worsens low temperature properties, improves solvation and reduces extraction by aliphatic
solvents. 44,79

138

D. L. Buszard

Alkyl chain length

Alkyl chain linearity

Separation of ester grouping

Reversal of ester grouping

Increasing alkyl chain length improves the efficiency of aliphatic

and phthalate diesters at equimolar
concentrations. Efficiency at equal
weight concentrations is, however,
largely independent of chain
length. 62
Increasing linearity improves lowtemperature flexibility and efficiency,
and
reduces
electrical
resistivity.80,81
Increasing the distance between
ester groups at a constant Ap/Po
ratio (see Section 5.6.1 and below)
increases
solvation,
softening
efficiency and effectiveness. 44
A change from a dibasic acid ester
to a dihydric alcohol ester of similar chain length leads to a decrease
in solvation, compatibility and
efficiency 44 (e.g. di-n-octyl adipate
is a better plasticiser than 1,4butylene glycol dipelargonate).

These parameters also influence the relative density and viscosity of

plasticisers,82 and a plot shows that plasticisers fall into very distinct
groups which are related to their plasticising properties (Fig. 5.4).
Van Veersen and Meulenberg showed that in addition to correlating
with the solid-gel transition temperature, SGTT, (Section 5.6.1) the
AJPo ratio also showed very distinct trends relating to efficiency (by
100% modulus), low-temperature properties (Clash and BergT 135 000), extraction resistance and plastisol ageing characteristics. 3?
These trends are summarised in Fig. 5.5.

5.8 AGEING OF PLASTICISED PVC

As every PVC technologist knows, the hardness and modulus of a PVC
compound increase measurably during the period immediately following processing. For this reason PVC test samples are usually stored at

139

5 Theoretical Aspects of Plasticisation

'00

.,

'00
0

...

~
N

50

o~elYI epoxy
slearale

"'*
I~...........

.....0 p\
"l!

Ilo'Q

,~~

Oi n heptyl
phthalate

ille.r

'0..

- 1----

~~

<-.,.

.o~

~ ;.",

'\; ~~<"~~"
~
",o~ o\~\"",J ~oi"

,I---.

'"

....

'i).

.....

$"\~

10

~ ~

"" '"
~.. 0"

'\",

~..<. ~
,.~~ ~~

10

....

.00.

09

095

10

t.'"

.,,'

..

$"tJ

-- f -

e\

011> 1l,,1I> ~II> 0,0"'" ~,o ,,0 ~,,,

\~ 0'''' 11> ..0
~<:J 11>*""

0",

085

Oetyl diphenyl phosphale

"'P4/.
OBP
~.L

~-.y

""
"..

\..

:rp~

('i},

..."

~~;-f-'"TTP . .04 f-"

~~4-

B;=t~
'e.r

1>-

~'-t-

:OJ-I.,,,..... 1'00..

~. ~
...

ri oelyl phosphale
0

~1iiiD

~r~,~

DOS

".1

----

"nlnll

10

,f;

105

11

1-15

HO

Relative density 25/25' C

Fig. 5.4 Relationships between bulk properties of plasticisers and their

plasticising properties. (Graph contributed by Mr T. C. Moorshead.)

room temperature for approximately 7 days before physical properties

are determined. In the past, when lower molecular weight plasticisers
were used, this effect was often attributed to plasticiser volatility.
However, this is impossible since the effect is reversible. Reheating to
the processing temperature and subsequent cooling causes the modulus
and hardness to revert to their initial values.
Several workers83 ,84 have followed the changes in elastic modulus
and density with storage time and temperature, and it has been
proposed that the stiffening is due to crystallisation of the PVC on
storage. This has been confirmed by DSC measurements which show
the development of endothermic peaks accompanying the stiffening. It
is suggested that the crystallites can be melted on reheating to the
processing temperature and re-form again slowly on cooling.

140

D. L. Buszard

130- 60

400

300

..

>.

,..."
' tI

..

c:

~
f-

...c:

>.
u

>

200~

5u

Q.

11

lle- ~c: 40

I-

ij

'z

c:
(

'u
W

I'oto~-...------.----------,
6

..

10

11

12

'00

13

Fig. 5.5 Relationship between Ap/Po ratio and physical properties of

plasticised PVc. 37

141

Theoretical Aspects of Plasticisation

90

60

-6050

60

-50-

40

50

40

30~
oil
oil

-40-

U
I

0
0
0

lCl
1'1

....
oil

.!!
-30...

..

'-

Q.

.
...
.

~30
oil

20~

.c:

.2

l:

...
..."x
...'"

.~

.
~
~

'-

20

>-

'Q.

..-:

!!

...J

.2

l:

'e"n
o'"

:;::;

...

10 ;

>

1-,0-1
6
7
8
9
----l.~ A p Po ratio

Fig.

10

5.~ontd.

11

12

13

142

D. L. Buszard

5.9 ANTIPLASTICISATION
The addition of small quantities of plasticiser (up to 20%) to a PVC
compound leads to an increase in modulus and tensile strength and a
reduction in impact strength and elongation at break. This is the
opposite behaviour to that which might normally be expected of a
plasticiser and has been termed 'antiplasticisation'.85 The phenomenon
has been known for a long time. Brous and Semon86 reported the
anomalous behaviour of PVC containing up to 18% TCP as early as
1935, and since then it has been examined by many other workers. 87- 99
An illustration may be seen in Fig. 5.6 from the work of Ghersa,87
which shows the effect of low concentrations of DOP on tensile
strength, elongation at break, tangent modulus and impact strength.
As in plasticisation, the mechanism has not yet been fully elucidated,
although the major features have been well researched. Horsley88
demonstrated by X-ray diffraction that systems containing low
concentrations of plasticiser possessed increased order on a molecular
scale, and attributed it to increasing crystallinity caused by the
increased freedom of motion induced by the presence of the plasticiser.
However, more recent X-ray and IR data have suggested that only
minor changes in crystallinity accompany antiplasticisation. 9o ,91
Bohn,92 using viscoelastic measurements, related the onset of
brittleness to the suppression of the viscoelastic f3 relaxation process.

'"E

3'0

80

~f

'5

0'"

25 E ~

2.0

~ 60

'C z

g, <D

c:

400
o

c:

2002

-.;,

1Il
01

1Il

Q.

+----'T--"T"'""--,---+o

10

20

30

Plasticiser cone. 010

40

c:
.Q

Fig. 5.6 Effect of low concentrations of DOP on the physical properties of

PVC (after Ghersa87).

Theoretical Aspects of Plasticisation

143

He showed that the brittleness was reasonably independent of

plasticiser type, whereas this had a marked effect on the concentration
at which brittleness disappeared. The more efficient plasticisers reduce
brittleness at lower concentrations. 92- 94 He therefore concluded that
the onset of brittleness and its subsequent disappearance were due to
two separate mechanisms. It is difficult to attribute the suppression of
the f3 peak to structural changes since Pezzin and his co-workers95 ,96
demonstrated that the f3 relaxation was not greatly modified by
increasing the crystallinity of PVC by either low-temperature
polymerisation or thermal treatments.
Robeson and Faucher97 ,98 considered that antiplasticisation was
attributable to the filling of the polymer free volume and hence the
restriction of molecular motion. Work by Mascia99 suggested that it is
time, temperature and stress dependent, that is, above certain critical
values the phenomenon assumes all the typical characteristics of
normal plasticisation.
Formulations containing less than 20% plasticiser are therefore
rarely encountered because of their poor physical properties. It is also
for this reason that copolymer processing aids are used for rigid PVC,
rather than low concentrations of conventional plasticisers. For
optimum physical properties levels of liquid epoxy and phosphite
stabilisers, and pigment dispersion aids, should be kept to an absolute
minimum in rigid PVC formulations.

REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.

10.
11.
12.

British Plastics Federation. (1982). Unpublished survey.

Kirkpatrick, A. (1940). J. Appl. Phys., 11, 255.
Clark, F. W. (1941). Chem. Ind., 60, 255.
Barron, H. (1943). Plastics (London), 7, 449.
Doolittle, A. K. (1954). The Technology of Solvents and Plasticisers, John
Wiley, New York, Ch. 14 and 15.
Doolittle, A. K. (1965). Plasticiser Technology, (Ed. P. F. Bruins),
Reinhold, New York, Ch. 1.
Leuchs, D. (1956). Kunststoffe, 46,547.
Stein, R. S. and Tobolsky, A. V. (1948). Text. Res. J., 18,302.
Alfrey, T., Wiederhorn, W., Stein, R. S. and Tobolsky, A. V. (1949). J.
Coll. Sci., 4, 211.
Walter, A. T. (1965). J. Polym. Sci., 9, 207.
Doty, P. M., Wagner, H. and Singer, S. (1947). J. Phys. Chem.,.51, 32.
Hengstenberg, J. and Schuch, E. (1964). Makrmol. Chem., 74, 55.

144
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.

D. L. Buszard

Crugnola, A. and Danusso, F. (1968). J. Polym. Sci., B6, 535.

Wales, M. (1971). J. Appl. Polym. Sci., 15, 293.
Kinjo, N. and Nagakawa, T. (1973). Polym. J., 5, 316.
Gugelmetto, P., Pezzin, G., Cerri, E. and Zinelli, G. (1971). Plast.
Polym., 398.
Gilbert, M. and Gray, A. (1975). Polymer, 16, 387.
Singleton, c., Isner, J., Gezovich, D. M., Tsou, P., Geil, P. H. and
Collins, E. A. (1974). Polym. Engng. Sci., 14,371.
Nakamura, K. (1975). J. Polym. Sci., Polym. Phys. Ed., 13, 137.
Gezovich, D. M. and Geil, P. H. (1971). Int. J. Polym. Mat., 1, 3.
Tsou, P. K. C. and Geil, P. H. (1972). Int. J. Polym. Mat., 1, 233.
Immergut, E. H. and Mark, H. F. (1965). Adv. in Chem. Series No. 48.,
ACS, Ch. 1.
Paton, C. (1972). Plasticisers, Stabilisers and Fillers, (Ed. P. Ritchie),
Iliffe, London, Ch. 4.
Stafford, T. G. (1972). 'PVC/Plasticiser Interaction. Pt I-General
Considerations', RAPRA Tech. Rev. No. 65.
Stafford, T. G. (1972). 'PVClPlasticiser Interaction Pt 2-Structure and
Properties', RAPRA Tech. Rev. No. 66.
Alter, H. (1959). J. Appl. Polym. Sci., 6, 312.
Newton, D. S. and Cronin, J. A. (1958). Brit. Plast., Oct., 426.
McKenna, L. A. (1958). Mod. Plast., June, 142.
Greenhoe, J. A. (1960). Plast. Technol., Oct., 43.
Wheeler, A. and Clifton, B. V. (1962). Brit. Plast., Dec., 640.
Critchley, S. W., Hill, A. and Paton, C. (1965). Adv. in Chem. Series No.
48, ACS, Ch. 14, 146.
McKinney, P. V. (1965). J. Appl. Polym. Sci., 9, 3359.
McKinney, P. V. (1967). J. Appl. Polym. Sci., 11, 193.
Van Veersen, G. J. and Dijkers, J. L. C. (1974). Kunststoffe, 64,292.
Mazzur, R. P. (1967). SPE Tech. Papers, 13, 177.
Graham, P. R. and Darby, J. R. (1961). SPE 1., 17, 91.
Van Veersen, G. J. and Meulenberg, A. J. (1972). SPE Tech. Papers, 18,
314.
Luther, H., Glander, F. O. and Schleese, E. (1963). Kunststoffe, 29,409.
Touchette, N. W., Seppala, H. J. and Darby, J. R. (1964). SPE 20th Ann.
Tech. Conf., January.
Sears, J. K., Darby, J. R. and Touchette, N. W. (1965). Paper presented
at the 12th Ann. It. Tech. Meeting of Sabine Area AICHE and the
Texas-Louisiana Gulf ACs, Orange, Texas.
Darby, J. R. and Sears, J. K. (1969). Encyclopedia of Polymer Science and
Technology, Volume 10, (Ed. H. F. Mark et al.), Interscience, New York,
p.237.
Jones, H., Hill, A. and Williamson, I. (1950). Trans. PI, 18.
Boyer, R. F. (1951). Tappi, 34, 357.
Van Veersen, G. J. and Meulenberg, A. J. (1967). Kunststoffe, 57,561.
Gee, G. (1946). Trans. Faraday Soc., 42B, 33; 42, 585.
Do~, P. and Zable, H. S. (1946). J. Polym. Sci. 1,90.
Burrell, H. (1955). Interchem. Rev., Spring, 3.

Theoretical Aspects of Plasticisation

145

48. Brydson, J. A. (1961). Plastics, 26, 107.

49. Gardon, J. L. (1969). Encylcopedia of Polymer Science and Technology,
Volume 3, (Ed. H. F. Mark et al.), Interscience, New York, p. 833.
50. Small, P. A. (1953). J. Appl. Chern., 3, 71.
51. Fedors, R. F. (1974). Polym. Engng. Sci., 14, 147.
52. Koenhen, D. M. and Smoulders, C. A. (1975). 1. Appl. Polym. Sci., 19,
1163.
53. Ciba-Geigy, unpublished data.
54. Severs, F. T. and Smitmans, G. (1957). Paint Varnish Prod., 47, 54.
55. Thinius, K. (1958). Plaste u. Kaut., 5,52.
56. Anagnostopoulos, C. E., Coran, A. Y. and Gamrath, H. R. (1960). J.
Appl. Polym. Sci., 4(11), 181.
57. DIN 53408-1967.
58. Bigg, D. C. H. (1975). J. Appl. Polym. Sci., 19, 3119.
59. Anagnostopoulos, C. E., Coran, A. Y. and Gamrath, H. R. (1965). Mod.
Plast., 43, 141.
60. Bigg, D. C. H. and Hill, R. J. (1976). J. Appl. Polym. Sci., 20, 565.
61. Van Veersen, G. J. and Meulenberg, A. J. (1966). Kunststoffe, 56,23.
62. Wiirstlin, F. and Klein, H. (1956). Kunststoffe, 46, 3.
63. Jasse, B. (1968). RGCP Plastiques, 5(6), 393.
64. Bell, K. M. and McAdam, B. W. (1967). Kunststoffe, 57, 526.
65. Paul, K. T. (1973). RAPRA Members J., November, 273.
66. Chemical Industry Bibliography. Annual Publication by Brabender OHg.,
Duisburg.
67. Frey, H. E. (1956). Kunststoffe, 46,81.
68. Reed, M. C. (1947). J. Polym. Sci., 2, 115.
69. Reed, M. C. and Connor, L. (1948). Ind. Engng. Chern., 40,1414.
70. Quackenbos, H. M. (1954). Ind. Engng. Chern., 46, 1335.
71. Small, P. A. (1947). J. Soc. Chern. Ind. Lond., 66, 17.
72. Royen, M. (1960). Bull. Am. Soc. Test. Mat., 243, 43.
73. Knappe, W. (1962). Kunststoffe, 52, 387.
74. Knappe, W. (1954). Z. Angew. Phys., 6, 97.
75. Hellwege, K. H., Knappe, W. and Lohe, P. (1961). Kolloid Z., 179(1),
40.
76. Titow, W. Unpublished work.
77. Moorshead, T. C. (1962). Advances in PVC Compounding and Processing,
(Ed. M. Kaufman), Maclaren & Sons, London, pp. 20-31.
78. Heaps, J. M. (1972). Plasticisers, Stabilisers and Fillers, (Ed. P. D.
Ritchie), Plastics Inst./Illiffe, London, Ch. 5, p. 68.
79. Lawrence, R. R. and McIntyre, E. B. (1949). Ind. Engng. Chern., 41, 689.
80. Wiirstlin, F. and Klein, H. (1955). Makromol. Chern., 16, 1.
81. Brice, R. M., Eakman, J. M. and Kaufer, D. M. (1963). SPE J., 19,984.
82. Private communication from T. C. Moorshead to W. Titow.
83. Juijn, J. A. (1972). Crystallinity in Atactic Polyvinyl Chloride, J. A.
Pasmans, s-Gravenhage, Ch. 4, p. 42.
84. Leharne, S. A., Park, G. S. and Norman, R. H. (1979). Brit. Polym. J.,
11, (March), 7.
85. Jackson, W. J. and Caldwell, J. R. (1967). J. Appl. Polym. Sci., 11, 211.

146

D. L. Buszard

86. Brous, S. L. and Semon, W. L. (1935). Ind. Engng. Chem., 27, 667.
87. Ghersa, P. (1958). Mod. Plast., 36(2), 135.
88. Horsley, R. A. (1957). Progress in Plastics, (Ed. P. Morgan), Iliffe,
London, p. 77.
89. Shtarkman et al. (1972). Polym. Sci. USSR, 14, 1826.
90. Tabb, D. L. and Koenig, J. L. (1975). Macromolecules, 8, 929.
91. Jacobson, U. (1959). Brit. Plast., 32, 152.
92. Bohn, L. (1963). Kunststoffe, 53, 826.
93. Nakamura, K., Hashimoto, F., Nakanishi, M., Kinjo, N., Komatsu, T.
and Nakagawa, T., (1970). Proc. 5th Int. Congo Rheol., p. 409.
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95. Pezzin, G., Ajroldi, G. and Garbuglio, D. M. (1967). J. Appl. Polym.
Sci., 11, 2553.
96. Pezzin, G., Ajroldi, G., Casiraghi, T., Carbuglio, C. and Vittadini, J.
(1972). J. Appl. Polym. Sci., 16,1839.
97. Robeson, L. M. (1969). Polym. Engng. Sci., 9, 277.
98. Robeson, L. M. and Faucher, J. A. (1969). J. Polym. Sci., B, 7, 59.
99. Mascia, L. (1978). Polymer, 19, 325.

CHAPTER 6

Commercial Plasticisers
D. L.

BUSZARD

6.1 INTRODUCTION

A large number of plasticisers are available to the PVC user and

confusion may be caused not only by the wide diversity of chemical
types but also by the widespread use of trade names. It is hoped that
the following sections will help to clarify the situation.

6.2 CLASSIFICATION OF COMMERCIALLY AVAILABLE

PLASTICISERS

In the past plasticisers have been classified in a number of ways: by

chemical constitution, by compatibility with PVC, i.e. primary,
secondary, etc., by molecular weight or by particular applicational
properties. All these systems have advantages and disadvantages. The
method adopted in this book is primarily a chemical classification.
However, the elements of other means of classification are apparent.
For example, Groups 1-4 are monomeric and Group 5 is polymeric.
Also, Groups 1-3 are largely primary plasticisers, Groups 4-5 are
frequently secondary plasticisers and Group 6 includes extenders. The
classification used is as follows:
Group
Group
Group
Group

1-phthalate plasticisers
2-phosphate plasticisers
3--trimellitate plasticisers
4--low-temperature plasticisers
147

148

D. L. Buszard

Group 5-polymeric plasticisers

Group 6-miscellaneous plasticisers: (a) epoxies, (b) chlorinated
paraffins, (c) monoesters, (d) glycol esters, (e) hydrocarbons,
(f) others.
6.3 GROUP CHARACTERISTICS OF MAJOR
PLASTICISER CLASSES

Table 6.1 summarises the major characteristics, including the advantages and disadvantages, of the main types of plasticiser available
commercially. It is intended to provide a convenient means of selecting
the type or class of plasticiser which should be considered for a
particular application.
6.4 SYNONYMS AND ABBREVIATIONS

There are a number of confusing synonyms and abbreviations in the

plasticiser field, and for convenience the most important are summarised in Table 6.2.
The preferred chemical names and abbreviations are those recommended by ISO 1043-1978(E) or, if not covered by the ISO standard,
those recommended by BS 4589: 1970. It should, however, be noted
that in some cases the preferred names or abbreviations differ between
the two standards. For example, BS 4589: 1970 proposed the prefix
'mixo' to define commercial mixtures formed from primary, branched
chain alcohols (e.g. DIOP, DIDA) since the prefix 'iso' should be
limited by the rules of IUPAC on chemical nomenclature. However,
this prefix (mixo) has not been included in the most recent ISO
standard.
The majority of the more common monomeric plasticisers are now
marketed by most manufacturers under their chemical name or
abbreviation, usually with a trade name prefix. The same products
from different manufacturers would be expected to give similar
performance, although there might be minor differences in raw
materials, process, purity and specification. The following sections
therefore attempt to cover these products in general terms by using
chemical names or abbreviations. Manufacturers' trade names are
referred to only where it will assist in defining the product more

Polymeric plasticisers
Epoxy esters and
oils
Chlorinated paraffins

Azelates and
sebacates
ACJS acid esters

Adipates

DTDP
BBP
Triaryl phosphates
Alkyl diaryl
phosphates
Trialkyl phosphates
Trimellitates

Very good low-temperature properties and

permanence
CJood low-temperature properties---cheaper than
other low-temperature plasticisers
CJood extraction and migration resistance, low
volatility
Improved heat stability, oils have reasonable extraction resistance
Low cost, reduced flammability

Very low volatility, excellent resistance to

aqueous extractants
CJood low-temperature properties

Used in the majority of applications not requiring

special properties
Improved low-temperature properties
Lower volatility, improved aqueous extraction resistance
Very low volatility
Rapid gelation, stain resistance
Excellent flame retardant and gelation properties,
good resistance to microbial attack
Moderate flame retardancy with improved lowtemperature properties
CJood low-temperature properties

C g phthalates

Linear phthalates
DNP, DlDP

Rapid gelation, ease of processing

Particular advantages or areas of usage

C 4 phthalates

Plasticiser
type
Disadvantages

May exhibit poor compatibility and poor low

temperature eroperties, high viscosity
Can be compatIbility problems particularly on
ageing
Poor efficiency and compatibility care needed
on stabilisation

CJenerally poor volatility and efficiency

CJenerally poorer volatility and extraction resistance

Expensive

Poor compatibility and processing

Expensive

Poor low-temperature properties

Poorer electrical properties

Less efficient-but may be an advantage in
some applications
Poor efficiency, expensive

Very high volatility normally limits their application

TABLE 6.1
Characteristics of the Major Types of Plasticisers

150

D. L. Buszard

TABLE 6.2
Plasticiser Abbreviations and Synonyms

Preferred chemical
name
Q

Preferred
abbreviationsQ

Other names and

abbreviations

AGS esters Mixed esters of adipic, glutaric and

succinic acids also known as
nylonates
ASE
n-Alkyl sulphonate
Alkyl sulphonic ester
BAR
Butyl-o-acetylricinolate
BBP
Butyl benzyl phthalate
Benzyl butyl phthalate
Butyl cyclohexyl phthalate BCHP
Butyl isodecyl phthalate
BIDP
Butyl nonyl phthalate
BNP
Benzyl octyl adipate
BOA
Benzyl 2-ethIlhexyl adipate
DA 79A
Di-Alphanol adipate, D 79A
Dialkyl (C/~) adipate
Dialkyl (C/~) phthalate DA 79 P
DAP, di-Alphanolb phthalate, D 79 P
DA 79S
Di-Alphanolb sebacate, D 79S
Dialkyl (C/~) sebacate
DA 79 Z
Dialkyl (C/~) azelate
Di-Alphanolb azelate
Dibutyl phthalate
DBP
DBS
Dibutyl sebacate
DCP
Dicapryl phthalate
DCHP
Dicyclohexyl phthalate
DEP
Diethyl phthalate
Digol benzoate
DGDP
Diethylene glycol dibenzoate
DHP
Diheptyl phthalate
Dihexyl phthalate
DHXP
Diisobutyl adipate
DIBA
Diisobutyl phthalate
DIBP
DIDA
Diisodecyl adipate
Diisodecyl phthalate
DIDP
Di-LinevoIC 79 phthalate
D~9P
Di-LinevoIC 911 phthalate D~llP
Diisononyl adipate
DINA
Diisononyl phthalate
DINP
Diisooctyl adipate
DIOA
Diisooctyl azelate
DIOZ
Diisooctyl phthalate
DIOP
Diisooctyl sebacate
DIOS
DITDP
Diisotridecyl phthalate
DITP, ditridecyl phthalate
DTDP
Di(2-methoxyethyl) phtha- DMEP
Di(ethylene glycol monomethyl
late
ether) phthalate
Dimethyl phthalate
DMP
Dibutyl adipate
DNBA
DNDP
Di-n-decyl phthalate
Di-n-octyl adipate
DNOA
DNOP
Di-n-octyl phthalate
Dinonyl phthalate
DNP
Di(3,5,5-trimethylhexyl) phthalate
Dinonyl sebacate
DNS
Di(3,5,5-trimethylhexyl) sebacate

6 Commercial Plasticisers

151

TABLE 6.2-contd.

Preferred chemical
name"
Dioctyl adipate
Dioctyl isophthalate
Dioctyl maleate
Dioctyl phthalate
Dioctyl terephthalate
Dioctyl azelate
Diphenyl cresyl phosphate
Dipropylene glycol
dibenzoate
Diphenyl octyl phosphate

Preferred
abbreviationsO

Other names and

abbreviations

DOA
DOIP
DOM
DOP
DOTP
DOZ
DPCP
DPCF
DPDB

DEHA, di(2-ethylhexyl) adipate

DPOP
DPOF
DUP
ELO
ESO
ODP
PPA
PPS
TBAC
TBEP

ODP, octyl diphenyl phosphate

DEHP, di-(2-ethylhexyl) phthalate

Di-(2-ethylhexyl) terephthalate
Di-(2-ethylhexyl) azelate
CDP, cresyl diphenyl phosphate;
tolyl diphenyl phosphate

Diundecyl phthalate
Epoxidised linseed oil
ESBO
Epoxidised soyabean oil
Di-Alfold 810 phthalate
Octyl decyl phthalate
Poly(propylene adipate)
Poly(propylene sebacate)
Tributyl a-acetyl citrate
Tri(2-butoxyethyl) phosphate
Tributyl phosphate
TBP
Tri(2-chlorethyl) phosphate TCEP
Tricresyl phosphate
TCP, TCF, Tritolyl phosphate (particularly
TIP
in UK)
TDBP
Tri(2,3-dibromopropyl)
'Tris', T23P
phosphate
Tri(2,3-dichloropropyl)
TDCP
phosphate
Triethyl a-acetyl citrate
TEAC
Triisooctyl trimellitate
TIOTM
Trioctyl phosphate
TOF
Tri(2-ethylhexyl) phosphate
Tetraoctyl pyromellitate
TOPM
Tetra(2-ethylhexyl) pyromellitate
Trixylyl phosphate
TXP,
Trixylenyl phosphate
TXF
3,3,5-Trimethylpentane 1,4- TXIB
Texanol' isobutyrate
diol diisobutyrate

The preferred chemical names and abbreviations are those recommended in

ISO 1043-1978(E) or BS 4589: 1970, or those widely accepted in the PVC

industry.
b Trade name of ICI-branched chain C,C9 alcohols.
C Trade name of Shell Chemicals-predominantly linear C,~ and GrC
ll
alcohols.
d Trade name of Continental Oil Co.-mixture of linear Cg and C IO alcohols.
e Trade name of Eastman Kodak.

152

D. L. Buszard

readily, or where that manufacturer has a pre-eminent position in the

field.
6.5 GROUP 1 PLASTICISERS-PHTHALATES

(X~-O-R
C~R

II

o
As mentioned earlier, the phthalates are the largest single chemical
group of plasticisers used in PVC, the majority being general-purpose
Cs phthalates of which DOP is particularly important. There are,
however, a wide range of other phthalates which offer interesting
properties to the PVC formulator.
Phthalates can conveniently be divided into the following groups:
lower phthalates; general-purpose phthalates; linear phthalates;
higher phthalates; miscellaneous phthalates.
A comparison of the properties of PVC compounds plasticised with
54 phr (35%) of the more important phthalates is shown in Table 6.3.
The majority of alcohols used in the production of phthalates and
other alkyl diesters are manufactured by the 'OXO process' or
carbonylation reaction. The principal commercial alcohols produced by
this process, together with their raw materials and feedstocks, are
shown in Table 6.4. 1
6.5.1 Lower Phthalates
DBP and DIBP were widely used in PVC in the early 1950s. They
exhibit good efficiency but unfortunately their very high volatility and
poor aqueous extraction resistance lead to poor permanence properties. They have been replaced in the majority of plasticised PVC
applications by higher molecular weight phthalates, the exception
being certain areas where their rapid gelation properties are required
and their high volatility can be tolerated.
Certain plasticisers can seriously affect the growth of plants. 2 DBP
and DIBP have been shown to be very bad in this respect because of

6 Commercial Plasticisers

153

their very high volatility. 3 It is important therefore that these

plasticisers are excluded from any formulations which may be used in
films, hoses and glazing strips, etc., for glasshouses or other
horticultural applications.
6.5.2 General-purpose Phthalates
The Cs phthalates are the largest class of plasticisers in use today. The
most important are DOP, based on 2-ethylhexanol, and DIOP, based
on isooctanol. DA79 P, which was based on a mixed C7 , Cs and ~
branched chain alcohol, has recently ceased manufacture. DOP, DIOP
and DA79 P have very similar properties and are generally regarded as
interchangeable, the choice being dependent on the current supply
position.
More recently, DINP, diisononyl phthalate, based predominantly on
dimethyl-l-heptanols, has become available, giving generally lower
volatilities and lower plastisol viscosities than the Cs phthalates. The
other ~ phthalate, DNP, based on 3,5,5-trimethylheptanol, is
markedly less efficient and finds particular application where low
platisol viscosities are desirable-especially for semi-rigid dip coatings,
slush mouldings and rotational castings.
6.5.3 Linear Phthalates
One of the more important developments in the use of phthalates as
plasticisers was the introduction and extensive use of linear or
predominantly linear dialkyl phthalates to improve low-temperature
performance. Since these products are available at little or no premium
over the general-purpose Cg phthalates, they have replaced a large
proportion of the more expensive diester market. The original linear
alcohols were by-products from the manufacture of detergent alcohols
by fat hydrogenation, e.g. straight chain C6-ClO alcohols from coconut
oil. The majority are now manufactured from synthetic hydrocarbon
feedstocks, as shown in Table 6.5. 4
Linear alcohols may of course be used in the manufacture of other
non-phthalate esters. It is however in phthalates that they have had the
most impact.
In addition to their improved low-temperature properties linear
phthalates have lower volatile losses than their branched chain
counterparts, as demonstrated by the apparent plasticiser loss on

0983
0968
0975

48

55

31

DA79P

DCP

DNOP

DNP

Dinonyl
phthalate

0970

0981

53

DIOP

80

0980

56

86

77

79

80

77

78

74

1042

29

DIBP

DOP

72

1035

IRHD

16

Liquid properties
at 25C
Viscosity
Density
(cSt)
(g mr 1)

DBP

Abbreviation

Dioctyl
phthalate
Diisooctyl
phthalate
Di-Alphanol
79 phthalate
Dicapryl
phthalate
Di-n-octyl
phthalate

Dibutyl
phthalate
Diisobutyl
phthalate

Name

26

38

36

36

39

37

45

48

BS
softness
No.

-8

-25

-17

-18

-16

-19

-5

-19

eC)

Cold
flex

02

07

13

10

10

10

13

17

Volatile
loss
(%)

24

25

23

23

24

24

20

23

Petrol

17

19

16

18

17

19

12

18

18

23

15

17

17

18

12

19

20

21

25

11

18

20

20

24

14

15

Extraction resistance
(% mass loss)
MinDetereral
Olive
oil Soap gent
oil

TABLE 6.3
Properties of Phthalate Plasticisers in PVC Compounds at 54 phr

'"::>~

1;

r--

.".

.....
Vl

DINP

Benzyl butyl
phthalate
Di(2-methoxyethyl)
phthalate

32

DMEP

1167

1124

0950

243

45

0947

0964

37

54

0971

33

0962

0962

49

85

0985

0976

33

BBP

Diisodecyl
phthalate
DIDP
Diundecyl
phthalate
DUP
Diisotridecyl phthalate
DTDP

Di-Linevol
79 phthalate
Dlq9P
Di-Linevol
911 phthalate
D~l1P
Di-Alfol610
(DROP)
phthalate
Di-Alfol 810
ODP
phthalate

Diisononyl
phthalate

76

79

95

91

84

81

77

87

76

80

40

35

13

20

26

34

38

27

42

35

38
10

-12

02

01

02

07

01

08

03

-7

-16

-26

-16

-25

-27

-27

-26

-14

12

26

21

25

20

21

26

24

16

14

16

25

18

22

18

20

23

21

16

15

18

25

22

25

18

19

30

21

15

16

14

+1

03

12

17

06

17

+02

+02

01

08

18

+08

09

Ul
Ul

;;;
'"

00'

~~.

'"
a

'"....

3
3

<:>

0-

()

D. L. Buszard

156

TABLE 6.4
Principal Commercial OXO Alcohols
Raw material

Feedstock

Propylene

(Propylene)

Propylene + butenes
Propylene
Isobutane
Propylene

'Heptenes'
'Nonenes'
'Diisobutylene'
'Dodecenes'

Paraffin wax

Co C8 olefines

Alcohol

{n-Butanol
Isobutanol
2-Ethylhexanol
Isooctanol
Isodecanol
Nonanol
Tridecanol
{AIPhanol79
Linevol79

TABLE 6.5
Major Producers of Linear Plasticiser Alcohols
Producer

Conoco

Raw material

Ethylene

Monsanto Ethylene

{ p"affin wox'

Shell

Ethylene

Process

Ethylene growth
followed by oxidation
Ethylene growth
followed by carbonylation
emking fnllow,d by }

carbonylation
Ethylene growth
(SHOP) followed by
carbonylation

Alcohol
Alfo16IO,
AlfolBIO
Santicizer 711
(phthalate)
Linevol79
Linevol911

Recently discontinued in favour of the Shell Higher Olefin Process (SHOP).5

milling,6 Fig. 6.1, and the changes in low-temperature flexibility of

plasticised PVC on ageing at 90C,7 Fig. 6.2. The compounds for the
latter were formulated to give equal Clash and Berg temperatures
(3410 kg cm- 2) of -30C.
The linear phthalates do however exhibit poorer electrical properties
(i.e. lower volume resistivities) which is undesirable in cable
formulations.
6.5.4 Higher Phthalates

DIDP is less efficient than the Cs phthalates, but gives appreciably

lower volatility and better aqueous extraction resistance.

157

6 Commercial Plasticisers
7

1,o.sl.' 2 ,ali- mill I

milling lim.: 15 min

Appa,.nl
plaslicis., loss
(%wIJ
6

OOP

OL 79P

OIOP

OL 911P

O+--_._---~----r_---_._---___r_

110

130

150

170

190

I.mp. S.tlin9 1 C)

Fig. 6.1 Apparent plasticiser loss as a function of milling temperature for

PVC compounds based on 50 phr of different plasticisers. (Reproduced by
permission of Shell Chemicals International Ltd from their technical
literature. )

DTDP, diisotridecyl phthalate, has a very low volatility and good

ageing characteristics, but has poor efficiency. It was used in
applications where the low volatility was advantageous, e.g. hightemperature cables, low-fogging leathercloth, etc. Its use in these
applications is now generally being superseded by that of trimellitate
plasticisers.

158

D. L. Buszard
to

If

l3'

f ,.,//

e...

r,,//
(//

:s;c

..

;;:

.
l!

-20

Cl.

it

...
0

If

-10

.. '
-30

50:50

DOP/DOA

60:40

DOP/DOA

70:30

DOP

610P

_._810P

~--.~---.
1

DOP/DOA

2
3
Time [days]

Fig. 6.2 Change of low-temperature flexibility of plasticised PVC on ageing at

90C. (Reproduced by permission of Condea Petrochemie GmbH from their
technical literature.)

DUP is again used for low-volatility applications, but is more

popular in North America than Europe.
6.5.5 Miscellaneous Phthalates
Benzyl butyl phthalate is one of the most rapidly fusing plasticisers for
PVC, and in compounding allows regular production rates at lower
temperatures or higher rates at similar temperatures. In addition, it
imparts good stain resistance to vinyl films and hence is frequently used
for clear wear layers in vinyl flooring.
More recently, dioctyl terephthalate (DOTP) has been introduced
commercially in the United States by Eastman Chemicals. This product
is claimed to have lower volatility, and improved permanence and
lacquer mar resistance, compared with DOP.
Modified phthalates, such as Hexaplas OPN (ICI) are also available
from some companies. These have similar low-temperature properties

6 Commercial Plasticisers

159

to the straight chain phthalates but inferior volatility. However, their

plastisol rheology and storage stability are superior and they are
claimed to give volume cost savings over most other phthalates.

6.6 GROUP 2 PLASTICISERS-PHOSPHATES

Phosphate plasticisers may be divided into four classes: triaryl

phosphates; trialkyl phosphates; mixed alkyl aryl phosphates; halogenated alkyl phosphates.
The triaryl phosphates as a group are by far the most important,
accounting for some 80-90% of the total phosphate plasticiser usage in
PVc. A detailed comparison of phosphate plasticisers has been given
by the writer elsewhere. 8

6.6.1 Triaryl Phosphates

The original triaryl phosphate plasticisers were TIP (tritolyl or
tricresyl phosphate) and TXP (trixylyl phosphate). However, in the
mid-1960s, the shortage and variable quality of the coal tar cresols and
xylenols, from which they were derived, led to the increasing
popularity of cresol diphenyl phosphate, and later to the development
of the Reofos range of synthetic triaryl phosphates based on
isopropylated phenol and introduced by Geigy (now Ciba-Geigy) in
1968.
The isopropylated phenyl phosphates are applicational equivalents
to the older TIP (TCP) , TXP and CDP, but offer more consistent
quality, much improved light fastness, better colour, lower odour and
lower toxicity. These products are now available in Europe and
elsewhere from Ciba-Geigy as Reofos 95, Reofos 65 and Reofos 50.
They are also available in the United States from FMC as Kronitex 100
and Kronitex 50.

160

D. L. Buszard

TABLE 6.6
Comparative Performance of Triaryl Phosphates
Reofos

TXP

Reofos

TTP

Reofos
50

95
1-131
87
25

95
1134
87
24

60
1-161
85
27

60
1158
82
31

50
1170
83
30

+5
05

+8
03

+4
05

+6
06

+3
10

15

15

15
11

12

15
13

15
13
12
11

11

12

95

Viscosity at 25C (cSt)

Density at 25C (g ml- 1)
IRHD (Shore A)
BS softness No.
Cold flex temperature
(BS 2782 method
104B) CC)
Volatile loss (%)
Extraction resistance:
weight loss (%)
Petrol
Mineral oil
Olive oil
Soap

11
11

11
11

65

13

Formulation: PVC 100, plasticiser 54, white lead paste 4, calcium stearate 1.

A comparison of these phosphates is shown in Table 6.6. As a group

triaryl phosphates offer excellent flame retardancy, good gelation
properties, very good high-frequency welding characteristics, good
microbial resistance, high extender tolerance and excellent compatibility even at high humidities. They do however suffer from poor
low-temperature properties, but since they are seldom used as sole
plasticisers, this may be offset by a careful selection of other
plasticisers.
The superior flame-retardant properties of triaryl phosphates in
comparison with the alkyl diaryl and the trialkyl phosphates are shown
in Fig. 6.3.

6.6.2 Trialkyl Phosphates

Trioctyl phosphate is the most popular of this group, but in general
trialkyl phosphates are little used in PVC today. They have poor
compatibility and rather poor flame-retardant properties-showing no
real improvement over phthalates-and are used primarily for their
excellent low-temperature properties.

6 Commercial Plasticisers

161

Oxygen index (%)

46f

36

~~
::1
28

26

24

22L__.- ' ~__-"----'----'----_..~"-:::=--~--;-!.

o

10

20

30

40

50

60

70

80

90

100

Concentration of piasticiser {phrl

Fig. 6.3 Effect of plasticiser concentration on oxygen index of phosphate

plasticisers. 5

6.6.3 Mixed Alkyl Aryl Phosphates

Octyl diphenyl phosphate (e.g. Santicizer 141-Monsanto Europe) and

isodecyl diphenyl phosphate (e.g. Santicizer 148) are the two mixed
alkyl aryl phosphates available commercially. They have properties
intermediate between the triaryl and trialkyl phosphates thus offering a
compromise in flame retardancy and low-temperature properties. Their
physical and flammability properties are comparable with a blend of
60% triaryl phosphate/40% adipate (Table 6.7).

IRHD
BS softness No.
Cold flex temperature
(BS 2782 method
104B) (0C)
Volatile loss at 82C (%)
Extraction resistance
weight loss (%)
Petrol
Mineral oil
Olive oil
Soap
Oxygen index (%)
15
13
13
12
34

17
16
18
12
27

-19
17

-50
17

3
10

76
41

78
38

83
30

22
21
21
19
29

(octyldiphenyl
phosphate)

141

Santicizer

TOF
(trioctyl
phosphate)

Reofos 50
(isopropylated
phenyl
phosphate)

20
17
16
17
29

-17
07

78
37

Santicizer
148
(isodecyl
diphenyl
phosphate)

20
17
18
12
29

-18
20

76
41

Phosphate
blend
(60% Reofos
50140% DOA)

TABLE 6.7
Performance of Different Phosphate Plasticiser Types in PVC Compounds at S4 phr

24
19
18
4
24

-19
11

78
37

DOP
(dioctyl
phthalate)

......

"'-

.,I:>

E;

tl:l

t""

Rl

6 Commercial Plasticisers

163

6.6.4 Halogenated Alkyl Phosphates

Products such as tri(2-chlorethyl)phosphate (TCEP) and the tri(monochloropropyl) phosphate for example, manufactured by Courtaulds, are effective flame retardants but exhibit poor compatibility
with PVC. They are of more interest as flame retardants in other
polymers (e.g. polyurethanes) but may occasionally be used as
additional flame-retardant additives in PVC.
6.7 GROUP 3 PLASTICISERS-TRIMELLITATES

C-o-R

~
R-o-C~C-o-R
II
II
o

Esters based on trimellitic anhydride have become very popular

primary plasticisers for PVC compounds, for use at high temperatures
or for applications requiring excellent resistance to aqueous extractants, e.g. washing machine parts. Table 6.8 gives a comparison of the
properties of various trimellitate plasticisers available commercially.
Since trimellitates are normally incorporated into PVC formulations
for high-temperature performance, most plasticiser manufacturers
supply them containing an antioxidant. Whether any additional
antioxidant is required will depend on the particular grade selected and
the ageing conditions to be encountered.
Branched chain trimellitates, such as Reomol ATM (Ciba-Geigy)
generally give better electrical properties, which are required for some
Cl.ble applications, whilst straight chain trimellitates, as with phthalates, give better low-temperature properties.
6.8 GROUP 4 PLASTICISERS-ALIPHATIC nIESTERS

The aliphatic diesters are generally known as the low-temperature

plasticisers since this is their prime advantage. They are secondary
plasticisers, made from a number of linear dibasic acids with the
general structural formula: ROOC(CHz)nCOOR.
The most popular dibasic acids are adipic (n = 4), azelaic (n = 7)

Tri-Alphanol 79
trimellitate
Tri-Linevol 79
trimellitate
Triisooctyl
trimellitate
Tri(2-ethylhexyl)
trimellitate
Tri-Alfol810
trimellitate

Plasticisers

0995
0993
0988
0985
0971

107

250

205
925

Density
25C
(gml- I )

181

Viscosity
25C
(cSt)

24
17

93

20

91
88

30

30

BS
softness
No.

83

84

lRHD

01
01
02
02
01

-15
-7
-10
-20

(%)

Volatile
loss

-10

Clash
and
Berg
("C)

26

22

22

21

21

26

12

19

14

14

22

14

14

15

14

+1

+04

+04

+02

+01

+08

+08

+07

+03

+03

Extraction resistance % mass loss

DeterMineral Olive
Petrol
oil
oil Soap gent

TABLE 6.8
Properties of Trimellitate Plasticisers in PVC Compounds at 54 phr

N
l:l

1:;

~
I:l:l

165

6 Commercial Plasticisers

and sebacic acid (n = 8). A mixture of acids, known as AGS or nylon

acids since they are a by-product of nylon production, and consisting of
adipic, glutaric and succinic acids, is also popular. Esters have also
been made from succinic acid (n = 2) (e.g. Reomol SD) and glutaric
acid (n = 3) (e.g. Plasthall DIDG-C. P. Hall), when they are
commercially attractive.
The majority of aliphatic diesters are manufactured from branched
chain alcohols, such as isooctanol, 2-ethylhexanol or isodecanol, the
latter being popular with the lower molecular weight acids. Linear
alcohols are generally avoided since their esters tend to crystallise at
relatively high temperatures, thus giving storage and handling
difficulties.
A comparison of the performance in PVC of the more important
linear diesters is given in Table 6.9.
6.9 GROUP 5 PLASTICISERS-POLYMERIC
PLASTICISERS

The maJonty of commercial polymeric plasticisers are saturated

polyesters resulting from the reaction of a diol with a dicarboxylic acid.
They differ basically from monomeric plasticisers such as DOP in that
their molecular structure contains repeat units and their molecular
weight is higher and can be varied. It is normal practice to include a
third reactant in a polyester to 'modify' or 'endstop' the product. This
is commonly either a monohydric alcohol or a monocarboxylic acid,
although isocyanates and even diazomethane have been used to modify
terminal hydroxyl and acid groups.
Thus there are three possible general structures for polymeric
plasticisers:
non-terminated
acid-terminated

RIf-O-C-RI-C4R-O-C-RI-e-1RIf alcohol-terminated

II

II

II

II

Diisodecyl
succinate
Isooctyl ester
of AGS acids
Isodecyl ester
of AGS acids
Dioctyl
adipate
Diisooctyl
adipate
Diisodecyl
adipate
Benzyl octyl
adipate
Diisooctyl
azelate
Dibutyl
sebacate
Dioctyl
sebacate
Diisooctyl
sebacate

Plasticisers

79
86
74
81
85
74
78
72

0928
0917
0924
0926
0912
0916
0913
0933
0911
0911

135

233

123

135

22

142

18

87

195

224

80

80

85

IRHD

0919

Density
at 25C
(g ml- 1 )

224

Viscosity
at 25C
(cSt)

05
04

-51
-46
34

48

37

35

04

-39

17

-48

-52

24

-45

06

10

-38

-47

75

-47

32

18

Volatile
loss
(%)

-38

Clash
and
Berg
(0e)

-36

45

27

33

46

25

37

26

BS
softness
No.

26

24

26

24

23

27

25

26

23

26

25

Petrol

27

24

26

22

23

26

21

22

23

23

24

26

25

27

25

23

25

21

26

24

24

24

04

18

14

17

13

75

35

15

45

Extractions (%)
Mineral Olive
oil
oil Soap

TABLE 6.9
Properties of Linear Diester Plasticisers in PVC Compounds at 54 phr

10

75

Og

45

19

Detergent

.....

s::.

!;;

t:x:l

t'"'

167

6 Commercial Plasticisers

There are therefore two main parameters which can be varied in

polymeric plasticisers-their constituents, including chain stoppers,
and their degree of polymerisation, Le. molecular weight-and since
both these factors are important in determining the resultant
properties, it can be seen that there is considerable scope for variation.
It also follows that polymeric plasticisers are not simple, readily
definable chemicals, as are the majority of monomeric plasticisers, and
hence they are invariably marketed under trade names rather than the
chemical names which indicate their constitution.
The most common raw materials are as follows:
dicarboxylic acids-adipic, phthalic, azelaic, sebacic;
diols-l ,2-propanediol, 1,3-butanediol, 1,4-butanediol,
1,6-hexanediol, neopentyl glycol, diethylene glycol;
monocarboxylic acids-acetic, caproic, caprylic, lauric,
myristic, palmitic, stearic, pelargonic, benzoic;
monohydric alcohols-isooctanol, 2 ethylhexanol, isodecanol,
Linevol 79 and 911 (Shell Chemicals)
The effect of molecular weight on the properties of a nonendstopped polypropylene adipate has been demonstrated by Moseley
and Dawkins9-Table 6.10. From these results it can be seen that
increasing molecular weight gives advantages of improved permanence
and lower volatility, but disadvantages of increasing viscosity, lower
plasticising efficiency and poorer low-temperature properties. In
addition, higher molecular weight products are more difficult to
process and often exhibit reduced compatibility with PVc.
TABLE 6.10

The Effect of Molecular Weight on the Properties of Polypropylene Adipate

Molecular weight
Viscosity at 25C (P)
Hydroxyl value (mg KOH g-l)
Compound properties
BS softness No.
Cold flex temperature eC)
Volatile loss (%)
Tensile strength (MN m- 2)
Extraction loss (%)
Hexane
Mineral oil
Soap solution (1 %)

2000
150
55

3000
250
45

4000
350
30

9000
850
25

27
-17
32
178

24
-15
27
198

23
+2
24
199

20
+58
23
208

04
10
90

03
04
68

01
01
47

01
0
38

168

D. L. Buszard

Moseley and Dawkins also demonstrated the effect of varying the

reactants as well as molecular weight in typical commercially available
polymeric plasticisers-Table 6.1l.
Endstopping will reduce the liquid viscosity of a polymeric plasticiser
of given molecular weight by reducing the hydrogen-bonding capability
of the terminal hydroxyl or acid groups. Similarly, this will increase the
high humidity compatibility and improve the extraction resistance to
aqueous media. It does, however, have an adverse effect on the
extraction resistance to non-polar media such as oils and fats. This is
demonstrated in Table 6.11 by comparing polymeric plasticisers 4 and
5, which are non-endstopped, with 1 and 2, which are alcohol
endstopped.
Mixed diols or dicarboxylic acids are frequently used to obtain a
desired balance of properties, as shown by examples 6 and 7, Example
8 may be regarded as a complex ester rather than a true polymeric
since essentially n = 1and there are no repeat units.
An interesting, fairly recent development in polymeric plasticisers is
the use of a lactone in place of a proportion of the dibasic acid and
diol. 1Q--12 These modified polyester plasticisers have the idealised structure:

The commercially available examples of this type of structure, based

on caprolactone, give plasticisers which have excellent compatability
with PVC, and extraction and migration-resistant properties which are
comparable with those of the medium molecular weight polyesters
endstopped with an alcohol. The caprolactone-based plasticisers,
however, have lower viscosities and much faster gelation properties.
They are therefore of particular interest in plastisols.
Most manufacturers of polymeric plasticisers offer a range of
products, from the low molecular weight complex ester types, such as
Uraplast W2 (Urachem) and Reoplex GL (Ciba-Geigy), to the high
molecular weight, harder to process products, such as Diolpate 150
(Briggs and Townsend), Reoplex 430 and Plastolein 9789 (UnileverEmery).
A further group of products which may be mentioned under the
classification of polymeric plasticisers is the 'solid polymerics'. These
are much higher molecular weight elastomeric polymers which may be

1,3-Butylene
glycol
Alcohol
3400
34
-75

211
37

8 X lO"

39
H
03
54
Moderate

1,2-Propylene
glycol
Alcohol
2300
32
-6

205
41

1 x 1012

42
39
02
61
Moderate

Diol

Chain stopper
Viscosity at 25C (cP)
BS softness No.
Cold flex eq
Tensile strength
(kgfcm- 2 )
Volatile loss (%)
Volume resistance
(0 em-I)
Extraction loss (%)
Hexane
Mineral oil
Water
Soap solution (1%)
Humidity (compatibility)

Adipic

Adipic

Acid

27
18
01
47
Moderate

6 X 10 13

10 12

37
Poor

z.l

07
01

210
29

1,3-Butylene
glycol
None
22000
25
-05

Neopentyl
glycol
Alcohol
5500
30
0
198
39

Adipic

Adipic

10 12

07
07
23
48
Poor

202
32

1,2-Propylene
glycol
None
24000
24
-15

Adipic

1013

57
55
06
93
Very
good

210
40

1,2-Propylene
glycol
Alcohol
800
36
-5

Adipic!
phthalic
anhydride

1013
28
34
06
69
Moderate

223
29

1,2-Propylene
glycol
Alcohol
32000
29
2

Adipic!
phthalic
anhydride

10 12
101
60
12
116
Excellent

191
67

Diethylene
glycol
Alcohol
700
33
-2

Phthalic
anhydride

1013
151
43
03
114
Very
good

210
120

1,2-Propylene
glycol
Alcohol
900
34
15

Phthalic
anhydride

TABLE 6.11
The Effect of Composition on the Properties of Commercially Available Polymeric Plasticisers

1013
350
160
0
130
Excellent

147
224

45
-20

72

~OP

10

0-

\0

....

'"
;;:

:::.

f
'"0;'

"tl

'"

3
3

0-

170

D. L. Buszard

more truly regarded as blending resins rather than plasticisers.

However, they have recently penetrated areas previously considered to
be the preserve of more conventional polymeric plasticisers by offering
improved permanence in addition to other advantageous properties
such as improved abrasion resistance and traction in shoe soles, etc.
Typical of these products are Elvaloy (Du Pont) ethylene interpolymer
resins and polyurethane elastomers such as Ultramoll PU (Bayer) and
Durelast 100 (Briggs and Townsend). They are extensions of the
long-established practice of blending nitrile rubbers with PVC.
6.10 GROUP 6 PLASTICISERS-MISCELLANEOUS
PLASTICISERS
6.10.1 Epoxy Plasticisers
This group of plasticisers contains the epoxy grouping:

They are usually derived from the reaction of unsaturated compounds

with peracids. The unsaturated compounds used are generally naturally
occurring oils or the alkyl esters of natural unsaturated fatty acids,
although some 'synthetic' triglycerides and esters are manufactured.
The resulting commercial epoxy products are primary or secondary
plasticisers for PVC and also exhibit an effective stabilising action (see
also Chapters 4, 9 and 10).
The epoxy oils are generally derived from soyabean oil (the most
popular) and linseed oil, both of which are triglycerides of unsaturated
fatty acids. They exhibit a good plasticising and stabilising action, and,
as suggested by molecular weights in excess of 900, their extraction and
migration resistance are comparable with many of the lower molecular
weight polymeric plasticisers. A disadvantage of the purer epoxy oils is
their high viscosity and their tendency to crystallise out at lower
temperatures, which can lead to storage difficulties. However, any
precipitation rapidly re-dissolves on heating to 30--40C for a short
period with no detrimental effect on the plasticising or stabilising
properties.
The alkyl epoxy esters are generally manufactured from tall oil acids

6 Commercial Plasticisers

171

(a by-product of paper manufacture), which contain a significant

proportion of unsaturated oleic and linoleic acids, or from purified
oleic acid. The most popular are the butyl and 2-ethylhexyl esters of
these acids, which are then epoxidised. The epoxy esters are
characterised by their good plasticising and low-temperature properties, as well as their stabilising action. The compatibility of epoxy
plasticisers with PVC is surprisingly good in comparison with the
non-epoxidised equivalents. However. once the epoxy groupings are
destroyed by undergoing a stabilisation reaction, their compatibility is
greatly reduced. Care should therefore be taken to ensure that certain
ultimate compatibility limits are not exceeded.
Typical commercial products are:
Epoxidised soyabean oil: Edenol D81 (Henkel)
Lankroflex GE (Diamond Shamrock)
Paraplex G62 (Rohm and Haas)
Reoplast 39 (Ciba-Geigy)
Edenol D72, B74, B35, H5235
Epoxy-alkyl esters:
Lankroflex ED3, ED6
Monoplex 5-71 (Rohm and Haas)
Reoplast 38, 42

6.10.2 Chlorinated Paraffins

In their early years chlorinated paraffin waxes acquired a reputation
for poor colour and low thermal stability. However, by employing
modern chlorination techniques and the use of straight-chain liquid
paraffin feedstocks, chlorinated products are now produced which are
water-white and have properties comparable to those of the octyl
phthalates. In the UK, ICI manufacture a range of chlorinated
paraffins, under the trade name Ceredor, which have gained
worldwide acceptance.
Within the Ceredor range are two grades, Ceredor 552 and Ceredor
545, which are specifically recommended for PVC applications. These
grades can be used as sole plasticisers in relatively hard products, such
as flooring compounds, but they are more normally employed as
partial replacements for phthalate or phosphate primary plasticisers.
Since they are available at lower prices than primary plasticisers, their
use in PVC compounds gives significant savings in raw material costs.
The properties of the finished compound are not impaired and the

172

D. L. Buszard

flame retardance may be improved when Ceredor is included in a vinyl

composition.
The important properties of these Ceredor grades are given in Table
6.12. Ceredor 552 is the general-purpose grade, suitable for most
applications, while the 45% chlorinate, Ceredor 545, was specifically
developed for use in PVC plastisols, where its lower viscosity is an
advantage, and for compounds having good low-temperature properties. The slightly higher volatility of Ceredor 545 still allows
compounds containing this grade to pass most international ageing loss
specifications.
TABLE 6.12
Properties of the 'Cereclor' grades
Grade

Chlorine content (%)

Average chain length
Density (g ml- I at 25C)
Viscosity (Pa s)
Volatility (% weight loss on
heating 4h at 180C)
Thermal stability (% HCI after
4h at 175C)
Toxicity

Ceredor 545

Ceredor 552

43-45
CI5
1-16
0154l25

50-52
CI5
125
1-2

28

14

006-01

007--012

Very low

Very low

The use of chlorinated paraffin secondary plasticisers is straightforward and, provided that compatibility limits are not exceeded, no
exudation occurs. The compatibility limit is of the order of 25-30 phr in
compounds of BS softness 40 (Shore A 75) based on octyl phthalates.
It is recommended, however, to refer always to the chlorinated
paraffin manufacturer's literature when reformulating. Normally PVC
compounds are reformulated to the same hardness. The lower
plasticising efficiency of the chlorinated paraffins and their higher
density mean, however, that phthalates are not replaced part for part.
Typically, 15 phr of Ceredor have to be included for each part of
replaced octyl phthalate. Table 6.13 shows that the physical properties
are relatively unaffected in compounds reformulated to contain either
Ceredor 545 or 552.
In addition to ICI, chlorinated products are also available from,
amongst others, the following manufacturers: Hoechst, Huls, Dynamit
Nobel, and Caffaro in Europe; Diamond Shamrock, Keil, and Dover

6 Commercial Plasticisers

173

TABLE 6.13
Properties of Compounds" containing 'Cereclor'
Plasticiser
OlOP
OlDP
Re%s 95
Ceredor 845
Ceredor 852

54

BS softness No.
Shore A
Tensile strength
(MNm- Z)
% elongation at
break
Cold flex (0C)
% ageing loss (24 h
at 100C)
Volume resistivity
(0 cm x 1013)

40
75

40
75

40
75

40
75

40
75

173

17-8

172

156

17-6

38

35
62

25

51

315
-20

66

30
35

40
75

40
75

40
75

162

201

193

15
30

300
-16

48

320
-16

20

315
-16

325
-18

330
-16

245
-6

290

-10

075

095

085

036

074

052

015

06

06

05

06

Formulated for constant BS softness by varying the plasticisers (amounts given in phr)
in otherwise the same formulation.

in the United States; and Toya Soda, Asahi Denka, and Ajinomoto in
Japan.
6.10.3 Monoesters
This group comprises a wide number of different plasticisers, the
majority of which are only of interest in certain specialist formulations.
Examples of these are butyl oleate, phenoxyethyl oleate and
tetrahydrofurfuryl oleate. They are claimed to be good lowtemperature secondary plasticisers with advantages in some plastisol
applications.
An exception which may be included in this class is Mesamoll, an
alkyl sulphonic acid ester, manufactured by Bayer and popular in
Germany. It is a good primary plasticiser with properties similar to the
general-purpose phthalates.
6.10.4 Glycol Esters
These also are of low interest and not very wide application. They
include aromatic glycol esters such as diethylene glycol dibenzoate and

174

D. L. Buszard

dipropylene glycol dibenzoate, which are popular in the United States

(e.g. Benzoflex 988-Velsicol Corp.) and which are used for rapid
solvating properties.
The unsaturated acrylic and methacrylic esters of glycols such as
diethylene glycol dimethacrylate are also included in this class. These
esters, together with other crosslinkable plasticisers such as dialkyl
phthalate and trialkyl cyanurate, are of interest for certain speciality
uses. Such applications include adhesion promoters in plastisol-coated
steel and rigisols, and there is now a renewed interest in them as
plasticisers for crosslinkable PVC cable insulation.
6.10.5

Hydrocarbon Extenders

A variety of hydrocarbon extenders and oils are available from a

number of manufacturers, including:

Dutrex (Shell);
Enerflex (BP);
Electrofine (D'Electro-Chemie);
Lipinol (Huls);
Mobisol (Mobil);
Ravolen (Manchester Oil);
Kenplast (Kenrich Petrochemicals, USA).
These oils are used as cheap extenders in certain PVC compounds
and plastisols. They are true extenders and have very limited
compatibility with PVC.
6.10.6 Other Miscellaneous Plasticisers

Citrate plasticisers such as acetyl tributyl citrate (Citraflex A 4-Pfizer)

are primary plasticisers with good low-temperature properties and a
low order of toxicity. They are of particular interest in products for
food contact and medical use.
A plasticiser of international importance not readily classifiable into
the previous categories is Texanol isobutyrate (Kodaflex TXIB),
manufactured by Eastman Chemicals Inc. This product is the
diisobutyrate of 2,2,4-trimethyl-l,3-pentanediol. It is of a particular
interest in non-stain flooring and plastisol applications such as
rotational casting, where low plastisol viscosities and good viscosity
stability are required. The high volatility of TXIB limits its use in some

175

6 Commercial Plasticisers

applications. Other esters of Texanol (e.g. Nuoplaz 1406-Tenneco)

are available but are much less popular.

6.11 STORAGE AND HANDLING OF PLASTICISERS

Plasticisers are supplied either in drums (e.g. 200 kg) or in bulk by
tanker. If large quantities of a particular plasticiser are used, it is
normally economically attractive to install bulk handling facilities
which can then be linked into automatic or semi-automatic weighing
and mixing equipment. Storage tanks and transfer lines can usually be
of mild or stainless steel construction and suitable epoxy finishes can be
applied if necessary. Cast iron or stainless steel gear pumps are
normally preferred, although centrifugal pumps can be used for low
viscosity or preheated plasticisers. Positive shut-off valves such as ball
valves or plug valves should be used.
Care should be taken in the selection of elastomeric materials for
contact with plasticisers, e.g. hoses, flexible couplings, a-rings and
seals. Table 6.14 summarises the effect of liquid plasticisers on many
TABLE 6.14
Suitability of Polymeric Materials for Use as Flexible
Seals, etc., in Contact with Plasticisers
Material

Butyl rubber
Ethylene propylene rubber
Chlorosulphonated polyethylene
Natural rubber
Nitrile rubber
Polyamide
Polychloroprene
Polyethylene
Polypropylene
Polytetrafluoroethylene
Polyurethane
Silicone
Viton

Ratinlf

1
2
4
4
3
1
4
2

2
1
3

2
2

1 = generally recommended; 2 = acceptable;

3 = possibly suitable under certain conditions; 4 =
unsuitable.

a Rating:

D. L. Buszard

176

10000

l'\.

r\ \ \

'f\.

5 OOO++-+-~~~-+l~-'--+-+--+--+--+--+--+--+--+---l
3000

\1\ r\. '\

\
\

2000

~\

\ \

I\.

\.

'\..

'\.

\.

1500t--t-l~......-\'~:-+--->ot--lI'Tt-+--+--+--+--+--+--+---+---i

1000

\\

-10

~\

10

\.1\ I\.

'\.

'\

'\..

20 30 40 50 60 70 80 90 100110120130140
Ttlmptlraturtl, C

Fig. 6.4 Viscosity-temperature relationships of a range of plasticisers. 1,

DOA; 2, DBP; 3, DIDA; 4, L79P; 5, Reofos 65 (isopropylated phenyl
phosphate); 6, DOP; 7, DIDP; 8, Reomol LTM (tri-Linevol 79 trimellitate);
9, DTDP; 10, Reoplex GL (low viscosity polymeric); 11, Reoplast 39 (ESO);
12, Reoplex 1102 (low viscosity polymeric); 13, Reoplex 903 (medium viscosity
polymeric); 14, Reoplex 430 (high viscosity polymeric).

6 Commercial Plasticisers

177

TABLE 6.15
European and US Plasticiser Manufacturers
Classes
manufactured

Company
United Kingdom
Albright & Wilson
B.P. Chemicals
Briggs & Townsend
Ciba-Geigy

1,2,4
1,3,4,6E
5
1,2,3,4,5,6A,6F

Trade names
Q

Pliabrac
Bisoflex, Enerflex
Diolpate
Reofos, Reomol,
Reoplast. Reoplex

Courtaulds
Diamond Shamrock
(Europe)
ICI
Robinson Bros
Scott Bader
Shell Chemicals

1,3,4,6A
1,4,6B
5
1,3,5
1,6E

Tenneco
Victor Wolf

2
5,6C

Lankroflex
Ceredor, Hexaplas
Arbeflex
Crestapol
Linevol, Dobane,
Dutrex
Wolflex

Austria
Chemie Linz

Mollan

Belgium
Argus Chemicals
Essochem Europe
Monsanto Europe
UCB-FTAL

6A
1
1,2,4,5,6F
1,3,4,6F

Drapex
Jayflex
Santicizer

1,3,4

Scandinol

1
6E
1,3,4
6D,6F

Gedeflex

1
1,2,4,5,6B

Plastifiant K
Garbeflex, Garbefos,
Alaiflex

1,4,5,6F

Palatinol, Plastomoll,
Palamoll

Denmark
Scandiflex
France
CdF Chemie
D'Electrofine-Chemie
ICI Europa
Nyco S.A.
Products Chemie Ugine
Kuhlman
Rhone Poulenic Polymeres

Hexaplas
Nycoflex

Germany
BASF

178

D. L. Buszard

TABLE 6.15-<:ontd.
Classes
manufactureda

Company

Bayer

1,2,4,5, 6E, 6F

Chemische Werke Hills

Deutsche Texaco
Dynamit Nobel
Henkel & Cie
Hoechst
Wacker-Chemie

1,4, 6B, 6C, 6E

1,3
1,3,4,5, 6B, 6C
1,4,5, 6A, 6C
1,6B
1,4

Trade names

Adimoll, Disftamoll.
Mesamoll, Ultramoll, Unimoll
Vestinol, Lipinol
Reproxal
Witamol, Witaclor
Edenol
Wacker

Holland
Akzo Chemie
Unilever-Emery

6A
4,5, 6A, 6C, 6F

Uraplast

1,4,5

Estabex
Emery, Plastolein,
Unem
Uraplast (formerly
Scadoplast)

Italy
Akzo Italia
Distillerie Italiane

4,5,6C,6F
1,4,5, 6A, 6F

Montedison
Sisas
Sprea

1,4
1
5

Estaftex
Diplast, Diepox,
Staftex
Sicol
Spreaftex

Sweden
Berol Kemi

1,4

Switzerland
Reichhold Chemie

1,4,5, 6A, 6E, 6F

Ricatyl, Contrastat

4,6C,6F
5
1,3
1
6B
6B

Kesscoftex

USA
Armak
Ashland Chemicals
BASF Wyandotte
Continental Oil
Diamond Shamrock
Dover Chemical
Eastman Chemical
International
Emery Industries
Exxon
FMC
C. P. Hall

1,3,4,5,6F
4,5, 6A, 6C, 6F
1,3
2,6A,6C
4,5,6F

Plastomoll, Palatinol
Chlorowax
Chlorez
Kodaftex, Texanol
Emery, Plastolein
Jayftex
Kronitex

179

6 Commercial Plasticisers

TABLE 6. 15-contd.
Company

Classes
manufacturedO

Harwick
Hercules

1,4,6F
1,5, 6B, 6F

ICI Americas
Keil
Monsanto

6B,6F
6B,60
1,2,3,4,5,
6A, 60, 6E, 6F
3,4,5,6F
4, 60, 6F
1,3,4,5, 6A, 6C, 6F
4,5, 6A, 6C, 6F
5,6A
2
6A
1,2,3,4,5
2, 6A, 60
1,3,4,5,6C
1,3,4, 6A, 6C
60

Pfizer

pva

Reichold
Rohm & Haas
Sherex
Stauffer
Swift
Tenneco
Union Carbide
Union Camp
USS
Velsicol

Trade names
Polycizer
Clorafin, Hercoflex,
Hercolyn
Cereclor, Hexplas
Aroclor, Santicizer
Citroflex, Morflex
Peroxidol, Staflex
Monoplex, Paraplex
Admex
Phosflex
Epoxol
Nuoplaz
Flexol
Uniflex
PX
Benzoflex

1, Phthalates; 2, phosphates; 3, trimellitates; 4, low-temperature plasticisers; 5,

polymerics; 6A, epoxies; 6B, chlorinated paraffins; 6C, monoesters; 60, glycol esters;
6E, hydrocarbons; 6F. others.

common sealing materials. In this context, confusion may occur over

the term 'compatibility'. In PVC technology it is used as has already
been discussed in Chapter 5. However, 'compatibility' is also used in
hydraulic fluids and liquid handling technology to indicate the resistance
of a sealing or gasket material to the particular liquid in question. In
practice, this is almost diametrically opposed to the conventional
plastics technology definition and confusion between them could have
serious consequences. If any doubt exists as to the suitability of a
particular material as a seal, etc., either the plasticiser manufacturer or
appropriate material manufacturer should be consulted.
It may be necessary to heat plasticisers to reduce their viscosity in
order to facilitate handling, particularly in colder weather. Figure 6.4
shows the viscosity-temperature relationship for a wide range of
common plasticisers.

180

D. L. Buszard

6.12 PLASTICISER MANUFACTURERS

A number of the more important European and US manufacturers are
listed in Table 6.15, together with the types of plasticiser manufactured
and their trade names. This list has been drawn from trade directories,
manufacturers' literature and published literature, and whilst every
effort has been made to make it so, it may not be completely
comprehensive.

REFERENCES
1. Murfitt, H. C. (1970). E.C.N. Polymer Intermediates, Oct. 30th.
2. Inden, T. and Tachibana, S. (1975). Mie Diagaku Nogakubu Gakujutsu
Hokoku, 1-10.
3. 'Plasticised PVC in Horticulture'. BASF Technical Bulletin.
4. Murfitt, H. C. (1979). PRI Symposium, Loughborough University, April.
5. Sherwood, M. (1982). Chern. Ind., 24,994.
6. Shell Chemical Int. Report on 'Vapour Losses During Processing of
Plasticised PVC', Fig. 2.
7. Condea Petrochemie, Information bulletin No. 3151, Fig. 6.
8. Buszard, D. L. (1978). Chern. Ind., 16,610.
9. Moseley, J. and Dawkins, P. (1978). Chern. Ind., 16,620.
10. Buszard, D. L. (1983). PVC Processing II Proceedings, PRI, 22.7.
11. British Patent No. 1455196.
12. British Patent No. 1455390.

CHAPTER 7

Properties of Plasticised pvc

D. L.

BUSZARD

7.1 INTRODUCTION

Chapters 5 and 6 have discussed the more theoretical aspects of

plasticisation, and the types and general properties of the classes of
plasticisers used commercially. It is the intention of this chapter to
investigate the properties of plasticised PVC and the effect of differing
plasticisers and plasticiser levels more thoroughly. The intention is to
give the reader a grounding in plasticised PVC technology and a guide
to formulating for specific end-use properties.

7.2 FORMULATION OF A PLASTICISED

PVC COMPOUND

At one time it was usual to use only one plasticiser in a PVC

compound, but this is much less common today, since a better balance
of properties or a reduction in compound cost may be achieved by
optimising the plasticiser system to the end-product requirements.
Although this is often a complicated task, generally requiring both an
intimate knowledge of and wide experience in plasticisation, there are
a number of ground rules which may aid the less experienced
technologist. The main points to be considered are as follows:
Constraints imposed by the method of processing: The main area
where this is of importance is in the processing of PVC plastisols,
where there are limitations on the choice and minimum concentration
181

182

D. L. Buszard

of plasticisers. Aspects relating specifically to plastisols are dealt with

in more detail in Chapters 21 and 22. Other processing techniques
generally have fewer restrictions, although problems may be encountered in, for example, the dry blending of high viscosity polymeric
plasticisers or in calendering operations where volatility must be a
consideration.
Special properties required in the final product: After an approximate
level of plasticiser has been established-normally judged by compound softness or 100% modulus-reference should be made to the
known properties of a general-purpose Cs phthalate, such as DOP, in
PVC and any additional properties required may then be assessed. For
example, these might be improved low-temperature or hightemperature performance, flame retardance or migration resistance.
Appropriate classes of plasticisers to give the required improvement,
either alone or as a blend, may be selected initially by reference to
Table 6.1 in Chapter 6. Depending on the nature of the final product,
it may be necessary to select a speciality plasticiser or merely 'shade'
the properties a little by using a related phthalate from a different
alcohol.
Inclusion of an extender or filler: Finally the possibility of including
an extender, such as a chlorinated paraffin, or a filler in the
formulation should be considered. There are obvious economic
advantages in doing so, providing that there would be no detrimental
effect on the properties of the final product.

Once the main parameters required for a particular compound have

been established, and an idea has been reached as to which, if any,
plasticisers should be blended, more detailed consideration must be
given to the particular properties, in order to permit plasticiser ratios,
levels, etc., to be chosen. In general, when plasticisers are mixed, the
resultant properties are approximately proportional to their relative
concentrations-always providing that compatibility limits have not
been exceeded. Although this is not an invariable rule, it is applicable
to most practical situations. For highest accuracy, ratios should be
determined by volume rather than by weight.
Even for the experienced PVC formulator the design of a compound
to fulfil a critical task is difficult because of the inevitable conflict in
desirable properties. For example, good low-temperature properties in

7 Properties of Plasticised

pvc

183

a plasticiser are inevitably accompanied by poorer oil-extraction

resistance and lower volume resistivities, and this obviously complicates the formulation of an oil-resistant cable for use at low
temperatures. A compromise has therefore to be reached in matching
the achievable properties to the desired specification whilst not
overlooking other effects which might be detrimental to the compound
in service. There are two 'theoretical aids' which may provide
assistance in this field-the 'desirability function' and computerassisted formulation.

7.2.1 The 'Desirability Function'

This useful concept has been put forward by Harrington! to assist in
the selection of plasticisers for applications requiring several properties
of the product, some of which may be conflicting. The method also
takes account of the price factor.
Briefly, the 'desirability function' is a single number representing the
combination of all the important property factors-each at least at the
minimum level of acceptability-for the application under consideration. For the purpose of the calculation, each of the properties being
considered is allocated a value representing its desirable or admissible
level in the compound. The scale of values is in arbitrary units;
therefore, both the measurable properties (e.g. cold flex temperature,
resistivity, etc.) and subjective ones (e.g. odour, irritation) can be
accommodated. Cost can also be one of the properties. One of the
attractive features of the method is that it gives a result strongly
reflecting the effect of a possible particularly low desirability value in
respect of a single property. This is analogous to the rejection by a
prospective user of an otherwise excellent compound because of, say,
poor transparency. It has been claimed for the method that compounds
within the (properly calculated) range of desirability values between
065 and 090 (100 represents maximum desirability) are virtually
certain to be suitable for the purpose for which they are being
formulated.

7.2.2 Computer-assisted Formulating

It is possible to handle laboratory data by computer to predict
reasonably accurately the performance of PVC formulations containing
a number of variables. This technique can be developed to enable the

184

D. L. Buszard

lowest cost formulation to be selected to meet a required

specification. 2 ,3 It can be particularly useful at times of rapid
price/availability fluctuations when a formulation originally selected for
low cost may have become uneconomic. The development of this type
of program is highly specialised and requires an extensive reliable data
base on the effect of plasticisers, extenders and fillers on all the
specification properties to be included in the system. This is generally
only within the scope of the larger PVC polymer and plasticiser
manufacturers and then only for the more common plasticiser
combinations and properties.
The following sections deal with the effect of plasticiser type and
concentration on the major properties of interest.

7.3 SOFfNESS AND TENSILE PROPERTIES

As was mentioned in Chapters 5 and 6, plasticisers are frequently
judged by their efficiency or the degree to which they soften a PVC
compound. Softness is therefore a very important property and it is
worth considering briefly the more popular methods of measurement.
Traditionally the rubber industry has measured it as 'hardness' using
either the BS scale (in the UK) or the Shore Durometer scales* (in the
USA--ef. ASTM D 2240-75) or, more recently, the International
Rubber Hardness scale (Method N of BS 903, Part A 26: 1969, in
technical agreement with ISO 48-1979; ASTM D 1415-68(74)). These
scales range from 0 to 100; the harder the compound the higher the
number. However, in the case of PVC, particularly in the UK, it is
normal to employ the BS softness number scale, where the higher
numbers represent greater softness (ct. BS 2782, Part 3, Method 365A:
197~formerly Method 307A of BS 2782: 1970). In practice the BS
softnes~ number may be determined either with a standard 'dead-load'
precision laboratory instrument (as in BS 2782, Method 365A: 1976) or
with a spring-loaded pocket instrument. The use, calibration, and
limitations of pocket-type instruments are covered by BS 2719: 1975.
*Two scales, A and D, are in use (respectively for softer and harder materials),
associated with two durometers of the same designations. Scale A is applicable
to most flexible PVC materials. ASTM D 2240-75 recommends that measurements with Type D durometer should be made where values above 90 are
obtained with the Type A durometer, and that Type A should be used when
values less than 20 are obtained with the Type D instrument.

7 Properties of Plasticised

pvc

185

Such instruments, if properly used, are suitable for routine checks of

BS softness values of PVC materials, but not for standard tests or rigid
laboratory or quality control.
At present, both the Shore hardness and the BS softness systems are
in use, and since a certain amount of confusion can arise, a conversion
graph is given in Fig. 7.1.
7.3.1 Effect of Plasticiser

The variation of softness with plasticiser level for nine common

plasticisers is shown in Fig 7.2 (BS softness number) and Fig. 7.3
(Shore A). The efficiency of the different plasticisers can obviously be
judged by the relative shapes of the curves (see Chapter 5, Section
5.6.2).
The measurements in these graphs have been made at 23C.
However, softness varies considerably with temperature. The degree of
change depends on the plasticiser type and content and it is therefore
possible to modify a compound by formulating it to have a desired
softness at a specific temperature. Figure 7.4 shows the effect of
temperature on the softness of PVC plasticised with DOP at three
concentrations.
It should be noted that, as the response of different classes of
plasticiser to temperature is not the same, compounds based on
different plasticisers but formulated to equal softness at one temperature may differ at another.
The effect of plasticiser type and concentration on tensile strength
and elongation at break is shown in Figs 7.5 and 7.6, respectively.
These properties also vary with temperature.
7.3.2 Compounding at Equal Efficiency

The general concept of effectivity was introduced in Chapter 5, Section

5.6.2. Comparisons between different plasticisers at equal efficiencies
may differ considerably from comparisons made at equal plasticiser
levels. An example of this is shown in Table 7.1 where a number of
plasticisers are compared at equal efficiency as judged by 100%
modulus. In particular the low-temperature properties of DA79P and
DNP should be noted. At equal plasticiser level (60 phr) the former
appears to be very much better. However, when compared at equal
efficiency, the difference is minimal.

D. L. Buszard

186

90

t-

80

'0

.e>

70

~'"~

%..

t-

...
E
....."
i"

<;,

~
'.j

.Q

::J

III

?..

-0
0

60

50

30

20

10

---,L-__...L.:-_ _----:-&:--_ _

_ _....L._ _

O~

50

IlO

70
80
Shore A durometer hardness

90

100

Fig. 7.1 ShorelBS softness correlation graph.

7 Properties of Plasticised

pvc

187

100

80
'-

Ci

.a

60

III
III
Ci

.5
'5III

40

Vl

1Il

20

20

40

60

Plasticis~r I~V<lI,

phr

80

100

100

80

...

CI

.a
E 60
:J
C

III
III
Ci

...,c

'5III

8
40

Vl

1Il

20

20

40

60

Plasticis~r l~v~l,

80

phr

100

Fig. 7.2 Effect of plasticiser level on BS softness number. 1. DOP; 2, DIDP;

3, DTDP; 4, DOA; 5, Reofos 65 (Ciba-Geigy); 6, TOTM; 7, ESO; 8, PPA;
9, PPA alcohol endstopped.

D. L. Buszard

188
100

90

<l:

80

L-

.c
VI

70

60

50

2
0

20

40

60

Plasticisar laval, phr

80

100

90

<l:

80

L-

.c
VI

70

60

9
5

50
0

20

40

60

Plasticisar laval, phr

80

100

Fig. 7.3 Effect of plasticiser level on Shore A hardness. 1, DOP; 2, DIDP;

3, DTDP; 4, DOA; 5, Re%s 65; 6, TOTM; 7, ESO; 8, PPA; 9, PPA alcohol
endstopped.

7 Properties of Plasticised

pvc

189

/10
100

~ 90l
:I

..

eoi

70l

60~

ID

I
!

so:

4d
I

I
30~
1

20
10

2O=------:30~---:40'::-----:S-::0:-------:'60'=""'"----:7:'::0:----='eo
Temperature.

Fig. 7.4 BS softness versus temperature.

The efficiency factor can be very useful in calculating the ratios and
concentrations of plasticisers necessary to replace one with another.
For example, if it is desirable to improve the low-temperature
properties of a compound containing 50 phr of TIP by replacing 20 phr
of it with DOA and yet retain the same modulus, then the 20 phr of
TIP should be replaced by (see Table. 7.1):
094
20 x 1.25

= 150 phr DOA

190

D. L. Buszard
25

20

15

....Ol
~

c:

til 10
~
iii

c:
~

20

40

60

80

100

40
60
80
Plasticisftr IftVftl, phr

100

Plasticisftr Iftvftl, phr

25

20

~15

....Ol
.t:

c:
....~
Ul

.5!
iii
c:
~

10

20

Fig. 7.5 Effect of plasticiser level on tensile strength. 1, DOP; 2, DIDP;

3, DTDP; 4, DOA; 5, Reofos 65; 6, TOTM; 7, ESO; 8, PPA; 9, PPA alcohol
endstopped.

7 Properties of Plasticised

pvc

191

500
4
1

1ii
c
o

~200
til

iii

100

20

40

60

Plasticiser level, phr

80

100

500

~~
8

20

40

60

Plasticiser level, phr

80

100

Fig. 7.6 Effect of plasticiser level on elongation at break. 1, DOP; 2, DIDP;

3, DroP; 4, DOA; 5, Reofos 65; 6, TOTM; 7, ESO; 8, PPA; 9, PPA alcohol
endstopped.

D. L. Buszard

192

TABLE 7.1
Comparison of Plasticisers at Equal Concentration and Equal Efficiency
Plasticiser

Efficiency
concentrationa

Efficiency
factol'

Properties at
60phr
Cold
Tensile
strength
flex
(MNm- 2 ) ("C)

Dibutyl phthalate
Dioctyl phthalate
Diisooctyl phthalate
Di-Alphanol 79 phthalate
Dinonyl phthalate
Tritolyl phosphate
Trixylyl phosphate
Dibutyl sebacate
Dioctyl sebacate
Dioctyl adipate
a
b

540
635
655
612
742
793
83-1
495
588
599

085
10
1-03
097
117
125
131
078
093
094

170
17-4
184
165
194
23-1
235
147
161
166

-25
-23
-22
-25
-125
-15
+l
-56
-47
-49

Properties at
efficiency concentration
Tensile
strength
(MNm- 2 )
179
159
17-1
159
160
176
172
169
163
165

Cold
flex
("C)

-21
-275
-30
-28
-245

-13
-]25
-39
-46
-49

phr to give a 100% modulus of 69 MN m- Z (1000 Ibf in- Z).

Efficiency concentration divided by the efficiency concentration of DOP (63,5).

7.4 LOW-TEMPERATURE PROPERTIES

All plasticisers improve the low-temperature performance of PVC but

some are more effective than others. Figure 7.74 shows the effect of
temperature on the rigidity modulus of PVC compounds plasticised
with four common types of plasticiser. It is apparent that the different
types exhibit very different responses: the highly solvating polar
plasticiser, TXP, shows a rapid change in modulus over a narrow
temperature range, whilst the less polar secondary plasticiser, DIOS,
gives only a very gradual change. Obviously the concentration of
plasticiser as well as its type affects the low-temperature flexibility of a
compound. The curves in Fig. 7.7 were obtained at 54 phr. Increasing
the concentration of the plasticiser displaces the curves to the left
without significantly altering the gradients.
A particular low-temperature performance may therefore be
obtained by varying either the plasticiser itself or the concentration of
a particular plasticiser. The latter will also have a significant effect on
other important physical properties, such as softness, and this may be a

7 Properties of Plasticised

pvc

193

~ 3
-'

:>

:f
>-

....

~
2
a:

<:>

-'

"- .....

-50

-~o

-30

-20

-10

10

20

"-

30

.....

~o

50

TEMPERATURE (OC)

Fig. 7.7 Log rigidity modulus versus temperature. 4

constraint. Figure 7.8 demonstrates the effect of concentration on the
'Clash and Berg' cold flex properties (according to BS 2782, Method
150B: 1976) for a number of typical plasticisers. In this test method
the temperature at which the sample is deflected through an arc oJ 2000
(equivalent to a modulus of rigidity of 1655 kg cm- z) is taken as the
cold flex temperature (see also Chapter 12, Section 12.2.1).
The effect of blending low-temperature plasticisers, in this case
adipates, with phthalates in different ratios is shown in Table 7.2. This
table also demonstrates the effect of volatility loss of plasticiser on the
change in low-temperature properties and highlights the advantages of
linear esters over branched chain esters in this respect (see also Fig. 6.2
in Chapter 6).
In addition to cold flex tests, other types of low-temperature test
methods are used in the PVC industry. These include cold bend tests,
e.g. BS 2782, Method 151A: 1984, and cold crack tests, e.g. BS 3424:
Method lOA: 1983. Obviously the actual results vary between the
different types of test method, but in general, similar trends are
observed (see also Chapter 12, Section 12.2.1).

194

D. L. Buszard
20

.
u

10

(:I

;l -10
nl

E-20
...
(:I

(:I

>< -30

....
(:I

1J

(5
U

-40

-50

10

-60+----r----r----r---~~____,

20

40

60

100

Plasticisar laval,

20
10

.u

~ -10

...
:J

nl

~ -20
a.

.3 -30
><

(:I

~-40

1J

(5

U_ 50

-60+---"'T'"'"--"---"'T'"'"--"---"
100
o
20
40
60
80
Plasticisar laval, phr

Fig. 7.8 Effect of plasticiser level on 'Clash and Berg' low-temperature

flexibility (BS 2782: 1970, Method 104B: NB Current revised version, BS 2782,
Method 150B: 1976). 1, DOP; 2, DIDP; 3, DTDP; 4, DOA; 5, Reofos 65;
6, TOTM; 7, ESO; 8, PPA alcohol endstopped; 10, ~9P,

7 Properties of Plasticised

pvc

195

TABLE 7.2

Effect of ,Linevol' Phthalates and Adipates on Low-Temperature Properties of

Identical PVC Formulationsa
Linevol 79 adipatel
Linevol 79 phthalate
(Ph,)

Linevol 911 adipatel

Linevol 911 phthalate
(Ph,)

2-EH-adipatel
2-EH-phthalate
(Ph,)

5010 3012020130 0150 5010 3012020130 0150 5010 3012020130 0150

Cold flex temperature

(BS 2782: 1970 M 104 B)("C) -44 -36 -31 -21 -23 -34 -30 -22 -35 -32 -24 -14
Cold flex temperature
after 7 days at 100C

(BS2782:1970MI04B)("C) -16 -15 -16 -13 -23 -30 -29 -22 +13

+9

-8

-5

a Extract

from technical literature of Shell Chemicals International Ltd, reproduced with their
permission.

7.5 PERMANENCE PROPERTIES

It is obviously desirable that once a product has been manufactured

from a flexible PVC formulation, it should continue to perform with a
minimum of change in properties throughout its service life. Failure to
perform satisfactorily may be the result of a number of factors:
(i)

inaccurate initial specification, e.g. insufficient low-temperature

properties;
(ii) degradation by heat, light or possibly radiation;
(iii) loss of plasticiser resulting in an undesirable change of
properties.

The latter may be as a result of extraction, migration or volatile loss of

plasticiser. The more practical aspects of these properties together with
t\l. 0 important related areas, cable ageing and fogging, will be
considered in this section.
As was mentioned in Section 5.6.3 in Chapter 5 the rate of loss of
plasticiser may be either diffusion- or surface-controlled. That is, the
rate-determining step controlling the loss may be either the rate at
which the plasticiser molecules can travel through the PVC matrix or
the rate of loss of plasticiser from the surface. The dominant step
depends on a number of factors but in general, where the overall rate
of loss is slow, e.g. the volatile loss of plasticiser during service life,
the process is surface-controlled. When the rate of loss is much higher,

D. L. Buszard

196

e.g. in a powerful extraction medium, the rate of plasticiser diffusion is

more important.
7.5.1 Extraction Resistance
One of the most important reasons for using polymeric plasticisers is
their resistance to extraction by solvents. Some figures giving details of
the physical properties and extraction resistance of various plasticisers
are shown in Table 7.3. The polymeric plasticisers all exhibit better
extraction resistance and, in general, somewhat inferior efficiency
when compared with monomeric plasticisers.
The high molecular weight non-endstopped Dio/pate 150 (Briggs &
Townsend) possesses particularly good extraction resistance to nonpolar solvents such as hexane and oils. The endstopped polymerics,
Dio/pate 214 and 917, show less resistance to nonpolar solvents, but
better resistance to aqueous extractants and also superior compatibility, especially at high humidity, and greater efficiency. The endstopped, mixed adipate/phthalate polymeric Diolpate 171, exhibits reasonable extraction resistance but improved processing behaviour, both
with respect to lower plastisol viscosities and faster gelation.
It is worth stressing that the good extraction and migration
properties of polymeric plasticisers are very dependent on achieving
full gelation. The high molecular weight non-endstopped products are
particularly difficult in this respect. If it cannot be guaranteed that the
TABLE 7.3
Properties and Extraction Resistance of Plasticisers at 60 phr

Viscosity at 25C (St)

BS softness No.
Cold flex temperature (0C)
Tensile strength (MN m- 2)
Elongation at break (%)
Volatile loss (%)
Extraction loss (%)
Hexane
Mineral oil
Olive oil
Water
Soap (1%)

DOP

BBP

TXP

ESO Diolpate Diolpate Diolpate Diolpate

150
171
214
917

05
45
-20
17-8
335
225

06
43
-12
115
195
163

09 5
41
41
+2 -12
203 165
280 365
69 90

35
158
235
01
128

140
124
154
05
196

155 186
67 107
9-6 145
+03 01
212 41

130

28
-3
187
320
29
12
+05
31

1-6
7-2

9
42
-6
180
315

3-6
7-6
73
98
04
82

35
41
-7
17-4
330
H
29

z.t

58
03
27

41

44
-4
169
350

3-3
24
19
38
01
29

7 Properties of Plasticised

pvc

197

appropriate compounding/processing equipment for a particular product will achieve full gelation, then it is preferable either to use a lower
molecular weight endstopped polymeric or to include a proportion of
rapid-gelling plasticiser, such as triaryl phosphate, in the formulation.
It can be seen that the replacement of an alkyl by an aryl group in a
dialkyl phthalate reduces the nonpolar extraction resistance of the
plasticiser. Triaryl phosphates and epoxidised soyabean oil exhibit
intermediate extraction resistance between the dialkyl phthalates and
the polymeric plasticisers.
As mentioned in Section 6.9 of Chapter 6, solid polymeric resins
have replaced high viscosity polymeric plasticisers in certain applications. Typical physical and extraction properties of a polyurethanebased solid elastomer are shown in Table 7.4. It will be noticed that
whilst such products impart excellent extraction resistance to a PVC
compound, they are far less efficient than conventional polymeric
plasticisers.
The thickness of a sample can also have an effect on its extraction
resistance. This is shown schematically in Fig. 7.9. With very thin
TABLE 7.4
Physical Properties of a PVC Compound
Containing a Solid Polyurethane Elastomer-'Durelast loo,a
BS softness No.
Cold flex temperature eq
100% modulus (MN m- 2)
Tensile strength (MN m- 2)
Elongation at break (%)
Tear strength (kN m- 1)
Volatile loss (%)
Extraction loss (%)
Hexane
Mineral oil
Olive oil
Water
Soap (1%)
Formulation:

a Trade

PVC
Durelast 100
ESO
Cd stearate

45
-225
56
15
530
59

02

+03
+01
-01
+07
+04
100
100
10
6

name of Briggs & Townsend.

D. L. Buszard

198

J.. --::l

.Q

,
._,. ,.
~

~ ,.'

1-

,.'

'

"

".

I
I

--- ---

1:C7l
.~

--_. '0
.,!!

~
~

.Q

---11

1:

Incrllaslng sampill thlcknllss -+

Fig. 7.9 Schematic representation of the effect of sample thickness on

extraction resistance.

samples the concentration gradient throughout the sample on extraction is very low (region A), whereas thicker samples exhibit a marked
concentration gradient with a reservoir of plasticiser in the centre of
the sample, thus resulting in the extraction being diffusion-controlled
(region B). Extraction resistance is normally quoted as % weight loss of
the sample (as in Table 7.3, etc.) or, less commonly, as % loss of
plasticiser. However, in certain cases, it has become accepted to quote
the results as actual weight loss per unit area of the sample tested. This
is so in a number of national and international directives relating to the
loss of additives from food-packaging materials into the contained
foodstuffs. For example, the EEC draft directiveS on overall migration
of plastics additives puts an upper limit of 10 mg per square decimetre
of packaging material when tested by a particular method using a range
of food simulants (distilled water, citric acid solution, aqueous alcohol
and olive oil). Expression of the results in this manner obviously means
that, as shown in Fig. 7.9, a particular compound may meet the
requirements when tested at one thickness, but may fail when tested in
a thicker section. In order to meet the olive oil extraction requirements
of the above directives, it has been necessary to reformulate the thin
PVC cling film to include a proportion of polymeric plasticiser as
shown in Table 7.5.

7 Properties of Plasticised

pvc

199

TABLE 7.5
Reformulation of Stretch Wrap PVC Food Packaging Films
to Include a Polymeric Plasticiser
Old
New
formulation formulation

PVC suspension polymer

DOA
Reoplex 430 (Ciba-Geigy)
ESO
Ca/Zn stabiliser
Antifogging agents
Overall migration resistance into
olive oil
days at 40C)
(mgdm- )

pO

100
25

3
1

100
10
20
5
3
1

32

7.5.2 Migration Resistance

The resistance of a plasticiser to migration from a PVC compound into
another material in close contact is often a very important requirement. For example, migration of plasticiser from a PVC refrigerator
gasket into a high-impact polystyrene (HIPS) refrigerator liner can
lead to cracking of the HIPS in high stress areas or even softening of
the HIPS resulting in it adhering to the gasket. Other examples include
PVC cables in contact with plastics electrical appliance cases,
self-adhesive PVC films, insulation tapes and the adhesion of print and
lacquer to PVC films.
The degree of migration will depend not only on the type and
molecular weight of the plasticiser but also on the nature of the surface
with which the PVC compound is in contact, in particular the
compatibility of the plasticiser with, and its diffusion coefficient into,
that material. This is highlighted in Table 7.6 where it can be seen that
plasticisers generally have a greater tendency to migrate into cellulose
nitrate than into natural rubber, and even less into polyethylene. It will
be noted that the relative tendency of different plasticisers to migrate
may be reversed when in contact with different surfaces. For example,
the acid endstopping of polypropylene sebacate increases its migration
into cellulose nitrate but markedly reduces its migration into natural
rubber (Table 7.6).

D. L. Buszard

200

TABLE 7.6
Migration Resistance of Plasticisersa
Cellulose Natural Polyethylene
nitrate
rubber

PPS
PPA
PPS/acid endstopped
PPAlacid endstopped
PPA/alcohol endstopped
Epoxidised oil

27
22
91

107
64
91
141

DOP
a Method

29
10

25
07
13
110

01
034
03
07
01
025
22

according to DIN 53405-1981.

Migration resistance is usually determined by DIN 53 405-1981, in

which pre-weighed discs of plasticised PVC are sandwiched between
discs of the relevant plastics material and placed between glass plates
with a 5 kg weight on top, in an oven at 70C. Table 7.7 shows the
migration (expressed as % weight loss of the PVC disc) of a range of
commercially available plasticisers into high impact polystyrene. The
resistance to migration of the different plasticisers varies widely and is
dependent on structure rather than molecular weight.
TABLE 7.7
Migration of Polymeric Plasticisers into Polystyrene
% weight loss of PVC disc a
Test
period
(days) Wolftex b 828 Wolflex 848 Wolftex 868 Wolftex PLA
1
3

7
14

0302
0623
0785
0956

0019
0027
0027
0037

0062
0114
0132
0157

0058
0127
0146
0173

a Modified
b

DIN 53 405-1981.
Trade name of Victor Wolf.

7.5.3 Volatile Loss

The volatile loss of plasticisers from PVC compounds is generally
studied in two ways. Compounds are aged under a given set of
conditions of temperature, time, airflow and sample size, and the
volatilisation assessed either directly by the loss in weight of the test

7 Properties of Plasticised

pvc

201

specimens, or indirectly by the changes in physical properties occurring

on ageing. The first method is very common and is the means by which
the volatile loss results quoted in Chapter 6 Tables 6.3 and 6.6-6.13
have been obtained. These tests may be carried out either directly in
ovens, preferably specially designed to avoid cross-contamination, or
with the samples in contact with activated carbon to absorb the
plasticiser vapours. Polymeric plasticisers, trimellitates and pentaerythritol esters are the classes of plasticisers exhibiting lowest
volatile losses. Figure 7.10 shows the weight loss of PVC plasticised
with a number of common plasticisers over an extended period. It is a
characteristic of monomeric plasticisers that volatile loss tends to be
reasonably linear with time up to fairly high losses. However, the
volatile losses from polymeric plasticisers tend to level off at relatively
low overall values, as the low molecular weight 'tails' are lost, and then
continue unchanged for an extended period.
The alternative method of assessing volatile loss is by following the
change in physical properties on ageing. It has already been
demonstrated by the changes in low-temperature properties on ageing,
in Fig. 6.2 (Chapter 6) and Table 7.2. This way of assessing plasticiser
volatility is obviously more compound-performance-orientated and is
much favoured in the various cable specifications, particularly for
high-temperature cables. The change in physical properties does not
40

30

HUG

Hcxaplal PPA

200

400
600
Houri at 100 0

800

1000

Fig. 7.10 Volatilisation of polymeric and other plasticisers.

202

D. L. Buszard

necessarily indicate just loss of plasticiser; particularly when the ageing

tests are carried out at high temperature, oxidation of plasticiser and
cross-linking and/or chain scission of the PVC molecules can also
occur. In these cases, the inclusion of an antioxidant in the formulation
can cause an apparent reduction in the plasticiser volatility.
In the case of cables, the choice of plasticiser is dependent upon the
conditions under which the cable is designed to operate. Generalpurpose insulation and sheathing compounds based on Cs phthalates,
often with a chlorinated paraffin, are normally limited to a maximum
continuous temperature of 6~5C. For continuous operation at
temperatures higher than this low-volatility plasticisers must be used.
Thus for a maximum rating of 75C, DIDP or perhaps a phosphate
plastieiser are suitable, whereas for 90C cables, DTDP is preferred.
Trimellitates, polymeries or pentaerythritol esters are required for
105C rated cables.
7.5.4 Automotive Fogging
One property relating to plasticiser volatility whieh is periodically of
interest to PVC technologists is automotive windscreen fogging. This
problem of the build-up of an oily condensation or fog on car
windscreens causing reduced light transmission, has been recognised
since the 1950s and was largely attributed to volatile plasticisers.
However, careful analysis of the fog by a number of laboratories
suggest that in addition to the PVC plasticisers from crashpads and
leathercloth, other additives may also cause problems. These include
plasticisers in adhesives, pigment-dispersing media and other
components of polyurethanes, antioxidants and even airborne hydrocarbons.
Although fogging has been around for many years, the car
manufacturing companies do not have a consistent approach to the
problem. Some companies have very strict requirements, whilst others
are influenced by the cost premium imposed by low-fogging leathercloth and crashpads. There are several different types of fogging tests
in use, and a number of different test temperatures, e.g. 60, 75 and
90C, depending on the part of the car for which the parts are destined.
The fogging performance of a compound has been shown to be
affected not only by the plasticiser but also by other constituents, e.g.
stabilisers and minor impurities such as residual emulsifying agent in
the polymer and free alcohol in the plasticiser. A selection of fogging
results on various typical formulations is shown in Table 7.8.

7 Properties of Plasticised

pvc

203

TABLE 7.8
Fogging Test Results on Typical PVC Formulations for
Automotive Use o
CRASH PADS
b

Breon S125/12
Blendexc 101
Chemigum d NB B1 A2
1rgastabe CH55
Titanium dioxide
Antimony trioxide
Reomof LTM
1rgastab 17M
Fogging at 90C

50
50
10
05
5
3
25
15
95%

CALENDERED SHEETING

Breon S125/12
Reomol LTM
Palatino! 911
Reofose95
Titanium dioxide
Calcium carbonate
Antimony trioxide
1rgastab 17M
Irgawax e 372
Fogging at 60C
Fogging at 75C
LEATHERCLOTH

Vinno[8 P70
Solvich 374 NB
ReomolLTM
Palatinol 911
Reofos 95
Titanium dioxide
Antimony trioxide
Irgastab 17M
Fogging at 60C
Fogging at 75C

100
50
2
5
5
1
03
98%
95%

100
30
20
2
5
1
03
97%
98%

33
66
70

33
66

33
66

70

2
5
1
99%
93%

2
5
1
96%
90%

45
25
2
1
98%
91%

Results by Volvo Fogging test method-minimum requirement 90% reflectance.

Ii Trade name of BP Chemicals.
C Trade name of Borg Warner.
d Trade name of Goodyear.
e Trade name of Ciba-Geigy.
fTrade name of BASF.
g Trade name of Wacker Chemie.
h Trade name of Solvay.
o

204

D. L. Buszard

Obviously the most stringent fogging test is that carried out at 90C,
which is for crashpad and window visor components. To meet the 90%
reflectance requirement, it is necessary to formulate with plasticisers
such as trimellitates, high molecular weight phthalates or other high
molecular weight plasticisers, as well as a carefully chosen polymer and
stabiliser system. Normal polymeric plasticisers are generally unsuitable since the low molecular weight 'tails' can fog severely.
Trimellitates are technically preferable to high molecular weight
phthalates, since it is far easier to strip Cg alcohols from the finished
product than C lO-C14 alcohols.

7.5.5 High-humidity Compatibility

Many plasticisers which have good compatibility under normal
conditions of usage can exhibit severe incompatibility under conditions
of high humidity, e.g. in refrigerators or in tropical climates.
Non-endstopped polymeric plasticisers such as polypropylene adipate,
are particularly bad in this respect. Phosphate plasticisers exhibit very
good compatibility at high humidity.
7.6 FLAME-RETARDANT PROPERTIES

Rigid PVC is the most flame-retardant of all the thermoplastic

polymers manufactured on a large scale. The addition of plasticisers
reduces this flame retardance to a greater or lesser extent, as is shown
in Fig. 6.3 of Chapter 6, in terms of the effect of plasticiser
concentration on the oxygen index. However, even with high
concentrations of non-flame-retardant plasticisers, flexible PVC exhibits a greater flame retardancy than other common polymers such as
polyolefins, polystyrene, PMMA, etc., and is often self-extinguishing
to small ignition sources.
In recent years a greater awareness of the fire hazards associated
with the extensive use of polymeric materials has led to increased
requirements for more highly flame-retardant flexible PVC compositions. Such applications include cables for use in power stations and
high-rise buildings, conveyor belting for coal mining, and wall
coverings with low flame-spread characteristics.
Flame retardancy in flexible PVC may be achieved either by (a)
using a suitable plasticiser, e.g. a phosphate or chlorinated paraffin, or
(b) incorporating a flame-retardant additive, such as antimony trioxide

7 Properties of Plasticised

pvc

205

or alumina trihydrate. The latter approach is often used in conjunction

with a flame-retardant plasticiser rather than alone.
Phosphate plasticisers, particularly triaryl phosphates which are very
effective primary plasticisers as well as good flame retardants, offer a
convenient means of achieving the necessary properties. They have the
additional advantage of being non-pigmenting and hence clear
flame-retardant formulations can be produced. Since triaryl phosphates
are seldom used as sole plasticiser, their poor low-temperature
properties can be offset by blending with other plasticisers. Figure 7.11
demonstrates the oxygen index and the cold flex properties of Reofos
95 (Ciba-Geigy) with di-Linevol 79 (Shell Chemicals) phthalate at
overall plasticiser contents of 40, 60 and 80 phr. If the di-Linevol 79
phthalate in the blend is replaced by another non-flame-retardant
plasticiser, e.g. an adipate, trimellitate, polymeric or other phthalate
plasticiser, then the oxygen index of the blends would be similar,
although the cold flex results would be different. The use of Fig. 7.11
35

20

o
o

0>(

ClI

"0

.!:
c
ClI

~
>(
025

,/

"0

-40

20'+-_ _,...-_ _~_ _r-_----I

o
25
50
75
100
100

Fig.7.11

75

0/0 Reofos 95

50

/oL79P

25

Oxygen index and cold flex temperatures of Reofos 95/di-LinevoI79

phthalate blends.

206

D. L. Buszard

in conjunction with the data in Figs 7.2 and 7.8 enables the properties
of other blends to be estimated.
The use of chlorinated paraffins particularly in conjunction with
phosphate plasticisers allows compositions with good flame retardancy
to be formulated economically, providing that a high degree of light
stability is not required. Alkyl diaryl phosphates can give formulations
with reduced smoke evolution. The partial replacement of triaryl
phosphates by chlorinated paraffins,6 particularly in the presence of
certain fillers, such as magnesium oxide and hydroxide. is also claimed
to give a reduction in smoke evolution;? see also Chapter 11, Section
11.5.
7.7 ELECTRICAL PROPERTIES

The electrical properties of greatest interest in flexible PVC are the

volume and surface resistivity, and the dielectric properties. Volume
resistivity and dielectric strength are naturally very important in wire
and cable insulation; high values in these properties enable thinner
coatings to be used. The effect of plasticiser type and concentration on
the volume resistivity of a PVC compound is summarised in Fig. 7.12. 8
Since, as is apparent from its molecular structure, PVC exhibits a
high dipole polarisation, the dielectric constant and power factor of its
compounds are very frequency- and temperature-dependent. This
limits the use of flexible PVC insulation to lower voltage and
low-frequency applications. However, the power losses at high
frequencies are successfully utilised in the high-frequency welding of
PVC sheet (see Chapter 20).
Outside the area of electrical insulation, low values of resistivity,
particularly surface resistivity, are often beneficial in reducing
problems of static build-up. A good review of the electrical properties
of polymers and the effect of plasticisers has been made by Coulson. 8
7.8 WEATHERING AND LIGHT STABILITY

These properties depend primarily on the stabiliser system (Chapters 9

and 12) but they are also affected by the plasticisers used. The
weathering and light stability of PVC compounds are usually assessed
either by long-term outdoor exposure tests or by more rapid

7 Properties of Plasticised

pvc

207

Eu
c:

13

> 10

>-

>
>-

.r>
.r>

10'2

....

:J

o
>

1010L..J~_ _~:----~:----~:---

40

50

60

70

PlASTICISEIl CONTENT (phr)

Fig. 7.12 Effect of plasticiser type and level on volume resistivity at 23C. 8

accelerated weathering techniques such as the Atlas Weatherometer*

or the Xenotest. t It is very difficult to compare the results of different
workers since both the climatic conditions and the accelerated ageing
techniques vary so widely, and this often leads to contradictory and
anomalous results.
Four phenomena are generally associated with the outdoor weathering of PVc. These are:
(i)

Discoloration-usually due to degradation of the PVc. This is

very dependent on the stabiliser system, but photo-oxidation of
plasticiser can accelerate the decomposition.

* Atlas Electrical Device Co.

t Hanau Quarzlampen GmbH.

208

D. L. Buszard

(ii) Loss of ftexibility-due to loss of the plasticiser by volatilisation, extraction Or photo-oxidation.

(iii) Light-induced exudation-plasticiser migrating to the surface
oxidises, leading to a discoloured, tacky surface layer. This is
particularly associated with plasticisers containing carboncarbon double bonds, chlorinated paraffins or high levels of
epoxy compounds.
(iv) Dirt pick-up-this is often associated with (iii) and is particularly a problem in PVC-coated steel for use in outdoor cladding.

In general, aliphatic diesters impart good light stability, providing

they are within their compatibility limits. Straight-chain phthalates are
superior to their branched-chain counterparts, although the high linear
phthalates exhibit poorer compatibility. Phosphates are poorer than
phthalates, except when included in phthalate-plasticised compositions
at low concentrations, when they apparently stabilise the
formulations. 9 Aromatic phthalates such as BBP have markedly poorer
light stability than dialkyl phthalates.

7.9 RESISTANCE TO MICROBIOLOGICAL ATIACK

This is particularly important in plasticised PVC products for use
outdoors, especially when in contact with soil or in warm humid areas,
Examples of products particularly at risk are: buried cables, swimming
pool liners and covers, foul-weather clothing, wallcoverings, and
shower curtains. Plasticisation increases susceptibility to microbiological attack and no plasticiser is completely immune. Much investigational
effort has been devoted to the problemy)"'15 Table 7.9 extracted from
the work of Burgess and Darby13 indicates the relative resistance of a
range of plasticisers to a mixture of five different fungi. Extensive soil
burial tests by Decoste 12 showed that in addition to type, plasticiser
concentration is also an important factor. Tests for plasticiser
suitability are time-consuming and the advice of manufacturers
provides a shorter route to the solution of specific practical problems of
formulation. This advice may include recommendations for the use of
such suitable chemical additives as fungistats or bacteriostats in the
PVC formulation (e.g. Irgasan DP 300/PA-Ciba-Geigy; Estabex
ABF-Akzo Chemicals; bioMET additives-M & T Chemicals).

7 Properties of Plasticised

pvc

209

TABLE 7.9
Fungal Resistance of Plasticisers13 ,a

Plasticise,P
TXP
D79P

DIOP

Polyester B
Polyester C
Polyester A

DIOA
DIOS
ESO

% plasticiser

% sample
shrinkage

o
o
o

loss

419
524
621
1458
1828
5313
5643
6383

32
22
27
85

107

150

Samples sprayed with a mixed spore suspension of: A. flavus; C. herbarum; P.

funiculosum; P. pullulans; T. viride; incubated for 14 days at 28C.
b Formulation: PVC, 100; Plasticiser, 54;
Epoxy, 15; BalCd stabiliser, 30.
a

7.10 RESISTANCE TO INSECT AND

RODENT ATTACK
This is also of interest in certain building and outdoor uses of PVC and
is particularly important in tropical climates. Plasticisation increases
the susceptibility of PVC to attack by insects and rodents. There is
some evidence that phosphate plasticisers may be more resistant than
others,lO,16 but effective remedies are not primarily a matter of
plasticiser selection. Special insecticides or repellants may be used in,17
or applied as coatings to, the PVC compound (e.g. Dieldrin-Shell
Chemicals; bioMED

7.11 STAIN RESISTANCE

Flexible PVC is susceptible to staining by many different substances
but particularly those which are oil-based (e.g. ball-point pen ink, shoe
polish, tar, etc.). It has been shown that the degree of staining
increases with the plasticiser content and that at equal levels of softness

D. L. Buszard

210

the type of plasticiser is also important. 18 Plasticisers which give

reduced levels of staining are 2,2,4-trimethyl-l,3-pentanediol diisobutyrate (e.g. Kodaflex TXIB-Eastman Chemicals), the monoisobutyrate monobenzoate of the above diol (e.g. Nuoplaz 1046-Tenneco),
benzyl butyl phthalate (e.g. Santicizer 16o-Monsanto) and triaryl
phosphates (e.g. Reolos So-Ciba-Geigy). The major applications
where stain resistance is important are in PVC flooring, and, to a lesser
extent, in wall coverings and claddings.

'.n
'.n.t

TOXICITY AND HEALTH ASPECTS

OF PLASTICISERS

Plasticisers for Food-contact Application

Plasticised PVC is often used in applications in which it comes into

direct contact with foodstuffs, e.g. packaging films, bottle seals, can
lacquers, conveyor belting used in food preparation, etc. In such
applications it is important that only those plasticisers-and indeed all
other constituents-which are known to be non-toxic are used. In
many parts of the world this is a requirement in law. In the USA for
example, only those additives specifically permitted by the PDA 19 may
be used. In other countries, such as the UK and Germany, there is
currently no specified list of legally approved products, but the
recommendations of the BPP20 and BGA,21 respectively, are voluntarily followed. It is likely that in Europe in the near future, the various
national lists of approved additives will be replaced by a single Council
of Europe or EEC directive. Table 7.10 summarises the more
important plasticisers approved in a number of countries and also
includes the draft proposals of the Council of Europe. However, this
list is not exhaustive and in certain applications additional limitations
may apply. For more detailed information a user should contact the
plasticiser manufacturer or study the appropriate published national
requirements/recommendations directly.
Recent studies22 .23 by the US National Cancer Institute (NCI) have
indicated that DOP and DOA could cause a statistically significant
increase in the observed liver tumours (hepatocellular adenomas and
carcinomas) when fed to certain rodents daily over a two-year period.
The high levels of dosage do, however, make interpretation of these
results difficult and it would not be possible on this evidence alone to

7 Properties of Plasticised

pvc

211

TABLE 7.10
Plasticisers Approved Q for PVC in Contact with Foodstuffs
DBP DOP DIOP DIDP DMEP DBS DOS DOA DIDA ESO Reop/ex Reop/ex
FG
430
Council of Europe
Federal Republic
of Germany
Franceb
HoUand b
Italt
UK
USA

x
x
x
x
x
x

x
x
x
x
x

x
x
x

x
x
x

x
x

x
x
x
x
x
x

x
x
x
x
x
x

x
x
x

x
x

x
x

x
x
x
x
x
x
x

x
x
x

x
x
x
x
x

Limitations not indicated in the table may apply to, for example, maximum permissible concentration, type of food to be packaged, form of finished product, etc.
b Subject to an overaU migration limit.

evaluate any potential carcinogenic hazard to man. Since it was evident

that these findings could have important implications affecting the
continued commercial use of these esters, the European Council of
Chemical Manufacturers Federation (CEFIC) recommended that
further scientific studies specifically designed to investigate the
possibility of adverse health affects resulting from human exposure
should be carried out. These studies sponsored by the European
Plasticiser Manufacturers under the auspices of CEFIC have now been
completed and reported. 24 The studies carried out on DOP included
DNA binding, dose/time response and a comparative assessment in
rodents (rats) and primates (monkeys). These results confirm that
there is sound evidence that the NCI study is not relevant to human
risk assessment and carcinogenic risk to man has not been demonstrated.
Further studies involving a wide range of phthalates and adipates are
currently in progress in the USA. This is a voluntary research
programme funded by the Plasticiser Manufacturers section of the
Chemical Manufacturers Association in conjunction with the FDA.

7.U.2 Health and Safety

The majority of plasticisers manufactured today are of a low order of
toxicity and constitute little hazard in use either from direct toxic
effects or dermatitic effects on handling. However, as with all organic

212

D. L. Buszard

TABLE 7.11
Vapour Pressure of Dialkyl Phthalates
Plasticiser Molecular
weight

DBP
DOP
DIDP

278
390
447

Vapour
pressure
(rnrnHg)

Concentration in
saturated air
at 160"C (g rn- 3 )

12
0121
0029

12
175
048

materials, good working practice should be employed. Adequate

ventilation should be ensured in the vicinity of heated equipment
where plasticiser fumes may be produced.
Table 7.11 indicates the concentrations of plasticiser vapour which
could occur in saturated air at 160C. Laboratory experiments25 and
actual measurements on industrial plastisol coating plants indicate that
25-50 kg h- 1 of plasticiser could be lost by volatilisation alone. This
indicates the need for good ventilation if the threshold limit value
(TLV) of 5 mg m- 2 , generally considered to he the safe maximum
concentration by the American Conference of Governmental Industrial
Hygienists 26 and adopted by HSE 27 and OSHA, is not to be exceeded.
REFERENCES
1.
2.
3.
4.

5.
6.
7.
8.
9.
10.
11.
12.
13.
14.

Harrington, C. E. (1965). Ind. Quality Control, 21,494-8.

Tang, Y. P. and Harris, E. B. (1967). SPE J. 23(11), 91-5.
Pugh, D. M. and Wilson, A. S. (1976). Eur. Plast. News, 3(9), 37-42.
Combey, M. (1972). Plasticisers, Stabilisers and Fillers, (Ed. P. Ritchie),
Iliffe/PRI, London, Ch. 12.
EEC Draft Directive on the overall migration limit for the constituents of
plastics, materials and articles intended to come into contact with
foodstuffs. Ref: R/1444178.
Ceasar, H. J. and Davis, P. J. (1975). SPE Tech. Papers, 21, 130-4.
Price, R. V. (1979). SPE Tech. Papers, 25,956--63.
Coulson, S. H. (1972). Plasticisers, Stabilisers and Fillers, (Ed. P. Ritchie),
Iliffe/PRI, London, Ch. 8.
Dolozel, B. (1963). Chern. Prurnysl., 13(38), 3, 160-5.
Wessel, C. J. (1964). SPE Trans., 4, 193-207.
Berk, S., Ebert, H. and Teitell, L. (1957). Ind. Eng. Chern., 49, 1115-24.
Decoste, J. B. (1968). Ind. Eng. Chern., 7(4),238-47.
Burgess, R. and Darby, A. E. (1964). Brit. Plast., 37(1), 32-7.
Burgess, R. and Darby, A. E. (1965). Brit. Plast., 38(2),2-6.

7 Properties of Plasticised

pvc

213

15. Wolkober, Z., Gyarmati, I. and Farkas, P. (1978). Int. Polym. Sci.
Technol., 5(4), no.
16. Bultman, J. D., Southwell, C. R. and Beal, R. H. (1972). Naval Res. Lab
Report No. 7417, Washington DC.
17. Anon. (1965). Mod. Plast., 42(5), 168.
18. Pinner, S. H. and Massey, B. H. (1963). Brit. Plast., 36(10), 564.
19. USA Food and Drugs Administration (FDA) Code of Federal Practice.
20. 'Plastics for Food Contact Applications-A Code of Practice for Safety in
Use', The British Plastics Federation.
21. 'Kunststoffe in Lebensmittelverkehr', Kunststoff-Kommission des Bundesgesundheitsamtes, Berlin, Federal Republic of Germany.
22. NTP Technical Report series 217. 'Carcinogenesis Bioassay of Di(2ethylhexyl)phthalate (CAS No. 117-81-7) in F 344 Rats and B6C 3F1 Mice
(Feed Study), NIH Publication No. 82-1773.
23. NTP Technical Report series 212. Carcinogenesis Bioassay of Di(2ethylhexyl)adipate (CAS No. 103-23-1); F 344 Rats and B6C 3F1 Mice
(Feed Study), NIH Publication No. 81-1768.
24. CEFIC. (1982). 'Di-(2-ethylhexyl)phthalate (DEHP), CEFIC Plasticiser
Toxicological Working Group Report on Developments in DEHP
Toxicology, Avenue Louise 250, Bte 71, B-1050 Brussels.
25. Poppe, A. C. (1980). Kunststoffe, 70(1), 38-40.
26. 'Threshold Limit Values for Chemical Substances in Workroom Air for
1978', American Conf. of Govt. Ind. Hygienists, Cincinnati, Ohio.
27. 'Threshold Limit Values 1980', Health and Safety Executive, Guidance
Note EH 15/80.

CHAPTER 8

Fillers in PVC
I. D. HOUNSHAM and W. V. TlTow

8.1 INTRODUCTION
For the purpose of this chapter fillers may be broadly defined as solid
particulate or fibrous materials, substantially inert chemically, incorporated in plastics compositions (including PVC) to modify the properties
or to reduce material cost. Cost reduction is often the primary reason
for the use of a filler, and because of this the term is occasionally
treated (incorrectly) as if it was synonymous with 'cheapening
extender'. In fact all fillers-when present in significant quantitiesaffect in some measure the material and/or processing properties of the
plastic, and some-which may be termed 'functional fillers'-are
indeed used, often at increased cost, expressly as property modifiers,
e.g. glass fibres as reinforcing filler in uPVC compositions, antimony
trioxide or alumina trihydrate as flame retardants in pPVc. It may be
noted that the functional aspect is emphasised in the standard
definitions of a filler (ct., for example, ISO 472-1979; BS 1755: Part 1:
1967; ASTM D 883-83).
In the ideal case the incorporation of a filler might confer the
combined benefits of cost reduction with increased output (involving
no processing difficulties and no rise in the process/production costs)
and some technical advantages in the properties and service performance of the plastic. In practice, usually only one, or some, of these
features can be secured, often at the expense of the others, and the
selection of a filler (or filler system) will thus be a compromise,
dictated by the balance of the technical requirements and cost
considerations. For example, whilst such low-cost fillers as ground
215

216

I. D. Hounsham and W. V. Titow

limestone and coarse ground whitings offer the highest material cost
savings in many flexible PVC compositions, they can also adversely
affect the processing, and some physical properties of the end product;
incorporation of glass-fibre reinforcement in uPVC upgrades mechanical
properties but increases the cost and affects the processing behaviour
of the material.
A wide variety of materials has been evaluated as fillers for PVC
compositions: in this chapter attention is centred on those which are of
current technical interest. Among these, certain kinds of calcium
carbonate and chrysotile (white) asbestos have attained particular
commercial importance.

8.2 MINERAL FILLERS

Certain minerals, especially some naturally occurring silicates and

natural (as well as synthetically produced) carbonates, provide some of
the most widely used fillers for PVC. These materials may be
considered under three general headings:
(i) silicates and silicas;
(ii) sulphates of the alkaline-earth metals;
(iii) calcium carbonates.
8.2.1 Silicates and Silicas

The silicate minerals of particular interest as filler materials for PVC

are asbestos, talc, and clay. Other silicate fillers used in some PVC
compositions, but not on a major scale, are wollastonite (a calcium
metasilicate 1 ,2 sometimes employed as a filler in floor tiles and plastisol
products), nepheline syenite (an anhydrous sodium/potassium/aluminium silicate, useful in some semi-transparent compositions because of
its low tinctorial power), mica (a general name for a group of complex
potassium/aluminium silicates with plate-like particles, of particular
interest in some electrical insulation applications), and slate flour (slate
is a complex composed of muscovite mica, chlorite and quartz, i.e. a
composite hydrated potassium/aluminium/magnesium silicate combined with silica).
The mineral silica fillers (quartz, sand, diatomaceous earth) are of
comparatively little interest for PVC compositions, although one

8 Fillers in PVC

217

form-novaculite-has been claimed to be useful in calendered sheet,

rigid compositions and foams. 3
(a) Asbestos
The only form of asbestos used as a filler in PVC is chrysotile (white
asbestos). Chemically this is a hydrated magnesium silicate
(3MgO.2SiO.2H zO). It is a fibrous material (fibre length 1-40 mm,
fibre diameter 001-1 tlm) with a very high fusion point (1500C) and
100% strength retention at temperatures up to 4000C. 1 Its main
applications in PVC are in flooring compositions (where a short-fibre
grade is used, improving melt cohesion in processing and providing
some reinforcement in the product, including improved hardness and
denting resistance), and as reinforcement in pressed sheet (e.g.
Duraform-Turner Brothers Asbestos, UK): a longer fibre grade is
used in the sheet, which finds application as internal and external
cladding material for buildings (especially industrial buildings),
corrosion resistant trunking and ducting, and the like. 4 ,5 Despite the
increasing stringency of various health and safety regulations, the
handling of asbestos and asbestos-filled PVC is still possible, if suitable
precautions are observed. 1 ,4 In formulating and processing asbestoscontaining PVC compositions it should be borne in mind that their
heat stability and colour may be affected by iron compounds present in
chrysotile as minor chemical constituents.
(b) Talc

This material also consists of hydrated magnesium and silicon oxides

(with admixtures of other minerals and impurities, neither of which are
completely removed in preliminary processing). The chemical composition and the particle shape of talc vary somewhat according to the
source; the shape may also be influenced by the grinding process: the
particles may be granular, plate-like ('platy' or 'scaly'), or needleshaped, with sizes in the range 1-50 tlm.1 Talc is used in some
calendered PVC floor tile compounds to increase melt cohesion and
the stiffness and hardness of the finished product: 1 its low tinctorial
power and its refractive index (which is close to that of PVC resin) also
make it of interest as a filler for translucent compositions.
(c) Clay
There are several varieties of clay, all essentially forms of complex,
hydrated alumino-silicates, with varying amounts of other minor

I. D. Hounsham and W. V. Titow

218

constituents (including potassium oxide, titanium dioxide, and iron

oxides). Of these only kaolinite ('kaolin', 'china clay') is of significant
interest as a filler for PVC. Whilst in some other plastics ground kaolin
is used directly, in PVC compositions it is normally employed in the
calcined form. Calcination refines the clay (by removing some
impurities and some iron compounds, which results in improved
whiteness), removes the water of hydration, and improves the
processing performance. The main use of china clay in PVC has been
in flexible compositions for electrical applications (insulation, cable
covering), and also in carpet backing compounds (in those based on
PVC latices bentonite clay, as well as kaolinite, may be used-see
Chapter 23), latex-based films, and plastisol products (especially
coatings on fabrics). However, in all these applications clay has yielded
ground to calcium carbonate fillers, which are normally cheaper, grade
90

.
z
...'"
...

&>

E
:>

5 50

Ul
Ul

ID

40

30

200~---"I""'O---2""'0--~30'--"l---"40'-----"50->o.---<60
0/0

by Weight of Filler

Fig. 8.1 BS softness versus filler loading. PCC: Precipitated calcium

carbonate; calcium silicate: wollastonite.

219

8 Fillers in PVC
400

300

c 200

C;arbon black'

II

'"o
C

iii

100

10

20

30

40

.,. By wllight of filler

50

60

70

Fig. 8.2 Elongation of a PVC compound versus filler loading.

for grade, whilst their effects on the properties of PVC compositions

are generally similar, and can be better in some respects (see, for
example, Figs 8.1 and 8.2, and Table 8.1). In broad terms, the particle
size of china clay (O2-8Ilm) is comparable with that of whiting, but
the particles are platelets, and the colour imparted to PVC materials
by clay fillers is comparatively poorer.
8.2.2 Alkaline-earth Metal Sulphates

Among the sulphates of the alkaline-earth metals (Be, Mg, Ca, Sr, Ba
and Ra) only barium sulphate (BaS04) is of some (albeit relatively
limited) practical interest as a filler for PVC. The two grades of barium
sulphate in use as fillers are both produced from the mineral barytes,

220

I. D. Hounsham and W. V. Titow

TABLE 8.1
Some Effects of Varying Filler Content in a PVC Componnd
Filler (% by weight)

Tensile
strength
(lbfin- z)

Cold flex eC)

Water absorction
(increase % y wt,
48h at 500C)

1700

-21

06

20
30
40
50

-20

60

1300
1210
920
750
500

15
15
15
12
12

20
30
40
50
60

1700
1400
1210
890
1090

20
30
40
50

-17

60

1450
1150
780
820
1100

Carbon black (MPC) 20

30
40

1920
1710
1760

-145
-11
-7

No filler
Precipitated
calcium
carbonate

Hard china clay

Calcium silicate
(wollastonite)

-19
-18
-18
-15
-9

-165
-16

28
37
49
51
65
113
83
68
65
71
12
09
09

The composition of the compound is based on 100 of polymer, 50 phr DOP,

and 7 phr basic lead carbonate, with filler as stated.
Q

the naturally occurring form of BaS04' They are: the natural material,
ground and purified; and precipitated BaS04' known as 'blanc fixe'.
Except where a high-density compound may be required for some
special reason, the high density of barium sulphate (about 4,5) is a
disadvantage because it makes the filler expensive on a volume-cost
basis. The advantageous features include high dry brightness (up to
995% reflectance) and low oil absorption (see Table 8.2). Flexible
PVC compositions incorporating this filler find use in specialised
applications where high acid resistance or opacity to X-rays is required.
Note: Calcium sulphate, found in nature as the minerals, gypsum
(CaS04.2HzO) and anhydrite (CaS04), can also be prepared

8 Fillers in PVC

221

artificially in the corresponding (hydrated and anhydrous)

forms, known by the same names. Gypsum loses most of its
water of hydration on heating at temperatures well within the
PVC melt-processing range:

Thus 'gassing' of the melt and void formation in the product is

a possibility to be considered in connection with its incorporation as a filler.
Anhydrous particulate CaS04 has recently been eliciting
some interest as a filler for plastics (e.g. Snow White-US
Gypsum Co., USA), and a microfibrous, crystalline form
(Franklin Fiber-United States Gypsum Company, USA) has
been suggested as a possible substitute for asbestos;8 however,
neither of these materials is used in PVC on an industrial
scale.
8.2.3 Calcium Carbonates
This group comprises a range of naturally occurring materials, as well
as prepared (precipitated) calcium carbonates. It provides the
following types of fillers, widely used in PVC compositions:
(i)
(ii)
(iii)
(iv)

whiting;
ground limestone, marble, and calcite;
ground dolomite;
precipitated calcium carbonate.

The mineral calcium carbonates are available at relatively low cost

and in large quantities from abundant natural sources. The energy
required for their processing (grinding and classification) is comparatively low. Their characteristics, desirable in fillers, include low
plasticiser absorption, absence of water of crystallisation and generally
good resistance to thermal decomposition during processing of the
plastics compositions in which they are incorporated, relative softness,
good white colour, and purity. The precipitated grades share these
properties (although their oil and plasticiser absorption is comparatively high); they are commonly used for specialised applications, notably
in rigid PVC compositions.

6
14

12

155
165
165

150
159
163
159
140

255

447
440

270

271

2.68

290
233

Calcite (Hydrocarb C )

Precipitated
Calcium silicate:
Wollastonite
Precipitated

26
360

15-65

18

34

40

158

240

Alumina trihydrate
(TrihydeC )
Asbestos (chrysotile)
Barium Sulphate:
Barytes
Blanc fixe
Calcium carbonate:
Dry-ground whiting
(stearate-coatedBritomya BSHC )

Oil
absorption b
(weight %)

Refractive
index

Filler materiaL

Specific
gravity

50
50

30

30

30

30
30

25-40

25

Moh
hardness

TABLE 8.2
Some Properties of Filler Materialsa

Crystalline
Crystalline

Crystalline

Crystalline

Crystalline

Granular
Granular

Granular or
crystalline
Fibre

Particle
shape

Particle size-mean
20 pm; top cut 15 Ilm
Particle size-mean
15Ilm; top cut 7 Ilm

Various particle
size grades

Remarks

152
151-152

150
159
160
145
154
1-40
155
155
159

250

249

021

275
260

220
200
265
265
265
280

Spheres, hollow
(thin-walledQ-cel 300c)

150
55-180
120
32
20-30
27-40

47
20

35 d

30

15

36
25

60
70
55
10-15

30
60

65

65

65

25
25

Spherical
Amorphous
Diatom
Crystalline
Amorphous
Platy

Platelet
Crystalline

Sphere

Sphere

Amorphous

Platelet
Platelet

Mean particle size

65,um (range 10-180 ,urn)

Various particle
size grades

IV
IV
W

Based in part on data from References 1, 6 and 7.

Some of the figures have been obtained by different test methods; however, most are the results of oil rub-out tests according
to ASTM D 281-31 (1974), and are thus generally comparable.
C Croxton and Garry Ltd, UK.
d Grams of oil per 100 cc of spheres.

Mica (muscovite)
Nepheline syenite
Silica:
Colloidal (pyrogenic)
Precipitated gel
Diatomaceous earth
Ground quartz (sand)
Novaculite
Talc (Garotalc C )

156
162

260
263

Clay (kaolin):
Ground
Calcined ground
Glass:
Ground
Spheres, solid
(Ballotin{)

224

I. D. Hounsham and W. V. Titow

8.3 CALCIUM CARBONATE FILLERS-NATURE,

PROPERTIES AND APPLICATIONS
8.3.1 General Types
(a) Whiting
This is a fine, white powder, produced by grinding and classifying
chalk,9 which is a fairly pure natural calcium carbonate found in the
form of deposits of aggregated, fossilised skeletons of microscopic
marine organisms of the group Foraminifera, known as coccoliths. The
deposits were produced, in the course of tens of millions of years, in
the Cretaceous period of the Mesozoic era (Latin creta = chalk). Apart
from its whiteness, the most characteristic features of whiting are its
particle size and shape. The particles are small-typically below 10 ,urn
in size: under suitable magnification some can be seen to have a fine
granular structure, with the granules (in most cases about 02-06 ,urn)
recognisable as elements of a coccolith skeleton; some of the particles
are actually complete, ring-shaped skeletons-roughly 4-8,um in
diameter-or parts of such rings. Basic dry grinding of chalk leads to
an end product with the majority of particles between 1 and 5,um in
size; this range is very well suited to the material's application as a
filler for PVc. Of particular interest are whitings from Northern
European chalks which are noted for their purity (especially the almost
complete absence of silicates).
(b) Ground Limestone, Marble and Calcite
Limestone is a very widely occurring natural calcium carbonate formed
from deposits of calcified Foraminfera, originally sedimented and later
consolidated by heat and pressure. Marble and calcite are hard,
compact crystalline varieties of limestone. 9,10 There are only a few
areas where the deposits of limestone, marble or calcite are pure
enough for grinding and processing into fillers for PVc. Of the ground
end products, limestone fillers are the coarsest (and hence have the
lowest oil and plasticiser absorption) and of, relatively, the poorest
colour. The colour (whiteness) of ground marble and calcite is very
good; their oil absorption is lower than that of whiting. The filler
grades available are produced by either wet or dry processing. The wet
ground materials are of higher quality, with finer particle size and more
uniform size distribution, but they are more expensive.

8 Fillers in PVC

225

(c) Ground Dolomite

Limestones containing about 45% magnesium carbonate, i.e. 55: 45
CaC03/MgC0 3 , are called dolomites (those with lower MgC0 3
contents are known as magnesian limestones). The filler grades of
ground dolomite have very good colour, and plasticiser absorptions
higher than those of their ground marble counterparts. Scandinavia has
the best deposits of dolomite.
(d) Precipitated Calcium Carbonates
These are available in two versions-as powders specially manufactured by controlled precipitation from solutions of calcium salts, and as
a by-product from water-softening plants. Both sources provide
powders of fine particle size-few particles exceed 1 pm, and the
average size is well below this level. For this reason the precipitated
calcium carbonates are normally supplied in the coated form (see
Section 8.3.2 below) to counteract agglomeration and aid dispersion in
polymer compositions: it is an advantage of the precipitation processes
that particle-coating treatments can be applied in the course of
manufacture (and not as an additional processing step). The process
also affords good control over the quality, particle size, and purity of
the product (albeit that from some water-softening plants may be
slightly alkaline), and the colour (whiteness) is normally very good.
However, the production cost of precipitated calcium carbonate fillers
is in general considerably higher than that of their ground counterparts.
Precipitated calcium carbonates are sometimes referred to as
'precipitated whiting' (especially in sales literature). This nomenclature
is incorrect (see description of whiting above).

8.3.2 Surface treatments

Calcium carbonate powders (as well as, occasionally, other inorganic
materials) used as fillers in PVC may be treated with substances which
make the particle surface organophilic (hydrophobic), thereby conferring certain processing and performance advantages. Thus moisture
absorption by the particles is reduced, and this improves dry flow of
the powder and reduces agglomeration; it has also been claimed to
improve the moisture resistance of PVC compounds filled with
surface-treated fillers (in comparison with similar ones incorporating
untreated grades)-an effect of interest, for example, in electrical wire

226

I. D. Hounsham and W. V. Titow

and cable coatings. The surface treatments improve interaction

('wetting') at the filler/polymer interface, promoting quicker and more
intimate dispersion of the filler in the polymer melt (better dispersion,
and 'wetting' of the filler particles by the melt, also make for easier
melt flow in processing). Plasticiser absorption ('plasticiser demand') is
reduced by the presence of the coating on the filler surface.
Improvements in the mechanical properties of the filled PVC
composition can also result (e.g. higher impact strength and flexural
modulus in uPVC in comparison with similar compositions containing
the same type of filler but without surface treatment): these may be
particularly noticeable in cases where the surface treatment affords
scope for actual bonding between the filler and polymer at the
interface (as, for example, when the filler is treated with some
organotitanate compounds-see below). However, the degree of such
property improvements is not so great as to constitute the main reason
for surface-treating fillers for PVC, and the substances most widely
applied are not primarily intended to act as coupling agents in the way
in which, say, certain silane compounds do when applied to glass fibres
for use as reinforcement in some polymers! (silanes are not, in fact,
used on either glass-fibre reinforcement or any other fillers for PVC).
It may be noted in passing that the surface treatments of commercial
fillers do not in practice attain the theoretical ideal of a complete
covering of the whole surface of every filler particle with a thin (ideally
molecular) layer of the coating substance. However, the general extent
of coverage is normally good enough to promote in significant measure
the advantages just mentioned: because the reagent in this type of
treatment is thinly distributed over the particle surfaces, the amounts
required are low (in general from fractions of a per cent up to about
2% on the weight of filler). The reagents used as surface treatments on
calcium carbonate fillers for PVC may be considered under three
headings: stearates, organotitanates, and miscellaneous (including
proprietary) treatments.
(a) Stearate Treatments
Stearic acid and some stearates are the oldest and still most widely
used reagents. They may be simply deposited on the particle surface,
or also additionally made to react with the surface material-at
suitably elevated temperature and/or pressure-to be positively
bonded thereto. Examples of commercial CaC03 fillers with such
surface-bonded stearate coatings are Polcarb S (English China Clay

8 Fillers in PVC

227

Sales Co. Ltd), Omya BLR/3 and Omyalite 95T (Pliiss-Staufer AG, or
Croxton and Garry, UK and Europe), and Gama-Sperse CS 11
(Georgia Marble Co., USA). Some CaC0 3 fillers are marketed as
'double-coated' grades, e.g. Britomya BSH 30 (Croxton and Garry
Ltd, UK); in comparison with the corresponding uncoated material
(Britomya M) the coating reduces oil absorption by about 25% and
DOP absorption by about 35%.11
(b) Organotitanate Treatments
Alkoxy organotitanates, introduced comparatively recently (1974/75)
in the USA as coupling agents for fillers in thermoplastics (as well as
some thermoset systems )4,12 have entered the commercial field, inter
alia, as surface treatments for calcium carbonate fillers and alumina
trihydrate flame retardants used in PVC. On the former filler certain
organotitanates (Ken-React TTOP-12 and TTOPP-38-Kenrich Petrochemicals Inc., USA) have been claimed 12 to improve substantially
the extrusion characteristics and impact resistance of 40%-filled rigid
PVC pipe compounds 4 ,13 and enable significant reduction in the
amount of lubricant used. In flexible PVC compositions the use of
TIOP-12 has been said to improve performance beyond that
achievable with stearate-coated CaC03 12 It has also been suggested
that the presence of an organotitanate coating on the CaC0 3 filler can
have some flame retardant effect in a compound. 13 Among commercial
calcium carbonate fillers for PVC surface-treated with organotitanates
are some of the grades supplied (in the USA) by the Sylacauga
Calcium Products Co., and the So/emite calcium carbonates from
Solem Industries Inc.
(c) Proprietary and Miscellaneous Treatments
The nature of proprietary surface treatments on some commercial
(ilC0 3 fillers (e.g. Super-Pflex 200-Pfizer Inc., Minerals, Pigments
and Metals Division, USA) is not generally disclosed, although some
are believed to be of the stearate type. Others include the so-called
'calcium resinate' treatment (as, for example, on Gama-Sperse
CR-12-George Marble Co., USA) and those involving the proprietary surface-active agents of Byk-Mallinckrodt (West Germany and
USA), as applied, for example, to some CaC03 filler grades of the
Calcium Carbonate Co. (USA). The opacifying surface treatment
(used, for example, on Omya BLR 2 and BLR 3-Croxton and Garry
Ltd., UK) may also be mentioned, although its function is not to

228

I. D. Hounsham and W. V. Titow

promote the effects discussed above, but to increase the refractive

index of the CaC0 3 filler and hence its whitening power in a
compound.

8.3.3 FDler Properties and Selection Criteria*

In order to select a CaC03 filler for a given PVC application, the

various properties of the filler should be understood in terms of its
effects on the compound (some of the considerations relevant here
apply also in the selection of other fillers). The most important features
are:
(a)
(b)
(c)
(d)
(e)
(f)
(g)

maximum particle size;

particle size distribution and mean particle size;
colour (whiteness)-dry brightness;
refractive index (opacifying effect);
oil and plasticiser absorption;
dispersion characteristics;
cost.

(a) Maximum Particle Size

This is very critical in terms of both the physical properties of the filled
compound and its surface appearance; the lower the maximum particle
size, the better these properties become. In fact, the presence of even
a small percentage of oversize particles can adversely affect performance. For most plasticised formulations for extrusions, fine-gauge
calendering, and injection moulding, a maximum particle size of 10 !Jm
is normally acceptable. Spreading plastisols can tolerate a still higher
maximum particle size, due to higher plasticiser content and less need
for good physical properties. In low-viscosity plastisols, large particles
can have a tendency to settle.
For rigid PVC compounds it had been long accepted that for both
good physical properties and surface appearance the maximum particle
size should be less than 1 !Jm. This effectively restricted this usage area
to precipitated calcium carbonates. However, recent improvements in
techniques for the milling and selection of natural calcium carbonates
have brought such fillers into contention for rigid PVc. Furthermore,
the development of better compounding equipment and improved
* Section closely based on a part of Ref. 14.

8 Fillers in PVC

229

formulatory knowledge have combined to increase the use of fillers

with particles of up to about 5 Ilm, with consequent cost advantages.

(b) Particle Size Distribution and Mean Particle Size

The particle size distribution will determine how well the filler particles
pack together. This is important in heavily filled compounds and
plastisols, since the better the packing, the higher the loadings
possible. In a heavily filled plastisol, not only can the correct selection
of the filler or fillers control the final viscosity but it is also possible to
control the rheological properties according to the final application. A
good example of this would be PVC plastisols for car-body underseals.
Here it is found that by using a blend of fine ground whiting and a
coarser ground crystalline calcium carbonate (calcite), it is possible to
achieve very high filler loadings, whilst the plastisol still remains
sufficiently free-flowing to be spray-applied, with the final coating
having excellent anti-sag characteristics.
The mean particle size also plays a part, and the finer this is, the
better the physical properties and surface appearance of the filled
compound. In PVC plastisols for slush or rotational mouldings, fine
fillers of mean particle size 1-3 Ilm are required to eliminate filler
settlement problems.

(c) Colour (Dry Brightness)

The dry brightness of a filler is normally expressed as the percentage of
light reflected from the smoothed surface of the filler powder,
compared with pure magnesium oxide considered as pure white with
100% reflectance. The results obtained give a useful measure of
whiteness (but do not necessarily indicate the opacifying effect) of the
filler. Very white fillers can afford cost savings by part replacement of
titanium dioxide pigments. There is a direct relationship between
particle size and opacifying effect. In general, the finer the filler, the
higher the dry brightness and the effective opacity. For comparison
typical dry brightness values would be: limestone, 80; UK-produced
whiting, 86; dolomite, 95; and calcite, 91.
(d) Refractive Index
The refractive index of a PVC polymer is about 155 and that of a
phthalate plasticiser may be in the range 147-150. Therefore, for a
typical plasticised formulation containing 50 phr DOP, the refractive
index of the homogeneous mix could be about 153. Addition of a filler

230

I. D. Hounsham and W. V. Titow

with a refractive index of 153 would lead to a transparent mix even

though the system would be heterogeneous.

Note: If the filler has not been sufficiently 'wetted-out' by the PVC
composition 'stress whitening' ('crease whitening') can occur
when the material is locally stressed. This is due to the
formation of minute voids as the solid phase of the filler
separates from the polymer.
As the refractive index of the filler increases from 153 the optical
transparency decreases.

(e) Oil (or plasticiser) absorption

This may be defined as the weight of linseed oil (or of a specified
plasticiser) required to 'wet out' completely 100 g of filler to a
putty-like consistency in a standard test. * The oil (or plasticiser)
absorption is related to, but is not a direct measure of, the 'plasticiser
demand', i.e. the extent to which the filler will absorb plasticiser when
incorporated in a compound. It is an important consideration in
deciding on a filler for a plasticised compound or plastisol.
The 'plasticiser demand' and oil absorption tend to decrease with
increasing particle size of the filler, and are directly related to the
surface area of the filler particles. Fillers with good particle packing
have lower oil absorption figures, and the more crystalline the particles
the less they absorb internally. The presence of a coating on a filler
reduces oil absorption and the actual plasticiser demand in a
compound (see Table 8.3). Thus, cost savings can be. effected through
the use of a coated filler, either by increasing the filler loading for the
TABLE 8.3

The Effect of Surface Treatment on Plasticiser Absorption by Whiting

Plasticiser (phr)
Filler loading (phr)
Plasticiser absorbed by ordinary
whiting
Plasticiser absorbed by coated
whiting (Omya BSH)
Reduced quantity of plasticiser
permissible in formula

* cf., for example, ASTM D 281-31(1974).

50
5

50
15

50
25

125

375

625

075

225

375

495

485

475

8 Fillers in PVC

231

same amount of plasticiser or reducing the amount of plasticiser for the

same filler loading, in comparison with an uncoated grade.
Oil (plasticiser) absorption has a direct bearing on the softness of a
flexible compound or the viscosity of a plastisol. Oil absorption of over
20 g per 100 g is generally regarded as high. Fillers exhibiting such
absorption will cause substantially more plasticiser to be required in
the compound than low-absorption fillers to achieve the same BS
softness. In a plastisol the oil absorption of the filler is directly related
to its effect on viscosity, whilst-in general-increased filler loadings
result in an increase in viscosity. If high viscosity is required but-to
limit the effect on final properties-only a relatively low filler loading
can be tolerated, then a filler with high oil absorption may usefully be
chosen to increase the viscosity to the required level. However, it is
more common to find examples where the upper viscosity limit is
reached before the limiting effect on physical properties. In such cases,
low-absorption fillers will effectively mean that higher loadings can be
achieved, with corresponding reductions in overall formulation cost.
(f) Dispersion Characteristics
Whatever the type of filler used, it is important to ensure good
dispersion, and some fillers disperse more easily than others. It usually
follows that fine particle size fillers are more difficult to disperse than
coarse ones. The presence of stearate surface treatments prevents very
fine particles from agglomerating. Where filler loadings are low, less
than 20 phr, say, the main 'dry' components, polymer and filler, should
be mixed together before the addition of plasticiser, to minimise the
risk of agglomeration. With higher filler loadings, it is better to add
plasticiser to polymer first; otherwise, the filler will tend to absorb
plasticiser to an undesirable degree, making it unavailable for its
plasticising function.
(g) Cost
In the majority of applications the primary reason for the addition of
CaC0 3 and some other fillers is to reduce overall costs. It is of
fundamental importance to consider not only the price of the filler but
also its nett cost effectiveness in the formulation. A low-price filler may
appear to fulfil its function adequately, but the price advantage could
easily be offset by low output, extra pigment costs (for the requisite
whiteness), increased plasticiser levels, and poor physical properties and
surface finish of the product.

232

I. D. Hounsham and W. V. Titow

Therefore, in choosing a filler, its cost should be very carefully

considered in relation to its effective productivity. The cheapest fillers
are the untreated ground coarse whitings and ground limestone. Large
quantities are used in low-cost flooring compositions but they are not
normally recommended for 'critical' applications (i.e. those in which
physical properties of the product are important). Their extra
plasticiser demand, poorer colour, and poorer dispersibility will cause
more plasticiser and pigment to be required, with longer or harder
mixing conditions, and consequent increase in the overall compound
cost. A coated filler will disperse more rapidly and completely than an
uncoated grade and can give up to 50% higher extrusion output, as
well as allowing reductions in lubricant content. Fine fillers can be used
at a higher loading for the same physical property level as given by
coarser fillers at lower loading, so that where special specifications
have to be met, the higher loading of a fine filler will help to reduce the
cost further. This is frequently the case with whitings in cable
compounds, where a fine-grade filler costs only marginally more than a
coarser grade, but can be used at much higher loadings, giving greater
savings on polymer and plasticiser.
When considering the savings of using a filler, the cost effectiveness
must be related to the volume cost (see Chapter 4). The relative
densities (SG) of mineral fillers are considerably higher than those of
the resin/plasticiser mix, and their cost per unit volume is the product
of unit weight cost and density in each case. Thus, for example, for
calcium carbonate, with a relative density of 27, the cost of 1 ml will
be 27 times the cost of 1 g; for barium sulphate the factor is about 45,
and so on (see Table 8.2). Figure 8.3 shows the effect of increasing
calcium carbonate loading on the specific gravity of a plasticised PVC
composition.
8.3.4 Applications, and Effects of Filler Loading

The main applications of CaC0 3 fillers in PVC are summarised in

Table 8.4. The following points may also be mentioned by way of
amplification.
(a) Flooring
This is a big usage area for fillers in PVC. Calcium carbonate fillers are
incorporated in flooring compositions not merely to save cost, but also
because substantial filler loadings increase weight, reduce shrinkage,
and improve impact indentation resistance.

233

8 Fillers in PVC
200

180

160

?:

'>II

tO>

120

100L.-_ _----1
o
100

----1

200

--J~_

300

CaC0 3 phr

Fig. 8.3 Specific gravity of a plasticised PVC compound as a function of

CaC03 filler concentration.
Note: As has been mentioned, chrysotile asbestos is widely used as a
filler in calendered flooring (sheet and tiles). This application
is also referred to in Section 8.4.1 below.

In backed flooring, made by spreading a plastisol on to asbestos

paper, or fabric, the correct choice of CaC03 filler type is important.
Crystalline types (calcite) are widely used; finely ground limestones
may also be employed. Filler loadings commonly range between 200
and 500 phr, subject to considerations of plastisol viscosity and
rheology generally. Ploss-Staufer AG have found that, with compositions incorporating their special ground calcite grade (Calibrite) ,
maximum output could be achieved at high spreading speeds with .
loadings in excess of 400 phr. Figure 8.4 illustrates some of their
findings* concerning the effect of the filler loading on the plastisol
viscosity at different shear rates: as can be seen, in that particular
*Data available to I. D. Hounsham via Croxton and Garry Ltd.

Ground whiting, s
Ground calcite

Precipitated, s

General

Dry blends

(a) Flexible:

2. Extrusion compounds
10

10
<4-

<1

10

200

30

Ground calcite (some

grades of ground limestone also suitable)

10-20

3-5

Ground calcite (s)

Nominal
maximum

60-75

Mean

Typical particle
size (,mt)

Relevant filler

13-15

Ground calcite

Type"

Rotational moulding; dip- Ground calcite (s)

coating

Spread-coated flooring
(base coals)

1. Plastiso/s
Fabric coatings; foams

Application

Good dispersion, low equipment abrasion, good flow, relatively low plasticiser demand

Fine particle size gives good surface

finish and physical properties

Filler fineness and crystalline structure

(and coating if present) give, respectively freedom from settlement and relatively moderate thickening

Good physical properties are not normally critical in this application, hence
relatively coarse filler can be used for
high loading and fast spreading rates

The finer filler gives good surface

finish; obviates possible settlement
problems

Low plasticiser demand, good rheological properties (for fast spreading)

Filler features and advantages/

Remarks

TABLE 8.4
Applications of CaC03 Fillers in PVC

Day/Cal;c
Hakuenka b

Britomya BSHb
Millicarbb

Millicarb;b
Omya D2 b

Omya D40b

Millicarb;b
Omya BLH b

Calibrite b

Examples
of
commercial
products

:-:::
:::J

s:>
~
s:>
;:,
l:l..

~
I':

i:l;:>0-

V>

tv

General

(b) Rigid:
Pipe fittings

Shoe-sole compounds

General

(a) Flexible:
10 } These fine-particle grades give good
balance of physical properties, ease of
10
dispersion and processability

Somewhat coarser particles acceptable

here

Small particle size and good dispersion

are particularly important (for good
physical properties and processability,
respectively)

Good physical properties and fast output promoted by filler fineness (fastest
production with coated grades). Special 'electrical' grades available

Good dispersion and physical properties

Generally as for extruded soil pipe and rain-water goods

Generally similar to those for rigid extrusion compounds, but fine particle size (especially
low maximum size) even more important (because of need to ensure good physical
properties of compounds based on polymer of lower K value)

Finest particle grades required for good wear properties, resistance to flex cracking, cut growth and other effects of damage in
service

Ground whiting, s

Ground calcite
Ground whiting (s)
Precipitated, s

Ground calcite

10

Ground whiting, s

Soil pipe, rain-water

goods

3. Injection-moulding
compounds

About 7
5

<5

10

1-2

Up to 2

7-10

Precipitated, s
Ground whiting, s

Ground whiting (s)

1-3

Pipe, cladding,
profiles

(b) Rigid:

Cable sheathing and

insulation

Ground calcite

Britomya BSHb
Hydrocarb b
Omyalite b

Millicarb b

Britomya BSH b

Super-Pflex 200d
Omyalite 95Tb

Britomya M or
BSH b

Millicarb;b
Hydrocarb b

N
W
VI

So

<:::

::!1

00

2-3

1-2

Ground whiting (s)

Ground whiting, s

Thick sheeting

(b) Rigid sheeting

Good dispersion, physical properties,

surface finish, and low plasticiser demand are the main requirements to be
met

5-10

10-100

Fine grades (coated for good dispersion) required, to give good physical
properties. Finest particle size for high
impact strength sheeting

Physical properties usually less critical,

hence less refined filler may be used.
Coarse ground calcite may be included
in some compositions to counteract
blister formation

= Stearate or other suitable surface treatment (desirable but optional if shown in brackets).
Croxton and Garry Ltd, UK.
C Harrison Enterprises, USA.
d Pfizer Inc., USA.

as

3
<5
2

Ground calcite (s)

Ground limestone (s)
Ground whiting, s

Thin sheeting
10
10
10

Millicarb b

:--

Britomya BSH;b
Omyalite 95Tb

Morden R;b
Britomya V/L b
Britomya BSH b

Pfinyl402 d
Britomya BSH b

;;;

15

:::'l

s::.
~
s::.
;:s

;:>-

'"~

Nominal
maximum

Examples
of
commercial
products

Mean

Typical particle
size (JJ11I)

Filler features and advantagesl

Remarks

(a) Flexible:

Type"

Relevant filler

0\

4. Calendering compounds

Application

TABLE 8.4-<:ontd.

237

8 Fillers in PVC
3

104
ll.

~
.~

9
8

'CIl

300

6
5

<:3"

10L.

500

1031......-~=-=-

300

~::--

-='="=--__--=-=~

400
500
Calibrite loading, phr

600

Fig. 8.4 Plastisol viscosity as a function of filler loading and shear rate.
system, viscosity decreased with increasing shear rate at all loading
levels; it also increased with loading levels for each individual shear
rate up to about 420 phr filler, but then dropped (with increasing
sharpness) at higher loadings and shear rates. The results suggest that
it should be possible to increase substantially the loading level without
a corresponding rise in viscosity if the shear rate (in practice the
spreading speed) is suitably increased. In actual manufacturing
operations the optimum loadings for maximum output should be
established in production trials.
(b) Plasticised Compounds
Fine ground whitings and calcites are the most suitable CaC03 fillers
for extrusion compounds. Filler loadings in the range 20-100 phr are
normal. Some typical effects of increasing filler loading are shown in
Table 8.5. As can be seen the effect of a fine whiting (in loadings up to
40 phr) on some physical characteristics of the compound is not very
great. Table 8.6 shows the effects of increasing loading level of a
coated whiting (Omya BSH). The coated whitings have good
dispersion characteristics and improve the processability of the
compound. They suffer little agglomeration and, being hydrophobic,
resist moisture pick-up in storage. The coating also improves the
free-flowing characteristics of the filler, making it particularly suitable

PVC resin
Plasticiser
Stabiliser: BalCd
Lubricant: stearic acid
Filler

100 phr
55 phr
2phr
05 phr
0-40 phr

-50

1234

2585
325
79

20
2500
325
81
1312
-35

-40

10

2605
335
80
1271

30
315
82
1350
-30

2465

305
83
1384
-30

40
2410

QPVC resin
Plasticiser: DOP
Stabiliser: dibasic lead phthalate
Lubricant: dibasic lead stearate
Filler

Filler (phr)
Tensile strength (lbf in-2)
Modulus at 100%
elongation (lbf in-2)
Elongation at break (%)
Tear. resistance (lb in-I)
Brittle temperature caq
1985
210
81
-19

2225
200
81
-20
100 phr
50phr
3phr
1 phr
0-150phr

10
2500

0
2700
1970
215
80
-19

12
2475
1965
210
78
-18

15
2425

1925
210
76
-18

20
2425

1850
200
75
-17

35
2225

1775
185
67
-14

50
2035

TABLE 8.6
Some Effects of Increased Loadings of a Coated Whiting ('Omya BSH') on a Plasticised Compound

Filler (phr)
Tensile strength (lbf in -2)
Elongation at break (%)
Hardness (Shore A)
Relative density
Brittle temperature (0C)

TABLE 8.5
Some Effects of Filler (3 Jim Whiting) Loading on Plasticised Compound

1950
125
47
-5

150
1925

'"

C>

:0::::

:'":l
'";:s"'-

~
;,-

l::

00

239

8 Fillers in PVC

TABLE 8.7

Effect of Surface-treated Whiting on Some Properties of a

Cable Compound
PVC resin
DOP
Lead stabiliser
Lubricant
Uncoated whiting
Coated whiting

100

Tensile strength (kg cm- z)

Elongation at break (%)
Brittle temperature ("C)

190
200

-17

Volume resistivity (0 cm)

at 20C

17xl014

Relative density

45

3
1

15

o
133

100
433
3

o
o

15

195

210
-18
133

for bulk-handling systems. In cable compounds, especially insulation

types, coated whiting offers some advantages over corresponding
uncoated grades, even at relatively low loading. Table 8.7 illustrates
the gain in volume resistivity: the small reduction in plasticiser content,
made to preserve the same level of mechanical properties for closer
comparison, demonstrates the lower plasticiser demand of the coated
filler.
(c) Rigid PVC
Fillers are not normally included in rigid compositions to reduce raw
material cost: their incorporation is usually aimed at an improvement
in processing, and/or physical properties of the end product. It is
known that such advantages do result at comparatively low loadings of
CaC03 fillers that are suitable for rigid applications, i.e. surfacetreated precipitated calcium carbonates and the ultrafine ground,
surface-treated natural chalk whitings. When selecting the latter,
attention should be paid to the percentage of particles coarser than
about 2 ,um: even a relatively small amount of comparatively coarse
particles can have a considerable detrimental effect on the mechanical
properties of the compound.
The presence of a fine CaC0 3 filler at a relatively low loading
increases the internal friction of the melt during compounding and
hence the mixing shear: this improves the dispersion of the other
additives (stabilisers, pigments, lubricants, etc.). Maximum dispersion

240

I. D. Hounsham and W. V. Titow

is important, to secure the maximum degree of stability, and optimum

mechanical, and other, properties in the finished product.
With precipitated calcium carbonates the dispersion characteristics
(of the filler itself, and in the sense of its effect on other additives
present) are very good at relatively low loadings; but as the loadings
increase, say beyond 10 phr, the internal shear in the melt increases
excessively due to the thickening effect of these very fine-particled
materials; the production rate is slowed down and the heat stability is
adversely affected. The effects are much less drastic with the so-called
ultrafine ground whitings which-despite the name-are relatively
coarser than the precipitated CaC03 grades. Because of this, even at
loadings substantially in excess of 10 phr, the number of particles
present in the melt, and the total particle surface, are much less, and
hence the rise in internal shear remains within acceptable limits.
Modern compounding machinery makes it possible to produce rigid
compounds (e.g. for extrusion) containing up to 100 phr of such fillers.
Whilst at such loading levels the use of the filler in a rigid compound
can bring significant cost saving, the increased density, and the possible
reduction of some physical properties (especially impact strength) must
be considered. In any particular case the choice of type of CaC03 filler
and the loading level will depend on the nature of the process and the
end-use of the product: it will be made in the light of experience and/or
advice from a reputable supplier of the filler. Final optimisation is a
matter for laboratory and production trials. Table 8.8 shows some
effects of fine CaC0 3 fillers in rigid PVC at 10 phr loading.
8.4 FUNCTIONAL FILLERS
The fillers discussed in this section are those whose primary function in
a PVC composition is to impart or modify a particular property or
group of properties: their use normally increases material costs, and
may also make processing more expensive.
8.4.1 Reinforcing Fillers
Most of these are fibrous, although glass spheres (and even
precipitated CaC03 when used in uPVC at low levels of loading) may
be included under this heading. With the partial exception of chrysotile
asbestos, none is of high commercial significance in PVC: however,
several merit a mention for the sake of technological interest.

None
Precipitated CaC03
Ultrafine ground,
coated whiting
Ground, coated whiting

Nature

TABLE 8.8

Filler

140
100
80
37

650
-

01
10
25
435

Elongation at
break (%)

Tensile strength
(kgfcm- Z)

(pm)

Mean particle size

Properties of compound

Some Effects of Fine CaC0 3 Fillers in a uPVC Compound at 10 phr Loading

11

12

7
12

Impact strength
(kgf cm cm- Z)

~
.....

(j

-.:::

'"tl

::J

00

242

I. D. Hounsham and W. V. Titow

(a) Asbestos (Chrysotile) Fibres

The applications of chrysotile asbestos as a reinforcing filler for PVC
have been mentioned in Section 8.2.1. It may be noted additionally
that, as in the case of most reinforcing fillers, good interfacial contact
(with the right degree of adhesion) between the fibre and the polymer
matrix improves the initial dispersion and the reinforcing effect. Some
surface treatments (notably with a polyethylene glycol) applied to the
asbestos fibre were found 15 to improve the impact strength and flexural
modulus of the filled PVC compound. The practical and commercial
repercussions of the concern about health hazards which may be
associated with the handling of asbestos in some processes and
products,1,4 have made themselves felt on both sides of the Atlantic;
inter alia, preoccupation is continuing with relevant safety measures
and regulations. However, whilst in Western Europe and the UK
emphasis is still on safer working with asbestos in its established
applications, in the USA considerable attention is focussed on
alternative materials and arrangements.
In a non-reinforcing application of chrysotile in PVC (as a
thixotropic additive for plastisols) operational safety can be improved
by using the material in the form of wet 'crumb', produced by
wetting-out the fibre with a plasticiser: in a commercial material of this
kind (Sylodex-W. R. Grace UK Ltd), DIBP is the wetting liquid (two
parts to one of asbestos).4
(b) Inorganic Microfibres
Those of the materials in this category which are of some technical
interest as reinforcements in PVC are all of American origin. They are:

(i) hydrated sodium/aluminium fibre (Dawsonite-ALCOA*);

(ii) potassium titanate fibre (Otsuka Chemical Co. Ltd);
(iii) 'Processed Mineral Fiber' (PMF-Jim Walter Resources Inc.),
produced from blast furnace slag.
Until 1974 a potassium titanate fibre was also available from the Du
Pont organisation, under the trade name Fybex, and Fybex-reinforced
rigid PVC compounds were marketed by commercial suppliers. 1
Dawsonite, in addition to its reinforcing effect, has some flameretardant and smoke-suppressant action (see Chapter 11, Section
11.5): its commercial progress has been retarded by the uncertainties
* Aluminum Company of America, Pittsburgh, PA.

8 Fillers in PVC

243

of the asbestos situation in the USA. The development of PMF

appears to have suffered relatively less from this factor. Some
properties of Dawsonite, Fybex and chrysotile fibres are compared in
Table 8.9. The effects of Dawsonite on some properties of rigid PVC
are illustrated by the data of Table 8.10.
TABLE 8.9
Some Properties of 'Dawsonite', 'Fybex' and Chrysotile Asbestos Relevant to their
Use as Fillers4

Fibre length O (,urn)

Fibre diarneterO(,um)
Density (g cm-3)
Refractive index
Surface areab (m 2 g-l)

Dawsonite

Fybex

Chrysotile

15-20
04-06
244
153
15-17

4-7
01-016
320
235
7-10

1000-40000
001-10
255
150-155
3-4

Typical dimensions of potassium titanate fibres from Otsuka Chemical Co. (the

only current source since supply of Fybex was discontinued in 1974) are: 16 length
20-30,um, average diameter 02,um. These fibres are claimed to have a higher heat
resistance than Fybex.
The dimensions of PMF (slag) fibre (cf. Section 8.4.1) are quoted!3 as: diameter
4-5 ,urn, aspect ratio 40-60.
b Surface area measurement by the BET N2 method.

(c) Glass Fibres

The incorporation of glass fibres in a rigid PVC compound can
substantially upgrade several 'short-term' mechanical properties, as
well as resistance to creep and fatigue. In PVC (and in other
thermoplastics) the degree of improvement (which can be substantialsee Table 8.11) depends on the orientation of the fibres in relation to
the direction of stress and-given that-also on the fibre length and the
amount of fibre present. The temperature of deflection under load of a
PVC composition for which the value of this property is normally low,
may be substantially increased by glass-fibre reinforcement (see Table
8.11). However, the highest values that may be attained through such
reinforcement are only marginally above the top figure for the general
range of unreinforced uPVC compositions (see Appendix 3). In this
general sense, therefore, glass-fibre reinforcement cannot be said to
have a significant effect upon the deflection temperature. uPVC

21-0 (1120'3)
5647 (389)
041 (2826)
11760 (81'0)
075 (5170)

1()6lbf in- 2 (MN m- 2)

ASTMD790

Flexural modulus

339 (180'8)

64

153 (68)

ft Ibf in-I (J m- 1)
Ibfin- 2 (MN m- 2)
1()6lbfin- 2 (MNm- 2 )
Ibfin- 2 (MN m- 2)

(J m- I)

10- 5 x C- 1

ASTM D 696
in- 1

OF

ASTMD648

COq

ASTM D 256(E)
ASTMD638
ASTMD638
ASTM D 790

47

ft Ibf

gper 10 min

Units

ASTM D 256(A)

ASTM D 1238-73F

Method
of
determination

Melt flow index

Deflection temperature
under load at 264 Ibf in- 2
(1,82 MN m- 2 )
Coefficient of linear
thermal expansion
lzod impact strength
(notched)
Izod impact strength
(unnotched)
Tensile strength
Tensile modulus
Flexural strength

Property

1-13 (7791)

181 (9656)
5900 (40'6)
054 (3723)
12420 (85 6)

300 (1600)

38

155 (69)

35

75

154 (10620)

165 (880 2)
6100 (42-1)
1-43 (9859)
12900 (88,9)

2-62 (1398)

3-l

160 (71)

32

15

Dawsonite content (% by weight)

TABLE 8.10
Some Effects of 'Dawsonite' in Rigid PVC 4

233 (16060)

104 (554,8)
6200 (42'7)
160 (11030)
13160 (907)

236 (1259)

21

163 (73)

27

30

i;

:::l

:0:::

I'>..

.,;:.,;:~

~
;::

:--

" Ethyl Corporation, USA.

ASTM D 648

638
638
790
256

ASTM
ASTM
ASTM
ASTM

Tensile strength
Tensile modulus
Flexural modulus
lin (H75mm) bar
Heat distortion at
264lbf in- 2 (1,82 MN m- 2 )

D
D
D
D

ASTM D 792

Method
of
determination

Specific gravity
Mould shrinkage

Property

'C

in in- 1
or
mmmm- 1
lbf in -2 (MN m -2)
Ibfin- 2 (MNm- 2)
Ibf in- 2 (MN m- 2)
ft Ibfin- ' (J m- 1)

Units

867

0001
14000 (96'5)
1200 000 (8273)
950 000 (6 550)
35 (186'71)

0002
9000 (620)
650000 (4481)
600 000 (4 136)
6 (320'08)

0'003-0'004
6400 (441)
420000 (2 896)
375 000 (2 585)
15 (80020)
817

153

145

140 002

706

20% glass

161

30% glass

878

0001
16000 (110'3)
1 300 000 (8963)
1100 000 (7584)
2 (10669)

Reinforced
(Ethyl 7042 compound)"
10% glass

Unreinforced
(Ethyl 7042
compound)"

TABLE 8.11
Effect of Glassfibre Reinforcement on Some Properties of Rigid PVC 4

(j

""

"1:l

:::l

00

246

I. D. Hounsham and W. V. Titow

compounds reinforced with glass fibre have been available commercially for some time,! recently in special grades (e.g. from B F Goodrich)
with the reinforcement coupled to the matrix.
(d) Carbon Fibres
If the magnitude of the reinforcing effect was the only consideration,
carbon fibres would offer advantages over glass-fibre reinforcement in
uPVc. However, their use in this polymer has never been an
economically sensible proposition. In round figures, the cost of carbon
fibre (chopped strand) is about 60 times that of PVC polymer (cf. cost
factor of about 17 times for glass fibre). Thus the cost of base polymer
in a compound containing, say, 25% carbon fibre is relatively
insignificant. For applications calling for the highest performance
(which would be the reason for considering carbon-fibre reinforcement
in the first place) a base polymer can be afforded with inherent stability
and 'engineering' properties better than those of PVC (e.g. nylon, or
polycarbonate).
(e) Glass Spheres
Neither hollow nor solid glass spheres are used to any significant extent
in PVC compositions. The former kind cannot, in any case, be
regarded as a reinforcing filler in the proper sense. Purely from the
technical standpoint, the main effects of incorporating solid glass
spheres as a filler in uPVC would be broadly similar to those in other
thermoplastics, viz. increased compressive strength, modulus, hardness
and abrasion resistance, reduced creep and shrinkage: the reinforcing
effects would be isotropic, as with the spherical filler orientation
cannot be a factor. In processing, the effect upon the viscosity of a
molten thermoplastic is normally less with glass spheres than with
comparable volumes of glass fibres or even inorganic fillers of irregular
particle shape.

(f) Fine-particle Calcium Carbonate

Reference has already been made to the reinforcing effects of this type
of filler in rigid PVC compositions, at relatively low loading levels (see
Section 8.3.4). Incorporation of precipitated CaC03 and some
ultra-fine ground whitings (especially when the particles have received
an organotitanate or stearate treatment) can improve the impact
strength and flexural modulus of uPVC compositions and products,
notably pipe and extruded profile.

247

8 Fillers in PVC

8.4.2 Flame-retardant and Smoke-suppressant FiBers

The flame-retardant and smoke-suppressant effects of materials
incorporated for these purposes in PVC compositions are mentioned in
Chapter 12 (Section 12.10) and discussed in Chapter 11 (Section 11.5).
Such additives are mainly of interest for plasticised PVC, as the
flammability of rigid compositions is inherently low (although smoke
suppressants can be useful in some uPVC products). Some of these
additives are liquids, and thus not relevant in the context of this
section. Of those which are particulate solids, the ones of greatest
practical significance are antimony trioxide (flame retardant), antimony
trioxide/zinc (or barium) borate mixtures (flame retardant), and
alumina trihydrate (flame retardant and smoke suppressant). The first
two are used in sufficiently low proportions (up to about 10 phr) not to
affect drastically the mechanical and physical properties of the PVC
composition: however, they do have an opacifying effect (somewhat
less pronounced with the borates, and generally reduced when
ultra-fine particle size grades of the additives are employed). The same
applies to some particulate smoke suppressants (e.g. molybdenum
trioxide, Mo0 3), with the notable exception of magnesium carbonate
which is used at relatively high loading levels (typically up to about
40 phr) for maximum smoke suppression effects. Substantial loading
with alumina trihydrate is also necessary to realise the effects of this
additive to the full (see Chapter 11, Section 11.5), and at the levels
used the effect on the mechanical and certain other properties of the
PVC composition can be considerable (see Figs 8.5 and 8.6), as is
25

250

IV

ll.

~~20

....r:.g'

200

i"

1ii 15
~

'iii

c:

~ 10

20

40

AI (OH)3

60

80

content, phr

Fig. 8.5 Tensile strength (1) and elongation at break (2) as functions of
alumina trihydrate content in a pPVC composition (50 phr plasticiser). Based
on data from Ref. 7.

248

I. D. Hounsham and W. V. Titow

100

.u...

90

'a.5 80
Ol

'c

...'0
~

en

Fig. 8.6 Vicat softening point (1) and hardness (2) as functions of alumina
trihydrate content in a pPVC composition (50 phr plasticiser). Based on data
from Ref. 7.
indeed the case with other particulate fillers (ct. for example, Figs
8.1-8.3). Apart from its flame-retardant and smoke-suppressant
action, which can be very effective at suitable loadings (say, broadly,
between 30 and 100 phr), alumina trihydrate can be especially useful in
certain compositions in that it does not impair the electrical properties
(tracking resistance in particular can actually be improved) and its
opacifying effect is comparatively slight (especially with ultra-fine
particle grades). As has been mentioned in the preceding section, the
fibrous mineral filler Dawsonite has some frame-retardant and
smoke-suppressant action in PVC compositions in which it also acts as
reinforcement.
8.4.3 Miscellaneous Functional Fillers

(a) Carbon Black

There are various kinds and grades of carbon black available for use in
a variety of application areas,17 of which incorporation in rubber and
plastics is one. As a constituent of plastics compositions carbon black
can have three main functions. It may be incorporated to impart black
colour, or to improve resistance to photochemical and thermal

Fillers in PVC

249

degradation, or to reduce electrical resistivity (in order to counteract

the build-up of static electricity on the surface of the plastic, or to
render the whole composition conductive). In the first two of these
three applications the amounts added are relatively low (commonly a
few phr), and the additive may be considered to function as,
respectively, a pigment (see also Chapter 11, Section 11.3) and a kind
of stabiliser. The stabilising effect is particularly widely utilised in
polyolefins, but significant also in some PVC compositions for outdoor
use (e.g. sheeting employed as anti-seepage lining for reservoirs, ponds
and canals): here too the fine, particulate carbon absorbs preferentially
UV radiation of all the wavelengths normally instrumental in
photodegradation of PVC polymer. It has also been claimed l7 . 18 that the
carbon, in fine, intimate dispersion in a plastics composition acts as a
free-radical terminator, this being the main mechanism whereby its
protective effect against thermal degradation is exercised. A mediumcolour furnace black is the type of interest for the stabilising
applications. The carbon black content in cases where the electrical
conductivity of this filler is utilised to reduce the surface and volume
resistivity of a plastic has to be relatively high, as the required effects
depend upon securing enough inter-particle contact to provide-in
sufficient measure---eonductive paths in the bulk and surface of the
material. For a reasonable degree of conductivity (say a volume
resistivity reduction down to about 1 Q cm) a carbon black loading of
about 30% by volume or over may be necessary. At such loadings the
effect on some mechanical properties may be similar to that observed
with other fine-particle fillers at comparable content levels (it may be
noted in passing that the kind of reinforcing effect that carbon black
exerts in natural rubber compositions does not arise in PVC).
Improvements in processability and conductivity of PVC compounds
filled with carbon black have been reported to result when a vinyl
chloride polymer was grafted onto the filler particle surface. 19
(b) Metal Powders
A metal powder may be used as an antistatic or conductivitypromoting filler in a plastics composition (in PVC the possible effect on
thermal stability is an additional practical consideration in selecting the
metal filler). The application, and mechanism of operation, are similar
to those just mentioned in connection with the use of carbon black,
and-when ordinary compounding methods are employed-similar
volume loadings of filler are required for comparable effect levels.

250

I. D. Hounsham and W. V. Titow

However, it has also been reported 20 that in compositions produced by

sintering suitable mixtures of graded metal powders with PVC (also in
powder form), conductive paths can be formed at relatively much
lower metal loadings: for example, a volume resistivity of 10 Q cm was
recorded 2o for a composition containing about 6% of nickel by volume;
this kind of composition with 5-8% Ni was also found to be rendered
stronger and more resistant to cracking by the presence of the filler.
(c) Wood Flour
Although the incorporation of wood flour in PVC compounds can
result in material cost savings, this filler is not merely a cheapening
extender but has a functional role in that it imparts a resemblance to
wood to the filled compositions which are used mainly in the
manufacture (by extrusion) of wood-substitute products, e.g. beading
(extruded profile) and sheet, for use in trim and light constructional
applications. Both the products (some of which are available in
cellular, structural-foam form with densities down to about 09 g cm-3)
and the compounds for their manufacture are available from
commercial sources. 4 The wood flour content of the materials can be
substantial (several tens phr) and, as would be expected, this can
reduce some mechanical properties (in particular extensibility may be
considerably lower) vis-a-vis similar unfilled compositions. However,
by and large, the effects are not unduly drastic, as indicated, for
example, by some values quoted 21 as typical for a well-known
commercial compound (Nordxyl-Nordchem SpA, Martignacco, Italy): tensile strength at yield, 350 kg cm- 2 (34 MPa) , at break,
390 kg cm- 2 (38 MPa); elongation at yield, 0; flexural strength,
657 kg cm- 2 (64 MPa). Another consequence of the presence of the
wool filler in the compound is an increased tendency to take up
moisture: drying before processing is good practice (several hours at
80C is sometimes recommended). Some modifications to the heads
and dies of standard extrusion equipment may be necessary for
optimum processing.

(d) Starch
A technically significant early use of starch in PVC compositions has
been as an extractable filler (removed by hydrolysis and dissolution
with dilute acid) in the production of porous rigid PVC sheet used in
the manufacture of battery separators and in some filtration applications (see Chapter 25). More recently, starch-filling of plasticised and

8 Fillers in PVC

251

semi-rigid PVC compositions was investigated as a means of promoting

biodegradability.22 The effects of the starch on the physical and
mechanical properties of these compositions were generally similar to
those of inorganic fillers at comparable loadings, but with less
opacification. The starch-filled PVC was found to be readily attacked
by a mixture of micro-organisms commonly occurring in soil.

(e) Synthetic Silicas

These fine-particle, amorphous silica powders include colloidal
(fumed) silica, silica aerogel, and wet-process silica. Because of the
very small primary particle size (in some grades within the range
001-01/-lm) these materials have an extremely large specific surface,
and hence the absorption-related effects they exert are strongly
pronounced even at low levels of loading (in some cases less than
1 phr). Thus some are extremely effective thickening agents for PVC
pastes (see Chapter 21), improve free flow of dry blends, counteract
plate-out of calendering compositions (see Chapters 9 and 18), reduce
surface gloss of (Le. act as matting agent in) coatings and films, and
also function as anti-blocking agent in plasticised products of this kind
(Le. counteract sticking together of their surfaces, especially under
pressure-e.g. in a stack).

8.5 SOME FILLER SUPPLIERS AND TRADE NAMES

The list in Table 8.12 is confined to fillers available from UK sources
(including some imported materials). It is neither complete nor
deliberately selective, but intended to identify a few materials often
referred to by their trade names.
The following publications may be consulted for information on
suppliers of fillers in the USA (a), (b) and (c) and Europe (d).
(a) Latest edition of Modern Plastics Encyclopedia, McGraw-Hill,
New York.
(b) List (relevant also to additives other than fillers) published in
Plastics Engineering, 33(5), 22-40 (May 1977).
(c) Plastics Technology (1980), Vol. 26, No.1, Manufacturing
Handbook and Buyer's Guide 1980/81.
(d) Latest edition of European Plastics Buyer's Guide, IPC Business
Press Ltd, London.

252

I. D. Hounsham and W. V. Titow

TABLE 8.12
Some Commercial Sources and Trade Names of Fillers

Supplier
Limestone

Trade name

Ben Bennett Jr Ltd

Derbyshire (Div Tarmac) Ltd
Longcliffe Quarries Ltd
Tilcon Gregory Ltd

Bennite
Calmote
Superlon

Blue Circle Industries Ltd

Croxton and Garry Ltd
ECC International Ltd
Microfine Minerals & Chemicals Ltd

Snowcal
Britomya
Polycarb
Microcarb

Croxton and Garry Ltd

Omya
Calibrite
Millicarb
Omyalite
Fordacal

Whiting

Calcites and Dolomites

ECC International Ltd

Microfine Minerals and Chemicals Ltd
Norwegian Talc (UK) Ltd
Tilcon Gregory Ltd

Precipitated Calcium Carbonate

Croxton and Garry Ltd

ICI Mond Division Ltd
John and E. Sturge Ltd

Clays

Croxton and Garry Ltd

ECC International Ltd

Alumina Trihydrate
Alcoa of Great Britain Ltd
B. A. Chemicals Ltd
Croxton and Garry Ltd
Barytes
Richard Baker Harrison Ltd
Vine Chemicals Ltd
Zach Cartwright Ltd
Tilcon Gregory Ltd
Synthetic Silicas
Joseph Crosfield and Sons Ltd
Degussa (UK) Ltd
W. R. Grace UK Ltd

Microdol
Hakuenka
Winnofil
Calofort
Calofil
Sturcal
Calopake
Burgess
MlOO, M501
Hydral
BacoFRF
Trihyde

Gasil
Aerosil
Syloid

8 Fillers in PVC

253

TABLE 8.12-contd.

Supplier
Antimony Trioxide
Anzon
Asbestos
A. A. Brazier & Company (Asbestos) Ltd
Cape Asbestos Fibres Ltd
Central Asbestos Company Ltd
Johns Manville (GB) Ltd
Marley Tile Company Ltd
Turners Asbestos Fibres Ltd
Cyprus Asbestos Mine Ltd
Henry Kiver & Partners Ltd

Trade name
Timonox

A list of glass fibre producers is given in Ref. 1, pp. 79-82.

Transport cost is a factor in filler price, and it can be useful in many
cases to consider the possibility of adapting a PVC formulation to
make the best use of materials from local sources. At the same time it
should be remembered that differences can and do occur in the
performance of apparently similar fillers from different manufacturers.

REFERENCES
1. Titow, W. V. and Lanham, B. J. (1975). Reinforced Thermoplastics,
Applied Science Publishers, London.
2. Fletcher, W. J. and Tully, P. R. (1967). 23rd ANTEC SPE Proceedings, p.
537.
3. Moreland, J. E. (Oct. 1971). In Modern Plastics Encyclopedia, Vol. 48,
No. lOA, McGraw-Hill, New York, p. 247.
4. Titow, W. V. (1977). In Developments in PVC Production and Processing-l, (Eds A. Whelan and J. L. Craft), Applied Science Publishers,
London, Chapter 4.
5. Private communication from TBA Industrial Products, Reinforced Plastics
Division, Rochdale, Lancashire, England.
6. Blumberg, J. G., Falcone, J. S., Smiley, L. H. and Netting, D. I. (1980).
In Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edn, Vol. 10,
John Wiley, New York, pp. 198-215.
7. Plastichem Ltd, Technical Bulletins and data sheets.
8. Rogan, J. (1979). Plast. Techno!., 25(8), 100.

254

1. D. Hounsham and W. V. Titow

9. 'Whiting: Notes on Origin, Manufacture, Properties and Uses', Research

Council of the British Whiting Federation, April 1962.
10. Lowry, T. M. (1946). Inorganic Chemistry, Macmillan & Co., London,
2nd Edn, pp. 732-3.
11. 'Britomya BSH 30 and Britomya M', Melbourn Whiting Company Ltd.
Data sheets 5.77.
12. Monte, S. J., Sugerman, G. and Seeman, D. J. (1976). 34th ANTEC SPE
Proceedings, pp. 27-39.
13. Naitove, M. H. and Evans, L. (1976). Plast. Technol., 22(8). 71-4.
14. Fillers for PVC-A Guide to Selection', Melbourn Chemicals Ltd,
Technical Bulletin 353/65, September 1977.
15. Axelson, J. W. and Kietzman, J. H. (1976). 34th ANTEC SPE
Proceedings, pp. 601-5.
16. Anon. (1980). Plast. Technol., 26(3), 38.
17. Dannenberg, E. M. (1978). 'Carbon Black'. In Kirk-Othmer Encyclopedia
or Chemical Technology, 3rd Edn, Vol. 4, John Wiley, New York, pp.
631-66.
18. Mascia, L. (1974). The Role of Additives in Plastics, Edward Arnold,
London.
19. Anon, (1979). Plast. Techno/. , 25(7), 95.
20. Kusy, R. P. and Turner, D. T. (1973). SPE J., 29(7), 56-9.
21. Anon. (1976). Mod. Plast. Int., 6(10), 14 and 15.
22. Westhoff, R. P., Otey, F. H., Mehltretter, C. L. and Russell, C. R. (1974).
Ind. Eng. Chem., Prod. Res. Develop., 13(2), 123-5.

GENERAL BIBLIOGRAPHY ON FILLERS

Wake, W. C. (1971). Fillers for Plastics, Plastics Institute Monograph,
Butterworth, London.
Ritchie, P. D., Critchley, S. W. and Hill, A. (Eds) (1972). Plasticisers,
Stabilisers and Fillers, Plastics Institute Monograph, Iliffe Books, London.
Mascia, L. (1974). The Role of Additives in Plastics, Edward Arnold, London.
Katz, H. S. and Milewski, J. V. (1978). Handbook of Fillers and
Reinforcements for Plastics, Van Nostrand-Reinhold, New York.

CHAPTER 9

Stabilisers: General Aspects

w.

V.

TITOW

9.1 INTRODUCTION
PVC polymers and copolymers are susceptible to degradation by heat
(the thermal degradation is sometimes referred to as 'thermolysis') and
by light (photolysis, also called photodegradation, and-in some
contexts-photochemical degradation): in both cases degradation is
rapid and more severe in the presence of oxygen. In the practical
context photochemical effects are of special concern in outdoor
exposure of PVC materials, where they may be accompanied by those
of other factors instrumental in weathering (see Chapter 12, Section
12.6) so that the overall deterioriation can be faster and more drastic
than that caused by exposure to light alone.
Heat stabilisers are incorporated in all PVC compositions to protect
the polymer against thermal degradation at the high temperatures of
processing (higher for uPVC, and generally ranging-depending on
composition and process-from about 170C to about 220C) and also
subsequently in service. UV-absorbing and antioxidant additives are
included where appropriate as stabilisers against photochemical
degradation. Many heat stabilisers have some antioxidant action. An
antioxidant is also often incorporated as a component in composite
commercial heat stabiliser systems.
Formulation components other than the base polymer may also
suffer degradation: e.g. chlorinated polyethylene (by dehydrochlorination and oxidation on excessive heating!), rubbery impact
modifiers (by disruption and oxidation-e.g. on weathering-of the
double bonds their molecules contain), and chlorinated paraffin
255

W. V. Titow

256

extenders (which can undergo dehydrochlorination with further

breakdown and formation of unsaturated compounds on strong
heating2). Like the PVC polymer, some of these additives can benefit
from the presence of stabilisers in the composition.
9.2 DEGRADATION OF PVC POLYMER
The degradation of polyvinyl chloride (and some copolymers), and the
ways in which various stabilisers counteract and modify the process,
have been widely studied for many years. The subject is complex and
much still remains to be elucidated and verified, inter alia, in regard to
the chemical and morphological effects of photochemical attack (and
weathering generally), and to the mode of action of stabilisers,
especially in systems involving some synergistic effects. However, at
least the basic features of degradation and stabilisation are now fairly
well understood, and there is reasonable general agreement as to the
principal underlying mechanisms. The extensive literature of the
subject includes useful reviews by Voigt,3 Silberman,4 Thinius,5
Onozuka and Asahina,6 the staff of Ciba-Geigy,7 Braun8 and Nass. 9
9.2.1 Thermal Degradation

The main outward manifestations of thermal degradation of PVC (at

temperatures sensibly below those of pyrolytic decomposition and
combustion, against which no stabilisation is possible) are the
evolution of hydrogen chloride, development of colour (progressing
with the extent of breakdown from light yellow, through reddish
brown, to almost black in severe cases) and deterioration of physical,
chemical and electrical properties.
It is widely accepted that dehydrochlorination involves progressive
'unzipping' of neighbouring chlorine and hydrogen atoms along the
polymer chain (although the actual mechanism of this process is still in
some doubt*): a double bond is formed between the carbons to which
the two atoms were originally attached-this constitutes an allyl
chloride structure with (i.e. is in the 3,4 position in relation to) the next
CI down the chain, which is thereby strongly activated (cf. Chapter 1,
* An ionic mechanism is favoured by some investigators/,8 and a free-radical
one by others. lO ,lI

257

9 Stabilisers: General Aspects

Section 1.5.1, and Ref. 31 in that chapter):

HHHHHHHHHH

~C-c=c-e-e-e-e-e-e-e~
I @) (j)~1 I I I I I I

<DCI H Cl H CI H CI

lenergy

HHHHHHHHHH

~C-C=C-;:~::;-CI-CI-el-e-C~
'Cl-H+'
I
HI
~.
~CI H
CI HI Cl

(1)

1energy
HHHHHHHHHH

~~-W-W-W-t-t-t~
I
I I I
~-----_.-:

H
HCl

L~l~_!t: CI H CI

and so on.
The development of colour is attributed to the conjugated double
bond systems formed in this process* (d. reaction scheme (1)), and
also, by some investigators,7 to the formation of strongly coloured
carbonium salt complexes (possible with an ionic mechanism of
dehydrochlorination) .

HH{H HfH H

I I I I
-C=C C=C

"c+iI

H ~ry H11

Cl-

(2)

~+-lL--i* Colour appears with as few as seven conjugated double bonds in a polyene,
whilst it is known 7 that sequences of up to about 30 can arise in the course of
dehydrochlorination of PVc.

258

w.

V. Titow

It has been suggested 7 that the mesomeric structure indicated in eqn

(2) accounts for the stability of these salts, which should also increase
with the length of the sequences involved.
Theoretical considerations, and the study of model compounds,7,8
indicate that-in the absence of sites of reduced stability in the
chain-PVC polymer should be stable enough to resist dehydrochlorination even at the high processing temperatures. The question of
which are the sites where dehydrochlorination is first initiated has been
receiving much attention over the years. In the light of all the
accumulated evidence it appears most likely that the process starts with
a chlorine atom activated by an adjacent allylic bond configuration
where that is already present in mid-chain (d. reaction scheme (1)); a
chlorine in the same position relative to an allyl end-group would also
be activated, albeit to a lesser extent. 8 Both mid-chain unsaturation
and allyl end-groups exist in PVC polymers (see Chapter 1, Section
1.5.1).
Note: That end-groups play a part in PVC stability is indicated by
the fact that---other factors being equal-the heat stability
increases with increasing molecular weight (K value) of the
polymer, i.e. with decreasing proportion of end-groups.
However, there is also considerable evidence that double
bonds within the chains activate the adjacent CI atoms in the
allyl chloride configuration more strongly, and hence reduce
the thermal stability more markedly, than do those in allyl
end-groups.

A labile 'tertiary chlorine' (i.e. a CI atom attached to a tertiary

carbon in the chain), such as would be present at one possible type of
junction between a branch and the main chain, is another likely
starting point-the CI in this position would be activated roughly to the
same extent as one adjacent to an allyl end-group.8 However, the
likelihood that a tertiary chlorine is the principal type of active site in
dehydrochlorination must be viewed in the light of the scarcity of
evidence for the existence in PVC polymers of the type of junction
which would involve its presence, or for any correlation between the
number of chain branches on one hand and thermal stability on the
other (see Chapter 1, Section 1.5.1).
Dehydrochlorination can occur at only moderately elevated temperatures (about 100C). It is catalysed by the HCI evolved (autocatalysis), and can also be promoted or initiated by other strong acids.

9 Stabilisers: General Aspects

259

Mathematical treatments of the dehydrochlorination process (including

calculations of reaction constants for particular conditions) have been
published by Woolley, 12 and by Troitskii et al. l3
In addition to dehydrochlorination, thermal degradation of PVC
polymer in the presence of oxygen also involves oxidation, with the
formation of hydroperoxide, cyclic peroxide, and keto groups, some of
which can provide additional active sites for initiation of dehydrochlorination. 7
Chain scission and cross-linking can also take place as degradation
proceeds, both in air and in an inert atmosphere (although some
investigators report no scission in nitrogen at 190C14). These effects
contribute to the general deterioration in properties.
If the thermal stability of PVC polymer or composition at a given
temperature is defined in terms of time required for one of the main
manifestations of degradation to reach a stated level (say, a certain
amount of HCI evolved, or intensity of colour developed: see Section
9.8.1 below) and if the degradation is treated as a unified process,
thermally activated in the classic manner (d. Chapter 12, Section 12.3),
the appropriate Arrhenius-type relationship may be written in the
form:

t = to exp (E/RT)

(3)

where: t is the duration of stability; to is a constant; E is the activation

energy for thermal degradation of the PVC polymer in the conditions
(and/or composition) concerned; R is the ideal gas constant; and Tis
the absolute temperature.
.
The activation energy for thermal degradation of a uPVC composition is quoted by Chauffoureaux et alY as 259 kcal mol-i. Rice and
Adam 16 give the following values, in the same units, for PVC and a
few other polYII!ers: PVC approximately 20; polystyrene 55;
p )lyethylene 46; polypropylene 65. This illustrates well the comparatively low thermal stability of PVc.
Susceptibility to thermal degradation varies with the process of
manufacture of the PVC polymer and also-even for the same
process-with the source of supply. Other things being equal, the
susceptibility increases (inherent stability decreases) in the sequence:

"

mass polymer ~ suspension polymer ~ emulsion polymer

This is normally attributable to the amount of impurities present,
which increases in the same sequence (the emulsion polymer in

260

W. V. Titow

particular contammg traces of surface-active agents used as emulsifiers), the amount of unsaturation in the chains and the kind of
end-groups (both the latter factors also differ in polymers from
different sources). As has been mentioned, higher molecular weight
makes for greater resistance to degradation. Homopolymers are,
generally speaking, more resistant than copolymers. 17 In compounds
the stability of the PVC resin can also be adversely influenced by other
constituents (e.g. phosphate plasticisers; antistatic agents; some
colourants-see Chapter 11). The ease of stabilisation and response to
particular stabilisers in particular conditions also vary with the above
features. Considered in conjunction with the requirements of processing
and service in any given case the variety and possible interactions of
these factors provide strong support for the often expressed view that
every PVC composition should be treated as in individual stabilisation
problem.
9.2.2 Photochemical Degradation
All the main external manifestations associated with thermal degradation of PVC appear also as a result of photolysis (i.e. dehydrochlorination, development of colour, and deterioration of properties).
In plasticised compositions, exudation of plasticisers (resulting in sticky
surface layers), embrittlement and cracking can also occur in varying
degrees. However, in comparison with typical thermal degradation,
there is greater variability in the occurrence of these effects (for
example, more often than not colour development is slight or absent
altogether) as well as in their onset, progress and respective intensities.
The situation can be further complicated where-as is often the case in
service~xposure to light is associated with weathering: this introduces a number of further destructive factors (see Chapter 12, Section
12.6).
The dissociation energy of a carbon-ehlorine bond is about
77 kcal mol- 1 : this corresponds to the energy of light of wavelength
375 nm. 8 In theory, therefore, light of this wavelength (in the near-UV
part of the spectrum) should be able to cause photodegradation of
PVc. In practice the process requires higher photo energies (UV light
of shorter wavelengths): it is known (cf. Chapter 12, Section 12.6) that
the UV band between about 290 and 315 nm is mainly responsible for
the photochemical degradation of plastics, including PVc. However,
the mechanisms of this process in PVC, alone or as part of weathering,

9 Stabilisers: General Aspects

261

are less well understood than those of thermal degradation: the main
features indicated by available evidence may be briefly summarised as
follows.
The first phase of photolysis of PVC in air appears to be
photooxidation,7 proceeding through a free-radical mechanism8,18,19and at a general rate proportional to the intensity of radiation (in the
appropriate UV region)-with the formation of hydroperoxide, keto,
and aldehyde groupS?,9,18 which undergo further light-induced reactions and breakdown:? the presence of these hydrophilic groups is
thought to playa part in the disruptive effects of atmospheric water in
weathering of PVC materials. 18 Dehydrochlorination also occurs at an
early stage7 ,8,20 (starting immediately, at a relatively fast rate, in an
inert atmosphere8), but usually proceeds more slowly than in typical
thermal degradation (although the rate, both in air and in nitrogen, is a
function of the intensity of irradiation and the temperature8):
conjugated double bond sequences are formed 7 ,8,18,19 (whose presence
may be expected to increase UV absorption l9) but these are liable to
be disrupted early in the process by reaction with oxygen 8,9,20
(probably resulting in the formation of carbonyl groups, themselves
light-absorbent and thus capable of accelerating the photolysis8), which
would counteract the formation of colour. Chain scission and
cross-linking also take place. 9,19,20 Exudation of plasticisers on
weathering of pPVC has been attributed 20 to their reduced affinity for
the cross-linked structures. Prior degradation by heat (even if not very
far advanced), e.g. such as may be allowed to arise by lack of strict
attention to conditions in heat processing (or through inadequate
stabilisation), can enhance and accelerate photodegradation: this
should be borne in mind in the formulation and processing of PVC
compositions for outdoor use. Impurities, and other adventitious
'additives' (e.g. residual solvents in films 8,21) can also have an effect in
this direction.

9.3 IDEAL REQUIREMENTS FOR A STABILISER,

AND GENERAL FACTORS AFFECTING
STABILISER SELECTION

Consideration of the main features of degradation of PVC, coupled

with the requirements of processing and service in various applications
and conditions, points to the following actions and characteristics to be

262

W. V. Titow

looked for in an ideal stabiliser: rapid binding of free HCl, high ability
to replace labile Cl atoms with stable groups, saturation of double
bonds, antioxidant action, disruption of chromophoric groups, absorption of free radicals, neutralisation of impurities and degradation
products, effective screening of UV radiation.
It is self-evident that the stabiliser itself, and any reaction products
resulting from the exercise by it of the above functions, should ideally
be innocuous, non-migratory, non-toxic, odourless, and should not
impair the colour, clarity or any other properties of the PVC
compound.
In addition, from the standpoint of processing and use, the ideal
stabiliser should also:
(i)

be readily dispersible in the PVC compound, and fully

compatible with all its constituents even after prolonged service;
(ii) have no adverse effect on processing properties;
(iii) be equally effective in PVC resins of all types and from all
sources; and
(iv) be inexpensive and effective in small proportions.
The ideal stabiliser does not exist. However, many of the available
stabilisers, and particularly composite stabiliser systems, can be highly
effective in compositions and applications for which they are
appropriate.
An important aspect of the suitability of a stabiliser, or stabiliser
system, which may be crucial in some cases (e.g. with PVC
compositions intended for food-contact or medical applications) is the
question of possible health hazards, both in the general handling and
processing in the factory, and in the subsequent use of the stabilised
PVC material. As in the case of other additives, much attention has
been given to this aspect of stabiliser usage, in particular in regard to
stabilisers based on lead and cadmium. The health hazard point is
mentioned briefly in connection with each group of stabilisers discussed
under the classification of the next section. It may be noted in general
that permitted material lists exist in several countries, and that limiting
regulations or legislation have been introduced. Information and
guidance on specific problems can be sought from the organisations
mentioned in Chapter 7, Section 7.12 and Chapter 12, Section 12.9 (ct.
also Chapter 11, Section 11.3.4). Suppliers will also advise on the
acceptability of their products.

9 Stabilisers: General Aspects

263

Cost, and the related consideration of cost-effectivity, are important

factors in the selection of stabilisers for PVC compositions processed
on any appreciable scale. Two other points of general importance may
also be mentioned. Firstly, the inter-relationship between stabiliser and
lubricant (in practice most often both are systems of more than one
component) is of special importance in PVC formulations: something
of this has been mentioned in the discussion of lubricants in Chapter
11. It cannot be too strongly emphasised that the choice of the
stabiliser system has an important bearing on that of the lubricant(s),
in view of such factors as lubricant action of some stabilisers, possible
synergistic or adverse interactions, and others-see Chapter 11.
Secondly, the physical state of the stabiliser system can affect the
processing and service properties of a PVC composition. Both liquid
and solid systems are available within each of the main stabiliser type
groups. In general, liquid systems tend to make for somewhat easier
processing of uPVC compositions, but lower softening and heatdistortion temperature of the products: the clarity of transparent
compositions is normally less affected-and may be improved-by
liquid stabiliser systems.
It is self-evident that a stabiliser (in practice normally stabiliser
system) chosen for a particular composition should-like any constituent-be compatible with all the others, as well as otherwise suitable
for the processing conditions and end-use envisaged: the importance of
cost and cost-effectivity has already been mentioned. Because-as
pointed out at the end of Section 9.2.1-virtually every PVC
composition (and certainly every type of composition) presents an
individual stabilisation problem, the choice of a stabiliser should be
made in consultation with the manufacturer (in the industrial context
'stabiliser' will normally mean a proprietary product, most often
composite, designed for the particular type of formulation, process,
and service conditions). The stabiliser so chosen should still be finally
evaluated in laboratory tests and plant trials (see also Chapter 10).

9.4 HEAT STABILISERS

All heat stabilisers and stabiliser systems in industrial use are of the
'external' kind in the applicational sense, in that they are additives

264

W. V. Titow

incorporated in the PVC by physical admixing. * Permanent 'internal'

stabilisation of the PVC polymer by introducing a stabilising
component into the molecular chain, or by attaching it to the chain
through a chemical reaction, is still more of academic interest than
practical significance. Examples of this approach to stabilisation
include: a vinyl chloride/lead undecylenate copolymer for which
substantially increased stability (in comparison with commercial PVC
polymers) has been claimed;22 treatment of PVC polymer with
triphenyl aluminium to substitute phenyl groups for labile CI atoms in
the chain for improved stability;17 and replacement of the labile CI by
mercaptide groups through reaction of the PVC polymer with
dibutyltin mercaptide salts, reported to result in improvements of
thermal stability by factors of 6 to 9. 23 .24 The chemical substitution in
the last-named treatment is of the same kind as those believed to
constitute one of the important mechanisms of stabilisation of PVC by
organotin stabilisers (see Section 9.6 below).
There is no formal, rigid classification of heat stabilisers, although for
the purposes of discussion or review of their properties and effects they
are very often grouped on a somewhat mixed basis relating partly to
the chemical nature and pa.rtly to the types and areas of application:
this kind of grouping is exemplified by the headings in the brief, basic
summary given in Section 4.4.1(b) of Chapter 4. The classification of
the present section follows more closely the lines of division by
chemical type; although no special intrinsic merit is claimed for this
particular approach, it is not regarded as any less convenient, or more
arbitrary, than other possible systems.
On this basis, the compounds used as heat stabilisers for PVC may
be divided into the following general groups:
(i)
(ii)
(iii)
(iv)

lead compounds;
organotin compounds;
compounds of other metals;
organic stabilisers.

* This is so even in the case of so-called 'in-kettle' stabilisation,25 in which the

stabiliser (normally an organotin) is added at the earliest possible stage, viz., to
the reactor during the polymerisation of the PVC resin. This method has been
introduced by some US companies manufacturing PVC pipes on a scale large
enough to warrant producing their own polymers. The benefits are a most
intimate dispersion of the stabiliser in the polymer for maximum stabilising
effect, and protection against heat degradation in the drying operations
concluding the polymer production cycle.

9 Stabilisers: General Aspects

265

In many instances (and with groups (iii) and (iv) predominantly)

individual members of these groups are used not singly, but in
combination with other compounds from the same or another group,
to make up composite stabiliser systems. The majority of commercial
stabilisers are such composites, specially designed for particular types
of composition and application, and with a view to utilising synergistic
effects between the components and avoiding undesirable interactions.
Stabilisers and stabiliser systems are also available in combination with
other PVC additives (lubricants, colourants, antistatic agents, etc.) in
'single-pack' additive systems marketed by suppliers for specific
purposes and types of PVC composition. The advantages and
limitations of such systems are mentioned in Chapters 10 (Section 10.4)
and 11 (Sections 11.1.3 and 11.3.3(iii)). The mutual effects of
stabilisers with lubricants (whether as members of the same
single-pack system or when incorporated individually in the PVC
composition) are of particular importance (see Chapter 10, Section
10.3; Chapter 11, Section 11.1.2; and Sections 9.4.1-9.4.4 below).
Other things being equal, the efficiency of a stabiliser increases with
the thoroughness of its dispersion in a PVC composition.
Useful concise reviews of stabilisers and their applications include
ones by Fernley,26 Grindley,27 and Thacker,28 as well as those in Refs
7 and 9 already cited.
9.4.1 Lead Compounds
These are either lead salts or lead 'soaps' (salts with stearic acid). The
main advantage of these old-established stabilisers are cost-effectivity,
good heat-stabilising power (in some cases combined with UV
absorption), and particular suitability for use in electrical insulation
(because of their complete non-conductivity and the inert nature of the
chlorides formed by reaction with HCI). However, they are not
suitable for clear compositions (although some may be used in
translucent ones), where freedom from sulphur staining is necessary
(ct. Section 9.7), or where their toxicity presents a hazard, as, for
example, in food-contact applications (e.g. packaging films, containers), products for medical use, or childrens' toys.
The handling (especially at the compounding stage) of lead
stabilisers can also present exposure hazards, and comes within the
scope of prescribed practice and regulation limits for occupational
exposure of workers to lead (e.g. in the USA 50~g of lead per cubic

266

W. V. Titow

metre of air over an 8-h weighted average is currently the maximum

under OSHA regulations). Lead stabiliser powders should preferably
not be used in 'open' handling and mixing operations, and certainly not
unless a first-class extraction system is available. In any case, the
powders may be difficult to disperse in comparison with the other
physical forms in which lead stabilisers are available. These are
'dustless' powders (stabiliser powders damped down with a small
proportion-varying with the absorptivity, but in general of the order
of 1%-of a plasticiser or mineral oil, or treated with PTFE) ,
granulates, 'co-precipitates' (of lead stabilisers with lubricants: coprecipitates tend to be amorphous rather than crystalline as the lead
stabilisers, and can also constitute synergistic systems), liquid dispersions (of the stabiliser(s) in a suitable plasticiser), and 'single-pack'
additive systems-see also Chapter 10.
In formulating with lead stabilisers, the PbO content and its
proportion 'safe' for reaction (without danger of gassing,* or liberation
of stearic acid from stearates) should be taken into account-see Table
9.1.
Basic lead carbonate (white lead): This well-known product has been
used since the early days of the industry, and it still retains its position
as one of the popular, low cost, general-purpose stabilisers for PVc.
Improvements in manufacturing processes have resulted in special
grades of white lead becoming available, with consistent properties and
exceptional purity, and having maximum heat stability for use in vinyl
compounds. White lead decomposes with the evolution of water and
carbon dioxide when heated to temperatures around 200C, and this
fact must be taken into account when processing compounds
incorporating this stabiliser. Care should be taken to avoid excessively
high temperatures, especially in the case of rigid or non-plasticised
materials subject to severe shearing forces, where the heat generated
by internal friction may result in temperatures high enough to cause
degradation and gassing due to the evolution of carbon dioxide.
White lead is suitable for use with all types of vinyl chloride
polymers, but in fast-rate processing (extruding, calendering, moulding) tribasic or tetrabasic lead sulphate is now preferred. The electrical
properties of white lead are good and it is therefore eminently suitable

* Release of gas, normally CO2 , during hot processing. Can be promoted or

aggravated by acidity of plasticisers in plasticised compositions. 29

267

9 Stabilisers: General Aspects

TABLE 9.1
Some Characteristics of Lead Stabilisers

Stabiliser
White lead

Tribasic lead
sulphate

Dibasic lead
phosphite

Specific
gravity

PbO
(totaf)

'Safe'
PbO

64-68

86

288

70

86

65

67

895

60

Lead silicate

267

89

665

Lead stearate
Dibasic lead
stearate

124
19

315
55

315
365

Tribasic lead
maleate

60

89

665

Quantity to use
(on 100 phr)
Extrusion
Rapid extrusion
Calendering
Spreading
Extrusion,
plasticised
Extrusion,
unplasticised
Calendering
Spreading
Extrusion,
plasticised
Extrusion,
unplasticised
Calendering
Moulding
Extrusion
Calendering
Used alone
Used in
combination

3-5
8-10
3-5
2-5
3-5
5-10
3-5
2-5
3-5
5-10
3-5
3-8
5-7
4-6
15-25
2-4
05-1
2-4

for stabilising cable compounds. As it is non-lubricating, the addition

of a lubricant is necessary; 05-1 % dibasic lead stearate has been found
satisfactory in most cases. The proportion used in PVC compounds is
not critical and as it has a high degree of long-term heat stability, the
problem of heat degradation during reworking scrap material can be
readily overcome if sufficient white lead is used. The quantities to be
used are indicated in Table 9.1.
Tribasic lead sulphate: Tribasic lead sulphate is a good stabiliser for
high-temperature working. It is in itself very stable to heat and can be
heated without decomposition to temperatures well in excess of those
normally encountered in compounding and fabricating PVc. For this

268

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V. Titow

reason it is suitable in such processes as high-speed extrusion or

manufacture of rigid products. Under these conditions the absence of
decomposition minimises the risk of porosity caused by evolution of
gases. Very good electrical properties are also a feature of compounds
stabilised with tribasic lead sulphate. It is especially useful for cable
sheathing purposes, as when it is used with suitable electrical grade
polymer, high values of volume and surface resistivity can be
maintained.
It is suitable for all pigmented compounds where long-period heat
stability is required, for rigid profiles, and rainwater goods, guttering,
downpipes, soil pipes and pipes for conveyance of gases and liquids.
A mixed stabiliser of tribasic lead sulphate and dibasic lead
phosphite has been found in practice to impart excellent weathering
properties, the dibasic lead phosphite having excellent resistance to
UV light. Tribasic lead sulphate is not self-lubricating and normally
requires the addition of a lubricant, such as lead stearate, to assist
fabrication. The amount of lubricant required is usually of the order of
0'5-10 phr.
Tetrabasic lead sulphate: This stabiliser is similar in general action to
tribasic lead sulphate, but somewhat more powerful. It provides the
highest proportion of available lead oxide of all the lead stabilisers. Its
low combined water content reduces the tendency for gassing in
extrusion of rigid compositions. It is a UV absorber, giving protection
to sensitive pigments. In combination with dibasic lead phosphite it
gives greater protection to PVC on outdoor exposure than does an
equivalent amount of tribasic lead sulphate in such combination.
Dibasic lead phosphite: This is one of the best stabilisers among the
lead compounds, also particularly effective against light and weathering (better than the sulphates), and hence widely employed in
compositions for outdoor applications (e.g. extruded profiles, cladding,
fencing), where its action as a UV-screening agent and its antioxidant
functionality are particularly useful. Like the lead sulphates, dibasic
lead phosphite is a strongly opacifying stabiliser: this should be
considered where translucent compositions are required.
Lead silicate: The refractive index of this stabiliser approximates to
that of PVC polymer; it is therefore suitable for translucent
compounds, promoting economy of use of colourants in translucent

9 Stabilisers: General Aspects

269

film, sheeting and fabric coatings. Lead silicate is an effective heat

stabiliser, in keeping with its high lead oxide yield: as it has no
lubricating action the amounts that can be added to PVC are not
limited by the possibility of over-lubrication (as are those of metal soap
stabilisers), whilst-by the same token-it is suitable for use in
compositions to be calendered or extruded where lubrication has to be
closely controlled. The main applications of lead silicate are in flexible
PVC, including some plastisol products. It does not normally cause
migration or blooming, which may occur with the use of metal soap
stabilisers.
Lead salicylate: This a good stabiliser against the action of light.
It is also a chelator for iron, used in compositions incorporating
iron-containing fillers to prevent the development of colour: one such
common application is in asbestos-filled PVC flooring. Lead salicylate
is normally employed in combination with another lead stabiliser, e.g.
basic lead carbonate.
Lead stearate: This is a stabiliser of only moderate power, but with
strong lubricant action, which is the main reason for its use-eommonly
as a component of a composite lead stabiliser system (most often
containing tribasic or tetrabasic lead sulphate as the main stabiliser). It
can also be used with other metal-stearate stabilisers (e.g. calcium and
strontium stearates). The proportions typical for normal usage are
05-15 phr, but above about 075 phr it will not normally give clear
compounds, so that dibasic lead stearate should be used. Over-addition
can cause blooming.
Dibasic lead stearate: A moderately good heat stabiliser and useful
high-temperature lubricant: it is used mainly in the latter capacity, as a
constituent of composite stabiliser systems (especially with the lead
sulphates) for pipe, profile and sheet compositions.
Dibasic lead phthalate: This is a good heat stabiliser, with some
light-stabilisation effect. It is readily dispersible in PVC resins. Its
refractive index is high so that its opacifying action in PVC
compositions is relatively strong. Dibasic lead phthalate is recommended for use in high-quality cable covering in which it promotes
good electrical properties (volume resistivity unimpaired by compounding and processing, and maintained during the life of the cable).

270

W. V. Titow

This stabiliser is also an effective activator ('kicker') for chemical

blowing agents in PYC foam compositions (cf. Chapter 25).

Tribasic lead maleate: This is an effective heat stabiliser with

light-stabilising (UY-screening) functionality, used in such products as
pipe and sheeting. It is suitable for translucent compositions, and a
good stabiliser for chlorinated PYC.
Tetrabasic lead fumarate: This compound has good stabilising action
and compatibility with PYC resin. Its main uses are gramophone
records and cable coverings.
9.4.2 Organotin Stabilisers

(a) Chemical Nature and Types

Commercial organotin stabilisers are mainly compounds of the general
formula, I, with some of those represented by formula II also in use
(commonly in mixtures with formula I compounds the respective
proportions being adjusted for particular effects-see Section 9.4.2(b)
below).

The nomenclature commonly employed in the industry for these

stabilisers is largely (though not exclusively-see further on) associated
with the nature of the substituent group R, as shown schematically
below, so that the compounds I and II may be referred to as di- and
mono-substituted respectively.
The tri-substituted compounds (R3SnA) are also formed in the
course of production of organotin stabilisers by the industrial
processes. 25 ,30 However, because their stabilising effects in PYC are
lower-and their toxicity higher-than those of compounds of types I
and II, they are normally regarded as undesirable by-products and the

production processes run so as to minimise their formation.

The following general classification scheme illustrates the nature and

271

9 Stabilisers: General Aspects

mutual relationship of the various types of commercial organotin

stabilisers (with reference to formulae I and II).
organotin stabilisers

I
Alkyltin compounds

(R = an alkyl group)

Methyltin
compounds

(R=-CH3)

Butyltin
compounds
(R=-C4~)

1_- - _ _,
1
Octyltin
Lauryltin
compounds

(R = -CsHd

Estertin compounds
(R = an ester group:
R'.OOC.CH2 CH2- )

compounds

(R = -C12H 2S)

The substituent groups A of formulae I and II are normally derived

from either:
(i) mercapto compounds (mercaptoacids and their esters; mercaptides), or
(ii) carboxylic acids and their esters (e.g. maleic or lauric acids;
maleic esters and half-esters).
Most commonly the A groups are all mutually the same, although
compounds in which they differ are not unknown among commercial
organotin stabilisers (e.g. Thermolite 17, M & T Chemicals, USAdibutyltin laurate-maleate).
Alkyltin stabilisers in which the A substituents are mercapto
compounds are usually referred to as thiotin stabilisers, or simply
'thiotins' (occasionally 'sulphur tins'), and those with A substituents of
the sulphur-free carboxylic acid or ester type as tin carboxy/ates: the
most numerous members of this latter group among commercial
stabilisers are dibutyltin carboxylates.
The estertin stabilisers are relatively new, having been first
introduced (by AKZO Chemie) in the mid-seventies. Since then
several commercial representatives have been available, e.g. in the
Stane/ere (AKZO Chemie), Irgastab (Ciba-Geigy), and Interstab
(Interstab Chemicals) ranges. The lauryltins-a Japanese development-are even more recent.
The preparation and evaluation of an interesting group of polymeric
p-benzoquinone-tin compounds was described recently by Yassin and
Sabaa,lO who claim a high degree of stabilising action in PVC for these
compounds.

272

W. V. Titow

(b) Characteristics and Applications

The organotins are powerful heat stabilisers, imparting excellent shortand long-term stability to PVC compositions, and-for the most
part-a high degree of clarity in transparent products. They are
relatively expensive, although the 'compounded' cost can be competitive with that of other types of stabilisers-especially when considered
on the basis of performance-because of the comparatively low
incorporation levels (rarely more than 2 phr, and only fractional phr in
many formulations). Most organotins are toxic: however, several
commercial tin stabilisers based on dioctyltin compounds* are allowed
in many countries (with restriction on maximum content), because of
their low level of toxicity, and good resistance to extraction. These
permitted tin stabilisers are important in the production of uPVC
food-packaging film and bottles for edible oils and beverages, where a
combination of non-toxicity with high degrees of heat stability and
clarity is a primary requirement. Some commercial estertins have also
gained qualified food-contact approval.
The stabilising action of organotin compounds is considerably
influenced by the nature of their A substituent groups (cf. formulae I
and U). In general, the thiotins-and especially dialkyl thiotins-are
the most powerful and effective heat stabilisers known, suitable for use
with PVC polymers of all types and grades (even emulsion resins
stabilised with alkali, which can give problems with some stabilisers of
other types), many copolymers, and blends with modifying polymers.
However, apart from their relatively high cost, the following factors
also impose some limitations on the use of the thiotins. As mercapto
compounds they impart an unpleasant odour to PVC compositions:
this is perceptible in the processing of both flexible and rigid PVC, and
persists in pPVC products (only rarely in uPVC). Because they contain
divalent sulphur, they are not normally suitable for compositions
incorporating lead or cadmium stabilisers or pigments, with which they
can react to form coloured metal sulphides ('cross-staining'). The
thiotins have relatively little light-stabilising action. Where good
stability to light, and weathering generally, is an important requirement, they are used in conjunction with tin carboxylates or other
light-stabilising additives, often epoxy stabilisers.
* e.g. di-n-octyltin maleate; or di-n-octyltin-bis(isooctyl thioglycollate), listed
in the US Federal Register as di-n-octyl-tin-S,S'-bis-isooctyl-mercaptoacetate.

9 Stabilisers: General Aspects

273

Note: Some commercial stabilisers are mixtures of this kind, e.g.

Irgastab T68 (a tin mercaptide with a dibutyltin carboxylate),
or Irgastab 170 MO (di-n-octyltin-bis(2-ethylhexyl thioglycollate) with epoxidised soyabean oil).
Addition of titanium dioxide (12-14 phr) to thiotin-stabilised
compositions for the production of extruded products also improves
weathering resistance. 25 In transparent compositions for outdoor use,
further augmentation of any stabiliser system with a UV absorber is
normal practice.
The heat-stabilising power of the sulphur-free tin carboxylates,
whilst generally good, is rather less than that of the thiotins, and their
cost tends to be higher. However, they impart good stability to light
(excellent in some cases, e.g. with some modified butyltin maleates).
Like the thiotins they are suitable for all types and grades of PVC
polymers. They are also odour-free and do not cause cross-staining
with heavy-metal compounds. When used in PVC pastes (in appropriate cases: pastes are not widely stabilised with organotins) they do not
increase the paste viscosity.
The first-generation estertins (all of the liquid thiotin type) are
comparable in performance with the established non-lubricating alkyl
thiotins in the major applications (calendering, extrusion, injection
moulding, blow moulding): they are also somewhat better than alkyl
thiotin stabilisers in regard to weathering resistance (although inferior
to tin carboxylates): low volatility and extractability are further general
advantages.
Organotin stabilisers are available in both liquid and solid forms.
Most liquid stabiliser systems of all types, including virtually all the
long-established liquid organotins, and the first generation of estertins,
have no lubricant action, and-in general-non-lubricating compounds
predominate among commercial tin stabilisers. Therefore lubricants
are required in most tin-stabilised rigid PVC compositions. In some
cases they may be introduced with the stabiliser (and possibly other
additives) within a multi-component 'single-pack' additive system, but
otherwise it is the task of the formulator to devise a suitable lubricant
system: mutual suitability of this with the stabiliser will be the most
important single factor to be considered in the general context of
processing characteristics, cost, and stability in service of the
composition. As mentioned in Chapter 11 (Section 11.1), inter alia, use

274

w.

V. Titow

can be made of synergistic effects that can arise between the thiotins
and some lubricants, notably internal lubricants of the partial glyceride
type. Conversely, these lubricants (both liquid and solid) can impair
the heat stability of compositions stabilised with tin carboxylates
(which give very good results when used in conjunction with lubricants
of the fatty alcohol ester type).
Lubricant capability can be built into methyl, butyl, and octyl tin
compounds by suitable choice of the ligand (substituent group A).
Thus some alkyltin mercaptides with a long aliphatic chain in the
ligand have lubricating properties (e.g. dibutyltin-bis(lauryl mercaptide), used in some rigid compositions in Europe), as have members of
the new group of 'reverse-ester' alkyltin mercaptides developed in the
USA for rigid pipe compositions, in which the A substituents are esters
of a mercaptan (such as thioethanol).
In lauryltin compounds the presence of the lauryl group is
conducive to lubricant action but the overall effect is governed also by
the nature of the A substituent.
The potential scope for imparting lubricant properties to the
estertins through chemical structure modification is considerable,
in that significant effects can be obtained by the appropriate choice
of the R' substituent in the ester groups25 (see classification scheme
above).
In the USA, where lead compounds are not permitted in PVC water
pipes, alkyltin stabilisers are used in this large-scale application. Their
relatively high cost, and the vigorous competition among their
manufacturers, prompted the development of new alkyltin stabiliser
systems effective in rigid PVC pipe compositions at very low
incorporation levels (down to about 03 phr). Among the main trends
in such systems have been the increased use of monoalkyl tins,
exploitation of synergists (e.g. some organotin sulphides), and
introduction of the lubricating tin stabilisers.
Note: The effect of the monoalkyl compounds in tin stabiliser
systems has been likened 25 to that of zinc in Ba/Cd/Zn
stabilisers (cf. Section 9.4.3 below), i.e. promotion of good
initial colour and long-term stability improvement. In some
blown-bottle and rigid-film formulations, an increased proportion of monoalkyl compound in the alkyltin stabiliser systems,
coupled with suitable lubricant choice, can reduce the
stabiliser requirement to below 1 phr.

9 Stabilisers: General Aspects

275

9.4.3 Compounds of Other Metals

(a) Metal Compounds with Stabilising Effects in PVC
Apart from those of lead and tin, certain compounds of the following
metals are of practical interest as stabilisers for PVC: lithium,
magnesium, aluminium, sodium, potassium, calcium, zinc, strontium,
cadmium, antimony, and barium.
The antimony compounds used in commercial stabilisers are
antimony mercaptides. Those of the other metals may be divided into
three general groups whose members are commonly known as 'soaps',
'salts', and 'complexes' (the salts and complexes are sometimes
grouped together under the latter name). The 'soaps' are metal
compounds of higher aliphatic carboxylic acids, typically stearic and
lauric, but also some others (e.g. myristic and palmitic): they are
usually solids, with some lubricating action in PVC compositions (but
liquid systems, in which the metal soaps are dissolved or pasted up in a
'carrier' are available among commercial stabilisers). The 'salts' are
compounds of relatively lower aliphatic acids, such as metal hexoates,
heptoates and octoates, occasionally also caprates and undecylates.
The 'complexes'* are metal derivatives of various aromatic acids,
phenols and petroleum acids, typically naphthenates, phenates, or
cresylates. Stabiliser systems based on the salts and complexes are
most often liquid, and usually non-lubricating.
Antimony mercaptides and calcium stearate are used alone (i.e. each
as the sole stabiliser) in some PVC compositions (although they are
also included as components in composite stabiliser systems-see
below). All the other metal compounds of this section are virtually
always employed in mixtures, compounds of two or three different
metals together forming a composite stabiliser system in which they
mutually supplement one another's effects (see (b) below). In most
cases the mixtures are further augmented by epoxy co-stabilisers and
phosphite-compound synergists ('chelators'), which are present as
constituents of some proprietary mixed-metal stabiliser systems, or
may be added separately to compositions stabilised with systems that
* The 'complex' terminology is not strict or universal: thus a combination of
metal compounds in a composite commercial stabiliser, whether in solid,
liquid, or paste form, is sometimes described as a 'complex stabiliser', or 'a
stabiliser complex', or simply 'a complex' (especially if synergistic additives
such as chelators or epoxy co-stabilisers are also included), even if the main
components are metal soaps.

276

w.

V. Titow

do not contain them (cf. (b) and Section 9.4.4 below, and Chapters 4
and 10).
ANTIMONY MERCAPTIDES

Liquid commercial stabilisers of this type, based on antimony

trimercaptide, were introduced in the USA in the mid-1970s. 31 Their
usage and effects are, in general, similar to those of conventional liquid
thiotins, which they resemble in their lack of lubricant effect and
general degree of toxicity, but over which they can offer cost
advantages. Some proprietary antimony mercaptide stabilisers, and
antimony-stabilised uPVC compounds, are now approved by the
National Sanitation Foundation (NSF) in the USA for potable-water
pipes (with restrictions on maximum content fixed at relatively low
levels-typically 03-04 phr).32 At such levels-which are suitable in
certain compounds formulated for twin-screw pipe extrusion, but
normally too low for single-screw extrusion-the antimony mercaptides
are more efficient than thiotins (the efficiency advantage is reversed
above about 08 phr content level-see Fig. 9.1); they can also be more
effective in compounds experiencing moderately high temperatures
over long time periods. However, the resistance to sulphur staining,
and to UV radiation (especially in transparent compositions) is, in
general, lower than that imparted by the organotins (in opaque
compositions adequate levels of addition of titanium dioxide will
promote good resistance); they may also form orange-coloured
antimony sulphide when exhausted. Strong synergistic effects are
possible when antimony mercaptide stabilisers are used in conjunction
with calcum stearate. 31 Stabilisers based on antimony/tin combinations
have also been developed for rigid pipe compounds for single-screw
extrusion and for thick-walled, large diameter pipe. 32 In Europe
antimony-based stabilisers are recommended, inter alia, for VCNA
copolymer gramophone record compositions. The use of antimony
mercaptides, whilst a relatively recent development in the commercial
context, is in fact a revival 33 made possible by improvements in PVC
compounding and processing techniques and by changes in the relevant
material costs. At the comparatively high levels of incorporation
normal in the early 1950s, when their application in PVC was first
explored, antimony mercaptides were less efficient than comparable
organotins. Their greater efficiency at low levels can now be utilised
thanks to the general lowering of the stabiliser proportions used, made
possible by the more thorough dispersion achievable with modern

277

9 Stabilisers: General Aspects

"'/
~"ti-'/

20
L.

.c

.~-\
~/

Co

0"0./
/

<1./

L.

ell

.a
11l

1ii

c
i= 10

25

1~

~O

Antimony stabiliser, phr

Fig. 9.1 Amounts (phr) of an antimony mercaptide and an organotin

stabiliser, at generally low incorporation levels in identical PVC compositions,
required for the same degree of improvement in dynamic heat stability (torque
rheometer). Marked points on the plot correspond to the improvement factors
shown, i.e. x15: x20; x25; and x30. Data from Ref. 33.

compounding equipment, and more efficient processing' on modern

machinery, especially twin-screw extruders.
Examples of commercial antimony mercaptide stabilisers are
Irgastab S 110 (Ciba-Geigy, UK) and in the USA Synpron 1027
(Synthetic Products Co.), with corresponding products in the Argus
Chemical and Ferro Chemical ranges (respectively, Mark 2115 and
Therm Check 1514).
CALCIUM COMPOUNDS

Some PVC-stabilising calcium compounds are available individually

from stabiliser manufacturers, e.g. calcium stearate and calcium
laurate. However, with the partial exception of calcium stearate, their
widest application is as regular constituents of composite commercial
stabiliser systems in which they are variously combined with zinc,
barium, and magnesium.

278

W. V. Titow

Calcium stearate can be used as a stabiliser in its own right, or as a

lubricating co-stabiliser (with synergistic effects in some cases) in
conjunction with other stabilisers, such as organotin and antimony
compounds (e.g. in rigid pipe compositions of the American kind).
Whilst it is not a highly powerful stabiliser, calcium stearate has a
reasonable heat-stabilising action, although with relatively little
light-stabilising effect. It is useful with emulsion-type PVC polymers
and finds use in certain paste formulations (especially in the UK). Its
non-toxic character also promotes certain applications. Thus uPVC
compositions for potable-water pipes in France are commonly
stabilised with calcium stearate, often in conjunction with organic
co-stabilisers (not epoxy compounds, which are susceptible to
microbiological attack). Calcium stearate is also a stabilising lubricant
constituent of some uPVC bottle formulations, sometimes in conjunction with a zinc compound (e.g. zinc octoate), added as a separate
component, and an epoxy co-stabiliser. Paste products for which
non-toxicity is a requirement (e.g. toys) are also stabilised with calcium
stearate.
ZINC COMPOUNDS

Zinc compounds are never used as sole stabilisers in PVC compositions. This is because PVC polymers are sensitive to zinc, in the sense
of increased susceptibility to degradation in its presence (amounting in
effect to a catalytic de-stabilisation by the metal). The degree of
sensitivity varies widely with the type and grade of PVC polymer, and
also in different compositions (e.g. plasticised, filled compositions of
vinyl chloride/acetate copolymers are among the least sensitive). The
variations in response of emulsion polymers used in PVC pastes to zinc
compounds and individual commercial zinc-containing composite
stabilisers are well known as a general fact (although the actual effects
in particular cases normally have to be ascertained by tests). Thus,
whilst individual zinc compounds (e.g. zinc octoate, zinc stearate) are
available within the regular ranges of many stabiliser suppliers, they
are always used in conjunction with other metal compounds (e.g. those
of cadmium, calcium, magnesium or barium), incorporated either
singly or in pre-combination (e.g. as barium/cadmium or calcium/
magnesium stabilisers). In such made-up combinations the zinc
compound improves initial colour, long-term stability, and resistance
to cross-staining with sulphur compounds (which can occur, for
example, with cadmium stabilisers). Liquid zinc compounds do not

9 Stabilisers: General Aspects

279

usually impair the clarity of transparent PVC composItions. Zinc

compounds (e.g. octoate) are also effective as activators ('kickers') for
chemical blowing agents in compositions for the production of PVC
foam (see Chapter 25).
The actions and effects of the zinc compounds are essentially the
same where they are present as components of commercial composite
stabilisers, such as proprietary barium/zinc, cadmium/zinc, calcium/
zinc, barium/cadmium/zinc and other systems of this general kind (see
(b) below).
Note: Calcium/zinc combinations are suitable for applications where
non-toxicity is a requirement.

The amounts of a zinc compound to be employed with other suitable

metal compounds or systems, as well as its proportions in proprietary
composite zinc-containing stabilisers (which may be differentiated into
low-zinc, medium-zinc, and high-zinc systems) can, typically, vary
within the range 01-05 phr, depending on the amount and nature of
the main stabiliser(s) used and the zinc-sensitivity of the PVC
composition concerned.
ALUMINIUM COMPOUNDS

The use of aluminium compounds in the stabilisation of PVC is

relatively very limited: it is normally confined to certain paste
compositions, and the aluminium compound is not the sole stabiliser.
Where it is added separately (i.e. not as a constituent of a composite
proprietary stabiliser) the compound will usually be aluminium
stearate, and a lead compound or calcium stearate will be used as the
main stabiliser in the paste. Some grades of aluminium stearate are
effective as thickening (gelling) agents for PVC pastes, and are
included in the formulation mainly in this capacity. In commercial
mixed-compound stabilisers aluminium may, typically, be combined
with calcium and zinc (d. (b) below).
In general terms, the stabilising effects of aluminium stearate may be
said to resemble those of zinc stearate.
CADMIUM COMPOUNDS

PVC compositions stabilised solely with cadmium compounds generally

[ave good initial colour hold, but their long-term stability is unsatisfactory, colour and eventual darkening developing with time. These
compounds are, therefore, not used alone as PVC stabilisers, although

280

W. V. Tilow

some are available from stabiliser manufacturers (e.g. cadmium

stearate, cadmium laurate, certain liquid compounds): these can be
added to compositions stabilised with composite, cadmium-containing
systems to increase the total cadmium content, or to some leadstabilised compositions (e.g. ones for pipe or extruded profile for
outdoor use) to improve initial colour, and light stability in service.
However, cadmium compounds are very important in PVC stabilisation, as one of the principal components of the widely used
barium/cadmium stabiliser systems (see (b) below).
A disadvantage of cadmium stabilisers is the toxicity of the
compounds of this heavy metal: this not only makes cadmiumcontaining PVC compositions unsuitable for 'non-toxic' applications,
but has been causing increasing concern as a hazard in the handling and
processing of cadmium stabilisers and pigments (cf. Chapter 11,
Section 11.3.4).
BARIUM COMPOUNDS

Barium compounds (such as, for example, the stearate and laurate
which are available from commercial stabiliser sources) can impart
good long-term stability to PVC compositions, but the initial colour is
poor and progressive yellowing usually takes place. The compounds
are thus unsuitable for use as sole stabilisers, but-as would be
expected from a consideration of the respective effects-they complement well the action of cadmium compounds. Moreover, when
compounds of the two types are used together synergistic effects also
arise, making the resulting stabilisation even more effective than would
be expected from a mere addition or superposition of their individual
contributions. These are the reasons underlying the wide use of
composite stabilisers based on the barium/cadmium combination, often
including also a zinc compound as the third component (see (b)
below). Barium/zinc systems, without cadmium, are also employed, as
are some barium/lead compositions in which the barium compound
improves long-term stability (see, for example, Durham Chemicals'
Durostabe S70 and S65, respectively, in Table 10.4, Chapter 10).
Barium compounds are not as toxic as those of cadmium, but they
are not suitable for use where non-toxicity is required.
LITHIUM COMPOUNDS

Lithium stearate is the single compound usually readily available from

stabiliser manufacturers. However, it is not used alone as a stabiliser,

9 Stabilisers: General Aspects

281

and even in combinations with other metal stabilisers its use is not
widespread. Like other stearates it has lubricant properties, and may
be regarded as a non-toxic substitute for other metal soaps in some
formulations (but its admissibility in particular cases should be checked
with the supplier or the appropriate organisations).
MAGNESIUM COMPOUNDS

Here again the stearate is commonly available from stabiliser supply

sources, but is not used alone in PVC stabilisation. In general,
magnesium compounds are mainly encountered as constituents of
composite proprietary stabilisers (usually for 'non-toxic' applications or
for certain paste compositions) in which they are combined with
calcium, or zinc, or both. Some commercial magnesium/zinc stabilisers
are recommended for a wider range of applications (see (b) below).
STRONTIUM COMPOUNDS

Strontium compounds are most commonly combined with those of zinc

in composite stabiliser systems. In such combinations they may be
regarded as substituents for cadmium compounds, offering lower
toxicity and freedom from sulphur staining. However, the systems are
less applicationally versatile than the cadmium analogues.
Individual strontium soaps (typically the stearate and laurate) are
available from stabiliser suppliers.
COMPOUNDS OF SODIUM AND POTASSIUM

These are of minor importance, and only occasionally encountered in

commercial stabilisers, as constituents of composite systems, e.g.
stabiliser CS 137 (originally in the range offered by F. W. Berk & Co.
Ltd in the UK)-a barium/sodium organic complex for transparent
compositions.
(b) Composite Metal Stabilisers

As has been indicated in the previous section, it is in certain recognised

combinations with one another that the metal compounds of that
section enjoy a prominent position as stabilisers for PVc.
The nature and applications of these composite systems are
illustrated by the examples of their commercial versions given in the
tables and sample formulations of Chapter 10. Only the salient points
and general features of the most important types are, therefore, briefly
outlined in the present set;tion.

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W. V. Titaw

Composite systems of the principal types are available in solid

(powder, flake), liquid, or paste forms. More recently concentrates of
some systems in PVC polymer have also been coming onto the market,
as have low-dusting (plasticiser-dampened) powder forms. Such
materials are exemplified, respectively, by some barium/cadmium
powder stabilisers 'encapsulated' in PVC resin at a 1: 1 ratio (in the
Poly-Chek MP series of Ferro Chemical, USA), and low-dusting
powder grades of the same metal system in the Mark 8100 series of the
Argus Chemical Corp., USA. The concentrates are added to PVC
compositions at twice the normal levels, with one part of PVC polymer
omitted from the composition for every 2 phr of concentrate.
These new developments parallel the forms in which some lubricants
and lead stabilisers are being offered, and involve similar advantages
(ct., respectively, Section 11.1.3 in Chapter 11 and Section 9.4.1 of the
present chapter).
BARIUM/CADMIUM AND BARIUM/CADMIUM/ZINC STABILISERS

In terms of the amounts used this is the most important group among
PVC stabilisers, although none of its members can equal the organotin
systems in stabilising power and versatility (in the sense of equal
suitability for use with all grades and types of PVC polymers).
However, systems of this type can impart high degrees of thermal
stability, good light stability, and be compatible with good clarity in
transparent compounds. Their effects are improved (and especially the
light stability increased) by the addition of epoxy co-stabilisers and
organic phosphite 'chelators' (see Section 9.4.4 below), and these
synergists are normally included either by the formulator or ab initio as
constituents of the composite proprietary system. Weathering properties are further improved by addition of UV absorbers (see Section
9.5 below). Liquid BalCd and BalCd/Zn systems are particularly
widely used in flexible PVC materials, typically at levels of 1-2 phr
(with about O5-10 phr of a chelator and up to about 5 phr of an epoxy
co-stabiliser where appropriate).
Solid (powder or flake) systems are combinations of the metal soaps,
with or without the further additives just mentioned. Whilst they can
be used in both rigid and flexible compositions they are of special
interest for uPVC as they have some lubricant action, and affect the
softening temperature less than do liquid stabilisers. In most cases they
are suitable for translucent (as well as opaque) compositions, but only
some are suitable for highly transparent ones. Typical incorporation

9 Stabilisers: General Aspects

283

levels are 2-3 phr, with a phosphite chelator (typically about 1: 3 on

the main stabiliser, i.e. about 07-10 phr) , for improved initial colour,
transparency and light stability: an epoxy co-stabiliser (about twice the
amount of the main stabiliser, i.e. around 4-6 phr) may be included for
further improvements in general stability and light and weathering
resistance. Combinations of solid and liquid systems may be used for
optimum flow and lubrication characteristics in particular compositions.
The main general limitations of BalCd and Ba/Cd/Zn systems are:
differing effectiveness in different types of PVC* (also influenced, in a
given type of composition, by the ratio-and respective contents-of
the Ba and Cd components, the amount of Zn component if present,
and the nature of the organic parts of the compounds); variable
tendency to plate-out in processing; and susceptibility to sulphurstaining (minimised in zinc-containing systems).
CALCIUM/ZINC STABILISERS

Members of this system are the most widely used non-toxic stabilisers
for PVC (although not all its commercial variants have approval, or the
same wide approval, in various countries). Stearates and octoates of
the two metals, and many of their proprietary combinations, are widely
permitted in most countries for use in rigid and plasticised compositions for the production of food-packaging materials and containers,
medical goods and toys.
Ca/Zn combinations are not very powerful stabilisers. Wherever
possible (and this is permitted in many 'non-toxic' applications) they
are used in conjunction with an epoxy co-stabiliser (which is a
component of many proprietary systems) to improve the stabilising
effects both against heat and light, and an organic phosphite synergist
(which improves initial colour and transparency, inter alia). Other
organic synergists available for use (in conjunction with organic
phosphites if desired) to improve the stabilising action and efficiency of
Ca/Zn systems include stearoylbenzoylmethane (Rhodiastab 50Rhone-Poulenc, France) and some proprietary polyol compounds (e.g.
those supplied by Perstorp AB, Sweden): stability improvements by
factors up to x2 can be obtained in some compositions through the
addition of these compounds (02-05% with solid CalZn systems).
The CalZn stabilisers are available in both solid and liquid forms. In
* Generally unsuitable for alkali-prestabilised emulsion grades.

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W. V. Titow

addition to the conventional powders, the solid versions now include

particulate concentrates in PVC polymer (e.g. Ferro-Check NT-3Ferro Chemical Corp.). Where a liquid sytem consisting of Ca and Zn
soaps in a liquid carrier is to be used for a 'non-toxic' application it is
necessary to ascertain that the carrier is acceptable for the purpose.
Typical incorporation levels may be illustrated by the following
figures: liquid Ca/Zn system for paste compositions-I'5 to 3 phr (with
up to 5 phr epoxy co-stabiliser); solid (powder) system for sheeting
compositions-l to 2 phr (rigid sheeting), 05-15 phr (flexible sheeting), in each case with the addition of an epoxy co-stabiliser.
Outside the non-toxic field, a common use for technical grades of
Ca/Zn stabiliser systems is in asbestos-filled PVC flooring. Such
compositions are subject to discoloration during heat processing, due
to the catalytic action of iron present in the asbestos. In compositions
otherwise adequately stabilised with BalCd or lead systems the
discoloration can be severe, but it can be effectively prevented by the
Ca/Zn stabiliser (see also Chapter 4, Section 4.6.2).
Apart from the special applicability of the non-toxic grades, the
advantages of Ca/Zn stabilisers include moderate price, and virtual
freedom from odour in finished products and from sulphide staining. *
The soap compositions have some lubricant action. The main
limitations are: the relatively low stabilising power already mentioned;
rapid progress of degradation, once commenced, in Ca/Zn-stabilised
compositions; unsuitability for outdoor applications; and limited
suitability for crystal-clear compositions. *
OTHER METAL-COMPOUND COMBINATIONS

Some of these have been mentioned in Section (a) above. Something of

the nature and applications of various mixed-metal stabilisers may be
illustrated by the following examples.
Note: Whilst there are, as yet, no official restrictive regulations
against the general use of cadmium compounds, the position
is under active review in some countries (ct. Chapter 11,
Section 11.3.4) and a trend has begun to consider technically
acceptable but potentially safer altenatives. In the stabiliser
field, certain cadmium-free metal combinations (some under
current development) are seen, or offered, as such replace* Haze may develop in transparent compositions in contact with sulphur
compounds-see Section 9.7.

9 Stabilisers: General Aspects

285

ments, at least in certain applications. These combinations

include some CalZn systems with improved light stability as
well as various BalZn, BaiCa/Zn, and MglZn compositions.
In such systems, as indeed in all mixed-metal stabilisers, the
principal factors governing the stabilising effects in a particular PVC composition and set of conditions are the proportions
of the individual metals, total metal level, nature of the
organic parts of the metal compounds, and nature and
amounts of any synergistic additives included in the composite
sytem. The mixed-metal stabilisers so far available as
substitutes for Ba/Cd systems do not, as a group, yet match
the collective applicational versatility of those systems.
MgIZn: Selected combinations of this type may be used (in
conjunction with phosphite chelators) for stabilising flexible and
semi-rigid compositions for many calendered, extruded and paste
products. A degree of UV-resistance and freedom from sulphur
staining are useful general features of compositions stabilised with
proprietary versions of this system. Its solid-soap variants (e.g.
Synpron 1534-Synthetic Products Co., USA) also have some
lubricant action.
BalZn: Examples of commercial versions of this system, currently
offered as replacements for Ba/Cd-based stabilisers in some applications, are listed below:
Synpron 1531: a liquid, low-Ba, high-Zn system incorporating a
phosphite synergist (for use in calendered, extruded and paste
products, at about 2 phr);
(ii) Mark 2181 and 4004 (Argus Chemical): both liquid Ba/Zn
combinations, for use in paste-produced PVC flooring (at
15-25phr, with 3-lOphr of epoxy co-stabiliser) where they
can confer good clarity (top 'wear' layers), initial colour hold,
stability to ageing at moderate temperatures and long-term
stability;
(iii) Stavinor BZ-329 (Rousselot, France), also for paste flooring
applications.

(i)

CdlZn: Systems of this type are useful in compositions for chemically

blown cellular PVC products (e.g. injection-moulded microporous
shoe soles; foamed layers of coated fabrics) in which they act both as

286

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V. Titow

stabilisers (alone or in conjunction with other stabilisers, usually BalCd

systems) and activators ('kickers') for the blowing agent (normally
azodicarbonamide). Typically (e.g. with a Ciba-Geigy commercial
version-lrgastab ABC 2) about 05 phr would be required for the
activator function, and up to about 25 phr for stabilising effects.
SrlZn: The commercial strontium/zinc systems are exemplified by
Sr/Zn laurate co-precipitates* (e.g. Lankromark M-Diamond Shamrock, USA and UK), used mainly in plasticised compositions (at about
2 phr, with about 5 phr of an epoxy co-stabiliser), where freedom from
sulphur staining, and low toxicity are of interest.
SrlZnlSn: This is another of the combinations offered as replacements for Ba/Cd-based systems in some applications. Resistance to
sulphur staining, and low tendency to plate-out (of some commercial
versions, e.g. Nuostabe V 1925-Tenneco Chemicals, USA) are
advantageous features.
CalSb: The already mentioned combination of antimony mercaptide
with calcium stearate effected by some formulators for its synergistic
and lubricant features, is also embodied in some proprietary stabilisers.
An example is stabiliser SB-739 of Rousselot-a liquid system for
high-fidelity gramophone records (a powder version is used in
lower-quality records, where initial high sound fidelity and fidelity
retention are less crucial).
CaIAlIZn: This system, and some of its uses, are exemplified by the
entries for Lankromark LA 105 and Lankromet LA 175 in Table 10.5
of Chapter 10.
9.4.4

OrganiclMiscellaneons Stabilisers

None of the organic, non-metal compounds used in the stabilisation of

PVC compositions can be described as a powerful primary stabiliser.

* Mixed-metal systems may be physical mixtures of the components (in which

the organic parts of each metal compound may be different, or mutually the
same) or 'co-precipitates' in which the organic portion is normally the same for
all the metal constituents present. This is the case also with composite lead
stabilisers and lead-based stabiliser/lubricant systems (ct. Section 9.4.1).

9 Stabilisers: General Aspects

287

However, some are used as sole stabilisers in composItions for

food-packaging products, whilst others (epoxy compounds and phosphite 'chelators') are very important as synergistic co-stabilisers used
with many primary stabilisers (notably BalCd and other mixed-metal
systems-see Section 9.4.3). Because some are liquids, and others melt
at PVC-processing temperatures, the organic stabilisers are uniformly
and intimately dispersible in PVC compositions (but some have limited
compatibility with plasticisers, or particular plasticiser/resin combinations in pPVC-see below).
(a) Esters of Aminocrotonic Acid
Typically these are aminocrotonates of the general formula
NHH 0

II

H 3 C-C=C-C-oR

Many commercial stabilisers based on these compounds are approved

for food-packaging applications in several European countries, including the UK, West Germany, France and Italy. They are used mainly in
uPVC compositions, based on suspension and emulsion polymers or
vinyl chloride copolymers, for use in the production of packaging film
and blow-moulded containers. Typical incorporation levels range
between 1 and 2 phr, in conjunction with an epoxy co-stabiliser (up to
about 4 phr) to improve both heat and light stability. Some proprietary
aminocrotonate stabilisers have limited compatibility with plasticisers
in pPVC-e.g. Irgastab Gl* is recommended for use mainly as a
co-stabiliser in plasticised compositions, at up to 04 phr to avoid
exudation, whereas Irgastab A70t causes no difficulties at normal
incorporation levels.
In most cases, uPVC compositions stabilised with the aminocrotonates require lubricants, although some proprietary versions may have
lubricant action.
* Ciba-Geigy: a solid (waxy flakes) mixture of esters of aminocrotonic acid
with 1,4-butylene glycol and some fatty alcohols (C 16-C 1S)'
t Thiodiethylene glycol-bis(f3-aminocrotonate), sold as a free-flowing
powder.

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W. V. Titow

(b) Urea Derivatives

Representatives of this group in common use are
H

II

phenyl urea (C6 H s)-N-e-N-H;

H

I II I
diphenyl urea (C6 H s)-N-C-N-(C6H s);
H S H
I II I
diphenyl thiourea(C6 H s)-N-C-N-(C6 H s).
These compounds may be used as heat stabilisers (with little
light-stabilising effect) for compositions based on alkali-prestabilised
emulsion polymers, and especially in plasticised compositions of this
kind (yellow discoloration may occur in semi-rigid and rigid PVC).
Typical incorporation levels are relatively low, around 03-05 phr,
because of the low compatibility of these stabilisers' with plasticised
PVC. Long-term stability can be substantially improved by the
presence of an epoxy co-stabiliser (up to about 3 phr). At temperatures
above 150C some commercial urea stabilisers may start decomposing
with evolution of ammonia: this point should be checked with the
supplier in individual cases (and preferably also by tests) with
reference to the processing method and equipment used, as such
gassing can give rise to porosity in products.
The main effect of stabilisers of this type is thought to be
neutralisation of any hydrogen chloride evolved as a result of thermal
dehydrochlorination: this mode of action would be in keeping with the
basic nature of these compounds. They are also thought to have some
antioxidant action.
(c) Epoxy Compounds
Epoxy compounds used as plasticisers for PVC are discussed in Section
6.10.1 of Chapter 6. These, as well as others (e.g. epoxy resins
marketed as components for thermoset systems), also have a stabilising
effect in PVC compositions. Whilst this effect is relatively mild in the
absence of other stabilising additives, epoxy compounds (and in
particular some of the epoxy plasticisers, e.g. epoxidised soyabean oil,
epoxy esters) are very important, and widely used, as strongly
synergistic co-stabilisers for metal-based stabiliser systems, as well as

289

9 Stabilisers: General Aspects

for organic stabilisers (see above). Mixed-metal stabilisers (especially

BalCd systems, but also other types) benefit particularly when used in
conjunction with an epoxy co-stabiliser (and a phosphite chelator-see
below). In all cases both heat and light stability are improved; the
latter improvement can be exceptionally marked in many instances.
Moreover, the presence of epoxy co-stabilisers/plasticisers can also
confer additional benefits. Thus in rigid compositions their plasticising
action (even at the 'stabilising' level of only a few phr) improves flow
properties in processing (although the softening point may be
lowered-d. Fig. 9.2), whilst the use of a suitable epoxy plasticiser in a
PVC paste can reduce viscosity where this effect is desirable in
processing, in addition to improving the heat and light resistance of the
product. Epoxy stabiliserslplasticisers are resistant to extraction and
migration: several (but not normally epoxidised soyabean oil) improve
the low-temperature flexibility and 'cold-crack' resistance of plasticised
PVC. Many proprietary products (notably epoxidised soyabean oils)
are approved in most countries for food-contact applications, and-at
incorporation levels of up to about 3 phr-do not affect the clarity of
transparent PVC compositions. The polarity of the epoxy groups
makes epoxy compounds effective as dispersion aids for solid additives
(pigments, fillers, polymeric modifiers) in both rigid and flexible
compositions.
Features which impose some limitations on the use of epoxy

....c

&80
Cl

'c
Ol

....ru
u

;;:

70

l:.- - - - - . . . . 1-----......L- - - - - - - o 1

ESBO

cont<2nt, phr

Fig. 9.2 Vicat softening point (DIN 53460) of a rigid PVC composition
stabilised with 2 phr of a liquid dibutyltin mercaptide as a function of the
amount of epoxidised soyabean oil co-stabiliser present.

290

W. V. TilOW

compounds in PVC compositions are their susceptibility to microbiological attack (see Section 12.7.1, Chapter 12). and the possibility of
exudation, with formation of tacky surface deposits, in some cases
where-in discharging its stabilising function-the compound loses its
epoxy groups through the chemical reactions involved, so that its
compatibility with PVC is reduced. This effect can be a potential
problem, especially in weathering or ageing situations. The compositional factors which promote it are the use of the epoxy compound as
the sole stabiliser and/or its presence in a relatively high proportion as
a component of the plasticiser system. Thus, to prevent this kind of
problem, an epoxy compound should not be used as the only stabiliser,
and its level of incorporation as a plasticiser should preferably not be
higher than about 25% of the total plasticiser system in PVC compositions likely to experience any but mild ageing or weathering conditions.
Note: Interaction of epoxy compounds with unsaturated additives in
a PVC composition (e.g. ricinoleates or oleates which might
be present in stabilisers or plasticisers) can also lead to
permanent chemical modification (loss) of epoxy groups, with
consequences similar to those just described. This was the
cause of development of surface tackiness in, for example,
calendered sheeting when, in the early days, the barium
component of Ba/Cd stabiliser systems then coming into use
was frequently barium ricinoleate, and addition of epoxidised
oils (and phosphate chelators) was beginning to be practised
as an effective way of improving heat and light stability. 34
Changing to the metal soaps (e.g. Ba and Cd laurates) and,
later, liquid complexes (e.g. Ba and Cd phenates) eliminated
the problem. However, inferior clarity and plate-out could
still be troublesome with the soap systems (especially in
high-speed, high-temperature processing), and yellowish colour and susceptibility to sulphur staining with both the soaps
and the complexes: incorporation of zinc compounds subsequently became a meanS of alleviating these disadvantages
(see Section 9.4.3(a) above).
(d) Organic Phosphites

These are not primary stabilisers, but valuable co-stabilisers, used

mainly with mixed-metal stabiliser systems (and widely with the

9 Stabilisers: General Aspects

291

principal types based on BalCd and Ca/Zn combinations). Many

proprietary organic phosphite co-stabilisers are acceptable (mostly at
levels of up to 1 phr) in conjunction with suitable Ca/Zn combinations
for use in food-packaging film and containers (e.g. blown bottles), and
in other 'non-toxic' applications. Numerous commercial stabilisers are
variants of this kind of composite system containing an approved
organic phosphite as one of the components, and in some cases also a
permitted epoxy co-stabiliser (see above).
It is well known that, when used in conjunction with suitable
primary stabilisers, the organic phosphites improve the clarity of
transparent PVC compositions, weathering and light stability generally, as well as heat stability (especially in pPVC). Although the
mechanisms of their action are not fully elucidated, the clarity
improvements are widely attributed to the formation by the phosphites
of PVC-soluble complexes with the normally insoluble chlorides of the
stabiliser metals (CdCl z, etc.) which are themselves formed as the
metal stabilisers exercise their main functions-see Section 9.6. It is
because of this that the phosphite co-stabilisers are commonly known
as 'chelators'. Their heat and light stabilising effects are believed to be
due to their own ability to react with hydrogen chloride,35 with labile
chlorine atoms, and with double bonds of conjugated systems. 36 They
are also credited with antioxidant action, albeit less pronounced than
that of some additives used as primary antioxidants in PVC7-ef.
Section 9.5.
Commercial organic phospite co-stabilisers (typically liquids, with no
appreciable lubricant effect in PVC) are either individual compounds,
or mixtures of compounds of the general formula:

in which R can be a simple (but relatively long-chain) alkyl, or aryl

(usually phenyl), or alkyl-aryl group, or a polyhydric alcohol derivative
(e.g. a partial ester of pentaerythritol); the R groups of the same
compound may not all be identical.
Examples of organic phosphites available as proprietary chelator
co-stabilisers for PVC include triphenyl phosphite, tridecyl

w. V. Titow

292

phosphite,37 distearyl pentaerythritol diphosphite, * tris nonylphenyl

phosphite, t and mixtures consisting of a dialkyl phenyl phosphite with
the corresponding alkyl diphenyl phosphite, triphenyl phosphite and
trialkyl phosphite (e.g. 1rgastab CH 300, CH 301, and CH 343).
The levels of incorporation of phosphite chelators are, typically,
about 1 phr (fractional phr in many cases). With solid BalCd systems it
is fairly usual to add one part of the chelator per three parts of the
metal stabiliser combination; but, in general, the optimum amount
should be verified by tests.

(e) Miscellaneous Organic Co-stabilisers

Stearoylbenzoylmethane and certain polyols have already been
mentioned (in Section 9.4.3(b)) as synergistic co-stabilisers for use with
Ca/Zn stabiliser systems. Another organic co-stabiliser of industrial
interest is 2-phenyl indole:

One use of this additive is as a co-stabiliser (at a level of about

O3-{j5 phr) in uPVC bottle compositions, frequently non-toxic ones
stabilised with a Ca/Zn stabiliser and containing also an epoxy compound
and phosphite chelator as the other components of the co-stabiliser
system. It is also used in some pipe and sheeting formulations.

9.5 ANTIOXIDANTS AND UV ABSORBERS

9.5.1 Antioxidants
As has been mentioned, oxidation (sometimes referred to as
'auto-oxidation') is one of the mechanisms instrumental in the
degradation of PVC polymers by both heat and light (cf. Sections 9.2.1
* Used in some formulations for PVC bottles in place of the common
combination of tris nonylphenyl phosphite and 2-phenyl indole.
t Commercial versions (e.g. Irgastab CH 55-Ciba-Geigy; Phosclere P315Interstab Chemicals Inc.) approved in many countries for food-contact
applications.

9 Stabilisers: General Aspects

293

and 9.2.2). Many heat stabilisers have an antioxidant action: this is

particularly marked in most of those which also exert light-stabilising
effects. Primary antioxidants (without heat-stabilising action) are also
used as additives in PVC, either incorporated individually or as
constituents of composite commercial stabiliser systems. These additives are typically phenol derivatives (with sterically protected phenolic
OH groups, popularly known as 'hindered phenols'). Examples of
commercial products include lrganox 1076* (Ciba-Geigy), and lonox
330t (Shell). Some aromatic amine derivatives are also available.
Incorporation is usually at low-fractional phr levels.
Of the so-called secondary antioxidants of general interest for
thermoplastics, the ones commonly encountered in PVC compositions
are the organic phosphites (which are not, however, incorporated
mainly in that capacity-see Section 9.4.4 above).
There is no detailed, generally accepted explanation of the
mechanism of operation of antioxidants in PVC (where the major role
of dehydrochlorination in the overall degradation process is a
complicating factor in this respect). However, it appears that the main
ways in which antioxidants act in PVC are analogous to those now
widely regarded as operative in other thermoplastics, notably
polyolefinsy,38,39 In line with this view, primary antioxidants are
essentially scavengers of free radicals, believed to interrupt-by this
type of action-the progress of oxidative degradation, generally
thought to proceed through a free-radical mechanism. 39 Additives with
secondary-antioxidant action, notably phosphites (including organophosphite chelators and dibasic lead phosphite), are able to remove
peroxide radicals and to decompose hydroperoxide groups (which can
act as free-radical initiators in the oxidative degradation process)
converting them to inactive derivatives through chemical reaction.
Since, in PVC, oxidation is both a degradation mechanism in its own
right and a factor increasing the rate of dehydrochlorination (cf.
Section 9.2.1), incorporation of antioxidants can improve the heat
stability of PVC compositions as well as-in many cases and types of
formulation-stability to light. Where they are added individually, and
not introduced as constituents of composite proprietary stabiliser
systems, primary antioxidants may typically be used at levels of about
01 phI.

* Octadecyi 3-(3,5-di-tert-butyi-4-hydroxyphenyi)propionate.

t 2,4,6-Tris(2,5-di-tert-butyi-4-hydroxybenzyi)-1,3 ,5-trimethyibenzene.

294

w.

V. Titow

Some antioxidants, e.g. Irganox 1010* (Ciba-Geigy), can be used in

very low proportions (about 200 ppm) as additives to the polymerisation mixture in the production of PVC polymers, to improve the
polymer's resistance to relatively intense heat treatment and thus
improve the efficiency of heat-stripping of VCM.

9.5.2 UV Absorbers
The cardinal role of UV radiation of wavelengths 290-315 nm in the
photodegradation of PVC polymer has been mentioned in Section
9.2.2 (310 nm is often quoted as the wavelength most damaging to PVC,
and 290-400 nm as the band instrumental in the photodegradation of
plastics generally). Light in the 'damaging' wavelength range excites
the PVC polymer molecules, in the sense of imparting excess energy
sufficient to break bonds in the molecular chains: the free radicals
formed as a result initiate, and participate in, the degradation process,
which is accelerated by the presence of oxygen (cf. Section 9.2.2).
Whilst many heat-stabilisers and antioxidants provide a measure of
protection against photolytic and photooxidative degradation of PVC,
they operate essentially after the process has started (in the case of
antioxidants mainly by disposing of the free radicals formed).
Moreover, they are used up as they exercise their protective functions,
so that the protection is of finite duration. The UV-protective additives
which are frequently included in PVC materials for outdoor use afford
additional and complementary protection, in that they absorb and
dissipate the incident UV radiation essentially before it can initiate
degradation, without themselves undergoing de-activating chemical
changes (see below).
The types of organic compound in widest commercial use as UV
absorbers for PVC compositions are modified benzophenones (especially certain alkoxy derivatives of 2-hydroxy or 2,2-dihydroxy
benzophenone), and benzotriazole derivatives. Proprietary additives of
the first type are exemplified by Cyasorb UV 9, UV 24, and UV 531
(American Cyanamid Co., Polymers and Chemicals Dept and
Cyanamid of Great Britain Ltd); Uvinul D408 (BASF Wyandotte
Corp.); UV-Chek AM 541A (Ferro Corp., Chemical Div.); Carstab
700 (Carstab Corporation). Benzotriazole compounds figure promin* Pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

9 Stabilisers: General Aspects

295

ently in the Ciba-Geigy Tinuvin light-stabiliser range (e.g. Tinuvin P,

320, 326, and 327).
Other organic compounds represented among proprietary UV
stabilisers available for PVC include substituted cyanoacrylates (e.g.
ethyl 2-cyano-3-diphenyl acrylate, cf. also Uvinul N-35 and N-559GAF Corporation), phenyl salicylate (Salol-Dow Cpemical Co.), and
oxalic anilide (Sanduvor VSU-Sandoz).
Polymeric UV stabilisers are exemplified by a polymer of 2,4dihydroxy benzophenone, originally prepared40 with a view to reducing
the ease of diffusional migration of the additive to the surface of a PVC
material (and subsequent loss by volatilisation, leaching and wear)
which may be regarded as a disadvantage of non-polymeric benzophenone UV absorbers. 41
The functional suitability and effectivity of the organic UV absorbers
just mentioned depends on the following combination of properties:
Generally high absorption coefficients for UV radiation in the
'damaging' range and in particular much higher than those of
PVC polymers.
(ii) Ability to re-emit the energy absorbed in the form of UV
radiation as lower-energy IR radiation (i.e. heat), relatively
harmless to the PVC composition.
(iii) Negligible absorption of visible light (so that there is no
appreciable effect on the colour and transparency of the host
PVC composition).

(i)

It is because of (i) that the organic UV stabilisers exert their effect at

relatively very low incorporation levels, typically between 02 and
08 phr. In most cases the degree of UV absorption increases with
concentration within the useful range. However, the protective effect is
also known to be dependent on the thickness of the PVC material, in
that-for the same concentration of stabiliser-it is markedly less in
fine fibres, very thin films, and surface layers of thicker products. This
phenomenon accords with the reported finding 42 that-at a given
stabiliser concentration-the amount of UV radiation reaching a point
in the substrate drops exponentially with the distance of the point from
the material's surface. These facts are in line with the expectation that
the degree of obstruction of the path of an incident ray by particles or
molecules of evenly dispersed stabiliser (i.e. the probability that one or
more particles or molecules will lie directly in the path) should increase

296

W. V. Titaw

fairly sharply with distance into the material: interaction of the radiation with the PVC material itself would also be a factor progressively
reducing the amount of radiation with distance of penetration. *
Note: The validity of this explanation is not affected (and is in fact
indirectly supported) by the frequently cited observation42-44
that the protective effects of two other kinds of additive with
light-stabilising action-viz., phenolic antioxidants, and the
nickel complexes used mainly in polyolefins-are independent
of material thickness. Neither of these two types of stabiliser
interacts with UV radiation. As has been mentioned, phenolic
antioxidants are essentially scavengers of free radicals. The
nickel complexes are known as 'quenchers' because they
de-activate, evidently by resonant energy transfer, some
groups in the polymer chain (e.g. carbonyl groups formed in
polyolefins in the course of photochemical degradation) which
have become 'excited', i.e. raised to a higher energy level by
absorption of UV radiation (and thereby primed to promote
chain scission).42,43 Thus both types of stabiliser act on
chemical species formed as a result of absorption of UV
energy by the polymer (i.e. only after this has already taken
place), so that, as would be expected, the only locational
factors influencing their operation are the distribution and
concentration of those species in the polymer, in relation to
their own distribution and concentration.

Compatibility with the rest of the PVC composition, and any

interactions that may occur, are considerations as relevant in the case
of UV absorbers as they are for any other formulation constituent. The
following practical points may be mentioned in this connection. Joint
use of organic UV absorbers with antioxidants can enhance the effect
of both in many PVC compositions. Their use in conjunction with a tin
carboxylate stabiliser (dibutyltin maleate) has been claimed to have no
beneficial effect on stability in outdoor exposure, and even to impair it
* In all materials the extent of degradation by light, and weathering generally,
is also dependent on thickness for purely geometrical reasons, in that whilst the
surface is the most directly exposed to attack, and therefore the material of the
outermost surface layer suffers the earliest and most extensive degradation,
that material will also represent an increasing proportion of the total as the
overall material thickness is decreased (the surface-to-volume ratio is
increased) .

9 Stabilisers: General Aspects

297

in some cases. 45 Some organic UV absorbers can form metal complexes

with certain metal-based stabilisers, giving rise to undesirable colour in
the PVC material, as in the following cases:
-Yellow coloration (overall or in spots) can develop, in the
presence of alkali, in compositions (especially flexible compounds)
stabilised with BalCd or BalCd/Zn systems in conjunction with
certain benzophenone or benzotriazole UV absorbers (normally
only those containing phenolic hydroxyl groups which are
'unhindered', i.e. not sterically protected and thus available to
participate in complex-formation): the alkalinity may be introduced
by the heat stabiliser system (e.g. some BalCd stabilisers, although
neutral versions are widely available), or where the PVC polymer
is an alkali-prestabilised emulsion resin, or adventitiously from
some external source.
-Pink to mauve colour can arise where a benzotriazole UV
absorber and a thiotin stabiliser are used together.
Some dihydroxybenzophenone compounds can develop a yellow colour
in the presence of nitrogen oxides (which may be produced in the
burning of gas, coal, or oil, or when air passes over incandescent
wires). This phenomenon is similar to the 'gas-fume fading' long
known to occur in man-made fibres dyed with aminoanthraquinone
dyes and certain others. 46-48 However, the alkoxybenzophenones,
benzotriazoles and salicylates used as UV absorbers in PVC are not
normally susceptible. Some UV absorbers can interfere with fluorescent
colourant effects.
Where non-toxicity is a consideration, selection of organic UV
absorbers should be made in the light of advice from the suppliers and,
if relevant, also from the appropriate authorities (cf. Chapter 7,
Section 7.12 and Chapter 12, Section 12.9).
Carbon black and titanium dioxide, widely used and important as
pigments for plastics, have a light-stabilising effect on many polymers,
including PVc. Because of their particulate nature, and their mode of
action, they are often referred to in this context as 'screening agents',
'screeners' or 'light screens'. Each functions as a physical barrier to
radiation, both UV and visible. Carbon black absorbs the radiation
over both these wavelength ranges and, like the organic UV absorbers,
emits the energy in the IR region: it is also believed to act as an
antioxidant by capturing free radicals (cf. Chapter 8, Section 8.4.3):
selected fine-particle grades should be used, typically at a few phr.

298

w.

V. Titow

Titanium dioxide also has some UV absorption but its screening action
is principally due to reflection and scattering of radiation (IR, visible,
and UV). This mechanism is less efficient than that of carbon black,
and higher loadings are needed (typically 5-15 phr) for appreciable
effect. It is self-evident that the use of both these pigments as light
stabilisers is ipso facto restricted to opaque compositions (and only
black ones in the case of carbon black).
Zinc oxide is another particulate, inorganic screening agent which
may be considered for those PVC compositions that are not too
zinc-sensitive (cf. Section 9.4.3 above): it is thought to benefit
synergistically from the presence of certain antioxidants, to the point
where suitable combinations of this kind can be more effective than
normal amounts of organic UV stabilisers.
As has been mentioned, UV absorbers incorporated in PVC
compositions are less effective in the outermost surface layers than in
the body of the products; yet it is the surface which needs the most
protection, as it is the most directly and extensively subjected to
photochemical attack on exposure. The problem is particularly
relevant in transparent compositions for outdoor service, in which UV
absorbers are widely used: surface application, rather than internal
incorporation of the stabiliser, can be a useful solution in some cases.
PVC sheeting, for example, may be surface-coated with a lacquer
containing a relatively high concentration (say 1-3%) of the stabiliser:
such lacquers, based on vinyl copolymer resins (cf. Chapter 24), acrylic
resins, or other binders, are available from commercial sources. This
approach can offer cost and protection efficiency advantages in suitable
circumstances. 49 Surface absorption (from solution) of a UV stabiliser
(MPB*) has also been claimed to give good results. 49
Such physical factors as the degree and uniformity of dispersion,
ease of migration through the composition, extractability, and
volatility, influence the performance of any additive in PVC: a useful
discussion of their effects on the performance of stabilisers, including
UV stabilisers, has been published by Allara. 23
Antioxidants, UV absorbers and screening agents are available
individually, as composite light-stabiliser systems, and as components
of polyfunctional 'single-pack' additive combinations. The individual
stabilisers or stabiliser systems are also supplied as ready-made or
* 2-(2'-Hydroxy-5' -methylphenyl)benzotriazole.

9 Stabilisers: General Aspects

299

custom-compounded concentrates in PVC polymer or other appropriate

carriers. Many sources are given in the publications mentioned in
Section 8.5 of Chapter 8.

9.6 MAIN MODES OF STABILISER ACTION

The subject of stabilisation of PVC is closely interrelated with that of
its degradation. Both have been investigated and discussed for a long
time, and various mechanisms have been put forward to account for
the observable effects of stabilisers. In the present state of knowledge
none of these mechanisms can be regarded as fully proven. However,
those mentioned below in connection with what might be termed the
major stabilising actions are based on a substantial body of evidence,
and enjoy considerable support. These actions, major in the sense of
their direct bearing on the factors believed by many to be of principal
significance in the degradation of PVC (see Section 9.2), are:
neutralisation of hydrogen chloride evolved in the course of dehydrochlorination; elimination of labile chlorine atoms from the polymer
chain (by substitution with more stably attached chemical groups); and
antioxidant action (mainly through inactivation of free radicals). Other
actions and mechanisms postulated in explanation of the effects of
some stabiliser types and systems are mentioned, as appropriate, under
the relevant sub-headings further on in this section.
9.6.1

Lead Stabilisers

Neutralisation of nascent hydrogen chloride is thought to be the main

mechanism whereby these stabilisers exert their effect. 7,9,11 This view
accords with their basic nature, their mode and rates of reaction with
HCI,5o and the formation of lead chloride during heat treatment and
service of lead-stabilised PVC compositions. Unlike the chlorides of
some other stabiliser metals, this salt does not promote degradation of
PVC polymer. The known fact that, in general, the performance of
lead stabilisers is not much improved by the presence of co-stabilisers
(especially the chelators, or metal carboxylates used as components of
mixed-metal stabiliser systems-see below), is probably associated-at
least to some extent-with the inactivity of lead chloride in this sense,
since de-activation of stabiliser decomposition products and impurities
is believed to be one of the main functions of such additives.

300

W. V. Titow

9.6.2 Organotin Stabilisers

These stabilisers are believed to function in several ways.
Dialkyltin chlorides have been identified among the volatiles evolved
in the heat-processing of PVC compositions stabilised with dialkyltin
compounds. A corresponding drop in the tin content of the
compositions has also been observed, increasing with time of
treatment. 7 These observations are consistent with the binding of
hydrogen chloride by the stabiliser, presumably in accordance with the
general reaction:

(4)
where A is a mercapto or carboxylic acid substituent (see Section
9.4.2(a. Like lead chloride, the dialkyltin chlorides do not impair the
stability of PVC polymer.
Work with model compounds (employed as PVC polymer
analogues)7,51 has shown that organotin stabilisers can replace labile
(allylic) chlorine atoms with their own ligand (A) groups, whereby
the stability of the thus substituted compound is significantly increased.52-54 The substitution could be either direct,l1 or possibly on
the carbon originally in the 4 position to the chlorine: 7

(5)

or

It has also been suggested7 that organotin stabilisers may be able to

form transitional complexes with 'instability centres' in the polymer.
It would appear that free-radical scavenging, proposed in the case of
some mercaptides,l1 may be among the modes of action of organotin
stabilisers.
Colour developed in PVC compositions as a result of heat-processing

9 Stabilisers: General Aspects

301

may be reduced, in some cases substantially, by post-treatment

(re-compounding) with an organotin stabiliser. This indicates that yet
another way in which these stabilisers perform their functions is to
react with chromophoric groups. The chemical transformations
suggested to account for the reduction of colour include reaction of the
stabiliser with any carbonium groups (cf. eqn (2)) formed in the course
of PVC degradation,? and with double bonds in conjugated systems.
The latter type of action would interrupt the conjugated double bond
sequences (thus reducing colour due to their presence) and also
increase the general stability of the polymer chain: two mechanisms
proposed for this are noteworthy. According to one, the carboxyl or
mercapto compound generated by the organotin stabiliser in its
reaction with HCl (cf. eqn (4)) may react with (presumably by adding
across) a double bond in the polymer chain: 7 ,1l
H H

~C=C~

+ HA -

H H

~C-C~

H A

(6)

Some support for the idea of this kind of effect is provided by an

experiment in which the colour of a heat-affected PVC material was
considerably reduced by re-processing with 1% ot the isooctyl ester of
thioglycollic acid (even though this entailed a further heat treatment at
180C).7 The other possibility suggested7,1l is that, where the
regenerated compound (HA) is a maleic acid derivative, it may enter
into a Diels-Alder reaction 55 with a diene section of the polymer
chain, thereby eliminating a double bond, and introducing into the
chain a relatively stable ring structure:

I
H~
HC

Hn-COOR
H6 + HC-COOR II

Hi

CH
HC/'

'cH-COOR
H~
tH-COOR
. . . . . . C H/

(7)

The fact that dibutyltin maJeate is a better heat stabiliser than the
corresponding succinate (which would not undergo a Diels-Alder
reaction) has been cited7 in support of this possibility.

302

w.

V. Titow

9.6.3 Other Metal-based Stabilisers

Displacement of labile chlorine atoms in the PVC polymer chain by
more stable groups appears to play an important part in the action of
the metal compounds of acids (salts, soaps, 'complexes', and mercaptides-see Section 9.4.3(a) above) used as stabilisers for PVc. Work
on model compounds has shown that such stabilisers can substitute
their acid groups for allylic (but apparently not tertiary) chlorine. 56
Substantial evidence that the acid groups of barium, cadmium and zinc
carboxylates are indeed transferred to PVC polymer in conditions
under which these stabilisers operate, was obtained in the radiochemical and IR-spectroscopic investigations of Frye and Horst. 57 Together
with other reported evidence,l1 these findings suggest a general stabilising mechanism analogous to that of eqns (5) or (5a).
Virtually all the metal compounds under the present heading react
with hydrogen chloride. This reaction is regarded as one of the modes
of their stabilising action. However, some of the chlorides formed,
notably those of zinc and cadmium, strongly promote decomposition of
PVC polymer: thus in these cases the HCI-acceptor action is not
entirely beneficial. As has been mentioned, the mixed-metal systems in
widest use are those combining barium and cadmium compounds, with
or without a zinc component. Some calcium/zinc carboxylate combinations are also popular for non-toxic PVC compositions, and certain
others (see Section 9.4.3). It appears most likely that the stabilising
action of-and synergistic effects in-both these general types of
composite system arise as follows. Chlorides and semi-chlorides (ct.
eqns (8) and (9) below) formed from the cadmium and zinc compounds
in the course of exchange of their acid groups for the labile chlorine
atoms of the PVC polymer (which may well constitute the main
stabilisation mechanism) are converted back to the original compounds
by exchanging the chlorine for the acid groups of the barium (or
calcium*) component of the system. This activity eliminates the harmful
cadmium and/or zinc chlorides, and regenerates the powerful cadmium
stabiliser. Direct reaction of the barium compound (or calcium
compound in Ca/Zn composite systems) with nascent HCI evolved
through dehydrochlorination of PVC polymer, whilst itself yielding a
* The suggestion has also been put forward 58 that in Ca/Zn carboxylate systems
the calcium carboxylate plays a part in the substitution of allylic chlorine atoms
by the carboxylate groups of the zinc compound.

303

9 Stabilisers: General Aspects

relatively innocuous chloride, would restrict similar direct formation of

cadmium and zinc chlorides: any CdCl z or ZnClz actually formed by
this route would also be expected to be re-converted in the way just
mentioned. These regenerative and protective processes should
proceed until all the barium (or calcium) compound has been used up.
Note: After heat treatment of sufficient severity and duration, PVC
compositions stabilised with Ba/Cd carboxylate systems tend
to darken rapidly to an almost black colour, much darker than
that characteristic of normal thermal degradation of similar
compositions without stabiliser. This is consistent with the
expected catalytic effect of accumulation of cadmium chloride, after the regenerative capcity of the barium component of
the system has been exhaused by its total conversion to BaClz.
Acceleration and aggravation of the degradation of PVC
polymer by the presence of CdCl z formed throughout the
material is also the most likely explanation for the well-known
fact that compositions stabilised solely with cadmium compounds darken badly after a relatively short time (cf. Section
9.4.3(a)). Formation and accumulation of zinc chloride
accounts, in an analogous manner, for the rapid, intense
darkening of PVC stabilised with Ca/Zn systems once the
stabiliser is exhausted.

Considering a BalCd carboxylate system as an example, and on the

assumption that the carboxylate group being exchanged for a labile
chlorine attaches itself to the same carbon in the PVC polymer chain
(i.e. that, in this respect, the exchanges of eqns (8) and (9) are
analogous to that of eqn (5) and not (Sa)), the above explanation is
illustrated by the following reactions: 7 ,1l,59,60

~C~

I
CI

~C~

~]

/OOCR
+Cd
--+
'-.....OOCR

/OOCR
+Cd
--+

~l

~C~

60CR

+ Cd

/OOCR

(8)

'-.....0

(9)

304

W. V. Titow

Cd

. . . . . . 'OOCR
. . . . . . CI

. . . . . . .O OCR
+ Ba
. . . . . . OOCR

OOCR
Cd"""""'"
+
'cl

Cd

. . . . . . .Cl
............

CI

OOCR

Bi

--+

"cl
. . . . . . .O OCR

+ Ba

............

. . . . . . .O OCR
. . . . . . .O OCR
Cd
+Ba
(10)
. . . . . . O OCR
'cl
. . . . . . .O OCR
. . . . . . .Cl
Cd
+B,
.........OOCR
CI
. . . . . . .O OCR

------.OOCR

--+ elf

OOCR

. . . . . . .Cl

+ Ba

............

(11)

(12)

CI

In eqns (8)-(12) the R group of the original cadmium compound may

be the same as, or different from, that of the barium compound.
The main functions of an epoxy compound when used as
co-stabiliser with mixed-metal stabiliser systems are thought to be
direct binding of nascent HCI and assistance in the transfer of labile
chlorine atoms to the main stabiliser (see below).
Auxiliary mechanisms thought by some authors to be operative in
the stabilisation of PVC with metal-compound stabilisers include
catalytic oxidation of chomophoric groups,7 and 'control of the
dehydrochlorination process' .61
9.6.4 Organic Stabilisers, Antioxidants, UV Stabilisers

The ways in which these additives are believed to operate have been
indicated in Sections 9.4.4 and 9.5. The following additional points
may be mentioned here.
Epoxy compounds are widely thought to bind HCI through their
oxirane groups: 7 ,9,11,62

-CH-CH- + HCI "0/

-CH-CHI
I
OH CI

(13)

These groups are also believed to participate in the role the epoxy
co-stabilisers may play in the transfer of HCI to the main stabiliser,62
and the exchange of the PVC polymer's labile chlorine atoms for
stabiliser groups. 11
The antioxidant action attributed to organic phosphite co-stabilisers
(cf. Section 9.4.4) may operate through the following kind of reaction

9 Stabilisers: General Aspects

305

with free radicalsY

~CH-CH2~

CI*

+ P(OR)3

----+ ~TH-eH2"""""

(14)

O=P(ORh + RCl

However, the function with which these additives are most widely
credited, and after which they are known as 'chelators', is the
formation of complexes with the metal chlorides arising as by-products
of stabilising reactions (see above). This 'complexing out' reduces the
deleterious effect of the chlorides on the PVC polymer, and also
improves the clarity of transparent PVC compositions (ct. Section
9.4.4). The mechanism of operation of po/yo/ co-stabilisers used, like
the phosphites, with mixed-metal stabilisers (cf. Section 9.4.3), is
believed to be similar.
9.7 SOME GENERAL EFFECTS AND COMMON FAULTS
IN STABILISED COMPOSITIONS

Some general effects of stabiliser-associated factors upon the properties of PVC compositions are summarised in Table 9.2.
The most common general faults to which certain stabilisers may
give rise in PVC compositions are plate-out and sulphide staining.
Both have been mentioned in passing: their principal features may be
summarised as follows.
9.7.1 Plate-out

This is the build-up of sticky deposits on the working surfaces of

processing equipment, which can occur in all the principal processes
(extrusion, calendering, moulding) as well as in some ancillary
operations (e.g. milling, embossing). The exact causes of plate-out are
still not fully elucidated, * but much practical experience is available
* Some interesting direct evidence has been produced by Lippoldt's78 investigation into the composition of plate-out deposited on an extruder die spider from
a tin-stabilised PVC compound containing-among the other constituentsthree types of lubricant (including Ca stearate), CaC0 3 filler, and Ti0 2
pigment. The organic material content of the deposit was found to be about 12
times that of the 'parent' compound. Calcium stearate lubricant and the tin
stabiliser were present (with the stearate: stabiliser ratio increased somewhat
over that of the compound), as well as a substantial proportion of resinous
material described as 'the result of accidental PVC particle contamination',
some pigment and filler. A tentative mechanism for plate-out formation has
been formulated by the author on the basis of the results (cf. pp. 687-8).

Selected octyltin compounds. Ca/Zn

systems (with permitted costabilisers) .
Organotin stabilisers. Selected Bal
Cd systems (with epoxy and phosphite co-stabilisers). Selected Cal
Zn systems (for non-toxic, clear
compositions).
Organotin stabilisers give best results. Some metal soaps can cause
problems.
In general, stabilisers should be
checked for effect on viscosity.
Liquid stabilisers should be used
for reduction (or least increase).
The pH of the stabiliser may have
an effect.

Processing and
service

Service (electrical insulation)

Service

Service

Heat welding

Processing

Lubrication

Electrical properties

Non-toxicity

Clarity

Weldability

Paste viscosity

In general, liquid stabilisers tend to

lower the softening point of the
composition.
Suitable choice and balance of the
stabiliser/lubricant system very
important, especially in uPVc.
Lead stabilisers are the usual choice
(ct. Section 9.4.1).

Relevant stabiliser types,

factors, and effects

Service

Significant
in:

Softening point
(uPVC)

Property

ct. Chapter 22.

Clarity is influenced by the refractive indices and mutual compatibility of all

components of the PVC composition
concerned. NB In damp conditions
cloudiness can develop in some Ba/Cdstabilised clear compositions.

decoration and heat-sealing properties

may be affected by stabiliser exudation.
Properties important in this connection
are high resistivity, low power factor
(esp. for high-frequency cables) and
high electric strength.

ct. Chapter 11, Section 11.2. NB Surface-

This consideration can be important with

many rigid PVC products.

Remarks

TABLE 9.2
Some General Effects of Stabilisers on Properties of PVC Compositions

:-::::

;:E:

...,

9 Stabilisers: General Aspects

307

relevant to its incidence and prevention. Thus it is known that the

nature and amount of the stabiliser is a factor, and that other
components of the PVC composition-especially the lubricant (with
particular reference to its balance and interaction with the stabiliser)can also playa significant part. Inter alia, plate-out can be associated
with the simultaneous presence of calcium compounds with those of
heavy metals (Cd, Zn, Ti, Mn, Pb).63 On the other hand it is known
that PVC compositions based on emulsion polymers are less prone to
plate-out than those in which the polymer is a suspension resin, and
that addition of emulsion resin to a composition of the latter type can
sometimes alleviate the problem. Incorporation of small amounts of
fine-particle pigments or fillers (e.g. titanium dioxide, precipitated
calcium carbonate, at 2-5 phr) can also be helpful, especially where the
plate-out is relatively light and there is reason to think that it may be
due to an imbalance of the lubricant or lubricant/stabiliser system.
Some manufacturers supply special grades of silicates as anti-plate-out
additives (e.g. Gasil 35-Joseph Crossfield & Sons Ltd, England).
The effect of fine-particle additives is thought to be due to retention,
by adsorption, of the compound responsible for plate-out deposits, and
to a direct 'scrubbing' action on the working surfaces as they come into
contact with the composition. 64 Pronounced plate-out can occur with
some compositions stabilised with lead and other metal soaps. Those
stabilised with organotins and certain liquid mixed-metal combinations
(and containing suitable, properly balanced lubricant systems) are the
least prone to this trouble.
A colour-transfer test may sometimes be useful as a means of
checking the plate-out tendency of a PVC composition. The principle
of such tests is that a test mix, made up to the particular formulation
and containing additionally a small amount of an appropriate
colourant, is run in suitable laboratory-scale equipment (e.g. a mixer;
roll mill) under conditions relevant to the intended full-scale processing
of the composition. The colourant should be one that will enter and
colour the plate-out deposit-a colourant supplier should be consulted
regarding the choice. After the test run the mix is completely removed
and a white scavenging mix run in the equipment. The plate-out from
the test mix is assessed on the amount of colour picked up by the
scavenging composition.
One variant of this kind of procedure is exemplified by the following
recommendations. 7

308

W. V. Titow

Colourant for test mix: Sico Red WRC* (0,1 weight % on the total
mix). Run the test mix for 7 min at 165C (without friction); sheet and
remove from the mixer. Run the scavenging mix for 3 min: remove and
judge the degree of red staining (related to the amount of plate-out) by
comparison with an unused portion of this mix. For increased accuracy
of assessment, the comparison specimens may be moulded into sheets
of identical size. Constant, uniform conditions are essential; in
particular the mixer should be in thermal equilibrium (achieved by
running for some hours prior to the test): the tests should be run by
one and the same operator as a continuous series, and each series
completed on the same day. The recommendations include the
following formulation for the scavenging composition.

100
PVC polymer: So/vic 239 (Solvay et Cie. SA, Belgium)
Stabiliser: Irgastab OM 18 (Ciba-Geigy) (dibutyltin maleate) 05 phr
Epoxy co-stabiliser: Reop/ast 39 (Ciba-Geigy)
50 phr
Plasticiser: DOP
300 phr
Lubricants: Irgawax 330 (Ciba-Geigy) (stearic acid)
08 phr
Irgawax 331
08 phr
White pigment: Kronos A (Titangesellschaft mbH,
West Germany) (Ti0 2-anatase)
15 phr
9.7.2 Sulphide Staining
PVC composItions contammg stabilisers (or other additives, e.g.
pigments) based on cadmium or lead can develop colour on contact
with sulphur compounds. This phenomenon is known as sulphide
staining. In cadmium-containing compositions the colour is yellow,
caused by the formation of yellow cadmium sulphide (CdS). Compositions incorporating lead compounds may tum black-in patches or
overall-due to the formation of black lead sulphide (PbS), or
sometimes dark brown ranging to black: this is probably attributable to
the presence of the reddish-brown lead sulphochloride, Cl.Pb.S.Pb.Cl.

Note: Zinc-containing additives do not give rise to dark sulphide

staining (zinc sulphide is white), and indeed the zinc
component of a Bd/Cd/Zn stabiliser may retard colour
development. However, turbidity may develop in clear
compositions if enough ZnS is formed (see also Table 9.3).
* BASF (originally a trade name of the Siegle company, West Germany).

Organic
sulphur - free

Organic
sulphur- ctg

Ca/Zn

Ba/Cd/{Zn)

Tin carboxylate

Thiotin

Lead

Organic
sulphur - free
Ca/Zn

Sulphide formation,
with visible effects
as indicated

No effect

Tin
carboxylate

Ba/Cd/{Zn)

Lead

TABLE 9.3
Visible Manifestations of Interaction of the Main Types of Stabiliser in PVC Compositions

'"'0;"'

'"~
a

<:>-

'0

310

w. v.

Titow

The sulphur compounds responsible for sulphide staining may be

encountered by the PVC as atmospheric pollutants, or as components
of materials (e.g. rubber) with which the PVC may come into physical
contact: they may also be present in the composition itself as its regular
components. Although simultaneous use of sulphur-containing additives with cadmium or lead compounds (e.g., say, thiotin or antimony
mercaptide stabilisers in conjunction with lead or cadmium ones) is
avoided in formulating practice, it can occur in the processing of PVC
scrap of different or uncertain origins. Where fresh stabiliser is to be
added to a batch of scrap material of unknown composition to
'post-stabilise' it for processing and service, or where two or more such
batches are to be mixed in processing, the possibility of internal
sulphide staining (cross-staining) should be checked beforehand (even
for black material). A simple compounding test, e.g. on the mill for
about 10 min at 180C, is regarded as satisfactory in most cases in
practice,64 and easier than analysis for heavy metals and sulphur.
Where the scrap material is to be post-stabilised with a lead-,
cadmium-, or sulphur-containing stabiliser, the test should be carried
out on a sample to which about 3% by weight of the stabiliser has been
added, and the sample then examined for colour development.
Absence of discoloration will indicate that the stabiliser is 'safe' for use
with the material: the appearance of colour (or milky haze in
transparent materials) provides not only evidence of interaction but,
from the nature of the manifestation, also clues for the choice of
suitable alternatives (see Table 9.3). The compounding test should also
be carried out where scrap from different sources is to be processed
with or without post-stabilisation.
Several standard tests are available for susceptibility of PVC
compositions to sulphide staining through external contact. BS 2739:
1975 (Appendix D) prescribes immersion (for 30 min) of a sheet
specimen (50 mm 2) in a freshly prepared solution of 55 g of hydrated
sodium sulphide (NaS.9H 20) in distilled water (1 litre), acidified with
concentrated hydrochloric acid (30 ml). In the method of ASTM D
1712-65 (1977) thin sheet specimens (preferably about 100 mm by
13 mm) are half-immersed (for 15 min) in a saturated solution of
hydrogen sulphide prepared by rapidly bubbling freshly produced H2S
gas through 10~150 ml of water for about 5 min. The method of DIN
53378-1965 involves exposure of film specimens to gaseous H 2S
(continuously generated by reaction of sodium sulphide with sulphuric
acid). In all three methods any staining is detected visually, and its

9 Stabilisers: General Aspects

311

intensity determined, where relevant, in terms of colour change in

comparison with untreated material or/and with the aid of the
appropriate standard grey scale for stain assessment (BS 2663; DIN
54001; see also Chapter 12, Section 12.6).
Note: The standard ASTM test method for the staining of PVC by
rubber-compounding ingredients (ASTM D 2151-68 (1977}ct. Appendix 1, Section 3.2(c) (ii)) caters for staining resulting
from actual migration of such compounds (especially certain
antioxidants) into PVC, whereupon colour may develop either
immediately, or after exposure to heat or UV radiation.

The development of milky cloudiness when a clear PVC composition

incorporating zinc in the stabiliser system is in contact with some
sulphur-containing gases or materials (see above, and Table 9.3), can
cause varying degrees of loss of transparency. This effect can be
quantitatively assessed with the aid of the standard methods of ASTM
D 1746 or DIN 53490. For a rough, qualitative assessment a simple
comparison may be made by viewing, in good light, a specimen of the
clouded compound, in thin sheet form, laid on a white page carrying a
few lines of sharp black print, side-by-side with a similar specimen of
the original (unaffected) material.
9.8 TESTING AND EVALUATION OF STABILISER
EFFECTS
9.8.1 Concept of Stability in Processing, Service and Tests
PVC is subject to degradation by heat and light in ways outlined in
Section 9.2. The ease and rate of degradation vary with the
composition and the conditions of treatment or exposure. Therefore,
in the practical context, the stability of a PVC composition may be
thought of, and measured, in terms of the length of time before
perceptible and/or measurable signs of degradation develop, or reach a
certain level, under the relevant conditions. In such terms the
well-known fact that the stability of unstabilised PVC is very poor can
be quantitatively related to the ease and rapidity of its degradation on
exposure to even relatively moderate heat or irradiation with light
containing a UV component.
Note: With regard to the effects of heat processing, it may be noted
that the activation energy for degradation of PVC polymer

312

W. V. Titow

(cf. Section 9.2.1) is considerably lower than the specific

energy required to generate a melt. 16 This alone would
necessitate stabilisation for melt processing.
Incorporation of suitable stabilisers may greatly increase the time for
the onset of appreciable degradation even under comparatively severe
conditions of processing and/or service. However, no practicable
amount of stabilisation can entirely prevent degradation where the
conditions are severe enough to promote it: the fact that primary
stabilisers are used up in reactions through which they exercise their
protective effects is a cardinal factor in this situation.
For practical purposes the stability of PVC materials may be
conveniently defined and compared in terms of stability time, or
induction time for degradation. The first of these is the length of time
up to the point when, under a particular set of conditions, selected
manifestations of degradation reach a level set as the acceptable
maximum: in tests the conditions are usually those of static heating, or
mechanical working with heating, of the material at a suitable,
elevated temperature, or exposure to light or weathering (see Section
9.8.2). The induction time is the period after which, in analogous
circumstances, the rate of degradation (as reflected in the manifestation selected for assessment) changes from an almost negligible to a
relatively high value. The definitions of stability time and induction
time are illustrated by the curve of Fig. 9.3.

r-----------------Maximum

acc~ptabl~ l~v~1

of

d~gradation

x
~
S

I
I

2ro

I
I
I

~
~

Tim~

Fig. 9.3

Induction time (tj) and stability time (ts) of a PVC composition

subjected to heat treatment: schematic representation.

9 Stabilisers: General Aspects

313

As mentioned in Chapter 12 (Section 12.3), the extent and/or

progress of degradation in PVC may be evaluated by determining
changes in selected physical properties (e.g. tensile strength, modulus),
or by various kinds of analysis (differential thermal, thermogravimetric, IR, chemical). However, for the purposes of direct
evaluation or determination of the effects of stabilisers, the degree and
rate of degradation are most often measured in terms of the two main
manifestitations of dehydrochlorination, viz. the development of
colour, or the amount of HCI evolved in the PVC composition.
Note: In stability tests in which colour development is used as an
index of degradation it may be relevant to make a distinction
between 'time to colour' and 'time to black'. 65 Blackening of
the composition, indicating extensive degradation, may develop gradually, or occur rapidly as a result of accumulation
of chlorides of stabiliser metals which can catalyse decomposition (e.g. CdClz-ef. Section 9.6.3).

Two concepts of practical significance in connection with the stability

of PVC in processing (and to some extent in service, especially at
elevated temperatures) are the heat life and heat history of a PVC
composition. The heat life is the period during which, under given
conditions (or successive sets of different conditions, as e.g. in hot
compounding followed by heat-processing into a product) the composition remains substantially free of significant degradation. Thus the heat
life is closely represented by the stability time (or the induction time,
depending on the way in which 'significant degradation' is defined),
and like the stability (or the induction) time it will be the shorter the
more severe the heat treatment(s) experienced, or the less effective the
stabilisation-see Figs 9.4 and 9.5. Implicit in the concept of heat life is
recognition of the fact, highly important in practice, that heat
treatment-or a number of consecutive heat treatments--of a given
nature, intensity and duration, Le. a certain 'heat history', may be
considered to use up a proportion of the heat life: the remainder then
represents the residual, shorter heat life still available. In this way the
extent and severity of its heat history determines how close a PVC
composition is to the point of significant degradation, Le. to the limit
of its total heat life. In the schematic illustration of Fig. 9.6 the three
curves represent the heat life (total stability time) of the same PVC
composition under the conditions of three different treatments (A, B
and C) of varying severity (A> B>C). If the composition is initially

314

X
eI .... - - -

"

W. V. Titow

_ ~a~i~u~ ~,=~t~b~ -.!.q::q!...O!..d!:g~~~on

.S
c:

:;:;
C1I

~
L.

Cl

eI

Timq--_.

Fig. 9.4 Effect of stabilisation (or severity of treatment) on the stability time
(t) of a PVC composition: schematic representation. A, No stabiliser (or most
drastic conditions); B, moderately effective stabilisation (or medium-severe
heating); C, highly effective stabilisation (or mildest treatment).

100
1

2
3

....
10

23

22

21

1/& , K- 1 x 103

20

Fig.9.5 Arrhenius plot (ct. Section 9.2.1) of log stability time (ts> minutes) as
a function of the reciprocal of absolute temperature (1/8) for three PVC
compositions of increasing stability (1) 2> 3): schematic representation (but
values roughly representative of some uPVC compositions, with HCl emission
as the degradation index).

9 Stabilisers: General Aspects

.g

.S

Maximum
accczptablcz

+----- --- Iczvczlof

dczgradation

"
~

01
(#

:
I

j--- -- -- -

I
I

315

---

I
I

tA

tT

Timcz

Fig. 9.6 Residual heat life (stability time), tA - tT, tB - tT , tc - tT, of PVC of
the same composition, processed under conditions of increasing severity
(A> B > C) after an initial heat treatment (T): schematic representation.

subjected to a heat treatment (say melt compounding), under

conditions A, or B, or C, or some other conditions, which uses up the
amount of its heat life corresponding to the initial portion tT of the
stability time, then the residual heat life (all that remains available
before significant degradation sets in during subsequent heat treatment) will be represented by t A - tT for conditions A, t B - tT for
conditions B, and tc - tT for conditions C.
9.8.2

Heat Stability Testing

Apart from their role in development and research work, heat stability
tests on PVC compositions and products are important in the practical
contexts of processing and service. Evaluation of the suitability and
effectivity of stabilisers, and stabiliser/lubricant systems, in protecting
PVC against degradation both under processing conditions and in use,
is one of their main applications. Others include direct assessment or
prediction of the stability of PVC compositions in various circumstances of treatment and/or exposure, with reference-where relevantto the effects of formulation components and/or heat history in this
regard. Investigation of PVC material failures, and 'trouble shooting'
generally, are related areas in which stability tests can be helpful.
A stability test normally comprises a suitable treatment of the PVC
material to induce degradation under controlled conditions, followed
by detection, or quantitative determination, of a significant level of the

316

W. V. Titow

manifestation of degradation which is being used as the degradation

index in the test. The determination methods employed in such tests
can also be applied to PVC materials degraded by means other than
the test treatment (e.g. in actual processing or service), but reference
to a relevant standard (e.g. results of appropriate calibration tests;
specimens exemplifying the effects of actual service in known, relevant
conditions) will normally be necessary to characterise the extent of any
degradation detected.
Stability tests are of two general types: dynamic and static. The
methods often used in the evaluation of stabiliser effects are
summarised, in a general way, in Table 9.4. Some details of standard
tests are given in Table 9.5.
In dynamic tests an appropriate weight of the PVC composition is
worked at an elevated temperature in sui~able equipment, typically a
torque rheometer, internal mixer, extruder, or mill. Stability is
assessed either by periodically checking the effect used as the
degradation index (commonly colour development in the material),
or~specially in a torque rheometer-determining the stability time as
the period from the commencement of test processing to the ultimate
rise in melt viscosity (and hence in torque) marking the onset of
substantial degradation ('decomposition point'). By their nature
dynamic tests are primarily relevant to the effects of processing on
PVC compositions. Indeed, the test equipment, temperature, and
running conditions are often chosen with a view to relating the test
results to a particular process. Because PVC cannot be processed
without stabilisers, dynamic methods are not suitable for the
determination of the heat stability of PVC polymers alone.
In a static test, the test treatment essentially consists in heating
specimens of PVC material at the test temperature. The specimens are
often pieces of sheet of standard size, but they may also be standard
weights of powder or pellets of PVC polymer or composition.
Note: Where the sheet from which specimens are cut for the test is

specially prepared, e.g. on a mill or by pressing, the

preparation should be carefully standardised, so that variations in heat history do not arise to affect any comparison of
results. The relevant standard test specifications (cf. Table
9.5) usually include the method and conditions of specimen
preparation. In the absence of specific recommendations the
following general method may be used 7 for preparing

9 Stabilisers: General Aspects

317

specimen sheet on a laboratory mill (35 x 15 cm), from about

100 g of composition.
uPVC: Process for 5 min at 180C into a sheet about 03 mm

thick.
pPVC: Process for 5 min at a temperature between 165 and

170C (depending on nature and amount of plasticiser) into a sheet about 05 mm thick.
The heating equipment may, typically, be an air-circulation oven,
containers for the specimens immersed in a heating bath, or-in some
cases-a press with suitable arrangements for heating and cooling the
platens. Stability is determined in terms of heating time to reach a
certain level of the degradation index used in the test (Le. stability
time in those terms): this may be the first appearance, or attainment of
a certain degree, of discoloration in the composition (ct. the example
below). Colour change of an indicator in continuous contact with
volatiles evolved by a specimen, or the other effects mentioned in
Tables 9.4 and 9.5, may also be used.
Note: A test method which can give rapid results, and in which the

degradative test treatment is combined with measurement of

induction time, is differential scanning calorimetry (DSC).
This may be applicable where the degradation process is
exothermic, so that on the usual DSC plot of heat flow rate
versus time the period Of stability (induction time) at the
heating temperature used is represented by a flat portion of
the curve, and a subsequent drop marks the end of that
period. 68
The results of static tests are more relevant to the effects of heat in
service than in processing of PVC materials. However, because the
equipment required and the test procedures are generally simpler than
those of dynamic tests, static tests are sometimes used also to obtain
indications of the likely stability in processing, albeit correlations with
actual process effects (or with those of dynamic tests) may not be very
good. Oven-heating involves free access of air to the PVC specimens,
whilst in the heating-bath methods the containers housing the
specimens can usually be continuously swept with air (cf. Table 9.5).
Thus either of these two methods may be employed where accessibility
to air is relevant to the purpose of the test, and their results are
sometimes taken as an indication of the PVC material's likely stability

Static

Colour change (to blue) of a

Congo Red paper, or universal indicator sensitive at
about pH 3, in contact with
volatiles evolved during the
test.
Reduction of colour of Ultramarine Blue incorporated in
the test specimens, continuously monitored (by
photo cell) during heat treatment in oven. Onset of significant degradation (end of
stability time) indicated by
sharp drop in blue-light
reflectance curve--cf. Fig.
9.8.

Colour change

Colour change

Evolution of HCI

Evolution of HCI

Static

Both static and

dynamic

Inspection after set time, or at

intervals, and comparison
with standards.

Method, and/or
stability criteria

Test treatment
for which
determination
method
is suitable

Visual

General means

Determination of degradation effects

Development of
colour in PVC
material

Manifestation
of degradation
detected or
measured

Nelson's Test: Ref. 67

ISO/R 182 (under revision);

BS 2782, Method BOA:
1976; DIN 53 381 Part 1

Static: ISO 305; ASTM D

2115; DIN 53 381 Part 2
Dynamic: Refs 7,65,66

References and remarks

TABLE 9.4
Heat Stability Tests Relevant to Practical Assessment of the Effects of Stabilisers in PVC

'"

::j

:00::::

00

Titration

Conductivity
determination

Torque-time
plot

Evolution of
HCI

Evolution of
HCI

Melt viscosity rise

with onset of
degradation of
composition in
torque rheometer

Volatiles evolved by specimens

in test treatment passed
through a standard KCI solution. Time for pH (continuously monitored) to drop
from about 6 to about 39
measured as stability time. a
Volatiles evolved by specimens
in test treatment absorbed in
NaOH solution and HCI determined by back titration.
Stability expressed as mg of
HCI evolved per g of sample
during heating period (30
min).
Absorption in water of volatiles
evolved by specimens in test
treatment. Stability time
measured as time for water
conductivity to rise by a
specified figure. a
Stability time determined as
time to reach point of torque
rise ('decomposition point')
on the torque-time graph.
Dynamic

Static

Static

Static

Ref. 66

Introduction of test of this

kind under consideration
for a revised version of
ISO/R 182

ASTMD793

ISO/R 182 (under revision);

BS 2782, Method l30B:
1976; DIN 53 381 Part 3

a Volatile alkyltin chlorides are formed on heating of PVC compositions containing alkyltin stabilisers (cf. Section 9.6).
These can dissociate in aqueous solution, and may thus interfere with HCI determination by conductivity and pH
methods.

pH determination

Evolution of HCI

\(:)

'-0

"<:;'"

{;

:J;.

'";::
'"
il

~
c:J

'"

(;;,

::::0

<:J-

is

v,

320

W. V. Titow

TABLE 9.5 Summary of

Basis of
test

Standard
specijications

Main particulars and features of

Test equipment
and reagents

Test specimens

Temperature

DeterminaISO 305-1976
Glass tubes for Discs of about
As agreed
individual
tion of col14mm dia(consistent
our developspecimens
meter, about 1 with signi(with closely
ment in
mm thick
ficant colour
fitting alumiPVC comdevelopment
position on
nium plug inwithin the test
heating
serts); oil bath
period)
ASTMD2115- Forced-draft
Squares of sheet 177 1C un67 (reapproved oven with aluabout 082 mm less otherwise
1974)
minium foil
thick; side at
agreed
supports for
least 254mm
PVC specimens
(on oven racks)
DIN 53 381,
Part 2-1975

Detection or
determination ofHCl
evolved by
PVC material on
heating

As in ISO 305

Glass tubes for

ISO/R 182individual
1970b Procedure A (Congo specimens,
with centrally
Red Method)
mounted strip
of Congo Red
paper 30mm
x lOmm: oil
bath

Essentially as
As in ISO 305
ISO 305, but
disc diameter 1
mm less than
that of the aluminium blocks

Enough material 180C prefersuitably comred; other

minuted, to fill
temperatures
may be used,
test tube to a
depth of 50 mm consistent
with completion of test
within time
limits stated

For specification titles see Section 3.2(c)(ii) of Appendix A.

Currently under revision.

321

9 Stabilisers: General Aspects

Standard Tests for PVC Stability

Remarks

specification
Test treatment
Time

Procedure: main
points

Assessment and/
or expression of
results

Visual assessment of
Test duration Specimens heated in
tubes immersed in oil colour developed, in
limits 60bath; one withdrawn
120 min
comparison with unfor inspection every
treated specimen
5 min (enough should
be used for completion ottest)
Specimens heated in
Relative heat stability
Up to 120
oven and removed
assessed visually, in
min
for inspection at suit- comparison with
able intervals, e.g. af- standard sample or
ter 30, 45,60,90 and control, in terms of
120 min
time for particular
degree of discoloration
As in ISO 305
As in ISO 305
Limits as in
ISO 305,
but test time
so selected
that the last
specimen to
be removed
is black

Stability time may

be defined as the
time after which
unacceptable intensity of discoloration first
reached

Specification
based on an earlier (1963) version of ISO 305

20 min to 5 h Tube with specimen

Mean of times
Certain minor
and indicator paper
obtained in duplicate modifications in
suspended above it
determinations for
conditions sugeach specimen is the
heated at test
gested to relate
temperature: time in
stability time (provid- the results of
minutes for red coling values lie within
different procesour to change to tran- 10% of their
sing methods
sient violet or perma- average)
nent blue recorded

TABLE 9.5Basis of
test

Main particulars and features of

Standard
specifications
Test equipment
and reagents

Test specimens
Temperature

As in ISO/R
BS 2782, Part 1, As in ISO/R 182 Powder, graMethod l30A:
nules, frag182
ments of sheet
1976c (Congo
Red Method)
(5-6mm
square), or
other formsamount as in
ISO/R 182
DIN 53 381 Part Substantially as the ISO and BS Congo Red Methods
1-1971
ISO/R 182-1970 Glass tubes for
10 g of commi- As in Proceindividual
Procedure B
nuted test
dure A
specimens with material
(pH Method)
provision for
passage of a
gas; heating
bath; supply of
gas (air or nitrogen); pH
measuring cells
(one for each
test tube); pH
meter
BS 2782, Part 1, As in ISO/R 182 As in BS
As in ISO/R
Method BOA
182
Method l30B:
1976d (pH
Method)
DIN 53 381 Part
Substantially as the ISO and BS pH Methods
3-1971
Specimen flasks 10 g of test
ASTM D 79349 (reapproved (250 ml Erlenmaterial cut
into pieces with
meyer) with
1976)
provision for
one dimension
passage of nitno larger than
rogen (pre1/16 in; spread
heated to test
evenly on bottemp.); HCl
tom of flask
absorption tube
with NaOH
soln; oil bath
C

In technical agreement with Procedure A of ISO/R 182-1970.

In technical agreement with Procedure B of ISO/R 182-1970.

contd.
specification

Remarks

Test treatment
Time

Procedure: main
points

Assessment and/
or expression of
results

As in ISO/R 182 As in ISO/R 182

Time in minutes (mean

of duplicate determinations) for first clear sign
of indicator change
from red to blue

As in Procedure Volatiles generated by

A
specimen swept by gas
stream from test tube
heated at test temperature into pH measuring
cell; graph of pH versus
time plotted: at least
duplicate determinations

Induction time, in minutes, given by the

period of heating for
pH drop to 39 01:
further decomposition
may be followed

As in ISO/R 182 As in ISO/R 182; gas

flow 6 litre h- I

As in ISO/R 182

30 min

'Short-time stability' expressed as mg of HCl

evolved per g of specimen in the test

Volatiles generated by
specimen heated in flask
swept into absorption
tube by nitrogen bubbling through at 2-4
bubbles S-I. After 30
min Cl pptd. with
AgN0 3 and determined
by titration with KSCN

324

W. V. Titow

in such 'open' processes as calendering and coating. Similarly, because

heating between the platens of a press substantially excludes air
contact, press-heating tests may be considered more relevant (within
the generally limited degree of correlation) to the stability of the
material in injection moulding or extrusion. The following
recommendations7 are fairly representative of conditions and methods
for a press-heating test. A sheet is prepared under standard conditions
from the PVC composition to be tested. Specimens of suitable size are
cut from the sheet and placed in a press (preferably a multi-daylight
one) preheated to the test temperature (typically 180C), between
chromium-plated metal plates, and within moulding frames to prevent
thickness reduction. Pressures of about 200 MPa (29000 lbf in- z) and
100MPa (14500lbfin- Z) may be used, respectively, for uPVC and
pPVC compositions.
The effects of calendering are among the most difficult to relate to
the results of tests, especially static tests: in-plant trials are the only
complete answer, where they are practicable and not precluded by cost
considerations.
Note: A milling test, at mill temperatures of up to 190C and
peripheral roll speed of 120 ft min -1 (with a tight nip),
developed in the late 1950s,69,70 has been claimed to give
reasonable correlation with the effects of calendering at
similar temperatures, and speeds up to 330 ft min -1. The
degradative effects of the test treatment at temperatures
within the range 17o-190C were found to be generally more
severe than those of a static (oven-heating) test at corresponding temperatures, with the difference greatest at the lower end
of the range.

An oven used for static heating tests must be reliable, with good
control, and even distribution, of temperature. ASTM D 2115 gives a
useful summary of requirements in this regard. In the interests of the
greatest uniformity of exposure, specimen carriers rotatable during the
test treatment should be provided inside the oven in preference to
ordinary shelves. These may take the form of self-levelling shelves
carried in a horizontally mounted cylindical frame after the manner of
a 'big dipper', or a turntable 67 (with the specimens placed around the
periphery). An oven test, employing discoloration of the specimens as
the degradation index, is illustrated by the following example. 71 Both
the test and its results are fairly representative of good early practice,

325

9 Stabilisers: General Aspects

reasonably in line with current standard tests of this kind (d. ASTM D
2115; ISO 305; DIN 53381/2 in Table 9.5).
A sequence of colour change was established by preparing a series of
strips of PVC sheet degraded to the colours listed below. The strips
served as standards for a quantitative expression of colour changes
produced by the test treatment in specimens of the composition tested.

O.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.

clear,
barely detectable change,
very slight change,
slight yellow tinge,
pale yellow,
yellow,
faint tinge of red,
pale red,
red,
deep red,
very deep red/black,
black.

Four test compositions were prepared (pbw):

A
B
C

PVC
resin

DOP

100
100
100
100

50
50
50
50

Barium
stearate

Zinc
stearate

Epoxidised oil
(Pliabrac A)

25
25

05
05

50

Dibutyltin
dilaurate

20

The compositions were made into sheets 006 in thick, and I-in squares
of the sheets were used as test specimens. The squares were placed on
aluminium mesh trays in an air-circulation oven at 180C. * One
specimen of each composition was taken out at IS-min intervals and its
colour number determined by reference to the standards. Figure 9.7 is
* Temperatures of 175-180C are most commonly used in static stability tests,
although higher ones are also sometimes recommended-e.g. 200C by the
French Centre Scientifique et Technique du Batiment. 72 For the same PVC
composition and test method, stability times at different temperatures should
normally conform to the Arrhenius relationship given in Section 9.2.1 (see also
Fig. 9.5).

326

W. V. Titaw
11
10

9
8
01

.S 7

-g6
u
L

54

10

20

30

40

50

60

70

80

90

100

110

H<2ating tim<2, minut<2s

Fig. 9.7 Colour changes in four PVC compositions on heating at 180C.

a plot of the results. It provides an actual example of the effects
illustrated in a general way in Fig. 9.4. Inter alia, the results
demonstrate the stability improvement resulting from addition of an
epoxy co-stabiliser to a PVC composition stabilised with a mixed-metal
stabiliser.
An oven test developed by Nelson 67 (originally for plastisol
materials) is noteworthy for the degree of precision achievable in the
determination of stability time, as well as the good control over the
heating conditions. An effectively insulated, dome-shaped oven is used,
in which a heated air-stream is directed, from above, onto a turntable
(revolving at one r min-I) on which the PVC specimens are mounted
over holes, so that they are accessible to a light beam directed at them
from below. The specimens are films spread on microscope slides: they
incorporate Ultramarine Blue RSl, compounded into the composition
to act as indicator, in an amount sufficient to make the colour change
(reduction of the blue colour) distinct when free HCI is evolved at the
onset of significant degradation (0,5 phr of the indicator exemplifies the
incorporation level). This degradation point, which defines the stability
time, is marked by the end of a sharp drop in the reflectance curve of
the blue component of the part of the light beam reflected by the
specimens onto an EEL selenium cell: the reflectance is continuously
measured and recorded from the start of the test (see Fig. 9.8).
In a typical procedure for a dynamic stability test in a torque
rheometer (Brabender Plasti-Corder), the appropriate mixing head is
selected, and the mixer pre-heated to the required temperature. A
weighed quantity of PVC composition is quickly introduced into the

327

9 Stabilisers: General Aspects

-!
o

ts
TimlZ., minutlZs

Fig. 9.8 Reflectance of blue light as a function of heating time in Nelson's

stability test with Ultramarine Blue RSI indicator: 67 schematic representation.
ts , stability time.

chamber (head cavity) with the rotors running. The amount of material
is selected in relation to the cavity volume: if it is desired to ensure
good exposure of the composition to air during mixing, the cavity
should not be filled completely. If colour development is used as the
degradation index, samples of the composition are withdrawn for
examination at suitably frequent intevals (say every two minutes).
Otherwise the time is determined from the start of mixing to the rise of
torque indicating the decomposition point. The roller speed and the
temperature are the principal variables; their values should be selected
in the light of the purpose of the test. The following may be mentioned
by way of example of combinations which have been used in
investigations of stability of PVC compositions in relation to their
behaviour in industrial processing: roller speeds of 35, 45, 55 and
65 r min -1 at temperatures of 165C, 180C and I85C;65 or 50 and
100 r min- 1 at 140C and I80C. 66
Note: An interesting study by Collins et ai. 65 provided evidence for
good correlation between Brabender thermal stability values
and those obtained with a capillary rheometer. Data obtained
with the latter instrument also demonstrated, inter alia, a

w.

328

V. Titow

correspondence between the 'time to black' of PVC compositions and a pronounced increase in melt viscosity (reflected by
the commencement of an upward sweep in a plot of the
extrusion load versus time).
A feature of properly designed dynamic stability tests employing the
Brabender torque rheometer or a suitable extruder, is that they can
bring out the important role of lubrication in the heat stability of PVC
in processing. The reduction of frictional heating by proper internal
and external lubrication can substantially increase the stability of a
generally adequately stabilised PVC composition (by reducing the heat
history and hence extending the heat life), in comparison with an
unlubricated, or poorly lubricated, but otherwise identical composition. This factor is not brought out by static tests, in which the stability
time depends essentially on the stabiliser system and is not significantly
influenced by the lubricants66 (unless these are of the stabiliserlubricant type--cf. Chapter 11, Section 11.1.2).
9.8.3 Light Stability Testing

The general format of tests for stability to light is the same as that of
heat stability tests-i.e. a test treatment producing degradation,
followed (or accompanied) by a determination of its extent. All the
test treatments in common use are static ones. In the practical context,
the ultimate significance of light stability tests is as sources of guidance
to resistance of the material tested to photodegradation in service
(although good correlations with actual service performance may be
difficult to establish-see Chapter 12, Section 12.6): this is implicit, at
least to some extent, even in the use of such tests for direct comparison
of the stability of similar materials, as criteria of specification
requirements, and in quality control. The usual test treatments consist
of exposure of suitable specimens to 'natural' light (with or without
accessibility to general weathering), or to artificial light sources in the
laboratory. The laboratory tests may also include exposure to heat and
water (liquid and/or vapour) to simulate the effects of these factors in
outdoor weathering. The popular tests in both these categories
(including international and national standard tests), their effects,
applications, significance, and limitations are discussed in Section 12.6
of Chapter 12, in connection with weathering resistance of PVc. As
mentioned in that section, laboratory tests which involve exposure to

9 Stabilisers: General Aspects

329

artificial light with a spectral distribution resembling that of daylight,

are not necessarily accelerated tests, as the degradation effects may
take as long to develop as they would on outdoor exposure. True
acceleration of photodegradative effects may be achieved by using UV
radiation of relatively high intensity (cf., for example, the QUV
test-Section 12.6), and/or running the test at elevated temperatures or
higher ambient oxygen concentrations (or both).
Such accelerated tests are particularly relevant where the object is
purely to achieve rapid photodegradation; or to examine the roles and
effects of the three factors just mentioned in the conditions of the test
(the effects may differ in magnitude or 'even nature under different
conditions); or where the stability of generally similar materials (e.g.
PVC of basically the same formulation but with modifications to the
stabiliser system) is to be directly compared.
The applicability of the test results as indication of the likely stability
of the material on long-term exposure in service will, in each individual
case, cardinally depend on the available evidence and records of the
relevant correlations.
A useful accelerated test for photochemical stability of polymers and
plastics, including PVC, has been developed at the TNO. * In this
method the time scale for degradation effects is reduced not only by
the use-in combination-of UV light, heat, and oxygen, but also by
specimen 'geometry'. The specimens are thin films: this makes for a
high surface-to-volume ratio, so that a large proportion of the total
material of each specimen is immediately and directly accessible to the
degradative influences. The films are mounted on the outer wall of a
cooling tube, of Duran 50 glass, which surrounds an inner tube housing
a high-pressure mercury lamp (TQ-150, Quartzlampen GmbH,
Hanau). The cooling tube also acts as a UV filter, absorbing
wavelengths below about 300 nm. The assembly is contained in a
cylindrical glass vessel, jacketed for temperature control by water
circulation: the test temperature is maintained by regulating those of
the cooling tube and the glass vessel. Test temperatures up to about
90C can be used, with UV radiation intensities between about 200 and
1100 W m- 2 . The progress of photooxidation of the specimens is
followed by continuous measurement of the uptake of oxygen from a
nitrogen/oxygen mixture filling the glass vessel. The oxygen concentration in this mixture may be used as a test variable to examine its effect

* Plastics and Rubber Research Institute TNO, Delft, Holland.

330

W. V. Titow

on the degradation of the material tested. In tests on PVC, the HCI

evolved is also continuously determined by absorption in water and
conductivity measurement.
Determinations of stability to photooxidative degradation of plastics
by the TNO test can be up to ten times faster than those in some types
of standard equipment (e.g. Xenotest--d. Table 12.7, Chapter 12).
They have also been claimed to correlate well with Xenotest results, as
well as those of some actual long-term exposures out of doors.
9.9 DETECTION AND ANALYSIS OF STABILISERS
Various methods of separation and analysis are used for the
identification and determination of stabilisers in PVC compositions.
Infra-red spectroscopy and gas chromatography are especially noteworthy among instrumental techniques. An outline of qualitative
analysis for commercial stabilisers and lubricants, published by Crowo
in 1967,73 is still of some interest. Other. more extensive, sources of
information include the well-known book by Haslam et at. on the
analysis of plastics,74 and that by Crompton on chemical analysis of
additives;75 the IR methods of identification of additives in plastics
are covered in the third volume of the publication by Hummel and
Scholf6 which includes many reference spectra.
Extractability of stabilisers from PVC materials is of special interest
in connection with the use of such products as food-wrapping film,
blown bottles for beverages, potable-water pipes and medical equipment. Product specifications, where available, contain appropriate
extractability tests. Useful general comments and some relevant data
have been provided by Brighton. 77

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Wiirrne, Springer Verlag, Berlin.
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5. Thinius, K. (1969). Stabilisierung und Alterung von Plastwerkstoffen,
Verlag Chemie, Weinheim.

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6. Onozuka, M. and Asahina, M. (1969). J. Macromol. Sci., Revs.

Macromol. Chern., C3(2), 235.
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11. Mascia, L. (1974). The Role of Additives in Plastics. Edward Arnold
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12. Woolley, W. D. (1972). Plastics and Polymers, 40(148),203-8.
13. Troitskii, B. B., Dozorov, V. A, Minchuk, F. F. and Troitskaya, L. S.
(1975). Eur. Polym. J., 11(3),277-81.
14. Abbas, K. B. and Sorvik, E. M. (1975). J. Appl. Polym. Sci., 19(11),
2991-3006.
15. Chauffoureaux, J. C., Dehennau, C. and van Rijckevorsel, J. (1979). J.
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16. Rice, P. and Adam, H. (1977). In Developments in PVC Production and
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17. Grassie, N. (1975). In Degradation and Stabilisation of Polymers, (Ed. G.
Geuskens), Applied Science Publishers, London, Ch. 1.
18. Summers, J. W. (1976). 34th ANTEC SPE Proceedings, pp. 333-5.
19. Rabek, J. F., Canback, G., Lucky, J. and Ranby, B. (1976). J. Polym.
Sci. Polym. Chern. Ed., 14(6), 1447-62.
20. Wilson, A. S., Biggin, I. S. and Pugh, D. M. (1978). 'The influence of
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Conference on PVC Processing, Egham Hill, Surrey, England, 6-7 April,
1978.
21. Rabek, J. F., Shur, Y. J. and Ranby, B. (1975). 1. Polym. Sci. Polym.
Chern. Ed., 13(6), 1285-95.
22. Braun, D. (1964). Kunststoffe, 54(3), 147-52.
23. Allara, D. L. (1976). 34th ANTEC SPE Proceedings, pp. 245-7.
24. Starnes, W. H. and Piitz, I. M. (1976). Macromolecules, 9(4),633-40.
25. Lanigan, D. (1978). 'Recent advances in organotin stabilisers,' paper
presented at the PRI International Conference on PVC Processing, Egham
Hill, Surrey, England, 6-7 April, 1978.
26. Fernley, A M. (1964). Plastics, 29(320),66-8.
27. Grindley, P. R. (1969). Chern. Processing, 15(3),8-11.
28. Thacker, G. A. (1969-1970). Modern Plastics Encyclopedia, McGraw-Hill,
New York, pp. 290-4.
29. Anon. (1976). Plast. Technol., 22(2), 12.
30. Hutton, R. E. and Oakes, V. (1976). In Organotin Compounds: New
Chemistry and Applications, (Ed. G. J. Zuckerman), Advances in
Chemistry Series, No. 157, American Chemical Society, Ch. 8.

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31. Dieckmann, D. (1976). 34th ANTEC SPE Proceedings, pp. 507-11.

32. Hartung, M. (1979). Plast. Techno!.. 25(8), 67-70.
33. Titow, W. V. (1977). In Developments in PVC Production and
Processing-I, (Eds. A. Whelan and J. L. Croft), Applied Science Publishers,
London, Ch. 4.
34. Rhys, J. A. (1962). In Advances in PVC Compounding and Processing,
(Ed. M. Kaufman), Maclaren and Sons Ltd, London, Ch. 3.
35. Worschech, K. F. (1978). 'Synergistic support of various stabilisation
systems during PVC processing by using lubricants,' paper presented at the
PRI International Conference on PVC processing, Egham Hill, Surrey,
England, 6-7 April, 1978.
36. Razuvaev, G. A., Troitskii, B. B., and Troitskaya, L. S. (1971).
Mechanism of Action of Some Stabilisers in the Thermal Degradation of
Polyvinyl Chloride, Proceedings of 7th IUPAC Symposium, Prague 1970,
Butterworths, London.
37. Hybart, F. J. and Rowley, G. N. (1972). J. Appl. Polym. Sci., 16,715-23.
38. Thacker, G. A. (1971-1972). 'Antioxidants', in Modern Plastics Encyclopedia, Vol. 48, McGraw-Hill, New York, pp. 21~14.
39. Hageman, H. J. and de Jonge, C. R. H. I. (1972). Kunststoffe, 62(10),
681-3.
40. Bailey, D., Tirrell, D., Pinazzi, C. and Vogl, O. (1978). Macromolecules,
11(2), 312-20.
41. Johnson, M. and Houserman, R. G. (1977). 1. Appl. Polym. Sci. 21(12),
3457-63.
42. Anon. (1976). Eur. Plast. News, 3(3), 28.
43. Thacker, G. A. (1971-1972). 'UV absorbers and light stabilisers', in
Modern Plastics Encyclopedia, Vol. 48, McGraw-Hill, New York, pp.
284-91.
44. Bonkowski, J. E. (1969). Text. Res. J., 39(3),243-7.
45. Szabo, E. and Lally, R. E. (1975). Polym. Engng. Sci., 15(4),277-84.
46. Asquith, R. S. and Campbell, B. (1963). 1. Soc. Dyers and Colourists,
79(12), 678-86.
47. Salvin, V. S. Ibid, pp. 687-96.
48. ISO 105-1978: Textiles-Tests for colour fastness. G05, Colour fastness to
burnt gas fumes.
49. Katz, M., Shkolnik, S. and Ron, I. (1976). 34th ANTEC SPE Proceedings,
pp.511-12.
50. Wypych, J. (1976). J. Appl. Polym. Sci., 20(2), 557-60.
51. Frye, A. H., Horst, R. W. and Paliobagis, M. A. (1964). J. Polym. Sci.,
A2, 1765, 1785 and 1801.
52. Klemchuk, P. P. (1968). In Stabilization of Polymers and Stabilizer
Processes (Ed. R. F. Gould), Advances in Chemistry Series, No. 85,
American Chemical Society, Ch. 1.
53. Ayrey, G., Poller, R. C. and Siddiqui, I. H. (1969). 'Reaction between
organotin compounds and chlorohydrocarbons in relation to the stabilisation of poly(vinyl chloride),' paper presented at the 4th International
Conference on Organometallic Chemistry, Bristol, England.

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333

54. Suzuki, T. and Nakamura, M. (1970). lap. Plast., 4(2), 16-21.

55. Fieser, L. F. and Fieser, M. (1944). Organic Chemistry, D. C. Heath &
Co., Boston, pp. 304-6.
56. Bengough, W. J. and Onozuka, M. (1965). Polymer, 6,625.
57. Frye, A. H. and Horst, R. W. (1959). l. Polym. Sci., 40,419; (1960). Ibid,
45,1.
58. Onozuka, M. (1967).1. Polym. Sci., AS, 2229-32.
59. McBroom, J. W. and Lally, R. E. (1971-1972). In Modern Plastics
Encyclopedia, Vol. 48, McGraw-Hill, New York, pp. 262-4.
60. Deanin, R. D., Foss, R. M., Gilbert, P. G., Guerard, R. F. and Muccio,
E. A. (1973). Polym. Engng. Sci., 13(2), 96.
61. Fuchsman, C. H. (1968). In Stabilization of Polymers and Stabilizer
Processes, (Ed. R. F. Gould), Advances in Chemistry Series, No. 85,
American Chemical Society, Ch. 2.
62. Wypych, J. (1975). l. Appl. Polym. Sci., 19(12), 3387-9.
63. Nass, L. I. (Ed.) (1976). Encyclopedia of PVC, Vol. 1, Marcel Dekker,
New York, pp. 344 and 670.
64. Gleissner, A. (1975). Kunststoffe-Plastics, 22(1), 11-12.
65. Collins, E. A., Metzger, A. P. and Furgason, R. R. (1976). Polym.
Engng. Sci., 16(4), 240-5.
66. Menzel, G. and Polte, A. (1975). Kunststoffe, 65(3), 149-55.
67. Nelson, J. H. (1978). 'A novel method of assessing heat stability', paper
presented at the PRI International Conference in PVC Processing, Egham
Hill, Surrey, England, 6-7 April, 1978.
68. Cassel, B. and Gray, A. P. (1977). Plast. Engng., 33(5),56-8.
69. Himmler, G. G. and Nissel, F. R. (1957), Plast. Technol., 3(4), 280-2.
70. Dodgson, D. P. and Pike, M. (1960). Svenska Plastforeningens Plasttenik,
Section TlF, 2.
71. Moorshead, T. C. (1957). Plastics, 22,243.
72. Fougea, D. (1971). Cahiers Centre Sci. Tech. Batiment, No. 124, p. 1070.
73. Crowo, J. A. (1967). Brit. Plast., 40(8), 84-6.
74. Haslam, J., Willis, H. A. and Squirrell, D. C. M. (1973). Identification and
Analysis of Plastics, 2nd Edn, Iliffe Books, London.
75. Crompton, T. R. (1977). Chemical Analysis of Additives in Plastics, 2nd
Edn, Pergamon Press, Oxford.
76. Scholl, F. (1981). Additives and Processing Aids: Spectra and Methods of
Identification, Vol. 3, 2nd Edn The Hummel/Scholl Atlas of Polymer and
Plastics Analysis, Carl Hanser Verlag, Munich, and Verlag Chemie
International. Deerfield Beach, Fla., USA.
77. Brighton, C. A. (1968). Plastics and Polymers, 36(126), 549-54.
78. Lippoldt, R. F. (1978). 36th ANTEC SPE Proceedings, pp. 737-9.

CHAPTER 10

Commercial Stabiliser Practice

P. S.

COFFIN

10.1 INTRODUCTION

There are a large number of stabiliser products available to the PVC

processor. The selection of the best stabiliser system for a particular
application depends very much on the specifications the PVC
end-product must meet and the fabrication process to be employed.
The situation is further complicated by the fact that individual
stabiliser compounds are being used less and less. Instead, many
processors take advantage of proprietary stabiliser brands which will
provide a complete stabiliser package. This has been established
practice for the 'barium/cadmium' and 'calcium/zinc' classes of
stabiliser, since these systems tend to be specific to individual
applications. In the lead stabiliser field the use of 'one-pack' systems,
incorporating all the stabilisers and lubricants for a particular
application, has become commonplace. Single-package products incorporating tin stabilisers with lubricants are now also becoming available.
Although certain general principles have been mentioned in Chapter
9, it is only by reference to the proprietary materials that the great
variety of PVC stabilisers available, and the relationship between their
nature and applications, can be illustrated. For this reason, the product
ranges of five principal UK stabiliser manufacturers are described at
the end of this chapter. The list is not meant to be complete, and it
does not imply that any material of any manufacturer not included is
inferior to those which are included. Nor is it intended to imply or make
any comparison between the materials of different suppliers. Not all
the products described are of UK manufacture; part of the product
335

336

P. S. Coffin

ranges referred to may be manufactured elsewhere. The main purpose

of the list is to demonstrate by reference to good commercial products
the range, nature and uses of principal PVC stabilisers. For this
reason, the fact that the products mentioned are mainly British is
immaterial, and the chapter should be of equal use to readers in other
countries. It is, in any case, a good plan for the prospective user,
TABLE 10.1
Some of the Larger Stabiliser Manufacturers World-Wide (Position c 1980)
UK stabiliser manufacturers
Associated Lead Manufacturers Ltd
Ciba-Geigy Ltd
Durham Chemicals Ltd

Ferro (GB) Ltd

Diamond Shamrock Ltd
Victor Wolf Ltd

Stabiliser manufacturers in Western Europe.

ASUA (Spain)
Hondorff, Block and Braet (Holland)
Akzo Chemie (Germany)
Meister (Switzerland)
BASF (Germany)
Metallgesellschaft (Germany)
BBU (Austria)
Penalmex (France)
Barlocher (Germany)
Polytitan (France)
Ciba-Geigy (Germany)
Reagens (Italy)
Cincinnati Milacron (Belgium)
Rousselot (France)
la Floridienne (Belgium)
SNEA (France)
Haagen Chemie (Holland)
Stabital (Italy)
Henkel (Germany)
Swedstab (Sweden)
Hoechst (Germany)
Stabiliser manufacturers in the USA
A and S Corp.
Argus Chemical Corp.
Associated Lead Inc.
Cardinal Chemical Co.
Ciba-Geigy Corp.
Cincinnati Milacron Inc.
Claremont Corp.
Cyanamid Co.
Eagle Picher Inc.

Emery Inc.
Ferro Chemical
Hammond Lead Products Inc.
Interstab Chemicals Inc.
M and T Chemicals Inc.
Stauffer Chemical Co.
Synthetic Products Co.
Tenneco Chemicals Inc.
Vanderbilt Co.

Stabiliser manufacturers in Japan

Adeka Argus
Dainippon Chemicals
Katsuta Kako
Kawamusa Kasei
Kikuchi Chemicals
Kyodo Chemicals
Mizusawa
Nitto Kasei

Sakai Chemicals
Saukyo Chemicals
Seido Chemicals
Shinagawa
Shin ChwQ Kagaku
Tannan Kagaku Kogyo
Toyko Chemicals

10

Commercial Stabiliser Practice

337

whether in the UK or abroad-after having clarified his requirements

and possibilities in the light of this chapter-to select and contact
suppliers with a view to asking for relevant details and preferably a
discussion. Many manufacturers will also specially formulate stabiliser
systems to suit individual needs. Table 10.1 gives a list of some of the
larger suppliers of stabiliser products in Western Europe, the USA and
Japan.
10.2 CHOOSING A COMMERCIAL STABILISER
The first step in selecting a stabiliser for a particular application i,s to
consider which of the basic stabiliser systems is most appropriate for
the particular conditions. Chapter 9 outlines the general performance
properties of the different stabiliser systems. No one stabiliser system
is equally suited to all the diverse uses of PVC, so the choice of
stabiliser is very much determined by which properties are of greatest
importance for the particular application in question. Cost, of course,
is also usually a critical factor in the final decision. However, it must be
remembered that the cheapest suitable stabiliser is not necessarily the
wisest choice. It is important to consider the total PVC compound and
manufacturing costs. For example, such factors as reject recycling
involve large hidden costs that may overshadow differences in stabiliser
prices. 1
Lead stabilisers are comparatively cheap. Although they are the
heaviest (costing is often on a volume basis) and are generally used at
high loadings, they can frequently prove most cost-effective. They are
efficient heat stabilisers; some are good UV absorbers and others (e.g.
stearates) have lubricant properties. Therefore, lead stabilisers are
worth considering first. They are particularly appropriate if the PVC
compound is required to have good electrical properties. However,
lead stabilisers will not be suitable if clarity, non-toxicity or
sulphur-staining resistance are of considerable importance. Typical
application areas where lead stabilisers are used include pipes, pipe
fittings, rainwater goods, interior and exterior profiles, cable coverings,
conveyor belting, and insulation tape.
Metal soaps* and 'complexes't are, almost without exception, most
effective in synergistic mixtures involving two or more metal salts
* Metal soaps used as stabilisers are typically commercial 'laurates' or
'stearates' (see Chapter 9).
t Metal 'complexes' are not complexes in the chemical sense of the word but
denote hexoates, octoates, benzoates, phenates, etc. (see Chapter 9).

338

P. S. Coffin

together with co-stabilisers such as organophosphites and epoxy

compounds. These systems, particularly those based on calcium/zinc,
tend to be specific in action and it is important to use the correct
system for a particular application. If the use of these stabilisers is
contemplated then the supplier's advice will certainly be of value.
There are many systems on the market based on various combinations
of different metals. In general, the barium/cadmium or barium/
cadmium/zinc products are the most efficient in performance. However, if the use of cadmium and possibly barium is not desired on the
grounds of toxicity, then the less effective barium/zinc, calcium/zinc or
combinations with other metals must be considered. The metal soap
systems are usually solids, and those based on stearates impart
significant lubricant action. On the other hand, the metal complex
systems are usually liquids. Mixed metal systems find use in a wide
range of applications, e.g. barium/cadmium stabilisers in shoes,
flooring, calendered sheet, leathercloth, flexible trimmings, and
flexible hose; and calcium/zinc stabilisers in articles for medical or
food-contact applications
The organotin stabilisers are, generally speaking, the most effective
of all compounds from a heat stability aspect, in particular for clarity
and colour hold. Some (e.g. maleates) also contribute light stability,
although UV absorbers are sometimes used in conjunction, especially
for transparent PVC articles for outdoor use. However, the organotin
stabilisers are the most expensive, and it is this factor that is
responsible for their use not being wider than it is at present, despite
their dosage level often being very low. Tin stabilisers would typically
be used for rigid sheet, clear sheet, plastisols and mouldings. Some tin
stabilisers (e.g. octyltins) have gained approval for food-contact
applications such as packaging film and bottles.
Having decided on the most suitable type of stabiliser or having
narrowed the choice to two possibilities, it is necessary to consider the
different forms and proprietary products within that system. As the
contents of this chapter will illustrate, there are often many individual
products of the same basic type within a supplier's range that have
been developed to suit differing circumstances.
Obviously, the supplier's description of his product will indicate its
principal performance properties. Further, for specialised applications
some suppliers are willing to formulate custom-fit products. However,
it is important to run practical trials in the laboratory and/or the
factory before the final selection is made.

10 Commercial Stabiliser Practice

339

10.3 THE IMPORTANCE OF A WELLBALANCED

LUBRICANT SYSTEM

Lubricants frequently have a large influence on the action of heat

stabilisers, particularly with regard to processing stability. For such
manufacturing processes as extrusion, injection moulding, blow
moulding and calendering, the selection of the correct lubricant system
can often be as important as the choice of stabiliser. PVC has a high
melt viscosity and lubricants must be added to facilitate processing. In
addition, PVC will stick to hot metal surfaces unless properly
lubricated. If an inefficient system is used, then the thermal history
experienced by the PVC compound will be greater because of the
higher shear necessary to process the material. This and the tendency
to stick to the metal parts of the processing equipment will strongly
encourage degradation. More of the stabiliser will be used up and the
possibility of a 'burn-up' will be considerably greater. Of course
some 'lubricants' such as lead stearate and calcium stearate are stabilisers
in their own right. Other lubricants, e.g. glycerol monostearate
and pentaerythritol esters, have been shown 2 to have stabiliser
action.
The lubricant system has, until recently, been the hidden art in PVC
technology which would differentiate between a successful processing
operation and a not so successful one. Lubricants not only influence
processing and stabilisation, but also the extent of gelation and the
physical properties of the fabricated article. The selection of the most
suitable lubricant system is a complicated matter, particularly for rigid
PVC applications. It is frequently necessary to employ a number of
individual lubricants simultaneously, with each performing a different
task during the processing operation and often showing subtle
interactions with the other lubricants. Laboratory tests rarely give good
correlation to processing conditions and it is usually necessary to carry
out development work on production plant. Laboratory equipment
that can give useful information, such as small scale extruders
and calenders, is expensive. It is, therefore, as important to
obtain recommendations from lubricant suppliers as from stabiliser
suppliers. Of course, with several stabiliser suppliers providing
one-pack stabiliser/lubricant products, the development work on the
lubricant system can be offered as part of the package. The various
types of compounds used as PVC lubricants are discussed in
Chapter 11.

340

P. S. Coffin

10.4 ONE-PACK SYSTEMS AND THE PHYSICAL FORM

OF STABILISER PRODUCTS
There are many advantages in a PVC processor obtaining his stabiliser
system as a one-pack product. The number of weighing operations
during compound preparation is reduced considerably. Products such
as antioxidants which are incorporated at low dosage levels would have
involved weighing small quantities. The formulation work on stabiliser
and lubricant systems is carried out by the stabiliser supplier, and the
processor does not need to carry out costly development projects. The
disadvantages are a loss of formulation flexibility and a higher stabiliser
price.
The use of a one-pack mixed metal stabiliser is almost obligatory
because of the complex synergistic effects between the individual
stabiliser compounds that necessitate lengthy development work to
optimise any system. Such proprietary products often incorporate
co-stabilisers such as organophosphites, antioxidants such as hindered
phenols, and chelators such as pentaerythritol. The solid metal soap
products, by virtue of the lubricant action of metal soaps, can be
formulated to give as well the complete lubricant system required for
the application in question. The one-pack lead stabiliser products,
either co-precipitate or composite, have been developed to offer a
complete stabiliser system in one product. This has been taken a stage
further by some suppliers with the incorporation of fillers, processing
aids, flame retardants and pigments within stabiliser composites. In the
USA the one-pack concept has extended into the tin stabiliser field
with the development of products containing both organotin stabiliser
and a complete lubricant system.
The physical form of a stabiliser product is another important aspect
to consider when selecting a stabiliser system. The ancillary equipment
available such as storage facilities, conveying equipment, and weighing
stations must be capable of handling the stabiliser. Most mixed metal
complexes and tin stabilisers are liquid and require dosing equipment.
Most lead stabilisers and mixed metal soaps are solid and can be
handled in equipment fundamentally the same as for the resin.
However, dust is a major inconvenience in handling a solid,
particularly when the dust can be harmful if inhaled. For this reason,
considerable development work has been carried out by the manufacturers of solid stabilisers on forms with low dusting tendencies.
Products can be <lamped with such liquids as plasticiser (e.g. the 'D'

10 Commercial Stabiliser Practice

341

grade from Associated Lead). Most lead stabiliser and mixed metal
soaps can be supplied as pastes dispersed in a suitable plasticiser.
Agglomerated forms such as granules and flakes are widely used
because of their reduced dusting tendencies. More recently, this type
of product has been taken a stage further with the introduction of
'strands' (see Section 10.6) and 'pearls'3 with considerably reduced
dusting tendencies and free-flowing characteristics. Finally, the stabiliser can be supplied packaged within a sealed polyethylene bag for
addition direct and whole into a high-speed mixer. The mixer shreds
the bag and the polyethylene then constitutes part of the lubricant
system.
10.5 HYGIENE AND ENVIRONMENTAL
CONSIDERATIONS

Most stabiliser systems are based on heavy-metal compounds, so

consideration must be given both to the handling of stabiliser products
within the factory from a hygiene viewpoint and the presence of
compounds of these metals within the final PVC article from an
environmental aspect. Most discussions centre on products containing
lead, barium and cadmium, although doubts have been expressed
about certain organotin stabilisers. 4 There have been considerable
improvements in the handling methods for lead-, barium- or
cadmium-containing solid stabilisers within the factory environment.
The previous section described the development of improved physical
forms with considerably reduced dusting tendencies. It is possible for
large processors to justify automatic or semi-automatic handling
systems so the stabiliser can be delivered in semi-bulk and conveyed
through the factory to weighing and mixing stations without any
worker needing to come into direct contact with the stabiliser.
Methods of monitoring such parameters as 'lead in air' and 'blood lead'
levels have also improved the situation, so that now, provided that
proper precautions are taken, it is possible to handle such hazardous
material in the factory with safety. Information on such matters is
usually readily available from stabiliser suppliers. 5
When considering the presence of heavy-metal compounds within
the final fabricated PVC article, it is important to remember that the
metal is present at low levels in the PVC compound and that it is
generally fixed within the PVC matrix. Thus lead stabilisers are

342

P. S. Coffin

approved for potable water pipe in all countries except the USA and
France. Extensive testing of the water extraction from lead-stabilised
pipe6 ,7 has shown that only a trace of lead is leached out during the
first pass through the pipe. Thereafter, the inner core is rendered
passive to the extraction of lead. Cadmium compounds give overall the
most problems of the various stabilisers, and at present considerable
restrictions on the use of cadmium in PVC are being considered in
Sweden. However, there are strong arguments for using barium/
cadmium stabilisers for certain applications, 8 and the restrictions are
under review.
For the applications where more stringent environmental restrictions
are necessary, such as medical or food-contact articles, the calcium/zinc
systems are generally acknowledged as non-toxic. The octyltin class of
stabilisers have wide approval for food-contact applications from such
bodies as the FDA (USA), BGA (West Germany) and BIBRA (UK).
The recently introduced estertin stabilisers are also claimed to be
non-toxic, but there is to date insufficient evidence for approval to be
given to this type of product.
10.6 UK STABILISER MANUFACTURERS-PRODUCT
RANGES AND APPLICATIONS

The types of stabiliser products available to the PVC compounder and

processor are illustrated by considering the product ranges for five of
the principal UK stabiliser manufactueres. No comment or comparison
is intended by the discussion of the various products described here or
by the omission of others. The purpose is solely to indicate the range,
nature and uses of commercial stabilisers by reference to good
commercial products.
10.6.1 Associated Lead Manufacturers Ltd

Associated Lead are the major UK manufacturer of lead stabilisers.

The product range is described in Table 10.2. The individual stabiliser
products are still used fairly widely, and these can be supplied in 'dry'
form, 'D' form when damped with small smounts of plasticiser, in
granule form, or as pastes dispersed in selected plasticisers. However,
many PVC processors now use composite lead stabilisers, and this type
of product is illustrated by the standard range of Associated Lead.
Such products, or if required a formulation to the customer's

10 Commercial Stabiliser Practice

343

specification, can be supplied in damped powder blend form, packaged

within individual heat-sealed polyethylene bags, or in granular form. In
certain cases it is possible to incorporate other additives such as fillers,
pigments, processing aids and impact modifiers within the composite to
constitute a total package. Associated Lead have recently launched a
TABLE 10.2
The Basic Stabiliser Range of Associated Lead Manufacturers Ltd
Individual stabiliser compounds

Tribasic lead sulphate

Tetrabasic lead sulphate
Dibasic lead phosphite
Dibasic lead phthalate
White lead (basic lead carbonate)

Dibasic lead stearate

Normal lead stearate
Calcium stearate
Barium stearate
Cadmium stearate

Stabiliser products for flexible PVC applications, e.g. cable covering

(a) Composite stabilisers
Trade
Main
stabiliser
name
present

Performance
characteristics

SQ, BQ or XQ

Basic lead
sulphate

SQ, BQorXQ

Basic lead
sulphate

SQ,BQorXQ
3103

Basic lead
sulphate

SQ orBQ
3104

Basic lead
phthalate

SQ orBQ

3105

Basic lead
phosphite

SQ orBQ

White lead

3101

3102

3106

High stabiliser action with balanced lubricant effect for applications with high thermal stability specifications
Good stabiliser action with efficient lubricant system; good general-purpose performance
High lubricant action for applications where
high shear and/or high linear speeds are
experienced
Designed for high electrical quality cable
and for cables used under high ambient
temperature conditions
Good weathering protection for cables subject to outdoor exposure during service
life
High-cost efficiency where low melt temperatures are maintained, particularly when
chlorparaffin extenders are used

(b) Stabiliser dispersions

Individual stabiliser compounds (or mixtures thereof) dispersed in selected
plasticisers to the required ratio are widely used in the manufacture of
lead-stabilised flexible PVC products.
Q

SQ, granular; BQ, powder blend; XQ, Strandex.

TABLE 1O.2-eontd.
Stabiliser products for rigid PVC pipe extrusion
Performance
characteristics

Trade
name

The selection of the correct stabiliser for pipe extrusion depends on the type of
extruder, the overall formulation and the specifications to be met. Associated
Lead offer the series of products below with varying but balanced lubricant
action, while retaining similar stabiliser effect:
XQ, SQ or BQ 3201
XQ, SQ or BQ 3202
XQ, SQ or BQ 3203
XQ, SQ or BQ 3204
XQ, SQ or BQ 3205

Very highly lubricating, both internally and

externally
Highly lubricating, both internally and externally
Medium lubricant effect suitable for a wide
range of processing situations
Medium internal lubricant effect with low
external action
Low lubricant effect for when extruders
must work hard for excellent physical
properties

The performance of each product can be further altered by varying the dosage
rate. For example, a stabiliser used at between 20 phr and 24 phr without
filler would be recommended at a higher dosage, 26 phr to 30 phr in the
presence of high filler loadings. Different balances between internal and
external lubricant action are also available within the Associated Lead's range.
Stabiliser products for convoluted drainage pipe

SQ or BQ3221

Balanced lubricant action and low PVC

melt viscosity-suitable for Drossbachtype process

Stabiliser products for rigid PVC profile extrusion

SQ or BQ3251
SQ or BQ 3252
SQ or BQ3261

Interior, thin-walled profile-low external

lubricant action
Interior, thick-walled profile-low external
lubricant action
Exterior profile, e.g. cladding or window
frames where balanced lubricant action is
important

Stabiliser products for rigid PVC injection moulding

SQ or BQ3301
SQ or BQ3303

Good early gelation performance for applications where physical properties are
critical
Basic lead phosphite based for mouldings
subject to outdoor exposure

10 Commercial Stabiliser Practice

345

TABLE 1O.2-eontd.

Mixed metal liquid stabilisers

Trade
name

Product
type

LF037

BalCd
liquid
BalCd
liquid
CalZn
liquid
Ba/Zn
paste
Pb liquid

LF114
LH 1671
PN 1678
LLOO5

Main
application
Flexible PVC moulding, e.g. footwear
Flexible PVC extrusion, e.g. tubing
Flexible PVC extrusion and calendering
Sulphur-staining resistant cable covering
Alternative to powdered lead stabilisers for
flexible PVC applications

new product, Strandex, which represents a significant advance towards

a granulated product with non-dusting and free-flowing properties but
with good dispersion characteristics into PVc. Associated Lead also
offer a range of liquid, mixed metal complex, stabilisers.
The following formulations illustrate the use of Associated Lead
stabilisers in a number of different applications (all amounts in phr).

Pipe extrusion
Pressure
pipe
100
PVC (Suspension K65)
CaC0 3 filler: (e.g. Omyalite
95T-Croxton and Garry Ltd)
1
XQ3204
22
XQ3203
XQ3221
Processing aid:
Paraloid K120N
(Charles Lenning Chemicals)
Pigment

Soil
pipe
100

Convoluted
drainage
pipe
100

10

28
40
1
As required

346

P. S. Coffin

Rigid PVC injection moulding

PVC (Suspension K60) 100

CaC0 3 filler: (e.g. Omyalite 95T)
Ti02 pigment: (e.g. Tioxide
R-CR2-BTP, Tioxide UK Ltd)
SQ 3301
SQ 3303
Processing aid: Paraloid K120N
Pigment
Rigid PVC profile extrusion

PVC (Emulsion K70)

PVC (Suspension K65)
CaC0 3 filler: (e.g. Omyalite 95T)
BQ 3252
Impact modifier: (e.g. Blendex 410Borg-Warner Chemicals)
Pigment
PVC cable covering

PVC (Suspension K65)

DOP plasticiser
CaC0 3 filler: (e.g. Britomya
BSH-Croxton and Garry Ltd)
XQ3102
White lead/DOP paste
Lubricant: calcium stearate
Pigment

Pipe
fittings
100
3

Exterior
mouldings
100

3
45

50

2
As required

Interior
profile
(twin-screw)
50
50
5
35

Interior
profile
(single-screw)
50
50
5
45

If required
As required

System A
100

40

System B
100
39

10
4

10
5
05

As required

10.6.2 Ciba-Geigy Ltd

Ciba-Geigy offer a wide selection of tin stabilisers. Their range (see
Table 10.3) includes four out of the five commercial types of organotin
compounds, namely methyltins, butyltins, octyltins and the recently
introduced estertins (produced under licence from Akzo Chemie). The

TABLE 10.3
The Basic Stabiliser Range of Ciba-Geigy Ltd
Heat stabiliser products
Trade
name

Product
type

Main
application

General
comments

Irgastab DIM

Methyltin
mercaptide

Bottles, extrusions and

pipes

Irgastab T4

Butyltin

Plastisols and rigid j'VC

carboxylate
Irgastab 1'9

Butyltin

Rigid PVC sheet and rigid

carboxylate
Irgastab 17M

Good light stability

sheet
Good light stability

PVC profile for cladding

Butyltin

Rigid PVC

Good heat stability

Non-toxic bottles and

Widely approved for

mercaptide
Irgastab 17MOK

Octyltin
mercaptide

sheet

food-contact applications

Irgastab T649}
Irgastab T

Estertins

Food packaging materials

Assessment of non-toxic
characteristics in

Irgastab BC445

BalCd/Zn

Semi-rigid and flexible

Some lubricant action,

Irgastab BCZ06

BalCd/Zn

Aexible PVC film and

liquid

sheet

BalCd

Rigid PVC for outdoor use,

progress
liquid

Irgastab BCZ8

PVC film

good plate-out performance

Good clarity
Available in dust-

solid

e.g. window frames

Irgastab BZ505} BalZn

Irgastab BZ529

Plastisols and flexible

PVC calendering

Good weathering
properties

reduced form

Irgastab CZ11 }
Irgastab CZ113

CalZn
pastes

Transparent flexible and

rigid PVC

For non-toxic applications

Irgastab A70}
Irgastab A80
Irgastab G1

Aminocrotonates

Rigid PVC film for food

packaging

Metal-free for non-toxic

applications

Irgastab S110

Antimony

PVC records

Low noise level

performance

Auxiliary stabiliser products

Trade name

Product type

Function

Reoplast 39
Reoplast 38

Epoxidised soyabean oil }

Epoxidised octyl oleate

Co-stabiliser

Irgastab CH55
Irgastab CH300
Irgastab CH310

Tris-nonyl phenyl PhosPhite}

Oi-alkyl phosphite
Oi-alkyl aryl phosphite

Co-stabiliser

Tinuvin P }
Tinuvin 320

Substituted benzotriazoles

UV absorbers

Irganox 1076}
Irganox 1010

High-molecular-weight
hindered phenols

Antioxidants

348

P. S. Coffin

only other class of commercial tin stabiliser, the lauryltins, are mainly
used in Japan. A range of mixed metal stabilisers, both of soap and
complex-type, are also manufactured. The products mentioned in
Table 10.3 illustrate the range of such products available. In addition,
aminocrotonate products are available as metal-free stabilisers for
non-toxic applications and Irgastab SlIO is an antimony stabiliser
specifically for PVC records. Ciba-Geigy's range of auxilliary stabilisers
is extensive, with epoxy oils and organophosphites as co-stabilisers, as
well as UV absorbers and antioxidants.

10.6.3

Durl.am Chemicals Ltd

Durham Chemicals manufacture three ranges of stabiliser products.

The individual metal soaps can be provided for those who wish to
formulate their own stabiliser systems. There is a Durostabe range of
single-package mixed metal stabilisers in solid, paste or liquid form
which have been developed by the company itself. In addition,
Durham offer the Nuostabe range of liquid stabilisers which are made
under licence from Tenneco Chemicals, USA. The main products in
the combined range are listed in Table 10.4. There are a large number
of barium/cadmium and calcium/zinc types, each developed for specific
application areas. The solid stabilisers containing cadmium or lead are
provided in flake or paste form to minimise dust hazards and aid
handling.
The recommended stabiliser systems given below demonstrate for a
number of PVC applications how the use of co-stabilisers complements
the main stabiliser in providing the required performance (all amounts
in phr).

Flexible calendered sheet

System A System B System C
Ba/Ca/Zn liquid: Nuostabe 979
2
Ba/Ca/Zn flake: Durostabe 2201
2
15
Ba/Cd/Zn liquid: Nuostabe 1500
075
Epoxy oil: (e.g. Reoplast
39-Ciba-Geigy)
3
3
Organophosphite: (e.g. Lankromark
LE98-Diamond Shamrock)
05
Lubricant: stearic acid
o to 05

TABLE 10.4

The Basic Stabiliser Range of Durham Chemicals Ltd

Individual metal soaps
Aluminium stearate
Barium laurate
Barium stearate
Cadmium laurate
Cadmium stearate

Calcium laurate
Calcium stearate
Nonnal lead stearate
Dibasic lead stearate
Lithium stearate

Magnesium stearate
Potassium stearate
Strontium strearate
Zinc stearate

Stabilisers based on solid mixed metal soaps

Product
type

Trade
name

Main
application

General
comments

Durostabe S59

BalCd (high Cd)

flake

Rigid and semi-rigid PVC

extrusion

Durostabe S64

BalCd (low Cd)

flake

Flexible PVC extrusion,

injection moulding and
calendering

Good general-purpose
performance

Durostabe 2048

BalCd
paste

Flexible PVC calendering

Good general-purpose
performance

Durostabe 2176

BalCd
flake

Injection moulding,
e.g. footwear

Durostabe 2230

BalCd
paste

Flexible PVC calendering

Durostabe 2240

BalCd
flake

Flexible PVC extrusion and

injection moulding

Durostabe 2201

BalCd/Zn
flake

High speed calendering of

flexible and semi-rigid PVC

Durostabe S70

BalZn
powder

Low asbestos, highly filled

flooring

Durostabe 2188

BalCd/Pb
flake

Translucent and pigmented

rigid PVC extrusion

Durostabe S65

BalPb
flake

Flexible PVC extrusion and

injection moulding

Durostabe 2090

CalZn
powder

Extruded packing film,

flexible PVC calendering and
plastisols

Non-toxic, FDA
approved ingredients

Durostabe 2147

CalZn
powder

Calendered or extruded sheet,

flexible or rigid

Non-toxic, FDA
approved ingredients

Durostabe 2236

CalZn
powder

Filled and vinyl asbestos

flooring

Durostabe S67

Zn/organic

Vinyl asbestos flooring

For use with high

Cable extrusion

Effective with

powder

asbestos loadings

Durostabe 2239

Pb

Durostabe 2248

3BLS'

Injection moulding

Durostabe 2270

3BLS'

Pipe extrusion

chlorinated extenders

flake

Based on tribasic lead sulphate.

Also used with Pb

stabilisers for rigid
PVC moulding

P. S. Coffin

350

TABLE lO.4-contd.
Mixed metal liquid complexes
Trade
name

Main
application

Product
type

General
comments

Nuostabe 979

BalCdlZn
liquid

flexible PVC

General-purpose
stabiliser

Nuostabe 1317

BalCdlZn
liquid

flexible PVC extrusion

Effective with
chlorinated extenders

Nuostabe 1500

BalCdlZn
liquid

flexible PVC calendering

extrusion and injection
moulding

Nuostabe 1515

BalCdlZn
liquid

Plastisols and organosols

Nuostabe 1842

BalCdlZn
liquid

Plastisols and flexible PVC

calendering, extrusion and
injection moulding

Nuostabe 3060

BalCdlZn
liquid

Plastisols and flexible PVC

calendering

General-purpose
stabiliser

Nuostabe 1471

BalZn
liquid

flexible PVC

For use with

phosphate plasticisers

Nuostabe 1829E

BalZn
liquid

Injection moulding for

Nuostabes 1223,
1627, 3029, 3044

CdlZn
liquid

Kickers for plastisols

Nuostabe 983

CalZn
liquid

Plastisols and organosols

Nuostabe 1420

CalZn
liquid

Plastisols and organosols

Good air release,

freedom from viscosity
build-up

Nuostabe 1602

CalZn
liquid

Plastisols

Good viscosity stability

Nuostabe 1830

CalZn
liquid

flexible and semi-rigid PVC

calendering and extrusion

Nuostabe 1839

CalZn
liquid

Plastisols

Good air release and

mould release

Nuostabe 1844

CalZn
liquid

Plastisols, and flexible and

semi-rigid calendering,
extrusion and injection
moulding

Alternative to Cdcontaining stabilisers

Nuostabe 1858

CalZn
liquid

Plastisol coatings, especially

vinyl wall coverings

Nuostabe 1465

Pb
liquid

flexible PVC and plastisols

Alternative to powdered
Pb stabilisers

Nuostabe 1251

Chelator
liquid

Auxiliary stabiliser

Composed of FDA
approved ingredients

Effective at high
temperatures

footwear

10 Commercial Stabiliser Practice

351

Clear flexible extrusions of calendered sheet

BalCd/Zn liquid: Nuostabe 1500
25
Epoxy oil: (e.g. Reoplast 39)
2
Lubricant: stearic acid
02-05
Plastisols or organosols
CalZn liquid: Nuostabe 983
Epoxy oil: (e.g. Reoplast 39)

3
3

Plastisols using FDA approved ingredients

CalZn paste: Durostabe S66
Organophosphite: Nuostabe 1251
Epoxy oil: (e.g. Lankroflex GE-Diamond Shamrock)

2
05-10
3

Flexible extrusions or calendered sheet using FDA approved ingredients

Ca/Zn stabiliser: Durostabe 2262
2
05-10
Organophosphite: Nuostabe 1251
3
Epoxy oil: (e.g. Lankroflex GE)
Clear rigid PVC extrusions or calendered sheet
2-3
BalCd flake: Durostabe S59
Organophosphite: (e.g. Irgastab CH300)
0-2
Epoxy oil: (e.g. Reoplast 39)
1
UVabsorber: (e.g. Tinuvin P-Ciba-Geigy) 05
Lubricant: stearic acid
02
10.6.4 Diamond Shamrock Polymer Additives Division

Diamond Shamrock Polymer Additives Division manufacture all

stabiliser types except lead-based systems, and their range now
includes the stabiliser products previously marketed by Lankro, SA
Argus Chemicals (Belgium), Manchem Ltd (products previously called
Manomet stabilisers) and Albright and Wilson (products previously
called Mellite stabilisers). The company also manufactures plasticisers
and surfactants which enables them to offer package systems in liquid
form (e.g. stabiliser-antistat blends), paste form (e.g. stabiliserantifogging agent) or in pellet form (e.g. stabiliser-lubricant blends).
Stabiliser development has been directed towards high quality
cadmium-free stabiliser systems, in particular through the use of the
matrix system. 9 the major products in the Diamond Shamrock range
are described in Table 10.5.

352

P. S. Coffin

TABLE 10.5
The Basic Stabiliser Range of Diamond Shamrock Ltd
Flexible PVC calendering

General category
(1) Stabilisers with low
lubricant effect, good
clarity and light stability
(2) Lubricating stabilisers,
good plate-out performance
(3) Stabilisers for semi-rigid
PVC
(4) 'Do-it-yourself system
using all three components
as required
(5) Non-cadmium stabilisers

(6) Non-toxic stabiliser

(7) Highly filled PVC flooring
(8) Asbestos-filled PVC
flooring

Trade name

Product type

Lankromark
Lankromark
Lankromark
Lankromark

LC 266
LC 145
LC 68
LC 442

Ba/CdlZn
Ba/CdlZn
BalCd
Ba/Cd/Zn

Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark

LP 15
LP 48
LP 125
LC 288
LZ 22
LE 98
LZ 253
LZ 242
LZ 341
LZ 330
LN 138
LP 103
LP 147
LP 301

Ba/Cd
BalCd
BalCd
BalCd
Zn
Chelator
BalZn

Ba/Zn
Ca/Zn
Ca/Zn
Ca/Zn
Ba/Cd

BalZn
Organic

Flexible PVC extrusion

General category
(1) Many of the above can also
be used for flexible PVC
extrusion
(2) Crystal clear PVC compound
(3) Stabiliser/anti-fogging
agent blends for cling film
(4) Sulphur-staining resistant
cable covering

Trade name

Lankromark
Lankromark
Lankromark
Lankromark
Lankromark

LC 431
A 3021
A 3131
LP 114
LP 356

Product type

BalCd
Ba/Cd
Ba/Cd

Flexible PVC injection moulding

General category
(1) Many of the above can also
be used for flexible PVC
injection moulding

Trade name

Product type

10

353

Commercial Stabiliser Practice

TABLE 1O.5-contd.
(2) Stabilisers for footwear
(3) Non-cadmium stabiliser for
footwear

Lankromark LP 378
Lankromark LP 257
Lankromark LP 422

Ba/Cd
Ba/Cd

Plastisols
General category
(1) Stabiliser/activators
-kickers for foamed PVC
(2) Clear wear layers
(good light stability)
(3) Vinyl wallpaper
(4) Rotational moulding
(good mould release)
(5) Coal Board belting
(6) General-purpose paste
stabiliser
(7) General-purpose leathercloth stabiliser
(8) Non-toxic stabiliser

Trade name

Product type

Lankromark LZ 440
Lankromark LC 101
Lankromark LC 90
Lankromark LZ 187
Lankromark LZ 473
Lankromark LZ 352
Lankromark LZ 528
Lankromark LT 41
Lankromark LT 19
Lankromark LZ 528
Lankromark LZ 110
Lankromet LA 105
Lankromet LA 175
Lankromark LA 247
Lankromark LA 105
Lankromark LP 301
Lankromark LC 310

Zn-fast action
Cd/Zn-fast
Cd/Zn-fast
Ba/Zn-slow
Ba/Zn
Ba/Cd/Zn
BalZn
Tin maleate
Tin
BalZn
CalZn
Ca/Al/Zn
Ca/Al/Zn
Ca/Zn
Ca/Al/Zn
Organic
Ba/Cd/Zn

Lankromark LZ 121

Ba/Cd/Zn

Lankromark LN 138 CalZn

Rigid PVC extrusion

General category
(1) Profile, e.g. PVC window
frames, with good
weathering properties
(2) Clear sheet and profile,
with good light stability
(3) General-purpose extrusion,
with good early colour,
e.g. pipes
(4) One-pack stabiliserl
lubricant system for pipe

Trade name

Product type

Lankromark LP 125

Ba/Cd solid

Lankromark LT 96

Butyltin maleate

Lankromark LT 118

Butyltin
mercaptide

Lankromark LN 468 Ca/Zn pellet

354

P. S. Coffin

TABLE 1O.5-contd.
Rigid injection moulding
General category

(1) General-purpose mouldings,

e.g. pipe fittings
(2) Co-stabiliser for leadstabilised mouldings for
improved flow characteristics

Trade name

Product type

Lankromark LT 162}
.
.
Lankromark LT 63 Butyltm mercaptide
Lankromark LP 103 BalCd solid

Blow moulding, e.g. bottles

General category

(1) Rigid PVC for food-contact

applications
(2) Rigid PVC for food-contact
applications
(3) Co-stabilisers for co-use
with above Ca/Zn systems

Trade name

Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark

LT74}
LT 85
LN 303}
LN 402
LE 87 }
LE 109

Product type

Octyltin
mercaptide
Ca/Zn
Chelators

Rigid PVC calendering

The above stabilisers (i.e. for blow moulding) would also be recommended for
rigid PVC calendering, but the lubricant system would be different.

The following formulations illustrate the use of Diamond Shamrock

stabilisers in a number of rigid PVC applications (all amounts in phr).

Profile extrusion for pvc window frames

pvc + impact {either 5% EVA copolymer
modifier
or Suspension K65 +
10% Paraloid KM323B
BalCd solid: Lankromark LP125
Epoxy oil: Lankromark G
Organophosphite: Lankromark L98
LOXiOI G3O-Hentel
Lubricants:
{ International GmbH
Loxiol G60
Processing aid: Paraloid K120N
CaC03 filler: (e.g. Omyalite 951)
Ti0 2 pigment: (e.g. Tioxide TC30)

100
3
2
05
05
10
10
40
40

355

10 Commercial Stabiliser Practice

Sheet extrusion for clear roofing

pvc (Suspension K65)
Butyltin carboxylate: Lankromark LT96
Combination lubricant: Lankroplast DP5982
.
.
{paraloid K175
ProcessIng aids:
Paraloid K120N

100
25
14

08
07
07

Benzotriazole UV absorber: (e.g. Tinuvin P)

Tinting violet
Pipe extrusion using twin-screw extruder
PVC (Suspension K65)
Butyltin mercaptide: Lankromark LT118
Calcium stearate
Lubricants: { Irgawax 367-Ciba-Geigy
AC 629 A
CaC0 3 filler: (e.g. Omyalite 951)
Ti0 2 pigment: (e.g. Tioxide RCR2)
Bottle blow moulding for food packaging

PVC (Suspension K60)

Octyltin mercaptide: Lankromark LT85
CalZn stabiliser: Lankromark LN303
Organophosphite: Lankromark LE89
Epoxy oil: Lankroflex GE
Combination lubricant: Lankroplast L234
.
.
{ParalOid K175
ProcessIng aids:
Paraloid K120N
MBS impact modifier: (e.g. Blendex BTA)
Calendered foil for food packaging

PVC (Suspension K60)

Octyltin mercaptide: Lankromark LT85
Ca/Zn stabiliser: Lankromark LN303
Organophosphite: Lankromark LE89
Epoxy oil: Lankroflex GE
ts: {wax E (montan ester)
Lub ncan
glycerol monooleate
.
.
{paraloid K175
ProcessIng aids: Paraloid K120N

As required

100
05
08
12
015
2

15

Tin
Ca/Zn
stabilised stabilised

100
15

10
12
10

100
12
05
35
08
12
13

Tin
Ca/Zn
stabilised stabilised

100
15

03
10
10
05

100

12
08
40
01
05
10
05

P. S. Coffin

356

10.6.5 Victor Wolf Ltd (owned by NL Industries, USA)

Victor Wolf manufacture a range of barium/cadmium/zinc, barium/
cadmium and calcium/zinc stabilisers. The principal products in their
range are given in Table 10.6. These are mainly of the liquid complex
TABLE 10.6
The Basic Stabiliser Range of Victor Wolf Ltd
Trade
name

Product
type

Vinco 348

Baled
liquid
Vinco 249C BalCdlZn
liquid
BalCdlZn
Vinco 265
liquid
Vinco 332 BalCdlZn
liquid
Vinco 374B BalCdlZn
liquid
Vinco 2810
Vinco 268
Vinco NlO

BalCdlZn
liquid
CalZn
liquid
CalZn
liquid

Vinco 654

CalZn
paste

Vinco 681

Phosphite
chelator

Main
application

General
comments

Extrusion

Good clarity performance

Calendering, extrusion and

plastisols
Plastisols, e.g. spreading
and dipping
Calendering and extrusion
of film and sheet

Good general-purpose
performance
Good resistance to
pigment plate-out

Calendering and plastisols

Good general-purpose
performance

Calendering, extrusion and

plastisols
Plastisols, e.g. spreading
and dipping
Plastisols, e.g. dipping

Good sulphur-staining
resistance
Low toxicity, good
sulphur-staining resistance
Low toxicity, good
sulphur-staining resistance
Rigid and flexible PVC, e.g. For non-toxic applications,
flexible dairy and
moderate lubricant action
beverage tubing
Rigid and flexible PVC
For non-toxic applications,
for co-use with Vinco 654

type, but also included are Vinca 654 and Vinca 681 which constitute a
mixed metal soap system for such applications as flexible dairy and
beverage tubing.

REFERENCES
1. Press, J. B. (1978). Paper presented at the PRI International Conference on

PVC Processing, Egham Hill, Surrey, England, 6-7 April, 1978.

10 Commercial Stabiliser Practice

357

2. Worschech, K. F. (1978). Paper presented at the PRI International

Conference on PVC Processing, Egham Hill, Surrey, England, 6-7 April,
1978.
3. Peter, W. (1979). Paper presented at the Krauss Maffei 8th International
Extrusion Symposium, Linz, Austria, September, 1979.
4. Nass, L. I. (Ed.) (1978). Encyclopaedia of PVC, Volume 1, Marcel
Dekker, New York, pp. 319, 320.
5. 'The Safe Handling of Lead Chemicals', Associated Lead Manufacturers
Ltd,1979.
6. 'Health Aspects Relating to the Use of PVC Pipes for Community Water
Supply', WHO International Reference Centre for Community Water
Supply, Holland, 1974.
7. Phillips, I. and Marks, G. C. (1961). Brit. Plast. 34,385-90.
8. Bredereck, P. (1979). Paper presented at the 2nd International Cadmium
Conference, London, February, 1979.
9. Donnelly, P. J. (1978). Paper presented at the PRI International
Conference on PVC Processing, Egham Hill, Surrey, England, 6-7 April,
1978.

CHAPTER 11

Some Miscellaneous Components of pvc

Formulations
W. V. TITaw

The major constituents of PVC compositions have been discussed in

some detail in the previous chapters. Others, which may be regarded
as relatively minor but common, and in some cases essential,
formulation components, are dealt with in this chapter, viz. lubricants, polymeric modifiers, colourants, antistatic agents, flame and
smoke retardants. Still other miscellaneous minor additives, some of
which were first mentioned in Chapter 4, are further considered in
other relevant chapters and sections of the book (e.g. blowing agents
in Chapter 25, antioxidants and UV absorbers in Chapter 9, thickening
agents for plastisols in Chapter 21, etc.).

11.1 LUBRICANTS
11.1.1 Functions, Nature and Effects
Lubricants are essentially processing additives-their primary role is to
influence some aspects of behaviour of PVC compositions under the
heat and shear experienced in the processing machinery, so that the
processing is made easier, whilst certain factors promoting thermal
degradation of the polymer are counteracted (see below). For
example, in the extrusion of a rigid PVC composition effective
lubrication can increase output for a given heat and power consumption, or reduce the heating and mechanical power required for a given
output rate. As constituents of a PVC composition, lubricants can also
influence some material properties. for example the thermal stability
359

360

w.

V. Titow

(either directly or through interaction with other components of the

formulation-see below), impact strength of uPVC, printability (which
may be impaired by the presence of a lubricant). The lubricating action
and effects can be divided into external and internal, but a
corresponding division of the lubricants themselves is not strictly
applicable as a firm classification, since some combine both functions in
varying degrees, and also because other additives in a PVC
composition can have lubricant effects, as well as-in some casesstrongly affecting the performance of (and requirements for) the
lubricants proper. 1
The principal external lubrication effect is reduction of friction and
adhesion between the hot PVC composition and the working surfaces
of processing machinery and moulds by the presence of the lubricant at
the interface: this makes movement of the composition through the
machinery easier, and prevents deposition of layers of PVC on the hot
metal surfaces.
Note: Avoidance of stagnant deposits is important in PVC
ing, as the polymer in them soon undergoes
decomposition, becoming a source of contamination
promoting further degradation in, the rest of the hot

processthermal
for, and
stock.

The basic internal lubrication effect is the lowering of internal (i.e.

inter-particle and inter-molecular) friction in the composition throughout processing, which reduces the effective melt viscosity and
frictional heat build-up under shear.
An additive, especially one of relatively low molecular weight, which
is dispersible in PVC on a molecular level (i.e. capable of 'dissolving'
in the PVC resin) may be expected to have some lubricating action. If
the additive is fully compatible with the PVC composition when
present in the amount appropriate to its purpose in the formulation
(say, for example, 80 phr of a primary plasticiser) then its lubricant
action will be of the internal type.
Note: Those polymeric processing aids and impact modifiers used in
PVC that do not lower (and in fact often raise) the melt
viscosity may be regarded as an exception: their compatibility
and relatively high molecular weight are factors in this
behaviour. It may also be noted that poly-a-methylstyrene (a
polmeric processing aid) and polymeric plasticisers do have an
internal lubricant action in that they lower the melt viscosity
of PVC compositions.

11

Some Miscellaneous Components of pvc Formulations

361

If the compatibility of such an additive is limited in the circumstances just mentioned, then it will have an external lubricant effect
(which may be combined with a degree of internal lubrication),
providing that its relevant chemical and physical properties make it an
effective 'slip agent' at the hot metal/PVC interface.
In broad terms, the compatibility of the common additives capable
of lubricant action, and their usual level of addition in PVC
compositions, decrease in the sequence:
primary plasticisers > secondary plasticisers and extenders >
impact modifiers* and processing aidst > stabilisers and
lubricants:j:
Thus the main operative features of additives incorporated specifically
as lubricants are:
(i) generally low compatibility with PVC (lowest for external
lubricants) ;
(ii) chemical nature enabling the lubricant effects to be exerted in
significant measure at the low level of addition (between O 2 and
about 30 phr for the total lubricant system, usually comprising
more than one lubricant).
Since the mode of a lubricant's action (internal or external) is closely
associated with its compatibility with PVC, several studies have been
made of the degree of compatibility of lubricants, measured in terms of
some relevant property of the lubricated PVC composition, with a view
to classifying the lubricants and/or predicting their suitability in
practical applications. 2 The properties measured included the amount
of haze introduced by the additive into a clear PVC compound3 (haze
being a manifestation of incomplete compatibility), and the reduction
of the glass transition temperature (Tg ) caused by its incorporation 4
(lowest Tg with the most highly compatible lubricant). The effect of
lubricants on the fusion behaviour of a PVC composition in a
*Some impact modifiers (e.g. extensively chlorinated polyethylene; nitrile
rubber; VC/EVA graft polymers) are highly compatible with PVC polymersee Section 11.2.
t Some processing aids are occasionally used in high proportions to increase
the resistance of PVC to deformation at elevated temperatures-see Section

11.2.

Lubricants with internal lubricant action are more compatible with PVC
polymer than typically external lubricants.

362

W. V. Titow

rheometer or an extruder has also been used as the criterion of the

type of lubricant action. In terms of behaviour under suitably
standardised mixing conditions in a torque rheometer the most
characteristic effects are:
Typical external lubrication: Fusion time (i.e. time to reach peak
torque-see also Section 11.1.3 below) substantially increased;5--7
torque value may be reduced (because of decrease in external
friction); NB in an extruder, increase of fusion time and torque
reduction are accompanied by a drop in back pressure.
Typical internal lubrication: Torque significantly reduced (in
consequence of drop in melt viscosity); little or no effect on fusion
time.

However, the effects of an external lubricant on the torque rheometer

fusion times of PVC compositions do not always correlate with the
corresponding melting rates in an extruder, 7 although limited prediction of extrusion characteristics may be possible from plots of
rheometer fusion time against mixing head temperature. 8
An increase of melt flow velocity at the wall face of an extruder die
(slip effect) was observed directly by Chauffoureaux and co-workers9
in the case of a PVC compound containing a lubricant with effective
external action: this effect was absent when the lubricant used was one
with a typically internal behaviour. Various studies directed to
characterising and classifying lubricant effects have been briefly
reviewed by Gale,? and by Logan and Chung. lO
The chemical structure of the lubricant is both the prime factor in its
compatibility with PVC and the link between compatibility and the
mode of lubricant action. Results of experimental studies in this area,
and in particular those of the authoritative work of Illmann l l are
consistent with the theoretical expectation that the molecular size
(chain length) and polarity (nature and number of polar functional
groups) of a lubricant are the main factors determining the compatibility and lubricant behaviour: broadly speaking, short chain length and
high polarity make for good compatibility and internal lubrication,
whereas relatively long-chain compounds (even with some polar
groups) tend to be poorly compatible and act as external lubricants.
The types of chemical compound used as lubricants in PVC are shown
in Table 11.1: among those, typical examples of low compatibility and
external lubrication effects are provided by, say, the polyethylene
waxes and calcium stearate, whilst relatively high compatibility and

11

Some Miscellaneous Components of pvc Formulations

363

TABLE 11.1
Compounds Used as Lubricants2,4,9
General type

Class of compound

Examples

Hydrocarbons

Natural hydrocarbons
Synthetic hydrocarbons

Paraffins, paraffin oils

Synthetic paraffins, low
molecular weight
polyethylene

Hydrocarbon
derivatives

Fatty acids
Fatty alcohols

Stearic acid
Cetyl, stearyl, octadecyl

Derivatives
of organic
acids

Metal salts (soaps)

Stearates of barium, calcium,

aluminium, and lead

Amides
Esters and partial
esters

Stearamide
Butyl stearate, glycerol
monostearate, glycerol
monoricinoleate;
Stearyl esters, montan acid
esters

Wax esters

associated internal lubricant action are exemplified by the partial esters

of glycerol.
Whereas rigid PVC compositions normally require both internal and
external lubricants (unless lubricating stabilisers and/or processing aids
are used-see below) only external lubricants will usually be
considered for flexible compositions, as in those the plasticiser will
provide internal lubrication (some external lubrication may also be
supplied by plasticiser extenders if present). However, an external
lubricant may be useful, or necessary, even in such heavily plasticised
compositions as certain plastisols, especially for intricate mouldings. 2
Because of the need to achieve the right measure of internal and
external lubrication, and to balance-in the particular, individual
composition-the effects of the lubricants with those of the other
additives present, more than one lubricant (i.e. a lubricant system) is
normally employed in rigid PVC formulations (where up to four
lubricants may be combined in some cases) and sometimes also in
pPVC. The mutual effects and interactions of the lubricants with the
other formulation components are important considerations, affecting
both the choice of the lubricant system and the design of the
formulation as a whole.

364

w.

V. Titow

11.1.2 Interaction and Co-action of Lubricants with Other PVC

Formulation Components
(a) Lubricant/Stabiliser effects
STABILISING EFFECfS OF LUBRICANTS

Direct stabilising action: Most lubricants of the metal soap type (see
Table 11.1) have some stabilising effect, and some can act as stabilisers
in their own right, albeit their action in this role is not as strong as that
of the more powerful 'primary' stabilisers. Thus certain metal soap
lubricants (e.g. calcium stearate) can be used in either capacity in PVC
formulations (but when employed as the sole stabiliser, a relatively
large amount will be needed to provide a reasonable measure of
long-term stability, and the overall stabilisation will not be as good as
that conferred by a smaller proportion of a strong primary stabiliser).
Lead stearate and dibasic lead stearate are widely used as lubricating
components of lead stabiliser systems.
Synergistic action with stabilisers: Some lubricants can enhance the
effectivity of some stabilisers by a synergistic effect. The synergistic
lubricants are of the internal kind (i.e. comparatively highly compatible with PVC) and usually contain reactive functional groups (in
particular hydroxyl) in the molecule. Typical examples are partial
esters of glycerol with relatively long-chain saturated or unsaturated
aliphatic acids. In those compositions where it occurs, the synergistic
effect depends, in a complex way, on several factors, including the
PVC resin (type and grade), the nature and amount(s) of stabiliser(s)
in the stabiliser system, and the amount of the synergistic lubricant
present. The stabiliser systems which benefit from the effects of
lubricant synergists are those based on sulphur-containing tin compounds (thiotin or tin mercaptide stabilisers) or on lead compounds. In
rigid compositions incorporating calcium stearate as the sole heat
stabiliser (e.g. in some pipe compounds for potable water in Europe)
most lubricants, whether synergistic or 'neutral' in their effects with
other stabiliser systems, can produce some stability improvement. 12
Calcium stearate used as a lubricant synergistically improves heat
stabilisation by antimony mercaptide stabilisers. 13 With BalCd,
Ba/Cd/Zn, CalZn and Ca/Mg/Zn stabiliser systems synergistic effects
are important, but they are provided by epoxy-compound co-

11

Some Miscellaneous Components of pvc Formulations

365

stabilisers, usually in conjunction with an organic phosphite (see

Chapters 4, 9 and 10), and the lubricants used do not make any
significant contribution in this respect. Improvements in heat stability
(mainly long-term) of compositions stabilised with sulphur-containing
tin compounds (e.g. rigid films, calendered or extruded) can be
promoted by the use, as lubricants, of glycerol partial esters (liquid
versions, e.g. glycerol monoricinoleate, are necessary for transparency).
Lubricants of this kind also enhance the stability of compositions
containing lead stabiliser systems (but discoloration can arise,
especially on outdoor exposure, with such inorganic lead stabilisers as
lead phosphite or sulphate*) Pentaerythritollfatty acid partial ester
lubricants can be particularly effective in synergistically enhancing the
long- and short-term stability of lead-stabilised rigid PVC compositions, allowing significant reductions in the amount of stabiliser
necessary in many cases. 12 Negative effects can also arise: for example,
the presence of glycerol partial ester lubricants can reduce the thermal
stability of compositions stabilised with sulphur-free tin stabilisers
(whilst very good stability may be maintained if the lubricant is an
ester of a monohydric alcohol and long-chain fatty acid-e.g. butyl
stearate).
Note: On the other hand, the heat stability of uPVC (dry blend)
compositions stabilised with a butyl thiotin stabiliser can be
impaired if cadmium stearate is included in the lubricant
system. 8
Indirect stabilising action: In discharging their primary functions, the
lubricants also affect the thermal stability of a PVC composition. By
lowering frictional heat build-up (through both internal and external
lubrication) and melt viscosity, and hence the effective processing
temperature, as well as limiting direct contact between the stock arid
hot metal surfaces whilst simultaneously preventing the formation of
stagnant deposits (through external lubricant action), lubricants reduce
the scope for immediate thermal degradation of the PVC in processing
and limit its 'heat history': the first of these two general effects is
equivalent to improving short-term thermal stability, and the second a
factor enhancing the long-term stability of the composition. 5 ,8 The use

* This is attributable to a reaction of these compounds, in the presence of light,

with free glycerol often contained in residual amounts in commercial glycerol
esters. 12

366

W. V. Titow

of an effective lubricant system can thus reduce the demands on the

stabiliser(s).
LUBRICANT ACTION OF STABILISERS

Several stabilisers have some lubricating action (usually mainly of the

external kind). This is greatest with some metal stearates: as indicated
above, certain compounds in this group (e.g. calcium and lead
stearates) may be regarded as lubricants with stabilising properties (see
also Chapters 9 and 10). Some tin stabilisers also exert lubricant effects
(e.g. dibutyltin dilaurate), as do Ba/Cd soap complex stabilisers.
Compositions containing such stabilisers will require less lubricant(s)
overall (none in some cases) and/or a different balance of the lubricant
system.

(b) Mutual Effects of Lubricants and Plasticisers

PRIMARY PLASTICISERS

The internal lubricating action of primary plasticisers has been mentioned (see Section 11.1.1 above): this makes the addition of internal
lubricants to plasticised compositions unnecessary in most cases.
However, if the external lubricant used is highly compatible with the
plasticiser(s), its lubricating action in the composition will normally be
reduced, necessitating an increase in the level of addition.
SECONDARY PLASTICISERS AND EXTENDERS

Some of these may exert external as well as internal lubricant effects.

However, the extent (or even the occurrence) of external lubrication
will depend on the nature (and given that, the amount) of the
plasticiser(s) or extender(s) present, and to some extent also on the
process. For example, in calendering compositions many polymeric
plasticisers, even when used near the compatibility limit, provide no
external lubrication so that external lubricants are required to
counteract 'stickiness' in processing: on the other hand, in some
compositions containing a chlorinated-paraffin extender this additive
can provide both internal and external lubrication in sufficient degree.
(c) Effects of Polymeric Modifiers (see also Section 11.2)
The polymeric additives incorporated in a PVC composition, in
relatively minor proportions, as impact modifiers or processing aids,
can, in any individual case, affect the total lubricant requirement

11

Some Miscellaneous Components of pvc Formulations

367

and/or that for the internaVexternal lubricant balance in a composite

lubricant system, if their own compatibility with the lubricant(s)
influences the latter's compatibility with the composition as a whole,
or-as, for example, in the case of some processing aids (see
below)-because of direct lubricant action.
PROCESSING AIDS

Many of these have no lubricant effect, internal or external, in that

they do not reduce the melt viscosity or the external friction and
'sticking' tendency of a PVC composition. However, some acrylicbased lubricating processing aids with pronounced external lubricant
action are available,14 and poly-a--methylstyrene (of the relatively low
molecular weight grade used as a processing aid) lowers the melt
viscosity of PVC compositions (i.e. has an internal lubricant effect).15
IMPACf MODIFIERS

Most ABS and MBS modifiers have no lubricant action. With those
highly compatible modifiers which may be incorporated in large
proportions to act as permanent plasticisers (nitrile rubber, chlorinated
polyethylene of high chlorine content, VClEVA graft copolymers)
lubricant effects may arise. The presence of some impact modifiers
increases the compatibility of external lubricants with the composition,
so that the external lubricant has to be carefully selected (and a
relatively high amount may have to be used) for optimum results.
(d) Effects of Fillers and Pigments
Fillers and pigments (especially fine-particle grades) can bind lubricants by absorption (ct. plasticiser demand-Chapters 4 and 8) so that
their presence in a PVC (especially uPVC) composition can increase
the lubricant requirement. However, this effect may be reversed-at
least with regard to external lubrication-if the filler carries a stearate
coating (see Chapter 8) as this can not only block absorption of
lubricants at the particle surface, but also actually provide additional
lubrication.
11.1.3 Assessment of Lubricant Effects

Reference has already been made in Section 11.1.1 to the evaluation of

the effects of lubricants in PVC compositions with the aid of a torque
rheometer or in an extruder; capillary rheometers are also sometimes

W. V. Titow

368

employed. The torque rheometer is widely used for this purpose (as
indeed, in general, for practically oriented studies of melt-processing
characteristics of PVC compositions): very popular and well-known
commercial equipment of this kind is the Brabender Plasti-Corder. * In
essence this consists of a thermostatically heated mixing chamber
housing two rotors mounted in a measuring head and driven by a
variable speed motor. The equipment is instrumented for continuous
measurement of the torque on the rotors (which is a function of the
resistance of the PVC composition to the mixing action) and the mix
temperature. A plot of torque against mixing time typically shows a
rise of the torque as the mix is fluxed, and something of a drop when
the fusion point is reached (see Fig. 11.1): the 'fusion time' taken to
reach this point is increased by external lubrication; the torque value
can also reflect lubricant effects. A standard method for carrying out

CJl~

:J

L.

f-

~ ~ - ~-

- - - -

- ----=-=_::"':_=-=_:":_==--=-=-=-=-=_:-

A
Time

Fig. 11.1 Schematic representation of a 'plastogram' recorded on a

Plasti-Corder chart for a uPVC composition. A, Torque (Nm); B, mix
temperature (0C); C, mixer temperature (0C).

* Marketed by C. W. Brabender Instruments Inc. (in North America),

Brabender OHG (in West Germany), and agents in most countries. The
Plasti-Corder is a larger, more sophisticated version of the original Brabender
Plastograph. Several models are available, with torque ratings between 100 and
400 Nm and different maximum rotor speeds.

11 Some Miscellaneous Components of pvc Formulations

369

this kind of fusion test is given in ASTM D 2538-79 (see Appendix 1,

Section 2.12). For determinations relevant to extrusion characteristics
of a PVC composition extrusion heads can be fitted to the
Plasti-Corder. 16 The RAPRA torque rheometer* is another wellknown instrument of the internal mixer type.
Determinations of melt viscosity (in many cases the value determined will be the apparent viscosity, if the melt behaves as a
non-Newtonian fluid) in capillary or, generally, tubular die rheometers
may be used to follow the reduction in viscosity brought about by
internal lubrication. A standard method, employing a piston plastometer, is given in ASTM D 3364-74 (1979) (see Appendix 1, Section
3.1(d; this can be useful for direct comparison of internal lubricant
effects in the same composition (or two closely similar compositions)
but correlation with processing practice may be variable, inter alia
because the shear rates imposed by the processing equipment can be
different (higher) than those in the plastometer, and the effects of melt
elasticity can affect the behaviour differently.
Highly sophisticated equipment has been described by Chaufoureaux and co-workers,9 not only capable of demonstrating the
overall effects of lubricants (as well as other constituents) on the
rheology of a PVC composition, but also providing data indicative of
the mechanisms of lubricant action.
The concept of 'lubricant value' (LV) has been put forward 17 as a
means of comparing-in a general, approximate way-the effectivity of
different lubricants and lubricant systems, including the stabiliser/
lubricant combinations formulated for use in particular applications.
To calculate the LV, appropriate data from standard determinations in
a Brabender Plasti-Corder are used in the formula:
LV = (lOOOE)/(T. md)
where: E is the total weight of lubricant additive (phr); T is the stock
temperature in the mixing compartment (0C); and md is the torque
(kgfm).
As can be seen, the LV is highest for the most effective lubricants.
The LV values of many lead-based stabiliser systems (Biiropan SMS
stabilisers-Otto Barlocher GmbH) were found 17 to lie between about
6 and 14.
Various laboratory methods of assessment of lubricants have their
* Developed in the UK by the Rubber & Plastics Research Association.

370

W. V. Titow

place in more fundamental studies as well as in the preliminary

selection and comparison for the purposes of practical formulation of
PVC compositions. In the latter case, however, actual processing trials
should always be conducted. Much of the development work on
lubricant systems for various types of compositions and processes is
done by suppliers of lubricants (and stabiliser suppliers, since
combined stabiliser/lubricant 'one-pack' systems properly formulated
can offer the advantages of optimum compatibility, component balance
and synergistic effects). A further extension of the one-pack concept is
the inclusion of other additives with the stabiliser/lubricant system, so
that the total additive content is tailored for particular requirements.
The advantages and limitations of this approach are mentioned in
Chapters 9 and 10. Another recent, interesting, line of development
has been the introduction of lubricant concentrates in PVC, in the
form of PVC particles heavily loaded (about 50% and over) with
calcium and barium stearates. The principal advantages of such
concentrates are that they are virtually dust-free, can be air-conveyed
and have dry-flow properties very similar to those of PVC resins.
The effects of incorrect balance, or total amount, of a lubricant
system in a PVC composition may include the following, in varying
degrees of severity:
Processing
Overlubrication:

(or wrong balance)

Underlubrication:

(or wrong balance)

Excessive slippage (resulting in lower output

or even disruption of
production); plate-out
High shear resistance
(resulting in lower output); degradation of
polymer in melt

Product

Surface bloom; haze (in

clear compounds); impaired printability
Impaired stability (because of excessive heat
history) or actual degradation

The presence of a slight excess of external lubricant can have some

useful effects. Thus surface gloss may be improved, and surface friction
and tendency to blocking reduced.

11.1.4 Sources of Information on Lubricants and Their Commercial

Suppliers
In addition to the references already quoted in this section, papers
published by Jacobson,18 Riethmayer,19 and Stapfer et al. 20 are
concerned with the nature, application and effects of lubricants.

11 Some Miscellaneous Components of pvc Formulations

371

Many suppliers of heat stabilisers for PVC (ct. Chapter 10, especially
Table 10.1) also supply lubricants. Listings of lubricant suppliers (as
well as those of most other additives) in the Western World will be
found in the publications mentioned in Section 8.5 of Chapter 8. Many
British suppliers are also listed in the Buyers' Guide for Plastics
Additives published by the British Plastics Federation. The following
may be mentioned by way of a few examples.

UK: Ciba-Geigy Plastics and Additives Co. Industrial Chemicals

Division (Irgawax); Diamond Shamrock Ltd (Lankroplast, Lankromark); Croxton and Garry Ltd (Lubriol, Syntewax).
Continental Europe: Henkel International GmbH, West Germany
(Stenol, Ceroxin, Loxiol); Otto Barlocher GmbH, West Germany
(Biiropan); Acima, Switzerland (Metawax, Metaglide).
USA: Emery Industries, Inc. (Emerwax); Interstab Chemicals Inc.
(Interstab); Nopco Chemical Division of the Diamond Shamrock
Chemical Co. (Metasap, Nopcowax); Witco Chemical Corp. (Lubraplus); Petrochemicals Co. Inc. (Monolube).
11.2 POLYMERIC MODIFIERS
As has already been mentioned in Chapter 4, the polymeric additives
incorporated in PVC compositions may be broadly classified into two
groups according to their functions, viz. processing aids and impact
modifiers. In general terms, the main differences which form the basis
of this classification are in the nature of the polymers used in each of
the two capacities (see Sections 11.2.1 and 11.2.2 below), in the usual
level of addition (normally substantially lower with the processing
aids), and in the type of effect: processing aids-as implied by their
name-serve to modify the properties of the PVC stock during heat
processing (but have relatively little effect on those of the finished
product), whereas the main function of impact modifiers is to improve
the impact resistance of the product. However, whilst the above
features do typify the group characteristics in a general way, they are
not rigidly definitive. Thus there is some overlap in the types of
polymer used for the two respective purposes; many impact modifiers
have some processing-aid action (albeit this often tends to be
manifested at temperatures somewhat higher than those at which
typical processing aids exert their effect); processing aids can affect
some product properties even at their usual, relatively low level of

372

W. V. Titow

addition. Certain of the polymeric additives are also used in

exceptionally high proportions to upgrade the heat-distortion properties of uPVC compositions (see Section 11.2.1), or to combine a
toughening effect with plasticisation of virtually ideal permanence (see
Section 11.2.2).
It is very important for its maximum effectivity (and hence also cost
economy) that any additive (and especially one used in relatively minor
proportions) should be dispersed as thoroughly as possible in the PVC
polymer. This applies to the polymeric modifiers discussed in this
section.
In the production of PVC pre-mixes for further (melt) compounding,
and dry blends for use as feedstocks in melt processing, the order of
addition of the formulation components (in conjunction with the
temperature at the various mixing stages) plays a significant part in the
ultimate degree of dispersion and effectivity of action of the polymeric
modifiers. The following guidelines for a particular procedural
sequence and conditions in hot high-speed mixing of a powder blend to
be used as extrusion feedstock,21 illustrate something of the points
important in practice (see also Chapter 13, Section 13.4.1, for a more
complete discussion of high-speed mixing):
-<:harge the PVC powder to the mixer and mix at the appropriate
(high) speed;
-add colourant and stabilisers at 45C, then impact modifier at
60C;
-add lubricant(s) at 80C;
-when the temperature reaches 100C add acrylic processing aid;
-<:ontinue mixing, and at l1o-112C discharge the batch into a cold
mixer (e.g. a water-jacketed ribbon blender); run till cooled to
40C and discharge.
Information on suppliers of polymeric modifiers will be found in the
sources mentioned in Section 11.1.4 above. Some commercial
materials are mentioned, by way of non-selective example, in Sections
11.2.1 and 11.2.2.
11.2.1 Processing Aids
The polymers used as processing aids in PVC are of the following
kinds:
(a) acrylates and methacrylates (acrylic processing aids);

11 Some Miscellaneous Components of pvc Formulations

(b)
(c)
(d)
(e)

373

styrene/methacrylate copolymers;
acrylonitrile/butadiene/styrene (ABS) polymers;
styrene/acrylonitrile (SAN) copolymers;
poly-a-methylstyrene (PAMS).

The molecular weight of the PAMS grades marketed as processing aids

for PVC (Amoco Resin 18-Amoco Chemicals Corp., USA) iS,low
compared with those of other processing aids. Some ABS polymers are
used also as impact modifiers (as are some acrylic polymers--see
Section 11.2.2 below). One of their composition-related properties,
viz. the modulus of elasticity, is sometimes cited as a rough index of
the type of their effect in PVC compounds: those useful as processing
aids have the highest moduli, whilst the moduli of ABS impact
modifiers are comparatively low (less than about 14 GPa).
Processing aids are employed in rigid PVC compositions, in
relatively low proportions (about 1-6 phr) to facilitate melt processing.
The typical effects of their presence on the stock are: 14 ,21-24
(i)
(ii)
(iii)
(iv)
(v)

increased rate of homogenisation and fusion, except in the case

of lubricating processing aids which extend fusion time (but
reduce torque and back-pressure in extrusion-cf. (v) below);
improved strength, cohesion and extensibility of the melt;
reduction of melt modulus and 'nerve', die-swell, and tendency
to melt fracture;
increased melt viscosity (except with PAMS by which it is
reduced in most types of uPVC composition);
tendency to increase torque and back-pressure in extrusion,
attributed to the faster, higher-shear character of the fusion
process 14 (PAMS is a partial exception here).

Effects (i) and (v) can be sensitive to the nature and amounts of the
lubricants present in the composition (especially where the processing
aid is PAMS23).
Note: In view of effects (iv) and (v) the practice-occasionally
encountered-of calling processing aids for PVC 'flow promoters' is questionable. It would be preferable to restrict the
latter term entirely to its original use as a name for the group
of additives sometimes incorporated in thermosetting resin
systems to reduce the rate of interaction of reactive groups by
a dilution effect. 25

374

W. V. Titow

Effect (ii) is a contributory factor in the improvement in thermoformability conferred on PVC sheeting by processing aids (especially of
the acrylic type).
The mechanism whereby processing aids produce their effects is not
yet fully understood. In certain respects their action is similar to that of
internal lubricants, but there are also important differences (e.g. the
opposite effect on melt viscosity in most cases): attempts to treat the
action of both these types of additive as a simple case of plasticisation
at high temperature,25 fall short of a complete explanation.
In addition to their role in the processing of uPVC, which is the
primary reason for their use, processing aids present at the normal
levels of addition can also affect some properties of the material.
Typically (e.g. with acrylic processing aids) such effects may include
improved surface finish (freedom from defects; improved gloss), better
colour stability of coloured materials, and improved transparency of
clear compositions.
Incorporation in uPVC compositions of high proportions (up to about
50 phr) of some polymers with processing-aid action (e.g. certain
styrene/acrylonitrile (SAN) copolymers) can improve the heat distortion temperature, increase the Vicat softening point and reduce the
linear thermal expansion. However, impact strength is also usually
reduced, and suitable impact modifiers should be included in the
formulation to counteract this effect. Such compositions may be used
in a number of applications calling for a higher than average degree of
resistance to heat distortion (e.g. some pipes and injection moulded
pipe fittings, some extruded profiles): transparent versions in which the
polymeric modifiers (as well as the other components of the
formulation) are approved for food contact are of interest for the
manufacture of containers (jars, bottles) for food products which are
still hot at the filling stage (e.g. jam, marmalade, some liquids). The
following formulation has been cited (by Sahajpat26 ) as a good general
basis for a transparent composition of this kind, with low haze and
yellowness index, a Vicat softening point (DIN 53 460, 5 kgf load) of
85C and impact strength (ASTM D 256) of 324 kgf cm cm- 2.
Suspension PVC polymer, K value 58
Stabiliser: Irgastab 17 MOK (Ciba-Geigy)
Polymeric modifiers: SAN
MBS
Lubricants: Sapchim Lubricant 4150
Sapchim Lubricant 6164

100

12 phr
20phr
10phr
07phr
05 phr

11

Some Miscellaneous Components of pvc Formulations

375

Some special ABS modifiers, * used in very high proportions, can

confer similar improvements in the temperature-dependent properties,
with good impact resistance and without substantial increase in
flammability.21

11.2.2 Impact Modifiers

(a) Impact Resistance-Its Nature, Significance and Measurement
Most PVC (as indeed other plastics) products are at risk of possible
damage by impact at some point during their lifetime, either through
accidental hits or drops (e.g. PVC pipes during transport and
installation; PVC containers in transport and storage), or in the course
of normal manipulation (e.g. PVC packaging film on high-speed
converting and packing machinery) and service (e.g. PVC swing doors
in factories and storage premises). For these reasons the degree of
resistance to breaking on impact, and its measurement, are of practical
importance in the selection and comparison of plastics materials for
particular applications, product design, and quality assessment and
control. On a more fundamental level, understanding the causes and
mechanisms of failure by fracture on impact of plastics materials and
products is equally important in the context of materials science.
The impact tests in general use measure directly the total energy
needed to break the test specimen by impact. This is one of the two
main general differences between such tests and the regular strength
tests, in which the force (load) which causes the specimen to yield or
break (in tension, compression, flexure or shear) is determined,
normally in conjunction with the load Ideformation curve. t
Note: Thus in this context 'strength' is the force (or the stress) for
failure. It is for this reason that the term 'impact resistance' is
replacing the formerly widely used 'impact strength' in the
titles of standard impact test specifications and references to
their results.

* These polymers are not primarily processing aids, and a formulation

containing even, say, 80 phr of such a modifier can benefit from the inclusion
of 2-4 phr of a good acrylic processing aid, e.g. Aery/aid K-120N (Rohm and
Haas Co., USA-the trade name Para/aid is used by Charles Lenning
Chemicals and affiliates in the UK and certain other countries: the product
coding is universal).
t The values of the stress at failure, and true stress/strain curves, can be
derived from such data.

376

W. V. Titow

The other difference lies in the respective test speeds (and hence
rates of deformation): those obtainable with ordinary strength-testing
equipment are much lower than the ones occurring in impact tests,
where the testing speeds are comparable with the speeds which can be
experienced by freely dropped objects (about 2-7 m S-I). These
differences do not mean that impact tests are fundamentally different
from strength tests. Although not measured directly in the latter, the
total energy to break can be computed from the area under the
stress/strain curve. Whilst the value so obtained will correspond to the
rate of deformation in the strength test concerned, and will thus
normally be numerically different from one furnished by a relevant
impact test (in which the deformation rate will be different), it has
been shown27 that both values can lie on the same smooth curve in a
plot of energy to break versus rate of deformation, if the mode of
failure (see below) is the same in the two tests.
Note: With special apparatus and instrumentation, tensile-strength

testing speeds can be brought up into the range involved in

impact tests. 28 29 One version of such a high-speed test is
covered by an ASTM standard. 30 However, certain difficulties
attendant upon this kind of testing, and the fact that the
stresses generated differ in state and distribution from those
arising in other impact tests, limit its relevance to impact
properties of plastics largely to the role of a supplementary
technique, of interest predominantly (though not exclusively)
in research.
The concept of toughness of a plastics material (or object) is based
on the definition of this property as the work necessary to break a
suitable specimen of the material (or the object). This is, of course, the
same as the total energy to break (given by the area under a
stress/deformation curve) and hence-in an impact test-the impact
resistance. However, any actual numerical value of impact resistance
obtained in a test is only an arbitrary index of toughness, relating
specifically to the single set of conditions and specimen characteristics
(including its dimensions and configuration) employed in the test. *
This is so because impact resistance is not a fundamental, constant
property of a plastics material (or its parent polymer) with which a
product made from the material may be expected to be fully and
* Such values are often referred to as 'single-point data'.

11

Some Miscellaneous Components of pvc Formulations

377

directly endowed. In both the material and its derivative products the
impact resistance is influenced-in a complex way-by many factors,
which may be grouped under the following headings:
'Internal' material factors: composition; morphology; fine structure (including crystallinity and molecular orientation); presence of impurities, nibs or gels.
(ii) Effects of processing conditions: modification of the material
properties (e.g. crystallinity, orientation, impurities, etc.) in
processing; heat degradation;* incomplete fusion;* incomplete
interdispersion of formulation components* (and especially
impact modifiers and particulate additives in the polymer); such
process-induced product features as 'skin-and-core' effects in
mouldings, presence of internal stresses (cooling and packing
stresses in mouldings); surface imperfections or faults; and
weak sites (e.g. weak weld lines in injection mouldings, or nip
closures in blow-moulded containers).
(iii) Design factors: In products:t abrupt changes in section
(especially sharp corners); moulded-in metal inserts; machined
holes and screw threads. In standard test specimens: 'geometry';
presence and characteristics of notches. In both: material flow
(direction and pattern) in the course of formation in relation to
the 'geometry' of the object (position and type of gates in
injection mouldings).
(iv) 'External' factors:+ energy and speed of impact (and hence the
rate of deformation); shape and hardness of impacting object;
point of impact; temperature; nature of environment (possible
presence of stress-cracking agents).

(i)

Whilst anyone of these factors can affect the magnitude of impact

resistance, and the way in which fracture occurs in a given situation,
the wide scope for their combined action or interactions can also
complicate the fundamental interpretation of impact test results, as the
same values of fracture energy may be obtained for materials or
products fracturing by different mechanisms. Data on the associated
stress/strain characteristics can be a great help in interpretation: some
modern, suitably instrumented impact testers of the falling-weight type
provide such information as well as other dynamic-property data. 31 ,32
* Of special significance in PVC.

t Features creating stress concentration

(some .crack-initiating).
:t:Operative in service conditions and/or tests.

378

W. V. Titow

Standard impact tests normally yield single-point data; but even

multi-point data provided by planned variation of the basic conditions
of a standard test, and/or the use of more than one test, cannot provide
a basis for a complete characterisation or prediction of impact
performance (although a well designed, comprehensive test programme
can go a long way in this direction, at least in some cases). Thus,
despite the comparability of the rates of deformation in standard
impact tests with those encountered in service, the degree of
correlation of the test results with impact resistance in service (or
between two different tests) is relatively limited. Nonetheless, a
standard impact test can be of practical value if its limitations in the
particular context are property recognised, and especially where-in
addition-experience of its use and a body of accumulated test data
relatable to service performance are available. It is on this basis that
standard impact tests are mainly employed in the industry.
Where a product or article can be tested in conditions realistically
approximating to the most severe likely service conditions the results
(even in the form of non-quantitative 'pass' or 'fail' information) can
provide valuable means of material comparison and production quality
control, as well as guidance on product design. This applies, for
instance, to drop tests on plastics containers* (some of which are
covered by standard specifications-e.g. ISO 2248 Part IV and the
corresponding BS 4826 Part 4; ASTM 0 2463), bird-impact tests on
aircraft canopies, or bullet-impact tests on safety screens or practice
targets.
Standard impact tests in general use for plastics materials or
products, and hence applicable, inter alia, to PVC, are listed in Table
11.2 (see also Appendix 3, Impact Resistance). Other relevant
standards, relating specifically to PVC materials and products, will be
found in the appropriate sub-sections of Appendix 1. The following
standard specifications give impact tests (all of the falling-weight type)
for extruded PVC products (pipe and cladding):

ISO 3127-1980. Unplasticised polyvinyl chloride (PVC) pipes for the

* Drop tests usually form the basis of impact resistance requirements laid down
by various national and international regulations governing acceptance for
transportation of filled containers (including plastics containers): ct., for
example, the International Maritime Dangerous Goods (IMDG) code; US
Department of Transport (DOT) regulations; International Air Transport
Association (lATA) regulations; or the RID regulations (Department of
Transport, UK) concerning carriage of dangerous goods by rail.

DIN 55448-1977

ASTM D 2289-69 (1976)

(high-speed test)

ASTM D 1822-79

Plastics compositionsa

Plastics compositionsa
(specimens as in
ASTM D 1822)

Energy to break in J
or ft lbf
Energy to break per
unit cross-sectional
area, in J m- 2 or
ftlbfin- 2
(NB Test also gives
tensile strength, in
Pa or lbfin- )
Energy to break, in
mJ mm- 2 or kJ m- 2

Rigid plastics compositions;a

rigid plastics sheet
Plastics compositionsa

DIN 53 443-1975 Parts

1 and 2

In the form of standard moulded specimens.

Tensile impact

Energy to break, in
J; kgf cm; or ft lbf
Mean tup weight for
failure, in kg or lb
Energy to break, in J

Rigid plastics compositions;a

rigid plastics sheet
Plastics sheet or parts

BS 2782:1970: Methods
306B and C
ASTM D 3029-78

Falling weight
impact

Expression of results
See Table 11.3

Applicable to:
Rigid plastics compositions;a
rigid plastics sheet

See Table 11.3

Relevant standards

Flexural impact
(Izod and Charpy
type)

Test type

TABLE 11.2
Types of Standard Impact Test in General Use

V.l

a6'

S"

l':

~
~

"tI

t:;

;:

~c

1:;

;:

t:;.

'"a::

~
::l

''-

380

W. V. Titow

transport of fluids-Determination and specification of resistance to

external blows.
BS 5255:1976. Plastics waste pipe and fittings.
ASTM D 2444-70 (Reapproved 1977). Impact resistance of thermoplastic pipe and fittings by means of a tup (falling weight).
ASTM D 3679-79. Rigid poly (vinyl chloride) (PVC) siding. *
It is a particular advantage of falling-weight impact tests that-in the
versions employing suitable equipment-actual products (mouldings;
sections of pipe, profiles or cladding; etc.) can be tested. Such tests
carried out on one of the modern testers with microprocessor
instrumentation,t in conjunction with similar tests on suitable material
specimens, can provide a great deal of information on the effects of
design and processing, as well as basic data on the fracture mechanism.
Impact testing of PVC pressure pipes with the aid of explosive
charges33 may be mentioned as an example of the use of a special
technique to obtain information on fracture characteristics under
deformation rates and stresses relevant to conditions which the pipes
may experience in service (e.g. in mines).
Two cardinal aspects of the fracture on impact of a plastics object in a
test or in service are the fracture mechanism and the mode of failure
(brittle, ductile or intermediate-see below).
A plastic (like its parent polymer) fractures through the initiation
and propagation of cracks, and the total energy to break is the sum of
the energies consumed in each of the two processes. A systematic
examination of the effects of notch sharpness in notched specimens on
their impact resistance (energy to break) in suitable impact tests can be
a useful basis for assessing a material's resistance to crack initiation
and propagation. As the sharpness of the notch increases the
proportion of the total energy to failure expended on crack initiation is
reduced:* tests on very sharply notched specimens (notch-tip radius
about l0.um or less) can give a good indication of the crack

* This is a product specification prescribing, inter alia, a falling-weight impact

test on a variable-height impact tester (Gardner Tester Model IG 1120Gardner Laboratories Inc., Bethesda, Md., USA).
t e.g. the 'Dynatup' impact tester, marketed by Effects Technology, Inc.,
USA,31 or the CEAST Fractoscope (CEAST S.p.A., Italy).
:j: The ratio of the impact resistance of unnotched specimens to that of notched
specimens is generally referred to as 'notch sensitivity'. Numerical statements
of notch sensitivity should always be related to the particular test (and the
notch radii) used.

11 Some Miscellaneous Components of pvc Formulations

381

propagation energy (as the crack initiation energy is drastically lowered

by the high local stress concentration created by the sharp notch).

Note: Stress concentrations occurring 'naturally' in plastics objects

(including unnotched test specimens) can be caused, inter alia,
by surface faults or damage, as well as the presence of gels,
nibs or large particles (e.g. undispersed aggregates of filler or
pigment particles, adventitious contaminant particles) in the
material. As pointed out by Vincent,34 a notch of 025 mm
radius approximates to the most severe defect likely to be
encountered in practice, whilst, at the same time, its use in
extended tests permits coverage of a wider range of temperatures than that of blunter notches which approximate better to
the most common service defects. The 025 mm radius notch
is used in several standard flexural impact tests (see Table
11.3).
Evaluation of the effects of an impact modifier in a rigid PVC
composition, or comparison of different modifiers, should be based on
investigations of this kind rather than-as often happens in the
industry~n single-point data from individual impact tests. The
temperature (and-if practicable-also the speed of testing) should
also preferably be varied in such investigations, to ascertain whether a
ductile/brittle transition in the mode of fracture (see below) may be
affecting the impact resistance within the relevant range of conditions.
Finally, supplementary information on the stress/strain behaviour of
the specimens at the rates of deformation and temperatures used in the
test is also relevant and helpful. The validity, as well as the practical
importance, of such investigations is illustrated, if illustration were
needed, by reports which crop up from time to time on the inadequacy
of single-point data from standard tests. The many examples which
could be cited include, for instance, three recent papers35 dealing,
respectively, with the insensitivity of a standard impact test (Gardner)
to the presence of impact modifier in uPVC sheet if crack-promoting
defects are absent; the need to vary the impactor velocity in the
standard (ASTM) Izod test-and to further supplement this by
high-speed tensile tests--for a better assessment of the toughness of
PVC materials; and the use of a three-point bend test on notched
specimens of uPVC sheet in preference to a falling dart test, for a better
evaluation of increased toughness of PVC with increased modifier
loading.

V
V
V

Specimen type A
Specimen type B
Specimen type C

ASTM D 25678, Methods A

andC

V
V

Notch type A b
Notch type B

ISO 180 (data from current revision draft document ISOIDIS

180, July 1980)
BS 2782:1970: Method 306A

Izod

Shape
(crosssection)

Specimen
or notch
designation

Standard specification

Test type

45

45
45
45

45
45

Included
angle

025

0.25}
100

Tip radius
(mm)

Notch characteristics

Remarks

tv

Four specimen types in

specification (type 4
preferred)
J or kgf cm or lbf ft per Notch moulded-in in
unit width of specispecimen A,
men (in m, cm and
machined in Band C:
width of specimen C
in., respectively)
is half that of A and B
J or ftlbf per unit
specimen width (in m
and in., respectively)
ckJ m- 2

Impact
resistance
unitsa

TABLE 11.3
Notch Characteristics and Impact Resistance Units in Standard Flexural Impact Tests

ClO

DIN 53 435-1977

DIN 53453-1975

ASTM D 256-78, Method B

BS 2782:Part 3: Method
351A:1977

ISO 179 (data from current revision draft document ISOIDIS

1979, July 1980)

Small standard
bar

Notch width:
2mm
Notch width:
08mm

45

Notch width:'
2mm orO8mm
45
45

Notch width: d
2mm or 08mm
45
45

Only unnotched specimens

U
U

V
V

Notch type B
Notch type C

Standard bar

V
V

Notch type Bb
Notch type C

Notch type A

Notch type A

Corner radii:
:/-01

Jm- 2

kJm- 2

kJm- 2

kJ m- 2 or
mJmm- 2

J or it Ibf per m or in.

(respectively) of
specimen width

*o.J

*01 }

Com"
"d;;'}
:/-02

025

Com",.iiii,
02
10

l-(lO

Com,,,.dii,
025

00

Three specimen sizes

in specification (size 1
preferred)

Four specimen types in

specification (size 2
preferred)

For unit conversions see Table 11.4.

This type preferred.
C i.e. energy to break in kilojoules per unit area of cross-section of the part of the specimen under the notch (total cross-sectional area in un-notched specimens).
d Respectively in Specimens 1 and 3.
, Respectively in Specimens 1 and 2.

Dynstat

Charpy

w.

384

V. Titow

TABLE 11.4
Conversion Factors for Common Units of Flexural Impact Resistance
Other units

SI unit

kJ m- 2

kgfcm cm- 2

ft [bf in- 2

ft [bf
(per inch of specimen
(notch) width O)

1
0981
210
524

102
1
214
536

0476
0467
1
250

0,191
0187
0401
1

Conversion factors for these units applicable only to rectangular specimens

with notch-tip radius of 025 mm and thickness of material under the notch of
1 mm (cf. ASTM D 256), on the assumption that-in general-the energy to
break is proportional to this thickness. 3

In the simplest, broad terms, the way in which a plastic fractures on

impact, i.e. the mode of failure, may be classified into brittle, ductile,
and intermediate (between the first two). The most characteristic
differences between typical cases of these three failure modes lie in the
appearance of the fracture surfaces and in the stress/strain effects as
shown up by the respective load/deformation curves. Typical brittle
failure produces a fracture surface which is smooth and shiny (although
overall it may be fragmented in the general plane of fracture). Fracture
surface typical of ductile failure exhibits ridges or strands of material
standing proud in varying degrees and configurations: these formations
may also show stress whitening. In the intermediate mode of failure
the surface characteristics are part-way between those of the other two
types: in some cases there may be a progressive transition marking the
original path of the developing crack. In terms of typical, basic
load/deformation behaviour, (which may be demonstrated with a
suitably instrumented impact tester 29 ,31) the three kinds of failure
mode are characterised by the following features. Since-by definition-brittle failure occurs (i.e. a crack initiates and propagates to the
point of complete fracture) before any bulk yielding of the material can
take place, the load/deformation curve is of the kind shown
schematically in Fig. 1l.2(A). In typical ductile failure (Fig. 11.2(B
the material yields before (in some cases well before) breaking, the
yield point being reflected by a bend or peak on the curve. The shape

11 Some Miscellaneous Components of pvc Formulations

385

o
Fig. 11.2 Load (L)/deformation (D) curves for the three general types of
failure mode. Schematic representation. A, Brittle failure; B, ductile failure;
C, intermediate failure.

386

W. V. Titow

of the curve after the yield point depends on the actual mechanism of
plastic deformation of the material in the particular case (e.g. necking,
cold drawing, etc.). With the mode of failure intermediate between
brittle and ductile there is some yielding in the region of failure before
or during the propagation of a crack (cf. the curve of Fig. 11.2(C)).
Although the diagrams of Fig. 11.2 are schematic, they do illustrate the
typical shape of the load/deformation curves for the different modes of
failure, and the fact that-other factors being equal-the energy to
break (as represented by the area under the curve) increases with the
mode of failure in the sequence brittle ~ intermediate ~ ductile.
Among the 'external' factors influencing impact resistance, the
temperature and the speed of impact (rate of deformation) have a
special significance, in that changes in their values which can occur
within the general range of possible service conditions can alter the
mode of failure of many thermoplastics from ductile to brittle (or vice
versa) and thus sharply reduce (or increase) the energy to failure. The
'internal' and processing factors most strongly affecting this transition
under service conditions (or in tests) are the basic composition (e.g.
presence or absence of impact modifiers in uPVC) , local stress
concentrations, and structural anisotropy. Lowering the temperature of
a thermoplastic which initially breaks in the ductile mode will normally
eventually result in a change to brittle fracture. Where the change is
sufficiently sharp, * the temperature at which it occurs is the
ductile/brittle transition temperature (Tb ), sometimes also referred to
as 'brittleness temperature', 'brittle temperature' or 'brittle point'. Its
value in any given circumstances is influenced by the various factors
affecting impact resistance (see above), and in particular by the
presence and magnitude of stress concentrators (surface faults or
damage in service, presence and tip radius of notches in tests): even
when all the main factors are kept constant the value assigned to the Tb
can be affected by the choice of criterion for identifying the change of
failure mode (e.g. whether sudden drop in impact strength, appearance
of fracture surface, load/deformation curve, etc.), and even by the
sensitivity of assessment under the same criterion (e.g. examination of
fracture surface with the naked eye, under the microscope, or by
electron scan). 29 However, these considerations do not invalidate

* With some plastics materials the drop in impact resistance with temperature
(and the associated evidence of transition from ductile to brittle deformation
on the fracture surface) may be very gradual, so that no definite Tb can be
established. 29

11 Some Miscellaneous Components of pvc Formulations

387

either the concept or the relevance of Tb in connection with the

understanding and assessment of impact behaviour of plastics,
providing that the limitations of its applicability are properly
understood.
Note: Bucknall et al. 29 use the Tb (in conjunction with notch sharpness) as the basis of a classification of plastics materials (into
five categories*) relevant to their impact behaviour in service.

Where no brittle/ductile transition occurs in the particular test or

service situation, the impact resistance of a plastic may remain constant
over a wide temperature range. This is demonstrated by the curves for
polystyrene and poly(methyl methacrylate) in Fig. 11.3: both polymers
251--~

----------., - - - - - --

pc------- ---------.

I
I

20~
I

PPO

....cen-

c
~ 10

ti

...

..
u

a.

~~~;;~;;;;:===::::=~:==::::::-

= _.....L
OL-_
_200

-150

L-_ _...L._ _---'

-100
-50
0
Tast tamparatura. 'C

PSPMMA

-:'::-_ _----:::-:---_~

50

100

150

Fig. 11.3 Impact resistance (in a Charpy-type test on notched specimens with
025 mm notch radius) as a function of temperature for five polymers. PC,
bisphenol-A polycarbonate; PPO, poly(2,6-dimethyl paraphenylene oxide);
uPVC, unplasticised polyvinyl chloride; PMMA, poly(methyl methacrylate);
PS, polystyrene. (Reproduced from Ref. 34 with permission of the copyright
holder, ICI, and the publisher, John Wiley and Sons Ltd).

* In order of increasing impact resistance: brittle, blunt-notch-brittle, sharpnotch-brittle, tough but crack-propagating, very tough, crack-arresting.

388

w.

V. Titow

are in the glassy state, and below their brittle temperatures (which
roughly coincide with the glass-transition temperatures), throughout
the entire temperature range covered, and hence break in brittle
fashion, with low energy to break.
Note: In contrast with the impact resistance, the tensile strength of
thermoplastics increases with decreasing temperature. * The
brittle point may be defined in terms of this property as the
temperature at which the yield strength is just equal to the
brittle strength (and below which the latter becomes
higher).34

The effect of increasing the speed of impact is similar to that of

lowering the temperature; it has been suggested that, with thermoplastics, a ten-fold increase in impact speed may be regarded as roughly
equivalent to a lOoC drop in temperature. 36
A full discussion of the impact behaviour of thermoplastics would be
outside the scope of this section (and not essential to its purpose).
Further information can be found in Refs 28, 29, 34 and 37, all of
which list numerous book and literature sources. A useful brief
summary of the main aspects of impact resistance relevant to the
design and service performance of plastics products is given in Ref. 36.
(b) The Impact Resistance of pvc
With PVC products the possibility of fracture by impact in service is of
much greater concern in the case of unplasticised compositions than
with pPVc. Whilst some plasticisers (notably tricresyl phosphate) can
make the plasticised material prone to embrittlement at temperatures
within a moderate range for service (even above OC for some
TTP-plasticised compositions), this can easily be avoided by suitable
formulation. Thus, in general, flexible PVC compositions are tough
materials, which do not normally fail by fracture on impact in service
or in tests (and give typically ductile breaks on failure in tension),
although plasticised sheeting-particularly thin films-may be punctured by falling weights (especially sharp-ended ones, like, for
example, dart impactors used in some tests).
* The tensile strength of a rigid PVC composition tested by Dyment and

Ziebland 38 increased from 77 x 103 1bf in- 2 at 20C to 197 x 103 1bf in- 2 at

-196C (with a corresponding increase, by a factor of 213, in Young's

modulus).

11 Some Miscellaneous Components of pvc Formulations

30

389
60

~~
20

20C
40

:::.
.:L

111

CI

'E
....,

'-

.0

.:L

E
~10

20

'CI
C

002
(05)

004
Notch radius, in
(10)
(mm, approx)

006

008

(1-5)

(20)

Fig. 11.4 Impact resistance of a uPVC composition as a function of notch-tip

radius in a Charpy-type test at various temperatures.

Note: Embrittlement in consequence of changes in the material

through loss of plasticiser, heat degradation, weathering, or

ageing is not directly relevant in the present context.
Rigid PVC is not intrinsically a brittle material at ordinary
temperatures: the brittle point of properly made un-notched uPVC
specimens in a flexural impact test can be as low as - 50C. 34
However, the material is sensitive to the presence of stressconcentrating features (as evidenced by its notch-sensitivity in impact
tests-see Fig. 11.4), and also to the rate of deformation, in the sense
that these factors-when operative at levels encountered in service
conditions and in tests-ean, singly or jointly, bring about a
ductile/brittle transition and thereby cause brittle failure to occur in
impact situations even at room temperature. A plastics material
susceptible in these two ways is sometimes referred to as 'notch-brittle'
and 'shock-brittle'.
This situation is illustrated by the curve for uPVC in Fig. 11.3: the
rapid drop in the impact strength of notched specimens within a

390

W. V. Titow

relatively narrow range of common service temperatures, is attributable to the onset of brittle fracture brought about by the relatively
severe 025 mm notches at the speed of impact employed in the test.
As has been mentioned, the effects of both these factors are
reasonably representative of those of stress-concentrating faults and
impact speeds which may occur in service.
Note: Notches, or 'natural' faults, in a polymeric material can raise
the Tb and thus promote brittle failure not only by causing
stress concentration, but also by limiting the amount of plastic
deformation which can take place locally before fracture
occurs, through a modification of the stress field at the
incipient crack tip (transition from plane-stress to plane-strain
conditions29 ). Contributory factors which can arise in practice
include incomplete fusion (gelation) of the PVC composition
(in consequence of inadequate heat processing), or degradation of the polymer (excessive heat processing).

Incorporation of impact modifiers in PVC compositions is a practical

way of increasing their impact resistance. The room-temperature
impact strength (notched Izod, ASTM D 256) of an unmodified PVC
based on a relatively low molecular weight polymer may be as low as
04 ft lbf in -], and perhaps about twice that with a polymer of high
molecular weight. Inclusion of, say, 15 phr of a suitable impact
modifier can raise these values to about 20 ft lbf in-lor even higher in
some cases, with considerable improvement also in low-temperature
impact resistance. In terms of the PVC graph in Fig. 11.3 such
upgrading amounts to a displacement of the curve upwards and to the
left.

(c) The Nature, Effects and Applications of Polymeric Impact

Modifiers for pvc

The following types of polymer are in industrial use as impact
modifiers in PVC:

(i) acrylonitrile/butadiene/styrene (ABS) polymers; *

(ii) methacrylate/butadiene/styrene (MBS) polymers;
(iii) ethylene/vinyl acetate (EVA) copolymers and EV ANC graft
copolymers;
* Normally of relatively high butadiene content (and hence comparatively low
modulus-see Section 11.2.1).

11

Some Miscellaneous Components of pvc Formulations

391

(iv) acrylic polymers (all-acrylic modifiers);

(v) chlorinated polyethylene (CPE);
(vi) acrylonitrile/butadiene copolymers (nitrile rubbers);
(viii) polyurethane (PUR) elastomers.
Other polymers, generally of an elastomeric nature, have been
patented, examined, or used as impact modifiers for PVC, including
butadiene/2-vinyl pyridine, butadiene/methyl isopropenyl ketone,39
butadiene/fumaric ester copolymers,39,4o and Hytrel 3495 (a copolyester thermoplastic elastomer produced by Du Pont).41
The normal levels of addition for straightforward impact modification of uPVC range between 5 and 20 phr (commonly 10-15 phr) but
some modifier polymers are sometimes used in very high proportions
to impart special properties to PVC compositions (see below).
Some fine-particle fillers (especially calcium carbonate-see Chapter
8, Sections 8.3.4 and 8.4.1) and pigments (e.g. titanium dioxide-see
Section 11.3 below) can, when properly dispersed, also improve the
impact resistance of uPVC.
At the normal levels of addition polymeric impact modifiers function
by forming a disperse phase in the matrix of the PVC polymer
(containing also those constituents of the composition which are fully
soluble in it, e.g. processing aids, internal lubricants, some stabilisers):
this interferes with crack development in the matrix, and can act as
internal energy absorber (the more effectively, the more rubbery the
nature of the modifier), in ways analogous to those in which
elastomeric modifiers function in toughened polystyrene. 25 Useful
early summaries of the mode of action of impact modifiers in PVC
have been published by Bramfitt and Heaps39 and Sisson. 42 The
impact-modifying particulate additives mentioned above have a
broadly similar action. Where, as with ABS and many other modifiers,
the refractive index of the continuous phase (PVC polymer matrix) is
appreciably different from that of the modifier, the latter has an
opacifying effect on the composition: hence in uPVC compositions for
clear products (e.g. blow-moulded bottles, packaging films) the
refractive indices should match as closely as possible at the appropriate
service temperature (the respective refractive index values, and hence
the closeness of match, can vary with temperature 21 ). Selected MBS
modifiers are widely used in clear compositions. In cases where the
refractive indices of modifier and matrix are close but not completely
matched (and where all other formulation components are chosen for

392

W. V. Titow

maximum clarity), if the refractive index of the disperse phase (which

may also include such components as, for example, some external
lubricants and stabilisers) is lower than that of the matrix the
composition will be yellowish and hazy in a degree proportional to the
difference in refractive indices: if the disperse phase has the higher
refractive index, blueing ('colour reversal') will result.
Some polymeric impact modifiers are highly compatible with the
PVC polymer, and are sometimes incorporated in very high proportions. Of these, those which interact strongly with (have a close
chemical affinity for) the PVC polymer act as true plasticisers of very
high permanence (e.g. EVNVC graft polymers rich in the VC
component; highly chlorinated polyethylene). Others, like, for example, nitrile rubber and some ABS polymers, also modify considerably
the properties of the blends they form with PVC at the high levels of
loading.
Side effects on the properties of uPVC materials exerted-in varying
degrees-by most polymeric impact modifiers at the normal levels of
addition, include the following: reduction of hardness, modulus,
strength (tensile and flexural), deflection temperature under load, and
chemical resistance; increased permeability; and impaired weathering
resistance (except with some acrylic and EVA/VC impact modifiers
which, whilst not positively improving the weathering properties, do
not affect them adversely in uPVC compositions formulated for good
weathering resistance). Some impact modifiers promote stresswhitening in uPVc. This phenomenon is usually attributed to the
formation of microscopic voids or crazes through local separation of
the disperse phase (including fillers-cf. Chapter 8, Section 8.3.3) from
the polymer matrix under strain; it is particularly undesirable in clear
compositions: modifiers for such compositions are selected, inter alia,
for minimum effect in this respect-several suitable MBS modifiers are
available.
Note: As measured in tests on transparent compositions, stress
whitening may be defined on the basis of the relationship

SW = 100 [1 - (Is/I)]
where: SW is the stress whitening (%), Is is the % light
transmission after stressing, and I is the % light transmission
before stressing.
In processing, many impact modifiers act as processing aids,

11

Some Miscellaneous Components of pvc Formulations

393

albeit-as has been mentioned in Section 11.2.1-this action is often at

its maximum at temperatures somewhat higher than those at which
regular processing aids are effective. In most cases the presence of an
impact modifier also increases die-swell in extrusion (except for some
acrylic modifiers, which have relatively little effect).
Polymers used as impact modifiers in rigid PVC may also be
incorporated in flexible compositions, where they can improve the melt
properties in processing as well as modify the material properties at
service temperatures, in ways which include reduction of brittle
temperature, increased stiffness, and improved surface properties and
emboss retention.
The effects of different impact modifiers on some properties of a
PVC composition are compared in Table 11.5.
The following further points may be mentioned about the individual
classes of polymeric impact modifiers.
ABS MODIFIERS
These modifiers are widely used in opaque, rigid compositions for
products not required to withstand weathering (e.g. pipes and pipe
fittings): in such compositions they can give high room-temperature
impact resistance and improved low-temperature resistance, with
relatively little effect on heat-distortion temperature and softening
point. Commercial compounds containing ABS modifiers in substantial
proportions are sometimes referred to as 'PVC!ABS alloys'.
Note: Typically, such commercial compounds may combine roomtemperature impact resistance (notched Izod) of about
10 ft lbf in-I with v-o rating in the UL94 flammability test,
and tensile strengths of about 5000lbfin- 2 .

Extrusion compounds of this kind are used, for example, for profiles,
and sheets for thermoforming (with particular suitability for deep draw
forming) into such products as panels, casings (e.g. computer
housings), and battery covers; injection moulding compounds are used,
inter alia, for electronic equipment covers and housings, television
cabinets and the like. Good surface finish and low SG are among the
useful features of these materials.
In semi-rigid sheeting ABS modifiers can also substantially improve
thermoformability and reduce post-forming shrinkage.
Very high proportions of suitable ABS polymers can be incorporated
in flexible PVC compositions (e.g. 65/35 ABS/PVC in some cases) if

10
15
10
15
10
15
10
15
10
15

Amount
(phr)

58
62
54
61
45
48
48
49
36
34

13-8
325
220
370
101
152
64
82
51
72

at -36C at 23C

Notched impact
resistanceb
(kgf cm cm- 2 )

PVC polymer (S grade, K value 65)

100
Modifier: as listed
10 or 15 phr
Stabilisers: Ba/Cd
3'Ophr
chelator
05 phr
30phr
epoxidised soyabean oil
13 phr
Lubricants
b Charpy type: DIN 53453.
cOIN 53460.
d Determined for a composition based on 20: 80 CPE:PVC blend.

CaC03 filler

Chlorinated
polyethylene
EVA/VC

ABS (Blendex 31Borg-Warner Chemicals)

MBS (Blendex 436)

Modifier

43
44
37 d

42
41

30-35

20-25 d
30-35
30-35

Brabender
rheometer,
30 rpm

30-35

oven

Heat stability at
2000C (min)

CC)

88
91
83
82
83
82
82
85
82
81

1 kg load

72
73
70
70
70
68
70
69
69
68

5 kg load

Vicat softening point

TABLE 11.5
Effects of Different Impact Modifiers on some Properties of a Rigid PVC Composition
(Summary of selected data from Ref. 26)

<:;

:::;j

:<:::

'R

...,

11

Some Miscellaneous Components of pvc Formulations

395

the plasticisers are chosen for compatability with the ABS component.
In such compositions it is the PVC which may be regarded as the
modifier for ABS, improving the latter's tear and abrasion resistance,
hardness and tensile strength, and reducing flammability.21
MBS MODIFIERS
Whilst modifiers of this class can be used in opaque formulations, they
are of particular interest for clear compositions (e.g. bottle, film and
sheeting compounds), as many have refractive indices in the right
range to promote good clarity: with several MBS modifiers this may be
combined with good colour and surface gloss as well as resistance to
stress whitening, good heat stability and low degree of odour and taste
transfer in containers. Increases in the room-temperature impact
strength of rigid compositions obtainable with some MBS modifiers can
be as high as 25-fold (e. g. from about 1 ft lbf in -1 to about 25 ft lbf in- 1
with Blendex 436 (Borg-Warner Chemicals) in a notched Izod-type
test).
EVA MODIFIERS
This group comprises EVA copolymers, and graft copolymers of vinyl
chloride with EVA. In general, the impact-modifying effect of EVA
copolymers in PVC increases with increasing vinyl acetate content.
Room-temperature impact strengths of about 20 ft lbf in-1 (notched
Izod, ASTM D 256) can be attained in some compositions at 10-15 phr
loadings.
The vinyl chloride component in EVAlVC polymers promotes
compatibility with PVC. Some graft copolymers of this kind (e.g. Du
Pont's Elvaloy resins 741 and 742) can be used as solid plasticisers of
exceptionally high permanence, in amounts as high as 80 phr. 13 ,43
Like some all-acrylic modifiers (e.g. Aeryloid KM 323B-Rohm and
Haas) EVA modifiers (e.g. Levapren 245O-Bayer; Hostalit HHoechst; Elvaloy 836 and 837-Du Pont) do not appreciably impair
the retention of physical properties (and, in many cases, colour) on
weathering of uPVC compositions which contain them: they are
therefore applicable in such products as window frames, cladding and
fencing profiles for external use, and rainwater goods.
Note: As has been mentioned in Chapter 1, a suitable EVAIVC
graft copolymer can be used on its own (instead of a PVC
resin/modifier combination) in uPVC products of this kind.

396

W. V. Titow

Similar uses are being developed for graft copolymers of vinyl

chloride on ethylene/propylene (E/P) copolymers and
ethylene/propylene/diene monomer (EPDM) terpolymers;44
the graft polymers form the basis of commercial PVC
compounds (Rueodur-Ruco Division of Hooker Chemical
and Plastics Corp., USA)45 for injection moulding, extrusion
and blow moulding which combine impact resistance in the
range 15-20 ft lbf in -1 with a UL94 flammability rating of
V-O.
ACRYLIC MODIFIERS

This group provides impact modifiers which, in addition to their

principal function in uPVC compositions, offer some processing-aid
effects, low die-swell in extrusion, and in service little impairment in
weatherability of products in which this is of primary importance (see
preceding paragraph). The acrylic modifiers are well represented by
the relevant products in the Aeryloid (Paraloid*) range of Rohm and
Haas in the USA and associate companies elsewhere.
CHLORINATED POLYETHYLENE

The chlorinated polyethylenes used as polymeric additives in PVC are

based on high density polyethylene. They are produced by chlorination
of this polymer, which may be carried out in suspension, solution, or
even in the solid phase. 46 The solution process gives the greatest
uniformity of distribution of the CI atoms in the polymer chains. 47 The
distribution is a contributory factor in the compatibility of CPE with
PVC polymer, which is mainly governed by the chlorine content.
Other factors influencing the compatibility and effects of CPE in a
given PVC composition are the molecular weight and degree of
crystallinity of the modifier. 48 Impact-modifier grades have chlorine
contents in the range 25-40%: they are used at incorporation levels
normal for polymeric modifiers in uPVC (up to about 20 phr, with
maximum impact resistance often reached at about 15 phr). Roomtemperature impact resistance (notched Izod ASTM D 256) of 20 ft lbf
in -1 can be attained (even higher in some cases), with considerably
improved low-temperature toughness: the modifier also has some
processing-aid action, and lubricant effects have been reported. 49

* The trade name Paraloid is used by Charles Lenning Chemicals and affiliates
in the UK and certain other countries: the product coding is universal.

11

Some Miscellaneous Components of pvc Formulations

397

CPE grades of higher chlorine contents are fully compatible in all

proportions with PVC polymer, due to the close chemical similarity.
They do not increase the flammability of PVC compositions, as do
polymeric additives without chlorine (or with relatively low CI
contents). The highly chlorinated CPEs can be used at very high
incorporation levels in PVC compositions to function as plasticisers of
excellent permanence.
In both capacities CPE is an additive which does not substantially
impair property retention on weathering of PVC compounds properly
formulated for weathering resistance. An important factor in this
desirable feature is the absence of double bonds (present in the
molecular chains of rubbery modifiers) which constitute vulnerable
sites in weathering and ageing situations (ct. also acrylic and EVA-type
modifiers).

Note: In an early evaluation of a CPE impact modifier (Modifier

PIM lOl-Allied Chemicals Corp.-a non-crystalline CPE
with 40% CI content) O'Toole and co-workers found,49 inter
alia, a 100% impact-resistance retention, with little deterioration of other properties, after natural weathering of a PVC
sheet containing this impact modifier. However, incorporation
of CPE modifiers does, in general, lower the strength
properties of PVC in comparison with unmodified material.
In such products as, for example, rigid profiles for outdoor use (and
especially in cellular versions) a CPE modifier can promote filler
acceptance. 13 The use of chlorinated polyethylene as plasticiser for
flexible sheeting for horticultural applications or reservoir lining can be
beneficial (but is restricted by cost considerations). Chlorine-rich
non-crystalline CPE grades are compatible with most plasticisers, and
can be incorporated-in moderate proportions-to increase the
modulus and reduce brittle temperature of pPVc. Crystalline grades are
said to be beneficial in plasticised flooring compositions. 50
NITRILE RUBBERS

Nitrile rubbers of suitable acrylonitrile content can be blended in

virtually any proportion with PVC homopolymers. Depending on the
proportion, on whether the composition has been vulcanised, and also
to some extent on the application, the material based on such a blend
may be regarded as rubber-modified PVC or PVC-modified rubber. In
a blend the two components modify each other's properties, and the

398

W. V. Titow

properties of the blend (and any composition in which the blend is the
base polymer) will reflect this mutual effect. The ratio of the components is the most important single factor governing the extent of
modification in a given case, but other factors also play a significant
part, e.g. the acrylonitrile content and Mooney viscosity of the rubber,
and the molecular weight of the PVC polymer,5! as well as the nature
and content of any other constituents of the composition (e.g. plasticisers, fillers). As a broad generalisation it may be said that in the blend
the PVC polymer contributes ozone, oil and fuel resistance, strength
(tensile and tear), and stiffness, as well as weatherability (with proper
stabilisation), abrasion resistance, flame resistance (which may be
enhanced by the presence of phosphate plasticisers and/or chlorinated
plasticiser-extenders in the composition) and higher electrical resistivity. Thus these properties of a nitrile rubber will be upgraded by
modification with PVC.
Note: The increase in strength (and especially tear strength) can be
maximised in vulcanised PVC-modified nitrile rubber compounds if the vulcanisation system is based on the total
polymer blend (not the rubber component alone).

The properties of PVC mainly upgraded by incorporation of nitrile

rubber are toughness (impact resistance), flex-crack resistance, lowtemperature flexibility, and resilience. Some of these effects are
illustrated by the curves of Fig. 11.5.
Nitrile rubber of grades used in blends with PVC is often regarded as
a plasticiser (highly permanent, non-extractable and non-migratory
because of its polymeric nature). In the practical context this is
consistent with its complete miscibility with PVC polymer, and its
principal effects on the properties of PVC compositions. The question
whether nitrile rubber indeed acts as a true plasticiser is therefore
more of theoretical than practical interest. It may be noted, however,
that-as observed by several investigators52-intimate blending (by
melt-compounding) of this modifier with PVC polymer in 'plasticising'
amounts does not result in a shift of the latter's Tg to a lower
temperature (as in the classic case of plasticisation) but gives rise to a
single, broad glass-transition region spanning the whole range between
the individual Tgs of the two components of the blend. Moreover, the
fine structure of the most intimate blends prepared by meltcompounding has been reported to be heterogeneous, with rubbery
domains of sub-micron size revealed by electron microscopy.39,52 With

11

Some Miscellaneous Components of pvc Formulations

399

40

(A)

(B)

10 20 30 40 50 60 70

'0 PVC

10

20

30

0'. PVC

40

50

Fig. 11.5 Some effects of PVC content in blends of PVC homopolymer with
nitrile rubber. (A) Tensile strength (TS) and modulus (M) of nitrile gum stock.
(B) Oil resistance of medium-acrylonitrile rubber.

regard to the toughening effect of nitrile rubber in PVC, the point has
been made39 that, whilst a rubbery additive capable of being dispersed
in PVC polymer on a molecular level could increase the impact
resistance by reducing the yield strength (promoting ductile failure) in
the same way as a plasticiser, a two-phase system is more effective in
producing a high degree of toughening.
In the production of blends of PVC polymer with nitrile rubber,
melt-compounding is necessary for maximum uniformity and completeness of inter-dispersion. However, availability of the rubber in powder
form enables it to be included in PVC compounding processes at the
pre-mix (dry blend) stage. Ready-made blends (in slab, chip, or powder
form) are also available from commercial sources: e.g. the Breon
'Polyblend' 500 series (BP Chemical International Ltd-blends of
butadiene/acrylonitrile copolymers of medium-to-high acrylonitrile
content with PVC homopolymer). The blends may be compounded
with additional nitrile rubber or PVC polymer (to adjust the ratio of
the two components to a value required for a particular purpose),
and/or with other materials appropriate to the intended application

400

w.

V. Titow

(PVC stabilisers, plasticisers, lubricants; vulcanising curatives and

reinforcing filler for the rubber; general fillers for the composition).
The main advantages claimed for the use of the commercial blends
vis-a.-vis direct blending of commercially available nitrile rubber and
PVC polymers, are better processing properties and reduced need for
high-temperature mixing. Some typical properties of Polyblend 503*
(sheet) are given in Table 11.6.
TABLE 11.6
Physical Properties of 'Breon Polyblend 503'
Tensile strength (lbf in -z)
Elongation (%)
100% modulus (lbf in- Z)
Hardness (Shore Durometer A)
Specific gravity
Crescent tear (lb in-I, ASTM D 624-54)
Rectilinear tear (lb in-I)
Low temperature brittleness (OC, ASTM D 746-64T)
DC volume resistivity (Q cm)

1850
430
1100
93
118
320
328
-51
26 x 109

Typical formulation for black press polished sheetings

Parts
Breon Polyblend 503
1000
Black (added as MB)
15
Acrawax C (Glyco Chemicals Inc.)
05-10
Lead stearate
02-03

Rubber-type processing of nitrile rubber/PVC blends and their

compounds can be carried out on ordinary rubber equipment, at
temperatures slightly higher than those typical for unmodified nitrile
rubber compounds. Compounds based on PVC-rich blends which are
not to be vulcanised are processed in ways normal for PVC
compositions-by extrusion, calendering, moulding, etc.
The use of nitrile rubber/PVC blends was pioneered by the cable
industry, where vulcanisation of the rubber component of cable-sheath
compositions based on the blends was an early development. Wire and
cable coverings, which continue to provide a considerable outlet for
* Described as a colloidal blend of medium acrylonitrile butadiene rubber and
a PVC homopolymer in the ratio of approximately 48 pbw rubber to
52pbwPVC.

11

Some Miscellaneous Components of pvc Formulations

401

the blends, are nowadays the subject of several standard specifications

(see Section 9 of Appendix 1). Other applications of nitrile
rubber/PVC blend compositions include integral covers for fuel hoses,
conveyor belting, and rollers, shoe soles, and flexible containers.
POLYURETHANE ELASTOMERS

Like nitrile rubbers, appropriate grades of these elastomers are widely

compatible with PVC, but the position with regard to their use in
combination with PVC differs somewhat in two respects from that in
the case of PVC/nitrile rubber blends. Thus, whereas the presence of
PVC polymer in nitrile rubber can substantially upgrade the latter's
resistance to ozone, oil, fuels and abrasion, the corresponding
resistance of some PUR elastomers is inherently good, so that
modification with PVC may not make much difference (although it
might cheapen some types of composition). Conversely, as an impact
modifier for uPVC, a PUR elastomer-even when potentially very
effective-has to compete on price with cheaper alternative materials.
Nevertheless, PUR modifiers for PVC are on the market (e.g. those in
the Landex range of the Story Chemical Corp., USA, Ultramoll PU of
Bayer and Durelast 100 of Briggs and Townsend, UK) and commercial
PUR/PVC blends have been used for the production of shoe soles and
moulded industrial boots (e.g. Ekalit M and Kombipur-VEB
Chemiekombinat, Bitterfeld, E. Germany): see also Chapter 7,
Table 7.4.

11.3 COLOURANTS
11.3.1 General Nature and Functioning

Colourants may be broadly divided into pigments and dyes. Both terms
can have somewhat differing connotations in different industries, but
for the purpose of this section-and without attempting a comprehensive description-the following working definitions are valid. Pigments
are colouring materials which are insoluble (i.e. not dispersible on a
molecular level) in the base polymer of a plastics composition, and
therefore remain in particulate form when incorporated in the
composition by proper compounding procedures: dyes are colouring
materials which are soluble in the above sense.

402

W. V. Titow

Note: The primary particles of a typical organic pigment may range

in size between about 05 and 5 ,urn, and may be made up-or
consist-of pigment crystals of sizes 0005-1,um. The

primary particles may form aggregates up to several tens, and

agglomerates up to several thousands, of micrometres in size:
these should be broken up into their constituent primary
particles in the compounding operation.
The colour of a coloured substance is due to selective absorption by
its molecules of some wavelengths from the incident light; the actual
colour seen by the eye is determined by the wavelengths remaining in
that part of the light which is transmitted or reflected. To be useful as a
colourant, a substance must be of a colour sufficiently intense to impart
it in the desired degree to the material to be coloured when
incorporated in relatively low proportions (in PVC compositions the
colourant contents normally range from fractions of a phr to a few phr
except for the special case of comparatively much higher loadings of
titanium dioxide or carbon black in certain compounds-see below): it
must also be compatible with the material and suitable in several other
respects (see below).
Where a colourant has an opacifying effect in a basically transparent
plastics composition, this is due to the scattering of light at the
colourant/plastic interface within the composition. It follows that the
effect will arise only if the colourant is insoluble in the composition,
and hence present in particulate from (i.e. acts as a pigment, not a
dye), and if-in addition-the particles are:
(i) large enough in relation to the visible light wavelengths
(0750-0400,um, respectively, for the extremes of the red and
violet spectrum bands) to permit scattering, as well as
(ii) either opaque or sufficiently different in refractive index from
the composition to enable significant internal scattering to occur.
It is because they do not entirely meet condition (i) that some
pigments of sufficiently small particle size can be used in translucentto-transparent compositions.

Note: Similar considerations apply to other formulation components

(fillers, flame retardants, impact modifiers): MBS modifiers

provide an illustration of the case where condition (ii) is not
fulfilled, i.e. where an additive forming an essentially discrete
disperse phase of effective particle size large enough for

11

Some Miscellaneous Components of pvc Formulations

403

interference with light, has no opacifying effect because its

refractive index matches that of the composition (cf. Section

1l.2.2(c)).
11.3.2 General Classification

As has been indicated in Chapter 4 (Section 4.4.1(g)) the following

general classification of colourants used in plastics may be made on the
basis of their nature and chemical composition:
Dyes (organic compounds)
Pigments
Organic pigments: substantially insoluble organic compounds; also
carbon blacks which consist essentially of elemental carbon,
occasionally tinted with an organic colourant.
Toners: Ba, Ca, or Mn salts of azo dyes.
Lakes: complex salts of basic dyes with certain acids, especially
phosphomolybdic, phosphotungstic, and phosphotungstomolybdic
acids.
Inorganic pigments: predominantly salts or oxides of certain
metals; this group includes the important white pigment, titanium
dioxide.

Several chemical types and combinations are represented among the

special effect pigments, which include: (i) metallic colourants (metal
flakes, usually aluminium for silver effects and copper or bronze for
gold; may be tinted with organic colourants for metallic colour effects);
(ii) pearlescent colourants (often based on bismuth and lead compounds; some on titanium/mica combinations, e.g. some Mearlin
Luster pigments of the Mead Corporation, USA, for which superior
weatherability is claimed); (iii) glossy and nacreous colour pigments (as
represented, for example, by the [riodin range of E. Merck, West
Germany); and (iv) fluorescent pigments, whose recent commercial
representatives have much improved heat resistance (up to about
300C in some cases) and light stability (cf., for example some Swada
Z/N and Day-Glo VC fluorescent colourants of, respectively, Swada
(London) Ltd, in the UK, and the Day-Glo Colour Corp. in the USA).
Most of the common dye classes (including azo, anthraquinonoid,
basic, nigrosine, indoline, quinophthalone, and aniline-black dyes) are
represented among dye colourants for plastics. Virtually all these
colourants have some solubility in common solvents, oils, fats and

404

W. V. Titow

plasticisers. For this reason they are relatively little used in flexible
PVC compositions in which their solubility can give rise to troubles
associated with migration ('bleeding', 'marking-off', 'blooming'). As
organic compounds with high degree of unsaturation the dyes (and
many of the closely related organic pigments) are fairly sensitive to
light (prone to fading or changes of shade). Their molecular state of
dispersion in PVC compositions also makes them more accessible to
light, and thus accelerates any photochemical effects they may suffer in
both pPVC and uPVc. Examples of commercial dye colourants for PVC
include Red HHR and Blue B (Hoechst) used in coloured gramophone
record compounds; Amaplast Yellow RRT (American Colour and
Chemical Corp.)-an azo yellow for use in rigid compos~tions; and
quinaphthalone yellows for uPVC (Mitsubishi Chemical Industries).
Rhodamine B has been evaluated53 as a fluorescent colourant for PVC
traffic cones, vacuum-formed emblems, point-of-sale displays, and the
like.
Commercial pigment colourants for PVC are discussed in Section
11.3.5; the main groups are listed, with some property data, in Table
11.7. In addition, the following general points may be noted. As with
other additives, the highest possible degree and uniformity of
dispersion* of a pigment in the PVC composition is very important, in
this case for maximum colour value and uniformity of coloration:
hence the form in which the colourant is used (see Section 11.3.3)
should be considered, inter alia, from the point of view of dispersibility.
Stability of PVC compositions may be reduced by some pigments
containing iron and zinc (especially salt-type pigments in which ions of
these metals are present, or pigments containing such ions as
impurities). Pigments containing barium, cadmium, lead, tin, or
calcium may have the opposite effect. Some pigments (notably carbon
black and titanium white-see Section 11.3.5) can improve weathering
resistance (d. also Chapter 12, Section 12.6, and Chapter 4, Section
4.4.1(g. Occasionally an interaction may be possible between certain
dyes and fillers: this effect is not very common, but in case of doubt
reliable advice can be had from the colourant supplier on this point.
Any colourant used should also be resistant to HCI which may be
liberated in the composition in processing or service: for example some

* A standard specification of interest in this connection is ASTM D 3015-72

(reapproved 1978). Microscopical examination of pigment dispersion in plastic
compounds.

11

Some Miscellaneous Components of pvc Formulations

405

iron oxides are susceptible to attack by Hel. Stability of the colourant

to the other formulation components, especially at processing
temperatures, is another relevant consideration. Some organic pigments, as well as the dye components of toner or lake pigments can
migrate, especially in plasticised compositions. For example, the older
monoazo pigments often caused trouble by migrating to, and
accumulating on, the surface of products, sometimes shortly after
manufacture or early in service: such effects are known as 'blooming',
'bleeding', 'chalking' or 'bronzing'. They occur usually where the
pigment is not sufficiently insolubilised, and can dissolve in the
polymer/plasticiser system. In such cases, by and large, the higher the
plasticiser content the worse the effect. Some monoazo pigments are
still notorious in this connection, but there are newer ones which are
sufficiently insolubilised to be fully suitable. Where the tendency
exists, high processing temperatures will accentuate 'blooming' and the
other effects; with rigid and semi-rigid products the problem would be
less acute because of the absence of, or the low, plasticiser content. It
may sometimes appear that where 'bleeding' occurs, transparent
compounds do not bleed as much as opaque ones. However, this is not
a basic difference and may be due simply to the fact that the
transparent compounds will normally contain less colour.
11.3.3 Forms in which Colourants are Available
A colourant is usually available in different physical forms. In any
given case the choice of a particular form-like that of the kind of
colourant to be used-will be made in the light of the various
considerations summarised in Section 11.3.4. The following forms are
available:
(i) 'Dry colours': These are colourant powders with no additives,
except for small amounts of lubricants, wetting agents, or
dry-flow promoters (anti-caking agents) which may be present in
some cases. Nowadays most dry colours are available in special
non-dusting powder grades or in granulate form.
(ii) Colour concentrates: A colour concentrate is a compound
consisting of a high proportion of colourant dispersed in a
carrier. Depending on the nature of the carrier the concentrate
will be either solid or liquid.

406

W. V. Titow

Solid concentrates in which the carrier is the same polymer as that of

the composition for which the colourant is intended, are known as
masterbatches. The term is also often applied to solid concentrates
whose carriers are polymers compatible, but not identical, with those
of the compositions to be coloured. Such 'universal' polymeric carriers
in some colour concentrates suitable for use in PVC can be vinyl
chloride/acetate copolymers (as, for example, in the Hoechst Hostavinyl pigment concentrate series) or EVA copolymers. A widely
compatible carrier is a feature of the Siscoversal concentrates (BASF)
which are suitable for use in PVC, inter alia, at up to 3 phr loading.
Non-polymeric carriers are also used in some concentrates (e.g. a fatty
acid or a lubricant wax, respectively in the Ciba-Geigy Microlith and
the Hoechst Remafin ranges). The solid masterbatch concentrates are
available in the form of standard pellets containing up to about 50%
colourant. Powder forms are also supplied-e.g. the Microspin dustless
concentrate powders of the Hilton Davis Chemical Co. in which the
colour (or titanium white) loading can be as high as 70% (in a
low-melting, heat-stable 'universal' carrier). In comparison with a dry
powder colourant the masterbatch offers ease and economy of
handling, freedom from dusting, and ease of dispersion in processing
(powder-form concentrates are, moreover, suitable for dry blending).
However, whilst the colourant in a masterbatch pellet or particle is
already 'wetted out' by, and intimately dispersed in, the resin carrier,
because of the high colourant content the viscosity of the molten
masterbatch in melt compounding is liable to be higher than that of the
composition to be coloured: thus, although problems in dispersing the
colourant as such are reduced, attention must be paid to ensuring that
the masterbatch compound is thoroughly blended with the composition. Since compounding a masterbatch with a composition to be
coloured amounts to a dilution of the former, it is common to refer to
the operation as 'letting down' the masterbatch: let-down ratios may
range from 100: 1 to 3: 1 (uncoloured composition or polymer to
masterbatch). Liquid concentrates of interest for PVC are normally
dispersions of colourants in plasticisers, often referred to as paste
concentrates.
(iii) Combinations of colourants with other formulation components
(stabiliser/lubricant systems and occasionally also other additives, e.g. antistatic agents, fillers) in single-pack systems;
'tailored' by the supplier for particular, specified types of PVC
compositions (see also Chapters 9 and 10). The main advantage

11

Some Miscellaneous Components of pvc Formulations

407

of such polyfunctional systems to the user is convenience (with

elimination of individual-component storage and metering or
weighing-out operations, and some pre-dispersion of colourants, fillers, etc., where present). The principal limitation is
on formulation flexibility; the price of proprietary single-pack
systems also reflects the supplier's blending, handling and
packaging costs.

Note: Broadly speaking, similar considerations apply to the use of

coloured compounds available from suppliers for direct
conversion into products by appropriate processes.

11.3.4 Choice of Colourant-Main Considerations

The principal considerations influencing the choice of colourant or
colourant system for a PVC composition (as for most plastics
compounds in general) may be grouped under the following headings.

(a) General Appearance and Colour Requirements

The relevant elements here will be the optical properties of the
composition (i.e. whether transparent, translucent, or opaque: ultrafine particle pigment grades may be suitable for all three categories),
the actual colour required, colour strength and brightness, and any
special effects (e.g. fluorescence, metallic or pearlescent effects).
Where various levels of colour strength may be required but
preservation of the same shade is important, the possibility of spurious
shade changes associated solely with differences in colourant concentration level should not be overlooked: such changes-which can occur
in PVC compositions coloured with commercial pigments-have been
attributed to dichroic effects. 54 Sophisticated microprocessor-based or
computerised colorimeters and colour analysers are available nowadays
to assist the plastics processor with colourant quality control, rapid
colour matching* and adjustments in formulation development, and
*Standard colours for matching are listed in the Dictionary of Colour
Standards originally contained in BS 543:1934, which no longer exists as a
standard, Other BS standards of interest are BS 381C-1964 (Colours for
specific purposes) and BS 4800:1972 (Paint colours for building purposes).
Colours for cables are given in BS 6746C:1969: in formulating coloured cable
compounds the possible effect of the colourant on the volume resistivity and
power factor should be considered; colourants specially produced for this
application are available.

408

W. V. Titow

the monitoring and control of colour quality and uniformity, and shade
consistency in production. The following equipment may be mentioned
by way of non-selective examples: the Gardner XL-80S colorimeter
system;55 the Vibrochrom FFR 2 colorimeter with companion computer (Chemiefaser Lenzing AG, Austria);56 the 7842 Color Analyzer II
(IBM Instrument Systems, USA); Match-Mate 3000 (Diano Corp.,
USA); and ACS 500 (Applied Color System, USA).57

(b) Processability and Stability in Processing

Considerations here will include ease of handling, conveying and
metering of the colourant; suitability for, and ease of dispersion in, the
relevant process(es) and type of PVC composition; own stability under
processing conditions (especially chemical and colour stability to heat
at PVC processing temperatures-general range approximately 170220C) and absence of adverse interactions with composition
constituents (or their decomposition products-e.g. HCI from PVC
polymer) under these conditions. An experimental scheme for the
evaluation of the suitability of pigments for use in polymers processed
at high temperatures proposed by Sonn58 is of interest in connection
with PVC (although the author does not include it among his 'high
temperature polymers').
(c) Stability and Permanence in Service
The points relevant under this heading will include permanence of
colour (no fading or shade changes) associated with resistance to such
environmental influences as heat, photochemical action, and other
weathering or ageing factors: resistance to migration and extraction
(e.g. on contact with such agents as detergents, polishes, oils); no
adverse interactions of the colourant (including any impurities therein)
or its decomposition products with the PVC polymer or other
constituents of the composition. Examples of pigments developed with
a view to compatibility with appropriate stabilising systems, and own
good weathering resistance in dark shades in such outdoor uPVC
products as window frames, cladding and profiles, are the BASF
Sicotan yellows and some pigments in the Ciba-Geigy Cromophtal
range. The former are Ni/Ti and CrlTi compounds which may be
combined with appropriate organic or inorganic pigments to produce
dark shades. The Ciba-Geigy materials (as represented, for example,
by the widely used Cromophtal Brown SR) are mainly organic
pigments with low IR absorption which limits heat build-up on

11

Some Miscellaneous Components of pvc Formulations

409

exposure to sunlight. Iron-free pigments recommended for outdoor

applications in PVC are available from several suppliers.

(d) Health and Safety Considerations

These include: (i) general safety in handling and processing (e.g.
possible explosion hazards associated with fine powders); (ii) possible
toxic or carcinogenic effects in handling and processing; and (iii)
similar effects on direct body contact or food contact with the PVC
product containing the colourant. With most colourants used on any
scale in PVC (and especially when in the form of concentrates or as
components of single-pack systems) (i) is not normally a cause for
special concern.
In the area of exposure hazards to processing operatives, and
possible hazards associated with use of end products (especially in
beverage and food contact applications), attention has been focusing
on three topics: inorganic pigments containing heavy metals which may
act as potential cumulative poisons; polychlorinated biphenyls, present
as impurities in organic colourants of the phthalocyanine and diarylide
type, and regarded as potentially carcinogenic; and organic colourants
based on benzidine, now widely recognised as a carcinogen.
Of the heavy metals present in colourants, lead is already subject to
stringent exposure limits in the USA and other countries: the
regulations thus affect lead chromate and lead molybdate pigments
(see Table 11.7) as well as lead-based stabilisers and lubricants. The
lead chromates are additionally suspect as a result of recent work in
the USA on the potential hazards of chromium (especially hexavalent
chromium).59,6o The question of the degree of hazard associated with
cadmium compounds affects both cadmium pigments and stabilisers.
Whilst the issue of appropriate official restrictions is still under
debate, any limitations (or outright bans as currently proposed in
Sweden 61 ) will adversely reflect on the usage of the cadmium reds and
yellows (see Table 11.7) so valuable technically for their heat and light
stability: many manufacturers are already looking into alternatives for
cadmium pigments and stabilisers. As with other PVC formulation
components, information and guidance on the latest thinking, and any
specific regulations, concerning the possible health hazards associated
with colourants are available from the various official and professional
bodies mentioned in Chapter 7, Section 7.12 and Chapter 12, Section
12.9. Organisations directly concerned with colourants include the
USA Dry Colour Manufacturers Association, the UK Society of Dyers

410

W. V. Titow

and Colourists, and Oil and Colour Chemists Association, and the
German Mineralfarben-industrie eV.
(e) Cost
This is an important consideration, applicable no less to the colourants
than to any other constituents of a PVC formulation.
11.3.5

Some Commercial Pigments*

There are many world-wide manufacturers of pigments and many

different chemical types; it would be a formidable task to list them.
Most of the manufacturers issue copious data on their products but
correlation of one range with others is not easy, nor is it a simple
matter to relate trade names with chemical constitution. Test data on
the other hand are fairly well standardised. Thus a simple compound is
used, e.g.
PVC polymer (e.g. Corvic H65/33-ICI Ltd)
Plasticiser: e.g. DOP or Reomol D79P (CibaGeigy)
Stabiliser: either basic lead carbonate paste or a
Baled soap and epoxidised oil in functionally
equivalent proportion
Colourant and titanium dioxide

100
50phr
8-10phr
as indicated

to evaluate the various properties as follows. t

Heat stability: A cut of hide from the mill is pressed between
polished steel plates for 30 min at 170C and the resulting sheet is
compared with one pressed for 5 min. Alternatively, portions of sheet
pressed for 5 min are further heated in a thermostatically controlled air
oven for 30 min at 170C or 10 min at 200C. Any difference is assessed
on the SDC Geometric Grey Scale (BS 2662: 1961) on a 5 to 1 rating,S
equalling no change, 1 equalling very considerable change. These
relatively long times are used to cover extremes of direct heating or the
cumulative effects Of reworking.

* This section, edited and supplemented for the present" edition, was originally
contributed (to the previous edition) by Mr H. G. White of ICI.
tThese tests were used by the compiler of Table 11.7. Other tests (some more
stringent) can be applied, e.g. those detailed by Ciba-Geigy in connection with
that company's rating of its pigments for PVc. 63

11

Some Miscellaneous Components of pvc Formulations

411

Migration: A specimen of coloured sheet is held in contact with a

piece of white PVC under a weight of 10Ibfin- 2 . The assembly is
placed .in an oven for 24 h at 70C and the degree of staining assessed
on a 5-1 scale.
Dry rubbing: A piece of coloured sheet is rubbed with a piece of dry
cotton fabric.
Wet rubbing: As for 'dry rubbing' except that moist cotton is used.
Soap fastness: A specimen of coloured sheet is placed between a
piece of cotton and a piece of wool. The assembly is rolled and
immersed in soap solution for 1 h at 60C. Staining is assessed on the
1-5 scale. (Solution prepared by dissolving 5 g soap flakes and 2 g
anhydrous sodium carbonate in 1 litre of water.)
Light stability: Coloured specimens are exposed to daylight and
assessed according to BS 1006: 1978 using the Blue Scale of Standards
against which the light fastness is rated (upwards) from 1 to 8.

The chemistry and properties of pigments available for and used in

PVC have been reviewed by White62 who originally compiled Table
11.7. The salient characteristics of the main chemical classes into which
the pigments have been grouped in the table may be summarised as
follows:
A. Toners: Alkaline earth metal salts of organic azo dyestuffs;
they give bright strong colorations but only moderate light fastness,
whilst the salt linkage gives susceptibility to colour change if the PVC
compound is changed. Newer types are giving better light fastness.
B. Disazo pigments: Mainly derived from substituted benzidine,
these are strong yellow to red pigments of good to very good light
fastness but may show a trace of solubility and colour change if
processed at high temperatures and low concentrations.

C. Condensed disazo pigments: These are made by condensing two

monoazo pigments, giving weaker but brighter colorations than
conventional disazo types with better light fastness and less solubility.

DCB/PCP

DCB-DA/PTMP

DCB/AA2MCA
DCB/PMP

TCB/AAMX
DCB/AAOA
DCB/AAMX

(A) Toners
Barium-2B
Strontium-2B
Manganese-2B
Calcium-2B
Calcium-4B
Ca-monoazo
Ba-monoazo
Ca-ONPSA
Ba-ONPSA
Ba-monoazo
(B) Disazos

Chemical type

P.Red 48
PoRed 48
PoRed 48
P.Red 48
P.Red 57
P.Red 134
P.Red 133
N.L.
P.Yellow 62
P.Red 151
P.Yellow 81
P.Yellow 17
P.Yellow 13
N.L.
PoYellow 83
Po Orange 13
N.L.
P.Red 111
P.Red 38

P.V.Fast Yellow HlOG

Irgalite Yellow 2GP
Vynamon Yellow GRES
Irgalite Yellow BAF
P.V.Fast Yellow HR
Vynamon Orange GS
Irgalite Orange F2G
Vynamon Red GES
Irgalite Red PYE

C.l. Ref. (Pt 1)0

Vulcafor Red AS
FW Rubine Toner BOS
Rubine Toner 2BRS
Irgalite Red RC
Vynamon Claret YS
Irgalite Red HGL
Irgalite Red HBL
Irgalite Yellow WSC
Irgalite Yellow WSR
P.V.Red H4B

Brand name

050
010
010
010
005
010
0075
005
005

015
015
010
010
010
10
05
05
05
025

Amt
for!
ISD
(%)

TABLE 11.7
Pigments for PVC and Some of Their Properties

05
05
05
05
05
05
05
05
05

05
05
05
05
05
10
10
20
20
05

001
001
001
001
001
001
001
001
001

001
0 01
001
001
001
002
002
0 04
004
001

% in
patterns b

6-7
7
6-7
7
7
6
6
5
5

4
5-6
6D
5
4
6
6-7
6-7
7
6

6
6
5-6
6
6
4
4
3
3

5-6

1-2
2-3
3
3
1-2
-

Light
fastness C

5
5
5
4
5
4-5
4-5
5
5

5
3-4
5
2Y
3Y
5
5
5
5
5

4Y
4Y
4Y
3Y
3Y
5
5
5
5
4

4
4B
4B
2B
5
4-5
2Y
2Y
2Y

Heat
stabilityd

(E) Polycyclics
Indanthrone
Dioxazine
Dioxazine
Thio indigoid
Perylene
Perinone
Flavanthrone
Quinacridone {3
Quinacridone a
(F) Isoindolinones
7th FAT/PEC
Congress
(1964), p. 61

(D) Insolubilised
Monoazos
No disclosures

(C) Condensed Disazos

See: JOCCA (1963),
p. 13, and (1968),
p.580

040
050
025
025

P.Yellow 109
P.Yellow 110
P.Orange 42
P.Red 180

Yellow 2GLT
Yellow 3RLT
Orange RLT
Red 2BLT

Irgazin
Irgazin
Irgazin
Irgazin

016
008
020
030
013
050

008
005

020
010
010
008
025
040
010
022

05
01
01
01
01
01

P.Blue 60
P.Violet 23
P.Violet 35
P.Red 88
P.Red 149
Vat Orange 7
P.Yellow 112
P.Violet 19
P.Violet 19

P.Orange 38
P.Red 185
P.Red 183
P.Red 171
N.L.
P.Yellow 105
P.Red 150
P.Red 187

P.Yellow 94
P.Orange 31
P.Red 139
P.Red 144
P.Red 140
P.Red 142

Vynamon Blue 3RS

Vynamon Violet 2BS
Irgazin Violet BLT
Cromophtal Bordeaux RN
P.V.Fast Red B
P.V.Fast Orange GRL
Cromophtal Yellow A2R
Cinquasia Violet RT 795D
P.V.Fast Red E5B

P.V.Red HFG
P.V.Carmine HF4C
P.V.Fast Bordeaux HFR
P.V.Fast Maroon HFM
P.V.Brown HFGG
Vynamon Yellow 8GS
P.V.Carmine HR
P.Y.Pink FL

Cromophtal Yellow 6G
Cromophtal Orange 4R
Cromophtal Red GR
Cromophtal Red BR
Cromophtal Red R
Cromophtal Rubine B

001
001
001
001
001
001
001
001
001
001
001
001
001

05
05
05
05

001
001
001
001
001
001
001
001

001
001
001
001
001
001

05
05
05
05
05
05
05
05
05

05
05
05
05
05
05
05
05

05
05
05
05
05
05

7
7
6
6
7
6-7
6-7
6-7
7

6
6
7
6-7
6-7
6-7
3
5

7
5
6
6
5-6
5

7D 6-7D
7D 7D
7D 7D
7D 7D

7
7
7
7
7
7
7
>7
>7

6-7
6-7
7
7
7
7
5
6

7
6-7
7
7
6-7
6-7

5
5
5
5

5
5
4-5
5
5
5
5
5
5

4-5
5
5
4-5
5
5
5
5

5
5
5
5
4-5
5

4B
5
4Y
4Y

4
5
1
3Y
4-5
3Y
4-5
4D
4Y

4Y
4-5
5
4-5
4Y
4-5
3-4
3Y

5
5
4-5
4-5
4Y
4Y

11

(G) Phthalocyanines
CPC, ll'form
CPC, stable ll'
CPC, f3 form
Chlorinated CPC
Brominated CPC
(H) Other Organics
Iron nitroso-f3-napthol
Aniline black
Carbon black
(I) Cadmiums
Cadmium sulphide

Chemical type

11

P.Yellow 37
Yellow P 3680
Primrose P 500
Lemon Yellow P 3682
Light Orange P 4701K
Deep Orange P 4702K

10
10
10
075
075

010
10
005

P.Green 8
P.Black 1
P.Black 7

Vulcafor Green LS
Monolite Fast Black LS
Kosmos 70

Cadmium
Cadmium
Cadmium
Cadmium
Cadmium

006
007
008
016
020

Amt
for!
ISD
(%)

P.Blue 15
P.Blue 15
P.Blue 15
P.Green 7
P.Green 41

C.l. Ref. (Pt l)a

Irgalite Blue BLP

Vynamon Blue LBS
Monastral Fast Blue BGS
Vynamon Green BES
Vynamon Green 6YS

Brand name

TABLE 11.7-eontd.

5
5
5
5
5

05
05
05

05
05
05
05
05

7
7
>7
7
7

6
7
>7

001
001
001
01
01
01
01
01

>7
>7
>7
>7
>7
001
001
001
001
001

5
5
5
5
5

6-7
6-7
6-7
6-7
6-7

5
5
5
5
5

3
5
5

4-5
5
5
5
7
>7

3Y
4Y
3-4Y
4-5
5

Heat
stabilityd

4-5
5
5
5
5
>7
>7
>7
>7
>7

P
F

Light
fastness C

%in
patterns b

P.V.Fast Brown G

Chrome Green DC 3593

Vynamon Yellow 6GNS

Supra Lemon Chrome 4GS
Vynamon Yellow CRNS
Supra Orange Chrome HYS
Supra Scarlet Chrome YS
Supra Scarlet Chrome MS

Light Red P 4703K

Scarlet P 4704K
Red P 4705K
Deep Red P 4706K
Crimson P 4707K
Maroon P 4708K

20
075
03

10
10
10
10
10
15

10
10
075
075
075
075

= Darkening.

P.Green 17
P.Blue 29
P.Brown 6

P.Red 104

II

P.Yeliow 34

P.Red 108

11

Colour Index (Part I) Ref: N.L. = Not listed.

Patterns: F = Full Shade; P = Pastel Shade in white plasticised PVC; D
C Light fastness: Daylight, Blue Scale 8-1 ratings BS.
dHeat stability: 10 min at 200C in air oven. Grey Scale 5-1 ratings.

(K) Other Inorganics

Chromic oxide
Ultramarine
Iron oxide

Lead molybdate

II

(J) Chromes
Lead chromate

Cadmium selenide

11

Cadmium
Cadmium
Cadmium
Cadmium
Cadmium
Cadmium

5
5
5

5
5
5
5
5
5

5
5
5
5
5
5

01
01
01

01
01
01
01
01
01

01
01
01
01
01
01

>7
7
>7

7D
7D
7D
7D
7
7

7
7
>7
>7
>7
>7

7
7
7

7D
7D
7D
7
7
7

6-7
6-7
7
7
7
7

5
5
5

5
5
5
5
5
5

5
5
5
5
5
5

5
4Y
5

5
5
5
5
5
5

5
5
5
5
5
5

416

W. V. Titow

Plate A Laboratory-scale equipment for PVC processing (Farrel Bridge

Ltd.). (1) Two-roll mill (swing-side, variable friction, rolls 6 in x 13 in).

D. Insolubilised monoazo: These are types in which heavy substitution of the simple monoazo pigment has suppressed solubility to very
acceptable levels; usually this is obtained at appreciable financial
expense.
E. Polycyclic compounds: These are offshoots of the vat dyestuffs
used on textiles; this highly selected group of colours give very high
strength, fastness and brilliance but at a very high cost.

11

Some Miscellaneous Components of pvc Formulations

417

Plate A-<:ontd. (2) Four-roll laboratory calender ('inverted L' type, rolls
6 in x 15 in).

F. Isoindolinones: These form a new group from the polycyclic class

with a shade range greenish yellow to bluish red of very good light
fastness and insolubility.
G. Phthalocyanines: These are a very old specialised type of
polycyclic giving the most stable blue and green pigments at
comparatively very low cost.
H. Carbon black: This term is often used as a general name for the
group of particulate carbon pigments, whose members are known
under names derived from the methods of their preparation (which
also affect the particle size, surface 'chemistry,64 and degree of
blackness), e.g. furnace blacks, channel blacks, lamp blacks (various
grades). Carbon blacks are characterised by small particle size,
outstanding tinting power and hiding strength, heat and light
resistance. The fine-particle furnace blacks have been increasingly
widely used in PVc. As indicated in Chapter 8, Section 8.4.3, apart

418

w.

V. Titow

from its action as a black pigment carbon black improves the

weathering resistance of plastics compositions and-in sufficiently high
loadings-eounteracts static electricity collection and can confer
conductive properties (see Section 11.4 below). A useful monograph
on carbon black, covering both the scientific and technical aspects of
the subject, has been produced by Donnet and Voet. 65
I. Cadmium sulphide and selenides: These form the main group of
yellow-orange-red-maroon inorganic pigments of very high light and
heat fastness with no solubility, but they are both expensive and
tinctorially weak.

J. Chrome pigments: For example, lead chromate and lead molybdate form a much less expensive greenish yellow to scarlet range of
pigments in which recent improvements have given light fastness
comparable with cadmium pigments, but they remain susceptible to
strong alkalies and to darkening by hydrogen sulphide.
K. Other inorganics: These include ultramarine, iron oxides and
chromic oxide, which are, respectively, the cheapest brightest reddish
blue, a source of very cheap and fast fawn to brown colours provided
very high processing temperatures are not involved, and the best base
for green colorations for the production of camouflage effects.

The above points are illustrated in terms of numerical data in Table

11.7, in which representative members of the pigment classes discussed
are listed with disclosures of their chemical constitution by reference to
the Colour Index or literature. A comparison of relative tinctorial
strength has been included by indicating the dosage of pigment
required in a clear plasticised PVC composition with 1% titanium
dioxide to give a uniformly strong coloration to 1/3 International
Standard Depth (BS 1006:1978). The light fastness and heat stability
ratings of the pigments as full and pastel shades in the same PVC
composition (with BalCd soap-epoxidised oil stabiliser system) are
then compared.
Titanium dioxide, the most widely used white pigment, has not been
included in Table 11.7. It is available in two crystalline forms-anatase
and rutile. In general rutile is the more stable to light (and hence,
broadly, preferable as a pigment for plastics, especially for outdoor
applications), whilst anatase has a stronger blue undertone. Both forms
are available in various grades differing in particle size and size

11

Some Miscellaneous Components of pvc Formulations

419

distribution, and in the presence (and nature) of surface treatments, so

that the supplier's advice should be sought regarding the choice of
grade for a particular application, although continuous development to
improve the ease of dispersion, blueness of undertone, durability and
resistance to moisture pick-up has made it possible to combine all these
features in a fine-crystal rutile grade.
In addition to its use as a white pigment, titanium dioxide is also
widely employed to enhance the brightness of a colourant. In
proportions appropriate to these two purposes (up to a few phr) this
pigment has no appreciable effect on the physical properties of PVC
compositions. At higher loadings (about 10-15 phr) it can enhance the
weathering properties of some PVC products (e.g. flexible films for
swimming pool and reservoir linings), or-especially when of the finest
particle size-improve the impact properties of rigid materials. 34
Useful information, respectively on the nature of organic pigments,
extractability of colourants (and some other additives) from PVC
compositions, and on all important aspects of the colouring of plastics
(including PVC), is contained in publications by Inman,66 Brighton,67
and Webber. 68

11.4 ANTISTATIC AGENTS

Like many other plastics materials, PVC products and articles may
readily accumulate static electricity charges under certain conditions.
Friction against, and separation after surface contact with, other
surfaces are common ways of charge generation. Since surface charges
leak away more easily in moist conditions, the highest and most
persistent charges result at lowest relative humidities. Charge build-up
is drastically reduced at relative humidities above approximately 80%.
Accumulated static charges can represent a serious potential hazard.
For example, when present on the cover or carcass of a PVC conveyor
belt, the charge may-on discharge-produce a spark which can cause
a fire, or an explosion in a dust-laden atmosphere: such circumstances
can arise in mines, where PVC conveyor belting is used. Charge
accumulation on PVC sheeting can constitute similar hazards in other
environments (including atmospheres containing flammable vapours or
gases). Charges built-up on PVC polymer particles (in conveying,
metering, etc.) can be troublesome; as can those acquired by dry blend
particles in the course of high-speed mixing (in that they can atfect the

420

w.

V. Titow

bulk density and handling properties, although they often eventually

dissipate in storage). Finally, attraction of dust and other atmospheric
pollutants to charged plastics surfaces (mouldings, etc.) can result in
dirty marks.
For all these reasons it is necessary to have methods of preventing
static electricity charge build-up. In general the methods employed
may be divided into two broad groups: chemical treatments and
physical treatments. The former treatments involve the incorporation
in the PVC material, or external application thereto, of a chemical (an
'antistatic agent') which will prevent the build-up of charge. The latter
are essentially means of ionising the atmosphere (either with the aid of
a radioactive source or electrical discharge) to enable any charge
build-up to be neutralised. These physical methods are mainly
applicable in the handling and processing of sheet materials. It will be
clear that they do not impart any antistatic properties to the material
itself, and require special apparatus. For all these reasons they are not
of great importance to the present subject and will not be considered
further here.
A recent BS Code of Practice 69 provides useful basic information on
the generation of static electricity, its measurement and control.
11.4.1 Static Electricity Charges on PVC: Phenomena and Tests

In common with many other plastics PVC is a good electrical insulant:

the volume and surface resistivities of the polymer (and many rigid
compounds) are, typically, in the range 1015 _10 17 Q cm and Q,
respectively (at room temperature and about 60% RH).7o Thus, as
mentioned above, the material can readily acquire static charges,
particularly in dry conditions, and retain them for long periods. The
charges on PVC are predominantly negative: as with other plastics, the
charge distribution may be 'patchy' and in some areas a local positive
charge may be present. In their discussion of charge distribution on the
surface of a plastic (polystyrene), Woodland and Zeigler71 suggest,
inter alia, that the widely accepted use of surface resistivity measurements as an indication of the 'static properties' of a compound is not
fully justified. However, in the PVC industry, surface resistivity
measurements still provide the most popular way of assessing the
effects of antistatic agents. Since conduction over the surface of the
material is the principal mechanism of electrostatic charge dissipation,
surface resistivity is indeed the most important single factor in 'static'

11 Some Miscellaneous Components of pvc Formulations

421

phenomena in plastics. Other ways in which static charge may be

dissipated are conduction within the material itself, and ion discharge;
the latter is in fact the mechanism of the previously mentioned physical
methods of combating static in some processes.
The scale and undesirable effects of static phenomena of interest in
practice are closely associated with the magnitude of the charge and
the rate of charge build-up and dissipation. Each can be measured
and-in any but a superficial investigation-they should be evaluated
jointly.
The magnitude of static charge can be measured, in terms of field
strength, by field meters and electrometers of various types. 69 ,72,73
With the proper instrumental arrangement, the field strength measured
is related to the charge density by the expression: 69

a=EoK
where: ais the surface charge density (Cm- 2), K is the field strength
measured (V m- 1), and Eo is the permittivity of free space (8,85 x
1O- 12 Fm- 1).
Field meters can also be used qualitatively to detect the presence of
a charge or locate the point(s) of highest density. A convenient hand
instrument is the 'Statigun',7 a gun-shaped, valve electrometer. The
rate of charge decay can be measured with the aid of electrometers,
but the important point that the charging method must be standard and
reproducible is frequently overlooked. In more fundamental investigations charging by rubbing is not satisfactory. Measurement of charge
decay in, say, factory conditions (e.g. on sheeting charged in the
course of a particular process) can be meaningful in the limited context
of that process and can give an indication of the efficiency of antistatic
agents and treatments. The figure usually quoted in connection with
charge decay results is the 'half-time', i.e. time required for the charge
to be reduced by a factor of 2.
Good reviews of the generation, nature and measurement of
electrostatic charges on plastics have been published by Quackenbos,74
Ferraris,75 and Gale and Pacitti. 7o
As already mentioned, in practice the 'static' properties of a plastic
are most often gauged and indicated in terms of surface and volume
resistivity, and several standards lay down their requirements in those
terms. Thus, for instance, the maximum resistivity (as determined in
prescribed tests) of PVC conveyor belting for underground use in coal
mines is laid down as 3 x 108 Q by both BS 3289:1960 and the

422

W. V. Titow

appropriate National Coal Board specification (NCB 158/1971), whilst

upper limits for antistatic products for use in hospitals (e.g. anaesthetic
tubing, trolley wheels, mattresses) and industry (e.g. flooring,
footwear, hose) given by BS 2050:1978 are, in many cases, about 106 Q
(5 X 104 Q for flooring in explosive-handling areas). The minimum
volume resistivity requirements for ordinary flexible PVC compounds
covered by BS 2571: 1963 range from 5 x 109 to 1 X 1014 Q (at 23C).
Standard specifications dealing with general methods of determining
resistivities of plastics are listed in Appendix 3. Methods suitable for
antistatic and conductive plastics (volume resistivities up to about
105 Q cm) are given in ISO/DIS 3915-1980 and BS 2050: 1978, and for
rubbers in BS 2044: 1978. The determination of antistatic properties of
plastics films (three methods, including one based on charge decay) is
covered by BS 2782: Methods 250 A, Band C: 1976.
The attraction of particulate dirt or dust by charge-bearing plastics
surfaces is the basis of a group of tests which, whilst not very precise,
do give some visual indication of the magnitude of the charge. Because
of their low accuracy and limited reproducibility their use should,
however, be confined either to rough, practical pointer assessments or
to strictly routinised checks under standardised conditions. Two
common tests of this kind are the ash test and the 'dirt chamber' test. 71
In the former the plastics material is charged by rubbing and the
amount of cigarette ash picked up by the surface is observed. In the
popular Procter and Gamble version of the dirt chamber test the
plastics article or material charged by rubbing is placed in a cabinet at
80F (27C) and 15% RH, and smoke (produced by burning a piece of
filter paper saturated with toluene) is introduced into the chamber.
The pick-up of the particulate combustion products by the material is
observed.
11.4.2 Nature and Use of Antistatic Agents

Antistatic agents .are chemicals which are either incorporated in a

plastics material, or applied externally, to reduce static charge build-up
and promote charge dissipation, by lowering the resistivity of the
material. They are cationic, anionic or non-ionic in nature, and
commonly belong to one of the following groups of compounds:
Amines and amides, e.g. Lubrol PE (ICI); Lankrostat LDN (Lankro Chemicals Ltd)

11

Some Miscellaneous Components of pvc Formulations

423

Quarternary ammonium compounds, e.g. Ethoquad e12 (Armour

Industrial Chemical Co. (USA) or Armour Hess Chemicals Ltd
(UK; Lankrostat QA T
Polyethylene glycol derivatives, e.g. Gafstat AE 610 (GAF Corp.)
Sulphates and sulphonates e.g. Querton 14 ES or 16 ES (Guest
Industrials Ltd)
Miscellaneous ethers and esters
Conductive polymers are also offered from time to time as antistatic
agents, for example, Resin QX2611 (Dow)-a copolymer of a
quaternary ammonium compound with styrene, or Ionac PE 100
(Ionac Chemical Co.).
Typically, about 2-5 phr of an antistatic agent may be incorporated
in internal application (but up to about 10 phr with some agents-see
below). External application (normally to semi-products, e.g. film, or
mouldings by spray, wipe or dip) is usually from solution of 01-20%
concentration; but soaking the pellets of a moulding compound in a
50% solution and drying has also been recommended (e.g. with
Ex-Static-Guinness Chemical Co., UK).
In both kinds of application the aim is to form a layer of the
antistatic agent on the surface of the product, which in turn attracts a
layer of moisture, ultimately responsible-in conjunction with the
conductivity of the agent-for conducting away charges. It is because
of this that the effectiveness of antistatic treatments drops at low
relative humidity.
Internal application of antistatic agents gives more permanent
results, because if the surface layer is removed (e.g. by friction against
another surface, or contact with liquids) it can be reinstated by more
reagent diffusing to the surface from the mass of the material. It has
been claimed that this process is detectable by measurement of the
contact angle of water on the plastic's surface. 76 An externally applied
layer of antistatic agent, if removed, can only be restored by
re-application. However, the external method may be reasonably
convenient and useful in appropriate cases: inter alia it affords the user
a simple means of keeping in check dust contamination of gramophone records.
It is well known that most antistatic agents reduce the thermal
stability of PVC (especially uPVC) compositions in which they are
incorporated. However, careful formulation, particularly the selection
of stabilising systems, can minimise the effect in many cases. Analytical

424

W. V. Titow

studies are claimed to indicate that nitrogen-containing antistatic

agents have the strongest adverse effect on heat stability. 77
The incorporation of a conductive filler (most commonly carbon
black, although metal powders-e.g. aluminium, * nickel-may be
used) produces an antistatic effect, or conductivity at sufficiently high
loadings. The use of carbon black for these purposes is old, having
originated in rubber processing. The proportions of the filler used are
high, up to about 35%. Various grades of carbon black differ in their
own conductivity: in general conductivity increases with decreasing
particle size, and with increasing structure, surface purity and
crystallite size and orientation. High-structure furnace blacks are
therefore particularly suitable. 78 t Whilst excellent permanent antistatic
effect or conductivity can be achieved, the method is obviously limited
to compositions acceptable in black.
Two further points may be mentioned. Firstly, plasticisers, and to
some extent also other constituents of PVC compositions, can affect
resistivity, and this should be borne in mind both from the point of
view of the resulting effect on static accumulation, and the insulation
properties in electrical applications. Secondly, certain antistatic agents
which have to be used in substantial proportions for their maximum
effect can have an appreciable plasticising action: examples are Antistat
A (Albright and Wilson) and Irgastat 51 (Ciba-Geigy), both used in
flexible compositions in amounts of up to 10 phr. The effect of Antistat
A on some properties of a flexible composition (Breon P13011+
plasticised with TXP and Pliabrac 987 in the ratio 70: 30) is illustrated
in Table 11.8
11.5 FLAME AND SMOKE RETARDANTS
11.5.1 General Mechanism of Burning of Polymers and Plastics

The mechanism of burning of polymers, alone or as base constituents

of plastics compositions, comprises two processes-pyrolysis and
* Conductive thermoplastic compounds (including PVC) filled with aluminium
alloy flake are commercially available, e.g. Emiblend (Howard Industries Inc.,
Clark, NJ, USA).
t Special proprietary brands are available for use in thermoplastics, including
PVC, e.g. Conductex 975 (Columbian Chemicals Co., Tulsa, OK, USA).
:j: Emulsion PVC polymer, K value 70-74 (BP Chemicals International Ltd).
Nonyl ester of saturated CC C6 dibasic acids (Albright and Wilson Ltd).

10
10
630
-33

5
20
720

-25 -29

Addition of Antistat A, (phr)

Surface resistance (Q x 107 )
Modulus at 100% elongation
(lbfin- Z)
Cold flex temperature
eC, Clash and Berg)
0
2500
830

70 phr

Plasticiser (total content)

-31

0
1000
640
-34

5
15
580
520

10

-37

80 phr
7

5
11
480

-36 -38

0
450
530

10
5
430
-40

90 phr

TABLE 11.8
Some Effects of 'Antistat A' in a pPVC Compound

-39

0
300
480

-41

5
7
420

100 phr

-43

10
4
390

Vl

i:>

3l::

ri

"t:l

to
~

1:;

~;::

!:;"

'"~

~
::i

......
......

426

w.

V. Titow

combustion. Pyrolysis is the breakdown (thermal degradation) of the

solid polymer material to products of lower molecular weight,
including simple, volatile, hydrogen-rich compounds, and conjugated
linear and cyclic compounds. Combustion is the process of exothermic
oxidation of the pyrolysis products. Both processes involve, inter alia,
the formation and re-combination of free radicals: it has been
suggested25 ,79 that flammability is considerably influenced by the ease
and rate of formation of HO* radicals. Both processes are complex,
and need suitably elevated temperatures to initiate and sustain them:
combustion additionally requires oxygen (pyrolysis can proceed
without it, although its absence will affect the temperatures involved
and the nature of degradation products formed). Pyrolysis starts first
(with many organic polymers the rate is appreciable at about 300C in
air), but once the amount of breakdown products generated and the
rate of their continued formation are sufficient for combustion to
commence (Le. for those constituents of the pyrolysate which are
present in gaseous, vapour, or fine-mist form to be ignited) and to
proceed, the two processes run concurrently, with the heat produced
by combustion actuating, or contributing to, further pyrolysis, which in
turn provides more degradation products for the combustion process
(see Fig. 11.6).
The pyrolysis products may be first ignited (Le. the combustion
process started) by contact with an external source of intense heat
(normally a flame, but, for example, incandescent-or simply very
hot-electric wires can also be the source in fire situations): this is
sometimes termed 'flash ignition'. Spontaneous ignition (self-ignition)
may also occur when the concentration and temperature of pyrolysis
products have reached suitable values. For a given polymer or plastic
these values will depend on the composition of the material and the
conditions (cf. Chapter 12, Section 12.10): 450C is fairly representative as the flash ignition temperature for rigid PVC (normal impact
strength grade) in the test of ASTM 1929-78 (cf. Chapter 12, Table
12.12). In general, as has been mentioned in Chapter 12, the burning
behaviour of a plastic is cardinally dependent on the conditions, to
which any descriptive terms (like 'non-flammable', 'slow-burning',
self-extinguishing', etc.) must relate. However, in many tests and
actual service situations where the plastic is not in continuous contact
with an 'external' flame, it may be properly described as self-

extinguishing if the burning process is not self-sustaining in the sense

that the heat generated by the material's own combustion is not

11

Some Miscellaneous Components of pvc Formulations

427

sufficient to maintain the high temperature required for, and the rate
of, pyrolysis at a level necessary to provide enough pyrolysate (in
suitable form-i.e. gaseous or fine mist) to keep the combustion going.
Any of the products of both pyrolysis and combustion (see Fig. 11.6)
may find their way into the smoke emitted by a burning plastic. In
terms of its physical nature smoke is a suspension of particles in a
mixture of air and the gases and vapours generated in the burning
process (and remaining uncondensed into liquid droplets or layers on
existing particles).8D-82 The particles of the particulate phase may be
solid or liquid (or some of each); some at least may have a solid
carbon 'skeleton'.83 Gases and vapours are invisible: hence, in any
given case (i.e. for a fixed total amount of matter in the smoke) the
smoke density, usually defined in terms of obscuration of light, will be
determined by the proportion of constituents present in the particulate
phase, and to some extent also by the particle size and size
distribution. In general, the greater the amount of pyrolysis products in
the smoke (i.e. the less complete the combustion) the greater the
visible smoke denisty (because the pyrolysis products tend to have
higher molecular weights than the final products of combustion and
hence condense more readily into droplets when mixed with relatively
cool air). In any particular case the actual nature and proportions of
the chemical constituents of the smoke will depend, in a complex way,
upon the chemical composition of the burning plastic and, given that,
upon the burning conditions (especially the temperature and the supply
of oxygen): the same factors also influence the parameters governing
smoke density.
11.5.2 Flame Retardance and Smoke Suppression in PVC
Compositions
It is the large proportion of chlorine they contain that is responsible for

the low intrinsic flammability of PVC polymers and those of their

compositions in which the overall chlorine content has not been
reduced too far by 'dilution' of the polymer with the additives used,
especially flammable plasticisers (see Chapter 7, Section 7.6, and
Chapter 12, Section 12.10). In terms of the mechanisms outlined
above, the presence of chlorine hinders burning through the formation
(mainly in the course of pyrolysis) of hydrogen chloride, which
interferes with the burning process in two ways: being incombustible
itself it prevents, or at least reduces, access of oxygen to the

w.

428

V. Titow

POLYMER

(or its dlZrivatlvlZ

plastic)

Pyrolysis +-

Liquid or
SlZmi-liquid
dlZgradation
products
('tar')

- - - - - - - -

GaslZous (vapour
phaslZ) dlZgradation
products

- - --

Solid or
SlZml-solid
dlZgradatlon
products
(primary 'char')

FurthlZr pyrolysis +-

--i
I

Solid
carbonaclZous
rlZsidulZ
(slZcondary 'char')

Combustion
\

\
Combustion
products (including
CO, CO2, H20 and
various oxidlZS)

I
I

I
I

I
\\

I
I
I

/" ,
<, HlZat ,/ - ,
/

I
-

_ ......

Fig. 11.6 Simple, schematic representation of the general mechanism of

burning of polymeric materials.

11

Some Miscellaneous Components of pvc Formulations

429

combustion zone; it also reacts with free radicals (especially HO*)

thus acting as terminator for the combustion propagation
reactions. 25,84
Thus, by virtue of its chemical nature, PVC achieves the kind of
flame-retardant effect that in other plastics has to be induced by the
addition-as flame retardants-of halogen derivatives of organic
compounds (sometimes in proportions so large that they affect
adversely the mechanical and other properties).
The effectivity of the flame retardancy mechanism just mentioned
can be preserved in soft and semi-rigid PVC compositions (i.e. those
containing substantial proportions of additives) by the use of
chlorinated paraffin plasticiser extenders or chlorinated polyethylene.
It can also be further improved by the synergistic effect of 'antimony
oxide' (antimony trioxide, Sb20 3) incorporated in relatively minor
proportions (up to about 10 phr). The improvement is usually
explained in terms of the following effects. The antimony trioxide
reacts with the hydrogen chloride generated by burning PVC polymer
(and any chlorinated additives)t to form antimony trichloride, volatile
at the combustion temperature. This is not only more effective than
HCI as a 'barrier' against oxygen, but can actually react with oxygen in
the flame zone (thus reducing the amount available even further). The
reaction products are antimony trioxide-regenerated in the form of a
fume (suspension of very fine particles in the combustion gases)-and
atomic chlorine. The presence of the Sb20 3 particles suppresses
somewhat the generation of the highly active HO* radicals by
reducing the excitation energy for the oxidative process (the so-called
'wall effect'25): the particles also generally catalyse the re-combination
of free radicals in the flame. 82 The chlorine is available to form more
HCl.
The action of zinc and tin oxides is similar to that of Sb20 3 but less
effective. Zinc oxide also functions as a smoke suppressant, but it
tends to impair the thermal stability of PVC. Zinc and barium borates
are sometimes used in flame-retardant products, mainly in conjunction
with Sb20 3 (as cheaper part-replacements13 ); synergistic effects can
arise in such combinations (notably with zinc borate85 ), which may also
have smoke-suppressing effects.
The borates are believed to inhibit burning in a manner similar to

t In other polymers flame retardancy can be conferred by Sb20 3 in a similar

way if a chlorine-containing organic compound is also incorporated.

430

W. V. Titow

that of borax (historically one of the earliest flame retardants, first used
in textiles), i.e. by fusing to form a protective layer which impedes
access of oxygen and heat to the PVC material;25,84 the fusion also
abstracts some heat from the system.
As particulate additives insoluble in PVC compositions the metal
oxides and borates just mentioned all have some opacifying effect
(rather lower in general with the latter compounds): this is minimised
with ultra-fine (sub-micron) particle grades (d. Section 11.3.1 above)
which are becoming increasingly widely available.
Note: The opposite approach to the same end is represented by a
version of Sb 20 3 of particle size considerably larger than in
the common, regular grades (1O-40/lm as against 1-3/lm):86
this is offered as a low-reflectance 'non-opaque' grade on the
basis that the comparatively lower number of coarse particles
present at a given level of loading by weight causes a lower
overall amount of interference with light.

Save for phosphate ester plasticisers in flexible compositions,

antimony oxide is the traditional flame retardant for PVC, still most
widely used today. However, its high cost has been providing incentive
for development of more economical alternatives. Some examples of
those already available commercially are 13 ,86 antimony-based additives
cheaper than Sb20 3 (e.g. antimony and antimony/zinc silicate compositions in the Oncor and Ongard ranges of Anzon America Inc;* d. also
CLarechem CLA-150o-Claremont Polychemical Corp.), and molybdenum-based compounds (e.g. a Mo/phosphate combination, MoLy
FR 36-Climax Molybdenum Co; and zinc molybdate/zinc oxide
combinations like MoLy White 101-Sherwin-Williams Co.). The
smoke-suppressant effect of molybdenum oxide, alone or in mixtures
with antimony oxide, has been known for some time (see below).
As has been mentioned in Chapters 7 and 12 the phosphate ester
plasticisers (especially the aryl phosphates which are primary plasticisers) are widely used to reduce the flammability of flexible PVC: they
are particularly useful in transparent compositions where Sb20 3 and its
above-mentioned combinations are unsuitable because of the opacifying effect. It is common to employ an aryl phosphate plasticiser in
* Associated with Anzon Ltd in the UK; now owning the PVC stabiliser and
fire retardant/smoke suppressant operations formerly belonging to National
Lead Co., USA.

11

Some Miscellaneous Components of pvc Formulations

431

conjunction with (as part replacement for) a cheaper primary

plasticiser (often DOP) or a plasticiser/extender combination, because-apart from the cost aspect-the low-temperature properties of
phosphate-plasticised compositions are relatively poor, whilst their
smoke emission on burning is rather high. The flame-retardant effect
of phosphorus compounds in polymers (including phosphate ester
plasticisers in PVC) is believed to operate mainly through the
formation of phosphoric acid residues, phosphorus pentoxide and its
hydrates, all of which strongly promote the generation of char during
pyrolysis and thus reduce the amount of matter available for
combustionZ5 ,84 (ct. Fig. 11.6). Chlorinated phosphate esters with
flame-retardant and general plasticising action similar to those of alkyl
phosphate plasticisers, but with lower smoke generatiOn and-in some
cases-better low-temperature properties, are also noteworthy (ct. e.g.
Fyroflex 2704 and 280o-Stauffer Chemical Co.): see also Chapter 6,
Section 6.6.4.
Cost is always a factor in the selection of a flame-retardant agent or
system for a particular PVC composition: in practice it is most often
flexible PVC that has to be 'flame retarded', as uPVC is inherently
resistant (see above). In the absence of special requirements (e.g. high
clarity), combinations of a chlorinated paraffin (plasticiser extender)
with antimony oxide (alone or in conjunction with, say, zinc borate as
cheaper part-replacement) can offer cost economy in pPVC compositions with good performance in flammability tests. 87 Where a
phosphate plasticiser forms a substantial part of the flame-retardant
system a smoke suppressant is also desirable: in filled compositions this
function may be discharged in a sufficient degree by the filler-for
example, calcium carbonate and talc can reduce the smoke generation
(and, as inert materials, also flammability) of PVC compositions. A
few outline examples of flame-retardant/smoke-suppressant systems of
the above kind are given in Table 11.9.
As has been mentioned in Chapter 8 (Section 8.4.2) alumina
trihydrate (AI(OHh or Al z0 3 .3HzO) is another additive, with both
flame-retardant and smoke-suppressing actions, of considerable use in
flexible PVC compositions. The main mechanisms whereby these
actions are exerted are considered to operate as follows. 88 ,89
The water of hydration present in high proportion (about 34%) in
alumina trihydrate is securely retained under PVC processing conditions (the amounts lost after heating for 10 min at, respectively, 170C and
220C, represent about 05% and 25%88). However, at the high

DOP
Epoxidised oil
{ Aryl phosphate ester
Chlorinated paraffin (52% Cl)b
{ Antimony trioxide
Zinc borate
Molybdenum complex c
{ Zinc/magnesium complex d

25
2
4

25

60

5
32
5

50

24

24

60
5

5
25

60

Used for its stabilising rather than plasticising action.

Cereclor S52 (lCI).
c Kem-Gard 91lA (Sherwin-Williams Co., Chemical Division).
d Ongard 2 (Anzon Ltd).

Smoke
suppressants

Flame
retardants

Plasticisers

Semi-rigid
formulations (phr)

Flexible formulations (phr)

TABLE 11.9
Outline Examples of Flame-retardant/Smoke-suppressant Systems for Flexible and Semi-rigid PVC

"'"

:::'1

o;;:

~
:'"

W
N

11

Some Miscellaneous Components of pvc Formulations

433

temperatures obtaining in burning it is rapidly split off as vapour or

steam, which obstructs the access of oxygen to the polymer, thus
hindering the combustion process.
2 AI(OH)3

h' h
18
)
temperature

Ah03 + 3HzO - 716 kcal

The action is supplemented by the insulating effect of the solid

alumina liberated in the decomposition. The alumina also acts as a
heat barrier which, in conjunction with the heat absorption in the
endothermic decomposition reaction, lowers the temperature and
suppresses pyrolysis, reducing smoke generation. It is also likely that
adsorption of smoke constituents (especially HCI) by the finely divided
alumina contributes to the reduction of smoke emission. 13
The double, flame- and smoke-retardant action of alumina trihydrate, and the fact that, weight-for-weight, it is cheaper than the main
flame retardants for pPVC, are considerable advantages. However, high
loadings are necessary for effective functionality (e.g. about 100 phr
may be required to raise the Oxygen Index of a typical composition
containing 50 phr DOP from about 22 to about 2788). At such loading
levels the effects on viscosity in processing and on physical properties
of the product can be substantial (see Chapter 8, Section 8.4.2).
The mode of action of the mineral fibre Dawsonite (d. Chapter 8,
Section 8.4.1) resembles that of AI(OHh- The material of the fibre, a
hydrated sodium aluminium carbonate, decomposes at combustion
temperature with essentially similar effects (supplemented in this case
by the evolution of non-combustible carbon dioxide in addition to
water vapour).
Magnesium carbonate is another smoke suppressant used at high
loading levels (up to about 40 phr) , at which its side-effects as a filler
become significant. It is a component of some proprietary flameretardant/smoke-suppressant compositions, e.g. Monsanto's Phosgard
LSV in which it is combined with a phosphate ester plasticiser
(Santiciser 148). The compositions are recommended for use in
compounds for electrical wire coatings, carpet backings and wall
coverings.
Molybdenum trioxide (molybdic oxide, Mo0 3) combines strong
smoke-suppressant action in pPVC at all plasticiser contents with some
flame-retardant effect: the latter is roughly comparable to that of
antimony oxide at low levels of plasticisation (e.g. 20-30 phr DOP),
but less at higher levels. The use of Mo0 3 in conjunction with Sbz0 3

434

W. V. Titow

(at 3 phr each) in medium-plasticised compositions can give good flame

retardancy and smoke suppression. 13 ,82 Mo0 3 is less dense than Sb20 3
(SG respectively, 45 and 5,7) and has lower pigmenting strength (in
comparable particle size grades); however it is an expensive additive.
The smoke-suppressant effect of Mo0 3 is associated with the
promotion of dehydrochlorination of the PVC polymer, and drastic
reduction in generation of benzene. 82 However, the actual mechanism
of its action is apparently different from that of Sb20 3 , as Mo0 3 has
been reported not to yield volatile metallic species in burning PVC. 82
Molybdates (e.g. combinations of calcium and zinc derivatives) also act
as smoke suppressants.
Note: Selected zinc compounds, especially in combination with
others, do not promote decomposition of PVC to the extent to
which zinc oxide does. Such combination, therefore, most
often forms the basis of commercial zinc-containing smoke
suppressants (e.g. Ongard 2-ef. Table 11.9) despite the
reasonable price and strong smoke-suppressing action of the
oxide.

Certain derivatives of ferrocene represent another group of smoke

suppressants effective in uPVC compositions. 82
Determination of the intensity of smoke generation (either by
measurement of 'optical density' in a standard chamber, or by
weighing the smoke substance collected on a filter in standard
conditions) is covered by several of the standards listed in Table 12.12
(Chapter 12). However, only one of these-ASTM D 2843 90-is
specifically and exclusively concerned with determination of smoke
evolution: the others merely feature this as one of the aspects of
burning behaviour under the test conditions. Another directly relevant
standard (centered on the so-called NBS smoke chamber) is ASTM
E 662,91 whilst an ISO standard, similar in principle, is in
preparation. 92 A useful review of smoke test methods has been
published in ASTM Standardisation News (August 1976, pp. 18-26).
Two other useful general sources of information ~n methods of
testing the flammability of, and smoke generation by, plastics materials
are Flammability Test Methods for Plastics: An International List,
published recently by the Chemical Industries Association Ltd, * and
ISO Technical Report 3814-1975 The Development of Tests for
Measuring 'Reaction to Fire' of Building Materials.
* Alembic House, 93 Albert Embankment, London SEl 7TU, England.

11

Some Miscellaneous Components of pvc Formulations

435

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77. Sheverdyaev, O. N., Slesarev, V. V., Tugov, I. I., Pudov, V. S. and
Zhuravlev, V. S. (1976). Plast. Massy, No.6, 53-5.
78. Garret, M. D. (1977). Kunststoffe, 67(1), 38-40.
79. Collington, K. T. (1973). Plast. Polym., 41(151), 24-9.
80. Titow, W. V. (1961). Trans. Plast. Inst., 29(84),186-95.

438

W. V. Titow

81. Gaskill, J. R. (1979). ASTM Standardisation News, 7(12),23-4.

82. Walker, A. G. (1980). 'Smoke from burning polymers', paper presented at
the PISA Symposium on Plastics in Transport, Durban, RSA, 21st-23rd
May, 1980.
83. Tadihisa, J. (1971). Res. [nst. Japan, 33, 40-4.
84. Grieveson, B. M. (1976). 'The fire hazard of polymers', paper presented at
the Polymer Symposium, British Association for the Advancement of
Science, Lancaster, England, 3rd September, 1976.
85. Cowan, J. and Manley, T. R. (1976). Brit. Polym. J., 8(2), 44-7.
86. Anon. (1980). Plast. Technol., 26(8), 71.
87. Colelli, C. C. and van Loenen, P. (1979). Plast. Technol., 25(7), 67-9.
88. Plastichem Ltd. (Croxton and Garry Ltd.), Technical Bulletin 3Ma/16,
'Trihyde' Fire Retardant Fillers in Plasticised PVC'.
89. Anon. (1977). Kunststoffe, 67(1), 34-8.
90. ASTM D 2843-77: Density of smoke from the burning or decomposition of
plastics.
91. ASTM E 662-79: Specific optical density of smoke generated by solid
materials.
92. ISOIDP 5924: Reaction to fire tests: Optical density of smoke using a dual
chamber box.

CHAPTER 12

Miscellaneous Properties ofSpecial Interest

in PVC Materials and Products
W. V.

TITOW

12.1 INTRODUCTION
All properties of a PVC material depend, in a more or less complex
way, upon the formulation, and to some extent also on the effects of
compounding and processing (including the 'heat history'). However,
some properties are more directly associated with the nature and
amount of a particular class of formulation component: for example,
softness, extensibility, tensile strength and modulus are particularly
strongly influenced by plasticisation, many mechanical properties are
substantially upgraded by incorporation of fibrous reinforcing fillers,
flame resistance improvement can depend directly on the incorporation
of suitable flame retardants, and so on.
In this book, properties linked in such a manner with individual
formulation components and factors are considered in conjunction with
them in most cases. Some general information and numerical data on
properties are also given in Chapter 1 and Appendix 3. The properties
discussed in this chapter are either those which might be described as
more 'composite' in nature or origin, or which are relevant in some
special context or application.

12.2 LOW-TEMPERATURE PROPERTIES

Many PVC products, both rigid (e.g. pipes, containers) and flexible
(e.g. PVC-coated tarpaulins and clothing, inflatables), are used in
conditions and climates where they may experience low (sub-zero)
439

440

w.

V. Titow

temperatures. It is necessary, therefore, that their properties should

not be affected by such conditions to the point where serviceability
would be impaired. Securing this objective is essentially a matter of
formulation, supplemented by proper compounding (to ensure good
inter-blending of all formulation components) and care in processing.
With uPVC the most important single consideration in the context of
low-temperature service is to preserve the toughness (avoid embrittlement) of the material. Without appropriate modifiers uPVC can be
brittle even at room temperature: suitable choice of modifier (and its
correct incorporation in the right proportion) can ensure that the
compound is, and remains, tough in sufficient measure. The effects
obtainable are largely a matter of degree, since uPVC compounds
(including the so-called high-impact grades) in most cases exhibit a
definite, often regular, dependence of impact strength (which is related
to toughness) on temperature, with, usually, a fairly well-defined
brittle point, i.e. a temperature at which the mode of failure in an
impact test changes from ductile to brittle (often with a corresponding
drop in strength). Brittle point, coupled with actual impact strength
values at the low temperatures concerned, can be used as a criterion of
low-temperature performance. Other things being equal, the brittle
point of a compound tends to vary inversely with the molecular weight
of the polymer and the amount of impact modifier present (up to a
practical usefulness limit in most cases). Although, in what might be
termed the more academic context, and also in connection with
product design, the fracture toughness approach l - 5 is playing an
increasingly important role in the understanding, determination and
prediction of the toughness of plastics, including PVC, in industrial
practice the results of impact strength tests are still widely used as a
measure of this complex property. This is so, partly because a large
body of relevant test data has been built up over the years, and despite
often comparatively poor correlation between the results of different
tests, and between test results and effects of particular service
conditions.
Standard impact tests of interest in connection with the determination of brittle point of PVC materials include the following:
ASTM D 759-66 (Re-approved 1976): Conducting physical property
tests on plastics at subnormal and supernormal temperatures.
ASTM D 746-79: Brittleness temperature of plastics and elastomers
by impact:

12 Properties of Special Interest in PVC Materials and Products

441

The method of this standard is technically similar to that of ISO/R

974:1969.
BS 2782:Part 1: Method 150 D:1976: Cold crack temperature of film
and thin sheeting.
The method of this specification is essentially Method 10 of BS
3424:1973, but modified to give more precise determination. Although
intended primarily for flexible film materials it can be used (with
special care) for uPVC film and thin sheet that can be bent into a loop.
Cold crack temperature is defined as the temperature at which cracks
are caused when a loop of film or sheet is flattened by a blow of a test
hammer under standard conditions. This temperature is usually related
to (but not the same as) the low-temperature limit for actual service.
ASTM D 1790-62 (Re-approved 1976): Brittleness temperature of
plastic film by impact.
Both in this method (which is suitable for films up to 025 mm thick)
and that of ASTM D 746 (in which thicker, die-cut specimens are
struck by a sharp edge), brittleness temperature is defined as that
temperature at which 50% of the test specimens fail (i.e. break or
shatter) under the conditions of the test. ISO 974-1980 gives a similar
definition in terms of its test. In this, specimens 16 mm thick are
struck a sharp blow which bends them round a shaped mandrel.
ASTM D 3029-78: Impact resistance of rigid plastic sheeting or parts
by means of a tup (falling weight).

The main effects of cooling of flexible PVC are stiffening, hardening,

and embrittlement. The temperature of onset, and the extent, of these
changes depend on the formulation. The stiffening and hardening are
much more pronounced than with uPVC; they are also more serious in
practice, since flexibility and softness are among the most important
properties for which flexible PVC is formulated. It is therefore
desirable that these properties should be retained under a wide range
of service conditions, including low temperatures. Correct formulation,
and especially choice of plasticiser(s) is again the key factor in ensuring
good performance in this respect. The best low-temperature properties
are conferred by plasticisers of the aliphatic ester type (see Chapters 6
and 7), whilst aromatic phosphates are among the least suitable
plasticisers (e.g. compounds plasticised with TIP can be quite hard
and stiff at freezing point).

442

W. V. Titow

It is clearly important to have tests available, the results of which can

assist in the evaluation and prediction of the stiffening and hardening
of flexible PVC at low temperatures. The results of relevant standard
tests are particularly useful in monitoring quality in production, or
assessing the effects of formulation modifications in basically the same
type of compound. Correlation between the results of tests by different
methods is not always good, and none of the methods can be said to
provide directly a value for the lowest temperature admissible in actual
service (albeit they do give useful indications in that direction). Useful
standard tests and the properties they determine include the following.

12.2.1 Cold Flex Temperature (Clash and Berg)

This is the lowest temperature at which a standard strip specimen can
be deflected through an angle of 200 under a fixed torque, in
prescribed test conditions. Clash and Berg are the originators of the
apparatus; the method is described in BS 2782: Part 1: Method 150 B:
1976. The cold flex temperature (normally quoted in 0c) is always
higher (Le. 'warmer') than the 'cold bend' temperature (see below).

12.2.2 Cold Bend Temperature

This is determined by the method of BS 2782:Part 1: Method
104A:1970: a strip specimen is cooled at the test temperature for
10 min and wound mechanically round a mandrel of prescribed
diameter, at a prescribed rate. The cold bend temperature is the
temperature at which this treatment causes the specimen to crack or
fracture in the standard test.

12.2.3 Low-Temperature Extensibility of Flexible PVC Sheet

This is the extension produced in a standard specimen at - 5C under a
prescribed load. It is determined by Method 150 C: 1983 of BS
2782:Part 1.
The effect of temperature upon the stiffness in torsion (apparent
modulus of rigidity) of plastics materials, including PVC, may be
determined by measurement according to the method which forms the
basis of the following standards: ISO/R 458-1965; BS 2782:Part 1:
Method 150 A:1976; ASTM D 1043-72 (Re-approved 1981); DIN
53447:1966. A version of the Clash and Berg apparatus is used in the
determination.

12

Properties of Special1nterest in PVC Materials and Products

443

U.3 HEAT RESISTANCE

This section is concerned with heat resistance of PVC materials and
products in service and service-related tests. Although 'heat resistance'
if often used synonymously with 'resistance to degradation by heat', in
the present context it has a wider meaning embracing the following
effects of heating:
(i)

degradation of the PVC material (outwardly manifested in

deterioration of properties and appearance);
(ii) loss of volatile components (especially plasticisers from pPVC,
with consequent hardening and stiffening, leading to deterioration of many properties);
(iii) temporary, mainly reversible, changes in properties (especially
mechanical properties) at elevated temperatures.

Degradation is the consequence of the breakdown of, and chemical

changes in, the PVC polymer. In practice it is usually detected and/or
monitored by detecting or measuring the evolution of HCI (the
principal breakdown product), colour changes, and changes in
properties. The methods used are discussed in Chapter 9, and some
relevant standards are listed in Section 3.2 of Appendix 1. Thermogravimetric analysis and various analytical methods of identifying
chemical changes in the polymer and its decomposition products are
also employed in more fundamental studies of thermal decomposition
of PVc. 6 Volatile loss is normally determined gravimetrically.
Degradation and loss of volatiles are usually concurrent at least to
some extent, and are often jointly termed 'heat ageing'. The greatest
possible resistance to heat ageing is clearly essential in PVC materials
intended for service above room temperature; it is also desirable in all
PVC products, since loss of volatiles and/or deterioration of properties
on heating in tests are frequently used as indication of likely long-term
performance in these respects in service at room temperature. Such
predictions, as well as those of the maximum acceptable service
temperature, are usually obtained by the following method.
A selected property (e.g. tensile or impact strength, modulus, etc.)
is determined in appropriate tests. Specimens are then heated
at a number of elevated temperatures suitably chosen in the light of
practical experience or other relevant information or requirements.
The property is re-determined at intervals during the heat treatment
(several properties may also be monitored in this way) and the

w.

444

V. Titow

100

~ 60------~
I
~

I
I

&
i!-

T(60),

I
I

Fig. 12.1 'Percentage retention' of selected property as a function of heating

time at various temperatures (81 ) 8z> 83 > 84 > ( 5), Schematic representation.
'percentage retention' (i.e. the value after a given heating time as a
percentage of the original value) is plotted against log time, to obtain a
family of curves as shown schematically in Fig. 12.1. The lowest
percentage retention value of the test property acceptable for service
purposes is decided (say, for example, 60%), and the corresponding
times for the test temperatures from Fig. 12.1 (intercepts of the 60%
retention line with the individual temperature curves) are plotted
against the reciprocal of absolute temperature to produce an Arrhenius
plot as shown schematically in Fig. 12.2.
Note: On the assumption that heat degradation is a simple
heat-activated 'reaction' the plot should represent the wellknown Arrhenius relationship, In k = -(E/RT) + constant
(here expressing the effect of temperature on the rate of the
notional 'degradation reaction') and should thus be rectilinear
in the ideal case. In practice curves concave to the
temperature axis may be obtained.

The time for the chosen test property to drop to the pre-selected
percentage retention value at a particular temperature can be read off
the curves of either of the two plots. The expected service time after
which the test property will reach the value at room temperature can be
found by extrapolating the curve of Fig. 12.2.

12 Properties of Special Interest in PVC Materials and Products

445

Reciprocal of absolute temperature, 11K

Fig. 12.2 Time to reduce percentage retention of selected property to 60%,

as a function of the reciprocal of heating temperature (j expressed in kelvin).
Schematic representation.
Methods of this type are used in deriving the 'temperature index'
values 7-widely used temperature limits for continuous service,
assigned to various polymers and plastics materials by Underwriters
Laboratories Inc. (and published in the Modern Plastics Encyclopedia,
McGraw-Hill Inc., and elsewhere).
The mechanism of heat degradation of PVC is discussed in some
detail in Chapter 9, in connection with heat stabilisation.
Some standard procedures and equipment applicable in the
determination and prediction of heat-ageing effects in plastics,
including PVC, are described in the following specifications:

ISO I137-I975. * Plastics-Methods of test for the determination of

the behaviour of plastics in a ventilated tubular oven.
ISO 2578-1974: Plastics-Determination of time-temperature limits
after exposure to prolonged action of heat.
BS 4618: Section 4.6:1974: The presentation of plastics design data.
The thermal endurance of plastics.
ASTM D 1870-67 (Re-approved 1978):* Elevated temperature
ageing using tubular oven.

* Mutually corresponding in technical content.

446

W. V. Titow

ASTM D 2115-67 (Re-approved 1980): Standard recommended

practice for oven heat stability of poly(vinyl chloride) compositions.
ASTM D 3045-79: Standard recommended practice for heat ageing
of plastics without load.

It may be noted in passing that some mechanical properties of

plasticised PVC (tensile strength, modulus) may appear to improve (in
that their values increase) in the initial stages of accelerated heat
ageing. This is associated with early loss of plasticiser: the tensile
strength and modulus of pPVC normally vary inversely with the
plasticiser content (except for some anomalous 'antiplasticisation'
effects which may occur at very low contents); their values thus
increase at first with the volatalisation of plasticiser, whilst at the same
time this process uses up heat that would otherwise be available for
thermal degradation (which reduces the strength and modulus).
Although loss of plasticiser may thus appear to bring some benefit in
the early stages of ageing of pPVC, it is in fact a contributory factor in
the overall deterioration caused by this process. Plasticiser loss is
accompanied by reduction of extensibility, flexibility and softness;
internal stresses may be set up (especially where the loss is locally
non-uniform) and these-either alone or in conjunction with any
external stress that may be encountered-<:an promote cracking of the
stiffened, hardened material; low-temperature properties (e.g. cold
flex temperature) can also be adversely affected.
Heat-ageing resistance is a significant consideration in connection
with the service performance of such important PVC products as
upholstery fabrics and cable compounds (insulation and sheathing). In
both these applications, and perhaps even more particularly in the
former, resistance to heat ageing of the PVC materials involved is of
interest not only per se, but also because it is normally associated with
good long-term stability in service at room temperature. 'Fogging' of
motor-car windscreens and interiors by plasticiser volatalised from
PVC-coated upholstery is an example of a special practical problem
associated with a formulational factor (nature, volatility and compatability of plasticisers used) instrumental in heat-ageing resistance. Tests
for stability to fogging used by motor-car manufacturers and plasticiser
suppliers to evaluate PVC upholstery coatings in this regard are
essentially heat-ageing tests at moderately elevated temperatures. The
problem of fogging is discussed in Chapter 7.

12

Properties of Special Interest in PVC Materials and Products

447

The performance of pPVC sheets, films and fabric coatings in tests

for loss of volatiles at elevated temperatures is of particular practical
significance, because it is often used as one of the criteria of technical
and commercial acceptability (the implication being that it gives an
indication of likely long-term behaviour in service at ordinary
temperatures). Several standards exist; all give test methods, and some
also lay down permitted loss limits: both the methods and the figures
(where prescribed) are somewhat arbitrary and do not correlate
particularly closely with actual service experience. The following
standards may be mentioned: ISO 176-1976,* BS 2782:1970 Method
107F,* ASTM D 1203-67 (Re-approved 1981),* BS 2601:1973,t BS
3424:1973,t BS 4216:1970,t AS:j: 1441:1973 (Method 8) and AS
1440:1973, Canadian Standard 4-GP-149:1972.
For a given formulation, the volatile loss from a plasticised PVC
sheet, or coating on a fabric, in standard conditions, is a function of
the specific surface (surface per unit volume) and hence the thickness.
Theoretical considerations8 suggest that in the kind of test prescribed
by most standards the total volatile loss in the test period (from 5 to
24 h, depending on the standard used) should conform to the
expression
L

= k(~+ ~)

(1)

where: L is the volatile loss; n is the thickness of the PVC sheet or

coating on a fabric; P is the perimeter length and A the area of the test
specimen; k is a coefficient dependent on the conditions (including
heating time and temperature) of the test method; and b is a numerical
factor dependent on the proportion of the specimen surface effectively
available for evaporation. For a given set of test conditions the value of
b may vary between 1 (for a coating on an impervious substrate) and 2
(sheet specimen with both sides freely accessible to the atmosphere).
Figure 12.3 shows a plot of loss of volatiles from PVC films of the
same composition but ranging in thickness between 01 and 0-4 mm,
determined by Method B of ISO 176-1976(E). The theoretical curve
(plot of eqn (1) with appropriate values) is superimposed (solid line).
The general agreement is good: the moderate departures from
theoretically predicted values at the extremes of the thickness range
* See Appendix 1, Section 4.2.
t See Appendix 1, Section 7.
:t: Australian Standard.

w.

448

V. Titow

2
L =0205 ( %- .008)

01

02

03

Nominal film thicknQ:ss (n), mm

04

05

Fig. 12.3 Volatile loss from calendered PVC film in test according to Method
B of ISO 176:1976(E), as a function of nominal thickness (~, dotted line).
Solid line: plot of eqn (1) with appropriate constants (PIA = 008 mm- 1 for
standard specimens in the method used; b = 2 for a sheet with both sides
exposed). PVC film formulation:
100
PVC resin (emulsion type)
70phr
Plasticisers: DIDP
45 phr
Polymeric
3phr
Stabiliser
05 phr
Lubricant

covered by the tests must be ascribed to experimental error (or some

other factor, possibly thickness-dependent); otherwise-if the two
extreme results were valid-extrapolation of the experimental curve
would predict that volatile loss should cease altogether at a film
thickness of about 05 mm, and that it should be only about 5% for an
infinitesimally thin film, when, in fact, with an almost infinite specific
surface, loss of most of the monomeric plasticiser can be expected,

12 Properties of Special Interest in PVC Materials and Products

449

(i.e. up to about 40% volatile loss from this particular compositionsee caption of Fig. 12.3).
Cable compounds are rated, inter alia, according to the conductor
temperature to be withstood in continuous service, but the effects of
still higher temperatures which may be experienced occasionally (e.g.
heat shock resulting from a short-circuit) are also relevant. The
pertinent standard tests typically involve heating specimens (which may
be under mechanical stress) for relatively short periods at high
temperatures-e.g. 1 h at 150C (the heat-shock test of BS 6746:1976,
in which no visible cracks must be caused by the treatment), or 40 to
120 min (depending on the type of insulation material) at 200C (the
thermal stability test of VDE* 0271/3.69, in which the pH indicated by
a standard indicator exposed to the volatile products evolved must not
be less than 3). Heat-ageing tests are also applied in which specimens
are heated for longer periods at somewhat lower temperatures, with
pass requirements in terms of permitted volatile loss and property
change maxima (as in BS 6746:1976) or absence of cracks (as in VDE
0271/3.69 after 7 days at 120C). Although such requirements may be
coupled with particular service-related temperature rating (e.g. for a
nominal 90C cable sheath compound, suggested volatile loss limit of
25 mg m- 2 on heating for 7 days at 115C9 ), the test results do not, in
the main, provide a reliable basis for firm predictions of behaviour in
service.
Apart from the question of thermal degradation and ageing
generally, the thermoplastic nature of PVC, coupled with its
comparatively low softening temperature (lowered still further by
plasticisation), is a limiting factor on the maximum service temperature. The limit for most types of cable compound is 70C (conductor
temperature). Some special, high-temperature cable compounds are
rated at 85C (and even up to 105C for limited periods under certain
conditions) but at high temperatures external damage to, or distortion
under pressure of, the heat-softened material, as well as the possibility
of outward penetration of the hot conductor through it, become
serious considerations. Susceptibility to damage, at room temperature,
by hot objects or materials (e.g. soldering irons, hot oil splashes) may
also have to be considered. The performance of PVC cable compounds
can be substantially improved in these respects by cross-linking the
* Verband Deutscher Elektrotechniker (specification of the German Electrical
Engineers Association).

450

W. V. Titow

cable covering, and this has been receiving attention in recent years,
with special reference to irradiation techniques, including the use of
electron beams. 10,11
Some of the direct (i.e. non-degradative) effects of heat on the
properties of PVC are illustrated by the data of Figs 12.4-12.6. As with
thermoplastics in general, mechanical properties are reduced at
elevated temperatures, as is resistance to creep and fatigue; however
90
80
1...
If

70

~60

Coo

::l

1/1

~40

~30

:g20
10

o
Fig. 12.4 Effect of temperature on tensile strength and BS softness number of
PVc. 6, uPVC (normal impact strength grade); 0, pPVC (50phr noP).

12

Properties of Special Interest in PVC Materials and Products

451

gmil

10

100 in2 24hatm

Fig. 12.5 Permeability of a uPVC (homopolymer) film to water vapour as a

function of temperature.
12

'"'Eu 10

-52

..x
I:

". '
3"
"~

....
.
1i
.....

Q,

I:

12

10

20

30

40
50 60 70
Tllmpcrraturcr. c

80 90

Fig. 12.6 Effect of fibrous reinforcement on the temperature dependence of

tensile creep of uPVC (ICl's Darvic 110). Curve A, material with 30% glass
fibres oriented parallel to the test direction; Curve B, as A, but fibre
orientation perpendicular to test direction; Curve C, unreinforced material.

452

W. V. Titow

uPVC is more thermally sensitive in this sense than the other common
'engineering' thermoplastics, and its softening temperature is comparatively low (see Appendix 3). The reduction of some of the mechanical
properties can be counteracted to some extent by incorporation of
fibrous reinforcement. Whilst improvement in the heat deflection
temperature under load is only moderate with, say, 30% glass-fibre
reinforcement (increase of 5-10C in some cases) creep at elevated
temperatures can be significantly reduced (see Fig. 12.6).
A non-degradative (though irreversible) effect of heat, which can be
a practical problem in service, is the longitudinal shrinkage of extruded
cladding and beading (finishing strip) sometimes occurring on buildings
and caravans. This is attributable to retraction of stretch imparted
during manufacture (extrusion and take-off).
The principal ways of securing the best practicable resistance of PVC
materials to heat degradation are proper stabilisation (by suitable
stabilisers in appropriate quantities, properly dispersed in the compound by suitable mixing-see also Chapters 4, 9 and 10) and-where
possible-the use of fillers and pigments which can afford additional
protection.
Volatile loss can be counteracted by proper choice of plasticisers
(polymeric plasticisers are particularly useful); use of polymeric
additives with plasticising action (e.g. copolymers of the Elvaloy* type,
highly chlorinated polyethylene, or nitrile rubber); ensuring that
plasticisers and all other constituents of the compound are of good,
consistent quality; and by general attention to the mutual compatability of all constituents.
12.4 PERMEABILITY

In the broadest sense permeability may be thought of as the ease (or

otherwise) with which a material will allow the passage of a penetrant.
In plastics this property is of special practical interest in connection
with barrier applications, Le. where these materials are used to exclude
or contain potential penetrants (most often fluids, i.e. gases, vapours
or liquids). For such purposes the lowest possible permeability vis-a-vis
the penetrant(s) concerned is desirable: examples of barrier applica* Du Pont trade name for a group of modified ethylene/vinyl acetate
copolymers.

12 Properties of Special Interest in PVC Materials and Products

453

tions of PVC are films (e.g. packaging films, rainwear, inflatables),

containers (e.g. blow-moulded bottles, sachets) and protective coatings
(e.g. on chain-link wire fencing, industrial gloves, tarpaulins). Such
applications may be regarded as particular instances of the general case
of the system penetrant(s)/plastics barrier in which low permeability is
required (for example the 'passage' of water through a good tarpaulin
is virtually nil), although it may be significant (as manifested, for
example, in loss of contents from a shampoo sachet made from badly
formulated PVC).
It can readily be seen, largely as a matter of common sense, that the
permeability of a plastic towards a given penetrant should be a
function of the chemical nature, morphology and composition of the
plastic, and that the barrier thickness and area involved must also be
factors. This is indeed so, and the relevant relationships may be
expressed, in a general way, by the following equation applicable in
steady-state conditions:
J/A

= P(F/L)

(2)

In this expression J is the flux of the penetrant, i.e. the amount (in
suitable units, e.g. of mass or volume, or in moles) passing through the
barrier in unit time; A is the area through which the passage takes
place; F is the driving force actuating the passage, e.g. the difference
between the concentrations (~c), pressures (~p), temperatures (~e)
or chemical potentials (~Il), of the penetrant at the 'upstream' and
'downstream' boundaries of the barrier; L is the barrier thickness, and
P is the permeability coefficient which embodies (i.e. whose value will
reflect) the effects of chemical and physical interactions in the system
(themselves dependent on the chemical nature and fine structure of the
barrier material).
As can be seen, F/L is the driving force gradient within the barrier.
The various quantities in eqn (2) may be expressed in any convenient
units, so long as those are mutually consistent; their choice will
determine the units (and hence will influence the numerical value)
of P.
In practice the permeability of plastics is commonly determined by
measuring-in standardised, steady-state conditions-the flux of a
penetrant (usually water vapour, oxygen, carbon dioxide or nitrogen)
through a film or sheet. Loss of contents (in terms of weight loss over a
period of time, i.e. average flux) through the walls of a container is
also often measured.

454

w.

V. Titow

The results of such determinations can normally be interpreted in

terms of a version of eqn (2), or some analogous expression, but they
may be (and usually are!) stated in various ways and in a variety of
units. This diversity complicates comparison of results from different
sources and can lead to confusion associated with, or compounded by,
the following factors.
(i)

Even if the same basic units are used (for flux, driving force,
film thickness, etc.), expression of the result of one and the
same determination (or results of separate determinations for
the same plastic/penetrant system in identical conditions) can
entail different combinations of the units and have different
numerical values, depending on the choice of the 'index' of
permeability (Le. whether permeability coefficient, rate of
transmission, permeance, etc.-see Table 12.1).
(ii) The same 'index' of permeability, expressing the result of the
same determination, will have different numerical values if given
in different units.
(iii) Values are sometimes quoted simply as 'permeability' without a
clear statement which 'index' is being used, so that units have to
be scrutinised to ensure correct interpretation of the figures.
Moreover, the same name is sometimes used for different
permeability indices.
This situation is illustrated by Table 12.1 in which the more common
ways of expressing permeability are listed, with the associated units
and an explanation of their mutual relationship (in terms of eqn (2)).
Since for a given penetrant/barrier system in defined conditions the
permeability coefficient should be a constant, expressing the relevant
intrinsic properties of the barrier material, this coefficient should-in
theory-be the best value to use as an index of permeability, especially
when comparing different plastics materials. It is often used for these
purposes, although here again the variety of units employed can cause
some confusion. The forms of permeability coefficient which are either
fairly widely used, or are of a more standard or fundamental nature,
are given in Table 12.2. A useful discussion of gas permeability
coefficients has been published by Yasuda. 12
However, the permeability coefficient is by no means solely or
universally employed as an index of permeability, because in practice
most plastics are multicomponent (often multiphase) materials; they
may be heterogeneous not only by virtue of these features per se, but

12

Properties of Special1nterest in PVC Materials and Products

455

also because the distribution of the various additives in the polymer

may not be uniform. Moreover, local differences in density and fine
structure may occur (e.g. due to orientation, or 'skin-and-core' effects
in, say, sheets and mouldings) as well as irregularities in thickness.
Thus the concept of uniform flux per unit thickness of a homogeneous
material, implicit in the definition of the permeability constant, may
not be applicable in practice, and it may be more realistic to quote,
say, transmission rates through a film or container wall of stated
average thickness, in strictly defined conditions.
The permeability considered so far is that of plastics materials in
continuous, i.e. non-porous form: even the cellular plastics mentioned
in Table 12.1 are of the kind in which the cells are separated by walls
of 'solid' material, and thus are not inter-communicating pores. In its
passage through a plastics barrier which is 'solid' (continuous) in the
above sense, the penetrant will normally be in a molecular state of
division:* it may be considered to dissolve in the plastic at the
'upstream' face of the barrier, diffuse through, and come out of
solution at the 'downstream' face. In this diffusional transport mechanism the chemical nature of the penetrant and the barrier material. as
well as the composition and fine structure of the latter, will be cardinal
factors. Moreover, the state of the plastics material (i.e. whether glassy
or rubbery) can affect the rate of diffusion. For a given composition
(e.g. a particular PVC compound) the state will depend on the
temperature and may also be influenced by the sorbed penetrant
concentration: this effect can be especially strong if the penetrant
interacts strongly with (i.e. is a good solvent or plasticiser for) the
polymer. 13
For simple gases, and many other penetrants sorbed from the vapour
phase, the solubility in the plastics barrier material will-under certain
conditions-be proportional to the partial pressure (i.e. Henry's law
will be obeyed), and the rate of diffusion will be directly proportional
to the concentration gradient (i.e. Fick's law will be obeyed). In such
cases permeability may be defined by the expression
P=DS

(3)

where P is the permeability coefficient (as in eqn (2)), D the diffusion

* Clustering may occur inside the barrier material in some cases, but this is
exceptional rather than typical.

J/A

J/A

J/A

J/(A.~p)

(J.L)/(A.~p)

Transmission
rate

'Permeability'

1. Transmission
rate

2. Permeance

3. 'Permeability'

Film or thin
sheet

Flexible
sheet

Sheet up to
about 1/8 in
thick

Water
vapour

Water
vapour

Water
vapour

Le. =P

J/A

In terms of eqn (2)

Transmission
rate

Name

Description

19.cm
m2.24 h.(mm Hg)

1 grain.in
ft 2.h.(in Hg)

Perm-inch =
Metric permcentimetre =

19
m2.24 h.(mm Hg)

1 grain
ft2.h.(in Hg)

grain
ft2.h

Metric perm =

Perm =

or

WVT

g
m2.24h

g
m2.24h

g
m2.24h

g
m2.24h

units

Constituent
simple

Special unit
name and/or
symbol

htdex of permeability

Film or thin
sheet

Plastics
barrier

Water
vapour

Penetrant

TABLE 12.1
Relevant determination
methods,
references and
remarks

Temperature
RH

Barrier thickness (L)

Temperature
RH

Barrier thickness (L)

Pressure differance (~p)
Temperature
RH

Barrier thickness (L)

Pressure difference (~p)
Temperature
RH

Barrier thickness (L)

Pressure difference (~p)
Temperature
RH

E 96-66(1972)

~ASTM

BS 3177: 1959

BS 2782:Part 8:
Methods 820 A to G
(in preparation)

ISO/R 1195-1970
Barrier thickness (L)
Pressure difference (~p)Q
Temperature
RH

Data required
in
conjunction

Some Common Ways of Expressing Permeability

:<::
:::l
0

.j:>.

'-"
a..

J/(A.t.p)

(J.L)/(A.t.p)
i.e. =p

J/(A.t.p)

J/(A.t.p)

(J.L)/(A.t.p)

1. Permeance
(for boards
with surface
skins)

2. 'Permeability'
(for boards
without
surface skins)

Transmission
rate

Transmission
rate (also
termed 'permeability')

1. Transmission
rate

2. Permeability
coefficient

Expanded
polystyrene
(board)

Films and
thin sheet

Films and
thin sheet

Film and
sheeting

Water
vapour

Gas

Gas

Gas

i.e.

=P

J/(A.t.p)

J/A

Rigid cellular Transmission

rate
plastic
(block)

Water
vapour

Punit
barrer

GTR unit

also

Barrier thickness (L)

Temperature
RH

Barrier thickness (L)

Temperature
RH

Temperature
RH

Barrier thickness (L)

Temperature
RH

As for ISO/R 1195

10- 10 P unit

Barrier thickness (L)

Temperature
RH
1 cm 3 (at STP).cm T
2
emperature
cm .s.(cm Hg) RH

1 cm 3 (at STP)
m2 24 h.atm

ml (atSTP)
m 2 .24h.atm

cm 3 (at STPj"
m2 .24h.atm

--

1 fm b
Pa.s

ng.m
N.s

SI unit

ng
N.s

g
m2 .24h

WVT

ASTM 01434-75
NB This specification
also recognises (and
gives conversion factors for) the following
units of P: (cm3 .mil)/
(m 2 .24 h.atm);
(cm 3 .mil)/(lOO in 2 .24 h.atm);
(cm 3 .mm)/(m2 .24 h.atm)

BS 2782:Part 5: 1970
Method 514 A (in
1979 replaced by new
method 821A of BS
2782 Part 8: 1979-see
also ISO 2556)

ISO 2556-1974
(identical with BS
2782 Part 8: Method
821A 1979)

BS 3837:1977
(prescribing tests by
the method of BS
4370: Part 2: 1973)
technically similar to
ISO/R 1663

ISO/R 1663-1970

...

-..l

Vl

!:;

"

$::

I::>..

;:<
I::>..

I::>

l:;-

...5'~

I::>

()

'"0

~
S

["
S'

.g>
'"

1'"?to

......
tv

Plastics
barrier

Resistance factor
Any plastics
lamina (in
practice film
or sheet)

Permeability
factor

Name

(A.t1p)/J
i.e. = lI(P/L)

(J.L)/A

In terms of eqn (2)

Description

p1

Special unit
name and/or
symbol

Index of permeability

Fixed in terms of the RH in standard determinations.

i.e. one femtometre per pascal per second = 8752 em' (at STP)/(m 2 .24 h.atm).
c STP: 760 mm Hg and 273 K.
d i.e. permeability factor at temperature I.

Any
(but
mainly
fluids)

Walls of
Any
(consti.
plastics contuents
tainer
of contents of
a plastics con
tainer)

Penetrant

N.s
mol

--

g.cm
m 2.day

Constituent
simple
units

TABLE 12.1-eontd.

Barrier thickness (L)

Temperature
RH

Temperature
RH

Data required
in
conjunction

Ref. 90

ASTM D 2684-73

Relevant determination
methods,
references and
remarks

:;;

:::J

00

Pressure"
difference (dp)

m2

"Or partial pressure, as applicable.

bAt STP.

g (24 h)-I

Water
vapour

Pressure"
difference (dp)

100in2

Gas or
vapour

cm 3 (24 h)-l

Gas or
vapour

Pressure"
difference (dp)

Pressure"
difference (dp)

cm 2

m2

mols- I

Concentration
difference (dC)

Concentration
difference (dC)

Nature

Pa(=Nm- 2 )

mol cm- 3

molm- 3

Units

mmHg

atm

cmHg

(F)

Driving force

cm3 S-I

cm 2

mols- I

Any

Gas or
vapour

m2

Area
(A)
units

mols- I

Flux
(J)
units

Any

Physical
state of
penetrant
in contact
with
barrier

(L)

cm

mil

cm

cm

units

Thickness

g
(mm Hg)
--=
p
24h.m 2
cm

mol
N
-=
Ps.m 2
m2 .m
b cm 3
(cm Hg)
--=
p--s.cm 2
cm
b cm 3
atm
=P24 h.l00 in 2
mil

mol
mol
--=
Ps.cm 2
cm 3 cm

mol
mol
-=
Ps.m 2
m3 .m

Equation (2)
in terms of
the units

TABLE 12.2
Some Common Fonns and Units of the Permeability Coefficient

g cm (24 h)-I
m- 2 (mm Hg)-I

cm 3 mil (24 h)-I

(100 in 2 )-1 atm- I

cm 2 s (cm Hg)-l

"tl

molms- I N- 1

.,..
ID

v.

I;;;

'"

i:

;:s

l::l

;;;-

l::l

:::!.

(j

-.::::

~
S

~
....

S-

'"~

"-

"....
::>.

.g

......

'"

cm 2 S-I

m 2 s- 1

Resulting
units of
permeability
coefficient
(P)

w.

460

V. Titow

coefficient (assumed to be constant or dependent only on concentration) and S is a solubility factor expressing the equilibrium content of
the penetrant in the plastics barrier material at the relevant
temperature.
If S is given in the form of a ratio, viz.
S

equilibrium concentration of penetrant in barrier material

concentration of penetrant 'upstream' of barrier

with both concentrations expressed in the same units, it becomes a

dimensionless partition coefficient, and P will have the same
dimensions and units as the diffusion coefficient (length2 time- 1-ef.
the first two entries in Table 12.2).
Solubility factors and Fickian diffusion coefficients can be determined fairly readily for plastic/penetrant systems of practical interest.
However, there is still no general, complete explanation of the way in
which the chemical structure and interactions of the components in
such systems influence the mechanisms of solubility and diffusion.
There is also no comprehensive theoretical treatment available for
diffusion of penetrants in polymers below the glass temperature (Tg ),
where complex time-, history- and concentration-dependence may
occur. This is relevant in connection with rigid PVC compounds which
are essentially glassy (non-crystalline) with Tg values well above room
temperature. Flexible PVC of medium and high plasticiser c;ontents is
normally rubbery, as plasticisation reduces the effective Tg
A more extensive discussion of the mechanisms and theories of
diffusion in polymers would be beyond the scope of a short section in a
technological book on PVC. Informative accounts are available in
publications by Fujita 14 and Meares l 5-17 (theory and various features
of diffusion), Crank and Park 18 (most aspects), Stafford and Braden 19
(diffusion of water in polymers).
The permeability of a porous plastics material (i.e. one containing
inter-communicating voids) is a matter of the rate of passage of the
penetrant concerned through the pores. On the assumption that the
pores are large in comparison with the size and the mean free path of
the penetrant molecules (the situation of practical interest in this
section), two general cases may be distinguished.
(i) The penetrant may be moving through a fluid (in practice most
frequently air or water) which fills the pores but does not itself
flow through them to an appreciable extent. The transport

12

Properties of Special Interest in PVC Materials and Products

461

mechanism will be 'straight' diffusion, or movement under a

directional driving force, e.g. the electrical force actuating the
passage of ions through the water filling the pores of a PVC
battery separator: apart from this example there are not many
instances of this kind of permeability relevant to practical
applications of PVC.
Equation (2) can be applied to describe the general
relationships in this case, but here the permeability coefficient
will represent essentially the effects of interactions between the
components of the system penetrant/pore-filling fluid integrated
with those of any other factors or constraints operative in the
system.
(ii) The penetrant, in this case itself a fluid, may be flowing through
the pores. The transport mechanism will be viscous flow (i.e. the
penetrant will continue to behave as a fluid whilst in the pores):
in practice the driving force will most often be a pressure
difference ('pressure drop') across the porous barrier.
In this case the relevant relationships can still be represented,
in general terms, by an expression closely analogous to eqn (2).
However, the expression must contain a viscosity factor, since
the viscosity of the fluid penetrant is an important parameter.
This is exemplified by the well-known D'Arcy equation which
may be written in the form
J/A

= K[~p/(L1])]

(4)

where 1] is the viscosity of the penetrant, K is the permeability

coefficient, and the other symbols have the same meanings as in
eqn (2).
For a given penetrant under standard conditions K represents
the combined effects of the internal structural characteristics of
the porous barrier (with the total volume, configuration and size
of the pores as especially important factors).
As can be seen, in neither of the above two cases are the chemical
and other intrinsic properties of the solid material of the barrier
particularly important. Hence, say, porous uPVC may be expected to
behave much like any other solid porous barrier of the same porosity
characteristics. For this reason the permeability of porous PVC will not
be considered further. The books by Carman20 and Scheidegger,21 and
the excellent papers by Rodebush and Langmuir,22 Davies,23 Iberall,24

462

w.

V. Titow

and Thomas 25 may be referred to for further information on flow of

fluids through porous media.
Many aspects of the permeability of 'solid' (i.e. non-porous) plastics,
with special reference to films and coatings, are discussed in a
collective publication edited by Hopfenberg. 26
Two useful, earlier publications by Lebovits,27 and Hennessy et al. 28
review the permeability of polymers and plastics to fluids. The latter
work deals in considerable detail with practical methods of determination.
In virtually all procedures for determining the gas permeability of
polymeric barriers, the amount of gas passing through in measured
time is determined from the volume change at constant pressure, or
the pressure change at constant volume (the manometric method), or
the contents of the penetrant gas in a carrier gas 'upstream' and/or
'downstream' of the barrier. The equipment used is normally an
appropriate 'gas cell' (e.g. a variant of the so-called 'Dow cell' as
employed in the method of ASTM D 1434-see Table 12.1). Various
types of apparatus and their commercially available embodiments are
mentioned in a paper by Pye et al. ,29 which also describes a particularly
versatile gas-permeability apparatus (of the manometric type) developed by the authors.
Water vapour permeability is most often measured by 'dish' or
'sachet' methods, prescribed by several of the standards listed in Table
12.1. In a 'dish' method the specimen forms the closure (secured with a
vapourtight seal) of a dish or beaker containing a desiccant. The
container is placed in an enclosure at a constant temperature and
controlled (normally high) relative humidity, and the passage of
moisture through the specimen is followed by repeated weighing. In
the sachet method, a sealed sachet containing water is placed in a
constant-temperature enclosure in which the humidity is controlled at a
low value. The sachet is weighed periodically to determine the rate of
loss of water. Other methods are also available. 28
Permeability to other penetrants may be determined by methods
similar to those used for gases and moisture. The container method of
ASTM D 2684 (see Table 12.1) is also used. In some cases the amount
of penetrant passing through a plastics barrier in measured time is
determined by chemical, chromatographic or gravimetric techniques. 28
Considerable success has been claimed for predictions of the
long-term barrier performance of plastics containers in service, based
on permeability coefficients calculated with the aid of the 'permachor'

12

Properties of Special Interest in PVC Materials and Products

463

concept, first developed-largely on an empirical basis-in the 1950s in

connection with the storage properties of blow-moulded polyethylene
bottles. 30 ,31 The method is to calculate a so-called 'permachor value'
for a given potential penetrant by summating appropriate values
allocated to its constituent atoms and/or functional groups: in this
respect the approach is somewhat similar to that involved in calculating
solubility parameters. 32 Certain corrections are applied, and the final
figure is substituted into the equation
log P = K - Rn

(5)

where P is the permeability coefficient, K is a temperature correction

factor and R is another correction factor associated with the polymer
(or polymer compound).
R values of 022 and 026 have been quoted 31 as appropriate for
polyethylene (apparently regardless of density) and polypropylene,
respectively, with values of K varying not only with temperature but
also with polymer density (for polyethylene) and nature (e.g. K = 23
for polyethylene of density 0945, and K = 42 for polypropylene, both
at 23o C).31 So far no analogous data appear to have been published for
PVC. Computer prediction of long-term gas transmission characteristics of polymers in service has been discussed by Horsfall and James. 33
Unplasticised PVC is a reasonably good barrier against simple gases
and water vapour. Taking the relevant permeability value of
unstretched uPVC 40,um film as unity in each case, some typical
comparative permeabilities of similar films of other polymers would be
as follows:
Nylons

O2
N2
CO 2
H2O

Polyolefins

66

11

HDPE

LDPE

PP

03
07
06
8

06
06
04
2

4
25
75
03

22
44
36
01

57
146
125
04

22
36
30
03

Permeability to other penetrants depends strongly on their chemical

nature.
To the extent to which it is valid to generalise over a broad range of
conditions and potential penetrants, the following points may also be

464

W. V. Titow

made. Other things being equal, PVC compositIOns based on

homopolymers are less permeable than those based on copolymers
with vinyl acetate, but more permeable than vinyl chloride/vinylidene
chloride copolymer compositions (ct. Table 12.4). Blending with other
polymers tends to increase permeability, but the opposite effect can
occur: even with the same component in a blend the permeability can
increase or decrease depending on the proportions and processing
conditions. Such effects have been observed, e.g. in the case of
penetration of oxygen and nitrogen through blends of PVC with
ethylene/vinyl acetate copolymer (EVA):34 they can be explained in
terms of the way in which composition and processing influence the
morphology and phase structure of a blend, both factors affecting the
rate of diffusion of penetrants. Stretch-orientation can reduce the
permeability of uPVC film by a factor of 2 (more in some cases).
Plasticisation, and generally incorporation of fully intermiscible
additives (e.g. impact modifiers, processing aids, internal lubricants)
tends to increase the permeability of PVC to most penetrants.
However, transmission of water vapour may be reduced in some
compositions by the inclusion of chlorinated plasticiser extenders.
Addition of fillers, which form a separate phase in the compound,
TABLE 12.3
General Order of Permeability of PVC to Some Common Penetrants at Room
Temperature

Units: cm 3 (at STP).cm.cm- 2 .s- I.(cm Hg)-I.

Units: g.mil.(lOO in 2 )-1.(24 h)-latm- 1.
C Typical, approximate factors representing order of change in comparison with values
for comparable uPVC compounds.
a

12

Properties of Special Interest in PVC Materials and Products

465

may have no effect on permeability, or it may reduce or increase it,

depending on the penetrant, and on the frequently complex effects of
the chemical nature, particle size and shape, distribution, orientation,
amount, and surface properties of the filler. The reduction in water
vapour transmission sometimes brought about by the incorporation of
relatively small amounts of certain waxes is probably associated with
the incomplete compatability and hydrophobic nature of this type of
additive.
Some permeability data are given, by way of illustration, in Tables
12.3-12.5.
TABLE 12.4
Permeability of PVC Homopolymer and Copolymer Compounds to Gases

TABLE 12.5
Water Vapour Transmission of Breon Films 0004 in Thick,
Containing Various Plasticisers
(Room temperature, dish method at 100% RH)
Plasticiser

DOP
Oetyl deeyl phthalate
Trioetyl phosphate
Tritolyl phosphate
Dioetyl adipate
Cresyl diphenyl phosphate

115
135
161
170
177
191

466

W. V. Titow

The rate of transmission of water vapour (in a dish test with desiccant,
at room temperature and 100% RH) through some commercial PVC
sheeting products is illustrated by the following figures (grams per
square metre per 24 h):
Rigid sheet (homopolymer-based) 0050 in thick:
Pipe-wrapping PVC tape with polyisobutylene adhesive layer
(PVC thickness 0013 in, adhesive layer 0008 in):
General purpose adhesive tape (PVC layer 0010 in thick):

01
06
25

It will be clear from what has been said in this section, that the
results of permeability tests are valid and their numerical expression
meaningful only for strictly standardised test conditions, which should
be specified. Moreover, even when these requirements are met, and
the results are given in appropriate units, comparison between sets of
data from different sources should be made with caution, as materials
of apparently the same kind (say two rigid PVC films of comparable
thickness) may differ in composition or nature of individual constituents (e.g. different lubricants, processing aids, stabilisers, may be
present), processing history and fine structure. Differences in the
performance of basically the same equipment in two different
laboratories may also be significant.

12.5 ENVIRONMENTAL STRESS CRACKING AND

CRAZING

Plasticised PVC is not normally susceptible to failure of this kind.

uPVC can be, albeit cases are not so common or frequent as to
constitute a serious practical problem: however, since they do occur,
the subject merits a brief discussion.
Crazing is a characteristic, localised deformation of a polymeric
material. A craze may be defined, after Kambour,35 as a thin,
plate-like region containing apparently continuous but in fact microcellular material, usually oriented, interconnected with the surrounding
'normal' material. Craze matter has the general characteristics of
open-cell foam. In most cases it is load-bearing, but-as would be
expected-its mechanical properties are different from (and generally
inferior to) those of the solid 'parent' material. 35,36 Thus crazes
constitute regions of comparative weakness in a polymeric material,
often discernible visually because of their opacity.

12

Properties of Special Interest in PVC Materials and Products

467

Cracking is a type of complete, local brittle failure. The term 'crack'

needs no special definition, but it may be recalled in passing that cracks
typical of environmental stress cracking of plastics are wedge-shaped,
and range in size from hair-cracks to large discontinuities, depending
on the material and conditions.
Environmental stress cracking and crazing may jointly be termed
'environmental stress failure' (ESF). The cardinal features of ESF are
that it occurs in the presence of an 'active environment' (a cracking or
crazing agent, which is normally a fluid, i.e. a gas, vapour or liquid),
and either in the absence of externally imposed stresses or at external
stress levels significantly below the normal short-term yield strength of
the material in air. In practice the stresses responsible (jointly with the
active environment) for ESF can be either internal, or external or (as is
often the case) a combination of both. As has been pointed out by
Ziegler,37 internal stresses may arise from the following causes:
(i)

differential cooling of the polymer in the final stages of

moulding (thermally induced moulding stresses);
(ii) molecular orientation, with or without crystallisation, arising as
a result of the flow and the cooling process in the course of
moulding (orientation stresses);
(iii) forced introduction of additional polymer into the mould when
that already present in the mould has begun to cool and
contract (packing stresses);
(iv) thermal shock either to the whole or to parts of the moulding,
caused by treatments such as, for example, machining (thermal
stresses).

The external stresses instrumental in ESF may be those encountered

in any processing or handling after moulding, or in service, or those
deliberately applied in tests.
Some environments (e.g. certain organic liq4ids), strongly active as
cracking agents for certain glassy polymers, can promote ESF under
stress two orders lower than the minimum cracking or crazing stress in
air at the same temperature. 36
Under given conditions the environmental stress failure of a plastic
will occur when local elongation within the material exceeds the
maximum such elongation that the material can accommodate without
failing. This is essentially the concept of critical strain, which has been
defined 38 as that minimum strain at which under a particular set of
conditions stress cracking or crazing is known to start. The main

468

W. V. Titow

factors making up the 'set of conditions' are the nature of the

environment (i.e. the cracking or crazing agent), the stress, the
temperature, and the rate of strain. Most of the methods used to study
ESF are ultimately concerned with the determination of critical strain
and the associated (critical) stress, by various means and in various
kinds of apparatus. 39 Practical tests, applied in production control and
occasionally in 'trouble-shooting' investigations, are mainly qualitative.
They usually involve immersion of a moulding in a liquid (frequently a
mixture of solvents) known to be active as a cracking or crazing agent
for the plastic concerned: development of cracks or crazes within a
prescribed period is taken as evidence of the presence of internal
stresses of unacceptable magnitude, and hence risk of failure in service
under conditions conducive to ESF. 39
Standards of main, general relevance to the understanding and
investigation of ESF phenomena in plastics include the following (some
still in draft form at the time of writing).
ISO 4600:1981: Plastics-determination of environmental-stresscracking resistance (ESCR)-ball or pin impression method.
ISO 6525:1981: Plastics-determination of resistance to cracking
under constant tensile force in the presence of chemical agents.

BS 4618: Subsection 1.3.3:1976: The presentation of plastics design

data. Environmental stress cracking.
British Draft Document 79/50196:3/79: Determination of environmental stress cracking resistance.
DIN 53 449:1970: Testing of plastics; evaluation of resistance of
thermoplastics to environmental stress cracking; steel ball impression
method. This specification is technically similar to ISO 4600.

Other standards (largely specific to particular materials and/or

products) as well as many literature sources on ESF are given in Ref.
39.
Two main hypotheses have been advanced to explain the origin and
mechanism of ESF in glassy polymers (of which PVC is one).
According to one, the 'active environment' reduces-by wetting-the
surface energy for crack or craze formation, and thus facilitates and
promotes growth of holes (craze cells and cracks) from minute voids in
the polymer which serve as nuclei. The second explanation is the

12

Properties of Special1nterest in PVC Materials and Products

469

so-called 'plasticisation hypothesis'. Currently this appears the more

firmly supported by the available evidence, although it is possible that
surface energy reduction may be a contributory factor. According to
the plasticisation hypothesis, the cracking or crazing agent actually
penetrates and plasticises the polymer. As is well known, plasticisation
reduces the temperature of glass-to-rubber transition (Tg ) as well as
the modulus and viscosity of a polymer. When operating locally at the
tip of a forming crack or craze these effects should make the polymer
yield more easily under the high concentration of stress obtaining at
that point, but because the degree of plasticisation is still relatively low
(in comparison with, say, that of bulk-plasticised flexible PVC
materials) the critical strain is not substantially increased: the net result
is that propagation of a craze or crack is facilitated and promoted.
In flexible (bulk-plasticised) PVC the plasticiser concentration, and
hence the degree of plasticisation, are relatively high. The material is
well above its effective Tg at room temperature (i.e. in the rubbery
state): it is thus able to relax sufficiently readily for internal stresses to
dissipate rapidly, so that this important contributory factor to ESF
(internal stress) does not normally exist in plasticised PVc. Moreover,
pPVC is extensible and its critical strain is consequently relatively high.
These are the main reasons why environmental stress failure is not
normally encountered in plasticised PVc.
Under suitable conditions (including sufficiently high contact
concentration of agent, and magnitude of stress) some aliphatic and
aromatic hydrocarbons (or their mixtures) in liquid or vapour form can
act as cracking or crazing agents for uPVc. This has been
demonstrated in the laboratory, e.g. for n-hexane and toluene. 4o In the
author's own recent experience, local cracking (and a subsequent
burst) in service of a 90-mm high-pressure uPVC water pipe occurred
in a section found to have been in temporary contact with toluene
(through accidental spillage). In an earlier case, investigated in
Holland in 1967 by Wolf,41 the appearance of hair-cracks in a uPVC
pipe conveying natural gas was identified as environmental stress
cracking promoted by naphthalene found to be present in the Dutch
gas in appreciable concentration.

U.6 WEATHERING RESISTANCE

Weathering may be broadly defined as the overall change in a material,
brought about by outdoor exposure. In PVC the change is the

470

w.

V. Titow

combined effect of several factors, interacting and affecting the

material in a highly complicated manner: thus from the technical
standpoint the weathering of PVC is a composite phenomenon,
complex in both its mechanism and nature. Some of the principal
factors instrumental in this process are listed in Table 12.6, with
indications of their main effects on PVc. However, it is a cardinal
characteristic of weathering that the factors never operate singly in
actual service conditions, but co-act and interact in many ways:
moreover their individual roles, and their contributions to the overall
result, can vary considerably depending upon the place and conditions
of exposure; seasonal variations at one and the same site also affect the
progress of weathering.
Extensive practical experience and data are available to aid
producers in formulating PVC compounds for good weathering
resistance, particularly important in such uPVC products as house and
caravan cladding, rain gutters and down-pipes, and window frames, as
well as in pPVC garden hoses, reservoir linings, tarpaulins and
outerwear. However, because of the complexity of the weathering
process and wide variability of service conditions, confident prediction
of the performance, and in particular of the likely length of useful
service life, is still very often difficult. Tests to help such predictions,
and to enable different compounds to be compared or effects of
formulation changes to be evaluated, are clearly desirable and
important. Any test method must include two elements:
(i) means of inducing in the material changes identical with, or
equivalent to, those caused by actual weathering in service over
relevant periods; and
(ii) means of assessing or measuring the degree of changes caused
(extent of deterioration).
There are three general ways of inducing weathering (or similar)
effects in a plastics material for test purposes.
1. Exposure of specimens at outdoor sites in locations and
conditions corresponding to (or correlating with) those to be
encountered in actual service, and for periods comparable with
the service life contemplated.
2. Outdoor exposure at selected sites, with the time scale substantially shortened by suitable intensification of at least some of the
main factors instrumental in 'natural' weathering (e.g. amount

12

Properties of Special Interest in PVC Materials and Products

471

and intensity of incident sunlight, amount or frequency of contact

with water), or by increasing the susceptibility of the material
specimens to weathering, or both.
3. Artificial ageing in the laboratory in conditions designed to
produce, in a much shorter time, changes similar to (and/or
sufficiently well correlating with) those caused by natural
weathering.
In all three cases the effect of exposure may be assessed in terms of
changes in optical properties (e.g. colour changes-with PVC often
darkening or yellowing-or changes in surface gloss, or in transparency), or differences between the 'before' and 'after' values of
other properties (with PVC products often tensile and/or impact
strength, modulus, elongation). Some standard methods relevant to
evaluating weathering effects in this way are given in ISO 4582
('Plastics-Determination of changes in colour and variations in
properties after exposure to daylight under glass, natural weathering or
artificial light') and many are listed in the Appendix to ASTM D
1435-79. In more fundamental investigations changes in some of the
properties and characteristics of the PVC polymer (e.g. the molecular
weight and its distribution, presence and nature of functional chemical
groups, IR absorption) .may also be followed, sometimes in conjunction with microscope or electron-scan examination of material surface,
and DTA or DSC determinations.
Whilst the long-term exposure approach (1 above) is the most
reliable it is in many cases impracticable as the sole means of testing,
because of the time periods involved. However, long-term exposure at
representative sites is often used to provide (eventually) reference data
against which the results of accelerated tests may be evaluated. Site
selection is important: sites in regions which provide severe conditions
are widely favoured (e.g. Arizona, the Australian interior, the
Transvaal in South Africa, for dry heat and maximum sunshine;
Florida, Natal for humid heat). More than one site may advantageously be used to allow for different types of conditions, although a recent
world-wide study of weathering of PVC42 has been held to suggest that
a reasonable correlation can be established between results from
different geographical locations. The mounting and positioning of
specimens playa part: backing with a good insulator (e.g. plywood)
helps to bring out the effect of temperature stresses; exposure racks
are normally south-facing (north-facing in the southern hemisphere)

Mainly effects of heat and temperature fluctuation, including:

(i) Heat degradation
(ii) Exudation and volatalisation
of components (especially
plasticisers)
(iii) Physical disruption by local
and general stresses caused by
temperature changes
(i) Mechanical erosion of surface
(especially by wind-borne
precipitation)
(ii) Leaching out of components
(especially plasticisers)
(iii) Mechanical disruption (especially
of surface) by repeated
absorption and desorption
(which may be aggravated by
presence of absorbent fillers
in the material)

Temperature

Water
(including
atmospheric
precipitation,
i.e. rain, snow,
hail, vapour
and condensate)

Degradation of PVC polymer by UV

component of the radiation
Fading of colourants

Typical action on PVC material

Sunlight

Factor
(environmental
agent)

1,5,7,8

1,8,9

1,3

6,8

1, 2, 3, 4, 5

1, 2, 3, 4, 5, 6,
7, 8

Main observable
effects a

Effects aggravated by the

action of other factors
(e.g. chemical reactions,
UV, heat)

Temperature effects can

promote and enhance those
of other agents

Direct sunlight is also a

source of heat and hence
can promote temperature
effects (see below)

Remarks

TABLE 12.6
Some Factors Instrumental in the Natural Weathering of PVC, and Examples of Their Main Effects

~;0

:0::::

dulling, marring and pitting of surface;

cracking (in severe or advanced cases);
stiffening;
discoloration (e.g. yellowing or darkening);
reduced strength;
6,
7,
8,
9,
10,

Effects can be accelerated

by heat and sunlight

Effects promoted and

enhanced by those of UV
radiation (instrumental in
creating reactive sites,
eS{J~cially double bonds)

reduced extensibility;
surface buckling or rippling;
distortion (various degrees and kinds);
development of microporosity;
environmental stress cracking or
crazing.

1,2,3,4,
5,6,8,9,10

(i) Leaching out of components

(ii) Chemical reactions with the PVC
polymer and possibly other
components of the material
(iii) Surface erosion (by wind-borne
particulate pollutants)

Atmospheric
pollutants
(in vapour,
liquid and solid
particle form)

1,
2,
3,
4,
5,

1,2,4,5,6

Oxidation of reactive sites in PVC

polymer and some other components

Air

1,2,4,9

(iv) Chemical effects of pollutants

(e.g. acids) dissolved in rain

-.I
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474

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V. Titow

with the specimens vertical, horizontal, or tilted at 45. In some

methods specimens are exposed under glass, so that the effects of
certain weathering factors (wind, rain) are excluded (ct. ISO 877-1976,
identical with BS 2782: Part 5: Method 540A: 1977; also ASTM G 24-73,
and DIN 53388). Outdoor exposure procedures and effects are the
subject of several international and national standards, including:
ISO 4607: 1978: Plastics-methods of exposure to natural weathering.
BS 4618: Section 4.2:1972: Resistance to natural weathering. Section
4.4:1973: The effect of marine exposure.

ASTM D 1435-75: Standard recommended practice for outdoor

weathering of plastics.
ASTM G 7-77: Atmospheric environmental exposure testing of
non-metallic materials.
DIN 53386:1974: Testing of plastics; testing of resistance to
weathering in nature (outdoor weathering).
British Draft Document 76/54334 (eventually to become method
828A of the revised version of BS 2782): Determination of resistance
to natural weathering.

Intensified outdoor exposure (2 above) can be effected in various

ways. A useful practical method developed by Caryl and Helmick43
involves boosting the amount of natural sunlight incident on the
specimen. In their apparatus, commonly known as 'EMMA' (Equatorial Mount with Mirrors for Acceleration), 10 mirrors direct extra
sunlight onto specimens, producing up to tenfold intensification. This
was found to be capable of accelerating by a factor of nine the
degradation of some uPVC materials: 44 the specimens are cooled
during exposure to prevent undue temperature rise. A further
development of this concept-involving the application of a water
spray and air stream to broaden and increase the weathering effects-is
embodied in the 'EMMAQUA' apparatus 45 in use in America at the
Desert Sunshine Exposure Test Station in Arizona. The rate of onset
of 'normal' weathering effects in PVC can also be effectively increased
(and hence the time scale of outdoor exposure shortened) if very thin

12

Properties of Special1nterest in PVC Materials and Products

475

films are used as specimens: in this form the surface-to-volume ratio

(specific surface) is large, so that most of the material of a specimen is
immediately and directly available to the agents instrumental in
weathering, and is affected by changes as soon as they begin to occur.
A potential disadvantage of this approach is that the exposure period
needed to bring about measurable changes may in some cases actually
be too short to encompass seasonal variations and sporadic effects
characteristic of the 'normal' weathering pattern in the particular
locality.
In accelerated artificial weathering (3 above) the aim is to reproduce
or match in suitable degree the effects of natural weathering by
laboratory treatment of comparatively short duration. As in the other
two approaches, evaluation of the results should, in the ideal outcome,
enable accurate predictions to be made of the useful service life of the
material concerned under given climatic conditions. Failing that it is
also of interest to be able to:
(i) place materials in order of qualitative relative merit with regard
to likely weathering resistance in actual service; and if possible
(ii) quantify the ranking, even if still on a relative basis.
The answers to (i) and (ii) would, of course, follow automatically if the
ideal could be achieved of reliably equating a period of standard
accelerated exposure in the laboratory to one in actual long-term
outdoor exposure (say, for example, 1 h in a Wether-Ometer to 50 h
outdoors in Arizona). Unfortunately this is not possible, especially
where long-term predictions are concerned. This well-known fact is
illustrated, for example, by the data of Kuist and Maxim,46 and
Grossman. 47 The former two investigators quote correlation coefficients for results of accelerated laboratory weathering tests and those
of outdoor exposure as 06--D9 (i.e. unavoidable variability approximately between 20 and 70%). It is also known, moreover, that
differences occur in the rates of failure between long-term outdoor
exposures at the same site. However, with good equipment the relative
performance of materials in accelerated weathering tests can give a
reliable, at least semi-quantitative indication of the relative performance to be expected in the field (i.e. (i) and (ii) above are attainable).
Three factors are employed to bring about 'artificial' weathering in
accelerated laboratory tests, viz. radiation, heat, and water (as vapour,

476

w. v.

Titow

liquid condensate or spray). * Exposure to radiation (light of wavelengths extending from about 280 nm into the visible region) is the
basic feature of all such tests: in most procedures this is combined with
the other two factors.
Radiation sources commonly used are listed in Table 12.7: the
emission characteristics of such equipment are discussed in a paper by
Allen et at. 48
It is generally recognised that, as far as radiation effects in the
normal weathering of plastics are concerned, it is the UV component
of sunlight which is the main operative factor.47-49 This is the basis of
the widely held view that the spectral distribution in the UV region of
the light used in accelerated laboratory weathering tests should be as
similar as possible to that of sunlight, t to reduce the possibility that
radiation-induced chemical (and any other) changes in the test
speCimens may differ in kind from the corresponding effects of natural
weathering. However, a strong case has also been made out for the use
of a source (fluorescent UV lamp) emitting intensely and almost
exclusively in the 290-340 nm region, where the intensity of sunlight's
spectrum is in fact comparatively low. This approach is based on the
view that most of the photochemical changes suffered by plastics in
natural weathering are attributable to the 290-315 nm UV band,47 and
that therefore exposure to a source with strong emission in this region
is both sensible and particularly effective as a means of accelerating
radiation effects in artificial weathering. Test apparatus employing this
type of illumination in conjunction with means of subjecting the
specimens to condensed moisture and elevated temperatures (see entry
No.4 in Table 12.7) has been claimed47 to give particularly rapid
accelerated weathering, and results which correlate well with those of
outdoor exposure (within the general limitations mentioned above).

* Resistance to other agencies, of specific interest in connection with

weathering in particular environments, is also sometimes assessed, in separate,
additional tests. Some examples are: Resistance to salt spray (relevant to
marine environments-see, for example, BS 3900:Part F4:1968); to marine
exposure generally (see, for example, BS 4618: Section 4.4:1973); to
microbiological attack (see Section 12.7 in this chapter); or to exposure to
damp heat, water spray, and salt mist (see ISO 4611-1980).
t For this purpose sometimes defined in standard terms as 'global radiation',
i.e. total radiation--direct, scattered, and reflected, incident upon a horizontal
plane in defined conditions (see, for example, Standard D65 of the
Commission Internationale de l'Eclairage).

12 Properties of Special1nterest in PVC Materials and Products

477

The following international and national standards are concerned

with the methods and apparatus of accelerated weathering of plastics:
ISO/R 878-1968: Plastics-Determination of resistance of plastics to
colour change upon exposure to light of an enclosed carbon arc.
ISO/R 879-1968: Plastics-Determination of resistance of plastics to
colour change upon exposure to light of a Xenon lamp.
ISO 4892-1981: Plastics-Methods of exposure to laboratory light
sources.
BS 3900: Methods of test for paints. Part F3:1979: Resistance to
artificial weathering (enclosed carbon arc).
BS 4618:Section 4.3:1974: Resistance to colour change produced by
exposure to light.
ASTM D 1920-69 (Re-approved 1976): Determining light dosage in
carbon-arc light ageing apparatus.
ASTM D 1499-64 (Re-approved 1977): Operating light- and
water-exposure apparatus (carbon-arc type) for exposure of plastics.
ASTM D 1501-71: Exposure of plastics to fluorescent sunlamp.
ASTM D 2565-79: Operating Xenon-arc-type (water-cooled) lightand water-exposure apparatus for exposure of plastics.
ASTM G 26-77: Operating light-exposure apparatus (Xenon-arc
type) with and without water for exposure of non-metallic materials.
ASTM G 53-77: Operating light- and water-exposure apparatus
(fluorescent-UV/condensation type) for exposure of non-metallic
materials).
DIN 53 387:1982: Testing of plastics; accelerated test of weathering
resistance (simulation of outdoor exposure by filtered Xenon-arc
radiation and artificial rain).
DIN 53389:1974: Testing of plastics; short test of the light stability
(simulation of global radiation behind glass by filtered Xenon-arc
radiation).
The results of accelerated weathering are assessed in the same way
as they are for natural weathering, i.e. in terms of colour changes,

Atlas Electric
Devices Co.,
Chicago, Ill. 60613
USA
Carl Zeiss Inc.
New York, USA;
Quartz-Lampen
GmbH, Hanau,
West Germany;
John Goodrich,
Ludlow, Shropshire,
England
(ii) Xenotesta

(xenon arc)

Weather-Omete~

(i)

Close

3. Xenon arc with

borosilicate
glass filter

Atlas Electric
Devices Co.,
Chicago, Ill. 60613
USA

2. 'Sunshine'
carbon arc
(open carbon
arc with
'Corex D'
filters)

Weather-Ometera
(Sunshine arc)

Poor

Fairly close

Suppliers

Atlas Electric
Devices Co ..
Chicago, Ill. 60613
USA

Name or
designation

Examples of weathering equipment in

which used

Fade-Ometera

Approximation of UV
spectral distribution
to sunlight

1. Enclosed carbon
arc

Nature

Radiation sources

TABLE 12.7
Radiation Sources in Common Use in Laboratory Weathering Equipment

ASTM D 2565

ASTM G 23;
ASTM G 25.

ASTM G 23;
ASTM G 25.

Remarks
and
References

o~

:::;j

:0::::

00

Microscal lightfastness tester

Close

Fair
(more intense
below 320 nm)

Fair

5. Mercury/tungsten
lamp

6. Fluorescent UV
lamp combined
with UV fluorescent
'black-light' source
(FSB unit)

7. High-pressure
mercury/quartz
arc with 'Corex
D' filters

Several models available.

bOriginated by American Cynamid Co., USA.
C Ciba-Geigy Technical Service Bulletin PL 9.1, January, 1977.
d Originated by National Starch and Chemical Corp., USA.

GP UVA ultra-violet
accelerometert

GP-PS/BL b

o-U-V accelerated
weathering tester

None, but source

effective in producing relevant
photochemical
degradation (see
text)

4. Fluorescent
UV lamp
(mercury arc
lamp phosphor
coated)

General Products
Manufacturing Co.,
Morristown, NJ,
USA

General Products
Manufacturing Co.,
Morristown, NJ,
USA

Microscal Ltd,
Ealing, London,
England

The O-Panel Co.

Cleveland, Ohio
44135, USA

Refs 46 and 48

Refs 48 and 50
One hour FSB exposure sometimes
approx. equated to
one day outdoors
in the UK c

Ref. 48

ASTM G 53;
Ref. 47

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5'
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~
~

"tl

S'

-t'

i;.

1"'

tv

......

480

W. V. Titow

deterioration of surface, or changes in other properties. In assessing

colour development (yellowing, darkening), colour changes, or
resistance to colour fading in artificial weathering, use is often made of
standard colour indices or scales, and colour fastness standards. Thus
the degree (and hence the development) of yellowness may be
measured and described by reference to the Yellowness Index (BS
2782:Part 5: Method 530A; ASTM D 192570 (Re-approved 1977)),
change in colour by reference to the Grey Scale (ISO 105-A021978(E); BS 2662:1961; BS 4618: Section 4.3:1974; ASTM D
2616-1967 (Re-approved 1979)), and colour fastness in terms of the
Blue Wool Standards originally set up for textiles (ISO 105-B011978(E); ISO/R 878-1968; ISO/R 879-1968; BS 1006:1971; BS 4618:
Section 4.3:1974). Other relevant standards include:
ISO 4582-1980: Plastics-Determination of changes in colour and
variations in properties after exposure to daylight under glass, natural
weathering or artificial light.
BS 2782:Part 5: Method 530B:1976: Determination of the colour of
near-white or near-colourless materials. *
ASTM G 45-75: Standard recommended practice for specifying
limits for fading and discoloration of non-metallic materials.

Thermal and thermomechanical analyses (DTA, DSC, TGA, TMA)

have been used as sensitive means of detecting and evaluating the
effects of artificial weathering of plastics; they have also been
employed as the combined means of both the thermal ageing itself and
the evaluation of its effects, useful results being claimed in the
prediction of service life of plasticised PVC formulations. 51
The weathering resistance of PVC is cardinally dependent on the
formulation, and in particular on the stabiliser system. The individual
roles of the major formulation components are mentioned in the
relevant chapters. Here the following general points may be made.
Much practical experience is now available to provide guidance in
the formulation of weathering-resistant PVC compounds for outdoor
service. However, by the same token, the limitations of even the best
formulations are recognised. Thus, in the extreme conditions encoun* This is also the subject of an ISO draft standard, ISO/DIS 3558.

12 Properties of Special Interest in PVC Materials and Products

481

tered in some hot-climate areas (e.g. in parts of Australia and South

Africa) where the intensity of incident sunlight, the proportion of
sunlight time, and the ambient temperature are all high, and where
other factors (e.g. severe hail or rain storms, large temperature
fluctuations) may also operate to aggravate the severity of exposure,
the durability-and hence the use-of even the most resistant PVC
compositions in long-term exposure situations is limited or precluded
altogether. Elsewhere PVC is successfully used in many outdoor
applications: e.g. rigid compositions for external wall cladding,
'ranch'-type fencing, road signs, rainwater goods and window frames;
and pPVC as coatings on chain-link wire fencing and tarpaulins, as well
as (in the form of flexible sheeting) for lining swimming pools and
reservoirs (although in this last application the long-term stability is
generally inferior to that of some alternative materials, e.g. butyl
rubber).
Among the formulational factors affecting the outdoor performance
of PVC materials, the following are particularly noteworthy. The PVC
polymer should have the highest molecular weight consistent with the
processing requirements applicable in the particular case. Homopolymers are generally preferable, although in certain compositions
(e.g. some PVC window-frame compounds) certain PVC graft
copolymers are used as impact modifiers (cf. Chapter 19, Section
19.4.3). The stabiliser system should be carefully selected, and should
preferably (with BalCd stabiliser systems invariably) include an epoxy
co-stabiliser (typically 2-8 phr): apart from the long practical experience of the beneficial effect of this type of additive, there is
investigational evidence for its useful role, inter alia, as an agent
facilitating the neutralisation of nascent HCI-evolved in the course of
degradation of the PVC polymer-by the main stabiIiser(s)
present. 52 ,53 As the main stabilisers, selected tin carboxylates can give
very good results, as can BalCd systems supplemented by epoxy
co-stabilisers and phosphite chelators. The carboxylates, too, benefit
from the presence of epoxy co-stabilisers, although there is some
evidence to show that the effect is less pronounced than with BalCd
stabilisers. 42 Where lead stabilisers are permissible, dibasic lead
phosphite is especially useful because of its UV-screening action and
antioxidant effect: combinations of this stabiliser with tribasic or
tetrabasic lead sulphate have also proved very effective for weatheringresistant compositions. UV absorbers are commonly included (sometimes in conjunction with antioxidants) in transparent compositions for

482

w.

V. Titow

outdoor use, to provide additional protection against photolytic

degradation. Polymeric impact modifiers for weathering-resistant rigid
compositions should be carefully selected from among the chlorinated
polyethylene, acrylic, and EVA types. Rubbery modifiers (ABS, MBS)
are not suitable in this application.
Two common pigments are noted for their beneficial effect on the
weathering resistance of PVC: carbon black and titanium dioxide. The
latter can also apparently enhance the effect of certain colourants
which are known to exert a stabilising action of their own: two
examples of such colourants are indanthrene blue and carbazole
violet. 54
The weathering resistance of plasticised compounds can be improved by keeping the plasticiser content as low as possible, using
selected high-permanence plasticisers (some polymerics can be
particularly useful), and incorporating epoxy plasticisers as already
mentioned.
To obtain the best weathering performance possible with a particular
formulation, attention should be paid to the processing conditions (in
particular excessive heating should be avoided), and preferably no
re-worked material should be included. Presence of solvent residues in
solvent-cast films can have an effect: residual tetrahydrofuran was
found to promote photodegradation of PVC in air. 55
External treatment (surface coating) may sometimes improve
weathering resistance: the lacquers applied as thin top coats to flexible
PVC sheet products (e.g. coatings on fabrics-see Chapter 22) can
have this effect. Such coatings, conventionally applied from solvent
solution, normally contain an acrylic polymer as a main component.
Co-extruded protective acrylic coatings on rigid PVC products have
also made their appearance: for example, improved weatherability is
among the advantages claimed for the German 'Vacuplast' PVC
window frame system56 produced from acrylic-surfaced extruded
profiles (with aluminium reinforcement). Application of UV absorbers
to the surface of transparent PVC sheeting by absorption, as well as in
surface coatings, has been suggested57 as a way of obtaining more
cheaply a degree of weathering protection comparable with that
afforded by the conventional incorporation into the compound. The
effectivity of internally incorporated stabilisers can be significantly
affected by their degree of dispersion, migration through the
compound, volatility and extractability. 58

12

Properties of Special Interest in PVC Materials and Products

483

12.7 RESISTANCE TO BIOLOGICAL ATTACK

12.7.1 Microbiological Attack (Biodegradation)
In the plastics context this normally means attack by fungi (mould,
mildew) or bacteria. Whilst infestation by algae might also be included
in the term in its widest connotation, it is not a major problem even
with such PVC materials as film linings for canals, reservoirs and
swimming pools.
The essential mechanism of microbiological attack is enzymatic
degradation of the substrate on which the micro-organisms groW. Both
bacteria and fungi produce enzymes capable of breaking down many
carbon compounds (those containing oxygen-bearing functional groups
can be particularly susceptible) to simpler substances utilisable as
nutrients. Some of the products of the breakdown process can be
coloured, so that the appearance of colour (in PVC often a
characteristic pink stain 59) or black spots, as well as deterioration of
some properties in consequence of the chemical degradation, are the
main outward manifestations of microbiological attack; others include
the development of offensive odours, surface tackiness (in soft pvq,
or surface cracking. The resistance of PVC materials can vary widely
depending on the formulation: some compositions stand up very well
to long exposure in the most unfavourable conditions, such as warm,
humid environments (indoors or out), soil burial or permanent
immersion in water. However, even a very resistant formulation can be
affected indirectly, through contact with a material that is prone to
attack: thus, for example, mildew may grow on the cotton fabric
backing of a PVC-coated protective glove (especially if kept moist with
perspiration for long periods) or on the moist paste layer of a
PVC-coated wall paper, or micro-organisms may flourish on surface
contaminants (grease, dirt) on PVC cladding.
In broad terms, the relevant characteristics and effects of the main
components of a PVC formulation may be summarised as follows. Like
many other synthetic polymers, the polymers and copolymers of vinyl
chloride are resistant to attack by micro-organisms. However, some
commercial PVC resins may contain residual amounts of emulsifying or
suspending agents used in their production, and these may be
susceptible. 44 ,60,61 Many plasticisers are vulnerable to microbiological
attack, as are some stabilisers and lubricants (especially epoxy

484

W. V. Titow

compounds, some stearates and waxes), and certain antioxidants,

although some organotin stabilisers and phosphite co-stabilisers
actually tend to inhibit microbiological growth. 6o The general ranking
of plasticisers, in order of increasing susceptibility, is:
-aryl phosphates and chlorinated paraffin extenders
-phthalates and trimellitates
-aliphatic esters (with sebacates and ricinoleates tending to be least
resistant in this group)
-polyesters (with some exceptions)
-epoxy esters and epoxidised oils
The resistance of plasticised PVC to microbiological attack is also a
function of plasticiser content in many cases. 62 Some fillers may be
vulnerable, e.g. wood flour in wood-filled PVC compounds used for
extruded profiles and trim. 6
Special protective additives are included in PVC formulations at risk
of microbiological attack. Those with a positive ability to destroy fungi
and bacteria are often referred to as fungicides and bacteriocides,
respectively (or, collectively, biocides): the terms 'biostat', 'fungistat'
and 'bacteriostat' are applied to substances which deter microorganism growth by whatever mechanism. Kaplan et at. 63 evaluated the
action of 32 biocidal compounds in PVC film: they concluded that of
those only one, 'copper 8-quinolinolate' (bis(8-quinolinolato)-Cu),
provided fully satisfactory protection. N-(trichloromethylthio)phthalimide also gave good results, but was considered less effective
and less widely compatible with PVC formulations. This ranking
appears to reverse the order that might be inferred from industrial
usage: although N-(trichloromethylthio)imides and the copper complex
are both used in commercial biostats, compounds of the former group
would be regarded as more versatile and possibly more effective at
least in some cases. Other compounds of practical interest are phenyl
mercury salicylates,6h and organic compounds of arsenic (e.g. Estabex
ABF-AKZO Chemie UK Ltd). Some commercial products are
claimed to give broad biostatic protection (e.g. TV-2-Sanitized Sales
Co. of America Inc.; Mikro-Chek 12-Ferro Chemical Division,
* The use of organomercury biocides in flexible PVC has been discontinued on
toxicological and environmental grounds despite their usefulness as the only
biocides of proven effectivity against Pseudomonas aeruginosa which can cause
problems in pPVc.

12

Properties of Special1nterest in PVC Materials and Products

485

USA). A bacteriostat of lower than average toxicity, highly effective in

plasticised PVC products (baby pants, curtains, flooring, gloves)
against both gram-positive and gram-negative bacteria, is
2,4,4'-trichloro-2'-hydroxydiphenyl ether (Irgasan DP 300--CibaGeigy): it is also active against certain fungi which grow on the skin,
e.g. athlete's foot. Its main function is to reduce growth and spread of
bacteria and to suppress odour, rather than to protect the PVC itself
against bacterial attack.
Amounts of biostats used in PVC formulations vary with the nature
of the reagent and the formulation itself, within the range of about
01-2% by weight of the formulation. The protection they afford is of
interest in many applications. In addition to those already referred to
in this section, electrical wire and cable coverings, PVC-coated
tarpaulins and foul-weather clothing, garden hose, and some pipe
formulations may also be mentioned.
Testing the resistance of a plastics material to microbiological attack
in the laboratory typically involves placing specimens in contact with
stock cultures of selected micro-organisms under controlled conditions
for a prescribed time, * and determining changes in a selected property
or group of properties. The appearance of the specimens before and
after the treatment is usually noted, either as part of the evaluation or
additionally. Some relevant standards are listed below. Of these BS
4618 gives a short bibliography, and ASTM G 21 lists in an appendix
several standard (ASTM) methods for determining changes in the
properties which may be monitored in the tests.
ISO 846-1978: Plastics-Determination of behaviour under the
action of fungi and bacteria-Evaluation by visual examination or
measurement of change in mass or physical properties.
BS 4618: Section 4.5:1974: The effect on plastics of soil burial and

biological attack.
ASTM G 21-70 (Re-approved 1980): Standard recommended
practice for determining resistance of synthetic polymeric materials to
fungi.
ASTM G 22-76: Standard recommended practice for determining

resistance of plastics to bacteria.

* Actual soil burial tests are also popular with investigators.

486

W. V. Titow

ASTM G 29-75: Standard recommended practice for determining

algal resistance of plastic films.

u.7.2

Insect and Animal Depredations

In practice the only problems of any significance under this heading

arise in connection with attack on PVC products by termites and
rodents.
(a) Attack by Termites
Although this only occurs in tropical and sub-tropical countries it can
be a problem with PVC products, especially soft PVC (e.g. electrical
wire insulation, cable covering, upholstery fabrics and foam). Experience appears to indicate that termites have a preference for soft
plastics generally, and hence high loading with hard fillers has been
suggested as a possible way to more resistant formulations (see, for
example, BS 4618). Other suggestions that have been made from time
to time included the use of phosphate plasticisers (regarded as more
resistant than other kinds),64 incorporation of lead naphthenate, and
incorporation of insecticides in, or their application in coatings to,
PVC materials. 65 The effectivity of such measures is by no means
established or universal: susceptibility can differ in different localities
and with different species of termite, and no PVC material can be
guaranteed to be generally immune from attack, even if it has
performed satisfactorily in a particular set of conditions. In some
countries a metal barrier (tape) is prescribed by regulations to prevent
termite and animal attack on the PVC covering of electrical cables, and
this is an effective solution in this particular case.
(b) Attack by Rodents
PVC materials are not, in general, palatable to rodents, and are not a
source of food. They are attacked, however, by mice and rats if they
form an obstacle on the way to food or water. Some apparently less
purposeful gnawing is also experienced from time to time on such PVC
products as electrical insulation and conduit, uPVC water pipes, and
reservoir linings.
Although barriers may be incorporated in some products (e.g. cable
coverings, see above) there is no generally applicable way of
preventing these depredations. However, they are neither sufficiently
frequent nor widespread to constitute a major problem.

12

Properties of Special Interest in PVC Materials and Products

487

12.8 CHEMICAL RESISTANCE

At ordinary temperatures PVC homopolymer is resistant to most of
the common inorganic reagents (including aqueous salt solutions),
oxidising agents (with the partial exception of concentrated nitric acid)
reducing agents, aqueous solutions of detergents, oils (mineral, animal
and vegetable), fats, aliphatic hydrocarbons and alcohols. Its solvent
resistance is, however, limited in certain respects: it can be dissolved
by some ketones (tetrahydrofuran, cyclohexanone, isophorone) and
swollen to varying degrees by others; some nitroparaffins can swell or
even dissolve it; and chlorinated hydrocarbons, aromatic hydrocarbons, aromatic amino compounds, as well as some other reagents
(e.g. acetic anhydride) are also swelling agents.
Copolymers are somewhat less resistant, especially to organic
solvents (cf. vinyl solutions-Chapter 24), save in the exceptional case
of copolymers of vinyl chloride with maleic acid imide derivatives (cf.
Chapter 1). However, their general resistance characteristics are
broadly comparable with those of the homopolymer.
As is usual with thermoplastic polymers, the susceptibility of PVC
homo and copolymers to chemical attack increases with increasing
temperature: the same behaviour is exhibited by uPVC and pPVC
compounds. The resistance of compounds can also be lower (in some
cases considerably so) than that of the PVC polymer alone, because of
the presence of the various additives. However, uPVC compositions
are not normally significantly inferior in this respect, although the
presence of some impact modifiers may increase solvent susceptibility
somewhat, whilst resistance to acids and alkalis may be affected by
heavy loading with certain fillers (e.g. whiting and wood flour,
respectively). Flexible (pPVC) compositions may be more readily
attacked by solvents; the increased susceptibility depends mainly on
the nature and amount of plasticiser(s) present. The general chemical
resistance characteristics of PVC compositions are summarised in
Table 12.8. Additional data for uPVC are given in Tables 12.9 and
12.10. ISO/DATA 7:1979 gives data on the resistance of uPVC pipes
to many fluids at up to 60C.
Apart from any direct chemical action, some reagents can affect the
properties of PVC materials by leaching or dissolving out important
components of the formulation (e.g. plasticisers, stabilisers) even if
only from the surface layer. Plasticisers may also be lost by migration
into materials in close contact with pPVC (e.g. adhesives, lacquers)
whose properties may be affected as a result.

S
S
S

Reducing agents
Detergent solutions
Inorganic salt solutions

:}

Remarks

Rigid PVC

No attack up to 60C, but

max. allowable design
stress should be lowered

No attack up to 60C;
allowable design stress
should be substantially
reduced
Allowable design stresses
should be substantially
reduced
No attack up to 60C

Attacked above 20C;

max. allowable design
stress should be reduced
substantially

:1

General
resistance
rating

Oxidising agents

Concentrated

Organic acids
Alkalis:
Dilute

Oxidising
(concentrated)

Concentrated

Inorganic acids:
Dilute

Reagents

S
S
S

:}

General
resistance
rating

No attack up to 60C

Some fillers may be

affected

Some plasticisers and

fillers may be affected

No significant attack up
to 20C; plasticisers and
some fillers may be affected
at higher temperatures
Plasticiser and some
fillers may be affected
Short-term contact may be
acceptable in some cases

Remarks

Plasticised PVC

TABLE 12.8
General Chemical Resistance Characteristics of PVC at Room Temperature

:::l
0

.j>-

oe
oe

U
U
U
M
M
M-U
U

S
U
U

U
U
U
M
M
S-M
U

Aliphatic hydrocarbons

Aromatic hydrocarbons
Chlorinated
hydrocarbons
Esters
Ethers
Ketones
Aldehydes
Amines
Liquid fuels
Turpentine
Oils:
Mineral
Vegetable and animal
Fats
See also Table 12.10

Rating key: S = Satisfactory.

M = Moderate (dependent on formulation and conditions).
U = Unsatisfactory.

S
S
S

U
U

Water

Allowable design stresses

should be substantially
reduced
Some softening possible at
elevated temperatures

M-U
M-U
M-U

U
U
U
M

U
U
U
S

Bromine
Fluorine
Iodine
Aliphatic alcohols

Little attack in the

absence of moisture

Halogens:
Chlorine

Softening, and some

effects on certain fillers
at elevated temperatures
Extraction of plasticisers
and some effects on other
components possible

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TABLE 12.9

Effects of Chemical Immersion on a High-impact uPVC Compound

30-day immersion
at room temperature

Chemical

Tensile
strength
(lbfin- z)

Weight
change

5200
4500
3600
5800
5900
5800
5300
4900
5700
5550
5450

081
199
448
050
043
022
032
040
048
004

5500
5600
5400

30-day immersion
at 60"C
Tensile
strength
(lbfin- Z)

Weight
change
329
825
1539
164
226

014
-007
-001

5000
2450
1450
5800
5700
4900
4700
5450
4200
4950
5250
4800
5900
5800
5700

148
098
659
172
-019
354
004
058
1278

4600
4100
5400
5200
5600

120
121
014
002
-002

2150
2400
5400
5900
5400

514
317
022
-005
-011

Carbon tetrachloride
Trichloroethylene

1850
1550

5914
10321

Excessive swelling
Excessive swelling

Benzene
Castor oil
Cotton seed oil
Glycerine
Hexane
Linseed oil
Salt solutions (sat.)
Barium sulphide
Ferric chloride
Potassium chloride
Sodium dichromate
Trisodium phosphate

5000
5300
5150
5450
3000
5150

73-11
044
018
007
424
007

Excessive swelling
5000
007
5400
026
5900
018

5000
5100
5000
5400
5050

061
025
022
023
046

5000
4700

080
153

2850
5200

387
061

Acetic acid
Chromic acid
Hydrochloric acid
Nitric acid
Oxalic acid (sat. soln)
Phosphoric acid
Stearic acid
Sulphuric acid

Butyl alcohol
Ethyl alcohol
Sodium hydroxide

Formaldehyde
Hydrogen peroxide
Phenol
Turpentine
Distilled water

20%
80%
(glacial)
10%
30%
40%
30%
30%
60%
75%
100%
20%
50%
80%

10%
30%
50%

(%)

(%)

4800

044

5450
4750
4800
5150
4800

311
032
020
018
078

4200
357
4800
167
Excessive swelling
1850
3549
5100
094

Acetaldehyde: 100%
40%
Acetone
Aluminium fluoride
Ammonia liquid, 100%
Ammonium hydroxide,
088
Ammonium fluoride, 20%
Ammonium sulphide
Amyl acetate, 100%
Aniline, 100%
Barium chloride
Benzaldehyde
Benzine
Bleach lye, 10%
Bromine gas, weak
Bromine liquid
Bromic acid, 10%
Butyl acetate
Butyric acid: 20%
cone.
Butanol: primary
secondary
Calcium chlorate
Calcium hypochlorite, soln
Carbon disulphide
Chloracetic acid, 100%

Chemical

S
S
U
U
S
U
S
S

S
S

S
S
S
S

S
U
S

U
S
M
S
S
S

U
S
U
S
S
U
S

U
M
U

60

20

(0C)

Temperature

Chloric acid, 1-20% soln

Chlorine: gas
moist gas
liquid
Chlorobenzene
Chloroform
Chlorosulphuric acid
Chromic acid
Citric acid, sat.
Copper fluoride, 2%
Copper cyanide
Cresol
Cresylic acid
Cupric fluoride
Cyclohexanol
Cyciohexanone
Dibutyl phthalate
Diethylene glycol
Diglycolic acid
Dioctyl phthalate
Ethyl acetate, 100%
Ethyl alcohol
Ethyl butyrate
Ethyl chloride
Ethyl ether
Ethylene chloride
Ethylene dichloride

Chemical

TABLE 12.10
Further Data on Chemical Resistance of Rigid PVCa

S
U
U
U

S
S
U
U
S
S
S
U
U
S

U
U
S
S
S
S
S

S
S
S

20

(0C)

U
U
U
S
S
S
S
U
S
S
U
U
S
S
S
U
U
S
U
S
U
U
U

S
S

60

Temperature

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;:,

'"

/;;'"

1:;'

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Ethylene glycol
Ethylene oxide
Fatty acids
Ferric sulphate
Ferrous chloride
Ferrous sulphate
Fluosilicic acid
Formaldehyde, 40%
Formic acid: 50%
conc.
Fruit juices
Fuel oils
Furfural
Glucose
Glycerine
Glycol
Heptane
Hydrobromic acid, 50%
Hydrochloric acid, 30% +
Hydrocyanic acid
Hydrofluoric acid: 40%
conc.
Hydrogen bromide, 10%
Hydrogen peroxide
Hydrogen sulphide
Hypochlorous acid

Chemical

S
U
S
S
S
S
S
S
S
S
S
S
U
S
S
S
S
S
S
S
S
M
S
S
S
S
M
M
S
S

S
S
S

S
U
S
S
S

U
U
S
S
S
S
S
S
M
U

Temperature
(0C)
60
20
Chemical

Kerosene
Ketones
Lactic acid: 10%
90%
Lead tetraethyl, 100%
Magnesium chloride
Magnesium hydroxide
Maleic acid, sat.
Mercuric chloride
Mercuric cyanide
Mercurous nitrate
Methyl alcohol, 10%
Methyl bromide
Methyl chloride, 100%
Methyl ethyl ketone
Methyl isobutyl ketone
Methylene chloride, 100%
Milk
Mineral oils
Molasses, commercial
Naphtha
Naphthalene
Nickel chloride
Nitric acid: 1-30%
70%
98%

TABLE 12.1().......ontd.

S
U
S
U
S
S
S
S
S
S
S
S
M
M
U
U
U
S
S
S
S
U
S
S
S
U

S
S
S
S
U
S
M
M

U
U

S
U
M
U
S
S
S
M
S
S
S
S
U

Temperature
eC)
20
60

<:;

:0::::

tv

\D

U
M
S
S
S
S
U
S
U
U
S
S
U
S
S
S
S
S
S
U
S
S
S
S
S
S
S
S
U
S
S
S
U
S
S
S
S
S
S
S

U
S

U
M
S
M
S
S
U
M

Sodium cyanide
Sodium ferrocyanide
Sodium fluoride
Sodium hypochlorite
Sodium sulphide, sat.
Stannic chloride
Stannous chloride
Sulphur dioxide: dry
wet
liquid
Sulphuric acid, 90%
Fuming sulphuric acid
Tanning extracts
Tartaric acid, sat.
Tetraethyl lead
Tetrahydrofuran
Thionyl chloride
Toluene
Transformer oil
Trichlorethylene
Triethanolamine
Turpentine
Urea, up to 30%
Vinegar
Xylene
Zinc chloride, sat.
Zinc sulphate

Key: S = Satisfactory.
M = Moderate (dependent on formulation and conditions).
U = Unsatisfactory.

Nitrobenzene
Octyl cresol
Oleic acid
Oxalic acid, sat.
Perchloric acid, up to 70%
Petrol, aliphatic
Petrollbenzene, 80/20
Phenol, 90%
Phenylhydrazine, 100%
Phosgene, liquid
Phosphoric acid
Phosphorus pentoxide
Phosphorus trichloride
Picric acid, 1%
Potassium bichromate
Potassium chromate, 40%
Potassium cyanide, sat.
Potassium hydroxide, cone.
Propyl alcohol
Propylene dichloride
Silver cyanide
Soap solution
Sodium acetate
Sodium bisulphite
Sodium bromide
Sodium chlorate, sat.
Sodium chromate

S
S
S
S
S
S
S
S
S
M
S
U
S
S
S
U
U
U
S
U
S
U
S
S
U
S
S

'"

"1:1

S
S

l:>..

'D
W

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"

l=:
0;

l:>..

<3

;:s

I:;"

::1.

"'"

~
~

"1:1

"s~

S'

"~'"

.g>

'"~.

~
~

tv

......

U
U
U
S
U
S
U
S
M

S
S
S
S
S
S
S
S
S
U
S
-

494

W. V. Titow

The good resistance of PVC to many chemicals is utilised in such

practical applications as, for example, uPVC wall cladding in chemical
plants, or the ducting and fans of fume-extraction systems, and
protective pPVC gloves and clothing for workers in the chemical
industry, laboratories and stores. The susceptibility of PVC compositions to attack by some solvents is also used to advantage in some
processes as well as for certain test purposes: apart from the various
applications of PVC polymer and copolymer solutions (see Chapter
24), such uses include, for example, the incorporation of isophorone as
a keying agent in printing inks for PVC sheeting and coatings, the
use of solvents in tests for the completeness of gelation of PVC paste
coatings on fabrics (see Chapter 22), and solvent-swelling tests (in
acetone or dichloromethane) for homogeneity and structural integrity
of uPVC pipe and other extruded products and mouldings (d., for
example, ISO 3472-1975; BS 3506:1969; ASTM D 2152-80; SABS
791-1975; SABS 966-1976).
The chemical resistance of plastics materials, including PVC, is
normally tested by determining changes in appearance, dimensions,
mass, and/or other properties of specimens after a period of contact
(usually by immersion) with the chemical(s) concerned. Some of the
relevant standards give a list of chemicals for determining the general
resistance and specify the properties to be used as assessment criteria
(see, for example, ISO 175 and 462; BS 4618: Section 4.1; ASTM D
543). Some basic requirements in respect of the general chemical
resistance of uPVC compound are laid down in Table 2 of ASTM D
1784-1981.
The international and national specifications of interest in connection with various aspects of chemical resistance of PVC include the
following:
ISO 175*-1981: Plastics-Determination of the effects of liquid
chemicals, including water.
IS0/R 462*-1965: (Later incorporated in ISO 175). Recommended
practice for the determination of change of mechanical properties after
contact with chemical substances.
ISO 3473-1977: Unplasticised polyvinyl chloride (PVC) pipesEffect of sulphuric acid-Requirement and test method.
* Essentially equivalent to parts of ASTM D 543.

12

Properties of Special1nterest in PVC Materials and Products

495

BS 2782:1970: Method 505A: Resistance to concentrated sulphuric

acid of rigid polyvinyl chloride compounds.
BS 4618: Section 4.1:1972: Chemical resistance to liquids.
ASTM D 543-67. (Re-approved 1978): Resistance of plastics to
chemical reagents.
ASTM D 1239-55. (Re-approved 1982): Resistance of plastic films to
extraction by chemicals.
ASTM D 1784-81: Rigid poly(vinyl chloride) (PVC) compounds and
chlorinated poly(vinyl chloride) (CPVC) compounds.

DIN 53476:1979: Testing of plastics; Determination of the behaviour against liquids.

DIN 53756:1974: Testing of plastics; Storage in contact with
chemicals.
DIN 53 428:1967: Testing of cellular materials; Determination of the
resistance to liquids, vapours, gases and solid materials.

U.9 HEALTH HAZARDS

Health hazards arise in the production, processing, use, and disposal of
most plastic materials, and PVC is no exception. Some of the hazards
are of a general nature, not directly dependent on the composition of
the plastic: e.g. risks of injury in operating plastics processing
machinery, or the well-publicised danger of suffocation to children
using plastics bags as substitute space helmets in play. This section is
concerned primarily with those health hazards which are specifically
associated with the chemical nature of PVC materials, although some
associated 'peripheral' hazards are also briefly mentioned. The main
hazard areas may be collectively identified as the risk of harmful effects
on contact with the PVC materials themselves, or their individual
constituents, or decomposition products, during any of the abovementioned phases of the materials' life history. The principal possible
harmful effects are poisoning (in the widest sense of the term),
carcinogenic action, irritation and tissue damage, and dermatitis. The
forms of contact through which they can arise are ingestion, inhalation,
absorption (e.g. through the skin or mucous membranes), or simple

496

w.

V. Titow

'external' contact (which may also lead to some absorption) especially

if prolonged or repeated.
12.9.1 Vinyl Chloride Monomer
In the case of PVC an important potential health hazard is
encountered at the earliest stage of the material's life cycle, in that the
vinyl chloride monomer (VCM) is a recognised carcinogen. The hazard
continues wherever residual amounts of the monomer are present in
PVC resins and compounds, before, during and after their conversion
into end products. This situation necessitates precautions against
exposure to free VCM in the production of PVC polymers and
copolymers, and measures to minimise residual VCM contents of such
polymers and the compounds and products based thereon. The general
objective is to reduce to an acceptable level the amount of the
carcinogen which can be transferred by direct contact, inhaled (or
absorbed) as vapour previously volatilised into the atmosphere, or
consumed in foods and beverages which can extract it from PVC
packaging films or containers. Among the most important problems
arising in this connection is the need to know what should be regarded
as the maximum permissible concentrations of VCM in PVC materials
and the atmosphere, and the associated requirement for suitable
methods of determination. Although the carcinogenic activity of VCM
(in animals) was first made known only in 1970,66 and links with a form
of liver cancer (angiosarcoma) and a rare cancer of the mouth in
humans first recognised in the mid-1970s,66,67 much effort has already
been devoted to meeting both these needs. Several analytical methods
for determining small amounts of VCM in PVC and in air are now
available, with sensitivity in many cases better than 1 ppm, and in some
down to a few parts per (American) billion. 68 Several commercial
detectors and monitors are on the market.69 Gas-chromatography
procedures, involving either direct or head-space sampling, can be
particularly useful,70-72 although IR spectroscopy and photodetection
are also utilised in monitors for VCM in air. 69 Clip-on badges have
been developed for the latter purpose.73 Interest continues in possible
ways of determining the actual extent of damage caused by VCM in
the body: inter alia, a very sensitive method has been reported based
on the alkylating action of VCM (as well as of certain other carcinogens) on amino acid constituents of haemoglobin. 74
Ideas on maximum concentrations representing 'acceptable risk'

12

Properties of Specia/1nterest in PVC Materials and Products

497

levels have undergone a considerable change in the past few years with
increasing volume and availability of relevant data.
The first limits recommended in the UK (in the mid-1970s) for
maximum VCM concentration in factory atmospheres started with a
time-weighted average figure of 25 ppm (by volume), soon to be
brought down to 10 ppm with the further proviso that wherever
possible zero concentration should be aimed at. 75 At the same time in
West Germany (North Rhine-Westphalia) the maximum concentration
limits for factories were being lowered from an initial 50 ppm to
5 ppm,76 whilst in the USA a limit of 1 ppm was being demanded, with
the US Food and Drug Administration (FDA) concurrently framing
regulations to prohibit the use of rigid and semi-rigid PVC for
food-packaging applications (bottles, films) unless it could be shown
that no migration of VCM into the contents would occur. Attention
was focused on unplasticised PVC, because available evidence
indicated that plasticisation reduces residual VCM contents to
undetectably low levels. A temporary standard was put out in the USA
by the Occupational Safety and Health Administration (OHSA) in
1974, followed by a finalised version in 1978: in the same year relevant
rules, limiting VCM emission in industrial plant, were formulated by
the US Environmental Protection Agency (EPA), and EEC directives
issued in Europe on VCM content in food-packaging materials.
These moves made themselves felt in the industry in several ways.
PVC resin production, as well as that of packaging films and bottles,
was curtailed by some manufacturers unwilling to face the difficulties
and expense of reducing VCM concentrations in their plants and
products in the face of uncertainty as to what limits might finally be
laid down. Prices of some PVC resins and products were affected as
production became more expensive where removal of VCM and tighter
control over its concentration were being instituted. Some resins, in
which the VCM content was reduced by heat treatment ('stripping'),
became more glassy and harder to process as a result of this addition to
their 'heat history'. On the positive side, R&D work was stimulated
towards methods of reducing VCM concentrations in PVC materials
and factory atmospheres, methods of determining such concentrations,
and the ways in which they were affected by production conditions.
Towards the end of the 1970s the practical improvements achieved in
production and processing, coupled with the results of the R&D
effort, led to a brighter outlook on the VCM risk. Further confirmation
has been forthcoming for the relative safety of plasticised PVC

498

W. V. Titow

materials, as has evidence of a substantial drop in residual VCM levels

in both PVC materials for food packaging and the foods packaged
therein. 67 ,77 It is now practicable to reduce the VCM content of
commercial PVC resins to a few parts per 109 (i.e. by a factor of nearly
106 since the early 1970s), and there is strong evidence (from the Ethyl
Corporation in the USA) that at, or below, 2 parts per 109 VCM will
not migrate into food from PVC materials at a significant rate. 78 ,79 The
latest FDA estimates based on this evidence indicate potential
maximum VCM levels of less than 5 parts per 1012 in PVC-packaged
food. 79 Thus, whilst the fact remains that only complete avoidance of
exposure to VCM can entirely eliminate all risk, a high degree of
confidence in properly processed PVC as food-packaging material may
soon be restored. An excellent review of the VCM problem in all its
aspects was published recently by Clayton. 8o
It may be noted in passing that exposure to VCM (admittedly in
minute quantities) from sources unconnected with PVC may be a real
possibility for large numbers of people both in the industry and
outside: vinyl chloride has been reportedly found in tobacco smoke
(albeit in very small concentrations-up to 003 ppm), and the
possibility has been mentioned that it may also be formed as a
combustion product of other plant materials, including vegetable
refuse. 8 !
U.9.2

PVC Compounds and their Regular Constituents

Aside from the effects of VCM, the main health hazard is possible
toxicity in food-contact applications involving such PVC products as
films and containers: this hazard is usually considered from the point of
view of the properties of the individual components of a formulation.
It is normal to 'clear' these, before the formulation is finalised and
made up, on the basis of experience, and/or information from the
manufacturers, and/or the relevant recommendations or rules of the
appropriate national authorities and organisations. In the USA the
organisations most directly concerned are the ones referred to in the
previous section (FDA, OHSA, EPA): the US Department of Health,
Education and Welfare (HEW) may also be mentioned in this
connection. In the UK and Europe the bodies with related interests
and functions (albeit largely different constitutions, and scope and
nature of operations) include the UK Health and Safety Executive,
British Plastics Federation (BPF) , the UK Chemical Industries

12 Properties of Special1nterest in PVC Materials and Products

499

Association, the West German Federal Health Office, and corresponding organisations in many other countries. Some of these organisations
(e.g. FDA, BPF) issue lists of materials (e.g. plasticisers, stabilisers,
colourants) approved (or forbidden) for food-contact applications:
such applications constitute the area of primary concern in the context
of this section.
Some aspects of the subject of toxicity of PVC materials are
discussed in a brief paper by Estevez. 82 An earlier review, by Phillips
and Marks,83 is also still of some interest. In the UK the BPF publishes
a code of practice for safety in use of plastics for food-contact
applications, based in part on extensive evaluation tests carried out by
the British Industrial Biological Research Association (BIBRA).
It is normally assumed that PVC homopolymers, vinyl chloride/
acetate and vinyl chloride/vinylidene chloride copolymers are non-toxic
in compounds. Several lubricants (in particular stearic acid) are
regarded as safe, as are some of the other two principal formulation
components, plasticisers and stabilisers, when used in prescribed
concentrations: acceptability, especially the concentration limits, may,
however, vary according to the conditions. For example, more
stringent requirements arise for food-packaging films to be used with
fatty foods (e.g. bacon, butter, etc.) capable of leaching out
plasticisers, than for non-fatty foods with a high water content (e.g.
fruits, vegetables). The packaging of children's toys is also an area of
special concern. Detailed, up-to-date information and guidance can be
obtained from the organisations mentioned in this section. Some
further general information is also given in the chapters on stabilisers
and plasticisers.

U.9.3 PVC Decomposition Products

If thermal decomposition of PVC is permitted to occur in processing,
and when PVC is burned (e.g. in an accidental fire, or as a means of
disposal), toxic and irritant fumes are produced. These contain a
considerable proportion of hydrogen chloride (usually appearing as an
acrid, highly irritant white fume), which is the principal product of
thermal breakdown of vinyl chloride homopolymers and copolymers: 84
a sooty, black smoke usually arises from the combustion of plasticisers
in flexible PVC compositions. Other pyrolysis products of PVC
materials include benzene, toluene, xylene, naphthalene, and certain
derivatives of these compounds: 6,84--86 with an adequate supply of

SOO

w.

V. Titow

oxygen, water vapour, CO and CO2 are also formed, as combustion

products. 84
U.9.4 Peripheral Hazards

The kinds of hazard that may be mentioned under this heading are
relevant to PVC, although not exclusive to it, * as they can arise in the
production and processing of other plastics. They are:
(i) fire and explosion hazards;
(ii) respiratory hazards;
(iii) toxic hazards;
These occur in the storage and handling of additives and other
formulation components (especially in powder form), and in processing
operations involving the use of solvents (e.g. making up PVC
solutions, printing on PVC materials, preparation and application of
solvent-based lacquers for PVC sheet materials).
The appropriate precautions are nowadays generally reasonably well
known in the industry, but it should also be remembered that many are
prescribed by law, and that the statutory requirements vary in different
countries. Advice and guidance is available from the organisations
mentioned in Section 12.9.2. Relevant information may also be found
in the current editions of the following publications:
Industrial Hygiene and Toxicology. F. A. Patty (Ed.), Interscience
Publishers.
Encyclopaedia of Occupational Health and Safety. International
Labour Office, Geneva.
Health Hazards of the Human Environment. World Health Organisation.
Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley &
Sons (under 'Industrial Toxicology' and other relevant headings).
* However, two specific points may be made regarding PVC: under certain
conditions the presence of fine PVC resin dust can lower the explosive limit of
VCM/air mixtures; potentially ignitable levels of VCM may arise in high-speed
mixing equipment. Guidance on safety in the operation of high-speed mixers is
provided in a booklet published jointly by the British Plastics Federation and

Chemical Industries Association Ltd, 'Vinyl CWoride Monomer. Guide to the

High Speed Mixing of PVC Resins and Compounds'.

12 Properties of Special Interest in PVC Materials and Products

501

Dangerous Properties of Industrial Materials. N. I. Sax, Van

Nostrand Reinhold.
Fire Protection Handbook. G. H. Tryon (Ed.), National Fire
Protection Association, Boston, Mass., USA.
Publications of the American Conference of Governmental Industrial
Hygienists, Cincinnati, Ohio, USA, including (i) Documentation
for Threshold Limit Values for Substances in Workroom Air; (ii)
Industrial Ventilation: A Manual of Recommended Practice.
Relevant HMSO Publications, (UK).

12.10 BURNING BERAVIOUR

Virtually all plastics are combustible: that is they will-under suitable
conditions (e.g. in a sufficiently intense fire)-undergo exothermic
oxidative decomposition, accompanied by flame and/or glowing and/or
smoke evolution as its main visible manifestations. However, the
nature and severity of the conditions required for ignition and
sustained combustion are different for different plastics and, conversely, the ignition and combustion behaviour will differ under identical
conditions: in both cases the differences are governed by differences in
chemical composition and physical state-e.g. a polystyrene film will
burn readily in circumstances in which a uPVC one will not; a uPVC
bar may have an oxygen index of 40 or only 25 depending on whether
it is solid or cellular, and so on. Thus meaningful comparisons can only
be made on the basis of tests relevant to the purpose of the comparison
and carried out under closely standardised conditions. Moreover,
because they are cardinally dependent upon the conditions, the results
of laboratory tests are strictly relative (as are any comparisons based
upon them) and should not be used as criteria for the prediction of the
degree of hazard in actual fire situations. Similarly, such apparently
definitive terms as 'self-extinguishing', 'non-flammable', 'flameresistant', 'slow-burning' can only have meaning in relation to a
specified set of conditions (e.g. a particular standard test). Even when
these principles are observed confusion can still occasionally arise
because the terminology of the burning behaviour of plastics is not
fully uniform: standardisation, and increasing awareness of the factors
and concepts involved, have done much to improve matters, but even
standard definitions of the same important term can still differ
considerably. For example, two sources of relevant standard defini-

502

W. V. Titow

tions, ISO 3261-1975 * and ASTM E 176-82, t define 'flammable',

respectively, as 'capable of undergoing combustion in the gaseous
phase with emission of light during or after application of an igniting
source' and 'subject to easy ignition and rapid flaming combustion'.
Note: Other publications containing relevant terminology are:
Addendum 2 (1983) to ISO 472, comprising definitions of
terms relating to burning behaviour of plastics; and Compilation of ASTM Standard Definitions published by the American
Society for Testing and Materials. Certain terms are also
defined in some of the standard specifications listed in Table
12.12.

The burning behaviour of plastics is of great importance in many

applications, and hence of interest to the user and technologist alike.
The key aspects with which the practically oriented tests are concerned
are ignitability, spread of flame, rate of heat release, and amount of
smoke generated. The chemical composition of the smoke, whilst not
investigated in standard tests, is also important and has been receiving
increasing attention as a toxic hazard in fires. In addition, the
Fennimore-Martin 'Oxygen Index,88,89 (based on the minimum
concentration of oxygen required to support candle-like burning of a
standard size specimen in specified conditions) provides a useful means
of rating the flammability (in the sense of ease of ignition and burning)
of plastics and other materials. Some typical oxygen index values for
plastics, including PVC, are shown in Table 12.11. Standard burning
tests relevant to (including some specifically devised for) PVC
materials and products are listed in Table 12.12. A British standard
covering the development, presentation and use of fire tests is now
available. 91
The' flammability of PVC (resins and solid uPVC compositions) as
determined in standard tests is one of the lowest among those of the
common plastics. However, the smoke emission is relatively high, and
the smoke is irritant and toxic (see Section 12.9.3). The low
flammability is due to the large chlorine content: like the other
halogens (cf., for example, PTFE in Table 12.11) chlorine acts as a
retardant in the process of combustion (see Chapter 11, Section 11.5).
* 'Fire tests-Vocabulary'.

t 'Standard definitions of terms relating to fire tests of building construction

and materials'.

12

Properties of Special Interest in PVC Materials and Products

503

TABLE 12.11
Oxygen Index Values of Some Plastics Materialsa

Material

PVC resin (homopolymer)

uPVC compound (medium impact strength)
uPVC compound containing 15% glass fibre
PVC floor tile (asbestos-filled)
pPVC compounds
PVDC
PTFE
Polyamide (nylon 6.6)
Polycarbonate
Polymethyl methacrylate
Polyethylene
Polypropylene
Polypropylene with flame retardant
Polypropylene asbestos-filled
Polystyrene
uPVC foam
pPVC foam
Polystyrene foam
Polystyrene foam with flame retardant
Polyurethane foam
Polyurethane foam with flame retardant
Polyisocyanurate foam

Oxygen indexb
(typical or
representative value)
45

40
40
30

21-26

60

95
23
23-27

17-18
17-18
17-18
22
21

18

25
22

18

24
19
22
26

Table based on data from Refs 88, 92, 94 and 95.

% Oxygen in the standard gas mixture, required to support candle-like
combustion of standard specimen in standard conditions (ASTM 2863).
a

The performance of PVC compositions in flammability tests falls with

decreasing chlorine content (see Fig. 12.7 here, and Fig. 6.3 in Chapter
6). This is the main reason for the well-known fact that plasticisation
increases flammability, albeit this effect is reduced where chlorinated
extenders or phosphate plasticisers are used, since the former
introduce their own chlorine, and the latter act as flame retardants in
their own right (see Chapter 11, Section 11.5; and Chapter 7, Section
7.6). An expression relating the halogen content of a polymer to its
carbon and hydrogen contents, known as the van Krevelen Composition Parameter, has been found to correlate well with the oxygen index
for many polymers, including polyvinyl chloride. 92 The flammability of

Flammability

Plastics: rigid (selfsupporting) sheet or

moulding

1. ISO 1210-1982
2. BS 2782: 1970
Method 508D
Burning time and/or rate and/ 1. BS 2782:1970:
or extent
Method 508A
2. BS 2782:1970:
Method 508B
3. ASTM D 635-81

1. ISO 871-1980
2. ASTM D 1929-77

Ignition properties

Plastics: pellets; sheet

or film

Standard
specifications

Incandescence resistance (be- l. ISO 181-1981

haviour during and after con- 2. BS 2782: 1970
tact with incandescent bar at
Method 508E
950C)
3. ASTM D 757-77
4. DIN 53459-1975

Property or
characteristic determined

Plastics: rigid sheet or

moulding

Material
or product

Remarks

1. Bar specimen held

horizontally
2. Relates specifically to
PVC compounds
3. Bar specimen held
horizontally

1. and 2. technically
equivalent: self-ignition and
flash-ignition temperatures
determined (in a hot-air
ignition furnace)

1. and 2. Intended for

thermosetting plastics
3. Recommended for materials
which are self-extinguishing
in the test of ASTM D 635
(see below)

All four specifications closely similar

technically (employ the 'Schramm!
Zebrowski' method)

TABLE 12.12
Standard Burning Tests Relevant to PVC Materials

;;

is

:::'1

VI

Flammability and/or burning

rate, and/or extent of bum

Plastics: cellular

Smoke generation
Horizontal burning characteristics
Smoke generation
Vertical burning characteristics (flame height, burning
time, mass loss)

Plastics: solid or cellular Oxygen index

(applicable also to
non-plastics materials
e.g. wood)

Plastics: film or thin

sheet

BS 5111:Part 1:1974
ASTM D 3014-76

BS 4735:1974

1. ISO 4589-1985
2. BS 2782:Part 1:
Methods 141 A to
C: 1978
3. ASTM D 2863-77
ASTM D 2843-77

4. ASTM D 1433-77

1. ISO/R 1326-1970
2. BS 2782:1970:
Method 508Ca
3. ASTM D 568-77

4. UL subject 94
Parts A & B
5. IBM CMH 6-0430102

The 'Butler Chimney' test

2. Restricted to solid
(non-cellular) specimens
NB Method D for electric cable insulation or sheathing-see below
Employing the XP2 smoke chamber

2. Relates specifically to
thin flexible PVC sheeting
3. Vertically suspended strip
specimen: test results
sensitive to thickness
4. Strip specimen supported
on 45 incline

4. and 5. Closely similar;

vertical bar specimens
ignited at lower end;
effect of dripping
(ignition of cotton by
flaming drops) taken into
account; tests more
severe than 1 and 2

2S
lJl

~
~
1:;

"'-

;::

'"

l:;'"

~.

r3

S'
"l:I

.:
S'

~
~

~.

.g~

.....
N

Property or
characteristic determined

Building materials (including plastics)

Various combustion characteristics (including smoke

generation in some cases)

Combustibility

Electrical insulation and Oxygen index

cable sheathing (mainly plastics)
Ignition and/or spread of
flame and/or rate and extent
of burning

Material
or product

Remarks

1. Agrees with lEC 332

(vertical specimen)
2. Test for rigid sheet and
2. ASTM D 299-82
plate insulation materials
3. Test for non-rigid PVC
3. ASTM D 876-80
tubing used for electrical
insulation
Test for duration of sustained
ISO 1182-1979
flaming
1. ISOrrR 3814-1975
1. Report on tests being
developed
2. BS 476
2. A multi-part specification
'Fire tests on building
materials and structures'
3. ASTM E 84-81
3. 'Underwriters tunnel furnace
test'. 25 ft specimens
4. ASTM E 286-69(1975) 4. The '8 foot tunnel' test
5. DIN 4102
5. A multi-part specification
'Behaviour of building
materials and components
in fire'

BS 2782:Part 1:
Method 141D:1978
1. BS 4066:1969

Standard
specifications

TABLE 12. 12-contd.

;e

:::J
c;

:0::::

Vl

Various combustion characteristics

'Materials' (some relevance to plastics)

Now superseded by BS 2782:Part 1: Method 140 D:1980.

Interior materials for

Burning rate and extinmotor vehicles (includ- guishing characteristics
ing PVC upholstery
and mouldings)

Duration of flaming and

afterglow, and/or length of
char (or melt), and/or flaming drips

Coated fabrics

ISO 3795-1976
(based on US Federal
Motor Vehicle Safety
Standard 302)

2. DIN 53 438-1977

1. ASTM E 162-81

4. DIN 54332-1975

3. ASTM D 2859-76

1. BS 3424:1973:
Method 17
2. BS 5790:1979

Requirements stated in terms of

rate of burning; specification much
used for PVC upholstery fabrics

1. Test with radiant energy

source: 'flame spread
index' and smoke
evolution measured

2. Specification for upholstery

fabrics, including PVCcoated woven and knitted
fabrics: flammability
tests by the Method of 1.
3. Flammability of textile
floor coverings (relevant
to PVC-backed carpets)
4. Burning behaviour of
textile floor coverings

1. Vertical strip specimen

Vl

I:l..

;::

I:>

5'
l:;-

~
~

"ll

~
~

;;-

~
~

~.

~
~

.....
N

W. V. Titow

508
45

40

25

03

004

el,

wt fraction

0-5

06

Fig. 12.7 Oxygen index (01) of a PVC composition as a function of its

chlorine content (fraction by weight of the total composition). Formulation of
PVC composition:
100
PVC resin
Plasticiser (DOP)
0-90 phr, as shown
White lead
7 phr
Ca stearate
O 75 phr
A,
B,
C,
D,
E,
F,

DOP 90 phr; all additives 9775 phr; CI content 0287;

DOP 60 phr; all additives 6775 phr; CI content 0339;
DOP 40 phr; all additives 4775 phr; CI content 0384;
DOP 20 phr; all additives 2775 phr; CI content 0445;
DOP 0;
all additives 775 phr; CI content 0527;
PVC resin alone; CI content 0568.

a PVC composition may be reduced, despite a reduction in the overall

chlorine content, through the incorporation of a non-combustible filler
(e.g. asbestos fibre), a flame-retardant compound, or a smoke
suppressant. The latter two types of additive and their effects are
discussed in Section 11.5 of Chapter 11.
Much useful information (including an extensive list of literature
references) on all aspects of combustion of polymers is contained in a
recent book by Cullis and Hirschler. 93 A comprehensive (10-volume)

12

Properties of Special Interest in PVC Materials and Products

509

report * by the National Materials Advisory Board of the USA

Academy of Sciences is an important source of reference on subjects
falling within the ambit of its title. A list of flammability test methods
for plastics (containing national standard tests of 18 countries, as well
as some ISO standards and those of the Underwriters Laboratory,
NCB) has been published by the Chemical Industries Association Ltd,
London.
Some data on the evolution of HCI and smoke from PVC (burnt
with wooden cribs) are given by Edgerley and Pettett. 84

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49.
50.
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55.
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60.

61.
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46(3), 267-8.
Sahajpal, V. K. (1978). 'PVC compounding for low organoleptics and
controlled bacteriological growth', paper presented at the PRI International Conference on PVC Processing, Egham Hill, Surrey, England, 6-7
April, 1978.
Mascia, L. (1974). The Role of Additives in Plastics, Edward Arnold,
London.
De Coste, J. B. (1968). Ind. Eng. Chern., 7(4), 238-47.
Kaplan, A. M., Greenberger, M. and Wendt, T. M. (1970). Polym.
Engng. Sci., 10(4),241-6.
Wessel, C. J. (1964). SPE Trans., 4(3), 193-207.
Anon. (1965). Mod. Plast., 42(5), 168.
McGinty, L. (1979). New Scientist, 183 (9th Aug.), (1167), 433.
Socrates, G. (1979). Plast. Rubb. Wkly, (9th March), p. 10.
Anon. (1975). Ibid, (21st February) p. 70.
Anon. (1974). Chern. Engng. News, (16th December), pp. 24-5.
Draft German Standard DIN 53743-1977. Testing of plastics:
Gas-chromatographic determination of vinyl chloride (VC) in polyvinyl
chloride (PVC).
Anon. (1979). Plast. Technol., 25(9), 13.
Berens, A. R., Crider, L. B. and Tomanek, C. J. (1975). J. Appl. Polym.
ScL, 19(12), 3169-72.
Anon. (1976). Chern. Engng. News, (8th March), p. 6.
Anon. (1979). New Scientist, 183 (April 19th), (1151), 185.
UK Health and Safety Executive. 'Vinyl Chloride-Code of Practice for
Health Precautions', Temporary Format (February 1975).
Anon. (1975). Plast. Rubb. Wkly, (18th April), p. 3.
Daniels, G. A. and Proctor, D. E. (1975). Mod. Packag., 48(4),45-8.
Anon. (1979). Plast. Technol., 25(5), 211.
Anon. (1979). Mod. Plast. Int., 9(12),28.
Clayton, H. M. (1977). In Developments in PVC Production and
Processing-I, (Eds A. Whelan and J. L. Craft), Applied Science
Publishers, London, Ch. 3.
Anon. (1977). Plast. Rubb. Wkly, (18th March), p. 15.
Estevez, J. M. J. (1969). Plast. Polym., 37(129),235-42.

512

W. V. Titow

83. Phillips, I. and Marks, G. C. (1961). Brit. Plast., 34, 319 and 385.
84. Edgerley, P. G. and Pettett, K. (1981). Plast. Rubb. Proc. Appl., 1(2),
133-7.
85. Iida, T., Nakanishi, M. and Goto, K. (1975). J. Polym. Sci. Polym. Chem.
Ed., 13(6), 1381-92.
86. Mitera, J. and Michal, J. (1976). Chem. Prum., 26(8),417-20.
87. Clark, C. A. (1972). SPE J., 28(7), 30-5.
88. Fennimore, C. P. and Martin, F. J. (1966). Mod. Plast., 44(3), 141-8.
89. Isaacs, J. L. (1970), J. Fire Flamm., 1(1), 36-47.
90. Oswin, C. R. (1975). Plastic Films and Packaging, Applied Science
Publishers, London.
91. BS 6336:1982. Guide to the development and presentation of fire tests and
their use in hazard assessment.
92. Grieveson, B. M. (1976). 'The fire hazard of polymers', paper presented at
the Polymer Symposium, British Association for the Advancement of
Science, Lancaster, England, 3rd September, 1976.
93. Cullis, C. F. and Hirschler, M. M. (1981). The Combustion of Organic
Polymers, Clarendon Press, Oxford University Press.
94. Titow, W. V. and Lanham, B. J. (1975). Reinforced Thermoplastics,
Applied Science Publishers, London.
95. Ahrens, H. W. and Zahradnik, B. (1973). 'Oxygen index rating of plastics
as a guide to their behaviour in fire', CSIR Special Report BOU 29.

CHAPTER 13

Industrial Compounding Technology ofRigid

and Plasticised PVC
W. HENSCHEL and P. FRANZ

13.1 INTRODUCTION
The compounding process represents the link between raw material
production and finished-article manufacture. Its function is to combine
the PVC resin with the various additives required for processing and
for the service properties of the final product, in accordance with the
formulation.
There are five general types of industrial PVC compounding

operation (Fig. 13.1)

-preparation of pre-mixes and dry blends,
-melt compounding and pelletising,
-compounding for the feeding of film and sheet calenders,
----,production of pastes (plastisols, organosols, plastigels),
-recycling.
As indicated schematically in Fig. 13.2, the equipment required can
be divided into the upstream section ahead of the compounder, the
compounder itself, and the downstream equipment. The upstream
units are more or less identical for all the five general types of
compounding operation, but the compounder and its downstream
equipment have to be adapted to the specific requirements of each
type. A typical line is shown in Fig. 13.3.
The upstream equipment handles the raw materials: it comprises silo
storage, conveying, weighing. Included in the compounding section are
the PVC pre-mixing operation, the actual compounding and, where
pellets are produced, the pelletising operation.
513

514

W. Henschel and P. Franz

PROCESSED PVC
MATERIALS

COmpounding
(mixing)

Compounding

IU~das feedstock -, Mtllt

,~r,

,Extrusion
,Blow moulding

d
I compoun Ing
I and .

~~~J~~_~~
i
1
1

Extrusion
caltlndtlring

II

..J

Furttitlr
compounding
and dirtlct
(in-lintl)
ftltldlng
to caltlndtlr

~~~~~

Iu~d asftltldstOek for~ 1

'Extrusion
i,Blow
Injtlction moulding
moulding

Rtl-cycling

calJdtlrlng
into

I
I
,

~O~~~I~ ~~~..J

Fig. 13.1 Industrial compounding of PVC: general schematic outline.

Table 13.1 indicates, for some important PVC products, the
proportions produced, respectively, from pre-mix and from pellets as
the feedstock. To interpret the table properly, one should bear in mind
that the production of film, sheet and board, and of products from
plastisols, involves processes with an in-line compounding step
between pre-mix and final product. Thus, in these cases final-product
processing follows directly on the compounding operation, and there is
no need either for pelletising or for the downstream equipment that
normally follows that operation.
The downstream equipment normally employed for pellets and
dry blends handles the cooling, conveying, storage and packaging of the
compound.

13.2 RAW MATERIALS

13.2.1 PVC Polymer and Fillers

In terms of the amounts used in PVC compounding, these are the two
principal solid raw material components; both are in powder form.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

515

r--T------------------,
~
RAW MATERIAL

STORAGE

5
a
w

RAW MATERIAL
HANDLING AND
CONVEYING

!L _~_

RAW MATERIAL
WEIGHING

a::
I t/)

r--T-------I
I
r - - - -.......- - - ,
I

t:

_..w-1

I
l-

Izl
I :::> 1
I
I
I <.9 I
1z 1
101
I z I
1

:::>

I ~ I
101
101

1L _ _ ...i.I

COATING
_

r~T-------I

I ~ I
151

I@I
I

~ I

: ~:
I~ !
I ~I 1
II II
L __

--------1

PRODUCT
COOLING

PRODUCT
CONVEYING

PRODUCT
STORAGE OR
BAGGNG

I
I
I

:
:
I

:
J

Fig. 13.2 PVC compounding: block diagram.

PVC polymer: The characteristics of PVC polymers, and their

significance in formulation and processing, are discussed in Chapters
1-4. From the standpoint of the compounding or extrusion operation,
it is improtant to emphasise those properties that are crucial to the
production of free-flowing, dry powder blends.

._-

.. {9.

D
Fig.13.3 Typical PVC compounding line. 1, Storage silo for PVC polymer; 2,
production or holding silo for filler; 5, storage tank for plasticiser; 6,
station; 8, weighing station for solid components; 9, weighing station for liquid
cooling; 13, storage silo for pellets; 14, bagging and palleting; 15, plant control

-_

t .._

_.1

15

~o ~~C ~
storage silo for filler; 3, production or holding silo for PVC polymer; 4,
production or holding tank for plasticiser; 7, minor components (additives)
components; 10, premixer; 11, melt compounding and pelletising; 12, pellet
system.

518

W. Henschel and P. Franz

TABLE 13.1
Proportions of Important PVC Products Produced, Respectively,
from Pre-mix and Pelletised Compounds (World-wide)

Products

Produced from:
pre-mix (%) pellets (%)

Extrusions
(pipes, profiles, tubes, hoses, siding)
Injection mouldings
Cables
Records
Blow mouldings (bottles)
Film and sheet
Plastisol products

90
25

75

70

100
100

10
75

100
25
30

Table 13.2 lists some of the relevant properties of commercial PVC

polymers produced by suspension polymerisation (S-PVC), emulsion
polymerisation (E-PVC) and mass polymerisation (M-PVC).
TABLE 13.2
Some Properties of PVC Polymers
Polymer type

Properties

Kvalue
(DIN 53726)
Processing
Particle shape
Particle size (/lIIl)

M-PVC

S-PVC

E-PVC

57-71

55-71

65-75
Sprayed
by special
process
Spherical, whole
and broken spheres

Dried with Sprayed

rolls
Riven,
porous
up to
1000

Bulk density (g litre -1) 54~30

(DIN 53468)
Good
Free-flowing
property
15-5
Plasticiser
absorption
(ml DOP per 5 g PVC)

Riven,
porous

Bead-shaped, Flaky
compact,
glassy
60-250
60-250
60-500

4~20

600-700

300

up to
200
30Q--4()()

Good

Good

Good

Poor

Good

J-5

05-1

J-5

up to
60

13

Industrial Compounding Technology of Rigid and Plasticised PVC

519

Fillers: The use and effects of fillers in PVC are discussed in

Chapters 4 and 8. The effect of fillers on the production of hot blends
depends on the loading, particle size and plasticiser absorption. High
loadings of fine-grained filler make blends flow less freely. Fillers with
a porous surface often absorb too much plasticiser, which in turn
results in dry mixes. One positive effect worth mentioning is the use of
very small amounts of colloidal silica for powdering poorly flowing
blends in the cold mixer.
13.2.2 Plasticisers

Plasticisers are the principal liquid components employed in PVC

compounding. The nature and classification of plasticisers, their
properties, applications, and effects in PVC, are discussed in detail in
Chapters 5-7 (also, passim, in Chapters 1, 4 and others).
13.2.3 Other Additives

The other constituents of PVC compositions, which-from the point of

view of compounding-may be regarded as additives to the PVC
polymer, are discussed in Chapter 4: some are also dealt with in
considerable detail in separate chapters or chapter sections, e.g.
stabilisers in Chapters 9 and 10; lubricants, colourants, and others in
Chapter 11.
13.3 UPSTREAM EQUIPMENT (SILO STORAGE
TO WEIGIDNG)
13.3.1 Silo Storage of PVC Polymer and Fillers

Storage of the solid raw material components calls for buildings

designed to house bagged or container goods, or for silo installations.
For economic reasons, preference is normally given today to batteries
of silos capable of holding several thousand tonnes. The lower limit for
economical silo storage of raw material components is a percomponent consumption of about 30 tonnes per month.
(a) Silo Sizes
Silos with capacities of 150 to 250 m3 are generally used for storing
PVC in the plastics industry. Whilst smaller silos are also used, those

520

W. Henschel and P. Franz

with volumes of less than 50 m3 are regarded as uneconomical. This

minimum size is set by the capacity of the rail tank cars normally
employed nowadays for delivering the raw materials from production
plants. The ability to discharge the entire contents of a tank car into an
empty silo in a single operation is essential. Otherwise, unnecessary
waiting time would result for the tank cars.
On the other hand, the maximum silo size depends on the transport
possibilities from the silo fabrication plant to the erection site. If
finished silos have to be transported by road or rail, the acceptable
volume is limited to 150 m3 . Typically, the design diameter of the silo
tank is 24 m, though 35 m silos are built occasionally. Larger
units-up to a volume of 400 m3 for PVC-can only be transported by
water or, if this is impossible, shipped in pieces and welded together on
site.
In the case of fillers (notably chalk), silos of volume greater than
150 m3 are hardly ever employed because of the relatively high bulk
density of the contents.
The size of a battery of silos (Plate B) in a plastics plant depends on
the procurement possibilities for the raw materials, raw material
consumption, the plant's geographic location, and not least the market
situation in the raw material sector.
(b) Materials of Silo Construction
Nearly all the silos erected out-of-doors today are fabricated from an
aluminium/magnesium alloy (AIMg 3). It is fair to say that the steel
silo with internal coating and external paint finish has been displaced
by the standard aluminium alloy silo in the field of PVC compounding.
Aluminium alloys are weatherproof, require no maintenance (as no
paint peels off and no rust develops) and have a virtually unlimited
service life. The plates used have a smooth surface, with a
peak-to-valley depth normally less than 20 f.lm. Silo walls of aluminium
alloy are much less prone to adhesion of contents than those of other
materials. There are no problems with electrostatic charges, because
unpainted aluminium is an excellent conductor of electricity. Because
the external wall reflects well, there is little product heating as a result
of exposure to sunlight.
For some years now, silos as large as 150 m3 have also been built of
glass-fibre reinforced polyester. This material is superior to aluminium
in terms of chemical stability and mechanical abrasion. The disadvantage of static charges causing dust to adhere to the silo wall is
countered by using antistatic additives in the material.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

521

Plate B Silo installation for PVC polymer and fillers.

(c) Raw Material Intake (Silo Filling)

With increasing use of silo storage facilities, the traditional practice of
purchasing solid raw material components in bags or other small
containers is being increasingly replaced by bulk purchase with delivery
by tanker transport. The advantages are:

-less labour;
-no loss of material in transport;
-lower raw material prices;
-no contamination of the materials and dust-free working conditions.
The filling of raw material silos is always accomplished with
pneumatic conveying systems. Both road tankers and rail tank cars are
used. The vehicle tanks are generally designed to resist conveying

522

w.

Henschel and P. Franz

pressures. Compressed air, and not a suction system, is normally used

to empty the vehicle tanks. Screw compressors are used to generate the
required flow of oil-free conveying air. Though most road tankers have
their own compressors, a stationary compressor installation is required
at the plant for emptying rail tank cars. These compressors have a
working pressure between 15 and 25 bar. Air flows lie between 400
and 800Nm3 h- 1 .* With the usual pipe diameters of 80 to 100mm,
depending on the material conveyed, this results in conveying
capacities of 15 to 30 Mp h -1. t
Generally, each silo has its own pipe leading from the connection
point for the filling hose.
In order to retain flexibility with regard to raw materials, and the
ability to handle small batches of different formulations and qualities
smoothly, most plants have an additional dumping station for filling the
storage silos (or holding bins, or both) with bag goods. Because the
amount of bagged goods is usually very small compared with total
plant throughput, a manual dumping station is normally sufficient for
this purpose. The hourly filling rate achievable by manual opening and
dumping of bags is about 3 tonnes. To eliminate bag scrap, it is
generally advisable to follow the dumping station with a suitably
dimensioned sifting machine before the raw material is conveyed
pneumatically to the storage silo through a rotary valve or a pressurised tank. The bag-dumping station must be arranged so that,
instead of escaping, the dust raised during dumping is drawn off to a
filter by a suitable exhaust system. As a rule these bag-dumping
stations are supplied with a built-on filter, so that the filter can be
cleaned mechanically after each filling operation to return the dust to
the raw material.
A proper exhaust system for a bag-dumping station should be laid
out for an air flow of about 20 m3 min- 1 at a vacuum of 200 mm w.g.
The resulting air withdrawal velocity during dumping is about
05ms- 1 .
If, in exceptional cases, larger quantities of bagged raw materials are
expected, it is advisable to plan for a semi-automatic or fully automatic
bag-dumping machine. Such machines are available on the market for
dumping rates of about 600 bags per hour.
Maximum and minimum level monitors are necessary in storage silos
* A German unit = cubic metres per hour at STP (i.e. 20C, one bar pressure).
t Megaponds per hour (i.e. tonnes per hour).

13 Industrial Compounding Technology of Rigid and Plasticised PVC

523

to prevent both overfilling and unplanned emptying. For more

sophisticated demands, it is also possible to use continuously operating
devices to monitor the filling level at all times.
(d) Raw Material Discharge
Raw material discharge is a very important factor in the operation of a
silo facility. Most conical silo outlets are built with a hopper angle of
60. Except for plastics pellets, additional discharge aids must be
attached to the outlet zone for virtually all fine-grained raw materials.
The familiar ability of many pulverulent products to flow freely when
fluidised with air is exploited with the aid of aerating devices. The
suitability of a product for aeration is determined by its bulk density,
angle of repose, grain size distribution and specific surface area.
Aeration plates are built based on a number of different systems. The
surfaces in contact with the product are made of an air-permeable
material. Nylon and polyester are generally used to cover the aeration
plates, but air-permeable ceramic materials, sintered metal, and
polyethylene board are sometimes used instead. Nozzles are occasionally employed to inject the air into the product, but it is important
to design them in such a way that no product can enter the tiny air
channels. Aeration plates are laid out to blow in the air successively in
different sections, thus achieving a pulsation effect. The air must be
completely free of dust or oil. Air pressures as high as 2 bar are
required, depending on material depth and bulk density. The
assumptions generally employed are a specific surface loading of
2-4 m3 of air per minute and m2 of aeration surface. (See Fig. 13.4).
Another important mechanical discharge aid is the vibration plate. It
is particularly suitable for products that tend to 'shoot over'. In such
cases, it is necessary to hold the products back while metering them to
the equipment that follows.
From the storage silos, the raw material components are conveyed
pneumatically to the weighing station. In small plants, this can be
accomplished with a ring pipe and discharge flap above the scale. In
larger plants, the raw materials are transported pneumatically from the
storage silos to the production (or holding) silos. The latter are located
directly above the weighing station in the compounding line.
The raw material components are normally metered into the
pneumatic conveying lines via blow-through rotary valves. Two-cycle
valves are sometimes used, particularly for low-velocity pneumatic
conveying or plug conveying.

524

W. Henschel and P. Franz

VI~W

A-A

v~nl

Qlr conl'lK\lon

flUldlSQ\lon

con~

Fig. 13.4 Storage silo for PVC polymer or fillers.

(e) Dust Removal System
As already noted, virtually all silo storage facilities in the plastics
industry are filled by pneumatic conveying systems. The product is
usually blown tangentially into the tank; cyclones are very seldom used
to separate the product from the air stream. The dust content of the air
differs, depending on silo size, filling level and particle size of the
product. Suitable filters have to be provided to remove the dust from
the air. Most silo installations are laid out with a filter for each tank

13 Industrial Compounding Technology of Rigid and Plasticised PVC

525

unit. The only exceptions are cases where the same product is stored in
a number of silos.
The filters are provided with fully automatic or semi-automatic
purging, depending on the dust loading and throughput. The difference
between the two is that fully automatic filters are purged by dust-laden
air during service, while semi-automatic filters are cleaned only when
the filling operation is complete. Either bag or sheet filters can be
used. The advantage of the sheet filter over the bag filter is that it
occupies less space. For lower dust loadings and coarse-particle dusts,
filters with mechanically actuated purging devices are generally
sufficient. For very highly loaded filters and those handling fine dust,
jet-type filters with pneumatic purging are generally used. In this case,
the dust is purged from the outside of the bags by applying compressed
air at about 6 bar pressure to the inside of the filter elements for
back-purging. Cotton can be used for the filter fabric, but synthetics
such as polyacrylonitrile or polyester are usually favoured. The filter
area to be provided is governed by the admissible filter surface loading.
Rule-of-thumb figures are: in the case of mechanically purged filter
elements, 1 m2 of filter area can handle 1 m3 min- 1 of dust-laden air: in
the case of pneumatically purged jet filters, 1 m2 of filter area can be
loaded with 3 m3 min- 1 of dust-laden air.
13.3.2 Conveying of PVC Polymer and Fillers

As already indicated, any two operations in a compounding process are

generally separated by a transport distance for the solid raw material
components, dry blend, finished pellets, or for recycled process or
start-up waste. The most suitable conveying system has to be found for
each material, depending on flow rate, conveying distance, and special
cleanliness requirements. It is also necessary to consider the material
temperature (and whether it cools down or heats up), as well as the
possibility of its segregation into various fractions. The decision
whether pneumatic or mechanical conveying (by means of screws,
bucket elevators, etc.) should be given preference will be made in the
light of these considerations.
(a) Pneumatic Conveying
Pneumatic conveying, i.e. the transport of bulk materials in closed
pipes with the aid of a stream of air, is standard practice in PVC
processing plants just as it is in other industries. The technique has

-1500

Piston
compressor,
radial
blower

Radial blower

Short to
medium
distances

30

150

Charging pellets into

bins and machines;
removing free-flowing
materials from tips
or containers
Silo filling,
suction pick-up
from grinding
mills

Silo filling

Filling of production or
holding silos from
storage silos or from
bag-dumping stations
Filling of holding silos

Filling of storage silos

from pressureproof tankers

Application

This system offers special advantages in conjunction with such process steps as drying and cooling.

10 000 mm w.g. = 1 kgf cm- 2 .

Suction/pressure
conveyor

Suction conveyor

Vacuum of about
-5000
Piston
compressor

Up to 50
(very limited)

Radial blower

<2000

200

Piston
compressor

4000-8000

Low pressure

Long
distances

Screw
compressor

15 000-25 000

(m)

High pressure
(generally employed
for high conveying
rates)
Medium pressure

Conveying
distance

Operating
pressure
range
(mm w.g.)O

System

Compressor

TABLE 13.3
Main Features of Conveying Systems

Cyclone with
rotary valve,
filter

Cyclone with
rotary valve,
silo filter

Material
delivery

Picked up
by suction

Picked up
by suction

Filter,
cyclone with
rotary valve

(1) Cyclone with

rotary valve,
filter
(2) Vacuum pot
with filter

Rotary valve,
Cyclone with
pendulum flap rotary valve,
filter

Rotary valve

Pressureresistant
silo

Material
pick-up

'"

;::

'"

;::
I'>..

'"

;:,-

"~

a..

Ul

13 Industrial Compounding Technology of Rigid and Plasticised PVC

527

decisive advantages, viz. easy adaptation of the system to a given

building, complete emptying of the conveying pipes, and the entirely
enclosed nature of the conveying system.
CONVEYING SYSTEMS

The basic division in pneumatic conveying is between suction and

pressure systems. There are also combinations, which are generally
known as pull/push systems. The main features of various types of
conveying systems and their applications are summarised in Table 13.3.
CONVEYING MODES

Flow conditions can differ widely in a conveying pipe depending on the

bulk material conveying rate, air velocity, particle size, and pipe
diameter. Four basic conveying modes are recognised: suspension,
stream, plug, and high-density conveying.
Traditional systems work on the suspension principle, with air
velocities between 15 and 30 m s-1, and material loadings up to 30 kg
of material per kg of air throughput. Typically, the individual particles
are distributed virtually evenly over the pipe cross-section and ricochet
from one side of the pipe to the other while being conveyed.
At air velocities in the range 5-15 m S-l, the materials no longer
ricochet; instead, they are pushed through the pipe in the form of
lumps and plugs.
Figure 13.5 illustrates the typical pneumatic conveying modes.
Figure 13.6 summarises the limits within which each of the four
conveying systems works. The basic advantages of the different
conveying modes are listed below.
Suspension and stream conveying:

-relatively inexpensive system,

-virtually all pneumatically conveyable products can be handled,
-<:onveying usually remains effective when products are modified,
-appropriate in cases where no extreme demands arise in terms of
operating time or conveying rates.
Low-velocity conveying:

-gentle treatment of material conveyed,

-avoidance of abrasion (dust, floss),
-low system wear,
-low energy consumption,

528

W. Henschel and P. Franz

Fig. 13.5 Typical conveying modes in pneumatic conveying systems. All

figures refer to a pipe of 100 mm nominal size. * Ratio of particle and air flow
rates (kg h- 1 particle/kg h- 1 air). ** Particle (pellet) velocity.

13

Industrial Compounding Technology of Rigid and Plasticised PVC

529

PrKs.n opftOtoon h.9!:! - dPnSI!y~

Shor1

c~

dlstoncu only

pulvHIAMt to granular products

R~lallVf'

Un$

workIng rang~s of Ih~

four conv~Ylng mod~s
IlIuslral~d In Flg.13.5

SlrfOlM and lumps

0-

PI.....-. opftObon. strfllJ'll

put-.."Mnl products

<l

~"9

'i'
\;V

SuctCln or prKSU'P opftOloon.

SU~Cln

CO!W!Y'..!.'9

granular ond ppllph

producls

",,"surP OpPf'Otoon - P.L"9~g

to tonP gronulor products

Variabl~ ~I

on ConVf'Ylng gas

Fr..

"'"w
'ir'9

Fig. 13.6 Curves of equivalent conveying rate: Generalised representation.

Fr = Froude's number (a dimensionless parameter); W = air velocity (m S-I);
D = pipe diameter (m); g = gravity constant (m S-2).

-low air consumption,

-low dust removal cost,
-stable conveying mode,
-low noise level along pipes and at separator,
-no serious problem with electrostatic charges.
The conveying modes usually employed in PVC processing plants
are the following:
E-PVC: Mostly suspension conveying, but some plug conveying,
because the fine powder cannot stick to the pipe walls when so
conveyed. In the case of suspension conveying, the solids loading is

= 10 kg h- 1 solids
kg h- 1 air

530

W. Henschel and P. Franz

S-PVC: Mainly suspension conveying; solids loading is

kg h -1 solids
20 to 25 k h-1 .
g
au
Fillers: Mainly suspension conveying, though for abrasive materials
such as untreated chalk, plug conveying is possible with solids loadings
of
1

60 to 80 kg h- sol~ds
kg h- 1 au
PVC pellets: Suspension conveying, though ftuidised conveying (low
velocity) is more effective in avoiding pellet abrasion. Pipe diameters
generally lie between the nominal sizes of 80 and 125 mm. Aluminium
alloys are usually used for the straight pipe sections while bends (with
radii between 1000 and 1500 mm) are normally made of stainless steel.

13.3.3 Storage of Plasticisers

(a) Tank Sizes
The installation of storage tanks can become an economical proposition at consumption levels of about 10 tonnes per month of a plasticiser
(or even at 5 tonnes per month in exceptional cases) for the following
reasons:
-lower purchase price for plasticisers,
-easier product handling,
-labour savings,
-less storage space required,
-easier surveillance of stocks.
A storage tank should be large enough to accept the entire contents
of one delivery vehicle. To ensure continuous withdrawal and complete
emptying, however, it is advisable to install a second tank of the same
size or possibly somewhat smaller. Typical storage tanks have capacities of 6, 12 or 24 m3 . If possible, the tanks should be set up in the
production plant to allow withdrawal of plasticiser entirely by gravity,
without using any pump or compressed air. In the case of larger
storage tanks, though, it is more advisable to install the tanks at
ground level: then the plasticiser is pumped into the production or
holding tank with a centrifugal pump (chemical pump), which is set up
in the compounding area above the metering and weighing station.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

531

(b) Suitable Construction Materials

Tanks
-corrosion-resistant steel;
-steel with paint finish resistant to the plasticiser;
-steel, sand-blasted, internal walls sprayed with plasticiser;
-aluminium;
-glass-fibre reinforced Palatal.

Pipes
-corrosion-resistant steel;
-steel;
-aluminium;
-glass-fibre reinforced Palatal.

Valves, ball valves

-corrosion-resistant steel;
-steel;
-aluminium;
-cast iron.

Pumps:
-cast iron.
The pumps should be equipped with single-acting mechanical seals,
because packing cords are attacked by the plasticiser.
(c) Plasticiser Delivery
Small consumers normally receive the plasticisers in drums, and
large-scale production plants in road tankers holding l(~20 tonnes (or,
under certain conditions, in tanker compartments holding 5 tonnes), or
in rail tank cars holding between 15 and 30 tonnes.
Road tankers normally have an outlet nozzle of 80 mm nominal size,
and are equipped with a pump or a compressor for emptying the
plasticiser. Maximum delivery head is 10 m, provided the piping is
straight.
Most rail tank cars have outlet nozzles of 100 mm nominal size. Here
the customer must provide the pump for emptying the car. A properly
dimensioned pump will drain a tank car in about one hour. The storage
tanks should be installed in the immediate vicinity of the siding.

532

vv. lfenscheland P. Franz

(d) Pointers on Pipe Laying

All piping should be laid so that it will run empty into the storage tank.
It is advisable to use 80 mm nominal size piping for empyting the
storage tanks, i.e. for pumping the plasticiser into the production or
holding tanks. If the plasticisers are highly viscous, the piping must be
heated.
13.3.4 Storage of Additives
Processing additives are delivered, and subsequently stored in the
processing plant, in small containers such as drums, bags or the like.
Additives required in the production line are emptied at dust-free bagor drum-dumping stations into the production or holding silos with
capacities between 05 and 2 m3 . These silos are normally made of
stainless steel. The additives are generally withdrawn with the aid of
metering screws, which feed them into the material flow as required by
particular formulations.
13.3.5 Metering and Weighing

(a) Fundamentals of Metering and Weighing Technology

If a material must be removed from a silo or tank at a steady rate, or if

a specified weight or volume must be removed, metering equipment is

required. Accurate metering of the individual raw materials is a crucial
prerequisite of precise formulation maintenance, and therefore of final
product quality. Generally, the raw materials and the final product are
the factors determining whether to meter gravimetrically or volumetrically, continuously or intermittently.
CONTINUOUS VOLUMETRIC METERING

The following volumetric metering equipment is available for raw

material components in powder or paste form, depending on the
physical properties of the product.
-Metering screws (in single-or twin-screw designs): Single screws are
employed in the form of simple helical screws, helical ribbons and
worms, sometimes with supplementary vibration or concentric
spirals in the inlet to break up the product;
-Belt metering devices;
-Vibrating chutes;
-Rotary valves.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

533

Liquid raw material components are metered by means of positive

displacement pumps (piston or gear).
In volumetric metering, high accuracy can be achieved only if the
physical properties of the metered material remain constant. Particulate materials should not be subject to bulk density variation such as
can occur through compaction or fluidisation in the course of filling
and emptying of the silos, or even inside the metering device itself. In
the case of liquids, temperature fluctuations can cause substantial
changes in volume.
Another requirement is that the mechanical and geometrical
parameters of the metering device remain constant. The quantity of
material delivered per unit time is constant if its conveying speed and
cross-section in transit are likewise kept constant. Depending on the
physical properties of the individual materials, volumetric metering
entails weight tolerances between 2 and 5%, or even higher.
Specified formulation accuracies normally do not permit the use of
volumetric metering for assembly of components, particularly where
powders are involved.
CONTINUOUS GRAVIMETRIC METERING

In the case of gravimetric metering-and in contrast with volumetric

metering-neither the various product properties, such as particle size,
particle shape, bulk density or flow behaviour, nor the specified
throughput rate, make any difference whatever. For many years, it has
been standard practice to use belt weighers for this work. Because the
materials can differ widely (pellets, beads, surging or poorly flowing
powders, fibres, etc.), the belt weighers are nearly always equipped
with feeding units that present a pre-metered stream of material to the
weigher. Belt loading is detected continuously by a load cell, and
the metering control system (set-point/actual comparison) keeps the
product weight (belt loading x belt speed) constant at a certain,
pre-selected level. Belt weigher systems work with a short-term
deviation from set-points of the order of 03 to 05%. Metering screw
weighers operate on the same principle.
The operating principle of a differential metering weigher is totally
different from that of the continuous belt weigher or metering screw
weigher. It is a refinement of the subtraction-type container scale that
has been modified to suit continuous operation.
The material being metered is withdrawn from a supply container by
a discharge unit-a metering screw, conveyor belt, vibration chute or

534

W. Henschel and P. Franz

pump. The metering control system operates this discharge device in

such a way that the material removed per unit time corresponds to a
pre-established set-point curve. When the container is empty, the
system switches automatically to a volumetric phase and the container
is refilled with product. During the volumetric phase, the scale's
discharge device operates at the last-established speed. Once the
container is back to maximum filling level, the system switches back to
gravimetric operation.
Despite its obvious advantages, continuous gravimetric metering has
yet to break into the PVC processing industry. One reason is the great
variety of formulations. Besides the large quantities involved (PVC,
fillers, some plasticisers), very small formulation portions, between 05
and 5% by weight, must be processed as well. But even more
important is the fact that the pre-mixing for PVC compoundingdry blend and agglomerate production-still works on the batch
principle. This makes it unnecessary to use continuous gravimetric
metering systems. Figure 13.7 summarises the different batch and
continuous weighing systems.
BATCH WEIGHING SYSTEMS

As a rule, a number of choices is available to a planner of batch

weighing installations, in terms of both weighing and metering
techniques. The decision is not always easy as the relevant evaluation
criteria may vary. Wherever final products are being produced in
automatically functioning systems, accuracy is almost always at the top
of the specification list. In other words, the components going into the
final product, often in widely varying proportions by weight, have to be
added as accurately as possible.
Because modern weighing systems can be produced with very high
resolution, offering high weighing accuracy with static measuring
methods, preference is often given to batch weighing in the layout of
new plants. We have already seen that this is the case in the PVC
compounding field. Three systems are available in current batch
weighing practice (see Fig. 13.8). Together with the various types of
scales, these systems-mechanical, hybrid and electromechanical-give
the user a broad range of alternatives. With the different transducer
systems available, i.e. mechanical and mechanical-electrical, and the
choice of analog or digital technology for analysis and display
equipment, the tendency in modern weighing and control practice is
towards the following combinations:

13 Industrial Compounding Technology of Rigid and Plasticised PVC

535

BATCH WEIGHING

mechanical

batch scales

II
II

hybrid

Ilelectromechanical

floor scales

Ir

vehicle scales

road vehicle
scales

I
I

container scales

solids

railway
scales

I bagging scales I

II

liquids

gross weight
baqqinq

net weight
baqqinq

CONTINUOUS
WEIGHING

I
I differential weighers I I
electromechanical

ICOOJE!'y'OI" belt weighers I

mechanical

belt weighers

lmetering belt weighers I

Fig. 13.7 Batch and continuous weighing systems.

-digital display of weight readings,

-handling separated from the weighing station,
-automatic control functions and calculations with the use of
microcomputers,
-data processing and display unit that can be placed anywhere,
-compatibility with peripheral computer and data processing
installations.

w.

536

Henschel and P. Franz

A.

a
I

~7

B.
f

(9
Ii

!l _._
c.

'

E-l r-icii
II

CJ

_._._ -'

~I

i
i

IL _e_ .

c
Fig. 13.8 Weighing systems. A, Mechanical; B, electromechanical; C, hybrid.
Key: a, load receptacle; b, lever system; c, force detector; d, junction box;
e, cable; f, weight display.

Solid raw material components: Depending on the formulation called

for by the final product, specific quantities of each raw material are
metered into a scale container. In this operation, the smallest possible
batch metering error is determined primarily by the accuracy of the
container scale. The only demands placed on the scale charging
equipment are that it should deliver a roughly continuous flow of bulk
material, and that this should be cut off virtually instantaneously when
the preset weight is reached. The metering accuracy of the piece of

13 Industrial Compounding Technology of Rigid and Plasticised PVC

537

equipment used to charge the scale has no influence on the batch

metering error. Container scales are charged with volumetric metering
devices such as rotary valves, vibrating chutes, single and double
metering screws, metering screws with agitators, or vibrating screws.
To prevent the scale reading from being falsified by the impact of the
falling bulk material, most container scale manufacturers recommend
that the momentary quantity of material during filling be limited to an
hourly rate that corresponds to 60 to 70 times the maximum scale
weight. But if peak accuracies are required in weighing, the maximum
product rate during filling should not exceed 10 times the maximum
scale figure per hour. In other words, a 100 kg scale could be filled
with a metering screw having a maximum product throughput of
1000 kg h- 1 .
In practice, weighing cycles are kept short (1-15 min), and high
accuracy is achieved at the same time by filling in about 90 to 95% of
the prescribed batch weight at the maximum admissible throughput
rate. Then the remaining 5 to 10% of the bulk material is metered into
the scale container at reduced throughput until the final weight is
reached. This approach is known as coarse/fine metering. It is achieved
by equipping the metering screws with a change-pole motor. The
cut-off of product flow upon reaching the preset weight is obtained by
mounting a pneumatically actuated closure flap on the outlet of the
metering screw. It is also essential that the scale container should be
emptied completely after its hatch is opened. This is done by mounting
a beater on the container or installing a flexible venting cloth inside it.
Many weighing errors are traceable to incorrectly installed scale
containers. Every scale container must be able to move freely in the
vertical direction, i.e. all incoming and outgoing pipes must be
attached to the scale container with elastic collars (Fig. 13.9). Efficient
aeration and venting of the scale container are also necessary.
Most PVC compounding plants have several batch weighing
installations. One is required to weigh-in the solid raw material
components according to the formulation (PVC, fillers, possibly
regrind). Scales with weighing ranges from 0 to 500 kg, or 0 to 1000 kg,
are normally found in this part of the plant. The individual components
are withdrawn from the production or holding bins according to a
preset programme in coarse and fine streams, and metered into the
scale container one after the other. The entire process-metering of
the raw material components in a specific order, weighing (set-point/
actual comparison), emptying of the scale into a holding container or

538

W. Henschel and P. Franz

Fig. 13.9 Weighing system for solids. 1, Container for solids; 2, discharge
plate; 3, metering screw, 4, pneumatic closure flap; 5, container scale; 6,
beater, 7, elastic collar; 8, vent.

preparation for pneumatic conveying or emptying of the scale directly

into the premixer, initiation of the mixed weighing process, batch
counting, and finally the pneumatic refilling of the production or
holding bins from the storage silos-runs completely automatically.
The batch weighing installation is rightly called the 'heart' of the
overall production line.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

539

Liquids: Figure 13.10 shows the main metering methods for liquids.
The most accurate metering is obtained by weighing the liquids as
indicated in Fig. 13.lO(A). In this case the material being metered
flows by gravity out of a storage tank into the scale tank, or else is
pumped into it from a lower level. Temperature, density and viscosity
fluctuations have no effect on metering accuracy here. Highly viscous
liquids are usually heated.
Where liquids are metered by volume, as illustrated in Fig. 13.lO(B),
they are again conveyed by gravity or a pump into a collecting tank. In
this case, the feed is cut off when a certain filling level is reached. This
is a very simple metering method, but density fluctuations result in
metering errors. Flow measurement, as illustrated in Fig. 13.10(C), is
based on measuring the volume of liquid delivered by a pump. Because
most flow meters react sensitively to fluctuations of the liquid's

A.

Weoighing

B.

Volumetric measuremeont

- -T-

flowmeter

\
C.

metering
pump

Flow rat~ m~asur~ment

D.

Volumeotric displac~ment

Fig. 13.10 Metering methods for liquids.

540

w.

Henschel and P. Franz

viscosity, metering installations of this type are sometimes heated up to

a constant temperature.
In the approach shown in Fig. 13.1O(D), the liquid pump itself is the
metering device. It delivers a specific volume of liquid at each stroke
with high accuracy. The number of pump strokes is exactly
proportional to the quantity of liquid metered. However, here again
metering failures can arise as a result of density changes in the liquids.
In a modern PVC compounding plant the second batch weighing
installation is found in the plasticiser metering area. The various
plasticisers are circulated from the production or holding tanks via
piping loops by gear-type pumps. Automatically controlled ball valves
direct the flow of plasticiser into the weighing tank. As soon as the
prescribed plasticiser formulation has been assembled in the weighing
tank, it is drained automatically into the downstream mixer or into a
holding tank ahead of the mixer. The plasticiser is called up for
charging into the mixer by the automatic programme control system.
Minor additives: These are the additives whose quantities assembled
for each batch are smaller than the quantity of PVC polymer by one or
two powers of ten, i.e. their total content in the overall formulation is
not more than 10% (and commonly 05-5%). For this reason, the
additives are handled in a number of different ways in the PVC
compounding field. Often they are weighed by hand by one person and
then filled individually into PVC pouches for incorporation into the
particular composition. The pouches are added in the production line
at a minor component station, where the mixing station calls them up
automatically for each batch of PVC. Labour shortages, rising material
and wage costs, ecological problems, and not least the increasing
quality requirements have fostered the development of fully automatic
batch weighing installations for handling the minor additives. Figure
13 .11 shows a concept developed by the Waschle Company. Conceived
along modular lines, the system provides for the metering and
weighing of up to 16 components at a batch weighing station. The 1 m3
containers arranged in a circle around a container scale are filled
manually from bags or drums by means of dust-free bag or drum
dumpers. Refilling of the containers can also be carried out
pneumatically from storage silos or bins. Individually adjustable
discharge and metering screws, which are equipped with a rapidclosing flap, meter the products into a container scale to satisfy the
particular formulation. Scales with several different weighing ranges
are used to enable the batch weighing installation to work optimally.

13

Industrial Compounding Technology of Rigid and Plasticised PVC

541

View A- A

level devIce

A
3000 d,a up to 16 contaIners
of O'S m3 each
3800 d,a up to 16 contaIners
of 10 m3 each

Fig. 13.11 Fully automatic weighing installation for additives.

542

W. Henschel and P. Franz

Control of the weighing procedure, i.e. input of the formulation, can

be accomplished via selector switches or punched cards. The additives
weighed in this manner are called up automatically by the pre-mixing
station for each batch of PVc. Another possibility is to fill the
additives automatically into PVC pouches, after which the pouches are
automatically heat-sealed. This approach has the advantage of allowing
the additive weighing to take place away from the production line.
Here again, the additive pouches are fed into the production line
automatically at a minor component station.
(b) Control and Monitoring Equipment
SYSTEM ACCURACY IN COMPOUNDING PLANTS

Even in a thoroughly planned metering installation, sizeable deviations

can occur under certain conditions. Figure 13.12 illustrates the control
loop for a weighing system.
Very roughly stated, the following sources of error exist in the
individual functions of the control loop:
-mechanical errors in the scale,
-cut-off errors in metering,
-discharge errors during emptying of the scale,
--errors in data input or acquisition.

Ulhmal.
conl,oll.d
,",I .al~

Fig. 13.12 Control loop of a weighing installation.

13

Industrial Compounding Technology of Rigid and Plasticised PVC

543

These potential sources of error deserve a great deal of attention in the

planning of batch metering and weighing systems, because they
represent the most frequent cause of malfunctions. Ultimately,
however, the crucial factors are the extent to which the material
weight obtained from a container weigher agrees with the set-point,
and the extent to which the recorded weight of a batch agrees with the
quantity drawn from the scale. The system error of a weighing
installation is obtained by comparing the deviation between set-point
and the amount actually weighed out with the maximum value of the
weigher's dial. System errors less than 2%0 are possible in weighing
installations with mechanical scale filling.
BATCH ASSEMBLY

As illustrated in Fig. 13.13 the control requirements for the actual

weighing of the components are relatively modest. The output signals
coming from the weighing installation comprise only the momentary
weight readings in digital or analogue form. The only input signals
required are the variables acting on the positioning elements, M1 and
M2, and on the closing device, M3, of the scale container. Only two
connections are required for the set-point input and the real value
recording.
Of course the inputs and outputs multiply with the number of
components being metered. But the factor that really complicates the
control system is the multitude of interlocks among the various
functions and pieces of equipment in a PVC compounding plant. For
one thing, the three batch-weighing installations described in the
foregoing have to be integrated into a master control complex.
The metering procedure in a plant designed along modern lines can
run as follows:
-Switch on plant in general.
-Set all scales to 'automatic'. If necessary, zero taring can be
carried out from the control desk. Automatic starting is only
possible when all scales are at 'zero'.
-Place punched cards in the reader.
-Release mixer filling system.
-Formulation is called for by the mixer control system.
-Metering of the individual components in coarse/fine stream with
'finished' report following the last components.
-Emptying of the individual scales in predetermined order and with
predetermined timing.

w.

544

Henschel and P. Franz

Real valuE'

oj

Convl'ntional
electrical

136

control systeom

247

conVE'ntional
.... eolE'ctrical
-,
control systeom

b)

[=-

Real valuE'
rE'COyding

Ig
0

Fig. 13.13 Control equipment for container scales.

-Transfer of batches (solid components, liquids, additives) to the

mixer calling for them.
-All scales move to 'zero', and the next weighing procedure can be
initiated.
Analog and digital remote displays at the control desk make it possible
to supervise the weighing installations.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

545

Table 13.4 provides a comparison of the main control functions of a

metering and weighing installation with conventional control technology and microprocessor technology.
The simplest type of control system is the one in which all batch
weight inputs are set manually. In this case, the operators perform the
metering and weighing of the materials, i.e. the accuracy with which
the individual components are added to the mixing operation depends
entirely on the reliability of the personnel. Though this system requires
a minimum of electrical equipment, the role of the human factor
makes the error quota relatively high.
In control systems working entirely automatically, all figures
required for the individual formulations are stored in punched cards. A
card reader then transmits these figures to the measuring heads of the
scales and to other measuring instruments and counters. Whilst other
storage systems, such as crossbar distributors, may also be used,
punched cards have proved effective in practice and are the most
common form of storage. In a fully automatic control system like the
one described above, the human factor is largely excluded. Moreover,
the punched cards can be run through once before the actual
production process starts, for verification of the punched figures.
Manual operation is necessary even in the case of fully automatic
control systems as a back-up, however, to allow operators to take a
hand in the process if things go wrong.
One of the most modern types of system is the freely programmable
control system under which all of the data leaving and entering the
weighing installation are fed to a computer unit. The logical sequence
of the successive switching operations, measurements, monitoring
operations and data outputs are laid down in the form of a computer
program. With this system, one can alter or adapt the control
procedure from one's desk.
Virtually unlimited possibilities for control, data acquisition, data
storage and data processing are offered by microprocessors, which are
essentially miniaturised computers and data memories.
Like a freely programmable control system, which is built around a
computer, a control system based on microprocessors is largely
indifferent to the particular application. The functional sequence of the
particular compounding line is described with a computer program and
then programmed. Control changes require nothing more than a
program modification. In microprocessor technology, the number of
data items stored is practically unlimited. Furthermore, a memory can
take on the data for several weighing installations and many different

Simplest scale
control system
for 1 weigher and
few formulations

Material balances

Output of
process data

Storage of
process data
Arithmetic
data processing
Supply of
process data

Formulation input, Digital switch or

potentiometer
weight input
Formulation storage
Selector switch
Component
or digital switch
preselection
Display on weigher
Acquisition of
process data
scale

Control
functions

Printout after
each batch

Remote digital
display of real
weight

Punch card
Punch card

Keypunch

Conventional scale
control system for
a number of weighers
and formulations

After every batch on demand

Sum of cumulated increments, total
Sum of cumulated increments,
each component
Printout after each batch
Printout on demand
Output of process data on screen
Balancing of daily, weekly and
monthly consumption
Inventory control
Quality control
Production control

Microcomputer

Remote digital display, total quantity

Remote ditital display, real weight
each component
Remote digital display, set-point
each component
Batch counter with digital display
Microcomputer

Microcomputer,
call-up via code
Microcomputer
Material matrix

General possibilities

Supplementary
possibilities

Data exchange with

external computers

Error acquisition
and diagnosis

Extension of
control system
for peripheral
functions

Microprocessor technology

Hardware possibilities

TABLE 13.4
Possibilities of Conventional Control Systems and Microprocessor Technology

'"~

""-

So

Vl

13 Industrial Compounding Technology of Rigid and Plasticised PVC

547

components. Formulations can be called up in extremely simple

fashion with code numbers. Individual weighings for a given component can be added as desired to provide a balance of the daily, weekly
or monthly raw material consumption at any time. These figures can
provide the basis for overall production control as well as stock
control.
With all of these possibilities, it is apparent that nothing remains to
stand in the way of the all-automatic, unmanned production operation,
but, like all other technical innovations, microprocessor technology is
still very expensive and accessible only to a few highly skilled
specialists.
At the present time, the freely programmable control system is
simpler to operate and offers nearly the same possibilities by
connecting process computers. The big advantage of both types of
control system is that modifications to the computer programs allow
them to be used indefinitely, regardless of changes to equipment and
processes.
13.4 MIXING
13.4.1 Blending of Bulk Materials in Overall Solid Phase

(a) Introduction
The processing of PVC compositions for the manufacture of products
(e.g. mouldings) or semi-products (e.g. sheeting) always involves
powder blending as an early process step. During this operation PVC
polymer powder is blended with the additives (fillers, lubricants,
stabilisers, pigments, plasticisers etc.) called for by the particular
formulation, plasticated to a greater or lesser extent and gelled, and
possibly agglomerated or pelletised. Depending on the way the
operation is carried out, the resulting blend of particulate formulation
components (and any liquid components present) can take one of the
following three forms, which are then processed further as indicated:
(i)

A free-flowing powder blend, subsequently used directly for

processing into products or semi-products.
(ii) A free-flowing agglomerate, suitable for subsequent direct
processing into products or semi-products.
(iii) A powder blend that is only relatively free-flowing: blends of this
type may subsequently be either melt-compounded and pelletised, with the pellets then being used in the production of

548

W. Henschel and P. Franz

products or semi-products; or melt-compounded for subsequent

direct conversion of the compound-by calendering-into sheet
or film.
A basic distinction is made between cold blends and hot blends. The
cold mixing of rigid PVC composition merely results in interdispersion
of the individual components of the mixture. In the cold mixing of
plasticised compositions, absorption of the plasticiser by the PVC
particles takes place in addition to the interdispersion process. The
mixing temperature in both these cases generally remains below 50C.
Cold blends are produced in slow-speed, unheated mixers. They
require long mixing times and are not dry, particularly where the
plasticiser content is relatively high. For this reason, their use is
recommended only in cases where the blend does not have to be
free-flowing or thoroughly dispersed, Le. where further plastication
will take place in subsequent melt processing on mixing rolls, in an
internal mixer, screw-type kneader or extruder.
The mixing with simultaneous heating of a PVC composition to a point
below the softening temperature is referred to as hot mixing, and the
product as dry blend, dry powder, fluidised powder, powder compound, pre-mix or dry mix. These terms are used rather loosely, and
there are no standard definitions. In some cases it may be clear what
mixing state is meant, but considerable confusion can also arise.
In hot mixing, the temperature is raised to 100C or higher. In the
case of rigid PVC this enables lubricants and liquid stabilisers to be
absorbed by the PVC polymer particles: in the case of plasticised PVC,
plasticisers are also similarly absorbed. The result in either case is a
dry, free-flowing blend.
The production of hot mixes involves the use of heatable, slow- or
high-speed mixers, in either case in conjunction with a cold mixer.
If the temperature of the hot mix is raised so that it is heated above
its softening temperature, a PVC agglomerate is formed as groups of
primary particles clump together to form enlarged secondary particles.
Agglomerate formation does not, however, involve a melt stage.
Agglomeration is obtained in mixers working with high-speed mixing
tools: it becomes attractive where difficult mixing functions are
involved, such as the incorporation of large percentages of plasticiser
or filler, and where the possibility of segregation before the next
process step is to be minimised.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

549

CONTINUOUS DRY BLENDING OF PVC COMPOSITIONS

Conventional dry blending in the hot or hot/cold mixers is a batch
process. One-step, continuous dry blending of uPVC and pPVC compositions has now also been introduced (inter alia for direct feeding of
extruders-d. Chapter 19, Section 19.3). Equipment developments
include an adaptation for powder blending of the Buss MT Turbine
(see pp. 657-9), and the Thyssen Henschel horizontal mixer Kontinuum TKlD250.

(b) Theoretical Aspects of Mixing, with Special Reference to Dry

Blending of pvc Compositions
In the simplest case, mixing implies the presence of at least two
substances with different characteristics. These may be totally different
substances, or variants of the same substance differing merely in
physical properties (e.g. particle size), temperature, or the like. In
more complex cases, a number of constituent substances may be
required for the desired final mixture.
The job of the mixer is to combine the substances in such a way that
extremely small samples of the mixture (of a size appropriate to the
particular application) do in fact contain the constituents in proportions as close as possible to those aimed at. Wherever mixing is done
on a commercial basis, i.e. by machine, the actual proportions will
always differ to some extent from the theoretical ideal.
The optimum mixture achievable in mechanical mixing is referred to
as the ideal random mixture: this can be calculated for specific
materials and mixing ratios. Samples can be taken from an actual
mechanically mixed composition to determine whether the ideal
random mixture has been approximated in the desired degree. The
methods of statistical probability are an important element of this
sample-taking and checking, and are integrated into the calculations
employed.
PHYSICAL STATE OF THE MIXTURE COMPONENTS

Table 13.5 shows how the difficulty of mixing materials in plastics

processing varies as a function of the physical state of the mixture
components.
EFFECT OF THE PHYSICAL PROPERTIES OF THE MIXTURE MATERIAL

The mixing process is greatly affected by the physical properties of the

mixture material, such as particle size, structure, angle of repose,

w.

550

Henschel and P. Franz

TABLE 13.5
Effect of the Physical State of Components upon the State of the Mixture and
Difficulty of Mixing
Physical state
Main components

Additives

Mixture

Solid
Solid, coarse-grained
(granulate)
Solid
Solid
Solid

Solid
Solid, fine-grained
(powder)
Liquid, viscous
Liquid, thin
Liquid

Liquid

Solid

Liquid

Liquid, viscous

Liquid,
viscous
Liquid

Liquid, viscous

Liquid

Liquid

Liquid

Liquid

Liquid

Degree of difficulty
in mixing

Solid
Solid

Easy
Fairly difficult

Solid
Solid
Liquid

Difficult
Fairly difficult
Easy to difficult,
depending on
particle size of
solid component(s)
Easy to fairly
difficult
Fairly difficult
to difficult
Easy to fairly
difficult
Easy

cohesion and adhesion to other components, adhesion to the working

surfaces of the mixer, melting point, softening point, electrostatic
properties, and moisture absorption. Any of these properties can be
decisive in the selection of a particular machinery system, and all
influence the level of sophistication called for.
DETERMINATION OF MIXING EFFECTIVITY: SAMPLING AND SAMPLE SIZE

In the plastics industry the effectivity of mixing is often judged merely

on the basis of final product reject rate, or material behaviour during
final processing. But since many other variables are involved, it is
impossible to tell on this basis whether difficulties have arisen as a
result of inadequate mixing accuracy or as a result of other factors
outside the mixing operation. Special measures should therefore be
taken to monitor the quality of mixing, particularly as the effect of this
on the final product can be much greater than generally assumed.
The obvious approach is to take samples and determine the
percentages of the individual components. This usually means
separating the components again. If such a separation is no longer

13 Industrial Compounding Technology of Rigid and Plasticised PVC

551

possible, colorimetry can be employed in cases where a new colour is

produced by mixing the components. Another method is to add test
components, but these should behave very similarly to the components
being mixed. Very reliable results are also obtained by mixing-in
isotopes, which are later counted with suitable equipment.
Sample size should be suited to the particular end product involved.
The larger the samples can be, the less critical are any errors, starting
with metering and moving on to mixing technology, sample taking and
evaluation.
Basically, to ensure comparability the sampling point should be
located within the mixer and the gross size of the sample should be
kept constant. The direction in which the sampling device is inserted
into the mixture also affects the results, particularly in the case of
large-scale mixing. When samples are examined, it is generally
sufficient to show that the minimum acceptable percentage of each
prescribed component is present.
SIDE EFFECTS OF MIXING

Energy consumption: The efficiency with which the energy employed

in mixing is used, as measured in terms of the uniformity of the final
blend, is extremely low-just as it is in size-reduction operations. The
bulk of the energy is converted into acceleration energy and heat. The
objective should always be to do the necessary job with the lowest
possible energy consumption per unit of final blend.
Temperature rise: The effects of heating as a result of energy
conversion differ greatly from one type of machine to another, as do
the final blend temperatures reached in different mixers. The shorter
the mixing time, i.e. the time required to impart the necessary mixing
energy to the material, the less time is available for loss of heat, and
the sharper the temperature rise. It has been found that suitable
intensification of the mixing operation in high-speed mixers is an
excellent way of heating up the material, so that heat need not be
introduced from external sources. Energy conversion in the mixture
can be increased by speeding up the mixing tools and altering their
configuration.
Particle size reduction: In the ideal case mixing should not change
the type or size of the particles being mixed. But because any

552

W. Henschel and P. Franz

commercial mixing process involves mutual abrasion or collision of the

particles, even the gentlest one results in a certain amount of particle
size reduction. Seldom occurring as actual particle breakage, this
phenomenon is generally a matter of extremely fine particle abrasion
as a result of 'circular grinding' of the particles. If there is a tendency
towards agglomeration in a mixture of fine powders, the forces
responsible for size reduction can break down the agglomerates under
certain conditions, which is entirely desirable.

Machine wear: During the mixing process, the material moves in

relation to the mixing chamber wall and the mixing tools. Wear of
these machine parts is therefore unavoidable. The degree of wear
depends partly on the material being mixed and very much on the
speed of the mixing tools. In general, the higher the speed the shorter
the mixing time but the greater the wear, because the wear usually
increases more than in direct proportion with the speed of the moving,
wear-inducing material particles. Virgin polymers normally cause very
little wear, but many fillers speed it up sharply. Wear and the desired
mixing tool speed are criteria in the selection of a mixer for a particular
process.
Bulk density change: Because of particle size reduction and abrasion,
some densification takes place in many cases, i.e. the bulk density of
the mixed material rises. Where such densification is desirable,
high-speed mixing machines are usually employed; but it can also be
achieved by partial agglomeration of the particles as a result of product
heating through energy conversion.

Particle segregation: In the mixing of particulate solid components,

continuous segregation is superimposed on the mixing operation
proper. Where components of sharply differing particle size are being
mixed (coarse granulate with powdered colourants or coarse granulate
with extremely small beads), the effect can be serious enough to make
successful mixing nearly impossible. In many cases it becomes
necessary to use certain additives in order to reduce or eliminate the
tendency to segregation.
Other side effects: Other side effects inevitable in any mixing

operation are those of adhesive, cohesive, and repulsive forces.

13

Industrial Compounding Technology of Rigid and Plasticised PVC

553

Because these forces tend to act selectively, they hinder the actual
mixing process. In some cases they can even render optimal mixing
impossible.

(c) Mixers for Plastics Processing

Virtually every type of mixer system on the market finds some
application in plastics processing. This section deals with mixers for
bulk materials in the solid overall phase, applicable to PVC
compositions. Mixer systems for primarily liquid phases used in the
production of plastisols are discussed in a later section. A mixing
operation is integrated into every kneading process for compounds in
the highly viscous, viscous/plastic, or paste-like overall phases handled
with internal mixers, screw-type kneaders or extruders. This aspect,
too, is dealt with in a later section.
GENERAL CLASSIFICAnON

Fundamentally, one can distinguish between two types of mlXlng:

mechanical mixing and pneumatic mixing. Mechanical mixers may be
subdivided into two groups: those with rotating containers and those
with rotating mixing tools. The static mixer may also be mentioned at
this point for the sake of completeness. Another classification can be
based on the mode of operation, i.e. whether the mixer operates
continuously or intermittently. Figure 13.14 lists and illustrates mixers
working on the batch principle.
MECHANICAL MIXERS

Mixers with rotating containers:

Operating principle: In rotating containers, the free-flowing bulk
material is carried along by the tank wall by means of friction, and
raised up, until it flows back down the incline formed (bulk cone). The
cascade motion produced at low speeds becomes a cataract motion at
higher speeds, whereby the particles are intermixed more intensively
and the mixing time is considerably reduced. All mixers of this type
produce a continuous interleaving and re-forming of the material,
which is thus repeatedly divided and reunited in a different
arrangement. The mixing process takes place virtually without shearing
forces and affords gentle product handling.

1&

1....1

T_1hel1
moeer

mixer

00l.tlIe ..".

1::-

a GyrootleeI
~-

Dn.wn
tumbler

belrrel

TlA'IlIlIong

Name

II. . . .

m,xong

IoIIrbcal scr_
solo lTIIXer

Orbbng_bcd
SC,....., lI'OXer

Low-I!l"d
tank mtx.,.

HIgh-speed
tonk m.....

Olonge-Qlf'I

nux..

I'IougI-.hore

A>ddle lTIIXer

mix.,.

RIbbon bar

m_r

...

II

~II

~-

~
~

f5?:l

II'"

II

~JkSi
IIOX.

mIX8'f'.

muun;

gronulat.

m.xlng

granulat.

c::dd

cold nuxer

hot mlx

PVC po5t"

cold

holnuxor

or

--

cold m,_

PIIC QlllllocotiOn

~- -

lI~trohon

with rotohng mixer tool

HMICoI rlbbon

Nome

lY0nulat.

pr-ong

pc>UIbly lor
oddll....

PIIC Qlllllocobon

""xer

c'rcUobng

PneumatIC

Name

j
ll~trotiOn

miXing

granulot.

P/C Qlllllcobon

PNEUMATIC MIXERS

Fig. 13.14 Batch mixers for bulk material in solid overall phase.

JS2D

~
n'\./
"1

Ml

~
~

ll~trotiOn

wrth rotating ITlIxer contolner

MECHANICAL MIXERS

'"

:"tI

;::

l:>

~s.

"'"

Ul
Ul

13 Industrial Compounding Technology of Rigid and Plasticised PVC

555

Applications in the processing of PVC:

-Pre-mixers for mixing plastic pellets with masterbatch pellets for
the colouring of PVC on injection extruders or cable insulation
extruders.
-Post-mixers for mixing PVC pellets following compounding and
prior to packaging for the purpose of batch homogenisation. This
makes it possible to equalise production-related quality variations.
Large-volume mixers such as double cone, tumbler or vee mixers
are used for this purpose.
Table 13.6 lists the main technical features of the mixers with rotating
containers shown in Fig. 13.14.
Mixers with rotating mixing tools:

Operating principle: The different mixer designs can be divided into

three groups on the basis of peripheral speed (Vu ):
slow-speed 'push' mixers with V u < 2 m S-l
slow-speed 'throw' mixers with Vu = 2-12 m S-l
high-speed intensive mixers with Vu = 12-50 m S-l
In the slow-speed push mixers, the mixing tool displaces the material
to the front and the side, so that it flows back into the resulting empty
space behind the tool and becomes mixed. The material is treated
gently and hardly any size reduction occurs.
If the speed of the mixing tool is raised until the centrifugal force
exceeds gravity, we have the throw mixer. The material particles are
thrown upwards by the mixing tools, follow intersecting trajectories,
and are thus mixed together. Mixing times are much shorter than they
are in push mixers.
Unlike push mixers, which are nearly filled with product, throw
mixers are filled to only about 60 or 70% of their volume, to provide
sufficient free space into which the mixture components can be thrown.
Velocity differences between the various trajectories produce frictional
forces that can help break up agglomerates, but friction-related
product stressing and heating remains within reasonable limits.
Still higher mixing tool speeds do not result in shorter mixing times,
but raise the energy absorption, with resultant heating of the material,
an effect that is desirable in many cases. Peripheral speeds between 30
and 50 m S-l are common in high-speed intensive mixers. The mixing

Twin shell mixer

(vee)

Wobble miX aod }

double cone mixer

Gyrowheel mixer

PVC application

Granulate mixing

Possibly for
additive premixing

Tumbling banel aud

drum tumbler
mixer

Name

50-10

2-30
60-70

50-10
(2-3)

2-30
(up to 60)

50-70

3-40000
(max. 100000)
2-30000

30-20
(up to 10)

5-10

50-75

30-20

Commonly
5-300
(max. 900)

5-10

(min)

Speed of
mixing
container
(r min-i)

50-75

(%)

(litres)

Mixing time

50-300

Filling level

Size,
total volume

TABLE 13.6
Technical Data for Rotating-tank Mixers

01--40

01-50
(up to 100)

01-10
(up to 30)

05-10

(kW)

Drive power

;:,

I:>

:-t'

;:,
I:l..

I:>

;:,~

(")

0\

Ul
Ul

13

Industrial Compounding Technology of Rigid and Plasticised PVC

557

tool produces an intensive impact effect, which tends to break up

particles besides dispersing the material components.
Applications in PVC processing (see Fig. 13.14):
-As hot or cold mixers for the blending of raw material
components. This function can be performed by helical ribbon
mixers, ribbon bar mixers, paddle mixers or ploughshare mixers.
It is also often carried out by tank-type mixers, alternatively
known as intensive mixers, fluidising mixers or turbo-mixers.
-Change-can mixers and orbiting vertical screw mixers are used for
the preparation of PVC pastes.
-Vertical-screw silo mixers are used for after-mixing of PVC pellets
following compounding for batch equalisation.
Table 13.7 and Fig. 13.15 contain the main technical data for the
mixers with rotating mixing tools shown in Fig. 13.14.
Because tank-type or intensive mixers are extremely important in
the processing of PVC, a detailed description of this type is provided in
the next section.

(d) Tank-type or Intensive Mixer

DESIGN AND OPERATING PRINCIPLE

Tank-type or intensive mixers, which are also known as turbo,

high-speed, or fluidising mixers, are used mainly as batch mixers for the
pre-mixing of the PVC raw material components to form a free-flowing
powder blend. Among the best-known designs are those marketed by
the following companies: Batagion, Caccia, Covema, Diosna, Fielder,
Thyssen, Mixaco, Moritz, MTI, Papenmeier, Spangenberg.
Tank-type mixers with high-speed mixing tools are generally built
with cylindrical tanks arranged vertically (Fig. 13.16) or horizontally.
Inside the tank, the mixing tools are mounted on a vertical or
horizontal mixing shaft. The tools, which generally operate at
peripheral speeds between 20 and 50 m s -1 differ depending on the
mixing job and manufacturer. They may take the shape of radial flights
in the form of bars, knives or propellers, or they may be ring-shaped or
paddle-shaped. In the vertical design, the tank bottom is either flat or
dished, and the ratio of tank diameter to height is approximately 1: 1.
The Diosna design employs two cylindrical tanks joined together to
form a figure-of-eight shell, which is equipped with two separate drives

Category

Helical ribbon mixer Cold mixer or

hot mixer
Ribbon bar mixer } Cold mixer in
combination
Paddle mixer
with hot mixer
Ploughshare mixer
Hot mixer
High-speed
tank mixer
Cold mixer
Low-speed
tank mixer

Name

60-70
40-50
80-90
40-50

200{}-{)000
100-3500
10-1500
25-4500

5-12

5-10

5-12

15-30

Size,
Filling level Mixing time
total volume
(litres)
(%)
(min)

TABLE 13.7
Technical Data for Rotating-tool Mixers

350-50

1000-250

350-100

50-15

rotational
(r min-I)

(10)
8-4

50-20

10-4

15

peripheral
(m S-I)

Mixing tool speed

15-45

3-300

5-45

10-25

(kW)

Drive power

U1
U1

;,.

s:>

:"t'

s:>
;,.
I:>...

00

13

Industrial Compounding Technology of Rigid and Plasticised PVC

559

, ....-1
5000

.000
3000

2000
1000
500
.00
300
200
100

50
.0
30

20

10
5

o-l---+--.-;..--I--...-----4-------l---;

:;m

.al

800

Mlx~r

800

1lXXl

tZlO

1.00

1800

1800

:IOOOmm

dl<lm~l~(

Fig. 13.15 Speed ranges of some mixers with rotating mixing tool.

and two separate, counter-rotating sets of mixing flights. This doubles

the useful volume with equal or better mixing quality, whilst staggered
starting of the two drive motors avoids high current surges. Another
interesting design is the Moritz 'Turbosphere' mixer (Fig. 13.17). In
this, the use of a spherical tank and large-diameter agitator forces the
material to run along the sphere wall in uniformly thin layers. The
result is a thorough comminution of the individual layers, which
promotes the dispersion and mixing effect. It also makes for
much-improved heat transfer between the material and the heating or
cooling medium circulating in the jacket. The spherical configuration

560

W. Henschel and P. Franz

Fig. 13.16 Tank or high-intensity mixer.

Paths of
product

mov.m.nl

Fig. 13.17 The Turbosphere intensive mixer (Moritz).

13 Industrial Compounding Technology of Rigid and Plasticised PVC

561

affords positive self-release of the material from the tank wall: build-up
on the internal wall surface is thus made more difficult, and cleaning of
the tank is facilitated.
The mixing tank of an intensive mixer is usually provided with a
jacket for heat control, and can be equipped with degassing
attachments. High-speed intensive mixers of the tank type are
sometimes built with a removable mixing tank or with a machine
superstructure that can be raised and lowered. The latter includes the
tank cover, rotor with mixing tool, and the entire drive.
The mode of operation of the intensive mixer stems from the speed
and shape of the mixing tool. The material particles are accelerated so
sharply by the mixing tool that they exceed the aeration velocity of the
fixed bed and are fluidised. The high peripheral speed of the mixing
tool imparts impact and friction forces to the material in the tangential
direction and centrifugal forces in the radial direction. The latter drive
the material against the tank wall in such a way that it can only escape
upwards: upon reaching the cover, it falls back into the centre of the
tank, which has been emptied of material. The result is the familiar
whorl of material, i.e. a circulating flow that is otherwise found only in
liquids.
Intensive mixers with long mixer shafts and high-set mixing tools
provide larger useful volumes (up to 90% of the total volume) than
low-set tool combinations (Fig. 13.18).
The high-speed mixers just described are generally used for batch
mixing, with drive ratings of 04 to 06 kW per kg of material. For
emulsion PVC blends with high percentages of plasticiser, drive ratings
as high as 1 kW per kg of material are employed. Extrapolation of

"
MIXing tool set high

MIXing tool set low

Fig. 13.18 Product whorl resulting from mixing tool setting.

562

W. Henschel and P. Franz

these drive power levels indicates that high-speed mixers are

economical only up to certain sizes. The largest known high-speed
mixers on the market have a tank volume of 1000 to 1500 litres, which
corresponds to a PVC batch size of about 800 kg.
In order to convey dry blend or agglomerate efficiently, and to be
able to store it at all, one must cool the heated product down to
storage temperature. Theoretically it would be possible to cool the
batch down in the high-speed mixer, but this would be unsuitable and
unprofitable in production practice. Moreover, the alternating stresses
on the machine in continuous operation would shorten its service life
considerably. Since it is obviously desirable to cool the dry blend or
agglomerate down to the storage temperature (40C to 50C) in the
shortest possible time to avoid thermal degradation, and because cold
shock is known to improve the free-flowing properties, it becomes
necessary to employ separate mixers in series, the so-called hot/cold
mixer combinations (Figures 13.19 and 13.20). Optimisation of this
Hot mixer
5PHd at 1001
Vu =20-S0 ms"

~"p~al

Fig. 13.19 Hot/cold mixer combination with hot mixer vertical and cold mixer
horizontal.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

563

-,

Cold m,"rr

:/

r~s

Joe rt lor
wolrr

eool~

:
:
-- --j
":.:: =:"

Fig. 13.20 Hot/cold mixer combination with both hot mixer and cold mixer
vertical.

combination in the production process dictates that both mixers should

operate with the same cycle times, and hence-because PVC is a poor
heat conductor-the cooling mixer must have a much larger volume:
this is usually two to four times that of the hot mixer, and the tank is a
cylinder arranged either vertically (whorl or plate mixer) or horizontally (throw mixer). The overall arrangement of the two units is
generally stepped, with the hot mixer placed high up on a machine
frame and the cold mixer set in front of it. Unlike the hot mixers
(intensive mixers), the cold mixers operate with tool peripheral speeds
of the order of only 4 to 8 m S-1.
Cold mixers are equipped with jackets for circulation of water as
cooling medium. Their mixing tools are relatively simple, and are
sometimes hollow to permit circulation of cooling water. The cooling
area is increased by installing water-cooled jacketed segments or baffle
rings inside the tank, i.e. directly in the flow of the PVC blend
undergoing agitation (Fig. 13.20). These inserts also direct the material
onto the cooled bottom at the centre of the tank. Some cold mixer
designs employ cooling air blown into the mixer with fans, in addition
to the water-cooling system. Whilst providing about 30% of the cooling
capacity, and thus reducing costs, the cooling air also serves to

W. Henschel and P. Franz

564

eliminate the undesirable condensation that often occurs when water is

used as the sole cooling medium.
The design principle of the cold mixer is aimed at providing as much
cooling surface as possible for rapid cooling. Relatively little product
movement is required for the heat transfer. The amount of heat
dissipated per unit time declines with rising mixing tool speed and
product velocity: when these reach sufficiently high values the material
is no longer cooled at all, because the amount of heat generated by the
energy of motion becomes equal to or greater than that dissipated
through the cooling surfaces.
Hot/cold mixer combination units are offered with various degrees
of automation. Frequently the basic control system is designed for
manual operation, but can be switched to the semi-automatic mode for
emptying the unit when the preset material temperature is reached.
More sophisticated systems are equipped with fully automatic process
control based on material temperature and time, and linked to the
overall plant control system. Data input is read-in either with punched
cards or programmable process control systems.
PROCESS ENGINEERING

Variables in the preparation of blends: Besides producing the PVC

composition, the mixing operation is intended to impart those
properties to it which will facilitate problem-free storage, conveying
and processing in the particular process. The most important of these
properties include:

(i)
(ii)

(iii)
(iv)
(v)
(vi)
(vii)

homogeneous dispersion of the individual components throughout the blend;

blend dryness, i.e. all additives, such as stabilisers, lubricants,
etc., should be comminuted, homogeneously distributed and
melted, and liquid additives such as plasticiser should be
worked into the PVC polymer particles: any existing moisture
should also be driven off;
good free-flowing properties;
low moisture absorption;
no tendency to segregate;
increased bulk density;
good shelf life of final blend.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

565

The main variables affecting the achievement of these properties

are: mixing tool shape, mixing tool speed, temperature of the material,
filling level of tank, and pressure in tank.
The mutual suitability of PVC and high-speed mixer processing is
remarkable. The polymer has to be combined with a great variety of
additives, into a wide range of compositions, and yet-because of its
thermal sensitivity-its 'heat history' must be kept to a minimum. These
objectives are achieved simply, efficiently and economically in
high-speed mixers, utilising the polymer in the form in which it is
produced (i.e. powder). The importance of external plasticisation,
coupled with the polymer's ability to absorb plasticisers on heating,
have been prime factors in the development of high-speed mixers.
Slow-speed mixers-which work with mixing tool peripheral speeds
only up to 10 m s-l-are not a viable alternative, as they are unable to
deliver a dry, free-flowing and sufficiently homogeneous blend after a
short period of mixing.
Mixing tool shape and setting: Mixing tool profiles have to be
designed to prevent undue overheating of the material and build-up on
the mixing flights. Tool profile is extremely important in high-speed
mixers in conjunction with the peripheral speed, which-as already
mentioned~an lie between 20 and 50 m s-1. Because the peripheral
speed determines the energy transmittable to the product, it is an
important factor to consider when selecting a mixing system. As the
peripheral speed of the mixing tools rises, so do the overall velocity of
the material particles, their velocities relative to one another, and the
resulting friction. This creates a solids-laden air stream that permits
sharp impact between PVC particles and metal if sharp-edged or
non-aerodynamic tools are used. Poorly designed tool profiles
therefore make it possible for build-up of mix components to occur at
the flight tips and their trailing edges where the material becomes
overheated. Scorching can also occur if the individual PVC particles
are heated by impact against the mixing tool: as this continues, the
stabilisation of the PVC may prove inadequate and flecks or streaks of
scorched material will appear in the final product.
To prevent overheating, it is important that flow along the mixing
tool surface should be uniform, enabling material particles lying
directly in the path of a mixing tool flight to evade it and follow the
flight profile without undergoing excessive impact or friction. For these

566

w.

Henschel and P. Franz

Fig. 13.21 Mixing tool cross-section.

reasons, the profile of an efficient mixing tool should be aerodynamic
(Figure 13.21), so that its flights allow the particles to flow off rapidly,
and overheating of material on its surface is consistently avoided.
The aerodynamic profiling and peripheral speed of the mixing tools
are matched, to provide rapid and intensive energy transfer to the
product, so that little time is required to produce fine blends and
homogeneous agglomerates with high bulk density and good flow
properties.
The angular position, projected surface and spacing of the individual
flights should be set optimally in relation to the mixing tank diameter,
so that the resulting flow forces prevent any material build-up on the
mixing tool and tank wall.
Power input and temperature pattern; general aspects of the process
sequence: The sequence of events in a high-speed mixer can be
described as follows: When the machine is started, turbulent
movement of material is set up immediately and the mixing of the
individual components begins. The material is spun against the tank
wall by the mixing tools and forced upwards. Thus it leaves the area of
the mixing tools, following a toroidal path to the centre of the tank, to
the bottom and back to the mixing tool area. Whilst undergoing this

13 Industrial Compounding Technology of Rigid and Plasticised PVC

567

horizontal-vertical motion in the direction of tool rotation, the

material starts to heat up.
Unlike some softer materials, particulate PVC is not comminuted to
any great extent when subjected to impact, friction, and high
mechanical stressing. The main effect is on the particle surfaces: sharp
corners and protruding fibres are flattened or bent over. As a result the
particles become smoother and rounder. This reduces the flow
resistance (and-to some extent-the size) of the individual particle.
The mechanisms contributing to heat build-up are:
-friction between material and mixing tool;
-inter-particle friction;
-friction between air and mixing tool;
-friction between material and tank wall;
-heat transfer from heated tank wall to air and material;
-heat generation by moving air and product;
-radiation heating.
The mixing progress is quasi-adiabatic, as the material is heated
primarily by the mechanical energy imparted by the effective surfaces
of the mixing tools (measured as the projections of flight surfaces at
right-angles to the direction of rotation) and by the mutual impacts of
the particles. Compared with these effects, the other heating
mechanisms contribute relatively little to the heat build-up.
If the mixing tools are properly designed, external heating (by means
of a heating jacket) is required only in certain cases; for example it is
advantageous where emulsion polymer is being mixed with a high
percentage of plasticiser.
Formulae are available describing the relationship between, on one
hand the power imparted by the mixing tool, and on the other, such
factors as the mass of material in the tank, the active tool-flight
surface, the height of material in the tank, the difference between tool
speed and product velocity, and the actual speed of the mixing tool.
Such a formula shows that the power input (and hence also the
mixing time) can be changed by modifying the effective mixing tool
surfaces, and even more sharply by altering the tool speed (see also
Fig. 13.22).
As the quality demands specified for final products become ever
more stringent, gentle treatment becomes increasingly important at
every stage of processing, and above all during mixing. The best way to
make mixing more gentle is to reduce the peripheral speed of mixing

,..- I

6,36
20,2
40.3
Effective (projected)flight area

oI

1.25 I

6O.5cm 2

:J
I

01
C

Q.

...

a>

min.

m:Q653 kg
39.5

r;:
40,3
6,36
2Q2
Effective (projected) flight area

~:

P: 760 Torr

60,5cm 2

Fig. 13.22 Power input and heating-up time to 90C as functions of the projected area of the mixing tool flights. No,
power consumption of the mixing tool without material (kW); N, total power consumption of mixing tool with material
(kW); P, pressure in the pre-mixer; OK, shell wall temperature.

Q.

t~

.E

'[ 2,5

kW

3,75 I

;:

I:>

;:
I:>..

I:>

";:,~

i;

Vl

13 Industrial Compounding Technology of Rigid and Plasticised PVC

569

tools. In this case, of course, the shape and configuration of the tools
must be adapted to the lower mixing speeds.
The mixing of a rigid PVC composition will normally proceed as
follows. The associated changes in power input (motor amperage) are
shown in Fig. 13.23.
The particulate components are homogenised by the turbulent
mixing motion immediately after the high-speed mixer motor is
switched on. As this occurs, the mechanical energy of the mixing tool
is converted into heat by material friction. The friction, and particle
impacts, bring about the particle surface changes previously mentioned
and the material flows more freely, causing the energy consumption
level to drop until a temperature of about 8SoC is reached. Around this
temperature the lubricants melt, and the material becomes sticky andflows
less freely, which again raises the energy consumption; this peaks when
the liquefied lubricants are being absorbed by the PVC grains:
thereafter the material again flows more freely and the energy
consumption falls. Another energy peak, this time a small one, is
observed at temperatures above 12SoC when the metallic stearates
melt.
A

I
I
I
I

III
Blending time

IV

VI VII :I
min.

Fig. 13.23 Power input during the blending of rigid PVC in a high-speed
mixer. Phase I, mixing and abrading; II, increase in free-flowing property; III,
melting of lubricants; IV, dry mixing; V, melting of metallic stearates; VI, hot
mixing; VII, cooling of blend in cold mixer.

I
5

10min.

f"/

15

I
I

20

tl50

:r

40-+

60-t

80

100

A! C

I \

1\

10min.

-----

--

15

-A

_oc

I
20

Fig. 13.24 Amperage input and temperature as functions of blending time in a high-speed mixer. A, Emulsion PVC
blend with 35% plasticiser; B, suspension PVC blend with 35% plasticiser. (Source: L. Schaffel, G. Spangenberg Co.)

oI

20-+

404

604

150

200

100

80

:>

~
l:l

l:l..

:>

l:l

'";:s~

Vl
-..J

13 Industrial Compounding Technology of Rigid and Plasticised PVC

571

When the motor amperage levels off, the mixing operation is over
and it is time to discharge the material into the cold mixer. Continued
mixing in this temperature range, but below the melting point of the
PVC, would merely impair the flow properties as a result of further
size reduction, accompanied-perhaps surprisingly-by a drop in bulk
density. Thermal degradation would also be initiated.
Changes in material temperature in the course of mixing are
illustrated, for various PVC compositions, in Figs 13.24-13.27.
Figure 13.24(A) shows the energy input and temperature curves of
an emulsion PVC blend with 35% plasticiser. In this case the cold
plasticiser was fed continuously into the preheated mixture. The start
O(OC)

120
110
100
90
80
70
60
50
40
30
20
10
0

10

11 I (min)

Fig. 13.25 Temperature change in a high-speed mixer as a function of

blending time. 1, S rigid PVC; 2, E rigid PVC; 3, S plasticised PVC 30% pi; 4,
S plasticised PVC 40% pi; 5, S plasticised PVC 50% pi; 6, E plasticised PVC
40% pI. (Source: Herfeld Mixaco.)

23'

A -.

o
Cool,n<l I,me

8m,n

Heohn<l lime

9m,n

17

Fig. 13.26 Temperature as a function of time in a hot/cold mixer combination (at approx. 15C cooling water inlet
temperature). A, Rigid PVC pipe blend; B, plasticised PVC shoe compound. (Source: MTI.)

60

70

80

90

100

110

120~

C
130

VI

i:l

s:>

s:>..
~

~
s:>
;:s

~
~
9-

id

60

10

20

30

40

UIII'I:;"

4
5

--

~ 1- ..... ~

1-

Blending and heating-l4' time

I'll...

.-

10

1-

11

Cooling time

I",

12

14

17

'. ~-

Cooling time

16

15

,~

~plasticised

IIV"IU ..........

"'

...

13

,.~

........

,~

"Coil""

~ ........

L/ I'

" "-

I~'

W'

~ l

Blending and heating-l4' time.

"

=vr

I"

t;'ITIUlV,IN

rigid PVC-/

IILI,nll.

18

~.

19

,...~

PVC

20

2 min.

Fig. 13.27 Temperature as a function of time in a hot/cold mixer combination. (Source: J. Bornemann, Rheinstahl
Thyssen.)

ell
~

f 50

Q.

Gi

~ 80
2 70

90

100

110

120

130

VI

-.]

"'tl

'"

!:;.

::>::I

~
~

;::

So

~o

......

574

W. Henschel and P. Franz

and finish of plasticiser feeding are apparent from the energy input
curve. Figure 13.24(B) is a similar plot for suspension polymer, but
with the cold plasticiser charged all at once into the mixture. Again,
the point at which this took place is reflected in the temperature and
energy curves.
Both diagrams indicate that the quality of a blend is affected by the
method and timing of the plasticiser addition. To obtain homogeneous
dispersion of the plasticiser, it is necessary to achieve a mixer
temperature of 70 to 80C. In this temperature range, the PVC
particles swell and absorb the continuously fed, and possibly
preheated, plasticiser more easily.
Figure 13.25 shows the temperature changes as a function of mixing
time for rigid and plasticised PVC with various amounts of plasticiser.
Figures 13.26(A) and (B) show the temperature curves, respectively,
for a rigid PVC pipe blend and a plasticised (60:40) PVC shoe
compound blend, both processed in a hot/cold mixer combination.
Figure 13.27 illustrates, in a generalised and highly simplified form, the
temperature changes of rigid and plasticised PVC compositions as
functions of mixing time in hot/cold mixer combinations.
Among factors contributing substantially to the achievement of
optimal properties in a PVC composition are the timing, sequence and
method of additive admixing, as well as the speed programme of the
high-speed mixer, mixing time and final temperature. It is therefore a
serious mistake to underestimate mixing technology and to regard the
mixing step as an unimportant preliminary to subsequent processing.
Influence of raw material components and processing conditions on
the properties of hot blends:
-PVC polymer. Particle structure, shape and size affect the blend
flow properties. Suspension and bulk polymers with porous
particles absorb the plasticiser easily. Fine-grained emulsion
polymers containing emulsifier, and their large-grained clusters
which are broken down in the mixer, usually result in pasty stock
when the plasticiser is added: this can only be used to produce
agglomerate.
-Type of plasticiser. Dry mixes are difficult to produce with
plasticisers of limited compatibility (which are poorly absorbed by
the polymer particles), and with slow-gelling plasticisers. Primary
plasticisers with good gelation effect give the best results.
-Plasticiser quantity. This is a crucial factor in producing a hot

13 Industrial Compounding Technology of Rigid and Plasticised PVC

575

dry blend. The maximum amount of plasticiser that the hot mixer
will tolerate depends on the type and K value of the polymer, as
well as the plasticiser type. In some cases high percentages of
plasticiser can only be handled by hot mixers to produce
agglomerate. The temperature of incipient agglomerate formation,
and then that of lump formation, decreases with increasing
plasticiser content. In other words: the higher the plasticiser
content, the lower the admissible final temperature. Cold mixing
at high plasticiser contents will normally result in damp or wet
mixtures lacking the ability to flow freely.
-Plasticiser viscosity. This mainly influences the diffusion rate into
the PVC particles (see Fig. 5.3 in Chapter 5). Medium- to
high-viscosity plasticisers therefore require longer mixing times,
unless their viscosity is reduced by heating before addition.
-Admixing the plasticiser. Understandably, it makes a difference
whether the plasticiser is placed in the mixer first and the solid
components then added or whether it flows into the cold or hot
pre-mix of the other components, and whether its introduction
into the running mixer is made in one shot, in portions, or
continuously. The best results are obtained by allowing the
plasticiser to flow slowly into the pre-mix of the solid components
at an elevated temperature (about 7o-S0oq. The feed rate should
be set in such a way that the amperage drawn by the drive motor
does not rise sharply. After the plasticiser has been added, mixing
should be continued for about one minute to make sure all of it
has been completely absorbed. If plasticiser is added to suspension
or bulk PVC of medium absorption capacity faster than it can be
absorbed by the particles, a highly viscous paste will form which
will then gel to produce large, tough lumps if mixing is continued.
This may cause the drive to cut out because of overloading: in any
case, the mixture is unusable and cleaning of the mixer is
unpleasant and time-consuming.
-Mixing temperature and mixing time. Mixing time depends upon
the required final temperature, which is given in the temperature/
time diagrams earlier in this section. For high-speed mixers it
ranges between 10 and 20 min, depending on the formulation and
whether a hot or hot/cold mix is involved. A reliable rule-ofthumb is that a temperature rise of more than 15C min -1 should
be avoided during mixing: otherwise local overheating can damage
the mix. Furthermore, the correct final temperature of the mix is

576

W. Henschel and P. Franz

also affected by the type and quantity of plasticiser employed, as

well as by the K value and particle structure of the polymer. It is
set correctly when the cooled blend emerging from the cold mixer
is dry and free-flowing.
-Lubricant: The effects of lubricants in the hot mix depend upon
their physical state (solid, liquid, paste), compatibility, melting
characteristics and quantity. A liquid lubricant (e.g. paraffin oil)
can produce a sticky, non-flowing hot mix if it is poorly compatible
with PVC and becomes concentrated on the particle surface.
PVC-compatible liquid lubricants are absorbed into the particles
with the plasticiser, unless the amount added exceeds the
compatibility limit. The melting range of solid lubricants should be
chosen in such a way that (1) the lubricant is molten before the
final mixture temperature is reached and is dispersed
homogeneously throughout all of the material, and (2) the solid
physical state has already been regained after the material has
cooled down to the cold mixer temperature (about 40C).
In the case of rigid PVC blends, all formulation components
except the lubricant are mixed at low speed: then the speed is
raised, and the lubricant is added about 20C below the desired
final temperature.
For the production of hot mixes, it is therefore advisable to
combine PVC-compatible internal lubricants with solid external
lubricants in the required melting range.
-Fillers: The effect of a filler on the production of hot mixes
depends on its amount, particle size and plasticiser absorption.
High percentages of very fine-grained fillers impair the freeflowing property. Fillers with porous surfaces usually have
undesirably high plasticiser absorptions, but, on the other hand,
promote dry mixes. Mixes poorly flowing in the cold mixer can be
improved by the addition of very small amounts of colloidal silica.
APPLICATION OF INTENSIVE MIXERS

Either high-speed mixers (hot mixers) or hot/cold mixer combinations

are used, depending on the production route followed for the final
product.
Hot mixers (high-speed mixers): Hot mixers are normally used alone
ahead of pelletising machines and for direct processing of PVC powder
blends. The advantages of hot mixing of PVC powders in high-speed

13 Industrial Compounding Technology of Rigid and Plasticised PVC

577

mixers are:
-optimal mix quality and homogeneity;
-short cycle times and high output rates;
-very free-flowing blends;
-pneumatic conveying of dry blends or agglomerates without
product segregation;
-up to 20-40% increase in bulk density as a result of sintering, thus
raising the output rates of processing machines;
-low-cost and effective lowering of the residual VC content, partly
because of the high mixing temperatures of more than 80C;
-nearly complete elimination of residual moisture in the material.

Hot/cold mixer combinations: Hot/cold mixer combinations have

won wide acceptance among PVC compounders in the past 15 years.
As already mentioned, they enable the hot mix from the high-speed
mixer to be transferred directly into the cold mixer and cooled down to
about 4Q-50C, whereby unnecessary 'heat history' (and hence thermal
degradation) of the material is avoided, tendency to agglomeration
during storage is counteracted, and the free-flowing property improved
by the cold shock.
Hot/cold mixer combinations are used both for feeding pelletising
extruders and for direct processing of the PVC powder blend for use in
injection moulding and blow moulding.
Virtually all rigid PVC blends are produced on hot/cold mixer
combinations, even if pelletising follows.
During mixing of suspension and bulk polymers, high friction
sometimes produces an electrostatic charge in the material, which
impairs flow properties, especially in batches with relatively low bulk
densities. One way to eliminate the charge is to cool the mix rapidly to
about 40C in the cold mixer. For certain purposes, e.g. the production
of large pipes, crystal-clear blown films and similar sensitive products,
which have to be absolutely free of moisture, the PVC batch can also
be de-gassed during mixing. This can be done by using vacuum mixers
or by blowing or drawing dry, filtered air under the hot-mixer cover
during the final phase of the mixing process.
13.4.2 Melt Compounding
In some production processes, such as the manufacture of records or
the extrusion of pipe and profiles, it is sometimes possible to use

W. Henschel and P. Franz

578

pre-mixes, produced as described in Section 13.4.1, directly as

feedstock for the processing machines. However, where only limited
homogenisation is achievable in the processing equipment (such as for
example, simple extruders, light-duty and heavy-duty calenders), or if
a simple pre-mix is not acceptable as feedstock (by reason of particular
material-handling arrangements or feed requirements), or where
stringent quality specifications for the final product necessitate the
highest degree of homogenisation of the composition, the material
must be melt-compounded.
Table 13.1 indicates the percentage of melt-compounded PVC used
in the main application areas. While dry blending interdisperses the
formulation components uniformly on a macroscopic, and down to the
microscopic scale, the level of interdispersion produced by melt
compounding may be described as microscopic to sub-microscopic, and
largely intermolecular for those components which are sufficiently
compatible. This degree of dispersion optimises the effectivity of
additives combined with the PVC resin in the composition. It can only
be achieved when the resin is in an elasto-viscous (melt) state during
the compounding: this is brought about by thermomechanical means.
PVC is a heat-sensitive material. The extent of thermal decomposition in processing depends on stock temperature and residence time, as
illustrated by Fig. 13.28; therefore both must be carefully controlled in
the compounding process. In this, thermomechanical stressing of the
PVC polymer changes the structure of the original particles and hence

104.11
T.mp.,otur.

UNACCEPTABLE FOR EXTRUSION

(OC)

EXTRUDABLE AND WEATHERABLE

2S

50

75

Uillmot. Proc.sslng TI_ (1041.....1)

100

AREA OF HEAT HISTORY

IN BUSS COMPOUNDING
AND PELLETISING LINES TYPE IIG

Fig. 13.28 Influence of processing conditions ('heat history') on the

processability and performance of melt-compounded PVc.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

579

the rheological behaviour of the material. Raising the stock temperatures and residence times results in more severe structural disruption,
and unravelling of the macromolecules, ultimately leading to a higher
degree of gelation. Where pellets are being fed to an extruder, for
instance, a higher degree of gelation requires higher melting energies
during extrusion. Because modern final-processing extruders are
pushed to the performance limit, raising the melting power may make
certain extrusion operations unprofitable as a result of reduced output.
Thus the compounding process has to be matched to the operating
conditions in the final processing (production) step, whilst achieving its
fundamental objective, viz. the maximum homogenisation and degree
of dispersion of the additives in the PVC resin, with the lowest possible
input of thermomechanical energy and minimum residence time, so
that the 'heat history' (and hence degradation) of the resin is kept to a
minimum.
Besides homogenising the composition, compounding converts it
into a physical form suitable for subsequent processing. In recent
years, too, sharply increased processing speeds on calenders and
extruders have added effective de-gassing of the PVC compoundoriginally effected on mixing rolls and in internal mixers-to the list of
the functions of compounding.
Whilst they are still in use in laboratories and in some small-scale
operations, mixing rolls and internal mixers find only limited
application in present-day industrial melt-compounding of PVC, which
is now largely the domain of screw-type compounding machines.
Continuous compounding on such equipment was introduced about 30
years ago with a view to better control of residence times, improved
efficacy of mixing, reduction of compound quality fluctuation (and
hence better reproducibility), process rationalisation, and elimination
of the effects of chance in batch and intermittent operation. In view of
this, the discussion in this section is confined to compounding processes
involving continuously operating screw-type machines.
In such machines, 80-90% of the energy required for fluxing the
polymers and homogenising the mixture is obtained by the conversion
of mechanical shearing energy. Only 10-20% of the total energy
requirement is provided by heating the barrels and screws. The main
job of the heating system is to ensure that the screw and barrel surfaces
in contact with the material are kept at a desired set-point
temperature; inter alia this prevents overheating and scorching of the
PVC stock as a result of wall slippage: thus the heating system must be

580

W. Henschel and P. Franz

capable of both supplying and dissipating heat. For this reason systems
based on the circulation of liquid heat-transfer media, such as water or
HT oil, in screws and separate barrel zones have gained wide
acceptance in industrial practice.
(a) Compounding and pelletising
Both rigid and plasticised PVC compositions are melt-compounded.
The general types of compound produced are shown in Fig. 13.29. The
characteristic curves of various rigid and plasticised PVC compositions,
obtained on a high-pressure capillary rheometer (Fig. 13.30), demonstrate the wide differences in rheological behaviour that have to be
coped with during the compounding process to obtain the necessary
degree of gelation.
The graph shows that with plasticised PVC compositions high
outputs are obtained within a relatively narrow (and generally low)
pressure range. This applies in melt compounding, so that-in the
context of this process-plasticised PVC may be regarded as relatively
insensitive to pressure and shear. For rigid PVC the graph shows a
pronounced influence of pressure on output, i.e. in this sense rigid
PVC compositions are sensitive to pressure and shear. Because energy
dissipation in screw-type machines is essentially a function of shear rate
and system pressure, adjustment of the degree of gelation of rigid PVC
calls for special elements to control these parameters in this kind of
equipment (see also further discussion below).

MELTCOMPOUNDED
PVC
COMPOSITIONS

FLEXIBLE

BOTTLE
EXTRUSION CABLE
COMPOUNDS COMPOUNDS COMPOUNDS

INJECTION
MOLDING
COMPOUNDS

EXTRUSION
COMPOUNDS

Fig. 13.29 Melt-compounded PVC compositions.

13

Industrial Compounding Technology of Rigid and Plasticised PVC

plasticised PVC
[k~] Oulpul

581

rigid PVC
6

21)

1,5

1,0

0,5

10

20

30

40

so

60

70

Fig. 13.30 Characteristic flow curves of some PVC compositions in a capillary

rheometer. 1, Shoe compounds; 2, water hose compounds; 3, general-purpose
extrusion grades; 4, cable compounds (insulation, sheathing); 5, 6, 7,
blow-moulding compounds; 8, general-purpose extrusion grades; 9, 10, profile
compounds; 11, window profile and siding compounds.
Both rigid and plasticised PVC are compounded for pelletising by
essentially the same process (Fig. 13.31). The free-flowing PVC blend
from the pre-mixer passes through a holding bin before being charged
into the feed hopper which serves as a product surge bin and a
volumetric metering element. In some cases the hopper is designed
additionally for powder de-aeration, but this does not eliminate the
need for de-gassing the fluxed stock. An agitator with suitably shaped
arms is employed in the upper part to prevent bridging (Fig. 13.32). A
separately driven twin-screw metering device is sometimes used below
the hopper (as, for example, in the feed section of the Plastifikator
machines). An alternative is to add a vertical metering screw to the
bottom of the agitator, a concept employed, for instance, in the design
of the Buss-Kneader and the Kombiplast machine. In either case, the
speed of the metering screws determines the volumetric flow of
product fed into the screw-type machine. In the intake zone of the
machine the metered blend is picked up and carried along to the
plasticating and homogenising zone. In this zone, part of the total
shear energy is converted into heat and the PVC is fluxed (plasticated).

582

w.

Henschel and P. Franz

Fig. 13.31 PVC pelletising: flow sheet. 1, Silos for solid components (resin,
filler); 2, tanks for plasticisers; 3, discharge and conveying devices; 4,
plasticiser supply pumps; 5, batch weighing station for solid components; 6,
batch weighing station for plasticiser; 7, pre-mixer; 8, compounding and
pelletising unit; 9, vacuum pump; 10, pellet cooler.

FEED HOPPER WITH

HORIZONTAL TWIN SCREW

FEED HOPPER WITH

VERTICAL 51 GLE SCREW

Fig. 13.32 Typical feed hopper designs.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

583

Another portion of the shear energy is used for breaking down and
dispersing the additives. The ways and means of imparting the energy
to the material are discussed in Section 13.4.4(a) ('screw-type
machines').
Homogenisation is one of the three objectives of the compounding
process, the other two being de-gassing and conversion of the
compound into a form suitable for further processing. In practice,
cylindrical pellets with diameters of 25-4 mm and lengths from
1 to 4 mm have proved optimal for feeding final processing machines.
To produce the pellets, it is necessary to force the plastic PVC stock
through a multi-hole die plate. One way to do this is to incorporate in
the screw-type machine a suitable metering and pumping zone, and to
mount the pelletising die plate directly on the end of such a machine.
This approach represents a rigid combination of compounding and
forming (i.e. pelletising).
Research and development work started at the end of the 1960s
demonstrated, however, that the optimal design and operating
parameters for compounding and forming, respectively, are often
diametrically opposed, so that it makes more sense to separate the two
stages clearly from one another in high-production compounding lines.
This approach resulted in the development of two-stage compounding lines, with one screw-type machine for compounding and a second
one for pelletising. Usually the pelletising screw is set up in cascade
fashion following the compounding screw. Pelletising machines are
normally single-screw designs, but the compounding step may be
handled by either single-screw or multi-screw machines. In some
cascade compounding units, the homogeneously fluxed PVC stock
drops in lump form through a connecting tube from the outlet end of
the compounding stage into the feed opening of the pelletising screw.
Vacuum can be applied to the connecting tube to de-gas the PVC
stock.
The pelletising screw proceeds to build up the pressure required for
extruding the compounded stock through the pelletiser's die plate.
With this separate arrangement, design and process parameters such as
speed, shear and temperature profile can be selected in such a way that
a minimum amount of energy is dissipated during the forming phase,
which is probably the most critical phase of the entire compounding
process.
As already mentioned, when compounding rigid PVC compositions
it is necessary to control effectively the system pressure in the

584

W. Henschel and P. Franz

BUSS-KNEADER

REGULA TlNG SCREW

PELLETISER

Fig. 13.33 Back-pressure control by regulating screw.

compounding stage in order to maintain the desired degree of gelation

in the PVC pellets. This control may be achieved in various ways.
Buss-Kneader compounding lines of the KG type employ a regulating
screw in place of the connecting tube between the compounding and
pelletising stages (Fig. 13.33). The speed of this 25 LID single screw is
separately and infinitely variable: its adjustment provides accurate
control over back-pressure in the kneader, and hence over energy
dissipation in the homogenisation zone and therefore over the stock
temperature and degree of gelation.
On the twin-screw ZSK Kombiplast machines both screws can be
shifted axially with a gear motor and adjusting spindle. This moves the
kneading elements at the discharge end (Fig. 13.34, shaded area) into
the outlet orifice to a greater or lesser extent, so that the back-pressure
can be varied infinitely without stopping production.
Another approach to controlling pressure conditions is adopted in
the twin-shaft MPC/v system. Two 'barrel valves' are employed (Fig.
13.35), one in the kneading disk area and the other at the discharge

Fig. 13.34 Back-pressure control by adjustable outlet orifice.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

585

Centreline
olugilulol shults - -

Fig. 13.35 MPCN barrel valve.

end. This kind of valve constitutes a movable saddle-shaped cut-out in

the barrel. When the valve body is turned manually, the saddle is set at
right angles to the direction of product flow, which closes the gusset
space between the two shafts and causes the pressure to build up. In
the open position the saddle piece in the valve body is lined up with
the barrel saddle, thus offering the least resistance to stock flow.
All three arrangements allow the composition to be de-gassed in
transit to the pelletising screw.
Two basic cutting arrangements are available for pelletising~entral
cutting and side cutting (Fig. 13.36). Side cutting has gained wide

KNIFE SHAFT At-() DIE PL ATE CONCENTRIC

KNIFE SHAFT NEXT TO DIE PLATE

Fig. 13.36 Basic cutting arrangements in pelletising equipment.

586

W. Henschel and P. Franz

acceptance among compounders because of the favourable cutting

conditions it provides. In both methods the plasticated PVC strands
forced through the multi-hole die plate by the pelletising screw are cut
into pellets by rotating knives on the outer surface of the die plate.
Pellet length can be changed by altering the speed of knife rotation.
The die head is enclosed in a collector casing that catches the pellets
chopped off on the die plate, pre-cools them, and feeds them to the
pneumatic conveying system.
Because of their relatively high melt viscosity and low stickiness,
most rigid and plasticised PVC formulations can be pelletised 'dry' by
the hot die-face cutting method, i.e. room air is sufficient for cooling
and conveying.
In special cases, such as heavily plasticised formulations for the shoe
industry or for medical purposes, record compounds with high vinyl
acetate content, or bottle compounds with low K value polymer, it may
be necessary to counteract pellet sticking by supplementing the
pre-cooling in the collector casing and the conveying line with low
levels of water mist. In this case, water and compressed air are mixed
in a mixing valve (Fig. 13.37) and injected into the collector casing.
The spontaneous evaporation of the water affords an additional
cooling effect, and prevents any direct contact between the PVC
pellets and free water. A flow meter is used to control the amount of
water atomised.
Particularly in the cable industry, impurities such as fibres, wood
chips, paper cuttings, etc., which enter the compounding process in the
raw materials, can seriously impair product quality and affect
profitability. It is therefore becoming common practice in the cable

COMPRESSED AIR

~+-"'T'"-DC::.t---

WATER

PNEUMATIC PELLET CONVEYING

Fig. 13.37 Water-mist cooling of cut pellets.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

587

DIE PLATE

PACK

Fig. 13.38 Die plate with strainer.

industry to filter such impurities out of the composition during
compounding. Because the contamination level is generally relatively
low, it does not always pay to use an automatic screen changer. An
economical solution is to insert behind a pelletising die plate a
sandwich screen pack consisting, for instance, of two 20 mesh support
screens flanking a 60 mesh strainer screen (Fig. 13.38). The die plate
must be designed to accept this screen pack. Experience has shown
that the screen pack has to be changed once per working shift. The line
is shut down, the die head swung out, and the contaminated screen
removed.
Wire and cable insulation is normally coloured all the way through.
The cable industry prefers to colour the cable with pigment
concentrates or masterbatches, which are normally prepared from a
complete pre-mix with all components. A compounding unit must
therefore be capable, in addition to its normal compounding duties, of
dispersing pigments in high concentrations uniformly without
streaking.
One aspect of masterbatch production is the preparation of
semiconductor PVC compounds, in which carbon black loadings as
high as 30% are dispersed in the PVC mixture. In this case, too, a
complete pre-mix of all components is supplied to the compounding
unit.
Apart from cable applications, these compounds are also used for
producing antistatically finished PVC film and sheet.
Another special demand placed on compounding technology by the
cable industry arises from the trend towards increased use of

588

W. Henschel and P. Franz

crosslinkable polyethylenes, either the traditional, peroxidically crosslinkable polyethylene or Sioplas (developed by Dow Corning, UK). A
modern compounding line must therefore be sufficiently versatile to
compound and pelletise these crosslinkable polyethylene compounds as
well as a broad range of PVC formulations.
The specific energy normally dissipated in the compounding step
is about 006-008 kWh kg- 1 for rigid PVC formulations and 004006 kWh kg- 1 for plasticised PVC formulations. In the forming step, i.e.
in the pelletising screw, additional specific energy is expended for
pressure build-up and extrusion of the PVC stock through the die
plate. A rule-of-thumb from actual practice indicates that the specific
energy requirement for extrusion through the die plate equals about
1/10 to 1/5 of the energy dissipated during compounding. The
introduction of energy causes the stock temperature to rise as it moves
through the kneader. Figure 13.39 shows typical stock temperature
profiles for various PVC formulations.
Compounding lines now available on the market cover a production
band from 100 kg h -1 to 6 t h -1. Besides these production units,
scaled-down laboratory units are offered for formulation development
and colour matching as a basis for production. Such units must employ

T (e)
200

180

160

140

120
100

eo
60
40

20

I.ENGlH

('tttot )

Fig. 13.39 PVC pelletisiing: temperature profiles. 1, Record compounds; 2,

plasticised PVC; 3, rigid PVC; 4, rigid PVC, US grades.

13

Industrial Compounding Technology of Rigid and Plasticised PVC

589

the same mixing and homogenisation process as their production

counterparts if the results are to be convertible.
(b) Compounding of pvc for Feeding Calenders
Calendering is a major process for the production of continuous film
and sheet. In this process the compounding step is arranged in-line, i.e.
the process runs from raw material through compounding to film or
sheet forming on a continuous basis.
The operation stages of a calender line as outlined in Fig. 13.40 must
therefore be well matched to form an integral, interconnected system.
These stages are common to regular calender lines, coating lines and
light-duty calender lines, so the following remarks on the calendering
process are intended to cover those processes as well. Because the
calender is essentially a forming machine with no substantial mixing or
homogenising effect, the compounding section must fulfil the
following functions in the interconnected system:
-fluxing of the polymers and homogenisation of the stock;
-achievement of an optimal degree of gelation for the calendering
process;
-de-gassing of the stock and straining (where necessary);
-conversion of the fluxed stock into a form suitable for feeding the
calender.
The provision of feedstock by the compounding section must, at any
given time, match the calender's throughput rate.

Fig. 13.40 Block diagram of a calender line.

590

W. Henschel and P. Franz

These requirements apply to the entire range of PVC film and sheet
formulations, which can be classified into three main groups according
to their plasticiser content:
-rigid (substantially without plasticiser);
-semi-rigid (10-25% plasticiser-Shore A hardness 95-85);
-plasticised (25-40% plasticiser-Shore A hardness 85-60).
For plasticised PVC film and sheet, a standardised calendering
practice has emerged in which a 'rolling bank' is set up in the calender
nip.
In the case of rigid PVC, processed at temperatures higher than
those in plasticised PVC lines, one of two calendering methodsrespectively known as the high- and low-temperature processes-may
be used, depending on the type of sheet or film being produced.
In the high-temperature process, the calender bowls are heated to
progressively higher temperatures with-typically-the intake bowls at
about 160C, and the last nip at about 210C. The film or sheet is then
passed through the usual cooling roll train.
In the low-temperature process the reverse heating order is used.
The temperature drops from, say, 175C at the intake to 145C at the
last bowls, i.e. the fluxed stock is formed in a relatively cool state.
Normally, the films produced by this method are fed directly to an
orienting calender, where they are heated rapidly on melting rolls
heated to about 240C, and then cooled sharply down to 110C. This
provides optimal film orientation. Known under the name of the
'Luvitherm process', this low-temperature process has gained acceptance in Europe for the production of tearproof films.
The calendering method also determines how the temperature will
be controlled in the compounding step. For the high-temperature
process, the PVC stock must be delivered to the calender fully
plasticated; for the low-temperature process, it should be barely
plasticated (crumbly), i.e. it has to be fed to the calender at a lower
temperature.
The calender design is determined essentially by the type of film and
sheet to be produced on it. The design determines, in turn, the overall
layout, position of the compounding unit relative to the calender, and
the necessary conveying and feeding elements.
Figure 13.41 shows the bowl arrangements in various four-roll
calender types. At the present time, the 'L' and inverted 'L' (also
called 'F') types are dominant.

13

(i)

(iv)

Industrial Compounding Technology of Rigid and Plasticised PVC

(iI)

(v)

591

(Iii)

(vi)

Fig. 13.41 Bowl arrangements in 4-bowl calenders. (i) Inverted 'L' type
(sometimes referred to as 'F' type); (ii) 'z' type; (iii) inclined '5' (or 'Z') type,
down-stack; (iv) inclined '5' (or 'Z') type, up-stack; (v) 'L' type; (vi) vertical
stack. Arrangements (i), (ii) and (iii) are widely used in PVC sheet production.

From a development history rich in tradition, two basic methods for

feeding calenders have emerged:
-direct feeding;
-feeding through a set of mixing rolls (two-roll mill) set up
between compounding unit and calender.
The mixing rolls are still justified where sport runs and a broad range of
formulations are handled on a given calender line. In this case the
mixing rolls serve as a material-surge unit, keeping the stock hot. This
makes it possible to change formulations without any interruption of
the calender operation in some cases. By passing through the roll nip
repeatedly, the stock can also be de-gassed to a limited extent.
However, it is necessary to keep the stock temperature in the

592

W. Henschel and P. Franz

compounding step lower because of the additional work done on the

mixing rolls and the longer retention time of the PVC stock at elevated
temperature. The endless ribbon of PVC emerging from the mixing
rolls is slit and fed to the calender in endless strips.
With direct calender feeding, which is undoubtedly the most
economical solution in terms of capital investment, labour and space
requirements, no mixing rolls are used. This type of feeding is
appropriate mainly for the processing of large runs and relatively
limited formulation ranges. The job of the compounding unit in this
case is to gel the PVC stock to the degree required for the calender
and to de-gas it effectively.
Whether the calender is fed directly or via mixing rolls, the stock is
delivered to the intake nip by conveyor belts. A separate wig-wag belt
is sometimes used just before the calender to achieve better
distribution of the stock acrosss the intake. These conveyor belts have
to be selected carefully with regard to thermal and abrasion resistance;
otherwise the stock can be contaminated and the quality of the PVC
film or sheet impaired. Another point to watch is that bits of metal can
sometimes enter the calender line with the raw materials. The
consequences of even the smallest metal particles entering the rolls of
the mixing bank or the calender can be much more serious for the
machinery than for film or sheet quality. To avoid such damage, it is
essential to set up a metal detector, capable of picking up
non-magnetic as well as magnetic particles, between the compounding
unit and the calender. Normally, the metal detector is located at the
beginning of the conveyor belt. Whenever it responds to a bit of metal
in the PVC stock, the belt is thrown into reverse for a preset period of
time to eject the foreign object.
It is a feature of the calendering process that the throughput varies
widely. The variation may be deliberate or random (sporadic). The
deliberate variation is a consequence of changes in (range of)
formulations and qualities handled on the calender line. These
determine calendering speeds and film or sheet gauges: since the full
width of the calender is normally used, the throughput (and hence feed
supply) required can be calculated roughly from calendering speed and
film or sheet gauge.
The random, momentary throughput variations stem from the nature
of the calendering operation. To ensure trouble-free running, a certain
amount of stock should always be maintained on the mixing rolls or at
the calender intake. Because degradation is a function of the intensity
and duration of heating (retention time) this buffer should be kept to a

13 Industrial Compounding Technology of Rigid and Plasticised PVC

593

minimum. If it starts increasing in size, the throughput of the

compounding line must be cut back, and vice versa.
Despite various attempts, no satisfactory method has been found as
yet to measure the buffer stock volume on the mixing rolls or at the
calender intake automatically, and to employ the resulting signal to
control the throughput of the compounding unit. Such monitoring and
throughput regulation must, therefore, still remain among the
operator's duties.
The compounding unit must be capable of delivering stock of
unvarying degree of gelation over the entire output range. The overall
variation can cover a ratio of 1: 10, i.e. the minimum throughput
equals one tenth of the maximum throughput.
As already described for PVC compounding generally, in compounding for the calender a free-flowing blend is first produced from
the individual raw material components, and then discharged into a
holding silo (Fig. 13.42). The blend leaves the holding silo-normally

Fig. 13.42 A typical compounding train for PVC calendering: flow sheet. 1,
Truck unloading station for solid components; 2, debagging station for solid
components; 3, pneumatic conveying system; 4, silos for solid components
(resin, filler); 5, day bins for solid components; 6, day bins for plasticisers; 7,
batch weighing station for solid components; 8, batch weighing station for
liquid components; 9, minor ingredients proportioning station; 10, pre-mixer;
11, buffer silo; 12, compounder; 13, conveying belt with metal separator; 14,
two-roll mill; 15, conveying belt; 16, calender; 17, edge trim cutter; 18, silo for
cut edge trimmings.

594

W. Henschel and P. Franz

under gravity-to enter a feed hopper serving as buffer bin and

volumetric metering element (see Section 13.4.2(a)). The metered
blend flows into the screw-type kneader, where it is densified,
plasticated and homogenised. To simplify operation and make it
possible to maintain optimal compounding conditions when the
throughput changes, systems have been developed for synchronising
the feeds of the feed hopper shaft and the kneading screw. The speed
ratio characteristic of the particular formulation is set on a potentiometer. When it is necessary to alter the throughput the operator needs
only to raise or reduce the kneading screw speed by pressing a single
pushbutton. The synchronisation system adjusts the metering rate
automatically, so that the specific plastication rate remains constant
regardless of the momentary throughput.
For effective de-gassing, where necessary, the screw-type kneader
is equipped with a de-gassing zone (Fig. 13.43), to which vacuum
(70-200 mbar) is applied. If allowed to remain, the air, moisture and
other volatiles introduced with the pre-mix can cause blistering of the
calendered film or sheet. Their withdrawal from the stock is promoted
and enhanced by the continuous creation and exposure of new surface
in the course of compounding. Figure 13.44 demonstrates the effect of
de-gassing on PVC stock.
A die on the end of the kneader forms the stock into one or more
strands. These can be fed either to mixing rolls or the calender. For

-~
~

BUSS-KNEADER

Fig. 13.43 De-gassing arrangements in screw-type compounders.

13

Industrial Compounding Technology of Rigid and Plasticised PVC

595

Fig. 13.44 Effect of de-gassing of PVC film/sheet stock (crystal-clear, rigid

composition). Samples taken at the outlet of a screw-type kneader. Left,
material processed without de-gassing (high bubble content); right, de-gassed,
bubble-free material.

simpler and more uniform nip feeding, the strands can be sliced into
chips with a cutting device working in conjunction with the die (Fig.
13.45).
Straining of the stock may be desirable, particularly for the production of plasticised PVC sheet and film, to remove foreign objects such
as fibres, paper cuttings, wood chips, etc., which may have entered the
mixture from the raw material packages.

Fig. 13.45 Kneader die with cutting device.

596

w.

Henschel and P. Franz

This is done by setting up a 'strainer extruder' following the

compounding unit. Normally a single-screw machine, it is equipped
with screen pack and die. Three basic alternatives exist for straining,
depending on the average degree of raw material contamination
expected:
-Use of automatic screen changer for high contamination levels
requiring an hourly screen change.
-Use of a tandem strainer head, i.e. a twin strainer head
arrangement permitting the contaminated strainer to be swung out
and the clean head swung in in a matter of minutes. This solution
is practical in cases where medium to low contamination of the
raw materials calls for just one screen change per shift.
-Insertion of a screen pack in the extruder head, a possibility that is
justified only in cases of minimal contamination, i.e. where a
screen change is required only at the end of a production run.
During the production of PVC film and sheet, the product is
trimmed twice: a hot trim on the calender, and a cold trim to the
desired width. The resulting trimmings are recycled.
Mixing rolls and internal mixers were widely used for compounding
in the early years of calendering. They are still sometimes included in a
compounding section which may be used intermittently, for particular
runs or formulations, as an alternative to the main compounding set-up
(see Chapter 18). The edge trim can be fed back to these machines just
as it is. However, attempts to feed it directly into continuously
operating screw-type machines have usually failed because of various
problems, including difficulties in metering. The usual current practice
is to grind the trim in grinding mills together with unsaleable starting
film and sheet to obtain 'regrind' particles with edge lengths of
5-10 mm. As a rule, this regrind is added to the virgin blend in the
pre-mixing operation at rates of about 10-20%.
In isolated cases-particularly where semi-rigid or plasticised film or
sheet is being produced-the regrind can be charged directly into the
kind of feed hopper shown in Fig. 13.32. The mixing effect of the
agitator arms designed to prevent bridging in the hopper is sufficient to
intermix the regrind with the powder blend adequately.
The specific energy required for compounding is in the 006010 kWh kg- I range. Typical stock temperature profiles resulting from
this energy input are shown in Fig. 13.46. The compounding units
available on the market cover a throughput range from 100 kg h -1 to
5th- I .

13

Industrial Compounding Technology of Rigid and Plasticised PVC

T (OC)

597

ZXl
180

1iO

v.o
lZ)

eo
60

IIJ
Z)

}1.

Fig. 13.46 Temperature profiles, PVC sheet and film stock. 1, Plasticised
PVC; 2, rigid PVc.

In the early 1970s some leading companies attempted to set up the

entire calender line, from pre-mixing to finished film and sheet, in the
form of an integral control loop employing a central process computer,
with the idea of saving labour and reducing out-of-tolerance film and
sheet (with consequent raw material and other savings). These projects
demonstrated, however, that the entire system is so complex and the
mutual interaction of the parameters involved so varied, that it makes
more sense to divide the calender line into three subloops, pre-mixing,
compounding, and calendering. Automation and control can be
applied in goal-oriented land comprehensible fashion in these subloops.
Automation in the pre-mixing operation is aimed at producing the
desired blend with the desired temperature, bulk density and flow
properties for delivery to the compounding line.
The compounding control system is responsible for maintaining the
throughput called for at any given moment in conjunction with the
prescribed outlet temperature and fluidity of the stock.
The control loops on the calender are essentially responsible for
guaranteeing film and sheet thickness and thickness tolerances in the
lengthwise and transverse directions.

Fig. 13.47

iii

...

-~ill

1'---

1--11

11

.111,,1

_~~_I

Bj

IlL

,
I

.-

--

f--------L.........

----

.
=

~-

r---l

PVC cascade extruder with sheeting line. 1, Extruder; 2, flat sheet die; 3, triple-roll smoothing system;
4, roller conveyor; 5, edge trimmer; 6, twin-roll haul-off unit; 7, length cutter; 8, sheet deposit.

Wren . .

n~r1l

Ul
\0

~
l:>

;:s

:"l'

l:l.

;:s

l:>

;,~

"

i;

00

13 Industrial Compounding Technology of Rigid and Plasticised PVC

599

(c) Extrusion of Film, Sheet and Board

Considerable progress has recently been made in work on production
of rigid and plasticised PVC film, sheet and board by extrusion. Film as
thin as 01 mm and board as thick as 10 mm have been produced on a
commercial scale. Maximum finished width at present is 12 m. As in
the case of calendering, these systems employ compounding equipment
in line with the extrusion set-up.
In the example shown in Fig. 13.47, a cascade extruder (here
equipped with a slit die for film formation) is used as the combined
melt compounding and extrusion unit (see also Plate Cl). The
operation of this machine is discussed in Section 13.4.4(a)).
Production systems of the type illustrated by Fig. 13.47 and Plate C2
are designed for outputs up to 500 kg h- 1 for film and 600 kg h- 1 for
sheet and board.

(d) Recycling
At the time of writing, no general strategy for recovery of plastics
scrap has yet gained wide acceptance. Undoubtedly this is attributable

-..
-

Plate C.l Cascade extruder (Barmag).

600

W. Henschel and P. Franz

Plate C.2 Sheeting line employing a cascade extruder.

to questions such as the possible applications and quality profile of

recycled plastics scrap, price and profitability, technological potential
and limits, the consumer mentality, and not least the problem of
communication among various industries.
Nevertheless, the current ecological situation is making it necessary
to assess technological progress not only according to increased sales
and profitability, but also according to recycling possibilities. We shall
probably wait a long time for a satisfactory solution to the problem of
reclaiming valuable substances from municipal refuse. From the
standpoint of PVC compounding technology, however, several interesting examples can be cited of recovery of scrap produced during a
manufacturing process.
The simplest and easiest problem to solve is the handling of in-line
scrap, so it is not surprising that recovery of the edge trim and starting
scrap produced in the manufacture of PVC film and sheet has been
practised (as described in Section 13.4.2(b virtually since the
beginning of calendering technology.
Recycling practice is similar in PVC pelletising operations when
products with the wrong composition or colour shade are produced.
Recently, two possibilities have been investigated for the recycling of
die-cutting scrap in the processing of PVC sheet, viz. production of

13 Industrial Compounding Technology of Rigid and Plasticised PVC

601

secondary sheet and production of extruded profiles or pipes. First the

scrap is ground up in a grinding mill. The stabiliser used in the original
process is added again in a pre-mixer, and pigments are often added to
achieve a uniform, desired colour. This pre-mix is fed into the
compounding unit.
If the regrind includes rigid, semi-rigid and plasticised PVC, the rigid
and semi-rigid fractions can be charged into the compounding unit
through a first inlet opening and plasticated in an initial kneading zone.
The plasticised portion is then fed into this fluxed stock, which ensures
the gentlest and most homogeneous processing (Fig. 13.48). Because
the plasticiser cannot diffuse in the PVC regrind within a reasonable
time, as it can in the case of virgin PVC, any additional plasticiser
required is injected directly into the kneading zone of the compounding unit by a pump. It is advisable to use a strainer in order to remove
any contamination from the stock. Afterwards, the calendering process
is carried out as usual.
For the production of profiles and pipes, the homogeneous stock is
pelletised (as described in Section 13.4.2(a following compounding.
Then the pellets are fed to an extrusion line.
In the cable sector, compounders were confronted with the problem
of recycling copperless insulation and sheathing scrap. The approach
taken in this case was to use this scrap for producing filling core
mixtures. The purpose of the filling cores is to fill out the cavities
between a cable's conductors (Fig. 13.49). Since their composition is
not subject to any special electrical or mechanical specifications, it is
normally made as inexpensive as possible, usually receiving up to 700
RIGID PVC SCRAP

PLASTICISED PVC SCRAP

PLASTlC~ ~

~~Wl
STRAINER

Fig. 13.48 Recycling of film scrap.

602

w.

Henschel and P. Franz

INNER SHEATHING
REINFORCEMENT
Fig. 13.49 Cable design.

parts of chalk filler. At this level of loading the PVC acts mainly only
as binder for the filler. The reground PVC scrap, with a particle size of
5-10 mm, is fed into the first inlet of a compounding unit designed
specifically for this application (Fig. 13.50). The regrind is plasticated
homogeneously in the first kneader zone, enabling it to absorb the high
filler loading metered in at the second inlet opening without any
problems. To plasticise the filler cores further (for increased flexibility)
plasticiser is injected into the kneading chamber by a pump. The
homogeneous stock is pelletised as described in Section 13.4.2(a).
PVC SCRAP

FILLER

PlASTIC~ ~
Fig. 13.50 Compounding of cable filler cores.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

603

Another feature of the equipment shown is that virgin blends can be

compounded on the same line.
Cork flour-obtained as a waste product in the manufacture of
bottle corks~an be admixed to either a PVC virgin blend or a PVC
regrind blend and compounded as described in Section 13.4.2(b) for
producing flooring materials on a calender. The presence of the cork is
believed to increase the resilience of such flooring.

13.4.3 Preparation of PVC Pastes

The preparation of PVC pastes consists in dispersing suitable PVC
polymer grades in plasticisers, or sometimes plasticisers and solvents,
together with fillers, colourants and stabilisers. Paste viscosities of the
order of 103-15x104 cP are required for ultimate processing. The
nature, properties and applications of PVC pastes are discussed in
detail in Chapters 21 and 22.
Because the pastes are viscous liquids suitable for further processing
and giving rise to homogeneous products when fused (gelled) by
heating, melt compounding is not relevant or appropriate. Indeed care
must be taken during paste preparation to keep any heat development
or temperature rise to a minimum in order to prevent premature
gelation. Thus screw-type machines of the type used for melt
compounding are not applicable.
For quite a long time, PVC pastes were prepared exclusively in
slow-speed mixers (see Table 13.8), as it was felt that the compositions
would gel if handled in high-speed mixers. In the mid-1950s, however,
TABLE 13.8
Mixing Equipment for PVC Pastes
Continuous

Batch
Vertical
Low speed

Horizontal

Horseshoe mixer Ribbon blender

Planetary mixer Paddle mixer
Perl mill
High speed

Dissolver

Roll mills

Vertical

3-Roll mill

Dissolver
Buss mixing turbine MT

604

W. Henschel and P. Franz

rationalisation efforts led to the first trials with such mixers: the use of
dissolvers with infinitely variable speed control eliminated such
recognised shortcomings as limitations on mixing tool speed and
inadequate coverage of the entire mixture volume, and marked a real
improvement in the efficiency of producing pastes on a batch basis.
Today, changing economic conditions have again evoked demands
for improved efficiency and automation, for better working conditions
and anti-pollution measures, for improved space utilisation and higher
per capita outputs.
To meet these demands, continuously operating units such as
continuous dissolvers and the Buss Mixing Turbine were developed.
Regardless of whether the continuous or batch approach is used,
industrial preparation of stock pastes can be broken down into the
following stages (Fig. 13.51):
-silo storage of components;
-metering of components;
-pasting-up and dispersion;
-filtering;
-de-gassing (de-aeration);
-ageing.
The preparation of pigment pastes, and stock paste colouring, run in
parallel with the preparation of stock pastes.
(a) Silo Storage
This is practised as described in Section 13.3.
(b) Metering
Because of the special nature and mixing requirements of PVC pastes
it is necessary to charge the components into the mixer in fractions. In
the simplest case, the components are batch-weighed and the portions
charged into the mixer manually.
In automated processes this manual operation has been replaced by
gravimetric metering devices for the bulk materials and metering
pumps for the plasticisers. For the bulk materials, either belt weighers
or differential weighers (loss-in-weight feeders) can be used. While the
metering devices used for batch operation operate intermittently, i.e.
are switched off after the desired amount of a component has been fed,
metering devices for continuous operation supply an uninterrupted
flow of material that remains constant per unit time.

TANK)

pASTE
BUFFER

AGEING

DE-GASSING

FIL TERING

DISPERSING)

(WETTING,

PREPARATIONI

METERING

Fig. 13.51

_g
_PL_A_STlCISER

I
I
I

----,-

FILLER PLASTICISER

STABILISER

9-~9~-c-Q -.~T~r~
PVC

CONTINUOUS

Flow diagram for industrial preparation of PVC paste.

I-M_:_~_Y_~_:_IG_AE_L_~__~_~__s_TA9_~E_R

BATCH

0;'

~.

:::!:!

I::>.

0~
~
::>;,
oQ.

~
;;;'
s.

~c

.:

::;

......
c..,

606

w.

Henschel and P. Franz

For batch operation, the gravimetric metering devices can be

program-controlled to deliver the desired metering sequence without
any difficulty. Metering accuracy is approximately 05%, which is
better than the accuracy normally obtained in manual weighing.
(c) Pasting-up and Dispersion
Although a distinction is made between these two operations one
follows the other in continuous sequence. In batch operation, the
liquid components are placed in the dissolver first, and the portionwise addition of the solid components is then commenced, with the
mixing tool rotating. This practice largely avoids the formation of
lumps, and promotes wetting-out of the solid particles. When the last
solids fraction has been charged and mixed into the plasticiser, the
pasting-up step is over. Dispersion is initiated by speeding up the
mixing tool to step up the stock's turbulence and hence the shearing
effect. The upper limit on speed is determined by the drive motor
rating and depends on the viscosity of paste.
In the case of the continuous-preparation system shown in Fig.
13.51, the bulk components are not charged in portions, but are
comminuted in the inlet head of the Buss Mixing Turbine by suitable
rotor elements. The plasticiser is sprayed in, so that the solid and
liquid phases intermix in finely dispersed form. Thorough wetting-out
of the surfaces of the solid particles is the result.
When low-viscosity plastisols are being produced by the batch
process, only part of the total amount of plasticiser is placed in the
mixer at the start: otherwise the shearing forces for the dispersion
operation would not be sufficiently high. The remainder is added, to
effect final dilution, only after the dispersion operation has been
completed. In the continuous-preparation equipment of Fig. 13.51, the
same result is obtained by spraying-in the plasticiser at various points
along the mixing turbine axis.
In the batch process, the pasting-up operation in the dissolver takes
8-10 min depending on batch size, and the dispersion operation about
5-8 min (i.e. 13-18 min total mixing time). The peripheral speeds of
the mixing tool during dispersion are between 20 and 30 m s-1. In the
continuous process employing the Buss Mixing Turbine, the average
residence times for the entire mixing operation lie between 15 and 30 s
at rotor peripheral speeds between 10 and 25 m S-I, depending on the
throughput and formulation. The very large time savings, at generally
comparable peripheral speeds, offered by the continuous process arise

13 Industrial Compounding Technology of Rigid and Plasticised PVC

607

because in the Buss Mixing Turbine the mix components come into
contact at individual particle (or plasticiser droplet) level. This
accelerates both the pasting-up and dispersion operations (particularly
the latter).
Batch mixing in the dissolver and continuous mixing in a turbine
both produce pastes so smooth that they are ready for use and
normally require no additional grinding step on mixing rolls (as
practised in some traditional, or small-scale, paste preparation
methods).
(d) Filtering
Paste quality can be impaired by the kind of contaminants mentioned
in the discussion of melt compounding, or by the presence of isolated
undispersed lumps. In cases where the paste is passed through mixing
rolls for grinding, partly gelled particles (small lumps) of paste can
cling to the ends of the rolls and get into the product at the end of the
grinding operation. All such impurities must be filtered out.
Although a number of filter devices are available, the vacuum filter
described below is the one most frequently used. It can either be
moved around the workshop on a portable frame and fitted onto the
vacuum-tight mixing and transport tanks as required, or set up for
stationary use between mixer and de-gassing tank. The PVC paste fed
into the hopper of the device (Fig. 13.52) passes through a screen pack
mounted in a quick-change frame: the screen packs are much the same
as those employed in automatic screen changers for thermoplastics

Fig. 13.52 Vacuum filter for PVC paste.

608

W. Henschel and P. Franz

processing. One pack is in operation while the second waits its turn.
The paste is drawn through the screen by vacuum in the tank below.
When the screens become clogged, the two packs are reversed and
the contaminated one replaced by a new pack. Clogging of a screen is
indicated by an increase in tank vacuum. The screen pack mesh must
be fine enough to retain particles larger than 200 tlm. The filtered paste
passes directly on to the de-gassing step.
(e) De-gassing
Air enters the mixing unit with the bulk materials. In addition, the
PVC particles contain air and moisture as a result of their structure.
Steadily rising quality requirements have been forcing producers of
imitation leather, floorings, toys, etc., to de-gas their PVC pastes
effectively, and this has how become standard practice. Low-viscosity
pastes are de-gassed by the application of a 5-50 mbar vacuum for
about 10 min (about 20 min for high-viscosity pastes).
Effective de-gassing requires that the surface of the stock be
continuously renewed, thus shortening the diffusion paths and the
evacuation time. That is why vacuum dissolvers or vacuum planetary
mixers are employed for the de-gassing of PVC pastes. For continuous
operation, appropriate continuous degassing units are available on the
market.
(f) Ageing
The procedure just described is typical of the preparation of medium
to large batches of stock (uncoloured) PVC pastes. Directly after
preparation the stock paste is pumped into a storage tank where it is
kept-under slow stirring-to serve as buffer stock between paste
production and subsequent processing. The storage may also serve as
an ageing period (of up to about 24 h) during which the paste viscosity
attains a desired value (see also Chapter 21).
(g) Colouring
PVC pastes are coloured by the addition of colour pastes, produced by
dispersing colourants in plasticisers (batchwise in planetary mixers or
dissolvers, or by the continuous method in mixing turbines), and
homogenising by milling (in ball or roll mills). The method of
preparation is thus similar to that used in the paint and varnish
industry.
Colour pastes are added to PVC stock pastes in high-speed mixers or
dissolvers with average mixing tool peripheral speeds of 10-12 m S-l,

13 Industrial Compounding Technology of Rigid and Plasticised PVC

609

peaking as high as 22-25ms- 1 . The stock paste is first stirred briefly,

and then the batch of colourant, appropriate to the paste formulation,
is added slowly into the vortex forming around the mixing tool. In
cases where smoothness is of cardinal importance (e.g. coating pastes
for the production of artificial leather) the paste may be milled after
colouring. If this is done on 3-roll mills, it is advisable to pass the
milled paste through a vacuum filter to preserve the high quality of the
ultimate coating by removing any gelled particles that may have
formed on the rolls.
13.4.4

~achinery

(a) Screw-type Machines

The compounding of PVC is a particularly difficult operation because
of the need to minimise the material's 'heat history', which is a
function of the time and temperature of treatment. PVC compositions
must not be compounded at high stock temperatures for long periods.
Consequently, the energy required for plasticisation and homogenisation must be supplied to the system by the gentlest possible shearing
within the shortest practicable stock residence time. Another complicating factor is the tendency of PVC compositions to slip on processing
surfaces. For all of these reasons, PVC compounding is normally
carried out by screw-type machines that operate with relatively little
wall slippage and have a sufficiently effective mixing action to
plasticate and homogenise the stock at the lowest possible level of
energy conversion. Some machines typical of equipment embodying
these features are listed in Table 13.9 and briefly discussed below. The
list is given by way of illustration only, and is not exhaustive.
THE PLASTIFIKATOR

Applications: Compounding and pelletising of plasticised PVC

compositions (cable, shoe, profile, hose, flooring compounds).
Equipment and operational sequence (Fig. 13.53): The pre-mix
passes through a holding tank to reach the stirred feed hopper, 1. The
variable-speed twin feed screws, 2, (intermeshing and co-rotating)
determine the rate of material feed to the shear cone in the
plastication section, 3. In smaller Plastifikator models, the
homogeneous stock is picked up by a discharge screw, 4, arranged
coaxially with the plastication cone and driven by the same shaft; this

Werner u. Pfleiderer, Stuttgart

West Germany
Buss Ltd, Basle, Switzerland
Barmag, Remscheid-Lennep,
West Germany

Manufacturer

Werner u. Pfleiderer, Stuttgart,

West Germany
FCM continuous mixer {Farrel Corp., Ansonia, CT, USA
David Bridge Co. Ltd, Rochdale, UK
Pomini-Farrel, Castellanza, Italy
Baker Perkins Chern. Machinery
MPCN
Ltd, Hanley, Stoke-an-Trent, UK
Bitruder BT
Reifenhauser KG, Troisdorfsiglar,
West Germany
Planetary
EKK Kleinewefers Kunstoff
PWE and ZSE
Maschinen GmbH, Bochum,
West Germany
Hermann Berstorff Maschinenbau
WE
GmbH, Hannover, West Germany

Twin screw
Kombiplast

Buss-Kneader
Cascade extruder

Single screw
Plastifikator

Machine type and

designation

X
X
X
X
X

X
X
X
X

X
X

Rigid PVC

Process

Extrusion

feeding

+ pelletising Calender-

X
X

Plasticised
PVC

Compounding

TABLE 13.9
Typical Screw-type Compounding Machines

.....

'"

l::l
;3

:-0

l::l..

l::l
;3

~
~
g.

0\

13

Industrial Compounding Technology

at Rigid and Plasticised PVC

611

Fig. 13.53 Plastifikator PK400. (See text for details.)

screw forces the stock through the pelletiser die plate. In larger
models, the discharge screw constitutes a separate unit with its own
drive, gear box, bearings and supports. Cutting knives, 5, offset from
the pelletiser die plate, chop the emerging strands into pellets by the
dry cutting process. The pellets are gathered in a collector casing, 6,
and conveyed pneumatically to the pellet cooler.
Working principle (Fig. 13.54): The plastication and homogenisation
comprises a shear cone, 1, rotating inside the conical housing,
2. The tapered part of the shear cone is fitted with spiral fins, 3. A
closed ring of powder formed, in the first part of the shearing gap
between the shear cone and housing, becomes sintered under the
influence of shear forces, and gels in the next section. The fins and
increasing shear cone diameter serve to divide the product into
individual strands; these are squeezed in the constricting gaps between
fins and housing wall to form thin layers, only to be re-formed again.
Axial displacement of the shear cone in relation to the housing varies
the shear gap and therefore the amount of shear energy dissipated.
s~tion

612

W. Henschel and P. Franz

2 1

flow

Fig. 13.54 Working principle of the Plastifikator. (See text for details.)
Temperature control system: The cone housing is equipped with an
electric heater. The barrel of the discharge screw is also electrically
heated, but is fitted with an air cooling system in addition. If the
machines are separate, the discharge screw can be cooled with a
separate heat transfer medium.
De-gassing: Where the plastication machine and discharge screw are
separate, a vacuum of 400 to 550 mbar can be applied to the transition
section between the two to de-gas the stock.
Operation and cleaning: During starting, a diverter can be placed
between the plastification section and discharge screw to remove any
PVC powder emerging; this prevents clogging of the die plate or screen
pack (if any). For cleaning, the plastification section and discharge
screw are run empty and purged of residual powder by passing warm
pellets through. The pelletiser head can be swung out to permit easy
removal of any product remaining on the screw tip or back of the die
plate. For extreme colour or formulation changes that call for a
thorough cleaning, the discharge screw with pelletising head of the
smaller models can be rolled away on an assembly dolly. Then the shear
cone can be pulled out in front of the barrel on a bar sliding in the
main shaft. On the larger models, the cone is rolled away together with
the transfer tube on guides, making the parts in contact with the
product freely accessible.
Energy input:

-cold pre-mix: 01-012 kWh kg-I;

-hot/cold blend (50C): 008-01 kWh kg-I;
-hot blend (85-90C): 006-008 kWh kg-I.
Output rates and technical data: See Table 13.10.

Production rate:
Plasticised PVC (kg h -i)
Drive rating:
Feed screw (kW)
Main drive (kW)
Pelletising (kW)
Fan (kW)
Separate pelletising screw (kW)
Speed range:
Feed screw (r min-i)
Shearing (r min-i)
Pelletising (r min-i)
Fan (r min-i)
Separate pelletising screw (r min-i)
Heating:
Cone barrel (kW)
Extruder barrel (kW)
Pelletising (kW)
Cooling:
Fan (m 3 h- i)
Water cooling, bearing (litre h- 1)
Water cooling, cone barrel (optional) (litre h- 1)
Water cooling, gear-box (optional) (litre h- 1)
Weight:
Plastifikator (kg)
Control cabinet (kg)

4
25
125
800

4
25
125
800

3200
270

3500
270

60

20-120
52
240-900
2800

20-120
42
204-900
2800

60

4
30
075
037

4
22
075
037

250-350

Model

PKlOOIV11

150-250

PK lOOIVI

TABLE 13.10
Technical Data for the Plastifikator

10
4
2

4500
500

800
100
-

30-150
88
230-1150
2800

4
55
15
037

450-900

PK 400/111

13100
700

2 x 800
200
500
500

20
16
48

29-117
75
312-1560
2800
35

55
160
3
2 x 037
37

1200-2400

PK lOoom

..

Vol

a......

(")

-<::

'1:l

$:>..

1:;'

'"
'"

::t.

'1:l

$:>..

l:>

..

:>::I

.Q,

;:0-

'"

;;;'l

s::

~c

f:..

s.

t:;

S'
$:>..

...........

614

W. Henschel and P. Franz

THE BUSSKNEADER

Applications:
-compounding and pelletising of (i) plasticised PVC blends (cable,
shoe, profile, hose, flooring compounds), and (ii) rigid PVC
formulations (bottle, profile, record compounds);
-compounding of rigid, semi-rigid and plasticised PVC blends for
calender feeding (packaging, deep-drawing, decoration, upholstery and engineering film and sheet).

Equipment and operational sequence (Plates D.l and D.2): The

pre-mix moves through a holding silo to the feed hopper, which is
equipped with an agitator. The bottom section of the agitator is
designed in the form of a vertical screw, so that speed variation of the
agitator shaft feeds product continuously at the desired rate into the
kneading section. If pellets are being produced (Plate D.l), the stock
homogenised in the kneader is transferred cascade-fashion to the
pelletising screw, which forces the product through the pelletising die
plate. Cutting knives supported next to the die plate chop the emerging
strands into pellets by the dry cutting process. The pellets are caught in
a collector casing and conveyed pneumatically to the pellet cooler. In
the case of calender feeding (Plate D.2), the homogeneous stock is
sliced into chips in a die mounted on the kneader; the chips are then
fed to the calender.
Working principle (Figs 13.55 and 13.56): The Buss-Kneader is a
continuously operating single-screw machine of special screw design.
Conventional single-screw machines have an uninterrupted
Archimedes' screw, which merely rotates around its longitudinal axis
(Fig. 13.55(a)). In the Buss-Kneader, each turn of the screw helix is
interrupted by three gaps to form the screw kneading tools, or 'screw
flights'. Their counterparts in the barrel, the kneading pins or teeth,
are arranged in three rows (Fig. 13.55(b)). An axial oscillation is
superimposed on the rotation of the screw. A special gear box
generates this characteristic Buss-Kneader motion. The mechanism
ensures that each turn of the screw is accompanied by one
back-and-forth movement.
The operating principle can be explained by reference to a
projection of the screw profile onto a flat plane (Figure 13.56(A)). The

13

Industrial Compounding Technology of Rigid and Plasticised PVC

615

616

W. Henschel and P. Franz

Plate D.2 Buss-Kneader PRKJE.

screw flight shaded in the figure is considered for this purpose, together
with the four marked kneading teeth which work in conjunction with
it. The sequence of drawings in Fig. 13.56(A)-(F) shows the tracks of
the kneading teeth relative to the screw flights. Each consecutive
drawing represents a quarter-turn of the screw shaft, i.e. the rotation
positions of 0, 90, 180, 270 and 360 angular degrees. In the drawings,
the screw rotation corresponds to movement of the screw flights from
bottom to top; the product is conveyed from right to left. The starting
position is shown in the first drawing.
In the course of a turn through 90 (Part (B, the dark kneading
tooth, which started at the top flight tip, has wiped past the long
left-hand flank of the screw flight. As it did so, the product was
sheared in the gap between the kneading tooth and shaded screw
flight, and the flank of this flight was cleaned at the same time. The
other marked teeth have not yet 'moved into action with the shaded
screw flight, but they have been working with other flights.
0

13 Industrial Compounding Technology of Rigid and Plasticised PVC

617

Fig. 13.55 The screw and barrel of: a, conventional single-screw machine; b,
the Buss-Kneader.

As the screw turns through another 90 (Part (e, so that it is

describing a half turn in relation to the starting position, the right-hand
kneading tooth of the two shown at the top of the projection in the
starting position wipes past the short right-hand flank of the shaded
flight, thus shearing the product and cleaning this flank. During this
rotary motion, the middle and the two upper kneading teeth pass
through their respective gaps between the screw flights and push the
product back into the next turn of the helix.
Note: Thus, superimposed on the conveying effect of the screw pitch
and right-to-Ieft movement, there is a backward movement of
material. This combined motion has been referred to in the
literature as 'pilgrim's step' (two steps forward and one back).

618

W. Henschel and P. l,ranz

D

c::::::::::::

619

13 Industrial Compounding Technology of Rigid and Plasticised PVC

c:::::::

-~~

620

W. Henschel and P. Franz

Naturally, the forward conveying effect produced by the pitch

and stroke of the screw is greater than the backward
movement of material actuated by the passage of the kneading
teeth through the gaps. The net material movement is thus in
the direction of the outlet of the machine.
The backward movement of material adds the crucial
benefit of axial mixing to the radial mixing effect. This is why
the homogenisation process in the Buss-Kneader takes less
time than in conventional screw-type machines.
In completing the 180 turn the screw has sheared the material and
performed a cleaning operation on both the left-hand (long) flank of
the screw-flight and the right-hand (short) flank.
In the course of the next 90 turn (Part (D the shearing of the
material proceeds as the left-hand (short) flank of the left-hand tooth
of the pair shown at the top in the starting position is being cleaned.
Axial product exchange takes place again as the kneading tooth passes
through the gap.
The result of the last 90 turn (Part (E, which completes one full
revolution of the screw, is tha,t the kneading tooth shown at the lower
tip of the shaded flight in the starting position (Part (A wipes past the
right-hand (long) flank of the flight, again shearing the material and
cleaning the flank. The interaction of the four kneading teeth with the
shaded screw flight during one full turn of the screw has thus sheared
the material on all four flanks of the flight, mixed it both axially and
radially, and mutually cleaned the screw flight and teeth. As can be
seen from the diagrams the same events-though with the roles of the
collaborating flanks and kneading teeth exchanged-take place on all
of the other screw flights. This is demonstrated by the enlarged detail
of the relevant projection: Part (F) shows that the coverage of the
kneading tooth tracks in relation to the screw surface is complete, with
no surfaces or spaces left unwiped. This is the basis of the thorough
mixing, kneading and self-cleaning action of the Buss-Kneader.
On the KG models, the regulating screw can be used to set the
back-pressure at the kneader outlet steplessly by remote control. This
provides finger-tip control of the energy input. On PRK models for
feeding calenders, the same back-pressure control is achieved with the
aid of a die with infinitely variable cross-section.

Temperature control system: The barrels of both the kneader and the

13 Industrial Compounding Technology of Rigid and Plasticised PVC

621

pelletising screws are fitted with jackets divided into several zones. The
screws are hollow right up to the tip. This design permits accurate
control of screw and barrel temperatures by means of liquid
heat-transfer media, usually HT oil. Pelletising die plates are heated
either electrically or with liquid.
De-gassing: On the KG and WKG models, which are used for
compounding and pelletising, de-gassing of the stock takes place at the
transition point between Buss-Kneader and pelletising screw. On
PRKlE models for feeding calenders, the Buss-Kneader is equipped
with its own de-gassing zone at the outlet end.
The de-gassing systems provide for vacuum as high as 50-60 mbar.
Operation and cleaning: When the KG and WKG pelletisers are
started up, the initial material can be eliminated with a diverter
between the Buss-Kneader and pelletising screw. In calender installations, the starting material can be eliminated at the kneader outlet.
Buss-Kneaders and pelletising screws are cleaned by running them
empty and purging residual powder with cleaning pellets. The
pelletising head can be swung out to allow easy removal of material
remaining between screw tip and die plate. For extreme product
changes requiring a thorough cleaning, the Buss-Kneader barrel flaps
open (Plate E), so that both screw and barrel are freely accessible. The
barrel of the pelletising screw can be drawn off the screw on an integral
roll-away chassis. Because all parts are fastened to the machine base
and therefore remain properly positioned, this cleaning procedure
requires no special tools, hoists or specially trained personnel.
Energy input:

-plasticised PVC: 0.04-006 kWh kg-I;

-rigid PVC: 005--008 kWh kg-I.
Output rates and technical data: See Tables 13.11 and 13.12, and Fig.
13.57.
THE CASCADE EXTRUDER

Applications:

-rigid and plasticised PVC film, sheet and board extrusion;

-pelletising.

622

W. Henschel and P. Franz

Plate E

The split barrel of a Buss-Kneader.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

623

Equipment and operational sequence (Fig. 13.58 and Plate Cl): The
cascade extruder is made up of two single-screw extruders, the fluxing
extruder and the discharge extruder. PVC pre-mix is fed into the
former through a simple inlet hopper without any agitator or metering
device. The fluxing screw mixes the blend and partly agglomerates the
stock into particles of approximately uniform size. The production rate
depends on the momentary bulk density of the pre-mix and the screw
speed. When the agglomerated stock emerges from the fluxing
extruder, it drops through a de-gassing tube (to which vacuum as high
as 80 mbar can be applied)' into the intake section of the discharge
extruder. Retention time in the de-gassing tube can be regulated by
altering the agglomerate level in the tube. The discharge extruder's job
is to complete plastication of the partially fluxed material, homogenise
it, and force it through the outlet die.
Working principle (Fig. 13.59): The energy required for agglomeration
and plastication of the PVC stock is supplied by heating the barrel and
by shearing the stock between screw core and barrel wall. The screws
are provided with a 'heat pipe' to prevent overheating and scorching.
To improve its intake characteristics, the fluxing extruder is fitted
with a cooled, grooved bushing in the inlet area. The intake section of
the discharge extruder is designed in the form of a tapered slot.
Temperature control: The barrels are heated electrically. Screw
temperature is controlled by the heat pipe system.
De-gassing: In the transition tube between fluxing and discharge
extruders.
Output and technical data: See Table 13.13 and Fig. 13.60.
THE KOMBIPLAST

Applications: Compounding and pelletising of plasticised and rigid

PVC.
Equipment and operational sequence (Fig. 13.61): The pre-mixed
material is fed into the feed zone of the twin-screw unit (ZSK or ZDS-K)
by a vertical force-feed screw. The compounded stock drops
cascade-fashion into the ES-A pelletising screw which forces it through

Rigid PVC (kg b- I)

Plasticised PVC (kg h- I)
(at elevated
PR screw speed)

Production rate:

Total weigbt' (kg)

No. of beating units
Heating capacity (approx. kW)

Dtive rating (kW)

Screw speed (r min-I)
Screw diameter (mm)
Screw lengtb (LID)
Heating zones
PeUetising:
Drive rating (kW)
Knife speed (r min-I)
No. of knives
Size of die boles (mm dia.)
Die beater (kW)

15
40-300
46
7
4

06
16-80
46
2

40
75

1000
3
30

PR

ET

GS

11
120-600
2
3/36
05

3
20-80
70
6
3

WKG46-7

Technical data for KGIWKG (rigid and plasticised PVC)

18
7-47
80
2

ET

400
750

4500
3
30

70
40-240
100
7
4

PR

GS

15
120-600
2
3/36
17

11
10-47
140
4
3

WKG1Q-14

3
4-30
140
25

ET

1500

BOO

1oo

3
60

107
40-120
140
7
4

PR
58
10-40
140
25
2

RS

KG 14-18

22
12(}..6()()
2
3/36
3

24
8-40
180
6
3

GS
45
4-30
215
2

ET

1600
3000

17500
3
60

210
40-120
200
7
4

PR

125
5-39
200
25
2

RS

KG2Q-25

TABLE 13.11
Technical Data For Buss-Kneader Models KG and WKG

3
120-600
2
3/36
4

52
8-40
250
6
3

GS

75
4-25
300
2

ET

3200
S-7ooo

38500
6
120

510
40-120
300
7
4

PR

23
5-35
300
25
2

RS

GS

75
100-1000
2
3/36
7

95
6-30
320
6
3

KG3Q-32

;:,

'"

;:,
!'>..

'"

";~,-

1;;

0"-

a
b

GS

ET
PR
70
40-240
100
7
4

750

18
7-47
80
2

75

11
12lHiOO
2
3
05

3
20-80
70
6
3

4500
3
30

IS
40-300
46
7
4
15
12Q-{;()(J
2
3
17

11
10-47
140
4
3

GS

WKGIO-14

1000
3
30

PR

ET

06
16-80
46
2

WKG46-7
ET
3
4-30
140
25

1500

8700
3
30

107
40-240
140
7
4

PR

22
12lHiOO
2
3
3

24
8-40
180
4
3

GS

WKGl4-18

Approximate figures, not including heating/cooling units, pellet cooling installation, control cabinet or main drive motor.
Approximate figures; may vary depending on formulation and operating conditions.

Total weight" (kg)

No. of heating units
Heating capacity (approx. kW)
Production rate: b
Plasticised PVC (kg h- I)

Drive tating (kW)

Sctew speed (r min-I)
Screw diameter (mm)
Screw length (LID)
Heating zones
Pelletising:
Drive rating (kW)
Knife speed (r min-I)
No. of knives
Size of die holes (mm dia.)
Die heater (kW)

Technical data for WKG (plastic/sed PVC)

ET
45
4-30
215
2

3000

60

15800
3

210
40-240
200
7
4

PR

3
12lHiOO
2
3
4

52
8-40
250
4
3

GS

WKG20-25
ET
75
4-25
300
2

6-7000

35000
4
120

510
40-120
300
7
4

PR

75
100-1000
2
3
7

95
6-30
320
4
3

GS

WKG30-32

Ul

'"tl

It

~.
0;.

;:,
I'>.

""

Ii;:

::tl
a;;.

g.

s::

~o

so

....
.......

626

W. Henschel and P. Franz

TABLE 13.12
Technical Data for Buss-Kneader Models PRK and PRK/E
PRK, PRKIE

PRK, PRKIE

PRK, PRKIE

100

140

200

Feed hopper:
Capacity (litre)
Screw diameter (mm)
Screw drive (kW)
Screw speed range (r min-I)

150
100
18
67-47

280 or 430
140
44
22-44

430 or 830
215
55
14-28

Buss-Kneader:
Screw diameter (mm)
Screw length PRK (LID)
Screw length PRKlE (LID)
Screw speed range (r min-I)
Gear box model
Kneader drive (kW)

100
7
12
120
G20
60

140
7
11
120
G45
120

200
7
11
120
G130
200

Heating/cooling equipment:
No. of units
Installed heating capacity (kW)

2
20

2
36

2
36

3800

6300

11700

Approx. total weight (kg)

(not including heating/cooling
units, control station or
kneader drive equipment)

the pelletising die. Cutting knives mounted next to the die plate chop
the emerging strands into pellets, which are conveyed pneumatically to
the pellet cooler.
Working principle: The ZSK is a twin-screw machine with intermeshing, co-rotating screws equipped with kneading discs (Fig. 13.62)
which shear and knead the product and change the local direction of
stock flow as it passes the barrel wall. The shearing occurs, and energy
is imparted to the stock, as a result of the velocity drop between the
kneading discs and the barrel wall and in the saddle area between the
two screws. Shearing intensity is determined both by the speed of the
screws and the inherent resistance of the kneading discs.
The configuaration and arrangement of the discs shown schematically in Fig. 13.62 give rise to squeezing forces which pass the material
forward along the screws while it is subjected to shearing and mixing
by the consecutive disc elements. The design ensures that the root of
each screw is wiped by the flight tip of the other. This self-cleaning

13

Industrial Compounding Technology of Rigid and Plasticised PVC

Output in kg h- 1
Model
PRK/E
2000

Output in kg h-1
Model
PRK
3000

1670
PRK/E 200
1350

1000

/~

670

330

o
o

627

-",

V
10-""-

~RK200

2500

2000

1500
PRK/E 140 ~

J/"
~ PRK140

-- -

20
40
60
80
Speed of Buss-Kneader screw

PRK/~ 100 I

1000

500

PRK100

100
r min- 1

120

Fig. 13.57 Output diagram for Buss-Kneader models PRK and PRKlE.

profile eliminates dead spots and normalises the residence time of the
material.
Temperature control system: The ZDS-K and ES-A barrels are
electrically heated. The ES-A unit is cooled by an air blower, whilst
the barrel of the ZDS-K unit has channels for cooling with liquid
heat-transfer media.
De-gassing: De-gassing is carried out at the transition point between
the ZDS-K and ES-A units.
Operation and maintenance: The starting product can be diverted
between the ZDS-K and ES-A units. For cleaning, both units are run
empty, and residual powder is purged with a cleaning material. The
pelletising head can be rolled away, which facilitates the removal of
product between screw tip and die plate. The barrel sections of the
ZDS-K and the barrel of the ES-A can be dismantled for more
thorough cleaning work.

628

W. Henschel and P. Franz

u
>
p..
...

sa...

-...
0

'0

;:I

>0<
0

'0
~

u
en
~

....0
U

l=:
.~
en
0

00

V)
~

......

oil

13 Industrial Compounding Technology of Rigid and Plasticised PVC

629

Standard Extruder
n

Process Steps

IVonabieland Fixed Operating Conditions

Fig. 13.59 Process steps and operating conditions of a standard cascade

extruder.

Energy input: 004-008 kWh kg-I.

Output and technical data: See Table 13.14.
THE FCM CONTINUOUS MIXER

Applications:

--<:ompounding and pelletising of plasticised and rigid PVC;

--<:ompounding of rigid and plasticised PVC for feeding calenders.

W. Henschel and P. Franz

630

TABLE 13.13
Cascade Extruder: Technical Data
Data

Screw diameter, D (mm)

Barrel length extruder (mm)
Screw speed:
Extruder (r min-I) 1 and 2
Drive power:
Extruder (kW)

Model

Number of heating zones

Heating power total (kW)
Number of cooling zones:
Barrel
Vacuum chute
Screws
Tempering devices-cooling capacity:
For barrel and vacuum chute (kcal h-I)
For screws (kcal h- I)
Vacuum pump:
Pumping capacity (with 60 torr), (m 3 h- I )
Drive power (kW)
Water consumption
(with 15C input temperature) (m 3 h- I)

1000
kg/h

900

E6K

E9K

E12K

2 x 60

2 x 90

2 x 120

2 x 150

9D
13D

9D
13D

9D
13D

9D
13D

100

80

70

60

20
12
5
144

48
32
5
273

87
60
5
486

140
100
5
740

4
1
2

4
1
2

4
1
2

4
1
2

20000
4000

30000
8000

40000
12000

50000
12000

36
12
023

46
19
026

97
22
045

97
22
045

Material' rigid PVC

800
700

.... 600
....5.500
::l

0400

300
200

100

~
E9K

E15K

E12K

E15K

Extruder size

Fig. 13.60 Output of the cascade extruder.

Fig. 13.61 The Kombiplast machine. 1, Screw barrel; 2, two co-rotating screw shafts; 3, thyristor controlled DC motor;
4, reduction gear; 5, duo gear which distributes the drive capacity between the two screw shafts; 6, screw barrel; 7, single
screw; 8, eccentric pelletiser; 9, die plate; 10, neck connecting the two machines; 11, quick acting lock; 12, pole-changing
three-phase motor; 13, spur gear.

0\

ri

t;;.

,,'

'[
;:
'"
I:>-

:;.;,

~
~

o
0-

;:

g.

;::
;:

~o

'""

......

W. Henschel and P. Franz

632

Fig. 13.62 Working principle of the Kombiplast ZSK and ZDS-K.

TABLE 13.14 Technical

KPl(}(}

Production rate:
Plasticised PVC (kgh- I )
Rigid PVC (kg h- I )
Screw:
Diameter (mm)
Length (UD)
Drive rating:
Main drive (kW)
Fan (kW)
Pelletiser (kW)
Speed ranges:
Screw (r min-I)
Fan (r min-I)
Pelletiser (r min-I)
Temperature control:
Barrel (kW)
Die plate (kW)
Heating cabinet (kW)
Cooling capacity of beating
cabinet (kcal/h)
Water consumption (m 3 h- I)
Air consumption (m 3 h- 1)
Weight:
Machine (kg)
Control cabinet (kg)

KP5(}(}

200-350
100-200

500-1100
350-700

ZSK57M23

ES-Al(}(}

ZSK90M58

ES-A150

57
13

100
6

89
115

150
6

3&-17

7/10
037
11

11-:>-50

17f27

82-360

21/42
2800
156-780

82-360

16/32
2800
23o-U50

96

30
3-15
45
10000

180

70
50
45
10000

45
14000

037
15

45
22000

04

01
800

07

015
800

1400
500

1500

2400
600

1900

13

Industrial Compounding Technology of Rigid and Plasticised PVC

633

Equipment and operational sequence: The FCM is fed not from a

hopper, but from one or more belt weighers, depending on the number
of components. The metered material is plasticated and homogenised
in the mixing chamber and discharged through a variable flap which
provides control over the outlet cross-section. For calender feeding,
the ribbon of product is passed to mixing rolls or a strainer extruder.
For the production of pellets, a suitable ribbon can be discharged for
subsequent dicing, or the product emerging through the FCM flap may
be passed to a pelletising extruder for hot die-face cutting.
Working principle (Fig. 13.63): Since the two screws (sometimes
referred to as rotors) of the FCM do not mesh, the operating principle
is comparable to that of the batch-type Banbury mixer. In the inlet
section, the shafts are designed in the form of Archimedes' screws. In
the mixing zone they are shaped like kneading paddles. The two shafts
are counter-rotating and are run at variable, different speeds. Besides
the shear occurring between barrel bore and screws, this also produces
shear and mixing action between the screws.
Energy dissipation and mixing effect can be controlled with the aid
of the flap for changing the outlet cross-section.
Data for the Kombiplast
Model
KP800

KP 1500

KP 2500

KP 3500

1200-2200
700-1300

1800-3600
1100-2100

3000-5000
1400-2800

4500-7500
2100-3800

ZSK 130M325

ES-A250

ZSK130M325

ES-A3oo

ZSK130M650

ESA350

89
115

200
6

130
14

250
6

130
14

300
6

130
14

350
6

10-100

25/36
2 x 037
22

1ll-180

40/56
2 x 15
4

24-240

62/90
2 x 15
55

355

90/132

36-360

16132

266-266

15130

36-360

15130

30-300

15130
2800
155-750

ASK90M120 ES-A200

2800

180
45
22000

160
72
45
10000

2800

200-1000

230-1150
320
45
22000

200
84
120
14000

2800

75

270-780
320
45
22000

220
96
150
14000

320
120
40000

120
360 + 180
30 000 + 14000

10

03
1600

15

05
2000

20

07
2000

30

30

3900
700

2500

5500
700

7500

5500
700

12000

6500
800

18000

634

w.

Henschel and P. Franz

Section A-A

Section B-B

Mixing

Feeding

Fig. 13.63 Working principle of the FCM compounder.

Temperature control system: The shearing forces generated by the

rotors and the mixing chamber walls permit adiabatic operation of the
FCM. To avoid product overheating, the rotor shafts are hollow and
the mixing chamber is provided with a jacket, so that water cooling can
be carried out. Since the outlet flap is plated for PVC products, there is
no need to control its temperature.

13

Industrial Compounding Technology of Rigid and Plasticised PVC

635

De-gassing: Vacuum can be applied to the connecting tube between

the FCM and pelletising extruder.
Operation and cleaning: The starting product can be eliminated at
the flap outlet. Because the machine is not self-purging, it is necessary
to dismantle the system for formulation changes where no intermixing
can be tolerated. This is done by shifting the mixing chamber barrel
away hydraulically and swinging it 60 away from the kneader axis.
This makes the rotors and barrel bores freely accessible for cleaning.
Energy input:

-plasticised PVC: 006--014 kWh kg-l;

-rigid PVC: 005-Q12 kWh kg- l .
Output and technical data: See Table 13.15.

TABLE 13.15

Technical Data for the FCM

Model

Volume (dm )
Max. torque (Nm)
Standard gear box:
Max. rating (kW)
Max. screw speed (r min-l)
Special gear box:
Max. rating (kW)
Max. screw speed (r min-I)
Dimensions with drive:
Length (m)
Width (m)
Height (m)

2FCM

4FCM

6FCM

9FCM

0344
187

270
1432

913
7162

308
28640

22
1150

735
100

257
350

882
300
1102
375

Weight without drive (kg)

20
15
28
2050

Production rate:
Plasticised PVC (kg h- I)
Rigid PVC (kg h- l)

165
90

42
16
2730

60
15
13
6700

70
20
16
9600

550
300

2000
1100

5000
3750

1-1

THE MPCIV

Applications: Compounding and pelletising of plasticised and rigid

PVc.

636

W. Henschel and P. Franz

DIscharge

SCrews

Vacuum

Connection

Extruder

To Pellellser

Fig. 13.64 MPCN design.

Equipment and operating sequence: PVC pre-mix is fed into the

twin-screw MPCN. The discharge screw elements (Fig. 13.64)
mounted on the end of the shafts push the homogeneous stock into the
pelletising screw, which is attached at right angles to the MPCN. Hot
die-face cutting is used for pelletising, but, in contrast to the other
processes, the pellets are cooled by being whirled into a cooling water
film. Finally, the pellets are dried.
Working principle: Shearing and mixing are carried out with the aid
of kneading disks similar to those described above for the Kombiplast.
A barrel valve (Fig. 13.35), located just ahead of the screw discharge
elements in the barrel, is used to control the back-pressure in the
kneading zone and hence the energy dissipation.
Temperature control system: MPCN systems are designed for
adiabatic operation.
De-gassing: De-gassing takes place in the pelletising screw immediately following the inlet opening (see Fig. 13.64).
Operation and cleaning: With this design there is no way to eliminate

13

Industrial Compounding Technology of Rigid and Plasticised PVC

637

starting product between the kneader and pelletising screw. Cleaning is

facilitated by the horizontally split barrel, which can be flapped open.
Output: See Table 13.16.
TABLE 13.16
MPCIV Output Rates
MPCIV
model

50mm
80mm
100mm
125mm
160mm

PVC

Drive

rigid flexible
(kg h- 1 )

(kW)

130
500
700
1400
2800

250
1000
1500
3000
6000

11
45
55
110
225

THE BITRUDER BT

Applications: Compounding and pelletising of rigid and plasticised

PVc.
Equipment and operational sequence: Unlike the systems described
thus far, Bitruders do not employ the cascade layout. In this case, the
operation steps of material intake, plastication, homogenisation and
discharge are carried out in a single, twin-screw machine (Plate F). The
PVC pre-mix enters the Bitruder either through a simple inlet hopper
without any internal devices, or through a feed hopper with agitator
and forcing screw. A barrel de-gassing arrangement is provided ahead
of the discharge zone as standard equipment. From the discharge zone
the screws force the homogenised stock out through a multi-hole
pelletiser die plate equipped with a torpedo. The pellets are produced
by the hot die-face cutting method and are conveyed pneumatically to
the pellet cooler.
Working principle: Bitruders are equipped with meshing, counterrotating screws. The energy required for plastication and homogenisation is dissipated primarily in the area where the screws mesh.
Temperature control: The barrel zones are heated by electrical

638

W. Henschel and P. Franz

Plate F

Bitruder GTlOO-18G.

heating circuits. The screws can be heated or cooled with a liquid

heat-transfer medium (HT oil).
De-gassing: De-gassing takes place in a section between the
agglomeration zone and the plastication/discharge zone. In this section
the screws are only partially filled and smooth product flow is aided by
a special insert.
Operation and cleaning: In this system start-up material cannot be
diverted ahead of the pelletiser die plate. The machine is cleaned by
running it empty and chasing with purging pellets. For major cleaning
operations the barrel is withdrawn with the aid of a rack-and-pinion
mechanism.
Output rates and technical data: see Table 13.17.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

639

TABLE 13.17

Technical Data for the Bitmder Range

Extruder

BT80-12G
BT 80-16G
BT 100-14G
BT 100-18G
BT 150-17G

Screw
diameter
(mm)

Screw
length
(LID)

77
77

12
16
14
18
17

98
98
150

Screw Heating
rating capacity
(kW)
(kW)

25
25
33
37
133

17
17
31
36
88

Output
rates
(kg h- J )

120-230
200-400
300-550
450-750
650-1200

THE PLANETARY EXTRUDER

Because the two makes listed in Table 13.9 are basically very similar,
they are discussed together in this section.
Applications:
-compounding and pelletising of rigid and plasticised PVC: ZSE
(EKK Kleinewefers);
-compounding of rigid and plasticised PVC film/sheet formulations
for calender feeding: PWE-AK and PWE-EV (EKK Kleinewefers); WE (Hermann Berstorff).
Equipment and operational sequence (Fig. 13.65): A force-feed
hopper feeds the PVC pre-mix into the filling zone; the material is then
passed into the planetary screw section for plastication and
homogenisation. This section is closed off with a retention ring which
prevents axial displacement of the planet screws (Fig. 13.66).
Models PWE-AK and WE typify the machines used for feeding
calenders without any de-gassing; the homogenised stock emerges from
the retention ring of the planetary screw section in the form of helical
strands, which are fed to the calender. If intensive de-gassing of the
stock is required, model PWE-EV is employed (Fig. 13.66). Basically,
this is a PWE-AK machine with a single-screw extension with
de-gassing and discharge zones. Here again, the planetary screw
section is terminated by a retention ring.
ZSE lines (Fig. 13.67), widely used for compounding and pelletising
rigid and plasticised PVC compositions, are basically cascade systems
made up of a PWE-AK machine followed by a single-screw discharge
extruder, with a de-gassing tube between the two units. The strands of

W. Henschel and P. Franz

640

Fig. 13.65 Planetary kneader design.

5

Fig. 13.66 The screw and barrel arrangement of planetary compounder

PWE-EV. 1, Feed zone 3L1D; 2, plastication zone (planetary system) 5L1D; 3,
discharge zone 2LID; 4, de-gassing zone 4L1D; 5, retention ring.

compound forced through a multi-hole die plate are cut into pellets by
the hot die-face cutting method and conveyed pneumatically to a
cooler.
Working principle (Fig. 13.68): The plastication and homogenisation
process takes place in the planetary screw section, which comprises
four interacting elements, viz. the driving main spindle, the follower
planet screws, stationary barrel, and retention ring.

13

Industrial Compounding Technology of Rigid and Plasticised PVC

641

30

Fig. 13.67 Planetary compounder ZSE. 1, Feed zone; 2, plastication zone

(planetary system); 3, de-gassing zone; 4, discharge screw; 5, retention ring.

When the main spindle is rotated, the planet screws rotate along
with it and roll around the inside of the barrel. As a result, the PVC
stock is sheared and squeezed between the tooth flanks and roots of
the main spindle, planet screws and barrel. Mechanical energy is
converted into heat and the stock is plasticated. External heating is
employed to aid the plastication work.

Fig. 13.68 Operating principle of planetary-type machines. 1, Main screw; 2,

planetary screw; 3, barrel; 4, retention ring; 5, discharge orifice.

642

W. Henschel and P. Franz

The replaceable retention ring serves two purposes:

-it prevents the planet screws from shifting axially, i.e. from being
screwed out of the barrel;
-it controls the level of back-pressure (and thus also the energy
conversion) in the planetary screw section: the control is exercised
by pre-selecting the internal diameter of the ring opening and
hence the proportion of outlet cross-section left open.

Anywhere from 6 to 18 planet screws can be employed, depending

on machine size and desired level of energy conversion.

Temperature control: The barrels have several temperature control

zones heated by means of a liquid heat-transfer medium (HT oil). The
main spindle and discharge extruder screw have the same type of
thermal control.
De-gassing: As mentioned under 'Operational sequence' above.
Output rates and technical data: See Table 13.18.
(b) Machine Drives
Present-day requirements in compounding technology call for variablespeed driving motors for the screw-type machines. The selection is
made from AC commutator motors, DC motors, and frequencycontrolled AC motors. All three types make it possible to alter screw
speed by remote control.
In Europe, DC motors are priced more favourably than commutator
motors for drive ratings above about 80 kW. The price advantage
begins at even lower ratings in the USA. This is one of the main
reasons why DC drives are preferred for most production installations.
Although such drives become expensive where explosion protection is
required, drive motors for PVC compounding seldom have to meet this
standard. Dustproof and splashproof motors are usually sufficient.
An interesting development is taking place in the area of
frequency-controlled AC motors, which exhibit DC-motor characteristics (such as constant torque over the entire speed range) despite the
use of AC. Another advantage is that explosion protection is no more
expensive than it is for commutator motors.
To protect drive motors from dust, it is advisable to draw cooling air
for self-ventilation through a generously dimensioned filter or to use
filtered fresh air in the case of separate ventilation.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

643

Small drives for peripheral equipment such as feed hoppers, cutting

knives, etc., are normally designed with single-speed AC motors. A
mechanical variator gear unit makes it possible to alter speeds. Where
the speeds of the main screw and the feed hopper are synchronised
(see Section 13.4.2(b, however, the hopper drive must also employ a
DC motor for technical reasons.
Power transmission from motor to gear box can be accomplished in
any of four different ways, viz. by direct drive with an elastic coupling,
V-belt drive, chain drive, or flat belt drive.
Direct driving by means of an elastic coupling is preferred for
machines with screw speeds higher than 200 r min -1 and in cases where
V-belt drives are impractical for technical reasons. Transmission with
V-belts, which provide an elastic link between motor and gear box, is
standard practice in the 50-250 r min- 1 screw speed range. The V-belts
should travel no faster than 30-40 m S-I. With today's materials and
V-belt structures, up to 35 kW can be transmitted per belt. Since it is
feasible to combine as many as 10 or 12 V-belts, drive ratings as high as
about 400 kW can be handled.
Drive chains are used typically for slow-turning screws, such as
pelletising screws. They are capable of transmitting high forces at low
speeds, Le. high torques. Chain speed is limited to 10-15 m S-I,
however.
Modern materials and improved designs are also opening up new
possibilities for flat belt drives, which date back to the beginnings of
industrialisation. Their low inertia forces and good elasticity are
desirable qualities for power levels up to about 40 kW.
(c) Control and Instrumentation
Process control of screw-type machines requires that the following data
be measured and recorded, and in some cases controlled automatically:
-temperature of the individual heating zones;
-material metering rate and screw speeds;
-energy input;
-stock temperature;
-pressures.
HEATING ZONE TEMPERATURE

Where liquid heat-transfer media are employed, a heat-exchanger unit

is provided for each heating zone. The temperature of the liquid is
maintained at the set-point adjusted on the electronic controller by a

Number of planetary screws

Main screw speed (min-I)

Planetary screw length (mm)

Screw length

Screw diameter, D (mm)

6 to 12
25-50 (70, 100,
120 and 150 EV)
3-60 (200 EV)
35-70 (170 EV)

6 to 18
2-40 (ZSE 300)
to
35-70 (ZSE 100)

5D1twin helix

6D (ZSE 300)
to
85D (ZSE 150)
500-1000

1-20 (ZSE 300)

to
3-60 (ZSE 150)

13D (170EV)
to
165D (100 EV)
260-1000

150 to 350

150 to 315

70 to 206

2nd stage
Single-screw system

PWE
70 EV to 200 Eva
(6 models)

1st stage
Planetary system

,ZSE 100 to 300n (4 models)

WE
100 to 2900
(5 models)
138 (120 AK)
to
315 (300 AK-N)
62D (300 AK-N)
to
88D(150 AK)
500 (100 AK-N); 700
(120 AK); 900 (150
AK); 1000 (all other
models)
7 to 18
2-40 (300 AK-N)
3-60 (all models)
to
35-70 (100 AK-N)

PWE 100 to 300n

Two series:
AK-N (4 models) and
AK (4 models)

TABLE 13.18
Technical Data for Planetary Compounders: Summary Table

9 to 40
6 to 22

12 to 49
9 to 31

Screw
Heating capacity (kW):
Barrel

85 to 2300
40 to 700

60 to 1400

77 to 81

3 (70 EV); 4 (100,

120 and 200 EV); 5
(170 EV) or 6 (150
EV)

12 to 280

Range limit data apply respectively to these range limit models, unless otherwise indicated.
b Approximate ranges.
c Figure for PWE 120 AK (the output of PWE 100 AK-N is the next lowest).

400 to 2800
500 to 3300
700 to 4000

1 to 2

Screw
Output ratesb (kg h- 1 ):
Rigid PVC
Semi-rigid PVC
Plasticised PVC
PVClABS blend

23 to 130

60 to 320

Drive rating (kW)

No. of heating/cooling zones:
Barrel

300c to 2800
350c to 3300
450c to 4000

21 (100 AK) to 72
(170 AK and 200 AK)

2 (100 AK) to 3
(all other models)

60 to 320

36 to 90

3 (all models)

50 to 400

646

W. Henschel and P. Franz

comparison in the controller between the desired and actual tempertures and subsequent correction, either by cutting-in electric heaters or
passing cooling water through the heat exchanger.
Electric heating systems are controlled in similar fashion. Thermocouples detect the temperature of the barrel wall in each zone, which is
then compared with the set-point. If the wall is too cool the electric
heater is switched on; if it is too hot, a liquid cooling medium is passed
through the particular jacket or else fans are switched on to provide air
cooling. Each heating zone represents a closed control loop with the
set-point temperature acting as command variable.
In contrast to final processing systems, compounding operations
generally do not require the command variable, i.e. the set-point
temperature, to be altered in line with the momentary stock
temperature.
Depending on the physical layout of a compounding operation, it
may be advisable to display the various zone temperatures in the
central control room or even to record them.
METERING RATE AND SCREW SPEEDS

In the equipment described in the preceding sections, in which

screw-type machines are fed via feed hoppers, the speed of the feed
screw governs the production rate. This rate, and the speed of the
main screw, are two of the variables on which the energy input
depends. If conditions are unfavourable, a screw-type machine can be
overfed so much that the feed screw or the main screw jams.
An added factor in the case of pellet production is that the
pelletising screw must extrude the stream of product emerging from
the compounder through the multi-hole die plate; again, this is a
question of screw speed.
It is therefore important to be able to preselect and control these
speeds from the central control station. Normally it is sufficient to
employ analog indicating instruments for showing the speeds
picked off by tacho-generators.
Where DC drives are used, the preset speed is automatically held
constant regardless of momentary motor load until the maximum
admissible amperage is reached. This, then, constitutes another closed
electronic control loop.
In the compounding operation, there is no need to control speeds on
the basis of stock temperature and stock pressure as is the case, for
instance, in injection moulding.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

647

ENERGY INPUT

The level of energy input is the main determinant of product quality. It

is expressed as specific kneading energy (work), i.e. that imparted to a
unit weight of stock, calculated by dividing the momentary driving
power by the output rate:
kWh)
e (kg

N(kW)

= G (kgh-I)

Hence the driving power levels of the kneading and pelletising

screws are among the most important variables requiring monitoring in
a compounding installation. Experience has shown that the input
power reacts more quickly and reliably to changes in process
conditions than do temperatures or pressures.
In the case of AC drives, the energy reading must be compensated
for reactive power to show only the active power imparted to the
product.
STOCK TEMPERATURE

After the specific kneading energy, heat history is the second

important determinant of product quality. Thus it is extremely
important to know the temperature profile of the stock as it moves
through the line.
A technical problem arises in this connection. In the screw-type
machines described, the temperature probes (usually thermocouples)
have to be inserted into the barrel wall without coming into contact
with the PVC stock (Fig. 13.69). However, the barrel wall is heavily
affected thermally by the heat-transfer liquid flowing through it, or by
electric heaters. Thus the temperature probe picks up not the true
temperature of the stock, but merely a reference temperature lying
somewhere between it and the heating zone temperature.
To obtain more accurate readings, probe rings (Fig. 13.70) have
been developed. However these can only be placed ahead of the screw
tip and thus do not provide a temperature profile along the barrel.
Moreover, although the measuring shoulder is streamlined, they raise
the resistance at the outlet of the machine and may even cause
scorching.
An exception to the foregoing is the temperature measurement in
the Buss-Kneader system described in Section 13.4.4(a). In this case
the barrel kneading tools ('teeth') are completely surrounded by the

648

W. Henschel and P. Franz

HEAT-TRANSFER MEDIUM

Fig. 13.69 Temperature probe in extruder barrel wall.

PVC stock (Fig. 13.71) and virtually take on its temperature. Thus the
thermocouples, which are inserted in the teeth and reach close to their
ends, are able to pick up the actual stock temperature at any point
along the barrel.
Because the stock temperatures are very important in assessing heat
history--or even only as reference data-it is advisable to record them
at the central control station. Multicolour chopper-bar recorders are
normally used for this purpose.

A-A

Fig. 13.70 Probe ring.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

649

Fig. 13.71 Temperature measurement in the Buss-Kneader.

PRESSURES

Measurement of pressure is not as important in compounding as in

final processing, because the compounding process can be controlled
with sufficient accuracy on the basis of power input and temperature
profile. The diaphragms of the pressure probes normally employed are
highly susceptible to inadvertent damage during cleaning operations,
and disastrous errors can result if this damage remains undiscovered.
For this reason, pressure probes are normally used in compounding
only for monitoring the clogging of strainer screens.
(d) Interlocks
A compounding installation, that reaches from pre-mix feeding all the
way to pellet bagging or storage, represents a complex, integral system
that may well cover several different sections or storeys of a production
plant. It is therefore of utmost importance that switching sequences be
maintained without exception both during starting and in the event of
an unplanned shutdown.
A mimic diagram is therefore provided at the central control station,
particularly in large scale production systems, to facilitate operation of
the equipment. Moreover, the individual pieces of equipment are
interlocked electrically on the counter-flow principle, so that start-up
must begin with the last link in the chain-e.g. the conveying air fan for

650

W. Henschel and P. Franz

carrying the cooled pellets to a storage silo-and move upstream, with

each unit being switched on in succession. If a given element in the
chain is omitted, none of the rest can be switched on. Should any
element stop because of a malfunction, all equipment upstream from it
is switched off according to a preprogrammed schedule. Trouble of this
kind is signalled acoustically and shown visually on the mimic diagram.
(e) Materials of Construction
Two main factors must be considered in the selection of materials for
PVC compounding machinery: corrosion and abrasion.
All PVC formulations are a possible source of corrosion. There is
always a latent hazard that traces of hydrochloric acid will form as a
result of power fajlure or incorrect plant operation. Hence all parts of
a compounding machine in contact with the product are made of
corrosion-resistant steels. For parts subject to severe mechanical
loading, designers prefer steels with 17% Cr because of their high yield
point and good fatigue strength. Chrome nickel steels are more
resistant to corrosion, but are suitable only for elements with lower
mechanical loading because the yield point is only half as high.
In the case of highly filled formulations, such as flooring compounds,
abrasion must be taken into consideration along with corrosion. It has
proven advantageous to employ element-type screws for such applications, i.e. the kneading tools are carried on short elements that are
mounted on a cylindrical arbour. When wear occurs, only the worn
elements need replacing. Abrasion resistance can be increased by
cladding the screw elements with high-wear armour materials by
welding, plasma spraying or cold spraying.
Barrels are protected against wear in similar fashion. Figure 13.72
illustrates the two basic possibilities. In machines with a one-piece
barrel (Fig. 13.72(a)), bimetallic liners are forced into the bore. As
soon as wear exceeds admissible limits, the barrel is taken off and the
liners are replaced.
In the case of the vertically split barrel of the Buss-Kneader (Fig.
13.72(b)), similarly split liner sections are installed in each barrel half.
These semi-cyclindrical liners are held in place by the kneading teeth
mounted in the barrel. Worn-out liner elements can be replaced
without taking the barrel off the machine; those not yet worn are left
in place.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

651

"0

8
Q)

"a
I

Q)

.0

652

W. Henschel and P. Franz

(f) Machines for the Production of Pastes

PLANETARY MIXERS

Planetary mixers (Fig. 13.73) are suitable for mixing stock pastes and
for colouring virgin pastes with colour concentrates. Because little
energy is imparted, no temperature problems arise, but this mixer is
not capable of dispersing solids thoroughly: additional sifting and
grinding steps are required for exacting specifications. Planetary mixers
are usually built as vacuum mixers to de-aerate the paste prior to final
processing. Anywhere from 6 to 40 mbar of vacuum is sufficient for this
purpose. Mixing aids, such as internal pin mills (Fig. 13.73(b)), can be
added without difficulty. Mixing tools can be raised up to permit
removal of the mixing tank and to facilitate cleaning. Planetary mixers
are particularly suitable for medium-size operations with a broad
product range.
HORSESHOE MIXER

This vertical mixer has a centrally mounted, slow-turning agitator,

shaped like a horseshoe. This sweeps the entire tank wall to make sure
all the contents are involved in the mixing process.
Baffles must be provided to prevent the paste from rotating along
with the agitator in laminar fashion, which would impair the mixing
effect. The simple version of the horseshoe mixer is limited to use as a
holding vessel for pastes. Lately efforts have been made to achieve a
mixing effect similar to that of the dissolver by adding a fast-rotating
second agitator mounted eccentrically in relation to the first (Fig.
13.74).
BALL MILLS

In these mills, the friction gaps required to achieve dispersion are

provided by balls moving past one another. Where ball diameters are
relatively large, it is sufficient to tumble them in drums. To meet more
exacting dispersion requirements, however, small spheres or beads of
glass, ceramic materials or steel, or silica sand, are used, kept in
motion by agitators (Fig. 13.75). Because energy input is relatively
high, ball mills are used mainly for producing colour pastes. In a recent
development cooled agitating disks and cooled housings are being tried
to eliminate excessive heating.
Ball wear and screening of the balls deserve special attention.

Because of cleaning expense, these mills are used only for long
production runs.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

653

Fig. 13.73 Planetary mixer. a, Basic; b, with internal pin mill.

~ .~
L.--

L.-.

t'--- L-----"
Fig. 13.74 Horseshoe mixer.

RIBBON BLENDERS

Ribbon blenders (Fig. 13.76) have a slow-turning agitator that works in

conjunction with counter-flow screws or counter-flow baffles to mix the
product axially and tangentially. Because hardly any kinetic energy is
converted to heat, these mixers require relatively low driving power.

654

W. Henschel and P. Franz

Fig. 13.75 Ball mill.

On the other hand, the energy is insufficient to produce the fineness of

dispersion called for in many cases. Sifting and grinding operations are
therefore used following, or between, mixing processes of this type.
These mixers make it possible to prepare large quantities of uniform
stock or finished pastes, but they suffer from the drawback of being
hard to clean. Axially removable agitators have improved matters
lately, however.

Fig. 13.76 Ribbon blender.

13

Industrial Compounding Technology of Rigid and Plasticised PVC

655

Ribbon blenders are used preferably for very long runs with
infrequent colour changes.
PADDLE MIXERS

The mixing tools of the paddle mixers (Fig. 13.77) dip down and bring
large, cohesive quantities of paste to the surface. In addition, the tool
surfaces beat alternately into the paste. The kneading and squeezing
processes combine to produce the mixing effect. However, for effective
operation the mixer should be no more than about 70% full. Because
the energy input is at the thermally tolerable limit, the mixing tank is
equipped with a jacket for cooling.
To reduce the labour required for cleaning, the mixing tools can
normally be withdrawn axially.
Though pin mills may be installed to improve the efficiency of
mixing, they should be used cautiously because of the energy
dissipation involved.
If the mixing tool speed is changed, paddle mixers can also be
operated under vacuum. Conversely, pressure can be applied to
accelerate emptying (even with the mixing tool stopped) and to feed
the contents to pressure or vacuum strainer units.

Fig. 13.77 Paddle mixer.

656

W. Henschel and P. Franz

ROLL MILLS

Three-roll mills with two shearing nips (Fig. 13.78) are normally used
for producing PVC pastes on this type of equipment. Nip pressure, roll
speed and roll speed differentials (which produce the shear) must be
set appropriately for PVC pastes. If the settings are not appropriate to
their rheological properties, the paste films carried on the rolls may be
broken in the nips.

I \...- '

t\

f\

./

Fig. 13.78 Three-roll mill.

Unlike single-roll mills, three-roll mills have no sifting effect. Roll

adjustment to maintain uniform nip clearance can be made automatic
(and thus independent of the operator) with the aid of hydraulic
systems so sophisticated that they are even capable of correcting
automatically for changes in nip characteristics resulting from thermal
expansion or other factors.
Current standard practice is to feed the raw paste to the roll mill
freely with a cut-off element or with the aid of pumps, regardless of
viscosity. The feed rate is controlled by the paste buffer in the inlet
nip.
DISSOLVERS

Dissolvers (Fig. 13.79) are mixers with high-speed, infinitely variable

disk agitators. They are used for the production of stock pastes and for
dispersion. Most dissolvers are vertical machines that work-especially
in large-scale production-with portable tanks. The main element is
the agitator disk, whose diameter should be half that of the tank.
Desirable peripheral speeds during the dispersion phase are in the

13

Industrial Compounding Technology of Rigid and Plasticised PVC

657

Fig. 13.79 Dissolver. a. Disc agitator; b, scraper.

range 22-25 m S-1. To achieve laminar flow, the final viscosity of the
paste should reach about 25 P. If low-viscosity pastes are being
produced, they should be mixed at a higher viscosity level (with some
of the plasticiser left out) and then diluted after the dispersion phase.
The mixing tanks are smooth on the inside, preferably with vertical
walls. Circulating scrapers (wipers) can be installed (Fig. 13.79) to
return powder or poorly wetted paste adhering to the tank wall to the
bulk stock.
Dissolvers with a vacuum facility make it possible to produce,
de-aerate and colour the paste in a single operation. In such cases
vacuum is applied only after the resin has been wetted-out. Continuous
dissolvers are being developed.
BUSS MIXING TURBINE MT

Unlike the mixers described thus far, the Buss mixing turbine is a
continuously operating unit for the production of stock, finished and
coloured pastes. The equipment (Fig. 13.80) consists of a vertical
stator containing a high-speed rotor. The solids are fed by a metering
device through the inlet tube, 2, into the atomisation zone, a, where
they are aerated and disintegrated for passage to the centre of the top
rotor, 4. While the solids are spun out radially by the rotor, the liquid
components are injected through nozzles on the bottom of the stator

658

W. Henschel and P. Franz

Fig. 13.80 Buss mixing turbine MT. 1, Drive motor; 2, inlet for solids; 3,
rotor shaft; 4, rotor; 5, stator ring; 6, casing; 7, spray nozzles for liquids; 8,
product outlet; a, atomisation zone.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

659

rings. The rotors are shaped in such a way as to propel the product
downwards as well as radially outwards.
The next stator ring directs the already wetted or partially dissolved
solid material toward the centre of the following rotor, and the process
is repeated. In some applications the entire quantity of liquid is
metered in through the top nozzle ring. In others, it is fed in fractions
to the successive mixing chambers.
The mixing turbine can be connected directly to a vacuum filter
system, in which case de-gassing can take place at the same time. The
finished PVC paste is then pumped continuously out of the vacuum
tank to the next operation.
The two-piece rotor can be swung open for easy cleaning when
drastic changes of formulation or colour are scheduled. Because the
machine is compact and easy to clean, it is economical for both short
and long production runs. Some technical data are given in Fig. 13.81.
I

r i1

~
I

Ii
I~

L.--

t:::
il-t

""f

H(mm)
B(mm)
T(mm)

I
i
i

:
i

Ii

Ii

Weight (kg)
Output (kg h- 1)

._.*

T
MTIOO

MT250

1200
300
500
110
lOG-2oo

2000
700

MT400

2800
1200
900
1100
1300
2000
60(}-1000 150G-25oo

Fig. 13.81 Technical data for the Buss mixing turbine.

660

W. Henschel and P. Franz

13.5 PELLET COOLING AND STORAGE

13.5.1 Pellet Cooling
(a) Nature and Outline of the Operation
It is necessary to cool down the hot pellets rapidly in order to prevent
sticking, deformation and possible thermal degradation. Since most
PVC compositions are in a dry, highly viscous state on leaving
the pelletiser, there is no need to employ water cooling (as
practised, for example, with polyolefins). Cooling in a strong air
stream is sufficient. This has the big advantage that there is no need to
superimpose a pellet-drying operation on the cooling process. Ambient
air is usually all that is needed, although in a tropical climate it may
sometimes be necessary to pass it through a cooler or even an air drier
before blowing it into the pellet cooler.
From the pelletiser head (where their temperature may be anywhere
from 130 to 190C depending on PVC type and formulation) the pellets
are conveyed pneumatically through a pipe to the pellet cooler. En
route, the pellet temperature will fall (by 40-50C depending on air
flow, pellet loading and distance): in the cooler it is lowered further, to
about 40 to 60C, to permit trouble-free storage. Most pellet coolers
operate on the fluidised bed principle, i.e. the pellets are cooled while
being held in turbulent suspension in a rising stream of air.
(b) Pellet Cooler Systems
Figure 13.82 shows two systems developed by Buss. In the first (Fig.
13.82(A)), the pellets leaving the pelletiser are collected in a casing
and carried to the pellet cooler through a pipe operating on the
pneumatic suction principle. A cyclone separator built into the cooler
separates the pellets from the conveying air. A rotary valve attached to
the cyclone then feeds the pellets into the cylindrical cooling chamber,
where they are distributed by a sheet-metal cone. The conical bottom
of the cooling chamber is made of perforated sheet-metal. A second
fan, which is connected to the cooling chamber by a pipe, draws the
cooling air (room air) through the perforated bottom so that it passes
upward through the slowly sinking pellets. The cooled pellets are
discharged by a second, variable-speed rotary valve attached to the
conical bottom of the cooling chamber. An equilibrium condition, i.e.
a constant fluid-bed height in the cooling chamber, is obtained by

13

Industrial Compounding Technology of Rigid and Plasticised PVC

661

A
or

I coolpr

rolar

YClIVPS

Fig. 13.82 Granulate discharge and cooling units. A, Suction conveying unit;
B, pressure feed unit.

662

W. Henschel and P. Franz

altering the rotary valve speed to match the momentary output of the
compounding line. Each of the suction conveying pipes contains a
butterfly valve for adjustment of optimal air conditions in the
conveying pipe and cooling chamber.
The alternative design (Fig. 13.82(B is similar to the first, except
that there are no mechanically moved parts (rotary valves) in the
cooler. Here again, the pellets are collected in a casing as they leave
the pelletiser. They are then blown by a fan directly into the cooling
chamber through a pipe attached to the casing (pneumatic 'push'
conveying). The conveying air escapes to the atmosphere through an
oversized pipe capped by a filter basket. A second fan blows cooling
air into the cylindrical cooling chamber up through the perforated,
conical base. Because the air velocity and pressure in the cooling
chamber are lower than those of the conveying air in the pipe, cooling
air cannot penetrate the pipe projecting into the cooling chamber. The
cooling air also escapes through the exhaust air nozzle at the top of the
cooler. A butterfly valve is provided to permit adjustment of the air
flow so that the pellets are kept in a state of gradually sinking
suspension. The cooled pellets leave the cooler through an adjustable
slide valve at the bottom.
Two other pellet cooler designs are shown in Fig. 13.83. Both are
chute conveyors employing the ftuidised bed principle, and both use a
cyclone separator ahead of the cooler to isolate the pellets from the
conveying air, a rotary metering valve at the bottom of the cyclone,
and adjustable diverter plates over which the pellets pass on their way
to the chute. The two designs differ in the mechanism employed to
obtain forward movement of the pellets in the chute.
In the version shown in Fig. 13.83(B), the chute, which has a finely
perforated sheet-metal base, is mounted on elastic vibration elements
(such as vibration mounts or helical springs): it thus functions as a
vibrating chute conveyor (here actuated by an eccentric motor) in
which the pellets are moved forward by micro-propulsion under both
horizontal and vertical acceleration, being whirled periodically upward
from the bottom of the chute in parabolic trajectories whose size and
shape depend upon the frequency and amplitude of the drive.
A fan connected by a pipe to the top of the chute conveyor draws
cooling air up through the perforated base, at right angles to the
conveying direction. Because the air flows over the entire surface of
each individual pellet, an intensive cooling effect is achieved. Pellet
residence time on the chute is adjustable over a broad range by
changing the chute's inclination or altering the amplitude of the

13

Industrial Compounding Technology of Rigid and Plasticised PVC

tr~,,

edlausl
OJr
~1~15

from

663

-"""""'........_b...1

~1~lo~r

cool~d
p~II~ls

~xhousl

OJr

~II~IS

from
~n~los~r

. ._-- -.......

8
coolong OJr
fan

Kcenlroc molor

I oor fan

Fig. 13.83 Horizontal granulate cooling units with: A, feeding system using
pulsation of air; B, feeding system using mechanical vibrations.

w.

664

Henschel and P. Franz

eccentric motor. The rate of cooling is regulated by varying the air flow
in conjunction with the pellet residence time. The pellet temperatures
normally achieved are some 5 to 10C above the ambient air
temperature.
In the Biihler-Miag design shown in Fig. 13.83(A), the pellets are
moved along the chute by means of pulsating cooling air, which is
blown into the chute by a fan, through a finely perforated base plate.
A pulsator in the form of a butterfly valve (driven by a variable-speed
motor) in the intake duct between the fan and the perforated base
produces an intermittent air flow that moves the pellets along the
chute. The cooling air leaves the chute through an oversized exhaust
pipe. Pellet residence time can be varied by altering chute inclination
or pulsation rate.
13.5.2 Pellet Mixing and Storage

The mixing of pellets with different characteristics or the homogenisation of pellets of a given type from different production batches calls
for large containers with useful capacities up to 1000 m3 .

(a) Pellet Mixer Designs

MECHANICAL MIXERS

A broad selection of mixers is available for mixing very small batches

of pellets up to about 10 m3 The main types of mixers used in the
plastics industry for larger batches are listed in Fig. 13.84 which gives
their capacities and corresponding driving power levels.

Note: Another type of mixer, not included in Fig. 13.84, is the pure
gravity mixer: the bulk material is withdrawn simultaneously
from various levels of the mixing silo and fed to a common
chamber, or else silo cells formed by vertical partitions are
filled successively and then simultaneously emptied. These
mixers, which require no energy input, cannot produce an
ideal (random) mixture but are adequate for certain purposes.
Mechanical mixers such as the orbiting vertical screw mixer (Fig.
13.85) are built with useful volumes as large as 75 to 80 m3 . This type
of mixer has a hopper-shaped container with a screw set parallel to the
hopper wall. The screw is supported at the bottom of the hopper and is

13

Industrial Compounding Technology of Rigid and Plasticised PVC

665

10000

1000
~

01
C

15
L-

a.o

10

L-

.
0.1

10lXlO

Capacity

m3

Fig. 13.84 Drive rating as a function of mixing volume in pellet mixers. A,

Orbiting vertical screw mixer; B, double cone mixer; C, vertical screw silo
mixer; D, pneumatic mixer.

driven by a crank arm at the top so that it both rotates and circles the
inner wall of the hopper simultaneously. (In the epicycloidal mixer, the
screw describes an epicyclic curve between the hopper wall and centre
instead of travelling in a circle around the periphery.) The PVC pellets
are carried upward by the screw to reach ever higher levels within the
hopper.
Double-cone mixers are built with capacities as high as 100 m3 . So
are vertical screw silo mixers of the type shown in Fig. 13.86.
In vertical screw silo mixers, the pellets are raised to the upper part
of the silo by a screw conveyor in the central pipe. Spreader arms
distribute the material evenly over the silo cross-section. The material
then proceeds to move downward in the silo, at a rate which is a
function of the conveying rate of the screw in the bottom part. A
hopper-shaped insert divides the pellets as they slide downward.
Ultimately they pass through the outer and inner annular spaces to the
bottom of the screw and are raised once again.

W. Henschel and P. Franz

666

P4!'II4!'llnl4!'1
from P4!'1l4!'1 cool4!'r

US4!'fui capacIty
Standard siz4!'s

0.05 to 30m 3
SP4!'cial SIZes
75 to 80m3

OrIY4!' rohng
1.51010 kW/m 3

- To sloraQ4!'
- To shipping

Fig. 13.85 Orbiting vertical screw mixer.

PNEUMATIC MIXERS

Pneumatic misers, which include both the fluidised-bed mixer for

powders (Fig. 13.87) and the recirculating mixer for coarse bulk
materials and pellets (Fig. 13.88), can be built in sizes up to about
1000 m3 . Pneumatic mixers are built with higher drive ratings and
larger capacities than mechanical mixers. They also handle the pellets
more gently. Figure 13.89 shows the operating pressure as a function of
mixer height for both types of pneumatic mixer.

13 Industrial Compounding Technology of Rigid and Plasticised PVC

667

P~Il~1 Inl~1

from

~II~I cool~r

S~od~r

U~ful

arms

copaclly

) 10 100m)
C~nlrol lub~

wllh

conv~y,ng scr~w

Orov~

roling

0.5 10 2kW/m)
Hopp~r-shop~

Ins~1 tor
dIvIdIng flow
01 ~1I~ts

Homo~nis~d
p~Il~IS

Fig. 13.86 Vertical screw silo mixer.

Fine bulk materials with particle sizes between about 30 and 200 J.lm
can be homogenised very economically in fluidised-bed silo mixers of
the kind originally developed for the cement industry, in which the
mixing process depends on different degrees of aeration of (different
rate of air supply to) different sections of the base of the silo. The main
design parameter is the fluidisation line. If a fluidised bed is aerated at
an air velocity above the point of incipient fluidisation, the bed
expands. The base of the silo mixer is designed to permit individual
sections to be aerated more strongly (or 'actively') than other
('inactive') sections. This causes the bulk material above the actively
aerated sections to expand and rise higher in the silo, so that it flows
down onto the material in the inactive sections. The material in the

w.

668

Henschel and P. Franz

Air oullt't

Filtt'r

".
USt'ful capacIty
up to 1000m)
and lar9t'r

...

,,

"'

:
'

II

,,
,

U
,

, .,
,.
,

I.
,
I

Circular a,r
Intakt' channt'ls

A,r
inactivt'
aCllvt'

Fig. 13.87 Fluidised-bed mixer.

bottom of the 'inactive columns' also tends to flow into the actively
aerated sections, because the actively fluidised 'columns' have lower
bulk density. The resulting circulation produces mixing, which can be
promoted by activating and de-activating a given section at regular
intervals. Fluidised-bed mixers of this type are used for homogenising
PVC powder following polymerisation.
Because the rate of air flow required for fluidisation rises with the
square of particle size, fluidised bed mixers become uneconomical for
coarse bulk materials with particle size larger than 500 pm, including

13 Industrial Compounding Technology of Rigid and Plasticised PVC

669

Aor oullE'1
PE'IlE" InlE'1
trom pE'IIE'1 coolE'r

a
b

c
d
E'
f

g
h
51,52

R'SE'r tubE'
MIXIng hoppE'f
Milling conE'
ChokE' SE'cl,on
Fan
Mlxong hE'Od
BUIIE'rfly valvE'
BailiE' conE'
ME'tE'f1ng gop

"

".

..

b
USE'ful capacIty
up 10 1000m)
and largE'r

DrivE' rot 109

-O,1kW/m)

HomogE'n,sE'd

V pE'IIE'IS

Fig. 13.88 Pneumatic recirculating mixer.

plastics pellets. For instance, pellets 3 mm in diameter with a solids

density of 1000 kg m -3 and a bulk density of 500 kg m -3, mixed with an
air fluidisation velocity of 1 m s -1 in a silo 5 m in diameter, would
require a minimum air flow rate of 70 000 Nm 3 h -1. *
The pneumatic circulating mixer provides a way of obtaining
satisfactory pellet homogenisation with less air. In this case the PVC
pellets are withdrawn at two points in the mixer outlet and conveyed
* A German unit = cubic metres per hour at STP.

w. Henschel and P. Franz

670

...

....
0

l/l
l/l

'"c:

.2
a

0.
D

'0
0

a:

..
...
~

jj

c
0
iii
ii

a.
E
0

AJ

11'1

30m
Mixer height

Fig. 13.89 Operating pressures for pneumatic mixers. a, Fluidised-bed mixer;

b, pellet recirculation mixer. (Source: Waschle leaflet.)
pneumatically back up to the top. In addition-as shown in Fig.
13.88-a mixing hopper (b) is built around the riser pipe (a). After the
pellet streams flowing between mixing hopper and riser and between
mixing hopper and mixing cone (c) have passed through a bottleneck
(d), in the form of annular metering gaps s1 and s2, they are metered
into the air flow for upward conveying. Together with the mixer
geometry, this metering step affords effective horizontal and vertical
mixing of the entire mixer contents. The metering gap s2 can be
optimised by shifting the riser pipe (a) vertically. A single-stage fan
generates the air pressure for the vertical conveying. It blows the air
into the mixing head (f), in which the PVC pellets are metered in
through the gaps s1 and s2. Because air velocities are low (about
12 m S-l), the pellets are conveyed very gently. Loadings of 7-12 kg of
pellets per kg of air are optimal. At the upper end of the riser pipe, the
pellets are spread on top of the mixer contents by a diverter cone (h).
In view of the low conveying velocity, this change in direction is also
very gentle. The conveying air leaves the silo through a central capped
opening in the mixer lid. Intelligent design of the riser pipe enables the
single-stage fan to raise the pellets at rates of 100 Mp h-h and higher.
Megaponds per hour (i.e. tonnes per hour).

13 Industrial Compounding Technology of Rigid and Plasticised PVC

671

The mixing process requires the pellets to be circulated 3 or 4 times

through the silo. The uniform random mixture obtained has a standard
deviation of the order of 2 to 3%.
Pneumatic circulating mixers have the following features:
-no moving parts in the mixing chamber;
-high-quality mixing;
-achievement of uniform, random mixture;
-same mixing quality throughout entire mixture;
-no segregation of different particle sizes;
---easy adaptation to process because of flexible mixing time;
-low-cost installation;
-virtually unlimited batch size;
-low energy consumption, even for large particle diameters;
-gentle product handling;
-low noise level;
-spray nozzles making cleaning easy at product changeover.
(b) Handling of pvc Pellets
Having been homogenised in the mixers, the batches of pellets can
now be delivered for processing. Most mixer silos are set on frames to
permit road tankers, container trailers or rail tankers to be driven
underneath for gravity filling. If the pellets are to be bagged, semiautomatic or fully automatic bagging installations are supplied directly
from the mixers. Fully automatic systems normally provide automatic
stacking of the bagged goods on pallets followed by fixation of the unit
load with PVC shrink film.
If the compounding operation is part of a final processing plant, the
pellets are conveyed to the injection machines or extruders through
distribution pipes or in boxes carried by fork lifts.

CHAPTER 14

Extrusion ofPVC-General Aspects

B. J.

LANHAM

and W. V. TITOW

14.1 INTRODUCTION

In the widest general sense, extrusion is a process for the conversion of

a plastics feed material into a continuous product with cross-section
shaped and dimensioned to particular requirements. In some operations the primary object is compounding and thorough mixing of the
plastics material (extrusion compounding-see Chapter 13).
Historically, plasticised compositions were the first PVC compounds
to be processed into products by extrusion. Single-screw extruders,
designed for rubber compounds, were used: these machines had very
low length-to-diameter (LID) ratios (down to 4: 1 in some cases), with
no provision for effective heating at the temperatures appropriate for
PVC (higher than those required for rubber processing) and for
temperature measurement. Improvements in these respects, together
with provision for acceptance of granular feedstocks, may be regarded
as the earliest steps in the evolution of PVC extrusion equipment (see
Chapter 1, Section 1.2). Even with these modifications the early
extruders were crude by modern standards: nevertheless, cable
coatings, tubes and sections were being produced towards the end of,
and shortly after, World War II.
Since those days the single-screw extruder has developed into
advanced equipment of a high standard of efficiency and reliability.
The growth of the use of rigid PVC-first extruded in the mid-1950sand especially rigid pipe production, was a prime factor in the
development of sophisticated twin-screw machines (and certain types
of multi-screw compounding extruders-see Chapter 13).
673

674

B. J. Lanham and W. V. Titow

The use of extruders in the compounding of PVC is discussed in

Chapter 13. Apart from its role in that application, and indeed even
more importantly, extrusion is a major production process, whereby
about one-third of all PVC polymers used are converted into products
of high industrial and applicational significance. The main rigid PVC
products made by extrusion are pipes (including water, soil, and
drainage pipes, rainwater goods, and electrical conduit), cladding for
buildings, profiles (including window frames), sheeting (including
packaging films), and blow-moulded containers. These products are
reviewed, together with others (including plasticised extrusions) in
Chapter 26; some are also discussed in Chapters 17 and 19. The most
important plasticised PVC extrusion products are electrical wire and
cable coverings, flexible film, flexible tubing and profiles. Protective
wire coating for chain-link fencing may also be mentioned.
14.2 THE EXTRUDER
14.2.1 Main Components and Their Functions, with Special
Reference to Extrusion of PVC

Figure 14.1 is a simple, generalised, schematic representation of the

basic processing parts of a single-screw extruder. The PVC feedstock
(pellets or powder~f. Chapter 13, especially Section 13.4.1(a); and
also Section 14.2.2 below) is charged into the hopper, whence it passes
to the feed section of the screw through an opening in the barrel (the
feed throat). The stock is conveyed forward by the screw and at a

Hopper

- - t -....

Fig. 14.1 General arrangement of a single-screw extruder.

14 Extrusion of PVC-General Aspects

675

Fig. 14.2 A typical twin-screw arrangement. (Intermeshing screws mounted

in horizontal plane; actual screw configuration of a Schleomann machine, ct.
Table 14.2.)
certain stage-depending on the composition, screw design and
operating conditions-fuses to a homogeneous melt. The conversion of
the solid PVC feed material to this state, and in particular the
morphological changes involved (see Section 14.3), is usually referred
to as 'gelation' or 'plasticisation'. The molten material is forced out
through a die at the outlet end. This extrudate is cooled, whereupon it
solidifies in the cross-sectional shape imparted by the die.
In a twin-screw extruder the two screws are positioned in the barrel
side-by-side, in a horizontal plane (cf. Fig. 14.2). The screws may be
either the regular cylindrical overall shape. or they may be conical,
tapering towards the die end of the extruder. In general. the screws
may be either co-rotating or counter-rotating (to the inside or the
outside)-in PVC processing commonly the latter. Twin-screw extruders for PVC usually have intermeshing screws: with segmented screw
construction (see (a) below) the flights may intermesh fully along some
segments, and only partially in others (some screw configurations may
also include non-intermeshing sections).
It is essentially a question of semantics, and in any case a largely
academic point, whether the twin-screw machine should be classified as
the simplest version of the multi-screw extruder. As a matter of
practical fact, twin-screw extruders-of various designs and makesare in wide industrial use for the processing of PVC (both
melt-compounding and manufacture of important products like pipe,
profiles, sheeting, etc.), whereas truly multiple-screw machines (e.g.
planetary extruders-cf. Chapter 13, Section 13.4.4, and Ref. 1 here)
are less common and employed principally in a compounding role. For
the purposes of this chapter, twin-screw extruders are regarded as a
group distinct from multi-screw extruders proper, and the latter are not

676

B. J. Lanham and W. V. Titow

discussed in any detail because of their essentially compounding

function, already covered in Chapter 13.
The heat necessary to fuse the stock to a melt, and to maintain that
at the appropriate temperature for the degree of fluidity required, is
supplied in part by heaters on the barrel (in some machines the screw
temperature may also be controlled by the circulation of a fluid), and
partly generated in the material itself by the shear and friction to which
it is subjected in the machine. In otherwise comparable operations the
work-heat generation is greater in single-screw machines, where it may
also lead to a temperature distribution in the material less uniform
than that obtainable in twin-screw extrusion.
(a) The Screw
Figure 14.3 illustrates some basic general structural features of a screw.
In broad terms, the functions of a screw-in conjunction with the
confining barrel-are to convey the feed forward, melt ('plasticise')
and mix (homogenise) it, and to meter the resulting melt, under

Fig. 14.3 Some general features of a screw and associated definitions. Depth:
the perpendicular distance from the top of the thread to the root surface.
Flight: the space enclosed by the thread and the surface of the root in one
complete turn of the screw. Helix Angle: the angle between the screw thread
and the transverse plane of the screw. Land: the surface at the radial extremity
of the screw thread constituting the periphery or outside diameter of the screw.
Lead: the horizontal distance travelled by the material in one complete
revolution of the screw, assuming 100% efficiency. It is equal to the pitch
multiplied by the number of starts. Number of starts: the number of separate
threads traced along the length of the screw. Pitch: the horizontal distance
between corresponding points of two successive lands. Root: the continuous
central shaft, usually of cylindrical or conical shape.

14 Extrusion of PVC-General Aspects

677

pressure, to the die. Originally PVC was processed with screws of

relatively simple design, comprising essentially three sections, each
associated with one of the above functions, viz. a plain(parallel)channelled feed section, a transition (compression) section with
gradually increasing root diameter (reducing flight cross-section) in
which the composition is melted and compacted, and a metering section
where the mixing of the composition is completed, and which acts as a
metering pump delivering the melt to the die at constant volume and
pressure. 2 Today, more intricate screw designs are widely used,
involving shear sections, special mixing sections, and sections forming
decompression zones in the screw/barrel assembly, from which
volatiles are vented off. Complex flight configurations and-in some
cases-special processing elements (e.g. mixing pins on the pin-type
screw of a single-screw extruder) are found in some of the sections. In
certain designs the elements may be in the form of demountable
bushings on an essentially plain screw shaft, so that screw configuration
can be varied for different extrusion or compounding operations: one
example is provided by the screws of the Werner Pfleiderer ZSK
compounding extruder3 (d. also Chapter 13, Section 13.4.4(a).
Other facts being equal, the ratio of the effective length of the screw
(the distance between the forward edge of the feed opening in the
barrel and the forward end of the barrel bore) to its diameter (taken as
equal to the barrel bore diameter) affects its processing capacity, as
well as the amount of heat generated and its transfer in the system
screw/material/barrel.
Note: This ratio, known as the LID ratio, is customarily expressed in
relation to unity: e.g. the LID ratio for a screw of 100 mm

diameter and effective length 25 m (i.e. 2500/100 = 25) would

be given as 25: 1.

LID ratios of screws in modern single-screw extruders for PVC can

range up to about 35: 1 (or even higher in some cases), although 24: 1
is fairly common. With twin-screw machines lower values are
practicable, because the co-action of the screws makes it possible to
attain the requisite material pressures and degree of homogenisation at
shorter screw length (aided also by the greater degree of contact
between the working surfaces and the stock in comparison with the
single-screw extruder).
Modern screws have internal channels for the circulation of cooling
liquid. With some thermoplastics only the feed section of the screw

678

B. J. Lanham and W. V. Titow

needs to be cored for cooling. For PVC this facility should be available
along the whole length.
As mounted in place in the extruder, the screw is driven by a motor
through a set of reduction gears to ensure sufficient torsional power
and to transform the high rotational speed of the motor into the much
lower rotational speeds required of the screw. A thrust bearing at the
rear end serves to accommodate the substantial back-thrust experienced by the screw as a result of back-pressure built up in operation,
by the restricting action of the die upon the forward movement of the
melt which the screw actuates.
Screws are made of steel, and surface-hardened (most commonly by
nitriding) for increased resistance to wear and some corrosion
protection. For increased protection against corrosion in PVC
processing the screw may be chromium-plated (at least on the flights 4 ):
hard chroming will also confer some wear resistance. Other means of
increasing resistance to abrasive wear are nitrogen ion implantation (a
relatively new treatment developed in the UK at AERE, Harwell, and
now in commercial useS), or coating with special alloys (of the kind
also used for lining extruder barrels-see below).
Note: It has been claimed that a Z-Core (Z-Core Inc., Trenton, NJ,
USA) alloy coating can increase the life of screw and barrel
by a factor of 35 over that of an otherwise comparable
nitrided set in a twin-screw extruder processing PVC pipe
compound and regrind containing untreated calcium carbonate filler. 6

The extent of mutual compatibility of the screw and barrel facing

materials can be a factor in the resistance to wear in operation (apart
from the effects in this regard of the plastics stock). The significance
and role of this factor have been discussed by McCandless and Maddy. 7
The mechanics of wear on plastics extrusion equipment, and the main
methods of improving wear resistance (as well as resistance to
corrosion in some cases) are listed in a useful brief review by Avery
and Csongor. 8 These authors point out, inter alia, that hard facings
(applied by various welding methods) of cobalt-ehromium-tungsten
alloys, although expensive, offer a very high degree of resistance to
surface wear (with particularly good stability at local frictional
temperatures high enough to soften conventonally hardened steels)
combined with high resistance to corrosion, particularly by hydrogen
chloride. Such facings can be applied in relatively thick layers resistant

14 Extrusion of PVC-General Aspects

679

to penetration and undermining in service. Nitriding provides some

corrosion protection, whilst hard chromium plating is both very hard
and corrosion resistant but comparatively thin and-if not carefully
applied-subject to cohesion and adhesion problems.
(b) The Barrel
The barrel is often a solid forging of high grade mild steel which is
prepared externally to receive the heaters and internally to receive the
liner. The latter is of the greatest importance and is usually made as a
one-piece, hardened and ground, nitralloy component, honed to a
mirror finish. The clearance between the screw and liner will often be
as low as 0001-0003 in. It may be necessary to run them in and not
place too great a load on them at the start.
The barrel should be provided with suitable positions for temperature sensors (usually deep-seated thermocouples), and venting port(s):
venting, which is standard in modern PVC extrusion, is particularly
important with powder feed because of its relatively low bulk density
(high air content). Each venting port (which in operation will usually
be connected to a vacuum system) is normally associated with a section
in the corresponding part of the screw where the material is not under
compression (a decompression zone) to ensure that it is not extruded
through the vent.
Barrel and screw lengths have increased considerably over the years,
particularly in single-screw extruders. Several factors have been
instrumental in this change. Thus, in both single- and twin-screw
machines, some length extension was the direct result of the
incorporation of venting zones: the introduction, in many cases, of
additional or modified screw sections-in consequence of advances in
screw design-was also a contributory factor. In single-screw extruders, the main route to attaining the desired higher output rates was by
increasing the screw diameter (as, other things being equal, the output
rate goes up in proportion to the square of this-see eqn (1) below). A
simultaneous increase in length was also necessary, however, to
prevent a reduction in the residence time of the material in the barrel
which would otherwise result as a consequence of the faster output
(and hence throughput) rate: such a reduction would entail the need
for a higher temperature and/or shear energy input in working the
material to ensure adequate fusion and homogenisation.
Note: With PVC, and especially uPVC, which is susceptible to

680

B. J. Lanham and W. V. Titow

thermal degradation, and whose heat history should always be

kept to a practicable minimum, the fact that the extended
residence time in a longer barrel enables the total amount of
energy necessary for the requisite plastification and gelation to
be imparted under less drastic conditions of temperature and
shear, is particularly significant in both single- and twin-screw
extrusion.
The barrel length is also, in its own right, a factor in the output rate.
Moreover, with a longer barrel, the output is less sensitive to changes
in back-pressure, as well as more closely linear with screw speed. The
following expression9 is a fairly good representation of the general
relationship between the rate of output of a single-screw extruder and
the main structural parameters (although the degree of its quantitative
applicability can be somewhat variable in practice):

Qex:D 2 LhN

(1)

where Q = output rate (weight per unit time); D = barrel (screw)

diameter; L = effective barrel (screw) length; h = flight depth in the
last metering section of the screw; and N = rotational speed of the
screw.
In practice, the volume (v) of molten material in the foremost flight
of the screw (which is proportional to h) is also a power function of D:
to a first approximation v ex: D n , where the index n depends on melt
viscosity, and can have values of about 08 for uPVC and 06 for
pPVC. 9 Since if v ex: D n then h ex: D n , it follows that the output per
revolution of the screw is proportional to iY+ n .
Equation (1) suggests that the output could be increased simply by
speeding up the screw: whilst this is correct, there is a top limit on
practicable screw speeds, imposed by the attendant shear and frictional
effects on the material.
(c) The Head and Die Assembly
The melt leaving the screw at the front of the extruder is fed through
the die head and die to form the extrudate. Most dies (the actual
shaping sections) need to be held in a head which provides the
passageway(s) for the melt delivered by the screw to flow evenly to the
die opening. Dies vary greatly in size and complexity, from very large
pipe dies which can dwarf the extruder, down to small dies for profiles
of simple, small cross-section. Dies for use with rigid PVC must have

14 Extrusion of PVC-General Aspects

681

smooth, fully streamlined flow channels, free from hang-up points for
the material. Requirements are less critical in this respect with flexible
PVC compositions, and the use of crosshead dies (that turn the melt
through 900 in relation to the extruder screw axis) is quite common.
Dies may be of the fixed type, in which no adjustment of the aperture
is possible, or they may be so constructed as to allow adjustment
during extrusion. Adjustment is usually necessary on dies of annular
cross-section (e.g. for pipe or channelled profile), where it is achieved
by displacement of either the control mandrel or the outer ring (the
two elements defining the aperture-see Chapter 19, Fig. 19.8). On
flat-sheet dies the die lips are normally adjustable, in automatically
controlled lines on signal from on-line product control devices (d.
Chapter 19, Sections 19.3-19.5).
For PVC processing, especially uPVC, the walls of the die channel
must be protected against acid corrosion, e.g. by chromium plating.
(d) Heating and Cooling
In extruders used for PVC processing, barrel heating is generally
achieved by electrical resistance heaters cast into aluminium or
aluminium/bronze blocks clamped around the barrel. The blocks also
contain cast-in stainless steel tubes for circulation of cooling liquid.
Some resistance heaters still in use are insulated in ceramic material
supported in ceramic wedges.

Note: The heaters form a number of heating zones along the barrel,
with temperatures separately controlled. Fairly typically,
there may be five heating zones for a 24: 1 LID extruder, and
six for a 30: 1 LID. Heaters on the die adapter and the die
form separate heating zones.
Mains frequency induction heaters-which entail a continuous coil
round the barrel-are also occasionally encountered, but they are not
common: such heaters give very good control of temperature, but are
expensive and can fail by short-circuiting initiated by various causes.
The barrel can be cooled by passing mains water through the cooling
pipes, incorporated in the heater blocks as just mentioned, or situated
in the barrel wall under the heaters. A closed-circuit liquid system may
also be used: in this, the cooling water (or another liquid) is circulated
through the barrel-cooling pipes and any channels in the screw, and is
itself cooled by passage through a heat exchanger. 10 Air cooling, which
is also practised on some machines, is effected by blowing cold air over
the extruder barrel from blowers situated underneath.

682

B. J. Lanham and W. V. Titow

Like the cooling and heating systems, the temperature control

instruments have grown in sophistication with the growth in scope and
extent of extrusion of products which must be kept to close tolerances,
e.g. pipe, film, complex profiles. Most temperature controls in use today
are of the relay-proportioning (anticipatory) type. Such instruments
are an advance on the simple on/off (two-step) controllers so often
used in the past, in that they damp down temperature variation.
(e) The Hopper
This is fitted over the feed throat of the barrel. The feedstock may be
dropped directly into it, but is more often introduced via a vibratory
delivery chute, or a pneumatic, vacuum, or screw metering device to
ensure a constant rate of feed (see also Chapter 13, Section 13.4.2(a)).
Feeds can be completely automated, with the material conveyed to a
number of extruders from a central point.
Pre-heaters for the feedstock, usually interposed between the hopper
and the feed throat, are available for use with twin-screw extruders ll ,12
(e.g. Kraus Maffei, Maize, Kan., USA; Maplan, Vienna, Austria).
The devices raise the temperature of the material, so that the
extruder's work in producing a melt is reduced: the resulting
advantages claimed include increased extruder output (by up to 50%),
reduced wear on screw, barrel and gears, as well as maintenance of
constant feed temperature irrespective of ambient conditions (see also
Chapter 19, Section 19.3).

Note: In an early test run over 5000 h the output of a twin-screw

90 mm Kraus Maffei extruder (KMD 90) producing uPVC
pipe from powder feed was reported to be increased by about
38% (from 705 to 970 lb h- 1 ) when a pre-heater was fitted
and operated to raise the feedstock temperature to 80C.
14.2.2 Some General Points Relevant to Extrusion of PVC

(a) Machine Outputs and Energy Efficiency in Modern Extruder

Practice
Figures exemplifying outputs of some extruders when used as
compounding machines for PVC are given in Chapter 13 (Tables
13.10-13.18). In the manufacture of PVC products by extrusion, the
regular production capacity of a good, modern twin-screw extruder may
be as high as about 800 lb h -1 on uPVC pipe or profile, and up to

14 Extrusion of PVC-General Aspects

683

about 12001b h -1 on flexible profile. The typical energy efficiency of a

modern single-screw extruder operating on PVC (averaged over a
range of common LID ratios, drive powers and screw designs) was
quoted (December 1980)13 as lO-lllb per horsepower per hour.
Figures from the same source, as well as others, show that the average
output of extruders of comparable size increased by factors of 3-4
between the late 1950s and 1980.
(b) Some Features of, and Aids to, Modern Extrusion
VENTING

This has already been briefly mentioned in Sections 14.2.1(a) and (b).
With many plastics materials vented extruders are used in order that
volatiles and moisture may be extracted before the melt is metered to
the die. With PVC, however, removal of moisture and voaltiles,
though relevant, is not the major consideration: venting is important
primarily in the extrusion of rigid compositions from powder blend
feeds, where its main function is to get rid of occluded air. The general
arrangement of a vented single-screw extruder is schematically shown
in Fig. 14.4: it will be seen that the screw is of the two-stage type, with
a decompression section immediately following the first metering
section. At this point the stock fills the flights of the screw only
partially, and is subjected to a vacuum applied through the venting
port. In a vented twin-screw extruder the vent may be positioned
before the compression zone. Two venting ports spaced along the
barrel are provided in some cases.

Decompression
zone

r---

2nd----j1-oo41----- 1st - - - - - - - 1__1

Stlge
Stlg.

Fig. 14.4 Principle of a vented extruder.

684

B. J. Lanham and W. V. Titow

Note: Machines with the so-called 'by-pass' venting arrangementinvolving a seal at the end of the first metering zone and a
separate channel in the barrel wall through which the melt
passes to the decompression zone-are not recommended for
use with rigid PVC. In such systems the by-pass channelling of
the melt entails the possibility of material hang-up and
consequent decomposition. Moreover, the amount of working
undergone by the material is increased, although an experimental investigation 14 indicated that the increase can be
relatively small.
GEAR PUMPS

The metering performance of a single-screw extruder (and hence the

output and-in some cases-product uniformity) can be improved by
interposing a gear pump between the extruder head and the die. Gear
pumps have been used inman-made fibre spinning (a form of
extrusion) since the early days of cellulose acetate fibre production 15
for the even, positive, smooth delivery of the spinning solution or melt
they effect owing to their positive-displacement action. In single-screw
extrusion of a thermoplastic (where the pumping and metering action
is less positive than in twin-screw extruders) a gear pump can similarly
serve to eliminate pressure surges, including those that tend to occur at
screw speeds above the normal optimum for a particular material and
set of conditions. This stabilising effect can enable screw speeds to be
increased with consequent increase of the production rate, whilst
maintaining or even improving product uniformity, and possibly
effecting net energy savings. With an extruder of sufficient capacity
one pump can be used to feed several dies. Microprocessor controls
are available to coordinate automatically the pump temperature and
intake/discharge pressures with extrusion speeds. In a case, quoted by
Rice,16 of extrusion of a uPVC precision profile on a 45 in extruder,
the installation of a gear pump* doubled the output by enabling the
screw speed to be substantially increased without unacceptable rise in
back-pressure, screen pack clogging, or material degradation, which
prior to the use of the gear pump was caused by such an increase. Gear
pumps can benefit extrusion of sheet and blown film,17 as well as
profile and pipe.
* A Thermorex gear pump, Luwa Corp., Charlotte, NC, USA.

14 Extrusion of PVC-General Aspects

685

COEXTRUSION

Production of multi-layer plastics packaging films by coextrusion has

been increasingly practised, with continuing technical advance, during
the past decade. The technique is also employed in the manufacture of
some blown plastics containers (where the resulting composite
structure provides the required combinations of mechanical and barrier
properties), as well as some pipes and profiles,18,19 and sheeting, where
it provides an advantageous alternative to coating and lamination. 2o
Specifically with regard to PVC, some sheets and profiles (in particular
for window frames) are 'capped' by coextrusion with protective or
decorative layers of acrylic polymers or-in some cases-highly
pigmented PVC compositions. Such applications are referred to in
Chapter 19 (Sections 19.4 and 19.5), in Chapter 26, and alsopassim----elsewhere in this book.
PURGING COMPOSITIONS

Effective and rapid cleaning of extrusion equipment is important for

the reduction in machine down-time it can effect, prevention of colour
and other contamination, and for reduction of material waste. The
plastics materials suitable for purging injection-moulding machines
used in PVC processing, which have been mentioned in Chapter 15
(Section 15.4), can also be used on extruders. The purging agents
specially developed for this purpose are also of interest for both these
kinds of equipment: most commercial sources supply a special grade for
use with PVc. Two such compounds may be mentioned by way of
non-selective example. In using the RapidPurge (Rapid Purge Corp.,
Trumbull, Conn., USA) pre-mix blend for PVC purging to purge a
rigid PVC pipe composition, the barrel and die are left at a
temperature near the operating temperature (say about 160C), the
barrel is emptied, and then filled with the purging compound. After
this starts emerging from the die, purging is continued until most of the
original PVC composition has been cleared out (say for about 15 s).
The screw is then stopped and the material allowed to 'soak' for about
5 min. This is followed by another 15-s purge and 5-min 'soak', the
cycle being repeated until all traces of contamination disappear,
whereupon the barrel is emptied and the new extrusion compound
purged through until the purging agent has been thoroughly
removed. 21 Like RapidPurge, ChemPurge (special grade for PVCEngineering Chemicals BV, Steenbergen, Holland; UK agent, Normandy Plastics, Sidcup, Kent) is said to be based on a thermally

686

B. J. Lanham and W. V. Titow

degradable nitrogen compound claimed to depolymerise by free-radical

attack the material being purged to products of low viscosity which are
readily removable: the use of this purging agent is said to involve no
health hazards,22 with full cleanliness achievable in about 15 min. The
nature, applications and sources of commercially available purging
agents of American origin have been reviewed recently by
Brockschmidt: 23 some of those of special interest for PVC, like Polyvin
(A. Schulman Inc., Akron, Ohio, USA) or 50-FT-50 (Wilson-Fiberfil,
Neshanic Station, NJ, USA)-the former re-usable, and suitable for
being left in machinery during shut-down and start-up-contain
scouring additives and stabilisers.
(c) Use of Computers
This has been growing in extent and importance in three areas:

computer modelling of the extrusion process 24 ,25 and of the

strategies of its automation;26
(ii) use of computer models and programs in the design of extruder
screws (d. Section 14.4 below), dies (cL Chapter 19, Section
19.3.2), and other parts;
(iii) practical application of microprocessors in automation of
extrusion lines, including automatic on-line monitoring of
product dimensions and quality, with necessary corrections by
automatic running adjustment of die apertures, as well as
automatic control of 'downstream' operations (e.g. cutting and
machining of pipes and profiles): several examples of this kind
of automation are given in Chapter 19.

(i)

(d) Some Material Aspects

FEED TYPE

The feedstocks used in PVC extrusion are of two physical forms:

powder and pellets. The powder feeds are usually dry blends, produced
by hot mixing of the formulation components, but powders mixed
without substantial heating-often called pre-mixes-are also used in
some extrusion operations: in a pre-mix the composition constituents
are less thoroughly and intimately blended with the PVC resin than in
a dry blend. Therefore the amount of overall homogenisation work that
must be done on the feed by the extruder decreases (whilst the cost of
the feed rises) in the sequence pre-mix> dry blend> pellets (which will

14 Extrusion of PVC-General Aspects

687

have been melt-compounded). The preparation of these types of PVC

compound is described in Chapter 13, Sections 13.4.1 (pre-mix and
dry blend powders) and 13.4.2 (pellets). Their use as extruder feeds is
further discussed in the introduction to Chapter 19.
PVC COMPOSITIONS FOR EXTRUSION
As in injection moulding of PVC, processing by extrusion is easier with
plasticised compositions, so that, in formulating, the processing
considerations (as against those associated with service requirements)
are less critical than in the case of uPVc. With the latter, the type of
extruder used (i.e. whether single- or twin-screw) also influences the
formulation. This, and other aspects of formulating uPVC compositions for use in the manufacture of major extruded products, are
discussed in Sections 19.3-19.5 of Chapter 19, in Chapter 4, and
Chapters 9 and 11 (in connection with the roles of stabilisers,
lubricants and other formulation constituents): they are also mentioned
at various other points in the book.

FORMULATION OF

PLATE-OUT

As mentioned in Section 9.7 of Chapter 9, plate-out-i.e. persistent,

sticky deposits on working surfaces of processing machinery--<:an
occur in extrusion, as well as calendering and other PVC processing. In
extruders, the deposits tend to appear and accumulate particularly in
areas where pressure or flow changes occur, as, for example, on the
wall and legs of the spider. Appreciable deposit build-up on these sites
causes surface marks on the extrudate: plate-out in the die can also
affect the extrudate dimensions. Cleaning-up operations on surfaces so
affected interrupt production, causing loss of time and output, and
material wastage (or at least creation of extra re-work) associated with
shutting down and starting up again. Moreover, cleaning merely
temporarily removes the symptoms, without remedying the cause of
the problem: this, albeit still not completely elucidated, is known to lie
in the interactions of some formulation components (certain lubricants,
stabilisers, pigments and fillers) in the particular processing conditions.
The first comprehensive explanation of the nature of plate-out and the
mechanism of its formation in extrusion to be proposed was put
forward by Lippoldt,27,28 on the basis of an analytical study of actual
plate-out deposits, and experimental preparation of 'synthetic' plateout material. The proposed explanation postulates a fairly complex
mechanism, involving six sequential steps, whereby a gel is formed by

688

B. J. Lanham and W. V. Titow

components of the lubricant and stabiliser system (one of which-a

hydrocarbon in this particular study-acts as a temporary solvent
above the 'critical solution temperature') occluding particles of
pigment and filler (Ti0 2 and CaC0 3), and is deposited on surfaces
whose temperature is below the critical value (put by Lippoldt as 175C
for the system examined). Loss of the temporary solvent after
deposition results in transformation of the deposit into a solid film,
resistant to re-dispersion in the PVC composition and forming a
receptive surface for further deposit build-up. Lippoldt suggests28 the
following measures for the prevention of plate-out: maintenance of
temperature in pressure-change zones well above the critical solution
temperature (CTS); reduction of the CTS by suitable selection of
lubricants and stabilisers; modification of the potential solvent/solute
system of the gel precursor of the plate-out deposit so as to hinder its
formation, e.g. by selection of a stabiliser with low capacity for
solubilising fatty acid salts (such as calcium stearate).
(e) Some Features and Common Faults of Extruded Products
MANIFESTATIONS OF INCOMPLETE GELATION

These can take various forms. Inadequate overall gelation (see Section
14.3 below) impairs the mechanical properties of the product.
Inhomogeneity of the melt arising from variation in the degree of
gelation produces corresponding differences in melt rheology, whichif sufficiently pronounced-ean be manifested as transverse undulations (in more drastic cases lines of transverse weakness) in the
product: such effects can show up, for example, as waviness in the bore
of an extruded pipe. This can take the form of a regular pattern, being
associated with release of strain (whose degree will be influenced by
melt rheology) imposed on the melt in the screw flights, and hence
related to the flight pattern. Given that the required degree of gelation
and homogenisation of the melt is being achieved in the process, the
pattern can be reduced or eliminated altogether by ensuring that the
die design and adjustment is fully suited to the pipe size being made
and the production rate (d. Chapter 19, Section 19.3.2).
Fine porosity may sometimes appear in the extruded product even
with adequate venting of the machine: this is usually caused by the
screw speed being too high, which can cause either some decomposition of the polymer (or of an additive) due to excessive shear, or
incomplete gelation (because the material moves out of the barrel

14 Extrusion of PVC-General Aspects

689

before full gelation has been attained). Reduction of screw speed,

or-in the case of porosity associated with incomplete gelation (which
can be shown up by appropriate tests)-also possibly increase of the
back-pressure (by suitable die design), are the remedial measures.
Longitudinal streaks or weld lines can sometimes arise if the melt
separated in its flow (e.g. by the spider legs) has failed to knit
properly: this kind of fault which results from incorrect die design is
rare in good modern extrusion practice (see also Chapter 19, Section
19.3.2).
IRREGULARITIES OF PARTICULATE APPEARANCE

These may be visible on the surface of an opaque extruded product, or

on the surface and in the body of a clear one (say film or sheet).
Dark-coloured specks or particles, especially if of irregular shape, may
be adventitious contaminants, or points where the polymer has been
degraded through overheating. More regularly shaped particles ('nibs')
roughly circular or oval in appearance, may be 'fish-eyes' introduced
into the composition with the polymer (see Chapter 4, Section
4.4.1(a)) or lumps of incompletely dispersed material remaining either
because the composition-itself of basically good quality-has not
been properly homogenised in processing, or because it contained
added material (possibly scrap or re-work) not completely dispersible
by normal processing. In the latter case the regularly shaped nibs may
also be discoloured if the added material has had an excessive heat
history.
VARIATION OR FLUcrUATION IN DIMENSIONS

These may arise from several causes, most commonly inadequate

extrusion die setting or adjustment: sizing die problems, take-off
irregularities, poor melt uniformity, and even operator error, can also
be factors. The sizing and uniformity control of some extruded
products are discussed in Chapter 19 (Sections 19.3.2, 19.4.2, 19.5.2).
14.3 PVC MATERIAL FLOW, HOMOGENISATION AND
GELATION (FUSION) IN THE EXTRUSION PROCESS

The PVC resins used in compositions processed by extrusion are either

of the suspension- or the mass-polymerised type. A particle (sometimes referred to as a 'grain') of either kind of polymer is an aggregate

690

B. J. Lanham and W. V. Titow

of much smaller primary particles (microgranules). The microgranules

within a particle form mutually adhering clusters with voids of varying
size between them: these voids may thus be regarded as internal pores
in the particle.
The microgranules, which are the primary structural units of a
particle, are closely comparable in size between the suspension and the
mass polymer, ranging in both from about 02 to about 2 J1.m (with the
majority around, and below, 1 J1.ffi). The mean sizes of the aggregate
particles are also similar for both kinds of polymer, typically around
150 J1.ffi, but the particle size distribution of a suspension polymer is
much wider-say about 95% of particles between around 50 and
250 J1.m, as compared with an analogous range of perhaps 100-170 J1.ffi
for a mass polymer, for typical polymer samples. In any given case the
actual mean and range values are influenced by polymerisation
conditions: 29 this is the main reason for differences between figures
quoted by different investigators, as illustrated by the following
examples.

Microgranule
(primary
particle)
size
'Approaching 1 JJrn'*
'Subrnicron'
'About 2 JJrn'
02-15 JJrn
05 JJrn
Approx. 1 JJrn

Grain (aggregate
particle)
size
About 100-500 JJrn*
50-250 JJffi
100-150 JJrn
100 JJrn
100 JJrn
Approx. 200-300 JJrn

Type of
polymer

Author

Mass
Suspension
Suspension
Unspecified
Suspension
Suspension

Marks29
ChartofPO
Surnrners et al. 31
Parey and Menges 32
Menges et al. 33
Benjamin34

A typical mass polymer particle has a higher degree of sphericity

than its suspension polymer counterpart, and its porosity is, on the
average, more uniform. The greatest morphological difference between the two types is the presence of a 'skin' on the suspension
polymer particles. This has been likened to a bag enveloping the

* Values cited as generally representative of those obtainable at high

conversion rates in polymerisation. Particle size distribution graphs also
given-as typical examples-in this reference indicate a total range of about
30-200 Iffil (with a mean of about 130,um) for a mass polymer, and about
4O-26O,um (with a mean of about 160 Iffil) for a suspension polymer.

14 Extrusion of PVC-General Aspects

691

microgranule clusters constituting the particle. 29 The skin is formed at

the boundary between the original monomer droplet (to which the
polymer particle corresponds) and the aqueous suspending medium
employed in the polymerisation process: hence, whilst the skin may not
be complete (seam-like gaps are a fairly common feature, for
example), and may vary in thickness (from about 05 to 5 fl1ll), it is
always present in suspension polymer particles and absent from those
of mass polymer, being clearly visible in photomicrographs of
suspension polymer particle sections and in electron-scan micrographs
of whole particles. Some excellent photographs of both kinds have
been published by Marks. 29 An interesting method for the determination of the internal particle structure of suspension PVC polymers by
analysis of the desorption rate of vinyl chloride has been described by
Daniels and Longeway.35
A uPVC powder compound (pre-mix or dry blend) will normally be
extrusion-processed for one of two purposes: to melt-compound it into
pellets for use as feedstock in further processing, or to convert it
directly into an extruded product (e.g. pipe, profile, etc.). In either
case, the powder-which originally consists of polymer particles mixed
with the additives called for by the particular formulation (in a
dry blend the mixture may have been heat-fluxed to some extent; cf.
Section 14.2.2(d))-must be transformed into a uniform, fused solid
containing the additives in intimate, thorough dispersion. The degree
of fusion (also referred to as 'gelation') actually achieved, and the
homogeneity (including uniformity of interdispersion of polymer and
additives) are important factors in the properties of the resulting
product. * The progress of the transformation of powder to uniform,
fused solid material, and the degree of fusion actually attained in the
latter in particular processing conditions, can be characterised in terms
of changes undergone by the polymer particles as the stock is moved
by the screw(s) down the extruder barrel. The transformation should
be completed within the dwell period of the material in the machine,
i.e. the time taken by a particle to traverse the barrel from feed port to
die outlet, which it should leave as an integral, no longer distinguishable part of the uniformly fused extrudate. In very round figures, this
time may be about 15 min.
In the light of a large body of relevant evidence obtained in
* A useful discussion of the effects of these factors on the quality of rigid PVC
pipes has been published by Benjamin. 34

692

B. J. Lanham and W. V. Titow

experiments and practical investigations30,33,34,3~2 the explanation of

the phenomenology of the transformation outlined below has gained
wide recognition. The central theme of this explanation is that the
cardinal feature of the transformation-in extrusion, and indeed in all
processes in which a melt is produced from PVC polymer powder by
mechanical working and heat-is progressive breakdown of the
polymer particles. For this reason, the mechanism formulated in these
terms has been referred to as the 'comminution mechanism'. Recently
it has been claimed* that this mechanism operates (or at least
predominates) only in equipment which subjects the material to very
vigorous mechanical working under high shear, such as internal
Banbury-type mixers and Brabender torque rheometers. Otherwise,
for what they regard as less vigorous processing in extruders and on
two-roll mills, a group of investigators* proposes a very different
mechanism, involving not breakdown but compaction, densification,
fusion and elongation of the polymer grains, followed directly by
melting (the 'CDFE mechanism').
According to the orthodox comminution mechanism, as the powder
compound is conveyed by the screw(s) from the feed zone of the
extruder, the temperature of the polymer particles is raised by the
friction and shearing they experience, and the heat provided by the
barrel heaters.
Note: Whilst friction is a factor in this heating process it (and in
particular that which occurs between the particles and the
working surfaces of the machine) also affects the conveying
efficiency in the screw/barrel system (especially in a singlescrew extruder, where there is no positive mechanical
pumping action). A study by Huxtable et at. 43 indicated that,
for several polymers, temperature was the most important
single physical variable controlling the particle/surface friction. The data of Isherwood and Katwiremu44 underline the
role of this 'wall' friction in the degree of compaction
undergone by the polymer particles. Riley and Klein 45 point
out that the coefficient of friction of pPVC is high and rises
with surface velocity: however, because of the material's heat
sensitivity, under some conditions the coefficient of friction on
the barrel surface may be lower than that on the screw
* ct. M. W. Allsopp In Manufacture and Processing of PVC, (Ed. R. H.
Burgess), Applied Science Publishers, 1982, Chapter 8.

14 Extrusion of PVC-General Aspects

693

surface, so that in the single-screw extruder no driving force

for conveying the stock forward will exist (see Section 14.5).
At this initial stage, the forward movement of the stock may be
envisaged as the sum total of the movements of the individual particles
as they tumble and slide over one another and over the working
surfaces in their progress. It is in this sense that the particles have been
said to constitute the 'units of flow'. 32 When the particles have been
heated to a high enough temperature they begin to break down under
the shearing and frictional forces they experience, into their constituent microgranules, which then become the units of flow. The
temperature above which this breakdown proceeds depends on the
shear rate. Most investigators regard 160C as this threshold in a
typical extrusion process (mainly on the basis of morphological
examination of under-processed stocks), but values as low as 9Q-lOOC
have been quoted. 46 It is at this stage that the additives in the
composition become more intimately dispersed, among and onto the
microgranules (having previously been attached to the surface of the
polymer particles or, in the case of liquid stabilisers, or plasticisers in
pPVC powder compositions, possibly partly penetrated into the pores).
With some solid stabilisers and lubricants the relatively high temperature reached may result in melting, and coating of the microgranules
by the molten substance. The breakdown of the aggregate particles
into their constituent microgranules is sometimes identified as the first
of the two stages in the gelation process: the rate at which it proceeds
(dependent on the temperature and the amount of mechanical
working, both of which also influence the rate of heat input) is
certainly an important parameter in the achievement of complete
gelation in the particular processing conditions. The second main stage
is the breakdown of the microgranules themselves and their merging
into a uniform mass. The main mechanisms involved are melting
(thermal disruption) of these primary particles followed by the
inter-diffusion-under the same thermal activation-of the molecular
chains initially confined within the boundaries of a particle, with those
similarly liberated by its neighbours. With uPVC compositions, this
second stage proceeds at temperatures above about 190C.
Note: This stage should not be regarded as demarcated with
absolute sharpness. Thus, depending on the processing
conditions, and in particular the amount of shear experienced,
the microgranules can undergo partial surface coalescence-at

694

B. J. Lanham and W. V. Titow

temperatures from about 175C upwards-before final

disruption. 31 ,41 It is significant, however, that a large increase
in the flow activation energy of a PVC compound has been
found 47 to take place at 195C indicating a change in the flow
mechanism. 48 The change is in line with morphological
changes noted in another investigation. 31 With pPVC powder
compounds the penetration of plasticisers into the microgranules is a factor in the gelation mechanism: inter alia, it tends
to lower the temperatures at which the morphological changes
just mentioned take place.
The second stage also involves further homogenisation with respect
to the additives (which-from their positions on the surfaces of the
microgranules-are now being distributed through the polymer mass)
to attain a still more uniform and intimate stage of dispersion in that, if
full gelation is reached, the polymer is in a molecular state of division.
The degree of completeness of the breakdown of the microgranules
and their inter-merging is the true 'degree of gelation' (or 'fusion') in
the context of melt processing. In this regard the concept is thus
virtually the same as that applicable in the case of fusion of PVC
pastes* (see Chapter 21, Section 21.2.5) given that there the
plasticiser is a substantial component of the system, so that when
complete fusion has been attained, its molecules are uniformly
interspersed with those of the polymer, jointly forming the matrix
within which the additives are distributed.
If the temperature is allowed to rise too high above 190C, or if the
stabilisation is poor, or the residence time of the melt in the machine
too long, the melting and fusion may be complete but degradation of
the polymer (in some cases also possibly some of the additives-d.
Chapter 9, Section 9.1) may also occur.

Note: The small crystalline fraction present in commercial PVC

polymers (see Chapter 1, Section 1.5.1) is assumed to remain
* It should be noted, however, that in the correct current paste-processing
terminology (ct. Chapter 21, Section 21.2.5) 'gelation' and 'fusion' are no
longer interchangeable to the extent to which they still are in the context of
melt processing: with pastes, gelation is the first stage of the conversion of the
paste to a homogeneous thermoplastic solid, whilst the progress of that
conversion is substantially different from that in melt processing, because of
differences in the structure of the polymer particles, absence of shear from the
heating stage in paste processing and-most importantly-the cardinal role of
the plasticiser in the conversion.

14 Extrusion of PVC-General Aspects

695

undisrupted after what is normally regarded as complete

fusion at safe processing temperatures, because of the
relatively very high melting point of crystalline polyvinyl
chloride (about 270C-cf. the section of Chapter 1 just
mentioned). It is also a reasonable supposition that the
crystalline material is distributed (first in the fused melt and
then in the resulting solid) in the form of the crystallites
(crystalline microdomains about 001 f1.m in size42 ,49) thought
to exist in the original polymer, and that these contribute to
the strength of the melt-processed product, possibly acting as
quasi cross-links after the manner of crystallites in other
polymers (cf. also Chapter 1, Section 1.5.1). However, such
contribution can certainly be outweighed by the adverse
effects of incomplete gelation; conversely, complete gelation
(without polymer degradation) ensures good properties of the
material.
The ideal result aimed at in the extrusion (and all melt processing) of
PVC is to achieve full gelation of the material, coupled with freedom
from voids, degraded polymer and external contaminants, any of which
can act as stress-concentrating flaws (ct. Chapter 11, Section 11.2.2).
As pointed out by Marshall and Birch,5o the correct balance between
good gelation (which optimises resistance to fracture) and introduction
of flaws (which reduce that resistance) is the essence of good
processing.
As in the case of PVC pastes, the completeness of gelation (fusion)
of melt-processed PVC (and especially uPVC compositions) is most
directly characterisable in terms of the material's morphology. The
morphological effects of processing just outlined have in fact been
worked out and demonstrated on the basis of examinations of the fine
structure of compositions, after various degrees of processing, by
optical and electron microscopy techniques. 30 ,31,34,36,37.39,41,49
On such a basis, full gelation may be sensibly equated with complete
absence of detectable granular structure in the material (including any
vestigial traces of such structure in the fracture surfaces). Similarly,
degrees of completeness of gelation may be assigned in terms of the
nature and extent of persisting granularity. Other factors (and in
particular the molecular weight of the resin) being equal, increasingly
perceptible granularity is associated with reduced mechanical strength,
impact resistance, and resistance to weathering. This is because the

696

B. J. Lanham and W. V. Titow

number of molecular chains participating in 'ties' across a perceptible

inter-grain boundary is smaller than that in a corresponding volume in
the interior of an incompletely dispersed granule: hence the boundaries
are planes of actual relative weakness.
Note: Moreover, the weakness may be accentuated by the presence
at the boundary of additives (in concentrations higher than
elsewhere in the material) which were originally reposing on
the microgranule surfaces.

This lower density of molecular ties is also the main factor in the
lower weathering resistance: photochemical disruption by incident UV
light of a number of these, even though small in absolute terms can,
because of their relative scarcity, cause cracking at the inter-grain
boundary under, say, normal thermal stresses.
As with PVC paste products, the relatively sophisticated methods of
morphological study are too time-consuming and elaborate to be
widely used in monitoring the completeness of gelation in industrial
operations. It is largely for this reason that more straightforward,
direct determination of some property of the product, influenced (like
some of those just mentioned) by the degree of completeness of fusion,
is usually resorted to. Whilst such determinations have the merit of
relative simplicity-and the property determined may be directly
relevant to service requirements (e.g. the hoop strength of extruded
pipe, which is sensitive to the completeness of gelation)-the
functional relationships of their numerical results to the fine structure
of the product are not normally linear. Thus such results are only
relative indices of the degree of gelation, and-whilst each may be
satisfactory for a particular purpose-they are not readily quantitatively relatable to one another. This is well brought out in the results
obtained in a study by Benjamin34 of the degree of gelation of an
extruded pipe of a relatively simple formulation. Benjamin's data are
reproduced in Table 14.1.
For practical purposes the completeness of gelation of extruded
products (pipe, profile) is usually assessed in terms of a solvent
immersion test (ct. Chapter 19, Sections 19.3.3 and 19.4.4), or a
strength or impact test.
A rheological method, giving numerical values for the degree of
gelation, has been developed,32,34,51 foreshadowed by ideas of Gonze 52
and Lamberty.53 With a series of melt-flow determinations in a
capillary rheometer (a standard melt-flow index apparatus may be used

14 Extrusion of PVC-General Aspects

697

TABLE 14.1

Degree of Gelation of a PVC Pipe as Reflected in its Various Properties

(Data of Benjamin, reproduced from Ref. 34 with permission of the author

and the copyright holder, The Plastics and Rubber Institute.)
Gelation level" (%)

32

44

68

90

Resistance to attack by
methylene chioride b

Severe
attack

Light
attack

No
attack

No
attack

Homogeneity
of microtome section C

Inhomogeneous

Some
inhomogeneity

Homogeneous

Homogeneous

Tensile strength, 20C:

yield (N mm- Z)
Elongation at break (%)

54
108

55
133

56
115

56
58

Tensile impact energy:d

OC, energy (Nmm mm- Z)
Elongation after break (%)
20C, energy (Nmm mm- Z)
Elongation after break (%)

381
3
624
15

706
15
763
19

711
16
733
18

656
12
697
16

Resistance to stress
cracking' 20C
Critical strain, Ec(%)

08

15

51

3-6

"Determined by the rheological method.

b By the method of KIWA KE 49.
C Section (approximately 10 J.LITl thick) taken across the pipe wall.
dDetermined by the falling weight method of KIWA KE 49.
Determined by the steel ball indentation test of DIN 53449.

in one variant5 !) a 'gelation curve' is constructed, representing changes

in flow characteristics with increasing degree of gelation, to serve as a
standard in determining the degree of gelation of a given specimen.
Where there is no prior knowledge of the processing which the
specimen has experienced (and thus a complete reference curve cannot
be obtained) it is still possible to assess the degree of gelation by the
following procedure. Part of the specimen is used for the flow
measurement under the appropriate conditions; the rest is heatprocessed (with periodical testing) until no further increase in gelation
is indicated by the rheological behaviour (e.g. the appropriate
extrusion pressure in the standard test conditions used remains
constant). On the assumption that the 'steady' value reached

698

B. J. Lanham and W. V. Titow

corresponds to 100% gelation, the gelation level similarly corresponding to the result obtained with the specimen in its original state can be
calculated.

14.4 SINGLE-SCREW EXTRUDERS

This section deals briefly with some features of, and developments in,
extruder design with special reference to those of interest in connection
with extrusion of PVc. Whilst twin-screw extruders have come into
their own in the compounding and extrusion of PVC, especially uPVC
from powder feeds, the single-screw machine is widely used,
particularly for processing plasticised PVc. The main advantages of
this type of extruder over the twin-screw machine are economic: lower
equipment capital cost; lower maintenance costs; on the average,
shorter down-time for repairs; lower rate of wear of screw, barrel and
gearbox. The theory of design and operation is also better developed
for single-screw machines.
Most suppliers provide a range of machines, varying from small
screw diameter (say 30 mm) to large (say 250 mm). It is also common
practice for a supplier to offer a range of screws not only for specific
materials but also for specific applications, e.g. uPVC pipe extrusion,
paper coating with polyethylene. It is in the area of screw design that
research and development have been most concentrated for a
considerable time. 54 The design of screws for the single-screw extruder
has been increasingly benefiting from the use of computers. An
important early step in this direction was the work carried out at the
University of Cambridge under a Ministry of Technology contract,
aimed at providing a suite of computer programs to model accurately
the single-screw extrusion process, and mathematical models for
prediction of the performance of screws of various configurations. 55 At
about the same time a company (Scientific Process and Research Inc.)
was being founded (by Klein and Tadmor, two eminent workers in the
field of screw design) to offer to industry a computer service for the
design of extruder screws. A feature of the service was a technique
whereby screw configuration and plasticating performance could be
simulated without need for any empirical information, prior experience
or laboratory experiments. 56 Initially, screws for flexible PVC have
usually been of the constant-pitch, increasing-root types; with a
compression ratio of 2: 1 (up to about 3: 1 for softer grades). This type

14 Extrusion of PVC-General Aspects

699

of screw (at the lower end of the compression range quoted) had also
been used for uPVC. Subsequently metering screws with mixing rings
fitted in the metering section came to be employed,S7 and thereafter
many variants of 'mixing' screws which may be broadly classified into
three groups: screws containing 'smearing' sections designed to
improve homogenisation of the stock; 'pin screws' with lines of pins in
the metering section9 designed to break up the flow pattern of the
stock for better homogenisation; twin-channel screws in which the
material already melting is periodically temporarily separated ('drained
away') from that still predominantly solid, for more effective working
of the latter and generally better overall homogenisation. Sophisticated
designs of the last-named type are represented by the 'barrier' screw, *
and the 'double-wave' screw;t the latter is claimed to be more efficient
than pin-type screws, to operate effectively with stock temperatures
significantly lower than those typical of a conventional single-screw
machine, and to make the single-screw extruder competitive with a
twin-screw one in the extrusion of pipe from dry blend. 58 Among the
other developments in single-screw extruder features (some already
mentioned in Section 14.2 above) the following should be mentioned:
increase of barrel length, screw speeds and torques; low noise level
drives; improvements in power transmission; increase in heat output of
barrel heaters. Some modern single-screw machines are among those
discussed in Sections 13.4.2 and 13.4.4 of Chapter 13.

14.5 TWIN-SCREW EXTRUDERS

As mentioned in the introduction, the development of twin-screw
extruders has been primarily associated with the processing of rigid
PVC, in particular, from dry blends: in this area the twin-screw
machine rapidly established supremacy in Europe and eventually also a
strong position in the USA, although there its advance vis-a-vis the
single-screw extruder has been rather slower. Twin-screw machines
used for the manufacture of extruded PVC products are normally of
the intermeshing screw type, with cylindrical or conical screws.
It is relevant to consider briefly the main differences in the way in
which the single-screw and intermeshing twin-screw extruders operate.

* Davis Standard-cf. Table 14.3.

t Patented by the HPM Corporation, USA-ef. Table 14.3.

700

B. J. Lanham and W. V. Titow

Single-screw machines work by virtue of the fact that the friction

between the stock and the extruder barrel is greater than that between
the stock and the screw: 2 this causes the material to be conveyed
forward. The twin-screw machine, on the other hand, moves the
material forward-on and between the screws-by positive displacement, i.e. it exerts a positive pumping action.
Note: A good illustration of the essential difference between these
two modes of operation is provided by the experiences of
Wyman's59 imaginary spider who finds himself in the screw
flight of a machine in motion (but empty of stock). If the
machine is a single-screw one, and the spider does not touch
the internal surface of the barrel (which-if he sits on the
screw root-he will see as a moving ceiling), he can relax
undisturbed on the spot he is occupying. Alternatively, when
he is ready, he can walk forward along the continuous helical
passage formed by the screw flights and the barrel bore
surface until he strolls out at the die. In either case he is not
impelled in any way by the movement of the machinery. If,
however, the spider sits on the root of a screw of an
intermeshing twin-screw extruder his situation will not be so
comfortable. He will realise that he is enclosed in a chamber
formed by the floor (screw root), two side walls (screw thread
walls), moving ceiling (internal surface of the barrel) and two
curved, convex walls at each end (lands of the other,
intermeshing screw). Moreover, he will see one of the end
walls rolling towards him and-if he is nimble enough to avoid
being crushed-soon pushing him along, unless he runs fast
enough ahead of it. If he runs too fast, he will catch up with
the other end wall (the 'rear' side of the second land of the
other screw) which is rolling away from him. He will thus be
forced to move forward (i.e. be positively displaced) at a pace
determined by the speed of movement of the end walls of his
prison (governed by the rate of rotation of the screws). When
he reaches the end of the barrel, the curved wall receding in
front of him will 'open up' and he will be forced out through
the die opening.
The difference between the material's friction against the screw and

barrel surfaces in a single-screw machine-whilst enabling the stock to

be moved forward-is also associated with some unevenness of the

14 Extrusion of PVC-General Aspects

701

stock temperature in the screw flight prior to complete homogenisation: the material is coolest in the centre of the flight and-particularly
in the absence of the kind of special mixing arrangements mentioned
above-that part fuses last. Relatively high screw speed is necessary to
promote uniformity of temperature distribution by the resultant high
shear, but this also generates considerable shear heating making it
necessary, in some cases, to run the machine with cooling constantly
on to keep the temperature to a safe level. The twin-screw extruders
produce much less in the way of shear heating and rely more on the
input of heat from the barrel. Single-screw machines are dependentparticularly for any mixing action-on the development of relatively
high back-pressures. Hence, since they have no positive pumping
action, with die openings of large cross-sectional area the achievement
of such pressures may be difficult: also in practice-for a given screw
speed-the output tends to decrease with decreasing die opening. The
performance of the twin-screw machine is little affected by the
cross-sectional area of the die.
With reference to the above points, and generally to its performance
and operation in PVC (and especially upvq processing, the
advantages of a twin-screw machine in comparison with a single-screw
one may be listed as follows:
(i)
(ii)

lower melt temperature;

more uniform melt flow (cf. also the paragraph on gear pumps
in Section 14.2.2(b) above);
(iii) less product variation.

These three features are consequent upon the positive pumping action
of the screws.
(iv)
(v)

higher outputs with less degradation;

possibility of using cheaper formulations (less expensive
stabilisation) .

These two points arise from the generally lower melt temperature in
processing.
(vi) better temperature control;
(vii) better mixing action and removal of entrapped air (hence
greater suitability for processing bulky feeds like dry blends);
(viii) insensitivity to the cross-sectional area of die opening in
operation.

702

B. J. Lanham and W. V. Titow

Various views have been expressed about the respective merits of

twin-screw extruders with conical (tapering) and cylindrical (parallel)
screws. Two points may be mentioned. The taper on conical screws
tends to produce a slight increase in compression, unless counterbalanced by suitable adjustment of the pitch and/or lead. The fact
that-with conical screws-the centres of the screw shafts at the rear
are more widely spaced than the screw tips, can be utilised in bearing
construction so that higher loads can be accommodated by the
bearings.
The design concepts of twin-screw extruders have been well
described by Prause,60--62 with references to machines produced by
various manufacturers. Some experimental work on this type of
machine, and its theoretical interpretation, have been published by
Jewmenow et al. 63 ,64 A theoretical model for the intermeshing
twin-screw extruder (including a comparison with a single-screw
machine) is developed in an interesting paper by Wyman. 59
An important difference among commercial twin-screw machines is
their choice of screw design. Table 14.2 indicates, in very brief
summary, the general nature and mutual direction of rotation of screws
TABLE 14.2

Types of Screw Used on Some Commercial Twin-Screw Machines

Manufacturer

AGM
Anger APM
Kesterman
LMP
Nouvelle
Mapre
Schloemann
Windsor

Screw
rotation

Type of screws

Tapered screws, large diameter at feed, small

diameter at meter
Three separated sets of flights, those in the feed
area having the largest pitch, a reduced pitch on
the second set and the smallest on the third
Features a single-flighted feed zone with a change
Counterto triple flights in the transition zone
rotating
Co-rotating Three-section screw with a different diameter in
each section, proceeding from large diameter at
feed to small diameter at meter
Single-flighted screws with increasing flight thickCounterness towards the die
rotating
CounterScrews are three-sectioned, constant pitch within
rotating
section, but decreasing in pitch from feed to
meter
Co-rotating Three-section screws are employed, having a
different diameter in each section, the large
diameter at feed and the small at meter
Counterrotating
Counterrotating

14 Extrusion of PVC-General Aspects'

703

in some extruders. In general terms, it is usually claimed that

counter-rotating screws provide a better mixing effect and that
co-rotating screws offer superior self-cleaning performance.
Another area of twin-screw design which aroused a good deal of
controversy at one time, is the service life and general robustness of
the thrust bearings. Where two shafts are running in close proximity,
the space available for the thrust bearings is clearly limited: the
advantage in this connection of the conical twin screws has already
been mentioned. Twin-screw machine manufacturers have developed
various bearing designs which permit higher loads to be borne than was
possible in the early days of twin-screw extrusion. Whilst-as has been
mentioned-most twin-screw machines are not operated at the high
back-pressures experienced with single-screw extruders, the loads that
the bearings are called upon to withstand have been increasing with the
progressive increase in operational screw speeds effected to increase
outputs.
Among the principal modern developments in twin-screw extruders
(which in many respects paralleled those in single-screw machines)
must be counted: increase in barrel and screw length (to secure better
controlled energy transfer with gentler heating, and ensure completeness of gelation at higher output rates); introduction and refinement of
barrel venting; increase in the speed range and torque capacity of the
screws; development of screw design (in particular the introduction of
mixing and decompression zones); improvement in the temperature
control systems for barrel and screws; improvement in drives and
reduction gears.
14.6 SOME COMMERCIAL MACHINES

Twelve extruder manufacturers from various countries, whose machines

are widely used in processing PVC, are listed-by way of non-selective
examples-in Table 14.3, together with brief indications of the
machines supplied. A comprehensive, worldwide survey of extrusion
machinery has been published in Plastics and Rubber Weekly, Nos 828
(15th March, 1980) and 829 (22nd March, 1980), and a shorter one,
with emphasis on Europe, in European Plastics News for April, 1982
(Vol. 9, No.4). Other sources of information include the current issues
of the Modern Plastics Encyclopedia (McGraw-Hili), the Plastics
Technology Plastics Manufacturinf( Handbook and Buyers Guide. and

HPM Corp., Mount Gilead,

Ohio, USA

Battenfeld Maschinenfabrik GmbH, Meinerzhagen, Westfalen, West

Germany
Herman Berstorff
Maschinenbau GmbH,
Hanover, West Germany
Cincinnati Milacron, Plastics
Machinery Division,
Batavia, Ohio, USA
Davis-Standard, Div. of
Crompton and Knowles
Corp., Pawcatuck, CT,
USA
EMS Industrie,
Bobigny, France

Manufacturer

S;T;M

Berstorff Ltd, Lancaster

S;T

International Corporation Ltd, Farnham,

Surrey

Loreburn Engineering
Ltd, Sheffield

D. Marks,b 2 Spicer Place, S

Bilton, Rugby,
T
Warwickshire
Davis Standard, Alderley S
Edge, Cheshire

S;T;M;
cascade

General type
of machineO

Battenfeld (England)
Ltd, Chesham, Bucks

UK associate or
agent

Claimed to be largest manufacturer in Europe; many models

of each main type of machine

Remarks

Specially designed complete production lines

and turn-key factories, with appropriate types
and sizes of extruders
50-90
Specialist in twin-screw
40-90 (the
(conical) extruders
'CM'range)
~30
Wide range of extruders and
extrusion lines; screw design
specialists-designers of
'barrier' screw
Extensive extruder range
30-300
includes special machines
combining single- and twinscrew construction
Provide custom-design control
50-250
systems; patentees of 'double
wave'screw

~40

Range of
screw sizes
(mm)

TABLE 14.3
Some Commercial Extrusion Equipment Widely Used for PVC Processing

~20

50-250

Francis Shaw and

Co. Ltd, Manchester,
England

Range of general-purpose
PVC extruders and downstream equipment
Special gear-box design for high
screw torque performance
Incorporates former Anton
Anger operation; single- and
twin-screw (conical) extruders with dual-circuit screw
temperature control; downstream equipment and complete lines
Inter alia, supplies a complete,
compact twin-screw line for
the production of PVC window profiles (continuous
output up to 130 kg h- 1)
Extruder range, and complete
lines for sheet extrusion,
cable and wire covering, and
compounding

Nearest representative: Cincinnati Milacron Austria AG, Vienna.

as = single-screw machines; T = twin-screw machines; M = multiple-screw machines (including planetary extruders).

60-120

S
T

60-100
50-90

S
T

Reifenhauser GmbH, Trois- Reifenhauser Ltd,

dorf, West Germany
Tewkesbury, Gloucs

~70

52-132

~40

~20

David Dryburgh and Co.

Ltd, Epsom, Surrey
Mr E. P. Hartmann,
Wakefield, Yorks

Mapre SA, Diekirch,

Luxembourg
Oswag Plastics Machines,
Linz, Austria

Maplan Maschinen GmbH,

Vienna, Austria

Regis Machinery (Sales) S

Ltd, Bognor Regis,
T
Sussex
Speedex Engineering Ltd, T
Bradford

Kaufman, Le Havre, France

706

B. 1. Lanham and W. V. Titow

the British Plastic Federation's Buyers Guide for Plastics Processing

Machinery and Equipment.
Information on some compounding extruders used for PVC is given
in Chapter 13, Section 13.4.4.
Plates G and H show two twin-screw extruders.
Technical data for a cascade extruder and the Bitruder machine
range are given in Chapter 13, Section 13.4.4(a). A few data are also
given for the Reifenhaser Bitruder BT 701-2-80-16V (shown in Plate
H) in Table 14.4 together with information on a PVC window profile
extrusion line incorporating this machine. Apart from their compounding uses the Bitruders are employed in a wide range of extrusion lines
for sheeting (single and multi-layer), pipes, profiles and coatings.
Twin-screw extruders designed basically for PVC are exemplified by
the Maplan r';lnge (see Table 14.3). All are produced to EUROMAP
sizes, with an extrusion height of 1 m. The screws are parallel,
counter-rotating, and temperature-controlled over the range S().....200C
by oil circulation. Barrel heat control-in the range SO-300C-is

Plate G Mapre twin-screw extruder Type E2.78.100: screw diameter 100 mm;
two models available, with LID ratios respectively 22:1 and 16:1. (Courtesy
Mr David Dryburgh-D. Dryburgh & Co Ltd., Epsom, Surrey, England.)

707

14 Extrusion of PVC-General Aspects

Plate H Bitruder BT 701-2-80-16V twin-screw extruder. (Courtesy of A.

Reifenhiiuser Ltd.)
operated by five heating zones (electrical heaters) and three oil-cooling
zones. Feedstock pre-heaters are supplied for the machines (cf. Section
14.2.1(e)). High, uniform screw torque is claimed to be provided by
the special gear transmission design, and a throughput per revolution
up to 50% higher than with conventional designs, so that the screws
can be run at relatively low speeds with consequent lower shear heat
generation and machine wear. The following data 12 relate to two of the
models.

Screw diameter (mm)

Screw LID ratio
Screw speed range (r min-I)
Torque (Nm)
Drive power (kW)
Output: rigid PVC pipe (kg h- 1)

Map/an DS 80

Map/an DS 100

80
24: 1
16--315
2 x 4000
13-26
250-300

24: 1
16--32
2 x 7500
26--52
400-500

100

708

B. J. Lanham and W. V. Titow

TABLE 14.4
Bitmder BT 7012-8016V Twin Screw Extruder: Some Technical Data for this
Model and for a Reifenhauser Window Profile Extrusion Line Based upon It
(Extracted, with the permission of A. Reifenhauser Ltd, from the technical
literature of Reifenhauser GmbH, Troisdorf, West Germany)
Technical and output data for Bitruder BT 70I280-I6V
Screw
diameter
length
(D, mm)
(D)

Nominal
torque
(daNm)
700

16

81

Drive
rating
(kW)

Screw
speed
range
(rmin- I )

Typical output (kg h- 1)

Corrugated
pipes

Sections

42-250

52-310

220

160

Compressed
air with
supply
pressure
5-6 bar
(Nm3 h- 1 )

Net
weight
(kg)

uPVC window profile extrusion plant data

Line components
Type
designation

BT701-2-80-16V

KKE-P0500-15-V3

A-P420D-2-175L
TSQ-P516A-220-450

ST-P710-00-300
Total

Description

Feed hopper
Twin-screw extruder
type 'Bitruder'
Temperature con
troller cabinet,
8 controllers
Profile die head
and sizing
Sizing unit base
with vacuum sizing
tank
Haul-off unit
Length cutting saw
with swarf
extraction
Discharge unit
Rail track

Installed
electric
rating
(kW)

Cooling water
consumption
with supply
water
12-I5C
(Nm 3 h- 1 )

700

05-08

10
3800
250

45
230

240
25-30

30
30

104"

30-38

2400

03
03-09

1800
520

01-03

450
250

07-1'2

9720

"The effective consumption for drives is up to approx. 75% and for heaters approx. 30% of the
installed rating.

A specification for a 45-in extruder is exemplified by the data given

in Table 14.5. The machine (produced by Melville Plastics Engineering
(Scotland) Ltd) is equipped with a one-pipe, bimetallic steel barrel
lined with a corrosion-resistant 'Brux' alloy, ground and honed to the

Screw diameter
Length/diameter ratio
Number of heating zones
Total heating load
Cooling system
Barrel zones (optional)
Individual blowers rated at
Feed section
Gear ratio
Gear type
Lubrication
Thrust bearing
Dynamic load capacity
B-10 life at 100 r rnin- 1 and
5000 lbf in- 2 head pressure
Motor power (suggested)
Screw speed
Installation area (approx.)
Extruder (excluding drive)
Control cabinet
Weight (approx).
Extruder (excluding drive)
Control cabinet

Specification
S450-24

450 in
24:1
4
601 kW
Air
595 ft 3 min- 1
Water
10:1
Single helical
Force feed
482 000 lb
56 000 h
1OQ-150hp
Up to 125 r min- 1
184 x 33 in
47 x 22 in
7900lb
850lb

S450-20

450 in
20: 1
3
501 kW
Air
595 ft 3 min- 1
Water
10: 1
Single helical
Force feed
482000lb
56000h
100--150 hp
Up to 125 r min- 1
165 x 33 in
47 x 22in
7100lb
850lb

Imperial

3225 kg
386 kg

420 x 84cm
120 x 56 cm

56000 h
74-112 kW
Up to 125 r min- 1

219000 kg

Air
17 m3 min- 1
Water
10: 1
Single helical
Force feed

115mm
20: 1
3
501 kW

S450-20

TABLE 14.5
Melville Plastics Engineering (Scotland) Ltd 45 in Extruder

219000 kg

Air
17 m 3 min- 1
Water
10: 1
Single helical
Force feed

115mm
24:1
4
601 kW

S450-24

3590 kg
386 kg

468 x 84cm
120)( 56 cm

56000 h
74-112 kW
Up to 125 r min- 1

Metric

-.I
'J:)

I :;

"'"

i:l

'"~

'";:s

?Cl

"1:l

c'
;:s

.....
.to,

710

B. J. Lanham and W. V. Titow

final bore diameter. Heating zones are individually controlled by

proportioning-type pyrometer controllers having a temperature range
of o-800F (0-400C). Each zone is equipped with a resistance-type
heater and air blower for cooling. Lightweight fibreglass-insulated steel
covers, designed for ease of removal, are fitted. The extrusion screw is
machined from high-grade alloy steel bored for fluid heating and
cooling, and fitted with a rotary union. Flights are flame-hardened and
the screw is plated with industrial hard chrome on all working surfaces.

14.7 ANCILLARY EQUIPMENT

For all extrusion processes, equipment in addition to the extruder and
its die is necessary to form, handle and collect the product. The major
uses to which the extruder is put in processing PVC are as follows:
(i)
(ii)
(iii)
(iv)
(v)
(vi)

wire covering;
hose and flexible pipe production;
blown and cast film;
rigid pipe;
rigid sheet;
profiles, rigid and flexible.

Common to most of these processes are the following items of general

ancillary equipment:
(a) sizing dies;
(b) a means of cooling the extrudate;
(c) a haul-off system.
The ancillary equipment required for wire covering is mentioned in
Section 14.8 below. The equipment used in the extrusion of uPVC pipe
and other rigid products is discussed in Chapter 19. In the case of hose
and profile65-67 the extrudate is passed into a shaping device
dimensioned to the size required for the final product: the device is
usually cooled in order to bring the extrudate to a temperature that
will ensure the retention of dimensions.
The methods of cooling and shaping of PVC film and sheeting
depend on the extrusion process employed, i.e. blowing or casting (see
Chapter 19, Section 19.5). A good description of both processes
appears in ICI Technical Service Note C 108.

14 Extrusion of PVC-General Aspects

711

Cooling of extrudates is usually achieved by the use of one or more

water baths or water sprays. Film is again a special case, in that with
blown film, air is used to cool the product: with cast sheeting the cold
metal surface of the casting roll achieves the required cooling.
Take-off systems may be of the caterpillar type, in which two or
more soft tracks or belts press against the extrudate and draw it off

Plate I Equipment for production of tubular (blown) film. (Courtesy of

Battenfeld Gloenco Extrusion Systems Ltd, Droitwich, England.) (1) Take-off
unit showing film bubble.

B. J. Lanham and W. V. Titow

712

Plate I-contd.

(2) Ring die with internal bubble cooling.

(see Chapter 19), or consist of wheels arranged in such a manner as to

exert a steady pull on the extrudate.
Screens are often employed in the extrusion of flexible PVc. These
screens are positioned on a metal support plate (the breaker plate)
fitted between the end flange of the extruder and the die, i.e.
immediately after the screw tip. The purpose of the screen is to

14 Extrusion of PVC-General Aspects

713

prevent foreign matter or ungelled particles from passing to the die,

and to provide a means of increasing back-pressure, thus improving
plastication of the melt. Typical screen selection might be as follows:
Medium grade PVC:

3 x 60 mesh

Hard grade PVC:

3 x 120 mesh

The use of screens has led to the development of an interesting piece

of ancillary equipment, viz. the automatic screen changer. Before the
advent of these units the changing of a screen involved stopping the
extrusion, opening up the head and replacing the screen. There are
many different screen changers available, working on several different
principles. The most common type simply has a slide block which
carries two breaker plates and screen packs, with a pneumatic or
hydraulic ram to slide the clean unit into position. The slide ram is
arranged at right angles to the barrel. Other methods use a continuous
screen which is fed very slowly across the face of the breaker unit.

14.8 EXTRUSION OF PLASTICISED PVC

14.8.1 Nonnal (Relatively Slow) Extrusion
The basics of extrusion procedures are common to all processing by
this technique, and in this sense all extrusion operations may be
considered to be normal. However, it is convenient to distinguish those
operations which require a marked change in common operational
procedure. For the purpose of this section, therefore, extrusions at
fairly low rates, say 5-200 ft min-I, will be classified as normal, and
those at rates significantly higher as fast extrusions.
It is impossible to be dogmatic about extrusion conditions in PVC,
or any other material for that matter. Every compound and even every
machine is different and extrusion conditions for each set of
circumstances must be worked out. However, it is possible to give
general guidance. The overall principle for slow extrusions is to have a
temperature gradient from the hopper end of the barrel to the die.
Some typical figures are given in Table 14.6.
The general principles are that the softer the compound the less heat
required, and the smaller the die orifice the more the heat required.
This is because the speed of extrusion will normally be greater the

B. J. Lanham and W. V. Titow

714

TABLE 14.6

Temperature Gradients for Slow Extrusions

eC)

Position in extruder
Type of extrusion

Soft compound, medium orifice

Hard compound, medium orifice
Soft compound, small orifice
Hard compound, small orifice

Hopper
end

Middle
of barrel

Head
end

110
120
130
140

125
140
140
155

135
150
150
165

Head Die

150
160
160
175

160
170
180
190

smaller the orifice so that greater heat input will be required. The
rotational speed of the screw will not yet be great enough to create an
excessive amount of heat. Higher temperatures are required on
twin-screw machines.
The cooling of the screw has to be controlled. Cooling is usually
unnecessary at the start of the extrusion since the aim is to build up
heat, not to take it away. After a time, however, a trickle of coolant in
the screw is often advantageous.
Before extrusion begins it is necessary to allow the extruder to
warm up to the required temperatures. The compound should then be
introduced gradually into the machine, the ammeter being watched
continually to ensure that the cold compound does not cause
overloading. If tubes are being made and a torpedo is in use, this may
also be capable of being heated. This is most advantageous and permits
really sensitive extrusion control, also allowing the barrel temperatures
to be kept lower than usual.

14.8.2 High-speed Extrusion

The principal difference between slow and high-speed extrusion is the
amount of mechanical heat developed. This can be so great that, once
extrusion has started, no external heat is required in the barrel (the
so-called adiabatic heating). This type of extrusion is fairly common,
particularly in the cable industry, and its successful practice is a matter
of obtaining a delicate balance between heating and cooling. Table
14.7 gives some typical temperatures for high-speed extrusion,
particularly associated with 20-24: 1 LID machines.

'715

14 Extrusion of PVC-General Aspects

TABLE 14.7
Temperature Gradients for Fast Extrusions

Type of extrusion

Medium compound, small orifice

(3,5 in extruder)
Medium compound, large orifice
(3,5 in extruder)
Medium compound and orifice
(2,5 in extruder)
Hard compound, medium orifice
(2,5 in extruder)

eq

Position in extruder
Hopper
Head
end
Middle end Head Die
300

300

300

300

300

110

120

130

130

150

150

150

160

150

150

140

140

150

150

160

There are some noteworthy points about Table 14.7 in that they are
contrary to convention. First, in general, the temperature gradient has
virtually been eliminated. Sometimes a little extra heat is necessary
just behind the head. The die temperature, however, can be varied
quite independently of all the other heaters and this is purely to control
the surface finish. This temperature can be quite high without causing
decomposition of the compound, largely due to the high speed of
extrusion.
With slow extrusions it is necessary to heat the hard compounds
more than the soft ones. With fast extrusions the opposite is the case
since the internal heat developed with the hard grade is much greater.
Cooling almost always needs to be applied. Its application should,
however, be judicious: it is not good enough just to turn the coolant
full on. The correct flow must be found by trial and error and, once
established, should be kept fairly constant. A flow meter can and
should be installed in the line so that the rate of flow can be regulated.
The amount of heat is the prime factor which determines whether or
not a good or poor extrusion will be obtained. There are many
symptoms of poor extrusions, two of the most common being 'lumps'
in the surface, or a 'grey' background instead of a fine deep colour.
Both of these troubles are caused by external overheating, usually of
the barrel. If an extruder is stripped after obtaining lumpy extrudate,
unplasticised lumps will be found behind the screen-the trouble is this
pronounced.
The natural tendency on seeing lumps is to increase the heat to

716

B. J. Lanham and W. V. Titow

obtain greater plasticisation. This has the opposite effect. The

compound is made more plastic so that less mechanical work is put into
it and less heat is developed. The external heating should be reduced
to increase the shear energy input.
All temperatures nowadays are controlled automatically, but great
care should be taken in interpreting the temperatures given by
automatic equipment. If when troubles of the above type arise and
overheating is suspected, a casual glance at the temperature recorders
indicates that this is not so, one of two things can have happened: (a)
the thermostatic control has gone wrong, or (b) the recording
instruments are such that the indicator needle cannot rise more than a
few degrees above the temperature at which the thermostat has been
set. If the restriction is momentarily removed it will frequently be
found that the temperature recorded will rise 20-30C above the value
at which it was set.
Whilst (a) above is not the usual cause of overheating troubles, if the
thermostat does break down and allows unrestricted heating at a point,
polymer degradation will occur, frequently to the point of carbonisation. However, this kind of problem is ultimately one for the maintenance electricians. In the case of (b) on the other hand, the situation is
quite different: it is also relatively common. The only answer is to
switch off all the heat and to apply cooling until a reasonable temperature is reached. Often it is advisable to set the initial heats rather lower
than those theoretically required so that with the heat developed
within the PVC itself, a reasonable balance will be achieved.
The recommendation given above about setting the extruder at a
lower temperature than normal may give rise to certain difficulties.
The principal one is that at the start of the extrusion cold compound is
fed to the extruder and with the low heats this is likely to place undue
strain on the extruder motor, and cut-outs may even be experienced.
The answer is to add a relatively small amount of stock at a time so
that the screw has a chance to work on it and develop some heat. In
other words, the screw should not be filled from an open hopper right
at the start of the extrusion. In actual practice, a schedule of
operations can easily be laid down to guide the extruder operator.
The information given above may appear contrary to theory and
usual recommendations. The conditions may not even be common to
all operators of high-speed modern extruders. Nevertheless, it is in line
with the experience of many users. The comments do emphasise the
point that in starting with a new extruder and/or raw material, it will be

14 Extrusion of PVC-General Aspects

717

necessary to find the best heat levels by a process of trial and error. In
doing this it should be appreciated that an increase or decrease in
temperature may achieve the desired results. These comments rarely
apply to the die (and often the head heats), which may be operated
independently of other heats to give the best finish.
14.8.3 Examples of Industrial Extrusion of Plasticised PVC

(a) PVC Coating of Wire and Cable

Plasticised PVC compositions are widely used as insulation on
domestic and industrial wiring cables, high-voltage transmission cables
(up to about 10 kV), short-haul telecommunication cables (switchboard
and inter-phone cables), and also as protective sheathing on most types
of cable. pPVC re-work and reclaimed material are employed as filling
core for composite cables.
pPVC has maintained its firm position in these major applications by
virtue of its good general dielectric properties, great formulational
versatility and low flammability. For very high voltage cables, and
high-frequency cables (e.g. telephone and coaxial cables) where
dielectric loss is of cardinal significance, polyethylene is preferentially
used because of its better dielectric properties (and its electrical
breakdown resistance, important in high-voltage applications). The
compounding of PVC compositions for the applications just mentioned
is discussed in Chapter 13, Sections 13.4.2 and 13.4.4.
The compositions are applied by extrusion-coating, involving the use
of crosshead dies in which the melt is turned through a 90 angle to
form the covering around the cable passing through the die. Useful
mathematical analyses of flow of the melt in wire-coating dies have
been published by Carley et al., 68 and by Fenner and Nadiri. 69
There are two basic kinds of internal die configuration, corresponding to two general ways of forming the insulation around the wire or
cable: these ways are pressure extrusion, in which the melt is fed more
or less directly onto the cable, and tubing extrusion in which the melt is
first formed into a tube inside the die and this is then collapsed onto
the cable. The latter method has operational advantages and is often
favoured, although pressure extrusion can give particularly good
tightness of the insulation or sheath, with effective filling of interstices
in composite cables.
A schematic diagram of a typical building-wire insulation and
sheathing line is shown in Fig. 14.5.

:Lcb=

14

~~

.1l'O'''~, ~

.~

""
""~
;:
""!:>.
is

:::1

;:-

;:

r-

!J:l

Fig. 14.5 A typical building-wire insulation and sheathing line. 1, Dual reel flyer pay-off for insulation or earth wire ;;;
when sheathing; 2, wire straightener; 3, rotating pay-offs for insulated core to make flat twin-sheathed cable; 4, cable
guides; 5, extruder; 6, hopper loader and colour masterbatch feeder; 7, control panel; 8, embossing unit; 9, multi-pass
capstan/cooling trough; 10, diameter control; 11, spark tester; 12, accumulator to control take-up speed; 13, high-speed
dual reel take-up; 14, stripping extruder. (Reproduced, with permission, from Ref. 9.)

~!
~-

, .."

;::J
00

14 Extrusion of PVC-General Aspects

719

Good accounts of extrusion-coating of wire and cable with PVC have

been published by Barnett,9 and Burton and Clarke. 7o
(b) Production of pPVC Hose with Braid Reinforcement
An example of a modern, continuous production operation is the
Maillefer line (Meillefer SA, Ecublens, Switzerland).?l A primary
extruder (operating on either pellet or powder feed) extrudes a tube
(the ultimate inner part of the hose): this is vacuum-sized, cooled and
dried, and thereupon enters an in-line winding section where filament
reinforcement is applied-in a braid configuration-by a counterrotating, multi-strand helical winder. The tube next passes through an
adhesive-coating station and a pre-heater, and then enters the
cross-head die of a second extruder, where it is coated with an outer
PVC layer. The composite tube emerging from the die is passed
through a cooling bath and caterpillar haul-off (which provides traction
for the whole operation), to a winding and cutting station. A typical
production speed (with 60-mm screw extruders) for 20-mm hose is
quoted as 15-20 m min- l depending on the PVC compound and the
reinforcement winding density.

REFERENCES
1. Anders, D. (1978). 36th ANTEC SPE Proceedings, pp. 726-31.
2. Fisher, E. G. (1964). Extrusion of Plastics, Illiffe Books Ltd, and The
Plastics Institute, London.
3. Titow, W. V. and Lanham, B. J. (1975). Reinforced Thermoplastics,
Applied Science Publishers, London.
4. Burbridge, J. (1973). In Developments in PVC Technology, (Eds J. H. L.
Henson and A. Whelan), Applied Science Publishers, London, Ch. 8.
5. Anon. (1982). Eur. Plast. News, 9(11), 3~.
6. Anon. (1982). Mod. Plast. Int., U(lO), 24.
7. McCandless, W. W. and Maddy, W. D. (1981). Plast. Technol., 27(2),
89-93.
8. Avery, D. H. and Csongor, D. (1978). 36th ANTEC SPE Proceedings, pp.
446-8.
9. Barnett, G. P. (1977). In Developments in PVC Production and
Processing, (Eds A. Whelan and J. L. Craft), Applied Science Publishers,
London, Ch. 8.
10. Grant, D. and Wilkinson, P. (1968). Plast. Polym., 36(124), 33~1.
11. Anon. (1979). Mod. Plast. Int., 9(1), 30-1.
12. Anon. (1982). Mod. Plast. Int.. 12(3), 20.
13. Anon. (1980). Plast. Technol.. 26(13). 62-4.

720

B. J. Lanham and W. V. Titow

14. Carley, J. F. (1968). SPE J., 24(2),36-41.

15. Yarsley, V. E. and Flavell, W. (1956). Cellulosic Plastics: Part 1: Cellulose
Acetate, Cellulose Esters, and Regenerated Cellulose, Plastics Monograph
No. C. 6., The Plastics Institute, London.
16. Rice, W. T. (1980). Plast. Technol., 26(2), 87-91.
17. Anon. (1982). Mod. Plast. Int., 12(11), 24-5.
18. Anon. (1981). Mod. Plast. Int., 11(11), 35.
19. Anon. (1981). Eur. Plast. News, 8(11), 37.
20. Kautz, G. and Schumacher, F. (1977). Kunststoffe, 67(10),585.
21. Brockschmidt, A. (1982). Plast. Techno!., 28(5), 35-7.
22. Anon. (1982). Eur. Plast. News, 9(11), 37.
23. Brockschmidt, A. (1982). Plast. Techno!., 28(3), 73-6.
24. Fenner, R. T. (1979). Plast. Rubb. Int., 4(5), 219-22.
25. Fischer, P. (1981). Plast. Rubb. News, January, 39-45.
26. Parnaby, J., Kochhar, A. K. and Wood, B. (1975). Polym. Engng. Sci.,
15(8), 594-605.
27. Lippoldt, R. F. (1978). 36th ANTEC SPE Proceedings, pp. 737-9.
28. Lippoldt, R. F. (1978). Plast. Engng, 34(9), 37-9.
29. Marks, G. C. (1973). Developments in PVC Technology (Eds J. H. L.
Henson and A. Whelan), Applied Science Publishers, London, Ch. 2.
30. Chartoff, R. P. (1976). 34th ANTEC SPE Proceedings, pp. 347-9.
31. Summers, J. W., Isner, J. D. and Rabinovitch, E. B. (1978), 36th ANTEC
SPE Proceedings, pp. 757-9.
32. Parey, J. and Menges, G. (1981). J. Vinyl Technol., 3(3), l52-{).
33. Menges, G., Berndtsen, N. and Opfermann, J. (1979). Kunststoffe, 69(9),
562-9.
34. Benjamin, P. (1978). 'The influence of processing on the properties of
PVC pipe,' paper presented at the PRI International Conference on PVC
Processing, Egham Hill, Surrey, England, 6-7 April, 1978; and (1980)
Plast. Rubb.: Mat. Appln, November, 151-{)0.
35. Daniels, C. A. and Longeway, G. D. (1979). Polym. Engng. Sci., 19(3),
181-9.
36. Hattori, T., Tanaka, K. and Matsuo, M. (1972). Polym. Engng. Sci., 12,
199.
37. Faulkner, P. G. (1975). J. Macromol. Sci. (phys.) , B11,251.
38. Khanna, R. (1977). Pigment Resin Techno!., 6(7), 11-14.
39. Krzewki, R. J. and Sieglaff, C. L. (1978). Polym. Engng. Sci., 18, 1174.
40. Kulas, F. R. and Thorshaug, N. P. (1979). J. App!. Polym. Sci, 23,
1781-94.
41. Summers, J. W. and Rabinovitch, E. B. (1981). J. Macromo!. Sci. (Phys.) ,
B20(2), 219.
42. Krzewki, R. J. and Collins, E. A. (1981). J. Macromo!. Sci. (phys.) ,
B20(4), 443.
43. Huxtable, J., Cogswell, F. N. and Wriggles, J. D. (1981). Plast. Rubb.
Process. Appln, 1(1), 87-93.
44. Isherwood, D. P. and Katwiremu, J. B. (1982). Plast. Rubb. Process.
Appln, 2(3), 253-63.
45. Riley, D. W. and Klein, I. (1978). 36th ANTEC SPE Proceedings, po.
525-8.

14 Extrusion of PVC-General Aspects

721

46. Press, J. B. (1978). 'The selection of PVC polymers, additives and fillers
and the choice of equipment to maximise output and quality and to
minimise cost,' paper presented at the PRI International Conference on
PVC Processing, Egham Hill, Surrey, England, fr-7 April, 1978.
47. Collins, E. A. and Metzger, A. P. (1970). Polym. Engng. Sci., 10, 57.
48. Logan, M. S. and Chung, C. I. (1979). Polym. Engng. Sci., 19(15),
1110-16.
49. Summers, J. W. (1981). J. Vinyl Technol., 3, 107-9.
50. Marshall, G. P. and Birch, M. W. (1982). Plast. Rubb. Process. Appln,
2(4), 369-79.
51. Parey, J. and Zajchowski, S. (1981). Plastverarbeiter, 32(6), 724-6.
52. Gonze, A. (1971). Chim. Ind., 104(4/5),422-7.
53. Lamberty, M. (1974). Plast. Mod. Elast., December, 82-9.
54. Lanham, B. J. (1969). Plast. Rubb. Wkly, (286), 10-11.
55. Martin, B. (1970). Plast. Polym., 38(134), 113-19.
56. Klein, I. and Tadmor, Z. (1969). Mod. Plast., 48(9), 16fr-70.
57. Sweetapple, L. (1968). Plast. Technol., 14(11), 75-83.
58. Anon. (1981). Plast. Techno!., 27(7), 15-17.
59. Wyman, C. E. (1975). Polym. Engng. Sci., 15(8), 60fr-11.
60. Prause, J. J. (1967). Plast. Techno!., 13(11), 41-5.
61. Prause, J. J. (1968). Plast. Technol., 14(2),29-33.
62. Prause, J. J. (1968). Plast. Technol., 14(3), 52-7.
63. Jewmenow, S. D. and Kim, W. S. (1973). Plaste u. Kaut. 20, 356.
64. Kim. W. S.,Statschkow, W. W. and Jewmenow, S. D. (1973). Plasteu. Kaut.,
20,696.
65. Korney, A. F. Jr. (1969). SPE J., 25(7),27-9; 25(9), 28-31.
66. Kramer, A. (1969). Kunststoffe, 59(7),409-16.
67. Anon. (1967). Brit. Plast., 40(12), 57-61.
68. Carley, J. F., Endo, T. and Krantz, W. B. (1978). 36th ANTEC SPE,
Proceedings, pp. 453-61.
69. Fenner, R. T. and Nadiri, F. (1979). Polym. Engng. Sci., 19(3),203-10.
70. Burton, V. A. C. and Clarke, J. J. (1978). 'Cable extrusion machinery for
PVC', paper presented at the PRI International Conference on PVC
Processing, Egham Hill, Surrey, England, fr-7 April, 1978.
71. Anon. (1979). Mod. Plast. Int., 9(1),20.

CHAPTER 15

Injection Moulding of pvc

The late L. W. TURNER

15.1 INTRODUCTION
Injection moulding is a commonly operated melt process, more
extensively applied to thermoplastics other than PVC than to PVC
itself, chiefly because of two inherent features especially appertaining
to the unplasticised PVC compounds. These features are thermal
instability and high melt viscosity, both of which create situations
which those responsible for the process must anticipate and control
carefully. There is little doubt that as moulding technology improves
and as the position with regard to VCM becomes less hazardous the
injection moulding of PVC will extend.
Injection moulding is a cyclic process in which precision in repetition
yields significant applicational, economic and quality returns. The
procedure by which an injection machine is used to produce adequate
components can best be envisaged in distinct stages: feeding the melting
cylinder with compound; preparing plastic melt by thermal and
mechanical effects; forcing the melt from the melting cylinder into the
mould; cooling the contents of the mould; finally emptying the mould.
While post-ejection processes may need to be applied-jigging,
trimming, decorating, assembling, cementing-these will not be dealt
with here. The two features that have been emphasised above as being
particularly significant with PVC, are especially so during melt
preparation and mould filling. For this reason attention will be largely
devoted to the behaviour of PVC in these two stages of the overall
cycle of operations. It is here that the plastic melt reaches its maximum
temperature and is forced to flow through restricting features such as
cylinder nozzle, sprue, runners and gates.
723

724

L. W. Turner

Concerning the other stages of the cyclic process of injection

moulding, it is generally satisfactory to consider PVC as one would
other thermoplastics. Thus, in the section below on trouble-shooting,
this approach is taken specifically, and the account emphasises the
effects which might be met with due to instability under melt
conditions.

15.2 MELT PROPERTIES OF PARTICULAR

SIGNIFICANCE, MELT BEHAVIOUR IN RELATION TO
MOULDING CONDITIONS, AND MOULDING COMPOUNDS
While, in many respects, PVC responds to the process of injection
moulding as do other thermoplastics, it is notable for two specific
reactions to moulding conditions which tend rather to set it apart.
These are: development of decomposition, in times of the order of
moulding cycles, at those levels of temperature found to be necessary;
and a tendency for the melt to have a higher viscosity than many other
materials at permissible temperature levels, when the polymer is
unaided by the presence of plasticisers or other flow promoters.
It is often stated that PVC shows a marked tendency to decompose
by reason of loss of HCI from the molecular chain accompanied by
darkening-at temperatures from, say, I80 a C upwards. But such a
description of its behaviour during moulding must be regarded as
oversimplistic. In fact degradative effects can become apparent over a
range of temperatures, including levels below I80 a C, in relation to the
time for which the melt is held at these levels. This leads to the concept
of residence time (often applied by moulders when setting up a
trouble-shooting programme) which also tends to be employed in too
simple a fashion in considering moulding performance. What has to be
taken into account is the integrated thermal input to the material (from
any input source) during both melt preparation and mould-filling
stages. The shear-work being done on a highly viscous polymer melt
can result in reduction of the molecular entanglements, thus aiding
flow; but this effect will not normally give rise to difficulties in
production control or in product quality. Rather more serious is the
molecular damage which high shear levels can cause, especially to
longer chains present in the melt. This latter degradative effect is
separate from, and additional to, the thermal degradative effect and is

15 Injection Moulding of pvc

725

almost always much less prominent and camouflaged by thermal

effects.
Firstly, to illustrate the straightforward effect of material temperature, the graph in Fig. 15.1 has been prepared from data given in the
literature! for three types of moulding compound (referred to again in
Section 15.6). The graph defines reasonable limits for residence times:
i.e. to the right of a given curve the residence time is too long for safe
operation with the compound concerned at a selected temperature; to
the left conditions are safe (no thermal/time decomposition).
The graph gives data for specific time-temperature pairs, but from
the discussion above it will be realised that to deal adequately with
degradative effects occurring during moulding, the broader picture of
integrated thermal input has to be considered.
Secondly, it is necessary to realise that the degradation which might
occur during moulding cannot be attributed to one specific timetemperature value pair.
The melt reaches the mould cavity by what might be regarded as an

230

220

V.

210

''"-

::J

,"200
'-

'"

a.
E

~190
180

lima,s

Fig. 15.1 Time-temperature behaviour of typical PVC compounds. A,

Pipe-fitting compound; B, rigid general-purpose compound; C, flexible
compound. Generalised representation, based on data from Ref. 1.

726

L. W. Turner

integration of a series of temperature-time steps which vary continuously as the plastic material proceeds from hopper to mould entry.
Shear-work, dissipated as thermal energy, raising the melt temperature, takes place in the melt in the forward zones of the screw and
barrel, in the nozzle, and finally in the gate. Thermal conductivity is
poor, and non-homogeneous build-up of temperature will occur. Poor
streamlining in the nozzle-to-gate region can exacerbate the situation
by causing local stagnation of flow, which adds seriously to the time
component of the thermal input.
The rheological behaviour of PVC2 is important in relation to
injection moulding because melt preparation usually involves an
extrusion screw and barrel arrangement. Melting and flow behaviour
during this heating process and flow during the moulding operation are
dependent on the rheology, which in turn depends on the composition,
i.e. the PVC polymer and the additives employed. Shear-work is
another feature dependent upon composition via slip and flow
behaviour.
15.2.1 Moulding Compounds

In the case of plasticised compositions, the general difficulties

associated with the high melt viscosity and susceptibility to thermal
degradation of PVC compounds are, to some extent, relieved by the
presence of the plasticiser(s) which makes for easier melt flow (lowers
melt viscosity) and hence for processability at somewhat lower heat
inputs and temperatures. It is thus the uPVC compounds that present
the greatest problems-a circumstance responsible for their general
unpopularity with moulders, and long operative as a restricting factor
on the scope and volume of the injection moulding of 'rigids'.
However, the problems can be considerably eased by suitable
formulation, and in particular by the use of special PVC homopolymer
resins of relatively low molecular weight (cf. also Chapter 4, Section
4.4.1(a)). 'Easy flow' rigid injection-moulding compounds* available
from most big suppliers are commonly based on such resins (in which
the lower molecular weight is also usually combined with fine particle
size and medium porosity). With good equipment and moulding
practice easy flow compounds permit production of relatively thinwalled mouldings of large surface area; deep draws, as well as normally

* e.g. Geon 110 x 346 (B. F. Goodrich); Ethyl 7042 (Ethyl Corp.).

15 1njection Moulding of pvc

727

difficult surface detail, can also be achieved in many cases. Although it

is sometimes claimed that the compounds can be successfully
run-with only a few modifications-on equipment set up for the
processing of materials less difficult than uPVC (e.g. ABS) it is
important for effective operation with any uPVC composition to pay
attention to the equipment and process considerations summarised in
Section 15.4.
Compounds based on vinyl chloride copolymers, or on combinations
of homopolymer with flow-promoting resins, may be used for ease of
processing, where the ultimate properties of the resulting products are
consonant with the end-use requirements.
Note: A standard flow test3 in a piston plastometer (melt index
apparatus with a modified die) provides a useful method of
comparison of PVC compounds with particular reference to
the effects of compositional factors and thermal and rheological stability. Whilst some correlation of the test results with
actual processing behaviour is also claimed3 (especially for
compounds of generally similar composition) the validity of
this claim in particular cases must be subject to such factors as
the differences in shear rates between test and processing
conditions (shear generally higher in the latter) and the effects
of the elastic nature of the melt (not normally brought out in a
plastometer test).

The mould shrinkage of rigid PVC moulding compounds is relatively

low: typically 01-07%. That of plasticised compositions is generally
more variable and much higher.
Note: Shrinkage of plastics mouldings can vary with the rate of
operation (cycle time). Useful general comments on the
practical aspects of mould shrinkage calculations for optimum
processing rates have been published by W. B. Glenn. 4

uPVC moulding compounds are not very sensitive to moisture and

do not require drying before use, except where significant moisture
pick-up may have resulted from prolonged explosure to humid
atmospheres. Even in such cases a hopper drier on the injection
machine may be sufficiently effective. Any oven pre-drying should
normally be done on shallow layers (up to about 4 cm), with the
temperature and time of drying preferably not exceeding 65C and 3 h,
respectively.

728

L. W. Turner

15.3 EFFECT OF PROCESS FACTORS UPON PRODUCT

PROPERTIES
Some reference to process factors affecting product properties, aside
from the effects attributable to thermal decomposition, is necessary.
PVC polymer, in common with other thermoplastics, by reason of its
characteristic long chain-like structure, yields melts of high viscosity
and poor thermal conductivity. These physical attributes give rise to
mouldings in which quenching stresses and orientation both exist.
These can have important effects upon product properties, though it is
not uncommon for moulders to be aware of and concerned about
orientation while neglecting to consider the effects of quenching
stresses.
Other morphological features of mouldings, e.g. skin and core
effects, also arise, and influence the properties. A useful summary of
methods of characterisation of injection mouldings was published
recently by Haworth et al. 5

15.3.1 Quenching Stresses

Injection into a mould which is much cooler than the melt results in
rapid chilling of surface layers of the moulding. Inner layers, by reason
of poor conductivity in the melt and the solid, cool more slowly and
stresses are set up within the moulding cross-section. Commonly,
compressive stresses of considerable magnitude arise in the surface
layers and balancing tensile stresses in the central zone; together these
are sufficient to affect mechanical behaviour and environmental
resistance of the moulding.

15.3.2 Orientation and Related Features

The flow pattern and the effect of the shear involved in melt flow give
rise to anisotropy of mechanical and other properties. Mouldings are
most resistant to fracture when deformed across the line of orientation
and less so along this direction. This situation can be exaggerated if
fillers are present in the compound, especially if they are fibrous.
Orientation is not uniform either along a flow path, or, at any given
point, through the moulding thickness.
Development of orientation relates to the shear stress required to fill
the mould cavity and through this physical parameter becomes related

15 1njection Moulding of pvc

729

to gate size, mould temperature, wall thickness, injection rate, melt

temperature, and so on. Thus the effective level of applied shear stress
can often be employed as an overriding control parameter and guide in
troubleshooting, enabling some of the complex inter-relationships
between various machine settings to be more simply recognised in so
far as moulding properties are being affected.
A useful reference to the effects of process conditions on
injection-moulded product properties is due to Gilbert et al., 6 who give
a description of the behaviour of a selected rigid formulation involving
typical ingredients. A low level of crystallinity in mouldings made from
this formulation is observed, as are differences between the skin and
core, layered structure developing during mould filling and cooling.
The distinct skin layer is highly oriented as shown by its strong
birefringence (when a thin cut section is viewed through the thickness),
whereas the core is largely unoriented. The skin layer decreases in
thickness from, say, 04 mm down to around 01 mm as moulding
thickness increases from 16 to 6 mm. Additionally, the thickness of
this oriented skin is governed by each of the commonly varied process
factors: filling rate, mould temperature, material temperature.
Unfortunately no reference is made to the quenching stresses which
must have developed in parallel with the oriented skin layer and for
this reason the consideration of the effects on product properties is not
too helpful to the reader. In referring to this paper it has to be
recognised that mould shrinkage data are not given though the word
'shrinkage' is used. Such 'shrinkage' data as are given relate to
recovery at an elevated temperature (130C).

15.4 THE MOULDING PROCESS: AVAILABLE

EQUIPMENT; PROCESS CONTROL; SOME
FEATURES OF uPVC MOULDING

The elementary principles of injection moulding (including machine

features, mould design and processing conditions) are outlined in an
leI publication. 7 Useful practical guidance on the equipment, the basic
process, process operation and control, and diagnosis and cure of
moulding faults is provided in a recent book by Brown. s A brief
general discussion of the main considerations in injection machine
selection has been published by Ireland and Smith. 9

730

L. W. Turner

Plate J Injection unit for the Peco-Loewy 20/90R injection-moulding

machine: shot weight 30 lb; 2500 ton locking unit. (Courtesy of the designer Mr
T. Seklecki, formerly of Peco, now with Gay's (Hampton) Ltd, Hampton,
Middlesex, England.)
The modern injection-moulding machine is a sophisticated piece of
equipment but, at the present moment, its design details are in a
transitional stage. Quite extensive changes are taking place, not so
much in the actual mechanics of the separate process stages which it
provides, but almost entirely in regard to the detailed control of these
process steps, their balance and integration. This is due to a
background already developed in monitoring and feed-back control
during the last decade, plus the well-nigh revolutionary possibilities
inherent in the use of microprocessors. By the use of these,
inexpensive integrated control can be achieved. Moulders involved in
large runs of closely related products (e.g. pipe fittings) can set up
processing units which are unique to the product in satisfying, at
optimum level, specific processing requirements. Having in mind the
nature of PVC and the specific nature of some of its applications, the
development in dedicated process control is most welcome to
moulders. Others, wishing to make a wide range of products, can gain
advantage from the greater ease of setting up and re-establishing
process conditions, thus achieving greater consistency of operation,
less rejects and less down-time.

15 Injection Moulding of pvc

731

Extensive surveys of injection-moulding machines are published

from time to time in the technical literature.
Note: Two recent surveys appeared, respectively, in the March 1983
issues of Plastics and Rubber Weekly and in European Plastics
News for June 1983.

The data provided for the various manufacturers' machines normally

relate to machine characteristics and construction, with the wide range
of equipment available divided into four groups according to the
mould-clamping force. Whilst manufacturers will advise how particular
machines can best be set up for PVC working, the following general
points may be mentioned by way of a few broad guidelines.
For moulding uPVC, the machine should preferably have a clamping
pressure capacity of up to 35 tons (UK) per square inch of proj~cted
area of moulding (i.e. about 55 MN m- 2 , in round figures), although
anything from about 2 tons upwards (i.e. about 30 MN m- 2 plus)
should normally be sufficient with most easy-flow compounds. In many
cases a shot size between about two-thirds and three-quarters of barrel
capacity will represent the practical optimum for melt residence times
sufficiently short to avoid undesirable heat effects or excessive heat
history when operating near the top limit of the relatively narrow melt
temperature range (see further on) desirable for ease of flow. With
screws specially designed for uPVC processing ('PVC screws') shot
sizes up to full capacity may be practicable. With decreasing shot sizes
(preferably not below about one-fifth of barrel capacity) the balance of
the effects of melt temperature, residence time, and cycle timealways important with PVC-becomes progressively more critical.
Several features of equipment and operation desirable or essential
for the best results in PVC moulding reflect the need to cater for the
two special factors which have already been emphasised, viz. the
susceptibility of the material to heat degradation, and the relatively
high melt viscosity (of uPVC). Thus streamlining right up to the nozzle
exit is important to avoid creation of points of increased friction in the
flowing melt, and pockets of stagnant material where thermal
decomposition may occur with consequent contamination of, and
destabilising effect on, the melt. For analogous reasons it is usually
considered essential for rigid PVC to have a conical extension
(smear-head tip) on the screw which-with a suitably shaped barrel
head-virtually empties the barrel at the finish of mould-fill, as it
attains its most forward position. Some relevant comments about screw

732

L. W. Turner

tip patterns for different circumstances have been published by Tulley

and Harris,I and about the moulding of rigid PVC generally by
Huber. lO The screw should preferably be of a design intended for
uPVC processing: LID ratios in the range 14-24: 1, and compression
ratios of 15-20: 1, may be regarded as optimal, although higher
compression ratios (up to about 3: 1) can be used if the effects of the
associated greater shear-heat generation are properly monitored and
controlled (by lowering the rotational speed and back-pressure of the
screw). Conversely, lower compression ratios allow a wider range, and
higher values, of back-pressures and rotational speeds. As an example,
the following values have been recommended for an easy-flow
high-impact uPVC compound (Ethyl 7042).11
Screw compression ratio
Back-pressure range (Ibf in -2)
Rotational speed range (r min-I)

l'S:l
20:1
2S: 1
G-1000 0-400 G-100
2G-100 2G-80 2G-SO

30: 1
G-SO
2G-30

It can be worthwhile to set the machine to operate under zero cushion

mode: otherwise a minimum cushion (say 2~ mm) is desirable.
The flow routes (nozzle, runners) should be as short and generous as
possible. The nozzle should preferably be reverse-tapered, to reduce
friction-heating possibilities in this area. Gates should also be generous
(and round wherever possible), with small lands and edges radiused
towards the component, for ease of flow, rapid mould filling and
reduction of pressure losses. Pin-gating is undesirable, although it may
be used in some cases (in particular for small parts moulded with easy
flow compounds). Adequate venting of moulds is important.
Maintenance of optimum stock temperatures at the various stages of
the material's processing in the machine is particularly important with
uPVC, for ease of flow, avoidance of decomposition, and minimum
heat history. Close attention should be paid to the proper setting and
control of all heater temperatures, as well as-and in conjunction
with-the factors influencing shear heating in the barrel (the
back-pressure and rotational speed of the screw-see above), and
frictional heating thereafter (size and configuration of nozzle, flow
channels and gates; rate of injection). The melt temperature should be
monitored directly, either through intermittent checks (e.g. with a
thermocouple inserted into melt flushing out of the nozzle while the
barrel is retracted from the mould) or continuously by a sensor
(thermocouple) so positioned that it does not cause additional friction

15

733

Injection Moulding of PVC

or stagnant spot in the flowing melt. It is generally advantageous to set

the barrel and nozzle heaters for a temperature profile rising fairly
sharply from the rear (feed) zone of the barrel to the nozzle. The set
temperatures should preferably lag somewhat behind the desired stock
temperatures, the heat needed to make up the difference coming from
the right amount of mechanical working of the material in the barrel
secured by appropriate speed and back-pressure of the screw.
For a given machine and mould set-up (and with a particular screw
type, speed and back-pressure) the heater temperature settings will
vary somewhat according to the composition processed (see examples
in Table 15.1), but an arrangement of this general kind offers the
following advantages. The final fusion of the stock takes place well
forward in the barrel, so that the amount and dwell time of the hottest
material are minimised, whilst any volatiles have an escape route
through the interstices between incompletely fused compound particles
in the rear of the barrel, with consequent reduction of the possibility of
porosity in moulding arising from this source. During a mechanical
stoppage, the material in contact with the cylinder walls (especially the
fused melt in the front part of the cylinder) will be hotter, at least
initially, than the wall surface, so that the immediate effect should be
its cooling-and not continued heating-with consequent delay of the
onset of decomposition.
TABLE 15.1

Examples of Recommendations for Temperature Regimes in the Processing of

Some uPVC Compounds
Type of compound

Temperature settings

eC)

Barrel zone heaters

General-purpose easy
flow, high-impact
Pipe-fitting compound
(Type 1)
Universal pipe-fitting
compound (Type 1/2)
See Section 15.5.

Nozzle
heater

Melt
temperature
(0C)

Rear
(feed
section)

Middle

Front

135

160

170

170-175

200-210

140

155

170

170-175

190-200

145

160

175

175-180

200-205

734

L. W. Turner

Note: In the case of stoppages of appreciable length, the heater

temperature settings should be reduced, and the barrel should
be pulled back from the mould and purged out slowly. If the
stoppage is prolonged, or when shutting down, the barrel
should be completely emptied and purged with a purging
compound (polystyrene, ABS, acrylic, or HDPE) at a
relatively low temperature (about 160C): uPVC should never
be allowed to solidify in the barrel.
If the temperature settings on the rear and centre zone heaters are
too low, the torque on the screw trying to work the relatively cold
material may be excessive: to prevent overloading the motor, an
upward adjustment should be made (say in steps of 5C) until the
screw is running normally.
The melt temperature should preferably not exceed 205C, and
should never be higher than 215C: the range 18Q-205C may be
regarded as typical for most processing.
The mould (inlet water) temperatures used are normally within the
general range 2Q-70C, with 2Q--40C usual for many easy-flow
compounds (the actual optimum depending on the composition, and
the wall thickness, flow length and moulding size), and the higher
temperatures for the older types of uPVc.
Temperature control techniques for injection-moulding machines are
summarised in a recent paper by Ingham. 12
The following further points may be mentioned.

15.4.1

Rate of Injection and Injection Pressure

The rate of injection should be the optimum for rapid, complete filling
of the mould, but consistent with avoidance of decomposition (first
manifested in the appearance of discoloration at and near the gate
point-d. Section 15.6) through excessive frictional heating.
Note: If the injection rate is reduced too far, weak weld lines, sink
marks, or even short shots may result. When the characteristic
signs of decomposition appear at a generally reasonable
injection rate, consideration should be given to enlarging (and
streamlining) at points where melt flow may be unduly
restricted (nozzle orifice, sprue, runners, gate). As a general
principle, automatic adjustment of injection rate (via a
closed-loop control arrangement) is highly desirable.

15 1njection Moulding of pvc

735

Injection pressure is interdependent with injection rate, and also

influenced by other factors, notably melt fluidity and the geometry and
temperature of the mould. As a general guide, for uPVC the first-stage
injection pressure can advantageously be within one-half to threequarters of the total pressure available on the equipment, and the
holding (dwell) pressure will usually be between one-half and
two-thirds of the first-stage pressure. It is desirable that the equipment
should be able to provide pressure up to 25000 lbf in -2 (about
172MNm- 2).
15.4.2 Working Surfaces

The working surfaces of machine and moulds must be resistant to acid

corrosion. Stainless steel moulds are desirable wherever the type of
work and run lengths can justify the initial expense.

Note: Galling can be a serious problem where stainless steel surfaces

in contact undergo repeated relative movement. For this
reason any moving parts in a stainless steel mould (ejector
pins, sliding cores) are usually of chromium-plated hardened
steel.
The mould surfaces, as well as those of the screw, may also be of
chromium-plated hardened steel, or of hardened steel nickel-plated (by
the electroless process) over-plated with chromium (the electroless
nickel finish alone may not provide sufficient corrosion protection,
especially where the mould contains deep recesses). Deep nitriding
may be adequate as the sole protective finish in some cases. It is
strongly preferable that all surfaces (those of the platens, etc.)
accessible to any gaseous products of decomposition of the PVC
material should also be suitably protected.

Note: For out-of-use periods (following the end of a run, before a

shut-down) the surfaces of the mould, including those of the
moving parts, should be treated to neutralise acidity and
inhibit corrosion. Suitable treatments (neutralisers and inhibitors, usually in sprayable form) are available on the market.
15.4.3 Interaction of PVC with Acetal Polymers and Copolymers

PVC and the acetal resins (e.g. Delrin-Du Pont; HostaformHoechst; Kematal-Amcel UK; Celcon-Amcel USA) interact strong-

736

L. W. Turner

ly at elevated temperatures, with resultant vigorous mutual degradation. The two materials should on no account be allowed to come
together in plastics processing equipment (injection-moulding
machines, extruders, melt-compounding mixers, etc.). It is highly
preferable that the same machine should not be used for the
processing-especially consecutive processing-of these materials: at
the very least extremely thorough purging must be carried out (with a
suitable purging compound-see above) before a change-over.
Two brief general summaries of considerations important in the
moulding of uPVC have been published recently by Whelan,13 and
Murrey and Dito. 14
15.5 MATERIALS AND APPLICATIONS
It should be obvious from what has been said concerning the rather

unique aspects of PVC moulding that the moulder, prospective or

current, is greatly aided if he has available to him property details of
the compounds he is intending to use. By and large, manufacturers can
help but it is not too wise to rely entirely on such sources and the
moulder would do well to look at some of the more fundamental
aspects of his activity.
The purposes for which PVC moulding compounds are used are
numerous and the compounds will range in type. It is, however,
possible to classify and thus to understand better what the main types
are and how they will mould. An excellent account of such a
classification is given in Ref. 1. The classification recognises two basic
types of unplasticised material, and a general category of plasticised
compounds:
Rigid (unplasticised)
Flexible (plasticised)

1. Typical for pipes and pipe fittings

2. Typical general-purpose
General: used for flexible demands

The differences. between the two types of rigid composition arise in

consequence of the requirements to be met.
Type 1: Mouldings usually thick-sectioned; high strength and
stiffness, high rupture strength, good corrosion resistance.
Minimum cost because of large number of items used,
runner stabilised.
Type 2: Designed for thinner sections and a wide range of

15 1njection Moulding of pvc

737

conditions. Higher level of stabilisation and better flow

properties for thinner, larger-area products.
The flexible (plasticised) grades, while considered as one broad type,
will vary widely in respect of types and amounts of plasticisers used.
In the moulding of PVC-and especially uPVC-pellets are used as
the feedstock in the majority of cases. This is mainly because they
consist of melt-compounded material which is already well homogenised and uniformly fused (d. Chapter 13), and thus-unlike powder
(dry-blend) feeds-does not have to rely for final homogenisation on
the treatment received in the barrel of the injection machine which is
not primarily designed as a mixing unit. This consideration normally
outweighs that of the more extensive heat history the pellets acquire in
consequence of the melt-compounding operation.
The most important area for the extension of injection moulding of
PVC undoubtedly lies in rigid mouldings of thinner sections. The
technical problems will be clear from the text above: the successful
development of new applications has depended upon improving
processing characteristics by increasing thermal stability and promoting
easier flow through the use of suitable PVC polymers and additives of
the appropriate types.
Availability of screw/ram machines has created better processing
conditions in making for better thermal homogeneity and reducing
residence times. It is not likely that piston machines will be employed
in the future in any significant way.
Where really thin disposable items are required (as in the packaging
field where PVC is regaining acceptance now that VCM concentration
hazards are controlled) these will not be made by injection moulding
but by forming of extruded sheet.
A process sometimes referred to as 'flow moulding'* enables large
mouldings to be produced on relatively small injection machines, by
utilising pressure developed by the. rotation of the screw (instead of
that produced by the injection stroke) as mould-filling pressure. Inter
alia, large (30 lb) PVC pipe fittings have been produced on a 250 ton
injection machine 15 by this process, which may be considered as a
combination of extrusion (as the means of supplying melt to the
mould) and injection moulding (in that a conventional-though
modified-injection-moulding equipment is used). The modifications
include adjustment of the hydraulics to keep the screw in the forward
* Developed by Durapipe Ltd, Cannock, UK.

L. W. Turner

738

position (feeding the stock through a gap between the screw tip and
the rear face of the nozzle); provision for adjustment of the size of this
gap (where the main working of the material to produce plastication is
effected through the shear imparted) to regulate the amount of shear;
special provisions for screw and barrel cooling; and overall control of
temperatures and pressures.
The process is claimed to be particularly suited to heat-sensitive
materials such as PVc.

15.6 TROUBLE-SHOOTING
Many processing and material factors have to be balanced in order to
achieve high outputs of good quality mouldings. Achieving an
acceptable balance can sometimes be a difficult task requiring
experience and skill. Two principles are here emphasised: good
knowledge of the material concerned (this is perhaps more important
with PVC compounds than with any other thermoplastic) and use of
such control aids as the equipment can provide.
Three groups of considerations which arise in aiming at continuous
in-balance quality mouldings are distinguished below. They relate to
machine selection; to those processing features pertaining more
specifically to PVC; and to those features which are of general
significance in injection moulding of thermoplastics.

15.6.1 Machine Selection

The moulder with a limited range of machines faces problems not
necessarily met with by the one who can match more closely machine
size to moulding shot-weight and cooling time. Here the essential
feature is 'residence time', or the 'temperature-time integral' to be
more accurate.
During operation it is important to maintain observation of heater
control indications (watching out, inter alia, for persistent and
increasing override), filling rate (to spot any tendency to increase with
running time), and changes in thickness of cushion layer.

15.6.2 Processing Features Specific to PVC

These relate almost entirely to the behaviour of the material, there
being an inevitable interaction between these features and those
mentioned in Section 15.6.1 above.

i5 injection Moulding of pvc

739

TABLE 15.2

Common Faults in PVC Mouldings

Observation
1. Splay marks or

silvery streaks
emanating from
the gate position

2. Dark centre to
sprue or internally in gate area

Significance
May be due to condensed moisture
but, more important, could be initial signs of decomposition due
to thermal input
increased above
acceptable level
Progressive overheating of material
(sometimes associated with hot spot
at screw tip)

3. Dark, streaky areas

on surface of sprue

Increasing overheating of material

4. More prominent
areas of darkened
material on sprue
surface often extending from sprue
into the moulding

Some decomposition
of material due to
overheating

5. Dark streaks spreading from gate point

High shear or
stagnation in this
region

6. Dark decomposition

Local 'burning'

spot at the same

point in each
moulding (sometimes in weld line)

Adjustment
Choice of reduction of forward band heater settings (especially nozzle
temperature), screw
speed, back-pressure,
filling rate, singly or in
various combinations

Adjust barrel temperature

and/or reduce backpressure, and/or screw
speed; if fault persists
attend to shape or
smooth runs of screw
tip; perhaps change to
distorted tip to give an
increase of local shear
Reduce band-heater settings, and/or backpressure and speed of
the screw
Retract barrel and make a
few air shots to remove
overheated stock. Return barrel, reduce heater settings; increase
cooling, lower screw
speed and/or backpressure; consider residence time
Better streamlining required: slow down input
rate, attend to streamlining if necessary; consider
enlarging nozzle and/or
gate(s)
First try reducing injection
rate; if fault persists
attend to proper mould
venting and radiusing of
corners

740

L. W. Turner

Observation of the product provides the clues from which process

adjustments can be decided upon. Table 15.2 lists the most frequent
manifestations of problems in the moulding of uPVC (1-4 may be
regarded as a sequence in order of increasing severity).
15.6.3 General Considerations

General moulding faults such as warping, sink marks, short shots,

flashing, weld lines and others can be treated as they would be for
other thermoplastics, so long as it is consistently borne in mind that
adjustments covering an increase in the temperature-time input must
be undertaken with caution by careful observation of signs of incipient
decomposition.
Mould filling rate should also be capable of being adjusted and
maintained at a specific level. Pressure control via feedback of data
obtained from pressure sensors in the mould cavity(ies) is a useful way
of controlling mould filling, since rates and pressures are interrelated.
Some control experts favour sensors mounted elsewhere.
Mould temperatures should be accurately maintained. This calls for
correct provision of cooling channels in the mould and control of the
fluid from circulating units of adequate performance.
Regarding the improvement of older equipment (again neglecting
piston machinery), in addition to improvements to the screw by
removal of unstreamlined non-return valves and the introduction of
conical extensions to the screw tip, it is often a simple matter to add
proprietary control features. The simplest and the best control
improvement which can be introduced by the addition of a single item
is cavity pressure control, though more specifically for PVC,
screw-advance rate control has some advantages especially where
forward-zone streamlining has proved difficult.

REFERENCES
1. Tulley, F. T. and Harris, B. C. (1979). In Encyclopedia of PVC, (Ed. L. I.

Nass), Marcel Dekker, New York, Ch. 24, p. 1313.

2. Shah, P. L. (1979). Ibid, Ch. 22, p. 1153.
3. ASTM D 3364-74 (Reapproved 1979). Flow rates for poly (vinyl chloride)
and rheologically unstable thermoplastics.
4. Glenn, W. B. (1980). Plast. Technol., 26(10), 73-5.
5. Haworth, B., Sandilands, G. J. and White, J. R. (1980). Plast. Rubb. Int.,
5(3), 109-13.

15 1njection Moulding of pvc

741

6. Gilbert, M., Marshall, D. E., Voyvoda, J. C. and Copsey, C. J. (1979).

Plast. Rub.: Process., 3,96.
7. 'The Principles of Injection Moulding,' ICI Technical Service Note G 103
(2nd edn), ICI Plastics Division, Welwyn Garden City, Herts, England.
8. Brown, J. (1979). Injection Moulding of Plastic Components-A Guide to
Efficiency, Fault Diagnosis and Cure. McGraw-Hill Book Co. (UK) Ltd,
London.
9. Ireland, R. A. and Smith, J. B. (1977). Plast. Rubb. Int., 2(5),225-7.
10. Huber, M. (1977). Plast. Rubb. Wkly, 18th February, pp. 2~23.
11. Technical Bulletins 8/73, Ethyl Corporation, Polymer Division, Baton
Rouge, Louisiana, USA.
12. Ingham, P. H. J. (1979). Plast. Rubb. Int., 4(5), 211-15.
13. Whelan, A. (1981). Brit. Plast. Rubb., April, p. 25.
14. Murrey, J. L. and Dito, A. J. (1981). Plast. Techno/., 27(12),79-82.
15. Anon. (1981). Mod. Plast. Int., 11(11), 36.

CHAPTER 16

Sheet Thermoforming and Related Techniques

for pvc

The late L. W. TURNER

16.1 INTRODUCTION
Sheet thermoforming has been described as the one method whose
development sprang uniquely from plastics technological history and
was not picked up from metallurgy. This contrasts with the case of such
solid-phase forming processes as forging, stamping, and certain others,
originally developed for metals and only relatively recently explored in
the plastics context. 1 Now super-plastic metals technology has taken up
the sheet-forming idea from the plastics industry. Plastic sheet
thermoforming is a secondary process, depending on, as primary
process, sheet extrusion to supply its starting material. In fact it is well
to bear in mind that extruded forms other than sheet (e.g. tubes), or
sheet produced by methods other than extrusion (e.g. cast as is PMMA
sheet, or laminated) can be thermoformed. It was in the early
Celluloid or Xylonite days of the plastics industry that methods of
shaping various sheet, rod or tube forms first came into industrial use.
For PVC it is largely the forming of extruded and calendered sheet that
must be considered.
Additionally, though, there are combination processes which start by
converting granules to a dimensioned pre-form of planar solid sheet
geometry and then form this into a 'drawn' article (the 'Topformer,2,3
process for example). .
There are three basic methods of sheet thermoforming:
(i) vacuum forming;
(ii) pressure forming;
(iii) matched-mould forming.
743

744

L. W. Turner

In each the sheet is softened by raising its temperature to an

optimum point in the 'rubbery' region to enable large deformations to
be achieved.
A persistent technological goal for forming operations with various
sheet materials is to save energy and promote rapid-cycle operations by
forming below the softening point. This is still not a widely established
technique and material formulation is especially important.
The methods of traditional sheet forming are quite distinct as a
group from injection moulding and blow moulding, although in certain
respects sometimes rival both. The advantages are that plant of lighter
construction can be used, which reduces capital investment in moulds
and equipment. Production can be very rapid indeed and it is
comparatively simple and cheap to change designs.
Apart from any financial considerations, there are a number of
technical advantages. It is possible to make quite large articles cheaply
and simply from thin sheets covering large areas. Design details not
involving sharp changes in thickness can be reproduced and preprinting of sheet is possible; this latter has no equivalent in injection
moulding and blow moulding, though in these processes in-the-mould
decoration is possible,4,5 but not too common.
It should not be thought that thermoforming is free from difficulties.
One of the major problems is that of the inevitable development of
considerable orientation as the 'rubbery' material is stretched, and
cooled in the stretched form. With deep forming, in particular,
orientation can be substantial and the objects produced will distort
excessively above certain temperatures. Extensive thinning of the
material can occur and control of distribution of thickness to maintain
stiffness and strength is a persistent difficulty. Some quenching stresses
may also be developed due to rapid cooling of the warm sheet. This
aspect is discussed in some detail later in this section. Sheet forming
was perhaps at one stage envisaged as being primarily suitable for
comparatively short runs of large objects. The scope has gradually
widened, however, and today fully automatic machines are available
which will produce small objects, e.g. beakers, at a high rate, and such
forming may be integrated with the sheet extrusion stage.
Sheet-forming equipment until recently has tended to be rather
poorly controlled, but this situation has now begun to change rapidly
due to the employment of improved engineering and, very recently,
microprocessor-based process monitoring and control. Good process
control is important in order to achieve economic operations with high
yields of good quality products.

16 Sheet Thermoforming and Related Techniques for

pvc

745

16.2 MATERIALS USED

Almost any thermoplastic which can be made into a satisfactory sheet
may be used for thermoforming provided that: (i) it does not
decompose at the processing temperatures, and (ii) it has properties
which make it suitable for the finished application. Materials which are
used do differ, however, in their response to the process conditions.
Many materials are used: commercially, the commoner ones are
ABS, HIPS, CA, PVC, PE, PP, and PMMA. In general, the
thermoforming performance of vinyl chloride homopolymer sheet
tends to be only moderate compared to ABS and HIPS, although
suitable formulation (and especially inclusion of appropriate polymeric
modifiers) can make a substantial difference. Whilst a copolymer-based
sheet (again without special compositional modification) will normally
be much easier to form than an otherwise comparable but homopolymer-based one, the lower softening point (and related ease of distortion
after processing) tends to make it less acceptable. In general,
chlorinated PVC is a better thermoforming material than unmodified
uPVC. It also offers better dimensional stability (at room and elevated
temperatures) of the finished product (see also Section 16.7).
Rigid, homopolymer-based PVC compositions incorporating
polymeric modifiers (including some regular high-impact compositions)
are widely used for thermoforming. It is this kind of composition that
is the main material considered here. One commercial example is
Kydex sheeting (Rohm and Haas-ef. Chapter 20), an acrylic-modified
uPVC material specially formulated for thermoforming.
Some thermoformable composite sheet materials, incorporating
PVC as one of the components, may also be mentioned. These are
exemplified by ABS/PVC solid-sheet laminates (represented, inter alia,
by some grades of Raya/ite sheeting3-Uniroyal Plastics Division), and
foam sandwich laminates with a PVC foam core and ABS sheet
facings, used for the production-by thermoforming-of interior
fittings for aircraft (side panels, window and door surrounds,
side-liners). 6
16.3 VACUUM FORMING OF SHEET
16.3.1 Principal Methods
A useful brief summary of the general types of thermoforming
processes and the main advantages and limitations of their industrial

746

L. W. Turner

embodiments was published recently by O'Neill,? and one of

thermoforming techniques and set-ups by Lubin et al. 8
Here forming methods relating to sheet are described in some detail
since sheet is by far the commonest prepared form processed in this
way; however-as has been mentioned-other forms, also made by
extrusion, or cast, can be shaped by adapted thermoforming
techniques.
There are five basic methods of vacuum forming. These are:
(a)
(b)
(c)
(d)
(e)

negative forming (or straight vacuum forming);

plug-assist forming;
drape forming;
bubble or blister forming; and
snap-back forming.

The essentials of each method are given below.

(a) Negative Forming (Fig. 16.1)
In this method the sheet is first fixed in a clamp frame over the mould.
It is heated from above and once it has reached the required
temperature is dropped onto the mould and sealed around the edges;
vacuum is applied from underneath and this draws the sheet down into
the shape of the female mould. When the sheet has cooled it may
either be removed by hand, or ejected by air pressure from
underneath. Method (b) is used for objects where drawing is greater
than 2 in. in depth.

(b) Plug-assist Forming (Fig. 16.2)

This technique is really an extension of method (a). A female mould is
again used but the drawing process is assisted by a plug very roughly
conforming to the shape of the moulding. The plug is forced down
onto the sheet, thus starting the forming process which is completed by
vacuum as in method (a). The plug has to be heated as well as the
sheet and the temperature of both has to be controlled fairly closely.
The plug also has to descend quite quickly.
(c) Drape Forming (Fig. 16.3)
This method is used for deeper drawing and thicker wall sections and
involves the use of a male mould. The male former can either be
pushed up into the heated sheet or alternatively the latter may be
pulled onto it. Vacuum is applied to complete the process once a seal

16 Sheet Thermoforming and Related Techniques for

pvc

747

Stoge I

Key

Heeter
B Clomping frome
C Plostics moteriol
o Former
E Gosket
F Vocuum box
G Pressure line
H Vocuum line
A

Stoge I-Heeter pleced over sheet

Stege 2-Vocuum opplied
Stoge 3-Heotor removed from sheet.
which is eliowed to cool before
vocuum is releosed

Fig. 16.1 Vacuum forming-negative forming. (BX Plastics Ltd.)

has been made. As in method (b) the temperature of the mould and
speed of ascent or descent is important. Speed is also essential in the
rate of air evacuation.
(d) Bubble Forming (Fig. 16.4)
In this method the sheet is heated, clamped over the vacuum box and a
specific air pressure applied to blow it into a bubble. A shaped male
plug is then forced into the bubble and vacuum is applied in the usual
way.

748

L. W. Turner

DT-.....IIIIIIIil_~iLE

'r-rSloge I

Stege 2

C-

c:..

Sloge 3

A
B
C
D
E
F
G

Heater
Plug
Plastics material
Clamping frame
Gasket
Former
Vacuum box

Stoge 4

Key
H Air inlet
I Air outlet
J Vacuum line
Stage 1 - Heater placed over sheet
Stage 2 - Plug partly down
Stage 3 - Plug fully down - no vacuum
Stage 4 - Vacuum applied

Fig. 16.2 Vacuum forming-plug assisted. (BX Plastics Ltd.)

16 Sheet Thermoforming and Related Techniques for

pvc

749

Stage 2

Key
A Heater
B Clamping frame
C

o
E
F

G
H
I

Plastics material
Gaskets
Former
Vacuum box
Air inlet
Air outlet
Vacuum pipe

Stage I-Heater over sheet

Stage 2-Drope up, no vacuum
Stage 3-Vocuum applied

Fig. 16.3 Vacuum forming-drape forming. (BX Plastics Ltd.)

Fairly deep draws with reasonably uniform wall thicknesses can be

achieved by this method.

(e) Snap-back Forming

This method is really the reverse of method (d). As before, the heated
sheet is clamped over a vacuum box and is sucked into the box by
vacuum, thus forming an 'upside down' blister or bubble. A male plug

750

L. W. Turner

Steg. 2

A
B
C
D
E
F
G

Heater
Clamping frame
Plastics material
Gaskets
Former
Vacuum box
Air inlet

Key
H Air outlet
I Vacuum pipe
Stage 1 - Heater over sheet
Stage 2 - Bubble blown
Stage 3 - Drape up, no vacuum
Stage 4 - Vacuum applied

Fig. 16.4 Vacuum forming-bubble forming. (BX Plastics Ltd.)

16 Sheet Thermoforming and Related Techniques for

pvc

751

or mould then enters this from above until it seals onto the sheet. The
vacuum is then released on the box side and applied to the male plug
side and the sheet 'snaps back' onto the mould.

16.3.2 Details of Methods

One of the important practical points is to apply vacuum as rapidly as
possible. If, however, a pump of sufficient self-capacity were used this
would be an extremely costly operation. The standard method
everywhere is to use an accumulator tank with a smaller pump than
would otherwise be required, as the vacuum is required intermittently.
In the case of some of the methods, particularly plug-assist forming,
a slip ring is used for clamping. This enables the material to slip
through the ring during the forming process, which has several
advantages. It makes more material available, which prevents
edge-tearing, buckling or undue thinning. When clamps are used there
must be a good seal between the mould edge and the material.
The drape and plug-assisted methods are ideally suitable for
producing sections with sharply radiused corners and intricate designs.
In the snap-back forming method the material has to be sucked down
to a predetermined length which nowadays is controlled by a
photoelectric eye.
The various aspects of heat control are most important in
vacuum-forming methods. Pre-heating may be effected by means of
radiant heaters or convection ovens. The former are almost invariably
used for thin sheets, particularly in continuous production, and a bank
of heaters placed about 2 in from the sheet has been found to be very
satisfactory. Convection ovens are usually used for thicker sheets in
view of the poor thermal conductivity of rigid PVC.
It has been generally established that the temperature at which the
sheet should be heated for optimum results is that temperature which
gives maximum elongation at break. Figure 16.5 illustrates the
principle for a calendered high-impact PVC sheet. In this particular
case the optimum temperature is about B2C, to which temperature
the sheet should therefore be uniformly heated. It may be noted that
although the material does not have a peak the curve is fairly sharp,
and some rigid vinyls give curves sharper than this. These would,
therefore, rapidly deteriorate if heated more than a degree or two
above the optimum elongation temperature.
Once the material has been brought to the correct temperature it

752

L. W. Turner
700

..
o
c

i.,. 400
c
o

iii

20'Cl!:--=--~~-----:-'----""""o:---~""""-_--:-:!
ioo
/10
120
130
140
150

Temperature,OC
Fig. 16.5 Variation of elongation at break with temperature.

should be formed as quickly as possible. A maximum forming time of

60 s should be imposed but it should preferably be below this,
particularly with sheets 0050 in. thick or less, when 30 s or shorter is
preferable.
Although moulds can be heated (and often are for some materials) it
is not general practice with rigid PVC, the relatively low softening
point being significant in this respect; whatever the choice it should be
consistent.
Another point of detail is a method of assisting the flow into the
required positions. Interference bars or plates can be placed at
strategic points to guide the material in the desired directions. Early
descriptions of some methods of producing vacuum formings of
uniform wall thickness have been published by Lee and Welham9 and
Bretton and Welham. lo

16 Sheet Thermoforming and Related Techniques for

pvc

753

16.3.3 The Moulds

The moulds are made from many types of materials; obviously the
cheapest consistent with adequate strength and inertness for service is
used. Any metal except copper or brass may be used and other
materials include phenolic resins and laminates, laminated wood,
hardwood, or even plaster for short runs. Light alloy castings are
frequently used for long runs.
As already explained, both male and female moulds are used,
although only one or the other is normally employed for a given
method. This keeps mould costs down to a minimum. The choice
depends on the method and other factors. For example, deeper forming
can be obtained better over a male than a female mould. However, a
female mould is best used if a design is incorporated on the outside of
the moulding, as this gives much sharper impressions. It is also used
for low depth of draw and where a number of cavities need to be
placed close together for large-scale production. On the other hand a
male mould is used if internal dimensions are of importance.
Some guidance can be given regarding the dimensions of the mould
compared with the depth of draw. In the case of a male mould the
height can be equal to the narrowest dimension and often greater. In
the case of a female mould the depth of draw should not exceed half the
minimum moulding width.
Wooden moulds, etc., are made by machining. Other types, which
are cast from metal for long production runs, are made by the use of a
wooden pattern. Here shrinkage considerations are of the utmost
importance; not only does the shrinkage of the metal used for the
mould itself have to be taken into account but also the shrinkage of the
formed article coming off the mould. Such moulds as these sustain no
damage, except by carelessness, and they are likely to last for a long
time. Those made from thermosetting plastics and the like are likely to
sustain much more damage even with metal spraying, metal fillers or
electroforming.
All the moulds must be vented to apply vacuum at various points.
The closer the detail, or wherever really close conformity to the mould
is required, the greater the number of vents needed. At most the holes
will not exceed 0030 in. in diameter, although half the thickness of the
material may sometimes be used as a guide. On the side away from the
material, the holes can be opened much wider and tapered to give
more rapid evacuation. Where moulds are made by any sort of casting

754

L. W. Turner

process the vent holes can be made by inserting wires into the wooden
pattern.
With large male moulds, particularly where large production runs
are involved, it may be necessary to have some method of cooling. The
mould is then cored for water circulation. Walls can never be exactly
upright; all must have a draft with a minimum of 3, a larger one giving
a better product. The radii should be as large as possible, certainly at
least the thickness of the material being moulded.
As with many moulding processes undercuts should preferably be
avoided. However, the comparatively simple moulds allow removable
parts to be used so that undercuts can be included. Inserts can easily be
incorporated in the mould surface and so can embossed lettering on
the surface.
In the case of large runs it is clearly preferable to trim the article in
the mould to avoid a subsequent deflashing process. For this purpose a
cut-off is required and the mould must be metal, preferably hardened
at the cutting edges.

16.3.4 Finishing
The finishing and decoration of vacuum-formed parts is frequently
necessary. In particular, it is necessary to remove flash, which can be
done by saw, trimmers, guillotine, or male and female dies in toggle or
clicking presses. Precisely which method is chosen will depend on the
size of the object and the rate of production.
Apart from deflashing, the cutting of various shapes in the
component is frequently necessary. It is advisable to employ .jigs for
such purposes to guarantee accuracy and speed up production; low- or
high-speed routers can be used for the cutting.
Other finishing operations are often necessary. Various parts have
often to be joined together; if high-frequency welding is not possible
(see Chapter 20) then parts have to be joined by adhesives. These may
simply consist of polymer solutions (in, say, cyclohexanone) or some of
the many proprietary adhesives available today (see Chapter 20). Some
impact adhesives may well be necessary if dissimilar materials are used.
Another type of finishing operation is the folding of edges, e.g. in
containers which have to receive a sliding top; for this purpose it is
possible to obtain heated folding or bending machines.
Decoration sometimes presents problems, but there is no problem in
decorating the finished object by masking and spraying or vacuum-

16 Sheet Thermoforming and Related Techniques for

pvc

755

metallising by conventional techniques. The problem arises when the

sheets are decorated before forming. This means that inks and paints
must be able to stretch, and stretch without much loss of colour. Far
more important, however, is the problem of allowing for the distortion
which takes place during forming.
One way of overcoming this is to form an object in the usual way
without decoration. It is then decorated or printed and heated, when,
because of the residual strain or elastic memory of the material, it
returns to its flat state. This gives a pattern of the distorted decoration
which can be converted into the printing block.

16.4 MATCHEDMOULD AND RELATED METHODS

An early review of these methods has been made by Mottram and
LeverY It is, of course, possible to use female and matching male dies
employing either conventional pressures or relatively low pressures of
say 200-100Ibfin- 2 . The actual pressure will depend on the flow
characteristics and thickness of the sheet.
In some instances it is possible to use a female die only. Shallow
mouldings can be made in this manner with thin sheet, examples being
0030-in. thick material and maximum draws of about 0250 in. Thicker
sheets could be used, but this would reduce the possible deformation.
A good example of the possibilities here is the production of printing
plates, illustrating that extremely accurate reproductions can be made.
The pressures used are only 100 Ibfin- 2 and the opposite side of the
material is backed with a rubber blanket.
A considerable number of small containers are made from rigid PVC
by the use of matched metal dies. Such methods are usually
continuous; the stock of sheet being fed from a roll, heated
continuously by radiant heat, stamped and removed by means of a
take-up roll. Because the dies are continually subjected to heat it is
necessary to core them for water cooling. In the design of the dies for
this purpose the corners and edges should be rounded if possible to
assist flow. The clearances between the surfaces of the male and female
dies should be at least equal to the thickness of the material, as this
avoids undue wear. Finally, it is preferable to introduce cut-offs at the
edges of the die to eliminate the necessity for a finishing operation.
It is necessary to employ clamping frames, particularly with deep
drawn objects. If the depth of draw is not great. then the edges of the

756

L. W. Turner

material may be clamped at once. If the draw is deep, some of the

drawing must be allowed to occur before the edges are clamped. If this
is not done, excessive thinning, undue strain or even tearing may
occur.
With both vacuum- and pressure-forming attention to detail is of the
utmost importance. Uniformity of heating is essential and the material
must reach the correct temperature just as it is removed from the oven
for pressing. The forming stroke should be quite rapid, but controlled,
and at the bottom of its stroke it should stay there long enough to cool
the material below its heat distortion point, usually a few seconds only.
Conditions will have to be varied according to the material and
thickness, and should be established at the start of a production run.
If the sheet used is too hot it will cause loss of embossing on an
embossed sheet; if it is too cold or the clamping is insufficient then
wrinkled mouldings will result. Even the cut-off must not take place
too soon, since, if there is insufficient cooling, warped mouldings will
result, or alternatively the edges will pull away. The cutting edges must
also be kept in good condition or rough trimming will result. The dies
must be properly aligned and be close together, otherwise air trapping
may occur with consequent shiny spots which look most unpleasant.
It is quite clear from all these methods that great care must be
exercised in establishing correct details of production. It is for this
reason that fully automatic production is so valuable, since conditions
can be set and maintained.
16.5 TOLERANCES IN DIMENSION AND DIMENSIONAL
STABILITY OF FORMED PARTS
It has already been indicated that if a thermoformed article is heated it

tends to revert to a flat sheet. This is not important for many

applications, where the components produced are unlikely to be
subjected to elevated temperatures. However, there are certain
applications where the problem can be serious. Some of these are car
parts, such as fascia panels, which are liable to be affected by strong
sunlight, illuminated displays and lighting fittings, etc. A careful study
of the subject is therefore required.
It has been established by experiment that the two factors which most
closely control the degree of distortion are the softening point of the
material used and the material temperature during the forming

16 Sheet Thermoforming and Related Techniques for

pvc

757

process. The amount of distortion which occurs (during a test, say, of

2 h at 70C) depends on the amount of distortion put into the
component in the first place. Thus shallow-formed articles will distort
much less than deep-drawn ones.
Having established the two most important factors influencing
distortion the next problem is what to do about it. There is no
complete answer but certain precautions can be taken. First, the higher
the softening point of the material used, the less the distortion; this is a
very important factor. Thus in choosing a vinyl compound, the one
with the highest softening point must be used.
The second important point is to use as high a forming temperature
as possible, for as long as possible. This allows more random
movement of molecules, i.e. relaxation to reduce excessive orientation.
Unfortunately there are several limits to the temperature which can be
used, not least of which is rate of production which has to be extended
when temperatures are high. High temperatures will destroy surface
finish and even partially destroy embossing, although in some cases
embossed sheet that can resist forming temperatures can be supplied.
The optimum temperature from the forming point of view is that at
which the elongation at break reaches a maximum. Obviously the
forming temperature cannot be allowed to exceed this.
16.6 EQUIPMENT SUPPLIERS
A number of thermoforming machines are made3,12-many automatic-as well as some completely integrated, computerised thermoforming lines. * A list of some suppliers is given in Table 16.1.
16.7 MATERIALS ASSESSMENT AND DESIGN ASPECTS
The term 'optimum temperature' was used earlier when the processes
of sheet thermoforming were being introduced and commented upon.
This relates to the fact that in uniaxial creep-type tests carried through
to rupture and in similar tests carried out in a biaxial-stretching mode
at different temperatures, the materials under discussion show

* e.g. the Shelley 'Linear Series' (M. L. Shelley and Partners Ltd, Huntingdon
in the UK, and Deacon North America, Bristol, cr in the USA).

TABLE 16.1

Some British and European Manufacturers of Sheet Thermoforming

Equipment
Anchor Plastics Machinery,
Weirvale Industrial Estate,
Denham Way,
Maple Cross,
Herts, UK

Stewart Machinery Sales,

The Old George,
Lavendon,
Olney,
Bucks, UK

Leesona Plastics Machinery,

Falkland Close,
Coventry,
CV48AU, UK

Engineering Developments
(Farnborough),
Belmore Road,
Farnborough,
Hants,
GUI47NW, UK

Ridat Engineering,
Fishponds Road,
Wokingham,
Berks, UK

Mortimer Plastics Machinery,

Coronation Road,
London,
NWlO 7PT, UK

Ataroth Plastics Machinery,

Unit A3,
Wem,
Salop, UK

Technoimpex,
Hungarian Foreign Machine Ind.
Trade Co.,
PO Box 183,
Dorottya u. 6 H,
1390 Budapest 62,
Hungary

Maschinenbau Gabler,
Niels-Bohr-Ring 5a,
PO Box 1690,
D-2400 Lubeck 1,
West Germany

Hanwood Engineering Services,

Unit B3,
Stafford Park 2,
Telford,
Salop, UK

M. L. Shelley and Partners,

St. Peters Road,
Huntingdon,
Cambridgeshire, UK

OMV Officine Meccaniche,

Veronesi Spa,
Lungadige Attiraglio 34,
Parona, Verona,
Italy

Bone Craven Daniels,

Bath Road,
Stroud,
Gloucestershire,
GL5 3TL, UK

VTM,
Ing Rudolf Wybranietz,
435 Recklinghausen,
Hubertusstrasse 41,
Postfach 1268,
West Germany

Meaf,
Groeninx van Zoelenstraat 33
(industrieterrein) ,
Yerseke 3622,
Netherlands

16 Sheet Thermoforming and Related Techniques for pvc

759

maximum elongation (before rupture) within particular 'optimum'

temperature regions depending on the material formulation. A broader
peak is preferable to a narrow one as the latter obviously allows less
processing tolerance.
Various relatively simple techniques can be used to compare
materials and to a degree assess forming characteristics. In Ref. 13
rapid creep tests are described comparing the forming behaviour of
two PVC sheet formulations. The tests consist of applying a
predetermined dead load to strips of sheet material at different
temperatures, the load being such that extension to high strains in the
range 4-5 or up to break-point can be achieved in about 14 s. As
described the creep curve is observed optically, but simpler means of
recording deformation can be employed to provide a useful evaluatory
procedure. In such a test a peak elongation at a certain temperature
can be observed (Fig. 16.6). The manner in which the data curve falls
away above and below this peak (operating region) gives useful
guidance as to the behaviour of the test material. The peak position on
the temperature scale, its sharpness and the shape of the overall curve
can be correlated with actual forming experiments.
A similar rupture test has been described,14 demonstrating the
effect of temperature on strain development. In this it is shown that
rapid uniaxial creep can be factorised into stress and time factors, and
a fracture envelope can be readily obtained. Correlation between such
creep data and actual thermoforming can usefully be made as in Refs
13 and 15. For this purpose the draw ratio becomes the significant
process variable to observe at various temperatures to correlate with
laboratory creep data.
16.7.1 Effect on Quality of Draw Ratio and Temperature

While it can be seen that acceptable forming can be conducted over a

reasonable range of temperatures, other factors can obtrude (process
rate, energy consumed, handling difficulties, discoloration and embritdement) so that, in practice, a processor would aim to conduct his
operation close to the shaded area in Fig. 16.7 which typifies the
product quality/forming temperature relationship. Overall the most
significant comparison between materials illustrated in this sketch is the
heavy-line boundary between good and bad forming; this can closely
be observed from uniaxial creep data, with due regard to the
differences between stretching one way and two.

L. W. Turner

760

optimum
Strain
l~v~1

c
.~

[Crl'Kld

Ar~a of
ruptur~

tim~

iii
Incr~sing

straining
load

rat~ und~r fix~d

T~mperatur~

Fig. 16.6 Effect of temperature on rapid strain (based on Ref. 13).

Biaxial creep data, such as might be obtained by blowing up a

clamped disc of sheet material, can be employed for similar
correlations, but uniaxial tests have the advantage of being the simplest
conceivable test pattern. It must be added that care should be taken if
the intention is to use creep data to indicate the effect of the pressure
employed in forming.

(Cold)
rupture

Holes

~
o

Discoloration
degradation
Details
not
reproduced

Temperature

Fig. 16.7 Quality aspects of correlation between draw ratio and temperature
(based on Ref. 15).

16 Sheet Thermoforming and Related Techniques for

pvc

761

16.7.2 Thermoformability of CPVC

The extensibility, uniaxial and biaxial, of chlorinated PVC (a simple

composition without polymeric modifiers) is good over a relatively
wide range of temperatures above the Tg This behaviour, and the
associated improvement in thermoformability over uPVC, must be
largely due to the reduction of inter-chain attraction brought about by
the presence of additional chlorine atoms in CPVC (ct. Chapter 1,
Section 1.6). These points are supported by the results of an
experimental study by De Vries and Bonnebat,16 which also demonstrated the molecular orientation imparted by stretching, and the
considerable improvements in some properties, notably impact resistance and barrier effects (i.e. permeability reduction), in biaxially
stretched CPVC sheet.
Note: Similar effects of biaxial orientation have been reported by
Brady17 for uPVC, where biaxial stretching under optimum
conditions to about 2 x 2 final extension could substantially
improve the impact resistance in the absence of polymeric
modifiers.

REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.

Kulkarni, K. M. (1979). Polym. Engng. Sci., 19(7), 474--81.

'Topformer', Literature from Bone Craven Daniels, Stroud, Glos, UK.
Anon. (1979). Plast. Rubb. Wkly, 23rd November, pp. 17-26.
Titow, W. V. and Turner, L. W. (1966). 21st ANTEC SPE Proceedings,
'Plastics in Europe', Paper No.2, pp. 1-5.
Titow, W. V. (1966). Plast. Technol., U(8), 3~0.
Anon. (1979). Mod. Plast. Int., 9(1), 35.
O'Neill, W. A. (1980). Plast. Rubb. Int., 5(5), 185-7.
Lubin, G., Mele, J. J. and Sheehan, M. J. (1978). 36th ANTEC SPE
Proceedings, pp. 50-6.
Lee, D. J. A. and Welham, F. A. (1959). Brit. Plast., 32(6), 265.
Bretton, R. H. and Welham, F. A. (1961). Ibid, 34(5), 244.
Mottram, S. and Lever, D. A. (1957). The Industrial Chemist, May.
Anon. (1981). Eur. Plast. News, 8(9), 66--74.
Harris, B. L. and Bruins, P. F. (1973). In Basic Principles of
Thermoforming, (Ed. P. F. Bruins), Gordon and Breach, New York,
p. 81.
Turner, L. W. (1958). Society of Chemical Industry, Monograph No. 17.

762

L. W. Turner

15. Malpass, V. E. and White, C. H. (1973). In Basic Principles of

Thermoforming, (Ed. P. F. Bruins), Gordon and Breach, New York,
p. 103.
16. De Vries, A. J. and Bonnebat, C. (1976). Polym. Engng Sci., 16(2),
93-100.
17. Brady, T. E. (1976). Ibid, 16(9),638-44.

CHAPTER 17

Blow Moulding of pvc

W. V.

TITOW

17.1 BASIC FEATURES AND HISTORICAL

DEVELOPMENT OF BLOW MOULDING

The general principle of blow moulding may be stated as follows: a gas

under pressure is introduced into the interior of an envelope of
heat-softened material, which is thereby expanded into conformity
with the cavity of a containing mould, to form a hollow article when
solidified on cooling. In the blow moulding of plastics the envelope is
normally tubular.
It is self-evident that to be useful for blow moulding, a material
must-when suitably softened by heating-have the right rheological
properties and sufficient cohesion at the processing temperature. It is
equally obvious that if the moulding is to be fit for use the material
must also possess the appropriate service properties. Other characteristics are also needed, e.g. sufficient thermal stability under processing
conditions. The thermoplastics first available on a large scale (cellulose
acetate, polystyrene) did not adequately meet the combination of
requirements relevant in the production and use of blow moulded
containers (a natural application for blow mouldings, first embodied in
glass bottles). Moreover, the earliest attempts at blow moulding these
materials, which were closely modelled on the blowing of glass bottles
(from a 'gob' of hot melt), were not very successful: as frequently
happens, direct transplantation of a technique from one technology
into another did not provide the best route.
A combination of two factors ultimately made possible, and
initiated, the development of blow moulding of plastics and its rapid
growth. The factors were:
763

764

W. V. Titow

(i) the advent of polyethylene-a thermoplastic with processing

characteristics well suited to blow moulding, and end-use
properties acceptable in containers for many purposes;
(ii) the introduction of the extrusion-blow method, pioneered after
the Second World War by the Plax Corporation and others in
the USA, l and by Kautex in Europe. *
Blow-moulded uPVC bottles (produced by the extrusion-based process)
first made their commercial-scale appearance around 1960. In the UK,
for example, a prestigious chain store began to market fruit squashes in
such containers in 1962. 2
As practised today, all the numerous variants of blow moulding
include the following essential elements:
The production of a tube of the thermoplastic material used. If
made by extrusion, the tube (which is initially open-ended) is
called a parison. If injection or dip moulded (in which case it is
always produced with one end closed) the tube is correctly
termed a preform.
(ii) Expansion of the hot tube (at this stage always sealed at one
end; sometimes at both ends) with compressed air inside a
mould.
(iii) Cooling the article so formed and removal from the mould.
(i)

Individual processes differ in the ways in which these basic operations

are performed, and in the number and nature of associated process
steps (see Section 17.2).
Some methods in which no parison or preform is used were explored
early in the development of blow moulding, but none has attained
industrial importance. In one example,3 two hot thermoplastic sheets
are clamped in a mould and thereby edge-sealed in the outline of the
shape required in the ultimate moulding. The envelope so formed is
expanded in the mould with compressed air, and the resulting
moulding cooled in the mould, removed and trimmed.
uPVC is one of the group of plastics important as blow-moulding
materials. The other members of this group are polyethylene
* Until the appearance of Kautex machines in the late 1950s blow-moulding
equipment in industrial use was custom-made for patented versions of the
process worked by the patent holders and their licensees. For example, in the
UK the patented Plax process (British Patent No. 516262) was for many years
operated, under an exclusive licence, by British Xylonite.

17 Blow Moulding of pvc

765

(especially the high density polymer), polyethylene terephthalate, certain modified acrylonitrile polymers, polypropylene, and polycarbonate. Some of these-notably HDPE and PET-eompete with uPVC in
many applications (see Section 17.4.1). A few examples of their
non-competitive uses are: HDPE petrol tanks for certain makes of
motor car, large cans and drums; PP header tanks for truck radiators;
PC baby-feed bottles.
Blow-moulded containers with composite walls made up of layers of
different materials are produced from coextruded parisons or-more
recently-eo-injection-moulded preforms. This is done to secure sets of
properties not obtainable with a single material: often the combination
of properties achieved in this way is low permeability with good
mechanical strength and stiffness. Typical examples of such composites
are HDPE with polyvinyl alcohol or with an acrylonitrile polymer (in
both cases an intermediate adhesive layer is normally also present).
PVC is not used as a component of such products.

17.2 BLOW-MOULDING PROCESSES AND THEIR

APPLICATION TO PVC
17.2.1 General Characterisation and Main Features of Process and
Systems
A blow-moulding process can be characterised by reference to three
features: the method of production of the first tubular precursor of the
ultimate moulding, the presence or absence of a stretching step in the
operation(s) whereby the tube is transformed into the moulding, and
the nature of the processing and equipment arrangements.
A broad classification on the basis of the first two features may be
illustrated by the simple schematic flow diagrams of Fig. 17.1. It is this
kind of classification that is implicit in such widely used terms as
'extrusion blow moulding', 'injection stretch-blow moulding', 'dip blow
moulding', and the like.
The processing and equipment arrangements comprise a number of
elements which may be combined in various ways in a particular
blow-moulding set-up. The nature of these elements and the way in
which they are combined may collectively be regarded as the third
main distinguishing feature of a blow-moulding process (cf. (c) below).

PLASTICS

extrusion

Fig. 17.1

FEEDSTOCK

PLASTICS

FEEDSTOCK

PLASTICS

by piston push on melt

in cavity:
)
complete silJlpmg of
pretonn round mandrel

dip mandrel into melt

mould,
stretch and blow, 0001

MOULDED
ARTICLE

PREFORM
(CLOSE-ENDED
TUBEWrrn
FULLY FORMED
NECK)

MOULDED
(ORIENTED)
ARTICLE

blow,oool

transfer to second
(article) mould,

transfer to second (article)

HOT MELT
IN CAVrrY

PREFORM
(CLOSE-ENDED
TUBE WITH FULLY
FORMED NECK)

MOULDED
ARTICLE

(article) mould,)
blOW, 0001

transfer to second

MOULDED
ARTICLE

PREFORM
transfer to second
(CLOSE-ENDED (article) mould, ) MOULDED
TUBE WITH
(ORIENTED)
stretch and blow,
FULLY FORMED
ARTICLE
0001
NECK)

enclose in mould.
blow, 0001

enclose in first
(pretonn) mould,
blow
(possibly 0001)

OPEN-ENDED
TUBE
(PARISON)

DIP (DISPLACEMEN1)
BLOW MOULDING

INJECTION
STRETCH-BLOW
MOULDING

INJECTION
BLOW MOULDING

EXTRUSION
STRETCH-BLOW
MOULDING

EXTRUSION BLOW
MOULDING

Characteristic operational elements in the main types of blow moulding process. Schematic outline.

or injection

moulding

injection

FEEDSTOCK - - +

:-:::
::l

17 Blow Moulding of PVC

767

(a) Main Characteristics of Extrusion, Injection, and Dip Blow

Moulding
EXTRUSION BLOW MOULDING

The typical sequence of operations in simple extrusion blow moulding

of a bottle is shown in Fig. 17.2A. As can be seen, a tube is extruded,
and immediately enclosed-while still hot-in a split mould. In the
action of closing upon it, the mould seals one end of the tube, leaving
outside a 'tail' of waste material (and in some cases also pinched-off
pieces or flash in other areas).
Note: In the arrangement shown in Fig. 17.2A the tube is closed at
the bottom, the neck being formed at the top, and the bottle
subsequently blown 'right-side-up'. The alternative arrangement is to have the bottom end of the parison tube descending
over a blowing mandrel: the tube is then closed at the top and
the bottle blown in the 'upside-down' position. See also
Section (c) below.

The parison tube is severed (before, during, or after the closing of

the mould) and expanded inside the mould by air pressure; the resulting
moulding is cooled in the mould and ejected. In some versions of the
process the flash (always formed in extrusion blow moulding) is
trimmed off in the mould; in others trimming is a separate,
post-moulding operation. In some cases such operations as printing or
labelling, filling, and closure application, are carried out in-line.
In a typical extrusion stretch-blow moulding process, schematically
illustrated in Figs 17.2B and 17.3, the extruded parison is first
blow-moulded in one mould into a complete preform (undersize in
relation to the ultimate moulding), and this is then stretched and blown
to final shape in a second mould. The stretching (longitudinal
extension) of the preform is commonly effected mechanically, by an
extending telescopic pin, and the radial extension by the final blow (cf.
Fig. 17.3). The object of stretch-blowing is to produce biaxial
molecular orientation in the moulding-the effects and advantages of
this are discussed in Section (b) below. For the best results the
orientation should be imparted at a temperature somewhat below the
extrusion temperature. In most industrial equipment provision is made
for temperature conditioning of the preform during and/or after its
cooling in the course of formation in the pre-blowing mould: the

W. V. Titow

768
A - Feedhopper
B - Extruder
C - ElI1ru ,on head

D
Mould buring d'stributor
E - Blower head.

Stege I - EXTRUSION
The parilon is ell1ruded
between two halfmouldl.

Stage 3 BLOWMOULDING
The blown perison
upands end Ilanans out
on tha mould ~vity wall.

Stege 2 CLOSINGIN
The parison
Is clamped into the mould.

Stege 4 EJECTION
Once cooled.
tha bonia i. immediately
ajacted from the mould.

Fig. 17.2A Extrusion blow moulding of PVC: schematic representation.

Direct blow moulding: a machine, and operational sequence. (SideI equipment
c. 1970: Courtesy of Sidel through their UK agents Engelmann and Buckham
Ltd.)

17 Blow Moulding of pvc

769

Fig. 17.2B A modern Sidel continuous-extrusion machine for stretch-blow

moulding of bottles. 1, Parison; 2, preform mould; 3, temperature conditioning
of preforms; 4, conveyor; 5, bottle mould; 6, demoulding.

conditioning may take place at a separate station (as, for example, on

the Sidel MSF machines 4).
Extrusion blow moulding was chronologically the first to come into
industrial use: stretch-blowing is a relatively recent development in this
method as well as in injection blow moulding. Apart from this
refinement, which is now available as an integral part of most leading
manufacturers' equipment (in some cases also as a retrofit modification-e.g. for the older versions of Kautex KEB machines 4 ), a modern
extrusion blow-moulding set-up usually includes parison programming.
This term is widely used for programmable adjustment of the wall
thickness of a parison in a number of zones along its length. However,
in its broadest sense, the expression may also be considered to include
certain other ways of parison modification and control now available.
In variable-thickness dies, both the central mandrel ('pin') and the die
ring interior are tapered, so that a relatively slight vertical movement
of the former (actuated by a suitable control mechanism) alters
significantly the annular gap between them at the die face. The number
of points at which parison thickness can be varied depends on the
particular programming system used. Many are available, from various
manufacturers: some of these systems are incorporated, as standard
components, in particular makes of blow-moulding equipment. The

W. V. Titow

770

Fig. 17.3 Operational sequence in a typical extrusion stretch-blow moulding

process. Schematic representation. 1, Extrusion of parison; 2, blow moulding
of preform; 3, transfer of preform to article mould; 4, mechanical stretching
(by extensible pin) and blowing of preform; 5, completion of formation of
article; 6, removal of article from mould.

17 Blow Moulding of pvc

771

systems range from relatively inexpensive, simple thickness programmers offering control at a limited number of points, adequate for
long-run production of simple blow mouldings (e.g. the Moog* system
for to-point thickness programming), to sophisticated computerised,
fully automatic systems for control at up to 50 points (e.g. the 49-point
parison programming facility of the MACa Vlt integrated microprocessor control system for extrusion blow-moulding equipment5).
Other examples are the 30-point parison programmer used on some
Bekum+ machines,6 and the Hunkar programmers (some with 32 set
points and higher). In the modern thickness programming systems
operated by microprocessors, the required thickness values at the
number of points available are pre-set on the control unit, which then
continuously automatically computes and executes the necessary
adjustments of the movable die elements. Programming capabilities
other than parison thickness control offered by some of the modern
systems include parison length control, parison stretch compensation,
parison ovalisation, and what is sometimes called 'deformable die
control'-provision for programming (through automatic control of
mutual movement of the die mandrel and bushing) for minimising the
amount of material in the pinch-off area(s) of the moulding. It is
largely self-evident that the main direct object of parison programming
is optimisation of the wall thickness and thickness distribution in the
finished moulding. The advantages this brings are two-fold: better
structure (with the attendant improvement in strength properties and
resistance to damage), and cost savings. The savings are in two
areas-reduction of the amount of material, and more effective
processing (especially easier and quicker cooling of mouldings which
contain no unnecessarily thick areas, and generally only the necessary
minimum amount of material). In an informative article (published in
1976), Hunkar7 gives, inter alia, the following figures (based on
p~rformance studies of over 800 blow-moulding machines) for the
economic gains resulting from parison thickness programming in the
* Moog Inc., Electronics and Systems Div., USA, and Moog GmbH, West
Germany: the group also supplies more advanced systems with full
microprocessor control, e.g. the Moog 40-point analog parison programmer.
t Barber-Colman Co. Industrial Instruments Div., Rockford, Ill., USA.
:\: Bekum Maschinenfabriken GmbH, Berlin, West Germany.
Hunkar Laboratories Inc., Cincinnati, OH, USA.

772

W. V. Titow

production of PVC bottles:

Nominal size
Average weight (g)
Material savings (%)
Production increase (%)

1 quart
546
158
133

1 litre
435
115

96

16-220z
223
193
298

Another source! quotes estimated savings of 20-30% in part weight

and cycle time with electronic parison-programming systems. The
above advantages of parison programming must be considered in
relation to the greater equipment cost and die complexity (undesirable
in principle with a heat-sensitive material like PVC). Thus, whilst
parison programmers are operated, and useful, with PVC, possibilities
sometimes exist-and should not be overlooked-of saving material
and securing good thickness distribution simply by suitable design of
the moulding.
INJECTION BLOW MOULDING

In this type of process a preform is injection-moulded around a metal

mandrel (core rod) in a closed mould. It is then transferred to a second
mould where it is blown to final shape, cooled and removed. In some
versions of the process the sequence is continuous, the temperature of
the preform being maintained for the blowing step which follows
directly after moulding. In certain others the preforms are cooled, and
may be stored, to be reheated and blown in a separate operation. In
either of these two general variants of the process the hot preform may
be stretched in the blowing mould to produce orientation in the
ultimate article in essentially the same way as in extrusion stretch-blow
moulding.
In comparison with extrusion blow moulding, the advantages of the
injection-based process may be summarised as follows. Exact,
pre-designed shaping of the preform with the attendant improvement
in product quality and material and processing cost savings, analogous
to the advantages of accurate parison programming in extrusion blow
moulding; lack of waste; virtually constant weight of mouldings (but
less easy to alter than in the extrusion-based process); a moulded neck
finish in bottles, giving accurate dimensions (and particularly useful for
crown closures); better quality finish, with no nip closure line (pinch
weld). The main disadvantages are: ratio of neck diameter of bottles to
the length limited in practice to about 1 : 12 (due to core rod deflection

17 Blow Moulding of pvc

773

problems); containers with handles not readily produced; highly oval

cross-sectional shapes not as successful as with extrusion blow
moulding; normally higher tooling costs.
Injection blow moulding originated roughly at the same time as
extrusion blow moulding, and some containers were being made-in
polystyrene and polyethylene-by early versions of this process
(involving manual transfer of a single preform on its core from the
injection to the blowing mould) from about 1948 onwards. 8 However,
large-scale production of injection blow-moulded PVC containers came
considerably later than industrial extrusion blow moulding of this
material, largely because of heat stability problems.
DIP BLOW MOULDING

Commercial equipment for this process (also called 'displacement blow

moulding') first appeared in the 1970s. The operational features of the
available machines differ in some respects, but the general essential
elements of the method are common to all. These may be outlined as
follows. A predetermined quantity of hot plastics melt is introduced
into a heated cavity, kept at a controlled, optimum temperature. This
may be done by horizontal extrusion (as in the original SchloemannSiemag equipment9 ), or vertical (downward) extrusion or injection (as
in the early Saum Systems design lO and its adapted version represented
by the Leesona displacement injection blow-moulding machine ll ), but
in all cases the cavity is not closed, so that the melt enters at relatively
low pressure. A metal mandrel (core rod), kept at the required
temperature by circulating heat-exchange liquid, is pushed---eentrally-into the melt in the cavity: this is done either by lowering the
mandrel or by raising the cavity. As it moves into the cavity, the
mandrel displaces the melt upwards, shaping it into an annulus defined
by the mandrel body and the cavity walls. The annulus being moulded
in this way is the body of the ultimate preform. The shaping of the
latter is finally completed-when full mandrel penetration has been
reached-by the upward movement of a piston positioned at the
bottom of the cavity, which ensures that the melt fills all available
space, thereby positively moulding the top (neck portion) of the
preform (inside a split mould, sometimes referred to as 'thread mould',
enclosing the top of the mandrel) and finalising the material
distribution.
The mandrel carrying the preform just produced is withdrawn (or
the cavity lowered away from it), and then enclosed in the article

774

W. V. Titow

(blowing) mould. Air at normal blowing pressure is admitted through a

channel in the mandrel, blow-moulding the body of the preform to the
shape of the cavity. The resulting article is cooled and ejected when
the blowing mould and the neck mould round the top of the mandrel
have opened.
The advantages claimed for dip blow moulding are: moderate cost of
machine and moulds (because they do not have to withstand high
pressures during the moulding of the preform); precision moulding of
the neck; no nip closure or gate marks on the article (which are
characteristic of, respectively, extrusion and injection blow-moulded
containers); virtual absence of scrap; ease of production of wide necks
in containers; close control over wall thickness by virtue of the method
of producing the preform and the fact that the preform diameter can
be close to that of the ultimate moulding.
(b) The Role and Effects of Stretching in Stretch-blow Moulding
The combination of longitudinal stretching with transverse expansion
effected in stretch-blow moulding imparts to the product a considerable degree of biaxial orientation. This improves several of the
properties particularly important in containers, which constitute the
vast majority of commercially produced PVC blow mouldings. The
properties concerned are: impact resistance (as measured in drop
impact tests, this property can be better by factors of 2-4 in
stretch-blow-moulded PVC bottles as compared with similar bottles
produced by simple blowing); bursting pressure; resistance to compression and to deformation by top loading (important in stacking);
rigidity; clarity of transparent containers; and permeability (which is
reduced by biaxial orientation). Some properties of biaxially oriented
PVC are discussed, in relation to those of CPVC, in a paper by De
Vries and Bonnebat. 12 Brady's study of the effect of biaxial stretching
upon the mechanical properties of uPVC13 (O015-in thick calendered
sheet) indicated, inter alia, that optimum property improvements are
obtainable at a stretch factor of x2 in each direction, and that lOOC
was the optimum stretching temperature.
The improvements in properties obtained by stretch-blowing make
possible significant savings in the amount of material used (because
container wall thickness can be reduced without sacrificing performance) and in processing costs (mainly because thinner walls make for
faster cooling). Furthermore, the material cost can be lowered in many
cases by 'reducing or eliminating impact modifiers. Savings-in

17 Blow Moulding of pvc

775

comparison with otherwise similar but unstretched blow mouldingsquoted as typical include, for example, weight reduction of 20-25% on
15litre mineral water bottles produced in rigid PVC on a Bekum
BMO-4D machine,14 an average material cost saving of about 10%
with typical bottle formulations through elimination of impact
modifiers,15 and possible overall production cost savings of up to 20%,
despite the somewhat higher equipment cost of stretch-blow
moulding. 16
At the same time it should not be overlooked that stretch-blow
moulding is applicable primarily to simple, symmetrical shapes (e.g.
not to containers with handles), and that stretch-blown PVC bottles
can still be no cheaper than bottles conventionally blown in, say,
high-density polyethylene which-despite their inferiority in some
properties-may be acceptable for many applications where clarity is
not a requirement.

(c) Processing and Equipment Arrangements

These arrangements comprise a number of elements which may be
combined in various ways in a particular blow-moulding set-up. The
elements and their particular combination collectively constitute
another general distinguishing feature of a blow-moulding process.
SINGLE- AND TWO-STAGE OPERATIONS

A blow-moulding process-whether based on extrusion or Injection

moulding-may be of the single-stage or two-stage type. That is, the
complete production may be carried out in the same machine, or on
two separate machines: in the latter case it is normally the blowing (of
a separately made parison or preform) that constitutes the second
stage. Industrial dip-moulding processes are normally all single-stage.
The version of simple extrusion blow moulding where the parison is
blown directly under the extruder head is an example of a single-stage,
single-station process. It may be noted that in this kind of operation
extrusion must be intermittent, to allow for completion of blowing,
cooling and ejection of the moulding, before the mould receives the
next parison.
In the widely used multi-station extrusion blow-moulding systems, a
mould receives the parison (which is severed at the appropriate point
in the sequence) and is moved out of the way while another is
presented to the extruder die. Here extrusion can be continuous, as
parison blowing and subsequent cooling of the resulting moulding in a

776

w.

V. Titow

direct blowing process, or-in a stretch-blowing process-the blowing

of a preform, its transfer to a blowing mould, and the stretch-blowing,
cooling and ejection of the final article, take place at stations away
from the extruder head. Continuous extrusion systems are preferable
for PVC (and other heat-sensitive materials) because they do not entail
stationary residence of the hot melt in the extruder, whilst optimum
melt temperature and uniform temperature distribution are easier to
maintain under constant, controlled flow conditions, so that the risk of
overheating is reduced. The simplest multi-station system consists of
two reciprocating moulds which are presented alternately to the
extruder die. More complex systems employ a number of moulds
mounted on a rotary support which may revolve in a horizontal or
vertical plane. Blow moulding on a multi-station system (even one with
many stations and process steps) will still be a single-stage process if
complete production takes place on the same machine, in a continuous
sequence of operations. If, however, the sequence is interrupted and
the moulding finished on separate equipment, then the process
becomes a two-stage one.
Note: In the context of blow-moulding processes, the terms 'step'
and 'stage' are sometimes used as if they were synonymous.
However, the usage adopted in this section is the most
common; it is also logical and avoids ambiguity if consistently
followed.

Examples of a two-stage process are the Marrick process and the

Corpoplast process. The former, developed in the 1960s,17 is now
mainly of historical interest. In its first stage PVC tubes were extruded,
cooled, and cut into parison lengths. The prefabricated parisons could
then be stored and transported to different locations as required. For
blow moulding, which took place on separate, special equipment, the
parisons were heated (on mandrels) to the required processing
temperature. The heating was carried out in ovens: as can be seen,
very close temperature control was essential for successful operation,
as well as accurate allowance for dimensional changes on heating. The
plant and 'know-how' for this stage of the process were provided,
under licence, by the Marrick Manufacturing Company Ltd (UK),
from whom parison tubes were also available. The advantages claimed
for the process included a low scrap percentage, and a potentially high
output (for the 1960s) made possible by the use of multi-cavity blowing
units: in a single-stage process these would have to be fed by

17 Blow Moulding of pvc

777

multi-head extrusion with its attendant increased risk of heat

degradation of the material. Thus the heat stability problem was eased
whilst the production rate at the moulding stage was not limited by the
rate of extrusion. However, the Marrick process, apart from lacking
the optimisation of wall thickness and economy of material use
available through parison programming in modern extrusion blowmoulding systems, was also generally less competitive in present-day
terms. None the less, it had played its part in the industrial production
of PVC bottles. It has also paved the way for the Corpoplast process in
which similar ideas have been given a sophisticated, modern format.
The Corpoplast system for the production of stretch-blown bottles in
PVC, polyacrylonitrile, and polyethylene terephthalate, originated in
West Germany. * In the first stage, preforms are produced either by
injection moulding, or from lengths of extruded tube (by heating the
ends and moulding a neck on one side and a rounded, closed bottom
on the other: 18 machines are available for either kind of operation.
The preforms are cooled for storage or transport. In the second stage
each preform is heated (on a mandrel telescopically extensible and
channelled for subsequent stretching and blowing operations) by IR
radiation. The heaters are specially designed for quick, effective
heating of the body of the preform to the optimum temperature for
orientation by stretch-blowing: one of the operational features is the
matching of the peak emission wavelengths to those at which the
plastics material absorbs most strongly.t The heating is uniform, as it
does not depend on conduction through the material. During the
heating step the pre-moulded neck is screened from the radiation. The
heated preform is stretch-blown in the way already mentioned.
Preform production and blowing may also be run in direct sequence.
The advantages claimed for the Corpoplast process are: high output
rates; versatility of equipment, permitting different arrangements with
good control over process variables; relative ease of setting up and
running bottle production at the filling plant (with preforms produced
at a different site transported more conveniently and cheaply than

* Initially marketed by Gildermeister Corpoplast GmbH: now KruppCorpoplast Maschinenbau GmbH, Hamburg. UK agent: Ritter Plastics
Machinery, Bracknell, Berks. In the USA exclusive rights held by Owens
Illinois, Toledo, Ohio.
t An early discussion of this way of increasing the efficiency of radiant heating
of polymeric materials was published by Grant and Foster. 19

778

w. v.

Titow

finished bottles); waste re-processing minimised (with injectionmoulded preforms); advantages associated with stretch-blowing (improved container properties, material and process economies). However, the costs of equipment and tooling are relatively high, and licence
fees and royalties are a factor.
Apart from the version of the Corpoplast process in which the
preforms are injection-moulded, injection blow moulding as commonly
practised is a single-stage operation. It must also, of necessity, involve
at least two stations, because the preform has to be transferred to
another mould for blowing. Indeed, the first machine designs to come
into industrial use operated on a two-station system. 1 Currently the
most popular configuration is a rotary three- or four-station arrangement: in a typical version, core rods are mounted on a turret which
indexes to the stations in turn. With a three-station turret these will be
the injection station, the blowing station, and the ejection station. A
four-station system may be set up to operate in various ways; some of
the common ones are given below.
Station 4
Station 1
Station 2
Station 3
Injection ~ Pre-blowing ~ Final blowing ------+) Stripping off the
core and ejection
Injection ~ Temperature----+ Stretch-blowing ----~ Stripping off the
conditioning *
core and ejection
) Surface decoration Stripping off the
Injection ~ Blowing
(e.g. printing)
core and ejection

Dip blow-moulding equipment currently available is single-stage and

typically one- or two-station,1 although the process involves several
steps (see (a) above).
BLOWING ARRANGEMENTS

In extrusion blow moulding of containers, such as bottles, the parison

is most often blown by means of a blowing mandrel (blowing 'pin')
through the neck opening, with the bottle formed either in the upright
position ('top blow') or upside-down in the mould ('bottom blow'). A

* This can be useful with PVC (ct. Fig. 17.2B), but not absolutely necessary
because PVC can be cooled directly to optimum orientation temperature,
unlike PET which needs a separate 'tempering' treatment of the preform
(normally at a separate station) for greatest property improvement on
stretching, or PP which must be conditioned for stretching within a narrow
temperature range.

17 Blow Moulding of pvc

779

hollow needle may also be used, being introduced-at any convenient

point-into a completely sealed parison through a suitable opening in
the mould. Needle blowing is useful with some container designs, e.g.
ones with neck openings too small to admit a regular blowing pin, or
where a portion is trepanned out after moulding (e.g. a domesometimes called a 'lost blowhead'-moulded, for operational convenience, over a very wide opening) in which case the blowing needle is
introduced through that portion. As with bottom blow, needle blowing
can start as the mould closes.
The bottom-blow arrangement is the simplest mechanically. The
open lower end of the parison descends over a blowing pin (often
called a spigot in this context). The mould closes around the parison,
its neck part (at the bottom) clamping on the lowest portion of the
tube which encloses the pin, and the top pinch-sealing the opposite
end. Blowing is commenced immediately, sometimes even before the
mould has completely closed (this can counteract any tendency for
parison sag, and help in the formation of a strong nip weld). The
general advantages of bottom blowing include fast operation, positive
forming of the outside of the neck (by the neck part of the mould
cavity against the blow pin), smooth internal neck surface, and
considerable latitude in the relationships between the thicknesses and
diameters of neck and body. The main limitations are that the internal
diameter of the parison must be large enough to fit, with reasonable
clearance, over the blowing pin, the external diameter must be greater
than the internal diameter of the neck portion of the mould, and
that-as a result-there is always flash on the sides and upper part of
the neck. This has to be removed, and the finish in this area is never
completely 'clean'.
In a top-blowing arrangement the parison must be severed from the
parent extrudate and clamped in a mould, completely closed, before
the blowing pin is brought into action. Typically (but not invariably)
the cutting follows the closing of the mould. If extrusion is continuous,
the mould enclosing the parison is moved away from the extruder die.
A blowing pin is introduced into the open top of the parison: the pin is
usually shaped and dimensioned to participate in forming the neck of
the bottle. Blowing, cooling and demoulding then proceed in the usual
way (often at separate, consecutive stations). It is an advantage of
top-blow arrangements that the bottle neck can be free from flash (if
the parison diameter is not greater than that of the neck part of the
mould cavity). However, the time lapse between parison formation

780

w.

V. Titow

and commencement of blowing increases the length of the cycle: the

possibilities are also increased (although these are adequately counteracted in good modern equipment) of parison sag and undesirable
surface cooling of material in the neck region.
In injection and dip blow moulding, blowing takes place through the
core rod on which the preform is moulded. The arrangement thus
broadly corresponds (but is not strictly analogous) to top blowing in
extrusion blow moulding. The blowing air pressures used in all
blow-moulding processes are typically within the general range of
05-10 MPa.
OTHER FEATURES

Mould venting: This is necessary to avoid impairment of surface

finish of the moulding by air trapped in the mould (in extreme cases a
pronounced 'orange peel' effect may be caused). Good surface contact
between the moulding and the cavity-without intervening air
layers-is also necessary for effective cooling. Vent slits are usually
provided along the mould parting line, and-if required-at other
points, according to the shape and design features of the article. Slight
plate-out (which may not be otherwise discernible) may collect in the
vents with some formulations. Such blockage should be removed with
a suitable solvent (e.g. a chlorinated hydrocarbon).
Multicavity moulds: These are used on some versions of blowmoulding equipment. In extrusion blow moulding they are operated in
conjunction with multiple heads on the extruder. In injection blow
moulding the number of cavities that can be operated has been
increasing over the years: equipment with as many as 8, 12 and 14
cavity moulds is in current industrial use. 8 ,20
Waste material removal: In extrusion blow moulding some waste is
always created as the mould grips the parison. This usually consists of
the 'tail' beyond the bottom nip closure, often with flash in the neck
region and-in containers with handles-handle pinch-off waste and
flash. The waste has to be removed. The removal operations are
automated to a large extent in modern equipment. 'Top and tail' waste
is trimmed in the mould in several systems: in some the removal is a
secondary operation carried out in-line-this is often the case with
handle pinch-off waste. In some equipment for stretch-blow moulding

17 Blow Moulding of pvc

781

of PVC the tail waste is torn off the preforms clamped in their moulds,
by sliding grippers. Examples of systems with automatic waste
trimming are the Hoover* Uniloy 300 CE line, the Automat Speed
3000 D and Maximat machines, and the Krupp-Kautex* KEB machine
range.
Part removal (take-off) systems: These too are largely automated,
especially in modern extrusion blow-moulding equipment. Typically,
mouldings trimmed of waste material (which may be automatically
routed to a granulator and from there to the extruder) are positively
deposited, in the required orientation, on a conveyor on which they
proceed to leak-testing, decorating or labelling, and packing.
(d) Cooling Methods
The blown article must be cooled in the mould before ejection.
Cooling is effected by circulation of a heat-exchange liquid (commonly
water and glycol) through drilled channels or milled labyrinth cavities
in the mould block. Blowing pins in extrusion blow moulding, and the
core rods in injection and dip blow moulding, are also channelled for
coolant flow.
Note: Preform temperatures prior to stretch-blowing can be controlled via the mould cooling system.
As in any moulding process, rapid cooling of the blow-moulded
article is desirabie for maximum output. However, in the interest of
product quality, the cooling should also be uniform and not so fast as
to set up stresses in the moulding. The relatively low wall thickness of
blow mouldings is conducive to quick cooling, whilst stresses arise less
readily in thin than in thick sections.
The rate of cooling of uPVC is faster than that of many other
thermoplastics (including PET and PP which, as materials of
stretch-blown bottles, compete with uPVC in some applications).
Note: The principal factor in this is uPVC's comparatively high
thermal diffusivity, which is the parameter governing the rate
of transfer of heat through a plastics material in transient (i.e.
non-steady) flow conditions, such as obtain during the cooling
*Hoover Universal, Plastics Machinery Div., Manchester, Michigan, USA.
t Automa SpA, Bologna, Italy.
t Krupp-Kautex Maschinenbau GmbH, Bonn, West Germany.

w.

782

V. Titow

of a moulding when the temperature is continually falling.

Heat flow in steady-state conditions is governed by thermal
conductivity. The thermal diffusivity (D) of a plastic can be
calculated from the relationship:
D

= (thermal conductivity)/(specific heat

x density)

The following calculated average values of D (in cm2 S-1) are

fairly representative for the temperature range over which a
moulding would be cooling. uPVC, 12 x 10- 3 ; PP (homopolymer), 06 x 10- 3 ; PET, 08 x 10- 3 .
Another practical advantage of uPVC over the polyolefins and PET
is its substantially lower mould shrinkage. The typical ranges are:
01--07% for uPVC; 15-5% for PE (all densities); 10-25% for PP
(homo- and copolymers); 2,0-25% for PET (blow-moulding grades).
It can be shown 21 that, under given moulding conditions, with no
undue fluctuation of the relevant operational parameters, the cooling
time (t) of a part in a mould will be proportional to the square of the
wall thickness (wZ), * i.e. t = const. x w2 . A plot of this equation (t
versus w) for a real situation (i.e. only positive values of w) will be the
positive arm of a parabola whose axis is the t-axis and whose vertex is
at the origin. A typical plot-given in Ref. 21-of actual cooling time
versus part thickness for preforms injection-moulded on an injection
blow-moulding machine has this form.
Removal of heat from a moulding via the mould walls by means of a
circulating coolant is the traditional and still the basic method of
cooling. Chilled water, at temperatures down to about 5C, can be
successfully used with PVC blow mouldings. However, the colder the
mould the higher the risk-especially in humid atmospheres-of
moisture 'sweating' on the cavity surface, with consequent impairment
of the surface finish of the moulding. Factors in the efficiency of such
cooling, more important than mould temperature alone, are the rate
and nature of the flow of coolant through the mould channels: for
* The derivation of this relationship in Ref. 21 is based on thermal conductivity
rather than thermal diffusivity (which is the proper parameter to consider).
However, in this particular case, this does not invalidate the method or the
equation derived. The author also suggests a practical way of using the
relationship to predict the cooling cycle for any thickness of moulding (in his
example an injection-moulded preform) on the basis of a demonstration with a
given thickness.

17 Blow Moulding of pvc

783

effective heat transfer the flow should be fast and turbulent. These flow
characteristics are achieved by a combination of appropriately high
pressures in pumping the coolant through, with suitable design of the
channels.
Since the shortest practicable cooling time is desirable for increased
outputs, various methods are available of supplementing the mould
cooling with internal cooling of the moulding. Reductions of cooling
time by up to 30% are claimed for some of these. The cost of the
techniques has been a restricting factor on their industrial use,
although they are of definite practical interest, particularly in the blow
moulding of large articles which normally require long cooling dwell
times in the mould. The following internal cooling methods may be
mentioned.
Liquid nitrogen or carbon dioxide cooling: In this, N2 or CO2 is
injected into the interior of the moulding directly after normal
blowing. Vaporisation and expansion of the originally liquified gas, and
its warming to the temperature of the cavity, abstract a substantial
amount of heat from the moulding.
Chilled-air cooling: With this system, a shot of air, cooled to a low
sub-zero temperature (about -50C), is injected under pressure into
the blown article through a special insulated nozzle.
Cooling with air and water mist: In the Hunkar variant of this
method (the Hunkar ILC process)* an amount of highly compressed
air and a metered quantity of water are simultaneously injected into
the interior of the moulding. The rapid expansion of the air as it leaves
the nozzle causes sharp cooling: the atomised water freezes, and
further heat is then extracted from the moulding as the ice particles
melt and the resulting water droplets evaporate.
Air flushing: There are several embodiments of this approach to
internal cooling. In the 'Interval Blowing' systemt a minimum air
pressure is maintained inside the moulding, whilst cool, compressed air
is additionally introduced and then vented out at intervals, 'flushing out'
* Hunkar Laboratories Inc. Also relevant here: the 'Frost Air' system (Ryder
Associates, Whippany, NJ, USA).
t Battenfeld-Fischer Blastformtechnik GmbH, Lohmar, West Germany.

784

W. V. Titow

some heat each time. In a simple continuous flushing system blowing

air is circulated through the moulding (after that has been blown in the
normal way): by controlled air feed and venting, a pressure near the
blowing pressure is maintained during the cooling period whilst heat is
continually removed. The necessary modifications to the blowing
circuit are relatively simple. A continuous cooling system has also been
developed* which can reduce substantially the time for cooling the
neck of a blow-moulded bottle.
17.2.2 Industrial Blow Moulding of PVC

(a) Some Process and Equipment Considerations

Both in the commercial and the technical sense, bottles are by far the
most important among blow-moulded PVC articles. Extrusion blow
moulding is the predominant method, a considerable proportion of the
mouldings being stretch-blown. Injection blow moulding of PVC is less
widespread, principally because the greater thermal severity of this
process has delayed and complicated its application to all heat-sensitive
plastics materials from which bottles are blown (modified polyacrylonitrile, multi-acrylic copolymers and PVC). However, PVC bottles are
being produced by this technique on an increasing scale, and the
problems are eased by the advent of special moulding compounds (see
Chapter 15). Relatively recent machine developments include injection
units in which the preform mould is filled at low pressure by rotating
the screw during injection:t this makes the treatment received by the
stock less drastic, and also reduces cycle time because the next
consecutive shot can be commenced before full screw recovery.
Multi-cavity injection blow moulding of PVC bottles has been operated
commercially for several years, with, for example, eight-cavity
production of round, 120 ml bottles at the rate of 48 per minute as
early as 1978. 8
The extruders used in the extrusion blow moulding of PVC are of
the general kind suitable for PVC extrusion (d. Chapter 14): LID
ratios around 25: 1 and compression ratios of 1 8 : 1-25 : 1 are fairly
typical for single-screw machines. The advantages and disadvantages
(mainly higher cost) of twin-screw extruders in the processing of PVC
are discussed in Chapter 14: the points made apply also to their use in
* By FGH Systems Inc., Dover, NJ, USA.
tRainville Co. Inc., Middlesex, NI, USA.

17 Blow Moulding of pvc

785

blow moulding. The relatively gentler processing and good stock

temperature control they afford are of particular interest in the
production of high-clarity bottles. Some blow-moulding machines are
available with a choice of twin-screw extruder (for PVC) or a
single-screw one (for polyolefins). One example is the Cincinnati
Milacron* BB3 equipment. Some equipment suppliers make a special
point of their twin-screw extruders' ability to process bottle compounds
based on PVC polymer of relatively high molecular weight (e.g. up to
K value 65 with the conical twin-screw machine of the Bellt
blow-moulding plant6). Certain features of equipment arrangement or
design, serving to reduce the risk of material hold-up and decomposition, are characteristic of extrusion blow moulding. Thus, in some
equipment, the extruder is mounted end-down for straight-through
vertical extrusion. With the more common horizontal extrusion set-up,
axial-flow crosshead dies are usual, equipped with a 'swan neck' curve
(cf. Fig. 17.2A) which preserves smooth melt flow at a constant rate
whilst changing the flow direction from the horizontal to the vertical.
Side-entry crosshead dies as used with polyolefins are not suitable for
PVC. The general, basic configuration of a typical die is similar to that
in pipe extrusion, with a spider~supported core to form the parison
tube. As in pipe extrusion, the spider legs should be suitably profiled
and the melt temperature high enough to ensure full merging of the
melt after its passage through the spider zone: otherwise flow lines can
result in the parison and the blown article (see Section 19.3.2(a) of
Chapter 19). The die head temperature is usually kept slightly below
that of the melt. All internal parts of the die should be streamlined and
smooth, with the number of joints kept to a minimum. A channel in
the core, opening into the interior of the parison, serves as a passage
for air which is blown in (usually through a connecting channel in one
of the spider legs) to provide shape support during extrusion.
Multi-parison extrusion-whether by means of multiple heads, each
producing one parison, or one multi-parison head-is attractive in
principle as a means of increasing production without a proportional
increase in machine space requirements. However, in practice it also
presents special problems of melt temperature and pressure control.
Close, accurate control is necessary, not only because of the thermal
sensitivity of PVC, but also to ensure even parison lengths (a hotter

* See Table 14.3 in Chapter 14.

t Bell Engineering Works Ltd,

Lucerne, Switzerland.

786

w.

V. Titow

portion of the melt will normally flow faster), and to prevent parison
curling (outward splaying) which may occur if the outside of the tube is
colder than the inside. The flow paths and lengths must also be suitably
balanced. Multi-parison heads are available on modern extrusion
blow-moulding equipment for PVC, e.g. four-parison ones on some
Bell* and Plastimact models. A production rate of 2400 I-litre bottles
per hour is claimed for the Bell two-station machine with the
multi-parison head. 6 'Universal' die heads suitable for both PVC and
polyethylene are also available, in single- or multi-parison versions.
Resistance of working surfaces to acid corrosion is as important in
blow moulding as it is in other melt-processing of PVc. Thus the
relevant points made in the chapters on extrusion and injection
moulding also apply here. With regard to the material of moulds for
blow moulding of PVC articles (including preform moulds), good heat
transfer and wear resistance are additional considerations. An
appropriate grade of stainless steel:j: would be the first choice for its
combination of very good resistance to corrosion and wear, unless cost
(high for stainless steel moulds), and/or the highest possible thermal
conductivity, and/or light weight were paramount considerations in the
particular conditions. In such cases the alternatives would be an
aluminium alloy (for light weight and fast heat transfer), or a zinc alloy
(for similar reasons) or beryllium/copper (for high heat transfer rate
with some corrosion resistance).
The following examples illustrate something of the features and
performance of some equipment in current industrial use for the blow
moulding of PVC containers.
(b) Extrusion Blow-moulding Equipment
An example of the smaller-size, continuous-extrusion machine is the
Bekum BMO 8, the smallest unit in the BMO range. Equipped with a
50-mm (2-in), 24: I LID extruder with a capacity of 40 kg (90 lb) of
PVC per hour it can produce single containers of up to I litre, or-with
a twin head-two containers up to about 113 litre. Production in a

*Bell Engineering Works Ltd, Lucerne, Switzerland.

t Plastimac SpA, Milan, Italy.
fA useful review of mould steels has been published recently by Hoffmann. 22
High capacity extrusion stretch-blow-moulding machines for the production
of biaxially oriented PVC and polyacrylonitrile bottles of up to 2 litre capacity.
The BM and BAE series comprise single-station machines producing
unstretched blow mouldings in the range 5-20Iitres.

17 Blow Moulding of pvc

787

typical run, with a twin head, of 230 ml (8 oz) PVC bottles (material
weight 12 g) can be at the rate of up to 2100 bottles per hour (3,4 s
cycle: dry cycle claimed 14 s). The containers are fully de-flashed in
the machine and leave in upright position for the secondary operations
of testing, surface decoration and filling and/or packing.
The single-station machines of the Battenfeld-Fischer VKl series
range from the VK1 07 model (maximum blown container size 07 litre)
to the 30 litre VK130 model. Capable of operation with a single
extrusion head or twin heads, these machines also provide complete
in-machine trimming, and delivery in upright position for secondary
operations. A typical output for the smallest unit (with twin extrusion
heads) on 12 g PVC bottles would be about 2000 per hour.
The Automa Speed 1500 SB machine, designed primarily for PVC,
can blow mould biaxially oriented containers up to 15 litre with
single-head and up to 1 litre with twin-head extrusion. Typical output
of I-litre (32 g weight) PVC bottles in a single-cavity mould would be
480 per hour. Other machines produced by Automa (in the Speed and
Maximat ranges) produce containers between 2 and 10 litres.
Some interesting features are embodied in the fully automatic
blow-moulding line produced by Sidel* (see also Table 17.1), and in
the Krupp-Kautex KEB 2-2 unit. In the former, rotary arrangements
of 24 moulds are operated to mould and temperature-condition
preforms (produced from continuously extruded parisons) and then to
blow them into bottles. The process is run under closed-loop computer
control involving automatic monitoring and adjustment of extrusion
rate, blowing pressure, temperatures, and product wall thickness. The
KEB 2-2 machine is a two-station unit equipped for both the
conventional blow moulding and stretch-blow moulding of PVC bottles
(typically about 1 litre capacity). In the former mode of operation, twin
heads are used with two two-cavity moulds: the problems of constant
parison delivery and uniform wall thickness and temperature distribution which-as has been mentioned-ean arise in multi-head extrusion
of PVC, are overcome by the use of two extruders, each feeding one
head.
(c) 1njection Blow-moulding Equipment
Two examples of commercial equipment of this kind suitable for PVC
are the Battenfeld-Fischer FiB injection stretch-blow-moulding equip-

* The Side) Division of SMTP, Paris, France.

VK1-2ESB
BM04
BM04D
KEB 2
MSFBO 3000
MSF BO 5000

Model

Material weight, about 30 g.

Can be converted for direct blow moulding.

Battenfeld-Fischer
Bekum
Bekum
Krupp-Kautex
Sidel (SMTP)
Sidel (SMTP)

Producer

Equipment

1
2

Cavities per mould

24 preform moulds and 24 bottle

moulds on two rotary wheels

1
1

Number

Moulds operated

500
900
1800
500
2600
10000

Typical production rate:

I-litre bottles per hour

TABLE 17.1
Typical Performance of Some Commercial Extrusion Stretch-blow-moulding Machines in Producing 1-litre PVC Bottlesa

--.)

:::l

ClO
ClO

17 Blow Moulding of pvc

789

ment range, and the Tri-Delta machines (Tri-Delta Technology, Inc.,

Middlesex, NJ, USA). Both types are four-station units. In, for
example, the Fischer FIB 517 machine the preform is temperatureconditioned at a station between the injection and the blowing stations:
the longitudinal stretch is imparted by pre-blowing (not mechanically):
the output (for bottle sizes up to 05 litre) is 500-600 per hour.
(d) Dip Blow-moulding Equipment
Industrial equipment for this process has been mentioned in Section
17.2.1(a) above. Another example is the Gamma series of machines
produced by Plastimac: this equipment is intended primarily for the
manufacture of small containers for pharmaceutical products. The
version specifically recommended for PVC (and polycarbonate) is a
three-cavity unit in which the melt shots are deposited by three
vertically mounted 35-mm screw extruders each driven by a 5-hp
variable-speed motor.
(e) Sources of Information on Blow-moulding Equipment
A survey of blow-moulding machines (with indications, inter alia, of
suitability for PVC proces&ing) has been published in Plastics and
Rubber Weekly for the 13th September, 1980. Up-to-date information
will also be found in the general sources mentioned in Section 14.6 of
Chapter 14.
17.3 PVC COMPOSmONS FOR BLOW MOULDING

The discussion in this section is centered on compositions for

blow-moulded bottles, since bottles are the most important PVC
products manufactured by this process.
Like any other PVC composition, a bottle compound is formulated
in the light of three key considerations: behaviour in processing,
properties for service, and cost. The formulation is normally a
compromise reflecting the relative importance of these three factors in
a particular situation.

17.3.1 The Processing Aspect

The PVC compositions used as feedstock in the production of
extrusion blow-moulded bottles may be in powder (dry blend) or pellet
form. A twin-screw extruder is preferable with powder feeds (see
Section 19.1 of Chapter 19). Pellet feeds are more common in injection

790

W. V. Titow

blow moulding of good quality bottles. The respective merits of the

two forms of feedstock are mentioned in the introduction to Chapter
19 and, passim, in Chapter 14 (Section 14.2.2(d. Ambient conditions
(especially possible high atmospheric humidity in transport and/or
storage) can be a factor in the choice of feed form, in that powder
blends absorb moisture more readily than pellets, and this can affect
their dry-flow properties as well as cause bubbles in the mouldings
(unless completely effective de-gassing can be guaranteed).
The basic processing considerations in formulating a bottle compound are substantially as those applicable to PVC extrusion or
injection-moulding compounds generally (see Chapters 14, 15 and 19),
although some points may acquire particular emphasis. These include
the use of relatively low K value polymer for ease of processing; need
for particularly good dynamic heat stability of the stock in the
manufacture of clear products; and desirability of complete freedom
from plate-out to avoid blockage of vents in blowing moulds.
Recommendations of the suppliers of the polymer and other
formulation constituents (or of the compound if purchased ready
made) can be useful as initial guidance on processing. In the light of
such recommendations the compound should be tested for processing
behaviour (as well as product quality) to establish the best operating
conditions. Some of the preliminary tests may usefully be conducted on
a suitable torque rheometer. The following properties are of direct
interest (especially in connection with extrusion blow moulding, or dip
blow moulding with extrusion feed).
Dynamic heat stability: A useful assessment of this can be made in a
torque rheometer test of the kind outlined in Section 9.8.2 of Chapter
9. The test conditions (temperature, shearing rate, and duration)
should be worked out in preliminary trials so that they relate to those
of production.
Melt viscosity: This determines the ease of melt flow in processing
(and the temperature for good flow: increasing temperature reduces
viscosity). It is also a factor in the amount of working the stock will
experience (which in turn influences the work-heat generation, degree
of homogenisation and fusion). Determinations can be carried out in a
torque rheometer or another suitable instrument. *
* A concise review of melt rheometry (with 78 references) has been published
recently by Dealy.z4

17 Blow Moulding of pvc

791

Rate of fusion: A bottle compound should be fast-fusing for good

homogeneity of melt with minimum heat history. Rates of fusion can
be determined in a torque rheometer (see Chapter 11, Section 11.1).
Melt swell: This is relevant in extrusion blow moulding, where the
extent to which the walls of a parison expand on leaving the die is a
factor in the ultimate weight of the moulding. The degree of swell is
determined by comparing the diameter of a rod produced under
relevant conditions from an appropriate die, with that of the die.
Melt fracture: This can occur, usually within a range of relatively
high rates of shear, in the extrusion of plastics compositions. In
extrusion blow moulding of PVC bottles it can cause varying degrees of
surface roughness. Tests may be carried out directly on the extrusion
equipment, or the relevant range of shear rates may be covered in
determinations with a rheometer.
Evolution of volatiles: The extent to which this occurs is a function of
the composition of the material and, to some extent, the processing
conditions. If the conditions are not so excessively severe as to cause
appreciable decomposition, the volatiles are often vapours of the more
labile components of the stabiliser system. The volatiles can condense
on the cold surface of the mould cavity: this can cause marring of the
bottle surface, with possibly also staining if the condensate darkens in
colour, as occasionally happens. Condensation of the fumes inside the
bottle can lead to tainting of the ultimate contents: this can be
counteracted by flushing with clean air directly after moulding;
'natural' airing in the course of storage can also help to reduce the
smell in some cases. However, the composition should in any case be
formulated with a view to preventing such problems. A test for
evolution and nature of volatiles can be run: this may consist in
processing the compound, under relevant conditions, in a torque
rheometer, collecting the condensate on a cold metal surface,
determining the amount produced, and taking an IR spectrum to
identify its nature. A version of the test, employing a Brabender
Plasti-Corder fitted for condensate collection, has been described by
Latham and Mendham. 23 These authors also give some information on
the application of this rheometer in the evaluation of the other
processing characteristics just mentioned.

792

w.

V. Titow

17.3.2 The End-use Aspect

Rigidity is a cardinally important property in blow-moulded containers,
since their relatively thin-walled structure is the better able to resist
distortion in service (under external forces, or the pressure of own
contents) the more rigid the walls. Moreover, the higher the rigidity of
the wall material the lower the thickness necessary (Le. the less
material need be used) to achieve the required degree of distortion
resistance. This is one of the main reasons why only unplasticised PVC
compositions are used for the production of PVC bottles. Other
important considerations are the better barrier properties and general
chemical resistance of uPVC in comparison with pPVC, and its greater
stability to extraction of formulation constituents by the bottle's
contents. The only plasticisers used commonly in PVC bottle
compounds are epoxy compounds (usually epoxidised soyabean oil)
which are incorporated, in low phr, as components of some stabiliser
systems: thus whilst they do ease melt flow to some extent,
plasticisation is not their primary function. Small proportions of dibutyl
phthalate are also occasionally included in some PVC compositions for
the production of bottles for mineral water: the functions of this
additive in such formulations (in which it may be associated with
benzoic acid) are to act as co-stabiliser and fungistat, and to assist
fusion.
Properly formulated uPVC has a number of properties which qualify
it as a good material for bottles for a large number of uses (see Section
17.4 below). These include a high degree of rigidity, toughness (in
impact-modified or biaxially stretched mouldings), resistance to
environmental stress cracking, high clarity and 'sparkle' of transparent
compositions, good barrier properties, and suitability (when formulated with approved constituents) for food contact. The points on
which uPVC compares less favourably with PET, its main competitor
in many blown-container applications, are relatively low maximum
service temperature, susceptibility to ketone and chlorinated hydrocarbon solvents, lower impact strength, greater susceptibility to stress
whitening (of some impact-modified grades) and permeability to some
penetrants.
PVC bottle compounds for the packaging of oil, beverages, and
pharmaceuticals must fulfil the requirements of the appropriate
regulatory authorities with regard to the suitability of all formulation
components. They must also be formulated to minimise odour and
taste effects and to resist microbiological infestation.

17 Blow Moulding of pvc

793

17.3.3 PVC Bottle Formulations

The basic formulation will comprise the following.
(a) PVC Polymer
Usually a suspension (sometimes mass) polymer, with particle
structure and size characteristics suited to ease of processing and rapid
fusion. Relatively low K value: normally 50-60 (number-average
molecular weight approximately 36000-55 OOO)-for low melt viscosity.
The polymer should be of good quality to secure freedom from gels
('fish-eyes' or 'nibs'), and its VCM content must be acceptably low (in
most countries under 1 ppm).

Note: The gel content is sometimes classified with processing

features. Its determination in bottle compounds can be carried
out on a suitably fitted torque rheometer, e.g. a Plasti-Corder
with extrusion attachment and bubble die assembly. A
free-blown thin-walled bubble is produced, in which the gels
should be plainly visible. 23 For a quantitative determination
the bubble size may be standardised and the number of gels
counted. Whilst gels may not be readily visible from the
outside in an opaque production bottle, they usually show up
as small protrusions on the inside surface. Their presence may
significantly impair strength properties, as they can act as
stress concentrators.
(b) Stabiliser System
This is usually liquid, to avoid increasing the melt viscosity. Most often
either a thiotin for good heat stability and high clarity (permitted
compounds for food contact), or a Ca/Zn system for reasonable clarity
and non-toxicity. In either case an epoxy co-stabiliser is usually
included, sometimes with a phosphite or another synergist.
(c) Impact Modifiers
Although in some cases the impact resistance of a conventionally
blown uPVC bottle of a particular design and wall thickness may be
considered sufficient for a particular end-use (and intended contents)
without impact modifiers in the formulation, these toughening
additives are important ingredients of most PVC compositions for the
blow moulding of bottles without biaxial stretching. Their nature, and

794

w.

V. Titow

effects in uPVC, are discussed in Section 11.2.2 of Chapter 11. As in the

compositions for other transparent products, the impact modifiers in
clear bottle compounds are of the MBS type. ABS, and some of the
other types, may be used for opaque bottles.
Impact modifiers can adversely affect, in varying degrees, such
properties as permeability and colour ,25,26 softening point, chemical
resistance, resistance to stress whitening,25 and resistance to photochemical degradation. It is, therefore, an important selection criterion
that the modifier chosen should combine the best toughening effect
with the least impairment of those of the properties which are the most
significant in the particular situation. In most cases, and especially with
clear bottle compositions, stress whitening potential will be a factor in
the selection. The impact resistance of blown bottles normally
increases with the proportion of modifier in the composition, up to
about 15 phr. Higher loadings produce no further significant improvement, and may be increasingly detrimental to other properties.
As has been mentioned, biaxial orientation imparted by stretchblowing can have a pronounced toughening effect, so that the amount
of impact modifier in compositions for stretch-blown bottles may be
substantially reduced, or the additive left out altogether in some cases.
(d) Lubrication
Both internal and external lubricants are employed in bottle formulations. Some proprietary composite lubricants, specially developed for
this application (e.g. Irgawax 368-Ciba-Geigy), can be particularly
useful. In general, all the points of lubricant action (and interactions
with other formulation components, especially stabilisers) discussed in
Section 11.1 of Chapter 11 are relevant to the formulation of lubricant
systems for bottle compositions. The question of permanence (i.e.
resistance to extraction and migration) is important: in this connection
(and quite apart from cost considerations) it is a good general principle
to keep the lubricant content to the necessary minimum. Impact
strength can also be significantly reduced by excess of internal
lubricant, whilst avoidance of the risk of plate-out through proper
choice of the nature, amounts and balance of the components of the
lubricant system is a further important consideration. Internal
lubrication is often provided in bottle compositions by calcium
stearate, whether incorporated solely for that purpose or as part of a
Ca/Zn stabiliser system: the addition level should preferably not
exceed 1 phr, and the effect on transparency of the moulding should

17 Blow Moulding of pvc

795

not be overlooked. Among lubricants with external action,

polyethylene waxes, synthetic waxes, and some fatty acid esters and
alcohols are of interest.
(e) Other Additives
Processing aids (commonly acrylic) are often included in bottle
compound formulations at levels of up tl) about 1 phr. At such levels
they can effectively discharge their functions in processing without
significant effect on the properties of the finished mouldings, except for
possible slight clouding of transparent products. For this reason any
processing aid to be used in a clear composition should have a
refractive index as close as possible to that of the PVC resin.
Colourants and pigments are incorporated in some bottle compounds, as appropriate.
Two examples of basic bottle formulations are given in Section 4.6.6
of Chapter 4. These, and the further examples in Table 17.2, illustrate
some of the points made in the present section.
The effects of some formulation and processing factors on the
quality of bottles blow-moulded from powder blends based, respectively, on a PVC homopolymer, and vinyl chloride/alkyl vinyl ether and
vinyl chloride/propylene copolymers, were investigated-with the aid
of dynamic stability tests-by Taylor and King. 27 These workers found
that the copolymer-based compositions gave bottles with a lower light
absorbance and yellowness index, and that certain product imperfections were related to the particle size distribution and volatiles content
of the resins.
Suppliers of PVC compounds market some blow-moulding grades.
One example is compound 9275 CI38 of the Ethyl Corp., formulated,
like others of its kind, for good heat stability and low melt viscosity in
processing, and for such product properties as good clarity (light
transmittance about 74%), impact strength and UV barrier action (to
protect light-sensitive contents in bottles).

17.4 PVC BLOW MOULDINGS

17.4.1 Applications
The vast majority of PVC blow mouldings comprises containers, used
for the packaging of a variety of products. The containers are mostly

Corvic D50116a
Stanclere 80C
22 phr
Paraplex G62f 28 phr
a--phenyl indole 06 phr
Kane Ace Bl2g 11 phr
Estol294h
Synthetic wax

Medium impact

1 phr
2phr

Kane Ace Bl2 14 phr

11 phr
01 phr

100 parts
Mel/ite 831c;d
Paraplex G62

High-clarity, high-impact

Fruit squash bottles

MBS
lrgawax 368;
PE wax

lOphr
12 phr
005 phr

Breon S90110 b 100 parts

Irgastab 17 Moe 12 phr

Clear bottles
(general purpose)

ICI. K value 50. Low MW polymer for blow moulding and film production. A special grade with low 'fish-eye' level
available.
b BP Chemicals. K value 57-60. A blow-moulding resin.
C AKZO. Liquid octyltin. BPF (British Plastics Federation) and BGA (Bundesgesundheitsamt-West German Federal Health
Office) approved for food contact.
d Albright and Wilson. Liquid octylin. BPF, BGA, and FDA (US Food and Drug Administration) approved.
e Ciba-Geigy. Di-n-octyltin bis(2-ethylhexyl thioglycolate) with 25% epoxidised soyabean oil.
f Rohm and Haas. Epoxidised soyabean oil (high MW grade). BPF approved.
g Kanegafuchi Chemical Industry Co.
h Joseph Crosfield and Sons Ltd, Warrington, Lancs.
; Ciba-Geigy. Composite lubricant for blow-moulding applications.

Impact modifier
Lubricants

PVC polymer
(suspension type)
Stabilisers

Formulation
components

TABLE 17.2
Examples of Basic Outline Formulations for Bottle Compounds

:::'!
0'

:0:::

-.J

17 Blow Moulding of pvc

797

bottles of various kinds, but wide-mouthed jars and the like are also
blow-moulded and find diverse applications in the packaging of some
foodstuffs (e.g. dried vegetables, syrup, honey), cosmetics and
toiletries (e.g. creams and ointments), small hardware items (e.g. nails,
screws) and others.
Large-scale application areas of PVC bottles comprise their use for
packaging consumable liquids (including fruit squashes, edible oils,
vinegar, cheaper varieties of table wine, mineral and natural spring
water, and carbonated drinks), liquids for household use (detergents,
bleaches, disinfectants, cleaners), cosmetics and toiletries (e.g. lotions,
oils, shampoos and other hair-care preparations, liquid soaps), and
pharmaceuticals.
In several of these outlets PVC competes with polyethylene
terephthalate (e.g. bottles for carbonated drinks, edible oil, some
cosmetics and toiletries), polyethylene (e.g. detergent and other
household liquid bottles, bottles for pharmaceuticals), polypropylene
(bottles for household liquids, some toiletries and pharmaceuticalse.g. mouthwash), and modified polyacrylonitrile (applications in which
barrier properties are of particular importance).
As an illustrative example, it may be mentioned that the consumption of uPVC for the production of blow-moulded containers in France
in 1972 and 1973 was reported 28 as, respectively, 110000 and 130000
metric tonnes. The main items making up the figure for the former
year were stated28 to be bottles for still mineral water (70000 tonnes),
for cooking oil (17000), for table wine (14000), for vinegar (3000), for
cosmetics (2000), and miscellaneous (1000).
17.4.2 Properties and Tests

The material properties of uPVC blow-moulding compositIOns,

which-together with the relatively moderate price-make containers
blown in this material attractive for many applications, have already
been mentioned.
Several processing factors also play a part in the properties of a
blow-moulded PVC container. Among these, perhaps the most
important single effcd is that of the nature and extent of molecular
orientation, especially when that is deliberately imparted in a
substantial degree by biaxial stretching. Some other factors have been
mentioned in Sections 17.2.1(c) and 17.3.1. Still others of considerable importance are the temperature of the parison or preform (and

798

W. V. Titow

the temperature distribution within it) during moulding, and the rate
and efficiency of cooling. The former factor can affect the dimensional
conformity and strength of the article and the surface finish; in
extrusion blow moulding it is instrumental in the strength of the nip
weld (also affected by the speed of mould closure, shape of the nipping
edges, and the blowing time and pressure). The cooling factor can also
influence the strength and dimensions.
Two properties normally monitored in the course of routine quality
control in production are the integrity (freedom from leaks) and wall
thickness of containers. Microprocessor-operated leak detectors are
available from several suppliers for on- or off-line use, in some cases as
part of the regular blow-moulding equipment (e.g. with Bekum or
Battenfeld-Fischer machines). A typical leak tester applies accurately
controlled air pressure to the interior of the container and measures
the rate of decay: this indicates the presence and size of any leaks.
Apparatus of this kind can also be used to test the dimensions of small
moulded orifices. An example of a fully automatic, computerised leak
tester is the BLT 1000 Leak Finder (South Bend Lathe Inc., USA 5 ),
capable of testing up to 50 containers per minute (test pressure about
Ollbf in- 2): the device can be programmed for automatic removal of
rejects from the line. Thickness gauges, working on the basis of
absorption of IR radiation, are available (e.g. from Oy G. W. Sohlberg
AB., Espoo, Finland): these can measure and record the wall thickness
of a blow-moulded container at 100 points within 2 s.
Service-related quality control tests widely performed on blowmoulded containers are those for impact resistance, resistance to
crushing, and permeability (barrier effect). Many manufacturers have
their own test specifications. ASTM test methods are also available in
the following standards: ASTM D 2463 (drop impact resistance),
ASTM D 2659 (column crush test), ASTM D 2684 (container permeability). Another ASTM standard (D 2911) lays down dimensional
tolerances for blow-moulded containers. Compatibility with the
intended contents is also sometimes determined, usually by relevant
mechanical property tests on containers before and after a prescribed
period of contact.
The above tests are normally carried out on samples of actual
production containers, although where the object is to compare or
evaluate moulding compounds the container specimens may be ones
specially produced in a prescribed design and size (e.g. the standard
750 cc Lesieur test bottle25 ). Compound property tests involved in such

17 Blow Moulding of pvc

799

comparison or evaluation may also include determinations of some or

all of the following properties, carried out on appropriate standard
moulded test specimens: deflection temperature under load; brittle
temperature; Vicat softening point; tensile strength and elongation;
flexural strength and modulus; density; hardness; and light transmittance (for clear compositions).
In the practical service context, the drop impact resistance is possibly
the most significant among the properties of a container. It is usually
determined by dropping the container-filled with water and closedonto a standard, hard surface.
Note: Some specifications include the same kind of test for a
multi-container pack, if the containers involved are normally
transported and stored in such groups.

In some versions of the drop test the height of the drop is fixed; in
others it is increased by prescribed increments until a stated percentage
(often 50%) of the drops results in failures, or-in some variants of the
method-until all specimens fail, the failure criterion being fracture or
defined damage. Both approaches are represented in ASTM D 2463
(together with a third procedure, known as the 'Bruceton staircase
method'). It may be noted that, as illustrated, for example, by Sisson's
data,25 whilst increasing the K value of the polymer (within the range
acceptable for processing) does raise somewhat the impact resistance in
a drop test, that rise is much less than one brought about by
incorporating in the composition an effective impact modifier in
suitable proportion. The design of the container is also a factor in drop
impact tests.
A non-destructive dynamic compression test of a few seconds'
duration may also be used to obtain a numerical index of the resistance
to flexure in the test conditions. With appropriate allowance for the
design, wall thickness distribution, and material of construction, the
index is claimed to be a reasonable measure of a bottle's relevant
mechanical properties, and to correlate well with the results of some
conventional destructive tests. 7
Bottles for carbonated drinks have to combine resistance to internal
pressure with a low enough permeability to CO2 to provide a
sufficiently long shelf life before 'carbonation loss' occurs. For a 2-litre
bottle in PET (a material somewhat superior to PVC in this
application) many soft-drink companies specify a carbonation-loss shelf
life of 16 weeks (with 8-12 weeks for a !-litre bottle). Biaxial

800

w. v.

Titow

orientation, combined with pressure-resistant design and material

weight for extra wall thickness, are necessary to meet such specifications with PVC bottles, especially where they are to be used in a hot
climate (PET carbonated drink bottles are also biaxially oriented). An
example is a round-shouldered, heavy weight (29 g as against 23 g for a
conventional design), biaxially oriented O'33-litre clear PVC bottle
with integrally moulded, internally rounded base (incorporating four
'feet' for stable standing without external support). This is capable of
containing-without distortion-drinks with up to 8 g litre- 1 CO 2 at
temperatures up to SOc. The bottles, and injection stretch-blowmoulding equipment on which they are produced, have been
developed by Voith-Fischer (now Battenfeld-Fischer) in collaboration
with 4P Rube Gottingen GmbH. 16,29
Apart from the pressure resistance and barrier requirements, bottles
for carbonated drinks and mineral water (as indeed those for wine and
other beverages) must be made from PVC compositions formulated for
the greatest possible resistance to development of taints and odours,
through the highest purity and resistance to extraction of all
constituents, and discouragement of bacterial growth. Some comments
on this formulation aspect are provided in a paper by Sahajpal. 30
REFERENCES
1. Anon. (1980). Plast. Techno!., 26(13), 66-7.
2. Couzens, E. G. and Yarsley, V. E. (1968). Plastics in the Modern World,
Penguin Books Ltd, Harmondsworth, Middlesex, England, p. 298.
3. British Patent No. 821 173.
4. Smoluk, G. R. (1981). Mod. Plast. Int., 11(2), 25-7.
5. Brockschmidt, A. (1982). Plast. Technol., 28(5), 78-81.
6. Anon. (1980). Mod. Plast. Int., 10(1), 25-7.
7. Hunkar, D. (1976). Plast. Rubb. Wkly, 12th November, pp. 30-1.
8. Crabtree, D. R. and Hart, R. J. (1978). Plast. Rubb. Int., 3 (6), 247-8.
9. Anon. (1975). Plast. Rubb. Wkly, 7th November, pp. 22-3.
10. Anon. (1979). Plast. Techno!., 25(2), 13-17.
11. Anon. (1982). Eur. Plast. News, 9(7), 8-9.
12. De Vries, A. J. and Bonnebat, C. (1976). Polym. Engng. Sci., 16(2),
93-100.
13. Brady, T. E. (1976). Polym. Engng. Sci., 16(9), 638-44.
14. Anon. (1981). Eur. Plast. News, 8(9), 64.
15. Anon. (1981). Plast. Rubb. Wkly, 26th September, p. 12.
16. Anon. (1980). Mod. Plast. Int.. 10(4), 36-8.
17. Anon. (1967). Packaging, 38(11), 95-9.

17 Blow Moulding of pvc

18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.

801

Anon. (1976). Plast. Rubb. Wkly, 12th November, p. 37.

Grant, R. and Foster, R. (1965). Mod. Plast., 43(2), 122-6,129,199.
Brockschmidt, A. (1981). Plast. Technol., 27(13), 55-60.
Valyi, E. I. (1981). Plast. Technol., 27(10),133-45.
Hoffmann, M. (1982). Plast. Techno!., 28(4), 67-72.
Latham, J. R. and Mendham, W. E. (1973). 31st ANTEC SPE
Proceedings, pp. 458-60.
Dealy, J. M. (1983). Plast. Engng, 39(3), 57-61.
Sisson, W. B. (1968). Plast. Polym., 36(125), 453-63.
'The blow moulding of Welvic PVC', ICI Technical Service Note W. 110.
Taylor, W. and King, L. F. (1970). Polym. Engng. Sci., 10(4),204-8.
Anon. (1974). Plast. Rubb. Wkly, 26th July, p. 19.
Anon. (1983). Eur. Plast. News, 10(1), 29.
Sahajpal, V. K. (1978). 'PVC compounding for low organoleptics and
controlled bacterial growth', paper presented at the PRI International
Conference on PVC Processing, Egham Hill, Surrey, England, 6-7 April,
1978.

CHAPTER 18

Calendering of pvc
W. V. TITaw

18.1 INTRODUCTION
According to Griffin 1 the word 'calender' shares a common Greek
antecedent with 'roller', and the first recorded reference to calendering
appears to be a description, in an 18th century publication, of a
smoothing treatment for textile fabrics, carried out by means of
individually operated, weighted rolls. The multi-roll machine of the
general type still represented by the modern calender, was developed
for the processing of rubber around the mid-1800s.
Today, in the thermoplastics context, calendering is very much a
PVC-processing operation, in that relatively little in the way of other
thermoplastics is processed on calenders, although some thermoplastic
rubbers, certain polyurethane compositions, talc-filled polypropylene,
and ABS have been calendered into sheeting. 2 ,3 More recently
chlorinated polyethylene sheeting produced by calendering has been
finding application as roof-lining material. In this context, therefore,
calendering may be defined, in general terms, as a process whereby a
hot mass of a thermoplastic is fashioned into a continuous sheet by
passage through a system of heated rolls (the calender). The sheet may
then simply be cooled (possibly after embossing-see below) and
wound up, or it may be deposited, while still hot, on a continuous base
material (e.g. fabric, paper) fed through the appropriate part of the
calender, to form an adherent coating. A calender may also be used to
laminate together externally fed sheets: however, this kind of
operation is lamination by calender, not calendering proper.
The general thickness range for typical calendered PVC products is
803

804

W. V. Titow

about 75-900,urn, although sheet up to about 15 mm thick can be

produced. Thus, whilst the products are often referred to as 'film and
sheet', according to the systematic terminology discussed and adopted
in Chapters 19 and 20, all the unsupported products of this kind should
properly be described as sheeting (or sheet), the top thickness limit for
PVC film being about 75/lom (and its normal method of production the
blown film variant of the extrusion process-d. Chapter 19, Section
19.5.2).
The main advantages of calendering over extrusion as a method of
sheet production are high outputs and production rates, good product
thickness control (and its relatively ready automation), and suitability
for long, continuous runs. These features are largely responsible for
the fact that most PVC sheeting is manufactured by calendering
despite the much higher capital cost of equipment and lower
operational flexibility for short runs in comparison with extrusion.
Suppliers of calenders and calender line equipment are included in
most of the main sources of information on commercially available
machinery for plastics processing. These sources are mentioned
elsewhere in this book (see, for example, Chapter 14, Section 14.6).
The following may be quoted as non-selective examples:
The Berstorff group: Berstorff Corp., Charlotte, NC, USA; Herman
Berstorff Maschinenbau GmbH, Hanover,
West Germany.
BKMllndustrieanlagen GmbH, Munich, West Germany.
The Farrel group: Farrel Bridge Ltd, Rochdale, Lancs, UK; Farrel
Conn. Div., Emhart Machinery Group, Ansonia,
CT, USA.

18.2 THE CALENDER

The machine comprises the arrangement ('stack') of rolls (also known
as bowls) mounted in bearing blocks supported by side frames
('gables'), equipped with roll drives, nip-adjusting gear, and heating
arrangements.
Calenders used for the general production of PVC sheeting are
commonly four-roll machines. Whilst there is no basic reason (other
than cost, space, and structural complexity considerations) for limiting
the number of rolls to four, five-roll calenders are not common, and

18 Calendering of pvc

805

only used for special purposes, such as the production of some types of
thin rigid sheeting where the extra nip can substantially improve the
surface finish. 1 ,4
Note: Three-roll (two-nip) calenders find some use in the manufacture of PVC flooring, and sequences of two-roll (single-nip)
units are used for processing certain highly filled flooring
compositions-see Section 18.4.2(a) below.

The various roll arrangements of a four-roll calender are shown in

Fig. 13.41 of Chapter 13. Their respective merits and drawbacks have
been discussed in some detail by Elden and Swan. 1 The advantages of
the 'L' configuration, widely favoured (especially in the inverted
form-d. Fig. 18.1(i for PVC processing, are usually quoted as
reasonable cost; good visibility and accessibility of all the rolls in the
stack; good rigidity imparted by the vertical superimposition of three
of the four rolls; good range of the available total lap ('wrap') of the
materials round the rolls (up to 540, depending on the positioning of
the offset roll of the stack and the stripper rolls); and ability to apply
thickness corrections at two material banks by crossing just one roll
(No.3 roll-the middle one in the vertical arrangement).

(ij)

(i)

'
Cf3
1

(iii)

"""

(iv)

Fig. 18.1 Customary roll numbering in calenders. (i) Inverted 'V type; (ii)
inclined 'z' Jype, downstack; (iii) 'V type; (iv) three-roll offset.

806

w.

V. Titow

Note: It is customary to designate the rolls of a calender by

numbers, starting from the first roll at the feed nip and ending
with the last one at the take-off (ct. Fig. 18.1).
Another roll configuration popular with manufacturers of PVC
sheeting is the inclined Z type (cf. Fig. 18.1(ii)): this too offers a
relatively wide range of the degree of lap, as well as easy aCCtSS for
fabric coating.
Note: In principle, the 'L', inverted 'L', and 'Z' configurations are

also convenient for bringing an embossing unit close up to the

last nip. Formerly this constituted an advantage, but is less
significant with the multi-roll stripper arrangements favoured
in modern practice (see Section 18.4.1(c) below).
The following typical features of modern calenders are instrumental
in their operational versatility and effectivity (including certain aspects
of product quality).
Roll face lengths up to about 3 m are available: large working face
length (sheet width) is a factor in output rate, and provides the option
of slitting the product into any lower widths required. Individual roll
drives, standard on modern machines, enable the roll speed ratios to
be widely varied, so that the calender can cope with a range of
compositions differing in rheological behaviour: the corresponding
available variation of friction ratios between the rolls makes possible a
high degree of control over the material in the rolling nip which, inter
alia, promotes a good surface finish in the product. In the modern
drilled rolls, the close proximity of the drilled channels for circulation
of the heating medium (high-pressure hot water or special heatexchange liquid), both to the working surface and the two ends of the
roll provides good temperature control, with fast response to
adjustments, which makes for improved processing and product quality
in comparison with those obtainable with older type cored rolls.
Another important feature is the provision for counteracting the
deflection of the rolls by the PVC compound being passed through the
nips. Because of its relatively high viscosity and compression resistance
the material tends to force the rolls apart, the effect being most
pronounced in the middle where the restraining effect of the bearings
is least, and also increasing with roll face length (sometimes also called
face width). The distorting forces developed can be quite high-up to
about 1 MN per linear metre of working face length in the production

18 Calendering of pvc

807

of thin rigid sheeting: 15 MN over the roll face of a 168-m (i.e. 66-in)
calender has been quoted as not unusual in such conditions. 1 ,2 With a
typical plasticised composition a representative range would be about
O 2-05 MN m -1. These forces actually deflect the rolls, so that-if the
deflection is not corrected or compensated for-the sheet produced can
be substantially thicker at the centre than at the edges. The rolls can be
suitably contoured (crowned) to counteract this effect on the product,
where the deflecting forces are known and remain reasonably constant.
In practice this means that roll crowning can be sufficiently effective
only over a rather limited range of compositions and processing
conditions. Outside this range the crowning will either undercom}.lensate (i.e. with deflecting forces significantly higher than those for which
the crowning was designed, the sheet will again be thicker in the
middle) or overcompensate (i. e. with deflecting forces significantly
lower than those allowed for, the sheet will get thicker towards the
edges). Systems are also available in which-to cope with a wider
range of deflecting force values-roll crowning is associated with
special arrangements for nip adjustment by a combination of lateral
and vertical movements of some of the rolls in the stack. * However,
the means of counteracting the effects of roll distortion that are the
most operationally flexible and widely used in current industrial
practice are the techniques known as roll bending and roll crossing
(sometimes also referred to as roll skewing or cross-axis roll
adjustment). A modern calender is normally equipped with facilities
for both these procedures.
Roll bending is effected by applying a hydraulic load to the roll
journal ends (extended for this purpose beyond the regular bearings);
this exerts leverage on the roll (against the bearings) which makes it
slightly concave or convex at the nip, the direction of the imparted
curvature depending on that of load application. The maximum extent
of effective compensatory crown increase or decrease with this method
is limited (typically to about 0075 mm 1 ) by the extra load that may be
safely exerted on the bearings.
Roll crossing is an angular shift of one or both rolls of a nip-forming
pair so that their axes, whilst remaining in their original horizontal
planes, are no longer parallel, but form a slight angle: this increases
the end clearance between the rolls and hence the amount of material
* e.g. the ES Profit Steering calender, developed by Wiik and Hoeglund,
Finland. s

808

w.

V. Titow

that can be accommodated in the resulting enlarged gaps, making for a

thickening towards the edges of the sheet being formed. The degree of
correction achievable in this way can-in particular conditions-be
equivalent to an apparent crown increase on radius of about 075 mm. 1
The roll-crossing facility is usually available at least on the last nip of
the calender (the gauge-determining or 'gauging' nip).

18.3 THE CALENDERING OPERATION: GENERAL

FEATURES, AND THEIR EFFECTS ON THE STRUCTURE
AND PROPERTIES OF CALENDERED SHEET
The operation of a four-roll calender has been said6 to constitute a
form of extrusion with rotating die lips, the material being moved
forward by friction against the roll surfaces in its passage through
the three consecutive nips, said to function, respectively, as the feed,
metering, and final sheet forming and finishing stages. Whilst the
calendering operation may indeed be considered in this way in general
terms, there is no close analogy with screw extrusion as, quite apart
from the different mechanical formats of the two processes, there are
essential differences between them in the state of the PVC material
and the way in which this is influenced by the processing. Thus, as
pointed out in Section 13.4.2(b) of Chapter 13, unlike the extruder, the
calender is not required to de-aerate, homogenise and fuse the PVC
composition: these functions are performed by the compounding
(upstream) part of the calender line, whose make-up and operation are
discussed in some detail in the section just mentioned. The calender
itself essentially only forms into sheet the homogenised fused (gelled),
hot PVC composition which it receives as feed.
Note: The amount of shearing and the temperature of treatment on
the calender can, in principle, be sufficient to homogenise and
gel even a powder feed, and some experiments have been
carried out in that direction. 1 However, quite apart from such
problems as ensuring adequate, uniform intake of powder
feedstock, and effective removal of entrapped air, the
residence time required to achieve a homogeneous, fully
gelled melt makes for a relatively slow rate of material
passage through the machine, and thus works against one of
the main advantages of calendering, viz. a high output rate.

18 Calendering of pvc

809

Furthermore, because of the way the final product is formed by the

calender roll nips it differs from extruded sheeting in some morphological features and in certain properties associated therewith. This is
brought out by the following brief consideration of the material's
passage through an inverted 'L' calender.
In operation, three banks of material are maintained at the three
nips (d. Fig. 18.1): a large relatively narrow feed bank at the first nip
(between No.1 and No.2 rolls) and progressively smaller but wider
banks at the subsequent two nips (with a full width bank between rolls
No. 3 and 4). Because the material is shaped essentially by surface
contact with the rolls. the surface of the ultimate product may be
regarded as having undergone two re-forming treatments (in the
second and the last nips), while the 'core' material inside the sheet is
not substantially re-worked after being given its laminar shape by the
first nip. In this sense, therefore, the core may be considered to be
formed by this nip. The properties of the core-and hence of the whole
product-are thus influenced by the uniformity of feed to the calender,
and uniformity and homogeneity of the first material bank. Differential
cooling of the sheet surfaces and the core tends to set up stresses in the
latter. These can be aggravated locally by non-uniform feed and
irregularities in the feed bank, such as, for example, parts of the feed
strip finding their way directly (without equalising residence in the
bank) into the material being formed by the feed nip: this can give rise
to cold streaks in the core with consequent creation of local stress. The
extent of development of skin-and-core morphology together with the
additional adventitious local strains and stresses, are factors in the
strength properties of the sheet and affect its ability to lie flat. They
can also cause problems in service (e.g. wrinkling) due to strain
recovery.
18.4 CALENDER LINES
18.4.1 General-purpose Line
A fairly typical calender line is schematically represented in Fig. 13.40
of Chapter 13, and something of its operation mentioned-with special
detailed reference to the pre-calender compounding train-in Section
13.4.2(b) of that chapter.
Line arrangements, and in particular those of the pre-calender

W. V. Titow

810

compounding and feed section, can differ in some respects, depending

on the type and range of calendering operations undertaken. The
schematic flow diagram of Fig. 18.2 illustrates a versatile arrangement
(of the kind shown in part in Plate K(1)) of a pre-calender section
which incorporates two alternative material paths for respective use
with plasticised and rigid (or semi-rigid) compositions.
Polymer
storage

Plasticiser
storage

Other additives
storage

Metering (weighing) devices

111

High-speed (hot) mixer

1
1

Cooling mixer

Feed (metering) hopper

......
....

Internal mixer

BussKneader

Two-roll mill

Metering
extruder/strainer

Two-roll mill

.)

feed conveyor
(with metal detector)

CALENDER
Fig. 18.2 An arrangement of the compounding and feed section of a calender
line providing two alternative material routes. A, Plasticised compound
processing route; B, rigid and semi-rigid compound processing route.

18 Calendering of pvc

811

(a) Pre-calender (Compounding and Feed) Section

Typical features of a compounding section of a calender line, and main
variations of the arrangements used, include the following.
The PVC formulation components can be metered in various ways
for the initial mixing (blending) operation (see Chapter 13). Of the two
main materials, the polymer is normally dispensed by weighing:
plasticisers can be metered by volume, but weights should also be
monitored for any dispensing adjustments necessitated by variation of
density with temperature.
The efficiency of the initial mixing, in which a powder blend is
produced, is a factor in the uniformity and homogeneity of the
calendered sheet. For this reason high-speed mixers are widely
employed with both rigid and plasticised compositions. However,
ribbon blenders are also sometimes used as the means of first
combining the polymer with plasticiser(s) and the other, minor
components of the formulation, especially where the subsequent
melt-compounding operation (sometimes also referred to as 'fluxing' in
this context) is carried out in an internal mixer.
As indicated in Fig. 18.2, the melt-compounding unit may be a
continuous-operation one, like a Buss-Kneader (or another one of the
suitable machines discussed in Chapter 13), or an internal mixer of the
Banbury type. Modern versions of these batch-processing mixers are
equipped with microprocessor controls which automate the mixing
cycle. Various basic models are available, with chamber capacities
within the approximate range 40-5001itres: in many cases a standard
model can be modified by the makers to suit a client's special
requirements. In comparison with a continuous compounder, the
advantages of an internal mixer in this application have been listed7 as
a relatively wide capacity range (although the output of a batch mixer
can be matched by that of a continuous compounder of appropriate
size); ease of loading re-work* (promoted by the large loading port
and ram operation) and its thorough re-dispersion; generally greater
heat transfer capacity; and comparatively moderate routine maintenance costs. The main comparative disadvantages include more drastic
working of the stock (a factor instrumental in confining the use of these
batch mixers in calender lines to those processing pPVC), and the need
to handle large discharged material batches; the connected-power
requirements are also relatively high, although the total energy
*In some operations re-work is freeze-ground and added to the high-speed
mixer-see Chapter 13, Section 13.4.2(b).

812

W. V. Titow

consumption is roughly comparable with that of an equivalent

continuous compounder. In general, the batch mixers are best suited to
calendering operations involving relatively short runs on different
formulations.
In an arrangement much used with flexible compositions in the past,
but now no longer very common, an internal mixer is followed by two
two-roll mills. The batch of compounded material is dumped directly
onto the first ('dump') mill where it is sheeted and taken off as an
unsupported strip into the nip of the second mill (the 'strip' mill). The
strip taken off this mill is carried on a conveyor to the feed bank of the
calender. A metal detector would be positioned either over the strip
between the two mills, or over that on the conveyor.
Note: In the early days of PVC calendering the material off the
dump mill might be fed to the calender manually in the form
of 'dollys'*, and even the melt-compounding might be carried
out on a mill.

Nowadays the arrangement of Fig. 18.2(A) would be fairly typical

for processing flexible compositions. In this, the two-roll mill which
receives the hot batches from the internal mixer links the batch-wise
operation of the latter with the continuous operation of the calender
by maintaining a reserve bank of hot, homogenised stock (the working
the material receives on the mill can further enhance homogeneity). A
continuous strip of material from the mill is fed to a short-barrelled
extruder (the extruder/strainer): the functions of this are to remove
from the stock extraneous contaminants and any material lumps and
particles (e.g. of pigment, filler) that may be present; to maintain the
material at a uniform, correct temperature; and to providecontinuously and at the appropriate rate-ealender feed in the form of a
flat or round strip (see also Section 13.4.2(b), Chapter 13).
Continuous compounders are equally suitable-and widely usedfor both plasticised and rigid PVC calendering compositions. With
uPVC this is the type of unit normally employed, in preference to an
internal mixer, ,because of its less severe processing action and very
good stock temperature control afforded by such machines as the Buss* This spelling is sometimes favoured over 'dollies' (also called 'pigs')-pieces
of hot hide cut from the mill and tightly rolled up to reduce heat loss: can
cause excessive bowl deflection in the first nip of the calender if not fully
integrated into the feed bank.

18 Calendering of pvc

813

Kneader. In some pre-calender line arrangements the compounding

machine may feed the calender directly, without the interposition of
another unit (see Chapter 13, Sections 13.4.2(b) and 13.4.4(a) for a
discussion of this and many other relevant points). It is quite usual,
however, for a continuous compounder to be followed in the line by a
metering extruder (extruder/strainer) or sometimes a mill (ct. Fig.
18.2(B, either acting in the capacity already mentioned. Where a mill
is used it makes a convenient addition point for edge-trim that is to be
re-worked, because of the manipulative ease, and to keep down the
heat history of such material (which has already experienced a full heat
processing cycle). The Buss-Kneader is very popular as the continuous
compounder in modern pre-calender trains. Planetary extruders have
also proved their worth in this application (see Chapter 13).
An interesting example of the use of a planetary extruder in a
purpose-designed but fairly basic calendering set-up is the Berstorff*
'Rollex' line,3 intended for what by general calendering standards is
comparatively small-scale manufacture of rigid calendered sheet for
thermoforming (at a quoted typical rate of up to 500 kg h -1), speciality
sheeting, and a wide range of rigid and flexible PVC sheeting for
limited local markets (e.g. in developing countries). The meltcompounding and feed section of the line comprises a planetary
extruder feeding directly into a single-screw metering extruder (LID
ratio 8: 1) which feeds its hot extrudate (formed into a strip by a simple
slot die) into the nip of a three-roll calender. Both extruders are
available in several sizes (the planetary screw size ranging from
100 mm to 290 mm, with rated outputs for the latter size of about
3300 kg h- 1 for uPVC and 4000 kg h- 1 for pPVq,3 but the metering
extruder always has the larger screw size (e.g. 200 mm if the planetary
machine's screw is a 140 mm one): this permits running at screw speeds
low enough to avoid substantial work-heat input into the stock. The
compounding extruder takes a powder blend feed introduced by a
hopper-mounted vertical force-feeder. The hopper also houses a metal
detector, particularly important if scrap is being processed (although
metal detectors are standard equipment in pre-calender trains-see
below). A special screw design featured by the planetary extruder is
said to make for good output rates with compositions based on PVC
polymers of high K value, and with highly filled compounds.
* Berstorff Maschinenbau GmbH, Hanover, West Germany-see also Table
14.3 in Chapter 14.

814

W. V. Titaw

Plate K Calender train (AECI Ltd Vinyl Products Division Midland Factory,
RSA-eourtesy Mr. W. B. Duncker). (1) Part of the compounding and feed
section.

As indicated in Fig. 18.2 (and discussed also in Section 13.4.2(b) of

Chapter 13), the final member of a typical pre-calender train is a
conveyor which carries the feed strip up to the calender feed bank. The
conveyor may consist of one or more sections. The final section is
usually swivel-mounted, so that the end can traverse the length of the
feed nip for uniform feed distribution. To help maintain its temperature,
the strip should have the lowest practicable specific surface (i.e. it
should preferably have a circular cross-section or, if flat, be thick and
narrow rather than thin and wide), and/or should be heated by some

18 Calendering of pvc

Plate K-contd.

815

(2) Rear view of calender.

means (for example by IR heaters) if it is carried over a long distance

(say more than about 2 m). Where heating is employed the material of
the conveyor should be suitably heat resistant.
The metal detector, always employed in the pre-calender train to
guard against damage to the calender rolls by any fragments of metal
that may find their way into the PVC composition, is commonly
positioned over the feed conveyor (although-as mentioned in passing
above-other locations may also be used): see also discussion of the
role of metal detectors in Section 13.4.2(b) of Chapter 13.

816

W. V. Titow

Plate L Calender train: part of the cooling-roll and take-off section (AECI
Ltd Vinyl Products Division Midland Factory, RSA-eourtesy Mr W. B.
Duncker).

(b) Calendering
Several features of the calender and its operation have already been
discussed in Sections 18.2 and 18.3 above. A few further important
points should be mentioned.
As the PVC composition fed to the calender is normally already
gelled and molten, the machine's main task is to form it into a uniform
sheet of the required thickness (although the material also receives a
certain amount of mechanical working-see below). The forming is
carried out gradually, in the course of passage through the consecutive

18 Calendering of pvc

817

roll nips. Two factors actuate the passage, their operation also
governing the route the material follows through the machine (referred
to as the 'sheet path') in that they determine whether the sheet
is or is not transferred from one roll of a nip-forming pair to the other.
These factors are the material's adhesion to the roll surfaces, and the
ratio of the roll speeds at a nip, usually called the friction ratio. Unless
it is grossly over-lubricated, a hot PVC calendering compound will
adhere to a hot roll surface: the adhesion is always stronger to a matt
than to a polished surface; it also usually increases with the roll
temperature, although some compositions may be formulated to
minimise or even reverse this effect by suitable selection of the
lubricant system. Where the speeds of the nip-forming rolls are
different, the material will run on the faster roll, if both have the same
surface finish. Otherwise the effect of the finish is strongly dominant,
that is to say if one of the nip-forming rolls is polished and the other
matt, the hot sheet will tend to remain on, or transfer to, the matt roll
irrespective of differences in speed and/or temperature.
In practice the sheet path is conveniently established-and changed
where necessary-by suitable settings of roll temperatures and friction
ratios. Save in the special case of the so-called low-temperature mode
of operation (see Section 13.4.2(b) of Chapter 13) it is usual to have
the roll temperatures (as well as the speeds) going up with roll
numbers.
Note: If the sheet does not lap the last roll (e.g. roll No.4 in the

arrangement of Fig. 18.1(ii then that roll will normally be run

at a lower temperature, and usually a lower speed, than its
partner (roll No.3 in the figure) which is required to retain
the sheet.
Some examples of roll temperature settings in particular runs on
particular machines are given in Tables 18.1 and 18.2. As can be seen,
the individual settings for a nip-forming pair can be very close: as a
general rule, the maximum difference between them should not
normally exceed lOe. If, with optimum friction ratio, a difference of
this order still does not make for satisfactory operation, the temperature measuring and control equipment should be checked and/or the
lubricant system of the composition re-formulated. The nature of the
compound, and in particular its lubrication, is always a factor in
the roll temperature settings: in general, for normal industrial

TABLE 18.1

Some mustrative Features of Industrial Production of PVC Sheeting on an 'L'

Type Calender with Highly Polished RoDs
(Based on data supplied by Mr D. J. Sieberhagen of Vynide Ltd.)
Composition type
Rigid
(crystal clear)

Flexible
(opaque)

Basic formulation
PVC homopolymer resin
Stabilisers
Lubricants
Plasticiser
Processing aid
Impact modifier
Filler
Pigment

Processing conditions
High-speed mixer
Tool tip speed
Mix temperature on
discharge
Cooler mixer
Tool tip speed
Mix temperature on
discharge
Buss-Kneader
Compound temperature at
die head
Internal mixer
Discharge temperature
Two-roll mill
Roll 1 temperature
Roll 2 temperature
Calender
Roll 1 temperature
Roll 2 temperature
Roll 3 temperature
Roll 4 temperature
Stripping device
Cieneral temperature
Embossing roll
Temperature
Cooling train
Temperature

87 pbw (K value 57)

25 pbw (organotin)
15 pbw (internal!
external)

100pbw (K value 71)

25 pbw (BalCd liquid)
05 pbw (external)
46 pbw (DIDP)

5pbw
8pbw
5 pbw (coated CaC0 3)
8pbw

TABLE 18.1-eontd.
Composition type
Rigid
(crystal clear)

Flexible
(opaque)

Sheet properties

Tensile strength (yield)"

Elongation at breaka b
Tear strength b (ASTM D 1922):
in machine direction
in transverse direction
Tensile impact strength
(DIN 53448)

49-60MPa

22-29MPa
206-273%

45--69 kgfmm- 1
6(}-84 kgf mm- 1

87-113 kgf mm- 1

121-129 kgf mm- 1

323--555 kgf cm cm- 2

a Dumbbell
b

specimens, with parallel central portion 10 mm wide.

Sheet 251-350 11m.

TABLE 18.2
Some Wustrative Features of a Laboratory Preparation of Flexible PVC
Sheeting on an Inverted 'L' Type, 61-cm (24-in) Calender Producing at
3mmin- 1
Formulation

PVC resin-Corvic R65181 a

Stabilisers: BalCd liquid complex
epoxidised oil
Plasticiser: DAP
Lubricant: stearic acid
Calender

Offset (No.1) roll temperature (0C)

Top (No.2) roll temperature COC)
Middle (No.3) roll temperature (0C)
Bottom (No.4) roll temperature (0C)
Mechanical properties of sheeting

Tensile strength (MPa):

in machine direction
in transverse direction
Elongation at break (%)
in machine direction
in transverse direction
Tear strength (N per mm of thickness):
in machine direction
in transverse direction

100 phr
2 phr
3 phr
47phr
0'5phr
For 0125 mm
sheeting

For 0500 mm
sheeting

155
155
160
165

158
164
168
170

0125mm
sheeting

0500 mm
sheeting

162
164

205
194

225
250

305
300

63
63

67
68

A high molecular weight VCNA copolymer containing 2% VA; porous, easyprocessing particles; recommended for extrusion and calendering of thick sheet.

820

W. V. Titow

production, these will be within the extreme overall range of

15O-195C.
The material of the banks at the roll nips experiences an amount of
shearing and friction increasing with roll speeds and speed ratios: when
these are sufficiently high the energy input can result in substantial
temperature rises. Such work-heating must be allowed for in the roll
temperature settings, to ensure that the composition is not overheated
(in some cases the rolls may have to be kept at temperatures below the
material temperature aimed at). Subject to this general consideration,
and any special ones that may arise in individual cases, it is normally
desirable to operate at the highest practicable material temperature for
ease of processing (lowest material viscosity) and good ultimate sheet
properties. With roll temperature settings and friction ratios increasing
from feed to delivery, the material temperature also rises: in the final
nip it can, for a short time, be as high as 200C (although accurate
measurement is difficult).8 For material coming off the last bowl a
fairly typical range is 17o-175C.
(c) The Post-calender Train
The post-calender section of a modern line is shown schematically in
Fig. 18.3, with the principal components clearly labelled. The figure is
largely self-explanatory, but the following additional points may be
mentioned.
STRIPPER ROLLS, AND OFF-THE-CALENDER STRETCHING

The hot sheet is removed from the calender bowl on which it runs after
the final nip by a stripper (pick-off) roll. Whereas formerly the use of a
single pick-off roll was quite common, in modern practice a set of rolls
is employed, in which the first stripper roll is backed by a large number
of similar rolls (see Fig. 18.3), temperature-controlled in groups of two
or more: this makes for good control over sheet thickness and for
uniform, gradual cooling, or close maintenance of temperature (with
provision for an extra heat boost by an IR heater as shown in Fig. 18.3,
or by passage over a hot drum) if the sheet is to be embossed in-line.
The fact that each side of the sheet is in contact with alternate rollers
(see Fig. 18.4) is a factor in the uniformity of temperature control. In
the common arrangement where the first pick-off roll counter-rotates
with respect to the calender roll, the stripping action takes place by
virtue of the greater peripheral speed of the stripper and the lapping of
the sheet round it (and the other rolls of the set-see Fig. 18.4).

18 Calendering of pvc

821

The running of the stripper rolls may be so regulated that the sheet
coming off the calender is stretched to a predetermined extent whilst it
is still at a temperature significantly higher than any that will be
reached in subsequent processing or in service (in conditions where
retraction of the stretch with consequent undesirable distortion is
possible). This procedure offers the following advantages. Greater
operational flexibility, in that a calender profiled, roll-loaded and set to
produce one thickness of sheet can also be used for a range of lower
thicknesses: furthermore, the lowest thickness limit is effectively
brought down below that for which the machine can be set.
Note: For example, sheet of thickness about 75 J.lIIl (a typical lower
thickness limit for calendered sheeting) would normally be
produced by stretching down a sheet calendered at a higher
thickness, say about 100 11m.

A setting of the final calender nip (the gauging nip) wider than
would be required for direct production of the sheet thickness that is
ultimately achieved by stretching, means lower distorting forces on the
rolls and somewhat less drastic working (and heating) of the material.
Calendering at greater thickness can also reduce the overall power
requirements.
Stretching of the sheet should not be allowed to cause a substantial
reduction in width, or be carried to the point of excessive uniaxial
orientation of the ultimate product: uniformity of thickness should also
be maintained. These considerations are factors which-together with
the composition of the sheet and the actual calendered thickness-limit
the extent of sensible stretch in a given situation. For suitably
formulated sheet, calendered at a thickness reasonably above the
minimum for which the machine can be set, stretching (and the
corresponding thickness reduction) by a factor of about 2 would not be
uncommon: say a sheet calendered at a nominal 280l1m might be
stretched down to 14(}-120l1m.
EMBOSSING

Although calendered sheeting can be embossed away from the

calendering line in an entirely separate operation (which involves
re-heating to a suitable temperature), embossing is often carried out
in-line. This obviates the need to set up separate equipment (which,
inter alia, has to duplicate sheet heating and cooling), saves heating
energy (as the sheeting does not have to be re-heated, but merely kept

822

W. V. Titow

Fig. 18.3 An 'L' calender with post-calender section. Schematic

hot on leaving the last nip of the calender), and avoids the acquisition
of extra heat history. Before the advent of multiple stripping rolls with
close temperature control it was usual to have the embossing station
positioned as closely as possible to the calender, for minimum heat loss
from the sheet, although a heat boost would still normally be given at
least to semi-rigid or rigid material which, for optimum embossability,

Fig. 18.4 Schematic representation of some stripper roll arrangements. A,

The lapping of hot sheet around the stripper rolls; B, a reverse stripping
arrangement.

18 Calendering of pvc

T'''''

823

,....-,--------,

representation. (Courtesy of Mr D. J. Sieberhagen, Vynide Ltd.)

must be at a higher temperature than that suitable for flexible sheeting.
A typical embossing unit consists of a chilled, metal roller engraved
with the emboss pattern, and a back-up roller-usually of substantially
larger diameter-covered with a synthetic rubber to provide the
requisite degree of resilience. It is normal for the backing roller to be
also cooled-internally and/or externally-to prevent distortion and
possibly deterioration of the rubber, and to maintain a reasonably
constant level of resilience. Other factors being equal, the definition of
the emboss pattern is the better the lower the temperature of the
embossing roller and the higher the nip pressure, although the
optimum pressure will vary with sheet formulation, as well as its
temperature and rate of passage through the unit. One (either one) of
the unit's two rollers is positively driven: the drive is independent of
those of the other parts of the line, but must be suitably synchronised
to avoid stretching the sheet.
Note: Prevention of uncontrolled stretching, and generally of
introduction of strain into the sheet in any part of the
post-calender train (after the initial, planned hightemperature stretching off the calender-see above), and
especially avoidance of such straining at relatively low
temperature (below about 100C), is an important considera-

824

W. V. Titow

tion in the running of the train. The presence of lowtemperature strain impairs the dimensional stability of the
sheeting in any subsequent heat processing (e.g. heat
lamination) and in service. A typical example4 of a problem
that may be caused by such strain is the wrinkling or
puckering of interior car door trim produced from calendered
PVC sheeting: during its manufacture, or in subsequent use,
the temperature inside a car can reach about 80a C (or even
higher in hot countries), giving rise to these unsightly faults as
a result of the reversion of any substantial strains originally
introduced at or below such temperatures.

COOLING

Since the early days of calendering the most common method of

cooling the sheet has been by passage around cooled drums (also
known as 'cans'), although air-cooling on conveyors has been tried,
and thick sheet has been cooled by passage through a water bath. l The
temperature of the drums is kept at the required level by circulation of
water through the annular space between the outer wall (which
constitutes the working surface) and an inner shell. Hollow drums
cooled internally by water sprays have been used in the past, but both
their temperature control and their balance in running are less
satisfactory for the precise cooling rate adjustment and fast, stable
rotation required with high production rates. Apart from the wide
adoption of the 'double-skinned' drum just mentioned, the other-and
indeed the main-developments over the years in the typical cooling
section of the post-calender train have been an increase in the number
of cooling drums, with improvement in their temperature control (in
small groups, or even individually), and improvements in the speed
drive. These developments were aimed at a better, more complete
attainment of the objects of the cooling operation, which are to bring
the temperature of the sheet gradually and evenly down to that of the
surroundings (or even somewhat below ambient), without thermal
shock (which can impair the sheet properties, especially with rigid
compositions) and without introducing low-temperature strain. In
typical modern practice these objects are achieved by passing the sheet
around a large number of cooling drums, running uniformly (under an
independent drive but in synchronisation with the rest of the train),
and temperature-controlled at gradually decreasing values: as an

18 Calendering of pvc

825

example, in the cooling section shown in Fig. 18.3, drums 1-3 might be
kept at 50C, drums 4-6 at 40C, drums 7-9 at 25C, and drums 10-12
at a temperature about 5-lOoC below ambient. As indicated in the
figure, the sheet is lapped around the drums in such a way that each of
its surfaces is alternately in contact with consecutive drum surfaces:
this promotes even, uniform cooling.
SHEET THICKNESS MEASUREMENT AND CONTROL

The monitoring of sheet thickness is a necessary part of production

control. For many years a ~gauge has been virtually standard
equipment for on-line thickness measurement. This device determines
continuously the extent to which the passage of a beam of electrons
from a radioactive source scanning across the moving sheet is
obstructed by the sheet material. Thus the sheet property actually
measured is the mass per unit area; but as this is directly proportional
to thickness (since the density of the material is fixed by the
composition) the read-out is in terms of thickness (and its variation
across the sheet).

Note: The nature of the measurement also means that the thickness
obtained is gravimetric thickness. * For a plain sheet this is the
same as the directly measurable 'geometrical' thickness. For
an embossed sheet-where the geometrical thickness cannot
be measured because of the surface contouring produced by
the emboss-the gravimetric thickness is the appropriate one,
and it is thus particularly useful that this is what is measured
by the ~gauge.
More recently, the scanning ~gauge has been integrated into a
complete, computerised on-line control system incorporating feedback
control loops: the thickness data from the gauge are utilised by
microprocessor-based controls which automatically make continuous
adjustments to the roll-crossing and roll-bending devices to keep the
* The notional average thickness (t) which, for a given piece or section of
uniform sheet is determined by the area (A), mass (m) and density (p), in
accordance with the relationships:
m/At = p;

t = m/Ap

Standard laboratory methods of measuring gravimetric thickness9-normally

prescribed for embossed sheeting-involve weighing a specimen of known area
and determining, separately, the density of the material.

826

w.

V. Titow

sheet thickness and profile within acceptable tolerances around the

appropriate set target values. This kind of sophisiticated, integrated
control system is exemplified by the well-known Measurex 2001/25
Vinyl Calender Control System *.10 In addition to the automatic closedloop control this provides multi-colour visual data displays and
print-outs of production and control data (including sheet profile plots
and figures in relation to the target values), process summaries, trend
plots, etc. A particular feature is the 'target adaptive control' (TAD):
this automatically adjusts the sheet thickness very close to a specified
percentage-of-nominal limit, so that the finished sheeting area or
weight per roll is optimised.
EDGE TRIMMING

The edges of the sheet are trimmed, to eliminate unevenness which

commonly arises in calendering. The trimming is normally done
towards the end of the line, after cooling (cold trimming), although hot
trimming on the calender is also possible. It is sometimes claimed that
the latter procedure is advantageous because of the particular ease of
re-circulating the hot trim by feeding it directly to the final two-roll mill
or metering extruder of the calender feed section, or even straight into
the calender feed nip. However, with a feed section of the kind
illustrated in Fig. 18.2 there is normally no great problem about
feeding the cold trim from rigid sheeting directly to the two-roll mill
(of the B route in the flow diagram), or that from flexible sheeting into
the internal mixer. In the former case, an end of the strip of rigid trim
(which is wound into a roll during the trimming operation) is fed into
the nip of the mill, where it is continuously melted and incorporated
into the bank of hot stock as it is being unwound. The rolls of flexible
trim strip can simply be dropped, without unwinding, into the internal
mixer, where the heat and shearing action during the mixing operation
will normally be sufficient to disperse them completely into the charge
of virgin material, providing that the proportion of re-work so
introduced is not excessive.
Thus hot trimming on the calender is not really essential for fairly
direct re-processing of trim, whilst it does present certain problems.
One is that a bead tends to form on the hot-trimmed sheet edges: this
can cause difficulties in the ultimate winding and-in any case-makes
the edge finish less neat than that produced by cold trimming. Another
*Measurex Corp., USA.

18 Calendering of pvc

827

disadvantage is marking of the calender roll surface by the trimming

knives.
Cold trim can also be comminuted (e.g. by freeze grinding) and
re-circulated by addition, in suitable proportions, to the high-speed
mixer, where it is incorporated into the powder blend being produced
from the components of the formulation (see Chapter 13, Section
13.4.2(b)).
WIND-UP

Most calendered sheeting is wound up into rolls for subsequent

storage, handling in post-calendering operations (e.g. printing or
lamination), transport, etc.
Note: The sheeting may occasionally be slit in-line prior to winding,
where a number of specified, narrower widths is required. It is
also sometimes cut into lengths or panels for further
processing (e.g. press polishing or lamination) or for use: in
such cases the roll-winding gear is replaced by cutting devices
(rotary kn:ves or guillotines) followed by any necessary
stacking and/or take-off arrangements.

The winding arrangement widely used in modern practice for both

rigid and flexible sheeting is a centre core wind-up unit, in which the
sheeting is wound onto a core (of wood or thick cardboad) mounted on
a mandrel turned by a constant-torque drive that keeps the winding
tension in the sheet at a constant, set value despite the rise of
peripheral speed as the roll builds up on the core. It is important that
the tension should be both constant and as low as possible (consistent
with the production of a reasonably tight, stable roll), to minimise the
introduction of low-temperature strain into (and its fluctuation in) the
sheeting. It is self-evident that the drive of any wind-up unit, whilst
independent, must be synchronised ('tracked-in') with the calender
speed and the other drives in the post-calender train.
A cheaper system, formerly in common use (and still employed in
some lines) for flexible PVC sheeting is contact batching. In this, the
core is not rotated directly, but driven round by surface friction
between the roll of sheeting being built up upon it and a revolving
wind-up drum. With this arrangement the tension in the sheet is more
variable, and the control over introduction of low-temperature strain
less good, than with a centre-core wind-up. Rigid sheeting is not
wound up by contact batching, because the surface friction between

828

W. V. Titow

the driving drum and the roll of sheeting is not sufficient to

maintain-in the relatively stiff material-even tension at the required
level, so that slipping occurs which disrupts and impairs the operation.
18.4.2 Special Lines and Arrangements

(a) Calendered Flooring Lines

Heavily filled vinyl/asbestos flooring compositions are difficult to
process on a conventional calender because of their stiffness, hardness
and relatively low resin content. Moreover, the thickness in which the
material is required may range up to 5 mm. For these reasons material
of this kind (for use as continuous flooring or cut into tiles) is
calendered on a sequence of two or three individual two-roll
calendering units, with vertical or inclined roll arrangement. The
compounding and feed section of a typical line may be similar to that
shown in Fig. i8.2(A), but with two mills between the internal mixer
and the first calendering unit. In the production of the familiar mottled
PVC flooring or tiles, multi-coloured vinyl chips are added either on
the first (dumping) mill, or the second (sheeting) mill which feeds the
first calendering unit. The functions of this and the subsequent units is
essentially to roll out the sheet as it makes its straight passage through
the nip, so that the sheet thickness is progressively reduced. The
operation is thus somewhat akin to the rolling out of ingots in sheet
metal production. The sheet emerging from the nip of the final unit is
cooled and wound or cut up, as required.
Fully flexible flooring compositions, whose relative resin content is
substantially higher, can be processed in the normal way: three-roll
calenders are quite often used, or four-roll calenders operated with a
'spinning' bank or a 'spewing' bank of stock before the second nip
(both these promote maintenance of material and temperature
homogeneity in the stock).
Sheets of suitable flooring compositions calendered in the normal
way on a three- or four-roll calender can be laminated-by various
techniques-to produce multi-layer flooring of the type conventionally,
if somewhat incongruously, styled 'homogeneous'. The individual plies
may be of the same or different composition. For example, a
three-layer laminate (which is fairly common, although flooring with a
higher number of plies is also produced), may be made up of a highly
filled base layer, a medium-filled middle layer with a decorated
surface, and a clear, tough, top (wear) layer: alternatively, three layers

18 Calendering of pvc

829

of sheeting of the same reasonably wear-resistant formulation, and

calendered to the same thickness (fairly typically about 05 mm), may
be laminated together, the sheeting with the best looking surface being
used as the top layer.
(b) Lamination on or at the Calender
Calendered PVC films can be laminated-on the calender or
in-line-to other continuous web materials, such as textile fabrics, felt,
paper and films. Lamination in an entirely separate operation is
mentioned in Section 18.7 below.
In principle, the range of PVC-coated fabrics and papers which can
be produced by lamination with flexible calendered film is equivalent
to that of similar materials made by paste coating. In practice the
coating route offers greater formulation versatility and operational
flexibility, especially for relatively short runs, for multi-layer coatings,
and where frequent formulation changes are made. Calender lamination can be economically attractive where long, continuous runs
without formulation changes are involved. Product properties are
broadly comparable, but the range and quality of cellular coating
layers are better in paste-produced coatings, whilst solid coatings of
this kind are completely free from orientation and strain, which may
not invariably be the case with some laminated film coatings.
There are three basic ways in which a freshly calendered PVC film
can be laminated to a continuous web of another material. These are
schematically illustrated in Fig. 18.5, which indicates the modifications
to the normal calender set-up entailed by each method. Additional
equipment is also normally necessary for unwinding the web to be
laminated (substrate to be coated) and its conveyance to the laminating
nip, as well as-especially with fibrous webs (fabrics and paper)arrangements for drying and pre-heating the web.
The in-line lamination method shown in Fig. 18.5(C) is of special
interest with heat-sensitive SUbstrates, or where an adhesive layer is to
be applied prior to lamination. In the calender nip lamination
arrangement illustrated in Fig. 18.5(A) the degree of penetration of
the hot film into a porous substrate, say a fabric being coated by this
method, increases with decreasing gap between the nip-forming rolls
and with increasing friction ratio between them: zero friction and a
suitably wide gap should be employed for minimum penetration.
Similar considerations apply to fabric lamination on the calender roll
with a squeeze roller, as shown in Fig. 18.5(B).

830

W. V. Titow

Fig. 18.5 Lamination or web coating with PVC film on an inverted 'L'
calender. Schematic representation. A, Nip lamination; B, lamination, with a
squeeze roller, against calender bowl; C, in-line lamination.

18.5 THE FORMULATION ASPECT

In formulating PVC compositions for calendering-as indeed with any

kind of PVC formulation for industrial processing-it is necessary to
take into account the considerations and requirements arising from the
nature and conditions of the process, together with the end-use
requirements and cost considerations, and to arrive at the best
practicable compromise.
The nature of the calendering process makes the lubricant system of
cardinal importance, especially the extent and balance of external
lubrication which is the formulation factor directly instrumental in the
degree of adhesion of the composition to (and hence also ease of its
release from) the calender rolls in the course of processing. External
lubrication is necessary in both plasticised and unplasticised formulations. The role of internal lubricant additives in rigid compositions,
whilst important, is more in line with the relevant general requirements
of melt processing (see Chapter 11, Section 11.1). The same is broadly
true of processing aids.

18 Calendering of pvc

831

Much calendered sheeting is surface printed, whilst some largeoutlet applications (e.g. as reservoir lining, upholstery material,
luggage covering) involve welding of the sheeting (ct. Chapter 20).
Print adhesion and bond formation in welding can both be impaired by
excessive external lubrication (as can the fusion in press laminationsee Section 18.7.2 below).
The intensive working and relatively high temperatures experienced
by calendering compositions in modern high-rate production entail the
need for good heat stabilisation. This is especially important with rigid
compounds, and most particularly those used in the production of
high-clarity transparent colourless foil and sheeting for packaging
applications. For these reasons clear, rigid PVC calendering compositions (as well as some pigmented ones) are commonly stabilised with
organotin stabilisers (where relevant, ones permitted for food contact
applications) .
Barium/cadmium systems, with or without zinc, are the stabilisers
most widely used in flexible calendering compositions. The liquid
versions are of particular interest for ease of metering for compounding, and good dispersibility. However, in highly plasticised compositions a solid system may be preferable to avoid lowering the melt
viscosity. This is the current position, although the question of toxic
hazards associated with the use of cadmium compounds has been
receiving increasing attention and development effort, which has
already produced some viable (albeit still not really fully operationally
equivalent) alternative stabiliser systems (see Chapter 9, Section
9.4.3(b)).
Lead stabilisers, historically the first to be used in calendering
formulations, are no longer employed on any scale because of their
toxicity, somewhat inferior effectivity in high-speed processing, and
generally limited suitability for clear formulations.
The PVC resins used in calendering compositions are grades of
suspension or mass polymers (the latter favoured for some high-clarity
sheeting), of particle size, size distribution, porosity, and bulk density
appropriate to the requisite high-rate processing suitability, inter alia,
with regard to such features as ease and uniformity of dry flow in
metering and dispensing, ready blending with other formulation
components in high-speed mixing (including fast, uniform plasticiser
absorption), and ease of fluxing and gelation. Flexible compositions
are normally based on high K value resins (see, for example, Tables
18.1 and 18.2). This promotes good physical properties important in

832

W. V. Titow

service, whilst the associated increase of melt viscosity in processing

(which prevents the use of high molecular weight resins in rigid
compositions) is actually helpful-especially with highly plasticised
formulations-as it compensates, at least to some extent, for the
opposite effect of plasticisers. Indeed, one of the functions of a filler in
a strongly plasticised material may be to bulk ('sludge') it up for higher
melt viscosity. In rigid compositions, the customary use of polymers of
relatively low K value is dictated (as also in other melt processes, e.g.
injection moulding, blow moulding-d. Chapters 15 and 17) by the
need to ease processing behaviour by all available means. The same
consideration lies behind the use of copolymer resins in some types of
composition-e.g. VCN A copolymers in calendered flooring, or in
sheeting for thermoforming-(although acrylic-modified, homopolymer-based compositions are also widely used for the latter), and
copolymers with vinylidene chloride (e.g. Breon CS lOOl30-BP
Chemicals Ltd) in some special formulations.
The choice of plasticiser(s) for a flexible calendering composition is
primarily influenced by end-use and cost requirements, but consideration should also be given to correct melt rheology in processing and to
possible effects (desirable or otherwise) of the plasticiser(s) upon the
degree and balance of lubrication. Chlorinated polyethylene of
appropriate (relatively high) chlorine content (cf. Chapter 11, Section
11.2.2) is being increasingly used as a solid plasticiser in calendered
sheeting, because of the resulting combination of permanence of
plasticisation with good resistance to weathering, important in such
products as, for example, reservoir linings. The cost of blends of this
kind can be reduced-without too drastic an impairment of properties-by the incorporation of phthalate plasticisers. An interesting
study by Young l l indicated that some compositions based on a blend
of PVC resin of relatively high molecular weight (Diamond 450Diamond Shamrock Chemical Co.) with a chlorinated HOPE (containing 42% or 46% chlorine: respectively, XO 2243.49 and 2243.51-Dow
Chemical Co.) incorporating diundecyl phthalate (Monsanto) or linear
phthalate esters (Santicizer 71l-Monsanto) compared favourably in
mechanical properties and long-term performance with ones plasticised
with polymeric plasticisers.
The fillers most commonly encountered in calendered products are
asbestos fibres in PVC flooring, and calcium carbonate, also used as a
particulate filler in some flooring compositions, and as a cheapening
filler with some processing-aid and reinforcing effects in certain other

18 Calendering of pvc

833

types of sheeting (e.g. supported or unsupported vinyl upholstery

material). The general use and effects of both these kinds of filler are
discussed in other chapters (see in particular Chapter 4, Section 4.6.2;
and Chapter 8, Sections 8.2.1, 8.3 and 8.4), with reference, inter alia,
to the special stabilisation requirements and rheology of asbestoscontaining flooring compositions, and to the principal effects of the
surface treatment and particle size characteristics of calcium carbonate
fillers. With regard to the latter, it may be recalled that whilst with
untreated grades plasticiser demand (and such reinforcing effects as
may arise) is normally an inverse function of paticle size, this effect can
be counteracted by surface treatment with stearic acid, some stearates,
and certain other substances. Apart from reducing plasticiser absorption by the filler (and hence the amount of plasticiser required in the
formulation) surface treatment can improve the filler's dry-flow
characteristics and dispersibility in dry blending and melt compounding. However, possible lubricating effects of the surface coating must
be considered and allowed for in the choice and formulation of the
lubricant system. Some useful data on the effects of particle surface
area and surface treatment of CaC0 3 fillers on the properties of
calendered flexible PVC sheeting have been published by Mathur et al. 12
The basic make-up of some calendering compositions is indicated by
the formulation examples in Section 4.6 of Chapter 4, and in Tables
18.1 and 18.2 here. However, successful formulating for the calender
calls for considerable skill on the part of the formulator as well as
knowledge not only of calendering and PVC materials generally, but
also of the special requirements (especially with regard to lubrication)
of the particular equipment concerned, as these may vary significantly
from one calender line to another.
18.6 SOME FAULTS AND DEFECTS OF CALENDERED
SHEETING

Several of these can also occur in extruded sheeting, in the same or

similar form (see Chapter 14, Section 14.2.2(e)).
18.6.1 Simple Dimensional Faults

These are rare with good modern equipment and correct operation.
However, the following may be mentioned for the sake of completeness.

834

W. V. Titow

Excessive thickness variation and profile irregularity: This fault can

result, possibly temporarily, from faulty operation of the monitoring
and/or control equipment, but would not continue undetected for long
on a modern line properly run.
Local dimensional irregularities: These are associated with 'bagging'
of the sheet in the transverse direction, or longitudinal sagging, on
stripping or in further passage through the post-calender train. These
faults, which are due to uneven or inadequate support of the sheet
while still hot, do not normally arise with modern equipment properly
operated.
Thickness generally too low or too high: Such faults can be caused by
incorrect calender setting, or-with plasticised compositions-may
sometimes arise as a result of, respectively, over- or underplasticisation, even if the setting is basically correct (for a properly
plasticised composition).
18.6.2 Structural Defects

Presence of strain imparted at relatively low temperature: The origin

and consequences of this fault are mentioned in various parts of
Section 18.4.1(c) above.
Unsatisfactory lay-flat behaviour: This can cause problems in winding
and in subsequent handling, processing and use of the sheet. The fault
may be associated with development of excessive skin-and-core
structure in the sheet (and/or irregularities of such structure) during
processing on the calender and subsequent cooling (see Section 18.3
above); it may also be caused or contributed to, by the kind of uneven
stretching or inadequate support of the hot sheet that leads to bagging
and sagging (ct. Section 18.6.1).
Excessive uniaxial orientation: This can be caused by over-stretching
the sheet on stripping from the calender. Although imparted at a
temperature which should be high enough not to lead to retraction
troubles in subsequent use (as in the case of low-temperature strain)
such stretch can result in unduly high differences in strength in the
machine and transverse directions (low tear strength lengthways; low
transverse tensile strength) and excessive longitudinal retraction at

18 Calendering of pvc

835

high temperature (high-temperature strain release). This fault is rare in

modern calendering practice.
Below-par mechanical properties: These are manifested as generally
low values of the properties most commonly measured, viz. tensile
strength, extensibility, and tear strength of sheeting (both flexible and
rigid), and low impact strength of rigid sheeting. The most likely cause
of this fault is insufficiently high processing temperature on the
calender.
18.6.3 Faults Manifested in Appearance
'Fish-eyes' (nibs): These hard, undispersed particles of polymer may
be introduced with substandard PVC resin, or persist in consequence
of incomplete gelation (see also Section 14.2.2(e) of Chapter 14).
Flecking ('fleck marking'): The flecks are a characteristic manifestation of an incorrectly functioning lubricant system (often excess of
external lubricant). The fault may be aggravated by (and in extreme
cases even due to) under-gelation of the composition, and/or incorrect
calendering temperatures.
Plate-out, on sheeting and/or equipment: The origins and nature of
this fault are discussed in Chapter 9 (Section 9.7) and Chapter 14
(Section 14.2.2(d. Some of the main factors responsible are the same
as those involved in flecking, although plate-out is a more complex
phenomenon.
Pluck marks: These are manifestations of poor release of the hot
sheet from the calender roll surface. The release difficulty can be
c~used by under-lubrication of the composition, or sometimes by
overheating in compounding and/or too high roll temperatures in
calendering.
Heat lines: These marks take the form of continuous fairly
close-lying lines running in the machine direction. They are usually
associated with difficulty of sheet release, commonly due to excessively
high calender roll temperatures; over-processing of the composition in
the compounding section may also be a factor. In severe cases heat
lines may be succeeded by pluck marks.

836

W. V. Titow

Surface roughness: In severe cases this may take the form of

pronounced rough surface marks. The fault is usually due to
under-gelation and attendant incomplete homogenisation of the sheet
material. The manifestation is broadly in line with extrusion experience, in that surface roughness in extruded products (if not caused by
purely rheological factors) can be reduced by increasing the processing
temperature and residence time, both of which promote gelation.
Bareich's discussion 13 of the form and measurement of surface
roughness in pPVC extrudates, and of the processing factors
instrumental in its origin, is of some interest here as part of the
relevant background. In some cases surface roughness may be
aggravated, or even caused, by incorrect operation of the calender.
Bank marks: Typically these have the form of irregular areas of
slight surface roughness, reminiscent of water marking of paper. In
severe cases the marks may merge into an overall orange peel effect.
The fault is caused by patches of compound cooler than the bulk of the
stock going through the roll nips: this can be due to incorrect size (too
large or too small) of the stock banks, or to temperature variation in the
stock as delivered to the feed nip.
Colour streaking (in coloured sheet): The streaks are due to poor
homogenisation of the composition, usually associated with undergelation (which may also be manifested in some of the ways mentioned
above).
Overall discoloration: Commonly this is a result of incipient or
substantial polymer degradation (the severity being reflected in the
depth of colour developed), attributable to inadequate stabilisation, or
overheating of the composition in compounding.
Dark specks: These may be either foreign particles small enough to
pass through any straining device employed in the feed section (e.g.
the screen of an extruder/strainer), or particles of partly degraded
material resulting from overheating at the compounding stage.
'Crow foot' marks: The marks (in some cases also referred to as
'pine trees'), which resemble a bird's footprint, are usually attributable
to poor dispersion of particulate additives (fillers or pigments).

18 Calendering of pvc

837

Pinholes: This is a fairly common fault in calendered sheeting,

especially the flexible type, often due to faulty gelation. Pinholing
adversely affects the barrier, strength and other properties of the
sheeting (including the appearance, in more severe cases). Large
pinholes, or substantial incidence of smaller ones, are normally
detectable at the inspection panel before the final wind-up (see Fig.
18.3). However, special automatic inspection by laser scanning 14 offers
a particularly effective means of detecting the presence and loation of
pinholes, as well as gauging their size; the time elapsing before any
necessary remedial action can be taken is also minimised.
18.7 FURTHER PROCESSING OF CALENDERED SHEET
18.7.1 Press Finishing
Substantial quantities of sheets produced by cutting up calendered
sheeting (especially rigid and semi-rigid) are finished by hot pressing
between suitably surfaced metal plates (polished or matt). A stack of
sheets, interleaved with the plates, is usually processed in one cycle.

Note: A typical cycle, which comprises a heating and a cooling

period of roughly equal durations, may last about 40 min, with
the set temperature peaking at about 175C, and the actual
material temperature only slightly lower.
The operation is sometimes referred to as press surfacing. The term
'planishing' has also made its appearance: 15 the question of its purely
linguistic appeal and merit apart, it is the more accurately descriptive
in the technical sense, in that the hot pressing not only imparts
particularly good surface finish to the sheets, but also regularises sheet
thickness and relieves internal stresses and residual strains. Pressfinished sheets are used for products in which the resulting properties
are important, e.g. offset printing plates, draftsman's instruments
(transparent curves, set squares, etc.), name plates, calculator cases,
computer floppy discs, and some thermoformed products.

18.7.2 Press Lamination

As will be mentioned in Chapter 20 (Section 20.1) this method is used
to combine a number of calendered sheets into one of greater thickness

838

w. v.

Titow

than the top limit for direct calendering. The process is similar to
press finishing, except that only two metal plates are used, on the top
and bottom of the stack, so that the sheets forming the stack are
laminated together and the surfaces of the resulting thick sheet acquire
the desired high-quality finish. The sheets to be combined, including
the outermost ones, need not be of particularly good quality except for
uniformity of thickness, necessary for straight, parallel-faced product.
Moreover, the pressed sheet may be matt on one side and glossy on
the other-a surface finish combination not obtainable directly by
calendering. This combination can also be obtained on individual thin
sheets by press finishing.
18.7.3 Surface Treatments

(a) Printing
Much calendered sheeting is printed with decorative designs, e.g. in
the production of vinyl wall coverings, self-adhesive decorative
surface-facing sheets (including imitation veneers), vinyl shower
curtaining, etc. The methods used are mentioned in Section 20.3.5(a)
of Chapter 20. Of these, rotogravure printing (with solvent-based inks)
is the most widely used, especially for plasticised sheeting.
(b) Coating

Coatings are applied to calendered sheeting-by variants of the

common roller or doctor blade techniques-for various purposes.
Plasticised sheeting is often coated with a lacquer for surface
protection (especially against soiling and abrasion) and/or to provide a
decorative finish. In general, the objects of lacquer coating, and the
lacquers and coating methods used, are the same as those described for
paste-produced PVC layers on fabric and other support in Chapter 22
(Section 22.2.6) and mentioned in Chapter 25 (Section 25.4).
Various adhesives are also coated onto sheeting as a preliminary to
lamination with certain other materials (see below), and in the
manufacture of self-adhesive surfacing sheeting, tapes, plasters,
flocked wall-coverings, and the like.
(c) Embossing
In some operations it is convenient to emboss away from the calender
line. The two rollers forming the embossing nip are essentially like

18 Calendering of pvc

839

those used in the post-calender train: the sheeting must be pre-heated

to a suitable temperature, and subsequently cooled evenly with
minimum strain.
18.7.4 Continuous Lamination

Continuous lamination of calendered sheeting to similar sheeting,

other plastics sheet materials, and various fibrous substrates (fabric,
paper) is often carried out on laminating equipment entirely separate
from the calendering line. This alternative to lamination on the
calender in many cases offers greater convenience and operational
versatility.
The key element in a typical operation is the bringing together of the
sheeting and the other web material and their joint passage, under
suitable pressure, through a laminating roller assembly. In heat
lamination the sheeting (and, where appropriate-as, for example,
with a textile fabric-also the other component) is pre-heated, and the
lamination takes place under further heating. With adhesive lamination, the adhesive layer may also require pre-heating (e.g. for activation of a melt adhesive, or gelation and softening of a PVC paste
coating serving as a bonding layer).
An example of heat lamination of two calendered PVC sheets is
provided by a common method of production of veneer-style facing
sheeting for furniture and panels. In this, flexible sheeting with a
wood-grain pattern printed on the surface is laminated with transparent
sheeting to serve as a wear layer and give good surface finish.
Typically, the clear facing sheet is pre-heated by passage over a hot
roller, and then brought into contact-under suitable tension and/or
pressure-with the base sheet, on the surface of a drum kept at about
170C. The resulting laminate, in which the two components should be
completely merged (so that it has the appearance and characteristics of
a single-layer sheet) is stripped off the drum by stripper rolls and may
be either cooled directly or first passed through an embossing station.
Cellular leathercloth may be produced by lamination of a base fabric
with calendered sheeting (as an alternative to the paste coating
methods discussed in Chapters 22 and 25). Various procedures are
used. In one type of process, specially formulated thin sheeting which
will act as a wear layer is assembled with sheeting containing a blowing
agent, and with the base fabric: the three are laminated together under
pressure at a suitable high temperature at which the blowing agent is

840

W. V. Titow

activated and controlled expansion initiated of the film constituting the

middle layer between the surface 'skin' and the fabric. Special
machines are available for this process, the 'Lembo' laminating unit
being a typical example. In this kind of composite lamination the two
PVC layers merge at the interface, but the fabric is usually bonded to
the middle layer with the aid of a thin coating of PVC paste deposited
on the surface of the middle-layer sheeting by a roller and fused in the
laminating step.
Note: The expandable sheeting may also be calendered directly onto
the base fabric and the 'skin' layer applied in a separate
operation. Expansion of the middle layer may also be carried
out after lamination, in a separate passage through an oven.

An interesting example of lamination by adhesive bonding is the

facing of calendered PVC sheeting (with or without fabric support)
with thin polyvinyl fluoride sheet. Outstanding resistance to soiling and
weathering is claimed for such laminates in use as, for example, wall
coverings, greenhouse sheeting and other outdoor applications.

18.8 PROPERTIES AND APPLICATIONS OF

CALENDERED MATERIALS
In addition to the continuous on-line monitoring and control of sheet
thickness and profile, and inspection for faults on- and off-line, some
properties of calendered sheeting are commonly determined in the
course of production quality control and for characterisation purposes
generally. These properties are listed in Tables 18.1-18.4 together with
numerical values that are either fairly typical of the product to which
they relate (Tables 18.1 and 18.2) or representative of minimum
requirements laid down in relevant standards (Tables 18.3 and 18.4).
Similar information relating to PVC-coated fabrics is contained in
Table 18.5.
Other properties are also assessed in tests, where they are of interest
in connection with the quality or suitability for service of particular
kinds of sheeting. Some examples are: surface hardness of plasticised
sheeting; print adhesion on printed sheeting; resistance to blocking of
flexible sheeting; ply adhesion of laminated sheeting; emboss retention
by embossed sheeting; electrical resistivity of sheeting for hospital use.
Standard test methods are available and-in some cases-minimum

15
50

8
50

21
9 (plain-surfaced
sheet)
11 (other surfaces, or
laminated sheet)

160

250-900
14
180
21
8

Up to 400 (inclusive)
13

11 (laminated sheeting)

21
9 (single sheeting)

160

Up to 900 (inclusive)
13

35

75-250
145-159
150

Each numerical property value quoted relates to the determination method appropriate to the standard specification concerned.
Medium stiffness general-purpose single or laminated thick sheeting with plain or embossed surface (one of the eight types of sheeting
covered by the specification).
c PVC sheeting for hospital-use; production method not specified.
d The calendered sheeting covered by this specification, which also covers extruded sheeting (Type II) and cast sheeting (Type III).

Low-temperature extensibility
(%, minimum)
Extensibility after heat ageing
(%, minimum)

Thickness (JlIIl)
Tensile strength (MPa, minimum)
Elongation at break (%, minimum)
Tear strength (N mm- 1 , minimum)
Dimensional stability: change in a
linear dimension (%, maximum)

BS 3878:1982 c

(Type 1
sheetingd )

sheetin!/,)

(Type 103
BS 1763:1975

ASTM D 1593-81

BS 2739:1975

TABLE 18.3
Some Standard Property Requirements for Calendered Flexible PVC Sheeting

00
.f>.

"1:l

.....
00

Softening point (minimum)

Dimensional change at 120C (maximum)
Heat deflection temperature (at
264lbf in- 2 fibre stress) (maximum)
Hardness (Rockwell R) (minimum)

Tensile strength (minimum)

Flexural strength (minimum)
Elastic modulus in f1exure c (minimum)
Impact resistance d

MPa
MPa
Number of
failures
in test
C

Units

--

60
15

38
2000
0

45
2500
Negotiable'

70
15

Type C3

Type Cl

50
Negotiable'

38
2000
Negotiable'

Type D

Numerical value for sheet type b

BS 3757:1978"

Ibf in- 2
Ibf in- 2
Ibf in- 2
ft-Ib per in.
of notch
(Izod)

Units

70
110

7000
11 000
400000
05

Type I

66
100

5000
8500
300000
30

Type Il

Numerical value
for sheet
type b

CS201-55"

C
R scale units

TABLE 18.4
Some Standard Property Requirements for Rigid PVC Sheeting

No failure in the mechanical splitting test prescribed

in the specification

%
%
%
%

%
%
%
%
increase
decrease
increase
decrease

increase
decrease
increase}
decrease

0
0
55

10

15

5
5

20
0
0
80

25

15
0

No delamination or disintegration in
the acetone immersion test prescribed

a Both standards are directed to rigid sheeting generally, but Types Cl, C3 and 0 of BS 3757 are specified as calendered or extruded sheets. CS 201 is a US
commercial standard.
b BS 3757: Type Cl-general-purpose sheet suitable for most applications and fabricating techniques.
Type C3--similar to Cl but with specific impact strength and possibly lower chemical resistance.
Type D-particularly suitable for deep vacuum forming.
CS 201: Type I-1:hemical resistant, normal impact resistance.
Type II-1:hemical resistant, high impact resistance.
C In BS 3757 applicable to sheet of minimum nominal thickness of 05 mm.
dIn BS 3757 applicable to sheet of minimum nominal thickness of 10 mm.
e Between supplier and purchaser.

Change in flexural strength (maximum)

After immersion in 100% acetic acid

Change in weight (maximum)

Change in flexural strength (maximum)

Property retention
After immersion in 80% sulphuric acid
Change in weight (maximum)

Resistance to delamination

Total mass per unit area (gm- Z , minimum)

Base cloth mass per unit area (g m- z ,
minimum)
Coating mass per unit area (gm- Z , minimum)
Tear strength (N per 50 mm, minimum)
Lengthways
Transverse

Property"

Standard

75
685

110
480

760

Grade V

110
685

795

Grade X

Type 2
(with PVC coating incorporating an expanded layer)

590

Type 1
(with solid PVC
coating

BS 5790:Part 1:1979
(for PVC-coated knitted fabrics)

TABLE 18.5
Some Standard Property Requirements for PVC-coated Upholstery Fabrics

40
40

300

550

Grade A

29
29

240

420

Grade B

BS 5790:Part 2:
1979 (for PVC-coated
woven fabrics)

127
114
700

109
097
700

33
400000
30
5

10

40

26

690

33
400000
30
5

26

380

33
400000
30
5

15
50

26

690

10
40

04

400000
30
5

580
26

04

300000
30
5

450
26

a Properties tested by the relevant methods of BS 3424, except for print wear, for which modified test methods are specified in both parts
of BS 5790.
b Requirements applicable to both lengthways and transverse strengths.
COn a Martindale-type abrasion apparatus, under prescribed test conditions.

Bursting strength (kPa, minimum)

Breaking strength (N, minimum b )
Coating adhesion (N per 50 mm, minimum)
Elongation (%, minimum)
Lengthways
Transverse
Tension set (% of actual elongation,
maximum)
Flex cracking (cycles, minimum)
Surface drag angle (degrees, maximum)
Heat ageing (% coating mass loss, maximum)
Print wear (chan~e of appearance) (grey
scale rating, mmimum)
Thickness (mm, minimum)
Mean
Individual reading _
Abrasion resistance (cycles,C minimum)

w.

846

V. Titow

requirement specifications (d., for example, BS 1763, BS 2739, BS

3878, and the relevant standards among those listed in Appendix 1 and
Appendix 3). However, producers, processors and purchasers of
calendered sheeting sometimes use their own tests. For example,
whereas a standard test for emboss retention (BS 1763 and 2739)
prescribes immersion in water at 100C for 10 min as the test treatment
(whereupon the emboss pattern should remain substantially unaffected),
other test treatments, involving different conditions and higher
temperatures (up to 180C in some cases), are also in use where they
are relevant to particular processing or service conditions that the
embossed sheet may experience. 1
The properties which are of interest in flexible calendered sheeting
for reservoir lining are listed in Table 18.6, together with some
relevant standard test methods and typical minimum requirements.
TABLE 18.6
Calendered Flexible PVC Sheeting 1 IDOl Thick, for Reservoir Lining and
Similar Applications: Typical Minimum Property Requirements
Property

Specific gravity
Tensile properties:
Tensile strength
Elongation at break
Modulus at 100% elongation
Tear resistance
Brittleness temperature
Dimensional stability
Q

Test method

ASTM D 792, Method A

ASTM 882

ASTM D 1004 (Die C)

ASTM D 1790
ASTM D 1204
(15 min at 100C)

Volatile loss

ASTM D 1203 Method A

Water extraction

ASTM D 3083

ASTM D 751 Method A

Hydrostatic resistance
Resistance to soil burial:
original property
retention
Tensile strength
Elongation at break
Modulus at 100% elongation
Q

In both the machine and transverse directions.

Numerical value

120
17MPa
300%
9MPa
50Nmm- 1
-30C
Linear dimensional
change Q not to
exceed 5%
Not to exceed
05% by weight
Weight loss not to
exceed 035%
690 kPa

95%
80%
90%

18 Calendering of pvc

847

The following are some of the main application areas of calendered

flexible PVC sheeting: Seepage barriers (swimming pool liners; lining
for water reservoirs, effluent lagoons and the like); film-packaging
applications; production of inflatables (both supported and unsupported film); production of baby pants; production of adhesive tapes
and labels; motor car trim (door panels, head liners, crash pads);
decorative surface coverings; awnings; furniture-facing sheet (veneer
effects and others); wall coverings; facing sheet for metal and board
panels for partitioning and building applications; production of book
bindings, document cases, folders; shower curtains; tablecloths;
mattress covers; floor coverings (continuous or tiles); luggage.
Rigid calendered PVC sheeting finds substantial outlets in thermoformed packs and containers (blister packs; packs and trays for
confectionery and sweets, pharmaceuticals, margarine tubs); lining
and trim for public transport vehicles, aircraft and marine craft; display
signs; production of venetian blinds; film-packaging applications.
Press-laminated sheeting is used in chemical plant construction; wall
cladding; tank lining; corrosion-resistant ducting; tunnel lining.
Uses of PVC sheeting are also discussed in Chapter 26.

REFERENCES
1. Elden, R. A. and Swan, A. D. (1971). Calendering of Plastics, Iliffe Books
and The Plastics Institute, London.
2. Stackhouse, N. (1978). 'Calendering and paste processing,' paper
presented at the PRI International Conference on PVC Processing, Egham
Hill, Surrey, England, 6-7 April, 1978.
3. Anon. (1977). Mod. Plast. Int., 7(7), 18.
4. Elden, R. A. (1977). In Developments in PVC Production and Processing-I, (Eds A. Whelan and J. A. Craft), Applied Science Publishers,
London, Ch. 10.
5. Anon. (1980). Plast. Rubb. Wkly, 13th December, p. 7 and (1981). Plast.
Rubb. Wkly, 24th January, p. 6.
6. Eighmy, G. W. (Jr) (1982). In Modern Plastics Encyclopedia 1982-1983,
pp.220-2.
7. Watkins, W. D. (1976). Plast. Engng, 32(6),23-5.
8. Private communication from Mr T. Hodgson, Storey Brothers and Co.
Ltd, Lancaster, England (1978).
9. ISO 4591-1979. Plastics-Film and sheeting-Determination of average
thickness of a sample and average thickness and yield of a roll by
gravimetric techniques (gravimetric thickness).
BS 2782: Part 6: Method 631A: 1982. Determination of gravimetric
thickness and yield of flexible sheet. (Identical with ISO 4591.)

848

10.
11.
12.
13.
14.
15.

w.

V. Titow

ASTM D 1593-81. Non-rigid vinyl chloride plastic sheeting.

ASTM E 252-78. Thickness of thin foil and film by weighing.
Anon. (1979). Plast. Techno!., 25(5), 24-9 and 49; and Technicalliteature
of Measurex Corporation, Cupertino, California 95014, USA.
Young, W. L. (1978). 36th ANTEC SPE Proceedings, pp. 750-3.
Mathur, K. K., Greenzweig, J. E. and Driscoll, S. B. (1978). Ibid., pp.
732-5.
Bareich, G. (1970). 28th ANTEC SPE Proceedings, pp. 569-72.
Anon. (1982). Eur. Plast. News, 9(10), 44.
Rusincovitch, G. (1982). Plast. Engng, 38(11), 31-3.

CHAPTER 19

Rigid PVC: Main Products-Production,

Properties and Applications
B. J.

LANHAM

and W. V. TITOW

19.1 INTRODUCTION
The properties, processing and applications of rigid PVC are
mentioned, in various contexts, in several parts of this book. Those
references are accessible via the Index.
In the present chapter, some salient technological and applicational
aspects of rigid PVC materials are focused more directly in a brief
review, with special reference to the most important products. The
rigid PVC compositions discussed are in fact almost exclusively
unplasticised (uPVC) materials. Although many compositions containing plasticisers in relatively low amounts might be classified as rigid
PVC on a strict, formal definition, * and could thus qualify for inclusion
here, the ways in which the presence of plasticisers affects the
properties of a PVC composition (including 'antiplasticisation' by small
proportions of plasticisers) are adequately covered in other parts of the
book (see, in particular, Chapters 5,6 and 7, and Appendix 3).
It may be noted in passing that in semi-rigid PVC compositions
(which may typically contain up to about 20-30 phr of plasticiser) the

* See Chapter 1, Section 1.1 in conjunction with ISO 472-1979 and ASTM D
883-80: both these standards define a 'rigid plastic' essentially as a plastics
material which, at a standard temperature and humidity (about 23C and 50%
RH respectively), has a modulus of elasticity (in flexure or in tension) greater
than 700 MPa (= 1Q5 Ibfin- 2). A 'semi-rigid' plastic is similarly defined as one
having a modulus of elasticity between 70 and 700 MPa (approximately
2
1Q4-1Q5 Ibfin- ). Typical modulus values for the material of main uPVC
products are given in Appendix 3.
849

850

B. J. Lanham and W. V. Titow

relationships between plasticiser content and degree of modification of

mechanical properties are often relatively complex and non-linear
('antiplasticisation' can be a factor in this). An early summary of some
of these relationships was published by Jacobson. 1 The effect of the
proportion of plasticiser in a semi-rigid composition (based on Pevikon
R335 PVC resin-Kema Nord, Sweden) upon the impact strength is
illustrated, for four plasticisers, in Fig. 19.1.
Note: Whilst, as shown by the curves of Fig. 19.1, the impact
strengths of these compositions pass through minima (not
quite reached by the TIP curve within the plasticiser content
range covered), the corresponding tensile strength plots pass
through maxima (at about 20 phr for TIP, and 5-10 phr for
DOP, DOA and DBS). The curves for elongation at break in
the tensile test also exhibit minima at about 10-15 phr
plasticiser.

As has been mentioned elsewhere in this book, uPVC compositions

120

DBS

11

DOA

:550
01

~40

+'
Ul

+,30
u

E
C1J

20
10

10

20

30

Plasticisar conttlnt I phr

Fig. 19.1 Effect of some plasticisers, at low content levels, on the impact
strength of a PVC composition.

19 Rigid PVC: Main Products-Production, Properties and Applications

851

may be based on homopolymers (in conjunction with suitable modifiers

where shear and heat processing is involved) or copolymers, which are
easier to process (but normally have lower softening temperatures and
are somewhat inferior in certain properties, especially mechanical and
thermal). The copolymers most frequently used are VCNA (e.g. in
gramophone records, flooring compositions, some vacuum-forming
sheet especially in the UK) and VCNDC (e.g. in some calendered
sheeting, some packaging films, and as extender polymer in special
paste compositions for rigid products). Copolymers of vinyl chloride
with propylene are also used in some uPVC compositions for ease of
processing (see Chapter 1, Section 1.5.2, and Sections 19.3.1 and
19.5.3 here).
Chlorinated PVC is often the polymer in rigid compositions for use
at temperatures higher than the service temperature of ordinary uPVC
(ct. Chapter 1, Section 1.6).
The feedstocks in the processing of uPVC are nowadays mainly
dry-blend powders, although melt-compounded pellet feeds are also
used, especially in the injection moulding of parts, and compression
moulding of gramophone records. Some extruded and blow-moulded
products are also made from pellet stock, particularly where processing
is by single-screw extruder, albeit dry blends are successfully run on
single-screw machines (suitably vented). For the production of-for
example-pipe or window frame profiles from powder (dry blend)
feedstocks, this kind of equipment may advantageously incorporate:
such features as special screw design (e.g. a 'wave' screw-see Chapter
14), and special feed arrangements (e.g. cram-feeders and vacuum
hoppers). A few examples of the uses of commercial uPVC compounds
representing both kinds of feedstock are given in Table 19.1.
The principal advantage of pellet feedstocks is that, having been
melt-compounded, they are fully homogenised (gelled) and thus the
processing they undergo in the course of conversion into products (by
extrusion or moulding) is not required to effect homogenisation (with
complete gelation-see Chapter 14, Section 14.3) but only melting: this
places less exacting demands on the processing effectivity of the
equipment.
The advantages of a dry-blend feed over pellets are:
(i) lower cost of the compound;
(ii) lower capital cost of production equipment for the compound;
(iii) less extensive heat history acquired by the compound.

Powder
Pellets
Powder

BS 3504 and 3506

BS 4514
BS 4576

Pressure pipe

Soil pipe fittings

Rainwater goods

Pellets
Powder

Pellets

BS 4607 Part 1}

High-impact conduit
High-impact profiles

Pellets
Powder

Form

Relevant standard

Profiles (normal impact)

Nature

Product

--

B.I.P. Ltd: VX 105

B.I.P. Ltd: VI 109

B.I.P. Ltd: VX 115

B.I.P. Ltd: VI 109

BP Chemicals Ltd: PA 182

BP Chemicals Ltd: RA 166

BP Chemicals Ltd: RA 126

BP Chemicals Ltd: PA 181

Source and gradeQ

PVC feedstock

144-146
148-152

147-149
148-152

142

148

148
146

SG

By way of non-exclusive, illustrative example. Numerous feedstock compounds available from many different sources.

Injection
moulding

Extrusion

Process

TABLE 19.1
Examples of the Uses of Some Commercial uPVC Feedstocks

'"

is

:::1

~
:0:::

;::,
l:>...

l:>

;:

l:>

;::,
;::,-

t-<
l:>

00

19 Rigid PVC: Main Products-Production, Properties and Applications

853

Various formulation aspects of uPVC compositions and their

significance in processing, material properties, and product performance, are considered in many of the other chapters. However, two
points may be reiterated here, viz. that in the absence of plasticisers
the molecular weight (K value) of the polymer (as well as its
nature-i.e. whether a homo- or copolymer) acquires additional
importance vis-a-vis processing, whilst the role of polymeric modifiers
(and hence their correct choice) with regard to effects in processing
and service also assumes primary significance, especially in homopolymer-based compositions.
Note: The physical characteristics of the polymer powder (including

particle structure, size and size distribution, bulk density) are

also important in such connections as flow and mixing
behaviour in dry blending, ease of gelation in melt compounding or melt processing from dry blend.
Other factors being equal, the K value of the PVC polymer
influences the ease of fusion and the melt rheology of a uPVC
composition. Hence relatively low K values are chosen where ease of
flow at reasonably non-degradative processing temperatures is particularly important (e.g. in injection moulding, extrusion blow moulding),
although a high K value is always desirable for best mechanical
properties of the product. Copolymers (in preference to homopolymers) are also used for ease of processing and good melt flow (as
required, for example, of gramophone record compositions), and
special purity grades of resin where high quality (high clarity in
transparent products) is a requirement-see Chapter 4, Sections
4.4-4.6 for more detailed discussion. Some of the characteristics of
PVC resins used in common types of uPVC compositions are
illustrated by the examples given in Table 19.2.
The role and functions of polymeric modifiers in uPVC compositions
are discussed in some detail in Chapter 11 (Section 11.2). Both the
increased ease of processing imparted by polymeric processing aids and
the improved impact resistance conferred on the ultimate product by
impact modifiers are important in all uPVC compositions. In the case
of some products for outdoor use-e.g. window-frame profiles,
cladding, some kinds of pipe-it is particularly desirable that the
polymeric modifier(s) should provide maximum process-aid effects at
the high rates of extrusion normally aimed at, with the greatest
weathering resistance in service. Some acrylic modifiers achieve this

100
9
02
015

H
S or M
57
580

Injection or
blow moulding;
calendered
sheeting

995
10
05

65-67
500-550

Sb

Hb

Largediameter
pressure
pipe

100
5
02
022

He
se
66
54{)

General
extrusion

100
99
02

H
E
72
480

999
5
02

C
S
62
510

Extruded or
calendered
sheeting (for
thermoforming)

= emulsion polymer.

Battery
separators

H = homopolymer; C = copolymer (VCNA); S = suspension polymer; M = mass polymer; E

e.g. Breon 5110110 (BP Chemicals Ltd).
e e.g. Corvic 5 6617 (AECI).
dAfter 30 min at 135C.

Polymer natureD
Polymer typeD
K value (Fikentscher: DIN 53726)
Apparent density (ISO 60) (g litre-I)
Particle size (ASTM D 1705):
% below 250 /lm
% below 75 /lm
Heat IOSSd (%)
Porosity (ASTM D 2873) (cm 3 g-I)

Polymer
characteristics

Typical application

TABLE 19.2
Some Characteristics of PVC Polymers Typically Chosen for Various Applications
(Based largely on data from Ref. 2)

997
15
18

C
S
47
780

Gramophone
records;
flooring

'l:

:::1

:<::::

;:,
l:l..

l:l

l:l

::.-

;:,

l:l

t--

"""

00
U1

19 Rigid PVC: Main Products-Production, Properties and Applications

855

TABLE 19.3
Impact Resistance and Tensile Strength of Typical uPVC Compounds at
Different Temperatures
Temperature

Impact resistance"
(notched lzod: ft lbfin- I )

COC)

Tensile strength b
(lbfin- Z )

Normal-impact
composition

High-impact
composition

Normal-impact
composition

High-impact
composition

03
04
09
40
160

10
40
160
180
190

12200
8900
6400
4100
2300

10400
7000
5500
2900
1500

-40

25
60
82

"ASTM D 256.
b ASTM D 638.

combination in a particularly high degree (see also Section 19.5

below).
The way in which the impact resistance and tensile strength of uPVC
compositions can vary with temperature is demonstrated by the data of
Table 19.3.
The comparison of room-temperature impact resistance of uPVC
compositions based on two copolymer resins, given in Table 19.4,
illustrates something of the effects on this property of the nature and
molecular weight of the resin.
TABLE 19.4
Influence of the Nature and Molecular Weight of the Copolymer Resin Used
upon the Room-temperature Impact Resistance of uPVC
PVC resin

VCNDC copolymer
(Breon CS 100/30)
VCNA copolymer
(Breon AS 70/42)

Relative
density

Specific
viscositya

K value

Impact
resistanceb
(J cm- 2 )

141

055

66

155

137

036

55

073

a 0.5% w/w in cyclohexanone.

In a modified Charpy test on notched specimens: the quoted values are

means over ranges representing considerable scatter of results.

856

B. J. Lanham and W. V. Titow

19.2 SOME MATERIAL PROPERTIES OF uPVC

Typical numerical values or value ranges for many properties of uPVC

materials are quoted in Appendix 3, together with corresponding
figures for pPVC. Further numerical data will also be found
throughout the book in connection with discussions of aspects of PVC
to which they are relevant (e.g. permeability of films in Chapter 12,
Section 12.4; effects of impact modifiers on the toughness and other
properties of uPVC in Chapter 11, Section 11.2; analogous effects of
fillers in Chapter 8; etc.). The data given in the present section are
offered as additional, complementary information, put forward by way
of general illustration or representative examples: in view of the great
variety of uPVC compositions and their derivative products a
comprehensive treatment cannot be contemplated within the space and
scope available.
PHYSICAL AND MECHANICAL ('SHORT-TERM') PROPERTIES

Many of these are represented, together with certain others, in Tables

19.5 and 19.6. Table 8.11 in Chapter 8 (Section 8.4.1) summarises
some typical properties of uPVC compositions reinforced with glass
fibres. In several of its properties uPVC approaches the so-called
engineering plastics (nylon, polyacetal, polycarbonate). The factors
which mainly restrict its use in 'engineering' applications are its
relatively low softening (and heat deflection) temperature and its
susceptibility to degradation by heat.
THERMAL PROPERTIES

Some of these are featured in Tables 19.5 and 19.6. The following
values have also been quoted 7 for We/vic (ICI) rigid PVC moulding
material:
Specific heat at 20C: 110 J kg- 1 (oq-l
Thermal conductivity at 20C: 017Wm- 1 COq-l
Approximate total heat (moulding): 270 x 106 J m- 3
ELECfRICAL PROPERTIES

Some electrical properties of two uPVC compounds, including some

effects of temperature, are illustrated by the figures of Table 19.7.

70 X 10- 5
Shore D: 85
002

5 x 10- 5

ASTM D 696
ASTM D 2240
ASTM D 570

73

77

140
6600
30
480000
11500
-

ASTM D 648
BS 2782

9500

490000
10500

139
6000

792
638
638
638
790
790
695

Injection
moulding:
general
purpose,
easY-flow b

D
D
D
D
D
D
D

Injection
moulding:
general
purposeQ

Compound type

ASTM D 256

ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM

Method of
determination

Breon RA 142/A (BP Chemicals International Ltd).

Ethyl 7042 (Ethyl Corporation: Polymer Division).
Ethyl 7020 (Ethyl Corporation: Polymer Division).

Relative density
Tensile strength (yield) (lbf in -Z)
Elongation at break (%)
Tensile modulus (lbfin- Z)
Flexural strength (yield) gbf in -Z)
Flexural modulus (lbf in- )
Compressive strength (lbf in-z)
Impact resistance, Izod
(notched, 1/4 in bar) (ftlbfin- 1)
Deflection temperature under
load (264lbfin- z stress) (0C)
Vicat softening point eC)
Coefficient of linear thermal
expansion (mm mm- 1 C- 1)
Hardness
Water absorption (24 h) (%)

Property and units

TABLE 19.5
Some Properties of uPVC Compounds for Melt Processing

71

17

63 X 10- 5
Shore D: 75
01

134
6500
30
400000
13000
375000

Extrusion:
high-impact
(for thin-section
products)C

VI
-J

00

:::.

"'-

;:s

l::>

'"3-.

"'tl
.,
.g

j:

~
"';::
:"::.
0

~
s
~
"';::
!:;'
"

"'tl
"<:::

"'-

~:

::I:l

.....
'0

ASTM D 2863

010 (020)
38"

60
R102-R113

6G--65
R115"

ASTM D 785

40-

77-83
015"

6(}...65
017"

ASTM 696
ASTM C 177

70"

8-18

134-136
6G-70
2-30
3,2-3,9
110"
32"
188

75"

137-1-45
7G-85
2-10
35-55
135"
40"
235

ASTM D 648

792
638
638
638
790
790

High-impact

0,7-3,0

D
D
D
D
D
D

Ordinary

upvc

ASTM D 256

ASTM
ASTM
ASTM
ASTM
ASTM
ASTM

Method of
determination

" Representative values (particular compounds).

b Homopolymer-eopolymer.
e Absorption after 24 h (ASTM D 570).

Impact resistance, Izod (notched)

(ft Ibfin- 1)
Deflection temperature under load
(264lbfin- 2 stress) (0C)
Coefficient of linear thermal expansion
(mm mm- t C- 1 X lO- S)
Thermal conductivity (W m- 1 K-')
Maximum temperature for continuous
service ("C)
Hardness (Rockwell)
Water absorption at equilibrium
(% at 20C (lOOOC
Oxygen index

Specific gravity
Tensile strength (lbfin- 2 x 10')
Elongation at break (%)
Tensile modulus (lbf in- 2 x 10")
Flexural strength (lbf in- 2 x 10')
Flexural modulus (lbf in- 2 x lOS)
Creep modulus at 1000 h" (lbf in- 2 )

Property and units

005 e
50"

90
Rl18-R120

38-65
014

1OG-105

2-3

152-157
82-85
8-15
4G-55
145-160
38-43

cpvc

80

70

000 (001)
17-18

R1G-R20

11-13
033--047

43--55

3--20

0941--{)965
3G-50
2G-8oo
06--18
3G-35
1G-20
40

HDPE

12-17
O 33--0 35

32-40

no break

091--{)93
1G-20
9G--650
02--{)4
1G-20
01--{)6
-

LDPE

000 (0'01)
-18

110
R8G-R110

68-110
010--{)22

55-60

2_lOb

090--{)91
3G-50
2G--600
1G-22
5G-80
17-25
60
(copolymer)

PP

105 (140)
-20

100
R3G-R118

6G-ll0
019--034

85-105

25-120

103--107
5,5-80
5-80
2G-40
6G-120
2G-35
172

ABS

TABLE 19.6
uPVC and Other Plastics Materials with Some Overlapping Applications (Especially in Pipes and Pipe Fittings)-A
General Comparison of Some Typical Properties
(Based in part on data from Refs 3 to 6)

;E

:::-J
C

:0::::

.,.,

s:>
;::

;:l

s:>
;::
;::s:>

t-<

00
1Il
00

19 Rigid PVC: Main Products-Production, Properties and Applications

859

TABLE 19.7

Some Electrical Properties of Two Rigid PVC Compounds (Breon RA 124 and
RA 170")
Volume resistivity
(Qcm)

Temperature
eC)

RA 124
23
40

60
80

90
100
aA

10
10
10
10
10
15

x 1014
x 1014
X

1014

x 1014
x 1014
x 1013

RA 170
10 X
25 X
70 X
20 X
90 X
50 X

1014
1013
1012
1012
1011
1011

Power factor at

Permittivity at

800 Hz

800 Hz

RA 124

RA 170

RA 124

RA 170

002
001
012
010
010
013

002
001
007
012
014
015

30
39
85
79
79

33
30
35
51
61
75

7-8

high-impact composition.

CHEMICAL PROPERTIES

These are discussed in Chapter 12 (Section 12.8), where data on

resistance of PVC to various chemicals are tabulated.
OPTICAL PROPERTIES

The light transmission characteristics of transparent uPVC materials

are similar to those of PMMA plastics. Compositions of high clarity
and 'sparkle' can be formulated (for use in, for example, the
production of transparent bottles or packaging films and sheeting).
Light transmission curves for clear and translucent (white) pigmented
uPVC (mass-polymerised resin) films, 0025 in thick, are shown in Fig.
19.2.
LONG-TERM MECHANICAL PROPERTIES

With the use of thermoplastics for engineering applications (i.e. ones

entailing service under stress, continuous or intermittent) now
widespread, their long-term mechanical properties-creep (including
creep rupture) and fatigue-have been extensively studied and the
results used to aid design, and prediction of behaviour in service.

Creep: Because of their viscoelastic rheological behaviour, polymers-and the plastics materials based upon them-are subject to creep,
i.e. increase of strain (deformation) with time under continued stress.
For a given polymeric material the creep strain will normally be the
higher the greater the applied stress, and the higher the temperature.

860

B. J. Lanham and W. V. Titow

100
A

80

..

c"60

o
"iii

III

'EIII
c

......~40
~

01

:J

20

o0""""'3~:--."L-,---0~''='5---0~"'="6---0~.=7---='0'-=8
WavlZllZngth.l!m

Fig. 19.2 Light transmission of O025-in uPVC films. A, Clear formulation; B,

translucent formulation (Ti0 2).
The creep rate-i.e. the slope at a given time of a plot of creep strain
versus time (cf., for example, Fig. 19.3)-ean also increase with
increasing temperature and/or stress. The creep strain or rate can
sometimes be influenced by other factors, e.g. relative humidity (which
can affect the moisture content of the material). For many thermoplastic materials the rate of creep can increase relatively suddenly after
remaining virtually constant for a considerable period under the same
applied load (cf., for example, the top curve in Fig. 19.4). Creep can
take place in any of the modes of deformation encountered by
polymeric materials in service, or employed in tests, i.e. tension,
flexure, compression, shear or torsion. Formal definitions of creep and
creep strain differ somewhat depending on whether the context is
scientific or engineering. 9 The 'engineering' type of definition is
favoured in standard plastics terminology, as represented by the
following versions.
Creep: 'The time-dependent strain resulting from stress'. 10
'The time-dependent increase in strain in a solid resulting
from force' Y

o~

I&l

>C

o
iii 30
c

Fig. 19.3

0'1

100

Time in Hours

'000

0'1

10

At 51C

100

Creep of a high-impact uPVC composition (Breon RA 170) at two temperatures.

10

50

5.0

60

60

1000

g;

i;

5"

'<:5

l:l.

;:s

l:l

~.

.g

j:s

g.

~~

1.:t

~
s
~

l:l.

~:

'0

......

862

B. J. Lanham and W. V. Titow

300kglcm 2

(42661bl i,;2)

100kglcm 2

(1422 Ibl i,;2)

1
10- L....,--...&.....,---'-:,..-----'-:----.J..,,---.....L..::,..----J

10- 2

10- 1

100
101
10 2
Timt und..r load, h

10 3

10 4

Fig. 19.4 Creep curves for a uPVC pipe composition at different loads.
Reproduced with permission from Ref. 8.
Creep strain: 'The strain at any given time produced by the applied
stress during a creep test'. 10
'The total strain, which is time-dependent, resulting
from an applied stress or system of stresses'. 12
'The total strain, at any given time, produced by the
applied stress during a creep test'. 13
Two further definitions are particularly relevant to data most
frequently quoted and used in connection with creep of thermoplastics.
Creep modulus: 'The ratio of initial stress to creep strain. It is given
by the equation Eo = alet, where a is the initial
stress in megapascals, and et is the creep strain at
time t,.10
'The ratio of applied stress to creep strain' .12
Creep rupture strength (sometimes called 'stress rupture strength'):
'(FL -2)-the stress that will cause fracture in a
creep test at a given time, in a specified constant
environment' .11
Early work by Turner 14 provided useful information on the creep of
rigid PVC at small levels of strain. The results showed, inter alia, that
the time at which the creep rate starts to increase sharply is dependent

19 Rigid PVC: Main Products-Production, Properties and Applications

863

on the heat history of the uPVC composition concerned. Later work by

Ogorkiewicz and Bowyer15 compared the tensile creep of rigid PVC
with that of some other thermoplastics: the findings indicated that at
low stresses and for relatively short times of their operation uPVC is
superior to polyacetal and polycarbonate, and that whilst it falls below
the performance of polycarbonate at higher stresses operating over
longer periods, some rigid compositions can still out-perform polyacetal. Some creep characteristics of uPVC are illustrated in Figs 19.3-19.5
and in Table 19.8.

Fatigue: Fatigue has been broadly defined 16 as '... the progressive

weakening of a test peice or component with increasing time under
load, such that loads which are satisfactorily accommodated at short
times produce failure at long times'. In the plastics context 'fatigue'
usually means dynamic fatigue, Le. fatigue resulting from the
application of periodically varying (cyclic) loads. Rupture (or other
failure) occurring as a result of fatigue under a steady, continuous
load, is-in relation to plastics, and especially thermoplastics-correctly termed creep rupture (or failure): the term 'stress
rupture' is also sometimes used. Two relevant standard definitions 17
may be noted.
40--------,------.------,.-------,-

en

~~ 10F======::f~=""'---+. . . ==:;;;;::;;~~D===d
ell
ell

..,~
VJ

10

10

Time,h

Fig. 19.5 Creep of a uPVC pipe composition: stress/time relationship for a

given strain. A, 3% strain; B, 2% strain; C, 1% strain; D, 05% strain.

864

B. J. Lanham and W. V. Titow

TABLE 19.8
Typical Values of Applied Stress to Produce Given Average Rates of Tensile
Creep in Some Plastics Materials

(Based on data from Ref. 6)

Material

Polyester resin with 60% glass fibre

Polycarbonate, glass fibre reinforced
Nylon 6, glass fibre reinforced:
as moulded
conditioned
Polycarbonate
uPVC
Polyacetal
Q

Tensile stress (MPa) producing

average creep rate of

1157
441
108

549
461 Q
343Q
304
177

90

These figures illustrate the effect of moisture absorbed during conditioning.

Fatigue: 'The process of progressive localised permanent structural
change occurring in a material subjected to conditions
which produce fluctuating stresses and strains at some
point or points and which may culminate in cracks or
complete fracture after a sufficient number of fluctuations'.
Fatigue life: The number of cycles of stress or strain of a specified
character that a given specimen sustains before failure
of a specified nature occurs.

In plastics, fatigue can be aggravated by temperature rises under

cyclic loading due to the high mechanical hysteresis and relatively poor
thermal conductivity of these materials. In some cases fatigue failure
can actually be caused by heat effects in the polymeric material
(thermal fatigue). The technical aspects offatigue in plastics have been
reviewed by Andrews. 18 ,19 A more recent series of brief review
articles20 deals with research on, and tests for, fatigue in materials
generally.
The molecular weight (K value) of the PVC polymer is a significant
factor in the fatigue resistance of a uPVC composition (the resistance
increasing with the molecular weight). However, this effect can be
overshadowed by that of processing, poor processing reducing fatigue
endurance. As would be expected, the presence of cracks and other

19 Rigid PVC: Main Products-Production, Properties and Applications

865

faults in a uPVC product (or notches in a test specimen) also reduces

fatigue resistance.
In general, the fatigue behaviour and resistance of uPVC-in a given
deformation mode, and for a given molecular weight of the polymer
and constant processing effects-are influenced by the wave form of
cyclic load application,21,22 the magnitude and amplitude of applied
stresses, and the cycle frequency.
Note: At high frequencies, the already mentioned factors of high
mechanical hysteresis and poor thermal conductivity of the
material are brought into play: this can cause a substantial
temperature rise, with consequent ready failure of the
heat-softened material.

The general appearance of a fatigue curve for uPVC subjected to

cyclic loading at a relatively low frequency (of the order of 1 Hz) is
schematically illustrated by the solid-line curve of Fig. 19.6, with
indications of the effects of such factors as the wave form of load
application, increased cycling frequency, poor processing, etc.
The range of stress or stress amplitude values (ordinates) and the
number of cycles to failure (abscissae) within which the curve might

Number of cycles to failure

Fig. 19.6 Schematic representation of a typical fatigue curve for uPVC. a,

Shift with lower cycling frequency, or higher K value of polymer; b, shift with
poorer processing, or introduction of notches or faults, or change from
sinusoid to square wave form of loading.

866

B. J. Lanham and W. V. Titow

typically lie would be, respectively, about 10-60 MPa and 10-106
cycles. It is usual to present fatigue data for plastics in the form
illustrated by Fig. 19.6, i.e. as a plot of stress (or stress amplitude)
versus the number of cycles to failure. This is the form of presentation
used for results' obtained with a sinusoid loading wave form which is
widely employed in experiments. However, with a square-wave form
of loading, the data can also be represented on a stress-time basis, * for
direct comparison with creep failure ('static fatigue') curves obtained
for the same material under continuous loading. The strength of uPVC
is normally higher under the latter conditions, so that, for the same
composition, the creep failure curve will lie above the corresponding
fatigue curve, as has been shown by Gotham 21 for calendered uPVC
sheet, and by Gotham and Hitch 22 for rigid pipe material. Two further
general points (made by Gotham 21 ) may be noted:
(i) Under cyclic loading a ductile-brittle transition in the failure
mode of uPVC may be expected after relatively short times,
whereas it may not occur at all under continuous loading (any
failure being of a ductile nature).
(ii) Brittle fracture occurs under cyclic loading at stresses much
lower than the corresponding yield stress.
The role of plastic deformation in the failure of PVC under stress
has been considered by Gotham and Turner;23 some data on fatigue
and creep behaviour of uPVC, and a discussion of their significance in
predicting long-term service behaviour of pipe materials, have been
published by Gotham and Hitch,22 and Moore et ai. 24
Fatigue (as well as creep) of uPVC pipes (especially those operating
under pressure) is of particular interest because of their large-scale use
in a number of important application areas. Cyclic loading arises in
service, e.g. as fluids are pumped through the pipes, or in consequence
of repeated opening and shutting of valves.

19.3 uPVC PIPES

The acceptance of rigid PVC pipes in a number of important
applications, coupled with their increasing utilisation, has been

* By summing up the time under load in the fatigue experiment over the
number of cycles to failure, so that a figure for time to failure is obtained. 21

19 Rigid PVC: Main Products-Production, Properties and Applications

867

cardinally instrumental in the general growth rate of usage of uPVc.

The fact that the pipes are produced by extrusion is a substantial factor
in the importance of this technique in uPVC processing. The usual
feedstock for pipe extrusion nowadays is a powder blend (dry blend):
most large-scale producers prepare their own powder compositions on
site, and feed them pneumatically to the extruders, usually via a drier.
Extruder-mounted compounding units are also available (e.g. compounder DCE/MSG-Colortronics, USA), which produce dryblend
powder and feed it in directly without cooling, at temperatures up to
about Boac. This arrangement offers the possibility of the following
savings and improvements: lower energy demand in the extruder and
reduced heat history of material (as the stock does not have to be
completely reheated); increased throughput and reduced screw wear
for the same rate of rotation, in comparison with operating on off-line
compounded feedstock.

19.3.1 Types of uPVC Pipe

These are associated with the main application areas, as follows:
(i)

pressure pipes for potable water supply (including water

reticulation systems below and above ground);
(ii) pressure pipes for irrigation systems;
(iii) pressure pipes for cold water services (including services in
mines);
(iv) pressure pipes for gas supply;
(v) non-pressure pipes for sanitary pipework in buildings: discharge pipes-main and branch-for soil water (toilets) and
waste water (bathrooms, showers, sinks); house drains;
ventilation pipes-main and branch;
(vi) non-pressure pipes for underground sewerage and waste-water
systems;
(vii) non-pressure, permeable drainage pipes (land and road
drainage);
(viii) pipes for chemical plant installations;
(ix) rainwater goods (guttering and down-pipes);
(x) conduit for electrical wiring and cables.
Several grades of pipe and appropriate fittings (injection moulded
from suitable uPVC compositions) are available for use in each of the
above applications, according to the particular conditions and

868

B. J. Lanham and W. V. Titow

requirements: relevant international and national standards abound

(see Appendix 1, Section 6).
Even in non-aggressive environments, uPVC pipes are not normally
suitable for continuous service at temperatures above 60-65C. Rigid
CPVC pipes extend the service temperature range to about 90C (cf.
Table 19.6).
A few additional points may be noted concerning the performance of
uPVC pipes in some applications.
Pipes made of compositions unmodified for impact resistance have
been used for town or natural gas distribution systems operating at
pressures up to 1 bar. However, the possibility of brittle fracture
(especially at low temperatures), susceptibility to environmental stress
cracking under the influence of trace contaminants present in the
gas25-27 (see also Chapter 12, Section 12.5), and the desirability-in
some cases-of operating at pressures up to 4 bar, have limited (and in
some countries excluded) the use of ordinary uPVC pipes in this
application. Pipes of impact-resistant 'ductile' uPVC (modified with
chlorinated polyethylene or ethylene/propylene copolymers26 ) have
proved more resistant to environmental stress cracking, and of
satisfactory toughness: they are acceptable in some countries (generally
for use at pressures up to 1 bar), but are not used in others (e.g. the
UK) on any significant scale.
Like other plastics pipes, uPVC ones have considerable structural
flexibility, that is to say they are able to withstand substantial axial
deformation without fracture or gross permanent distortion, and-by
flexing under load-can 'shed' a considerable part by transmitting it to
the soil28 side-fill in a trench. Their interior surface is smooth initially
and to a large extent remains so in service, minimising 'furring' which
can greatly impede flow in non-plastics pipes (in metal ones the effect
can also be aggravated by corrosion)-cf. Table 19.9. These features
represent important service advantages of uPVC pipes over such
competitive products as pitch-impregnated fibre pipes, concrete pipes
(including asbestos/cement pipes) and clay pipes, used in drainage
(sewage and waste) systems and sub-soil drainage. As clean-water
conduits uPVC pipes score over the metal pipe alternatives in
corrosion resistance and ease of flow.
Note: For sub-soil drainage, non-porous pipes (uPVC, pitch-fibre)

pipes must be suitably perforated: the clay pipes used in this

application are permeable, in contrast with glazed clay sewage

19 Rigid PVC: Main Products-Production, Properties and Applications

869

TABLE 19.9
Typical Ease-of-flow Characteristics of Pipes (AU Values Relate to Flow
Through a New uPVC Pipe, Taken as Unity)
Pipe material

uPVC
Cast iron
Steel
Asbestos/cement

Relative ease of flow a

New pipe

After 30 years'
operation

1
087
093
1

093
027
029
073

% retention of
original ease of
flow

93
31
31
73

Based on the Hazen-Williams hydraulic roughness factors for 100-mm bore

pipes carrying water.

pipes. Particular effectivity has been claimed for uPVC

drainage pipes with perforations in the form of circumferential
slots. *
From the point of view of transport, handling and installation, the
much lower weight of PVC in comparison with other, non-plastics pipe
materials is a great advantage.
uPVC pipes can stand up to interior wear by some mineral process
slurries, e.g. a large-diameter pipe line has been used to carry away
slurry from a tin mine.
19.3.2 Production of uPVC Pipe
(a) Equipment and Process
A typical basic pipe extrusion set-up is schematically shown in Fig.
19.7, and sections of actual extrusion lines (twin-screw machines) in
Plate M. The elements of the pipe extrusion line are labelled in Fig.
19.7.
Note: An on-line inspection unit may be included to monitor the
pipe wall thickness. This is usually an ultrasonic scanner
continuously measuring the time lag between reflections of an
ultra-sound beam from the outer and inner surfaces of the
pipe. The unit may form part of a computerised control set-up

* Extrudex uPVC pipes-Turner and Newall Ltd, Ayecliffe, UK.

SAW
MACHINE

MARKING

OFF

HAUL

WATER
BATH

DIE AND
SIZING
DEVICE
EXTRUDER

HEATER
OlE BODY

BREAKER
PlATE

TORPEDO

BARREL

MELT FROM
- - THE EXTRUDE:R

Fig. 19.8 Typical pipe extrusion die. (Reproduced, with permission, from Ref. 8.)

APERTURE

MANDREL

OlE RING

THERMOCOUPLE

Fig. 19.7 A typical pipe extrusion line: schematic representation. (Reproduced, with permission, from Ref. 8.)

TABLE

DISCHARGE

o:E

:::j

:<:::

l::l..

l::l

So

l::l

t"'"

19 Rigid PVC: Main Products-Production, Properties and Applications

871

Plate M Pipe extrusion line (Superocla (Pty) Ltd, Rosslyn, Tv!., RSA). Top,
general view. Bottom, extruder (Cincinnati Milacron CM65 conical twin-screw
extruder), die, and spray cooling unit.

872

B. J. Lanham and W. V. Titow

which converts the readings into wall thickness and pipe

concentricity data (that may be displayed, printed out, and/or
stored on tape), and automatically applies corrections, via a
closed-loop system, by changing the haul-off speed or other
settings. With some control equipment it is possible to set the
controls for running close to the minimum wall thickness limit
for material economy. The Buhl controller* is an example of
such a complete control system, and the Rota-Sonict scanner of
a commercial thickness-monitoring unit.
Features of computer-aided automation of pipe production
(from raw materials intake and compounding to the monitoring of final product and requisite process adjustments) are
outlined in an article by Smith. 30
THE DIE

As shown in Fig. 19.8, a typical die for pipe extrusion consists of an

outer member comprising the die ring/die body assembly, concentrically enclosing a mandrel (with a torpedo-shaped end on the inlet side)
supported in position by three or more 'legs' of a 'spider'. The internal
annular gap between these two main components of the die is the flow
channel for the melt. Appropriately shaped and dimensioned, it tapers
conically towards the exit end, terminating in a parallel-sided annulus
defined by the mandrel body and the die ring: it is this annulus which
determines the cross-sectional dimensions of the tubular extrudate
issuing from the die and hence to a large extent also those of the
finished pipe, although the annulus is normally slightly oversized in
relation to the pipe dimensions required, to allow for the effects of
draw-down and of the sizing/cooling operation. At the spider, the die
channel is spanned radially, at intervals, by the spider legs. The
reduction factor in the cross-sectional area of the channel between the
spider and the die orifice (outlet), resulting from the conical taper,
may-as a rough guide-be about X 8: a high degree of reduction is
necessary to ensure that the melt is considerably compressed, and thus
enabled to 'knit' thoroughly, after being divided by the spider legs. To
the same end, the legs should be kept to a minimum size consistent
with securing the necessary strength and rigidity of the mandrel
mounting, and hence of the whole die assembly, and should be suitably
streamlined. Failure of the melt to re-unite properly after passing
* Buhl Automatic, 24 Topstykket, 3460 Birkeroed, Denmark.

t Sonic Instruments Inc., USA. 29

19 Rigid PVC: Main Products-Production, Properties and Applications

873

round the spider legs can result in the presence of weld lines in the
pipe, which may become failure sites under impact or pressure.
Note: This potential cause of weld-line formation does not present
any serious problems in good, modern pipe production
practice. In some extrusion operations even the possibility can
be eliminated by the use of a spiderless die. A commercial
example is the Cuvar* straight-flow die (with mandrel support
from the rear) originally designed for the production of
co-extruded plastics pipes. 31
Other considerations important in die design include the following.
The die 'geometry' is responsible for a substantial part of the
back-pressure generated in the extruder, and hence affects such
important process features influenced by the back-pressure as energy
consumption, extrusion rate, and the completeness (as well as the rate)
of gelation of the PVC stock. The constructional factors principally
instrumental in the generation of pressure in the die are (a) the
configuration and dimensions of the conically tapering section of the
channel, and (b) the length and cross-sectional area of the annulus: this
length is usually referred to as the land length, and its ratio to the
width of the aperture as the land length ratio. Values of 8-12 are fairly
typical for land length ratios of pipe extrusion dies. Obviously, the
smaller the cross-section and the greater the land length, the higher the
pressure developed.
The die design must promote generation of back-pressure at the
appropriate level: sufficient to secure the required throughput and
good gelation of the stock, but not so high as to result in excessive
generation of frictional heat in the material or cause abnormal wear of
screw thrust bearings. In relation to the throughput aimed at, the die
channel volume and configuration must be such that the dwell time of
the material in the die is optimised to ensure that the homogenised
melt is uniformly distributed in the parallel-sided annular gap which
imparts its shape to the emergent pipe.
The pressure that is likely to be developed in the die head can be
calculated if the melt viscosity of the compound at the extrusion
temperature, the die channel geometry and dimensions, and the output
rate are known. The calculation (especially with regard to the section
of the die channel between the spider and the annulus) is complex:
computer programs are available for use in working out the best die

* Cuvar Inc., Rexdale, Ont., Canada.

874

B. J. Lanham and W. V. Titow

configuration and dimensions to suit the combination of a particular

pipe size and output rate required.
Ideally, for optimum economy of operation and product quality at a
given throughput, each pipe grade (representing a given combination
of outside diameter and wall thickness) should be produced with a die
designed for that particular grade. However, this would entail a heavy
outlay on equipment not normally justifiable on grounds of overall
process economy. In practice modern die designs extend the effective
and economical working range of one die over a number (typically 3 or
4) of standard pipe diameters and wall thicknesses. In some cases the
adjacent pipe dimension ranges covered in this way by two dies can
overlap to some extent, so that for pipes of certain sizes either die can
be used. Equipment manufacturers provide charts and tables setting
out the effective working ranges and performance characteristics of
their dies.
SIZING (CALIBRAnON) SYSTEMS

Sizing is an operation of cardinal importance in pipe manufacture, in

that it finalises the bore, or the outside diameter, and circularity of the
pipe. It is performed on the hot tubular extrudate emerging from the
die orifice. The four main methods of calibrating uPVC pipe are as
follows:
(i) Mandrel sizing: An extended mandrel protrudes from the die and
is cooled with circulating water. This system yields pipes with very
smooth, calibrated bore, but can be troublesome to run and is less
versatile than the other systems.
(ii) Pressure sizing: In this system the tubular extrudate passes
directly into a metal tube (the sizing die or 'sleeve') having a bore
equal to the OD required for the finished pipe. Air pressure is applied
through the mandrel via one of the spider legs. The tube being
extruded is sealed by means of a plug attached by a wire to the
mandrel, and an internal pressure is built up sufficient to keep the pipe
pressed against the metal tube (about 2lbf in-2). The tube is usually
double-walled and cooling water is passed through the cavity. Such
sizing dies are usually quite short (6-18 in) and the pipe being extruded
passes directly from the die into a cooling bath.

(iii) Vacuum tube sizing: A similar arrangement to the pressure

19 Rigid PVC: Main Products-Production, Properties and Applications

875

sizing die is used, but in this method a vacuum is applied to the outside
of the extruded hot pipe via a number of small holes in the sizing tube.
This obviates the need for a sealing plug.
(iv) Vacuum ring and cooling tank: In this system the tubular
extrudate is passed through a vacuum ring (a short vacuum tube) which
effects the initial sizing of the pipe whilst cooling proceeds in a water
bath kept under reduced pressure. The atmospheric pressure inside the
pipe maintains its circularity during its passage through the bath.
Modern vacuum sizing tanks can handle a range of pipe sizes, up to
about 900 mm diameter. 32
As can be seen, mandrel sizing calibrates directly the bore of the
pipe, and the other systems, the external diameter (the dimension
particularly important vis-a.-vis pipe fittings and jointing requirements).
COOLING BATH

High-velocity, finely atomised water sprays are used as the cooling

medium in modern practice. Flooded immersion water baths are
suitable only at very low take-off speeds: otherwise inordinate bath
lengths would be necessary to achieve the requisite heat transfer. In
some modern take-off trains for the production of uPVC guttering
(e.g. the Technoform PPZ process by Reifenhauser) the extruded pipe
can be slit longitudinally and post-formed in the cooling tank, the two
halves forming guttering profiles of the desired shape.
HAUL-OFF (TAKE-OFF)

The main functions of this equipment are to pull the pipe away from
the die and through the sizing and cooling units at the required rate
and in such a way that it is kept straight during calibration and cooling;
it also feeds the cooled pipe forward to the marking and cutting
sections of the line. The haul-off is usually of the caterpillar or
pneumatic-tyre type, employing these elements to grip the pipe
securely and impart the necessary traction. The haul-off speed is
normally set slightly in excess of extrusion speed, to achieve the
requisite degree of draw-down. As is largely self-evident, the wall
thickness of the pipe will decrease with increasing draw-down
(increasing take-off speed), whilst the uniformity of take-off rate is an
important factor in wall thickness uniformity. For these reasons close
controllability and fine adjustment of haul-off speed are of cardinal
importance in the process.

876

B. J. Lanham and W. V. Titow

MARKING EQUIPMENT

This is normally a unit which prints on the pipe, at intervals, such

information as the manufacturer's trade mark and/or name, grade
designation, batch number, any standardisation mark, etc.
CUT-OFF EQUIPMENT

Pipes are usually cut by so-called flying saws. A flying saw is a circular
saw which travels along with the pipe as it makes the cut. The saw is
generally activated by a limit switch touched off by the end of the pipe
when a desired length has passed under the saw position. On large
pipes (diameter> about 150 mm) peripheral ('planetary') saws are
used, which do not cut right across the pipe but move around the
circumference, cutting through the wall: such saws may be associated
with a chamfering device.
Complete 'downstream handling' systems for pipe or profile
extrusion operations are available, comprising take-off and all
subsequent units (including on-demand cutters, transport, packaging
and automatic control equipment) for use on- or off-line. Automatic
perforating equipment may be used as part of an extrusion train for the
production of sub-soil drainage pipe. 32
For certain kinds of jointing (rubber-ring joints in common use in
some large-diameter pipe lines; solvent-cemented joints of the
spigot-and-socket type) a shaped socket is required at one end of a
length of pipe, with internal diameter equal to (or slightly greater than)
the external diameter of the pipe. Such sockets are produced by a
'belling' operation, in which the pipe end is heated to a suitable
temperature (quite commonly 160-165C), moulded on an expanding
mandrel of appropriate shape, and cooled. The operation may be
partly or fully automated. Some automatic belling equipment can
operate in-line with the extrusion train. 32
(b) Some Formulation Aspects

In very round figures, the cost of raw materials can amount to as much
as 60-70% of the total production cost of uPVC pipe. This is the main
reason behind the importance of material cost economy in pipe
compound formulation. At the same time, the fact that the fastest
practicable production rates are desirable for the process economy they
offer, imposes a need for considerable sophistication in formulation to
ensure stability, completeness of gelation and good rheological

19 Rigid PVC: Main Products-Production, Properties and Applications

877

behaviour in processing, as well as the requisite service properties: in

many cases these requirements preclude the use of the cheapest
formulation constituents, or introduction of cheapening fillers. The
most economical approach may involve formulating with not the
cheapest, but the most functionally effective additives for the PVC
resin, so that they may be used in minimum quantities. An illustration
of this is the trend towards increased effectivity, permitting low levels
of incorporation (fairly typically 03-04 phr) of organotin stabilisers
(as well as some antimony ones) used in uPVC pipe compositions in
the USA (ct. Chapter 9, Sections 9.4.2 and 9.4.3). Similar considerations are also behind the careful selection and balancing of lubricant
and lubricant/stabiliser systems for pipe formulations, including the
finer points of the merits in this connection of lubricating stabilisers
vis-a-vis combinations of non-lubricating ones with particular lubricant
systems.

Note: Some high-efficiency methyltin stabilisers combine relatively

moderate cost with functional effectivity-and a degree of
lubricity-in uPVC pipe compositions at incorporation levels
down to 025 phr in some cases (e.g. Mark 1939-Argus
Chemical, USA: a liquid methyltin).
The crucial importance of the lubricant system, well understood
from practical experience, is brought out by the results of an
experimental study by Zechinati et al. 33 In this, the effects of the seven
additives in the following American-type* formulation were investigated in terms of changes in extruder response (drive amperage,
thrust-bearing load, and output rate), Brabender torque curve, and
properties of pipe produced.
PVC polymer (pipe-extrusion grade)
Stabiliser: methyltin mercaptide

lOOpbw
03 phr

* A fairly typical basic formulation for a pressure pipe (non-impact-resistant

grade) in countries (or for applications) where lead stabilisers are permissible,
might be:
PVC polymer (pipe-extrusion grade)
Stabiliser/lubricant (co-precipitate): tetrabasic lead sulphate
calcium stearate
polyethylene wax
Filler: CaC03

100 pbw
12 phr
12 phr
0,1 phr
2-3 phr

878

B. J. Lanham and W. V. Titow

Lubricant system:
External lubricants: paraffin wax (MP 71 0c)
partially oxidised polyethylene
(MP 104C)
Internalluhricant: calcium stearate
Acrylic processing aid
Pigment: Ti02
Filler: CaC0 3

12 phr
02 phr
08 phr
10 phr
15 phr
25 phr

The investigators found, inter alia, that the greatest changes in

processing behaviour and product quality resulted from varying the
amounts and proportions of the components of the lubricant system.
19.3.3 Pipe Properties and Their Determination
The importance of some properties of uPVC pipes is relative to the
end-use: e.g. high bursting strength and fatigue resistance are required
in pressure pipes, but not in electrical conduit (which, on the other
hand, should have a relatively high degree of impact resistance), etc.
However, mechanical properties relevant to all applications are
strongly influenced by the degree of gelation of the pipe material. For
this reason, this structural characteristic may be regarded as the most
important single property of uPVC pipe. The mechanism and role of
gelation in extrusion of uPVC are discussed in Chapter 14 (Section 14.3).
In pipes the completeness of gelation is usually assessed by a solvent
immersion test (although inadequate gelation will, of course, also be
shown up in several mechanical property tests-e.g. those for impact
resistance, bursting strength, tensile strength, resistance to stress
cracking, and others). The solvents used in such tests are acetone (ISO
3472; BS 3505 and 3506; ASTM D 2152) or dichloromethane (KIWA *
KE 49; SABS 966). Typically, a section of pipe is immersed for about
30 min in the solvent and, after removal, examined (especially at the
edges) for signs of white efflorescence, delamination or disintegration
(respective manifestations of increasingly serious under-gelation). A
desirable refinement, employed in many versions of the test, is to cut at
the end of the specimen, across the full wall thickness, a continuous
taper of an acute included angle (say 5-10). This helps reveal any
layer-wise differences in homogeneity within the pipe wall. Examination under the microscope for grainy appearance and inhomogeneity
(frequently involving comparison with standard specimens or photo-

* Keuringsinstituut voor Waterleiding Artikelen, Delft, The Netherlands.

19 Rigid PVC: Main Products-Production, Properties and Applications

879

micrographs) is also often carried out as a means of (or aid to)

assessment of completeness of gelation.
Note: On the basis of a study of the mechanism of failure of uPVC
pipe materials, Marshall and Birch34 concluded, inter alia,
that the combination of the dichloromethane test on tapered
specimens with fracture toughness determinations provides a
good means of evaluating the completeness of gelation of such
materials.

The property tests commonly carried out on uPVC pipes for some
typical applications are cited in Table 19.10. Analogous or corresponding tests are also performed on the appropriate fittings. Some of the
tests are applicable only to the fittings or only to pipes (see the list of
relevant specifications in Appendix 1, Section 6.1).
As has been mentioned, resistance to creep (including creep
rupture) and fatigue are long-term properties very important in the
service performance of uPVC pipes operating under internal pressure.
Pipe design, and prediction of behaviour in service on the basis of
evaluation tests rely to a considerable degree on extrapolation-in
accordance with established procedures-of plots of relevant test data
(cf., for example, ASTM D 1598 and D 2837, and Refs 35 and 36).
Much is now also available in the way of actual results obtained in
long-term service. 35 ,37
Note: Evidence has been produced35 indicating that the bursting
strength of uPVC pipe can increase significantly after a long
period under steady internal pressure (as experienced in a
creep test or in service). It appears possible that such
improvement might be attributable to molecular orientation
effected by the prolonged stress, andlor possibly also to some
annealing effects.
19.3.4 Some Special Pipe Products
FOAMED uPVC PIPE
Rigid pipes with cellular (structural foam) walls are not produced or
used on a large scale because of the unfavourable difference in
mechanical properties in comparison with solid-walled pipes. However,
in some areas where the property requirements are less critical (e.g.
certain types of electrical conduit), or where the superior heat
insulation performance of cellular wall structure is relevant, foamed

V
V

V
V

v
v

Solvent immersion
(acetone or CH2 C12 )
Chemical resistance

Water-extractable content

Water absorption

v'

V
-

Vb

Vb

Vb

Vb

v
v
-

Rainwater
goods

Above-ground
sanitary piping

Sewerage
and drains

Industrial
uses

Application area of pipe

Cold-water
services"

Temperature cycling

Vicat softening point

Temperature of deformation
underload
Resistance to heat
Thermal reversion

Nature of test, or property

tested

Electric wire
conduit

TABLE 19.10
Tests Commonly Performed on uPVC Pipes for Various Applications

Decrease in length on
heating
Alternating hot and
cold water cycling
Test for completeness of
gelation
Weight change after
immersion in acid and
alkali, sometimes also
other reagents
In some cases checked
for Sn and Pb

Remarks

t-<

:::'1
0

:0::::

;:
l::l..

;::,

;::,

;:-

;::,
;:

00

1/

1/

1/

(tensile
impact
resistance in
some cases)

Including pressure piping in mines.

Check for blistering or splitting in the heat reversion test, or after special heating test.
Ball indentation (BS 4607).
Particularly for impact-modified grades.

Electrical insulation properties

Stiffness
flammability

Resistance to creep and creep

rupture under hydraulic
pressure
Suitability for end-beUing

1/

1/

1/

Resistance to flattening or
crushing
Bursting strength
Tensile properties
(of pipe material)

(often only
high-impact
grades)

Impact resistance d

v'

v'

v
v
v

Absence of splitting when

heated end expanded on
standard conical former

Normally tensile strength

and elongation

Usually a falling-weight
test method, but sometimes special tests
(ct. Chapter 11,
Section 11.2.2(a))

00
00

'"

;:

5"

l:l

'"'

~:::-:

;:
I:l..

l:l

'"
~.

'"'
S"
.?
'1:l
.,
.g

;::

I:l..

;j

'1:l

'C;"'

;::

I:l..

;j

'1:l

-.:::

'1:l

I:l..

~:

'0

'-

882

B. J. Lanham and W. V. Titow

pipes are of interest. They can certainly offer cost advantages over the
solid-walled pipes in view of the already mentioned high share of
material cost in the total cost of pipe production. A good summary of
the main aspects of production of foamed pipes (including formulation,
extrusion conditions, and economics) and their properties has been
published by Szamborski and Marcelli. 38
'HOLLOW-WALLED' uPVC PIPE
Sewer pipes have been produced incorporating closely spaced
longitudinal channels in the wall (formed by the extrusion die of
special design used to produce the pipe):* weight reduction of up to
about 30% in comparison with a solid pipe has been claimed, with
corresponding cost reduction of around 20%, and only moderate
sacrifice of the relevant mechanical properties. 39 This last feature-also
said to make the strength superior to that of foamed-wall pipes-has
been attributed to the fact that the structure of the pipe wall (as readily
demonstrated by a cross-sectional view) resembles a circumferential
assembly of 'I-beams' joined at the edges: this beam shape is well
known for its high strength-to-weight ratio.
HIGH-STRENGTH, ORIENTED uPVC PIPE
Controlled, partially biaxial molecular orientation induced in the wall
material by modifications of the production process involving a
stretching operation, can result in substantial improvements in bursting
strength, impact resistance and fatigue resistance of the pipe in
comparison with standard pipe of similar diameter and pressure rating
but nearly double wall thickness. The first commercially available pipe
of this kind was developed and produced in the late 1970s. t

uPVC PIPE
Large-diameter pipes for culverts and sewers, having a corrugated
wall, are manufactured (in PVC and other thermoplastics) by extrusion
directly followed by air-pressure expansion against corrugated sectional
mould blocks. In a variant of the process a continuously extruded strip
is helically wound and fused together to form a continuous pipe. The
patented* production process can also be used to make double-walled
CORRUGATED

* Wavihol pipe-Wavin Overseas BV, Zwolle, The Netherlands.

t Superpolyroc pipe-Yorkshire Imperial Plastics, UK.

:j: By

the Corma company (Toronto, Canada).

19 Rigid PVC: Main Producls-Producliun, Properlies and Applicalions

883

pipe (with a smooth inside wall and corrugated outside wall, or vice
versa), or conventional smooth-walled pipe.
RIBBED PIPE

Pipes with integral external ribs (circumferential flanges)* are

produced-in a range of diameters including ones of 1 m and over-by
a novel injection-moulding technique. The process has been called
'grow-moulding', because the pipe is made stepwise, each consecutive
section being moulded (over a mandrel positioned in the mould) so
that it welds onto the end of the previous section (left in the mould
when that section has been partially pushed out by an ejector ram). Of
the materials so far used in the manufacture of these pipes
(polyethylene, polypropylene, uPVC) , uPVC is-as would be expected-the most difficult to mould, especially in the large sections for
big pipes. The problem is eased somewhat by using foaming
compositions producing structural-foam pipe walls with relative density
down to about 1 (from about 14 for solid uPVC). The main general
advantage claimed for the ribbed structure is that the pipe's ability to
withstand external loads within the normal service range is on a par
with that of a conventional pipe containing over twice the amount of
material per unit length. Also, when laid in a back-filled trench, a
ribbed pipe has been found to be more resistant to deflection or
damage under an external load (such as might be imposed by the
passage of a heavy vehicle on the surface) than steel, or steelreinforced concrete sewer pipes of the same diameter. 40 Applications
of 'Ribstruct' pipes include non-pressurised sewers and effluent drains,
ventilation ducting, multi-core cable ducting, shuttering for concrete,
chemical silos, industrial box gutters, pneumatic conveyance of
materials, and others.
19.4 uPVC PROFILES
19.4.1 Main Types and Applications

Extruded profiles range from simple strips for use as beading or trim,
e.g. with PVC panelling, through more intricate cross-sectional shapes
(including channels and the like) for various trimming, finishing and
* Ribstruct pipe-Duropenta (Pty) Ltd, New Germany, RSA.

884

B. J. Lanham and W. V. Titow

mounting purposes, to very complex hollow-section multi-channel

products for use in modern uPVC window-frame systems.
Note: uPVC casings have been extruded over timber profiles for use
as window- and door-frame components, where the covering
serves as a permanent protective and decorative surface finish.
uPVC window-frame profiles covered by an integral layer of
acrylate resin have been produced by coextrusion (e.g. the
Trocal Colour profile-Dynamit Nobel, West Germany41).
The acrylate 'skin', which may be coloured, provides
protection, inter alia, against weathering.

Among the uses of solid (i.e. non-cellular) uPVC profiles,

window-frame systems are the fastest growing and possibly technically
the most interesting, representing as they do a combination of
sophisticated design, material formulation and extrusion technology.
Other products include components of demountable partitioning
systems (cloaking head channels and mitre pieces, angle trim and
skirting, some of which may incorporate a flexible PVC lip extruded
onto the rigid section to provide a dust and draft seal), solid rods and
various angle sections for general applications.
Cellular (structural foam) profiles have been replacing traditional
wood products in such applications as skirting boards and architraves;
furniture, boat, and caravan trim; and picture frames. Wood-flour
fillers are often incorporated in products of this kind. The foam density
and skin thickness is governed by the intended application and the
design of the profile. In general, the thinner the cross-section and
the greater the stresses and impacts expected in service, the higher
the density. The approximate overall density range within which the
cellular profiles fall is 0SD-O80gcm- 3 , with thick-sectioned purely
decorative beading fairly typically near the lower limit and, say,
relatively thin-section skirting board around O 70 g cm -3.
Note: Foam-filled uPVC window- and door-frame profiles (of
relatively simple cross-section) are produced by the 'Coexcel'
process, * in which a foaming composition for the core is
coextruded within the one forming the solid profile walls.

* Developed by GKN. Commercial 'Coexcel Thermal Clad' profiles manufactured by a subsidiary, Scope Aluminium Products Division of BKL
Extrusion Ltd, UK.

19 Rigid PVC: Main Products-Production, Properties and Applications

885

19.4.2 Production
The production process and typical extrusion line for profiles are
generally similar to those for pipes, the greatest degree of equipment
complexity and refinement being called for in the manufacture of
hollow multi-channel profiles of complex cross-section used for modern
uPVC window frames: sophisticated extrusion dies and calibrating and
cooling equipment (with the associated pumping gear) are employed in
lines for this product, which also include-as do extrusion trains for all
kinds of profiles-haul-off, marking, and cutting equipment. Whole
lines specially designed for window-frame profile are available from
manufacturers of this type of machinery, incorporating advanced
control systems and cutters. In the USA, production of window-frame
profiles from pellet stock on single-screw extruders is still common,
whilst dry blend extrusion on twin-screw machines is widely practised in
Europe. Typical production rate capabilities are in the range
15-3 m min- 1 , with pellet extrusion on single-screw machines near the
lower end. The main restricting factors on speed of production are the
sizing and cooling operations: both require elaborate arrangements and
sufficient time to ensure effective heat removal from the complex,
multi-channel profile, and its accurate dimensioning to close tolerances.
Foamed profiles are normally extruded from powder feedstocks to
avoid subjecting the blowing agent to extra heat processing at the high
temperatures involved in the melt-compounding of pellet feeds. Since
foaming takes place on emergence from the extrusion die (cf. Chapter
25, Section 25.2.1), a sizing die ('former') is used-normally positioned
in the cooling bath-to control the final size: the sizing operation also
determines the density of the finished profile. As a rough general
guide, the respective cross-sectional areas of the extrusion die orifice
and the sizing die should be in the same ratio as the product density
aimed at and the density of the solid (unexpanded) uPVC composition.
The density of the final product is also influenced by other factors, in
particular the distance the extrudate travels before entering the cooling
bath and sizing die. Torpedoes and spreaders used in the extrusion of
uPVC compositions into solid pipes and profiles are not normally
necessary with foaming compounds. A useful discussion of foamed
profile extrusion has been published by Davies,42 and one of methods
of production of structural foam in general (by extrusion and injection
moulding) by Harris. 43

886

B. J. Lanham and W. V. Titow

Among refinements available for modern extrusion lines are special

foam-faced traction belts in haul-off units, for delicate profiles,32 and
on-line tooling and fabrication systems (mounted on travelling work
tables), for automatically routering, milling, drilling, notching and
punching the moving profile before it is cut. 44
19.4.3 Some Formulation Aspects

In general, the processing considerations in the formulation of

compositions for simple profiles are similar to those arising with pipe
compositions. However, vis-a-vis the end-uses, virtually all profile
formulations must provide for some degree of impact resistance: in
many cases provision is also necessary for good resistance to
weathering.
Formulations for window-frame profiles embody the greatest degree
of sophistication, and also, incidentally, provide a good illustration of
the importance of harmonising the properties and effects of the
individual components. Broadly speaking, the formulations are
designed principally to satisfy the following cardinal technical requirements: good processing at fast rates of production, high impact
resistance of the product, and the highest possible degree of resistance
to weathering. Other considerations, including the usual economic
ones, are also involved. Window-frame profiles have been produced
for well over a decade, but the expansion in their use (notably in the
UK and the USA) is more recent. Development and improvement of
formulations is still going on and is far from complete, although some
very good compositions are available. The best current formulations
are, naturally, not made public by their users, but the general trends
are known, as are the main differences in the stabiliser systems
favoured in Europe (where the window profile technology originated
and first came into large-scale practice, especially in Germany) and the
USA. The subject is extensive, and only some salient points can be
indicated within the scope of the present section: useful general
reviews have been published recently dealing with several aspects in
reasonable detail. 45-47
There are three general formulation routes-based on three
different impact modification systems*-used to obtain compounds
* uPVC compositions without impact modifier have also been used (chiefly in
France), based on a Solvay suspension homopolymer. Whilst such compositions
give stiffer, harder and higher-softening profiles, they tend to be more brittle
than modified types.

19 Rigid PVC: Main Products-Production, Properties and Applications

887

with the requisite combination of good impact resistance and

weathering performance, coupled with adequate levels of other
relevant properties (including sufficiently high softening point and
temperature of deflection under load; low thermal expansion; and
good processing characteristics).* These approaches are represented by
the following types of composition.
(i)

Compositions modified with EVA copolymers, commonly graft

copolymers of EVA and vinyl chloride (e.g. Levapren-Bayer;
Elvaloy-Du Pont).
(ii) Compositions incorporating conventional acrylic impact modifiers (e.g. Aeryloid KM 323 B-Rohm and Haas), or ones
modified with acrylatet/vinyl chloride graft copolymers (e.g.
Vestolit P1982K-Hiils, or Vinnol K-Wacker Chemie).
(iii) Compositions modified with chlorinated polyethylene (e.g.
Hostalit Z-Hoechst).

The stabiliser systems commonly used in Europe in window-frame

compositions are BalCd combinations (often selected liquid grades, for
ease of processing) usually incorporating also some dibasic lead
phosphite, or all-lead systems, again normally including dibasic lead
phosphite. In the USA organotins are employed-ehiefly methyltins,
but also butyltin and some estertin stabilisers. Whilst one of the
cardinal criteria for the use of the particular impact modifier types is
that they do not significantly impair weatherability, the stabilisers are
certainly chosen with a view to enhancing this important property: the
objective is also further promoted by incorporation of titanium dioxide
(typically about 4-12 phr, depending on the stabiliser-Iower proportions with the BalCd/Pb and all-lead systems, highest with organotins).
Acrylic processing aids are also used: e.g. the well-known Aeryloid
K120N or K125 (Rohm and Haas Co., USA), sometimes in
conjunction with a lubricating grade (e.g. Aeryloid 175). Lubricant
systems vary: some involve calcium stearate for internal lubrication,
and a wax, e.g. paraffin or ethylene bisstearamide ('bisamide').
* An example of some property levels acceptable in practice is provided by
values for an industrial powder compound (RP lDO--Conoco Chemicals Co.,
USA) claimed to meet the specification for rigid PVC compound of the
Window and Door Committee of the SPI. 48 Tensile strength, 6200 lbf in -2;
tensile modulus, 329800 lbf in -2; Izod impact resistance, 20 ft lbf in- \ Vicat
softening point, 82C; deflection temperature under load (264lbf in -2 stress),
72C; Shore hardness, D 83; water absorption (24 h), 02%. (All results
obtained by the appropriate ASTM test methods.)
tUsually butyl acrylate.
.

888

B. J. Lanham and W. V. Titow

Calcium carbonate fillers are included in some formulations, the usual

claims being made regarding impact strength improvement with the
very fine grades normally used: low loadings (up to about 4 phr) are
favoured, but much higher ones (about 20 phr) are also occasionally
encountered.
The actual proportions of constituents in a particular formulation
depend on their nature. As regards the popularity of the three basic
formulation types, acrylic-modified compositions have been gaining
ground largely because of their tolerance for temperature and pressure
variation in processing and tractability at high production rates.
However, profiles made from this type of composition can have an
excessively shiny surface (this tendency may have to be counteracted
by incorporation of matting agents). Compositions with EVA-type
modifiers-for a long time the leaders in Europe-have been suffering
some loss in popularity in the face of claims, challenged by the
modifier suppliers, that these modifiers have an excessive plasticising
effect when present in amounts optimal for the required high impact
resistance (especially the relatively high proportions needed for this
purpose in cold climates) and that they are inferior to the best acrylics
in weathering performance: the generally somewhat better processing
of acrylic-modified compositions, especially at high production rates, is
100

, ...

,,

80

.
.......

II

r.

II

,,

"

60

',/"

.",.,,----..

',/

40

-/-

CPE modiflad

'../.....

20

/"

/"

/"

/"

/"

/"

/"',

'

........

- --....

..........
"

EVA modiflad

'<

Acrylata
mOdiflad

Unmodifiad

014.......==I:::::::t=::t=I:::::c::::c:c:~_==::x=6.........J...--I.......J
1965'66 '67 '68 '69 '70 '71 72 '73 '74 '75 '76 '77 '78 '79 'SO '81 '82 '83 '84 '85
Yaar

Fig. 19.9 Percentage shares of the three basic types of impact-modified PVC
window profile compositions in the West German market. (Reproduced from
Ref. 46 by courtesy of the editor of Plastics and Rubber Weekly.)

19 Rigid PVC: Main Products-Production, Properties and Applications

889

also a factor. The use of CPE-containing compositions-historically the

earliest type-has also been declining: need for close control to avoid
over-processing, and alleged susceptibility to yellowing of white
profiles in some circumstances, are usually cited as the main reasons.
Figure 19.9 shows the respective market shares of the three types of
composition in West Germany.
19.4.4 Testing and Specifications
The tests carried out on profiles are normally related to the end-use.
The properties evaluated may be broadly divided into material
properties (determined on standard specimens moulded from the
profile composition) and product properties, evaluated in tests on the
finished profile. The material properties frequently determined include
tensile and flexural strengths with the corresponding moduli, impact
resistance (commonly Izod or Charpy), softening point, temperature of
deflection under load, and coefficient of linear thermal expansion.
Product property tests often include those for impact resistance
(usually by a falling weight method), thermal reversion, and completeness of gelation (by solvent immersion), as well as any special
determinations particularly relevant to end-use.
Window profiles are also tested for property retention after heat
ageing and weathering as well as for weldability and weld strength.
Made-up window assemblies are subjected to the various tests
prescribed by relevant building specifications (e.g. tests for thermal
insulation, air and water ingress, sound insulation, etc.).
The national standards of direct interest to uPVC window profiles
are:
DIN 53 419 (1977) -see Appendix 1, Section 11.2.
NEN 7034 (1976) -Unplasticized PVC profiles for constructing
window frames, windows and doors in facades.
41-GP-19 Ma: 1978-Rigid vinyl extrusions for windows and doors.
Work has been under way since August 1980 on a British standard
for uPVC windows. Some of the numerical requirements included in
the draft standard prepared by the Plastics Windows Group of the
British Plastics Federation are listed in Ref. 45. A technical schedule to
BS 5750 Part 1 deals, inter alia, with the design and properties of
plastics windows, including the related hollow uPVC profiles. The
ASTM specification (D 3679) for uPVC siding is also of some interest.

890

B. J. Lanham and W. V. Titow

19.5 uPVC SHEET AND FILM

19.5.1 Terminology
The meanings of these terms in industrial usage and their standard
definitions are discussed in the introduction to Chapter 20. As pointed
out there, the common usage and standard terminology do not fully
coincide, the demarcation in thickness between thick film and thin
sheet is not very precise, and the description of certain kinds of thin
sheet as 'foil' is not free from ambiguity. However, if the context in
which they are being used is clear, the terms-though not associated
with strict, universally accepted thickness limits-are fairly consistent
and understood; with regard to PVC, common usage is reasonably in
line* with the following classification, which is adopted for the purpose
of this chapter.
She~
A

Aim

Foil

.....

----001.-'- ----)~f-oT,1---- r--r1'O--------..,-h.-~~

0075mm
(0003 in)

075mm
(003in)

19.5.2 Production
uPVC film is usually made by the blown-film extrusion process. Some
solution-cast film is also produced, for applications where high clarity
and/or freedom from orientation are important (see Chapter 24).
Sheeting is made by calendering, or by extrusion (from a flat sheet die
into the nip of cooling and polishing rolls-sometimes referred to as
extrusion casting). Calendering of PVC is discussed in Chapter 18: in
comparison with this process, extrusion involves lower equipment cost
* It may be recalled that the relevant British nomenclature standard puts the
demarcation point between PVC film and sheet at 0003 in (76Ilm), whilst
other standards give 250 Ilm as the upper thickness limit for film for all plastics
(ct. Chapter 20). It may also be noted that in industry the thickness range
for PVC foils is sometimes quoted as, or implied to be, 01--06 mm, or
01--07 mm.

19 Rigid PVC: Main Products-Production, Properties and Applications

891

and is more flexible, in the sense that calendering is best suited to long
runs on the same thickness and width of product. Very thick sheets (up
to about 25 mm and even thicker in some cases) for such applications
as, for example, glazing, chemical plant, etc., are made by compression-laminating a number of thinner sheets (see Chapter 20, Section
20.1).

Note: Equipment combining elements of both extrusion and

calendering is also available for the manufacture of uPVC
sheet (e.g. for thermoforming applications). In the 'Calandrette'* system, a planetary extruder homogenises the composition-at a melt temperature somewhat below that usual for
conventional extrusion-the extrudate is automatically cut
into lumps (to increase the specific surface for ease of
subsequent de-gassing) and dropped into the feed zone of a
vented single-screw metering extruder. This re-forms the melt
and extrudes it as a series of strands, which are spaced out
horizontally by an adjustable comb and passed on to form a
bead in the nip of calendering rolls (a stack of three, of
diameter up to 50 cm). The rolls form the bead into a
continuous web whose width (which may range between 60
and 140 cm) is determined by the number and original spread
of the strands. The spaced-strand form of feed to the rolls is
claimed to reduce the thermal stressing of the material, giving
a better flow, and to facilitate die adjustment.
Blown-film extrusion of PVC follows the general pattern of this type
of process. The melt is extruded through a tubular die, and the
resulting tube is taken off vertically upwards whilst being inflated-by
compressed air (which may be chilled for a better cooling effect) fed in
through the centre of the die-so that it forms an elongated bubble
closed at the top by the nip of a pair of rollers. Cooling air is also
blown through an air ring onto the outside of the tube above the die.
For a given die orifice size and extrusion rate, the final film thickness is
determined by the rate of take-off, and the amount of radial expansion
of the bubble (controlled by a sizing frame). These two parameters
also govern the degree of biaxial orientation undergone by the film.
The bubble is collapsed (folded flat) by a guide frame operating in
* EKK Kleinewefers, Bochum, West Germany.

892

B. J. Lanham and W. V. Titow

conjunction with the above-mentioned rolls at the top of the take-off

tower. The resulting flattened tube of film may be slit longitudinally
(commonly to produce two sheets separately wound up) or it may be
wound up directly as 'lay-flat tubing'.
An extrusion line for PVC sheet is shown schematically in Fig. 13.47
of Chapter 13. The essential elements of a set-up of this kind
are-from the extruder out-a sheet die, cooling and polishing rolls
(commonly a vertical stack of three, but up to five may be used), a
conveyor and haul-off unit (normally a relatively simple two-roll nip
arrangement) usually incorporating an edge trimmer for the sheeting,
and sheet collection equipment: for thick sheeting (say upwards of
about 15 mm) the collection equipment would normally be that shown
in the figure, i.e. sheet cutting and stacking units; thinner sheeting
would usually be reeled up on a winder.
The sheet die, connected to the extruder via an adapter, usually has a
manifold of the 'coat-hanger' type* and adjustable lips for control of
sheet thickness. For coextruded sheet the die is preceded by a
coextrusion block to introduce the input from the satellite extruder(s)
supplying the additionallayer(s).
Note: In the case of one kind of uPVC sheet (0,46 mm thick)
'capped', by coextrusion, with an acrylic layer (0,076 mm) for
decorative and protective effects, it was calculated49 that this
method of production could offer a material cost saving of up
to about 36% in comparison with extrusion lamination to
acrylic film.

Extrusion lines for blown film and for extrusion-cast sheeting are
available from several equipment manufacturers, e.g. inter alia,
Barmag (blown film, and sheeting, including coextruded productsEurope and USA), Francis Shaw (blown film, and sheeting-UK and
Europe), Kestermann (sheeting-Europe), and Windmoler and HOlscher (blown film-Europe and USA).
Apart from conventional thickness gauges (radiation, and other
types) long established in industrial use, advanced equipment for
continuous, on-line monitoring and-in some cases-automatic control
of product quality is available for use on film and sheet extrusion
trains. Examples include the following. The 'NC-P' thickness control

* The geometry of a coat-hanger die design with uniform flow rate and
residence time across the die width is discussed in a paper by Matsubara. 5o

19 Rigid PVC: Main Products-Production, Properties and Applications

893

system (Windmoler and Holscher, West Germany and USA) for blown
film,51 utilising IR transmission as the property monitored, and
automatic adjustment of individual cooling sectors in the ring to effect
corrections. The Sussex pneumatic system (Sussex Instruments Ltd,
UK) for continuous monitoring of film or sheet thickness 52 with a
feedback control loop operating on the extruder or line speed controls.
The 'Intec 500' laser-based inspection system (Intec Corp., USA)53 for
detection of defects (fish-eyes, gels, wrinkles, streaks, holes, contaminants, and surface imperfections). Sheet or film profile control
systems,54,55 which-like that forming part of the 'Profitmaster 5510'
extruder control system (LFE Corp., USA)-eouple detection of
irregularities in profile with automatic correction through adjustment
of the sheet die lip. Microprocessor-based systems for web width
control are also available, e.g. the 'Sigmat 770' system (TMS Systems
Ltd, UK), originally offered for blown film of width up to about 10 m.
19.5.3 Applications and Properties

The main uses of thick uPVC sheet are mentioned in Chapter 20. The
applications as cladding may be considered to encompass both sheet
and profile, in that some cladding systems involve the use of panels
(which may be of the pressed, and/or thermoformed56 variety) and
others of extrusions narrow enough to be classed as profiles. The main
service performance requirements applicable to external cladding are
similar to those that window-frames have to meet, including good
resistance to impact and weathering. Similar formulating approaches
are used (d. Section 19.4.3 above), with acrylic and chlorinated
polyethylene impact modifiers popular in formulations.
Note: Particularly good performance has been claimed57 for a type
of modified acrylic impact modifier commercially represented
by Durastrength 200 (M & T Chemicals Inc., USA).
Some aspects of the service behaviour of external cladding are
related to the effects of processing. Apart from any detrimental effects
of incomplete gelation, shrinkage and surface distortion can take
place-in consequence of recovery of production-induced stresses-at
elevated temperatures resulting from solar heating. The surface
distortion (local rippling and bulging) is sometimes referred to as 'oil
canning'. uPVC materials with high enough heat distortion temperatures (say about 87C) tlre less prone to this effect. The stress

894

B. J. Lanham and W. V. Titow

relaxation behaviour can be studied and assessed by thermomechanical

analysis: the results can have practical relevance to selection of cooling
conditions in processing, or suitable annealing temperatures if such
treatment is being considered. 58
uPVC foils and films find their principal outlets in various areas of
packaging. Foils are used mainly in the production of thermoformed
packaging elements, e.g. support containers and trays for chocolates
and confectionery, blister (bubble) packs, boxes, etc.
Films of, typically, semi-rigid compositions are employed for
shrink-wrapping of a wide range of articles and goods.
Shrink-wrap films are stretched in production to effect various
combinations of longitudinal (machine direction) and transverse
stretch, suited to the requirements of the intended use. The objects to
be shrink-wrapped are first overwrapped or sleeve-wrapped in the film:
this is normally done on semi or fully automatic equipment. The
wrapping is heat-sealed, to form a closed bag, and the package is
passed through a heating tunnel ('shrink tunnel') where the stretch
imparted in production is caused to retract as the film reaches the
appropriate temperature (roughly corresponding to that at which it was
stretched), with the result that the film shrinks onto the contents. The
degrees of retraction built into the film are said to be 'balanced' if they
are the same in both directions. Fairly typically, shrink-wrapping films
may range in thickness between about 12 and 30 .urn. The temperatures
in the heating tunnel may be up to about 180C depending on film type
and thickness and the residence time: higher temperature settings are
needed with shorter times and/or thicker films. Some typical property
data for commercial shrink-wrap films are given, by way of illustration,
in Table 19.11.
The formulations for uPVC sheeting and film compositions are
legion, varying with the nature, production method and end-use of the
product. The following two basic types are mentioned purely by way of
general, illustrative examples.
uPVC foil for deep-draw thermoforming:
VCNA copolymer resin (low K value,
10% vinyl acetate)
Stabilisers: Ba/CdlZn
epoxidised soyabean oil
Lubricant: stearic acid

100
3phr
3phr

05 phr

BS 2782:1970-515B
BS 2782: 1970-515A

30/30

100-160

90
1

4500

40

39-58
150-200
230

Food items b
(including ones
for deep-freeze)

40/20
30/30
10/10

100-160

90
1

1700

25

54-64
150-200
100

Non-food
articlesC

10/10

40/20
30/30

100-160

90
1

4600

50

49-69
175-250
300

Heavier or
sharp-pointed
objects d

Typical wrapping application area

Based on data from technical and sales literature for Vinophane films (BCL Films Division, Bridgwater, UK).
b e.g. tray-borne or unsupported fruit, fish, meats (fresh or cooked), cheeses, bakery products, sandwiches.
C e.g. toys, games, cards, table mat or coaster sets, small textile items.
d e.g. cutlery, sharp-cornered toys, tools, stationery, clothing, household textiles.
e 25-llm film. f 19-1lm film. g 125-llm film.

Examples of available shrink characteristics:

LongitudinaVtransverse shrinkage (%)

Heat-sealing temperature range Cc)

BS 2782:1970-514A

Optical properties:
Gloss (%)
Hazeo(%)

BS 3177

ASTM D 882-67
ASTM D 882-67
BS 2782:1970-306F

Test method

Barrier properties: g
Water vapour transmission (at 25C, 75% RH)
(g m- 2 (24 h)-I)
O 2 transmission (at 21C, 44% RH)
(cm 3 m- 2 (24 h)-I atm- I)

Physical properties:
Tensile strength (MPa)'
Elongation at break (%)e
Impact resistance at OC (g(

Properties and units

TABLE 19.11
Some Typical Properties of Commercial Shrink-wrap PVC Films (Relative Density 13; Thickness 12-25 pm)Q

f2
U1

2
g"
a

l'>..
~

.g
...;:t.'"

l'>..
;:

"g.
:s
::p

"tl

l'>..

;:.;,
~:

.....
'0

896

B. J. Lanham and W. V. Titow

American-type cladding (siding) composition:

Homopolymer PVC resin (K value 66)
Stabiliser: a butyltin mercaptide
Impact modifier: acrylic type
(or chlorinated polyethylene)
Lubricants: calcium stearate
paraffin wax (MP 74C)
fatty acid ester
Pigment (UV screen): TiO z

100
16 phr
6phr
19 phr
08 phr
09 phr
12phr

A basic formulation for extruded (blown) uPVC film is given in

Section 4.6.1(c) of Chapter 4.
Apart from the use of VCNA copolymers as the resin components
in some thermoformable sheet compositions, two copolymers of vinyl
chloride find their way into certain packaging films. Vinyl chloride/
propylene copolymers have been used (for their greater ease of
processing-d. also Chapter 1, Table 1.2) in films for food wrapping
(especially for fresh meat) and in over-wrap films for cigarette
packets. 59 Vinyl chloride/vinylidene chloride copolymers are used as
components of some packaging films where very low permeability is a
requirement (see also Chapter 1, Section 1.5.2). Laminated sheets of
polyvinyl fluoride and PVC have been used in the production of
vacuum-formed containers for some packaging applications where the
superior barrier properties and stability of PVF were of particular
benefit. 59
Many national and international standards relating to uPVC sheet
and film are listed in Section 5 of Appendix 1. An ISO standard for the
designation and classification of PVC film and sheeting is in
preparation. *
19.6 GRAMOPHONE RECORDS

Gramophone records are one of the only two uPVC products of

industrial significance to be manufactured by compression moulding
(the other being pressed sheets).
The dominant requirements for record compositions are reasonable
* ISO draft proposal 6236: Plastics-PVC film and sheeting-Part 1: Designation.

19 Rigid PVC: Main Products-Production, Properties and Applications

897

rigidity and high compositional homogeneity of the product, combined

with ease of flow in production. The latter two requirements are
dictated by the need for the best possible replication of the intricate
groove pattern of the record mould, necessary for fidelity and good
quality of sound reproduction. For the same reasons it is important
that the polymer should be free from fish-eyes and particulate
impurities, and the carbon black used as the pigment (as well as all
other formulation components) should be well dispersed with no
coarse aggregates of particles, lumps, or other inhomogeneities, for
maximum freedom from surface defects. The frictional characteristics
of the composition must also be such as to ensure freedom from 'hiss'
in playing, and smooth running of the stylus generally-this, as well as
the processing characteristics, are factors in the choice of lubricant.
To meet this combination of requirements, record compound
formulations are based on a high-purity grade vinyl chloride/vinyl
acetate copolymer of a low K value and vinyl acetate content of about
15%-say Breon AS 60/40 (K value 47-50), or Corvic R46/88-with
the minimum number and amounts of additives. An example of a basic
formulation is given in Chapter 4, Section 4.6.5: this example shows
the use of a lead stabiliser-other stabiliser systems are also employed
(liquid ones for best melt flow and completeness of dispersion), e.g.
calcium stearate/antimony mercaptide (see Chapter 9, Section
9.4.3(b)). Melt compounding is invariably used. The original processstill practised in some places-involves an internal mixer~ mill~
extruder sequence to produce pelleted compound from the formulation components; a weighed amount of the pellets is fluxed to form
a coherent, hot slug, which is fed to the mould and pressed into a
record with little or no flash; the moulding is briefly pre-cooled in the
mould, and cooling completed (in an air stream) after removal. A
typical slug temperature would be 165-170C, and mould temperature
about 95C. Flow behaviour of the compound is checked with a
plastometer to ensure uniform quality. In more modern versions of the
process a dry blend is melt-compounded in a compounding extruder,
and metered portions of the melt fed to the mould.

19.7 INJECTIONMOULDED uPVC ARTICLES

These are mainly fittings for pipe systems of various kinds. Some other
mouldings are mentioned in the summary review of PVC products in

898

B. J. Lanham and W. V. Titow

Chapter 26. Injection moulding of uPVC is discussed in Chapter 15.

An example of a basic formulation for injection-moulded pipe fittings
is given in Section 4.6.7(a) of Chapter 4.
The fine structure of uPVC injection mouldings is influenced by the
moulding conditions in a way generally similar to that observed with
other materials. For example, a study by Copsey and Gooding60
indicated a 'skin-and-core' structure, (with some molecular orientation
in the skin and little in the core), increasing density of the mouldings
with higher melt temperatures and injection rates, and a correlation
between the processing conditions and shear moduli of the mouldings
(see also Section 15.3 of Chapter 15, and Section 1.5.1 of Chapter 1).

REFERENCES
1. Jacobson, U. (1959). Brit. Plast., 32(4), 152.
2. Corvic Vinyl Chloride Polymers (1982). Technical publication of AECI
Chlor-Alkali and Plastics Ltd, Johannesburg, RSA.
3. Howie, J. A. (1971). Chem. Brit., 7(10), 428-33.
4. Mining: Why PVC Now? Technical booklet; AECI Ltd, Plastics Division,
Johannesburg, RSA.
5. Properties of Plastics (1976). Technical booklet, Shell Chemicals UK Ltd,
London, England.
6. Titow, W. V. and Lanham, B. J. (1975). Reinforced Thermoplastics,
Applied Science Publishers, London.
7. Plastics: The Principles of Injection Moulding. ICI Technical Service Note
G103 (2nd Edn), ICI Plastics Division, Welwyn Garden City, Herts,
England.
8. Press, J. B. and Trebucq, D. A. (1977). In Developments in PVC
Production and Processing-i, (Eds A. Wheelan and J. Craft), Applied
Science Publishers, London, Ch. 9.
9. Handbook of Plastics Test Methods (1981). (Ed. E. Brown), George
Godwin Ltd and The Plastics and Rubber Institute, London, 2nd Edn,
p.189.
10. ISO 899-1981. Plastics-Determination of tensile creep.
11. ASTM E 6-81. Standard definitions of terms relating to methods of
mechanical testing.
12. BS 4618. Recommendations for the presentation of plastics design data. Part
1: Mechanical properties. Section 1.1: 1970: Creep.
13. ASTM D 2990-77. Tensile, compressive, and flexural creep and creep
rupture of plastics.
14. Turner, S. (1964). Brit~ Plast., 37(6), 322-4, and (12), 682-5.
15. Ogorkiewicz, R. M. and Bowyer, M. P. (1969). Brit. Plast.. 42(9), 125-8.
16. Bucknall, c., Gotham, K. V. and Vincent, P. I. (1972). In Polymer
Science, (Ed. A. D. Jenkins), North Holland, Amsterdam, Vol. 1, Ch. 10.

19 Rigid PVC: Main Products-Production, Properties and Applications

899

17. ASTM E 206-72 (Reapproved 1979). Standard definitions of terms relating

to fatigue testing and statistical analysis of fatigue data.
18. Andrews, E. H. (1968). In Testing of Polymers, (Ed. W. E. Brown),
Interscience, New York, Ch. 6.
19. Andrews, E. H. (1973). In The Physics of Glassy Polymers, (Ed. R N.
Haward), Applied Science Publishers, London, Ch. 7.
20. 'Spotlight on fatigue' (7 brief papers by different authors), ASTM
Standardisation News (1980), 8(2), 8-27.
21. Gotham, K. V. (1974). In Thermoplastics Properties and Design, (Ed. R.
M. Ogorkiewicz), John Wiley and Sons, London, Ch. 4.
22. Gotham, K. V. and Hitch, M. J. (1975). Pipes Pipelines Int., February,
pp.10-17.
23. Gotham, K. V. and Turner, S. (1973). Polym. Engng. Sci., 13(3),113.
24. Moore, D. R, Gotham, K. V. and Hitch, M. J. (1978). 'The mechanical
properties of PVC and how these are influenced by changes in processing,
formulation and polymer type', paper presented at PRI International
Conference on PVC Processing, Egham Hill, Surrey, England, fr-7 April,
1978.
25. Benton, J. L. and Brighton, C. A. (1965). IGE J., March, pp. 185-202.
26. Benjamin, P. (1979). Plast. Rubb. Int., 4(5), 269-73.
27. Swiss, M. (1976). Plast. Rubb. Wkly, 17th September, pp. 33-4.
28. Stephenson, D. (1979). Pipes Pipelines Int., December, pp. 9-17.
29. Cist, J. D. and Smith, J. G. (1978). 36th ANTEC SPE Proceedings, pp.
548-50.
30. Smith, M. (1976). Plast. Rubb. Wkly: 24th September, pp. 25-7; 1st
October, pp. 1fr-17; 8th October, p. 29.
31. Anon. (1981). Mod. Plast. Int., 11(11), 35.
32. Smoluk, G. R (1982). Mod. Plast. Int., 12(11),44-7.
33. Zechinati, J., Harvey, B. and Despain, C. R (1978). 36th ANTEC SPE
Proceedings, pp. 740-4.
34. Marshall, G. P. and Birch, M. W. (1982). Plast. Rubb.: Process. and
Appln, 2(4), 369-79.
35. Hucks, R. T. (Jr) (1981). AWWA J., July, pp. 384-<:i.
36. Janson, L.-A. and Valimaa, P. (1973). Pipes Pipelines Int., January and
February.
37. Gaube, E., Diedrich, G. and Miiller, W. (1976). Kunststof!e, 66(1),2-8.
3:. Szamborski, E. C. and Marcelli, R A. (1976). 34th ANTEC SPE
Proceedings, pp. 324-6.
39. Anon. (1976). Mod. Plast. Int., 6(10), 22; and Plast. Rubb. Wkly, 16th
July, p. 8.
40. Anon. (1979). Prospect (AECI Quarterly), 18(3), 2-6; and private
communication from K. R Hart, Research Director, Duropenta (Pty)
Ltd.
41. Anon. (1976). Brit. Plast. Rubb., November, p. 70.
42. Davies, B. (1975). Plast. Rubb. Wkly, 3rd October, pp. 20-1.
43. Harris, W. D. (1976). 34th ANTEC SPE Proceedings, pp. 154-<:i1.
44. Anon. (1982). Plast. Technol., 28(4), 19.
45. 'Special Window Frame Feature', Plast. Rubb. Wkly, 6th June, 1981.

900

B. J. Lanham and W. V. Titow

46. Anon. (1982). Pfost. Rubb. Wkfy, 13th November, pp. 8-9, and 20th
November, pp. 8-11.
47. Neudell, D. H. (1982). Pfost. Techno!., 28(8), 31-5.
48. Anon. (1981). Mod. Pfost. Int., 11(9), 8 and 69.
49. Johnson, J. E. (1978). 36th ANTEC SPE Proceedings, pp. 36-40.
50. Matsubara, Y. (1979). Pofym. Engng. Sci., 19(3), 169-72.
51. Anon. (1981). Mod. Pfost. Int., 11(11), 11.
52. Anon. (1979). Pfost. Rubb. Int., 4(3), 115.
53. Anon. (1981). Pfost. Technof., 27(2), 15-17.
54. Rudd, N. E. (1978). 36th ANTEC SPE Proceedings, pp. 565-8.
55. Anon. (1981). Mod. Pfast. Int., 11(7), 10.
56. Acton, J. (1976). Pfost. Rubb. Wkfy, 23rd April, pp. 17-19.
57. Stoloff, A. (1979). Pfost. Engng, 35(7),29-31.
58. Changfoot, J., Dickson, A. G., Noel, F. and Stark, W. M. (1976). 34th
ANTEC SPE Proceedings, pp. 42-4.
59. Briston, J. (1976). Packag. Rev., 96(3),71-4.
60. Copsey, C. J. and Gooding, V. J. (1977). 'Effects of processing on the
morphology and properties of injection moulded PVC', paper presented at
the Institute of Physics Conference on Processing, Structure, Properties
and Performance of Polymers, University of Nottingham, July 1977.

CHAPTER 20

PVC Sheet and its Fabrication

W. V. Trrow

20.1 INTRODUCTION
Very few people nowadays can be unfamiliar with plastics sheet or
film. However, it may be of some interest to consider briefly the actual
meanings of these terms, and the significance of the distinction
between the products they designate.
The main English-language standards of plastics nomenclature l - 3 all
base their definitions of sheet on the obvious cardinal feature, viz. that
this laminar product is thin in relation to its length and width. Some2 ,3
also relate the term to a single piece of such product? which may have
been individually produced or cut from sheeting, the latter term being
defined as sheet in continous form (e.g. a long length supplied as a
roll 1,2). One of the standards 1 recognises synonymous use of 'sheet'
and 'sheeting'.
On the above basis a film is clearly a kind of sheet (or sheeting).
Indeed the only distinction between the two-both in standard
terminology and in common usage-is purely a matter of thickness,
and not actually precisely defined in industry. Thus whilst the general
sequence (in order of decreasing thickness) sheet~ thin sheet~ film is
universally recognised, the actual demarcatory thickness value between
thin sheet and film (or, for that matter, thin and thick sheet) is not
uniformly quantified and can vary in practice depending on the
material, the field of application and even the country concerned.
However, in an attempt at standardisation, the general thickness limit
below which a plastics sheet should be referred to as a film is set by the
three above-mentioned standards at 250.um (0010 in). The arbitrary
901

902

W. V. Titow

nature of this figure is actually pointed out in the ISO standard, l and
illustrated by a note in the BS specification to the effect that in the case
of some materials the term 'film' should be reserved for still thinner
sheet, and that specifically for unsupported rigid PVC film the upper
thickness limit should be 0003 in (about 76,um).
The term 'foil' is also sometimes applied in certain practical contexts
to plastics film and thin sheet materials, although it is not defined in
the nomenclature standards, only one of which2 mentions it as a
(discouraged) alternative to 'film'. Thus the thin films (plastics or
metal) used in the so-called hot-foil stamping method of surface
decoration (see Section 20.3.5(a) below) are commonly referred to as
foils: this is quite logical in view of the long-standing (and
standardised) relevant terminology for thin metal films* as well as
common usage in the packaging field where such films (employed e.g.
for wrapping chocolate) are known as foils. Less obviously logical (and
vis-a.-vis the accepted meanings just mentioned even somewhat
contradictory) but none the less fairly widely encountered in
commercial and industrial contexts, is the use of 'foil' for thick plastics
film or thin sheet (with PVC roughly 0003-003 in) for such packaging
applications as thermoformed insert trays, blister packs, etc. Finally,
the word foil occasionally crops up in contexts where it is clearly
employed as a loose synonym for plastics film in general.
Note: It appears possible that the use of 'foil' in English in the latter
two connotations may owe something to the influence of
relevant plastics terminology in other languages (ct. Foliethe correct German term for 'film', and French feuille for
'film' or 'sheet', in the plastics context).

PVC sheeting is commonly produced by calendering or extrusion.

Sheet for certain purposes (vacuum forming, special decorative surface
effects), and thick sheets (panels) are also made by compression
moulding: uPVC sheet up to about 25 mm thick can be produced in
* The four definitions of 'foil' in the Compilation of ASTM Standard
Definitions (3rd Edn: 1976) are, respectively, 'a thin sheet of a material,
usually a metal, not exceeding 0005 in in thickness'; 'a rolled product,
rectangular in cross section, of thickness less than 0006 in (0'15 mm)'; 'any
strip of sheet less than 0005 in (013 mm) in thickness'; and 'a term often
applied to thin sheet or strip usually 0005 in (0,13 mm) or less in thickness'.
This is in substantial agreement with the definitions of aluminium foil, and
copper and zinc alloy foil, in BS 4342: 1968.

20 PVC Sheet and its Fabrication

903

this way (by heat-laminating a number of thinner sheets under

pressure): the thick sheets are used for such applications as, for
example, the construction of fume scrubbers, chemical plant, covers
and linings for chemical storage or processing tanks, special trunking
and ducting resistant to chemical corrosion, and the like. Pressed sheet
reinforced with a long-fibre grade of chrysotile asbestos (e.g.
Duraform-TBA, UK) is used in some of these applications, as well as
for external and internal wall cladding of some industrial premises
(including flush wall lining of food factories), motorway signs, etc. The
nominal thickness range of rigid PVC sheet (produced by any of the
three main methods) covered by BS 3757: 1978 is 025-240 mm.
In the plastics industry the term 'fabrication' is usually understood to
cover a range of techniques by which such intermediate products as
sheet or rod are processed into finished products. It is a characteristic
feature of many fabrication techniques that, despite the wide extent of
automation, they often involve a certain amount of more or less direct
manipulation by an operative. Some fabrication techniques find their
main application where the dimensions of the finished product are too
large for production by other methods and/or where final operations
have to be carried out on site. Examples are production, by welding, of
chemical ducting from rigid PVC sheet; lining of chemical tanks (metal
or GRP) with PVC sheeting (which may have to be cut to shape, and
then joined by welding); and welding of PVC flooring or reservoir
linings (of flexible PVC sheeting).
Although such operations as cutting and welding (as well as printing)
are widely performed on PVC pipes, the greatest variety of fabrication
and surface decoration techniques is used in the processing of PVC
sheet materials in their various forms (unsupported sheet and film,
rigid and flexible; fabric-supported sheeting; sheet laminates, flooring,
etc.). It is for this reason that a discussion of the main fabrication
methods is coupled with a brief consideration of PVC sheet in this
chapter. Among sources of information relevant to fabrication, an
early review by Zade,4 and the Plastics Institute Monograph by
Estevez and Powell, 5 are still of some interest in addition to newer
publications on such topics as solvent welding6 and machining7 of
plastics (including laser machining8 ).
The nature, properties and applications of unsupported PVC sheet
and film are briefly dealt with in the next section, with reference to
some commercial products. The manufacture of sheet and film is
discussed in Chapters 18 (calendering) and 19 (extrusion); film casting

904

W. V. Titow

from solution is covered in Chapter 24. PVC layers (coatings) on fabric

support are dealt with in Chapters 22 and 25.

20.2 UNSUPPORTED PVC SHEET MATERIALS

There are many primary manufacturers of PVC sheet and film for use
in a variety of direct applications (e.g. tank lining, wall cladding,
glazing, roofing, with sheet; article and pallet stretch-wrapping with
film) or for further conversion (e.g. production of ducting and chemical
plant from rigid sheet; bags, blister packages, table cloths, decorative
self-adhesive surface coverings from film).
The main general types of product represented in the manufacturers'
ranges are:
-rigid PVC homopolymer sheet and film;
-rigid PVC copolymer sheet and film;
-plasticised PVC sheet and film;
-plasticisedlrigid PVC sheet laminates;*
-PVC sheet laminates with other materials (see e.g. Chapter 16,
Section 16.2).
Most types of sheet and film are available in clear and pigmented
grades, and many in various embossed finishes. Special products, such
as corrugated or wire-laminated sheeting, and uPVC sheeting laminated-or 'capped' by coextrusion-with relatively thin decorative or
protective layers (e.g. of acrylic polymers, for weathering resistance)
are also on the market.
Some characteristics and applications of commercial PVC sheet
materials are illustrated in Table 20.1 by reference to a number of ICIt
Darvic and Flovic products. Although the data quoted are not the

* This type of laminate was specially developed for lining metal tanks for heavy
chemical duty. Bonding large areas of rigid PVC sheet to mild steel presents
serious problems. However, when the laminate is bonded (by means of a
special adhesive) with its plasticised layer to the metal surface, and inter-sheet
joints are sealed by welding with a uPVC welding rod, satisfactory adhesion is
achieved, coupled with the overall effect of an all-uPVC internal tank
surface. 10
t Currently manufactured by a subsidiary, Weston Hyde Products Ltd, formed
by the recent amalgamation of Wallington Weston and the ICI PVC sheet
product manufacturing operation at Hyde.

20 PVC Sheet and its Fabrication

905

latest for these ranges,9 they provide a valid general indication of the
kind of materials concerned and their uses. The following may also be
mentioned by way of further examples.
Roofing and wall-cladding sheet: Sintaclad (ICI)-rigid corrugated
sheet for roofing applications* and for cladding of buildings exposed to
corrosive chemical atmospheres: good retention of light transmission
(several years in moderate climates) is claimed for the transparent
version (tinted in 'solar bronze' to reduce heat build-up). Both the
transparent and opaque versions have Class 1 ratings in the
spread-of-flame test of BS 476: Part 7. Biaxially oriented uPVC
sheeting (clear or translucent) developed by Solvay & Cie., Belgiumt
(based on their Bellvic emulsion resin grades claimed particularly
suitable for outdoor applications) offers improved impact resistance
imparted by the orientation, coupled with retention of this property
down to very low temperatures (-40C is claimedll). Cobex 1350
(Storey Bros,:j: UK)-sheet for interior wall cladding in food factories,
bottling plants and the like (meets the requirements of BS 3757, Part 1,
and BPFIBIBRA Code for food-contact materials).
Linings for chemical or food-storage tanks and reactors: Vybak
(Storey Bros, UK)-pressed PVC sheet (service temperatures up to
95C claimed for GRP-clad installations). Armodur (Societe la
Cellophane, France)-rigid PVC sheet made by pressing from
calendered sheeting based on a mass-polymerised resin grade. Telcovin
TL (Telcon Plastics, UK)-flexible PVC sheet.
Safety doors: Astraglass (Dynamit Nobel, West Germany and
UK)-flexible PVC sheet.
Sheet and film for thermoforming: Kydex (Rohm and Haas, USA:
European Licensee Mazzucchelli Celluloide, Italy)-acrylic-modified
PVC sheet. Fromopack (Wallington Weston, UK)-range of thermo-

* A summary of general data on the span of corrugated PVC sheeting in roof

construction in relation to maximum safe stress and deflection, and to modulus
reduction with temperature, has been published by Gamski. 12
t cf. also Oriex, biaxially stretched PVC sheeting of Tenneco Chemicals Inc.,
USA.
:j: Now part of the Wardle Storeys group.
See the earlier footnote on Darvic sheet products.

Limited number of colours. Scratched-plate

surface finish
Grey green

05-190mm
(002o.l in)

08-254mm
(&-1 in)

16-48mm
(rl,-rl,in)

CF standard grade

Industrial grade

Unplasticised/
plasticised grade
(laminate)

Nature and/or
colour'
Various colours; two
types of surface finish
(matt or polished)
Various colours; two
types of surface finish
(matt or polished)

Thickness range

05-12,7 mm
(0020-~ in)

Darvic sheet
Standard grade

Type and/or
grade

Main applications

More flexible than the

industrial grade

Tank lining

Contains no known tox- Interior lining (including

vehicles) and exterior
ic ingredients
cladding
High resistance to
weathering. Not recommended for foodcontact use
Not normally recomChemical plant
mended for foodcontact use (but a special, suitable grade can
be supplied)

Special features

TABLE 20.1
Some Properties and Applications of 'Darvic' and 'Flovic' PV-c Sheeting

:::J

:<:::

All standard grade colours

Up to 0'76mm
(0,003 in)

075-45 mm
(0030-0180 in)

Darvicfilm

Flovic sheet
(vinyl chloride/vinyl
acetate copolymer)

Various transparent col- High impact strength.

ours
Good weathering.
High clarity. Not for
food-contact use. Incorporates wire mesh
reinforcement

10-65 mm
(0040-0260 in)

Clear wire laminate

Glazing (including safety

glazing), lighting,
machine guards, windscreens, illuminated
signs
Glazing (including roofs)

Multi-colour, and opaque-clear laminates are available.

Stronger in longitudinal Packaging

direction. Suitable for
shaping, but not
vacuum forming
Opaque-white and some Contains no known tox- Vacuum forming food
colours
ic ingredients
packaging

Various transparent col- High impact strength.

ours
Good weathering.
High clarity. Not for
food-contact use

05-65mm
(0.020-0.260 in)

Clear grade

;:,

6"

l:>

F;.

0-

i;'

;:,
I:l..

l:>

'"~

v,
;:r-

."

I\,)

20 PVC Sheet and its Fabrication

909

formable packaging sheeting in clear, rigid PVC, for blister packs, skin
packs, etc. Vinophane (British Cellophane, UK)-clear PVC film for
various shrink-wrap packaging applications.

Road Signs: Pacton SQ (ICI)-impact-resistant rigid PVC sheet.

Interior wall coverings for buses and aircarft: Storeytrim (Storey
Bros, UK)-self-adhesive PVC sheeting. Kydex (some versions).
Bondene (Storey Bros, UK)-aluminiumJPVC sheet laminate.
Miscellaneous: PVC-Glas (Simona GmbH, West Germany)high-transparency natural and coloured sheets (in 1-20 mm thicknesses). Simona-PVC-EL antistatic sheet (surface resistivity down to
106 Q).
Information on manufacturers and suppliers of PVC sheet and film
for their numerous applications is available from various sources (some
mentioned in other connections in this book), including the following:

International: The current editions of:

(i) International Plastics Directory (Handbuch der Internationalen
Kunststoffindustrie), Verlag fur Internationale Wirtschaftsliteratur, Zurich.
(ii) European Plastics Buyers' Guide, IPC Industrial Press, London.
UK:

(i)

British Plastics Federation Buyers' Guides.

Plate N Applications of rigid PVC sheet. (Top) Processing-solution tanks in

an automatic colour film processor. Tanks fabricated from Darvic by Refrema
NS, Roskilde, Denmark. Darvic was chosen because it is unaffected by the
colour-processing chemicals and because it can be shaped, machined and
welded accurately to make strong, durable tanks which fit precisely into place
in the processors. (Courtesy of ICI Plastics and Petrochemicals Division and
Weston Hyde Products Ltd.) (Bottom) Instrumentation panel: complete wall
cladding of Duraform reinforced sheet with decorative (unreinforced) surface,
chosen-as a replacement for steel sheets-because of its combination of good
load-bearing and non-conductive properties. (Phillips Petroleum Company's
North Sea Gas Terminal at Bacton, Norfolk-courtesy of TBA Industrial
Products Ltd.)

910

W. V. Titow

(ii) The current edition of Packaging Review, IPC Business Press,

London.
(iii) The current edition of Buyers' Guide to Plastics Products used
in Agriculture and Horticulture, British Agricultural and
HOHicultural Plastics Association, London.
USA:

(i) The current edition of Modern Plastics Encyclopedia, McGrawHill, New York.
(ii) Films, Sheets and Laminates: Desk-top Data Bank, International
Plastics Selector Inc., San Diego, California.

20.3 MAIN FABRICATION TECHNIQUES APPLICABLE

TO PVC SHEET MATERIALS AND PARTS

20.3.1 VVelding
The international standard for plastics nomenclature l defines welding
as 'the process of uniting softened surfaces of materials, generally with
the aid of heat', and points out that in some countries the term
'sealing' (rather than 'welding') tends to be applied to processes in
which the surfaces of films are united by the application of heat and
pressure.
All the main techniques employed in the welding (as distinct from
bonding or cementing-see Section 20.3.2) of PVC involve the
application of heat to, or its generation in, the material at the site of
the joint. Hence the main factors instrumental in weld formation are
the welding temperature, amount of heat, duration of heating, and the
pressure applied. As in all processing of PVC, it is important to
minimise the risk of direct thermal degradation (which in this case
would be largely localised in the area of the welded joint) and
generally to ensure the minimum practicable increase of the heat
history of the material in this area. The recommended general
temperature ranges for welding rigid and flexible PVC are, respectively, 180-210C13 and 250-300c. l4 Below the lower limits of the two
ranges incomplete or faulty welds are likely, whilst exceeding the
upper limits can cause unacceptable degradation of the polymer.

20 PVC Sheet and its Fabrication

911

Hot-gas welding: In the main embodiment of this method the edges

of sheets to be joined are softened by a stream of hot air or other gas,
and a similarly heated filler rod (of the same or similar material) is laid
into the gap to complete the joint. In a variant of the technique,
known as hot-gas overlap welding, the welding nozzle is passed
between the faces of overlapping sheet pieces to be joined: no filler rod
is used, but the joint is made, between the heated surfaces in the
overlap area, under pressure applied manually or mechanically. A
development of the hot-gas method, called extrusion welding, employs
a heavy-duty hot-gas gun to pre-heat the work pieces, in conjunction
with a miniature extruder (comprising a screw and barrel, a reduction
gear box and an electric motor drive developed from an industrial hand
drill) which lays a bead of hot filler material into the gap of the joint as
the device is drawn along it. The ultimate strength of joints made
manually by any variant of hot-gas welding is cardinally dependent on
the operator's skill.
Hot-gas welding is used where fully mechanised or automated
techniques are not suitable because of the size and/or complexity of the
workpieces, or where the number of joints required is small and simple
enough to favour a manual method. Examples are seam welding of
PVC flooring, liners for refrigerated vans, chemical or food-storage
tank linings, wall linings in hospital operating theatres, industrial clean
rooms, food halls, etc.
Heated-tool (hot-plate) welding: In this method those surfaces of the
parts to be joined which are to form the joint interface are heated by
contact with the hot surfaces of a metal tool (often a relatively simple
platten with built-in electrical resistance heaters), and subsequently
pressed together to form the joint.
Indirect heated-element welding: In this method, which is normally
confined to the heat welding (heat sealing) of thermoplastic films and
thin sheeting, insulated* heating elements are applied (with simultaneous application of suitable pressure, either via the elements
themselves or by some other means) to the outer surfaces of the
workpieces to be joined, so that the corresponding inner surfaces

* The insulation (commonly PTFE) serves as a parting layer preventing

disruption (through sticking) or marking of the plastics surface by the hot
element.

912

W. V. Titow

participating in joint formation are heated indirectly, through the

thickness of the material. The elements may be heated only during the
bonding operation (thermal impulse welding) or may be constantly
maintained at the appropriate temperature (as in some continuous
film-sealinG operations).
Friction welding: The two variants of this method are spin welding
and vibration welding. In both the surfaces to be joined are softened by
heat generated when they are rubbed together, but in spin welding the
rubbing is actuated by complete rotation, and in vibration welding by
reciprocating, lateral displacement, linear or angular 15 (commonly at
about 100 cycles per second). In both variants the parts are ultimately
joined under pressure. Vibration welding is more versatile than the
spin variant which is normally restricted to parts of which at least one
(and preferably both) must be symmetrical and rotatable.
Although in principle friction welding is applicable to both rigid and
flexible PVC, in practice difficulties can arise with the latter, and the
technique is largely used for suitable uPVC parts.
High-frequency welding: In this technique, also known as dielectric
welding or radio-frequency (RF) welding, the bond areas of the parts
to be joined are subjected to an electric field of high frequency: this
induces molecular vibration causing internal heat generation within the
material. The contacting surfaces of the parts so heated are joined
under pressure (relatively light). It has been estimated 16 that over a
half of all the bonding in industrial conversion of flexible PVC film and
sheeting into products (see Section 20.3.1(c)) is carried out by the
high-frequency method, and that around 90% of all plastics products
manufactured with the aid of this technique are made of PVC.
Note: To be suitable for high-frequency welding, a thermoplastic
material should have a loss tangent (dissipation factor) of at
least 001 (at 1 MHz and 20e) to ensure sufficient heating in
a high-frequency field. Hence, among PVC materials, the
method is primarily applicable to those based on flexible
compositions (cf. loss tangent values in Appendix 3). It may
thus be regarded as mutually complementary with ultrasonic
welding, which is normally suitable only for rigid compositions
(see below).

20 PVC Sheet and its Fabrication

913

Ultrasonic welding: With regard to the bond-formation mechanism

this may be considered a special case of frictional welding. Intense
mechanical vibration of one of the surfaces to be bonded against the
other is caused by placing the material in contact with the 'sonotrode'
or 'horn' of an ultrasonic generator (often vibrating at 20 kHz, but in
general up to about 40 kHz). The vibration at the interface, which is of
relatively low amplitude, produces frictional heat, and softens the
surfaces which merge under applied pressure (normally maintained
throughout the welding operation). Possibly the greatest single
advantage of ultrasonic welding is the short bonding time required
(typically 0-1-1 s). The main limiting factors are the sound transmission characteristics of the material (which should be good, with the
least possible energy loss), its softening point, modulus, and coefficient
of friction. The technique is more suitable for rigid than flexible PVC
(in general, the softer the thermoplastic material the more difficult it is
to weld).
Ultrasonic welding equipment is supplied by some manufacturers of
high-frequency welders, and also by companies specialising in this line,
e.g. Ultrasonics Ltd (UK); Branson Sonic Power Co., their USA
associate; Dukane Corp. (USA); or Telsonic (Switzerland and UK).

Good summaries of most welding methods applicable to PVC are

given in Refs 13 and 14. Some of the techniques are also described in a
booklet published by the Institute of Welding in the UK (Data on the
Welding of Thermoplastics). Two DIN specifications list (with drawings
and brief explanations) respectively, the processes for the welding of
plastics (named in German, English and French)17 and their technical
principles. 18 The following standards are also of some peripheral
interest.
ISO 2553-1974. Welds-Symbolic representation on drawings.
BS 499. Welding terms and symbols.
Part 1: 1965. Welding, brazing and thermal cutting glossary.
Part 2: 1980. Specification for symbols for welding.
BS 2759: 1956. Glossary of terms used in industrial high-frequency
induction and dielectric heating.
Published reviews of welding methods for thermoplastics of interest
here include a relatively early one by Streese,19 and a more recent one
already referred to. 16 An excellent account of the use of welding

914

W. V. Titow

techniques (thermal-impulse, heated-tool, ultrasonic, and highfrequency welding) for the production of welded seams in coated
fabrics has been published by Koehler. 20
Analyses of some welding processes for thermoplastics in terms of
their principal parameters are given in papers by Frankel and Wang21
(ultrasonic welding), and Potente and Reinke 22 (heated-tool, ultrasonic, and friction welding).
Some of the welding methods and their applications in the
fabrication of PVC products are discussed further in the following
sections.

(a) Hot-gas Welding*

Mass production of articles from PVC often involves welding of
complicated shapes. This is usually best done by high-frequency
welding machines. Plastics film and thin sheeting (PVC, polyethylene,
polypropylene and others) are also commonly welded by the indirect
heated-element method. Hot-gas (in practice normally air or nitrogen)
welding remains a favourite method for batch production (especially
where the products are large and/or complicated), for many on-site
operations (particularly where those involve the jointing of sheet
materials to form continuous large-area layers, as, for example, with
PVC flooring), and for butt-welding of relatively thick sheets (as, for
example, in wall lining, or the production of tank linings). The welding
of pipes by the hot-gas technique in the construction of pipelines is also
practised. These, and many other applications stem from the general
versatility of the method and portability of the equipment. Inter alia, it
is of considerable practical significance that the rate, extent and degree
of heating of the material in the course of the welding operation can be
readily varied, for best results, in line with the operator's knowledge
and experience of what is required with a particular material in
particular circumstances. The factors directly relevant in this connection are the temperature and rate of flow of the hot gas, the distance
between the nozzle of the welding torch and the material, the rate of
formation of the joint (speed of the welding operation), and the
magnitude and method of application of pressure.
* This section is based in part on an earlier version-here extensively edited,
revised and supplemented-contributed to the previous edition by Mr R. W.
Berman of Welwyn Tool Co. Ltd, UK.

20 PVC Sheet and its Fabrication

915

WELDING TORCHES

A welding torch is basically a simple instrument, but a large range of

designs, developed for different purposes, is available. * There are two
general types: 'self-blowing' torches, and lightweight torches which
require an external gas supply.
Self-blowing torches, often called 'welding guns', are self-contained
in that they incorporate a motor and a small turbine, housed in the
handle together with a heating element. A typical modern version of
the latter is a ceramic block, pierced by a large number of channels
through which the gas (normally air) passes on its way to the nozzle,
and where it is heated by contact with resistance wires threaded
through the channels. The heating element is encased in an element
holder of special heat-resisting steel which can withstand temperatures
in excess of 600C and become red-hot without distortion. The steel
holder terminates in an air outlet nozzle. The nozzles, or nozzle/holder
assemblies, are normally exchangeable: designs include wide-slot and
multiple outlet varieties (the latter enabling a skilled operator to work
at considerably increased speed). It is usual to have a temperature
control (e.g. a ring switch) on the handle, whereby the temperature
can be varied (in some designs stepwise by activating consecutive
sections of the heating element). The motor-actuated turbine of the
welding gun delivers a steady air stream. In normal models the air flow
and pressure cannot be altered. However the flow is sufficient for all
common operations. It may be noted that it is the flow which is the
directly important factor. The operating pressure is normally relatively
low, say about 1-2Ibfin- z.
Torches of the other general type ('non-self-blowing') are frequently
referred to as 'welding pistols'. Their heating elements, element
holders and gas outlets are similar to those of self-blowing torches, and
in many cases these parts are interchangeable between the two types.
The welding pistol can be connected either to an air blower or to a gas
(air or nitrogen) bottle. The advantages this tool offers in some of its
industrial uses include the ability to employ an inert gas (nitrogen)
where oxidative degradation of the plastic undergoing heating is to be
minimised, and reducibility of the gas flow to levels below those
normal for the welding gun; most models incorporate a reduction valve
(in its simplest form a flow-restricting screw mounted in the handle)
* In the UK, for example, from the Welwyn Tool Co. Ltd, Rediweld Ltd, or
Goodburn Plastics Ltd.

916

W. V. Titow

and/or a gas flow meter. The gas should be free from oil, water and
other contaminants.
WELDING TECHNIQUE

The basic technique is similar to that of arc welding of metals, in that

the operator uses the hand-held gun to heat a welding rod and the
workpiece simultaneously, with the rod being drawn along the line of
the weld and part of the hot gas stream softening the plastics material
in front of the weld area. The operation thus involves suitable filling of
the gap between two workpieces (sheets) butted together. A strip of
the material concerned may be used as the welding rod, but special
extruded rods are available, and preferable for most purposes. In
contrast with metal welding, there is relatively little risk of fire,
explosion, or injury to the operator.
The welding rods used for most purposes are unfilled, but should
otherwise be as close as possible in composition to the material to be
welded: the right grades are normally obtainable from the material
producer or from suppliers recommended by him. In either case-and
particularly the latter-it is necessary to identify clearly (preferably by
sample) the material for which the rod is to be used. Rods for
industrial welding purposes (as distinct from floor welding) are
supplied in various cross-sectional shapes. The advantage of this is that
the groove (see further on) can be filled with one line of suitably
shaped (say triangular or trefoil) welding rod, where several lines of
cylindrical welding rod might otherwise have been necessary.
Floor-welding rods are normally plasticised and hence flexible. It is
for this reason that they are often referred to as 'welding cables'.
The materials (sheets, floor tiles, etc.) to be welded must be
prepared. With sheets of kin thickness or more, a single 'V' shape
groove of 60 angle is made, either by a hand tool or-for industrial
unplasticised material-with the aid of a grinding wheel and inclined
table. For plasticised floor tiles the groove can be produced by a
motor-driven chamfering tool. One version runs on four rollers, two of
which engage in the gap between the two sheets (and in the groove as
soon as the machine starts chamfering). This self-guiding arrangement
makes the use of a straight edge unnecessary. With thick sheets, or if
convenient generally, a double groove can be used. Before welding,
the sheet edges and the welding rod should be wiped with methyl ethyl
ketone or another suitable solvent.
As to the welding operation itself, a distinction may be made
between industrial welding and floor welding.

20 PVC Sheet and its Fabrication

917

INDUSTRIAL WELDING

Before the welding operation proper, it is advisable to tack the

material (normally relatively thick sheets or sections) together so as to
create a bottom to the groove. This is done with the aid of a tacking
jet which can be pushed onto the nozzle of the welding gun or pistol.
In the early welding method the welding rod was held in one hand
and the welding tool (pistol or gun) in the other, the rod being pressed
into the groove as the immediately concerned sections of both became
sufficiently softened by the hot gas. The method is known as the
'pendulum' method of welding because the hot-gas outlet of the tool is
swung up and down during the operation; it is still used for welding
difficult corners. In all other cases the welding is facilitated and
speeded up by the use of speed-welding nozzles (see Fig. 20.1). A
speed-welding nozzle is an attachment, push-fitting the end of the
welding tool, consisting of a sleeve ending in a tongue and a hot-gas
outlet. The sleeve holds the welding rod so that it is pre-heated, and
then pressed by the tongue into the heated groove. The use of this
attachment not only speeds up the welding, but in many cases enables
it to be performed with one hand. Speed-welding nozzles are available
for welding rods of various diameters and cross-sectional shapes (e.g.
triangular, trefoil).

Fig. 20.1 Speed-welding nozzles.

For plastics films and thin sheets, where the material is too thin for
grooving, overlap welding is used. This operation can be considerably
mechanised for many applications (e.g. production of tarpaulins, in situ
joining of films used as seepage barriers, etc.) and the mechanisation
adapted to so-called 'tape welding' in which the film edges to be joined
are butted together and sealed with special thermoplastic tape which
overlaps the joint on both sides.
The lining of a metal tank with PVC sheeting (which may be the
uPVClpPVC laminate previously mentioned) can be examplified by the
following sequence of operations.
(i)

Hammering out, grinding out, or filling-as appropriate-of

any dents, bulges, high points (e.g. welds) or depressions in the
metal.

918

W. V. Titow

(ii) Shot- or sand-blasting the surface, followed by de-greasing (e.g.

with trichloroethane).
(iii) Preparation of the sheet (including pre-shrinking by heating if
recommended by the supplier) and cutting to size.
(iv) Application of an appropriate adhesive (most manufacturers'
ranges-e.g. Bostic, 3M-include suitable compounds) to the
tank walls (in some cases also to the sheet) strictly in
accordance with the adhesive supplier's instructions.
(v) Attaching the pre-cut sheet to the walls: the usual order of
covering is sides, floor, and lip edges.
(vi) Hot-gas welding of all joints (butt and corner).
The completed joints of a lining should be checked for freedom from
flaws, cracks and other leak-promoting faults. This is usually done with
the aid of an electrical spark tester, obtainable from most suppliers of
hot-gas welding equipment and some general sources of industrial test
equipment.
For the production of PVC linings for reinforced plastics tanks, a
British Standard covering the construction of such vessels23 recommends a minimum PVC sheet thickness of 3 mm, and specifies that the
tensile strength across a weld should be not less than 90% of that of
the sheet itself. A corresponding figure, given in DIN 1693013 as the
general minimum 'valence ratio' for hot-gas welded joints between
rigid PVC sheets is 06 (i.e. tensile strength across the weld at least
60% that of the sheet), whilst ASTM D 178924 stipulates a general
minimum of 75%. The latter specification lists, and illustrates, the
main causes of poor welds.
FLOOR WELDING

This is carried out in premises with PVC tiled floors, especially where
considerations of hygiene make a continuous surface particularly
desirable, e.g. in hospitals. In essence, the operation consists in
grooving the joint lines between the tiles and sealing by welding in the
normal way. In manual operation the welding rod (welding cable) may
be fed and laid in with the aid of a feed roller, with the handle
hollowed out to take the cable, and a grooved wheel to apply it to the
groove. However, here too the process can be considerably speeded up
by the use of a speed-welding nozzle (suitable for the cable diameter
employed). A still faster rate of working is made possible by floor
seam-welding machines, which run automatically, following a groove,

20 PVC Sheet and its Fabrication

919

laying a weld, and shutting off upon reaching a wall, so that the
operator's function is reduced to moving the equipment over into
consecutive grooves, and general supervision. Welding rates of
30 it min- 1 are possible with this kind of automatic operation, if the
grooves are properly made, preferably by a mechanised chamfering
tool.
Felt- or foam-backed PVC flooring was originally welded from the
back, after chamfering away the backing layer. The modern method
permits the welding of such flooring in position, i.e. when stuck down
in the normal way. Exact chamfering with a motorised tool engaging in
the gap between the sheets enables a groove to be produced which is
accurately centred and of a depth so pre-adjusted that the felt or foam
layer remains virtually undisturbed. The welding can then be carried
out manually or with an automatic machine.
In all floor welding, the seam (original welding cable) will remain
protruding above the tile or sheet surface on completion of the welding
operation. These protrusions must be removed, to make the floor
surface flat and even. This can be done with a sharp knife ('spatula') or
another hand tool (e.g. a spatula fitted with a cable-cutting slide), but
is best accomplished with a trimming plane whose knives can be set to
cut no deeper than is necessary to ensure that the seam does not 'sink
in' afterwards.
(b) Extrusion Welding
This modification of the hot-gas welding method was developed in
Germany. The main general features of the extruder component of a
typical extrusion welder have already been mentioned. The second
main component of this tool is a heavy-duty hot-air gun (usually
mounted on the side of the extruder): this pre-heats the material in the
area of the joint to be formed as the tool is moved along the groove
and just before the nozzle of the extruder head lays-in a line of melt.
In comparison with conventional hot-gas welding, extrusion welding
enables welds to be produced in one operation where otherwise the
sheet thickness and width of groove would necessitate the consecutive
laying-in of several welding rods, and can give much higher weld
strengths. Heat degradation of the material can also be reduced with
this technique.

(c) High-frequency Welding

The principle of this technique has already been mentioned: Some of

920

w.

V. Titow

Plate 0 Autodex MK V automatic feed and RF welding unit, with standard

6 kW generator: 30 x 20 in (760 x 508 mm) overall working area; high-speed
automatic production, with manual option; platen pressure load variable
between 200 and 1500 lb (91-680 kg); indexing accuracy 05 mm. (Courtesy
Radyne Ltd, Wokingham, Berks., England.)

its features and applications are reviewed in Ref. 16. The appropriate
sections of the parts to be joined are subjected to an alternating
high-frequency field by positioning them suitably between two
electrodes. The induced internal molecular vibration generates heat
within the material which becomes softened to the point where it can
be welded under pressure. The electrodes may be flat or threedimensionally shaped, depending on the configuration of joint
required, and should be temperature-controlled so that they do not
become overheated (by heat transfer from the material) during
welding. In commercial equipment they also serve as the means of
applying pressure to the joint. Various arrangements and electrode
designs are used. For more efficient material heating (through
reduction of heat loss to the comparatively cooler metal of the
electrodes) thermal barriers are normally interposed between the

20 PVC Sheet and its Fabrication

921

electrodes and the work. Originally the material commonly used for
this purpose was a hard paper known as 'Pertinax', but a variety of
others have proved more successful, e.g. silicone-impregnated glass
fabric, PTFE sheet, etc.
The internationally recognised standard operating frequency for the
welding equipment is 2712 MHz, with a tolerance limit of only
06%. The narrow margin this leaves for variation necessitates a high
degree of built-in frequency control (which is reflected in equipment
cost), inter alia, to ensure (commonly through the use of auto-tuners)
that any change in capacity caused by reduction in the thickness of
material between the electrodes as fusion takes place in the course of
welding, does not result in frequency drift beyond the prescribed
limits. Purely from the technical standpoint, production may in fact be
improved by operating at frequencies higher than the standard (cf., for
example, the 50 MHz machines originally available from StanelcoThermatron Ltd*). The optimum power for welding depends very
much on the sheet thickness. In general, the thinner the material the
higher the power required to compensate for the proportionately
greater heat loss from the plastic to the metal of the electrodes (which
are colder than the plastic heated up in the course of welding). It is
because of this that at very low material thicknesses welding may not
be possible at all. The already mentioned use of thermal barriers is
aimed at reducing the heat loss and thus redressing the balance to
some extent. As an example, for film 0003 in thick, tOO MHz is
necessary, and the length of heating time makes little difference,
although it does, of course, above 0010 in. As a general, approximate
guide, 1 s may be regarded as about right for the heating time of films
up to 0005 in. For sheets about 0020 in thick (for example) a time of
6 s should be aimed at, although less would be preferable if the power
is available. The best seam is obtained by using a short time cycle
(excess will cause plasticiser loss and embrittlement), a light pressure,
a reasonable heat dosage, and electrodes with suitably radiused edges.
Sharp edges will cause a field concentration and overheating.
The nature of the compound influences the weld obtained. Metallic
particles and furnace blacks can give conducting paths and serious
troubles on thin sheets. Really first-class dispersion should, therefore,
be obtained if these types of fillers are to be employed. Generally, the
lower the filler content (including pigment) the better the result.
* Member of the International Group Wilcox and Gibbs Inc.

922

w. v.

Titow

Excess material can make welding more difficult and weak seams may
result. Highly filled cheap products should therefore be used with
caution, particularly with inflatable goods where good seams are vital.

Note: Arcing-a potential source of serious damage to the electrodes and danger to the operator-was a real possibility with
early versions of welding equipment, especially when processing thin films. In modern machines the hazard has been
virtually eliminated by the incorporation of arc-sensing units.
High-frequency welding machines are available from a number of
manufacturers. Stanelco-Thermatron (with its parent group) and
Radyne Ltd are among those whose equipment represents wide ranges
of size and power rating, and includes complete production lines, in
many cases incorporating also printing and other operations.
The products welded on the equipment typically include the
following: Blood-transfusion and other PVC medical equipment; liquid
packaging; clothing (including protective garments and rainwear);
footwear; stationery covers, folders and binders; book covers; fancy
goods; handbags; luggage; garden and other furniture covers; upholstery; inflatables; baby wear; pram covers; quilted goods; tarpaulins;
large welded sheets; car trim.
The welding press platen sizes range from, say, about 25 x 3 mm
(for welding blood-transfusion equipment) to 3 x 2 m (for inflatable
rafts), with generator power ratings of the order of 100 W at the lower
end of the range up to 100 kW at the higher end.
(d) Heated-tool Welding
As has been mentioned, in this method the surfaces to be welded are
heated by direct contact with an electrically heated element which may
be quite intricately shaped to give the type of weld required. In
practice the surfaces are actually pressed against the element
(pre-heated to the appropriate temperature), allowed to remain in
contact for the appropriate time, the heating element is withdrawn and
the surfaces are brought together under the appropriate pressure to
form a weld. It is claimed25 that heated-tool welding is one of the
quickest and most economical methods of heat-welding thermoplastics.
Apart from the properties of the material itself, the following points
are of crucial importance to the quality of the weld: the tool
temperature and surface condition, pressure during pre-heating, time

20 PVC Sheet and its Fabrication

923

of heating and tool withdrawal time ('change-over time'), welding

pressure, and the cooling rate and time.
Thermostatic control of the heating element is important for good
results. A popular form of heating tool is the heating mirror type
supplied, for example, in the UK by Bielomatik London Ltd, or the
Welwyn Tool Co. Ltd.
A good early outline of the heated-tool welding method has been
provided by Neubert 26 of Bielomatik Leuze and Co. (West Germany)
who, through their subsidiary Bielomatik London Ltd, supply what is
probably the biggest heated-tool machine range in the UK, with a
number of machines for the hot-welding of plastics sheeting, pipe and
the like.
Automatic welding machines specifically for the welding of PVC
window-frames are available (e.g. Urban AKS 3313-Elu Machinery).

20.3.2 Bonding

In this chapter a distinction is made between the welding of plastics

parts, sheets, etc., in which heat is the principal agent promoting the
union between the two parts of a joint, and bonding, wherein the
union is brought about with the aid of solvents, solvent cements or
adhesives.
Note: The state of attachment achieved between the two joint
surfaces when the union is completed is referred to as the
'bond' irrespective of the method employed in making the
joint.
This nomenclature, convenient for the present purpose, is broadly in
line (but not in full conformity) with the relevant IS0 27 and ASTM*
standard definitions.
(a) Solvent Bonding
This operation (sometimes also referred to as 'solvent welding') may
be broadly defined as the formation of a joint wherein a self-bond
between two polymeric components is promoted by the presence of a
solvent in temporarily high concentration.
The type of joint best suited to solvent bonding is a lap joint. The
* Source referred to in the footnote on p. 902.

924

w.

V. Titow

method is not normally used for butt joints where these are likely to
experience significant stresses (especially bending stresses) in service.
The essential features of bond formation in this method are the
interdiffusion of polymer molecules across the original interface
between the two components of the joint, and the promotion and
acceleration of this process by the swelling (increase of the free volume
content) of the polymer of the joint components at the interface,
caused by sorption of the solvent. The solvent concentration in the
polymer, originally high, is ultimately reduced to a low constant value,
mainly by further penetration inwards (away from the joint line),
and-to a minor extent-also by evaporation from the 'edges' of the
bond zone. 6
As normally practised, the solvent bonding operation involves the
following main stages:
(i)

The surfaces to be joined are pre-cleaned by wiping with a

cleaning solvent (not a strong swelling agent for the polymer).
Methyl ethyl ketone or carbon tetrachloride may be used with
PVC.
(ii) A suitable solvent or mixture of solvents is applied to the
surfaces. With PVC parts brushing-on is a common method, but
dipping may be possible in some cases (especially if the parts
are small). In solvent bonding of PVC the solvent usually
contains some dissolved PVC polymer or compound (commonly
up to about 10%, but up to 30% in some special 'strong'
cements). Such compositions are known as solvent cements
(also sometimes called 'bodied cements' or 'solvent dopes'). In
comparison with neat solvents, the use of solvent cements for
bonding offers the advantages of reduced evaporation loss at
the time of application, better manipulative control and less
tendency to spread outside the intended contact area.

Note: It is sometimes thought that, by virtue of its polymer content,

a solvent cement is gap-filling. This is not the case with
solvent cements for PVC (and indeed not with most such
cements formulated for other plastics) mainly because the
amount of polymer they contain is proportionately low. It is
therefore essential for good results that the surfaces of parts
to be joined should fit closely together with no gaps.
(iii) The joint is left 'open' for a short time. In this period the

20 PVC Sheet and its Fabrication

925

solvent is sorbed into the surfaces, producing a softened,

swollen polymer layer. In some cases a second application of
cement may be made, followed by another short 'open' period.
(iv) The components are brought together to close the joint. Where
practicable this is usually done under positive pressure, which
may be maintained for some time.

Note: The main function of the pressure is to promote intimate

surface contact between the components. Where-as, for
example, in the cylindrical joints betwen pipes, or pipes and
their fittings-application of pressure perpendicular to the
joint interface is not readily practicable, it is especially
important that the initial fit between the surfaces concerned
should be gap-free.
The assembled joint must be left for a suitable time (normally
at least 24 h *) as the strength develops gradually, in step with
the progress of interdiffusion of molecular chains across the
original interface, and progressive reduction of solvent concentration in the bond zone. Where practicable-e.g. with an
essentially planar joint between parts which can be held in a
pressure jig-elosing pressure may usefully be maintained
during this period. Suitable heating can accelerate the development of full strength.
The ultimate strength of a properly made solvent joint may equal
that of the bulk material of the components, but the initial 'green'
strength is normally quite low (cf. Table 20.2)
A discussion of the mechanism of bond formation in solvent-bonded
joints has been published. 6 Some practical aspects of solvent bonding
of plastics are featured in papers by Mittrop,28 and Trauernicht. 29
Detailed instructions for bonding procedures are also normally
provided by suppliers of solvent cements, and-in some cases-by
manufacturers of products (especially pipes and pipe fittings) bonded
with such compositions.
The main advantages of solvent bonding are the relative simplicity of
the method which-in its common variants-does not require special
* For pressure-pipe joints (pipe-to-pipe or titting-to-pipe), made with good
solvent cement, and assembled and aged at room temperature, it is a
reasonable 'rule of thumb' to allow at least H hours' ageing for each
atmosphere of service pressure (within the rated limit for the pipe).

926

W. V. Titow

TABLE 20.2
Strength Development in Joints Between Rigid
PVC Parts Bonded with Solvent Cement"
Time from
assembling
(h)

05
1
4
8
16
32
48
96

Breaking load (in shear)

(lbf(kN

113 (0503)

120
220
290
400
495
505
580

(0534)
(0979)
(1290)
(1779)
(2202)
(2246)
(2580)

a PVC

resin (Breon AS 70142), 5%; tetrahydrofuran, 70%; cyclohexanone, 25%.

equipment or power and heat sources, and the good ultimate bond
strengths obtainable. It is for these reasons that the method has been
widely used in the bonding of rigid PVC pipes and fittings. However, it
should be noted that the quality of joints depends critically on the skill
and conscientious working of the operator, as well as on good fit
(absence of gaps) between the surfaces to be joined. Other limitations
are the volatility, somewhat toxic nature, and flammability of the
solvents used (which may become particularly significant when
operating in confined spaces and/or near potential sources of ignition).
The already mentioned fact that a solvent-bonded joint cannot be
subjected to normal service stresses for some time after assembly is
also a consideration.
In general, solvent bonding may be regarded as more suitable for
rigid than for flexible PVC parts, because of the possibility of local
effects of the solvent(s) on the plasticiser content and distribution in
the area of the joint, which may lead to hardening and other
undesirable consequences. However, where this possibility has been
properly taken into account (and-preferably-the level of any adverse
effects shown to be acceptably low by suitable tests) flexible PVC
products may be successfully joined by the solvent method. An
interesting, if minor, example is the solvent bonding of flexible PVC
tubing and fittings, stitched into certain types of high-altitude flying
suits to serve as conduit for a liquid heat-exchange medium.

20 PVC Sheet and its Fabrication

927

Many commercial solvent cements have been marketed for a large

number of years. The original Tensol Cement No. 53 (ICI, UK) and
Tangit (Henkel International, West Germany) may be mentioned by
way of example.
In addition to BS 4346: Part 3: 1982 and ASTM D 2564-80, listed in
Appendix 1 (Sections 6.1 and 6.3 respectively), the following standards
are of interest in connection with solvent cements for PVC products
and their application.
ASTM D 2855-81. Making solvent-cemented joints with poly(vinyl
chloride) (PVC) pipe and fittings.
ASTM F 402-80. Safe handling of solvent cements used for joining
thermoplastic pipe and fittings.
ASTM F 656-80. Primers for use in solvent cement joints of
poly(vinyl chloride) (PVC) plastic pipe and
fittings.
ASTM F 545-80. PVC and ABS injected solvent cemented plastic
pipe joints.
ASTM D 2846-82. Chlorinated poly(vinyl chloride)(CPVC) plastic
hot- and cold-water distribution systems.
(b) Adhesive Bonding

In general, adhesive bonding of uPVC-whether to itself or other

substrates-is easier than that of pPVc. In the latter case plasticiser on
or at the surface may act as a parting layer preventing the formation of
a bond by some adhesives, or the formed bond may be weakened by
subsequent migration of plasticiser into the adhesive layer (which can
be appreciably softened thereby) whilst the local loss of plasticiser may
leave the PVC surface less uniform and hence more prone to
disruption under the influence of temperature changes and some other
environmental effects. Some of the solvents used in solvent-based
adhesives can also have an adverse effect on the PVC surface (of both
rigid and plasticised compositions).
However, a number of adhesives are available, based on certain
suitable polymer systems represented in the ranges of most major
suppliers. Table 20.3 gives a general indication of the main types of
adhesive systems, with a few examples of their commercial versions
and references to some applications. Advice is available-and should
be sought-from adhesive manufacturers on the applicability of
adhesives for any specific purpose, and on the suitability of any given
adhesive for any stated use and method of application.

General
applicability

Both uPVC and pPVC

Polyurethanea
can be bonded with
(single- or twosuitable versions
component systems:
i.e. resin, or resin
and hardener)
Both uPVC and pPVC
Cyanoacrylate
can be bonded with
suitable versions
(but with pPVC
bonds are weaker
and time to handling strength longer)

Type

Loctite IS 414}
CyanolitC 811
Eastmand 910

Bostik PA 779

Bostik 3250

Adhesive

Various rapid bond

applications

Footwear (especially
soles to uppers)
Film laminates

Some typical
uses

Examples of commercial products

TABLE 20.3
Main Types of Adhesives for PVC

Cyanocrylates have fast

setting times (of the
order of 10 s) and
give strong bonds

Basically two-pack systems, but the resin

component can be
used alone

Remarks

tv

\0

'"

:::J

:-::::

00

For uPVC and pPVC

bonding

For uPVC and pPVC

bonding

Nitrile
rubber

Hot-melt
(several polyesterbased)

InstawelcV

Selected members of
the Permabond e C
and F ranges
Bostik 4141 and 4142
(water-based: emulsion types)
Bostik M890 (a modified'two-part acrylic
system)
Bonding pPVC to
polyurethane foam
(e.g. in motor car
upholstery), Flooring adhesives
Mainly uPVC

Bonding uPVC
(various products) to
itself and certain
substrates

Some suppliers:
a Bostik companies in most Western countries. Hager & Kassner-West Germany.
b Loctite-USA and UK.
C Industrial Science Ltd-UK.
d Eastman Kodak, and associated companies in most Western countries.
e Permabond Adhesives-UK, and associate companies.
f National Adhesives and Resins Ltd-UK.

Predominantly uPVC

Acrylic
(acrylate
copolymers)
Acrylic adhesives are
used in some PVC
pressure-sensitive
products (e.g. tapes)

\0

tv

\0

"

""<

~.

l'>..

;l
~

"l:I

930

W. V. Titow

20.3.3 Machining

Although ordinary engineering workshop equipment can be successfully used for machining plastics, including PVC, certain tool characteristics, speeds and settings may be used to advantage. A useful review of
the subject has been made by Korani. 30 Special tools, including
portable equipment, are available for machining plastics sheet, etc. In
the UK a range of such equipment is supplied, for example, by
Interwood Ltd. This includes, inter alia, routers, trimmers, edgeclipping trimmers, and shears. Some general pointers concerning the
most common operations are briefly summarised below: most of these
relate primarily to typical rigid PVC sheet. Wherever possible,
asbestos-filled uPVC sheeting should be cut to the required size(s) by
the suppliers, most of whom offer such service.
CUTTING

Ordinary scissors or shears can be used for cutting thin material.

Electrically operated nibbling shears are particularly suitable for sheets
up to about 0080 in thick.
Guillotining can be carried out quite successfully, although commercial power-operated machines should be slowed down. The bevel
angles should be 60-80, the higher figure being for blades which are
not often sharpened. For normal thicknesses cutting temperatures
should be 2G-30C, but for sheets of, say, 025 in a temperature of
50C is of great assistance.
DRILLING

For drilling the included point angle should be 140 and a quick spiral
should be employed. Without lubricant a peripheral speed of
100 ft min -1 is satisfactory but this can be increased to 200 ft min- 1
with lubricants. For holes over 05 in the drills and feeds used with
steel can be employed.
ENGRAVING

Spindle speeds of about 5000 r min -1 with a low rate of feed should be
employed. The included angle of the cutter should be 45-60 tending
towards the higher figure. A clearance angle of about 40 or larger is to
be preferred and the material should be chilled before work begins.
Apart from soluble oil, a suitable silicone emulsion may be employed.
If a coolant is not used the swarf may be prevented from sticking to the
sheet (by static) by wiping with an antistatic agent.

20 PVC Sheet and its Fabrication

931

PLANING AND POLISHING

The surfaces cannot be planed, only buffed. Ordinary woodworking

planes can be used along edges. For polishing normal calico buffing
mops may be employed with suitable compounds. Speeds below
5000 ft min -1 are usual.
ROUTERING

The following are the recommended conditions: the sheet temperature

should be greater than 20C; use a high-speed steel cutter (not tungsten
carbide), Z-shaped, preferably l-iin in diameter; a smooth feed and
maximum machine speed are desirable; machine vibration should be
avoided. A fixed head router is preferable.
SAWING

Sawing presents no special difficulties, but hollow ground blades

should be used for sheets thicker than rl; in. Lubricant is not normally
necessary, but vibration must be avoided otherwise chipping may
occur. Speeds of 5000-10000 ft min- 1 should be used with circular
saws and with sheets over rl; in thick the blade should not be less than
kin thick. There should be a slight negative rake with no front or top
bevel and there may be six to nine teeth per inch. A typical feed rate is
4ftmin- 1 .
SCREW-THREAD CUTTING

Threads can be cut on screw-cutting lathes or by using standard taps

and dies. When cutting a male thread, chamfer the end of the rod so
that the thread does not continue to the end. When cutting a female
thread, countersink the top of the hole. Turpentine substitute is an
effective lubricant.
TURNING AND MILLING

The simplest turning tool is a profile cutter, and increasing the front
rake angle reduces the amount of heat generated. With a straight
turning tool a 10 top rake and 20 front clearance give good results.
The following are general rules: the included cutting angle should be
about 60; the tool tip must have a radius of 0025 in for a side cutter
and more for a rou,nd-nosed cutter; the tool faces must have a high
polish; the tool must be sha~ilicon carbide can be used to
advantage; the speed of the work should be about 500 ft min -1.
If troubles are experienced, it is because the correct conditions are
not being used. For example, chipping and shattering are chiefly

932

w.

V. Titow

caused by low top rake; overheating is caused by low front rake;

chipping and rough surfaces are caused by too fast a feed.
Milling is similar to turning and a 10 positive front rake and 20 top
rake is suitable.

20.3.4 Conversion and Manipulation of PVC Film and Sheeting for

Packaging
There is a variety of techniques and machines for these purposes. The
subject is, however, within the scope of packaging rather than PVC
technology. A relatively early review published by Bippus and
Ackermann (Mechanical Processing of pvc Foils in the Packaging
Sector)31 is still of interest. Other sources of information include books
by Briston and Katan,32 Oswin,33 and Bruins,34 some relevant RAPRA
Abstracts, and the current edition of Modern Packaging Encyclopedia
(McGraw-Hill).

20.3.5 Surface Decoration, Marking, and Other Surface Processing

of PVC Materials and Products

In terms of surface area processed, films and sheeting-both

unsupported and fabric-supported (Le. where they constitute coating
on textiles or paper)-are probably the most important single group
among the PVC products to which the various surface threatments are
applied. It is for this reason that the present section, which is intended
to give a brief, general outline of the main processes involved, has
been placed in this chapter. However, as should be evident from the
contents, the processes are no less significant in their application to
many other products made from PVC compositions.
(a) Surface Decoration
PRINTING

The rotogravure process-popular for continuous sheet materials

('webs' in printers' parlance) in both plastics and textiles-is
particularly widely used for printing PVC sheeting, coated papers (e.g.
vinyl wall-coverings) and fabrics, on machines usually specially
designed for these products. Solvent-based inks are commonly

20 PVC Sheet and its Fabrication

933

employed: in some cases these are prepared on the premises. The

solvents are, typically, ketones: often methyl ethyl ketone is a major
constituent of the solvent system, which usually also contains a
keying-solvent component, still more aggressive towards PVC (e.g.
tetrahydrofuran, isophorone). The binder resins of the inks may be
PVC polymers or copolymers in combination with others (e.g. acrylic
polymers).
Note: Some commercial inks of the emulsion type (i.e. water-based)
are also used for PVC sheet printing (cf., for example, the
crosslinkable Vinaprint GV inks (Claremont Polychemical
Corp., USA) for PVC-coated fabrics and wall-coverings).

Some PVC articles and mouldings (especially bottles) are printed by

the silk-screen and offset techniques. Pad-printinj35 has also been
coming into use: this can be particularly useful for very thin-walled
parts, and for convex, concave, textured or irregular surfaces. Various
specialised versions of the basic equipment are available. An
interesting example is a rotary pad-printer for in-line application of
wood-grain surface print to extruded profile. 35 Inks for pad-printing on
PVC are commonly based on PVC resins and acrylic binders.
HEAT TRANSFERS

In this method, a pre-printed image (which may be multi-coloured)

carried on a special release-coated support (usually a paper or plastics
strip) is applied to the surface of the article to be decorated under heat
and pressure, whereupon the image is transferred to the surface and
fused-on (the inks of the original print having been formulated to be
compatible and fusible with the surface material).36,37 The carrier strip
is moved out of the way (usually by winding up) after the image has
been fixed.
The method is advantageous for the decoration of articles (especially
blown bottles and containers) in that it allows multi-colour images to
be deposited in one pass, at relatively low cost. However, not every
commercial heat-transfer process is suitable for every type of plastics
article. Examples of those processes applicable to PVC bottles are the
Therimage process (Dennison Manufacturing Co., USA), the D/-NACAL process (Diamond International Corp., USA), and the DR/-CAL
process (Dri-Print Foils Inc., USA). In general the heat transfer
method of surface decoration is more economical for large volumes of
production.

934

W. V. Titow

HOT-FOIL STAMPING

This method is also sometimes known as 'hot-foil marking', 'hot

stamping', 'gold blocking', 'gold stamping' or 'dry printing'. It is
similar in some respects to the heat-transfer method, in that the
image-forming material is carried on a release-coated tape (usually a
polyester film 0020-0030 in thick) and is eventually fused (after
separation of the material from the carrier tape in the image area) onto
the surface of the plastics article, under pressure and heat. In most
cases the image is actually also impressed to some extent into the
surface, somewhat after the manner of an inlay-emboss print. The
image-forming material is a thin foil (hence the common name for the
process) of appropriate plastic, suitably coloured with heat-resistant
and generally fast colourants (for application to PVC surfaces the foil
is usually a film of vinyl chloride polymer or copolymer composition),
or-for metallic effects-a metal foil (normally aluminium). With
metal foils a hot-melt adhesive layer must be used, appropriate for the
article's surface. The make-up of a tape for hot-foil stamping is shown
schematically in Fig. 20.2.
The basic difference between the heat-transfer process and hot-foil
stamping is that in the latter there is no pre-printed image: the
image-forming material extends over the whole surface of the carrier,
and an image is formed-in the shape of a die (of metal or silicone
rubber) which also actuates its transfer to the article-only at the
actual time of transfer. Thus, for multi-colour effects, several passes
are necessary--one for each colour-and this increases the cost of the
operation. The technique is, therefore, usually employed for one- or
two-colour designs. Other limitations are that no half-tones are

S
R
C

Fig. 20.2 Two basic structural variants of hot-foil stamping tape: schematic
representation. C, carrier base; R, release layer (e.g. wax, silicone); S,
protective surface layer for image (polymeric); F, metal foil; A, hot-melt
adhesive; P, coloured polymer composition layer.

20 PVC Sheet and its Fabrication

935

possible in the image, and that the article's wall thickness (at least in
the image area) must be uniform and not too low, to withstand the
heat and pressure of the transfer operation. The main advantages of
hot-foil stamping are that it is the only method of true metallic printing
on plastics, that suitably embossed dies can produce inlay-emboss
print effects (on smooth or irregular surfaces) and that high quality
prints are obtainable without any after-treatment.
EMBOSSING

The thermoplasticity and general nature of PVC compositions make

them suitable for embossing. Depending on the form and thickness of
the material and the process conditions, the operation may affect only
the surface (thick sheets, thick-walled products) or result in overall
texturing (thin sheets and films). Sheet products are normally
embossed in the hot state (fairly typically at 140C or higher), by a
passage through the nip of a pair of rollers (commonly an engraved
metal roll and a rubber backing roll). For calendered sheeting the
operation may be run in-line (see Chapter 18). Separate embossing is
also practised, with extruded sheeting, or with calendered sheeting
where only short embossing runs are involved, or where very deep
emboss and/or especially high temperatures are called for. Other
factors being equal, a low-gloss embossed finish is obtained if the
embossing roller is heated, and a high-gloss one with a cool roller.
Local surface embossing of PVC products (e.g. for marking
purposes) may be carried out with special versions of high-frequency
heating equipment incorporating suitably surface-shaped dies. The
so-called 'chemical' embossing of cellular PVC flooring, wall coverings
and the like is dealt with in Chapter 25.
(b) Surface Marking
This is normally carried out for the purposes of product coding (e.g.
date and batch marks), identification (e.g. marking with the manufacturer's name and/or trademark), and quality marking (e.g. the 'kite'
mark of the British Standards Institution).
Suitable direct printing techniques are widely used (as, for example,
in the in-line marking and coding of PVC pipes, electrical conduit,
cable covering, etc). Local embossing with a heating die is also
practised, as is spray-painting (through a stencil).
Etching-in of code marks on articles (e.g. PVC bottles) by means of
a pulsed laser beam impinging on the cut-out of a suitable stencil forms

936

W. V. Titow

the basis of a modern marking system. * The advantages of this method

are relative operational simplicity, cleanliness, and insensitivity to any
surface contamination on the article being marked. Marks of area
0010-1 in 2 can be produced.
Apart from the references already cited in the text, articles by the
following authors are relevant to various methods of surface decoration
of plastics: Kiihne 39 (an early review of processes), Jolley40 (hot-foil
stamping), Clayton41 (gravure printing on PVC sheeting).
(c) Surface Processing
The kind of processing fa:Iling under this heading consists of treatments
carried out to protect the PVC surface, or to upgrade some of its
properties by chemical modification.
Surface coating (typically with lacquers based on acrylic, epoxy, or
polyurethane resins) of PVC layers on wall-coverings, upholstery, etc.,
is one example. This application is further discussed in Chapter 22.
Reference has also already been made (in Chapter 9) to the
incorporation of UV stabilisers in surface-coating lacquers for PVC
materials for outdoor service, as a means of protection against
weathering, alternative to the inclusion of such agents in the PVC
composition itself.
Another kind of surface treatment is exposure to an electron beam,
or contact with plasma. In the former case, controlled irradiation in an
electron accelerator (several industrial versions of this equipment are
now operational) can bring about a predetermined degree of
cross-linking of the PVC polymer either in the immediate surface
layer, or to a considerable depth (roughly up to about 1 cm with many
compositions), improving resistance to heat and weathering, hardness
and modulus, and reducing permeability. Examples of PVC products
benefiting from such treatment are films for some packaging or medical
applications, roofing sheets, and electrical cable insulation. Similar
effects (but confined to a relatively thin 'skin') are produced by plasma
treatment.

REFERENCES
1. ISO 472-1979. Plastics-Vocabulary.
2. BS 1755. Glossary of terms Used in the plastics industry. Part 1: 1967.
Polymerization and plastics materials.

* The 'Lasermark' system-Lumonics Inc., Kanata, Ontario, Canada. 38

20 PVC Sheet and its Fabrication

937

3. ASTM D 883-78a. Standard definitions of terms relating to plastics.

4. Zade, H. P. (1959). Plastics, 24, 136.
5. Estevez, J. M. J. and Powell D. C. (1960). Manipulation of Thermoplastic
Sheet, Rod and Tube, Iliffe and Sons Ltd, London.
6. Titow, W. V. (1978). In Adhesion 2, (Ed. K. W. Allen), Applied Science
Publishers, London, Ch. 12.
7. Kobayashi A. (1967). Machining of Plastics, McGraw-Hill, New York.
8. Machining with Lasers (1973/74). In Modern Plastics Encyclopedia,
McGraw-Hill, New York, pp. 504-5.
9. ICI Technical Service Note D106 (Second Edn): Darvic Price List, March,
1970.
10. Bateman G. T. (1970). Brit. Plast., 43(5), 96-9.
11. Anon. (1981). Mod. Plast. Int., 11(3), 44.
12. Gamski, K. M. (1978). 36th ANTEC SPE Proceedings, pp. 20-2.
13. DIN 16930: 1964. Welding of rigid PVC (rigid polyvinyl chloride);
Directions.
14. DIN 16931: 1959. Welding of flexible PVC (flexible polyvinyl chloride);
Directions.
15. Mengason, J. (1976). 34th ANTEC SPE Proceedings, pp. 594-7.
16. Anon. (1979). Eur. Plast. News, 6(3), 11-28.
17~ DIN 191~Part 3: 1977. Welding: Welding of plastics: Processes.
18. DIN 16 96~Sheet 1: 1974. Welding of thermoplastics: Principles.
19. Streese, G. (1969). Kunststoffe, 59(11), 679-84.
20. Koehler, T. J. (1970). Mod. Plast., 174-7.
21. Frankel, E. J. and Wang, K. K. (1978). 36th ANTEC SPE Proceedings,
57-60.
22. Potente, H. and Reinke, M. (1981). Plast. Rubb.: Process. Appln, 1(2),
149-60.
23. BS 4994: 1973. Vessels and tanks in reinforced plastics.
24. ASTM D 1789-65 (Reapproved 1977). Welding performance of poly(vinyl
chloride) structures.
25. Bielomatik London Ltd, Technical Publication HV-310.
26. Neubert, W. Welding Machines for Assembling Plastic Parts,
Technical Publication, Bielomatik Leuze (Bielomatic London Ltd).
27. ISO 6354-1982 (ElF). Adhesives-Vocabulary.
28. Mittrop, F. (1969). Kunststoffe, 59(10),685-7.
29. Trauernicht, J. O'R. (1970). Plast. Techno!., 16(8),43-9.
30. Korani, R. (1969). Kunststoffe, 59(10), 688-9.
31. Bippus, W. and Ackermann, H. (1968). Kunststoffe, 58(3), 197-206.
32. Briston, J. H. and Katan, L. L. (1974). Plastic Films, Butterworth,
London.
33. aswin, c. R. (1975). Plastic Films and Packaging, Applied Science
Publishers, London.
34. Bruins, P. F. (1975). Packaging with Plastics, Gordon and Breach, New
York.
35. Rogers, M. (1979). Plast. Technol., 25(10), 73-7.
36. Titow, W. V. (1966). Plast. Technol., 12(8), 38-40.
37. Frazier, J. F. (1978). 36th ANTEC SPE Proceedings, pp. 212-4.
38. Anon. (1981). Mod. Plast. Int., 11(10), 21.

938

w.

V. Titow

39. Kuhne, G. (1969). Kunststoffe, 59(10), 697-9.

40. Jolley, R. A. (1978). Plast. Rubb. Int., 3(6), 255-7.
41. Clayton, F. R. (1978). 'Printing techniques relating to the gravure
process', Paper presented at the PRJ International Conference on PVC
Processing, Egham Hill, Surrey, England, 6-7 April, 1978.

CHAPTER 21

PVC Pastes: Properties and Formulation

W. V.

TITOW

21.1 INTRODUCTION
The processing of PVC in paste form constitutes an important,
long-established area of the technology of this versatile polymer.
Pastes are made with emulsion-type PVC resins (although suspension
resins are sometimes added for special effects-see Sections 21.2.2 and
21.3.1 below). In the early days such resins were selected for the
purpose from among the standard grades: subsequent availability of
special paste-making emulsion polymers did much to further the
advance of the technology and applications of PVC pastes.
In the PVC context, the word 'paste' may be regarded-and is used
in this book-as the broadest generic term for a suspension comprising
particulate vinyl chloride polymer or copolymer as the principal, or the
only suspensoid, and liquid plasticiser(s) as the main, or the sole
constituent of the suspending medium. The suspension will normally
contain stabiliser(s), and may also incorporate various other relatively
minor constituents (e.g. colourants, fillers, etc.). *
A PVC paste is also often called a plastisol, the two terms being
treated as completely synonymous. * In view of this very common
usage, the question whether they are properly interchangeable is
largely academic, although it should be noted that pastes incorporating

* Although the term 'paste' is quite common in the UK, it is not included in
the main relevant English-language nomenclature standards (ISO 472-1979;
BS 1755: Part 1: 1967; ASTM D 883-80) all of which define 'plastisol' and
'organosol' .
939

940

W. V. Titow

organic solvents as constituents of the liquid dispersion medium

additional to the plasticiser(s) are widely known as 'organosols', whilst
pastes thickened (by the addition of thickening agents) to the point
where they are no longer free-flowing are occasionally referred to as
'plastigels'. Organosols are useful in applications where low initial
viscosity but a hard final product with a low plasticiser content are
required: this ultimate condition is achieved by evaporation of the
solvent in the final stages of processing. However, the presence of a
solvent in the original composition, as well as the need for its eventual
removal, can complicate production operations, and thus constitute a
restriction on the use of organosols.
Plastigels, which may vary in consistency from that of butter to
putty, and may be highly thixotropic, are used in applications where
such rheological properties are desirable (e.g. in some spread-coating
operations).
Yet another variant of PVC paste is a rigisol. * The term was coined
to describe plastisols (i.e. solvent-free pastes) so formulated that they
are free-flowing at plasticiser content levels which would normally result
in high viscosity.l,2 This means that a rigisol can be processed like an
ordinary plastisol giving, however, much harder ultimate products:
inter alia, this can afford cost savings as thinner sections may be
produced to meet particular hardness and stiffness requirements.
As with solid PVC compounds (cf. Chapter 4), the main considerations in formulating a paste are the effects of composition upon the
service properties of the ultimate product and on the behaviour of the
paste in processing. The end-use aspects of paste formulation are
substantially the same as those of the solid compounds, but differences
arise in the processing context, principally as a result of the liquid state
of the paste. Factors important in this connection include paste
viscosity, viscosity stability over reasonable periods of time (resistance
to ageing-see Section 21.2 below), and viscosity changes under shear
(in stirring, spreading, etc.-see Section 21.2.2(iii) below).
21.2 PVC PASTES: RHEOLOGICAL PROPERTIES
AND THEORY
'Paste' is a technical term, much less precisely definitive than such
scientific terms as, say, 'emulsion' or 'solution'. The definition varies,
* Not to be confused with Rigidsol, the original trade name for a brand of PVC
pastes of the Watson-Standard Co. USA.

21

PVC Pastes: Properties and Formulation

941

as does the nature of the paste, according to the field of application.

For example, wallpaper-hanging paste may be an aqueous colloidal
solution of a cellulose derivative or starch, whereas toothpaste is
essentially a suspension of particulate solid(s) in water, containing
certain soluble additives. Most pastes are in fact basically suspensions,
and many are characterised by a comparatively high concentration of
the suspensoid. As has already been indicated, PVC pastes belong to
this category, consisting as they do essentially of a comparatively high
proportion of PVC resin particles suspended in a plasticiser or
plasticiser mixture.
The unique suitability of PVC pastes in many applications, and
hence their technical importance, rest essentially on two general
characteristics: the fact that pastes are liquid (even the plastigels will
flow or spread under moderate shear) and can readily be processed in
this state in a number of applications, and the fact that on heating
(which can be applied at the appropriate stage of the technical process)
they are irreversibly converted (fused) to very highly viscous solutions
of polymer in plasticiser. On cooling these solutions solidify; the
resulting product is plasticised PVC.
It should be clear, even from the above brief summary, that the
knowledge and control of rheology of PVC pastes is of great
importance. The essential practical requirements are:
(i) that -as prepared-the paste should have the right rheological
properties for application;
(ii) that these properties should be constant for reasonable periods
of time in storage, and should either remain so through
processing to the time where heat is applied to gel the paste or
should change as required at the appropriate point;
(iii) that the fusion (and the gelation which precedes it) should
proceed at the right rate and generally be controllable.
Unfortunately, the rheological factors associated with the above
points are not simple, and are influenced in a complex way by the
nature and composition of the paste system.
21.2.1 Viscosity of a Simple Suspension

In general, the viscosity of a suspension might be a priori expected to

be a function primarily of the amount of suspensoid present and the
viscosity of the suspending liquid. In the simplest case of dilute,

942

W. V. Titow

substantially monodisperse suspensions in which there is no appreciable interaction between the suspensoid and the medium, those are
indeed the two governing factors, and such systems closely obey
Einstein's expression:
'TJs
'TJo

= 1 +2.5cp

(1)

where 115 and 110 are, respectively, the viscosities of the suspension and
the suspending liquid and cp is the volume fraction of the suspensoid.
The ratio 1151110 is the relative viscosity (11r).
At suspensoid volume fractions higher than about 0025 the relative
viscosity predicted by the above relationship rapidly becomes much
lower than that actually observed. Other more complicated expressions
of a similar nature, e.g. the modified Einstein equation:
'TJs - 'TJo
'TJo

= 2.5cp + 14.1cp2

(2)

and the Mooney equation:*

11r =

(l+05cp)1/2
125cp
1
exp - -cp
1 -cp

(3)

have been shown by Johnston and Brower'! to give a better fit with
actual experimental results, but even with those the viscosity values
predicted for suspensoid volume fractions over about 02 decreased
sharply and progressively in comparison with actual experimental
figures. 3
21.2.2 Main Compositional Factors Influencing the Apparent
Viscosityt of PVC Pastes
At this point it will be useful to list the important compositional
characteristics of PVC pastes which distinguish them from the simple
suspension system so far considered, and complicate their theoretical
treatment as well as the rheological properties in practice.
(i) In PVC pastes the suspensoid volume fraction can be quite high
(considerably in excess of 02); it will also be particularly high in
rigisols, and in plastisols to which 'extender' polymers have
been added. The latter are non-paste-making PVC polymers of
* Originally derived for the viscosity of rubber latices.

t i.e.

viscosity measured at a single, constant rate of shear.

21

PVC Pastes: Properties and Formulation

943

large particle size; when used to replace part of the paste

polymer they usually lower the viscosity of the paste (ct. Section
21.3.1 below).
(ii) PVC pastes are not simple, monodisperse suspensions. When
prepared by the usual methods (ct. Chapter 13, Sections 13.4.3
and 13.4.4(f); and Chapter 22, Section 22.1.1) which give a
dispersion of the polymer particles in the plasticiser(s) good by
ordinary industrial standards (but which do not employ special,
powerful means-such as, for example, ultrasonic vibration-to
secure complete particle separation), the pastes will normally
contain some particle aggregates ('secondary particles') in
addition to completely separated primary particles. The primary
particles of paste-making PVC resins range in size between
01 f-lm and 2 f-lm: aggregate sizes of 18-70 f-lm have been found
in pastes prepared from typical representatives of such
polymers. 4 Whilst some commercial paste resins have particle
size distributions so narrow that the resulting pastes may be
regarded as practically monodisperse, a broad particle size
range (polydispersity) is a feature of others; substantially
bimodal primary particle size distributions are also
encountered4 ,5 (whereas pastes containing added extender
polymer, of particle size normally in the range 8~140 f-lm, are
certainly grossly bimodal systems). The particle size and size
distribution of the paste polymer strongly influence the viscosity
and flow behaviour of the paste (see Section 21.3.1 below).
(iii) Paste polymer particles are resistant to, but not completely
immune from, attack (swelling or even solution) by plasticiser
at room temperature. The interaction, though limited and slow,
can result in a rise of the paste viscosity through an effective
increase in the volume fraction of the solid (swelling of polymer
particles) combined with increase in the viscosity of the
plasticiser brought about by dissolution of some of the polymer
(the finest particles). Such effects are normally collectively
termed 'ageing'.
21.2.3

Expressions for the Apparent Viscosity of Pastes

As can be seen, the ageing of pastes is an extra complicating factor in

the theoretical prediction of their rheological behaviour, as well as in
their application and quality control.

w.

944

V. Titow

All the above factors must be taken into account in a theoretical

treatment of paste viscosity. The treatments outlined here all relate to
apparent viscosity at a given, constant (and normally low) rate of
shear. The reason for this is explained in the following section.
According to the findings of Ram and Schneidero certain modified
forms of the equations of Mooney7 and Eilers8 with some empirical
corrections, describe well the relationship between the apparent
viscosity and the suspensoid volume fraction for certain plastisols at
constant shear rates, even when ageing effects are taken into
consideration. Ram and Schneider also proposed the following
simplified empirical relationship:
TJ

=A

;WJ

B
exp [1_

(4)

where 1/ is the apparent viscosity of the plastisol, A and B are empirical

constants, W is the polymer weight fraction and Wp the 'critical' weight
fraction (weight fraction at gelation, when the viscosity becomes
extremely high).
The concept of critical weight (strictly: critical volume) was also
independently advanced by Johnson and Brower,3 who used it to
develop what is one of the best expressions available for the
relationship between the apparent viscosity of a plastisol and its
suspensoid fraction; the equation was demonstrated to hold for several
resin/plasticiser systems (including plastisols containing extender
resins) and thus not to be invalidated by considerable variations in
particle size and size distribution of the suspensoid. The equation was
also shown to be equally applicable to suspensions of glass beads in
plasticisers; in conjunction with the other data this demonstrates that
the equation is not invalidated by ageing effects within reasonable
limits. Moreover, the authors suggested a simple way of estimatingwith the aid of the critical volume concept-the extent of the volume
increase of polymer particles in plastisols as a result of plasticiser
absorption. Their estimates indicate volume increases from about
0-13% for stable resins to 1 76% for less stable ones.
The equation of Johnston and Brower3 is:
10gloTJr=

(1-33-0-84!t)(~)
<Pc

<Pc

<P

(5)

where ({Jc is the critical volume fraction, and other symbols are as
defined above.

21

PVC Pastes: Properties and Formulation

945

The critical volume fraction is defined as the volume fraction of

polymer particles when those have absorbed the plasticiser to the point
where it no longer fills completely the interstices between the particles
and consequently the viscosity becomes extremely high. Assuming that
the equation and the master curve which can be plotted from it
(lOglO l1r versus the 'relative volume fraction' cp/CPc) do not change, the
critical volume for a particular system can be calculated from viscosity
measurements at a known volume fraction, and the critical volume
fraction thus determined. This provides ready means of characterising
and/or predicting the apparent viscosity, at least at low shear rates, for
plastisols based on a given resin, over a wide range of compositions
and with various plasticisers. Ageing properties of plastisols, and the
effects of extender resins can also be similarly characterised.
21.2.4 Variation of Paste Viscosity with Rate of Shear, or with Time
at Constant Shear Rate
The preceding section dealt with the ways in which the main
compositional properties of PVC pastes influence their viscosity even
when that is determined at a single, constant rate of shear. It is
because of this simplifying limitation that the viscosity was described as
'apparent'. The qualification is necessary, because-and this is a very
important rheological characteristic of PVC pastes-their viscosity also
varies with the rate of shear; both the phenomenon and the manner of
the variation (which is complex) are of course also functions of the
nature and composition of the paste. The subject is extensive, and a
full discussion would be beyond the scope of this book. However, a
few important points of particular significance to technological practice
may be briefly mentioned. In order to do this it is useful to define a few
essential concepts.
Consider a thin layer of liquid of thickness d.x, between two parallel
plates, each of area A (Fig. 21.1). If the bottom plate is held and the
top one moved in the direction of the arrow with a force F, the liquid

~A

dV/-A-7----='
1

Fig. 21.1

946

w. V. Titow

layer will be subjected to shear. The shearing force will be opposed by

the internal cohesion or viscosity of the liquid. Let the force F impart a
velocity V to the top plate. Then the thin lamina of the liquid in
immediate contact with the surface of the plate will move with the
same velocity; a similar lamina adjacent to the surface of the stationary
bottom plate will be at rest, and any lamina of liquid in a position
intermediate between the two will be moving with a velocity which will
be greater than zero but smaller than V. In laminar (Le. not turbulent)
flow, that velocity will also be proportional to the distance of the
lamina from the bottom plate. In other words a velocity gradient dVldx
will be set up. For the purpose of the present consideration the
simplifying assumption may be made that the velocity gradient is equal
to the 'shear rate' (i.e. the change of shape of the whole liquid layer
under the action of the shearing force); this equality does in fact exist
in the conditions of simple shear.
In mathematical terms the relationship is dVldx = y, where y is the
shear rate.
As the force F is acting over the area A the shear stress may be
defined as:
F
T=(6)
A
It might reasonably be expected that the extent of deformation of the
liquid layer (the shear rate) should be proportional to the magnitude of
the shearing force per unit area (the shear stress), i.e.

ret: y or r = y times a constant

(7)

This is indeed so for many liquids; such liquids are called 'Newtonian'.
Their behaviour conforms to eqn (7) in which the proportionality
constant (usually given the symbol 'YJ) is called the Newtonian viscosity;
Le. for Newtonian liquids:
T

-=7j

"Y

(7a)

and the graph of r versus y is a straight line of slope 'YJ, passing through
the origin (Fig. 21.2).
Liquids for which the shear rate is not directly proportional to shear
stress (Le. the ratio r/y is not a constant) are called non-Newtonian. In
such liquids the ratio of the shear stress to shear rate varies in some

21

PVC Pastes: Properties and Formulation

947

Shear
stress
(T)

Shear rate

("y)

Fig. 21.2 Viscosity relationship for Newtonian liquids.

manner with the shear rate, i.e.

T

- == "'('Y)
'Y

(8)

or with time at constant shear rate, i.e. r:ly == 1jJ(t). PVC pastes belong
to this group.
It is worth noting in passing that the value of the ratio determined
for single, specified values of r: and y is called 'apparent viscosity' and
this is the sense in which this term was used in the preceding section.
Unlike Newtonian viscosity which is a constant, apparent viscosity
values will depend on the shear rate. In practical terms this means
that a PVC paste will flow (or spread, or drain) differently in
processing according to the amount of shear it is experiencing.
The relationship between r:lyand yor time (i.e. the nature of 1jJ(y)
and 1jJ(t) , or the manner of variation of apparent viscosity with shear
rate and time) in non-Newtonian fluids can assume various more or
less complex forms, corresponding to certain known types of
rheological behaviour. Those most important or common in PVC
pastes will now be briefly mentioned.
'BINGHAM BODY' BEHAVIOUR

This is the case where a certain minimum stress is necessary before

appreciable flow will start, but-once this point (known as the 'yield
point' or 'yield value') has been reached-the behaviour becomes
Newtonian. The mathematical statement of this is:
r: == 77Y + K

(9)

948

W. V. Titow

Shear
stres/s
(T)

Yield
value

Shear rate

(1')

Fig. 21.3 Bingham body behaviour.

where K is a constant associated with the yield value (cf. for example
Ref. 8). The relationship is illustrated in Fig. 21.3. The yield value is
important in the application of PVC pastes to vertical surfaces (e.g. in
spraying or dipping) for which the paste should be formulated for
Bingham body behaviour, with a yield point most suited to
the particular conditions. 9
DILATANCY AND PSEUDOPLASTICITY

Where the apparent viscosity rJa( = -r/y) changes with the rate of shear,
the function (-r/y) = 'ljJ( y) (cf. eqn (8) above) is a power function which
may be written in the form: 9
rJa = Kyn-l

(10)

where the value of n in the power index reflects the nature of the
rheological behaviour. As can be seen, if n = 1 the apparent viscosity
will be constant and therefore the behaviour Newtonian. With n > 1
the shear stress and the apparent viscosity will increase with increasing
shear rate (see Fig. 21.4(a) and (b), respectively). Such behaviour is
known as shear thickening or dilatancy.
With 1 > n > 0 the shear stress and the apparent viscosity will
decrease with increasing shear rate (see Fig. 21.5(a) and (b),
respectively). This behaviour, which is the opposite of dilatancy, is
known as shear thinning or pseudoplasticity. Pastes with high polymer:
plasticiser ratios tend to be dilatant, especially in process conditions
involving high rates of shear. This may, for example, make them
difficult to spread in a coating process, but will also counteract

21

949

PVC Pastes: Properties and Formulation

Apparent
viscosity

Shear
stress

(77 8 )

(T)

Shear rate (')')

Shear rate (')')

Fig. 21.4 Dilatant behaviour in which increasing shear rate is accompanied by

an increase in shear stress (a) and in the apparent viscosity (b).

Shear
stress

Apparent
viscosity

(T)

(77a)

Shear rate

("y)

Shear rate

("y)

Fig. 21.5 Pseudoplasticity behaviour (the reverse of dilatancy): increasing

shear rate is accompanied by a decrease in shear stress (a) and in the apparent
viscosity (b).

excessive penetration into the substrate. 9 A study by Cawthra et ai. 1O

has shown that Breon P 13011-TXP plastisols tend to be dilatant.
Pseudoplastic pastes give good spreadability and surface finish in
certain coating operations involving high shear rates.
THIXOTROPY AND RHEOPEXY

If the apparent viscosity varies with time at constant rate of shear

(TJa = r:/y = 1jJ(t two principal types of behaviour may be exhibited.
The apparent viscosity (and the shear stress) may decrease with time,
or it may increase with time. These two cases are known respectively

W. V. Titow

950

Shear
stress

(T)

or
Apparent
viscosity

(71a)

Time
Fig. 21.6 Thixotropic behaviour: the shear stress and apparent viscosity
decrease with time.
as thixotropy and rheopexy (also sometimes termed negative thixotropy
or antithixotropy): they are illustrated in Figs 21.6 and 21.7.
An example of thixotropic behaviour is 'non-drip' paint which will
spread and flow on stirring and/or brushing, although it is gel-like when
not worked. The viscosity of thixotropic PVC pastes (which may
appear to thicken excessively on storage) may similarly be reduced by
stirring. Pastes thickened as a result of true ageing cannot, of course,
be restored in this way.
Rheopectic behaviour is also sometimes observed in PVC pastes.
Figures 21.3 to 21.7 are schematic illustrations of the main general
types of behaviour mentioned here. Explanations and discussions of
these phenomena (which are not of course exclusively associated with
PVC pastes) abound in the literature, textbooks and reference books;
see, for example, accounts by Mendelson,11 Lodge,12 Reiner 13 and

Shear
stress

(T)

or
Apparent
viscosity
Time

Fig. 21.7 Rheopectic behaviour: shear stress and apparent viscosity increase
with time.

21

PVC Pastes: Properties and Formulation

951

Fredrickson. 14 Actual plots from experiments on pastes have been

published by Cawthra et al. 10
In the type of suspension exemplified by a basic form of PVC
plastisol (dispersion of resin in plasticiser(s)), non-Newtonian flow
behaviour is attributable to modes of interlocking of the particles
(flocculation mechanisms) which impart various degrees of 'structure'
to the generally liquid system. For the purposes of a systematic
treatment the particle interactions may be regarded as weak mechanical linkages, increased or reduced under various rates and durations of
shear. 9 In such terms, dilatancy of a plastisol will arise as a result of a
build-up of structure, and pseudoplasticity will be the result of
breakdown of structure already present,15 when shear is applied. In
Bingham body behaviour the breakdown begins only at a certain,
sufficiently high shear stress (the yield value). As would be expected
from these considerations (and as demonstrated in investigations and
actual processing), dilatancy, pseudoplasticity, thixotropy, rheopexy
and Bingham body behaviour of PVC pastes are reversible phenomena. For a suspension containing a high proportion of suspensoid
particles closely packed, a special kind of ordering of the packing array
may be necessary to allow the cooperative movement of particles
required for flow: otherwise the particles may be forced together in a
way which will hinder flOW. 16 ,17 As pointed out by Rangnes and
Palmgren,18 the need for cooperative particle movement to facilitate or
enable flow is greatest in monodisperse systems, and hence-other
factors being equal-such systems have a greater tendency to dilatancy
than polydisperse systems in which the smaller particles can be
accommodated, and can move, in the interstices among the larger
particles.
Apart from the amount of PVC resin particles present, their size and
size distribution, the rheology of a paste is also influenced by the
amounts and characteristics of the other constituents. These effects are
discussed in further sections of this chapter. It should also be noted
that, under different conditions, one and the same paste may exhibit
more than one type of rheological behaviour.
21.2.5

Gelation and Fusion of PVC Pastes

A PVC paste is transformed into the solid substance of the ultimate

paste-derived product by heating at an elevated temperature. As the
temperature of the paste rises, the plasticiser penetrates into the

952

W. V. Titow

polymer particles which swell and merge, first loosely and then
progressively more fully, until-if the temperature is sufficiently high
and the time adequate-the process culminates in complete mutual
solution of polymer and plasticiser with the formation of a
homogeneous plasticised PVC melt: on cooling this solidifies into the
familiar plasticised PVC material. Overall, the transformation may be
regarded as a phase inversion: a change from a suspension of
particulate polymer in the continuous phase of liquid plasticiser, to a
dispersion (solution) of plasticiser in a continuous polymer matrix,
solid at room temperature.
.
It is usual to distinguish two main, consecutive stages in the
transformation-gelation and fusion of the paste.
Note: Either of the two terms (and particularly 'gelation'), has
sometimes been used to denote the whole transformation
process. However, with better understanding of the phenomena concerned, usage has progressively tended to conform with definitions which may be formulated on the
following lines.
Gelation (or gelling) of a PVC paste is the process whereby
absorption of the plasticiser(s) by the polymer particles, which is the
first major consequence of heat treatment (or sometimes the result of
drastic ageing), brings about the formation of a relatively weak gel. The
state attained by the material with the formation of the gel is also
sometimes referred to as 'gelation'. This state may be considered to
exist until further heating results in fusion.
Note: ASTM D 833-80 defines 'gel' in this context as 'a state
between liquid and solid that occurs in the initial stages of
heating, or upon prolonged storage'.
Fusion is the process whereby (or the state attained when), as a
result of heating, the polymer particles of a PVC paste, permeated by
the plasticiser(s) which they have entirely absorbed, become fully
merged to form a physically homogeneous plasticised PVC material
with mechanical and other properties developed to the full.
Thus the gelation and fusion of a PVC paste are marked by
morphological changes, which are paralleled by changes in properties.
From the practical standpoint of industrial processing and use of pastes
and their products, the properties are of more immediate significance
than the morphology. Even for the purposes of more fundamental

21

PVC Pastes: Properties and Formulation

953

study of the gelation/fusion process, following the changes in some

selected, relevant property offers the advantages of continuous, rapid,
relatively simple monitoring, none of which would be readily attainable
in direct examination of changes in the morphology of the composition
processed. In the present state of knowledge, major changes in certain
relevant properties can, in any case, be related to important stages of
modification of the fine structure of the paste material.
Of particular interest in investigations involving continuous examination of changes in a selected property of the paste is the identification
of the fusion temperature or fusion point (still sometimes referred to as
'gelation temperature'), i.e. that temperature (reached in processing
after a period dependent on the rate of heating in the particular
conditions employed) at which fusion of the material is achieved. It
may be noted that the actual value of the fusion point depends to some
extent on the method of determination, which should, therefore,
always be stated when such figures are quoted. Fusion points
determined in instrumental measurements of such properties as
viscosity, modulus, and others (see below) are often several degrees
lower than the temperatures to which the particular pastes must be
heated to attain the highest tensile strength (as measured after cooling
to room temperature). In general, complete fusion (and full strength
development) will not normally be achieved in paste products heated
to temperatures below 160C, irrespective of the heating rate and time.
The paste property systematically examined in the greatest number
of studies of the gelation/fusion process has been the viscosity, often
measured indirectly in terms of torque in a torque rheometer (most
frequently a Brabender Plastograph or Plasti-Corder).19-24 In investigations of this kind a constant rate of heating is usually employed
(with the paste undergoing shear mixing under controlled conditions)
and the torque is plotted as a function of temperature. The main peak
in the curve is usually taken to indicate the fusion point (sometimes
called the 'relative fusion point'), although the material may not yet be
completely fused at this stage (see Chapter 5, Section 5.6.1). The
magnitude (torque value) of this peak depends on paste composition,
and in particular the compatibility of the plasticiser(s) used: the higher
the compatibility the lower the torque-cf. Chapter 5, Section 5.6.1.
Some plastograph curves obtained by Cayrol et ai. 25 with plastisols*
* Based on Pevikon PVC resins of the PE and PS series (Kema Nord,
Sweden).

954

W. V. Titow

containing between 50 and 100 phr DOP are shown in Fig. 21.8 by way
of general illustration. The same investigators also used a balance
rheometer (the Contraves instrument) to follow changes in the
viscosity, shear modulus and loss angle of their plastisols. The viscosity
effects are illustrated in Fig. 21.8 and shear modulus changes in Fig.
21.9: the fusion points as indicated by the curve peaks for each of the
two properties are fairly close for one and the same plastisol. The
authors noted that the temperature position of the fusion peaks did not
appear to be dependent on the nature of stabilisers or other additives
in the plastisols. Other equipment used to investigate changes in
viscosity of pastes undergoing gelation/fusion on heating included the
Brookfield viscometer, 26-28 and the Bendix Ultra Viscoson
viscometer. 29 An oscillatory, parallel-plate rheometer (Rheometrics

..'"
Q.

1'0

";e

Ui

..-

.o
u

.;

::>

CI'

'"
o 3

.J

05

50

100
T~mp~ratur~

150

, 'C

Fig. 21.8 Viscosity (Contraves balance rheometer) and torque (Brabender

Plastograph) versus temperature for three plastisols. Heating (or cooling) rate:
3C per minute (not linear for the Plastograph). One sample (PE 709) cooled
to 120C after fusion and then re-heated. For the torque curves the times of
fusion are shown. , Plastisol based on Pevikon PE 709 emulsion resin; f:::"
plastisol based on Pevikon PE 712 emulsion resin; plastisol based on
Pevikon PS 690 suspension resin. (Reproduced from Ref. 25 by courtesy of the
editor of Polymer Engineering and Science.)

21

PVC Pastes: Properties and Formulation

955

'l'e
u

'"

"

::I

"Eo
01

...J

50

100

150

Tqmpqraturq. C

200

Fig. 21.9 Shear modulus versus temperature for the three plastisols of Fig.
21.8 during gelation and fusion in a Contraves balance rheometer. Conditions
and coding as for Fig. 21.8. One sample (PE 709) cooled to 120C after fusion
and then reheated. (Reproduced from Ref. 25 by courtesy of the editor of
Polymer Engineering and Science.)
Mechanical Spectrometer)* was employed by Nakajima et al. 30 to
follow the effects of heating not only on the viscosity but also on the
elastic and loss moduli of a plastisol, in the temperature range
55-195C. Some of their results are shown in Fig. 21.10.
The rate of the morphological transformations involved in the
gelation and fusion of a PVC paste, as well as the actual temperatures
at which distinguishable phases of the overall process will occur in a
particular case, depend principally on the nature of the PVC polymer
and plasticiser(s) and the resultant compatibility between them (often
simply referred to as plasticiser compatibility). A general outline of
plasticiser/polymer interactions in processing is given in Chapter 5
* As is pointed out in the second paper of Ref. 30, viscoelastic
measurements carried out with this apparatus on gelling and fusing paste do
not suffer from two shortcomings to which torque rheometer measurements
are subject. Thus, although the torque rheometer provides a good 'fingerprint'
of the gelation/fusion process, it subjects the material to mechanical working
(not experienced in most cases of industrial processing), whilst the torque
values alone give no indication whether the material is in a rubbery or a more
fluid state.

W. V. Titow

956

W : 0628 rad

sl

...

Q.

;,

"..c

G'

10

12

TimG,min

14

16

18

20

Fig. 21.10 Viscoelastic properties of a PVC plastisol on gelation and fusion.

G', elastic modulus; Gil, loss modulus; "'I, viscosity; w, angular frequency.
(Reproduced from Ref. 30 (first paper), by courtesy of the editor of Polymer
Engineering and Science.)

(Section 5.5): this certainly applies also to the gelation/fusion of pastes,

but the process may usefully be considered in more detail here.
The first effect of heat treatment applied to a PVC paste to gel and
fuse it is a short-term reduction of paste viscosity. This is attributed to
a drop, with increasing temperature, in the viscosity of the plasticiser
before the polymer particles become sufficiently swollen (and the
plasticiser 'bodied-up' by any dissolved polymer) to counteract this
effect by increasing the viscosity of the paste as a whole. Other factors
being equal, the magnitude of the initial viscosity drop will thus
depend on the nature of the plasticiser. This is illustrated by the curves
of Fig. 21.11. The same figure also demonstrates that the paste
viscosity soon begins to rise steeply with rising temperature as heating
proceeds: the ascending portions of the curves in fact correspond to the

21

PVC rnin 100

PI..licill' 15

PVC Pastes: Properties and Formulation

957

=
I:

:0

to-

Fig. 21.11 Variation of gel rate curves with plasticiser choice. 31 A,

Dipropylene glycol dibenzoate; B, butyl 2-ethylhexyl phthalate; C, di-2ethylhexyl phthalate; D, di-2-ethylhexyl hexahydrophthalate; E, tri-2ethylhexyl phosphate; F, diisodecyl phthalate; G, di-2-ethylhexyl adipate; H,
diisodecyl adipate. (Reprinted from SPE J., 17(2), 1961.)
initial, near-vertical parts of the viscosity, torque, and modulus plots in
Figs 21.8 and 21.9). The sharp increase of the viscosity and modulus of
the paste reflected in these mutually corresponding features is caused
by progressive absorption of the plasticiser into the polymer particles
(with some, relatively minor, contribution from viscosity increase of
temporarily remaining 'free' plasticiser, due to dissolution of some
polymer). These phenomena are salient elements of the gelation
process: the temperature at which the sharp viscosity rise occurs (or,
more accurately, the mean of the temperature range-admittedly very
narrow in most cases in practice-over which it takes place) is usually
called the 'setting' (or 'set') temperature, or sometimes the gelation
temperature. Its actual value will be governed principally by the
compatibility of the plasticiser and resin, in which the chemical nature
of the plasticiser is a cardinal factor (cf. Fig. 21.11 where the relatively
good compatibility of phthalate and phosphate plasticisers in comparison with the adipates is reflected in the positions and shapes of the
rising portions of the corresponding curves). In general, the higher the
compatibility of the plasticiser(s) with the polymer in a paste the easier
and faster the gelation (and the ultimate fusion): the best solvating
plasticisers (BBP, triaryl phosphates) lead in this respect, followed by
some of the widely used phthalates. In practice this affords scope for

958

w.

V. Titow

lowering the gelation and fusion temperatures for the same duration of
heat treatment, or reducing treatment times at the same temperatures,
by substituting some or all of the plasticiser in the formulation with one
of higher compatibility (e.g. a general-purpose phthalate with a triaryl
phosphate) if other processing requirements (e.g. paste rheology,
which is also affected by plasticiser compatibility-see Section 21.3.2),
cost considerations, and ultimate service performance requirements do
not preclude such substitution.
The end of the steep rise of the viscosity, torque and modulus curves
of Figs 21.8 and 21.9, marked by a small peak in most of these plots, is
regarded by some authors25 as corresponding to the 'dry point' in the
gelation process, at which all the plasticiser is assumed to have been
absorbed by the polymer but the strength of the resulting solid material
is still very low. However, some comparative curves published by
Greenhoe,26 who has distinguished and named a number of sub-stages
in the gelation/fusion process, suggest that it is more likely to be the
'gel point', or even possibly the 'haze point' or 'elastomeric point' (in
Greenhoe's nomenclature-cf. Refs 26 and 32, and Chapter 5, Section
5.5)-states reached consecutively at temperatures progressively higher
than the dry-point temperature (but still considerably lower than the
fusion-point temperature).
The next point of interest-and major importance-in the progress
of the gelation/fusion process is the fusion temperature. As already
mentioned, this is the temperature corresponding to the main, final
peaks of the curves of Figs 21.8 and 21.9. The drop in the curves at the
still higher temperatures to the right of this peak has been attributed to
the disruption (melting) of centres of ordered structure (microcrystallites) believed to form in the plasticised PVC polymer (d. Chapter 5,
Section 5.4), and thought-when present-to act in the same way as
microcrystalline regions in naturally crystalline polymers, i.e. as quasi
cross-linking points stiffening the structure. However, as has also been
mentioned, the fusion point indicated by the main peaks of the
viscosity or modulus versus temperature curves does not necessarily
correspond to the development of the highest room-temperature
tensile strength appropriate to the composition. * In many cases that

* In material which has lost a significant amount of plasticiser in the course of

heat treatment such loss may (if no substantial polymer degradation has yet
occurred) produce an increase of tensile strength beyond the value normal for
the properly fused composition. However, in such a case there will also be an
appreciable reduction of extensibility and increase of stiffness (ct. Chapter 12,
Section 12.3).

21

PVC Pastes: Properties and Formulation

959

ultimate strength level is attained only by heating to a somewhat higher

temperature for an appropriate time.
A method originated by McKenna33 and subsequently employed by
Greenhoe 32 (cf. Chapter 5, Section 5.5) to investigate the course of
gelation and fusion of PVC pastes (in the form of cast films) provided
the basis for a practically orientated laboratory test used in industry as
an aid in the formulation and evaluation of paste compositions,
and-in some cases-production control. The method is variously
known, in its main versions, as the 'hot bench' test, the 'gel block' test
or the 'temperature-gradient bar' test: some literature references
relevant to these tests and their results are given in Section 5.5 of
Chapter 5. All the tests employ a metal element (bar, block, etc.)
whose surface is differentially heated to produce several zones kept at
increasingly higher, closely controlled temperatures. A thin layer of
paste is placed on the surface so that it spans the heating zones. After
an appropriate time (which may be one ofthe variables investigated) the
PVC layer-now solidified in varying degrees along its length-is
removed and the degree of gelation/fusion attained by the consecutive
sections determined, by a tensile strength test or in other ways.
Note: A plot of tensile strength (from the point where that becomes
high enough to be measured) versus temperature is similar in
shape to the curves of Figs 21.8 and 21.9.

Because of its usefulness as an indicator of completeness of fusion

and its relevance, as a material property, in many service situations,
tensile strength is widely employed as the criterion in assessing the
results of heat treatment of PVC pastes in tests and actual processing.
Note: The appearance of the surface of a paste-derived product can
provide a useful general clue to the completeness of fusion. A
dull, matt surface is a strong, positive sign that fusion has not
been complete.

Other tests of interest in the practical context include the solvent

immersion test (several versions), and the 'clear point' test (also
several variants). Solvent immersion tests for paste-derived PVC
products are discussed in Chapter 22 (Section 22.1.2). As originally
conceived, this kind of test was a pass-or-fail check to determine
whether the material of such products (very often the PVC coating on
a fabric) had been completely fused in processing, the criterion of
complete fusion being absence of any sign of disruption by the solvent
used as test medium.

960

W. V. Titow

However, some solvent immersion tests for paste products can also
give an indication of the extent to which the state of the material falls
short of complete fusion (as reflected in the time of onset and severity
of solvent attack).34 The clear point test-discussed in Chapter 5,
Section 5.6.1-gives a relative index of the compatibility of a plasticiser
with the PVC polymer: this can be used as an indication of the relative
ease (and to some extent, especially in the light of relevant experience
and background data, the likely temperature) of gelation and fusion of
a paste based on the particular polymer/plasticiser system.
The results of appropriate tests, carried out and interpreted in the
right context, can provide guidance relevant in the formulation and
processing of pastes, but no laboratory test can be a full substitute for
practical production trials.
21.2.6 The Measurement of Viscosity of PVC Pastes

Reference has already been made in the preceding section to the role
of viscosity measurement as an important technique in the study of the
gelation and fusion of PVC pastes, and to the equipment employed for
this purpose.
Another important application of viscometry in PVC paste technology is its use in the determination of rheological properties relevant to
such aspects of industrial production as paste formulation and quality
control (including evaluation of ageing characteristics), applicational
suitability, and trouble-shooting. Two types of viscometer are of
particular interest in this connection-the Brookfield rotational
viscometer (for determination of the apparent viscosity of pastes at
relatively low rates of shear) and the Castor-Severs viscometer (an
extrusion rheometer used for apparent-viscosity determinations at high
shear rates).
The Brookfield instrument measures viscosity in terms of the
arresting torque on a spindle rotating in the composition under test.
The models used with PVC pastes (RV and LV) are available in a
number of variants (e.g. RVF, RVT, RVT-lOO, LVF)35,36 offering
different (though overlapping) spindle speed ranges: those recommended by the relevant ASTM standard36 are models RVF and LVF.
The combination of spindle size (designated by a number) and spindle
speed-which should be chosen in accordance with the viscosity
characteristics of the material and the desired precision of measurement-should be stated when quoting the 'Brookfield viscosity' of a

21

PVC Pastes: Properties and Formulation

961

paste: this is expressed in conventional units (Pa s; P; cP), the value

being calculated from a formula involving factors representing spindle
speed (for a particular spindle size) and the dial reading on the
instrument.
Cone-and-plate rotational viscometers (e.g. the Haake-Rotovisco
instrument)37 are also sometimes used with PVC pastes. Useful
comments on the determination of viscosity of polymer dispersions,
emulsions and solutions with a rotational viscometer are given in
ISO 3219.
The Castor-Severs viscometer is a rheometer in which the paste is
extruded by gas (normally nitrogen) pressure under standard conditions, through a die of standard dimensions. Several determinations
are made, each at a different pressure value (in the relevant IS0 38 and
ASTM39 standards, respectively, within the ranges 100-2500 kPa and
69-690 kPa), and the apparent viscosity ('YJa) is calculated-in appropriate units (Pa s; P; cP)-for each pressure (and hence shear stress) level
as the ratio of shear stress (r or a) to shear rate (y or e), the values of
these two factors being given by the relationships:
r = Prl2l and

y = 4WI!r?pt

where P is the pressure used in a determination, r is the die channel

radius, l is the die channel length, W is the weight of paste extruded in
time t, and p is the density of the paste (all in appropriate units).
The results may be represented as a graph of r versus y, or 'YJa versus
y (d. Section 21.2.4).
For the monitoring of paste viscosity in fully routinised industrial
operations, simpler equipment-giving viscosity values in relative
terms-may be adequate in some cases. Two examples are the
Gardner viscometer and the Ford Cup viscometer. In the former, the
time is measured for a plunger to fall, under a standard load, through a
cylinder containing the paste; modified versions (e.g. with perforated
plungers) have also been used. With the Ford Cup the time which the
paste takes to run out of a standard-size cup through an orifice of
standard dimensions is measured. It need hardly be pointed out that in
tests of this kind the conditions and method of operation must be very
strictly standardised if reproducible and comparable results are to be
obtained. In practice this means, inter alia, that the paste should always
be prepared in the same way, stored in the same conditions, and
viscosity measurements should be taken each time after the same
storage time and by eactly the same procedure.

962

W. V. Titow

21.3 PASTE COMPONENTS AND FORMULATION

Pastes are PVC compounds, and therefore all those normal constituents of a PVC compound necessary for its intended end-use are
found in pastes. These ingredients are discussed in Chapters 4-11.
They are the polymer, plasticiser(s), stabiliser(s), colourant(s), filler(s);
external lubricants are also occasionally included, and speciality
additives required in processing (e.g. blowing agents) or end-use (e.g.
antistatic agents).
The principal differences between pastes and solid PVC compounds
are, of course, in their physical state and in processing. Therefore
those ingredients which are added because of special requirements
arising in connection with these two aspects will be different in the two
types of compound. Thus polymeric modifiers are not used in pastes
and neither are lubricants with exclusively internal-lubricant action. On
the other hand pastes will contain viscosity modifiers, diluents or
thickeners which are absent from solid compounds, because their
functions are specifically associated with the liquid character of the
pastes. This factor also influences in a marked way the choice of some
of the other 'major' components.
The individual components of a paste formulation will now be briefly
discussed.

21.3.1 The Polymer

(a) Paste Polymers
As has already been mentioned these must both:
(i) be resistant at room temperature to the plasticisers used (this
makes for good paste stability), and
(ii) have good affinity for the plasticisers in order to rapidly fuse
with (dissolve in) them at the appropriate elevated temperature,
for good gelation and fusion.
These are conflicting requirements, but modern paste-making
polymers achieve a reasonably successful compromise, assisted by the
high sphericity of the particles (which mades for relatively low
surface-to-volume ratio) and their fairly dense surface (an obstacle to
plasticiser penetration at room temperature).
The particle size and size distribution characteristics of different
paste polymer grades are also suited to different rheological require-

21

PVC Pastes: Properties and Formulation

963

ments. Thus resins recommended for high-viscosity pastes tend to have

comparatively small particles and narrow particle size distributions
verging on monodispersity: such distributions, with means between
about 01 f.lm and 06 f.lm, have been reported for some resins,S and
means in the range 023-046 f.lm for others. 4 Medium-viscosity paste
resins are more typically polydisperse: broad size distributions of both
primary particles and aggregates (which were also present) have been
reported for some commercial products, with primary particle size
medians in the range 08-15 f.lm, i.e. somewhat larger than in some
typical high-viscosity paste resins. Bimodal distribution of primary
particle sizes is a feature of some paste resins,6 notably certain
commercial polymers recommended for low-viscosity pastes (characterised also by a secondary-particle content relatively higher than that of
typical high- and medium-viscosity paste resins).4
(b) Extender Polymers
Reference has already been made to these in Section 21.2.2. They are
homopolymers or copolymers made by the suspension method, with
particle sizes generally in the range 80-140 f.lm. Extender polymers are
usually included in pastes, replacing part of the paste polymer, to
lower paste viscosity whilst preserving the overall polymer content.
Homopolymers with a non-absorbent particle surface, and copolymers
with low co-monomer contents are used for this purpose. The
viscosity-reduction effect is illustrated in Fig. 21.12. It arises, and is at
maximum at about 50% replacement, because the paste now behaves
as a system of the coarse extender-resin particles, suspended in a
'liquid' consisting of the dispersion of the paste resin in the
plasticisers. 40 ,41
The viscosity effect is reasonably permanent and the ageing
properties of the paste may even be improved in some cases, as shown
b."/ Fig. 21.13.
Occasionally suspension homopolymers with absorbent surfaces, or
copolymers with high co-monomer contents, are used as extender
polymers. In such cases the viscosity of the paste increases sharply, and
ageing properties deteriorate; both effects are due to the absorption of
some of the plasticiser into the extender-polymer particles.
Viscosity-lowering extender polymers are employed in pastes for
coating, spraying and rotational casting applications (ct. Chapter 22).
They are also utilised in rigisols. The selection and use of extender
polymers are discussed by Park. 42

W. V. Titow

964
100000

Polym~r

/ plasticisar

80000
Q.

,., 40000

'iii

..
o

':>

20000

10

20

30
./.

40

50

60

70

60

90

100

past~ polym~r r~plac~d

Fig. 21.12 Effect of replacing a paste polymer (Breon P130/1) by a

suspension-type VCNnC copolymer (Breon CS 100/30).

...

A.

>-

'w

..
o

10000

.!!

>

5000

Ag. of

10
IIlStl,

15

days

Fig.21.13 Ageing characteristics of Breon P130/l :CS100/30 blends (polymer:

plasticiser, 60: 40).

21

PVC Pastes: Properties and Formulation

965

21.3.2 Plasticisers
In addition to the properties important from the point of view of
end-use, which are discussed in Chapter 7, the choice of plasticiser for
pastes is governed by the paste viscosity and general rheological
characteristics which the plasticisers will impart; this includes also the
gelation and fusion properties, as has been illustrated in Section 21.2.5.
In addition to the studies of these effects already mentioned in that
section, there are several earlier publications on the effect of
plasticisers on the rheology of pastes. 43--47
Other factors being equal, the initial viscosity of the paste is
significantly influenced by the bulk viscosity of the plasticiser(s), but
this may be overshadowed by the effect of plasticiser affinity (solvating
power). As would be expected in the light of the relevant considerations already discussed, highly solvating plasticisers will normally tend
to produce higher paste viscosities. In those normal pastes which are
subject to appreciable ageing effects, the main viscosity increase will
commonly take place within a few hours from the completion of
mixing; it is therefore reasonable to measure paste viscosities for
routine control purposes 12-24 h after preparation.
As has been mentioned in Chapter 7, a plasticiser mixture will
normally impart to the compound physical properties and end-use
characteristics intermediate between those imparted by its individual
components. This is so also in pastes where, moreover, the principle
extends to such properties of the liquid pastes as flow properties and
ageing characteristics. An illustration of this is provided by the
examples in Table 21.1.
The effect of some individual plasticisers on the viscosity of PVC
pastes is illustrated by Table 21.2.
Solvating power of plasticisers as a factor in paste ageing is discussed
in a paper by Bigg and Hill. 49
The following further comments may be made on the effects of
various plasticisers in pastes.
In general, the phthalate plasticisers give medium-viscosity pastes,
with low to medium setting (gelation) temperatures. Most phthalates,
and especially general-purpose Cs phthalates, impart some thixotropy
to the paste even when used alone in a relatively low concentration
(down to about 50 phr) so that the paste is very viscous. This feature is
useful where pastes are required which will not flow easily without
being worked (i.e. without shear), but which must spread readily under

w. V. Titow

966

TABLE 21.1
Viscosity of Pastesa with Mixed Plasticisers48
Plasticiser composition

Relative apparent viscosity at indicated shear

stress (DOP 18 h viscosity = 1(0)
0159Ibfin- 2

DOP-l00%
DOP- 90%: Polyester (Flexol R2Hy
DOP- 80%: Polyester (Flexol R2H)
DOP- 70%: Polyester (Flexol R2H)
DOP- 90%: 1TP
DOP- 80%: 1TP
DOP- 90%: Chlorinated paraffin
(Halowax 4004Y
DOP- 80%: Chlorinated paraffin
(Halo wax 4(04)
DOP- 70%: Epoxy compound
(Paraplex G60)d

30days b

223Ibfin- 2
30days b
18h 30days~

18h

30 days

l8""h

10%
20%
30%
10%
20%
10%

100
141
246
259
123
133
158

175
196
351
351
196
186
214

175
1-40
143
136
160
137
135

100
174
344
309
217
213
173

145
281
354
398
295
301
202

145
161
103
129
136
141
117

20%

158

196

124

186

217

1-17

30%

175

205

116

149

186

125

PVC resin Bakelite QYNV 100 pbw, total plasticiser 60 pbw.

b This ratio is an index of the viscosity stability.
C Union Carbide.
d Rohm and Haas.

TABLE 21.2
Effect of Plastieisers on Ageing Characteristics of Pastes (ICI 'Come'
Polymer)
Plasticiser

Viscosity
(Gardner)
1 day 28 days

DBP
DAP
DOP
Bisoflex 791 a
DNP

TIP

TXP
TOP

DAS
HexapLas PPL b
HexapLas PPA

B.P. Chemicals.
ICI.

Too viscous
72
120
80
124
68
110
69
69
410 1200
320
480
13
48
6
4
1030
300
Too viscous

21

PVC Pastes: Properties and Formulation

967

shear, as, for example, in coating operations. However, it should be

noted that some plasticisers thixotropic in their effect at moderate rates
of shear (e.g. DOP, DOS) may promote dilatant behaviour when the
paste is subjected to high shear rates.
As would be expected, plasticisers whose own viscosity is high tend
to make viscous pastes. Paste viscosity is also promoted by plasticisers
with good solvating power (e.g. DBP-see Table 21.2). Moreover,
such plasticisers usually tend to promote dilatancy, which may be
pronounced at low rates of shear: triaryl phosphates, and some
aromatic esters of glycols (e. g. diethylene glycol dibenzoate) are
examples of plasticisers with this kind of action. These general
considerations are relevant in paste formulation, as neither high
viscosity (unrelieved by thixotropy) nor dilatancy is normally desirable
in a paste.
Note: Some pastes for the production of flexible PVC foams

constitute an exception here: a relatively high viscosity, either

natural to the formulation or-as may be preferableresulting from dilatant behaviour in processing, can promote
uniformity and stability of the foam cells during their
formation, and help to maintain these features until the
structure is fixed by gelation. Promotion of a measure of
dilatancy to these ends is one of the advantages of inclusion of
suitable, rapidly solvating plasticisers (usually BBP; in some
cases DBP as part of the plasticiser system-d. Chapter 25) in
pastes for foaming, although rapidity of gelation and fusion to
solidify the foam quickly may be regarded as their main
function.
Viscous and/or dilatant pastes are more difficult to stir, de-aerate
and transfer in production and directly prior to application; they do not
flow or spread easily. This can make for problems in casting and
coating operations, and cause difficulties where smooth, even coatings
(especially thin ones) are required. Both high viscosity and dilatancy
can be counteracted by incorporating in the paste a suitable plasticiser
(usually as part of the plasticiser system); some aliphatic diester
('low-temperature') plasticisers are particularly effective for this
purpose and selected phthalates can also be useful, e.g. DINP (which,
in addition to lowering paste viscosity, also offers lower volatility in
comparison with Cs phthalates). Other phthalate plasticisers noteworthy from the point of view of advantageous paste rheology and

968

W. V. Titow

viscosity stability in storage are dicapryl phthalate (DCP) and Hexaplas

OPN. * Where relatively high temperatures and long times of setting

and fusion may be required, such higher phthalates as DDP and DLDP
should be considered: their comparatively low solvating power also
confers good ageing stability on the paste.
The strong solvating ability of triaryl phosphate plasticisers accounts
for the fact that their inclusion in a paste formulation makes for
increased viscosity and, in most cases, dilatant behaviour. At the same
time they promote rapidity and ease of gelation and fusion, and their
tolerance of extenders is good.
The 'low-temperature' (aliphatic diester) plasticisers lower the paste
viscosity, very considerably in some cases (e.g. DIDA; some 'nylon
acid' esters-d. Section 21.4.2), and impart thixotropic properties
(some dialkyl sebacates and adipates are particularly effective). The
ability of several members of this group to promote a large drop in
paste viscosity with increasing temperature makes them useful in
formulations for rotational casting. Pastes containing aliphatic diesters
(normally-in view of their secondary-plasticiser character-as one
component of the plasticiser system) tend to have good ageing
resistance and relatively high setting temperatures.
Epoxy plasticiser/stabilisers are employed in pastes for the same
end-use effects as in solid compounds. Some (epoxidised soyabean
oil) will generally tend to increase paste viscosity, whilst others (epoxy
alkyl esters) normally have the opposite effect.
Polymeric plasticisers tend to give fairly high viscosity and may
promote dilatancy. However, the ageing properties imparted are good.
These plasticisers are used in pastes essentially for the permanence of
properties in end-use which they confer.
Crosslinkable and polymerisable plasticisers have a special application in some pastes, where their use permits a relatively low initial
viscosity to be combined with conversion to a semi-rigid or even fully
rigid ultimate product. However, their incorporation in paste formulations gives rise to special considerations. Unless radiation can be used
as a means of effecting polymerisation or cross-linking of the plasticiser
in the fused product (and this additional treatment, usually expensive
in any case, may not be practicable) an initiator or cross-linking agent,
commonly a peroxide, will usually be included, and this may affect
the stabiliser system or have some effect on properties. These specialist
* Proprietary product of ICI: see Chapter 6, Section 6.5.5.

21

PVC Pastes: Properties and Formulation

969

plasticisers and their uses are mentioned in Section 6.10.4 of Chapter 6.

Examples of such constituents of PVC compositions include diallyl
phthalate (e.g. Bisomer DALP-BP Chemicals International Ltd),
certain glycol dimethacrylates,50 trimethylol propane trimethacrylate,
Santoset (a proprietary product of Monsanto), and the Sartomer plasticisers (Ancomer Ltd, UK).
Some other paste-relevant properties and effects of various plasticisers and extenders are pointed out in the discussion of these materials in
Sections 6.5 and 6.10 of Chapter 6.

21.3.3 Stabilisers
In this respect the service-suitability aspect of paste formulation is very
similar to that of solid compositions, whilst the effects of stabilisers on
paste rheology are associated largely (though not exclusively) with
their physical state: liquid stabilisers and stabiliser systems are used
where the least effect on the flow properties (minimal viscosity
increase) is desired.
A comparison of some common stabilisers in a paste compound
(Breon P13011, 100 parts; TIP, 33 phr; DOP, 33 phr; stabiliser,
167 phr) on the basis of the Congo Red test is given below.
Dibasic lead phosphite
Basic lead carbonate
Calcium stearate
Barium ricinoleate
Lead stearate
Cadmium stearate
Control (no stabiliser)

Time to breakdown (min)

101
83

39
27
19
14

Stabiliser systems based on combinations of Ba, Cd and Zn

compounds (see Chapter 9) are more widely used in PVC pastes than
any other stabiliser type. Liquid Ca/Zn and Mg/Zn systems are useful
in pastes where risk of sulphur staining in end-use is a consideration:
they are also advantageous to paste rheology. Some are approved for
non-toxic applications. Some Ca/Zn and Cd/Zn as well as certain lead
stabilisers function also as 'kickers' for the blowing agent in flexible
foam production from pastes. Liquid organotin stabilisers (especially
the sulphur-free systems) are of interest where maintenance of

970

w.

V. Titow

reasonably low paste viscosity, or viscosity reduction, is an important

consideration.
Good heat and light stability can be obtained in paste products
stabilised with basic lead carbonate and dibasic lead phosphite; the
former stabiliser has been useful for opaque formulations in the
absence of non-toxicity requirements. Calcium or lead silicate have
been used in translucent formulations. Calcium stearate functions as
stabiliser/lubricant for transparent compositions. However, in formulating with stearates it should be remembered that they tend to
increase initial paste viscosity and can intensify viscosity increase on
ageing.

21.3.4 Fillers
Fillers are included in pastes for the same end-use purposes as in solid
compounds, but their effects on paste rheology and ageing characteristics must be considered, as most can increase the viscosity and reduce
the shelf life of the paste, or modify the response to shear. Films and
coatings produced from filled pastes are usually less tacky and harder
than those made from unfilled ones, but other physical properties may
be inferior. In some cases the optical effects of a filler in the finished
product are particularly important, e.g. the achievement .of the correct
degree of translucency to impart a life-like appearance to pastemoulded PVC dolls.
Other factors being equal, paste viscosity tends to rise with
increasing filler loading and with decreasing particle size. The former
factor increases viscosity partly as a result of the increase in the
particulate phase content (and modification of its size distribution) in
the paste (cf. Section 21.2.4), and partly because more particles are
available to adsorb some plasticiser onto their surface. Particle size
reduction also increases plasticiser adsorption by the filler because the
specific surface (surface-to-volume ratio) goes up. The surface
adsorption effects can be considerably modified if the filler particles are
coated (see Chapter 8, Section 8.3.2). The amount, distribution and
chemical nature of the coating all play their role, the most common
overall effect being a reduction of plasticiser adsorption-and hence of
viscosity increase-by the presence of the coating. Some of the effects
of organic titanate coatings on fillers upon the viscosity and other
properties of filled PVC pastes are discussed in a paper by Monte and
Sugerman. 51

21

971

PVC Pastes: Properties and Formulation

TABLE 21.3

on Absorption of Fillers
Filler

Oil absorption number

16
30
33
36

Barytes
Slate powder
Dolomite
Whiting
China clay (medium fine)
China clay (very fine)
Silica
Water-ground mica

35
55

42

79

An indication of the likely magnitude of the effect of a filler on paste

viscosity is given by its oil absorption avalue (cf. Chapter 8, Section
8.3.3), which is influenced by the factors just mentioned. A few oil
absorption values of common fillers are shown, by way of example, in
Table 21.3, and others in Table 21.4 where some effects of fillers on
the viscosity of a paste and on the mechanical properties of the
ultimate product are also illustrated. The table indicates, inter alia,
something of the paste viscosity response to the incorporation of
precipitated calcium carbonate fillers of, respectively, low and high oil
TABLE 21.4
Effect of Some Fillers on a PVC Pastea and its Ultimate Product
Filler
Nature

None
Calcined clay
Blanc fixe
Ppted CaCO/
Ppted CaC0 3c
Barytes
Diatomaceous earth
Lithopone

Viscosity Tensile Modulus Elongation

Oil
(cP: 1 day) strength at 100% at break, absorption
(lbfin- 2 ) extension
phr
(%)
(No.)
(lbfin- 2 )

0
20
31
21
20
34
18
33

10000
17000
15000
18000
40000
7000
40000
40000

2400
2050
2250
2100
2250
2220
1900
1750

1000
1125
1100
1000
1100

950
1175
1000

350
340
320
350
370
420
270
320

66

38
36
45
16
148
37

a Breon P1301l, 100 parts; DOp, 667 phr; filler as shown (each weight represents a
volume equivalent to that of 20 phr calcined clay).
b Low oil absorption grade.
c High oil absorption grade.

W. V. Titow

972
1500

Sturcal L
_ - - - - - - - - 3 3 phr

_ - - - - - - - - - - C a I O f i l A.4
33phr

ll.
>,
....
"iii

ou

III

:>

__

---------Sturcal L
8phr
~_ _- - - - - - - - - - - - C a l o f i l A.4
8phr

__------------NO filhzr

10
TimlZ, days

15

Fig. 21.14 Effects of two CaC03 fillers on viscosity of a PVC paste. Sturcal L
(John E. Sturge Ltd), medium oil absorption filler; Calofil A4 (John E. Sturge
Ltd), low oil absorption, resin-coated filler.
Paste formulation:
PVC resin (Breon P130/1)
DOP

TIP

Filler
Stabiliser (white lead paste)

lOOpbw
33 phr
33 phr
as shown
1.7 phr

absorption. The rheological effects of two commercial grades of

CaC03 filler are also shown in Fig. 21.14; the main features
demonstrated by the curves of this figure are fairly typical, viz. higher
paste viscosity with higher loadings of both fillers, and generally lower
viscosity with the coated filler (except for the slight initial reversal at
the higher level of filler loading, where the early viscosity of paste
containing the uncoated filler is somewhat lower, because of the slower
rate of wetting out). Filler grades specially recommended for pastes are
available from many suppliers. As with other major components of
pastes (e.g. plasticisers) the effect of fillers on viscosity stability is of
interest to the formulator and processor: this is often expressed in

21

PVC Pastes: Properties and Formulation

973

terms of the ageing index (sometimes called the viscosity stability

index--d. Table 21.1) calculated as a ratio VL: V S , where VL is the
viscosity measured after an appropriate, long period (say 15 days) and
Vs is the viscosity value obtained in an earlier measurement (say the
24 h or 48 h viscosity).
21.3.5 Thickening Agents (for Thixotropic Plastisols and Plastigels)
Thixotropic plastisols are used in various dipping processes, where
one-dip coatings are required or where no-drip coatings are essential,
and in spreading processes to reduce penetration and mobility. Normal
pastes can be made thixotropic or converted into plastigels by the
addition of various thickening agents. These include certain grades of
precipitated or fumed silica, e.g. Gasil 23 and Neosyl (Joseph
Crosfield and Sons Ltd), Cab-o-Sil (Cabot Corp.), Aerosil 200 (Bush,
Beach and Segner Bailey), special bentonites, some grades of
aluminium stearate, e.g. Higel No.1 (Albright and Wilson Ltd), and
Sylodex (W. R. Grace (UK) Ltd)---ehrysotile asbestos fibres in the
form of 'crumb' produced by wetting out with plasticiser (2 parts DIBP
to 1 part of asbestos). Some fillers can also have similar effects, e.g.
very fine whitings and carbon blacks.
The normal method of working is to pre-gel the plasticiser with the
agent and use the resultant product for preparing the paste. The
process is very simple and consists of dispersing the agent in the
plasticiser and warming until a clear solution is obtained (with soluble
thickening agents). A marked increase in viscosity also takes place.
After cooling the plasticiser is ready for use.
In the case of aluminilJm stearate (Higel No.1), a 25% solution
(pre-gel) is made in the plasticiser and the amount on the plastisol is
2-10%, a good average being 5%. DOP and DOS can readily be
pre-gelled in this way but TIP cannot be. The sort of increase in
viscosity which can be achieved (Breon P130/1 100; DOP 667 phr;
white lead paste 1 phr and 5% pre-gel Higel No. 1 in DOP) is from
10 000 cP to 106 000 cPo Aluminium stearates G and 2027 (Durham
Raw Materials Ltd) behave in a similar way. The latter will gel at a
lower temperature, the actual gelation temperature depending on the
type of plasticiser used. The recommended use levels for both grades
are 1% upwards.
Aerosil is a useful material for plastisols. It increases the degree of
thixotropy by about 60%, it can be easily dispersed (by stirring into the

974

w.

V. Titow

plastisol or dispersing in the plasticiser) and it gives a stable product.

Sedimentation of filler is also prevented and the addition of 0'5-1 % is
required. Bentone 27 (F. W. Berk and Co. Ltd) is another suitable
material.
Sometimes plastigels of putty-like or even modelling consistency are
required. Suitable materials here are Santocel C (Monsanto Co.,
USA), a fine diatomaceous silica, and Neosyl C, used to the extent of
5-15%. For modelling purposes 30-50% of fillers such as French chalk
or kieselguhr are employed. Again 10-30% of a finely divided china
clay or calcium carbonate may be used or titanium dioxide in
plasticiser.
Some recipes are (in phr):
Corvic P65150
Dialkyl 70 phthalate or similar phthalate
Tritolyl phosphate
Aluminium stearate
Santocel Cor 54
Lead carbonate
Pigment

A
100
40
40
4
6

100

100

80

55

4
6

4
As required

25
25
4

As indicated by the above formulations, in general the higher the

plasticiser content, the more thickening agent is required. Mixing
procedure is as follows.
As aluminium stearate does not dissolve in tritolyl phosphate, the
soap must first be dispersed in a phthalate plasticiser. This is done by
making a paste with the soap and some of the plasticiser, adding the
remaining plasticiser to form a slurry, then heating this to about
120-140C (248-284F) with slow stirring. When this temperature is
reached, a clear mobile solution is formed, which on cooling changes
to a soft jelly. To this jelly is added any additional plasticiser
necessary, the Corvic P65150, heat stabilisers and pigments, mixing
being carried out in a dough mixer which can be water-cooled. About
10-15 min mixing is required and the temperature of the mix should
not be allowed to exceed 35-37C (95-98F). In the later stages of
mixing, Santocel C should be added, the result being a firm putty-like
mass. The mixed compound should be stored for 24 h or so at room
temperature before use, to allow full thixotropic properties to be
developed. Within this period marked thickening occurs, but thereafter
changes are slow. Over a period of months plastigels may harden
slightly but they may be used safely some months after manufacture.

21

PVC Pastes: Properties and Formulation

975

The gelled material has the same good ageing properties as normal
PVC compounds.
21.3.6 MisceUaneous Paste Components
These include the following.
(a) Viscosity Depressants
These are used when it is essential, for end-use properties, to employ a
particular plasticiser system and plasticiser: polymer ratio which at the
same time give unduly high paste viscosities. Viscosity depressants are
usually surface-active agents of various kinds. The effect of a particular
depressant in a particular formulation cannot be entirely predicted and
therefore tests are necessary. Most viscosity depressants also retard the
ageing of the paste. These compounds are added in low quantities (of
the order of 1%) in order not to upset the formulation, and to avoid
exudation. Polyethylene glycols and Lubrol MOA (non-ionic surfaceactive agent: fatty alcohol/ethylene oxide condensate-ICI) are
examples.
(b) Diluents
These are usually organic solvents producing a thinning effect on the
paste, and are mainly used in organosols (see Section 21.4.1).

(c) Other Minor Additives Occasionally Included

These include colourants, blowing agents, fungicides and bactericides,
tire-resisting agents, odourants and deodorants.
21.4 PASTES FOR RIGID PRODUCTS: ORGANOSOLS
AND RIGISOLS
Apart from the use of cross-linking plasticisers in plastisols, the
requirements of initial low viscosity and semi-rigid tinal products can
be met by organosols and rigisols. Brief reference has been made to
both in this chapter; a few more details may now be given.
21.4.1

Organosols

These are essentially plastisols containing additional diluents. The

diluents may be aromatic hydrocarbons (e.g. xylene and toluene),
aliphatic hydrocarbons (e.g. white spirit), or certain ketones (e.g.

976

W. V. Titow

methyl ethyl ketone, methyl isobutyl ketone); alcohols, glycol ethers

and chlorinated hydrocarbons have also been used. The diluents are
employed in circumstances somewhat similar to those in which
viscosity depressants are used, but, unlike the depressants, they are
volatilised orf in the course of processing. Accounts of their use were
first given in early literature. 52-54
Organosols have their place where the process demands a paste
combining low viscosity with high solids content, to yield a relatively
rigid final product. For example, sprayable compositions can be
formulated, with the aid of suitable volatile thinners, containing as
much as 60% non-volatile matter, with up to 150 phr filler, and very
low plasticiser content (down to a few per cent if necessary).

21.4.2 Rigisols
As mentioned in Section 21.1, these are plastisols specially formulated
to achieve low viscosity for processing, but combining this with high
polymer content and hence rigidity of the ultimate products. The
factors which are adjusted and controlled to achieve this result are the
following.!
(i)

Selection (and if necessary blending) of paste-grade PVC

polymers with particle size and size characteristics best suited to
give the kind of particle packing system in the paste that will
promote the lowest practicable viscosity combined with highest
polymer content. Selected suspension-grade homopolymer resins may be included, or some vinyl chloride/vinylidene chloride
copolymers, as extenders for the paste-grade resin(s) to reduce
the viscosity of the system still further.
(ii) Selection of plasticisers which promote low viscosity and
thixotropy in a paste, so that the plasticiser content can be
reduced to a minimum. Several aliphatic ester 'lowtemperature' plasticisers are especially suitable, in particular the
AGS ('nylonate') esters.
Note: It has been suggested! that the packing of the polymer
particles achieved by suitable blending is a close multimodal
packing with the smaller particles almost filling the interstitial
spaces among the larger ones, and that the amount of
plasticiser should be that which then fills the remaining
inter-particle voids, just preventing the particles from
touching. It is further suggested that such a 'lubricated' system

21

PVC Pastes: Properties and Formulation

977

is considerably different from an ordinary plastisol in which

the polymer particles may be regarded as floating in the
plasticiser: it obviously contains proportionately less
plasticiser. !
(iii) Careful attention to the choice of stabilisers and fillers. The
stabilisers should preferably be liquid with no thickening effect
on the plasticiser, and the filler loading should not exceed
15 phr.
(iv) Use of viscosity depressants: polyethylene glycol (400) monolaurate has been recommended as particularly effective.!
(v) Use of diluents. It is an academic point whether the inclusion of
a solvent in a paste otherwise formulated as a rigisol makes it
into an organosol. In practice, white spirits and aliphatic
naphtha (free from aromatics) are diluents useful in lowering
the viscosity of a rigisol.
It has also been stated! that the speed of mixing in the course of
preparation is a factor in successful production of rigisol pastes.
High-speed mixing is preferable in the first ('dry' or 'thick' stage-see
Chapter 22, Section 22.1.1) to ensure that any aggregates that may
tend to form are thoroughly broken up, but once the composition has
been homogenised the mixing speed should be reduced.
Useful advice on basic rigisol formulations for specific purposes is
available from manufacturers of paste resins and plasticisers. One
2
Parts by weight
example is given below:
PVC resins: paste-grade emulsion polymer,
low viscosity (K value* 65)
50 50
100
suspension polymer (K value* 55)
50 50
Plasticisers (AGS esters): Reomol MDt
25
30
Reomol MNt
25
Stabilisers: BalCd liquid system
2
2
2
epoxy co-stabiliser
2
2
2
2
2
2
Viscosity depressant: Lubrol MOA
Apparent' viscosity of paste (at low shear rate) (P)
18 22
42
after 1 day
after 7 days
18 20
98
BS softness No. of ultimate product
6
7
9
* 05 g polymer in 100 ml dichloroethane at 25C.

t Ciba-Geigy.

978

W. V. Titow

REFERENCES
1. Goodier, K. (1960). Proceedings of the International Congress on the
Technology of Plastics Processing, Amsterdam 17th-19th October, N.C.
V't Raedthuys, Amsterdam.
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24. Buckley, C. D. (1971). J. Cell. Plast., 7,23.
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21

PVC Pastes: Properties and Formulation

979

30. Nakajima, N., Ward, D. W. and Collins, E. A. (1979). Polym. Engng.

Sci., 19(3), 210-14; and Nakajima, N. and Ward, D. W. (1983). J. Appl.
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34. Titow, W. V. Unpublished work.
35. ISO 2555-1974. Resins in the liquid state or as emulsions or dispersionsDetermination of Brookfield RV viscosity.
36. ASTM D 1824-66 (Reapproved 1980). Apparent viscosity of plastisols and
organosols at low shear rates by Brookfield viscometer.
37. Ciba-Geigy Technical Service Bulletin PL 9.1 (1977).
38. ISO 4575-1978. Plastics-Polyvinyl chloride pastes-Determination of apparent viscosity using a Severs rheometer.
39. ASTM D 1823-66 (Reapproved 1979). Apparent viscosity of plastisols and
organosols at high shear rates by Castor-Severs viscometer.
40. Lewis, T. B. and Nielson, L. E. (1968). Trans. Soc. Rheol., U(3), 421-4.
41. Farris, R. J. (1968). Trans. Soc. Rheol., U(2), 281-93.
42. Park, R. A. (1975). Plast. World, 33(1), 48.
43. Severs, E. T. and Austin, J. M. (1954). Ind. Eng. Chem., 46(2), 369.
44. Darby, J. R. and Graham, R. R. (1955). Mod. Plast., 32, 148.
45. Newton, D. S. and Cronin, J. A. (1958). Brit. Plast., 31, 426.
46. Werner, A. C. (1957). Mod. Plast., 34, 137.
47. Todd, W. D., Esarove, D., and Smith, W. M. (1956). Mod. Plast., 34, 159.
48. 'Bakelite Vinyl Dispersion Resin QYNV' (1956). Union Carbide
International Co., Technical Release No. 14.
49. Bigg, D. C. H. and Hill, R. J. (1976). J. Appl. Polym. Sci., 20(2),565-8.
50. British Patent No. 694444, Union Carbide and Carbon Corp.
51. Monte, S. J. and Sugerman, G. (1978). 36th ANTEC SPE Proceedings,
pp.781-4.
52. Werner, A. C. (1959). Mod. Plast., 36, 126.
53. Nielson, E. R. (1950). Mod. Plast., 27, 97.
54. Powell, G. M., Quarles, R. W., Spessard, C. I., McKnight, W. H.
and Mullen, I. E. (1951). Mod. Plast., 28, 129.

CHAPTER 22

Preparation, Processing and Applications

ofPastes
W. V. TITaw

22.1 INTRODUCTION
22.1.1 Preparation
In the early days, with old-type resins,. grinding was essential to
produce satisfactory pastes. With modern paste polymers 'stir-in'
techniques in good mixing equipment are effective. The method and
equipment used in the industry for paste preparation are discussed in
considerable detail in Chapter 13 (Sections 13.4.3 and 13.4.4(f)).
The use of an effective mixer and proper technique should ensure
that the paste is free from lumps, with all constituents uniformly
distributed, and not excessively aerated (to facilitate the postpreparative de-aeration which will usually be carried out). Of the two
possible general modes of operation, continuous mixing is in practice
confined to industrial processes: batch mixing is practised on both
industrial and laboratory scale. Modern equipment (e.g. a planetary
mixer) makes it possible to prepare a satisfactory paste batch in a
one-step operation, and versions of this kind of technique are laid
down in standard specifications (ISO 4612-1979; DIN 54800-1979) for
the preparation of standard pastes to be used in the control and
evaluation of formulation factors (especially the nature of the PVC
resin) and the rheological properties of pastes. However, this does not
detract from the practical value of a good two-stage method of paste
preparation, especially for low-viscosity pastes, both in the laboratory
and for production purposes. The following is a brief, general outline
of one such method.
981

982

w.

V. Titow

All dry components (pigments, fillers, solid stabilisers, etc.) are

thoroughly pre-dispersed in a small quantity of the plasticiser (say
between 1 and 3 pbw plasticiser to 1 pbw dry materials). This is best
done on mill-type equipment (say three-roll or five-roll mills, cone
mills) or by ball milling. The polymer is then placed in the mixer with
the addition of plasticiser in quantity just sufficient to form a paste,
and into this the pre-dispersed dry components are added. This is the
first stage of mixing known as the 'thick stage' and the aim is to have
just enough plasticiser to ensure mixing at maximum shear. The
shearing action will produce heat, and care should be taken that the
temperature of the paste should not exceed about 30C, otherwise the
plasticiser will start to attack the polymer and the ultimate viscosity of
the paste will be higher than it should. The mixer can be water-cooled
if necessary. The 'thick-stage' stirring should be continued for some
time (roughly 10-30 min depending on conditions). At the end of this
period the gradual addition of the rest of the plasticiser (and any
diluents that may be employed) is commenced. This marks the
beginning of the 'thin stage' of the mixing process. The plasticiser
addition may conveniently be made continuous from, say, a suitable
funnel arrangement. The thin stage mixing may take very roughly
about 1 h.
The stirring action traps air in the paste, which is undesirable for
most processes, and it must be removed. One of the best ways of
effecting this is to mix under vacuum. If this is not possible the finished
paste is subjected to vacuum or, for the thinner types, allowed to stand
for 24 h.
Storage is important and should receive careful consideration. If the
pastes are prepared and formulated correctly they will store satisfactorily for long periods. They must, of course, be stored in a cool place.
The material of the container is also important. Iron or zinc should be
avoided unless the former is protected by a lacquer which is not
attacked by the paste. Glass, aluminium and tinplate are satisfactory.
The above method is suitable for both laboratory and work-scale
preparation of pastes. For very small quantities the whole operation
can be effected on a mill mixer (say a triple-roll mill) by a suitable
number of passages.
22.1.2 Conversion to Products

As discussed in Section 21.2.5 of the preceding chapter, the conversion

of the liquid paste to a solid PVC product involves gelation and fusion,
actuated by heat. The initial drop in viscosity which precedes the

22

Preparation, Processing and Applications of Pastes

983

'setting' of the paste can also be significant in some processes. The

state reached by a paste which has set to a considerable extent but has
not fused, is sometimes called 'semi-gel' or 'pre-gel'. These essentially
practical terms are not very precise, and in fact relate to what is a fairly
advanced degree of gelation, in which the paste may be sufficiently
cohesive to withstand some handling: this is sometimes utilised in, say,
multiple dipping or coating techniques, where each consecutive paste
layer is 'pre-gelled' after application, and then the whole coating is
finally fused at an appropriate, higher temperature. As has been
mentioned, the temperature necessary for complete fusion cannot be
lower than 160C (and will be appreciably higher for many paste
compositions). Heating above the appropriate lowest temperature of
complete fusion will effect fusion in a shorter time. If the temperature
is too high, some plasticiser loss will first occur, and then decomposition of the polymer may follow if heating is prolonged.
It is important for the purposes of process and quality control to test
the completeness of fusion of paste-derived products. Determination of
relevant physical properties (tensile strength, hardness, etc.) is one
obvious way of doing this, but it can be cumbersome as a routine
check. Solvent tests have been proposed from time to time,
particularly for use with PVC coatings on fabrics, and some of those
are convenient to use and quite reliable. The tests include the ethyl
acetate immersion methods of Kling! and Schimke? and the acetone
test widely used with PVC-coated gloves. The general principle of such
tests is that a test strip, or a complete article (e.g. a PVC-coated
glove), is immersed in the solvent either in a strained condition (e.g. a
strip bent into a loop) or freely suspended, and the PVC is watched for
signs of flaking, i.e. rising of small fragments of the solvent-swollen
material away from (i.e. above) the surface (in the case of a coated
fabric, sometimes also away from the fabric surface). In some versions
of the test the flaking site is predetermined by a nick made in the
specimen, but spontaneous flaking will normally occur in material
which is incompletely fused. If they form, the flakes are clearly visible
and unmistakable in appearance: severe flaking may result in the flakes
becoming completely detached: in the case of under-fused PVC
coatings partial stripping from the supporting layer may occur. In
solvent tests of this kind it is usual to regard the PVC material as
satisfactorily fused if no flaking is observed in a specified period of
time: this may be anything from about 5 to 30 min, depending on the
aggressiveness of the solvent used and the presence or absence of
imposed strain in the specimen.

984

W. V. Titow

In the course of a study3 of gelation and fusion effects in the coating

of fabric-backed PVC gloves produced by a dip-coating process, the
author showed that an acetone immersion test* normally used to
check~n a pass or fail basis-whether satisfactory fusion has been
achieved in an industrial operation, could also provide data on the
degree of fusion (where fusion complete in terms of the test had not
been attained), and an indication of the minimum temperature
necessary for complete fusion of the particular paste composition
under the heating conditions employed.
Substantially identical fabric glove liners were dip-coated (on
production formers, in a standard way) with the same PVC paste (a
standard production formulation). Groups of three of the paste-coated
liners withdrawn at random from the batch so produced were subjected
to heat treatment, each group at a different temperature/time
combination. After the heat treatment, followed by a cooling and
conditioning period, the acetone test was carried out on two gloves
from each group (the third being retained for reference). Where
flaking occurred, the time for the first flake to appear was noted (these
times were in excellent mutual agreement for the duplicate determinations on gloves from the same group). The test results were plotted as
shown in Fig. 22.1. In the figure each point represents the result of one
test (duplicate determination) on gloves from the group which had
undergone heating at the temperature and for the time given,
respectively, by the relevant abscissa and ordinate values. Points
marked with crosses correspond to tests in which flaking occurred: the
time (minutes) of appearance of the first flake is shown by each point.
The circled points represent those tests in which no flaking took place
during an immersion period of 24 h: i.e. where the PVC coating could
be regarded as properly fused in terms of the test. The regions of the
plot occupied by the circles and the crosses correspond to heat
treatment conditions producing, respectively, complete and incomplete
* The specimen used in this test is a complete glove with a circular hole of
25 cm diameter cut in the middle of the back, about 2 cm above the finger
base line (to admit the solvent to the interior of the glove). The specimen is
suspended, fingers downwards, in a beaker, and acetone is quickly poured in
until it surrounds and fills the glove, with the surface level standing about
25 cm above the edge of the hole. Timing is commenced from the moment this
level is reached, the surface of the glove being closely watched for signs of
flaking. In a popular industrial version of this test the fusion of the PVC
coating is considered complete if no flakes appear within 30 min.

985

22 Preparation, Processing and Applications of Pastes

45
40

n3

35

...

30

..

25

.!

20

15

'j

-..

10
5

o ---- \

)(

x
4-5

25

26

x
HI

1"4
160

170

180

190

x
2-3

)(

22

200

OVln tllllperltlill

)(

33

32
I

210

220

230

240

(C l

Fig. 22.1 Effects of heating time and temperature on the completeness of

fusion of PVC coating on dip-coated gloves. Each point on the plot relates to
an acetone immersion test on gloves 'cured' under the conditions (time/
temperature combination) given by the appropriate ordinate and absicissa
values. x, Tests on gloves 'cured' under these conditions resulted in flaking
after the number of minutes indicated by the numericals (e.g. x3.:r-first flake
appeared after 33 minutes); 0, gloves 'cured' under these conditions did not
flake during 24 h continuous immersion.

fusion. The curve constituting the boundary between the two regions is
thus the locus of the minimum time/temperature conditions for
complete fusion in the particular process. The steeply rising portion of
this curve may be regarded as asymptotic to the 172C temperature
line: this indicates that 172C is the minimum temperature for
complete fusion of the paste (and in the conditions) used.
Figure 22.1 also demonstrates that the test is sensitive enough to
distinguish between degrees of fusion where fusion had not been
complete. This is shown by the fact that the times to flaking increase
with increasing oven temperature and with increasing oven time.

986

W. V. Titow

22.2 APPLICATIONS
22.2.1 Rotational Casting
This is the main process for producing hollow moulded articles (dolls'
heads and body parts, hollow 'squeaky' toys, playing balls, etc.) from
PVC paste, offering several advantages over slush moulding which is
the alternative method (see the next section). The development of
rotational casting began around 1950, and the first descriptions of
machinery4-6 are of that vintage. The principles and early practice of
this process were described by Meazey.7
Modern rotational casting equipment, of various sizes, numbers of
moulds and capacities, is available from several manufacturers in the
UK, USA and Europe, most of whom will be found in the current
editions of the relevant directories. 8
Rotational casting (also known as rotary casting, roto-casting, or
rotational moulding) has gained popularity for the following reasons,
most of which represent advantages over slush moulding. Rotationally
moulded hollow articles can be produced with uniform wall thickness
and fine surface detail, from a pre-metered amount of paste. Virtual
absence of flash minimises trimming operations, and the amount of
material waste is also minimal. The equipment and operation are
automated to a large extent, whilst the capital expenditure on
machinery and moulds is moderate by present-day standards.
The principle and basic process of rotational casting are simple,
although in their modern embodiments the equipment and technique
have attained considerable sophistication and versatility. Typically,
multiple moulds-earried on one or more arms indexed to move
between operational stations-are each charged with the appropriate,
metered amount of paste at the filling station, and closed. Transfer to
the heating/cooling station follows, the moulds being spun in one plane
and simultaneously rotated at right angles to the spin direction at the
outset and throughout the heating period. The heat treatment takes
place in an oven powered by electricity, gas or oil, employing hot air or
IR radiation as the heating medium. The complex two-directional
rotation of the moulds spreads the paste evenly over their interior
surfaces, where it is gelled and fused by the heat. The rotary
movement is continued during cooling (by an air stream and/or water
spray) in a cooling chamber, after which the moulds are returned to
the filling station where they are unloaded prior to the commencement

22 Preparation, Processing and Applications of Pastes

987

of the filling step of the next cycle. A typical cycle time may be about
15 min. Spinning rates of 5-16 r min- 1 are fairly representative, with
the ratio of these to the rotation rates between about 1: 1 and 1 :4. For
a given product, the best rates and their combinations are established
on the basis of trials. Simple moulds can be quite satisfactory, made by
the electrodeposition technique (e.g. nickel on copper for good release
properties and thermal conductivity), or cast or machined in
aluminium.
Some rotational mouldings (e.g. playing balls) are inflated after
manufacture with air introduced through a hypodermic needle, the
resulting hole being heat-sealed. Rotationally cast products may also
be filled with foam generated from a polyurethane composition poured
in through a hole foamed in situ whilst the hollow moulding is
supported in a retaining mould. This method has been widely used in
the production of car arm-rests with outer 'skins' rotationally moulded
from PVC paste. However, in that particular application, it is being
strongly challenged by essentially one-step moulding of the arm-rests in
structural polyurethane foam. The following basic formulations
illustrate the kind of pastes used for some rotationally cast products.
Rotational casting formulation for soft dolls or playing balls (paste
viscosity about 12P):

PVC resin: Corvic P65/54*

Plasticisers: DAP
DNP
Stabiliser: Cd/Ba liquid system

l00pbw
40phr
50phr
3phr

Rotational casting formulation for harder objects:

PVC resins: Corvic P65/54

Corvic D55/3t
Plasticiser: Pliabrac 810t.
Stabiliser: CdlBa liquid system
Viscosity depressant: Lubrol MOA

50pbw
50pbw
25 phr
3phr
2phr

* Medium-viscosity, paste-grade resin (ICI).

t Suspension resin

(leI) here used as extender polymer.

:j: Proprietary plasticiser of Albright and Wilson (a dialkyl phthalate, prepared

from a blend of straight-chain octyl and decyl alcohols).

Non-ionic surface-active agent (ICI).

988

W. V. Titow

Rotational casting formulation for car arm-rest 'skins':

PVC resins: Corvic P65/54

Corvic D55/3
Plasticisers: DNP
Reomol MN*
Paraplex G62t
Stabiliser: Irgastab TI50*
Viscosity depressant: Lubrol MOA

70pbw
30pbw
50phr
lOphr
2phr
15 phr
2phr

Rotational mouldings are sometimes surface-finished by spraying

with a lacquer to provide a decorative, tack-reducing finish which also
improves resistance to soiling. The lacquers used are the same as those
applied, for similar purposes, to PVC coatings on fabrics (see Section
22.2.6).
22.2.2 Slush Moulding
This technique may be regarded as the precursor or rotational casting,
to which it has yielded considerable ground over the years. In comparison with rotational casting, slush moulding is more labour-intensive,
whilst repeated handling of the same paste, which also experiences
warming in the process (see below), can cause aeration and adversely
affect the rheological stability. These and other points of comparison
will be apparent from the following brief ol,ltline of the process.
The principle of slush moulding is that the paste is poured into a
lightweight, open mould, and then poured out leaving a layer on the
inside surface of the mould. The thickness of the retained layer may be
governed entirely by paste rheology, or it may be increased by heating
to effect a degree of gelation. In either case the gelation and fusion of
the retained material (which becomes the hollow slush moulding) is
completed by a final heat treatment. The mould is cooled sufficiently to
enable the moulding to be removed without damage or permanent
distortion, but not to a temperature so low that removal may become

* An AGS ester 'low temperature' plasticiser (Ciba-Geigy).

t Epoxidised soyabean oil (Rohm and Haas).

:j: A modified, sulphur-free tin carboxylate stabiliser (Ciba-Geigy).

22

Preparation, Processing and Applications of Pastes

989

difficult: in practice a temperature of about 35C will usually be

suitable. The moulding is most often blown out of the mould by a jet
of compressed air. With shapes which make removal more difficult,
vacuum can be applied to the opening of the mould to collapse the
moudling first.
The main practical variants of the basic method are outlined below.
In one, sometimes referred to as the 'one-pour' method, the moulds
are filled with paste and passed on a conveyor through an oven or
heating bath in such a way that only the body of each mould is heated
(not the paste surface exposed in the open top). The object is to gel
the desired thickness of paste adjacent to the mould wall, and the
heating time (dwell period) and temperature will be adjusted to this
end in accordance with the gelling properties of the paste and the
relevant thermal characteristics of the mould. After the heat treatment
the moulds are emptied of the ungelled paste (this may be by inversion
on the conveyor, so that the paste runs into a catchment trough
underneath) and conveyed to a second heating station-normally an
oven-operated at a temperature required to complete, in the course
of a convenient dwell period, the gelation and fusion of the material
remaining in the mould. The arrangement should be such that both the
mould and the material inside it (accessible to heat through the mould
opening) are uniformly and effectively heated: slow rotation of the
moulds may assist in this, but should not be necessary with an efficient
heating set-up. The temperatures of treatment will vary considerably
depending on the paste composition and conditions, but will normally
be within the range 17D-230C. After leaving the oven the moulds are
cooled (by water or air) in a cooling chamber to a temperature most
appropriate to easy removal of the mouldings (see above), which is
then effected.
In another variant the moulds are pre-heated at around 170C for a
time depending on their size and thickness. They are then filled with
paste and allowed to stand (this may be on a moving conveyor) for
1-2 min. After this the moulds are inverted so that the paste, other than
that of the layer gelled on the mould walls, drains out. The gelled
layer, which may be up to 3-4 mm thick, is then fused by heating the
moulds in a fusion oven. Cooling and de-moulding follow as before.
A method combining elements of both above variants, known as the
'two-pour' method, is also used. In this, cold moulds are filled with
paste, and inverted immediately after filling so that whilst some paste
remains on the interior wall surface the layer is thin. The draining may

990

W. V. Titow

take place on a conveyor, into a catchment trough, as described

previously. The moulds are placed in (passed through) an oven where
the paste layer is pre-gelled. In practice this treatment is short (a few
minutes) at a temperature of 17~220C. On leaving the oven, the
moulds are re-filled with paste and then emptied almost directly,
but-because they are hot-a paste layer of fairly substantial thickness
is gelled onto the previous, thin coating. The actual thickness of the
second layer will be determined by the characteristics of the paste, its
residence time in the hot mould and the temperature of the mould.
The combined paste layer inside each mould is then fused by heating in
a second oven, and the moulds cooled down and emptied as before.
In slush moulding, moderate variation in various paste and process
factors is not absolutely critical, but once suitable conditions have been
established they should be adhered to as closely as possible. Attention
must also be paid to the condition of the paste which is being
re-used, particularly with regard to air bubbles and adventitious
contamination that may have been introduced, and any gelled
particles, as well as to the prevention of any water from the cooling
process entering the paste (as this can cause blistering in the
mouldings). The re-circulated paste should be passed through a
fine-mesh screen on its way into the holding tank, where it should be
de-aerated, preferably under vacuum.
The following formulation exemplifies a basic composition for the
production of PVC overboots by slush moulding.
PVC resins: Corvic P65/54
Corvic D55/3

Plasticisers: DIOP
Pliabrac 810

Stabiliser:
Colourant:

Cd/Ba liquid system

Blue Masterbatch C

70pbw
30pbw
55phr
15phr
3phr
075 phr

Blue Masterbatch C

PVC resin:
Plasticiser:
Stabiliser:
Colourants:

Corvic P65/54

DNP
Calcium stearate
Reckitt's:
ultramarine blue M 6925
blue 8651

100pbw
60phr
4phr
1 phr
2phr

22 Preparation, Processing and Applications of Pastes

991

22.2.3 Paste Casting

This is a relatively straightforward technique, employing comparatively
simple moulds; however a large number are needed for mass
operation. The main types of product manufactured by paste casting
are shock-absorbent pads moulded onto the ends of air and oil filters
for vehicle engines, printing rollers, and various kinds of mats (table
mats, doilies, anti-slip under-mats for rugs). The end-pads for filters
are made in open dish moulds, by pouring the required amount of
paste into the mould in which the filter is standing on one of its ends,
gelling and fusing the paste around the filter 'insert' by placing the
mould with its contents on a hot plate or in an oven, and finally cooling
and removing the filter with the moulded-on pad. The whole operation
is then re-run to mould a pad onto the other end of the filter. In the
production of printing rollers, a metal core is first coated with a thin
priming layer (typically an acrylic and/or epoxy resin composition) to
promote positive interfacial adhesion to the ultimate paste-produced
pPVC roller body. The core is placed axially in a cylindrical mould, the
paste is poured in, and the assembly transferred to an oven where the
paste is gelled and fused, and then removed for cooling and
de-moulding. The heating conditions must ensure complete fusion
throughout the PVC body of the roller, to develop maximum structural
uniformity and durability: these, together with the correct degree of
softness and resilience (which, for properly fused material, are
determined by the paste formulation), are important in this application. The roller (in particular the ends) may require final machining for
correct size: this may necessitate freezing the PVC if it is too soft. Like
the filter mounting pads, mats and like products are produced by open
casting, usually into a shallow dish mould. Excess paste may be
removed by passing a doctor blade across the top of the mould, and
the moulds subjected to a vacuum if the filling operation has
introduced air bubbles. Gelation and fusion are carried out in an oven
(or sometimes on a suitable hotplate or heated conveyor) as for the filter
mounting pads. In the heating operation, a longer treatment at a lower
temperature (providing that this is not below the minimum temperature for complete fusion) will normally be preferable to a shorter
period at a higher temperature, to avoid under-fusing the inside with
possible overheating of the outside of the products.
PVC films are cast or spread from paste onto a suitable base (e.g. release

992

W. V. Titow

paper) in fabric coating operations: this application is discussed in

Section 22.2.6.

22.2.4 Dip Coating and Moulding

(a) Hot-dip Coating
This is a useful method of producing ppve coatings on metal objects
suitable for dipping in paste. In essence, the article to be coated is
heated, dipped into the paste, allowed to drain for an appropriate
time, and heated to complete the gelation and fusion of the coating
layer.
Articles of thickness substantially below 3 mm (e.g. thin wire) will
not normally be suitable for treatment by this process, because low
heat capacity hampers satisfactory fusion. For similar reasons it is
difficult to obtain a good coating on sharp edges. The two essential
items of equipment are an oven (with air circulation or other means of
ensuring maintenance of uniform temperature distribution) and a
dipping tank equipped with a slow-speed stirring arrangement. Oven
temperature of 175-200o e will usually be satisfactory. Stirring the
contents of the tank, whilst necessary to maintain general paste
uniformity, cannot prevent some lumping and viscosity rise brought on
by the continual dipping of hot objects: the state of the paste must
therefore be monitored.
The objects to be coated must be thoroughly cleaned and degreased
before dipping. This gives some adhesion but of relatively low degree:
if positive interfacial bonding is required the surface of the object must
be primed by application of a priming coat of the kind mentioned in
Section 22.2.3, deposited from solution in a solvent. Two commercial
examples are Deckor Primer (Scott Bader, UK) and Vinatex Adhesive
MP7A (Vinatex Ltd, UK). The primed article to be coated is first
heated in an oven to a temperature between 900 e and 130oe:
depending on the thickness this may take 5-10 min. It is then dipped in
the paste and left long enough to build-up the desired (or maximum
practicable) thickness of coating: the time required for this is normally
quite short-typically 1-2 min. On wire, coatings 05-08 mm can
usually be obtained in one dip. The temperature of the paste may be
between about 17e and 300 e depending on the composition. The
speeds of entry into the paste and of withdrawal are factors in the
process. If the object is withdrawn too quickly a poor coating will

22 Preparation, Processing and Applications of Pastes

993

result-ideally the rate should be the same as that at which the paste
drains off. Not much heat should be left in the object: the final fusion
is effected in a separate step. 'Dip marks' (paste drips) usually formed
at the bottom of the article may be brushed off before the heat
treatment for fusion. This will be appropriate to the paste composition,
coating thickness and other relevant process factors. An under-fused
coating which may appear matt and be weak or even crumbly, may be
returned to the oven for further treatment, providing that the fault is
not due to the oven temperature being generally below the minimum
necessary for complete fusion.
Articles PVC-coated by the hot-dip process include fence posts and
fittings, handles, thick wire baskets and trays, mounting brackets and
the like.
(b) Hot-dip Moulding
This process is closely similar to hot-dip coating, except that the object
being dipped is a suitably shaped metal former (which may be treated
with a release agent), and the coating becomes a hollow moulding
when it is stripped from the former after fusion and cooling.
Two procedural variants are in use. In one, the formers are
pre-heated in an oven and dipped into the paste in the dipping tank at
a controlled rate: this is usually quite fast (say about 10 s to submerge
the former to the required depth) to avoid differential cooling with
consequent uneven paste layer build-up. The immersed formers are
left for the time necessary for the coating layer thickness required: this
residence period may be quite short. They are then withdrawn at a
uniform rate (normally slower than the dipping rate) so regulated as to
avoid excess paste being dragged out of the bath through viscosity
effects. Once out of the bath, the formers are inverted to let any drips
merge back into the coating layers, and transferred to a second oven to
fuse the coatings. This treatment is followed by cooling (which may be
forced), stripping, and any trimming operations that may be necessary.
The second variant involves the same dipping and withdrawal
procedures, but the pre-heating of the formers and gelation/fusion of
the paste coatings picked up are both done by immersing the formers
in a tank of a liquid heating medium. More effective heating for
shorter periods (e.g. completion of gelation and fusion about 2-3 min
in many cases) are claimed as the main advantages over the method
involving oven heating, with consequent faster cycles and reduced

994

W. V. Titow

tendency to the formation of 'drips' and 'runs' of paste on the articles

directly before and in the early stages of the gelation/fusion treatment.
Disposable, unsupported PVC gloves (typically produced from a
basic plastisol composition containing about 100 phr DOP), tool and
handlebar grips, golf club covers, and covers for cable terminals, are
examples of mouldings produced by the hot-dip process.

(c) Cold-dip Coating

In this process the object undergoing dipping is cold. The advantage of
this is that the viscosity and general condition of the paste in the
dipping tank remain stable, and there is no accumulation of partly
gelled lumps and particles. Although on some metal objects the finish
obtainable may not be as good as that from hot dipping, cold dipping
can be useful in some cases where the object is of irregular thickness:
in hot dipping the thicker parts, having greater heat capacity, will tend
to build up a thicker coat.
Cold-dip coating is important as the method of production of
fabric-lined PVC work gloves. These are made by drawing knitted
fabric gloves (the 'liners' for the ultimate composite articles) onto
hand-shaped formers (usually metal, but sometimes also ceramic), cold
dipping the liners on their formers fingers-downwards into the PVC
paste, withdrawing, allowing to drain, inverting to let any drip marks
at the ends of fingers and thumbs flow back into the coating, and then
gelling and fusing the paste layer by passage through an oven under
suitable conditions of oven temperature and dwell time. Operation in
modern plants is continuous and highly automated. The thickness of
PVC coating and degree of its penetration into the fabric of the liner
are influenced by the fabric's construction, the rheological properties
of the paste, the rates of dipping and withdrawal of the formers, the
length of the draining period, and the gelation/fusion conditions. An
appreciable degree of penetration is desirable for good union between
coating and liner, but a layer of free fabric should remain on the
inside of the glove to fulfil the moisture absorption and cushioning
functions important to the wearer's comfort. For these reasons any
extensive 'strike through' of the paste to the inside of the glove is a
fault.
A glove-dipping plant is shown in Plate P.
Other fibrous products cold-dip coated with PVC paste, in which a
degree of mechanical keying through partial penetration of the coating
into the surface of the substrate contributes to the strength of union

22

Preparation, Processing and Applications of Pastes

995

Plate P Fully automatic dipping plant for PVC-coated industrial gloves.

(Comasec SA, Paris, France-Courtesy Mr A. Charnaud.)

between the two, are household clothes lines and some types of cords
and ropes.
Cold-dip coating of metal objects-where there is no surface
anchorage effect of the kind afforded by a fibrous substrate-is
generally more difficult to operate and control than the hot-dip
process. A low-viscosity, non-dilatant paste may be used to build up
the required coating thickness, by multiple dipping, from a number of
thin layers, each pre-gelled before the application of the next one. In
this kind of procedure enough heat must be applied at each gelling step
to soften the previous coat sufficiently to ensure good merging with the
one undergoing gelation. The combined layer is ultimately fused as a
whole in a final heat treatment. In some cases a one-dip coat may be
given with a viscous paste formulated to be strongly thixotropic at the
relatively low shear rates involved in the dipping process: such a paste
will 'set-up' in the form of a fairly thick coating, with very little
draining, directly after withdrawal from the tank.

996

W. V. Titow

An example of a basic formulation for a low-viscosity, cold-dip paste

is given below:
PVC resin: Breon P 130/1
Plasticiser: DOP
DOS
Stabiliser: White lead paste

100pbw
65phr
16phr
2phr

22.2.5 Spray Coating

The area of application of this method is similar to that of dip coating.
It is, however, particularly useful for objects which are either too large
to be easily manipulated in dipping, or of intricate shape. Plastisols for
spraying should have low viscosity and be non-dilatant. A definite yield
point for flow (Bingham body behaviour) is also desirable as it restricts
flow after deposition, although it also makes levelling more difficult:
this is, in any case, not normally as easy as with paints for spray
application where the solvent vehicle promotes the necessary degree of
mobility. Raising the temperature of application can assist the levelling
of the paste coating by reducing its viscosity. The incorporation of a
small proportion (say about 10 phr) of solvent (e.g. white spirit) can
also be helpful in this connection. However, if too much solvent is used
a two-stage heat treatment may be necessary, to remove the solvent
and then to gel and fuse the coating. Limiting the proportion of solvent
added to well below the level usual for a true organosol also enables a
thicker coating to be achieved in one operation: as an example, say
025-125 mm depending on the paste formulation and application
conditions, as against 003-006 mm with some true organosols. For
thick organosol-applied coatings, multiple application may be necessary, with solvent evaporation after the deposition of each layer to
avoid blistering or orange-peel effects in the final product.
The spraying method and equipment may be of the air-spray or
airless variety. In the former, the spray gun used should be of the
external mix type. A commercial example is the De Vilbiss JGA gun
fitted with a No. 306 air cap and size D fluid tip, and connected to a
pressure feed container for the paste. Pressure feed is normally more
efficient than gravity feed, although the latter type can be used
satisfactorily in relatively small-scale operations for spraying organosols of suitably low viscosity. A typical capacity range for pressure feed
containers would be 05-40 gal.
The airless method uses a high hydraulic pressure, in the region of

22

Preparation, Processing and Applications of Pastes

997

2000 lbf in- z, to force the paste through a small spray orifice (typically
OOB-in bore) and thereby obtain the right atomisation.
Electrostatic spraying of PVC paste may be carried out by either of
the above two general methods, with appropriate arrangements for
charge generation. This mode of operation, which is particularly useful
with metal objects, can offer economies in paste consumption and
coating time: uniformity of coating of intricately shaped surfaces is
another advantage of a properly run electrostatic spray-coating
process.
Problems which may be experienced in spray coating with pastes are
generally similar to those encountered in paint spraying. Some of the
more common ones are: a 'pebble' finish caused by excessively high
line pressure or the gun being held too far from the work; runs which
may form if the gun is too close or the paste too fluid; wrinkles or sags
on vertical surfaces where the coating has been applied too thickly.
After spraying, the coating is gelled and fused by a heat treatment.
This may be preceded by drying if an organosol has been used. The
drying temperature should be kept to a reasonable minimum to
prevent bubbling by the departing solvent, and to keep down the
polymer's heat history. The gelation/fusion of coatings on metal
substrates may take about 5-10 min at an oven temperature of around
180aC. Higher temperatures may be used to shorten the time, but
caution is necessary, as hot spots can develop (especially in a large
oven) which can lead to local overheating.
The following are two examples of basic formulations for spraycoating pastes:
Plastisol
PVC resin:
Plasticisers:

Stabiliser:

Corvic P 65/54A
DAP
DNP
Paraplex G62
Stanclere80(AKZO, Chemie, Sarl, France)

100pbw
40phr
50phr
2phr
075 phr

Breon P 130/1
DOA
Mellite131 (Albright and Wilson Ltd, UK)
MIBK
white spirit
TiO z paste (1 : 1 in DOP)

100pbw
25phr
2phr
15phr
15 phr
5phr

Organosol

PVC resin:
Plasticiser:
Stabiliser:
Solvents
(diluents) :
Pigment paste:

998

W. V. Titow

22.2.6 Coating of Sheet Materials (Fabrics and Paper)

PVC pastes find a very important commercial outlet in the coating of
fabrics and papers in the manufacture of such products as tarpaulins,
tent fabrics, awnings, upholstery materials, wall-coverings, bookbinding fabrics and papers, leathercloth for travel and fancy goods and
garments (protective and fashion), floor coverings, conveyor and drive
belts, and adhesive tapes.
The coating procedures fall into two general groups-direct coating
and transfer coating (also known as reverse coating*). In procedures of
the first kind the paste is applied directly to the substrate to be coated
(textile or non-woven fabric, paper), whilst the essential features of a
transfer method are that the coating is first deposited on a carrier
material with an easy-release surface, the substrate proper is laminated
to the deposited layer (which may be composite), and the carrier
removed.
Extrusion coating, and lamination to a preformed PVC film, are
alternatives to paste coating as methods of manufacture of some of the
above mentioned products (as well as others-e.g. decorative surface
coverings such as imitation veneers and the like). In the film
lamination method, a calendered film may be laminated to the
appropriate substrate in-line, i.e. as the hot material leaves the
calender (see Chapter 18). A finished film (manufactured by
calendering or extrusion) can also be applied to a substrate in an
entirely separate operation. In this case the film will be heated or
treated with an adhesive for bonding to the substrate: the latter may
itself be carrying a tie coat to facilitate bonding, or a coating (say a
foamable layer) directly applied, so that the operation becomes a
combination of direct coating and film lamination techniques (see also
further on in this section).
The common basic arrangements for applying a coat of PVC paste to
a continuous sheet material are schematically illustrated in Figs 22.2
and 22.4. Their practical embodiments form the paste-application
sections of various industrial coating units and lines. In the laboratory,
paste layers can be hand-cast with a simple film-coating frame, with a
fixed or adjustable gap under the spreading edge.
* Not to be confused with reverse roller coating which is one of the ways
whereby paste is applied to a sheet material by means of an arrangement of
rollers-see Fig. 22.4 and the associated text.

22

Preparation, Processing and Applications of Pastes

999

The suitability of each basic type of industrial coating arrangement

in a particular situation will depend on several mutually interacting
factors, especially the nature of the substrate (with particular reference
to its permeability, and extensibility under the tension experienced in
processing), paste rheology, thickness of coating and degree of
penetration required.
Note: In some cases (e.g. certain tarpaulins and ground sheets,
conveyor belts, some types of rainwear and protectivegarment fabrics) complete impregnation of the substrate may
be required. With most true coatings on fabrics a depth of
penetration of 1/3-1/2 of the fabric thickness will normally be
aimed at to combine good 'keying' of the coating with the
preservation of satisfactory flexibility and 'handle' of the
finished product.
For a given application system and paste rheology, the thickness and
degree of penetration of the coat (and, to some extent, the rate of
coating) are influenced by the size and configuration of the gap
between the substrate and the coating element (doctor blade or roller)
as governed by the setting and (especially with a doctor knife) the
profile of the latter, the tension applied to the substrate, and the
nature and positioning of any support under the substrate at the
coating point.
Some of the ways in which the factors just mentioned will affect the
casting operation and its results are fairly obvious. Thus a thick,
heavily filled, non-thixotropic paste will tend to produce thick coatings
with relatively limited penetration, and will make for comparatively
slow rates of application. A light substrate with an open structure and
substantial extensibility will be more prone to penetration by a given
paste in a given coating process than a dense, heavy, stiff one. A
doctor knife with large radius of the leading edge, set at an angle to the
substrate, will tend to produce a heavier coating than a vertically set,
finely radiused blade. Such general considerations provide useful broad
guidelines, and a few more are mentioned below among further
comments on the knife and roller coating arrangements. However, the
individual factors do not operate in isolation: they invariably interact,
and the effects of the interaction must be taken into account (and the
results confirmed by practical trials) in any given case.

1000

w. v.

Titow

(a) Paste Coating (Spreading) by Doctor Knife

The basic variants of this method are represented schematically in Fig.
22.2.
In coating with a doctor knife the blade is set over the substrate and
the paste is poured or pumped from a reservoir so that it forms a
constantly replenished uniform 'roll' or 'coil' in front of the blade
across the width of the substrate 'web'. Depending on the properties of
the latter, and the coating characteristics required, the consistency of
the paste may range from that of a fairly free-flowing liquid to a thick
dough: the knife blade profile and setting (i.e. whether vertical or
inclined), and the effective spreading gap will also be chosen
accordingly. Some typical profiles are illustrated in Fig. 22.3, with an
indication of their applications. The coating speed is subject to the
factors just mentioned: depending on the conditions, the speeds for a
fairly representative range of operations may vary between about 10
and 100 it min-I.
In the knife-over-roller and knife-over-plate arrangements, the
support roller may be of steel or rubber, and the plate is usually steel.

Fig. 22.2 Knife coating (spreading) arrangements: schematic representation.

A, Knife over roller; B, air knife; C, knife over plate; D, knife over blanket.

l. I
E

Fabrics: over rubber

roll or blanket

Fabrics: as D

Fabrics: as air knife, or

over rubber roll or
blanket
Heavy fabric: over
blanket
Paper: over steel roll
Paper: over metal roll

Substrate, and coating

arrangement

Typical uses

May be angled
(up to about
4)
AsD

Vertical, or
angled up to
3
Usually vertical

Vertical

Usual knife
setting

Heavy (suitable for

thick, heavy pastes)

Suitable for range of

coating weights
(with range of paste
viscosities)
Heavy and/or penetrating

Thin (including antiqueing on embosssee text)

Thin (especially priming or tie coats)

Thickness and/or weight

of coating

Good surface finish;

typical products: floor
coverings, brattice
cloth

Appropriate for highspeed coating; good

surface finish

Remarks

Fig. 22.3 Some common doctor blade profiles: schematic representation. Substrate movement from
left to right. Other factors being equal the amount of coating will increase with increasing radius of the
leading edge of the blade.

r r
$::>

--

-~

.Q.,

$::>

<"'>

:=::-:

).

s::..

;:,

~.

'"

<"'>

C3

"1:l

.r

6'"

i:l

$::>

!OO2

W. V. Titow

In both these arrangements there is a fairly direct relationship between

the setting of the doctor blade and the coating thickness: this is a help
in setting up and controlling a coating operation. With a knife-overblanket system the situation is more complicated, as the tension of the
rubber belt and the speed of its movement also have a considerable
effect. Similar considerations apply in connection with the tension in
the fabric and its rate of advance in the air knife arrangement where,
however, absence of support under the knife creates further complications: the tension generated in the fabric by the pressure of the knife is
comparatively high, and more variable than with the knife-overblanket system. With relatively light and extensible fabrics this can
lead to excessive weight and/or penetration of coating, as well as
variability in these respects. Hence, in practice the arrangement is best
suited to the coating of fairly substantial substrates of reasonable
strength and low extensibility, with pastes of medium or high viscosity
which are not greatly thixotropic or pseudoplastic.
The general effects of incorrect selection or setting in the matter of
such basic process parameters as knife profile and positioning, fabric
tension and rate of advance, and paste rheology, are broadly
predictable; and conversely, their manifestations should be fairly
readily traceable back to these causes. Faults originating in this way
will most commonly take the form of deviations from the desired
weight per unit area (or thickness) of coating and/or the extent of its
penetration into the substrate. The magnitude of such defects in a
given case will depend on the degree of departure from the optimum
processing arrangements and the relative importance-in the paticular
operation-of the factor(s) responsible. Thus, for example, a highly
dilatant paste may (especially with an unsuitable knife profile and
setting) flow so poorly that areas of the substrate will remain uncoated
(a fault sometimes known as 'missing').
Other faults, whose origins in particular cases may not be
attributable to basic process parameters, are also encountered. Those
usually known as 'streaking' and 'blobbing' are possibly the most
characteristic. Streaking takes the form of lines or streaks caused by
the drag of particles under the doctor blade. The particles may be
present for various reasons: they may be relatively coarse particles (or
aggregates) of pigment or filler (or even polymer) persisting from the
original preparation of the paste; they may be polymer agglomerates
formed in the high-shear region under the blade (especially in
high-viscosity pastes at excessive spreading rates); in some composi-

22

Preparation, Processing and Applications of Pastes

1003

tions the compatibility of constituents may be affected by the

high-shear conditions under the blade to the point where separation
and agglomeration can occur-this particular problem can be prevented by suitable formulation in the light of relevant experience.
Otherwise the first practical remedy to be considered when streaking
occurs is milling the paste on an efficient mill. In general, use of good
quality components (especially polymer(s), pigment(s) and filler(s
and proper compounding of the paste to ensure thorough dispersion
and homogenisation are purposeful preventive measures. Blobbing is
the presence of blobs on or in the otherwise smooth and level surface
of the coating. The immediate cause of this fault is local build-up of
paste at the back of the doctor blade and periodic dropping off of the
accumulations, but the reasons for the build-up are not entirely clear:
it is believed to be associated in some way with the high pressure
experienced by the paste under the blade, but the differences between
conditions, respectively normal (i.e. resulting in fault-free operation)
and abnormal in this regard have not been fully elucidated. In some
cases too-high paste viscosity and/or insufficient thixotropy are
definitely instrumental in the origin of the fault, in that it may be
remedied by appropriate adjustments of paste rheology: milling the
paste or changing the profile of the doctor blade may also be helpful
on occasion. Turbulence in the paste under the blade may occasionally
arise, and cause air trapping.
Two other well-known faults, which can occur with any coating
method, are pinholing and blistering. A common cause is excessive
evaporation of a volatile substance when heat is applied to the
paste-coated material in processing to gel/fuse the coating, causing
blowing of expandable layers, etc. The culprit may be moisture present
in the substrate, or originally present in a formulation constituent (e.g.
polymer, filler) and introduced with it into the paste, or (less
commonly) acquired by the paste during or after preparation. It may
also be a volatile impurity or low-molecular-weight residue in a paste
component. In all such cases the fault is frequently batch-related. In
organosols, pinholing or blistering can sometimes be caused by
untimely or too rapid evaporation of solvent. Occasionally the
appearance of pinholes may not be traceable to any of the above
factors. In such cases, and if the fault is not of catastrophic
proportions, it may be helpful to use two coating stations in series (Le.
apply the coating in two consecutive layers) so that the number of
pinholes penetrating the total coating thickness is reduced in

1004

W. V. Titow

proportion to the chance that a pinhole in the first layer will coincide
with one in the second.

(b) Paste Coating by Roller

In roller coating, a uniform layer of paste is first formed on the surface
of a roller (the transfer roll) whence it is transferred to the substrate as
the latter passes through the nip of the transfer roll and a backing roll
(commonly of rubber, or rubber-sleeved).
In the simplest practical arrangement (not much used in PVC paste
coating) the transfer roller picks up the coating material directly from a
trough in which it is partly immersed, excess is removed by a suitably
positioned doctor knife, and the resulting fairly uniform layer then
transferred to the substrate.
The most popular roller sytem for applying PVC paste to continuous
sheet substrates is known as reverse roller coating. Its main advantage
is good control of the weight (and thickness) and uniformity of coating
applied, by virtue of the fact that a layer of the coating material is
accurately pre-formed before transfer to the substrate: the amount
actually transferred can also be further adjusted by the setting of the
nip between the transfer and backing rollers (see Fig. 22.4). The
nature of the substrate is also less critical than in knife spreading as a
factor in the process and the characteristics of the resultant coating. A
nip-fed version of a reverse roller coating station is schematically
shown in Fig. 22.4.

Fig. 22.4 A reverse-roller coating arrangement (nip feed): schematic

representation; only basic components shown.

22

Preparation, Processing and Applications of Pastes

1005

In modern roller-coating equipment additional control over the

thickness uniformity of coating across the width of the substrate is
afforded by provision for roll crossing as a means of adjustments in this
regard. Such means of controlling the profile of a plastics sheet
material undergoing processing by rollers are a feature of some
calenders, and are discussed in Chapter 18.
(c) Direct-coating Process
A typical basic direct-coating unit will comprise a paste application
section (of either knife- or roller-coating type) and a gelation/fusion
oven. This assembly, with appropriate unwinding and wind-up
arrangements for the substrate, and paste reservoir and feed, may
constitute the entire set-up for siinple single-coat application. However, a modern coating line can comprise a number of coating units
(including double-sided coaters in some cases, e.g. for the production
of completely sealed or impregnated fabrics), with the appropriate
gelling ovens and cooling stations (cooled drums or chambers).
Embossing and over-lacquering units may sometimes be included in a
line (with the coating being embossed directly after fusion, while still
hot enough to take the impression), but such surface decoration and
finishing is often done in a separate operation (see below).
Tensioning control and drive systems for the substrate, incorporating
unwinding, compensating, rewinding and wind-up gear, are typical
features of good industrial equipment, as are measuring devices (e.g.
~ray gauges) for the monitoring of coating thickness and its running
adjustment via a link-up to the coating station(s).
Substrate widths of over 1 m (e.g. for wall-coverings or heavy-duty
fabrics) to about 4 m (e.g. for floor coverings) are processed. Coating
speeds, say with some wall-coverings, may be over 600 ft min-I.
Oven temperatures can, and should, be controlled closely with
regard to both level and distribution, for uniform gelation/fusion
throughout the coating and across its full width. Temperature zoning
should be available to regulate the temperature rise in the coating (and
the operation of the blowing agent in expanded coatings) for best
results. With organosols, pre-heating in a relatively low temperature
zone is practised to prevent skinning of the paste layer which can lead
to blistering as the temporarily trapped volatiles eventually escape.
Some ovens are provided with integrated exhaust incineration to
prevent air pollution, and with heat recovery systems.

1006

W. V. Titow

(d) Transfer(Reverse )-coating Process

The modern versions of this process are capable of close control,

producing good-quality uniform, multi-layer coatings. The process is
also particularly useful where such coating is required on a weak or
easily distorted substrate (e.g. a relatively light knitted fabric). The
principle of the transfer-coating method is to produce-by a direct
application method-a layer (which may be composite) of paste
material(s) on the smooth surface of a continuous support (which may
incorporate or carry a release agent), laminate the substrate to be
coated to the paste layer, and remove the laminate. The temporary
support may be a stainless steel band or, very commonly, a strong
paper coated with a silicone release agent. An excellent surface finish
which is usually obtained is an additional advantage in transfer coating.
A procedure for the production of a typicalleathercloth9 ,10 (for, for
example, fancy goods, upholstery or garments) provides an example of
transfer coating where the finished product will be a fabric carrying a
coating comprising an expanded (foamed) intermediate layer, and a
'skin' (wear-resistant layer) with or without a thin bonding layer
between the foam layer and the fabric.
Note: The three-layer construction is also common for fabric-based

PVC flooring (normally produced by reverse-roller coating,

not the transfer method).

In this kind of operation, the paste formulated for the skin layer is
spread ('cast') on the surface of strong kraft paper treated with a
silicone release agent. The layer may be gelled before the next
operation, or it may be left ungelled. The next step is to cast a second
layer of suitable foamable paste composition onto the skin layer: if the
latter has been gelled in the meantime, this second step will constitute
a 'wet on dry' application; if not, then the application will be 'wet on
wet'. The second coat (or both if the application has been wet on wet)
is then usually pre-gelled at a temperature low enough not to cause
foaming or excessive hardening. The base fabric is applied to the 'free'
surface of the second coat and fixed in place by a heat treatment which
will gel and fuse the PVC and produce expansion of the intermediate
layer (by activating the blowing agent-see Chapter 25). In another
variant, gelation/fusion and blowing may be accomplished before the
application of the fabric, and a third thin bonding coat of paste

(without blowing agent) may then be applied and the fabric laminated
to this to be finally fixed by heating. In either case the material is then

22

Preparation, Processing and Applications of Pastes

1007

stripped from the paper (with the original first PVC/paper interface
becoming the top surface of the coated fabric).
Where only simple, single-station coating equipment is available, the
wet-on-dry procedure will be followed, each coating step being
effected in a separate passage. In modern large-scale coating practice
the whole process can be carried out on a single line with multiple
coating, heating and cooling stations, and usually incorporating the
facilities and refinements mentioned above in connection with direct
coating. The final stripping of the substrate/coating laminate from the
carrier may also be carried out in-line, or on a separate machine. In
the latter mode of operation faster coating speeds may be possible (say
up to about 500 ft min-I) as stripping is, in general, slower than
coating.
Cellular leathercloth may also be produced by a variant of transfer
coating involving a film lamination step. In this method the foamable
paste is first cast onto the carrier (release paper) and the fabric
applied to this layer (which may be pre-gelled). The laminate is passed
through an oven to foam and fuse the PVC, then through a cooling
station, and the carrier is stripped off. Next a thin layer of paste is
applied to the coating's surface; this paste is formulated (often on the
basis of a vinyl chloride copolymer) to fuse at a relatively low
temperature at which the foamed layer will not collapse. A thin
calendered film, formulated to function as the skin layer of the
composite coating, is then laminated to the assembly and fixed on by a
heat treatment which fuses the thin adhesive layer.
(e) Promotion of Adhesion between Coating and Substrate
The use for this purpose of a tie (bonding) or priming coat has already
been mentioned. Such coats may be applied to a substrate (fabric,
paper, metal) to be subsequently coated by a direct or transfer
method, or to the 'free' surface of a transfer coat deposited (if
composite, assembled) on a carrier prior to the final lamination to the
substrate, or to a film in the film-lamination coating method. In some
cases, especially with direct coating, a priming coat can serve as both a
bonding layer and a barrier restricting penetration into a porous
substrate of the material of the main coat. Such priming costs on paper
or fabric substrates may be thin latex-deposited PVC layers (see
Chapter 23.)
Certain adhesion promoters may be incorporated in the coating
paste. For instance, special liquid isocyanurates (e.g. Vulcabond

1008

W. V. Titow

VP-ICI) have been used as such additives in PVC pastes for coating
nylon and polyester fabrics in the production of tarpaulin and
protective clothing materials.

(f) Surface Decoration and Finishing of pvc Paste Coatings

The surface of many products manufactured by paste coating of
continuous substrates is structured by embossing for such decorative
effects as, for example, grain and leathercloth, or various raised
patterns on wall-coverings (so-called 'chemical emboss' achieved by
selective control of foaming is discussed in Chapter 25). Sometimes the
surface is printed (commonly by a gravure printing process)l1 either as
the only decorative treatment or prior to embossing. The printing and
embossing may be carried out as a separate operation after coating.
With some products (e.g. flooring, decorative surfacing materials) the
intermediate layer of the composite coating may be printed, so that the
print is protected by a clear skin layer which is applied after printing.
A thin top coat of a lacquer is commonly applied to paste-produced
PVC coatings, especially those of high plasticiser contents (say roughly
above 50 phr). The lacquer layer may have (or combine) any of the
following functions: prevention of plasticiser migration (and the
resultant surface tackiness), increasing resistance to abrasion and
soiling, imparting or reducing surface gloss, modifying surface colour,
imparting special decorative effects (especially in conjunction with
embossing-see below). Many commercial lacquers are dilute solvent
solutions of acrylic resins often in conjunction with a PVC copolymer,
e.g. some of the Deckor lacquers (Scott Bader, UK), or Argutop LG
(Argus Chemical Corp., USA; Argus Chemical GmbH, West
Germany). Some processors make up their own lacquers: a fairly
representative example of a basic formulation would be: *

Copolymer (VCNA) resins: Breon 202

Breon 425
Polymethyl methacrylate resin:
Solvents: toluene
methyl ethyl ketone

2pbw
3pbw
5pbw
40pbw
40pbw

Heat and light stabilisers may be incorporated to protect the resin

(especially the PVC) components of the lacquer itself and also-where
required-the PVC coating underneath. In the latter case, say where
* See also Chapter 24, Section 24.4.

22

Preparation, Processing and Applications of Pastes

1009

exposure to sunlight will occur in service, the lacquer may serve, inter
alia, as a vehicle for an extra light stabiliser interposed in this way
between the incident radiation and the PVC coating. Colourants are
also common additives. Matting agents are incorporated in lacquers for
matt finishes. The resin components of a lacquer may also be (or
include) polymers other than those already mentioned, such as
polyurethanes (e.g. Argutop LV), polyamide (e.g. Argutop LN
1060-a high gloss commercial lacquer), or cellulose acetate butyrate
(for surface slip and anti-blocking).
Keying solvents (e.g. cyclohexanone, isophorone, tetrahydrofuran)
may be included in the lacquer formulation for better ultimate
adhesion to the PVC surface, but care must be taken that their
presence does not disfigure the emboss during heat treatment.
Whilst the lacquers have traditionally been solvent-based, aqueous
polyurethane and acrylate systems (colloidal dispersions) have also
made their appearance among the commercial products. Two examples
are Neo-Rez R-900 (Polyvinyl Chemical Industries Inc., USA) and
Laqua WB 240 (Bee Chemical Co., USA).
Lacquers are usually applied by an engraved (gravure) roller or
doctor knife. Special effects may be achieved on embossed surfaces if
the colour of the lacquer is different from that of the coating. Thus,
most emboss patterns may be 'topped' by applying a coloured lacquer
by roller in light contact with the surface so that only the protruding
portions are covered and thereby made to contrast with the
depressions. The speed of passage of the coated, embossed material
under the roll, and its presentation to the roll surface, can be arranged
to deposit the lacquer predominantly on the 'slopes' to one side of the
tops of the raised portions of the emboss. This effect is known as
'shading'. With suitable heavy emboss patterns a coloured lacquer can
also be applied (usually by a doctor blade suitably profiled and set-ef.
the caption of Figure 22.3) so that it is deposited in the depressions,
whilst the tops of the raised elements of the embossed pattern are
wiped substantially clean and thus retain their original colour. This
effect, produced on some leathercloths used for decorative purposes, is
referred to as 'antiqueing' or 'antique finish'.
(g) Testing of Coated Materials
Completeness of fusion of coating may be determined by a solvent test.
In some cases a test of coating-strength properties may be practicable
(e.g. a bursting-strength test on the coated material, or a tensile

1010

W. V. Titow

strength and elongation test on the coating removed from the substrate
with the aid of a leather-splitting machine).
Most of the other tests and determinations commonly carried out on
coated materials, including conveyor belting, will be found in the
standard specifications listed in Section 7.1 of Appendix 1. The
properties of most frequent interest include weight of coating per unit
area, breaking strength (bursting strength with some coated knitted
fabrics), resistance to flexural fatigue, adhesion of coating, abrasion
resistance, tear strength, low-temperature properties of coating
(cold-crack, cold-bend, etc.-see Chapter 12, Section 12.2), water and
air permeability, volatile matter content (cf. also ISO 176-1976; BS
2782: 1970, Method 107F; AS 1441.8: 1973; Canadian Standard
4-GP-149: 1972), the effects of weathering and ageing, and various
performance tests directly relevant to end-use. An early summary of
some test techniques and equipment was published by Dalton,12 and a
useful test for soiling resistance (carried out on an abrasion tester) by
Kratschmann. 13
Note: Resistance of flooring materials to staining by contact with
rubber (shoe soles, ferrules) or shoe polish, and by other
agencies, is assessed in various ways, some used as standard
tests, e.g. by plasticiser manufacturers. 14

Test data on some properties of PVC-coated nylon and polyester

fabrics, with special reference to creep resistance, are contained in a
paper by Blumberg et al. 15
22.2.7 Miscellaneous Paste Processing Methods of Minor Significance
The methods mentioned in this section have never been of primary
industrial importance. In some cases their interest has become more
historical than current as a result of increasing applicational scope of
modern solid flexible PVC compounds for injection moulding and
extrusion.

(a) Low-pressure Injection Moulding

Split moulds (usually of aluminium or chromium-plated steel), gated
on the parting line (and clamped during the moulding and heating
operations) may be employed, the paste being injected by air pressure
(the simplest and cheapest way in most cases), ram, or screw. The
greatest single application of the process has been in the moulding of

22 Preparation, Processing and Applications of Pastes

1011

soft PVC soles onto the uppers of certain types of cheap footwear.
Fairly typical conditions would be: injection of paste under about
50 lbf in -2 pressure into a mould pre-heated to about 170C and
thereafter maintained at that temperature for the time required to
complete the gelation/fusion of the moulding (normally a few minutes).
Soft sealing gaskets for tin box lids have also been produced by
low-pressure injection moulding. Direct injection of a paste into the
gap of a joint between metal components (inter alia, in vehicle
construction) to act as a caulking medium (after gelation/fusion by
external application of heat) is another example of the application of
this kind of process.

(b) Compression Moulding

This is not a paste-processing method of any substantial practical
significance. Whilst it has been used to make-in a controlled,
reproducible way-moulded sheets serving as a source of specimens for
evaluating and monitoring the properties of paste products, it is
common practice to make sheets for the same purpose by casting (and
fusing) a layer of paste on a metal plate (in some cases on a 'hot bench'
or 'gel block'-see Chapter 21, Section 21.2.5). A typical compressionmoulded sheet of this kind would be a disc of a size and thickness
appropriate to the dimensions and number of test specimens required,
moulded in a flash mould. In outline, a suitable moulding procedure
would comprise pre-heating the mould to about 80C, filling with
paste, closing, heating to about 170C (or such higher temperature as
may be necessary for complete fusion) and keeping at that temperature
for about 10 min under a pressure of about 40 tons, then cooling under
a somewhat higher pressure (say 45-50 tons) to counteract shrinkage.
(c) Extrusion
Extrusion of plastisols-with the extruder barrel, screw and die heated
to effect gelation/fusion of the paste in the equipment-was explored
relatively early in the development of paste processing, but it cannot
be regarded as a technique significant in the present-day industrial
context. The position is substantially the same with regard to the cold
extrusion of plastigels which, by virtue of their consistency, can retain
the shape imparted by the die without gelation, so that the extrudate
can be gelled and fused subsequently, by passage through an oven or a
hot liquid (e.g. oil, glycerol) bath.

1012

W. V. Titow

Note: The shape retention ability of a plastigel is the property

utilised in the application of specially formulated pastes of this
kind as modelling compounds. Some early applications of
plastigels are mentioned in Ref. 5.

REFERENCES
1. Kling, A. (1951). Kunststoffe, 41(8),240-2.
2. Schimke, F. (1956). Kunststoffe, 46(11), 537-9.
3. Titow, W. V. (1958). Investigation into the validity of the claims of British
Patent 624 795 (James North and Sons Ltd). Unpublished.
4. Anon. (1949). Plast. Ind., 7, 11.
5. Anon. (1951). Mod. Plast., 29,87.
6. US Patents 2629131,2629 134 and 2 681 472.
7. Meazey, A. C. (1959). Brit. Plast., 32,55.
8. European Plastics Buyer's Guide, IPC Business Press Ltd, London.
Buyers Guide for Plastics Processing Machinery and Equipment, British
Plastics Federation, (Machinery and Engineers Group), 5, Belgrave
Square, London SWIX 8PH, UK.
Plastics Manufacturing Handbook and Buyers' Guide: Plastics Technology
Magazine, Rubber/Automotive Division of Hartman Communications Inc.
(a subsidiary of Bill Communications Inc.), 633 Third Ave., NY, NY
10017, USA.
9. Meazey, A. C. (1968). Brit. Plast., 41, 133-40.
10. Schmidt, P., and Polte, A. (1967). Kunststoffe, 57(1),25.
11. Clayton, F. R. (1978). 'Printing techniques relating to the gravure
process,' paper presented at the PRI International Conference on PVC
Processing. Egham Hill, Surrey, England, 6-7, April, 1978.
12. Dalton, W. K. (1960). Plastics, 25(268), 71-81.
13. Kratschmann, F. (1960). Kunststoffe, 50(9), 534-5.
14. Ciba-Geigy Technical Service Bulletin PL 1.1.1, 1976.
15. Blumberg, H., Krummheuer, W. and Nebe, J. (1976). Kunststoffe, 66(2),
97-103.

CHAPTER 23

PVC Latices
Revised and edited by W. V. TlTaw

23.1 INTRODUCTION
In the previous edition the nature and properties of PVC latices were
discussed in this chapter principally by reference to one commercial
range of products of this type-the Breon vinyl latices. With the
permission of the suppliers, BP Chemicals International Ltd, the text
was based to a substantial extent on the appropriate part of their
relevant publication (Technical Manual No.5). This was done because
its technical scope and depth of treatment of the subject were
considered to make that part of the manual useful as a good account of
the technical and applicational aspects of PVC latices generally, even
though actual data quoted by way of illustration did relate to members
of the Breon range.
These considerations, and the relevance of the basic technical
information presented, remain valid irrespective of the changes
consequent upon the take-over of BP's PVC production operations by
ICI in the early 1980s. The chapter is, therefore, still essentially based
on the former text, although some editorial changes and additions have
been made. The original references to Breon latices have been retained
in their former role of illustrative examples: whilst other good
commercial PVC latices, e.g. those of the Geon (B. F. Goodrich) or
Lutofan 200D (BASF) ranges, would provide illustrations more
current in the purely commercial sense, it will be understood that
corresponding grades of latices from different sources, and the finished
products of their conversion, all differ among themselves, but none
fundamentally.
1013

1014

W. V. Titow

As in the case of the Breon latices, references to other commercial

materials (ingredients of latex compositions, and others) are by way of
example only. In this connection it may be noted that not all material
trade names or sources of supply mentioned may be current: specific
up-to-date information on compounding ingredients for PVC latex
compositions, and other relevant materials, can be obtained from
manufacturers of PVC latices, or suppliers of the types of additive
concerned.
A latex may be defined as a stable dispersion of fine polymer
particles in water, containing also some non-polymeric constituents
(emulsifiers and others-see following sections of this chapter). * Of
the three general types of liquid PVC composition-solution, paste and
latex-the last two are both dispersion systems. However, they differ
in several important respects, the most fundamental difference being
the nature of the liquid dispersion medium-water in the latex, and
plasticiser (or plasticiser/solvent mixture) in a paste. This difference is
a cardinal factor in the respective processing and uses of the two types
of system. Although in both cases the ultimate product is a solid PVC
material, with a latex this is obtained by evaporation of the dispersion
medium, whilst a paste undergoes a phase inversion without substantial
loss of plasticiser which remains as an important component of the final
product. In broad terms, the polymer contents of latices and pastes are
comparable, but latices have lower viscosities which may be varied by
dilution; their compounding versatility is also greater in some respects.
In comparison with solutions, PVC latices have much higher solids
contents in the viscosity range employed in processing. Unlike that of a
solution, the viscosity of a latex is independent of the molecular weight
of the polymer component (so that higher molecular weights may be
used for better mechanical properties of the final product), whilst its
liquid component is relatively cheap and innocuous. However,
generally speaking, latices are less stable and more variable in
processing behaviour than solutions, with greater variability in the ease
of wetting of some substrates.
PVC latices are produced by emulsion polymerisation. The particle
size of the solid (polymer) phase is typically around 01-025 ,um.
The total amount of PVC processed in the form of latices is
relatively small: the bulk is worked-for the major outlets-by the
* The ISO definition is 'a colloidal, aqueous dispersion of a polymeric material'
(ISO 472-1979).

23

1015

PVC Latices

main processes (extrusion, calendering and moulding of solid compositions; paste coating). All industrially significant uses of PVC latices
involve their application to some kind of substrate, whereupon a deposit
of solid polymer is ultimately formed after the water has been removed
by evaporation (with or without some intermediate absorption into the
substrate). The general mechanism of deposit formation is virtually the
same for all polymer latices 1,2 (including PVC ones-d. also Section
23.4.2 below): it may be regarded as comprising several stages, each
characterised by the corresponding state of the latex layer on the
substrate and the associated changes in the rate of evaporation of the
aqueous phase. 2 The layer of latex as originally deposited on the
substrate (cf. Fig. 23.1(A)) loses water relatively rapidly by evaporation at a rate comparable with that for pure water. This reduces the
water content comparatively quickly to the point at which the layer
consists of polymer particles in fairly loose mutual contact, with the
interstitial spaces containing residual water (Fig. 23.1(B)). In this state
the interfacial area between the water and ambient air is substantially
B

Fig. 23.1

Formation of a polymer film from a latex layer: schematic

representation (after Vanderhoff et at. 2).
A, Latex layer as applied to substrate; B, particulate deposit in loose packing
array: advanced stage of drying; C, substantially dry, consolidated deposit:
particles deformed, close packing; D, polymer film formed after full
coalescence of particles.

1016

W. V. Titow

reduced, resulting in a decrease in the rate of evaporation. Further loss

of water eventually leads to very close packing of the particles with
extensive inter-surface contact (the closer the softer and more easily
deformable the polymer), amounting to the formation of a granular
polymer layer with little free liquid water remaining (Fig. 23.1(C)). At
this stage the rate of loss of residual water becomes relatively very
slow, being governed by that of its movement through capillary
channels between deformed polymer particles, or diffusion through the
polymer substance. In most cases the particles of the granular layer
finally coalesce fully into a continuous film of essentially uniform
structure (Fig. 23.1(D)). Depending on the nature of the polymer (and
the presence or absence of plasticisers) the coalescence may have to be
accelerated by the application of heat (heat fusion), occasionally also
aided by pressure.
Whilst the closest, most complete mutual contact among the polymer
particles of the granular layer is a prerequisite to effective film formation, the basic mechanism of particle coalescence is that responsible for
all self-bonding of polymers generally, viz. the diffusion of polymer
chains (or their parts) across the original boundaries in areas of surface
contact. In practice this does not take place to a sufficient extent below
the glass-transition temperature of the polymer, whilst above the Tg
the process is accelerated by heating and enhanced by pressure. 3 Most
applications of PVC latices involve heating to accelerate the removal of
the aqueous phase and subsequent fusion of the particles.
23.2 TYPES OF PVC LATICES

PVC latices may be classified according to the nature of the polymer of

the particulate phase, i.e. vinyl chloride homopolymer or copolymer
latices, and the presence or absence of external plasticiser(s), i.e.
plasticised or unplasticised latices.
In common with any other form of vinyl chloride copolymer material
or product, the particles of a copolymer latex may be regarded as
'internally' plasticised by the presence of comonomer units in their
molecular chains (see Chapter 1, Section 1.2; and Chapter 5, Section
5.2). In the practical context of latex technology the main effects of
this chemical modification are similar to those of inclusion of external
plasticiser(s) in a homopolymer latex, in that the temperature needed
for particle fusion is lowered, and the ultimate product (fused film)
becomes softer and more extensible. External plasticisation-necessary
for satisfactory film formation by vinyl chloride homopolymer

1017

23 PVC Latices

latices-is also not uncommon with copolymer latices in which it

increases still further the effects of the internal plasticisation.
Plasticised PVC latices, whether homopolymer or copolymer, are
either supplied with the plasticiser(s) already incorporated, or
prepared by the user from the unplasticised versions (see further on in
this section and Section 23.4.2.)
Some properties of PVC latices are shown in Table 23.1.
TABLE 23.1
Some Properties of PVC Latices
Breon latex
General nature
Minimum pH value
% tolal solids
Brookfield
viscosity" (cP)
Specific gravity
a

151
Homopolymer

351
352
Unplasticised
copolymer

80
52-55

80
54-58

80
55-59

12-28
117-119

20-40
117-119

30-42
117-119

576
599
Plasticised
copolymer
80
55-59

80
54-58

35-55
30-40
112-1-14 112-114

652
Unplasticised
copolymer
70
49--53
7-12
123--125

No.1 spindle, 60 r min-I; 25C.

23.2.1 Homopolymer Latices (e.g. 'Breon 151')

These are not normally film-forming in the absence of plasticisers,

tending to give rather powdery deposits on drying even at elevated
temperatures. External plasticisation promotes particle coalescence
after deposition in processing, but temperatures of about 160C are
needed for satisfactory fusion, assisted by pressure in some cases.
23.2.2 Unplasticised Copolymer Latices

Depending on the nature and proportions of co-monomer present,

particle fusion may require elevated temperatures (e.g. 13o-140C for
Breon 351; 14o-150C for Breon 352), or the Tg may be low enough for
coalescence, with satisfactory film formation at room temperature. The
fusion properties of a copolymer latex of the latter kind (e.g. Breon
652) are, therefore, not improved by external plasticisation, although
for applications where extra softness is required in the ultimate film a
plasticiser may be incorporated. Neither do the film properties of a
room-temperature fusing latex apparently benefit from processing at
elevated temperatures, as indicated by the data of Table 23.2.

w.

1018

V. Titow

TABLE 23.2
Physical Properties of Films from Plasticised 'Breon 352' and 'Breon 652'
Heating
temperature
(oc) for 2 min

25
90-100
150

23.2.3

Plasticised Breon 352

Tensile
Elongation
strength
at break (%)
(lbfin- 2 )

1052
1673
3823

180
270
480

Breon 652
Tensile
Elongation
strength
at break (%)
(lbfin- 2 )

2445
2255
2600

760
620
750

Plasticised Copolymer Latices

Some vinyl chloride copolymer latices supplied in plasticised form are

claimed to offer greater efficiency of plasticisation than that obtainable
by post-plasticising an otherwise similar originally unplasticised version
(even if plasticisation is effected by addition of plasticiser preemulsified in water-d. Section 23.4.2). This is the case with Breons 576
and 599, the plasticised counterparts of, respectively, Breon 351 and
352, each incorporating about 35 phr of a phthalate plasticiser.
Blending an unplasticised latex with the corresponding plasticised
version enables the stiffness of the final product to be varied within
limits represented by that obtainable with each of the two components
used alone. Further plasticiser (pre-emulsified in water-d. Section
23.4.2) may be added to a plasticised latex if required. The plasticised
Breon copolymer latices (576 and 599) were developed to supplement
the range of applications covered by their unplasticised counterparts,
especially where lower fusion temperature, good colour and resistance
to yellowing of the final product under the influence of heat or UV
light are of primary importance. However, these improvements are
gained at a slight sacrifice of strength and rigidity in comparison with
products of Breon 352.
23.3 SOME PROPERTIES OF POLYMERIC PRODUCTS
FROM PVC LATICES
23.3.1 Mechanical Properties
PVC polymers deposited from latices requiring heat treatment (with
pressure in some cases) for effective particie fusion, attain the

1019

23 PVC Latices

maximum strength only after the appropriate treatment of this kind.

Films should be fused under conditions as near the ideal as possible. In
collecting laboratory data, cast film testing is subject to many errors.
To obtain a true comparison of properties and to overcome these
difficulties Breon vinyl latices were dried out at 23C and the polymer
moulded in the form of a disc 6 in in diameter, 003 in thick. Pressing
conditions were 5 min at 165C under 1 ton in- 2 pressure. Breon 151,
351 and 352 powdered before pressing, but the plasticised grades
formed continuous film. Table 23.3 indicates the results obtained when
dumbbell samples cut from the moulded films were pulled at 5 in min- 1
on an Instron tensile machine. Optimum strength may be approached
simply by heating but unplasticised latices normally require between 10
and 20 parts of added plasticiser to form unpressed films.
TABLE 23.3

Physical Properties of Pressed Films from 'Breon' Vinyl Latices

Breon latex

151
351
576
352
599
652

Tensile
strength
(lbfin- 2 )

7075
8030
2140
7575
2115
1360

Elongation at
break (%)

Modulus (lbfin- 2 ) at
elongation
100%

300%

230

1825

860
380

1850
760

500%

10

15
330
20
240
570

1200

23.3.2 Toxicity Considerations

Where PVC latices or their products are required to come into contact
with foodstuffs, clearance (and general advice) should be obtained
from the manufacturers.

23.4 COMPOUNDING
There are two categories of compounding ingredients for vinyl latices:
(i) stabilisers, wetting agents, thickeners, anti-foaming agents and
pH modifiers affecting latex properties;

1020

w.

V. Titow

(ii) heat stabilisers, plasticisers, fillers, pigments and anti-blocking

agents affecting polymer end properties.
Latex stability must be maintained when compounding ingredients
are added, and the manufacturers' recommendations on the preparation of compounding additives should be followed. Attention must be
given to the physical form and pH of the additive and its compatibility
with the basic latex. The mixing process must give thorough
intermingling of the components under conditions of shear below the
critical level. The slow, even speed paddle or turbine mixers are
recommended, but care must be taken to avoid 'vortexing' or
'cavitation' which introduce excessive air. Careful preparation of
additives reduces the need for excessive mechanical agitation and the
dangers of flocculation.
23.4.1 Latex Property Modifiers

(a) Latex Stability

Vinyl latices are treated with stabilisers to ensure adequate
chemical and mechanical stability for normal handling, compounding
and processing. Stabilisers are carefully chosen to cover a wide range
of applications and quantities kept to the minimum practical level.
Certain factors which adversely affect the stability of PVC latices
should be avoided. These are:
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)

high concentrations of monovalent ionic salts;

small amounts of polyvalent cations;
strong inorganic and organic acids;
water-soluble solvents such as alcohols and ketones;
prolonged exposure to freezing conditions;
excessively high temperatures;
conditions of very high shear, such as pumping via closeclearance gear pumps.

Materials improving stability include protective colloids and certain

surface-active agents. When choosing a suitable stabiliser, wetting
properties of the latex compound, water sensitivity of the dried film
and the nature of likely destabilising influences must be borne in mind.
Chemical stability of PVC anionic latices is improved by anionic
surface-active agents.
Surface tension drops in proportion to the amount of surface-active

23

PVC Latices

1021

agent added, thereby increasing the wetting power of the system. This
factor can be advantageous for covering impermeable surfaces and
penetrating fibrous substrates. However, reduced surface tension gives
rise to increased foaming and the higher the level of added surfactant
the greater the sensitivity of the dried film to water. Non-ionic
surfactants, such as ethylene-oxide/fatty-alcohol condensation products, offer the greatest protection against chemical destabilisation and
a degree of mechanical stability. Protective colloids such as casein or
Lytron 820 (Monsanto Co., USA) improve the stability of the latex
under conditions where mechanical shear can cause breakdown of the
emulsion system.
Table 23.1 shows that the minimum recommended pH for Breon
vinyl latices is 7-8. It is important to maintain this level during
processing and ingredients added to the latex must be adjusted to a
minimum pH 8 before addition.
(b) Wetting Agents
Anionic and non-ionic surfactants which efficiently reduce tension
improve wetting characteristics. Those recommended include alkyl
sulphosuccinates and polyoxyethylene alkyl phenol derivatives.

(c) Thickeners
Several types of polymeric substances which form viscous solutions in
water when dissolved in relatively low concentrations, are of interest as
latex thickeners. Among those successfully used with Breon PVC
latices have been cellulose derivatives (methyl cellulose, sodium
carboxymethyl cellulose), polyacrylates (including some sodium and
ammonium polyacrylate salts), and colloidal solutions of casein and
sodium alginate. Different types of thickener, and even individual
thickeners within the same type, can differ considerably in their effects
on a given PVC latex, or on different latices: this is illustrated, by way
of examples, by the data of Figs 23.2-23.7. Some latices can be
adversely affected (destabilised) by certain thickeners. Specific advice
on thickening agents most suitable for use in a particular latex (and its
given application) is available from latex manufacturers. In general,
polyacrylates have been said4 to be particularly useful with Breon PVC
latices, and less prone to causing sedimentation than cellulose
derivatives.

100000

so 000

--_.......
-.- --

..........
I

p........- .... ~--.

to 000
e

-. -..
i
...... -..

5000

..

", I

_..I - ._.-..

,~

I __
iiiiiiiit_ _

7;

1-,-

1-_-1-

e-

~,

~:...-

",-.-

_.

.
I

MC (2-5)
MC (1-5)
$CMC (ZS)
MC (0'15)
SCMC '1-5)

SCMC {0'75}

1000

50 0

10 0

Fig. 23.2 Cellulose thickeners in Breon 151. Figures in brackets indicate dry
parts per 100 parts dry polymer by weight. Me, Methyl cellulose; SCMC,
sodium carboxymethyl cel!~lose.

100 000
~

50 000

...

"""Iiii

--...:.:.:
PA (z.s)

/
10000

c::::;;,;;liiii

o....

5000

--

'A (125)

PA (015)

.
u

.;

...

..!
.;

1000

I
I

-1
I

500

I
I
II I

.1

100

I
J
Mltllring lilll. (dlYs II '00

I
I

--

IIr.1pllllllr. ZJ' C)

Fig.23.3 Polyacrylate thickeners in Breon 151. (NB Sodium and ammonium

polyacrylates adversely affected Breon 151.) Figures in brackets indicate dry
parts per 100 parts dry polymer by weight.

100 000

50000

-_.-....

10000

~.:.":

.
.....
ii

5000 1---

1--

...
-;

--.--',--.--._.- --_.--.....------- .-. -.

-- - ..
~_.

~.- ~.-

--...-

~-- ~--

MC (25)
MC (15)
MC (015)
SCMC (2'5)

--

SCMC (1-5)

---

SCMC(O'15)

::0

.a

1000

500

100

Fig. 23.4 Cellulose thickeners in Breon 351. Figures in brackets indicate dry
parts per 100 parts dry polymer by weight.

100000

--

50000

"""Iii

10000

--.-...

...o

..

5000

-.r:;..

IL

.-..

- -

10"-

-- =:::
~..:: ..
~j

..-.J--

......

.;

..

APA (H)
SPA (H)

=- -

l--

PA (N)
APA (1'U)
SPA (1-25)
SPA (0'15)
PA (1'25)
APA (075)

PA (OlS)

oM

.;

1000

500
I

100

Fig. 23.5 Polyacrylate thickeners in Breon 351. Figures in brackets indicate

dry parts per 100 parts dry polymer by weight. APA, Ammonium polyacrylate;
SPA, sodium polyacrylate.

tOO 000

50000

10000

oN

5000

iii

...
u

._-"'-- --.--,.-- -- .....

_.- .--...---- .. -- ---.---"""--- '-_.-- ----'"----.,--._-- -.....=w

~~

1000

--

SCMC (2'5)
SCMC (1-5)

MC (z.s~
SCMC (0 5)
MC (t 5)

.....

-. --

I
I

MC (015)

500

100

Matyri"_ t,ma (4arl at '"

tamparatura 23'C I

Fig. 23.6 Cellulose thickeners in Breon 576. Figures in brackets indicate dry
parts per 100 parts polymer by weight.

100000

50000

' ..... .. -'

.......
.....

~.

...

1---

I'

_-..-

-- --

e-

o
N

5000

II.
u
~

.;
o

--- --

----

r-

10000

..-

~;

~_

APA (2-5)

PA (z.s)
APA (1 25)
SPA (1-25)

~--'

PA (1-15)
APA (015)
.sPA (0 7S)

=:=.~
j

SPA US)

..
u

.;:

,,

...
D

~
::Ii

PA (015)

1000

500

i
I
I

100

MIIUlinlllill1 1~IYs II loom Ilmperlluil 2J"C)

Fig. 23.7 Polyacrylate thickeners in Breon 576. Figures in brackets indicate

dry parts per 100 parts dry polymer by weight.

1028

W. V. Titow

Note: Sedimentation of PVC latices is analogous to creaming ot

rubber latices: both are manifestations of destabilisation, but
the relatively heavy PVC particles (SG > 1) settle downwards
through the aqueous medium, whereas the particles of a
rubber latex, which are of relatively low SG, rise to the
surface to form a 'cream'.

The basic rules for introducing a thickener into a PVC latex are the
same as for other latices. The best dispersion and maximum efficiency
are obtained when the latex is added slowly, under constant, slow
agitation, to a solution of the thickener. An alternative method is to
'masterbatch' the thickener. This involves thoroughly mixing the thickener solution for a large compound batch with a small amount of the
latex mix in an efficient small mixing vessel. This added to the main
batch will disperse when stirred to give maximum efficiency. When
very large batches of highly filled latex are prepared it is sometimes
possible to add the thickener solution directly. Effectiveness depends
here largely on the agitator efficiency.
(d) Anti-foaming Agents
Both silicone and non-silicone based anti-foams have been used
effectively with Breon vinyl latices. It is important that the most
suitable type is chosen with each latex for maximum efficiency. Silicone
Antifoam A and RD have good general-purpose efficiency. The Nopco
and Bevaloid grades most suitable for each Breon latex are given in
Table 23.4.
TABLE 23.4
Anti-foaming Agents for 'Breon' Latices
a

Breon latex

151
351
352
576
599
652
a

Bevaloid
Type
566 or
942
6250
6250
6250
60
6250

Amount (% on
latex)
03-05
02-D3
01-D2
01-D2
005-D1
01-D2
O2-D3

Bevaloid Ltd (in the UK).

Diamond Shamrock Chemicals (UK) Ltd.

Nopco b
Foamaster
Type at 025% on total
latex
NDW or 8034
DNH-1 or 8034-E
NX2 or NDW
DNH-1 or 8034-E
DNH-1 or NXZ
DNH-l or NXZ

23

PVC Latices

1029

(e) pH Modifiers and Buffers

The pH of dispersions, emulsions or solutions of additives to be
compounded with PVC latices must be adjusted to a value of at least 7,
or 7-8. Alternatively the pH of the base latex should be raised and
buffered to prevent destabilisation by neutral or slightly acid additives.
Strongly acid substances must not be added to anionic latices in normal
circumstances.
The pH modifier most often used is ammonium hydroxide. This has
the advantage of not causing flocculation if added in concentrated
solutions, and of evaporating on drying. Alternatives are 'fixed' alkalis,
such as sodium or potassium hydroxide. However, whilst these do raise
the pH effectively, their use in concentrations above 5% (2% in some
cases) causes flocculation: less concentrated solutions may dilute the
latex mix to an undesirable extent. Moreover, fixed alkalis remain in
the latex film, impairing its water resistance and increasing moisture
transmission. The alkali phosphates or sodium bicarbonate also act as
pH modifiers.
Common buffering agents are phosphates such as trisodium
phosphate or sodium hexametaphosphate (Calgon-Albright and
Wilson). Phosphate addition to a latex sytem partially counteracts the
effects of sharp pH changes, aids dispersion of solid ingredients and, to
a certain extent, sequesters the harmful cations of calcium, zinc, and
magnesium. A more powerful sequestering agent is ethylene diamine
tetra acetic acid. This material does not have the economic or buffering
advantages of phosphate, but used carefully in small quantities it helps
prevent the insolubilisation of stabiliser soaps by calcium, zinc and
magnesium.

23.4.2 Polymer Property Modifiers

The compounding ingredients discussed in the preceding section are

used primarily to balance the latex properties for processing, with
relatively little effect on those of the solid end product. Additives
incorporated into PVC latices to modify the properties of the polymer
in the end product (and, in the case of plasticisers, also to facilitate its
production in continuous film form) serve essentially the same
purposes as they do in PVC compositions processed in solid or paste
form. The main ones are heat stabilisers, plasticisers, fillers, and
opacifying pigments and colourants.

1030

W. V. Titow

For some applications PVC latices may be used as supplied, without

further modification.
(a) Heat Stabilisers
The particulate (solid) phase of a PVC latex, consisting as it does of a
vinyl chloride polymer or copolymer, is prone to heat degradation on
exposure to elevated temperatures. In practice this may occur in the
course of formation of the solid end product (dried film, binder deposit
in bonding applications) or thereafter. The manifestations and likely
mechanisms of degradation of PVC are discussed in Chapter 9.
With the exception of those which are film-forming at room
temperature (ct. Breon 652), solid deposits from PVC latices develop
their maximum strength only after fusion at an elevated temperature.
The detrimental effects of heating on the polymer should be minimised
by initially drying off the water from a latex layer on a substrate (ct.
Fig. 23.I(A at around 100C and then ensuring a rapid rise to fusion
temperature, followed by a cooling cycle. In many processes PVC
latices are applied in very thin layers which dry readily and require
fusion times of only a few seconds: heat stabilisation is usually
unnecessary in such cases. In general it will be required where very high
temperatures or prolonged treatment times at about IS0C or over are
to be used. The choice of stabiliser will be made-from the wide range
available (see Chapters 9 and lO)-in the light of the processing and
service conditions, as well as suitability of the stabiliser(s) for
conversion to a fine dispersion in water-the form in which it should be
added to the latex. A solid stabiliser must, therefore, be capable of
being comminuted (commonly by ball-milling) to a fine aqueous
suspension, and a liquid one of being emulsified in water. Thorough
dispersion of a stabiliser in the aqueous phase of a latex may not
necessarily lead to a significant improvement of the heat stability of the
PVC polymer: it is essential for the stabiliser to be intimately
associated with the polymer.
The main points to be considered when choosing heat stabilisers for
PVC latices are:
(i) effectivity of heat-stabilising action;
(ii) ease of dispersion or emulsification in water and stability of the
dispersion formed (including stability after mixing with the
latex);
(iii) compatibility with the latex system (including absence of

1031

23 PVC Latices

coagulant effects and non-interference with other compounding

ingredients) .
Not many stabilisers satisfy all these conditions, but organotin
compounds as a class are acceptable, especially when used in
conjunction with an epoxy co-stabiliser. Heat stabilisation of PVC
latex products does not follow exactly that of dry compositions, and a
stabiliser effective in the latter will not necessarily be so in a latex
system. Reasons advanced for this relate to the influence of water, as
well as emulsifiers and dispersing agents introduced in processing.
Two heat stabiliser systems have been found 4 to give excellent
results with Breon PVC latices. These are based, respectively, on a
liquid dibutyltin mercaptide (Mellite 39) and dibutyltin dilaurate, with
the addition of an epoxy plasticiser (Lankroflex ED3):

Components
Mellite 39 (Albright and Wilson Ltd, UK)
Lankroflex ED3 (Lankro Chemicals
Ltd, UK)
Tween* 20 (Honeywill-Atlas Ltd, UK)
Spant 20 (Honeywill-Atlas Ltd, UK)
Dibutyltin dilaurate
Morpholine oleate
Water

System 1
System 2
(pbw, wet)
2860

The emulsified heat stabiliser system should be added to the latex

early in the compounding cycle; under constant slow stirring. The
Mellite 39 system has proved slightly more effective than the DBTD
system, but in either case optimum results can be expected at
approximately 4 parts of mixed organotin/epoxy system per 100 parts
of PVC polymer (dry).

(b) Plasticisers
PVC homopolymer latices dry out to hard, normally discontinuous
deposits. Softness and flexibility can be achieved only by the use of
copolymer (internally plasticised) latices, or by external plasticisation,
* Polyoxyethylene sorbitan monolaurate (emulsifier).
t A sorbitan fatty ester (emulsifier).

1032

W. V. Titaw

or both. In the Breon PVC latex series, deposit softness increases in

the sequence Breon 151 < 352 < 351 < 599 < 576 < 652: in comparison with deposits from Breon 351 and 352, those from Breon 599 and
576-which are their plasticised versions (cf. Section 23.2)-demonstrate the further softening and flexibilisation brought about by the
presence of external plasticiser.
Incorporation of about 25 phr DOP in a PVC homopolymer latex
typically gives a hard and stiff (but generally cohesive) film after drying
and heat fusion of the deposit (at about 150-160C); 50 phr DOP
imparts appreciable flexibility to the fused film; 75 phr produces a
highly flexible film; and with 100 phr DOP the fused film is very soft,
flexible, and slightly tacky.
Note: In an externally plasticised PVC latex, the plasticiser is not

normally absorbed to any substantial extent by the polymer

particles with which it is co-suspended in the aqueous phase.
Plasticisation is only effected when the water has been driven
off and the polymer deposit heated to the appropriate
temperature.
Differences in softness between particles of different PVC latices are
sometimes demonstrated by electron micrographs, in which some
copolymer particles (e.g. of Breon 352) may be seen to have been
deformed from the original spherical shape by the impact of the
electron beam, while the harder homopolymer particles (of Breon 151)
maintain their original sphericity. 4
In most latex applications the end product is a continuous polymer
film, obtained after the removal of water from the system and
coalescence of the polymer particles. A latex will normally contain
30-50% of polymer particles by volume. Film formation is believed to
proceed as follows. As the water evaporates to the extent roughly
corresponding to that represented by Fig. 23.1(B), the particle content
increases to about 70% (for the normal latex particle size range of
01-025 llm). The particles pack closely together, but intimate surface
contact is hampered, for a time, by forces of repulsion set up as a
result of interaction of electrical surface-charge layers. 2 ,4,5 Further
evaporation of the water results in the contraction ('necking-in') of the
water/air interface between the packed particles (commencing in the
surface layer): this creates forces (sometimes referred to as the
'capillary forces'6) drawing the particles closer together. The capillary
forces eventually exceed the electrostatic repulsion and the particles

23 PVC Latices

1033

move together into close mutual surface contact. At this stage the
capillary forces are supplemented in their action on the particles7 by
forces arising from the polymer/water interfacial tension ('surface
tension forces'S). If the particles are sufficiently soft, they deform as
they pack tightly under the influence of these forces (as, for example,
in the case of rubber and some PVC copolymer latex particles),
achieving intimate, extensive surface contact. The quality of softness
which makes this possible is also usually associated with relative
freedom of movement of the polymer chains. The combination of good
surface contact and chain mobility plays a cardinal part in the ease of
coalescence of the particles (cf. Section 23.1) through the basic
mechanism of inter-diffusion of polymer chains across particle
boundaries. Coalescence (and the attendant development of cohesion
in the polymer layer) will-in favourable circumstances-proceed until
the layer is transformed into a homogeneous film. The term
'autohesion' has been coined for this kind of effect. 9 In the context of
the morphology of latex deposits, autohesive cohesion may be
.contrasted with the much weaker one produced in a layer of closely
packed but essentially discrete polymer particles by capillary and
surface tension forces developed on drying. With hard particles,
coalescence sufficient for the ultimate formation of a continuous film
may occur only at suitably elevated temperatures (heat fusion). The
very hard particles of a PVC homopolymer latex (e.g. Breon 151)
require the addition of plasticiser for satisfactory fusion even at high
temperatures. External pressure is also employed in some cases. The
presence of a plasticiser in the polymer deposit facilitates fusion, as its
penetration into the polymer increases the free volume and reduces the
effective Tg , thus effectively increasing chain mobility (as well as particle
softness).
The likely performance of a plasticiser in the ultimate latex film may
be estimated from a knowledge of its effects in solid PVC
compositions. However, with base polymers of the same type it may be
necessary to reduce the amount of plasticiser used in a latex
formulation, because of the greater inherent flexibility of thin films.
The main factors to be taken into account in selecting plasticisers for
latex formulations include all those relevant in the formulation of
solid compositions (cf. Chapters 4 and 7), with-additionally-ease of
emulsification for blending with the latex. Where nitrile rubber is to be
used as a plasticising modifier of high permanence in the ultimate film
(cf. Chapter 11, Section 11.2.2) this is introduced by addition to the

W. V. Titow

1034

TABLE 23.5
Physical Properties of Films from 'Breon' Vinyl Latices after the Addition of
Plasticiser

Latex
Breon 151

Breon 352

Breon 599

Plasticiser (35 phr)

Tensile strength
(lbfin- 2 )

Elongation at
break (%)

DAP
TIP
Breon 1562a
Acetyl tributyl
citrate (ATBC)
DAP
TIP
Breon 1562a
ATBC
Phthalate-preplasticised grade

1800
3200
2780

150
150
150

2000
1850
2400
2700
1750

210
300
210
100
250

1700

350

Nitrile rubber latex.

PVC latex of the appropriate nitrile rubber latex (e.g. Breon 1561
high-nitrile latex, or 1562 medium-nitrile latex which imparts somewhat better low-temperature flexibility to the ultimate film).
It is essential in latex working to obtain an even, stable plasticiser/
latex mixture. Pre-emulsification is the most common method used for
ester types. Sometimes it is possible to emulsify the plasticiser directly
into the latex compound. This involves adding a carefully controlled
type and amount of emulsifier to the latex and agitating the oil in
slowly. Type and amount of emulsifier vary according to the plasticiser
and the base latex used. Optimum association of polymer and
plasticiser is not often possible by this method because of limitations
on the shear rate which can safely be applied to emulsion latex
systems. Other ingredients such as fillers and thickeners assist in
maintaining an even mixture and preventing phase separation.
The addition of pre-emulsified plasticiser to Breon vinyl latices at 35
parts per 100 parts of dry polymer affects the physical properties of the
dried, fused polymer film according to the type of plasticiser chosen.
The data in Table 23.5 were obtained on thick films cast on glass
plates, dried at 23C and fused at 160C. The higher plasticising
efficiency obtained by pre- as against post-plasticisation is demonstrated by the higher elongation and lower tensile strength of film from
Breon 599 vis-a-vis that from Breon 352 post-plasticised with 35 phr

23 PVC Latices

1035

DAP (as the nature and contents of the polymer and plasticiser of the
two latices are closely comparable).
In general, for a given base polymer, the higher the plasticiser
content the lower the tensile strength and the higher the elongation of
the resultant film. As with solid compositions, epoxidised oils are not
commonly used as primary plasticisers in PVC latices, but they may be
included for improved heat stability.
The hard PVC latices, Breon 151,351 and 352, require plasticisation
and/or pressure, in addition to heat fusion, to form films. The
minimum amount of general-purpose phthalate plasticiser which has to
be added to render Breon 151 film-forming varies, according to
processing conditions, from 15 phr to 20 phr; it is slightly less for Breon
351 and 352. Where-as is sometimes necessary-a very hard film has
to be formed of lower plasticiser content (and without use of pressure),
a temporary, 'fugitive' plasticiser may be used. An example is
polypropylene glycol, which evaporates from PVC at fusion temperatures of about 160C but assists film formation at about lOOC in the
earlier stages of processing.
(c) Fillers
Fillers are added to PVC latices for one or more of the following
effects on the final product: cost reduction; reduction ('flattening') of
gloss; increase of hardness and stiffness; reduction of tack. The fillers
most commonly used are calcium carbonate, clay, barytes, and some
types of particulate silica. Relatively small amounts of filler (up to
about 20 phr) modify latex-produced PVC films without too drastic an
effect on their physical properties. The actual amount of filler to be
used in given circumstances will depend on its type and particle size, as
well as the nature of the polymer and the plasticiser level. However,
there is a volume concentration of filler (or pigment) for a PVC latex,
as there is for a surface-coating emulsion in the paint industry, above
which a sharp drop occurs in a number of physical properties of the
ultimate film. Experimental evidence indicates that at this 'critical
pigment volume concentration' (cpvc) the filler becomes the major
structural component of the film, with the role of the polymer changing
from that of a continuous matrix to one of a binder holding the filler
particles together without enveloping them entirely. Whilst the binding
power of PVC in such a system is quite good, the resulting cohesion is
inferior to that of a continuous film. 4 The cpvc may be determined for
the latex-produced filled (or pigmented) films of most polymers by

1036

W. V. Titow

measuring a physical property, such as tensile strength or elongation at

break, at various filler loadings, * and plotting the results. Although the
actual property values will depend on several factors (and especially
the nature and binding power of the polymer in the particular system)
the general form of the plot is fairly universal: it is typified by the curve
of Fig. 23.8, in which the cpvc is marked by the change of slope.
A water sorption method, described by Liberti and Pierre Humbert,1O
may also be used to detect the cpvc. This indicates that while 'free'
polymer is present in the system afer the surface area of the filler has
been covered, a coherent film retaining most of the polymer properties
is maintained. But at the point where all the polymer is adsorbed onto
the filler surface the film loses coherence as its structure becomes
discontinuous. Therefore the cpvc may be defined as a function of the
particle surface area of the filler, its ability to adsorb polymer, and the
amount and particle size of the polymer.
700
600
500
;: 400
".

~ 300

.c

to

c:

~200

iii

I
I

'"oc:

I
I
I
I

100~2---:3~-4~~5~-:-6~7-:8~9;;-:'0~---+1-:2i::-0---:!::---;J40:---:50=Plgmcmt conc..ntratlon l vol. ".

Critical plgm"nt volum ..
conc..ntration (cpvc)

Fig. 23.8 Elongation at break of a latex-produced, pigmented PVC film

versus pigment loading.

* The % volume concentration of filler in the dry film is given by:

weight of filler
weight of film

x SG of filler x 100
x SG of film

23

PVC Latices

1037

In many applications small amounts of filler below the cpvc level are
used, to cheapen the mix, modify flow characteristics, or reduce the
gloss of the final product. The relevant points made in Chapter 8
concerning the properties and effects of fillers apply here. Thus, for
economy, whitings followed by clays are the most widely available and
attractively priced fillers in most countries. Whitings are available in
many different particle size forms according to the method of
manufacture and mineral source: the cost varies depending on particle
size and size distribution, chemical purity, and presence or absence of
surface treatment. Similar considerations apply to clays which,
however, are more expensive grade for grade. Mica fillers, also
occasionally used, are the most expensive. In general, whitings are the
softest fillers and cause the least stiffening, whilst clays impart
intermediate hardness-and micas high hardness-at the same loading
levels. Barytes is sometimes incorporated in PVC latices to increase
the density and weight per unit area of the ultimate coatings, as only
relatively small loadings of this high-density filler with good covering
power (see Chapter 8, Section 8.2.2) are needed to produce significant
increases. Where barytes is used, the latex viscosity must be adjusted
to prevent the filler settling out and forming a compact, hard-todisperse layer at the bottom of the container.
Gloss reduction may be brought about by the incorporation of small
amounts of fine-particle-size silica. The water absorption and soap
demand of these finely divided particles must be satisfied before
addition to the latex in order to prevent flocculation.
Bentonite clay may be used to modify flow characteristics of latex
mixes. This clay has a layered plate-like structure which readily
absorbs water, imparting 'body' to the compound. The yield value
developed can be usefully employed in coating mixes where restricted
flow, low penetration and good dimensional stability in the wet state
are required. Initial difficulty in wetting-out bentonite may be
overcome by treating it with a small amount of alcohol before water
dispersion.
Small amounts of filler used well below cpvc must be in fine particle
form, well dispersed in water to minimise depression in polymer
strength. Coarse aggregates or large particles form points of weakness
in the structure which start or propagate physical breakdown. It is
normal to predisperse these fillers in water with an added dispersing
agent and pass the resultant slurry through a cone or high-speed colloid
mill to de-aggregate the particles. When very small amounts of extra

1038

W. V. Titow

fine dispersions are needed, ball mills may be used to achieve fine filler
slurries but this process is too slow and uneconomic for large-scale
production.
Near to the cpvc point when the polymer becomes a binder, choice
of filler becomes more critical. Fine particles have large surface area
and therefore a greater binder demand but give increased covering
power. They may be tolerated where binding power is the prime
requirement in a surface coating, but where economy is the main
consideration coarse fillers may be added in greater amounts before
the film cracks and fails physically. China clay is normally preferred for
dense, high-hardness coatings, and coarse whitings for maximum filler
levels and economy.
(d) Pigments
Unfilled and unpigmented vinyl latices produce transparent colourless
films, and for some applications it is necessary to pigment the polymer
or improve the appearance of filled compositions with opacifying
pigments or colours. Choice of pigments is restricted as certain metallic
ions such as iron and zinc under some circumstances catalyse the
decomposition of PVC. Reaction depends on the chemical form of the
ion and service temperature. Many grades of metal oxide pigments
may be safely used with PVC but care is needed in the choice of grade.
Where there is a danger of small proportions of latent metal ions
existing in the pigment or being generated during its preparation for
addition to the latex, oxides of iron, zinc or copper are best avoided.
Titanium dioxide is the preferred pigment for a white base but
Iithopone and blanc fixe could be used. It is advisable to incorporate a
white base in filled and unfilled stocks required in pastel shades.
A wide range of colours is possible with vinyl latex base, as the
polymer itself is clear and does not discolour under normal
circumstances. Some care is needed in the use of Breon 652 which does
discolour more readily during service exposure to UV light or elevated
temperatures. The normal range of organic pigments is usually
satisfactory for coloured compositions, especially aqueous pastes
prepared for use in latex systems.
Pigments and dyes, like many compounding ingredients, are
prepared in aqueous dispersion prior to addition for the greatest
efficiency.

23

PVC Latices

1039

23.5 ANTI-BLOCKING TECHNIQUES

Blocking is unintended surface adhesion between plastics films (or

sheets) or between such films (or sheets) and other surfaces. The films
or sheets may be either the regular, unsupported kind, or coating layers
on substrates. *
Blocking occurs most commonly between continuous, flat surfaces of
soft, tacky polymers forced into close contact under pressure. The
magnitude of the effect (which may be measured by determining the
force required to separate the surfaces 1Z) is a function of the pressure
and the degree of tackiness.
Films produced from latices of soft PVC copolymers, or ones
containing high proportions of external plasticiser(s), are prone to
blocking in circumstances favourable to this effect. The tendency is
best counteracted by the addition to the original latex of one producing
a harder film (e.g. Breon 151 or 351) providing that the extra hardness
and stiffness thus imparted to the resulting film can be tolerated. In
this way clarity is unaffected and gloss retained. Blocking may also be
reduced by breaking up the flatness of the film surface through
embossing. Its thermoplastic nature makes the latex-produced PVC
layer suitable for this treatment which, in the simplest form, may
consist of subjecting the layer (usually a coating on a substrate) to
radiant (IR) heat and then passing the material through the nip of cold
embossing rolls (a hard rubber backing roll nipping under pressure on
a suitably engraved steel roll).
These two methods do not involve basic compounding modifications
(except for latex blending in the first) but the problem may also be
tackled by suitable additives. Most fillers reduce surface tack, and
blocking is seldom encountered in filled formulations. The most
efficient anti-blocking filler is finely divided silica which, in small
proportions up to 20 parts per 100 parts of polymer by weight flattens
the surface gloss and reduces tack with the minimum effect on
transparency. Another method is to incorporate a wax emulsion into
the latex formulation: e.g. paraffin or amide waxes have limited
solubility in PVC and reduce surface tack by blooming. Because of low
compatibility, physical properties of the polymer are unaffected as long

* This definition is closely in line with those given in relevant standards ll ,12

(some of which are somewhat less comprehensive).

1040

W. V. Titow

as the wax concentration is below 10%. Blocking may also be reduced

by increasing the fusion temperature above the minimum required.
23.6 APPLICATIONS

pvc

latices provide an advantageous alternative to the other two

liquid PVC systems-pastes and solutions-for a number of applications. In many they are the only type of liquid system suitable in
practice. The main use areas are the bonding and coating of certain
textiles, some paper treatments, leather finishes, and heat-activated
adhesive applications.

23.6.1 Textile Applications

(a) As Bonding Agents in Non-woven Fabrics
In this capacity PVC latices can provide good bonding strength,
chemical resistance, and colour. Copolymer latices, usually with
external plasticiser (e.g. Breon 576), are normally favoured for ease of
fusion and high flexibility of the product, but a plasticised homopolymer latex (or unplasticised copolymer one) may be used where greater
product stiffness is required and higher fusion temperatures are
admissible. Where plasticiser permanence is of particular importance,
a nitrile rubber latex may be blended into the PVC latex in place of a
conventional external plasticiser. The type of basic formulation
concerned is illustrated by the following examples: 4
Formulation 1 Formulation 2
(pbw, dry solids)

Plasticised vinyl chloride copolymer

100
latex (Breon 576)
Unplasticised vinyl chloride copolymer
latex (Breon 351)
60
Nitrile rubber latex (medium acrylonitrile-Breon 1562)
40
Wetting agent
025
025
Antifoaming agent
010
010
The latex compositions for bonding non-woven fabrics are normally
diluted with water to a degree governed by the method of application
and the required properties of the finished product. These factors also
determine the admissibility of fillers and pigments in the formulation.
Various application methods are employed,13-15 depending on the

1041

23 PVC Latices

nature and intended use of the textile, including full saturation of fibre
mat by immersion (followed by removal of excess latex by squeezing or
suction), impregnation with foamed binder latex, spraying, printing,
and others.
A review of the properties, applications, and structural effects of
vinyl chloride copolymer latices used as binders for non-woven fabrics
has been published by Schlauch and Caimi. 16
(b) For Coating or Impregnation of Fabrics
Applications of PVC latices in this field include backings for carpets
(tufted and woven), flame-retardant finishes, water-proofing finishes
(e.g. for tarpaulins and tent fabrics), priming (keying, bridging or tie)
coats on fabrics to be coated with PVC pastes and/or made into belting
or other composite structures (wherein the priming coat reduces
penetration of the main coating composition into the fabric and
improves its adhesion), and impregnation coatings for shoe-lining and
book-cover fabrics (to impart heat-bonding properties, or/and moisture
resistance, or/and stiffness). The following basic formulations are
illustrative of some of the types used (figures are pbw dry solids):
(i) High-quality, stiff backing for woven carpet

Vinyl chloride copolymer latex

(Breon 351)
Nitrile rubber latex (carboxylated,
high acrylonitrile-Breon 1571)
Sodium carboxymethyl cellulose
(added as 5% solution)
Water

40
60

Amount required to make

total solids in composition 30%

(ii) Flame retardant fabric finish

Vinyl chloride copolymer latex
(Breon 351)
Stabiliser (dibasic lead phoSphite)
Plasticiser(s)
Whiting
Antimony trioxide
COlourant}
Thickener

100
5
50
100

25
As required

1042

W. V. Titow

Compositions based on formulation (ii) may be used to impregnate or

coat a fabric, and the viscosity is adjusted accordingly. Heating at
140C will normally be required to fuse the PVC properly (for full
development of mechanical properties and wash resistance). A latex of
a room-temperature fusing copolymer (Breon 652) may be used instead
of Breon 351 in this formulation for 'on site' applications or generally
where no heating equipment suitable for fusion is available.

Note: Coatings produced with Breon 652 may yellow on outdoor

exposure. Suitable dark-coloured pigments should therefore
preferably be incorporated to mask the effect where
appropriate.
23.6.2 Paper Treatments
Paper may be treated with PVC latices-alone or in conjunction with
nitrile rubber or certain acrylic polymer latices-in various ways, for a
number of purposes.
Thus a suitable latex composition may be added to the pulped fibres
before sheet formation ('wet-end' addition on the paper-making
machine) ultimately to impart to the paper (after appropriate fusion
treatment, say press finish at about IS0C) improved strength, stiffness,
water resistance, flame retardance, and thermoformability.
Finished paper may also be impregnated or coated for similar
effects, as well as to provide protection against fats, greases, moisture
and abrasion, e.g. for such products as drinking cups, ice-cream
cartons, book covers and wall-coverings. In the latter two applications,
smooth surface finish promoted by the latex treatment may be a
desirable decorative effect, or alternatively, an embossed finish may be
produced by a suitable treatment utilising the thermoformability
imparted by the polymer deposited from the latex. Latex coatings on
paper can introduce heat-bonding capability (see Section 23.6.4
below). Where applied as priming coats they playa role analogous to
that of such coatings on textile fabrics.
Improvements in paper strength which can be produced in some
cases by suitable latex treatment are illustrated by the figures of Table
23.6.
The following formulations have been recommended4 for the base
coat of a scrub-resistant vinyl wallpaper (to be applied by the air-knife

23

1043

PVC Latices

TABLE 23.6

Some Strength Characteristics of Paper Before and After Impregnation with a

Blenda of PVC and Soft Acrylic Polymer Latices
(Data from Ref. 4)
Material

Tensile
strength
(kgfcm- 2 )

Bursting
strength
(kgfcm- 2 )

Tear
strength
(kgcm- I )

Bending
length
(cm)

155

105

58

110

223

121

90

52

20

33

58

21

37

1. Paper impregnated with

latex blend and dried at

90C for 10 min
2. Same paper, treated as
under 1, and then pressed
for 3 min at 170C under
124 kgf cm- 2
3. Original paper as used for
1 and 2, without latex but

A. Heat-treated as under 1
B. Heat-treated and pressed
as under 2

60

Breon 352, 6 parts; Breon 2671 2, 4 parts. Solids content of impregnation bath: 40%.
Pick-up (% of dry fibre weight): 666 17.

technique and top-coated with uncompounded Breon 576):

Breon 576
Breon 151
65% Dialphanyl phthalate emulsion
Coalescing solvent (Bisol
DPS-BP Chemicals)
40% Calcium stearate
Pre-ground pigment dispersion *
Water

Formulation 1 Formulation 2
(pbw, wet)
100
65
22

07

5
5
100
100
Amount. required for a
viscosity rating of 20s with
No.4 Ford cup

* A 50% aqueous pigment 'grind' produced by stirring together the following

components (in the order given), and colloid-milling prior to use (pbw):
Water
Polyacrylate dispersant (Dispex 115-Allied Colloids)
Sodium hexametaphosphate (Calgon-Albright and Wilson)
Clay (water dispersible grade)
Titanium dioxide (Tioxide R-HD-Laporte Chemicals)

46.6
02
02
30
20

1044

w.

V. Titow

23.6.3 Leather Finishes

In some of these the polymeric (binder) component may be provided
by a blend of a PVC latex with a nitrile rubber one, as exemplified by
the following formulation (intended to be combined 1: 1 with a suitable
aqueous pigment dispersion):4

pbw, wet (dry)

Breon 1562
Breon 652
Triethanolamine oleate (latex stabiliser)
10% aqueous tetra sodium pyrophosphate
(buffer against residual acidity in
leather)
Water

135

(55)

90
10

(45)

to pH 10
10

On application of the finish the main functions of binder are to bond

the pigment(s) to the leather, whilst providing some surface protection
against moisture and abrasion, and enhancing appearance (increasing
gloss).

23.6.4 Adhesive Applications

Because of their thermoplasticity and polar nature, PVC films
deposited from suitably formulated latex compositions on such
substrates as paper, cardboard, fibreboard, some textile fabrics and
certain wood products can serve as effective heat-activated adhesives in
applications where bonding through a paste coating or via pre-formed
sheet lamination is unattractive or impracticable. Simple radiofrequency (rt) welding of substrates precoated with a latex-produced
film is a useful route to some products for the automotive industry,
packaging, and upholstery applications. Thus, for example, PVCcoated boards may be rf-welded to PVC foam and film to form a range
of soft decorative finishes for automotive and domestic purposes. Their
ability to retain the padding and durable PVC leathercloth finishes in a
rigid construction makes the products attractive, whilst the rf-welding
production route is cheap to operate.
Breon 151 is claimed4 to be a versatile, cheap basic component for a
range of adhesive formulations for work with porous, polar substrates:
in such adhesives it may be used alone, or in blends with other PVC,
nitrile rubber, or acrylic latices. A starting formulation for a latex

23

PVC Latices

1045

coating to enable PVC sheeting to be rf-welded onto fibreboard or

wood for applications in vehicle production or furniture, is illustrated
by the following example4 (figures are pbw (dry)):

65
30

Breon 576
Breon 151
Breon 1562
Antifoaming agent
Non-ionic stabiliser
Pigment
Thickener (ammonium polyacrylate)

10
01
05
10
05

Blends of Breon 351 or 352 with a nitrile latex may be used as

heat-sealable coatings on paper, or-with addition of suitable tackifying resins-as water-based adhesives with applications in the
building industry.

REFERENCES
1. Blackley, D. C. (1966). High Polymer Latices, Vol. 1, Applied Science
Publishers, London, Ch. 1.
2. Vanderhoff, J. W., Bradford, E. B. and Carrington, W. K. (1973). J.
Polym. Sci., Part C (Polymer Symposia), No. 41, 155-74.
3. Titow, W. V. (1978). In Adhesion 2 (Ed. K. W. Allen), Applied Science
Publishers, London, Ch. 12.
4. Breon Latices: Technical Manual No.5. BP Chemicals (UK) Ltd, London,
1969.
5. Glasstone, S. (1948). Textbook of Physical Chemistry, 2nd Edn, Macmillan
and Co. Ltd, London, p. 1220.
6. Brown, G. L. (1956). J. Polym. Sci., 22,423.
7. Vanderhoff, J. W., Tarkowski, H. L., Jenkins, M. C. and Bradford, E. B.
(1966). J. Macromol. Chem. 1, 361.
8. Dillon, R. E., Matheson, L. A. and Bradford, E. B. (1951). J. Colloid Sci.
6, 108.
9. Voyutskii, S. S. (1963). Autohesion and Adhesion of High Polymers,
Polymer Reviews, Vol. 4, Wiley-Interscience, New York.
10. Humbert, L. and Humbert, P. (1959). Official Digest, 181,413, 736.
11. ISO 472-1979. Plastics-Vocabulary.
ASTM D 883-78a. Standard definitions of terms relating to plastics.
12. ASTM D 1893-67 (Reapproved 1978). Blocking of plastic film.
ASTM D 3354-74 (Reapproved 1979). Blocking load of plastic film by the
parallel plate method.
BS 2782: 1970: Method 31OA. Blocking offlexible PVC sheet.

1046

W. V. Titow

13. Krcma, R. (1971). Manual of Nonwovens, Textile Trade Press, Manchester, England, and W. R. C. Smith Publishing Co., Atlanta, Ga., USA.
14. Gillies, M. T. (1979). Nonwoven Materials, Noyes Data Corp., NJ, USA.
15. Whitehead, D. A. (1980). Tex. Ind. SA, February, pp. 5-11.
16. Schlauch, W. F. and Caimi, R. J. (1974). Text. Chern. Color., 6(10),
223-9.

CHAPTER 24

PVC Solutions and their Applications

W. V. TITaw

24.1 INTRODUCTION
The applications of vinyl chloride polymer and copolymer solutions are
less extensive than those of solid compounds or pastes. However, the
solutions-and the special resins from which most are made-are well
established in the application areas where they are utilised, and the
advantages they offer are recognised. The principal uses are in surface
coatings (including certain paints, corrosion-protective coatings, and
overlacquers for PVC), some printing inks, adhesives (solvent
cements) for PVC, the production of PVC fibres, and solution-casting
of PVC films. These applications are discussed in more detail in the
following sections.
Although standard suspension-, emulsion- and mass-polymerised
PVC resins dissolve in the appropriate solvents, they are not too well
suited for much of the solution work where special processing and
end-use requirements have to be met: the common ones include ready
solubility in mixed-solvent systems (up to high solids content levels for
some applications), tolerance for diluents (especially aromatic hydrocarbons), good compatability with other polymeric solutes, solution
viscosities suitable for particular uses, good adhesion of solutiondeposited films to substrates (especially metals), and high strength and
toughness of the films and other end products. Resins-mainly
copolymers of vinyl chloride with other monomers (especially vinyl
chloride/acetate copolymers)-are available to meet these and other
special requirements. These polymers are 'solution' resins in two
senses: they are produced for solution applications, and most are made
1047

w. v.

1048

Titow

by solution polymerisation which gives uniform molecular weight

(narrow molecular weight distribution-d. Chapter 1, Section 1.5.1)
controllable at the desired level (low, medium or high), and high purity
of the polymer-all features particularly desirable for solution use.

24.2 COMPONENTS OF PVC SOLUTIONS

By definition, the two essential components of a PVC solution must be
PVC polymer(s) and solvent(s). The solutions used for some practical
applications (e.g. some solvent cements, film-casting solutions) are just
such simple systems. Solutions for other purposes can be multicomponent compositions (see below and Section 24.4).

24.2.1 The PVC Polymer

Depending on the application, the polymer component of a PVC
solution may be a vinyl chloride homopolymer, a copolymer, or a
terpolymer produced either directly from the appropriate monomers or
by a post-modification of a copolymer (e.g. hydrolysis of a proportion
of the acetyl groups of polyvinyl chloride/acetate to hydroxyls), or a
mixture of any of these. As well as the polymer type, the molecular
weight will also be chosen in the light of the intended use: it will
normally represent a compromise between ease of solution (and
achievement of a high solids content, where required) combined with
manageable viscosity (all promoted by low molecular weight) and good
mechanical properties of the final product which normally improve
with increasing molecular weight.
(a) Homopolymers

In broad terms, these offer better service properties (including strength

and heat-softening characteristics) than the copolymers, but have more
restricted solubility and, in products, lower flexibility, with poorer
adhesion to substrates (usually no air-dried adhesion to metals).
Hence, in the absence of special considerations, homopolymers are
preferable for film-casting solutions and copolymers or terpolymers for
most other applications, especially coatings.
(b) Copolymers
Vinyl chloride/acetate copolymers are widely used in solutions for
surface coating applications. Some information relevant in this context

24 PVC Solutions and their Applications

1049

is given in Table 24.1 by reference to members of a well-known

commercial range.
A copolymer of vinyl chloride with triftuorochloroethylene, as well
as copolymers with vinyl isobutyl ethers, are also available for
solution-coating applications. Both types have good solubility characteristics and the former particularly good service properties (but poor
adhesion to metal unless stoved after application at a high temperature). The air-dried adhesion of the VIBE copolymer to metal is good.
Solution-applied coatings of vinyl chloride/vinylidene chloride
copolymers of high VDC content serve as barrier layers on packaging
materials.

(c) Terpolymers
The terpolymers in general use as solution resins are vinyl chloride/
vinyl acetate copolymers containing either maleic acid or vinyl alcohol
residues as the third component. The maleic acid is introduced by
using maleic anhydride as the third comonomer in polymerisation; the
vinyl alcohol groups are produced in situ in the usual way, by
hydrolysis of some of the acetyls of a VCNA copolymer. Some
information on commercial representatives of both kinds of terpolymer
is given in Table 24.1. In both, useful properties result from the
presence of the additional functional groups. The hydroxyl groups
provide reactive sites through which cross-linking can be effected by
reaction with amino resins (urea- or melamine-formaldehyde) or
isocyanates. 1 The -OH groups also improve compatibility with other
polymers (e.g. nitrocellulose and alkyd resins in surface-coating
formulations l ). The carboxyl groups in acid-modified VCNA copolymers improve solubility in relatively weak solvent systems and impart
good air-dry adhesion for a number of substrates (especially metals and
paper), important in coating and adhesive applications (ct. Table 24.7).
24.2.2 Solvents and Diluents

The solubility characteristics of PVC solution resins vary with their

chemical type (i.e. whether homopolyer, copolymer or terpolymer,
and the nature and amounts of the co-monomers where present), as
do tolerance for diluents, and solution viscosity at a particular
concentration in a given solvent or solvent system. These aspects of
solubility are also affected by the molecular weight: in general, for a
given chemical make-up of the polymer, the ease of solution, diluent

13-16

12-13

Approx.
10

118-142 08-12

84-87

87-88

Approx.
90

85-88

VYHD

VYLF

VYNS

VMCH

maleic
acid

Other

14-15

Vinyl
acetate

85-86

Vinyl
chloride

% Composition

VYHH

Desig
nation

60

Best solvents include

some ketones,
especially MEK and
MIBK; relatively
low tolerance for
aromatic
hydrocarbons
Similar to VYHH

82

Medium-high

Medium

Soluble in some
ketones and esters

Soluble in some
ketones, esters,
chlorinated
hydrocarbons, alone
or in combination
with aromatic
hydrocarbons
As VYHH (higher
solids content
solutions possible)

Solubility
characteristics

16

36

57

Solution
viscosityb
(cP)

Medium-low

Medium
(lower than
VYHH)

Medium

Molecular
weight

TABLE 24.1
Ucar" Solution Resins

General coating uses

(alone or in
combination with
other resins)

General coating uses

(where highest
toughness and
durability not
essential)
Blending with
VYHH to increase
solids content, gloss
and 'build' in paints
Overiacquers for
PVC coatings;
strippable coatings;
protective coatings

General coating uses

(especially where
high toughness and
durability required)

Some typical uses

Good air-dry
adhesion of coatings
to metal, paper and
other substrates;
tough, durable
coatings.

Poor air-dry adhesion

of coatings to
unprimed metal
surfaces (improved
by baking)

Acceptable in some
food-contact
applications

Acceptable in several
food-contact
applications

Remarks

155-189

2~53

79-82

895-915

89.5-91.5

79-83

VMCA

VAGH

VAGD

VROH

Medium

Medium
(lower
than
VAGH)
Low

5.2--6.5
vinyl
alcoholc

Approx.
5 vinyl
alcohol

Similar to
VMCC

H-25
maleic
acid

52--65
vinyl
alcoholc

Medium
(lower than
VMCH)

08-11
maleic
acid

17

43

87

20

37

Acceptable in several
Similar to VMCH,
Similar to VMCH
food-contact
but higher tolerance
(but where
applications
for aromatic
toughness and
hydrocarbons and
durability
higher solids content requirements lower)
solutions possible
Good solubility in
Coating and adhesive Recommended for
ketone/aromatic
use in conjunction
applications
solvent mixtures
with cross-linking
systems (esp.
VERRd )
Soluble in some
Coatings (alone or in Acceptable in several
ketones, esters and
food-contact
combination with
applications;
chlorinated
other resins)
hydrocarbons;
crosslinkable by
virtue of hydroxyl
tolerance for
content
alcohols in the
solvent systems
Acceptable in several
Similar to VAGI:>.
Similar to VAGH,
food-contact applicabut higher solubility
tions; crosslinkable
and maximum solids
by virtue of hydroxyl
contents in solutions
content
As VAGH, but lower
Similar to VAGH
Similar to VAGD,
costs in coatings as
but still easier and
higher applied solids
greater solubility
and cheaper solvent
systems can be used

The former. Bakelite (Vinylite) range of vinyl chloride copolymer resins for solution applications (Union Carbide Corp. in the USA, and
associate companies elsewhere). Table based on data from Union Carbide technical literature.
b 15% resin in 1: 1 MEK: toluene at 25C.
C Formed by hydrolysing part of the vinyl acetate component.
d See Note on pp. 1058-9.

Approx.
12-16

2.~5.3

144-177

815-845

VMCC

w.

1052

V. Titow

tolerance and maximum achievable concentration, all increase, and

solution viscosity decreases, with decreasing molecular weight.
Although all PVC polymers are susceptible, in varying degrees, to
many ketone, chlorinated hydrocarbon, and ester solvents, as well as
to some aromatic hydrocarbons (cf. Chapter 12, Section 12.8), the
homopolymer will give solutions of reasonable concentrations and
workable viscosities in only relatively few solvents. Of those,
tetrahydrofuran and cyclohexanone are the most important in the
technological context. Methylcyclohexanone and isophorone are also
relevant, especially for mixed solvent systems, and dimethylformamide
is an effective 'booster' for solutions of PVC polymers of high
molecular weight. Methyl isobutyl ketone is a useful co-solvent in some
systems.
For copolymers used in solution applications, the range of effective
solvents increases, as does general ease of solution, with increasing
proportion of co-monomer(s) present and activity of chemical groups
brought thereby into the polymer chain. Solvents effective at room
temperature include many ketones, some aliphatic esters, chlorinated
hydrocarbons, and nitro compounds. Certain other compounds also act
as solvents or co-solvents, e.g. the cellosolves (ethylene glycol
monoalkyl ethers), and some aromatic hydrocarbons (benzene,
toluene, xylene) can have a marked swelling action. Some solubility
data for commercial copolymers are given in Tables 24.2 and 24.3.
Tolerance for diluents in solvent systems also becomes greater in the
main (although it varies from one copolymer to another): for example,
considerable proportions of toluene or xylene can be included in some
TABLE 24.2
Saturation Concentrations of a Commercial Vinyl Chloride/Acetate
Copolymer (Breon AS 70/42) in Various Solvents
Solvent

Weight
(g/lOO g
solution)

Solvent

Weight
(g/lOO g
solution)

Acetone
Methyl ethyl ketone
Methyl isobutyl ketone
Cyclohexanone
Methylcyclohexanone
Mesityl oxide

25
30
25
30
27
32

Isophorone
Benzene
Toluene
Xylene
50/50 acetone/xylene
50/50 MEK/xylene

28
1
1
1

28
28

24 PVC Solutions and their Applications

1053

TABLE 24.3
Solubility (in 10% Concentration) of a Commercial Vinyl Chloride/Acetate
Copolymer for Solution use (Vinylitea VYHH)
Solubility

Solvent

Acetone
Butyl acetate
Carbon tetrachloride
Cellosolve solvent
Cellosolve acetate
Dibutyl phthalate
Dichloroethyl ether
Dimethyl phthalate
Dioxane
Ethanol
Ethyl acetate
Ethylene dichloride
Ethylene glycol
Ethyl ether
Dioctyl phthalate
Isophorone

at
25C

at
95C

S
S
I
I
S
S
S
S
S
I
S
S
I
I
I
S

S
S
I
I
S
S
S
S
S
I
S
S
I
I
PS
S

Solvent

Solubility
at
at
25C 95C

Isopropanol (anhydrous)
Isopropyl acetate
Mesityl oxide
Methanol
Methyl acetate
Methyl ethyl ketone
Methyl cellosolve acetate
Methyl isobutyl ketone
Propylene dichloride
Propylene oxide
Tricresyl phosphate
Hydrogenated naphtha
(diluent)
Xylene (diluent)
Toluene

I
S
S
I
S-CI
S
S
S
S
S
I
SO

I
S
S
I
S-CI
S
S
S
S
S
PS
PS

SO
SW

PS
S

Key: S, soluble; I, insoluble; PS, partially soluble; CI, cloudy solution; SO,
softens.
a Materials of this range now marketed under the trade name Ucar-see
footnote to Table 24.1.
surface-coating formulations. All these points are illustrated by the
examples of compositions given in Section 24.4, which also demonstrate that the choice of solvent, or solvent/diluent, system in any given
case is determined by the nature, mode of application and end-use of
the composition. Aliphatic hydrocarbons, alcohols, and water have
precipitant action on PVC solution copolymers, but alcohol diluents
can be tolerated in moderate amounts by hydroxyl-containing polymers
(especially when dissolved in good solvent(s) in relatively low
concentrations) .
In general, the solubility of PVC solution resins tends to increase
with rising temperature. Highly concentrated solutions may become
thixotropic or gel permanently (especially when prepared at an
elevated temperature and then cooled down to room temperature).
Viscosity increases with the solute content (cf. Fig. 24.1), and-for

1054

W. V. Titow
10000

.i

0..1000
u

'iii
0

l/l

;;:
c

(f)

.
/

I .:/
:/

-:

.: / /

I
I.

I'

1/
I

:1

,. '"
.
'
"
.
!/ ,.

//

100

....Q
(5

....
::J

..

<

",,7

....-

.... ..-7
....-

10
0

10

15

20

010 Polymer

25

30

35

Fig. 24.1 Solution viscosity (Brookfield) versus concentration for some

commercial copolymers.
Ucar VYNSIMIBK; _ . Ucar
VYNSIMEK;
Ucar VAGHIMIBK; + + + + Ucar VAGDlMIBK;
----Breon AS 70142 in MEK:xylene, 1: 1.

many systems, but not invariably-with iQcreasing percentage of

diluent at the same solute concentration.
The requirements applicable to solvent systems are those for
surface-coating or film-casting solutions generally, embodying such
considerations as applicational functionality (including evaporation
characteristics), health and fire hazards, and cost.
24.2.3

Other Solution Constituents

Like any other PVC composition, a solution may incorporate several

of the additives commonly included in PVC formulations. However,
the nature and applications of PVC solutions modify considerably the
need for, or relative importance of, some of the usual formulation
constituents. Thus heat stabilisers, essential in heat-processed compounds, may be omitted from many solution formulations, except

24 PVC Solutions and their Applications

1055

those for stoving finishes or where the product may experience

significant heat in service. In these cases the choice of stabiliser should
be made in the light of advice from suppliers (of both stabilisers and
solution resins) and its suitability verified by tests.
With polyvinyl chloride/acetate copolymer, or modified copolymer,
solution resins the following general points are relevant. Selected tin or
BalCd stabiliser systems can be particularly suitable, preferably used in
conjunction with an epoxy co-stabiliser. However, BalCd stabilisers
are not recommended for solutions of hydroxyl-modified copolymers,2
and metal soap stabilisers generally can impair adhesion in surfacecoating and adhesive compositions; blooming can also be a problem in
some cases, and possible opacifying effects should be borne in mind
where transparent final products (e.g. coatings) are required. Basic lead
carbonate, satisfactory for some applications (in the absence of nontoxicity requirements) is not suitable for clear formulations: a further
consideration with this kind of s.tabiliser is possible development of
alkalinity which may be troublesome particularly with acid-containing
terpolymer resins. Urea- or melamine-formaldehyde resins can have a
stabilising action in clear baking finishes, when present at the level of
about 3 phr. A tin mercaptide in conjunction with an epoxy resin (e.g.
Bakelite Resin ERL 2774-Union Carbide) has also been
recommended2 as a typical stabiliser system for a baked surface coating
(in the respective proportions of 1 phr and 5 phr). With polyvinyl
chloride/acetate copolymer resins, including hydroxyl-modified grades,
zinc stabilisers can cause rapid colour development on heating, especially in unplasticised compositions, or those of low plasticiser content.
Stabilisation against light is normally effected by suitable pigmentation, in particular with titanium dioxide used in substantial proportions
in many coating formulations, or with carbon black (up to about 6 phr)
where a black colour is acceptable. In the absence of protective
pigments the resistance of copolymer and modified copolymer solution
resins to photochemical degradation is not sufficient for prolonged
outdoor service, although a clear film or coating may withstand limited
exposure if an effective light stabiliser system is included in the
formulation, say about 1 phr of a good UV absorber (e.g. Cyasorb
UV-24*-see Chapter 9, Section 9.5) in conjunction with 3-5 phr of a
suitable epoxy co-stabiliser (e.g. Bakelite Resin ERL 4221-Union
Carbide).
* American Cyanamid Co., USA, and associated companies elsewhere.

1056

W. V. Titow

Plasticisers may be incorporated in PVC solutions, for increased

flexibility of the ultimate products. The compatability of the usual PVC
plasticisers both with the solutions and the PVC polymers or
copolymers in the final, solid products is adequate for the purposes of
the established applications. In practice, therefore, the plasticiser(s)
will, as usual, be chosen for the final properties required (in the light of
cost considerations), the main technical limitation on the amount
incorporated being development of tackiness in films and coatings and
impairment of the adhesion of such products to substrates (especially
metals). To the extent to which a meaningful generalisation is possible,
about 40 phr may be regarded as the top plasticiser content limit for
tack-free coatings based on vinyl chloride/acetate copolymers. The
amounts used in solution-deposited coatings based on hydroxylmodified copolymers may typically range between about 15 phr and
30 phr. In some cases, plasticised films and coatings may be improved
by a short heat treatment at about 70C.
The already mentioned UV-protective action of pigments (best with
carbon black and titanium dioxide, but exerted by all otherwise
suitable pigments at sufficiently high loading levels) is one of the
reasons for their inclusion in PVC solution-coating formulations,
additional to the functions of colouring the end product and
imparting covering power to the coatings. Many of the pigments
discussed in Chapter 11 (Section 11.3.5) are used, several in relatively
high loadings. A few examples of pigment contents of surface coating
solutions based on vinyl chloride/acetate copolymers (including
hydroxyl-modified grades) are given below. Selected soluble colourants
can be used in solutions for clear coatings or films, in rather lower
concentrations, as their role is confined to imparting colour.

Pigment
Titanium dioxide
Carbon black
Lead chromate
Lead sulphate (white lead)
Chrome orange
Chrome green (chromic oxide)
Iron oxide brown
Phthalocyanine green
Phthalocyanine blue
Aluminium powder

Typical loading range (phr)

50-90
4-6
75-125
75-125
75-100
50-75
40-75
10-20
10-20
30-50

24 PVC Solutions and their Applications

1057

For applications involving heating (e.g. baked finishes), pigments

containing zinc should be avoided, as should-preferably-also iron
pigments, because of possible promotion of polymer degradation
mentioned above in connection with zinc stabilisers. Similarly, alkaline
pigments can cause problems in compositions based on acid-modified
vinyl chloride/acetate copolymers. Conversely, some lead pigments can
have a stabilising action (e.g. white lead).
At the high loading levels at which many pigments are used in some
PVC solution-coating compositions they may, in some respects, also be
regarded as fillers, in that their modifying effects on the properties of
the resin in the final product will be broadly in line with those of
particulate fillers, as discussed in Chapter 8. In view of the rather
specialist applications of PVC solution compositions, fillers with a
purely extender (cheapening) function are used only to a relatively
limited extent (e.g. clay in some coating formulations) although there
are no general technical reasons precluding their incorporation in that
role.
The properties of PVC solutions and their ultimate products are also
influenced by polymeric materials, other than the PVC solution resins,
that may be included in some formulations (e.g. for many surface
coatings), which may incorporate, for example, epoxy resins, certain
cellulose derivatives, or alkyd resins (see also Section 24.4). Such
formulations are, however, more properly in the province of surfacecoating technology rather than that of PVC.
Lubricants are not included in PVC solution formulations since the
processing of this special type of PVC composition does not involve the
kind of manipulation of the polymer under heat and shear in which
these additives are beneficial (see Chapter 11, Section 11.1.1). Indeed,
the presence of a lubricant in, say, a solution-coating composition
could impair the ultimate adhesion to substrates.
24.3 PREPARATION OF PVC SOLUTIONS AND
SOLUTION COMPOSITIONS FOR
PARTICULAR APPLICATIONS

The viscosities of simple PVC solutions used directly (e.g. for film
casting) or in the preparation of composite surface coatings are, in
most cases, sufficiently low for paddle or impeller mixers to be
employed in their preparation, both on the laboratory and industrial

1058

W. V. Titow

scale. The mixer should preferably be covered to reduce solvent loss,

and a reflux facility is desirable where heating is applied to assist
dissolution of the polymer and keep solution viscosity down for ease of
stirring (although heating for these purposes will normally be
mild-say at about 35C). Where the solution is to be heated to assist
solvent removal after application, and especially if a deposited film will
be post-treated by heating (as with baked finishes), consideration must
be given to inclusion of a heat stabiliser in the formulation; in any case,
the temperature and duration of heating should not exceed the lowest
values necessary for good results. The generally lower heat stability of
copolymer resins in comparison with homopolymers should be borne in
mind in these connections. Since thermal degradation of PVC resins
can be promoted by the presence of iron, the working surfaces of
mixing equipment or those of storage containers should not be of mild
steel: stainless steel, glass or enamel are the preferred materials.
In simple solution preparation involving only the PVC resin and
solvent(s), with no other solid constituents (other polymers, pigments)
to be incorporated, a useful technique is to add the resin portionwise
into the vortex produced in the solvent(s) by the rotation of the stirrer,
each portion being allowed to dissolve before the next is added, to
avoid lumping. If the solvent system includes also a diluent, the resin
may be wetted out with this first, before being stirred into the
solvent(s). Alternatively, the diluent may be added slowly, with
vigorous stirring, to the solution of resin in the solvent(s); but the
pre-wetting method can be particularly useful in preventing lump and
gel formation. Where the amounts of solvent(s) and diluent called for
by the formulation permit it, the resin should first be dispersed in the
diluent, and the solvent added gradually, with vigorous stirring to the
resulting suspension, the stirring being continued until solution is
complete. As with any polymer solution for clear products, or products
of low thickness-e.g. films, fibres-where the presence of even small
particulate impurities, gels, or bubbles can seriously affect the
properties and appearance, PVC solutions for film casting and clear
coatings should be filtered and de-aerated.
Note: Ready-made solutions of some vinyl chloride copolymers are
commercially available. Two examples are Ucar* vinyl resin
solution VYNC (a clear, 40% solution of a hydroxyl-modified

* Formerly Bakelite.

24 PVC Solutions and their Applications

1059

vinyl chloride/acetate copolymer in isopropyl acetate) and

Ucar vinyl resin solution VERR-4(j3 (a 40% solution of an
epoxy-modified vinyl chloride/acetate copolymer of low
molecular weight in MEK: toluene). The VYN C solution is
recommended for use in coatings incorporating nitrocellulose
or nitrocellulose/alkyd blends, as well as coatings modified by
reaction (via the hydroxyl groups) with amino resins or
isocyanates. The VERR-40 solution, in combination with an
acid-modified VCNA copolymer (e.g. Ucar YMCA) can be
used for high-solid baked coatings with very good adhesion
to metal, hardness and gloss. Examples of another kind of
commercial PVC solutions are proprietary solvent cements for
bonding pipes and fittings (see Chapter 20, Section 20.3.2).
Because of the nature of the solvents and diluents used, the
precautions to be taken in the preparation, storage, transport and
handling of PVC solutions are substantially the same as those called for
with flammable liquids generally.
The preparation of pigmented PVC solution compositions (for use as
paints and the like), which may also contain other constituents, e.g.
plasticisers (cf. Section 24.4), may be carried out in more than one
way, depending on the equipment available. Advice is readily
obtainable from the resin or pigment suppliers in particular cases. A
useful general approach, which can give compositions producing
coatings of good gloss, is to prepare first a solution of the PVC resin(s)
in the solvent(s) as outlined above. The pigment (and stabiliser, if
used) is then pre-dispersed in the diluent and plasticiser(s), withpreferably-some grinding aid, in the ball mill. The resin solution is
finally added to the mill and grinding continued for the requisite time.
For coatings of maximum gloss, a suitable pigment concentrate should
be used. This may be a solid masterbatch (highly pigmented chips of
the appropriate resin) or the appropriate pigment concentrate paste.
The paste need only be diluted with the resin solution in the required
proportion to make the complete coating composition (if plasticisers
are to be included, these can be stirred into the resin solution before
blending with the pigment concentrate). Masterbatch chips must be
dissolved in solvent (part of the total amount called for by the
formulation): the quantity of solvent used should be the minimum
necessary to form a thick, pasty (but complete) solution. This solution
is then blended with the resin solution (by stirring-in the latter). Where

1060

W. V. Titow

good gloss of the final coating is not a primary requirement, the

plasticiser(s), pigment, and grinding aid (and stabiliser if used) may be
pre-dispersed directly in the resin solution (in a high-speed disperser,
two-roll mill, or other suitable equipment), and the dispersion ground
in a paint or ball mill in the usual way.
Details of the preparation of paints in which PVC resins are
modified by, or serve as modifiers for, other polymeric binders, and
oils, belong to the field of surface coatings, and are thus outside the
scope of this book. It may be mentioned, however, that the following
types of paint binder materials are among those with which vinyl
chloride/acetate copolymer and terpolymer resins are compatible (in
varying degrees, but generally adequate for paint formulation):
urea-formaldehyde resins, phenolic resins, alkyd resins, epoxy resins,
polyketone resins, castor oil and other oils, urethane prepolymers.
Note: The urethane prepolymers react with the -OH groups of
hydroxyl-modified VCNA copolymers, giving tough coatings
with very good adhesion. The reaction can proceed at a
significant rate at toom temperature, so that the storage life of
mixtures is limited to 8-24 h,z For this reason, surface-coating
compositions based on urethane prepolymers and the modified copolymers (e.g. Ucar VAGH or VAGD) are formulated
as two-component systems, to be mixed directly before use.

24.4 APPLICATIONS
Solutions of vinyl chloride/acetate copolymer resins find a number of
applications as surface coatings, of which the following are typical:
overlacquers for PVC coatings on fabric and paper in such products as
leathercloth, floor-coverings and vinyl wallpapers (see also Chapter 22,
Section 22.2.6); strippable coatings (sprayed or dipped) for temporary
protection of metal surfaces and various products during transport and
storage, cocooning compositions (applied by spraying) for equipment
and article protection in similar circumstances; protective coating
(resistant to chemicals and moisture) for concrete, wood and metal in
the building industry. Some relevant starting formulations are given,
by way of example, in Table 24.4.
Solutions of the modified copolymers (whose carboxyl or hydroxyl
groups variously improve adhesion to substrates and reactivity with

1061

24 PVC Solutions and their Applications

TABLE 24.4
Vinyl Chloride/Acetate Copolymer Solutions for Some Coating Applications:
Examples of Basic Formulations
(Based on data from the technical literature of Union Carbide Corp.)

Component

Formulation (Pbw)
Overiacquer
for vinyl
coatings

Ucar VYNS
Ucar VYHH
Methyl methacrylate resin
Cellulose acetate-butyrate resin'
Plasticiser
Aluminium powder
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
Toluene

50-75 a
25-50
02-04

40d
60d

Strippable Cocooning
coating
solution
solution
10
5

16b

8
6
70

27
27
27

a Toughness,

flexibility and adhesion improve with increasing resin content.

For bridging large gaps (say about 40 cm) 2 parts of the resin should be
replaced with polyvinylidene chloride resin of high molecular weight.
'May be omitted if surface slip and blocking resistance not required, or
replaced with amorphous silica if the attendant matting effect acceptable.
d The amount of the solvent system used may be varied according to viscosity
required for application and the desired solids content (but the ratio of 4: 6
MEK:MIBK should be preserved).
b

other resins) alone or in combination with one another and/or with the
unmodified copolymers, are used in a variety of coating applications
where moisture and chemical resistance, toughness and gloss are of
interest. The applications include primers and top coats for wood and
fibre or particle board (in which the copolymers-especially the
hydroxyl-modified resins-are usually combined with other resins, e.g.
alkyd, nitrocellulose, urea-formaldehyde, urethane prepolymer), and
various paper coating uses, notably coatings for food-packaging papers
in which the hydroxyl-modified copolymers (offering particularly good
adhesion) may be used alone or in blends with vinyl acetate and other
polymers. The same copolymers are also especially useful in decorative/protective coatings for paper labels in view of their excellent
adhesion to a variety of print types, and the gloss obtainable after
drying at about 105-120C (enhanced further by a short baking
treatment). 2

W. V. Titow

1062

Industrial maintenance and marine paints for steel and other

substrates constitute a long-established, important area of application
of solution systems based on the vinyl chloride/acetate copolymers and
terpolymers. 4 Such systems, nowadays normally of the high-build
variety, offer some adyantage over each of the rival types of coating
(alkyd, epoxy, or chlorinated rubber) in handling, performance
(especially corrosion and weathering resistance) or costs. Something of
the nature of the formulations, and the suitability of different resins for
particular kinds of these finishes, is indicated by the examples given in
Table 24.5.
Baked finishes (solution-applied by roller or spray) for tinplate or
sheet iron, based on hydroxyl-modified VeNA copolymer in conjunction with the previously mentioned co-reactive resins (UF, MF, epoxy,
TABLE 24.5

High-build Vinyl Marine and Maintenance Paints: Examples of Basic

Formulations
(Based on data from Ref 4)

Formulation (Pbw)

Component

Cellosolve acetate
Methyl butyl ketone
Toluene
Xylene
VM & P naphtha
Ucar resin VAGH
Ucar resin VYHH
Ucar resin YMCA
Ucar resin VYHD
Tricresyl phosphate
Didecyl phthalate
Thixotropic agent
Red lead
Rosin
Cuprous oxide
Dispersant
Titanium dioxide
Clay extender
Zinc phosphate

Red lead
primer

Shipbottom
antifouling

White anticorrosive
primer

White
topcoat

4445
635
698
444
127
1318

1315
188
207
132
038

3676
525
578
367
105

3820
546
600
382
109

249

136

227

196
2001

1-39

2190

1566

392
092

390
105

1153

027
1095
1360

975
6530

922

24 PVC Solutions and their Applications

1063

urethane prepolymer) offer excellent protective properties combined

with adhesion good enough to withstand drawing, stamping and
forming operations involved in the formation into containers, closures
and the like. 2
Solutions of vinyl chloride homopolymer of relatively high molecular
weight (for good mechanical properties) are used (at about 30% solids
concentration) for the production-on a limited scale (because of the
relatively high cost in comparison with calendering or extrusion)-of
high clarity PVC film for special packaging applications. The solution is
cast onto a stainless steel band in the way originally developed for
casting cellulose acetate film. 5 ,6 Lack of molecular orientation, and
hence freedom from mechanical and optical anisotropy (which, inter
alia, virtually eliminates retraction on heating and affects optical
properties) is a special feature of cast polymer films.
The polymeric components of PVC solutions used as solvent
cements for bonding pipes, pipe fittings, and certain other PVC
products may be homopolymers, copolymers, standard PVC
compounds,7 or the actual compositions of the mouldings, etc., to be
bonded. Solvent cements for PVC are discussed in Section 20.3.2 of
Chapter 20, where attention is drawn to some relevant standard
specifications. Two further ones, not mentioned either in that section
or in Appendix 1, are:
ASTM D 3138-80 Solvent cements for transition joints between acrylonitrile-butadiene-styrene (ABS) and poly (vinyl
chloride) (PVC) non-pressure piping components.
ASTM F 493-80 Solvent cements for chlorinated poly (vinyl chloride)
(PVC) plastic pipe and fittings.
PVC fibres are spun from solvent solutions of suitable copolymers. 8
24.5 ADHESION OF SOLUTIONAPPLIED PVC COATINGS
TO SUBSTRATES

In general, the adhesion of vinyl chloride homopolymers and vinyl

chloride/acetate copolymers to smooth substrates (especially metal, but
also others) is poor, although it can be improved in some cases by a
baking treatment (cf. Table 24.6). The presence of carboxyl or
hydroxyl groups in the modified copolymers improves the adhesive
properties of these resins substantially, as indicated in Table 24.7.

1064

W. V. Titow

TABLE 24.6
Adhesion of Vinyl Chloride/Acetate Copolymer Resin (Breon AS 70/42) Film
Solution -deposited onto Aluminium Sheet
Q

Stoving conditions

Solution solids

Resin (20 g)

None
30 min. at 50C
15 min. at 150C

Resin (15 g) + maleic acid (5 g)

Resin (10 g)

None
}
30 min. at 50C
30 min. at 150C

+ maleic acid (10 g)

None
30 min. at 50C }
30 min. at 1500C

Adhesion

Air-dried film peeled

easily
Slight adhesion
Adequate adhesion
Air-dried film peeled
easily
Adequate adhesion
Air-dried film peeled
easily
Adequate adhesion

Solution: solids, 20 g; acetone, 40 g; toluene, 40 g; phosphoric acid, 05 g.

TABLE 24.7
General Adhesion Characteristics of Commercial Vinyl Copolymer Resins for
Solution Use
(Based on data from Ref. 2)
Resin type

Surface

Metal (clean, smooth)

Phosphated metal
Wood
Glass
Paper
Cloth
PVC
Polyvinyl butyral
Phenolic resins
Urea-formaldehyde
resins
Methacrylates and
acrylates
Q

Vinyl chloride
acetate (Ucar
VYHHor
VYHD)

Carboxylated
VClVA (Ucar
YMCA, VMCC
or VMCH)

Hydroxylated
VCIVA (Ucar
VAGH or
VAGD)

P
P
P
P
P
P
E
P
P
P

E
E

P
F

F
E
G
F-E
E
F
F
F

F
F
G
G
E
E
G
G

1065

24 PVC Solutions and their Applications

TABLE 24.7-eontd.

Surface

Resin type
Vinyl chloride
acetate (Ucar
VYHHor
VYHD)

Carboxylated
VCIVA (Ucar
VMCA, VMCC
or VMCH)

Hydroxylated
VCIVA (Ucar
VAGH or
VAGD)

P
P
F
P

F
F
F
P

P
E
F

G
G

Nitrocellulose
Alkyd resins
Chlorinated rubber
Oleoresinsa
Shellac
Concretea
Plastera
Key: E

F-E

= excellent; G = good; F = fair; P = poor.

a Adhesion

can vary with type.

Notably, the air-dried adhesion of carboxyl-modified copolymer is

particularly good, e.g. Ucar VMCH adheres well, on air-drying, to
iron, steel, cadmium and brass, although on zinc a phosphate pretreatment or a wash primer is desirable (wash primers are useful in
many other cases). Admixing with the VMCH resin can improve the
adhesion of other vinyl chloride/acetate copolymer coatings.

REFERENCES
1. Bakelite Vinyl Resin Solution VYNC, Union Carbide Corp. Technical
Bulletin, 1971.
2. Bakelite Hydroxylated Vinyl Resins VAGH and VAGD, Union Carbide
Corp. Technical Bulletin, 1971.
3. Bakelite Vinyl Chloride-Acetate Resin Solution VERR-40, Union Carbide
Corp. Technical leaflet, 1978.
4. High-build Vinyl Maintenance Paints, Union Carbide Corp. Technical
Bulletin, 1973.
5. Yarsley, V. E. and Flavell, W. (1956). Cellulosic Plastics: Part 1: Cellulose
Acetate, Cellulose Ethers, and Regenerated Cellulose, Plastics Monograph
No. C6, Plastics Institute, London.
6. Couzens, E. G. and Yarsley, V. E. (1968). Plastics in the Modern World,
Penguin Books Ltd, Harmondsworth, Middlesex, England.
7. ASTM D 2564-80: Specification for solvent cements for poly (vinyl chloride)
(PVC) plastic pipe and fittings.
8. Cook, J. G. (1964). Handbook of Textile Fibres, Merrow Publishing Co.,
Watford, England.

CHAPTER 25

Cellular PVC Materials and Products

w.

V. TITaw

25.1 INTRODUCTION
Neither the terminology nor its usage in the field of cellular plastics is
as yet fully standardised. The principal nomenclature standards* offer
definitions of some basic terms, but these are by no means mutually
identical. Moreover, none of the definitions can be said to be fully
comprehensive, and they are not adhered to strictly in industrial usage.
For the purpose of the present chapter the most important relevant
terms are defined as follows.
Cellular PVC: A PVC material or product whose apparent density is
significantly lower than that of its parent PVC composition by virtue of
the presence of numerous cells (voids) dispersed throughout its mass.

This definition conforms closely with those of 'cellular plastic' given in

the ISO and ASTM standards. *
Cellular vinyl:t A cellular PVC whose solid material is a flexible
PVC composition.
PVC foam = expanded PVC: A cellular PVC in which the cells have

* ISO 472-1979; ASTM D 883-80; BS 1755: Part 1: 1967.

t As

mentioned in Chapter 1, the use of 'vinyl' for 'PVC', especially 'flexible

PVC', is widespread, although it might be questioned on strict terminological
grounds (see Chapter 1, Section 1.1). In the context of cellular PVC the
'flexible' connotation of 'vinyl' is particularly strong.
1067

1068

W. V. Titow

been formed by a gas evolved in, or introduced into, the parent PVC
composition in the course of production or processing.
Vinyl foam = expanded vinyl: A PVC foam whose solid material is a
flexible PVC composition.
Blown PVC: A PVC foam in which the cell-producing gas has been
generated or expanded within the parent PVC composition (and not,
say, mechanically admixed at atmospheric pressure).
Blown vinyl: A blown PVC whose solid material is a flexible PVC
composition.

In both the commercial and the technical sense PVC foams form the
most important group among cellular PVC products. They are also
significant among plastics foams generally, with several applications
where their processability and/or properties offer special advantages
over alternative cellular materials including those (like, for example,
polyurethane foams) whose volume of use is much greater in many
areas. Two characteristic examples are the foam layers of composite
coatings on vinylleathercloth (d. Chapter 22), and rigid foam cores of
GRP or other sandwich panels used in the construction of vehicle
bodies (e.g. refrigerated vans, modern high-speed train cabs l ). In the
former application, processability in paste form-unique to pPVCand good bonding to the skin and anchor layers of the coating are
cardinal advantages; as are the strength of rigid PVC foam (greater
than that of polyurethane or polystyrene foam) and its low flammability in the constructional sandwich panels.
Note: The floor in the cab of the British Rail high-speed train is a
GRP/PVC foam panel. In the prototype a more complicated
sandwich was used, with a composite PVC/polyurethane foam
core layer in which the PVC foam (of density about
40 kg m-3) was the strength-imparting component.

Like other expanded plastics PVC foams are usually classified by

reference to type, i.e. flexible or rigid, and density. The size and
nature (open or closed) of the cells is also a significant characteristic,
influencing such properties as, for example, the resilience and
compression behaviour of flexible foam or the heat conductivity and
moisture permeability of rigid foam insulation.
The description of a plastics foam as low, medium, or high

1069

25 Cellular PVC Materials and Products

density, very common in practice, is not exact, as the density ranges

corresponding to each of these terms are not strictly defined. The
following figures can, however, serve as a rough, general guide.
Low density range
Medium density range
High density range

kg m-3

lb /t- 3

10-50
50-350
350-900

06-3
3-21
21-54

Expanded PVC can be produced in a variety of densities. Most of

the commercial rigid foams which find application in vehicle and
marine construction, cold-store insulation and some aircraft interior
fitments, are of low to medium density, say, in general terms,
30-400 kg m -3, with densities of 80-120 kg m -3 fairly typical for the
PVC foam cores of constructional sandwich panels for vehicle bodies.
Many types of flexible foam fall within the same general density range,
but higher densities, up to about 800 kg m -3, are also practicable. Such
high densities are fairly typical for (and may even be exceeded in)
flexible injection-moulded microcellular shoe soles, or certain types of
permeable coatings on leathercloth (cf. about 1250 kg m- 3 for solid
flexible PVC). Some rigid structural foam products (e.g. extruded
cellular PVC profiles, injection-moulded parts) are also in the high
density range.
The production of vinyl foam from plastisols provides the basis of
important industrial processes and such large-tonnage commercial
products as coated fabrics, flooring and foam-backed carpets. These
processes and outlets are dealt with in the following sections, as are
other applications and production methods of cellular PVc. The
production of expanded vinyl coatings on fabrics is also mentioned in
Chapter 22.
Microporous PVC sheets with intercommunicating cell structure,
which are used as battery separators and filter media, may be
mentioned as an example of a cellular PVC material manufactured by
methods other than foaming (see Section 25.2.2 below).

25.2 PRODUCTION METHODS AND PROCESSES

25.2.1 Foams
(a) Dispersed-gas Blowing
The general principle of this method is the incorporation of an inert
gas, usually a halogenated hydrocarbon or CO2 , into a PVC plastisol at

1070

w.

V. Titow

low temperature and high pressure (the gas usually dissolves in the
plasticiser(s) under these conditions), followed by pressure release and
heating, carefully controlled to bring about synchronised expansion and
solidification (fusion) of the composition, which is finally cooled.
The principle has been utilised in several commercial processes,
including the Elastomer process2 ,3 (originated in the USA, but also
used in Europe), the Dennis process4 (sometimes known as the 'Fay
Foamer' process) and the German Trovipor process of the Dynamit
Nobel company. 5 The PVC foam manufactured by processes of this kind
is flexible, mainly open-cell (about 90% of the cells intercommunicating), and of low to medium density (typically 60-270 kg m- 3). It is
normally produced in the form of continuous sheet (slab) several
inches thick, which is usually slit into thin layers (e.g. for use in
upholstery). The sequence of operations in the Trovipor process is
schematically shown in Fig. 25.1. Machines have been available since
the mid-1960s capable of slitting the foam slab into layers of thickness
down to 15 mm (0,050 in) with a tolerance of about 025 mm
(0,010 in).6 The layers may be bonded to textile fabrics with adhesives,
for use, for example, in the proquction of foam-backed clothing~
However, such techniques will not produce cellular PVC leathercloth,
partly because of the comparatively coarse nature of the foam, and
partly because the thickness of coating on many types of leathercloth is
only about 0040 in or even less. It is also very difficult (and costly) to
produce cellular layers of this thickness by direct deposition of 'wet'
dispersed-gas-blown foam onto a fabric. Cellular leathercloth is not,
therefore, made from this type of foam, although it is a major field of
application for foams produced by other processes, as described below.
The most important application of foams made by dispersed-gas
blowing was for many years in the automobile industry as padding and
cushioning material, especially in car seat upholstery, where the
open-cell nature (and hence 'breathability') of the foam, its good
resilience, and-perhaps most importantly-its suitability for highfrequency welding to PVC sheet materials used for seat surfacing, were
important advantages. However, over the past ten years the use of
vinyl seating and trim in motor cars has declined drastically in favour
of fabrics, now widely used for this purpose (in conjunction with
polyurethane foam cushioning). Vinylleathercloth is currently installed
in only a few per cent of European cars (the percentage is substantially
higher in cars for export to, or made in, some overseas countries,
notably in Africa). Vinyl foam produced by dispersed-gas blowing still

25

1071

Cellular PVC Materials and Products

(B)

____ --.l...-

~I
()

Inlrt gu

(C)

P
s

,q

()

Fig. 25.1 Schematic representation of the Trovipor process. * A. Paste

preparation: a, PVC; b, plasticiser; c, additives; d, mixer. B. Gasification
plant: e, gas circulation pump; f, cooler; g, autoclave; h, paste; i, gas stream;
k, perforated plate; I, paste feed pump; m, paste feed container. C. Spray and
fusion plant: n, spray tower; 0, h.f. heating; p, after-heating; q, cooling tunnel;
r, to transverse or longitudinal cutters; s, conveyor belt.

features prominently in such major end-uses as travel and fancy goods,

certain types of foam-backed clothing, embossed quilting, and some
types of furniture upholstery (especially where low flammability is of
particular importance).
(b) 'Chemical' Blowing
This method is used industrially in the manufacture of many cellular
PVC products (see Table 25.1), but it is also convenient for small-scale
preparation of PVC foams, e.g. in laboratory operations. A blowing
H. V. Finkmann et al. (1969). The foaming of plastics, Kunststoffe, 59(9), 695;
reproduced by kind permission of the publishers, Carl Hanser Verlag.

Free
~
blowing

The sheet may be laminated

with a fabric and topped
with a dense skin. Sheet or

Calendered sheet
(produced by compounding and pro-

Sheet
blowing

Solid (gelled) skin usually

formed first by rotational
casting from ordinary plastisol. Mould (vented to prevent pressure build-up during blowing) then partially
filled with foaming composition (amount adjusted to
give foam filling mould but
with atmospheric pressure
within cells), heated in hotair oven, and finally cooled

Plastisol

Deposition of plastisol layer

on sheet support (e.g. release paper or conveyor
band) for subsequent lamination with a fabric, or direct
onto a fabric; heating to expand and gel (hot-air or IR
oven); cooling. Posttreatments: embossing, lacquering, printing

Cavity
filling

Principal production
operations
or process
stages

Plastisol

Form of
composition
(starting
material)

Direct
expansion

Method type

Carpet and flooring underlays, embossed wallpapers,

cellular leathercloth, upholstery, cushioning

Typical products

Largely closed cell at

medium densities, largely
open-cell at low densities

Foam flooring, cellular

leathercloth

Soft: low to medium density, Foam filling for arm rests,

mainly open-cell structure,
handlebar grips, dolls and
but mixed in some products soft toys

Largely closed cell at

medium densities, largely
open-cell at low densities
(could be described as mixed
cell structure)

Characteristics of
foam produced

TABLE 25.1
Main Production Methods Involving Chemical Blowing

~~

:<::

-.l
IV

pounds

E"ru,;on
<om
b

Plastisol (incorporating polymerising

component, e.g.
methyl methacrylate)

Substantially the same as in

general extrusion of PVC
compounds, but preferably
with finer screen packs and
land-less dies (for good surface finish). Temperature

Porous irrigation tubing,

filtration
Electrical cable sheathing,
pipe, weatherstrip and other
foamed profiles

Medium to high density,

mainly closed cell

Buoyancy blocks, fishing

floats, structural laminates insulation (thermal and acoustic), shock-absorbent materials

Shock-absorbent material
for crash pads and helmets,
life jackets, packaging

Medium density, mainly

open cell

Rigid, medium density,

closed cell

Rigid, low density,

closed cell

Semi-rigid or soft, low to

medium density, mainly
closed cell

A strong mould is filled completely ('105%') with plastisol. It is then placed in a

press (with a covering gasket) and pressure applied
sufficient to keep mould
closed during blowing.
Platens are heated at the required temperature for the
required time, then cooled
to cool the moulding to below 30C (surface temperature) before removal. The
pressures, temperatures and
times are established in
pointer trials. Expansion of
the moulding is completed
by heating in boiling water
or circulating-air oven (at
about 100C)

Plastisol

Plastisol (incorpor.
ating volatile or
Pressure blowmg { cross-linking plasticiser)

l
laminate then conveyed with (could be described as mixed
positive support through
cell structure)
heating tunnel (hot air) at
the temperature necessary to
fuse the material and effect
blowing

cessing the composition at temperatures

below the decomposition point of the
blowing agent)

-.J

......
0

l::>I::

~
"

;:,

'"I::>-

l:;"

;:l.

"'"

C"'l

-.:::

...

::::::
I::
;:;-

Moulding compoundsb

Form of
composition
(starting
material)

Characteristics of
foam produced

Essentially as in normal inNormally medium to high

jection moulding, but exdensity, mixed cell structure
pandable-cavity moulds or
short shots usually employed. The following factors are also important: careful temperature control, injection time (preferably
short), mould gate size

(and hence rate of decomposition of blowing agent)

and cooling and take-off rate
should be particularly carefully controlled. The hot extrudate emerging from the
die is weaker than in extrusion of 'solid' PVC

Principal production
operations
or process
stages

Shoe and slipper soles; rigid

structural foam mouldings

Typical products

In each case containing the appropriate quantity of blowing agent, properly dispersed (d. also Section 25.3 below).
These may be purchased as special blowing grades, or produced in-plant either by a complete compounding operation (from individual
formulation components) or by compounding the blowing agent(s), or blowing agent masterbatch, into an appropriate PVC
composition. In all cases the temperatures should be so controlled that the blowing agents are not activated.
In compounding dry blends the blowing agent(s) may be added either pre-dispersed (if solid, by milling) in the plasticiser(s), or in
powder form with the drying agent (flow promoter). In the latter case the addition may be made after the cooling of the mix, as a further
safeguard against activating the blowing agent prematurely; however, the resulting degree of dispersion may not be as good as when the
blowing agent is pre-milled in plasticiser.
A good solvating plasticiser (e.g. BBP) should be included in the plasticiser system of any plasticised composition for blowing.

Blowing in extrusion and injection

moulding

Method type

TABLE 25.1-eontd.

o'l:

:::'1

:-::

......

25

Cellular PVC Materials and Products

1075

agent (a chemical which decomposes on heating to generate a gas) is

intimately dispersed or dissolved in a PVC composition. Subsequent
heating causes evolution of gas with consequent cell formation in, and
expansion of, the material. The products are described as free blown if
foamed unconstrained at atmospheric pressure, or pressure blown if in
a mould at a higher pressure.
Blowing in the course of extrusion (e.g. in the production of foamed
profiles or pipes-ef. also Chapters 14 and 19) may be regarded as
intermediate between these two modes: although the blowing agent
decomposes in the hot stock inside the extruder barrel, the gas evolved
is believed to remain in solution in the melt under the prevailing high
pressure, and blowing takes place only when the pressure is released as
the melt leaves the die. 7 Similarly, in injection moulding of cellular
articles (e.g. microcellular PVC shoe soles) the blowing agent decomposes in the melt, but-although blowing is effected in the
mould-expansion takes place only when pressure is reduced either
because a reduced shot volume is used (initially underfilling the cavity)
or if the mould incorporates a movable base plate8 or other means of
expanding the cavity. These are the two most common arrangements
for injection moulding of foamed PVC parts. The material of both
injection-moulded and extruded cellular PVC products is high-density
foam encased in an integral skin. Such foam is known as 'structural
foam'. The general characteristics of structural foams, and methods of
their production by extrusion and injection moulding are summarised
in Refs 9 and 10 (the latter being particularly concerned with injection
moulding of fibre-reinforced thermoplastic foams). Successful operation of the two processes for foam production, and the quality of the
products, are cardinally dependent upon proper control over cell
formation: the key factors instrumental in this are the chemical nature,
physical state, and degree of dispersion of the blowing agent; the correct
relationship between its decomposition characteristics (temperature
range, rate of gas evolution and total amount generated) and the
processing temperature(s) of the plastics host material;ll the melt
viscosity of the plastics material;1l,12 and other factors influencing cell
stability during formation, e.g. the presence of cell control agents.

Note: Some commercial additives of this kind are effective, at low

incorporation levels (about 1 phr) , in promoting cell uniformity and eliminating 'overblow' even in foaming compositions
heavily filled with mineral fillers (cf., for example, product
VS-I03-Air Products and Chemicals Inc., USA).

1076

W. V. Titow

There are several commercial systems for the continuous production

of chemically blown structural foam injection mouldings, based on
consecutive presentation to the injection unit of moulds carried on a
rotary table (cf., for example, the Schloeman-Siemag equipment
originated in Europe,13 or the rotary version of the Hettinga set-up l4
developed in the USA *), or a multi-station line (as, for example, in
another version of the Hettinga equipment I4).
A method claimed to produce-on largely conventional equipmentparticularly smooth-surfaced extruded sections in rigid PVC structural
foam (of densities 500-1200 kg m3) was patented in the mid-1970s in
France by CDF Chemie. 15 The causes and mechanisms of formation of
the well-known 'swirl' patterns in the surface of structural foam
products are summarised in a paper by Gross and Angell. 16
Table 25.1 gives an indication of the physical form of the PVC
composition appropriate to the various modes of 'chemical' blowing,
together with the main operations or process steps, the types of foam
produced, and typical applications. Many applications overlap in some
areas with those of PVC foams produced by the other methods
discussed in this chapter. It will be self-evident that all the
compositions in column 2 of the table will contain blowing agents,
normally introduced at the compounding stage (and nowadays very
commonly in masterbatch form: see also Section 25.3 below).
For the sake of convenience, dry blends for foam production have
been mentioned in conjunction with extrusion and moulding compounds (in the footnotes to Table 25.1). However, two points should
be noted. The preparation of dry blend powders for foam production is
very similar to that of 'ordinary', non-foaming versions (say, for use as
extrusion feed stock), except for the addition of blowing agent(s). At
the same time, the foamable dry blends may be processed in various
ways, notably by doctor-knife spreading as in the production of carpet
backings, which have been a significant outlet for such compositions.
Other application methods have included ftuidised-bed coating or
spraying (e.g. for expanded protective coatings on metals). A good
account of foams from dry blends has been given by Hartman et al. 17
(c) Gas Entrainment ('Mechanical Frothing')
In this method a PVC plastisol is expanded into a stable 'wet' foam
(froth) by vigorous mechanical agitation or whipping to entrain a gas,

* The reM ('thermoplastic cellular moulding') system, marketed by the Foam

Moulding Corporation, USA.

25 Cellular PVC Materials and Products

1077

usually air. The foam is fused by heating. The plastisol must contain a
surface-active agent to facilitate foaming and stabilise the froth, which
is usually spread on a support (frequently a fabric, to form a laminate,
or release paper for subsequent lamination to fabric-...cf. Chapter 22).
Fusion is effected in a hot-air, IR or rf oven. The method normally
produces soft foams, with largely open-cell structure; the cells can be
very fine. A wide range of densities, roughly 300-800 kg m- 3 or even
higher, may be achieved by varying the plastisol formulation, and
adjusting the production procedure. The foam may be embossed and
surface-coated (e.g. with a lacquer). The main applications are similar
to those of PVC foam produced by the direct expansion of a plastisol
in the free-blowing technique; they include cellular leathercloth, carpet
backing and garment padding.
The Vanderbilt process3,11l and its variant developed by Scott Bader
and Co., Ltd,6 exemplify industrial processes utilising the gasentrainment method.
(d) In-situ Gas Evolution and Cross-linking
This is not a general principle on a par with, say, 'chemical' blowing or
mechanical frothing, but the cardinal feature of a process* for the
production of rigid cross-linked PVC foam (Vinylcel). The superior
thermal and dimensional stability, chemical resistance, mechanical
strength and stiffness claimed for this material in comparison with
conventional rigid PVC foams are attributable to the cross-linked
structure. Preparation of the foam is said to start with a composition
comprising a PVC resin, vinyl monomer, maleic anhydride, a
diisocyanate, and a free-radical catalyst, and to involve, as its main
phases, copolymerisation of the monomer with the anhydride,
evolution (on heating) of CO2 (with consequent blowing) concurrent
with hydrolysis of the anhydride and its reaction with the diisocyanate
which gives rise to the cross-linked structure.
Foams in the density range 32-64 kg m-3 (2-4lb ft-3) produced by
this process found applications in sandwich panels and thermal
insulation.

(e) Solvent (Monomer) Blowing

This is not an established process, but a technique once devised 19 for
the production of expanded beads from vinyl chloride/ethylene
* Originally operated by Kleber Colombes SA in France, and Johns Manville
Corp. and B. F. Goodrich Chemical Co. in the USA.

1078

W. V. Titow

copolymers. The beads may be consolidated into cellular sheet or

moulded articles by surface 'welding' under heat and pressure: they
have also been proposed for use in the production of syntactic foams
through bonding with resins or other suitable media. The beads are
made from particles of the suspension-polymerised copolymer swollen
in the monomer mixture and expanded by rapid volatilisation of the
permeant on heating under reduced pressure, i.e. in a way somewhat
similar to the solvent blowing of polystyrene beads. The method
cannot be used with PVC homopolymer as, quite apart from the health
hazard presented by vinyl chloride monomer (see Chapter 1, Section
1.2; and Chapter 12, Section 12.9.1), the homopolymer is not dissolved
or appreciably swollen by it.
25.2.2

Other Cellular PVC Materials

The commercial applications of materials produced by the methods

mentioned in this section are much less extensive and numerous than
those of PVC foams.

(a) The 'Lost Filler' Method

This is one of the oldest methods of producing cellular plastics
materials. Its essential features are that a particulate additive, capable
of being subsequently removed by dissolution, is intimately and
uniformly dispersed in a polymeric composition, the filled composition
is formed into the desired product (e.g. sheet, moulding, etc.), and the
additive is dissolved or leached out. In practice the level of loading is
such that there is substantial mutual contact between the particles of
the soluble filler to enable effective dissolution on immersion in the
appropriate liquid medium: the finished cellular product thus has an
intercommunicating pore structure, the cell size being influenced by
the degree of dispersion and particle size of the soluble filler. The
earliest fillers used in practice were finely comminuted mineral salts,
dissolved out by immersion of the filled material in water.
In the PVC context an early practical embodiment of the method
was the original Porvic process20 for the production of porous sheeting.
The method was also used in the manufacture of PVC battery
separators21 (although nowadays these are normally made by sintering
of powder-see below). In both cases the removable filler was starch:
this was leached out of the formed products by hydrolysis and
dissolution with dilute sulphuric acid.

25 Cellular PVC Materials and Products

1079

An interesting variant of the general method-with finely dispersed

droplets of water constituting the 'filler'-has been proposed22 for the
production of porous PVC film from a plastisol. The paste may contain
up to 50 phr of water, the voids being formed as this evaporates when
heat is applied to gel and fuse the material. The process is claimed to
be controllable so that the vaporisation causes comparatively little
expansion, and the main proportion of the voids arise simply as a result
of the disappearance of the dispersed water from the composition.
(b) Sintering of Powder
The principle of this long-known method, by which porous sheets and
mouldings can be produced from plastics powders, is surface fusion of
the particles (appropriately size graded for good processing and pore
size of the product) at an elevated temperature, and sometimes also
under pressure. Solvents or plasticisers may be present to facilitate the
bonding.
With PVC and other plastics powders to which variants of the
method are applicable,2,23 intercommunicating cell structures are
usually obtained.
The only industrially significant application of powder sintering in
modern PVC technology is the production of battery separators, where
the method has been used for a long time. 21 The production is
continuous, the powder being preformed on a moving belt-typically
co-acting with another element, e.g. a roller (as in the Jungfer
roll-coating process)-and sintered in the familiar ribbed form of the
separator plate. A special grade of emulsion homopolymer is used,
with particle size range and distribution suited to good dry flow and
giving a high angle of repose to maintain sharp rib definition during
sintering. The molecular weight is relatively high, for good product
strength and stiffness, whilst the generally small size and uniformity of
the particles characteristic of emulsion-type resins make for fine,
uniform ultimate porosity. As heat stability is not a service requirement,
stabilisers are not normally used: in their absence the heating during
sintering can turn the product a fawn or light brown colour, but it does
not degrade the relevant properties significantly. Apart from the
moisture content (a few per cent, conditioned into the powder as it
helps smooth fusion) the only additive present is a small amount of a
surface-active agent which promotes wetting of the separator plate by
the aqueous acid solution in the battery.

1080

w.

V. Titow

25.3 FORMULATION AND PROCESS FACTORS IN

FOAM PRODUCTION
The properties of all PVC products are governed by the formulation
and, in varying degrees, also by the processing method and conditions.
The effects of these factors are particularly pronounced in the case of
cellular PVC, and especially foams.
25.3.1 Effects of Formulation and Processing Variables on Foam
Properties
Other factors being equal, increasing the molecular weight (K value)
of the polymer will improve the mechanical properties of a cellular
PVC product by upgrading those of the solid substance of the cell
walls. The effect is greatest in rigid materials and at high densities, and
relatively less marked in flexible materials especially at low densities.
However, the processing characteristics of a PVC composition (e.g.
melt viscosity of a rigid compound, gelation/fusion properties of a
plastisol) are also influenced by the K value of the polymer. This
influence, where sufficiently pronounced (and not counteracted by
adjustments in the formulation and/or processing conditions) may be
ultimately reflected in such characteristics of the final product as its cell
size and structure: these characteristics are also factors in the mechanical properties of the cellular material as a whole, and their effect may
modify the direct one of molecular weight of the polymer on the
properties of the solid walls of the cells.
In flexible foams produced from pastes by chemical blowing or
mechanical frothing, the main polymer component will be an
emulsion-type PVC resin: its grade (as determined by the particle size
and size distribution) will influence paste viscosity and general
rheological behaviour in processing (see Chapter 21, Section 21.3.1),
including cell formation in foaming (which, in turn, affects the finished
foam properties). The presence of any extender polymer will also have
an effect in these regards.
It has long been known, as a matter of practical experience, that the
foaming behaviour of a paste of one and the same formulation can be
significantly affected by the make (Le. source of supply) of the
emulsion polymer used. There is good evidence24 that such effects are
attributable to differences in the nature and content of emulsifier
residues present in vinyl chloride polymers and copolymers produced

25

Cellular PVC Materials and Products

1081

by the emulsion method by different manufacturers: the differences are

reflected in the degree and extent to which the residual emulsifiers
interfere with the action of the surface-active agents used as cell
stabilisers in paste formulations for foaming (particularly important in
foam production by the mechanical frothing method-see below).
In general, any factor affecting paste rheology can influence cell
formation in processing and hence the properties of the ultimate foam
product.
The amount of plasticiser(s) is a cardinal factor. In general, softer
foam, with decreasing modulus and strength, is obtained with
increasing plasticiser content. The choice of plasticisers is also
important: for low-density foams the presence of a good solvating
plasticiser is essential, to promote rapid setting of the cell structure at
the appropriate, early, point of the heat treatment, and good
gelation/fusion characteristics generally. Such plasticisers are also
beneficial, for the same reasons, in higher density foam compositions.
BBP or the triaryl phosphates, as well as some other strongly solvating
plasticisers (e.g. propylene glycol dibenzoate), are included in foam
formulations for this reason, commonly in conjunction with cheaper
phthalate plasticisers like DOP, DAP, etc.
Fillers also affect foaming behaviour and the ultimate foam
properties.
Whilst cell stabilisers are significant as processing additives in PVC
compositions for foam production by chemical blowing or dispersed-gas
blowing (ct. Section 25.2.1 above), they are cardinally important
components of paste formulations foamed by mechanical frothing. In
such formulations the special surface-active agents used as cell
stabilisers also promote the initial mixing-in of the air. To discharge
both functions properly, the agent must have the right chemical
structure to combine the requisite degree of solubility in the plasticiser
system with correct alignment of its molecules at the air/paste interface
of the cell (bubble) walls, in a way optimal for effectivity in three
relevant actions characterised by Acton and Debal25 as:
(i)

lowering the interfacial tension between paste and air (to

reduce the energy required for frothing, and to promote
stability in the bubbles formed);
(ii) increasing surface elasticity;
(iii) promoting surface plasticity.
The effect of (ii) is seen by these authors as reduction of the

1082

W. V. Titow

tendency of paste forming a cell wall to flow, under gravity, towards

the bottom of the cell and thus cause local attenuation at the top which
may culminate in rupture and collapse. That of (iii) is increased
resistance to similar but longer-range draining of paste down the liquid
columns formed by the interconnecting walls of vertical 'stacks' of
cells.
In view of the complexity of the mechanism of their actions, it is not
surprising that the surface-active agents used as frothing aids/cell
stabilisers in PVC pastes can differ in their effectivity in different
formulations. In the absence of relevant practical experience, suitable
selection will be aided by advice from suppliers (of surfactants for use
in plastics compositions, * or of PVC polymers or plasticisers) and
finalised on the basis of trials. Examples of commercial additives of this
kind are Atmer 152 (a mixture of surface-active agents in a phthalate
plasticiser carrier, supplied by Atlas Chemical Industries); the range of
silicone-based surface-active agents marketed by the Dow group of
companies; and products in the Dekor Cellset range (Scott Bader &
Co. Ltd).
The main processing factors governing cell formation-and hence
the quality and properties of the ultimate foam product-in the
manufacture of structural foam by chemical blowing have been
mentioned in Section 25.2.1. Closely similar considerations apply to
foams chemically blown from pastes (ct. Table 25.1) where, however,
the gelation/fusion properties of the paste constitute an additional
factor of primary importance. This is so also in the foaming of pastes
by dispersed-gas and mechanical frothing methods where, in analogy
with the operation of a chemical blowing agent, the dispersion of the
gaseous blowing medium should be as thorough, initimate and uniform
as possible. In mechanical frothing of pastes the air is normally
entrained by means of a mixing head into which it is fed, under
pressure, simultaneously with the paste. The air pressure at the head,
and the back-pressure of the discharging air/paste stream are
parameters influencing the ultimate foam density, 2S ,26 with the
air-to-paste feed ratio as another important factor. 2S The foam density
can also vary with the thickness of the 'wet' froth layer before gelation
and fusion: with froth deposits on a fabric backing, Acton and Debal2s

* See, for example, the British Plastics Federation's Buyers Guide for Plastics
Additives (section on antistatic, viscosity control, depression and wetting
agents), or the Plastics Technology Buyers' Guide.

25

Cellular PVC Materials and Products

1083

found density increases after fusion which were most pronounced for
the thinnest layers.
The relationship between the formulation and processing conditions
on one hand and properties of chemically blown flexible foam on the
other has been receiving a considerable amount of attention over the
years. A study by Renshaw et al. 27 demonstrated that increasing
concentrations of plasticiser, filler and blowing agent all reduce the
tensile strength of the foam and that the plasticiser concentration is the
principal factor determining foam elongation (the latter being directly
proportional to the former). Elongation was also found to increase
with processing temperature within the investigated limits but, as might
be expected, to decrease with the concentrations of filler and blowing
agent. Other findings were that the compression deflection is inversely
proportional to the blowing agent concentration, that the compression
set values are governed mainly by the plasticiser and filler content
(increasing with the former and decreasing with the latter), that the
foam density is a function almost exclusively of the blowing agent
concentration, and that the use of a good solvating plasticiser is
necessary for good quality foam of the type studied.
Similar work by Deanin et al. 28 indicated that for chemically blown
vinyl foams with open-cell contents in the range 0-90%, the
open: closed cell ratio correlated directly with low-temperature
flexibility and volume resistivity, and inversely with modulus, strength,
elongation, permanent set, resilience and abrasion resistance. Modulus
and strength also varied inversely with the plasticiser content, whilst
decreasing foam density produced decreasing modulus, strength and
elongation. In an extension of this work,29 the effects of plasticiser
content and foam density were found to be generally similar also in
substantially open-cell foams produced by mechanical frothing of
plastisols of a simple basic formulation. However, at comparable
densities (in the range 19-751b ft- 3 ), the mechanical properties of the
latter foams were considerably inferior to those of their chemically
blown, partly-open-cell counterparts.
In his investigation of the effect of formulation and processing on the
properties of foams blown with azodicarbonamide (Genitron A C/2
-Fisons, UK) Visnovsky30 has evaluated such parameters as the
nature of the PVC resin, the activator, plasticiser, and ambient
temperature during expansion. His results show how variations in all
these parameters can affect foam properties, and illustrate particularly
well the effect of molecular weight (K value) of the resin.

w.

1084

V. Titow

Molecular weight is also an important factor in cellular PVC

produced by the 'lost filler' method, in which high molecular weight
polymers should be employed for best results.
The effects of formulation variables on the properties of expanded
vinyl flooring were the subject of a thorough study by Jones and
Lavender. 31 Modern vinyl flooring-a product of very considerable
commercial importance-is usually a two- or multi-layer material
incorporating an expanded foam layer produced by chemical blowing.
The two-layer construction consists of a vinyl wear layer, which may
include a transparent vinyl coating for print protection, backed by a
fairly thick foam layer; the multi-layer construction comprises
essentially a clear wear layer, a thinner foam layer and a fabric layer
with, in some cases, an additional barrier layer between foam and
fabric. The fabric layer may serve as a backing layer to the foam or it
may be contained between the foam and the wear layers. 31 ,32 The main
service requirement to be met by vinyl flooring is rapid recovery after
compression; other service properties which, although of primary
importance, are not unique to vinyl flooring, include composition
stability (no migration or evaporation of plasticiser), dimensional
stability, good wear and soiling resistance. The above-mentioned study
was primarily concerned with the effects of formulation variables on
recovery properties, but the work and its results are a good general
illustration of the way in which the formulation parameters can
influence the properties of a foam.
Some of the conclusions of Dietz33 are also of interest in connection
with the compression and other properties of plastisol foam (blown
with azodicarbonamide) as functions of the formulation variables. The
main results indicate that-all other things being equal-better
compression recovery properties are shown by foams with:
(i)

lower plasticiser contents;

(ii) higher densities; and

(iii) higher filler loadings (over the minimum of 20 phr).
Dietz also found that a maximum of 30% of blending (i.e.
non-paste-forming) resin could be used in plastisol formulation without
affecting the compression properties, lower foam densities resulting at
high blending resin levels. This latter effect is attributable to the
reduction in plastisol viscosity and lower melt viscosity permitting
better utilisation of gas. Finally, higher molecular weight resins were
considered more difficult to process into good foam products.

25 Cellular PVC Materials and Products

25.3.2

1085

Chemical Blowing Agents-Nature and Operation

The blowing agent is a cardinal component of PVC formulations for

the production of foams by 'chemical' blowing. Blowing agents are
compounds which decompose on heating within a defined temperature
range, to generate a large volume of gas. They can be solid or liquid,
and inorganic or organic in nature.
In general terms, the principal requirements to be met in sufficient
degree by a blowing agent for any plastics composition may be listed as
follows:
(i) stability at ordinary temperatures (good shelf life);
(ii) compatability with the plastics composition and good dispersibility therein (down to solution where appropriate);
(iii) gas evolution at a high but controllable rate in a suitable,
preferably narrow, temperature interval within the normal
processing temperature range of the plastics material concerned;
(iv) innocuous nature of the gas(es) evolved;
(v) no excessive temperature rise (exotherm) in decomposition;
(vi) non-toxicity of the blowing agent itself, combined with
maximum volatilisation of decomposition products and innocuous (non-toxic and non-corrosive) nature of any residues
left behind in the expanded material: such residues should also
be permanently retained (no exudation or 'blooming'), have no
adverse effect on the properties of the foam, and impart no
colour or odour.
Just as in the production of flexible foam by the dispersed-gas
process it is important to synchronise properly the expansion of the gas
with the temperature and rate of gelation of the PVC paste, so in
chemical blowing the temperature and rate of gas evolution by the
blowing agent should be similarly synchronised. The requirement that
the blowing agent must generate the gas(es) at the temperature and
rate suited to the expansion of the plastics material concerned at the
appropriate stage in processing, is in fact a general one, applicable to
any given composition.
Inorganic blowing agents are not much used in PVc. The most
common one, sodium bicarbonate, albeit a cheap material, is rather
difficult to disperse finely and intimately in PVC compositions, whilst
its temperature range for gas evolution is low as well as relatively

1086

W. V. Titow

broad-a combination of features disadvantageous from the point of

view of what is desirable in the processing of PVC (including the
gelation and fusion of pastes). The use of sodium borohydride has
been explored, but not implemented on a significant scale.
Thus the chemical blowing agents in industrial use for the production
of PVC foams are organic ones. Their main qualifications for this
application are that their operating temperature ranges fit in with
those of the relevant PVC compositions (either directly, or when
modified by the presence of activators-see below) and that their
compatibility with these compositions is good. Their other advantages
include availability of the solid ones in uniform particle sizes (including
very fine ones in some grades) for control of final cell size and
uniformity, and relatively narrow decomposition ranges (see Fig. 25.2).
The organic chemical blowing agents also tend to be self-nucleating
during decomposition, which makes for cell uniformity.
The blowing agent most widely used with PVC compositions,
including pastes, is azodicarbonamide (ADA), sometimes called
azobisformamide (ABFA). It comes close to meeting all the principal
general requirements mentioned above and, in addition, is not
flammable in ordinary conditions. The general operational temperature
range (i.e. the range of plastics stock temperature in processing) for
which unmodified ADA is suitable is about 20o-250C (d. its
decomposition range in Fig. 25.2). This would be rather high for PVC
processing (especially pastes), but the range can readily be extended
downwards to about 165C (or even lower in certain special cases) by
the presence of activators, introduced either as formulation components external to the blowing agent, or as modifying additives
incorporated in the commercial version. Thus 165-230C can be
regarded as the typical operational range in PVC of most commercial
ADA blowing agents (see Table 25.2).
The use of activators (sometimes referred to as 'kickers') in
conjunction with ADA (as well as some other blowing agents-see
below) is an important feature of plastics foam production by chemical
blowing. The principal effect of an activator is to lower the
decomposition (gas evolution) temperature of the blowing agent: many
also increase the decomposition rate. Lead, zinc, and cadmium
compounds, including several used as PVC stabilisers or components
of stabiliser systems, act as activators for ADA. This long-known fact 34
is widely utilised in formulating compositions for chemically blown
PVC foams: as little as 05 phr of a kicker can be sufficient for

25
250

1087

Cellular PVC Materials and Products

200
I

en

E 150

XX

'0

....IIIto

l...

..:-'-x

x
x

I
I

~1oo
to

en

CIl

III

<!>

50

I
;" /

xX

x
xX

xx

o
250
B

200
'en

E 150
'0
to

....

'"to
~

.
f

215C

185'C

-----

l...

en

170C
..............................

100

170C

CIl

III

<!>

50

o
Fig. 25.2 Volume of gas generated by some blowing agents, as a function of
temperature (A), and time at a constant temperature (B). - - Azodicarbonamide (ADA); x x x ADA non-plate-out grade; ... ADA activated with
a liquid CdlBalZn stabiliser system; - - . - - ADA activated with a liquid Pb
stabiliser system; ------ a commercial hydrazide-based blowing agent;
- - 4, 4'-oxybis(benzene sulphonylhydrazide) (OBBS).

EF (profile,! sheeting;
EF (profile,! sheeting;
EF (profile,d wire and

165-230
165-180
165-230
From 145
160-200

AZNP130

AZ760

AZ3990

AZ754

AZRV

Modified:
Non plate-out

Non plate-out
(coml?ounding
grade)
Flow-treated

Activated

Activated

Kempore FF

Kempore 125N

Genitron (or
Ficel) EP
Kempore MC

Genitron
(or Ficel) AC
Azocel
Porofor ADC
Kempore

Materials

Fisons Industrial
Chemicals, UK
(Genitron)
Haake Inc., USA
(Ficel)
Fairmount Chemical
Co., USA (Azocel)
Bayer, West Germany
and Mobay Chemical,
USA (Porofor)
Stepan Chemical Co.,
USA (Kempore)

Sources

Examples of other similar

commercial products b

Based in part on data from Uniroyal Chemical technical literature.

Not necessarily directly equivalent.
CSome applicatIOn, with sUitable activation.
d A main application.
A main application, with suitable activation.
fS ome application.
Key: ER, rigid extrusions; EF, flexible extrusions; SR, rigid structural foam mouldings; SF, flexible structural foam mouldings; R,
rotational mouldings; C, calendered sheeting; P, paste products.

SF d R" p . CC
E~ (fiJm' and sheeting;
wire and cable)
ERd (profile, pipe,
sheeting); SRQ

cabl~;

wire and cable')

wire and cable')

ERe.. (profile, pipe,

sheeting)
EF (sheeting,C wire and
cabled)
SR;c C;< P"

165-230

AZ130

Regular

Application areas

Approximate
operational
range Cc)

Celogen
grade

General type

:::l
S

:0::::

00

TABLE 25.2
Operational Temperatures and Applications of Some Commercial Azodicarbonamide Blowing Agents, with Special .<=>
Reference to the 'Celogen' Range (Uniroyal Chemical)Q
00

25 Cellular PVC Materials and Products

1089

activation (i.e. much less than required for stabilisation, in normal

circumstances, with Pb, Zn and Cd stabilisers). Selected liquid or
paste-form stabilisers containing the above metals can be particularly
effective as activators, and are featured in the ranges offered by all
major suppliers (d., for example, Irgastab L600, ABC 2, or CZ
ll-Ciba-Geigy). Certain organotin stabilisers also have an activating
effect (e.g. Mark 1915-Argus Chemical, USA).
Note: In formulating a PVC composition for blowing with ADA (or
another blowing agent sensitive to activation) the relevant
considerations will thus include, inter alia, the following
points: whether the blowing agent is internally activated; if
not, the best stabiliser system to give the required activation;
whether any other formulation components can interfere by
spurious activation (e.g. lubricants like lead or zinc stearate,
pigments based on Pb, Zn or Cd, or even certain carbon
blacks)-in case of doubt practical trials should be carried
out.

The effect of le.ad activator* concentration on the density of

extruded PVC foam is illustrated in a paper by Wells. 35 The use of
isocyanates as retarders (i.e. the opposite of activators) in certain
foams blown with borohydrides was patented in the USA some time
ago,36 although isocyanates have also been considered as indirect
blowing agents, generating carbon dioxide through reaction with water
in processing.
The principal gaseous products generated-in a high yield (cf. Fig.
25.2)-by ADA at the decomposition temperature are nitrogen,
carbon dioxide and carbon monoxide. A small amount of ammonia is
also evolved, and this should be borne in mind where the processing
surfaces of equipment may be susceptible to corrosion by this reagent
(e.g. beryllium copper moulds). Although azodicarbonamide is a solid,
insoluble in plasticisers, it can be satisfactorily dispersed in PVC
compositions, being available as powder or as dispersion (paste) in
plasticisers. Both forms are supplied in several particle size grades (e.g.
Fison's Genitron ACI2, AC/3 and AC/4 are powder grades of ADA of
progressively finer particle size), and the pastes in different plasticisers.
In general, the rate of decomposition in processing increases with
decreasing particle size: this behaviour is particularly marked in the
* Dibasic lead phthalate (Dythal-National Lead Co.).

1090

W. V. Titow

presence of activators. Hence the coarser grades afford better control

over blowing (although, with good control, smaller cell sizes can be
obtained with finer grades).
Examples of commercial versions of azodicarbonamide are given in
Table 25.2.
Apart from modification to the decomposition temperature and
decomposition rate of ADA by incorporation of suitable activators in
some commercial versions (as well as through differences in particle
size as just mentioned), the other principal variations available are
represented by plate-out resistant and easy-flow grades.
Note: As with some lubricants and stabilisers, plate-out is deposition
of residues on the processing surfaces of equipment: in the
case of compositions blown with ADA the deposit consists
essentially of cyanuric acid or its compounds, appearing as a
whitish powder or sticky layer. Cyanuric acid is a residual
solid product of decomposition of ADA. Inclusion of finely
divided silica in the blowing agent is a common way of
counteracting the formation and deposition of this substance
without materially affecting the generation of gaseous decomposition products, except for nucleating action which the fine
particulate additive can exert.

The following blowing agents are also of interest in the production of

PVC foam.
4,4'-Oxybis(benzene sulphonylhydrazide) (OBBS or OBSH): The
general operational temperature range of this agent is 13o-170C, the
blowing gases generated being mainly nitrogen and water vapour. Its
main industrial applications in PVC are in the production of flexible
foams (extruded profiles and sheeting, injection-moulded structural
foam, and paste-derived foam products). Examples of commercial
versions are Genitron OB (Fisons, UK), Celogen OT (Uniroyal,
USA), Nitropore OBSH (Stepan Chemical, USA), Sulfocel (Fairmount Chemical, USA).
Azobisisobutyronitrile (AZDN): This blowing agent decomposes
between about 80C and HOC in PVC compositions (in which it is not
normally responsive to activation), evolving principally nitrogen, but
also generating some toxic volatiles. It can be used in the production of
foam from pastes. Some of its commercial versions are Genitron

25 Cellular PVC Materials and Products

1091

AZDN (Fisons, UK), Porolor N (Bayer, UK and Europe), Poly-Zole

AZDN (Stepan Chemical, USA).
Blow~ng agents with decomposition temperatures low enough to
coincide with the gelation temperature range of PVC pastes are of
particular interest for the chemical blowing of paste-produced foams.
A commercial example (with an operational temperature range of
about lOS-BOaC) is Celogen TSH (Uniroyal Chemical, USA).
Another blowing agent in this general category, originally marketed by
Du Pont under the name Nitrosan, is N,N'-dimethyl-N,N' -dinitrosoterephthalamide (DMDNT). This compound decomposes at about
lOOC, with an exceptionally low exotherm, which makes it particularly
interesting for the production of thick-section foam from paste, where
excessive heat build-up can affect the polymer. At the same time, the
fact that the decomposition temperature is low also restricts the main
use of DMDNT primarily to pastes. This is because there it can be
incorporated by dispersion at room temperature, whereas where
heating is necessary with other types of composition the DMDNT may
begin to decompose at temperatures in excess of 50C.
A technique has also been developed 36 for foam production by
room-temperature blowing of PVC paste with a liquid blowing agent of
the azo type whose decomposition is initiated by an organic acid. A
polyfunctional monomer (e.g. trimethylolpropane trimethacrylate) is
also included in the composition (together with a peroxide catalyst) to
help stabilise the foam by polymerising to form a three-dimensional
network at the appropriate stage in the process before the final fusion
of the PVC composition. The liquid state of the blowing agent makes
for ease and homogeneity of dispersion in the paste. An example of a
blowing agent of this type is 2-t-butylazo-2-hydroxybutane which
generates nitrogen as the main blowing gas (up to about 140 ml g-l):
this reagent is one of the commercial Lucel range (Pennwalt Corp.,
USA).
Dispersibility in plasticised PVC compositions amounting to solution
has been emphasised as a feature of a group of liquid blowing agents
which are esters of azodicarboxylic acids,37 soluble in many plasticisers. Decomposition into nitrogen gas and entirely liquid residues which
are colourless, non-toxic, non-staining, non-blooming and odourless
are further features of interest.37
Incorporation levels of blowing agents range fairly widely, from
about 05-08 phr in structural foam compositions for injection

1092

W. V. Titow

moulding, to 2-10 phr in foamable paste coatings on substrates for

flooring with 'chemical' emboss effects (see Section 25.4). The form in
which the blowing agent is introduced, and the method of incorporation depends on the nature of the PVC composition and general
operational and cost considerations. Most commercial blowing agents
in large-scale industrial use are solids, available as powders (in various
particle sizes), concentrates, and masterbatches. Liquid dispersions (in
plasticisers or oils) are also supplied. The incorporation method used
(e.g. tumbling of powder with injection-moulding compound followed
by subsequent dispersion in the melt in the barrel of the injection
machine, or stirring or milling into paste) must result in dispersion of
the blowing agent in the composition which is sufficiently intimate and
uniform to avoid uneven blowing with consequent variability in cell
size, or formation of holes.
25.4 SOME SURFACE TREATMENTS-EMBOSSING AND
LACQUER COATING OF FLEXIBLE CELLULAR
SHEET MATERIALS

Embossing is a major decorating technique for such commercially

important vinyl sheet products incorporating foam layers as floor and
wall coverings ('cushioned' by virtue of the presence of such layers)
and certain leathercloths. The processes used are of two general kinds:
mechanical embossing and the so-called chemical embossing. An
emboss-like effect can also be obtained by printing a pattern in
foamable paste and then expanding and fusing the printed deposits.
25.4.1 Mechanical Embossing

Relatively coarse embossing and/or quilting by application of heat and

pressure came into practice in the manufacture of PVC upholstery
linings: 5 ,6 however, in that kind of application the main object was to
structure the material in a particular way, rather than to decorate or
improve its surface in the sense in which this is done by embossing
PVC flooring, wall-coverings, and leathercloth for certain fancy goods.
Cellular leathercloth is embossed by the general process mentioned in
Chapter 22 (Section 22.2.6), but preferably with a fixed gap between
the pattern roller and pressure roller, and with both rollers watercooled, the surface layer of the leathercloth being softened by the

25 Cellular PVC Materials and Products

1093

application of heat before the material enters the nip of the rolls. 38
Other methods include 'direct' embossing as the material emerges from
the fusion oven (this is mainly applicable to cellular leathercloth with a
woven fabric base), and the use of embossed release paper on which
the foam layer is cast (cf. Table 25.1).38 In all cases care must be taken
that heat applied to the foam, and/or roll pressure, do not cause
uncontrolled collapse of the cell structure.

25.4.2 Chemical Emboss

This is effected by printing on the surface of a foamable PVC layer
(commonly a pre-gelled layer of paste on an appropriate backing) a
composition incorporating a reagent which modifies locally the extent
of expansion when heat is applied. The modifier may be an activator
for the blowing agent, in which case the expansion will be greater in
the areas of the printed pattern, and these areas will form the raised
portion of the resulting emboss effect. Alternatively, it may be an
inhibitor either for the activating action of a kicker present in the layer
(but not for its heat-stabilising action if the kicker is also the stabiliser),
or for the blowing agent itself, in the sense of reducing its susceptibility
to activation by the kicker: in either case the printed pattern areas will
form the 'valleys' of the emboss effect resulting from differential
expansion, on heating, of the foamable layer. Where the blowing agent
is ADA and-as is normal-a suitable kicker is also present, external
deactivators for the kicker may be, for example, trimellitic anhydride
or fumaric acid. In the alternative variant the ADA itself may be
locally desensitised against activation by the kicker if the printed pattern
contains a suitable reagent, say thiourea, which can react with the azo
group to form a stable compound.
The modifying agents are usually incorporated in coloured printing
inks, so that the two modes of surface decoration (coloured printed
pattern and emboss) are combined in the finished product, the
decorative value of the combination being enhanced by the excellent
mutual register inherent in the process. The inks are usually applied by
rotogravure. The height of the raised portions and depths of the
depressions of the emboss can be varied selectivity, to produce
multi-level effects, by appropriate variation of the depth of engraving
on the printing roller. The amount of activator or retardant in the ink
(which may vary within the range of about 5-20%), and the
permeability of the PVC layer (affected-for a given composition-by

1094

w.

V. Titow

the degree of pre-gelation), are also factors influencing the emboss

pattern depth. Clear, non-foaming wear layers are normally applied to
flooring over the printed pattern before the final heat treatment which
effects foaming and fusion.
Variants of the chemical emboss method, which has been in
industrial use for a considerable time, have been patented by
Congoleum-Nairn Inc. 39 and Fisons Industrial Chemicals. 4o

25.4.3 Emboss Effects by Screen Printing of Paste

In this method, a foamable paste is printed onto the appropriate base
layer (fabric, paper, etc.) with the aid of a seamless cylindrical printing
screen of the kind originally developed for applying coloured printing
compositions to textiles. * The principle of the method is an adaptation
of the flat screen printing technique: the screen cylinder contains the
paste which is forced out through the pattern areas by an internally
mounted squeegee as the cylinder rotates in contact with the moving
web. An unpatterned screen cylinder can be used to deposit a
continuous coating.
A fairly common procedure in the production of, say, a floorcovering by the printing method is to deposit a layer of foamable paste
as a base coat on the substrate with a plain screen cylinder, then print
the pattern also with an expandable paste composition which may be
suitably coloured (where appropriate the pattern may be built up by a
number of printing stations). The printing may be wet-on-wet, or
wet-on-dry (with pre-gelling before each new step). A wear layer may
finally be printed on, and blowing and fusion (preceded by gelation if
printing had been wet-on-wet) effected by a heat treatment.

25.4.4 Lacquer Coating

A coat of lacquer may be applied over the wear layer of sheet
materials with PVC foam coatings, or-in some cases (e.g. certain
wall-coverings or leathercloths where a wear layer is not required)directly over the expanded layer (with or without emboss effects). The
role and functions of the lacquer coat, and some typical compositions,
have been mentioned in Chapter 22, Section 22.2.6. It may be noted
* The Stork rotary screen system. originated by M. de Vries: Stork Brabant
BV, The Netherlands: Stork Inter America Corp., USA.

25

Cellular PVC Materials and Products

1095

that the 'breathability' of cellular leathercloths which are required to

be permeable may be impaired by the lacquer layer.
25.5 EXAMPLES OF BASIC FORMULATIONS

The best formulations for pastes used in the production of flexible PVC
foam by the dispersed-gas blowing method-which is the domain of big
manufacturers operating under patents and licences-are rarely
disclosed. They are in some cases the results of extensive development
work involving, inter alia, gelation/fusion and viscosity studies of the
kind mentioned in Chapter 21, Sections 21.2.5 and 21.2.6. Such pastes
normally contain fairly high proportions of plasticisers and include a
good solvating plasticiser: they are thus similar in general type to
pastes used for the production of flexible foam by chemical blowing.
Basic formulations for chemically blown foams are exemplified by
those shown in Table 25.3. Some examples relating to foams produced
by gas entrainment are given in Table 25.4.
Basic formulations for the individual layers of a composite coating of
a cellular leathercloth are included among the examples at the end of
Chapter 4.
25.6 EVALUATION AND TESTING

Apart from such general tests as determinations of heat stability,

viscosity and gelation behaviour of pastes, etc., some evaluation and
test methods are of special relevance or sole applicability to
compositions for the production of cellular PVC, and the resulting
products.
Thus, gas evolution by a blowing agent (and the effects of
activators in this connection) may be examined by heating the agent
(with the appropriate proportion of activator, where relevant) in
dispersion in a plasticiser (say 1: 10 solids in DOP) at temperatures
relevant to processing, and collecting the volatiles formed in a gas
burette. Thermogravimetric analysis-over the appropriate temperature interval-of a sample of an actual foaming composition can yield
similarly relevant data on foaming behaviour, as can differential
thermal analysis and thermomechanical analysis. The latter can also be
applicable where the foaming and gelation effects in foamable pastes

PVC paste-forming resin

PVC calendering resin
Dibutyl phthalate
Dioctyl phthalate
Butyl benzyl phthalate
Dialphanyl phthalate
Chlorinated paraffin
(plasticiser extender)
Whiting
Azodicarbonamide
(Genitron AC/2)
Genitron CR
CdlZn stabiliser
White lead paste
(7:1 in DBP)

Formulation (Pbw)

Method and technique

25

25

20
5

60

100
-

Calendered
sheet (foam
layer)

Free blowing

100
65
20
-

Coated
plastisol
(foam layer)

TABLE 25.3

20

05

18
4

50

50

100

05
10

20

55

100

Blowing in
injection
moulding

05

100

Extrusion blowing

120

100
-

Pressure
blowing

100

145

100

Cavity
fillings b

Specimen Formulations for Chemically Blown FoamsD

:::'j

.....

Coated
fabric and
unsupported
sheet;
leathercloth;
flooring;
wall-covering

Soft
12-40 Ib ft- 3
Mixed

Laminated
and unsupported
sheet;
leathrcloth;
flooring

Medium/soft
20-40 lb ft- 3
Mixed

025

Soft toy
filling

Soft
Variable
Mixed, fine

Kindly supplied by Fisons Industrial Chemicals.

b This application is included as an illustration, but its commercial significance is very limited.

End application

Type
Density
Cell structure

Foam characteristics

Stearic acid
Zinc oxide (active)
Epoxidised oil
Ca stearate
Pb stearate
Pb silicate

Cushioning

Soft
SIb ft- 3
Mainly
closed
Profiles

Medium/soft
37lb ft- 3
Closed

Profiles/pipe

Rigid
56lbfc 3
Closed

05
05
30

Shoe sole
mouldings

Medium/soft
43lb ft- J
Closed

20

05

12-

s::.

1:;"

~.

r:s

."

t;:

50

30
55

30
55

100
(Breon P130/I)

100
(Breon P130/l)

Recommended for cellular leathercloth.

Recommended for permeable cellular leathercloth.

Dialphanyl phthalate
Butyl benzyl phthalate
Nylonate plasticiser
(Monoplas 230)
Foam promoter
(Deckor Cellset 5)
Paris whiting

PVC paste-forming resin

20 lb [t- 3
and higher

10-30 lb [t- 3

45
40

100

30-50 lb [t- 3

(Norvinyl PlO)

10

20
30

100
(Breon PI30/I)

50 lb [t- 3
and highe~

Formulation (phr) to give resultant foam density or

TABLE 25.4
Specimen Formulations for Foams Produced by Gas Entrainment26

is
<:

:<::
:::1

;:e

00

......
~

25

CelluLar PVC Materials and Products

1099

are to be followed. Some suggestions regarding the use of thermal

analysis techniques for the determination of such formulation components as stabilisers, fillers, impact modifiers and others in foam
compositions (not specifically PVC) have been put forward by Breakey
and Cassel. 41 The effects of formulation variables on the foaming
characteristics of a paste composition and the resultant cellular product
can be examined by casting a film of about I-mm thickness on a metal
or glass plate and heating at constant temperatures for different times,
and/or similarly casting onto a gel block and differentially heating for
suitable constant times: in each case the results are evaluated in terms
of the extent of foaming (foamed layer thickness) in conjunction with
cell size and uniformity obtained.
As in the case of solid PVC products, most of the tests normally
carried out on cellular ones are property tests relevant to product
comparison and service performance. National and international
standard specifications are, collectively, the most relevant source of
applicable test methods. Although the tests contained in the four main
groups of standards (ISO, BS, ASTM and DIN) listed in Section 8 of
Appendix 1 do overlap to some extent in nature and scope, they are
also complementary in many directions: that section should therefore
be considered and consulted when a particular test is required. A few
salient or additional points are mentioned below, as well as some
references not listed in Appendix 1.
The properties of rigid PVC foam relevant to its applicationsalready mentioned-in building, vehicle, and marine construction,
include density, compressive strength, cross-breaking strength, dimensional stability, heat conductivity (the K factor, indicative of insulation
value), permeability to moisture, and flammability. Many of the
appropriate British standard test methods are contained in BS 4370,
the general test specification for rigid plastics cellular materials. BS
3869 is specifically directed to rigid PVC foams for use in thermal
insulation and building applications. Friability of rigid cellular insulation materials may be measured by a tumbling test (ASTM C 421)
which has been claimed42 to correlate well with abrasion resistance
determined on a Taber Abraser. Standard methods are also available
for determining the resistance of such materials to damage by dropping
(ASTM C 487), their impact resistance (ASTM C 589) and indentation
hardness (ASTM C 569). Two relevant water vapour transmission
methods (ISO 1663 and BS 4370: Part 2: 1973: Method 3) are included
in Table 12.1 (Chapter 12).

1100

W. V. Titow

The test methods of BS 4443 are useful for the determination of

many service-relevant properties of flexible plastics foams. Although
not directed specifically to PVC foams, these methods may be used for
determining such properties of these materials as tensile strength and
elongation, compression set and stress/strain characteristics in compression: the latter two are particularly relevant to upholstery
applications, although it has been argued 43 that compression set, as
measured in many standard tests, is a doubtful criterion for
characteristing flexible, closed-cell foams. Flexible, cellular PVC
sheeting is specifically covered by BS 4023. Determination of heat
shrinkage of cellular soling material is given in BS 5131: Part 2.
The completeness of fusion is an important factor in properties of
products made from PVC pastes, including paste-produced foams. The
use of solvent tests for the completeness of fusion of solid products is
discussed in Chapter 22 (Section 22.1.2). A similar approach was
adopted by Carey and Rogers 44 in their tests on flexible PVC foam, in
which the foam was treated with ethyl acetate, and its tensile strength
then determined to provide an indication of the 'degree of fusion'.
It is occasionally of interest to know the total volume of voids and/or
the respective volume percentages of open and closed cells in a cellular
material. The determination methods given in standard specifications
differ in the form of apparatus and in the shape and size of the
specimens. However, they are all based on the same principle, which is
an application of Boyle's Law: when a specimen of cellular material is
placed in the chamber of the test apparatus, the closed cells and the
solid material (cell walls) displace their own volume of air, causing a
proportionate increase in pressure: this is measured, and the value
used to calculate the percentage contents of closed cells, open cells,
and solid material in the specimen. The methods include those of
Remington and Pariser45 (for a time the subject of ASTM Standard D
1940-62T, now withdrawn) and Payne and Stephenson46 (sometimes
known as the 'ICI method'), the air pycnometer method of ASTM D
2856-70 (Reapproved 1976), and the method of BS 4730: Part 2: 1973
(Method 10). The last two methods are technically similar to those of
ISO 4950. All the above standard methods are intended for rigid
cellular materials.
With porous PVC sheets or mouldings used as battery separators or
filters, the properties commonly determined by tests are water and/or

gas permeability,21 the pore size (an average value may be determined
according to BS 1752 or, for air filters, BS 2577), total pore volume

25 Cellular PVC Materials and Products

1101

(determined by the absorption of a suitable liquid21 ) and mechanical

properties (in particular tensile and flexural strengths, determined by
the standard test methods). For battery separators, electrical resistance
and chemical resistance are also of interest. 21

REFERENCES
1. Gotch, T. M. (1979). Plast. Rubb. Int., 4(3), 119-24.
2. Elastomer Chemical Corporation US Patent 2666036; British Patents
767465; 770237.
3. Ward, D. W. (1969-70). Modern Plastics Encyclopedia, pp. 256-9.
4. Dennis, I., US Patent 2763475.
5. Fuchs, 0., Heckalt, F., and Herz, A. (1965). Kunststoffe, 55(9), 717-23.
6. Anon. (1967). Brit. Plast., 40(8), 64-9.
7. Dilley, E. R. (1966). Trans. J. Plast. Inst., Feb., pp. 17-21.
8. Challenger, P. (1970). Polym. Age, 1,9-12.
9. Harris, W. D. (1976). 34th ANTEC SPE Proceedings, pp. 154-61.
10. Titow, W. V. and Lanham, B. J. (1975). Reinforced Thermoplastics,
Applied Science Publishers, London. Ch. 10.
11. Shea, F. C. (1978). 36th ANTEC SPE Proceedings, pp. 205-7.
12. Nakajima, N., Ward, D. W. and Collins, E. A. (1976). J. Appl. Polym.
Sci., 20(4), 1187-98.
13. Anon. (1976). Plast. Rubb. Wkly, 27th August, p. 10.
14. Anon. (1982). Plast. Rubb. News, October, pp. 45-7.
15. Anon. (1975). Plast. Rubb. Wkly, 22nd August, p. 12.
16. Gross, H. L. and Angell, R. G. (1976). 34th ANTEC SPE Proceedings,
pp.162-5.
17. Hartman, J. V., Kozlowski, R. R. and Podnar, T. (1966). J. Cell. Plast.,
2(4),214-17.
18. R. T. Vanderbilt Co. Inc., US Patent 3288729.
19. Bartl, H., and Wingler, F. (1970). Kunststoffe, 60(1), 19-22.
20. Titow, W. (1961). J. Plast. Inst., Dec., pp. 186-93.
21. Collins, D. H. (Ed.) (1963). Batteries, McMillan, New York, p. 16-17.
22. Greenhoe, J. A. (to Monsanto Chemical Co.), US Patent 2864777.
23. Laskowski, W. and Skowronski, T. (1969). Polim. Tworz. Wielk. 14(8),
389-94.
24. Simonik, J. (1978). 36th ANTEC SPE Proceedings, pp. 773-fJ.
25. Acton, J. and Debal, F. (1976). Plast. Rubb. Wkly, 18th June, pp. 22-3.
26. Deckor Cellset 5, Vinyl Foam Stabiliser, Scott Bader & Co. Ltd, Technical
Booklet.
27. Renshaw, J. T., Cannon, J. A. and Minchen, J. D. (1970). SPE J., 26,
47-50.
28. Deanin, R. D., Kapasi, V. C., Georgacopoulos, C. N. and Picard, R. J.
(1974). Polym. Engng. Sci., 14(3), 193.

1102

W. V. Titow

29. Deanin, R. D., Calcuttawala, A. H. and Kapasi, V. C. (1976). 34th

ANTEC SPE Proceedings, pp. 501-2.
30. Visnovsky, L. (1970). Brit. Plast., September, pp. 90-3; October, pp.
109-12.
31. Jones, P. W. and Lavender, C. M. (1969). Expended Vinyl Flooring: A
Study GJ ' Variables in Foam Formulation, Published by Fisons Industrial
Chemicals, March, (ref. GIB/2).
32. Conger, R. P. (1968). SPE J., 24(3), 43-5.
33. Dietz, G. R. (1968). Ibid. 24(9), 49-52.
34. Nass, L. I. (1963). Mod. Plast., 40(7), 151-65.
35. Wells, J. N. (1968). J. Cell. Plast., 4(3), 109-12.
36. Gallagher, R. B., Kamens, E. R., Lanse, F. W. and Kamath, V. R.
(1978). 36th ANTEC SPE Proceedings, pp. 777-9.
37. Sheppard, C. S., Schack, H. N. and Mageli, O. L. (1966). J. Cell. Plast.,
2(2), 97-111.
38. Cellular Leathercloth, Fisons Technical News. GIB/9, 1969.
39. Congoleum-Nairn Inc., US PateHts 3293094 and 3293108.
40. Fisons Industrial Chemicals, US Patent 3464934.
41. Breakey, D. and Cassel, B. (1979). Plast. Technol., 25(12), 75-8.
42. Hilado, C. J. (1969). J. Cell. Plast., 5(1), 5fr8.
43. Baumann, H. (1977). Kunststoffe, 67(9), 509-13.
44. Carey, R. H. and Rogers, E. A. (1956). Mod. Plast., 33(12), 139-46 and
22fr9.
45. Remington, W. J. and Pariser, R. (1958). Rubb. World, 138,261-4.
46. Payne, N. and Stephenson, C. E. (1969). Brit. Plast., 42, July, 135-6.

CHAPTER 26

Applications of pvc
w.

V. TlTaw

Although PVC runs second to the polyolefins (considered collectively)

in terms of total tonnage utilised, it has a much wider spectrum of uses.
Some of its numerous and diverse applications are exclusive to it,
whilst in many others it competes successfully not only with other
plastics but also with older materials.
The wide and varied applicability and usage of PVC are due to a
combination of relatively moderate cost with a number of technical
factors which include:
its useful general properties as a plastics material (strength,
chemical resistance, low flammability, suitability for foodcontact and medical applications, good electrical properties,
and others);
(ii) the fact that the properties can be widely varied, and the
applicational scope of the material thus greatly increased, by
suitable formulation, and in particular incorporation of plasticisers;
(iii) the processing versatility: whilst PVC can be processed-and
converted into important products (e.g. pipes, sheeting,
floor-coverings, wire and cable insulation, etc)-by the standard
plastics processing techniques of extrusion, injection moulding,
blow moulding, and thermoforming, it is also particularly suited
to calendering and finds important applications because of its
processability in such special forms as paste (which is unique
to PVC) and latex.

(i)

The preceding chapters will-it is hoped-have demonstrated to the

1103

W. V. Titow

1104

reader something of the significance, role, interaction and effects of

these and many other relevant factors operative in the technology and
utilisation of PVc.
The purpose of the present chapter is to summarise in brief outline
the main applications of PVC materials and products, as well as many
of its miscellaneous uses including some ranging from the less common
to the unusual. Numerous references to, or descriptions of, the forms
and ways in which PVC is used will also be found throughout the book
in the sections on subjects to which they are relevant.
The most substantial single outlet for PVC is in rigid pipes and
fittings. Other big application areas are sheeting and film (rigid and
flexible), and-for plasticised compositions-electrical wire and cable
coverings, and coated fabrics. An extensive list of applications of PVC
(as well as other plastics) in building has been published by JCL I The
subject is also discussed in an article by Fischer2 and the main
applications of PVC in general have been briefly reviewed by Smith. 3
The classification scheme adopted for the purpose of the summary
review contained in the following sections is somewhat arbitrary; it is,
however, not highly unconventional; it is also considered reasonably
logical, as is the designation as 'primary' of those products which-like
PVC sheeting, profile or pipe-are manufactured in continuous form,
and are either used directly, or converted, fabricated, or assembled
into secondary, derivative products.
26.1 MAIN APPLICATIONS OF PRIMARY PVC
PRODUCTS
Some of the secondary products manufactured from the primary ones
are also mentioned under the various sub-headings of this section:
others are included-as appropriate-in further sections.
26.1.1 Pipes and Tubing
(a) Rigid (uPVC) Pipes
Rigid pipes (with corresponding ranges of appropriate fittings usually
produced by injection moulding) are widely used in the following
application areas (see also Chapter 19, Section 19.3).
Building (including some ship and aircraft applications): Sanitary

26 Applications of pvc

1105

pipework (soil, waste water and ventilation pIpmg, waste traps for
basins, baths, showers and sinks); potable water supply pipes;
rainwater systems (guttering and down-pipes); electrical conduit and
trunking.
Note: Chlorinated PVC (CPVC) is among the rigid plastics pipe
materials fulfilling the main conditions for use in domestic
hot-water systems. 5 The other materials are polybutylene6 and
cross-linked polyethylene.
Water distribution systems: Pressure pipes for potable water
distribution (below and above ground), for cold-water services
(including cooling water in mines), and for irrigation systems.
Sewage and waste-water drains: uPVC pipes have been particularly
successful in underground sewage systems. Competitive pipe materials
include pitch-impregnated fibre ('pitch fibre'), glazed clay, concrete
(including asbestos-reinforced cement) and high-density polyethylene.
Drainage gullies have been moulded in uPVc. *
Aeration systems in sewage-treatment installations
Land (sub-soil) drainage
Pipes for compressed air and vacuum lines:t For example, in mines
and industrial premises. ABS is a competitor in this application, among
common non-metal pipe materials.
Gas supply pipelines: Here the use of uPVC pipes (even of the
preferred impact-resistant 'ductile' compositions) is limited to some
countries (and generally tends to be restricted to pressures not much
above 1 bar in practice, although the nominal ratings can be
considerably higher). Possibility of environmental stress-cracking is a
technical consideration (see Chapter 12, Section 12.5). Mediumdensity polyethylene is a competitive plastics material in this
application.

* A multi-component moulded uPVC drainage gully won a British Design

Council award in 1976. 4
t For some high-pressure applications the uPVC pipe may be strengthened by
an outer casing of GRP. 3

1106

W. V. Titow

Pipes for chemical plant and other industrial installations: This is

another successful application area for uPVC. Competitive thermoplastics are high-density polyethylene, polypropylene, and-at the expensive end-polyvinylidene fluoride.
(b) Flexible Tubing
The use of extruded flexible PVC tubing as garden hose is well known
and widespread.
Heavy-duty versions, reinforced with polyester or nylon braid and
overcoated with another pPVC layer formulated for abrasion resistance, find applications as pressure hose in mining (some types have
bursting strengths of up to about 7 MPa), irrigation or industrial lines,
on building sites, etc.
Flexible PVC tubing with a 'concertina' structure is used as conduit
in many applications. This type of tubing is manufactured by
simultaneous extrusion, through a special die, of a flexible compound
and a strip of harder composition which becomes embedded as a
reinforcing helix in the wall of the resulting flexible tube. 7 Varieties of
this tubing are marketed, under the trade name Heliflex, by A. G.
Petzetakis of Athens (and associates outside Greece): the company,
founded by the patentee of the original process, claims to be the
world's largest producer of PVC hose (over 30000 tonnes said to have
been manufactured in 1981).
Vacuum-cleaner hose is another application of flexible PVC tubing.
Transparent PVC tubing is used in general laboratory and plant
applications.
Tubing for medical applications is mentioned in Section 26.4.6
below.
26.1.2 Extruded Profiles and Channels (see also Chapter 19, Section
19.4).
Rigid extruded profiles used for external cladding of buildings (siding)
represent a substantial outlet in North America: some are 'capped' by
coextrusion with a layer of acrylic polymer for colour effects and
improved weathering and wear resistance. uPVC window frames and
complete window systems, produced from special compositions
formulated for resistance to weathering and impact, have made great
gains-originally in Europe (especially West Germany and Austria),
and more recently in the UK and USA-in capturing this application

26 Applications of pvc

1107

from the main traditional materials (wood and aluminium). In West

Germany, where uPVC is currently the leading window construction
material, the PVC polymer consumption for this application exceeded
100000 tonnes already in 1979. However, uPVC windows are not yet
suitable for long service in hot countries with high intensity of sunlight
(Australia, central South Africa), although continuing improvement in
formulations may alter the position in a few years' time. In most uPVC
window systems the profile sections (assembled by welding) are
reinforced with metal (commonly aluminium): GRP rod reinforcement
is also featured (e.g. in the Thermassive system-Schock GmbH, West
Germany8), and uPVC-covered wood profiles have been used. Door
and window frames for internal use in buildings (where the service
requirements are less exacting than for external windows, and profiles
of simpler cross-sectional shape can be used) are also made from
uPVC, as are internal window ledges. Other uses of rigid profiles
include framing and trim for uPVC cladding panels, and expanded
beading, mouldings, picture frames, and furniture trim. Solar collector
panel housings have also been made from uPVC profile, for service in
moderate climates. 9
Flexible PVC profiles find a major application as waterstops
(waterbars) for the leak-proofing of joints in concrete structures (dams,
reservoirs, sewage works, basements, retaining walls, etc.): quite
intricate cross-sectional shapes, including ribbed, fluted and hollow
sections are available.
Other uses include edge trim, treads and nosings for stairs, draft
excluders and the like, as well as application in vehicle fittings (seat
welting; decorative and protective trim strips).
26.1.3

Unsupported Sheeting and Film

(a) Rigid Sheet (see also Section 19.5 of Chapter 19, and Chapter 20)
Rigid PVC sheeting is produced by extrusion or calendering: thick
sheets are made by compression laminating layers of either kind of
sheet. The following are the main application areas.

Building: Roofing; corrugated and wire-laminated sheeting is used,

as well as plain; many transparent versions.
Note: Among the many examples of uPVC-roofed structures is the
pool section of the Leisure Centre in Sunderland (UK)

1108

W. V. Titow

covered by a 2025 m2 barrel-vaulted roof, glazed in Sindlon

Stratum ICI transparent plain uPVC sheeting.
Cladding, external and internal (including partitioning): in the UK
as well as in other countries these applications are subject to the
requirements of the relevant Building Acts. Safety doors and glazing
(clear sheeting); light fittings (mainly translucent); fabrication into
chutes and ducting.
Chemical and other plant: Lining of tanks for chemical or food
storage; absorption towers; casings for high-speed air washers in
air-conditioning plant; fabrication into chutes, ducting and extraction
hoods.
Other uses: Interior wall covering and lining of vehicles, aircraft and
boats-an interesting example is the interior cabin trim in Jetstream
light aircraft (British Aerospace): the cabin side walls and upper side
walls are lined with Fromoplas (Wallington Weston, UK) toughened
uPVC sheet. 10 Thermoforming into parts and containers (VCNA
copolymer sheet, or acrylic-modified sheets used in this application);
thermoformed cabin fittings for aircraft are produced from ABS
sheet/PVC foam laminates (see Chapter 16, Section 16.2). Road signs
and sign boards.

(b) Flexible Sheet

Sheeting used as lining for water reservoirs, tanks, effluent lagoons,
and other large-scale seepage barrier applications, * swimming pool
linings; damp-proof coursing and roof lining* for buildings. Fabricated
products include: safety swing doors (usually transparent) for factory
and storage premises (typically about 5 mm thick or over); suspendedstrip curtain doors (strips typically about 4 mm thick and 200-300 mm
wide) for air-conditioned premises, cold rooms, and the like; products
fabricated from thin sheeting-shower curtains; table covers; some
types of rainwear and inflatables; mattress covers for general use
(camping, hostels) and medical applications (water-beds used for
patients suffering from burns or bed sores).
Note: The mattress and water-bed cover sheet formulations contain
biocide additives.

* Blends of PVC with chlorinated polyethylene (acting as a solid, permanent

plasticiser) are being increasingly used for these applications.

26 Applications of pvc

1109

Self-adhesive decorative surface coverings, and wall-coverings of the

unsupported kind (paper- or fabric-supported PVC wall-coverings are
mentioned in Section 26.2.3 below).
(c) Foil and Film
RIGID FILM AND FOIL

The main applications of these materials are in packaging. PVC foil is

thermoformed into blister (bubble) packs, nesting trays for confectionery and biscuits, nesting packs for medicinal tablets, containers, etc.
PLASTICISED FILM

Semi-rigid film is used for shrink-packaging a variety of articles (see

Chapter 19, Section 19.5.3), including food items.
Special plasticised PVC compositions are among the common
plastics materials of 'clingwrap' films familiar in their household and
catering applications (the competitive materials are LDPE and EVA).
pPVC films are also formulated for stretch-wrapping applications.
The principle of stretch-wrapping may be regarded as in a sense the
reverse of shrink-wrapping, in that the film is stretched under the pull
exerted in the wrapping operation: the resulting tight grip is actuated
by the material's elasticity, which also promotes good holding
performance with contents which may be subject to shifting, settling or
shrinking (in this respect PVC is superior to its main competitors in
this application, EVA and LDPE). The film is wrapped around the
contents several times: it is fastened either by virtue of the self-cling of
the overlapping layers, or in some cases-depending on the material
and wrapping system used-by means of a heat seal or mechanical
crimping. The holding force obtainable with stretch-wrapping is
normally greater than that in shrink-wrapping. Another advantage is
the absence of a heat treatment: this is particularly significant with
large loads or goods that are sensitive to heat. On the other hand a
shrink-wrap conforms better to the shape of the contents, provides a
greater degree of protection from the environment, and is less sensitive
to load irregularities (sharp corners, etc.). The biggest single outlet for
stretch-wrapping film is the packaging of goods-loaded pallets (e.g.
palleted textile yarn packages, bagged materials, etc.); another use is
in bundling (wrapping groups of products to 'unitise' them for
wholesale distribution). In some application areas the uses of shrinkand stretch-wrapping overlap (notably in pallet wrapping). PVC film

1110

W. V. Titow

has been used in stretch-wrapping since the mid-1970s. As formulated

for this application, the material offers clarity, good strength and
abrasion resistance, and a considerable degree of self-cling. However,
in wrapping, it starts at a lower effective stress than LDPE, and its
percentage stress retention with time is also lower, as illustrated by the
following typical figures:

Initial
stress
(MPa)
LDPE
PVC

137
74

Stress (MPa) retained after

time shown
2 min 5 min IOmin

Ih

24h

112
49

98
32

96
32

104
39

100
34

This makes LDPE a better choice for wrapping heavy loads, but the
lower initial stress of the PVC film means that it is easier to wrap (less
force required).
Apart from LDPE film (used for stretch-wrapping since about 1970),
and the recently introduced linear LDPE, PVC's other competitor in
this field is EVA: such copolymer films of low vinyl acetate content
came into use contemporaneously with PVC, and the tougher high-VA
copolymer films towards the end of the 1970s. The lower density of all
these olefinic films in comparison with PVC is a general advantage;
some also have higher elongation. The biggest suppliers of PVC films
for stretch-wrapping are the Resinite Division of Borden Chemical,
and Goodyear (Films Division) in the USA, with their subsidiaries
abroad. A useful, brief review of stretch-wrapping (with special
reference to its comparison with shrink-wrapping, and to the properties
of the films used) was published recently by Johnson and Langford. 11

26.1.4 Foam
(a) Rigid Foam
Used as the cellular layer of some sandwich and multi-layer panels for
the construction of refrigerated vans, other transport vehicles (see
Chapter 25, Section 25.1) al)d some boat hulls.

26 Applications of pvc

1111

Note: The hull construction of the yacht Eclipse, top individual

points scorer in the 1979 Admirals Cup series, was: resin gel
coat/aramid fibre (Kevlar 49) cloth (02 mm thick)/continuousfilament glass cloth (07 mm thick)/the Kevlar 49 cloth/uPVC
foam layer (25 mm thick)/the> Kevlar 49 cloth/the glass
filament cloth/the Kevlar 49 cloth/gel coat. 12

Materials of some types of buoys and floats; cellular profiles and

certain types of pipe (see Chapter 19, Sections 19.3.4 and 19.4.1).
(b) Flexible Foam
Once widely used as the cushioning material in car upholstery: this use
has declined drastically in the last ten years. Still used widely as the
foam layer in coated-fabric flooring and cellular leathercloth (see
Section 26.2.1 below). Material of injection-moulded microcellular
soles, certain types of carpet-backing, crash pads, and some toy fillings.

26.2 COMPOSITE PRODUCTS (COATED, LAMINATED,

OR FILLED)
26.2.1 Coated Fabrics (see also Chapters 22 and 25)
This is a big outlet for flexible PVC. The main types of product (mostly
produced by paste coating) are:
leathercloth of all kinds (both solid and cellular coatings) used
in the production of upholstery, protective and foul-weather
clothing, travel and fancy goods;
(ii) tarpaulins (usually with a synthetic-fibre base, commonly nylon
or polyester), inflatable buildings, * other inflatables, t brattice
cloth;
(iii) some types of water barriers, hovercraft skirts, life rafts, bulk
liquid freight bags (some produced by hot lamination of
PVC/nitrile rubber blend sheeting to nylon fabric 13);

(i)

* Very large air-inflatable structures (usually from PVC-coated nylon) may be

delivered to the site in sections, and finally fabricated by welding before
erection.
t e.g. large inflatable air bags for breaking the fall in rescue situations-an
example is the bag developed (originally for use by a film stuntman) by
Greengate Polymer Coatings Ltd in the UK14 (similar products are also
available in continental Europe and the USA).

1112

W. V. Titow

(iv) PVC backing on carpets (see Chapter 23);

(v) continuous fabric- or felt-backed flooring;
(vi) fabric-backed PVC adhesive tapes for electrical insulation,
medical and other uses;
(vii) PVC-impregnated sectional blinds for picture windows;
(viii) PVC-coated gloves;
(ix) PVC-coated glass-fibre fabric, used, for example, in the
building industry for ducting (wrapped over flexible wire
helical frames). 15

26.2.2 Conveyor Belting

This might be classified as a kind of coated fabric, but is in fact much
more substantial and heavy than coated fabrics for all other uses. The
main application of PVC conveyor belting is in mines, although some
grades are also used in manufacturing processes.
The two main structural types of conveyor belting are known as
multi-ply and solid-core belts. Multi-ply belting is produced from layers
of fabric (cotton duck, and/or synthetic fibre) individually coated on
both sides with flexible PVC (applied in paste form) and laminated
together: the resulting multi-layer band is over-coated on both sides
with an outer coat (typically about 1 mm thick) formulated for
toughness, abrasion resistance, and low electrical resistivity (antistatic
property). The outer coverings may also be calendered sheets
heat-laminated to the interply assembly: the latter may typically
contain 3 piles (common with synthetic fibre fabrics) or 5 plies (with
cotton duck fabric). To obtain the necessary shape and smoothness of
edge contour, an extruded flexible profile may be applied under
heating, or a paste of suitable composition moulded on. A common
continuous method of producing multi-ply belts is the Rotocure
process,16 in which the pre-coated plies (with the coating pre-gelled by
passage through an oven) are combined, under pressure, on the
surface of a slowly rotating, heated drum of large diameter, where the
fusion of the paste layers in the resulting laminate is completed.
Stepwise lamination in a daylight press may also be used, but this is
generally slower than the continuous method.
Solid-core belting consists of a fabric layer encapsulated by
coating/impregnation in paste-applied flexible PVC, over-coated with a
harder surfacing composition. In some versions the yarns of the core
fabric may be pre-impregnated with PVC. 16

26 Applications of pvc

1113

26.2.3 Sheet-type PVC Interior Wan-Coverings

The salient features of this kind of wall-covering have long been
known: the main ones are-in combination-distinctive appearance
with many possible decorative effects, durability, and washability (in
all but a few cases of special composite effects, like a flocked or
metallised finish).
The majority of PVC wall-coverings consist of clear vinyl coatings on
the more traditional materials such as paper, or cotton fabric, but
laminates of PVC with woven acrylics, hessian, and even silk, or
metallised layers, are also represented. Further variants include
wall-coverings with embossed PVC layers, which mayor may not be
cellular.
Note: Non-coated, special wall-coverings are also made; these are
panels thermoformed in rigid PVC, and might thus be
classified as wall cladding for interior use. The panels are
made-in three-dimensional effects-to resemble brickwork
or stone walls. A commercial example is Stone Decor
(Triplastic Gesellschaft, Niederheim, West Germany).
In general, the wall-coverings fall into two categories: supported and
unsupported products. In the supported products the base material
carrying the polyvinyl chloride layer may be paper (of varying
thickness and substance) or fabric of varying weave and consisting of
various types of fibre (synthetic fibres, cotton, jute or silk).
The PVC layers of the supported products, and the 'body' of the
unsupported products, are essentially the same in nature, appearance
and physical characteristics. They consist of plasticised PVC compositions and may be either solid or cellular (expanded). The PVC
composition may be bulk-coloured, or natural, or white.
The surface of the PVC layer, or of the PVC sheet in the
unsupported wall-coverings, may be plain or embossed. It may also be
printed with a design.
The wall-covering, whether supported or unsupported, may carry a
separate surface layer which may be a thin coating of metal or a
protective plastics film or a lacquer coating.
The commercial products represent many combinations of the above
principal structural features. The following may be quoted as
illustrative examples:
Mural Mousse Somvyl Decor 5106 (Sommer Exploitation, Neuilly,

1114

w.

V. Titow

France): An unsupported, cellular, bulk-coloured material with a

printed embossed surface, produced by paste-coating on a carrier (cf.
Chapter 22).

Suwide Placo 180-182 (Helmonde Textile Co., Helmond, The

Netherlands): Fabric-supported solid PVC layer, bulk-coloured,
embossed, surface-protected by Tedlar (Du Pont) fluoropolymer layer.
The Ferralon range (Chamberlain Plastics, Rushden, Northants,
UK): Paper-supported, thin, solid, colourless PVC layer with metallised surface (plain or embossed). The Ferralon range is not
recommended for large-scale wall covering, but is fully illustrative of
the similar (but cotton scrim-backed) Metalon range which is.
The Galan range (Galon AB, V. Frolunda, Sweden): Fabric-based
PVC wall-covering produced by extrusion of a plasticised sheet and
integral bonding to the fabric support.

26.2.4 PVC Coatings and Coverings on Metal Substrates

(a) Wire and Cable Insulation and Coverings
Some aspects of this subject are also covered in Chapters 12 (Section
12.3), 13 (Section 13.4.2.4), 14 (Section 14.8), and mentioned
elsewhere in the book.
Suitably formulated PVC is a good electrical insulator: * this fact
coupled with the relative ease of application (by extrusion), good
mechanical properties, and low flammability, have been instrumental
in making wire insulation and cable covering into major applications of
pPVC compositions. The relatively low heat resistance and maximum
service temperature of PVC is a limitation, but these can be
substantially increased by cross-linking: specially formulated compositions containing radiation sensitisers are applied by normal extrusioncoating procedures, and the coatings are subsequently cross-linked by
exposure to high-energy radiation (an electron beam, or emission from
a cobalt-60 source). Some cross-linked coatings suffer no cut-through
after application for 5 min of a weighted soldering iron at 350C. 18
Other property improvements include increases in toughness, abrasion
* The factors affecting the volume resistivity of a PVC composition have been
discussed in some detail in a paper by Wingrave. 17

26 Applications of pvc

1115

resistance, tensile strength at elevated temperatures (e.g. about 3 MPa

at 150a C for a Type 5 hard insulation to BS 6747 18), and resistance to
cracking under stress, as well as a reduction in creep and improved
solvent resistance. Examples of some applications of wire with
cross-linked PVC insulation are: flexible cord for hot domestic
electrical appliances, jumper wires in telephone exchanges (specified,
for example, by the UK Post Office); under-the-bonnet wiring in some
quality motor vehicles (including, for example, Jaguar cars).18
A useful brief review of the service requirements for modern cables,
mentioning several applications of PVC in this area, has been
published by Nye. 19
In certain types of power cables (10 and 20 kV) corrugated polyester
film is used as a binder and thermal insulation in the form of a helical
wrapping between the inner PVC covering of the core and the outer
PVC sheathing. 2o
Note: Wire for the production of chain-link fencing is also
extrusion-coated with PVC compositions.

(b) PVC/Metal Sheet Laminates

As with any other PVC coatings on metal where positive adhesion is
required, a primer is first applied to the metal: typically, the primers
are epoxy- and/or acrylic-based. The main functions of the PVC layer
are decorative and protective. With suitable priming the metal sheet
may be formed without dislodging the PVC layer. Steel plate and
aluminium sheeting are available with PVC coating (e.g., respectively,
Hishi-metal-Mitsubishi Plastics Industries Ltd, Japan,21 and
Bondene22-Storey Brothers and Co. Ltd*): applications of the former
include electronic equipment casings, electric cookers, refrigerators,
lighting apparatus and show cases: 21 the PVC/aluminium sheeting is
also used for electronic equipment casings, interior and exterior signs
and display panels, and road-tunnellinings. 22
26.2.5 Laminates of PVC with Non-metallic Materials
(a) Sandwich Panels
PVC-sheet-faced panels with insulant filling (non-PVC foam or other
porous material) are used for some constructional and partitioning

* See footnote :j: on p. 905.

1116

W. V. Titow

applications (for use of PVC foam cores in composite panels see

Section 26.1.4(a) above).
(b) PVC/Polystyrene Sheet Laminate
This type of laminate, comprising a decorative PVC film on a
polystyrene sheet backing carrying a pressure-sensitive adhesive layer
is manufactured* for use as surface finish (wood and other effects),
e.g. in the radio and television industries, furniture and interior fitting
applications.

(c) PVc/Polyacetal Laminated Sheeting has also been produced. 23

26.2.6 Unsupported PVC Flooring and Floor Tiles

This is a substantial application. The flooring (continuous, or cut into
tiles) is produced by calendering from compositions based on VCNA
copolymers and filled with asbestos fibres (see also Chapter 4, Section
4.6.2; Chapter 8, Section 8.2.1; Chapter 9, Section 9.4.3(b); and
Chapter 18).
Note: These PVC flooring materials can occasionally suffer embrittlement, shrinkage and cracking under conditions of heavy use
in industrial applications (some of these effects have been
attributed to the use of solvent-gel cleaners and strong
detergents). However they are widely used in hospitals and
schools, and domestic kitchens and bathrooms, where they
offer wide choice of colours and patterns, ease of cleaning,
good cushioning, insulation and reasonable price (the last
three features represent advantages over linoleum).

A special type of dust-capturing flooring with a permanently tacky

surface (achieved by deliberate formulating for limited plasticiser
migration) is commercially availablet for use in premises where
dust-free atmosphere is important-e.g. production premises for
pharmaceuticals or electronic components, operating theatres and
intensive-care units in hospitals. The material is also offered as an
alternative to chemically impregnated rugs in offices, with the claim

* In the UK, for example, by Matcon Ltd, Mayland, Essex.

t In the UK from

Dycem Ltd, Bristol.

26 Applications of pvc

1117

that the latter require shampooing, on the average every 6-8 weeks,
whereas the special flooring should perform satisfactorily if cleaned
about every 20 months. 24

26.3 PVC FIBRES AND FIBRE PRODUCTS

Apart from the vinyl chloride copolymer fibres mentioned in Chapter
1 (Section 1.5.2) homopolymer fibres are also produced (by solution
spinning). There are many commercial products. Some examples are:
Rhovyl (continuous filament and staple-originally produced by
Societe Rhovyl SA, France) and other fibres from the same makers (e.g.
Thermovyl, Fibravyl, Retractyl); Movil (Montecatini, Italy) and PeCe
(Agfa Wolfen, West Germany) fibre.
PVC fibres have been used in the production of filter cloths, wadding
and braiding for use in the chemical industry. Other applications
include protective clothing (in which the low flammability and chemical
resistance of the fibres are utilised), tarpaulins, fishing nets, and
awnings.
Blends with other fibres are also used: one example is the use of
shrinkable Retractyl fibre yarns in cloque fabrics, where retraction
under heating of this PVC yarn produces special effects. The use of
fibres of VCNA copolymer modified with maleic acid has also been
proposed 25 in heat-sealable thermoplastic papers to improve fibrillation, sheet formation and sealing.

26.4 MISCELLANEOUS PRODUCTS AND APPLICATIONS

26.4.1 Gramophone Records
These are discussed in Section 19.6 of Chapter 19. An example of a
modern record-production plant-daimed to be the most modern in
the EEC-is that operated by CBS Records at Aylesbury, Bucks, UK.
The automatic compounding line, utilising a Buss KoKneader KG
20-25 compounder and other Buss AG equipment (supplied by
Buss-Hamilton Ltd, Cheadle Hulme, UK) has a capacity of 1625 kg
h- 1 for free-flowing granulate: output (in mid-1982) was 100000 per
day of both 7-in and 12-in discs (produced by 66 presses).26

1118

W. V. Titow

26.4.2 Blown Bottles and Containers (see Chapter 17)

The development and growth of this application was given impetus first
by the development of suitable uPVC moulding compositions combining stability in processing and service with good clarity, strength, and
suitability for food-contact applications (cf. Chapters 9, 10, 11 and 17),
and then by developments in processing (cf. Chapter 17).
26.4.3 Footwear (see also Chapter 11, Section 11.2.2, and
Chapter 25)

Microcellular moulded pPVC, and PVC blend soles have been in use
for a considerable time, as have pPVC uppers in some types of
footwear. The main synthetic materials competing with PVC in the
former application are polyurethane, some thermoplastic rubbers, and
EVA (as well as natural rubber), and in the latter mainly
polyurethane. 27 ,28 Complete units (boots, shoes and sandals) are
produced from PVC by injection moulding,29 including all-weather golf
shoes (from a PVC/nitrile rubber blend30).
26.4.4 Battery Separators (see Chapter 25, Section 25.2.2)

The main competitive materials in this application are resin-bonded

papers and porous polyethylene.
26.4.5

Powder-coated Products and Mouldings Produced by

Powder-coating Methods

Along with other thermoplastics, PVC is suitable for powder-coating

applications. The two main techniques by which PVC powders are
applied are dip-coating (in fluidised beds )31-33 and electrostatic
deposition (electrostatic spraying) ,31,33,34 which started to be practised
more recently, with the advent of compositions of suitable particle size
and high resistivity. * The formulational versatility of PVC is a factor in
its applicability by the powder techniques. Plasticised compositions are

* e.g. in the UK, Vyflex PC 80 ES-Plascoat Systems, (formerly Plastic Coating

Systems). Typically sprayed (with object earthed) at a negative potential of
60-100 kV, followed by oven treatment at 220-260C to fuse the powder
deposit.

26 Applications of pvc

1119

normally used, commonly in the form of dry blends, but meltcompounded compositions-eomminuted by freeze-grinding-have
been employed: these offer the usual advantages of this type of
compound but the cost differential is even higher than between
dry blend and pellet feedstocks, because of the expense of the grinding
operation. Because of the lack of adhesion between PVC and metal
surfaces priming is necessary in powder coating as in other coating
techniques.
The main considerations in the two techniques, brought out well in
Newton's summary,31 may be listed as follows:
Electrostatic
deposition
Typical coating thickness (mm)

Preferred particle size of

powder (Ilffi)

Pre-heating of part to be
coated

Automation

0075-02
(tends to be selflimiting)
30-80
(oversize particles
tend to accumulate
on recirculation)
Not normally necessary
(powder coating held
by electrostatic
attraction
until sintered)
Readily effected with
suitable equipment

Fluidised bed
dipping
025-075
(not self-limiting)
Over 100
(some oversize particles
acceptable)
Required

Possible, but needs

careful design

The useful features of powder coating in comparison with other

methods are the 'dry' nature of the process (absence of liquid media
like solvents or plasticisers), feasibility of required thickness build-up
in a single pass, and suitability for coating difficult shapes (especially
sharp corners and edges-particularly with electrostatic spray).
Articles powder-coated with PVC include wirework (special coating
formulations are available with the requisite resistance to hot detergent
solutions, for caoting dishwasher baskets), metal furniture and vehicle
seat frames,32 pipework,35 road signs, railings and posts of
balustrading. * An interesting application is a clear coating on

* Including ones for use in heavy weathering conditions, e.g. the safety
balustrading and fog detector hood of the Bull Point lighthouse at
Woolacoombe, Devon, UK have a PVC powder-applied protective coating. 36

w.

1120

V. Titow

laboratory glassware l4 to retain the pieces in the event of breakage:

the coating also increases the resistance of the object to impact (e.g. in
accidental dropping) and provides some first-line protection against
abrasion.
Compositions can be formulated for the production of cellular
coatings by the fluidised-bed technique.
Mouldings can be produced with PVC powders by methods
analogous to those used with PVC pastes (see Chapter 22, Sections
22.2.1, 22.2.2 and 22.2.4), i.e. rotational moulding, slush moulding
(usually referred to as 'static moulding' when a powder is used), and
dip moulding (sometimes also called 'fusion moulding'3? when
practised with a powder composition) employing a fluidised bed.
26.4.6 Medical Applications

Plasticised PVC compositions are the materials of many kinds of tubing

(drainage, endotracheal, infusion), blood-collection and transfusion
sets, stopcocks, aprons and sheeting.
Note: In one case of blood-storage containers made of DOP-

plasticised composition (with a Ca/Zn stabiliser) some plasticiser was leached out, and even detected in patients' bodies
after repeated, large-scale transfusions (no adverse effects
were found attributable to its presence). 38
Special extrusion lines are available for the production of
medical-grade PVC tubing. *
Bags fabricated from clear, flexible PVC sheeting have been used for
enclosing wounded limbs to provide an environment controlled in
terms of bacteria content, humidity, temperature and pressure, to
secure suitable conditions for healing without ordinary dressing
(whilst the transparent nature of the bag allows the wound to be
observed).t
Thermoformed PVC trays, designed specially to accommodate the
* e.g. Model 116 line of Betol Machinery Ltd, Luton, Beds, UK designed for
the production of soft, radio-opaque PVC tubing for surgical use: the tubing,
with an inside diameter of 12mm and wall thickness of O'12mm, has an
internal web, off-set so that it divides the interior into two unequal
compartments. 39
t Sterishield bag, developed in the UK by the Biomedical Research and
Development Unit of the Department of Health and Social Security.40,41

26 Applications of pvc

1121

contents (which may be sealed-in with a transparent PVC film) are

available with single-use medical devices-e.g. anaesthetic handventilation circuit assemblies for chest operations.
Rigid, transparent compositions based on vinyl chloride/propylene
copolymers are used for moulding and extrusion of components for
medical applications.3
Flexible PVC film tapes with a pressure-sensitive adhesive layer are
widely used as water-resistant sticking plasters.
26.4.7 Applications in Motor Cars

Apart from its virtually universal use as insulation on electrical wiring,

the usage of PVC in motor cars tends to vary somewhat from country
to country, and also to a certain extent from model to model. *
However it is one of the three materials which-on the averagejointly account for about 75% of the plastics content of a car (the other
two are polyurethane and ABS). With the decline in popularity of
PVC leathercloth upholstery (ct. Chapter 25, Section 25.2.1)although it is still used in some parts of the world-the main interior
applications of PVC in a typical western motor car are door panels (in
some cases a 2-mm PVC foam-backed sheeting adhesive-bonded to a
filled polypropylene materia!), rear parcel-shelf covers, head-linings
(usually with a polyurethane foam backing), crash pads (also
foam-backed), seat trim, and-in some cases-arm rests (ct. Chapter
22, Section 22.2.1). In some models the steering wheel and gear-lever
knob may also be PVC-covered.
PVC paste compositions are used as underseals and for corrosion
protection in wheel arches and other vulnerable areas.
26.4.8 Tubularframe Furniture and Related Applications

Interest has been growing on both sides of the Atlantic,42 and also
overseas (e.g. in Australia and South Africa)43 in furniture-mainly for
outdoor use-playground equipment, balustrades, and the like, made
from rigid PVC pipe specially formulated for impact and weathering
resistance. The pipe may be plain or externally patterned-in some
cases to resemble bamboo, cane, reed or wicker. t Special 'furniture
* e.g. the total PVC content (including electrical insulation) in the current
model of the VW Golf motor car is about 15 kg.
t e.g. the Ramboo tubing of Plastirama, Mexico.

1122

W. V. Titow

grade' uPVC compounds have come onto the market formulated on

lines similar to those of window-frame profile compositions.

Note: For example, Geon 80 x 3 (B. F. Goodrich) is said to be42 an

acrylic-modified composition with about 7 phr Ti0 2 . Another
example is Conoco RPlOO (Conoco Chemicals).

In fabricating the pipe into the products it is cut into lengths and
suitably shaped (after pre-heating). Shaped surface effects, e.g.
bamboo, etc., can be produced by expanding the hot pipe inside a
mould by air pressure. The products are then assembled with the aid of
solvent bonding or special couplings. Good weathering performance
with respect to appearance and strength retention over two years'
exposures in Florida and Arizona has been reported. 42
26.5 SOME SPECIAL, UNUSUAL, OR MINOR PRODUCTS
AND APPLICATIONS
Baby pants: These are made from thin pPVC sheeting (about
01 mm thick), and usually incorporate some form of foam
(polyurethane) padding, fabric-covered elastic band, and fastening
studs. The sheeting is formulated for resistance to hardening by loss of
plasticiser through washing and wear in use, tear and staining
resistance, and good weldability. Typically, DIDP is used as the
plasticiser together with Cd/Ba/Zn stabiliser systems with very low
susceptibility to sulphide staining. A tear strength (Elmendorf test, e.g.
to BS 1763) of 180 g per 01 mm of thickness is a reasonable practical
minimum value.
Fishing lures: PVC lures moulded in the shapes of sand eel,
lugworm, squid and pilchard have been reported to be highly
successful as aids to commercial fishing in Cornwall. 44 The lures are
produced from metal-pigmented compositions, in moulds made from
highly accurate carved acrylic models of the animals. Coupled with the
paint-spray finish this results in very realistic appearance. Hooks larger
than practicable with live bait can be used.
Simulated skin: A PVC composition developed by the UK Ministry
of Defence (Stores and Clothing Research and Development Establishment) has been successfully used-in the form of a sheet about
015 mm thick (produced by Storey Bros, Lancaster, UK)-as a

26 Applications of pvc

1123

simulant for human skin in the evaluation of clothing for protection

against molten metal. 45 The material has a weight per unit area of
230 g m- 2 . The formulation is given as:
PVC resin
Di-alphanaphthyl phthalate

TIP

Chlorinated paraffin
White pigment
Lead tartrate
Lead stearate
Calcium stearate

100
26phr
1375 phr
1250 phr
10phr
175 phr
100 phr
075 phr

pPVC selective membranes: Films of PVC plasticised with tributyl,

dibutylcresyl, and dicresylbutyl phosphates have been found to have
selective permeability for uranyl nitrite, with the diffusion rate of the
compound strongly dependent on the chemical nature of the
plasticiser. 46 ,47
PVC-based plastic from waste products: Bags, biogas (methane)
generators, pond linings, moulded solar collector panels and other
sheet and moulded products have been produced from a composition*
combining scrap PVC with two waste products-'red mud' (a residue
from the processing of bauxite ore in the production of aluminium) and
used engine oil. The 'red mud' is claimed to provide considerable
reinforcement and act as stabiliser for the resin (by virtue of its metal
salt and oxide content).48
PVC cricket pitch surface: Green pvc sheeting (Ruberoid, UK),
laid between the stumps in two 33 ft lengths, each 6 ft wide, on a
smooth concrete base, has been shown-in extensive use 49-to provide
a robust, wear-resistant surface with playing characteristics similar to a
medium to fast grass pitch.
Industrial duckboard: Embossed or smooth heavy pPVC duckboard
is commercially availablet for use in industrial premises, milking sheds,
trucks for animal transport, and the like.
*Developed at the Taiwanese Industrial Technology Research Institute.
t e.g. in the UK the Heron duckboard manufactured by Plastic Extruders Ltd:
a softer, hollow-section version is also made for use on worktops where a
cushioning effect is required.

1124

W. V. Titow

Rug and mat underlay: Two special PVC products are noteworthy. A
rayon mesh coated with PVC fibre flock which provides a surface grip
(Ako-Stop, developed in West Germany50), and a highly plasticised
PVC material in the form of sheet or netting for use as dust-capturing
floor mat or non-slip underlay (Protect-A-Mafl-Dycem Plastics Ltd,
Bristol, UK).
Ball valves: These have been produced in PVC (for use in food and
chemical industries)52 and PVC/polyacetal combinations (for use with
water and other non-corrosive liquids).53
PVC bricks: Several designs have been proposed in the UK,
Germany and Sweden, most with channels to take cement (so that the
brick structure ultimately becomes a framework strengthened by a
cement core). The British-developed Inca-Brick (Inca Construction
Company Ltd) aroused particular interest. Despite claims that costs
compare favourably with those of conventional brickwork, with
building times cut by a factor of 10 or more,54 the bricks have not come
into widespread use.
Protective sheath for hydrophones: Specially formulated PVC tubing
has been used as protective sheathing for lines of hydrophones (about
100 m long) towed by geological survey vessels engaged in mapping the
sea-bed by echo-sounding techniques.55 The equipment, sealed inside
the tubes, is surrounded by paraffin which acts as a protective medium:
the tube material must thus be resistant to paraffin and sea water, and
retain its properties at near-zero temperatures (for use in the North
Sea and other cold waters).
Various minor applications and products: Reflective, self-adhesive
vinyl tape for clothing, walls, etc., for use in mines and other sites and
work situations. Hazard-warning labels (self-adhesive, PVC-film backed)
bearing symbols for radio-activity, poison, inflammable material,
and other hazards.
Ear-protection pads covered with flexible PVc.56 Decoy dummy
aircraft fabricated in PVC (some equipped with radar reflectors for
correct response).57 A low-density core material in sheet form, for
decorative and some constructional applications has been made by a
novel sheet-drawing process, from various thermpolastics, including
PVC (Nor-Core, Norfield Corp., Conn., USA).58 Heat-shrinkable

26 Applications of pvc

1125

end-caps and harness clips for cables (e.g. the Heatshrink fittings
range, Thomas Ness Ltd, UK).59 Cellular PVC monofilament has been
used as the bristles in rough-duty brushes. 60 Safety goggles, moulded in
high-clarity PVC compound (We/vic X16/909-ICI). Composting bins
for garden-use, made of interlocking, perforated rigid PVC profiles. 61
Extruded, fluted PVC curtain rods covered (by an in-line operation
during production) with vacuum-metallised polyethylene terephthalate
sheet. 62

REFERENCES
1. Plastics in Building, ICI Plastics Division, Technical Publication G.25
(revised periodically).
2. Fischer, P. (1968). Kunststoffe, 58(1), 21-5.
3. Smith, P. I. (1969). Appl. Plast., 12(7), 17-19.
4. Anon. (1976). Plast. Rubb. Wkly, 2nd April, p. 10; 25th June, p. 11.
5. ASTM D 2846-81. Chlorinated poly(vinyl chloride) (CPVC) plastic hotand cold-water distribution systems.
6. ASTM D 3309-81b. Polybutylene (PB) plastic hot- and cold-water distribution systems.
7. Petzetakis, A. G. British Patent 984247, and corresponding patents in
other countries.
8. Anon. (1981). Eur. Plast. News, 8(9), 109.
9. Anon. (1976). Plast. Rubb. Wkly, 20th August, p. 7.
10. Anon. (1981). Plast. Rubb. Wkly, 29th August, p. 5.
11. Johnson, F. M. and Langford, A. J. (1982). Plast. Rubb. Int., 7(6),
217-20.
12. Anon. (1980). Plast. Rubb. Int., 5(1), 11.
13. Anon. (1976). Plast. Rubb. Wkly, 17th December, pp. 12-13.
14. Anon. (1982). Eur. Plast. News, 9(7), 29.
15. Anon. (1982). Plast. Rubb. Int., 7(6), 205.
16. Breon P. 130/1 Paste Resin: Technical Manual No.2, B.P. Chemicals (UK)
Ltd, 1969, p. 61.
17. Wingrave, J. A. (1978). 36th ANTEC SPE Proceedings, pp. 580---5.
18. Matheson, A. F. (1981). Electrical Times, 5th June.
19. Nye, H. F. (1976). Plast. Rubb., 1(2), 87-90.
20. Anon. (1976). Plast. Rubb. Wkly, 5th November, p. 26.
21. Anon. (1976). Plast. Rubb. Wkly, 10th September, p. 9.
22. Anon. (1976). Plast. Rubb. Wkly, 16th April, p. 11.
23. Kubitzki, C. and Schulz, G. (1965). Kunststoffe, 55(9), 727-8.
24. Anon. (1982). Mod. Plast. Int., 12(11), 6.
25. US Patent 2899351; Morse, E. A. (Assignor to Personal Products
Corp.).
26. Anon. (1982). Eur. Plast. News, 9(8), 6.

1126

27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.

W. V. Titow

Anon. (1977). Plast. Rubb. Wkly, 20th May, p. 18.

Pettit, D. (1981). Plast. Rubb. Int., 6(5), 205-10.
PVC for Footwear, ICI Technical Service Note W.109.
Anon. (1976). Plast. Rubb. Wkly, 17th December, p. 10.
Newton, D. S. (1978). Plast. Rubb. Int., 3(5), 203-6.
Anon. (1976). Plast. Rubb. Wkly, 16th April, p. 9.
Anon. (1979). Mod. Plast. Int., 9(2), 8-11.
Cross, U. (1981). Chern. Britain, 17(1), 24-6.
Anon. (1976). Plast. Rubb. Wkly, 5th November, p. 36.
Anon. (1976). Plast. Rubb. Wkly, 30th April, p. 1.
Anon. (1979). Plast. Technol., 25(5), 135.
McHattie, G. V. 'General aspects of use ot polymers in biomedical
applications', Paper presented at the Symposium on Polymers in
Biomedical Applications, BruneI University, 2nd May, 1974.
Anon. (1982). Eur. Plast. News, 9(12), 41.
Anon. (1977). Plast. Rubb. Wkly, 28th January, p. 1.
Anon. (1977). Plast. Rubb. Wkly, 21st January, p. 14.
Anon. (1982). Mod. Plast. Int., U(12), 50-1.
Anon. (1982). Plast. Rubb. News, November, p. 24.
Anon. (1975). Plast. Rubb. Wkly, 3rd October, p. 19.
Metha, P. N. and Willerton, K. (1977). Text. Inst. Ind., 15(10), 334-7.
Bloch, R., Finkelstein, A., Kedem, O. and Vofsi, D. (1967). Ind. Engng.
Chern.: Process Design Develop., 6,231.
Vofsi, D., Kedem, 0., Bloch, R. and Marian, S. (1969). J. Inorg. Nucl.
Chern., 31,2631-4.
Hao, L. c., Tang, H. S. and Hsu, W. W. (1978). 36th ANTEC SPE
Proceedings, p. 768.
Anon. (1976). Plast. Rubb. Wkly, 19th November, p. 4; and Anon. (1979).
Plast. Rubb. Int., 4(6), 248.
Anon. (1982). Plast. Rubb. News, November, p. 43.
Anon. (1975). Plast. Rubb. Wkly, 27th June, p. 14.
Anon. (1975). Plast. Rubb. Wkly, 5th September, p. 18.
Anon. (1976). Plast. Rubb. Wkly, 23rd July, p. 11.
Anon. (1968). Australian Plast. Rubb. J., 23(2), 12.
Anon. (1975). Plast. Rubb. Wkly, 17th October, p. 21.
Anon. (1979). Plast. Rubb. Wkly, 27th July, p. 1.
Anon. (1976). Plast. Rubb. Wkly, 17th September, p. 35.
Anon. (1975). Plast. Rubb. Wkly, 5th September, p. 16.
Anon. (1976). Plast. Rubb. Wkly, 26th November, p. 16.
Anon. (1976). Plast. Rubb. Wkly, 23rd January, p. 12.
Anon. (1975). Plast. Rubb. Wkly, 16th May, p. 16.
Anon. (1975). Plast. Rubb. Wkly, 10th January, p. 12.

APPENDIX 1

Standards Relevant to PVC Materials

and Products
Compiled by N. HERBERT and W. V. TITOW

With the exception of Sections 1, 7 and 8 (and a few individual entries

in other sections) the standards listed in this appendix are those
relating specifically to PVC (and-in some cases-major constituents,
e.g. plasticisers). Many general 'plastics' standards which are used in
the testing of PVC are mentioned in the relevant chapters and (some)
in Appendix 3.
Copies of ISO standards and national standards of countries foreign
to one's own are available from (and in fact must be ordered through)
the local national ISO member body which acts as sales agent in that
country for ISO and for all other ISO member bodies. These bodies
are normally the individual countries' own national standardising
bodies.
As new standards are being reviewed, revised or amended,
standardising bodies provide the means to maintain up-to-date records.
The four bodies regarded as the most important (cf. Chapter 1, Section
1.7) are given below together with some observations on certain
general aspects of the standards listed in this appendix.

International Organization for Standardization (ISO)

Headquarters: 1, Rue de Varembe,
Case Postale 56,
CH-1211 Geneve 20,
Switzerland.
The ISO publishes a Catalogue of all its standards annually. The ISO
Bulletin is published monthly and includes a list of newly published
1127

1128

N. Herbert and W. V. Titow

standards and draft international standards. The ISO technical

committees dealing with plastics are TC 61 Plastics and TC 138 Plastics
pipes, fittings and valves for the transport of fluids. Plasticisers are
found under TC 47 Chemistry.

United Kingdom
British Standards Institution (BSI),
Linford Wood,
Milton Keynes MK14 6LE.
The annual British Standards Yearbook gives a list of all British
standards with a short summary of each one, and an alphabetical
index. The BSI News is published monthly and may be used for
manual updating of the Yearbook. In addition to lists of all new and
revised standards and amendments to standards published during the
month, draft standards and 'new work started' are also given.
A comprehensive list of standards received from all parts of the
world is contained in BSl's Worldwide List of Published Standards
which is issued monthly.
A large number of standard specifications is contained in BS
2782:1970 Methods of testing plastics, which is currently (1984) under
revision. Many of the specifications in this collection have already been
published in the revised form, and some entirely new ones have been
added. Work is in progress on others. The relevant revised and new
specifications have been included in this appendix, as have those
originally published in the 1970 edition which have not yet been
revised.
Note: In the body of this appendix the degree of equivalence of a
British Standard to an ISO standard is indicated where
possible according to the coding used in the BSI Yearbook,
viz.

= identical in every detail;

1- technically equivalent though the wording and presentation

may differ quite extensively;
a related standard; covers subject matter similar to that
covered by a corresponding international standard.

Al Standards Relevant to PVC Materials and Products

1129

United States of America

ASTM

American Society for Testing and Materials,

1916 Race Street,
Philadelphia,
Pennsylvania 19103.

Until recently, the Annual Book of ASTM Standards consisted of 48

parts, each part containing the standards covering a specific main
subject or an aspect of that subject. The division has now been
restructured into 16 sections subdivided into 66 volumes. Section 8
contains the volumes directly relevant to plastics:

Volume

~::~:}
08.03

08.04

Subjects covered

Plastics-General test methods,

nomenclature
Plastics-Materials, films, reinforced
and cellular plastics; high modulus
fibres and composites
Plastic pipes

Corresponding
parts in former
classification

Part 35
Part 36
Part 34

Other volumes of interest in connection with some PVC materials and

products, and the Index volume, are:

::::: }
10.03

00.01

Electrical insulation-Test methods:

solids and solidifying fluids
Electrical insulation-Specifications:
solids, liquids, and gases;
protective equipment
Index-Subject index; alphanumeric list

Part 39
Part 40
Part 48

The parts and the individual standards are obtainable from the ASTM.
Note: Where an ASTM designation is followed by a number in
brackets, this indicates the year of the latest reapproval by the
committee concerned.
ANSI: The national standardising body in the United States of

1130

N. Herbert and W. V. Titow

America is the:
American National Standards Institute (ANSI),
1430 Broadway,
New York,
New York 10018.
A great many individual standards issued by the ASTM have been
adopted by the ANSI as national standards. These adopted standards
may be purchased through a local national ISO member body.
West Germany
DIN Deutsches Institut fUr Normung,
Burggrafenstrasse 4-10,
1000 Berlin 30.
The DIN-Katalog is published annually, most of the German titles
being given in English as well. The catalogue may be kept up to date
by Ergiinzungen (Supplements) which are published monthly and are
cumulative. Further information on standards is given in DINMitteilungen (DIN-reports), which is also a monthly publication. The
latter two are in German only.
DIN standards on plastics which have been translated into English
are available in ring binders in the following collections:
Sales no. 10053 Plastics 1. Test standards for mechanical, thermal and
electrical properties
10056 Plastics. Duroplast resins and duroplast moulding
materials
10705 Plastics 2. Test standards on chemical, optical, usability and processing properties
10789 Plastics. Semi-finished products of thermoplastic
plastics
10790 Plastics. Pipes, pipeline components and pipe joints
of thermoplastic plastics
The collections of DIN standards in German are reduced in size and
bound into Taschenbiicher (Pocketbooks) in A5 size, and cover the
same classification of the collections translated into English, viz.
TAB 18 Kunststoffe 1. Prtifnormen tiber mechanische, thermische
und elektrische Eigenschaften

Al Standards Relevant to PVC Materials and Products

1131

TAB 21

Kunststoffe 3. Duroplast-Kunstharze und DuroplastFormmassen

TAB 48 Kunststoffe 2. Prtifnormen tiber chemische, optische Gebrauchs- und Verarbeitungs-Eigenschaften
TAB 51 Kunststoffe 8. Halbzeuge aus thermoplastischen Kunststoffen
TAB 52 Kunststoffe 5. Rohre, Rohrleitungsteile und Rohrverbindungen aus thermoplastischen Kunststoffen

Japan
Japanese Industrial Standards Committee,
c/o Standards Department,
Agency of Industrial Science and Technology,
Ministry of International Trade and Industry,
1-3-1 Kasumigaseki, Chiyodaku,
Tokyo 100.
In view of Japan's standing as a major producer and consumer of
PVC, the existence of many relevant Japanese Standards should not be
overlooked (e.g. JIS K 6720 (1977), Polyvinyl chloride resins; JIS K
6741 (1975), Unplasticised polyvinyl chloride pipes.
It has not been practicable to include them in this appendix.
However, from the technological standpoint, they do not cover any
important specifications or methods or materials not dealt with by
standards from one or more of the four sources represented here. It is
useful to remember that Japanese Standards are regularly included in
the already mentioned BSI Worldwide List of Published Standards and
that they are available (generally in English translation) from the BSI.

1 PLASTICS TERMINOLOGY, PROPERTIES AND

TESTING: GENERAL
1.1 Terminology
(a) General
ISO 472-1979
Plastics-Vocabulary
BS 1755
Glossary of terms used in the plastics industry

1132

N. Herbert and W. V. Titow

Part 1: 1982 (=t= ISO 472)

Polymer and plastics technology
Part 2: 1974
Manufacturing processes
BS 3558: 1980
Glossary of rubber terms
BS 4815: 1972
Glossary of generic names for man-made fibres
BS 5168: 1975
Glossary of rheological terms
ASTM C 168-80
Definitions of terms relating to thermal insulating materials
ASTM C 274-68 (1980)
Definitions of terms relating to structural sandwich construction
ASTM D 16-80
Definitions of terms relating to paint, varnish, lacquer and related
products
ASTM D 883-80
Definitions of terms relating to plastics
ASTM D 907-82
Definitions of terms relating to adhesives
ASTM D 1418-81
Recommended practice for rubber and rubber latices-Nomenclature
ASTM D 1566-82
Definitions of terms relating to rubber
ASTM E 6-81
Definitions of terms relating to methods of mechanical testing
ASTM E 12-70 (1981)
Definitions of terms relating to density and specific gravity of
solids, liquids and gases
ASTM E 41-79
Definitions of terms relating to conditioning
ASTM E 206-72 (1979)
Definitions of terms relating to fatigue testing and the statistical
analysis of fatigue data
ASTM E 284-81
Definitions of terms relating to appearance of materials

ASTM F 17-76
Definitions of terms relating to flexible barrier materials

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1133

ASTM F 141-79
Definitions of terms relating to resilient floor coverings
ASTM F 412-81
Definitions of terms relating to plastic piping systems
DIN 7732
Part 1 (1963)
Standardized terms and definitions relating to plastics; summary
(b) Common Names and Abbreviations
ISO 1043-1978
Plastics-Symbols

BS 3502
Schedule of common names and abbreviations for plastics and
rubbers
Part 1: 1978
Principal commercial plastics
Part 3: 1978
Rubber and rubber lattices

BS 4589: 1970
Abbreviations for rubber and plastics compounding materials
ASTM D 1600-83
Abbreviations of terms relating to plastics
DIN 7723 (1971)
Abbreviations for plasticizers
DIN 7728
Part 1 (1978)
Symbols for terms relating to homopolymers, copolymers and
polymer compounds
Part 2 (1980)
Symbols for reinforced plastics
(c) Equivalent Terms in Various Languages
ISO 194-1981
Plastics-List of equivalent terms
DIN 7730
Part 1 (1965)
Plastics, equivalent terms in German, English, French and
Russian following ISO/R 194-1961

1134

N. Herbert and W. V. Titow

1.2 General Test Conditions and Methods

(a) Conditioning and Testing Conditions
ISO 291-1977
Plastics-Standard atmospheres for conditioning and testing
ISO/R 483-1966
Plastics-Methods for maintaining constant relative humidity in
small enclosures by means of aqueous solutions
ISO 554-1976
Standard atmospheres for conditioning and/or testing-Specifications
ISO 558-1980
Conditioning and testing-Standard atmospheres-Definitions
ASTM D 618-61 (1981)
Conditioning plastics and electrical insulating materials for testing
DIN 50013 (1979)
Climates and their technical application; preferred temperatures
DIN 50014 (1975)
Atmospheres and their technical application; standard atmospheres
DIN 50015 (1975)
Atmospheres and their technical application; constant test atmospheres
DIN 50016 (1962)
Testing of materials, structural components and equipment;
method of test in damp alternating atmosphere
DIN 50017 (1982)
Climates and their technical application; stress in condensed water
containing climates
DIN 50018 (1978)
Testing of corrosion; methods of test in condensation water
alternating atmosphere containing sulphur dioxide
DIN 50019
Part 1 (1979)
Climates and their technical application; climates with regard to
technology, sign and cartographical graph of the open-air climates
Part 2 (1963)
Testing of materials, structural components and equipment; open
air climates; data on climates

Al Standards Relevant to PVC Materials and Products

1135

Part 3 (1979)
Climates and their technical application; climates with regard to
technology; climatic patterns based on statistics
Supplement to Part 3 (1979)
Climates and their technical application; climates with regard to
technology, geographical survey for open-air climate patterns
based on statistics
(b) Some General Test Methods
ISO 62-1980
Plastics-Determination of water absorption
ISO 171-1980
Plastics-Determination of bulk factor of moulding materials
ISO 3451/1-1981
Plastics-Determination of ash-General methods
2 VINYL POLYMERS AND COPOLYMERS (Chapter 2)
2.1 General (Designation, Coding, Characterisation Tests)

ISO 1060/1-1982
Plastics-Homopolymer and copolymer resins of vinyl chloride.
Part 1: Designation
ISO 1060/2-1978
Plastics-Homopolymer and copolymer resins of vinyl chloride.
Part II: Determination of properties
ISO 1163/1-1980
Plastics-Unplasticized compounds of homo- and copolymers of
vinyl chloride. Part 1: Designation
ISO 6186-1980
Plastics-Determination of pourability
ASTM D 1755-81
Specification for poly(vinyl chloride) resins
Note: This specification gives test methods referred to in some of the
ASTM standards listed in the sections that follow, e.g.
Sections 2.2 to 2.9, etc.

ASTM D 2474-81
Specification for vinyl chloride copolymer resins

1136

N. Herbert and W. V. Titow

ASTM D 2873-70 (1982)

Test for interior porosity of poly(vinyl chloride) (PVC) resins by
mercury intrusion porosimetry
ASTM D 3591-77
Recommended practice for determining logarithmic viscosity
number of poly(vinyl chloride) (PVC) in formulated compounds
DIN 7746
Part 1 (1979)
Vinyl chloride (VC) polymers; homopolymers; classification and
designation
Part 2 (1979)
Vinyl chloride (VC) polymers; homo- and copolymers, determination of properties
DIN 7747 (1979)
Vinyl chloride (VC) polymers; copolymers, classification and
designation

2.2 Viscosity
ISO 174-1974
Plastics-Determination of viscosity number of PVC resins in
dilute solution
ISO/R 1628-1970
Plastics-Directives for the standardisation of methods for the
determination of the dilute solution viscosity of polymers
ISO 3219-1977
Plastics-Polymers in the liquid, emulsified or dispersed stateDetermination of viscosity with a rotational viscometer working at
defined shear rate
BS 2782
Part 7
Rheological properties
Method 730A: 1979 ( ISO/R 1628)
Determination of reduced viscosity (viscosity number) and
intrinsic viscosity of plastics in dilute solution
Method 730B: 1978 (= ISO 3219)
Determination of the viscosity of polymers in the liquid,
emulsified or dispersed state using a rotational viscometer working
at a defined shear rate
ASTM D 1243-79
Test for dilute solution viscosity of vinyl chloride polymers

Al Standards Relevant to PVC Materials and Products

1137

DIN 53726 (1983)

Testing of plastics; determination of viscosity number and K-value
of vinyl chloride (VC) polymers
2.3 Chlorine Content
ISO 1158-1978
Plastics-Vinyl chloride homopolymers and copolymers-Determination of chlorine
ASTM D 1303-55 (1979)
Test for total chlorine in vinyl chloride polymers and copolymers
DIN 53474 (1976)
Testing of plastics, rubber and elastomers; determination of the
chlorine content
2.4 Vinyl Acetate Content in VCIVA Copolymers
ISO 1159-1978
Plastics-Vinyl chloride-vinyl acetate copolymers-Determination
of vinyl acetate
2.5 Ash and/or Sulphated Ash Content
ISO 1270-1975
Plastics-PVC resins-Determination of ash and sulphated ash
BS 2782: Part 4
Method 454A: 1978
Determination of ash
Method 454B : 1978 (= ISO 1270)
Determination of sulphated ash
2.6 Volatile Matter (Including Water)
ISO 1269-1980
Plastics-Homopolymer and copolymer resins of vinyl chlorideDetermination of volatile matter (including water)
BS 2782: Part 4
Method 454D: 1978 (= ISO 1269)
Determination of volatile matter (including water) of PVC resins
ASTM D 3030-79
Test for volatile matter (including water) of vinyl chloride resins

1138

N. Herbert and W. V. Titow

2.7 Impurities and Foreign Matter

ISO 1265-1979
Plastics-PVC resins-Determination of number of impurities and
foreign particles
ASTM D 2222-66 (1978)
Test for methanol extract of vinyl chloride resins
2.8 Bulk Density

ISO 60-1977
Plastics-Determination of apparent density of material that can
be poured from a specified funnel
ISO 61-1976
Plastics-Determination of apparent density of moulding material
that cannot be poured from a specified funnel
ISO 1068-1975
Plastics-PVC resins-Determination of compacted apparent bulk
density
BS 2782: Part 6
Method 621A: 1978 (= ISO 60)
Determination of apparent density of moulding material that can
be poured from a funnel
Method 621B : 1978 (= ISO 61)
Determination of apparent density of moulding material which
cannot be poured from a funnel
Method 621D : 1978 (= ISO 1068)
Determination of compacted apparent bulk density of PVC resins
ASTM D 1895-69 (1979)
Tests for apparent density, bulk factor, and pourability of plastic
materials
NB Method A equivalent to ISO 60
Method C equivalent to ISO 61
2.9 Particle Size

ISO 1624-1978
Plastics-Vinyl chloride homopolymer and copolymer resinsSieve analysis in water

Al

Standards Relevant to PVC Materials and Products

1139

ISO 4576-1978
Plastics-Aqueous dispersions of homopolymers and copolymers-Determination of gross particle content by sieve analysis
ISO 4610-1977
Plastics-Vinyl chloride homopolymer and copolymer resinsSieve analysis using air-jet sieve apparatus
BS 2782: Part 4
Method 454F: 1978 (= ISO 4610)
Sieve analysis of vinyl chloride homopolymer and copolymer
resins using air-jet sieve apparatus
ASTM D 1705-61 (1980)
Particle size analysis of powdered polymers and copolymers of
vinyl chloride
2.10 Bromine Number

ISO 3499-1976
Plastics-Aqueous dispersions of homopolymers and copolymers
of vinyl acetate-Determination of bromine number
2.11 pH of Aqueous Extract

ISO 1264-1980
Plastics-Homopolymer and copolymer resins of vinyl chlorideDetermination of pH of aqueous extract
BS 2782: Part 4
Method 454C: 1978 (= ISO 1264)
Determination of pH of aqueous extract of PVC resins
2.U Miscellaneous Properties Relevant to Processing

ASTM D 2396-79
Recommended practice for powder-mix test of poly(vinyl chloride) (PVC) resins using a torque rheometer
ASTM D 2538-79
Recommended practice for fusion test of poly(vinyl chloride)
(PVC) resins using a torque rheometer
ASTM D 2873-70 (1982)
Test for interior porosity of poly(vinyl chloride) (PVC) resins by
mercury intrusion porosimetry

1140

N. Herbert and W. V. Titow

ASTM D 3367-75 (1980)

Test for plasticizer sorption of poly(vinyl chloride) resins under
applied centrifugal force
ASTM D 3596-77
Recommended practice for determination of gels (fish eyes) in
general purpose poly(vinyl chloride) (PVC) resins
2.13 Methanol Extract
ASTM D 2222-66 (1978)
Test for methanol extract of vinyl chloride resins
2.14 VCM Content
DIN E 53743 (1979) Draft
Testing of plastics; gas chromatographical determination of vinyl
chloride (VC) in polyvinyl chloride (PVC)

3 VINYL COMPOUNDS (Chapter 3)

3.1 General (Designation, Coding, Characterisation Tests)
(a) Rigid Compounds
ISO 1163/1-1980
Plastics-Unplasticized compounds of homopolymers and copolymers of vinyl chloride. Part 1: Designation
ASTM D 1784-81
Specification for rigid poly(vinyl chloride) (PVC) compounds and
chlorinated poly(vinyl chloride) (CPVC) compounds
ASTM D 2124-70 (1979)
Analysis of components in poly(vinyl chloride) compounds using
an infrared spectrophotometric technique
ASTM D 3010-71 (1981)
Recommended practice for preparing compression-moulded test
sample plaques of rigid poly(vinyl chloride) compounds
DIN 7748
Part 1 (1979)
Plastic moulding materials; unplasticized PVC moulding materials;
classification and designation
Part 2 (1979)
Plastic moulding materials; unplasticized PVC moulding materials;
determination of properties

Ai

Standards Relevant to PVC Materials and Products

1141

(b) Flexible Compounds

ISO 289811-1980
Plastics-Plasticized compounds of homopolymers and copolymers
of vinyl chloride. Part 1: Designation
ISO 2898/2-1980
Plastics-Plasticized compounds of homopolymers and copolymers
of vinyl chloride. Part 2: Determination of properties
BS 2571 : 1963
Flexible PVC compounds
ASTM D 2124-70 (1979)
Analysis of components in poly(vinyl chloride) compounds using
an infrared spectrophotometric technique
ASTM D 2287-81
Specification for non-rigid vinyl chloride polymer and copolymer
molding and extrusion compounds
DIN 7749
Part 1 (1979)
Plastic moulding materials; plasticized polyvinyl chloride (PVC)
moulding materials; classification and designation
Part 2 (1979)
Plastic moulding materials; plasticized polyvinyl chloride (PVC)
moulding materials; preparation of specimens and determination
of their properties
(c) Pastes
ISO 4612-1979
Plastics-PVC paste resins-Preparation of a paste
DIN 54800 (1979)
Testing of plastics; preparation of polyvinyl chloride (PVC) paste
for testing purposes
DIN 54801 (1979)
Testing of plastics; determination of apparent viscosity at high
rates of shear of polyvinyl chloride (PVC) paste by Severs
capillary viscometer

(d) Miscellaneous
ASTM D 729-81
Specification fOr vinylidene chloride molding compounds
ASTM D 3364-74 (1979)
Test method for flow rates for poly(vinyl chloride) and rheologically unstable thermoplastics

1142

N. Herbert and W. V. Titow

3.2 Properties and Tests

(a) Bulk Density and Pourability

ISO 60-1977
ISO 61-1976
BS 2782: Part 6: Method 621A: 1978
BS 2782: Part 6: Method 621B: 1978
ASTM D 1895-69 (1979)

For titles see Section

2.8 above

DIN 53466 (1960)

Testing plastics. Determination of bulk factor of moulding
materials
DIN 53467 (1960)
Testing plastics. Determination of apparent density of moulding
material that cannot be poured from a specified funnel
DIN 53468 (1974)
Testing plastics. Determination of apparent density of moulding
material that can be poured from a specified funnel
(b) Water Absorption
BS 2782: Part 5
Method 502e: 1970
Water absorption and water soluble matter of polyvinyl chloride
extrusion compound
See also DIN 7748: Part 2 (1979) in Section 3.1(a) of this Appendix.
(c) Temperature Effects
(i) PHYSICAL
BS 2782: Part 1
Method 122A: 1976
Determination of deformation under heat of flexible polyvinyl
chloride compound
Method 150B: 1976
Determination of cold flex temperature of flexible polyvinyl
compound
Method 150C: 1983
Determination of low temperature extensibility of flexible polyvinyl chloride sheet
ASTM D 746-79
Test for brittleness temperature of plastics and elastomers by
impact

Al

Standards Relevant to PVC Materials and Products

1143

ASTM D 1043-72 (1981)

Stiffness properties of plastics as a function of temperature by
means of a torsion test
ASTM D 1593-81
Specification for non-rigid vinyl chloride plastic sheeting

(ii)

CHEMICAL

ISO/R 182-1970
Plastics-Determination of the thermal stability of polyvinyl
chloride and related copolymers and their compounds by splitting
off of hydrogen chloride
ISO 305-1976
Plastics-Determination of thermal stability of polyvinyl chloride,
related chlorine-containing polymers and copolymers, and their
compounds-Discoloration method
BS 2782: Part 1
Method BOA: 1976 (=f:. ISO/R 182)
Determination of the thermal stability of polyvinyl chloride by the
Congo red method
Method BOB: 1976 (=1= ISO/R 182)
Determination of the thermal stability of polyvinyl chloride by the
pH method
ASTM D 793-49 (1976)
Test for short-time stability at elevated temperatures of plastics
containing chlorine
ASTM D 2115-67 (1980)
Recommended practice for oven heat stability of poly(vinyl
chloride) compositions
DIN 53381
Testing of plastics; determination of the thermal stability of
polyvinyl chloride and related copolymers and their compounds;
Part 1 (1971)
Congo red method
Part 2 (1975)
Discoloration method
Part 3 (1971)
pH method
(d) Mechanical Properties
BS 2782: Part 3: Method 365A: 1976
Determination of softness number of flexible plastics

1144

N. Herbert and W. V. Titow

(e) Miscellaneous Properties and Analysis

ASTM D 2124-70 (1979)
Analysis of components in poly(vinyl chloride) compounds using
an infrared spectrophotometric technique
ASTM D 2151-68 (1977)
Test for staining of poly(vinyl chloride) compositions by rubber
compounding ingredients
ASTM D 2538-79
Recommended practice for fusion test of poly(vinyl chloride)
(PVC) resins using a torque rheometer
ASTM D 3421-75
Extraction and analysis of plasticiser mixtures from vinyl chloride
plastics
ASTM D 3596-77
Recommended practice for determination of gels (fish eyes) in
general purpose poly(vinyl chloride) (PVC) resins

4 PLASTICISERS (Chapters 5-7)

4.1 Bulk Properties

Specifications for individual plasticisers (as chemical materials) may be
found in the various catalogues of standards under the appropriate
compound names. Some of these are given here, as are some general
tests on plasticisers and some specifications covering groups of
compounds used as plasticisers.

ISO 1385/1-1977
Phthalate esters for industrial use-Methods of test-Part 1:
General
ISO 1385/2-1977
Phthalate esters for industrial use-Methods of test-Part II:
Measurement of colour after heat treatment (Diallyl phthalate
excluded)
ISO 1385/3-1977
Phthalate esters for industrial use-Methods of test-Part III:
Determination of ash

Al Standards Relevant to PVC Materials and Products

1145

ISO 1385/4-1977
Phthalate esters for industrial use-Methods of test-Part IV:
Determination of acidity to phenolphthalein-Titrimetric method
ISO 1385/5-1977
Phthalate esters for industrial use-Methods of test-Part V:
Determination of ester content-Titrimetric method after saponification
ISO 2520-1974
Tritolyl phosphate for industrial use-List of methods of test
ISO 2521-1974
Tritolyl phosphate for industrial use-Determination of acidity to
phenol red-Volumetric method
ISO 2522-1974
Tritolyl phosphate for industrial use-Determination of apparent
free phenols content-Volumetric method
ISO 2523-1974
Adipate esters for industrial use-List of methods of test
ISO 2524-1974
Adipate esters for industrial use-Measurement of colour after
heat treatment
ISO 2525-1974
Adipate esters for industrial use-Determination of acidity to
phenolphthalein-Volumetric method
ISO 2526-1974
Adipate esters for industrial use-Determination of ash-Gravimetric method
ISO 2527-1974
Adipate esters for industrial use-Determination of ester content-Volumetric method
BS 573, 574, 1995, 1996, 2535, 2536, 3647: 1973
Plasticizer esters
Comprises: BS 573 Dibutyl phthalate
BS 574 Diethyl phthalate
BS 1995 Di-(2-ethylhexyl) phthalate
BS 1996 Dimethyl phthalate
BS 2535 Dibutyl sebacate
BS 2536 Di-(2-ethylphenyl) sebacate
BS 3647 Dimethoxyethyl phthalate
BS 1998: 1970
Triphenyl phosphate

1146

N. Herbert and W. V. Titow

BS 1999: 1964 ( ISO 2520/2)

Tritolyl phosphate
BS 4835: 1973 ( ISO 1385, ISO 252417)
Methods of test for plasticizer esters
BS 4968-70: 1973
Di-isobutyl phthalate, di-isooctyl phthalate and di-isooctyl sebacate
ASTM D 1045-80
Sampling and testing plasticizers used in plastics
ASTM D 1249-81
Specification for octyl ortho-phthalate ester plasticizers
ASTM D 2288-69 (1980)
Test for weight loss of plasticizers on heating
DIN 53400 (1970)
Testing of plasticizers; determination of density, refractive index,
flash point and viscosity
DIN 53401 (1975)
Determination of saponification value
DIN 53402 (1973)
Determination of acid value
DIN 53404 (1952)
Testing of plasticizers; determination of saponification rate
DIN 53409 (1967)
Testing of plasticizers and solvents; determination of Hazen colour
(platinum cobalt colour, APHA method)
4.2

Properties in Association with PVC (Compatibility, Volatility,

Migration)

ISO 176-1976
Plastics-Determination of loss of plasticizers-Activated carbon
method
ISO 177-1976
Plastics-Determination of migration of plasticizers
BS 2782: Part 4
Method 465A and 465B: 1979 (= ISO 176)
Determination of loss of plasticizers (activated carbon method)
BS 2782: Part 5
Method 51lA: 1970
Effect of polyvinyl chloride compound on the loss tangent of
polythene

Al

Standards Relevant to PVC Materials and Products

1147

ASTM D 1203-67 (1981)

Tests for loss of plasticizer from plastics (activated carbon
methods)
ASTM D 2134-66 (1980)
Test for softening of organic coatings by plastic compositions
ASTM D 2383-69 (1981)
Recommended practice for testing plasticizer compatibility in
poly(vinyl chloride) (PVC) compounds under humid conditions
ASTM D 3291-74 (1980)
Test for compatibility of plasticizers in poly(vinyl chloride) plastics
under compression
ASTM D 3421-75
Extraction and analysis of plasticizer mixtures from vinyl chloride
plastics
DIN 53405 (1981)
Testing plasticizers; determination of migration of plasticizers
DIN 53407 (1971)
Testing plastics; determination of loss in weight of plasticized
plastics by the activated carbon method
DIN 53408 (1967)
Testing plastics; determination of solubility temperature of
polyvinyl chloride in plasticizers

4.3 Effects on PVC

ISO 4574-1978
Plastics-PVC resins for general use-Determination of hot
plasticizer absorption
ISO 4608-1977
Plastics-PVC resins for general use-Determination of plasticizer
absorption at room temperature
BS 2782: Part 4
Method 454E: 1978 (= ISO 4608)
Determination of plasticizer absorption at room temperature of
PVC resins for general use
ASTM D 2396-79
Recommended practice for powder-mix test of poly(vinyl chloride) (PVC) resins using a torque rheometer
ASTM D 3367-75 (1980)
Test for plasticizer sorption of poly(vinyl chloride) resins under
applied centrifugal force

1148

N. Herbert and W. V. Titow

DIN 53408 (1967)

Testing of plastics; determination of solubility temperature of
polyvinyl chloride in plasticizers
5 PVC SHEETING AND FILMS (Chapter 20)
5.1 Rigid
BS 3757: 1978
Rigid PVC sheet
BS 4203: 1980
Extruded rigid PVC corrugated sheeting
ASTM D 1927-81
Specification for rigid poly(vinyl chloride) plastic sheet
ASTM D 2123-81
Specification for rigid poly(vinyl chloride-vinyl acetate) plastic
sheet
DIN 16927
Part 1 (1977)
Sheets of rigid polyvinyl chloride (rigid PVC), normal impact
strength; technical delivery specifications
Part 2 (1977)
Sheets of rigid polyvinyl chloride (rigid PVC), raised impact
strength; technical delivery specifications
DIN 16929 (1965)
Tubes and sheets of rigid PVC (rigid polyvinyl chloride);
resistance to chemicals; recommended practice
5.2 Flexible
BS 1763: 1975
Thin PVC sheeting (calendered, flexible, unsupported)
BS 2739: 1975
Thick PVC sheeting (calendered, flexible, unsupported)
BS 2782: Part 6
Method 643A: 1976
Shrinkage on heating of film intended for shrink wrapping
applications
BS 3878: 1982
Flexible PVC sheeting for hospital use

Al Standards Relevant to PVC Materials and Products

1149

ASTM D 1239-55 (1971)

Test for resistance of plastic films to extraction by chemicals.
Discontinued in 1980
ASTM D 1593-81
Specification for non-rigid vinyl chloride plastic sheeting
ASTM D 1893-67 (1978)
Test for blocking of plastic film
ASTM D 3083-76
Flexible poly(vinyl chloride) plastic sheeting for pond, canal and
reservoir lining
ASTM D 3354-74 (1979)
Test for blocking load of plastic film by the parallel plate method
DIN 16937 (1971)
Sheets of bitumen-resistant nonrigid PVC (nonrigid polyvinyl
chloride) for waterproofing of buildings; requirements, testing
DIN 16938 (1971)
Sheets of non-bitumen-resistant non-rigid PVC (non-rigid polyvinyl chloride) for damp-proofing
DIN 53372 (1970)
Testing of plastics films; determination of break at low temperature of films of nonrigid polyvinyl chloride
The following list gives further DIN specifications on the testing of
plastics sheet and film (short titles):
DIN 53353
DIN 53365
DIN 53366
DIN 53369
DIN 53370
DIN 53374
DIN 53375
DIN 53377
DIN 53378
DIN 53380
DIN 53488

(1971): Tear test

(1974): Mass per unit area
(1975) Draft: Blocking
(1976): Shrinking stress
(1976): Thickness
(1959): Flexure
(1972): Coefficients of friction
(1969): Dimensional stability
(1965): Colour fastness to hydrogen sulphide
(1969): Gas transmission rate
(1963): Hole test

5.3 Sheet and Film Fabrication and Products

BS 1776: 1951
Fabrication of lightweight articles (other than rainwear) from
polyvinyl chloride sheeting

1150

N. Herbert and W. V. Titow

BS 3501: 1962
Dinghy buoyancy equipment
ASTM D 1789-65 (1977)
Test for welding performance of poly(vinyl chloride) structures
DIN 1910
Part 3 (1977)
Welding; welding of plastics, processes
DIN 16930 (1964)
Welding of rigid PVC (rigid polyvinyl chloride); recommended
practice
DIN 16931 (1959)
Welding of nonrigid PVC (nonrigid polyvinyl chloride); recommended practice
DIN 16995 (1976)
Packaging materials; plastics films, main properties, special
properties, test methods
Note: Some properties of PVC films and sheeting are covered by
general plastics film and sheeting standards. Such standards
are mentioned in the appropriate chapters and in Appendix 3.
Some examples are water vapour permeability, gas permeability, electrical properties and flammability. BS 1133 Packaging
Code; Section 21: 1976 Regenerated cellulose film, aluminium
foil and flexible laminates is also relevant to plastics films for
packaging (cf. DIN 16995 above).

6 PVC PIPES, TUBING AND PIPE FITTINGS

6.1

Rigid Pipes and Fittings, Including Pressure Pipes

ISO DATA 7-1979

Unplasticized polyvinyl chloride pipes and fittings-Chemical
resistance with respect to fluids
ISO 580-1973
Moulded fittings in unplasticized polyvinyl chloride (PVC) for use
under pressure-Oven test
ISO 727-1979

Unplasticized polyvinyl chloride (PVC) fittings with plain sockets

for pipes under pressure-Dimensions of sockets-Metric series

Al

Standards Relevant to PVC Materials and Products

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ISO 2035-1974
Unplasticized polyvinyl chloride (PVC) moulded fittings for elastic
sealing ring type joints for use under pressure-Pressure resistance
test
ISO 2043-1974
Unplasticized polyvinyl chloride (PVC) moulded fittings for elastic
sealing ring type joints for use under pressure-Oven test
ISO 2044-1974
Unplasticized polyvinyl chloride (PVC) injection-moulded solventwelded socket fittings for use with pressure pipe-Hydraulic
internal pressure test
ISO 2045-1973
Single sockets for unplasticized polyvinyl chloride (PVC) pressure
pipes with elastic sealing ring type joints-Minimum depths of
engagement
ISO 2048-1973
Double socket fittings for unplasticized polyvinyl chloride (PVC)
pressure pipes with elastic sealing ring type joints-Minimum
depths of engagement
ISO 2505-1981
Unplasticized polyvinyl chloride (PVC) pipes-Longitudinal reversion-Test methods and specification
ISO 2507-1982
Unplasticized polyvinyl chloride (PVC) pipes and fittings-Vicat
softening temperature-Test method and specification
ISO 2508-1981
Unplasticized polyvinyl chloride (PVC) pipes-Water absorption-Determination and specification
ISO 2536-1974
Unplasticized polyvinyl chloride (PVC) pressure pipes and fittings,
metric series-Dimensions of flanges
ISO 2703-1973
Buried unplasticized polyvinyl chloride (PVC) pipes for the supply
of gaseous fuels-Metric series-Specification
ISO 3114-1977
Unplasticized polyvinyl chloride (PVC) pipes for potable water
supply-Extractability of lead and tin-Test method
ISO 3460-1975
Unplasticized polyvinyl chloride (PVC) pressure pipes-Metric
series-Dimensions of adapter for backing flange

1152

N. Herbert and W. V. Titow

ISO 3472-1975
Unplasticized polyvinyl chloride (PVC) pipes-Specification and
determination to resistance to acetone
ISO 3473-1977
Unplasticized polyvinyl chloride (PVC) pipes-Effect of sulphuric
acid-Requirement and test method
ISO 3474-1976
Unplasticized polyvinyl chloride (PVC) pipes-Specification and
measurement of opacity
ISO 3603-1977
Fittings for unplasticized polyvinyl chloride (PVC) pressure pipes
with elastic sealing ring type joints-Pressure test for leakproofness
ISO 3604-1976
Fittings for unplasticized polyvinyl chloride (PVC) pressure pipes
with elastic sealing ring type joints-Pressure test for leakproofness under conditions of external hydraulic pressure
ISO 3606-1976
Unplasticized polyvinyl chloride (PVC) pipes-Tolerances on
outside diameters and wall thicknesses
ISO 4434-1977
Unplasticized polyvinyl chloride (PVC) adapter fittings for
pipes under pressure-Laying length and size of threads-Metric
series
ISO 4439-1979
Unplasticized polyvinyl chloride (PVC) pipes and fittingsDetermination and specification of density
BS 3505: 1968 (1982) (oF ISO 2505, ISO 3114, ISO 3472-3, ISO
3474)
Unplasticized PVC pipe for cold water services
BS 3506: 1969
Unplasticized PVC pipe for industrial purposes
BS 3943: 1979
Plastics waste traps
BS 4346 ( ISO 2035, ISO 2043-5, ISO 2048)
Joints and fittings for use with unplasticized PVC pressure pipes
Part 1: 1969
Injection moulded PVC fittings for solvent welding for use with
pressure pipes, including potable water supply
Part 2: 1970
Mechanical joints and fittings principally of unplasticized PVC

Al Standards Relevant to PVC Materials and Products

1153

Part 3: 1982
Solvent cement
BS 4514: 1983
Unplasticized PVC soil and ventilating pipe, fittings and accessories
BS 4576
Unplasticized PVC rainwater goods
Part 1: 1982
Half-round gutters and circular pipe
BS4607
Non-metallic conduits and fittings for electrical installations
Part 1: 1970
Rigid PVC conduits and conduit fittings. Metric units
Part 2: 1970
Rigid PVC conduits and conduit fittings. Imperial units
Part 3: 1971
Pliable corrugated, plain and reinforced conduits of selfextinguishing plastics material
Part 5: 1982
Rigid conduits, fittings and components of insulating materials
BS 4660: 1973
Unplasticized PVC underground drain pipe and fittings
BS 5481 : 1977
Specification for unplasticized PVC pipe and fittings for gravity
sewers
BS CP 312
Plastics pipework (thermoplastics materials)
Part 2: 1973
Unplasticized PVC pipework for the conveyance of liquids under
pressure
ASTM D 876-71
Testing non rigid vinyl chloride polymer tubing used for electrical
insulation
ASTM D 1785-76
Specification for poly(vinyl chloride) (PVC) plastic pipe, schedules
40, 80 and 120
ASTM D 2152-80
Degree of fusion of extruded poly(vinyl chloride) (PVC) pipe and
molded fittings by acetone immersion
ASTM D 2241-80
Specification for poly(vinyl chloride) (PVC) plastic pipe (SDR-PR)

1154

N. Herbert and W. V. Titow

ASTM D 2464-76
Specification for threaded poly(vinyl chloride) (PVC) plastic pipe
fittings, schedule 80
ASTM D 2466-78
Specification for poly(vinyl chloride) (PVC) plastic pipe fittings,
schedule 40
ASTM D 2467-76a
Specification for socket-type poly(vinyl chloride) (PVC) plastic
pipe fittings, schedule 80
ASTM D 2665-81
Specification for poly(vinyl chloride) (PVC) plastic drain, waste
and vent pipe and fittings
ASTM D 2672-80
Specification for bell-end poly(vinyl chloride) (PVC) pipe
ASTM D 2729-80
Specification for poly(vinyl chloride) (PVC) sewer pipe and fittings
ASTM D 2740-80
Specification for poly(vinyl chloride) (PVC) plastic tubing
ASTM D 2846-81
Specification for chlorinated poly(vinyl chloride) (CPVC) plastic
hot- and cold-water distribution systems
ASTM D 2949-78
Specification for 325-in outside diameter poly(vinyl chloride)
(PVC) plastic drain, waste, and vent pipe and fittings
ASTM D 3033-81
Specification for type PSP poly(vinyl chloride) (PVC) sewer pipe
and fittings
ASTM D 3034-81
Specification for type PSM poly(vinyl chloride) (PVC) sewer pipes
and fittings
DIN 1187 (1982)
Drain pipes of unplasticized polyvinyl chloride; dimensions,
general requirements, test methods
DIN 3441
Valves of unplasticized polyvinyl chloride
Part 1 (1982): requirements and tests
Part 2 (1977): ball valves, dimensions
Part 3 (1977): diaphragm valves, dimensions
Part 4 (1978): oblique pattern valves, dimensions

Al

Standards Relevant to PVC Materials and Products

1155

DIN 3543
Part 3 (1978)
Tapping valves for plastics pipes, dimensions
DIN 4279
Part 7 (1975)
Internal pressure test of pressure pipelines for water, pressure
pipes of unplasticized PVC
DIN 6660 (1980)
Pneumatic tube systems; conveyor tubes of rigid PVC
DIN 6661 (1979)
Pneumatic tube systems; sleeves of rigid PVC
DIN 6664 (1980)
Pneumatic tube systems, conveyor tube bends 900 of rigid PVC
DIN 8061
Part 1 (1974)
Pipes of rigid PVC; general quality requirements, test methods
Part 2 (1971)
Pipes of high impact PVC; general quality requirements, test
methods
DIN 8062 (1974)
Pipes of rigid PVC; dimensions
DIN 8063 Parts 1-11
Pipe joints and their elements for pipes of unplasticized PVC
under pressure
DIN 8079 (1974) (Preliminary Standard)
Pipes of PVC-C (chlorinated polyvinyl chloride) dimensions
DIN 8080 (1974) (Preliminary Standard)
Pipes of PVC-C; general quality requirements and test methods
DIN 16450 (1975)
Socket-fittings for pressure main lines of rigid polyvinyl chloride;
symbols
DIN 16451 Parts 1-7
Socket-fittings of cast iron with lamellar graphite for pressure main
lines of rigid polyvinyl chloride
DIN 16929 (1965)
Tubes and sheets of rigid PVC; resistance to chemicals, recommended practice
DIN 19531 (1980)
Pipes and fittings of unplasticized PVC, with rubber ring sockets,

1156

N. Herbert and W. V. Titow

for waste and soil installation inside buildings; dimensions,

technical specifications for delivery
DIN 19532 (1979)
Pipe-lines of unplasticized PVC for drinking water supply; pipes,
pipe connections, fittings for pipe lines
DIN 19534
Part 1 (1979)
Pipes and fittings of unplasticized PVC (polyvinyl chloride) with
sockets for elastic sealing ring joints for sewage; dimensions
Part 2 (1979)
Pipes and fittings of unplasticized PVC (polyvinyl chloride) with
sockets for elastic sealing ring joints for sewage; technical delivery
specifications
DIN 19538 (1980) Draft
Pipes and fittings of chlorinated polyvinyl chloride (PVC-C) with
rubber ring sealed sockets for hot water resistant waste and soil
installations inside buildings; dimensions, technical specifications
for delivery
DIN 86012 (1978)
Pipe lines of unplasticized polyvinyl chloride (unplasticized PVC)
on ships, cemented type joints; summary of components
DIN 86013 (1978)
Pipes of unplasticized polyvinyl chloride (unplasticized PVC) on
ships with pipe fittings for solvent cement joints
DIN 86015 (1976) (Preliminary standard)
Pipe lines of unplasticized polyvinyl chloride on ships, cemented
type joints; application, processing, laying
6.2 Flexible Tubing
BS 1882: 1976
Specification for flexible polymeric tubing and drainage sheeting
(radio-opaque) for medical use
BS 3746: 1964 (1983)
PVC garden hose
BS 4607
Non-metallic conduits and fittings for electrical installations
Part 3: 1971
Pliable corrugated, plain and reinforced conduits of selfextinguishing plastics material

Al Standards Relevant to PVC Materials and Products

1157

ASTM D 876-80
Testing nonrigid vinyl chloride polymer tubing used for electrical
insulation
ASTM D 922-80
Specification for nonrigid vinyl chloride polymer tubing
ASTM D 3150-81
Specification for crosslinked and noncrosslinked poly(vinyl chloride) heat shrinkable tubing for electrical insulation
DIN 16940 (1964)
Extruded hoses of nonrigid PVC (nonrigid polyvinyl chloride);
permissable deviations for dimensions for which tolerances are not
indicated
DIN 16942 (1966)
Water-hoses of nonrigid PVC (nonrigid polyvinyl chloride);
dimensions
6.3

Miscellaneous Standards Relevant to Pipes

ISO 3514-1976
Chlorinated polyvinyl chloride (CPVC) pipes and fittingsSpecification and determination of density
ISO 3608-1976
Chlorinated polyvinyl chloride (CPVC) pipes-Tolerances on
outside diameters and wall thicknesses
ISO 4065-1978
Thermoplastic pipes-Universal wall thickness table
BS 4962: 1982
Pipes for use as light sub-soil drains
BS 5556: 1978 ( ISO 161/1)
Specification for general requirements for dimensions and pressure
ratings for pipe of thermoplastics materials (metric series)
BS CP 312
Plastics pipework (thermoplastics materials)
Part 1: 1973
General principles and choice of material
ASTM D 2152-80
Test for degree of fusion of extruded poly(vinyl chloride) (PVC)
pipe and molded fittings by acetone immersion
ASTM D 2564-80
Specification for solvent cements for poly(vinyl chloride) (PVC)
plastic pipe and fittings

1158

N. Herbert and W. V. Titow

ASTM D 2855-81
Recommended practice for making solvent-cemented joints with
poly(vinyl chloride) (PVC) pipe and fittings
ASTM D 3036-73
Specification for socket-type poly(vinyl chloride) (PVC) plastic
line couplings
ASTM F 409-81
Specification for thermoplastic accessible and replaceable plastic
tube and tubular fittings
ASTM F 412-81
Definitions of terms relating to plastic piping systems
DIN 16929 (1965)
Tubes and sheets of rigid PVC (rigid polyvinyl chloride);
resistance to chemicals, recommended practice

7 PVC-COATED MATERIALS AND PRODUCTS

Several standards covering plastics-coated fabrics generally are relevant to PVC-coated fabrics, and have been included in this list.
7.1

Coated Fabrics, Including Conveyor and Transmission Belting

ISO 1419-1977
Fabrics coated with rubber or plastics-Accelerated ageing and
simulated service tests
ISO 1420-1978
Rubber and plastics coated fabric-Determination of resistance to
penetration by water
ISO 1421-1977
Fabrics coated with rubber or plastics-Determination of breaking
strength and elongation at break
BS 351: 1976 (=1= ISO 22)
Specification for rubber, balata or plastics flat transmission belting
of textile construction for general use
BS 490
Conveyor and elevator belting
BSO 490
Part 1: 1972 (=f:. ISO 282, ISO 283, ISO 703, ISO 1121)
Rubber and plastics conveyor belting of textile construction for

Al Standards Relevant to PVC Materials and Products

1159

general use (of either multi-ply, single-ply or solid woven

construction)
Part 2: 1975 ( ISO 251, ISO 252, ISO 282, ISO 283, ISO 432, ISO
433)
Rubber and plastics belting of textile construction for use on
bucket elevators
BS 3424
Parts 0-7: 1982
Testing coated fabrics
BS 3546
Parts 1 and 2: 1981
Coated fabrics for water resistant clothing
BS 5790
Coated fabrics for upholstery
Part 1: 1979
Specification for PVC coated knitted fabrics
Part 2: 1979
Specification for PVC coated woven fabrics
ASTM D 751-79
Testing coated fabrics
ASTM D 2136-66 (1978)
Testing coated fabrics-Low-temperature bend test
ASTM D 2137-75
Test for rubber property-Brittleness point of flexible polymers
and coated fabrics
DIN 16922 (1981)
Flexible sheet materials, manufactured using plastics; technological classification.
DIN specifications relating to coated fabrics generally-not specifically PVC-coated-(short titles):
DIN 53352 (1982):
DIN 53353 (1971):
DIN 53354 (1981):
DIN 53356 (1982):
DIN 53357 (1982):
DIN 53358(1971):
DIN 53359 (1957):
DIN 53360 (1982):
DIN 53361 (1982):
DIN 53362 (1980):

Mass per unit area

Thickness
Tensile test
Tear growth test ('trouser-leg' specimen)
Adhesion
Mass per unit area of coating
Cracking on repeated flexing
Elongation
Cold creasing
Determination of stiffness in bending

1160

N. Herbert and W. V. Titow

7.2 Other Coated Materials and Products (including chain-link

fencing, powder-coated wire and other products)
BS 1651: 1966
Industrial gloves
BS 4102: 1971
Steel wire for fences
DIN 3036
Part 1 (1978)
Plastic coated steel wires
Part 2 (1978)
Plastic coated steel wires
8 CELLULAR VINYLS (Chapter 25)
Standards relating specifically to cellular vinyls are still comparatively
few, and those covering cellular plastics generally are frequently used.
For this reason most of the latter standards have been listed here.
Specifications relating to fabrics coated with cellular vinyls are given
in Section 7 of this Appendix.

8.1 Rigid CeDular Materials

ISO 844-1978
Cellular plastics-Compression test of rigid materials
ISO 845-1977
Cellular rubbers and plastics-Determination of apparent density
ISO 1209-1976
Rigid cellular plastics-Bending test
ISO 1922-1981
Cellular plastics-Determination of shear strength of rigid material
ISO 1923-1981
Cellular plastics and rubbers-Determination of linear dimensions
ISO 1926-1979
Cellular plastics-Determination of tensile properties of rigid
materials
ISO 2581-1975
Plastics-Rigid cellular materials-Determination of 'apparent'
thermal conductivity by means of a heat-flow meter

Al Standards Relevant to PVC Materials and Products

1161

ISO 2796-1980
Cellular plastics-Test for dimensional stability of rigid materials
ISOrrR 2799-1978
Cellular plastics-Determination of the temperature at which fixed
permanent deformation of rigid materials occurs under compressive load
ISO 2896-1974
Rigid cellular plastics-Determination of water absorption
BS 3869: 1965
Rigid expanded polyvinyl chloride for thermal insulation purposes
and building applications
BS 4370
Methods of test for rigid cellular materials
Part 1: 1968 (=1= ISO 844, 845, 1923)
Methods 1-5
Part 2: 1973 (=1= ISO 1922; ISO 1926)
Methods 6-10
Part 3: 1974
Methods 11-13
ASTM D 1621-73 (1979)
Test for compressive properties of rigid cellular plastics
ASTM D 1622-63 (1975)
Test for apparent density of rigid cellular plastics
ASTM D 1623-78
Test for tensile properties of rigid cellular plastics
ASTM D 2126-75
Test for response of rigid cellular plastics to thermal and humid
aging
ASTM D 2842-69 (1975)
Test for water absorption of rigid cellular plastics
DIN 53421 (1971)
Testing of rigid cellular plastics; compression test
DIN 53423 (1975)
Testing of rigid cellular plastics; bending test
DIN 53424 (1978)
Testing of rigid cellular plastics; determination of dimensional
stability under heat in the case of flexural load and compression
load
DIN 53425 (1965)
Testing of rigid foams; creep-depending-on-time compression test
under heat

1162

N. Herbert and W. V. Titaw

DIN 53427 (1976)

Testing of rigid cellular plastics; determination of shear strength of
rigid cellular plastics in the form of a sandwich between metal
plates
DIN 53430 (1975)
Testing of rigid cellular plastics; tensile test
DIN 53432 (1977)
Selfskinning rigid foams; test methods
DIN 53433 (1979)
Testing of rigid cellular plastics; determination of water absorption
by dipping in water
8.2 Flexible Cellular Materials

BS 4023: 1975
Flexible cellular PVC sheeting
BS 4443 (~ ISO 485, 1794, 1798, 1856,3386)
Methods of test for flexible cellular materials
Part 1: 1979
Methods 1 to 6
Part 2: 1972 (= ISO 2439)
Method 7-Indentation hardness test
Part 3: 1975
Method 8--Determination of creep
Method 9-Determination of dynamic cushioning performance
Part 4: 1976 (;zf ISO 2440)
Methods 10-12
Part 5: 1980
Test for dynamic fatigue by constant load pounding
Part 6: 1980
Methods 14-16
ASTM D 1565-81
Specification for flexible cellular materials-vinyl chloride polymers and copolymers (open-cell foam)
ASTM D 1667-76 (1981)
Specification for flexible cellular materials-vinyl chloride polymers and copolymers (closed-cell vinyl)
DIN 53570 (1981)
Testing cellular materials; determination of linear dimensions
DIN 53571 (1978)
Testing of flexible cellular materials; test of the tensile strength

Ai Standards Relevant to PVC Materials and Products

1163

DIN 53572 (1979)

Testing of flexible cellular materials; determination of compression set after constant deformation
DIN 53574 (1977)
Flexible cellular materials; test for dynamic fatigue by constant
load pounding
DIN 53576 (1976)
Testing of flexible cellular materials; hardness testing by indentation techniques
DIN 53577 (1976)
Testing of flexible cellular materials; determination of compression stress value and compression stress-strain characteristics
DIN 53578 (1974)
Testing of flexible cellular materials; testing of ageing
DIN 53579
Part 1 (1980)
Testing of flexible cellular materials; hardness test on finished
parts, compression test on shaped parts
Part 2 (Draft) (1977)
Testing of flexible cellular materials; hardness test on finished
parts, compression test on profiles

8.3 MisceUaneous Standards (including those relevant generally to

cellular plastics materials and products)
(a) Definition and Classification
DIN 7726
Part 1 (1966)
Cellular materials; definitions of terms, classification
(b) Physical Properties-General
DIN 53420 (1978)
Testing of cellular materials; determination of apparent density

(c) Thermal Properties-General

ASTM C 177-76
Test for steady-state thermal transmission properties by means of
the guarded hot plate
ASTM D 696-79
Test for coefficient of linear thermal expansion of plastics

1164

N. Herbert and W. V. Titow

(d) Flammability and Burning

ASTM E 84-81
Test for surface burning characteristics of building materials
ASTM E 162-81
Test for surface flammability of materials using a radiant heat
energy source

(e) Chemical Resistance and Permeability

ASTM E 96-80
Tests for water vapor transmission of materials
DIN 53428 (1967)
Testing of foams; determination of the resistance to liquids,
vapours, gases and solid materials
(f) Insulation Materials
(i) THERMAL
ASTM C 351-61 (1973)
Test for mean specific heat of thermal insulation
ASTM C 421-77
Test for tumbling friability of preformed block-type thermal
insulation
DIN 18164
Part 1 (1979)
Foamed plastics as insulating building materials; insulating
materials for thermal insulation
Part 2 (1979)
Foamed plastics as insulating building materials; insulating
materials for impact sound insulation
(ii) ELECfRICAL
ASTM D 149-81
Tests for dielectric breakdown voltage and dielectric strength of
electrical insulating materials at commercial power frequencies
ASTM D 257-78
Tests for D-C resistance or conductance of insulating materials
ASTM D 1673-79
Tests for relative permittivity and dissipation factor of expanded
cellular plastics used for electrical insulation

Al

Standards Relevant to PVC Materials and Products

1165

(iii) ACOUSTICAL
ASTM C 384-77 (1981)
Test for impedance and absorption of acoustical materials by the
impedance tube method
ASTM C 423-81
Test for sound absorption and sound absorption coefficient by the
reverberation room method
(g) Cushioning Materials
ASTM D 1596-78
Test for shock absorbing characteristics of package cushioning
materials
ASTM D 2221-68 (1979)
Test for creep properties of package cushioning materials
(h) Sandwich Structures
ASTM C 273-61 (1980)
Shear test in flatwise plane of flat sandwich constructions or
sandwich cores
ASTM C 393-62 (1980)
Flexure test of flat sandwich constructions

9 PVC WIRE AND CABLE INSULATION, CABLE

SHEATHING AND JACKETING
BS 6004: 1975
PVC-insulated cables (non-armoured) for electric power and
lighting
BS 6231: 1981
Specification for PVC-insulated cables for switchgear and controlgear wiring
BS 6346: 1969 (1977)
PVC-insulated cables for electricity supply
BS 6485: 1971 (1977)
PVC-covered conductors for overhead power lines
BS 6746: 1976
PVC insulation and sheath of electrical cables

1166

N. Herbert and W. V. Titow

BS 6746C: 1969 (1979)

Colour chart for PVC insulation and sheath of electric cables
ASTM D 876-80
Testing nonrigid vinyl chloride polymer tubing used for electrical
insulation
ASTM D 922-80
Specification for nonrigid vinyl chloride polymer tubing
ASTM D 1047-79
Specification for poly(vinyl chloride) jacket for wire and cable
ASTM D 1755-81
Specification for poly(vinyl chloride) resins
Section 13:
Electrical conductivity of water extract
(This test distinguishes between electrical and non-electrical grades of
unprocessed PVC resin)
ASTM D 2219-81
Specification for poly(vinyl chloride) insulation for wire and cable,
60C operation
ASTM D 2220-80
Specification for poly(vinyl chloride) insulation for wire and cable,
75C operation
ASTM D 2405-81
Specification for general-purpose acrylonitrile-butadiene/poly(vinyl chloride) (NBRlPVC) jacket for wire and cable
ASTM D 2432-81
Specification for heavy-duty acrylonitrile-butadiene/poly(vinyl
chloride) (NBRlPVC) jacket for wire and cable
ASTM D 2633-82
Testing thermoplastic insulated and jacketed wire and cable
ASTM D 2708-81
Specification for extra-heavy-duty acrylonitrile-butadiene/poly(vinyl chloride) (NBRlPVC) jacket for wire and cable

General: Test methods for electrical properties of plastics insulation

materials are given in the following collections of standards:
BS 2782: Part 2. Electrical properties
ASTM Book of Standards: Volumes 0802, 1001-1003
DIN Handbook Plastics 1. Mechanical, thermal and electrical
properties

Al

Standards Relevant to PVC Materials and Products

1167

10 PVC FLOORING
BS 3260: 1969
PVC (vinyl) asbestos floor tiles
BS 3261
Unbacked flexible PVC flooring
Part 1: 1973
Homogeneous flooring
BS 4902: 1976
Specification for sheet and tile flooring colours for building
purposes
BS 5085
Backed flexible PVC flooring
Part 2: 1976
Cellular PVC backing
DIN 16950 (1977)
Flooring materials; vinyl-asbestos-tiles, requirements, test
methods
DIN 16951 (1977)
Floor coverings; polyvinyl chloride (PVC) flooring without
backing, requirements, test methods

11 VARIOUS PRODUCT STANDARDS AND TESTS

11.1 Colour Bleeding and Staining
ISO 183-1976
Plastics-Qualitative evaluation of the bleeding of colorants
BS 2782: Part 5
Method 542A: 1979 (= ISO 183)
Qualitative evaluation of bleeding of colourants
ASTM D 2151-68 (1977)
Test for staining of poly(vinyl chloride) compositions by rubber
compounding ingredients

11.2 Miscellaneous
ISO 580-1973
Moulded fittings in unplasticized polyvinyl chloride (PVC) for use
under pressure-Oven test

1168

N. Herbert and W. V. Titow

BS 3887: 1965
Regenerated cellulose and unplasticized PVC pressure-sensitive
closing and sealing tapes
ASTM D 2301-73 (1979)
Specification for vinyl chloride plastic pressure-sensitive electrical
insulating tape
ASTM D 3005-73 (1979)
Specification for low-temperature resistant vinyl chloride plastic
pressure-sensitive electrical insulating tape
DIN 16941 (1964)
Extruded profiles of nonrigid PVC (nonrigid polyvinyl chloride);
permissable deviations for dimensions for which tolerances are not
indicated
DIN 53419 (1977)
Extruded profiles of unplasticized polyvinyl chloride (unplasticized
PVC); test method of the behaviour against methylene chloride

APPENDIX 2

Quantities and Units: The SI System:

Unit Conversion Tables
Compiled by W. V. TITOW

The measurement and expression of the properties of the great variety

of PVC materials and products in existence today, as well as the
description of their performance in their numerous applications,
involve the use of various units from a number of scientific disciplines
and technical fields. The conversion tables and other information
provided in this appendix are offered as relevant and-it is hopedpotentially useful in these connections.
Sources of further information include the following standards and
publications:
ISO 31*
Covering the general principles concerning quantities, units and
symbols (ISO 31/0-1974), the quantities and units of space and time
(ISO 31/1-1978), periodic and related phenomena (ISO 31/2-1978),
mechanics (ISO 31/3-1978), heat (ISO 31/4-1978), electricity and
magnetism (ISO 31/5-1979), light and related electromagnetic
radiations (ISO 31/6-1973), acoustics (ISO 31/7-1978), physical
chemistry and molecular physics (ISO 31/8-1973), atomic and
nuclear physics (ISO 31/9-1973), nuclear reactions and ionising
radiations (ISO 31/10-1973), and solid state physics (ISO 31/13), as
well as mathematical signs and symbols for use in the physical
sciences and technology (ISO 31/11-1978), and dimensionless
parameters (ISO 31/12-1975).

* ISO Standard Handbook 2: 'Units of Measurement', contains the texts of all

relevant ISO standards.
1169

1170

W. V. Titow

ISO 1000-1973. * 'SI Units and recommendations for the use of their
multiples and of certain other units'.
BS 350. 'Conversion factors and Tables'
(Part 1 :1974, Part 2: 1962 with Supplement No.1: 1967).
BS 1991. 'Letter symbols, signs and abbreviations'
Covering general aspects (Part 1: 1976), chemical engineering,
nuclear science and applied chemistry (Part 2: 1961), fluid mechanics
(Part 3: 1961), structures, materials and soil mechanics (Part
4: 1961), applied thermodynamics (Part 5: 1961), electrical science
and engineering (Part 6: 1975) with a list of subscripts for electrical
technology (Supplement No.1: 1973 to Part 6).
BS 3763: 1976. 'The International System of Units (SI)'
ASTM Metric Practice Guide (1976). US National Bureau of
Standards.
Changing to the Metric System. (1969). Anderton, P. and Bigg, P. H.,
HMSO.
The International System of Units (1973). HMSO.
The Use of SI Units (1969). British Standards Institution.
Quantities, Units and Symbols (1975). The Royal Society.
A Dictionary of Scientific Units. (1964). lerrard, H. G. and McNeill,
D. B., Chapman and Hall.

Standardisation of units, with emphasis on the use of those of the SI

system, has-for some time now-been strongly promoted in the
science and technology of plastics. The SI units are, therefore, given
prominence in this section.
The SI system is based on seven so-called base units. It also contains
two supplementary units, and a number of derived units with special
names. Multiples and sub-multiples of all SI units are, of course, also
within the system.

* ISO Standard Handbook 2: 'Units of Measurement', contains the texts of all

relevant ISO standards.

A2

Quantities and Units: The Sf System: Unit Conversion Tables

1171

Named Units of the SI System

Quantity
(usual symbol(s) in
brackets)

Unit
Name

Common
Equivalent in
equivalent
base (and
Symbol
in Sl
supplementary)
units
Sl units

Length (L, I)
Mass (M, m)
Time (T, t)
Electric current (I)
Thermodynamic temperature
(e, T)
Luminous intensity (J, I)
Amount of substance
(N, n)

metre
kilogram
second
ampere

m
kg
s
A

kelvin
candela

cd

mole

mol

Supplementary
units

Plane angle (cr, {3, y, 0,

Solid angle (Q, w)

radian
steradian

Tad
sr

Derived units
with special
names

Absorbed dose (ionising

radiation)
Electric capacitance (C)
Electric conductance (G)
Electric potential,
tension (V, U)
Electric resistance (R)
Energy (E), Work (W, w),
Quantity of heat (Q, q)
Force (F)
Frequency (v, f)
illuminance (E)
Inductance (L, M)
Luminous flux (4))
Magnetic flux (4))
Magnetic flux density (B)
Power (P), Energy flux (E",)
Pressure (P), Stress (a, r)
Quantity of electricity,
Electric charge (Q, q)

gray
farad
siemens

Gy
F
S

J kg-I
Cy-l
Ay-l

m2 s- 2
s' A 2 m- 2 kg-I
S3 A 2 m- 2 kg- 1

volt
ohm

WA- 1
YA- 1

m2 kgs- 3 A- 1
m2 kgs- 3 A- 2

joule
newton
hertz
lux
henry
lumen
weber
tesla
watt
pascal

J
N
Hz
Ix

Nm

m2 kg S-2
m kgs- 2
S-I

WbA- 1

1m
Wb
T
W
Pa

Ys
Wbm- 2
J S-l
Nm- 2

coulomb

Base units

!p,

etc.)

cd srm- 2
m2 kgs- 2 A- 2
cd sr
m2 kgs- 2 A- 1
kgs- 2 A- 1
m2 kgs- 3
kg m- I S-2
As

Decimal multiples and sub-multiples of units in the SI and other

systems are denoted by adding directly (i.e. without a space or hyphen)
the appropriate prefix to the name of the unit, or the appropriate
symbol to the unit symbol. The use of multiples and sub-multiples
which are not powers of 1000 (indicated by parentheses in the list
below) is discouraged in the SI system.

1172

W. V. Titow

Multiple
Prefix
Symbol

x 1018
exa
E

x 1015
pela
P

Sub-multiple
Prefix
Symbol

x 10- 1 x 10- 2
(deci) (cenli)
d
c

1012
lera

10- 3
milli
m

109
giga
G

10- 6
micro

/.l

6
X 10
mega
M

10- 9
nano
n

x 1cP
kilo
k

x lOZ
(hecla)
h

10- 12
pica

10- 15
femlo
f

xlO
(deca)
da

10- 18
atto
a

Unit Conversions: Time

Other common units

SI unit
s
1
3155 6926 x 10'
8640 x 1Q4
3600
60
a

year
3169 x
1
2738 x
1141 x
1901 X

10- 8
10- 3
10-4
10- 6

d
(solar day)b

h
(hour)

min
(minute)

1157 X 10- 5
36524
1
4167 X 10- 2
6944 X 10- 4

2778 X 10- 4
8766 x 103
24
1
1667 X 10- 2

1667 X 10- 2
5259 x lOS
1440

60
1

Units recognised for use with the International System.

1 sidereal day = 86164090 6 seconds; 1 year = 36625 sidereal days.

Unit Conversions: Electric Current

Only the SI unit (ampere) or its multiples or sub-multiples in use.
Unit Conversions: Luminous Intensity
Only the SI unit (candela) or its multiples or sub-multiples in common
use.
Unit Conversions: Amount of Substance
Only the SI unit (mole) now in common use (mainly in calculations in
chemistry and physics).
The mole is the amount of substance of a system which contains as
many elementary entities as there are atoms in exactly 0-012 kg of 12c.
The entities (which must be specified in each particular case) may be
atoms, ions, molecules, electrons, or groups of such units.

1000
10
1
1 X 10- 3
1 X 10- 7
9144
3048
254

100
1
01
1 X 10- 4
1 X 10- 8
9144
3048
254

1
001
1 X 10- 3
1 X 10- 6
1 X 10- 10
09144
0304 8
00254
254
X

10

1 X 106
1 X 104
1 X 103
1
1 X 10- 4

jimQ

1X
1X
1X
1X

1010
108
107
104
1

(angstrom)

QThe name 'micron' for this unit (micrometre) is discouraged.

mm

cm

Sf units

Unit Conversions: Length

328084
0032808
32808 X 10- 3
3
1
0083333

1
0333333
0027778

ft
(foot)

1093610
0010 936
1093 6 X 10- 3

yd
(yard)

Other common units

36
12
1

393701
0393701
0039370

in
(inch)

?3

-.I

........
'"

if

c::r-

;:;'J

;:l

'"5't::l

-<:

;:l

~.

~
too>

'"

;;l

~.

~:

K:l

1
1 X lO-4
1 X lO-6
08361
009290
6452 X lO-4

mm
1 X 1()6
100
1
8 361 27 X lOS
92903 X 10'
645-16

1 X 10"
1
001
8361 X 10'
929
64516

cm 2

SI units

Unit Conversions: Area

1196
1196xlO- 4
1196 X 10- 6
1
01111
7716 X 10- 4

yd

10764
1076 X 10- 3
1076 X 10- 5
9
1
6944 X lO-3

it>

Other common units

1550 X lO3
01550
1550 X lO-3
1296 X 10'
144
1

in 2

:0::::

......
......

cm3
UK gal
(UK gallon)
2200
2-2 X 10- 4
22 X 10-7
1
08327
0-2200
6-229
3605 X 10- 3

mm 3

1 X 109
1 X 103
1
4-546 X 106
3-785 X 106
1 X 106
2-832 X 107
16387 x 104

Unit recognised for use with the International System.

1 x 106
1
6
1 X 101
1 X 10-3
1 x 10- 9
4546 X 10-3 4-546 X 103
3-785 x 10-3 3-785 X 103
1 x 10- 3
1 X 103
0-02832
2832 x 104
1-6387 x 10- 5
16-39

m3

Sf units

Unit Conversions: Volume

264-2
2-642 X 10- 4
2642 X 10-7
1201
1
0264 2
7-4805
4329 X 10- 3

US gal
(US gallon)
1 x 103
1 X 10- 3
1 X 10- 6
4-546
3785
1
2832
001639

(litre)a

fr3

35-32
3-532 X 10-5
3532 X 10- 8
0-1605
01337
0-03532
1
5787 x 10- 4

Other common units

6-1024 x 104
0061024
61024 x 10- 5
2774
2310
61024
1728 x 103
1

-.l
V1

........

1r

<::>-

o
;:s

~
;,..

""

'"~

~.

in 3

S
S.
:::to

to

343775 x 1cP
60
1
00166667
54
54 X 103

572958
1
00166667
277778 x 10- 4
09
90

1
00174533
2908 88 x 10- 4
484814 X 10- 6
00157080
157080

206265 x
36 X
60
1
3240 x
3240 X

10
105

10
103

"
(secondt

Other units
g

636620
111111
00185185
308642 x 10- 4
1
100

(grade)

Units recognised for use with the International System.

The degree and the second may be subdivided decimally, e.g. 57.2958 = 5717'44.8".

(minuteY

(degree)ab

rad
(radian)

S1 unit

Unit Conversions: Plane Angle

0636620
0011111
1851 85 x 10- 4
308642 x 10- 6
001
1

(right angle)

:-=:::

a-

--.I

--

123457 x 10- 4
1

1
081

The solid angle of a sphere (=4n).

4052 85 x 10

328281 x 1<>3

0079577 5
1

1
125664
3046 17 x 10- 4
246740 x 10- 4

(square grade)

OK

00
(square degree)

sp
(spat)a

Other units

sr
(steradian)

SI unit

Unit Conversions: Solid Angle

-J
-J

--

ff

0-

;:

0"

'"C::l"

;:

~
::::

'"

;:J

S.
~

l:l

s:~

10

~
N

1 x lQ3
1
1 X 106

1
1 x 10- 3
1 x 103
101605 x 103
907185
508023
0453592
0028350

f'

1 x 10- 3
1 X 106
1
101605
0907185
005080
45359 x 10- 4

(tonne)
1102 3 x 10- 3
1102310
112
1
0056
500 X 10-4

0984207
1
0892857
005
44643 x 10- 4

US tone

9842 1 x 10- 4

UK ton b

196841
20
178571
1
89286 x 10- 3

0019684

cwt
(hundredweight)

Other common units

lb

220462
220462 x 10- 3
220462 x 103
224 x 103
2 x 103
112
1
00625

(pound)

352740
0035274
352739 x 104
3584 X 104
32 X 104
1792 x 103
16
1

oz
(ounce)

Also known as 'metric ton' or 'metric tonne'. Unit recognised for use with the International System. 1 t = 1 Mg (which is an SI unit).
The 'long' ton.
e The 'short' ton.

508023 x 10
453592
283495

g
(gram)

kg

Sf units

Unit Conversions: Mass

:::1

-..l
00

.....
.....

A2 Quantities and Units: The Sf System: Unit Conversion Tables

1179

Unit Conversions: Density

51 units

Other common units

kgm- 3

gcm- 3

kgl- 1

Ibin- 3

Ibft- 3

lb UKgal- 1

1
1 X 1<P
1 X J(}l
276799 X lO'
160185
99776

1 X 10- 3
1
1
27-6799
00160185
0099776

I X 10- 3
I
I
276799
00160185
0099776

36127 X 10- 5
0036127
0036127
I
57870 X 10-'
3-604 6 X 10- 3

0062428
62-4280
62-4280
1728XI<P
I
622884

0010022
100224
100224
277-419
0160544
I

Unit Conversions: Mass Flux

SI unit

Other common units

1
2777 6 x 10- 4
0,16666
13561 x 10- 3

3600

60000
488243

16666 x 10- 3
1
81370 x 10-3

73734
020481
12289
1

Unit Conversions: Force

51 unit

Other common units

kg!
(kilogram-force)"

dyn
(dyne)

UK tonf
(UK ton-force)

lbf
(pound-force)

pdl
(poundal)

I
9807
I x 10- 5
9964 x I<P
4448
01383

01020
I
1-02 X 10- 6
1016 x 1<P
04536
00141

I X lOS

1004 X 10-'
9842 x 10-'

02248
22046
2248 X 10- 6
2240 x I<P
I
00311

7233
7093
7233 X 10- 5
7207 x 10'
32174
I

Called 'kilopond' (kp) in Germany.

1
4464 x 10-'
1390 x 10- 5

bar

1 X 10- 5
1013
1
09807
006895
2-491 X 10- 3
1333 X 10- 3
1 X 10- 6

atm
(standard
atmosphere)b

9869 x 10- 6
1
09869
096708
006805
2458 X 10- 3
1316 X 10- 3
9869 X 10- 7

1 Pa

1450 X 10- 4
1470
1450
1422
1
003613
001934
1450 X 10- 5

clbfin- z

Other common units

foo atm.

1020 X 10- 5
1033b
1020
1
007031
2540 X 10- 3
1360 X 10- 3
1020 X 10- 6

kgfcm- z

= 1 N m- z ; 1 MPa = 1 MN m- z = 1 N mm- z .
1 atm = 1033228 technical atmosphere (at); 1 at = 1 kgf cm- z.
C Often denoted by 'psi'.
dOften referred to as 'inches water gauge' (in w.g.).
C 1 mm Hg = 1 torr (to within one part in seven million); 1 torr =

1013 X 105
1 X 105
9807 X 104
6895 X 103
2491
1333
0100

PaO

SI unit

Unit Conversions: Pressure, Stress

4015 X 10- 3
4068
4015
3937
2768
1
05352
4015 X 10- 4

in HZO d
(inches of
water)

7501 X 10- 3
760
7501
7356
5171
1868
1
7501 X 10- 4

mmHgC
(millimetres
of mercury)

10
1013 x
1x
9807 x
6895 x
2-491 x
1333 X
1

106
106
105
104
103
103

dyn cm- z

~
:0:::

10-7

2724 X 10- 6
1163 X 10- 6
29307
2931 x 10- 4
3766 X 10-7

2778

kWh
(kilowatt
hour)
01020
3671 x 105
1
04270
10759 x 107
10759
01383

kgfm

02388
85985 x 105
23420
1
25200 x 107
25200
03238

cal
(calorieY

1 X 10- 5
1285 X 10- 8

9478
003412
9294 x 10- 8
3968 X 10- 8

X 10- 9

therm

Other common units

1285

X 10- 3

9478 X 1034121 X 103

9294 X 10- 3
3968 X 10- 3
1 X 105

Btu
(British
thermal unity

07376
26552 x 106
72330
30880
77817 x 107
77817
1

ftlbf

The
The
The
The
The

4C calorie, cal4 == 42045 J.

I5C calorie, calIS == 41855 J.
mean (0-100C) calorie, cal (mean) == 41897 J.
thermochemical calorie, cal (thermochem) == 41840 J.
mean (32-2I2P) Btu, Btu (mean) == 105579 J.

In this table these units have their International Table values, now in general use (1 cal == 41868 J; 1 Btu == 105506 J.
These values are always implied when the unit is written without a specifying subscript (i.e. simply 'cal' or 'Btu') but the
notation 'cain' and 'BtuIT' is still sometimes employed. Other values occasionally used are:

1
3600 X 106
98066
41868
1055 06 x 108
1055 06 x 103
13558

SI unit

Unit Conversions: Energy, Work, Heat

--

:-:l

"
~
~.

'

'"

'"
~

~.

'

;:0

s:

lC

::t>.

""

W. V. Titow

1182

Unit Conversions: Power

Sf unit

W
1
7355
9807
4187
7457
029307

Other common units

metric
horsepower'

kgfms- I

cal S-I

hpb
(horsepower)

Btuh- 1

x 10- 3

010197
7500
1
04268
7604
002988

02388
1757
2343
1
1781
006999

1341 x 10- 3
098632
001315
5613 x 10- 3
1
3929 x 10- 4

34128
2510 x 103
33-47
1429
2545 x 1Q3
1

1360

1
0013 33
5692 x 10- 3
10139
3984 x 10- 4

No symbol for this unit in English-speaking countries (in France ch or CV; in Germany
PS). Unit now regarded as obsolescent.
b Unit traditionally used in the UK and USA. Now regarded as obsolescent.

Unit Conversions: Frequency-Units in Common Use

Quantity

Sf unit

hertz (Hz)
reciprocal second (s-I)

Periodic frequency
Rotational frequency
(i.e. number of rotations
in unit time)
Angular frequency

Other units
cycle per second (c s-I)a
revolutions per second;
minute, etc. (i.e. r S-I,
rOlin-I; etc.)b

reciprocal second (s-I)

Equivalent to Hz but discouraged (both equivalent to S-I).

bThe notation 'rev' for 'revolution' (as in rev/min) is now discouraged.

Unit Conversions: Temperature

As a unit of temperature (temperature interval) I K a = IOC = lgoR

= lgoP
equivalent
to
A
temperature
reading of

(kelvin)

(degrees
Celsius)

OR
(degrees
Rankine)

yKa
xOC
uOR
zOF

y
x + 27315
ul18

y - 27315
x
(ul1'8) - 27315
(z - 32)/1'8

l'8y
l'8(x + 27315)
u
z + 45967

is

Ka

(z + 45967)/18

o~

The SI unit of temperature.

b Unit recognised for use with the International System.

of

(degrees
Fahrenheit)

18y-45967
18x + 32

u - 45967
z

2388 X 10-3
02388
1
2778 x 10- 3
4134 x 10- 3
3445 X 10- 4

1 X 10- 2
1
4187
001163
001731
1442 x 10- 3

1
08598
8598
3600
1
1488
01240

kcal h- 1 m- 1 K- 1

Other common units

05778
5778
2419
06720
1
008333

aBtu h- 1 [t- 1 F- 1

6933
6933
2903 x 103
8064
1200
1

Btu in h- 1 [t- 2 F- 1

Where they form part of the units in this table, the calorie and Btu have their international table values (see the Energy
Unit Conversion Table).

100
4187
1163
1731
01442

acal S-l cm- 1 K- 1

Wcm- 1 K- 1

Wm- 1 K- 1

51 unit

Unit Conversions: Thermal Conductivity

00

.....

......
......

~
~

;;l

'

.~

~
[

~
to>

'"
:::z

~.

s::...

I:>

::>.
::>.

lC

tv

W. V. Titow

1184

Unit Conversions: Thermal Resistivity

This is the reciprocal of thermal conductivity, and the unit conversions
can be found by using the reciprocals of the appropriate units and
values in the thermal conductivity table, e.g. for the thermal
conductivity of 1W m- 1 K- 1 the corresponding thermal resistivity is
1 K m W- 1 == 1I6933Fft2 h in- 1 Btu- 1

= 014423 of ft2 h in- 1 Btu- 1

Unit Conversions: Thermal Conductance (Heat Transfer Coefficient)
Sf unit

Other common units

085984
1
36001 x 104
488240

1-16301
41868 x 104
567827

238846 x 10- 5
2 7777 x 10- 5

017611
0204 81
7372 9 x 103
1

13562 x 10- 4

a Where they form part of the units in this table, the calorie and Btu have their
international table values (see the Energy Unit Conversion Table).

Unit Conversions: Thermal Resistance

This is the reciprocal of thermal conductance, and the unit conversions
can be found by using the reciprocals of the appropriate units and
values in the thermal conductance table; e.g. for the thermal
conductance of 1 W m- 2 K- 1 the corresponding thermal resistance is
1 K m 2 W- 1 == 11017611 OF ft2 h Btu- 1

= 5678 2rF ft2 h Btu- 1

Unit Conversions: Viscosity
Kinematic viscosity

Dynamic viscosity
Sf unit

01
1 x 10- 3

Other common units

Sf unit

pa
(poise)

cP

m 2 s- 1

(centipoise)

10
1
001

1 X 103
100
1

1
1 X 10- 4
1 X 10- 6

Other common units

(stokes)

sf>

cSt
(centistokes)

1 X 104
1
001

1 X 106
100
1

APPENDIX 3

Some Material Properties of pvc Products

and Compounds
Compiled by W. V.

TITOW

Nm- 2 (=Pa);
lbf in- 2 (psi);
kgf cm- 2 ;
For fibres: g per
denier, or g per
tex

Maximum stress which the

material will withstand before failure (yield or break)
NB Comments on common
types of failure in
strength tests are given
in BS 4618: Section
1.3: 1975

Tensile
strength

arb

kgm- 3
gcm- 3
Ibin- 3
lb ft- 3

Common
units

Mass of a unit volume. For

practical purposes numerically equal to relative density (also sometimes called
specific gravity), which is
the ratio of the density of a
material to that of water at
the same temperature.

Brief definition

Density
p

Property arid
usual symbol

M; S: 130145 g cm- 3
M(G): approx
15gcm- 3
F: approx 14
gcm- 3
PVC homopolymer: 14
gcm- 3

Rigid PVC

M: 110-135 g
cm- 3

Flexible PVC

Typical values or value ranges

for pVC'

M: 31-60 MPa M (and other compounds): 10-25

(BS 2782 or
BS 2782: Part 3:
ASTM D 638)"
MPa
Methods 320 A to F: 1976
M(G): approx
(BS 2782)
Methods 326 A to C: 1977 (for 110 MPa
S: 15-21 MPa
films);
(ASTM D
(ASTMD 882)
ASTM D 638-82;
638)
ASTM D 759-66 (1976) (at low S: 38-45 MPa
and elevated temperatures); F: 27-30 g per
ASTM D 882-81 (for thin sheet
denier
and films);
( = 330-370
ASTM D 1708-79 (microtensile
MPa approx)
specimens) ;
DIN 53 455-1981

ISO/R 527-1966;
ISO/R 1184-1970 (for films);

BS 2782: Part 6:
Methods 620A-D: 1980;
BS 4618: Section 5.1: 1970;
ASTM D 792-66 (1979)
(Displacement method);
ASTM D 1505-68 (1979)
(Density gradient tube);
DIN 53479-1976

ISO/R 1183-1970;

Some standards relevant to

determination in plastics

ISO 6383-1983;
BS 1763: 1975 (thin sheeting:
Elmendorf test);
BS 2739: 1975 (thick sheeting);
BS 2782: Part 3: Method 36OB:
1980 (trouser-tear test);

Very low values

for normally
plasticised PVC
materials

M: 62-100
MPa
(ASTMD
790)
M(G): approx
138MPa
(ASTMD
790)

S: 20-100 N mm- 1

M: 150-400%
S: 120-250%

M: 2-40%
M(G): 1-2%
S: 5-35%
F: 10-20%

b.d

(continued)

M = mouldings; M(G) = mouldings with 25% glass fibre; S = sheeting and/or film; F = fibre.
Symbol not in wide general use.
c Specification numbers in brackets after numerical property values indicate the source of standard test(s) by which the values were
obtained, not that the values are numerical requirements laid down in the particular specification(s).

N; kgf; lbf;
or
g; oz; lb;
or
Nmm-\ kgf
mm- 1

Force or load (stated directly or per unit specimen

thickness) required to initiate tearing orland propagate
a tear in specified test
conditions.

Tear resistance (tear

strength) of
sheeting and
film

OF

ISO 178-1975;
BS 2782: Part 3:
Method 335A: 1978;
ASTM D 790-81;
DIN 53452-1977

Maximum stress in the outer As for tensile

strength
fibre of a specimen at the
moment of break in bending
(in specified conditions).
NB Flexural strength at
yield is the analogous
stress at yield (calculated from a formula
appropriate to the test
method).

As for tensile strength (measured in the same tests)

Flexural
strength

Normally % of
the original
length; occasionally units of
length

The increase in ~he length of

a test specimen caused by
the tensile stress at the
moment of rupture (or
yield)

Elongation at
break (or
yield)
eTd

Impact
resistance
(Impact
strength)

Tear resistance
(contd)

Property and
usual symbol

Energy required to break a

standard test piece by impact in a standard test.
NB A useful outline of
impact behaviour of
plastics is given in BS
4618: Section 1.2: 1972
(with special reference
to design data)

Brief definition

Nm (=J);
kgfcm;
lbfft;
per unit length of
notch (for notched specimens) or
per unit area of
the cross-section
of the unnotched
part, or (for unnotched specimens) per unit
specimen width
or crosssectional area.

Common
units

ISO 179-1982 (Charpy test);

ISO 180-1982 (Izod test);
BS 2782: 1970: Method 306A
(Izod test);
BS 2782: Part 3: Method 351A:
1977 (Charpy test);
BS 2782: 1970: Methods 306B
and C (falling weight test);
ASTM D 256-81
Methods A and C (Izod
test);!
Method B (Charpy test);
ASTM D 1822-79 (tensile
impact);
ASTM D 3029-78 (falling
weight test);
DIN 53 443-1975 (falling weight
test);

ASTM D 1004-66 (1981);

ASTM D 1922-67 (1978)
(Elmendorf test);
ASTM D 1938-67 (1978);
ASTM D 2582-67 (1978) (snag
resistance) ;
DIN 53363-1979

Some standards relevant to

determination in plastics

Flexible PVC

M: 05-25 lbf
With small
ft in- I
amounts of plasticiser impact
(ASTMD
strength can be
256)
M(G): approx
very low 05
llbfft in- I lbfft in-I) the
embrittlement
(ASTMD
256)
being caused by
the so-called
'antiplasticisation'
effect. Very high
at normal plasticiser contents

Rigid PVC

Typical values or value ranges

for PVC'

:::'l
0

:0:::

00
00

Ability of material to resist

indentation under rigidly
specified conditions (including particular, specified
combinations of indentor
and stress).
NB Determination of hardness by scratch resistance is not relevant to
PVC.
Completely arbitrary, related to
arbitrary hardness scales used
in particular test
methods (e.g.
Shore, Rockwell, Barcol specified scale
units).
ISO 868-1978 (Durometer
hardness);
ISO 2039-1973 (Ball indentation);
ISO 2039/2-1981 (Rockwell
hardness);
BS 2782
Method 365A: 1976 (BS softness numberS);
Method 365D: 1978 (ball indentation hardness);
Method 1001: 1977 (Barcol
hardness h ) ;
BS 2719: 1975 (pocket-type
meters: Shore Durometer);
ASTM D 785-65 (1981) (Rockwell hardness);
ASTM D 2240-81 (Durometer
hardness);
ASTM D 2583-81 (Barcol hardnessh );
DIN 53456-1973 (Ball indentation hardness);
DIN 53 505-1973 (Durometer
hardness)

ASTM test essentially similar to ISO 180, but differs (in root radius of notch) from that of BS 2782.
Applicable mainly to pPVc.
Relevant to glass-reinforced plastics.

Hardness

DIN 53448-1977 (tensile impact)

DIN 53453-1975 (Charpy test)
M (and other
compounds):
Durometer
(Shore D
scale):
65-85
Rockwell
(R scale):
110-120
Ball Indentation
(DIN 53
456): 75155

(continued)

M (and other
compounds):
BS softness No.
15-90
Durometer
(Shore A
scale): 50-95
Rockwell (R
scale) 5-80

t;-

~c

I::l

"tl

.s;,

~
::to
~

.g

~
E:.:

I::l

v,

)..
...,

As for tensile (or

shear) strength

As for tensile (or

flexural) strength

'Modulus of rigidity'. Ratio

of shear stress to shear
strain in reversible conditions.
NB In practice usually determined by torsional
methods

Ratio of stress to corresponding strain in bending,

in reversible conditions

(b) in shear
G

(c) in flexure
EB

Common
units

As for tensile
strength

Brief definition

Ratio of tensile stress to

tensile strain in reversible
conditions.
NB Secant modulus: The
ratio of stress to corresponding strain at any
given point on the
stress-strain curve

Elastic
moduli:
(a) in tension;
E

Property and
usual symbol

ISO 178-1975;
ISOITR 4137-1978 (Alternating
flexure method);
BS 2782: Part 3:
Method 332A: 1976 (stiffness
of film);
Method 335A: 1978;
ASTM D 790-81;
DIN 53457-1968

ISO 537-1980 (Torsion pendulum method);

ASTM D 1043-72 (1981);
ASTM D 2236-81 (Torsion
pendulum method);
DIN 53447-1981 (Torsion
pulley method)

ISO/R 527-1966;
BS 2782: Part 3: Methods 320A
to F: 1976;
ASTM D 638-82;
ASTM D 882-81 (for thin sheet
and films);
DIN 53457-1968

Some standards relevant to

determination in plastics
Flexible PVC

Very low at norM: 20-35

GPa
mal plasticiser
(ASTMD
contents
790)
M(G): approx
85 GPa
(ASTMD
790)
S: 20-30 GPa

Very low at norM (and other

commal plasticiser
pounds):
contents
10-18 GPa

Very low at norM (and other

commal plasticiser
pounds):
contents
25-35 GPa
(ISO, BS,
ASTMor
DIN
methods)

Rigid PVC

Typical values or value ranges

for pVC'

:::l
S

>-'
>-'

:g

Also known as Young's modulus, elastic modulus, or modulus of elasticity.

(ASTMC 177)

Wm-1K- 1

;:

it

l:>

<">
1;;

(continued)

f}

;:s

(ASTM C 177) ]

Wm- 1 K- 1

M (and other
compounds):
014-017

M (and other
compounds):
014-028

BS 874: 1973 (1980);

BS 4618: Section 3.3: 1973;
ASTM C 177-76;
DIN 52612-1979

See relevant conversion table in

Appendix 2

The quantity of heat which

passes in unit time through
unit area of a slab of
uniform material of infinite
extent and unit thickness,
when unit difference of
temperature is established
between its parallel faces

Thermal conductivity

k;)"

M (and other
~
compounds): ~
General-purpose It
plasticised com- ~
pound typically ~
about 40, but
i:!-.
the range is wide ~
(ASTM D 1525 .Q.,
does not recom- ~
mend the test for ~
pPVC for that
~
reason)
~
M (and other
compounds):
65-100C
(ISO 306:5
kg load)

ISO 306-1974;
BS 2782 : Part 1: Methods 120A
to E: 1976;
ASTM D 1525-76;
DIN 53460-1976

Vicat softening point

"'"

:t.

Cor OF

Low at
normal
plasticiser
contents

The temperature at which a

flat-ended needle of specified dimensions penetrates
a specimen to a prescribed
depth under a prescribed
load (usually 1 kg or 5 kg),
in standard test conditions

M: 22-35
GPa
(ASTMD
695)

ISO 604-1973;
ASTM D 695-80;
DIN 53457-1968

As for tensile (or

compressive)
strength

'Bulk modulus'. Ratio of

change in external pressure
to fractional change in
volume, in reversible conditions

(d) in compression
K

(BS 2782:
Method
335A)

BS 4618: Section 3.1: 1970;

ASTM D 696-79

K- 1 ; 0C- 1 ; F- t

C; of

Change in length per unit

original (reference) length
per degree temperature
change; i.e.
a= 6.LI(L o . 6.T)

The temperature at which,

in specified test conditions,
a test specimen (bar of
prescribed dimensions)
undergoes a specified deflection under a flexural load
causing a maximum fibre
stress in the specimen of
either 182 MPa (2541bf
in -Z) or 0455 MPa (66lbf
in- Z)

Percentage deformation of a
sheet specimen of prescribed dimensions by a
specified load at 70C,
under stated test conditions

Coefficient of
linear thermal
expansion

Deflection
temperature
under load

Deformation
under heat of
flexible PVC
compounds k

BS 2782 :Part 1: Method

122A:1976

ISO 75-1974;
BS 2782: Methods 121A and
B: 1976;
ASTM D 648-72 (1978);
DIN 53461-1969

Some standards relevant to

determination in plastics

Common
units

Brief definition

Property and
usual symbol

Very low at normal plasticiser

contents (pPVC
not normally
tested for this
property)

M (and other
compounds) :
15-65%
(BS 2782)

M (and other
compounds) :
10 x 10- 5_
25 x
10- 5 K- 1
(ASTMD 696)

Flexible PVC

M (and other
compounds):
6O-80Ci
(ISO, BS,
ASTMor
DIN)
M(G): 7085Ci
(ISO, BS,
ASTMor
DIN)

M (and other
compounds):
5 x 10- 5_
15 x 10- 5
K- 1
(ASTMD
696)
M(G): 27 x
10- 5
(ASTMD
696)

Rigid PVC

Typical values or value ranges

for pvc'

'l:

:::'l
S

:<::;

to.>

'0

......
......

Ratio of the capacitance

(Cx ) of a given configuration
of electrodes with the particular material as the
dielectric, to the capacitance
(C v ) of the same electrode
configuration with vacuum
(or air) as dielectric; Le.
k' = C)Cv

The ratio of true power

dissipated to the apparent
power absorbed during the
passage of an alternating
current through a dielectric

Permittivity'"
(dielectric
constant)
k'; '

Loss tangentn
(dissipation
factorO)
tan 0
None
(a ratio)

None
(a ratio)

J g-IK- 1 ;
Ical g-l 0C-\
IBtu Ib- 1 F- 1

BS 2782: 1970: Method 207A;

BS 4618: Section 2.2: 1970;
ASTM D 150-81;
DIN 53 483-1969, 1970

BS 2782: 1970: Method 207A;

BS 4618: Section 2.1 : 1970;
ASTM D 150-81;
DIN 53 483-1969, 1970;
(NB ISO 1325-1973 PlasticsDetermination of electrical properties of thin sheet
and film)

BS 4618: Section 3.2: 1973;

ASTM C 351-61 (1973)

M (and other
compounds):
45-85 at 50
Hz
35-45 at
1 MHz
(ASTMor
DIN)

M (and other
compounds):
1.0--2.0 J g-l
K- 1

~.

~
~
::t
'"

..,<;;

'"

~
3

.....
.....
\D

.,

~o

M (and other
M (and other
-s;,
comcompounds) : ."
pounds):
0OS-O15 at ~
60Hz
0007-0017
004-014 at ~
at 60Hz
0006-0019
1 MHz
at 1 MHz
(ASTM D 150)
.,."
(ASTMD
150)
~

M (and other
compounds):
33-36 at
50Hz
29-31 at
1 MHz
(ASTM or
DIN)

M (and other
compounds):
0S-O9 J
g-l K-1

At 254Ibfin- 2 .
k The temperature of heat distortion (extension or shrinkage), under tensile load, of 00025-15 mm thick, relatively stiff plastics
sheeting (room-temperature elastic modulus >69 MPa) may be determined by the method of ASTM D 1637-61 (reapproved 1976).
I Numerically identical.
m Strictly, relative permittivity (see, e.g. BS 4618 or ASTM D 150).
n Term favoured in the UK.
o Term favoured in the USA and Europe.
(continued)

Amount of heat required to

raise the temperature of a
unit mass of material by one
degree (within a specified
temperature range)

Specific heat
c

Resistivity
p;s

Property and
usual symbol

BS 4618: Section 2.3: 1975;

BS 2782: 1970: Methods 202A
andB;
ASTM D 257-78;
DIN 53482-1967

BS 4618: Section 2.4: 1975;

BS 2782: 1970: Method 203A;
ASTM D 257-78;
DIN 53482-1967

Qm
Qcm

Volume resistivity: The electrical resistance between

opposite faces of a unit-side
cube of the material.
NB May also be defined in
terms of potential gradient and current density (see, e.g. ASTM D
257 or BS 4618 Section
2.3)

Surface resistivity: The resistance between surfacemounted electrodes of unit

width, at unit spacing.
NB May also be defined in
terms of potential gradient and current per
unit width of surface
(see, e.g. ASTM D 257
or BS 4618 Section 2.4)

Some standards relevant to

determination in plastics

Common
units

Brief definition

M (and other
compounds) :
1012_10 15 Q
cm at 60%
RH; room
temperature
(ASTM;DIN)

Flexible PVC

M (and other
M (and other
comcompounds):
1011_10 12 Q
pounds):
1013_10 14 Q
at 60% RH;
at 60%
room
RH;
temperature
room
(DIN)
temperature
(DIN)

room
temperature
(ASTM;
DIN)

RH',

M (and other
compounds):
About
1016 Qcm
or higher
at 60%

Rigid PVC

Typical values or value ranges

for PVC"

is

:::;j

:-:::

.j:o.

\0

--

The amount of water

absorbed by a standard
specimen in prescribed test
conditions

Water absorption
g; mg; mass %
(volume % for
cellular plastics)

Vm- I ; Vcm-I;
Vmm- I ; V mil-I
(1 mil = 0001 in)

(continued)

M (and other
M (and other
compounds) :
compounds):
3O-150mg
(48 h)
8-50mg
(BS 2782:
(48 h)
Method
(BS 2782:
502e)
Method
015-10%'
502e)
007-040%' (ASTMD 57024h
(ASTMD57024 h
specimen
0125 in
specimen
thick)
0125 in
thick)

ISO 62-198()"q (cold water

absorption; boiling water
absorption) ;
BS 2782: 1970
Method 502C (absorption by
PVC compounds)
Methods 502F and G P
Methods 503B and C q
ASTM D 570-81;p,q
ASTM D 2842-69 (1975) (for
cellular plastics);
DIN 53471-1976;q
DIN 53473-1979 (absorption
from humid atmosphere);
DIN 53 495-1973P

M (and other
compounds:
25D-400V
mil-I
(ASTMSpecimen
125 mil thick)

M (and other
compounds):
400-500 V
mil-I
(ASTMSpecimen
125 mil
thick)

BS 2782: 1970: Methods 201;

ASTM D 149-81;
DIN 53 481-1974

Methods closely similar technically (cold water absorption).

q Methods closely similar (absorption on immersion in boiling water).
, Highest absorption is exhibited by some filled compounds.

Field strength (ratio of applied voltage to thickness)

required to produce breakdown of the material under
specified test conditions

Dielectric
strength

......
......

\0
VI

1}

l::
;>

~o

!i

f2

.s;,

'"
i;.

.g

~
.:

.......

)..

Fo

required to initiate sliding;

= minimum force required
to maintain it (at a particular
speed); and L = the force
(usually gravitational) acting
normally to the surfaces to
maintain their contact

/is

= FsIL
Ilo = FoIL
where Fs = the minimum force

BS 2782: 1970: Method 311A;

BS 4618: Section 5.6: 1975;
ASTM D 1894-78 (/is and Ilo of
plastics film and sheeting);
ASTM D 3028-72 (1978) (Ilo of
plastics solids and
sheeting)

None
(a ratio)

The two coefficients of friction,

static' (/is) and dynamic' (Ilo)
are defined by the expressions:

Coefficients of
friction

Il

ASTM D 1044-78 (Taber

abraser);
ASTM D 1242-56 (1981);
ASTM D 673-70 (1982) (Mar
resistance) ;
DItol,53 754-1977

No conventional units.
Measured in
terms of mass
loss by the
specimen, or
visual effects,
e.g. marring
of surface,
loss of transparency.

Some standards relevant to

determination in plastics

Common
units

Resistance to surface damage

or wear caused by rubbing by
prescribed abrasives in strictly
specified conditions.
NB Abrasion resistance (adhesion) of print on thin PVC
sheeting prescribed in BS
1763: 1975 (measured
according to BS 2782 :
1970: Method 310B)

Brief definition

Abrasion
resistance

Property and
usual symbol

Flexible PVC

:::J
<s
The values of friction coefficients
of PVC depend cardinally on the
formulation, and generally decrease with increasing rigidity
M (and other
M (and other
comcompounds);
pounds);
also S: about
also S:
02-20
normally
<02

Abrasion resistance of PVC materials and products varies widely

depending, inter alia, on formulation and test conditions. As an
example, loss by calendered
sheeting in a version of the Taber
test may be 10-80 mg per 1000
~
cycles under a 1 kg load (with a
:0:::
CS-10 wheel).

Rigid PVC

Typical values or value ranges

for pVC'

Ratio of the velocity of light in

particular material

vacuo to the velocity in the

None
(a ratio)

Also known as the starting coefficient of friction.

Also known as the kinetic or sliding coefficient of friction.

/-l;n

Refractive
index
ISO/R 489-1966;
BS 4618: Section 5.3: 1972;
ASTM D 542-50 (1977);
DIN 53 491-1955
PVC resin:
approx
155
M: 152-155

!:;-

;:s

s::

~o

f2-

."

.g
~.

The refractive index is often lowered by plasticisation, but the

effect (like com- ~
pound clarity)
v...
depends on the ~
plasticiser (and 3
the formulation '"
~
generally) .

INDEX 1

General

Acrylic
impact modifiers, 99,107,391,395,
396,482,887
lacquers, 1008-9, 1061
light-protective coatings, 482
processing aids, 98, 108, 372-5,
395,396,795
thickeners for PVC latices, 1021,
1023, 1025, 1027
Acrylonitrile butadiene styrene
(ABS) copolymers
blends with PVC, 99, 393,395
impact modifiers, as, 99,113,114,
390,391,393-5,482
processing aids, as, 373
sheet laminates with PVC, 745
Activators ('kickers'), see under
Blowing agents
Adhesion
promoters for PVC coatings, 62,
174, 1007-8, 1119
solution-deposited copolymer films,
of, 1047, 1049-51, 1061,
1063-5
Adhesive bonding of PVC, see under
Bonding of PVC
Ageing of pastes, 943-5, 963,964,
966
AGS acid ester plasticisers (see also
under Aliphatic diester piasticisers), 149, 165, 166,976,
977

Alcohols for plasticiser production,

156
Aliphatic diester plasticisers, 163-6
adipates, possible health hazard,
211
PVC compounds, performance in,
166
Alumina trihydrate
effects in PVC, on
electrical properties, 248
hardness, 248
tensile properties, 247
Vicat softening point, 248
flame and smoke retardant, as, 215,
247,248,431,433
properties of, 222-3
Anti-blocking (see also Blocking)
agents, 251
techniques, 1039
Antimony stabilisers, 275-7, 348
calcium stearate, synergism with,
276,286
organotin, comparison with, 277
Antimony trioxide, 215, 247,429,
430,432
Antioxidants, 255, 292-4
Antiplasticisation, 142-3, 849-50,
1188
'Antique finish' ('Antiqueing'), 1001,
1009
Antistatic agents, 83, 419-25
nature and use, 422-5

1199

1200

Index I General

Antistatic agents-contd.
thermal stability, effect on, 106,
260,423-4
A p / Po ratio (of plasticisers), 130-1,
140-1
physical properties of PVC, effect
on, 140-1
Asbestos
filler, as, 216, 217, 242, 243
surface treatments for, 242
flooring, in, 109-10, 217, 233
hazards of, 242
heat stability of PVC, effect on,
217
properties, 243
sheet reinforced with, 217, 903,
908-9
.
thixotropic additive, as, 242
AZDN,1090-1
Azobisformamide (ABFA), see Azodicarbonamide
Azodicarbonamide (ADA), 108(r90
Baby pants, 1122
Barium
stabilisers, 91, 109, 113--15,275,
280,303-4,338,341,345,
347-54,356
sulphate, 219-20, 222-3, 282-3, 285
Barrier properties of
blown bottles, 458, 462-3, 798-800
PVC compositions, see Permeability
shrink-wrap PVC films, 895
Barytes, 219, 222
Battery separators
passim, 1069
polymer for, 854
production, 1078, 1079
property tests, 1100, 1101
PVC's competitor materials, 1118
Biaxial stretching effects on
impact resistance, 19, 27, 761,
774-5, 794
permeability, 19,29,464,774-5
'Bingham body' behaviour, 947-8,
951,996

Biodegradation, see Microbiological

attack
Blanc fixe, 220, 222
Bleeding (colourants), 404
Blends of PVC with
ABS polymers, 375, 393--5
nitrile rubber, 397-401, 1118
other polymers, 21, 24
polyurethane, 170, 197,401
SAN polymers, 374
styrene/maleic anhydride copolymers, 24
Blocking
definition, 1039
determination of, 1039, 1045, 1149
films and coatings, 1039
standard tests, 1039, 1045, 1149
Blooming
colourants, of, 404
surface tack reduction by, 1039
Blow moulding
basic elements, 764
blowing arrangements in, 778-80
bottom-blow, 779
dip (displacement) process, 764,
766, 773-4, 778, 780, 789
equipment and process arrangements, 775-80
extrusion process, 764, 76(r72, 788
equipment, 784-7, 789
methods, 775-7
parison control in, 769, 771-2
waste trimming in, 780-1
formulation aspects, 112-13, 793--7
general principle, 763
historical development, 763-4, 769,
773
injection process, 766, 772-3, 777,
784, 787, 789
equipment, 787, 789
methods, 778
'lost blowhead' technique in, 779
main process features, 765-84
materials, 764-5, 784, 797
multicavity moulds for, 780, 785
multi-station, 775, 778, 789
product
cooling, 781, 784

Index I

Blow moulding-eontd.

product-eontd.

removal systems, 781

PVC compositions for
end-use aspect, 792
formulation aspect, 793-5, 796
processing aspect 789-91
single-stage processes, 775-8
stretch-blow methods 766-7, 769,
770, 772, 774-5, 787, 789
extrusion, 766-7, 769, 770
injection, 765-66, 772, 778
product properties, effects on,
767,774-5,797,800
terminology, 764, 767, 769, 776,
778-9
top-blow, 778-9
two-stage processes, 775, 776-8
Blow mouldings
applications, 764, 795-7
composite walls, with, 765
properties, 792, 797-800
tests for, 789-99
Blowing agents, 1071, 1074, 1075,
1085-92
activators ('kickers') for, 115,270,
279,286,350,353
commercial azodicarbonamide,
1088
decomposition of
products, 1085, 1089-90
rates, 1075, 1085, 1087
temperatures, 1085, 1087, 108891
incorporation levels, 1091-2
operational temperature ranges of,
1085-8, 1090-1
performance requirements for,
1085
retarders for, 1089
test for gas evolution by, 1095
volumes of gas generated by, 1087
Bonding of PVC
adhesive, 918, 927-9
distinction from welding, 923
solvent and solvent cement, 923-7
compositions, 927, 1063
mechanism, 924-5

General

1201

Bonding of PVC-contd.
solvent and solvent cement-eontd.
procedures, 924-5
specifications relevant to, 927,
1063
Brittle-ductile transition, 386-8, 866
Brittle fracture, 384-5, 866, 868
Brittle point, 386, 388, 440
Brittle temperature, 386-8
Brittleness temperature, 386, 440,441
Bronzing, 405
BS softness
fillers, effect of, 218
measurement, 65, 184-5
number scale, 184, 186
plasticisers, effect of, 162, 172, 185,
187
rubber hardness, and, 184, 186
Shore hardness, and, 184,186
temperature, effect of, 189,450
values of pPVC, 72-7, 1189
Bulk (mass)
polymer particle characteristics, 46,
47,690-1
polymerisation, 40
Burning (see also Flammability)
plastics, of, 424, 426-7, 428, 501-2,
508-9
PVC, of
effect of plasticisers, 161,204-6,
503,508
products of 499-500
role of chlorine in, 161,427,429,
502-3,508
Cable and wire insulation and coverings (see also under Compounding)
application (by extrusion), 717-19
compounds, 72-3,111,346,581
cable design, and, 602
cross-linkable, 72, 449-50, 1114
formulation, 111, 202, 346
production, see under Compounding
PVC/nitrile rubber, 400,1166
reclaimed PVC in, 601-2

1202

Index 1 General

Cable and wire insulation and coverings-contd.

compounds-contd.
stabilisation of, 90, 266-7,269,
337,343,349
heat tests for, 449,1115,1165-6
properties and applications, 401,
1114-15
Cadmium compounds
pigments, as, 409, 414-15, 418
stabilisers, as, 91-2, 278-80, 282-3,
384-5,831
stabilising action of, 302-4
toxic hazards of, 280, 342, 384,409,
831
UVabsorbers, interaction with, 297
Calcium carbonate fillers, 100-1,
221-40,252,832-3
applications, 100, 232-40
cost considerations, 232
dispersion characteristics of, 231
loading, effects of, 233, 238
plastisols, in, 233, 234, 237
precipitated, 220-2, 225, 241,252
properties, 228-31
surface-treated, 220, 222, 225-8,
234-6,238,241,833
types, 224-5
uPVC, in, 235, 236, 239-41, 246
Calcium resinate, 327
Calcium stearate stabilisersnubricants, 93, 104, 114, 275,276,
277,278,286,305,349,
364-6
synergism with antimony mercaptide, 276, 364
Calcium sulphate, 220-1
Calcium/zinc stabilisers (see also
Zinc-containing stabilisers),
283-4
Calender, 589, 591, 804-8, 815, 822,
828
compounding and feed for, 589-99,
810-15
main components of, 804-5
roll (bowl), 804-8
arrangements, 591, 805, 806, 828
bending, 807

Calender---eontd.
roll (bowl)---eontd.
crossing, 807-8
crowning, 807
deflection, 806-7
number in stack, 804-5, 828
numbering, 805-6
stripper rolls, 820-1, 822
suppliers, 804
Calendered sheet
applications, 847, 1107-9
defects and faults in, 809, 823-4,
833-7
flooring, for, 828
lamination of, 829-30, 837-8, 839-

40

low-temperature strain in, 823-4,

827
morphology of, 809
press-finished, 837
properties and tests, 809, 84Q-6
surface treatments applied to, 8389
thickness
gravimetric, 825
stretch-down effect, 821
typical range, 803-4
Calendering, 589-91, 597, 803-48
advantages over extrusion, 804
broad definition, 803
Calandrette system, by, 891
formulation aspects, 830-3
general features, 803, 808-9
historical development, 803, 812
lines
automated, 597
flooring, 828-9
general purpose, 589,809-28
small-scale, 813
material temperature in, 590, 820
materials processed by, 803
operation outline, 808-9, 816-17,
820
roll
speed (friction) ratios in, 806,
817,829
temperature settings in, 590,
817-20

Index I

Calendering-eontd.

scrap reprocessing, in, 596, 826-7

sheet path in, 817
sheet production aspects in
cooling, 824-5
edgetrimrning, 596,826-7
embossing, 821-3
lamination, 829-30
stretch-down, 821
thickness control, 825-6
wind-up, 827-8
techniques (general), 590
Carbon black
colourant, as, 102, 248-9, 414,
417-18
compounding into PVC, 587
conductive filler, as, 249,424
light stabiliser, as, 105,249,297,
418,482,1056
types, 248, 417-8
Cell stabilisers (for foam production),
1075, 1081-2
Cellular PVC (see also Foams and
Blowing agents), 1067-102,
1110-11
applications, 1068-74, 1076-9,
1084, 1092-4, 1096-101,
1110-11
evaluation and testing, 1095, 1099101, 1160-5
rnicroporoussheet, 1069, 1078-9
production methods
blowing and foaming techniques,
see under Foams
'lost filler' technique, 1078-9
sintering of powder, 1079
rigid, properties of, 1099
terminology, 1067-8
Chalking, 405
Chemical blowing agents, see Blowing
agents
Chemical blowing of foams, 1071-6,
1085-92
Chemical embossing, 1093-4
Chemical resistance of PVC, 48795
data, 488-93
tests for, 494-5

General

1203

Chlorinated compounds
paraffins
degradation of, 255-6
flame retardants, as, see under
Flame retardants
plasticiser extenders, as, 171-3
polyethylene (CPE)
calendering of, 803
chemical structure of, 396
degradation of, 255
impact modifier, as, 396-7, 887,
888
plasticiser, as 397, 832
polyvinyl chloride (CPVC), 24-9
applications, 5, 25, 28, 851,868,
1105
chemical structure of, 25-7
commercial compounds of, 25,
27,28,832
fibres from, 5,25
production of, 5, 24-5
properties of, 26-9, 858, 868
solvent cements for, 1063
thermoformability of, 745, 761
Chromium pigments, 409, 415,418,
1056
Citrate plasticisers, 174
Cladding, 452, 893-4
Clay
filler, as, 100, 101,216,217-19,
220,223,971,1037
oil absorption of, 971
thickener for pastes, as, 973-4
Clear point temperature, 127-9,959
commercial plasticisers, of, 129
Coated fabrics
applications and products, 1111-12,
1113--14
production, 829, 998-1009, 1072,
1077,1094
properties and tests, 844-5, 100910
Coating, see under Lacquers, Pastes,
and Surface
Coextrusion, 482, 685, 765, 884, 892
Cold bend temperature, 193,442
Cold crack temperature offilm, 193,
441

1204

Index 1 General

Cold-dip coating, 994-6

Cold flex (Clash and Berg) temperature
definition, 442
determination, 193,442
effect of
'Antistat A', 425
plasticisers, 166, 169, 173, 192--4,
195,205
phthalate-plasticised PVC, of, 156
Colourants, 82, 102-3, 401-19, 10567
choice considerations, 407-10
commercial,412-15
dispersion, test for, 404
fluorescent, 403--4
formulating with, 102-3
general types,403
health and safety considerations, 409
migration of, 102-3,404
nacreous, 403
pearlescent, 403
physical forms, 103,402,405,410
PVC stability, effects on, 103,260,
404,482,1056-7
service properties, 410-11
stability, 408
Compounding, 513-671, 810-14, 867,
1019-38, 1057-60
cable compounds, of, 586-8,601-2
continuous
Buss Turbine, by, 549, 605,
657-9
paste dissolvers, by, 606-7, 656-7
powder blends, of, 549-5
de-gassed melt in, 594-5
downstream' equipment associated
with, 513-15, 660-71
extruders use in, 599, 609-51
ingredients (PVC formulation components), 81-3, 86-103, 51419
conveyance of, 525-30, 531
metering and weighing of, 53247,604,606
mixing of, 550, 556, 558, 574-6
sequence of addition, 372, 574
storage of, 516-17, 519-25, 530-2

Compounding~ontd.

in-line
calendering, for, 589-97, 81014
extrusion, for, 549, 867
latex compositions, of, 1019-38
masterbatches, of, 587
melt, 577-603
equipment for, 609-51
pellet production and handling
in, 526, 530, 557, 582-6,
587,588
mixing aspects of, 549-51
operations, general nature and
objectives of, 79, 513-14
pastes, of, 603-9, 981-2
continuous, 605, 657-9
equipment for, 652-9
laboratory-scale, 981-2
standards for, 981
powder blends, of, 547-77
cold,548
continuous, 549, 867
effects of fillers, 519
hot, 548-9,551,574-6
mixers used, 554
high-speed (intensive), 557-62,
564-71,576-7
hot/cold combination, 562--4,
572-3,577
re-cycled material, of, 599-603
schematic outline, 514, 515
solution compositions, of, 105760
typical line, 516-17
'upstream' equipment associated
with, 513, 515, 519--47
Compounds (see also PVC compositions)
commercial,59-77
costing of, 83-5
definitions, 1--4, 79
injection moulding, 726-7
pellet (granulate), melt compounded
designation of, 64
feedstocks, as, 518, 686-7,7367, 789-90, 851-2

Index I

Compounds-contd.
pellet (granulate), melt compounded-contd.
production of, see Compounding,
.
Melt
physical forms, 80, 514
powder, see Powder compounds
production of, see Compounding
Compression moulding
gramophone records, of, 896-7
pastes, of, 1011
thick sheets, of, 837-8, 891, 902-3
Congo Red test, 320, 322, 1143
Conveyor belting, 421-2, 1112
Cooling of PVC mouldings, 781-4
Copolymers
abbreviations for, 4
ABS
blends with PVC, in, 375
impact modifiers, as, 99, 367,
373,390,39>'-5
processing aids, as, 373
butadiene/acrylic ester, 20
butadiene/acrylonitrile, see Nitrile
rubber, and under Impact
modifiers
butadiene/fumaric ester, 391
butadiene/methylisopropenyl
ketone, 391
butadiene/2-vinyl pyridine, 391
copolyester elastomer (Hytrel
3495), 391
EVA, 96, 99,390,395
MBS, 99, 367, 390, 394-5
SAN, 373, 374
styrene/maleic anhydride, 24
vinyl chloride, of, 19-21,22-3,832,
855
commercial, 5, 41
emulsions (latices) of, 1016-18
graft, 20, 41, 887
morphology of, 21
properties of (general), 20
solution type, 1048-9, 1050-1,
1052, 1053, 1054
VC/acrylic ester, 23, 887
VC/acrylonitrile (fibres), 20, 22
VC/ethylene, 22, 41

1205

General

Copolymers-contd.
vinyl chloride, of,-eontd.
VCIEVAt 20,23, 99, 367,392,

394-~,887

VClfumaric ester, 23
VC/itaconic ester, 23
VC/maleic ester, 23
VClmaleinimide (N-substituted),
20
VClpropylene, 22, 41, 795,851,
896
VCltrifluorochloroethylene
(TFCE), 23, 1049
VC/vinyl acetate, 5, 19,22,39,
41,42,50,832,851,894,
897,904,907,1008,1048-9,
1050-1, 1052, 1053, 1060-2
1064-5
VC/vinyl alkyl ether, 23,795
VClvinylidene chloride, 19,20,
21, 22, 41, 832, 851, 896,
964
Co-precipitates, 266, 286, 340
nature, 286
Sr/Zn laurate, 286
Co-stabilisers
epoxy compounds, see under Epoxy
stabilisers
organic, 278, 283, 285, 292
phosphites, 282-3, 290-2, 304-5
polyols, 305
CPVC (chlorinated polyvinyl chloride) see under full name
cpvc (critical pigment volume concentration), 1035-6
Crack initiation (see also Fracture)
nibs and impurities, by, 381
notches, by, 381,387,390
role in impact resistance, 380-1
Creep, 859-63
coated fabrics, resistance to, 1010
data for uPVC, 451, 861-3, 864
definitions, 860, 862
modulus, 862
PVC pipe, of, 863, 866, 879
rate, 860
rupture, 862
strain, 859, 862

1206

Index I

Creep-contd.
temperature, effect of, 450, 451,
759
tests on thermoforming sheet, 75960
Cricket pitch surface, 1123
'Critical solution temperature' (in
plate-out), 688
Cross-staining, see under Sulphide
staining
Crystallinity
plasticised PVC, in, 12~1, 139, 142
PVC polymers, in, see under
Polyvinyl chloride
VCIVDC copolymers, in, 21
Degradation of PVC, see under
Photochemical degradation
and Thermal degradation
Dilatancy, 948-9, 951, 967
Dip coating, 992-6
Dry blends (see also Powder compounds, and powder blends
under Compounding)
commercial, 61, 64, 70, 795
conveyance of, 562, 564
feeds, as, 518
blow moulding, in, 789-90, 795
extrusion, in, 686, 691,867
foamed product production, in,
1074,1076
nature,79,80,548-9,564,574-6
passim, 1,513,514
production of, 372, 547-53
standard designation of, 63, 64,65
uPVC processing, in, 851, 852, 867
Dry colours, 405
Dry point, 122, 123
Duckboard, 1123
Electrical insulation, see Cable and
wire insulation
Electrical properties of PVC, 73,
90, 101, 107, 206, 207,
859,1114-15,1165-6,
1193-5

General

Embossing, 821-3, 935, 1008-9,

1092-4
calendering, in, 821-3, 838
cellular sheet materials, of, 1092-4
'chemical' 1093-4
direct, 1092
PVC paste coatings, of, 1005,
1008-9
screen printing, by, 1094
Emulsion
polymerisation, 39, 40, 41
polymers
applications, 54, 86, 87, 107, 854
particle characteristics of, 46-8,
943,962-3
purity of, 87,259-60
PVC pastes, in, 962-3
latices, in, 1014
Environmental stress cracking and
crazing, 466-9
cracking agents for PVC, 469, 868
definition, 467
mechanism, 468-9
PVC pipes, of, 469, 868
resistance, tests for, 468
Epoxy plasticisers, 17~1, 290
Epoxy stabilisers, 93, 107,278,282,
287,288-90,347
formulations, in, 109, 110, 112,
113,115,289,347,348,351,
354,355
interaction with unsaturated additives, 290
mode of action, 304
Estertin stabilisers, 271, 273, 347
Extenders
fillers, as, 215, 231,232
plasticisers, for, 94, 96-7
chlorinated paraffin, 171-3
hydrocarbon, 174
Extruded film
applications, 894-5, 1063, 1109-10
production of, 599, 891-2, 1063
Extruded sheet
applications, 893, 904-9, 1107-8
production of, 598-9, 891-2
Extruders
blow moulding, use in, 784-7

Index I

Extruders-contd.
cascade, 583, 598, 599, 600,610,
621,623,628-30,706
commercial, 609-51, 698, 703-10
compounding, 609-51
heating and cooling, 579-80, 612,
623,627,634,642,676,677,
678,681-2
LID ratio, 673, 677
main components of, 674-82
manufacturers of, 704-5
output
factors affecting, 680
PVC compositions, 599, 630,
632-3,635,637,639,645,
682-3, 707, 708
planetary 610, 639-42, 644-5, 813
single screw, 673, 677, 698-9
energy efficiency with PVC,
683
screw configurations, 698-9
twin screw, 675, 699-703, 706-8
mode of operation: differences
from single-screw, 700-1
screw arrangements, 675, 702
venting of, 677, 683-4
Extrusion, 673-721
ancillary equipment, 710, 713,
718-19,870-1,874-6,885-6,
891,892
blow moulding, 766-72, 784-7
compounding, see under Compounding and Extruders
(compounding)
computers, use of, 686, 698
dies, 680-1
blown film, 712, 891
cross-head, 717, 785
pipe, 870-1, 872-4
sheet, 892
variable-thickness (for blow
moulding), 769, 771
feedstocks for, 514, 518,686-7,
789-90,851-2
feedstocks pre-heating, for, 682,
687
formulation aspects, 274, 687, 853,
876-8,886-9,894,896

General

1207

Extrusion-contd.
fusion and gelation in
completeness, 688, 694-8, 878
phenomenology, 692-4
general nature of process, 673
high-speed, 714-7
historical development, 6, 7, 673,
699
lines, 704-5, 706
cable and wire coating, 718
pipe, 869-76
PVC hose (braid-reinforced), 719
sheet, 598, 600,892
window frame profiles, 706, 708,
885
normal, of pPVC, 713-14
pastes, of, 1011
pipes, of, 869-78
products, common faults in, 688-9
profile, of, 884-9
sheet, of (see also under Extruded
sheet)
advantages over calendering,
890-1
equipment, 598, 600, 892
melt temperature profiles, 597

Fatigue, 863-6
data for uPVC, 865-6
definition, 863, 864
dynamic, 863
life, 864
resistance of uPVC, 864-866
temperature, effect of, 450
Feedstocks for PVC processing, see
under Compounds and Powder compounds
Fillers (see also under individual
names and types), 99-102,
215-54
conductive, 248-50
cost considerations, 100,215,216,
221,231-2
definition, 215
effects in PVC, on
BS softness No., 218
density, 100, 220, 233

1208

Index I

Fillers---contd.
effects in PVC, on-eontd.
paste rheology, 228, 229, 237,
251,970-3
tensile properties, 219, 247
fibrous, 217,240,242-6
flame retardant (see also under
Flame retardants), 842-3
functional, 215, 240-51
glass, 243, 245, 246
latices, in, 1035-8
loading, effects of, 220
microfibre, 242-4
mineral, 216-23
oil (plasticiser) absorption by, 104,
221,222-3,226,230-1,971-2
pastes, in, 970-3
properties (general), 222-3
reinforcing, 240-6
silicaceous, 216-19, 251
smoke suppressant, see under
Smoke
starch, 250-1
suppliers, 251-3
surface treated, 104, 225, 228, 242,
833, 970, 971, 972
trade names, 221, 222-3, 226,227,
252,253
wood flour, 250
Film (see also under uPVC)
applications of, 893-6, 1109-10
conversion and manipulation of
(for packaging), 932
definition, 890, 901-2
extruded, see Extruded film
latex, from, 1015-16, 1018, 1019,
1034
properties, 860, 893-6, 1064, 11867, 1190, 1197
shrink-wrap, 894-5
solvent-cast, 890, 1058, 1063
stretch-wrap, 199, 1109--10
thickness
measurement and control, 892-3
normal range, 890,901-2
'Fish-eyes'
count, specification for, 89, 1140,
1144

General

'Fish-eyes'-eontd.
melt-processed compositions, in,
49, 689, 793, 835
nature, 49, 89
passim, 51
standard tests for, 89, 1140, 1144
Fishing lures, 1122
Flame retardants, 83, 424-34, 508
chlorinated paraffins as, 204-6, 432
fillers, as, 206, 242-3, 247-8,431,
433
modes of action, 429--31, 433-4
phosphate plasticisers, as, 160-3,
204-6,430-2
special additives, as, 427, 429--34
Flammability (see also Burning)
definition, 502
PVC, of (see also under Burning),
161,204-6,427,429,502-3
terminology, 424, 426, 501-2
test specifications, 426, 434, 502,
505-7, 509
Flooring (see also under Asbestos and
Calendered sheet)
antistatic, 422
asbestos-filled, stabilisers for, 10910,349,352
calendered,828-9
coated, 1005, 1006, 1010, 1084,
1094
dust-capturing, 1116
embossed, 1092, 1094
expanded, 1084, 1092
fillers in, 109-10, 217,232-4
formulations, 109--10
linoleum, advantages of PVC over,
1116
stain resistance of, 210, 1010
unsupported, 1084, 1116-17
Flow moulding, 737-8
Flow promoters
dry (powders), 251
melt, definition, 373
Foams (see also Cellular PVC, and
under Pastes), 1069-78,
1080-92
cross-linked, 1077
definition, 1067-8

Index I

Foams---eontd.

density
general ranges, 1069
values for PVC, 1068, 1069,
1070, 1076, 1077,1083,
1097, 1098
evaluation and test methods, see
under Cellular PVC
formulations for
chemically blown, 1097
mechanically frothed, 1098
microcellular, 1069, 1075
production methods
'chemical' blowing, 1071-6, 1080,
1085-92
dispersed-gas blowing, 1069-71
mechanical frothing (gas entrainment), 1076-7, 1081-2
products, 1068-77, 1079, 1084,
1088, 1094, 1096-7, 1099,
1100,1110-11
properties of
blowing agent, effect of. 1083
cell stabilisers, effect of, 10812
factors affecting, 1080-4
plasticisers, effect of, 1081, 1083,
1084
PVC polymer, effect of, 1083-4
structural, 1075
'Fogging', 157, 202-4, 446
leatherc!oth, role in, 202
tests, 202-4
Foil
applications, 894, 1109
definition, 890, 902
stamping, see Hot-foil stamping
thermoforming, for, 894
Footwear,76-7,89, 401, 581,586,
1011, 1069, 1074, 1096-7,
1118
Formulation, 79-115
components
kinds, 81-3
mutual effects, 103-6,265,3347,339
nature and functions (general),
86-103

General

1209

Formulation---eontd.
components---eontd.
side effects, 105-6,296-7,305-7,
308-9,364-7
costing, 83-5
examples
blow mouldings, 112-13,355,
374, 796
flooring, 109-10
foam compositions, 115, 1096-8
gramophone records, 112
injection mouldings, 113,346
miscellaneous, 348, 351, 1008,
1123
pastes, 114-15,972,974,977,
987, 988, 990, 996, 997
pipes and tubing, 110,345,355,
877
profiles, 114, 346, 354
sheet and film, 107-9, 199, 203,
348,355,818-9,894-6
solutions, 1061-2
wire and cable coverings, 111, 346
general considerations, 80-81
Fracture
impact, on, 375, 376, 377, 380, 384
modes of, 380, 384-6
uPVC, of, 387, 388-90, 866
Fusion point (pastes), 853, 854
'Gassing'
calcium sulphate, by, 221
lead stabilisers, by, 266
Gear pumps, 684-5
'Gel block', 122, 959,1011,1099
Gelation/fusion
melt processing, in, 132, 688,
689-98
pastes, of, 122,694, 951-60,982-5,
1095
stages in, 951-2, 956-9
solvent tests for degree of, 696,
697,878-9
foams, in, 1100
paste products, in, 959-60, 983-5
pipes and profiles, in, 697,878-9,
889

1210

Index 1 General

Gels, 89, 689, 793

Glass transition temperature, see Tg
Global radiation, 476, 477
Gloves
dip coating of, 994-5
solvent tests on, 983-5
Gramophone records
colourants for, 404
compounds for, 586
formulation, 112, 897
polymers for, 853, 854
production, 896-7, 1117
stabilisers for, 112,270,276,286,
348,897
Gravimetric thickness, 825
'Grow moulding', 883
Hardness (see also BS softness)
data for PVC, 1189
Durometer (Shore), 65, 184, 186
international rubber scale, 184
plasticisers, effect of, 188
tests, 184, 1183
Heat (see also under Stability)
ageing, 443
degradation, see Thermal degradation of PVC
history, 80, 313-15, 578, 851
life, 313-15
non-degradative effects of, 450-2
resistance, 443-52
transfers, see Transfers
Heat stabilisers (see also under

individual and type names)

activators for blowing agents, as,

see under Blowing agents
blow mouldings, in, 291, 793, 796
calendering, in, 831
chelator, 275, 282, 285, 287, 291-2,
352,354
commercial, 335-57
applications, 342-56
cadmium-free systems, 284-5,
351,353
suppliers of, 336, 342-56
trade names of, 280, 281, 282,
283-7,292,343-6

Heat stabilisers-eontd.
complexes, 275, 337
composite metal, 91-3, 281-6, 335,
337-8,345,347-56
cross-staining by, 272, 278, 309
detection and analysis of, 330
evaluation of, 311-28
hazard and hygiene considerations,
265-6,280,341-2
latices, in, 1030-1
lubricants, and or as, 95-8, 104-5,
265,269,274,278,281,282,
283,286,306,339-40,364-6
metal soaps and salts as, 275, 337-8
mode of action, 291, 299-305
non-metallic, 93, 286-92, 348
non-toxic, 92, 106,272,278,279,
281,283-4,287,291,348
one-pack systems, in, 335, 340-1,
348,351
organic, 286-92
pastes, in, 969-70
physical forms, 266, 273,275,
282-3,340-1,343,345,347,
348-51,353-4,356
polymeric, 271
selection criteria, 262-3, 335, 337
single-metal compounds as, 275-81,
343,348,349
types, 89-93, 264
window-frame formulations, in, 887
Hose, see Tubing
'Hot bench', see Gel block
Hot-dip coating and moulding, 992-4
Hot-foil stamping, 934-5
Hydrocarbons, plasticiser extenders
as, 174
Impact modifiers (see also under

individual type names) 98-9,

371,390-401,793-4
evaluation of effects, 381
fillers as, 226, 236, 241, 246, 391,
419
mode of action, 391
polymeric, 99,105,390-401,853-4
side effects of, 392-3

Index I

Impact modifers-eontd.
window-frame compositions, in, 20,
482,88~

Impact resistance (impact strength),

375-90
biaxial stretching, effect of, 19,27,
761, 774, 793-4
blow mouldings, of, 774, 793-4,
798-9
definition, 375-6, 1188
factors affecting, 377
mode offailure, and, 384-7
notches, effect of, 380-3, 389,390
PVC polymer, effect of (in compositions), 855
temperature, effect of, 855
tests, 375-6, 378-81, 382-3, 799,
1188
units, 382-3, 384, 1188
uPVC, of, 387-90, 855, 1188
Injection moulding, 723-41
compounds, 726-7, 736-7
commercial, 61, 62, 64, 68,70,
76-7,726,852
'easy flow', 726
formulation, 726
melt flow test for, 727
time-temperature behaviour of,
725
types, 733
equipment, 729-35
features relevant to PVC, 730-3,
735
general considerations, 740
selection, 738
faults, 734, 739
feedstocks, 514, 518, 737, 852
melt properties important in, 724-6
process
factor effects on products, 728-9
stages and operation, 723-4,
731-5
temperature
effects, 724-6
settings, 732-4
thermal input in, 724
trouble shooting in, 738-40
uPVC, of, 723, 731-5, 738-40

General

1211

Injection mouldings, 62, 68, 70, 76-7,

897-8, 1118, 1121, 1122
faults in, 734, 739
formulations for, 113
morphology of, 19,729,898
orientation in, 19,728-9
property data, 1185-95
quenching stresses in, 728
shrinkage of, 727
Intensive mixers, see under Mixers
Internal mixers, 596, 810-12, 818
International Rubber Hardness
(IRH),184
Kvalue
cellular PVC, effects in, 1080, 1083
concept, 14,43
effect on properties and processing,
86,793,799,853,855,1080,
1083
fatigue resistance, and, 864
Fikentscher, 15, 43, 44,854
gelation/fusion of plastisols, effect
in, 1080
ICI,86-7
molecular weight, and, 15,44-5,86
specific viscosity, and, 14,44-5
viscosity number, and, 14,44-5
'Kickers' , see under Blowing agents
(activators for)
Lacquer coating, 298, 1008-9, 1094-5
compositions, 298, 1008-9, 1050,
1060,1061
methods, 1009
objectives of, 298, 1008
rotational mouldings, of, 988
Latices, 1013-46
acrylic, 1044
definition, 1014
film formation by, 1015-16
nitrile, 1040, 1041, 1042, 1043,
1044,1045
vinyl (PVC)
anti-foaming agents for, 1028
applications, 1040-5

1212

Latices-eontd.
vinyl (PVC)-contd.

Index I

compounding ingredients and

techniques for, 1019-38
products from, 1019, 1034, 1036
sedimentation in, 1028
stability of, 1020-1
types, 1016-18
Lead stabilisers, 90-1, 265-70, 337,
343-6,349,350
applications, 265-70
chemical nature, 265-70
electrical insulation, suitability for,
90
hazards, 265-6, 337, 341-2
mode of action, 299
physical forms, 266, 340-1, 343
Leathercloth, 998, 1006, 1007,1008,
1009, 1069, 1070, 1072,
1092,1094,1095,1096-7,
1098
applications, 1111
'fogging', role in, see under Fogging
Light stability, see under Stability
Limiting oxygen index, see Oxygen
index
Lithium stabilisers, 280-1, 349
Loop test, 131, 135
Low-temperature plasticisers, 97,
163, 165, 166, 193
Low-temperature properties of PVC,
192-5,388-90,393,394,
400,439-42
'Lubricant value', 369
Lubricants, 82, 95, 98, 359-71
blow mouldings, for, 794-5
calendering, role in, 95, 817,
830-1
chemical structure, 362-3
commercial sources, 371
compatibility with PVC, 360-2
compounds used as, 95, 104, 105,
362-3
concentrates, 370
formulating with, 95, 98
functions and effects, 95, 98,
359-63
mutual effects with
fillers and pigments, 367

General

Lubricants-eontd.
mutual effects with-eontd.

plasticisers, 366
polymeric modifiers, 366-7
stabilisers, 95, 104, 364-5
one-pack systems, in, 98, 339, 340,
370
stabilising effects of, 95, 105,339,
364-5
Lubrication
effects of
plasticisers, 82, 360, 363, 366
polymeric modifiers, 367
stabilisers, 269, 274, 278, 281,
282,283,284,286,366
evaluation of effects, 361-2, 367-70
external, 82, 95, 359-63
internal, 82, 95
rheological effects of, 360-2, 368,
369
Machining of rigid PVC, 930-2
Magnesium carbonate, 247, 433
Mass polymerisation and polymers,
see under Bulk
Masterbatches
colour, 406
compounding of, 587
Maximum swelling temperature, 123
Maximum torque temperature, 132
MBS impact modifiers, 99, 390, 391,
392,394,395
Microbiological attack, 208-9, 483-6
definition, 48~
manifestations and mechanism, 483
protective additives, 208, 484-5
resistance to
plasticisers, of, 208-9, 483-4
PVC, of, 208, 483, 484
vinyl chloride polymers, of, 483
testing of resistance, 208, 485
Migration of
colourants, 404, 411
plasticisers, 135, 175, 199-200,
1146-7
Mills
ball, 652, 654
roll, 656

Index I

Mixers (see also under Compounding), 554, 556, 558, 603,

605
continuous, 549, 605, 657-9,
867
dissolver, 656-7
general types, 554-7
horseshoe, 652, 653
hot/cold, 562-4
intensive, 557-62, 564-71, 576-7
paddle, 557, 655
planetary, 652, 653
pneumatic, 666-71
ribbon blender, 557, 653-5
rotating, 556, 558
vertical screw, 666, 667
Modacrylic fibres, 20
Molecular weight
definitions, 13-14
distribution, 15-16
polymeric plasticisers, of, 165, 167,
168
PVC, of
K value, and, 15,43-6
p. value, and, 125
polymerisation temperature,
and, 16,46
processing and properties, effect
on (see also under Kvalue),
86
Molybdenum trioxide, 247, 430, 4334
Mould shrinkage
other polymers, of, 782
PVC, of, 727, 782
Moulding
blow, see Blow moulding and Blow
mouldings
compression
pastes, of, 1011
solid PVC, of, 837-8, 891, 896-7,
902
dip, 993-4
injection
pastes, of, 1010-11
solid PVC, of, 723-41
rotational,986-8
slush,988-90
p. Value, 125-6

General

1213

Newtonian viscosity, 946-7

'Nibs', 49, 689, 793, 835
Nitriding, 678, 679, 735
Nitrile rubber
blends with PVC, 170,397-401
cable compounds, in, 400, 1166
commercial, 399-400
footwear, in, 1118
latices, in, see under Latices
(nitrile)
processing of, 399-400
modifier, as, 99, 397-401
plasticiser, as, 96, 367, 398
Non-toxic additives for food contact
applications, 106
Non-toxic colourants, 409
Non-toxic plasticisers, 210-11
Non-toxic stabilisers, 92-3, 272,2834,287-92
'Nylonate' (nylon acid) plasticisers,
see AGS acid ester plasticisers
Oil absorption, see under Fillers
'Oil canning', 893
'One-pack' additive systems, 98, 265,
266,273,298,339,340,348,
351,370,406-7
Organosols, 940, 975-6, 996, 997,
1005
Organotin stabilisers, 92-3, 270-4,
300-1,338,346-8,353,354,
355
antimony, comparison with, 277
characteristics and applications,
272-4
chemical nature, 270-4
effects, 272, 306
mode of action, 300-1
polymeric, 271
'reverse ester', 274
single-pack systems, in, 273, 340
types, 270-1
'Oxo' process, 152, 156
Oxygen index, 502
plasticisers, effect of, 161,205,508
plastics, values for, 503
test methods, 505, 506

1214

Index I

Pastes (see also Organosols, Plastigels, Plastisols, and Rigisols)

car body undersealing, for, 229,
1121
casting of, 991-2
coating of sheet materials with,
998-1010
common product faults, 1002-4
techniques, 998-1002, 1004-7
commercial, 60, 62, 69
components and formulation of,
962-75
compression moulding of, 1011
definition, 939-41
dip coating with, 992-3, 994-6
dip moulding of, 993-4
extrusion of, 1011-12
foam production from, 115,967
formulations, 1095-8
methods and effects, 1069-77,
1080-4, 1091
foamable coating layers, 115, 1006
gelation/fusion of, see under Gelation/fusion
low-pressure injection moulding of,
1010-11
preparation, processing and applications, 981-1012
production,603-9,981-2
products, 114-15,284,987-8,990,
991,993,994-5,999,1006,
1007, 1010, 1011
properties and formulation, 939-79
rheological properties of, 228-9,
237,945-51
room-temperature blowing of, 1091
rotational casting of, 986-8
slush moulding of, 988-90
spray coating with, 996-7
standard specifications for
preparation, 51, 981, 1141
viscosity determination, 51, 9601,1141
terminology, 939-40
viscosity of, see under Viscosity
Pellets, see under Compounding and
Compounds
Permachor, 462-3

General

Permeability, 452-66
biaxial orientation, effect of, 19,
27, 761, 774, 799
blow mouldings, of, 774, 798,799
coefficient
definitions, 453, 455, 461
units, 459
definition, 452, 453, 455, 460
determination
containers, on, 462, 798
plastics, on, 462
standard methods, 456-8
porous materials, of, 460-2
PVC, data for, 451, 463-6
units, 453-4, 456-9, 460
Phosphate plasticisers, 94, 96-7, 15963
flammability, effect on, 160-3,
204-6,430-1,432,503
halogenated alkyl phosphates, 163,
431
mixed alkyl aryl phosphates 161
PVC compounds, performance in,
160, 162
thermal degradation, effect on, 260
trialkyl phosphates, 160
triaryl phosphates, 159, 160
Phosphite stabilisers, see under Costabilisers
Photochemical degradation, 260-1
impurities, effect of, 261, 482
mechanism, 261
protective additives, see UV stabilisers, Antioxodants, Carbon
black, and Titanium dioxide
relevant tests, 328-30, 476-80
weathering, in, 472, 474-5
Phthalate plasticisers, 93-7,152-9
flammability, effect on, 161,205,
508
general-purpose, 153
higher, 156-8
linear, 153, 156
lower, 152-3
miscellaneous, 158-9
modified, 158-9
possible health hazard, 210
PVC compounds, performance in,
154-5

Index I

General

1215

Pigments (see also Colourants)

Plasticisers-contd.
chemical nature of, 119-20, 136-9
latices, in, 1036, 1038
behaviour in PVC, and, 136-9
solutions, in, 1056-7, 1059
citrate, 174
weathering, effect on (see also
classification of, 147-9
Carbon black and Titanium
commercial, 147-80
dioxide), 482, 1056
compatibility
Pipes, see under uPVC
expressions, 125-32
Plasticisation
external materials, with, 175
external,5-6,117-18
high humidity, at, 204
internal, 5, 20, 118, 1016
mechanisms of, 120, 121, 122, 124
tests, 123, 127, 131-2
TXP isomers, of, 128
theories of, 120-2
cross-linkable, 174, 968-9, 1073
vinyl latices, of, 1016-17, 1018,
definition, 117
1031-5
desirability function, 183
Plasticised PVC (pPVC)
diffusion in PVC, 135-7
ageing of, 138-9
effectivity (efficiency), 132-4, 185,
chemical resistance of, 487, 488-9
189, 192
definition, 2-4, 590 (calendered
effects in PVC compositions, on
sheet)
(see also under individual
filler loading, effects of, 233, 238-9
flammability of, 161, 204-6, 427,
properties)
430-1,432,433,503,508
BS softness No., 187-9,450,
products, 986-98,1072-4,1106,
1189
electrical properties, 156,206,
1108, 1109-10, 1111, 1112,
1114-15, 1118, 1120, 1121,
207,1193-4
1122-3, 1124
elongation at break, 191,850,
properties of (see also under indi1187
flammability, 204-6, 508
vidual property names), 65,
67,69,72-7,118,154-5,
impact strength, 388, 441-2, 850,
157,158,160, 161, 162,164,
1188
166,173,187-212,441-2,
low-temperature performance,
447-9,464,465,469,472-3,
94,192-5,205,439-42
483-4,487,488-9
modulus, 193, 1190
stain resistance of, 209-10,1010
softness, 184-5, 187-9, 1189
weathering of, 261, 472-3, 482
tensile properties, 190-1,450,
Plasticiser absorption
1186-7
fillers, by, see under Plasticiser
efficiency factor, 134, 189
demand of fillers
extraction, 135, 196-8
PVC polymer particles, by, 47, 48,
exudation, tests for, 131
123, 125, 127
flexible seals, in contact with, 175
Plasticiser demand of fillers (see also
foams, effects in, 1081, 1083-4
under Fillers (oil absorpfood, contact considerations, 106,
tion)), 226, 230-1, 970-2
210-11
Plasticisers (see also under individual
formulating with, 93-7,105,149,
or type names)
181-4
bulk properties of, 139, 160, 164,
fusing, rapid, see solvating (below)
166,167,172, 1144-6
glycol ester, 173-4
cellular PVC, effects in, 1081,
handling and storage of, 175, 179,
530-2,539-40
1083-:4

1216

Index I

Plasticisers-contd.
health and safety aspects, 211-12
history of, 5-6
interaction,
parameter (Flory-J{uggins), 128,
130
PVC polymer, with, 122-32
'low temperature' , see aliphatic
diester plasticisers
migration, 135, 199-200
tests for, 200
miscellaneous, 170--5
monoester, 173
monomeric, definition, 119
names and abbreviations, 148-51
pastes, in, 153, 159, 265-9,976-7
permanence, 195-204
polymeric, 96-7,165-70
compositions, in, 199
definition, 119-20
nature, 165-70
solid, 169-70, 197,394-401
polymerisable, 174,968-9,1073
primary, definition of, 118
producers of, 177-9
properties in PVC, 118, 140-1,
154-5, 158, 160-2, 164, 166,
169, 173
rapid fusing, see solvating (below)
resistance to
insect and rodent attack, 209,
486
microbiological attack, 208-9,
483-6
secondary, definition of, 118
selection of, 96-7,124-5
solubility parameters of, 127
solvating, 94, 97,115,158,174,
1074,1081
synonyms, 148-52
types, 119, 149
usage features (general), 96-7
vinyl latices, in, 1031-5
viscosity-temperature relationship,
176
volatilisation, 135, 157,200-2, 212,
446-8
Plastigels, 973-5

General

Plastisols (see also Pastes), 945,

953-5,973,997,1069,10723, 1076-7, 1079, 1084, 1096-

basic form of, 951

nature, 939
synonymity with pastes, 939
Plastometers, see under rheometers
Plate-out, 91, 251, 305, 307-8,687-8,
780, 835, 1090
blow moulding, in, 780
blowing (foam) compositions, with,
1090
calendering, in, 835
deposits, composition of, 305,688,
1090
extrusion, in, 687-8
test for, 307-8
Polymeric modifiers, see under Impact modifiers and Processing aids
Polyurethane
lacquers, 1009
modifiers, 168-70, 197,401
Polyvinyl chloride (homopolymer)
chemical structure, 13-18
crystallinity, 18-19, 121,694-5
fine structure (morphology), 18-19
glass transition temperature
effect of blending with nitrile
rubber,398
typical values, 18
molecular orientation, 19
syndiotactic, 18, 121
Porous materials
permeability of, 460-1
production methods, 250, 1078,
1079
Powder
coating and moulding, 61, 111820
compounds, 514,518,852
as feedstocks in
blow moulding, 789-90
calendering, 808
extrusion, 686-7, 851, 885
injection moulding, 737, 852
gelation of, 691-2

Index I

Powder---eontd.
compounds---eontd.
production of (see also under

Compounding), 372, 547-9,

867
sintering of, 1079
types, 548, 686-7
pPVC, see Plasticised PVC
Printing, see Surface decoration of
PVC
Processing aids, 98, 372-5, 392-3
blow mouldings, in, 795
effects in PVC, 373-4
impact modifiers, action as, 373,
392-3
mode of action, 374
polymers used as, 372-3
Pseudoplasticity, 948--9
Purging
extruders, of, 685-6
injection machines, of, 734
materials for, 685-6, 734
PVC
applications (see also under relevant

individual headings) 1103-26

ball valves, 1124

bricks, 1124
cellular, see Cellular PVC
compositions (see also under Compounding and Compounds)
commercial,59-77
melt compounded, 79, 80
production of, see Compounding
definitions, 1-4
expanded, see under Cellular PVC
fibres and fibre products, 5, 20, 22,
1117
flexible (see also Plasticisation and
Plasticised PVC)
definition, 2, 3
products (see also under Plasticised PVC (products) and
Pastes (products, 1106,
1108, 1109, 1110, 1111
foams, see Cellular PVC and
Foams
general definition, 1
health hazards, 495-501

General

PVC---eontd.

1217

historical development, 4-7

IR spectrum of, 34-5
laminates with other materials, 745,
909,1111-16
medical applications, 1120--1
motor cars, use in, 1121
plasticised, see Plasticised PVC
polymer particles
morphology,46,48,51,689-91
size, 46, 47, 51, 690, 943, 962-3
polymers (resins)
characterisation tests, 50--2
characteristics, 41-9, 86-9
commercial
producers and trade names,
55-7
properties, 54, 854
high purity, 89, 853
history, 4-5
kinds, 38-41,53,86-8,1047-8,
1050--1
production processes, 37-41, 47
properties and tests, 47, 50-4,
852, 1135-68
quality, 89
standard designation, 49, 53
'red-mud' filled, 1123
reprocessing, 9-10, 310, 599-603
rigid, see Rigid PVC
sheet, see Sheet
solutions, 1047-65
applications of, 1050--1, 1060--3
cocooning, for, 1061
film casting, for, 1063
miscellaneous components of,
1054-7
pigments, in, 1056, 1057, 1059,
1060
polymers used in
adhesion to substrates, 1049,
1059, 1061-5
nature, 1048--9, 1050--1, 1052,
1053
preparation of, 1057-60
ready-made, 1058--9
solvent-cements, as, 924-7, 1063
solvents used in, 1049-54

1218

Index I

General

PVC-contd.
solutions-contd.

Roll test, 131, 135

Rotational casting, 986-8

Re-cycling
compounding, and, 599-603
general problems, 9, 10
sulphide staining in, 310
'Red mud' (as reinforcing filler), 1123
Relative melting temperature, 123
Rheometers
balance (Contraves), 954, 955
capillary, 327-8, 369, 580,581
oscillatory (parallel plate), 954-5
plastometers
Macklow-Smith, 65
piston (ASTM), 369, 727
review (passim), 790
torque
evaluation of lubricants, use for,
362,368-9
extrusion characteristics, determination in, 369
fusion time and rate, determination in, 362, 368, 790-1, 954
Plasti-Corder, see under
Brabender in Index 3
Plastograph, see under
Brabender in Index 3
RAPRA, see Index 3
stability tests, use for, 316, 319,
326-8
Rheometry, reference to review of,
790
Rheopexy, 949-50
Rigid PVC (see also uPVC)
chemical.resistance of, 487,488-9,
491-4
definition, 2, 3, 849
feedstocks, 851-2
typical property value ranges,
1185-97
Rigisols, 940, 976-7
Rodent attack, resistance of PVC to,
209,486

Screeners, see UV stabilisers

Selective membranes, 1123
Semi-rigid PVC
definition, 2, 590 (sheet), 849
properties, 849-50
Sheet
applications of, 847, 893-Q, 903-9,
922,1107
calendered, see Calendered sheet
conversion and manipulation of
(for packaging), 932
definition, 803-4, 890, 901-2
embossing, 821-4, 838-9,935
extruded, see Extruded sheet
fabrication of, 910-36
'planishing' (press finishing) of, 837
press-laminated, 837-8, 891, 902-3
property data, 819, 841, 842-3,
846, 1185-95
tank lining with, 917-18
thermoforming, see Thermoforming of sheet
thickness
measurement and control, 82~,
892-3
values and ranges, 804, 890-1,
901-3
types 904, 906-907
Shore (Durometer) hardness
BS softness, and, 184, 186, 188
determination of, 184, 1189
typical value ranges for PVC, 1189
Siding, see Cladding
Simulated skin, 1122-3
'Single-pack' additive systems, see
'One-pack' additive systems
Single-screw extruders, 673, 674, 677,
679-80,698-9,704-5,709
Slush moulding, 988-90
Smoke
density, 427, 434
evolution
enhancement by some additives,
431

surface coatings, as, 1059-63

viscosity of, 1054
usage statistics, 8, 10-11
Pyrolysis, 424, 426, 427, 428

Index I

Smoke-contd.
evolution-contd.
plastics, by, 427, 502
tests for, 434, 505-7, 509
nature, 427
PVC, from burning, 499, 502, 509
suppressants, 83, 242, 247-8, 42934
Softness (see also BS softness)
measurement, 184-5
plasticisers, effects of, 185,187-9,
450,1189
Solid-gel transition temperature, 123,
127,131
Solubility parameter, 125-7
plasticisers, of, 126, 127
PVC polymer, of, 127
Solution polymerisation, 39, 42, 1048
Solution polymers, 1048-9, 1050-1
Solutions, see PVC solutions
Solvation point, 123
Solvent cements, see under Bonding
of PVC, Chlorinated polyvinyl chloride, and PVC
(solutions)
Stabilisation (see also Heat stabilisers,
UV stabilisers and Antioxidants)
blow moulding compositions, of,
793 (see also Non-toxic stabilisers)
calendering compositions, of, 831
effects, evaluation of, 312-30
external,264
'in kettle', 264
internal, 264
mechanisms, 264, 291, 299-305
Stabilisers, see under functional types
(e.g. Heat stabilisers, UV
stabilisers, Antioxidants)
Stability
heat, to
adverse effects of formulation
components, 260
concept, 311-15
induction time, and, 312
polymer nature, effect of, 259-60
stability time, and, 259, 312-15

General

1219

Stability-contd.
heat, to-contd.
testing, 315-28
light, to
testing, 328-30
Stain resistance of pPVC, 209-10,
1010
Standards
institutions, 29, 1127-31
test specifications, 29-30, 1134-68,
1185-95
Static electricity charges, 420-2
electrical resistivity, and, 420-2
measurement, 421-2
Stress
concentrating features, 377, 381,
386,695
cracking, see Environmental stress
cracking
rupture strength, 862
whitening
filled compositions, in, 102, 106,
230
impact-modified compositions,
in, 392, 794
mechanism, 392
Strontium stabilisers, 249, 281
Sulphide staining
cross-staining, 91, 105,272,278,
309,310
occurrence, 91, 106,276,308-11
tests for, 310-11
Surface decoration of PVC, 838-9,
932-5, 1005, 1008-9, 1092-5
Surface marking of PVC, 935-6
Surface processing of PVC, 936
Surface treatment of
fillers, see under Fillers and Calcium carbonate fillers
PVC
cellular coatings, 1092-5
paste coatings, 1005, 1008-9
sheeting, 838-9, 932-6
Suspension
polymer particle characteristics, 46,
47,690-1
polymerisation, 39-40, 41
Syndiotactic PVC polymer, 18, 121

1220

Index 1 General

Synergism
co-stabilisation, in, 91, 104,276,
283,340
lubricant/stabiliser, 104,274,364-5
calcium stearate/antimony mercaptide, 276, 364
glycerol esters/thiotins, 364

Tg

PVC polymer and compounds, of,

18,361,398,460
role in
film formation from latex, 1016,
1017
mode of fracture, 388
Talc, 217, 223
Tank lining with PVC sheet, 917-18
Temperature gradient bar, see Gel
block
Temperature index (UL), 445
Tensile strength
paste products, of, 959
plasticisers, effects of, see under
Plasticisers and Effects in
PVC
temperature, effect of, 388, 450
typical values for PVC, 1186
Termite attack, 209, 486
Thermal decomposition products
plastics, of (general), 426-7,428
PVC, of, 256-8, 259, 499-500
Thermal degradation of PVC, 256-60
activation energy for, 259
and specific energy for melt
generation, 311-12
different PVC polymers, 259-60
mechanisms, 256-9
nature and measurement, 313, 326,
327
time/temperature effects in melt
processing, 578, 725
Thermal diffusivity, 781-2
Thermoforming of sheet, 743-62
advantages, 744
basic methods, 743
combination processes for, 743
CPVC properties relevant to, 745,
761

Thermoforming of sheet--eontd.
creep tests relevant to, 757, 75960
equipment for
integrated lines, 757
suppliers, 757, 758
materials used
assessment of, 757, 759--60
nature of, 745
products
distortion of, 756-7
finishing of, 754-~
quenching stresses in, 744
related processes, and, 746
techniques
matched-mould and related, 755-

pressure, 756
vacuum, 745-54
temperature
draw ratio, and--effects on product quality, 759--60
role in process, 751-2, 756-7, 760
Thickening agents
latices, in, 1021-8
pastes, in, 251, 973--5
Thixotropy, 949-50, 973, 976
Time/temperature effects in melt
processing, see under Thermal degradation
Tin stabilisers, see Organotin stabilisers
Titanium dioxide
clay, in, 218
light stabiliser, as, 108,297,419,
482,1056
types, 418
white pigment, as, 102,418--19,
1062
Toners, 411
Torque rheometer, see under Rheometers
Toughness, 376, 399, 440
Transfers (surface decoration), 933
Trialkyl phosphate plasticisers, 149,
160, 161, 162
Triaryl phosphate plasticisers, 149,
159-60, 161, 162

Index I

Trimellitate plasticisers, 96-7, 149,

163, 164
PVC compounds, performance in,
164
Tubing (flexible), 674, 719, 1106,
1120
Underlays (rugs and mats, for), 1124
uPVC
chemical resistance of, 487, 488-93,
494
definition, 2, 3
fillers in, 235, 236, 239-40,241,
242-6,250
film (see also Extruded film),
890-2,894,895,1109
injection moulded articles, see
Injection mouldings
pipes
applications, 867-9, 882, 883,
1104-6, 1121-2
formulation aspects, 853, 876-8
production of, 869-78
properties and tests, 378-80, 697,
878-9,880-1
special forms of, 879,882-3
types, 867-9
water flow, through, 869
profiles
applications,883-4,1106-7
cellular, 884, 885
formulation aspects, 886-9
production of, 884-6
specifications and tests, 889
types, 883
window frame, 20, 482, 883, 884,
885,886-9,1106-7
properties (see also under indi-

vidual property names), 65,

66,68,71,463-4,466,
469,489-94,849,850,85566,878-9,899,893-5118595
sheet, see under Calendering,
Calendered sheet, Extruded
sheet, Extrusion, and Sheet
UV stabilisers, 255, 292-9

1221

General

Vacuum forming, 745-54

Venting of extruders, 612, 621, 623,
627,629,635,636,638,677,
683-4
Vinyl chloride
copolymers, see under Copolymers
homopolymers, see under Polyvinyl
chloride
Vinyl chloride monomer (VCM)
detection and determination, 496
explosive limits, 38, 500
hazards of, 9, 38, 496-7, 500
polymerisation of, 38-41
production, 7, 37-8
properties, 38
regulatory measures, 9, 38,497
'stripping' from PVC polymer, 39,
41,497
Viscometers (see also Rheometers),
954,960-1
Bendix Ultra Viscoson, 954
Brookfield, 954, 960
Castor-Severs, 961
cone-and-plate (Haake-Rotovisco),
961
Contraves balance, 954, 955
Ford cup, 961
Gardner, 961
Viscosity
depressants for pastes, 975-7
expressions and terms, 14, 44-5, 52

(passim),960-1

melts, of, 369, 581, 790

number, see under K value
pastes, of, 941-51, 953-8
ageing index, see stability index
(below)
extender polymers, effect of,
943,963,964
fillers, effect of, 970-3
measurement of, 51, 953-5,9601,1141
plasticisers, effect of, 957, 965-8
thickening agents, effect of, 9735
solutions, of, 14-15,44-5,50,
1050-1, 1054
specific (see also under K value)

1222

Index I

Viscosity-eontd.
stability index (pastes), 966, 973
standards and definitions, 14,44-5,
50,52,1136-7
Volatile loss, 200-2, 447-8

Wall coverings (interior), 998, 1005,

1042-3, 1113-14
Weathering (see also under Photochemical degradation),
206-8, 469-82
definition, 469
effects, 206-8,261,471-3,476,480
factors instrumental in, 470, 472-3,
474,475-6, 481-2
plasticisers, effects of, 207-8, 482
resistance
assessment, 471, 474-7, 480
formulating for, 107, 480-2,
886-8
processing, effect of, 482
solvent residues, effect of, 482
tests
methods, 470-1, 474-5, 477, 480,
1134
radiation sources in, 476-9
WeldIng of PVC (see also Bonding)
definition, 910, 923
flooring, 914,916,918-19

General

Welding of PVC-eontd.
recommended temperature ranges,
910
specifications relevant to, 913, 918
techniques
dielectric welding, 912
extrusion welding, 911, 919
friction welding, 912
heated tool welding, 911, 922-3
high frequency welding, 912,
919-22
hot gas welding, 911, 914-19
indirect heated element welding,
911
radio-frequency (RF) welding,
912
spin welding, 912
thermal impulse welding, 912
ultrasonic welding, 913
vibration welding, 912
White lead, 266-7
Whiting, see Calcium carbonate fillers
(types)
Zinc-containing stabilisers, 91, 93,
106, 109-10, 112, 113, 115,
283-4,286,302-3,309,325,
338,345,347-53,355,356,
364,793,831,969,1086,
1087,1096

INDEX 2

Material and Product Trade Names

Beetle PVC resins, 23, 57

Bennite, 252
Bentone, 974
Benvic PVC resins, 905
Benzoftex plasticisers, 174, 179
Bevaloid defoaming agents, 1028
bioMET, 208, 209
Bisoftex plasticisers, 35, 177, 966
Bisol DPS, 1043
Bisomer DALP, 969
Blendex modifiers, 203, 346, 355,
394,395
Blue B, 404
Bondene,909,1115
Borden PVC resins, 56
Bostik adhesives, 918,928-9
BQ stabilisers, 343, 344,346
Breon
latices, 1013, 1014, 1017-19, 10218, 1030-2, 1034, 1035, 1038-45
PVC compounds, 399, 400, 857,
859,861
PVC resins, 57, 203, 424, 465, 796,
832,854,855,897,926,964,969,
971,972,973,996,997,1008,
1052, 1054, 1064, 1098
Britomya, 222, 227,234-5,236,252,
Baco FRF, 252
Bakelite PVC resins (see also Ucar) ,
346
56,966,1051,1055
Brux alloy, 708
Ballotini,223
Burgess clays, 252
Baropan stabilisers, 369, 371
BZ 329 stabiliser, 285
1223

Acryloid modifiers
equivalence to Paraloid, 375,396
formulations, in, 108, 395, 887
Adimoll plasticisers, 178
Admex plasticisers, 179
Aerosil, 252, 973
Airco PVC resins, 22, 56
Ako-Stop, 1124
Alaiftex plasticisers, 177
Alfol alcohols, 151, 156, 164
Alphanol 79 alcohols, 150, 156, 164
Amaplast Yellow RRT, 404
Amoco Resin 18, 373
Antifoam A, 1028
Antistat A, 424, 425
Araclor plasticiser extenders, 179
Arbeftex plasticisers, 177
Argutop lacquers, 1008, 1009
Armodur, 905
Artevyl PVC resins, 56
Astraglass, 905
Atmer 152, 1082
Azocel blowing agents, 1088

1224

Index 2

Material and Product Trade Names

Cab-o-Sil, 973
Cadmium colourants, 414, 415
Calgon, 1029, 1043
Calibrite, 233, 234, 237, 252
Calmote, 252
Calofil, 252, 972
Calofort, 252, 972
Calopake,252
Carina PVC resins, 56
Carstab 700, 295
Celanese (Courtaulds) plasticisers,
163,177
Celcon, 735
Cellosolve, 1052, 1053, 1062
Celogen blowing agents, 1088, 1090
Cereclor plasticiser extenders, 127,
128, 130, 171, 172, 173, 177, 178,
432
Ceroxin lubricants, 371
Chemigum N8, 203
ChemPurge, 685
Chlorafin plasticiser extenders, 179
Chlorez plasticiser extenders, 178
Chlorowax plasticiser extenders, 178
Chrome Green DC 3593, 409
Cinquasia Violet RT 795 D, 407
Citroflex plasticisers, 174, 179
Clarechem CLA-1500, 430
Clorafin, 179
Cobex 1350, 905
Conductex 975, 424
Conoco
PVC compounds, 63, 1122
PVC resins, 56
Contrastat, 178
Corvic PVC resins, 34, 35, 52, 54, 56,
410,796,819,854,897,966,974,
987,988,990,997
Crestapol plasticisers, 129, 177
Cromophtal colourants, 408, 413
Cyanolit 811, 928
Cyasorb UV stabilisers, 294, 1055
Dacovin PVC resins, 57
Darvic,451,904,906-7,909
Dawsonite, 242, 243, 244, 248, 433
Day/Cal, 234

Day-Glo pigments, 403

Deckor
Cellset, 1082, 1098
lacquers, 1008
primer, 992
Dekadur,28
Delrin, 735
Denkavinyl PVC resins, 56
Diamond 450, 832
Dieldrin, 209
Diepox plasticisers, 178
Diolpate plasticisers, 129, 168, 177,
196
Diplast plasticisers, 178
Disflamoll plasticisers, 178
Dispex 115, 1043
Dobane plasticisers, 177
Drapex plasticisers, 177
Duraform, 217, 903, 909
Durastrength 200, 893
Durelast 100, 170, 197,401
Durostabe stabilisers, 280, 348, 349,
351
Dutrex plasticiser extenders, 174, 177
Dynel fibre, 20, 22
Dythal, 1089
Eastman 910, 928
Edenol plasticisers, 171, 178
Ekalit M, 401
Ekavyl PVC resins, 56, 57
Electrofine plasticiser extenders, 174,
177
Elvaloy, 170, 395, 452, 887
Emerwax lubricants, 371
Emery plasticisers, 178
Emiblend, 424
Enerfiex plasticiser extenders, 174,
177
Epivyl PVC resins, 56
Epoxol plasticisers, 179
Estabex ABF, 208, 484
Estabex plasticisers, 178
Estaflex plasticisers, 178
Estol 294, 796
Ethoquad C12, 423
Ethyl PVC compounds, 63, 726, 732,
795,857

Index 2 Material and Product Trade Names

Etinox PVC resins, 57

Exon PVC resins, 57
Ex-Static, 423
Extrudex pipe, 869
Ferralon wall coverings, 1114
Ferro-Check stabilisers, 284
Fibravylfibre, 1117
Ficel blowing agents, 1088
Flexol plasticisers, 179, 966
Flovic, 904, 907
Fordcal, 252
FPC PVC resins, 57
Franklin Fiber, 221
Fromopack sheet, 905
Fromoplas sheet, 1108
FW Rubine Toner BOS, 412
Fybex,242,243
Fyroflex flame and smoke retardant
plasticisers, 431
Gafstat AE 610, 423
Galon wall coverings, 1114
Gama-Sperse, 227
Garbeflex plasticisers, 177
Garbefos plasticisers, 177
Garotalc, 223
GasH, 252, 307, 973
Gedeflex plasticisers, 177
Genitron blowing agents, 1083, 1088,
1089, 1090, 1096
Geon
compounds, 28,53, 726,1122
CPVC resins, 25, 28
PVC latices, 1013
PVC resins, 56
flakuenka, 234, 252
flalowax 4004, 966
flalvic PVC resins, 57
fleatshrink fittings, 1125
fleliflex tubing, 1106
flercoflex plasticisers, 179
flercolyn plasticisers, 179
fleron duckboard, 1123

1225

flexaplas plasticisers, 158, 177, 178,

201,966,968
fligel,973
flishi-metal, 1115
flostaform, 735
flostalit PVC compounds, 63
flostalit PVC resins, 20, 56, 395
flostalit Z, 887
flostavinyl colour concentrates, 406
flydral, 252
flydrocarb, 222, 235
flytrel3495, 391
Igelit PC, 25
Inca-Brick, 1124
Instaweld adhesives, 929
Interstab
lubricants, 371
stabilisers, 271
Ionac PE 100, 423
Ionox antioxidant, 293
Irgalite colourants, 412, 414
Irganox antioxidants, 293, 294, 347
Irgasan DP 300, 208,485
Irgastab stabilisers, 108, 109, 113,
114,115,203,271,273,277,286,
287,292,308,347,348,351,374,
796,988, 1089
Irgastat antistatic agents, 424
Irgawax lubricants, 108, 110, 113,
203,308,355,371,794,796
Irgazin colourants, 413
Iriodin pigments, 403
Irvinil PVC resins, 57
Jayflex plasticisers, 177, 178
Kane Ace B 12, 796
Kaneka PVC resins, 56
Kematal, 735
Kem-Gard 911A, 432
Kempore blowing agents, 1088
Kenplast plasticiser extenders, 174
Ken-React, 227
Kesscoflex plasticisers, 178
Kevlar,1111

1226

Index 2 Material and Product Trade Names

Kodaflex plasticisers, 174, 178, 210

Kohinor PVC resins, 57
Kombipur, 401
Kosmos 70, 408
Kronitex plasticisers, 159, 178
Kronos Ti0 2 , 308
Kydex,745,905,909
Lacqvyl PVC resins, 56
Landex modifiers, 401
Lankroflex plasticisers, 171, 177, 351,
355,1031
Lankromark stabilisers, 286, 348,
352-4,355,371
Lankromet stabilisers, 286, 353
Lankroplast lubricants, 355, 371
Lankrostat antistatic agents, 115,422,
423
Laqua WB 240, 1009
Levapren modifiers, 395, 887
LF, LH, LL, stabilisers 345
Linevol alcohols, 156, 167
plasticisers, 110, 150, 164, 177,205
Lipinol plasticiser extenders, 174, 178
Loctite IS 414, 928
Lonzavyl PVC resins, 57
Loxiollubricants, 110, 354, 371
Lubraplas lubricants, 371
Lubriollubricants, 371
Lubrol, 422, 975, 977, 987, 988
Lucalor CPVC compounds, 28, 63
Lucel blowing agents, 1091
Lucovyl PVC resins, 56
Lutofan PVC resins, 56, 1013
Lytron 820, 1021
Manomet stabilisers, 351
Mark stabilisers, 277, 282, 285, 877,
1089
Marvinol PVC resins, 57
Mearlin Luster pigments, 403
Mellite stabilisers, 351, 796, 997, 1031
Mesamoll plasticisers, 130, 173, 178
Metaglide lubricants, 371
Metasap lubricants, 371
Metawax lubricants, 371

Microcarb,252
Microdol, 252
Microlith colour concentrates, 406
Microspin colour concentrates, 406
Mikro-Chek 12, 484
Millicarb, 234, 235, 236,252
Mirvyl PVC resins, 57
Mobisol plasticiser extenders, 174
Modifier PIM 101, 397
Mollan plasticisers, 177
Moly flame and smoke retardants,
430
Monastral Fast Blue BGS, 414
Monolite Fast Black LS, 414
Monolube lubricants, 371
Monoplas 230, 1098
Monoplex plasticisers, 171, 179
Morden R, 236
Morflex plasticisers, 129, 179
Movil fibre, 1117
Mural Mousse Somvyl Decor wall
coverings, 1113-14
Neo-Rez R900, 1009
Neosyl, 973, 974
Neralit PVC resins, 56
Nipolit PVC resins, 56
Nitropore blowing agents, 1090
Nitrosan, 1091
Nopco Foamaster Defoaming agents,
1028
Nopcowax lubricants, 371
Nor-Core 1124
Nordxyl, 250
Norvinyl PVC resins, 56, 1098
Nuoplaz plasticisers, 175, 179,210
Nuostabe stabilisers, 286, 348, 350,
351
Nycoflex plasticisers, 177
Omya, 100,227,234,237,238,252
Omyalite, 227, 235, 236, 252, 345,
346,354,355
Oncor flame retardants, 430
Ongard flame retardants, 430, 432,
434
Oriex, 905

Index 2 Material and Product Trade Names

Pacton SQ, 909

Palamoll plasticisers, 129, 177
Palatinol plasticisers, 177, 178, 203
Pantaprene L, 23
Paraloid modifiers
equivalence to Acryloid, 375, 396
formulations, in, 345, 346, 354,355
Paraplex plasticisers, 133, 171,179,
796,966,988,997
Pe-ee fibre, 5, 1117
Pekevic PVC resins, 57
Permabond adhesives, 929
Peroxidol plasticisers, 179
Pertinax, 921
Pevikon PVC resins, 57, 850, 953, 954
Pfinyl 402, 236
Phosclere stabilisers, 292
Phosftex plasticisers, 179
Phosgard LSV, 433
Plaskon PVC resins, 57
Plasthall DIDG, 165
Plastifiant K, 177
Plastolein plasticisers, 129, 168, 178
Plastomoll plasticisers, 177, 178
Pliabrac plasticisers, 159, 177,424,
987,990
Pliovic PVC resins, 23, 57
PMF (slag fibre), 242, 243
Polyblend 500 (Breon), 399,400
Polycarb, 226, 252
Poly-Check stabilisers, 282
Polycizer plasticisers, 179
Polydon PVC compounds, 63
Polyvin, 686
Poly-Zole blowing agents, 1091
Porofor blowing agents, 1088, 1091
Protect-A-Mat, 1124
PVC-Glas, 909
PV colourants, 412-13, 415
PX plasticisers, 179
Q-ce1l300, 223
Querton antistatic agents, 423
Quirvyl PVC resins, 57
Ramboo tubing, 1121
RapidPurge,685

1227

Ravinil PVC resins, 57

Ravolen plasticiser extenders, 174
RedHHR,404
Remafin colour concentrates, 406
Reofos plasticisers, 129, 159,160,
162,176,177,187,188,190,191,
194,203, 205,210
ReoP1ol plasticisers, 110, 129, 163,
165,176,177,203,410,977,988
Reoplast plasticisers, 171, 176, 177,
308,347,348,351
Reoplex plasticisers, 110, 129, 168,
176,177,199,211
Reproxal plasticisers, 178
Resin QX-2611, 423
Retractyl fibre, 1117
Reynosal PVC resins, 57
Rhenoftex, 25
Rhodamine B, 404
Rhodiastab 50, 283
Rhovyl filament, 1117
Ribstruct pipe, 883
Ricatyl plasticisers, 178
Ricon PVC resins, 57
Rigidsol, 940
Royalite, 745
Rubine Toner 2BRS, 406
Ruco PVC resins, 57
Rucodur PVC compounds, 396
Salol,295
Sanduvor VSU, 295
Santicizer plasticisers, 129, 161,162,
177,179,210,433
Santicizer 711, 156, 832
Santocel,974
Santoset plasticiser, 969
Sapchim lubricants, 374
Saran fibre, 22
Sartomer plasticisers, 969
SB 739 stabiliser, 286
Scadoplast, 178
Scandinol plasticisers, 177
SCC PVC resins, 56
Scon PVC resins, 57
Shinetsu PVC resins, 56
Shintech PVC resins, 56

1228

Index 2 Material and Product Trade Names

Sico Red WRC, 308

Sicol plasticisers, 178
Sicotan colourants, 408
Sicron PVC compounds, 63
Sicron PVC resins, 56
Simona-PVC-EL, 909
Sintaclad,905
Sintilon Stratum sheet, 1108
Sioplas, 588
Siscoversal colour concentrates, 410
Snow white, 221
Snowcal,252
Solemite, 227
Solvic PVC resins, 56, 203,308
Span 20, 1031
SPC PVC resins, 56
Spreaflex plasticisers, 178
SQ stabilisers, 343, 344, 346
Staflex plasticisers, 178, 179
Stanclere stabilisers, 271, 796, 997
Stenollubricants, 371
Sterishield, 1120
Stone Decor panels, 1113
Storeytrim, 909
Strandex, 343, 345
Sturcal, 259, 972
Sulfocel blowing agent, 1090
Superlon, 252
Super-Pflex 200, 227, 235
Superpolyroc pipe, 887
Supra colourants, 415
Suwide Placo wall coverings, 1114
Swada pigments, 403
Sylodex, 242, 973
Syloid,252
Synpron stabilisers, 277, 285
Syntewax lubricants, 371
Tangit solvent cement, 927
Telcovin TL, 905
Tenneco PVC resins, 56
Tensol solvent cement, 927
Texanol plasticisers, 151, 174,175,
178
Therm Check stabilisers, 277
Thermolite stabilisers, 271
Thermovyl fibre, 1117

Timonox, 253
Tinuvin light stabilisers, 108, 109,
295,347,351
Tioxide Ti0 2 , 346, 354, 355, 1043
Trihyde, 222, 252
Trocal Colour profile, 884
Trovidur HT, 25
Trovipor PVC resins, 57
TV-2 biostat, 484
Tween 20, 1031

Ucar PVC resins, 1050-1, 1054,

1058-61, 1062, 1064-5
Ultramoll plasticisers, 129, 170, 178
Ultramoll PU, 170,401
Unem plasticisers, 178
Uniflex plasticisers, 179
Unimoll plasticisers, 178
Uraplast plasticisers, 168, 178
UV-Chek AM 541A, 294
Uvinullight stabilisers, 294, 295

Vacupiast, 482
Varian PVC resins, 56
Vestinol plasticisers, 178
Vestolit PVC resins, 23, 56,887
Vinamold hot-melt compounds, 63
Vinaprint GV inks, 933
Vinatex Adhesive MP 7A, 992
Vinco stabilisers, 356
Vinidur PVC resins, 56
Vinnol PVC resins, 23, 56, 203, 877
Vinoflex PVC resins, 56
Vinophane, 895,909
Vinychlon PVC resins, 56
Vinylcel, 1077
Vinylite PVC resins, 1051, 1053
Vinyon HH, 22
Vipla, Viplavil, PVC resins, 56
Viton, 175
Vixir PVC resins, 57
VS-103 (foam cell stabiliser), 1075
Vulcabond VP, 1007
Vulcafor colourants, 412, 414
Vybak,905

Index 2 Material and Product Trade Names

Vyflex powder-coating compounds,

63,1118
Vygen PVC resins, 57
Vynamon colourants, 412-15

Winnofil, 252
Witaclor plasticisers, 178
Witamol plasticisers, 178
Wolflex plasticisers, 177, 200

Wacker plasticisers, 178

Wavihol pipe, 882
WaxE,355
Welvic PVC compounds, 63,70-7,
856,1125

XO 2243 (CPE), 832

XQ stabilisers, 343-6
Z-core alloy, 678

1229

INDEX 3

Named Equipment and Processes

ACS 500 colour analyser, 408

Automa Speed blow-moulding equipment, 781, 787
Banbury internal mixer, 811
Battenfeld extrusion and blowmoulding equipment, 704, 787,
788
Bekum blow-moulding machines,
771, 775, 786, 788
Bell blow-moulding equipment, 786
Bendix Ultra Viscoson viscometer,
954
Berstorff calendering and extrusion
equipment, 704, 804, 813
Beta gauge, 825
Betol Model 116 extrusion line, 1120
Bitruder, 610, 637-9, 706, 707,708
BKMI calendering equipment, 804
BLT 1000 leak finder, 798
Brabender
Plasti-Corder, 326, 327, 328, 368,
791,953
Plastograph, 132, 368, 953, 954
Brookfield viscometer, 954, 960-1,
1017
BuW controller, 872
Biihler-Miag pellet cooler, 663-4
Buss-Kneader, 581, 584, 594, 610,
614-23,624-5,626,627,647,649
650,810,811,813,1117

Buss mixing turbine, 549, 605,606-7,

657-9
Butler chimney apparatus, 505

Calandrette system, 891

Cascade extruder, see under Extruders (Index 1)
Castor-Severs viscometer, 960, 961
Cincinnati Milacron extrusion and
blow-moulding equipment, 704,
785,871
Clash and Berg method, 193, 194,442
Coexcel process, 884
7842 Color Analyzer II, 408
Contraves rheometer, 954, 955
Corex D light filter, 478,479
Corpoplast process, 776-8
Cuvar extrusion die, 873
Davis-Standard extrusion equipment,
699, 704
DCEIMSG compounder, 867
'Dead Load' hardness tester, 184
Dennis process, 1070
De Vilbiss JGA spray gun, 996
DI-NA-CAL process, 933
Dow cell, 462
DRI-CAL process, 933
1231

1232

Index 3 Named Equipment and Processes

Durometer (Shore) hardness tester,

184, 186, 1189
Dynatup impact tester, 380

Elastomer process, 1070

EMMA apparatus, 474
EMMAQUA apparatus, 474
EMS Industrie extrusion equipment,
704
Fade-Ometer, 478
Farrel group calendering equipment,
804
Fay Foamer process, 1070
FCM compounder, 610, 629, 633-5
Fischer blow-moulding equipment,
787, 788, 789
Ford cup, 961
Francis Shaw extrusion equipment,
705,892
Gardner
colorimeter XL 805, 408
impact tester, 380, 381
mixer, 6
viscometer, 961, 966
Haake-Rotovisco viscometer, 961
Henschel mixers, 549
HPM Corporation extrusion equipment 699, 704
Hunkar control systems, 771
Hunkar ILC process, 783

ICI method for foam cell content

determination, 1100
Intec 500 inspection system, 893
'Interval blowing' cooling system for
blow mouldings, 783
Jungfer (sintering) process, 1079

Kaufman extrusion equipment, 705

Kautex blow-moulding machines, 764
Kombiplast, 581, 584, 610, 623,
626-7,629,631,632-3
Kraus Maffei extrusion equipment,
682
Krupp--Kautex KEB blow-moulding
machines, 769, 781, 787, 788
Lasermark system, 936
Leesona blow-moulding machine, 773
Lesieur test bottle, 799
Luvitherm process, 590
Macklow-Smith plastometer, 65
Maco VI control system, 771
Maillefer extrusion equipment, 719
Maplan extrusion equipment, 682,
705,706-7
Mapre extrustion equipment, 702,
705, 706
Marrick process, 776-7
Match-Mate 3000 colour analyser,
408
Maximat blow-moulding machine,
787
Measurex 2001/25 control system, 826
Melville Plastics Engineering Extruder, 708-10
Mesco process, 10
Microscal apparatus, 479
Moog control systems, 771
MPCN compounder, 584-5, 610,
635,636-7
NBS smoke chamber, 434
NC-P thickness control system, 892
Oswag extrusion equipment, 705
OXO process, 152, 156
Planetary extruder, see under Extruders (Index 1)

Index 3 Named Equipment and Processes

Plasti-Corder, see under Brabender

Plastifikator, 581, 609, 610, 611, 61213
Plastimac blow-moulding equipment,
786,789
Plastograph, see under Brabender
Porvic process, 1078
Profitmaster 5510 control system, 893
QUV apparatus, 476, 479
RAPRA torque rheometer, 369
Reifenhauser extrusion equipment,
705, 707
Rheometries 'Mechanical Spectrometer', 954
Rollex calender line, 813
Rota-Sonic scanner, 872
Rotocure process, 1112
Saum Systems blow-moulding equipment, 773
Schloemann-Siemag blow-moulding
machine 773
Schramm-Zebrowski method (in
flammability tests), 504
Shell higher olefin process (SHOP),
156
Shelley 'Linear Series' thermoforming
line, 757
SIDEL blow-moulding machines,
768, 769, 787, 788
Sigmat 770 control system, 893
Speed blow-moulding machines, see
Automa Speed

1233

Statigun, 421
Stork system, 1094
Sussex thickness control system, 893
Taber Abraser, 1196
TCM foam moulding system, 1076
Technoform PPZ process, 875
Therimage process, 933
Thermassive window frame system,
1107
Thermorex gear pumps, 684
Topformer process, 743
TQ-150 mercury lamp, 329
Tri-Delta blow-moulding machines,
789
Trovipor process, 1070, 1071
Turbosphere mixer, 559, 560
Ultra Viscoson viscometer, see Bendix Ultra Viscoson
Underwriters tunnel furnace test, 506
Uniloy 300 blow-moulding line, 781
Urban AKS 3313 welding equipment,
923
Vanderbilt process, 1077
Vibrochrom FFR 2 colorimeter, 408
Weather-Ometer, 207, 475, 478
Werner Pfleiderer ZSK extruder, 623,
626, 632, 677
Xenotest apparatus, 207, 330, 478
XP-2 smoke chamber, 505