W. V. Titow M. Phil., PH.D., C. Chem., F. R. S. C., F. P. R. I., C. Text., A.T.I. (Auth.) - PVC Plastics - Properties, Processing, and Applications-Springer Netherlands (1990) PDF

PVC PLASTICS
Properties, Processing, and Applications

PVC PLASTICS
Properties, Processing,
and Applications
W. V. TITOW
M.Phil., Ph.D., C.Chem., F.R.S.C., F.P.R.I., C. Text., A. T.I.
ELSEVIER APPLIED SCIENCE

LONDON and NEW YORK
ELSEVIER SCIENCE PUBLISHERS LTD
Crown House, Linton Road, Barking, Essex IGll SJU, England
Sale distributor in the USA and Canada

ELSEVIER SCIENCE PUBLISHING CO., INC.
655 Avenue of the Americas, New York, NY 10010, USA
WITII 120 TABLES AND 149 ILLUSTRATIONS
© 1990 ELSEVIER SCIENCE PUBLISHERS LTD
British Library Cataloguing in Publication Data
Titow, W. V. (Witold Victor) 1926-

PVC plastics.
1. Polyvinyl chloride
I. Title
668.4236
ISBN 1-85166-471-8
Library of Congress Cataloging in Publication Data
Titow, W.V.
PVC plastics: properties, processing, and applications/
W. V. Titow.
p. em.
Includes bibliographical references.
ISBN 1-85166-471-8
1. Polyvinyl chloride. I. Title.
TPll80.V48T58 1990
668.4'237-dc 20 89-71512
CIP
No responsibility is assumed by the Publisher for any injury and/or damage to persons
or property as a matter of products liability, negligence or otherwise, or from any use or
operation of any methods, products, instructions or ideas contained in the material
herein.
Special repletions for readen in the USA

This publication has been registered with the Copyright Clearance Center Inc. (Ccq,
Salem, Massachusetts. Information can be obtained from the CCC about conditions
under which photocopies of parts of this publication may be made in the USA. All other
copyright questions, including photocopying outside the USA, should be referred to the
publisher.
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, photo-
copying, recording, or otherwise, without the prior written permission of the publisher.
Preface
This book originated from my Publisher's request for anew, concise

account of PVC plastics in terms of their nature, properties, process-
ing, and applications. There is thus, inevitably, an extensive thematic
overlap with my-still relatively recent-PVC Technology (4th edi-
tion), and I have drawn liberally on that source for a substantial
amount of relevant basic material. However, the present book is by no
means merely an abridgement of the earlier one: whilst indeed
considerably shorter, it is not only comparable in scope and general
coverage of the subject, but also contains much new information. I
have made a point of again strongly featuring the numerous standards
relevant-and in many cases cardinal-to the testing and characterisa-
tion of PVC materials and products, and to the evaluation of their
properties and performance: these standards are an indispensable part
of the technology of PVC plastics, and nobody concerned with any
aspect of this complex subject should fail to recognise that fact.
It is ever a pleasure to express appreciation and thanks where they
are due.
I am grateful to Dipl-Ing. H. E. Luben of Brabender OHG,
Duisburg, FRG, not only for the up-to-date information he provided
on Brabender equipment, but also most particularly for his exception-
ally friendly, helpful attitude in all our contacts, and for the trouble he
took to make some illustrations and figures available in the form
convenient for direct reproduction. The courtesy of those other
persons and/or companies to whom I am indebted for the photo-
graphic illustrations is, in each case, acknowledged in the relevant
caption.
Myoid friend and former colleague Mr David Mugridge, of the
Yarsley Technical Centre, Redhill, UK, kindly obtained for me some
v
vi Preface
additional information I needed for Chapter 20. I am most grateful for

this help.
My appreciative thanks go to Mrs Micky Kruger, who typed the
manuscript and provided other secretarial assistance.
As on previous occasions, I have experienced-and much
appreciated-the friendly, courteous cooperation of every member of
the Publisher's team concerned with the preparation and production of
the book.
W.V.T.
Contents
Preface. . . . . . . . . . . . . . . . . . . . . . . . . . v
Section I-Introductory 1
Chapter 1 . . . . . . . . . . . . . . . . . . 3
General Introduction . . . . . . . . . . . . 3
1.1 Some Key Terms, Definitions, and Concepts 3
1.1.1 What is PVC? . . . . . . . . . . 3
1.1.2 The Nature and Make-Up of PVC Materials 4
1.1.3 Abbreviations and Symbols for Material Names 5
1.2 Material and Test Standards . . . . . . . . . . . . 6
1.3 Origins, Historical Development, and Present Position of
pvc . . . . . . . . . . . . . . . . . . . . . 8
1.3.1 Early History . . . . . . . . . . . . . . . . 8
1.3.2 Present Position: (a) PVC as a major, highly
versatile thermoplastic; (b) some topical concerns-
vinyl chloride as a health hazard; some PVC for-
mulation constituents as potential health hazards;
health hazards associated with combustion products
of PVC; disposal of waste PVC products . . . . 10
1.3.3 The PVC Industry-Outline of General Structure 16
References 17
Bibliography 18
Chapter 2 . . . . . . . . . . . . . . . . . . . . . . . . 22
Constitution and Formulation of PVC Materials. . . . . . . 22
2.1 PVC Compositions (Compounds) and Their Formulation 22
vii
viii Contents
2.1.1 General Features and Main Categories . . . . . 22

2.1.2 Constituents of PVC Compositions (Formulation
Components) . . . . . . . . . . . . . . . 24
2.2 The Basics of Formulating PVC Compositions . . . . . 25
2.2.1 General Considerations: (a) processing require-
ments; (b) service requirements-food-contact and
medical applications; outdoor applications; electrical
insulation; (c) material and process cost economy 25
2.2.2 Selection of the Principal Individual Constituents of
a PVC Composition: (a) PVC polymer; (b) heat
stabilisers; (c) plasticisers; (d) lubricants; (e) poly-
meric modifiers; (f) fillers; (g) colourants; (h) other
components of PVC formulations . . . . . . . 27
2.2.3 Some Aids to Formulating: (a) computer-aided
formulating; (b) 'desirability function' in plasticiser
selection for pPVC formulations . . . . . . . . 35
2.2.4 Some Interactions and Mutual Effects of Principal
Components of PVC Formulations: (a) compatibility
effects; (b) synergism; (c) other mutual effects . . 36
2.2.5 Side-Effects of Formulation Components: (a) 'sec-
ondary functionality' effects; (b) undesirable side-
effects. . . . . . . . . . . . . . . . . . . . 37
2.2.6 Examples of Basic Formulations: (a) pipes and
tubing; (b) extruded profiles; (c) sheeting and film;
(d) calendered PVC/asbestos flooring (tiles); (e)
cable covering and insulation; (f) injection mould-
ings; (g) blow-moulded bottles; (h) paste formula-
tions . . . . . . . . . . . . . 38
2.3 Materials Cost of a Formulation . . . . 45
2.4 Compositional Analysis of PVC Materials 46
References . . . . . . . . . . . . . . . . 48
Section 2-Constituents of PVC Compositions 51
Chapter 3 . . . . . . . . . . . . . . 53
PVC Polymers . . . . . . . . . . . 53
3.1 Homopolymers of Vinyl Chloride. 53
3.1.1 Chemical Structure and Molecular Weight. 53
Contents ix
3.1.2 Polymer Morphology and Some Related Properties 59

3.1.3 Production of PVC Polymers: (a) vinyl chloride
monomer (VC); (b) polymerisation processes-
suspension polymerisation; mass (bulk) polymerisa-
tion; emulsion polymerisation . . . . . . . . . 61
3.1.4 Physical Forms of PVC Polymers: (a) suspension
polymer particles; (b) mass polymer particles; (c)
emulsion polymer particles . . . . . . . . . . 67
3.1.5 Effects of Some Polymerisation Process Factors on
Polymer Characteristics 73
3.2 Copolymers of Vinyl Chloride 73
3.2.1 Kinds and Applications 73
3.2.2 Production . . . . . 78
3.3 Commercial PVC Polymers . 78
3.3.1 Polymer Properties Cardinal to Processing and/or
Service: (a) chemical composition; (b) molecular
weight (viscosity number; K value); (c) polymer
particle characteristics; (d) quality (purity) 78
3.3.2 Characterisation and Designation of Commercial
PVC Polymers. . . . . . . . . . . . 81
3.3.3 Some Commercial Sources and Materials 90
3.4 Chlorinated Polyvinyl Chloride (CPVC) 90
3.4.1 Origins and Production Methods 90
3.4.2 Chemical Structure . . . . . . 95
3.4.3 Material Properties. . . . . . 96
3.4.4 Formulation and Processing of CPVC Compositions 97
3.4.5 Commercial CPVC Compounds and Their Applica-
tions 99
References 99
Chapter 4 . . . . . . . . . . . . . . . . 102
Stabilisers . . . . . . . . . . . . . . 102
4.1 Degradation and Stabilisation of PVC. 102
4.1.1 General. . . . . . . . . . . 102
4.1.2 Thermal Degradation: (a) outward manifestations;
(b) chemical aspects-dehydrochlorination and col-
our development; chemical basis of other property
changes; vulnerable sites in the PVC polymer chain;
(c) thermal degradation in melt processing and static
x Contents
exposure to heat; (d) effects of polymer molecular

weight, and some impurities and additives . 103
4.1.3 Photochemical Degradation 109
4.2 Purposes and Functions of Stabilisers in PVC 111
4.3 Heat Stabilisers . 112
4.3.1 General Classification of Heat Stabilisers 114
4.3.2 Lead Compounds 115
4.3.3 Organotin Stabilisers: (a) chemical nature and types;
(b) characteristics and applications; (c) mode of
action. 119
4.3.4 Other Metal-Based Stabilisers: (a) nature, and some
general applicational features; (b) antimony stabili-
sers; (c) calcium stearate; (d) mixed-metal
stabilisers-barium/ cadmium and barium/ cadmium/
zinc stabilisers; calcium/zinc stabilisers; other
mixed-metal stabilisers; mode of action of mixed-
metal stabilisers 124
4.3.5 Organic and Miscellaneous Stabilisers: (a) esters of
aminocrotonic acid; (b) urea derivatives; (c) epoxy
compounds; (d) organic phosphites; (e) other or-
ganic stabilisers 135
4.3.6 Stabiliser/Lubricant Balance and Interactions 140
4.4 Antioxidants and Light Stabilisers 141
4.4.1 Antioxidants. 141
4.4.2 Light Stabilisers: (a) organic UV absorbers; (b)
inorganic (particulate) UV-screening agents; (c)
free-radical scavengers; (d) chromophore quenchers;
(e) some general features of the action of light
stabilisers and antioxidants 143
4.5 Stabilisers in Single-Pack Additive Systems 149
4.6 Some Commercial Stabilisers . 151
4.7 Some General Effects of Stabilisers on Various Properties
of PVC Compositions . 151
4.8 Some Stabiliser-Related Problems 151
4.8.1 Sulphide Staining. 151
4.8.2 Plate-Out . 157
4.9 Testing and Evaluation of Stabilisation Effects 160
4.9.1 The Concept of Stability in Processing, Service, and
Tests. 160
4.9.2 Stability Testing: (a) heat-stability tests-dynamic
Contents xi
stability tests; static stability tests; (b) light-stability

~~. 1~
References 174
Chapter 5. 177
Plasticisers 177
5.1 General Definition and Nature of Plasticisers . 177
5.2 Plasticisation Mechanism, and some Relevant Features of
Plasticiser Structure. . . . . . . . . . . . 179
5.3 Main Outward Manifestations of Plasticisation . 182
5.3.1 Effects of the Level of Plasticisation 182
5.3.2 Stages of Plasticiser-Polymer Interaction 184
5.3.3 Ageing of Plasticised PVC after Processing 185
5.4 Principal Functional Parameters of Plasticiser Action 186
5.4.1 Compatibility and Miscibility: (a) the 11 value; (b)
solubility parameter 6; (c) clear-point temperature
(solid-gel transition temperature); (d) interaction
parameters: Flory-Huggins (X) and Bigg (a); (e)
Api Po ratio; (f) loop and roll compatibility tests; (g)
maximum-torque temperature (fusion point) in con-
trolled mixing . . . . . . . . . . 186
5.4.2 Effectivity (Efficiency) of Plasticisers . . . . . 193
5.4.3 Permanence of Plasticisers. . . . . . . . . . 195
5.5 Plasticiser Types, Their Characteristics and Commercial
Versions. . . . . . . . . . . . . . . . . . . . . 196
5.5.1 General Type Classification . . . . . . . . . 196
5.5.2 Plasticiser Nomenclature: Names, Synonyms, and
Abbreviations . . . . . . . . . . . . . . . . 198
5.5.3 Properties of Individual Plasticiser Types, and Their
Main Effects in PVC: (a) phthalate plasticisers-
lower phthalates; general-purpose phthalates; linear
phthalates; higher phthalates; miscellaneous phtha-
lates; (b) phosphate plasticisers-triaryl phosphates;
trialkyl phosphates; mixed alkyl aryl phosphates;
halogenated alkyl phosphates; (c) trimellitate plas-
ticisers; (d) aliphatic diester plasticisers; (e) polyme-
ric plasticisers; (f) miscellaneous plasticisers-epoxy
plasticisers; chlorinated paraffins and olefins; mono-
esters; glycol and polyglycol esters; other mis-
cellaneous plasticisers; hydrocarbon extenders . . . 201
xii Contents
5.5.4 Transport, Handling, and Storage of Plasticisers 223

5.5.5 Some Commercial Sources and Trade Names of
Plasticisers . . . . . . . . . . . . . . . . 224
5.6 Plasticiser-Inftuenced Properties of PVC. . . . . . . 224
5.6.1 Formulating Considerations-General Points. 224
5.6.2 Softness and Tensile Properties: (a) softness; (b)
tensile strength and elongation at break 230
5.6.3 Low-temperature Properties . 237
5.6.4 Electrical Properties . . . . . . . . 239
5.6.5 Flammability. . . . . . . . . . . . 239
5.6.6 Permanence Properties: (a) volatile loss-
automotive fogging; plasticisation of cable cover-
ings; (b) extraction resistance; (c) migration resis-
tance; (d) high-humidity compatibility . . . . 239
5.6.7 Stain Resistance . . . . . . . . . . . . . . 248
5.6.8 Resistance to Weathering and Photodegradation 249
5.6.9 Resistance to Biological Attack . . . . . . . 250
5.7 Toxicity and Health Aspects . . . . . . . . . . . . 250
5.7.1 Plasticisers in Food-Contact and Medical Applica-
tions . . . . . . . . . . . . . . 250
5.7.2 Plasticiser Handling and Processing. 251
5.8 Standards Relevant to Plasticisers . 255
References . . . . . . . . . . . . . . . . . 255
Chapter 6. . . . . . . . . . . . . . . . . . 258
Fillers . . . . . . . . . . . . . . . . . . . 258
6.1 Definition and General Functions of Fillers 258
6.2 Particulate Mineral Fillers . . . . . . . . 259
6.2.1 Silicates and Silicas: (a) clay; (b) asbestos; (c) talc;
(d) other silicate fillers-wollastonite; mica; nephe-
line syenite . . . . . . . . . . . . . . . . . 259
6.2.2 Alkaline-Earth Metal Sulphates; (a) barium sulph-
ate; (b) anhydrous calcium sulphate . . . . . . 265
6.2.3 Calcium Carbonate Fillers: (a) general: types and
characteristics; (b) whiting; (c) ground limestone,
marble, and calcite; (d) ground dolomite; (e) pre-
cipitated calcium carbonates; (f) filler properties and
selection criteria-maximum particle size; particle
size distribution and mean particle size; dry bright-
ness; refractive index (opacifying effect); oil (plas-
Contents xiii
ticiser) absorption; dispersion characteristics; cost;

(g) applications, and some effects, of filler loading-
flooring; plasticised compounds; rigid compounds 266
6.3 Functional Fillers. . . . . . . . . . . . . . . . . . 281
6.3.1 Reinforcing Fillers: (a) asbestos (chrysotile) fibres;
(b) miscellaneous inorganic microfibres; (c) glass
fibres; (d) microspheres; (e) fine-particle calcium
carbonate. . . . . . . . . . . . . . . . . 281
6.3.2 Flame-Retardant and Smoke-Suppressant Fillers 286
6.3.3 Miscellaneous Functional fillers: (a) carbon black;
(b) metal, or metallised particles and fibres; (c)
wood flour; (d) cellulose fibres; (e) starch 286
6.4 Surface Treatments for Fillers . . . . . . . 288
6.4.1 Stearate Treatments . . . . . . . . 289
6.4.2 Treatment with Silane Coupling Agents 289
6.4.3 Organotitanate Treatments . . . . . 290
6.4.4 Proprietary and Miscellaneous Treatments. 290
6.5 Commercial Fillers 293
References . . . . . . . . . . . . . . . . . . . . 293
Chapter 7. . . . . . . . . . . . 294
Lubricants . . . . . . . . . . . 294
7.1 Functions, Nature, and Effects 294
7.2 Interaction and Co-action of Lubricants with Other PVC
Formulation Components . . . . . . . . . . . . . . 301
7.2.1 Lubricant/Stabiliser Effects: (a) stabilising effects of
lubricants-direct stabilising action; synergistic ac-
tion with stabilisers; indirect stabilising action; (b)
lubricant action of stabilisers. . . . . . . . . . . 301
7.2.2 Mutual Effects of Lubricants and Plasticisers: (a)
primary plasticisers; (b) secondary plasticisers and
extenders . . . . . . . . . . . . . . . . . . 303
7.2.3 Effects of Polymeric Modifiers: (a) impact modifiers;
(b) processing aids . . . . . . 304
7.2.4 Effects of Fillers and Pigments . . . . . . . . . 304
7.3 Assessment of Lubricant Performance. . . . . . . . . 305
7.3.1 Test Methods: (a) sheet 'fluidity' test; (b) two-roll
milling; (c) flow in the moulds and dies-flow in a
spiral mould; flow in a Rossi-Peakes flow tester;
xiv Contents
flow in a piston plastometer; the ASTM capillary

rheometer test; (d) tests using the Brabender Plasti-
Corder-fusion test in a roller mixer attachment;
processability test in a Brabender Extrusiograph
with a rheometric head . . . . . . . . 305
7.3.2 Some Research Equipment and Methods 309
7.3.3 'Lubricant Value' . . . . . . 309
7.4 Some Effects of Incorrect Lubrication 310
7.5 Commercial Lubricants 310
References . . . . . . . . . . . . . . 312
Chapter 8 . . . . . . . . . . . . . 313
Polymeric Modifiers . . . . . . . . 313
8.1 Nature and Functions-General 313
8.2 Processing Aids. . . . . . . . 314
8.3 Impact Modifiers . . . . . . . 316
8.3.1 Impact Resistance-Definition, Significance, and
Measurement . . . . . . . . . . . . . . . . 316
8.3.2 The Impact Resistance of PVC . . . . . . . . . 322
8.3.3 The Nature, Effects, and Applications of Polymeric
Impact Modifiers for PVC: (a) ABS modifiers; (b)
MBS modifiers; (c) acrylic modifiers; (d) rubber-
modified styrene/maleic anhydride copolymers; (e)
nitrile rubbers (acrylonitrile/butadiene copolymers);
(f) E/VAC modifiers; (g) chlorinated polyethylene
(CPE); (h) polyurethane (PUR) elastomers 323
References 333
Chapter 9 . . . . . . . . . . . . 335
MisceUaneous Additives . . . . . 335
9.1 Additives Active in Processing 335
9.1.1 Chemical Blowing Agents for PVC Foams. 335
9.1.2 Cell-Control Agents for PVC Foams . . 343
9.1.3 Minor Additives for PVC Pastes . . . . . 344
9.2 Additives Incorporated for End-Use Properties . . " . 345
9.2.1 Colourants: (a) general; (b) choice of colourant-
colour; processability; stability and performance in
service; health and safety considerations; (c) some
Contents xv
practical tests-heat stability; stability to light and

weathering; colour migration . . . . . . . . . 345
9.2.2 Flame Retardants and Smoke Suppressants . . . 351
9.2.3 Additives for Antistatic and Conductivity Effects:
(a) antistatic surface-active agents; (b) polymeric
antistatic additives; (c) conductive fillers; (d) some
relevant test methods and specifications . . . 354
9.2.4 Odour Control Agents . . . . . . . . . . 359
9.2.5 Matting ('Flatting') and Anti-blocking Agents 360
References 361
Section 3-Production (Compounding) of Solid PVC Composi-

tions. . . . . . . . . . . . . . . . . . . . . . . . . . . 363
Chapter 10 . . . . . . . . . . 365
Solid ('Dry') PVC Compositions 365
10.1 General . . . . . . . . 365
10.2 Types and Forms of PVC Compounds 367
10.3 Some Material Properties of PVC Compounds 370
10.3.1 Physical and Short-Term Mechanical Properties 370
10.3.2 Creep and Fatigue in Rigid Compositions: (a)
creep; (b) fatigue. . 370
10.3.3 Thermal Properties . 379
10.3.4 Electrical Properties 379
10.3.5 Chemical Properties 379
10.3.6 Miscellaneous Properties: (a) optical; (b) water
absorption; (c) others. . . . . . . . . . . . 385
10.4 Characterisation and Standard Designation of Commercial
PVC Compounds . . . 387
10.4.1 Characterisation 387
10.4.2 Designation 388
References . 392
Chapter 11 . . . . . . . . . . . . . . 393
Compounding: Operations and Equipment 393
11.1 General . . . . . . . . . . . . 393
xvi Contents
11.2 Industrial Production of Solid Compounds . . . . . . . 396

11.2.1 Upstream Equipment and Operations: (a) han-
dling, storage, and conveying-polymer and
fillers; plasticisers; other formulation components
(additives); (b) metering-general; major for-
mulation components; minor formulation com-
ponents; control and accuracy in metering in-
stallations; batch assembly. . . . . . . . . . . 396
11.2.2 Compounding Operations and Equipment: (a)
general; (b) production of powder mixes-batch
mixing; continuous mixing; (c) melt-
compounding: objectives and general features; (d)
melt-compounding machinery: continuous
compounding-the Plastifikator (shear-cone com-
pounder); the Buss kneader; the cascade ex-
truder; the Kombiplast equipment; the FCM
continuous mixer; the MPC/V compounder; the
Bitruder BT; the planetary compounder; machine
drives and controls; machine working surfaces and
parts; on-line operational and melt quality con-
trol; (e) further processing-pelletising; pellet
cooling; mixing (blending) of pellets; final han-
dling and delivery; (f) batch compounding in
internal mixers; (g) compounding some recycled
materials . . . . . . . . . . . . . . . . . . 412
11.2.3 Compounding for Direct Feeding of Calenders. 455
11.3 Compounding of Liquid PVC Compositions. . . . . . 455
11.4 Small-Scale (Laboratory) Compounding . . . . . . . 455
11.4.1 General: (a) usual objectives; (b) scope of discus-
sion in this chapter . . . . . . . . . . . . . . 455
11.4.2 Laboratory Compounding Equipment and Its
Uses: (a) some laboratory and pilot-scale counter-
parts of industrial compounding equipment-
powder mixers; two-roll mills; Kombiplast; Buss
Kneader; compounding extruders; internal
mixers; (b) specialised instrumented equipment
for investigation and study of compounding be-
haviour and effects 456
References . 463
Contents xvii
Section 4---Processing of Solid PVC Compositions into Products 465
Chapter 12 . . . . . . . . . . . . . . . . . . . . . . . . 467
Main Types of PVC Products and Methods of Their Production 467
12.1 PVC Products of Greatest Industrial Importance-General 467
12.2 Rigid PVC Products . . . . . . . . . . . . . . " 467
12.2.1 Pipes and Conduit: (a) types of PVC pipes-
principal general kinds; some special pipe forms;
(b) some formulation aspects; (c) important pipe
properties and their determination . . . . . . . 467
12.2.2 Profiles and Cladding (Siding): (a) types and
applications; (b) some formulation aspects; (c)
testing and specifications . . . . . . . . , . 475
12.2.3 Sheeting and Film: (a) terminology; (b) produc-
tion types; (c) some formulation aspects; (d)
properties and applications 481
12.2.4 Blow Mouldings . . . 486
12.2.5 Injection Mouldings . 486
12.2.6 Gramophone Records. 486
12.3 Plasticised PVC Products . . . 486
12.3.1 Electric Cable and Wire Coverings: (a) types and
applications; (b) properties and tests 486
12.3.2 Sheeting and Film . 489
12.3.3 Flooring. . . . . . 493
12.3.4 Tubing and Profiles. 493
12.3.5 Fabric Coatings 495
References 496
Chapter 13 . . . . . . . . . . . . . . . . . . . . . " 497

Extrusion. . . . . . . . . . . . . . . . . . . . . . . . 497
13.1 History and Significance of Extrusion in PVC Processing 497
13.2 Extruders Used in PVC Processing. . . . . . . . . . 498
13.2.1 General. . . . . . . . . . . . . . . . . . 498
13.2.2 Basic Operational Features: (a) the screw; (b) the
barrel; (c) the head and die assembly; (d) the
hopper; (e) main operating characteristics of
single-screw and twin-screw extruders for PVC
processing. . . . . . . . . . . . . . . . . . 499
xviii Contents
13.3 Some General Points Relevant to PVC Extrusion 504

13.3.1 Working Surfaces 504
13.3.2 Use of Gear Pumps. 505
13.3.3 Purging. . . . . . 506
13.3.4 Coextrusion. . . . 507
13.3.5 Extrusion of CPVC . 507
13.3.6 Computerisation and Automation of Extrusion
Lines. . . . 508
13.4 Material Aspects. . . 508
13.4.1 Formulations 508
13.4.2 Feed Types . 508
13.4.3 Stock Transformations in the Course of Extrusion 509
13.4.4 Some Extruded-Product Faults: (a) manifestations
of incomplete gelation; (b) irregularities of par-
ticulate appearance; (c) variation or fluctuation in
dimensions; (d) plate-out . . . . . . . . 511
13.5 Basic Extrusion Lines for Important Extruded PVC
Products . . . . . . . . . 513
13.5.1 Rigid Pipe Extrusion 513
13.5.2 Profile . . . . . 516
13.5.3 Sheeting and Film . 516
13.5.4 Wire Covering. . . 519
13.6 Some Commercial Extrusion Equipment 522
References . 522
Chapter 14 . 524
Calendering. 524
14.1 Origins, and Current Position in the PVC Industry 524
14.2 Equipment and Process: General Aspects. . . . 524
14.2.1 The Calender . . . . . . . . . . . . 525
14.2.2 The Calendering Operation: Main Features and
Their Effects on the Structure and Properties of
Calendered Sheet . . . . . . . . . . . . . 529
14.3 Calender Lines . . . . . . . . . . . . . . . . . . 530
14.3.1 Regular General-Purpose Lines: (a) pre-calender
(compounding and feed) section; (b) calender
section; (c) post-calender section-sheet take-off
and stretching; embossing; cooling; measurement
and control of sheet thickness; edge trimming;
wind-up. . . . . . . . . . . . . . . . . . . 530
Contents xix
14.3.2 Other Lines and Arrangements: (a) lines for

calendered flooring; (b) 'Calandrette' lines; (c)
lamination on or at the calender . . . . . . . 542
14.4 Formulation of PVC Compositions for Calendering 546
14.5 Some Faults and Defects Occurring in Calendered Sheet-
ing. . . . . . . . . . . . . . . 549
14.5.1 Simple Dimensional Faults 549
14.5.2 Structural Defects . . . . 549
14.5.3 Faults Manifested in Appearance -. 550
14.6 Further Processing of Calendered Sheet 552
14.6.1 Press Finishing. . . 552
14.6.2 Press Lamination. . . . . . . 553
14.6.3 Surface Treatments. . . . . . 553
14.6.4 Continuous Lamination away from the Calender 553
14.7 Calendered-Sheet Products: Properties and Applications 554
References . . . . . . . . . . . . . . . . . . . . . . . 559
Chapter 15 . . . . . 560
Blow Moulding . . . 560
15.1 Basic Features. 560
15.2 Blow-Moulding Processes and Their Application to PVC 562
15.2.1 General Characterisation and Principal Features
of Blow-Moulding Techniques and Systems: (a)
extrusion blow moulding-general operational se-
quence; parison programming, and other control;
(b) injection blow moulding; (c) dip blow mould-
ing . . . . . . . . . . . . . . . . . . . . 562
15.2.2 Stretch-Blowing in Blow Moulding. . . . . . 569
15.2.3 Process and Equipment Arrangements in Blow
Moulding . . . . . . . . . . . . . . . . . 570
15.2.4 Cooling Methods. . . . . . . . . . . . . . 571
15.2.5 Miscellaneous Features: (a) mould venting; (b)
removal of waste material; (c) part removal
(take-off) systems; (d) blowing pressures 573
15.3 Industrial Blow Moulding of PVC . . 574
15.4 PVC Compositions for Blow Moulding 577
15.4.1 The Processing Aspect . . . 577
15.4.2 The End-Use Aspect . . . . 579
15.4.3 Formulations: (a) commercial compounds;
xx Contents
(b) formulation components-PVC polymer; sta-

biliser system; impact modifiers; lubrication; other
components . 580
15.5 PVC Blow Mouldings . . . 583
15.5.1 Applications . . . . 583
15.5.2 Properties and Tests 584
References . 586
Chapter 16 . . . . . . . . . . . . . . . . . . . . 588
Injection Moulding . . . . . . . . . . . . . . . . 588
16.1 The Process and its Application to PVC-General 588
16.2 The Material Aspect . . . . . . . . . . . . . 589
16.2.1 PVC Melt Properties and Behaviour . . 589
16.2.2 Moulding Compounds: (a) general points; (b)
'easy flow' moulding compounds; (c) melt flow
tests for moulding compounds . . . . . . . . 591
16.3 Equipment and Process Considerations . . . . . . . . 594
16.3.1 Equipment: (a) features and operation; (b) work-
ing surfaces . . . . . . . . . . . . . . . . 594
16.3.2 Processing: (a) stock temperature, and tempera-
ture settings; (b) rate of injection and injection
pressure; (c) interaction of PVC with acetal
polymers and copolymers . . . . . . . . . . 597
16.3.3 Flow Moulding. . . . . . . . . . . . . . . 600
16.3.4 Moulding Quality Maintenance, and Some Com-
mon Faults . . . . . . . . . . . . . . . . 600
16.4 Some Effects of Processing on the Morphology of Injec-
tion Mouldings . . . . . . . . . . . . 601
16.4.1 Quenching Stresses. . . . . . . 603
16.4.2 Orientation and Related Features 603
16.5 Injection Moulding of CPVC 604
References . . . . . . . . . . . . . . . . . 605
Chapter 17 . . . . . . . . . . . . 607
Other Processes. . . . . . . . . . 607
17.1 Compression Moulding of PVC 607
17.1.1 General . . . . . . . 607
17.1.2 Industrial Applications: (a) production of gramo-
Contents xxi
phone records; (b) compression moulding of thick

sheets (press lamination) 607
17.1.3 Sheet Moulding for Samples and Test Specimens:
(a) unplasticised PVC sheet-preparation of mill
sheet; compression moulding of final sheet in a
picture-frame mould; (b) plasticised PVC sheet 610
17.1.4 Compression Moulding of PVC Paste 613
17.2 Thermoforming 614
17.2.1 General Features . 614
17.2.2 Plastics Materials Used in Thermoforming . 615
17.2.3 Assessment of the Thermoforming Characteristics
of Materials . 616
17.2.4 Thermoforming Methods: (a) main types and
variants; (b) some processing considerations . 619
17.2.5 Thermoforming Equipment: (a) machinery; (b)
moulds-mould materials; applicational features
of main mould types; mould construction 627
17.2.6 Finishing Operations 630
17.2.7 Thermoformed Parts: (a) general design con-
siderations; (b) dimensional stability, and effects
of temperature and draw ratio on part quality 630
17.3 Powder Sintering and 'Lost Filler' Methods in the Produc-
tion of Porous PVC Sheets 632
17.3.1 Sintering of Powder 632
17.3.2 The 'Lost Filler' Method 633
References . 634
Section 5---Liquid PVC Compositions: Nature, Preparation,

Processing, and Applications . . . . . . . . . . . 635
Chapter 18 . . . . . . . . . . . . . . . . . . . . . . 637
PVC Pastes. . . . . . . . . . . . . . . . . . . . . . 637
18.1 The Nature and Terminology of PVC Pastes-General 637
18.2 The Role and Basics of Paste Rheology . . . . . . 638
18.2.1 Viscosity of PVC Pastes: (a) features relevant to
behaviour in processing; (b) basic modes of
rheological behaviour: effects of shear rate, and of
time under constant shear . . . . . . . . . . . 638
xxii Contents
18.2.2 Rheological Effects of the Polymer Component in

a PVC Paste: (a) polymer particle content ('poly-
mer fraction'); (b) polymer particle
characteristics-particle size and size distribution;
particle interactions. . . . . 643
18.3 Measurement of PVC Paste Viscosity . . . . . . . . . 645
18.4 Gelation/Fusion of PVC Pastes . . . . . . . . . . . . 646
18.4.1 General Features of the Transformation of a Paste
into a pPVC Material. . . . . . . . . . 646
18.4.2 Polymer-Plasticiser Interactions during the
Gelation/Fusion of a PVC paste . . . . . 647
18.4.3 Practical Determination of the Completeness of
Fusion in Paste Products . . . . . 651
18.5 The Composition of PVC Pastes. . . . . . . . . . . 653
18.5.1 Paste Formulation-General Points. . . . . . 653
18.5.2 Components of PVC Pastes: (a) paste polymers;
(b) plasticisers; (c) stabilisers; (d) fillers; (e)
additives modifying paste rheology-thickening
agents; viscosity depressants; diluents; (f) mis-
cellaneous additives. . . . . . . . . . . . 653
18.5.3 Pastes for Rigid Products: (a) organosols; (b)
rigisols . . . . . . 659
18.6 Preparation of PVC Pastes . . . . . . . . . . . 661
18.6.1 Some General Points . . . . . . . . . . 661
18.6.2 Small-Scale (Laboratory) Paste Preparation 662
18.6.3 Industrial Production of Pastes. . . . . . 664
18.7 Application of PVC Pastes: Processes and Products 666
18.7.1 Moulding Processes: (a) rotational casting; (b)
slush moulding; (c) dip mOUlding. . . . . . 666
18.7.2 Coating of Objects and Articles: (a) dip coating-
hot-dip coating; cold-dip coating; (b) spray coat-
ing . . . . . . . . . . . . . . . . . . . 668
18.7.3 Coating of Fabrics and Paper: (a) coating pro-
cesses and methods; (b) quality and testing of
paste-coated materials-some coating faults; test-
ing . . . . . . . . . . . . . . . . . . . 670
18.7.4 Paste Casting . . . . . . . . . . . . . . 678
18.7.5 Other Paste-Processing Methods of Minor Sig-
nificance 681
References . 681
Contents xxiii
Chapter 19 . . 683
Solutions. . . 683
19.1 General 683
19.2 Composition of PVC Solutions 683
19.2.1 The PVC Polymers: (a) homopolymers; (b) co-
polymers and terpolymers. . . . . 684
19.2.2 Solvents and Diluents. . . . . . . 688
19.2.3 Other Constituents of PVC Solutions 689
19.3 Preparation of PVC Solutions 692
19.4 Applications 694
References . . . . . . . . . . . 697
Chapter 20 . . . . . . . . . . . . . . . . . 698
PVC Latices . . . . . . . . . . . . . . . . 698
20.1 The Nature and PVC Versions of a Latex 698
20.1.1 Definition and General Characteristics 698
20.1.2 Basic Processing Features 700
20.2 Types of PVC Latices . . . . 702
20.2.1 General. . . . . . . 702
20.2.2 Homopolymer Latices 703
20.2.3 Copolymer Latices . . 703
20.3 Commercial PVC Latices . . . 706
20.4 Formulation and Compounding of PVC Latices 706
20.4.1 General Considerations . . . . . . . 706
20.4.2 Constituents Controlling Latex Stability and Pro-
perties: (a) latex stabilisers (emulsifiers); (b)
wetting agents; (c) thickeners; (d) anti-foaming
(defoaming) agents; (e) pH-modifiers and buffers 707
20.4.3 Additives Incorporated for End-Product Pro-
perties: (a) heat-stabilisers; (b) plasticisers; (c)
fillers; (d) pigments; (e) miscellaneous additives-
matting agents; anti-blocking agents; flame retar-
dants; biostats . . . . 711
20.5 Applications of PVC Latices . . . . . . . . . . . 719
20.5.1 Typical Uses-General . . . . . . . . . . 719
20.5.2 Examples of Basic Formulations for Particular
Applications. . . . . . . . . . . . . 723
20.6 Some Standard Test Methods for Polymer Latices 725
References . . . . . . . . . . . . . . . . . . . . 725
xxiv Contents
Section 6----Post-production Processing of PVC Products . . . . 727
Chapter 21 . . . . . . . . . . . . . . . . . . . . . . . 729
Fabrication, Conversion and Related Processing of PVC Sheet
and Parts. . . . . . . . . . . . . . . . . . . . 729
21.1 Fabrication and Related Operations-General . 729
21.2 Welding of PVC Products. 733
21.2.1 General. . . . . . . . . . . . 733
21.2.2 Hot-Gas Welding. . . . . . . . 734
21.2.3 Heated-Tool (Hot-Plate) Welding 735
21.2.4 Indirect Heated-Element Welding 737
21.2.5 Friction Welding: (a) spin welding; (b) vibration
welding . . . . . . . . 737
21.2.6 High-Frequency Welding . . . . . . . . . 738
21.2.7 Ultrasonic Welding. . . . . . . . . . . . 740
21.3 Bonding of PVC with Solvents, Solvent Cements, and
Adhesives . . . . . . . . . . . . . . . . 741
21.3.1 Solvent and Solvent-Cement Bonding 741
21.3.2 Adhesive Bonding 745
21.4 Cutting and Machining 745
21.4.1 Cutting. . . . . 745
21.4.2 Machining. . . . 750
21.5 Manipulation and Conversion of PVC Film and Sheeting
for Packaging 750
References . . . . . . . . . . . . . . . . . . . . . . . 750
Chapter 22 . . . . . . . . . . . . 752
External Treatments of PVC Products 752
22.1 Decorative Surface Treatments 752
22.1.1 Printing. . . . . 752
22.1.2 Heat Transfers. . . . 754
22.1.3 Hot Foil Stamping . . 755
22.1.4 Embossing: (a) general; (b) emobssing of foamed
sheet products-mechanical embossing; chemical
embossing. . 756
22.2 Surface Marking. . . 759
22.3 Protective Treatments 759
22.3.1 Lacquering . 759
Contents xxv
22.3.2 Other Protective Coatings. . . . . . . . . . 761

22.3.3 Film and Sheet Lamination . . . . . . . . . 762
22.4 Treatment with High-Energy Ionising Radiation (Irradia-
tion for Cross-Linking) . . . . . . . . . . . . . . . 762
22.4.1 Effects of High-Energy Radiation on Essentially
Saturated, Linear Polymers . . . . . . . . . 762
22.4.2 Irradiation of PVC Products: (a) PVC composi-
tions for products cross-linkable by high-energy
radiation; (b) property improvements in irradiated
PVC products; (c) the irradiation treatment 764
References . 768
Section 7-Applications of PVC Products, and Some Important

Application-Related Properties . . . . . . . . . . 769
Chapter 23 . . . . . . . . . . . . . . . . . . . 771
Miscellaneous PVC Products and Their Applications 771
23.1 Cellular PVC Products . . . . . . . . . . . 771
23.2 PVC Fibres and Fibre Products . . . . . . . 777
23.3 Laminates or Laminate-Like Products Involving PVC
Layers . . . . . . . . . . . . . 778
23.4 Sheet-Type Interior Wall Coverings 779
23.5 Powder Coatings and Mouldings. 779
23.6 Medical Applications. . . 781
23.7 Applications in Motor-Cars . . . 782
23.8 Footwear Applications . . . . . 783
23.9 Some Special, Unusual, or Minor Products and Applica-
tions . 783
References . . . . . . . . . . . . . . . . . . . . . . . 785
Chapter 24 . . . . . . . . . . . . . . . . . . . . . . . . 787
PVC Properties of Special Significance in Some Important Usage
Contexts . . . . . . . . . . . . . . . . . 787
24.1 Mechanical and Related Properties . . . . . . . 787
24.1.1 Principal Mechanical Properties . . . . . 787
24.1.2 Environmental Stress Cracking and Crazing 788
24.2 Properties Relevant to Electrical Applications . . . 792
xxvi Contents
24.2.1 Electrical Properties 792

24.2.2 Other Relevant Properties . 793
24.3 Properties Relevant to Some Effects of the Environment
in Service. 798
24.3.1 Properties for Outdoor Applications: (a) stability
to light (UV resistance); (b) resistance to
weathering-definition of weathering; factors in-
strumental in the weathering of PVC; manifesta-
tions of weathering of PVC; ways of promoting
weathering resistance of PVC; evaluation of the
resistance of PVC to weathering 798
24.3.2 Behaviour at Low and High Temperatures: (a)
low-temperature properties; (b) high-temperature
effects-general; maximum 'safe' temperature for
continuous service (in the absence of mechanical
stress); heat ageing of flexible PVC; effects as-
sociated with the thermal softening of PVC at
elevated temperatures. 813
24.3.3 Resistance to Biological Attack: (a) microbiologi-
cal attack (biodegradation); (b) attack by insects
and rodents 819
24.4 Properties Relevant to Barrier and Protective Applications 821
24.4.1 Permeability . 821
24.4.2 Chemical Resistance 833
24.5 Health Hazard Aspects . 833
24.5.1 Vinyl Chloride Monomer 834
24.5.2 PVC Compositions and Their Regular Constitu-
ents. 835
24.5.3 Peripheral Hazards in Production, Processing, and
Bulk Conveyance. 836
24.6 Burning Behaviour, Flammability, and Combustion Pro-
ducts. 836
24.6.1 General Burning Mechanism. 837
24.6.2 Flammability of PVC. 838
24.6.3 Products Generated by Burning PVC: (a) chemi-
cal nature; (b) smoke emission. 840
24.6.4 Burning Tests: (a) small-scale laboratory tests; (b)
larger-scale tests . 842
24.6.5 Tests for Smoke Emission and Properties: (a)
smoke density; (b) acid index; (c) toxicity . 845
Contents xxvii
24.6.6 Some Relevant Publications 847

References . 847
Appendix 1 . . . . . . . . . . . . . . . . . . . . . . 851
Some Material Properties of PVC Products and Compounds 851
Appendix 2 . . . . . . . . . . . . . . . . . . . . . . . 864
Quantities and Units: The SI System: Unit Conversion Tables 864
Appendix 3 . . . . . . . . . . . . . . . . . . . . . . 877
Abbreviations (Letter Symbols) Used in This Book for Some
Polymers, Their Derivative Plastics, and Certain Monomers 877
Index . . . . . . . . . . . . . . . . . . . . . . . . . . 881
Section 1
INTRODUCTORY
CHAPTER 1
General Introduction
1.1 SOME KEY TERMS, DEFINITIONS,

AND CONCEPTS
1.1.1 What is PVC?
In common, widely employed usage, the abbreviation 'PVC' has one
of two meanings, depending on the context in which it appears, viz.
(a) 'polyvinyl chloride', i.e. the homopolymer of vinyl chloride, or

(b) as a noun: a member (or, collectively, the whole) of the large
family of plastics materials based on polyvinyl chloride and/or
vinyl chloride copolymers;
as an adjective: of the nature of, or pertaining to, such member
or family.
In the sense of (b), the term 'vinyl' is also often used in the place of
'PVC' , e.g. in such phrases as 'vinyl flooring', 'flexible vinyl' ,
'processing of vinyls'.
The quality of meaning and its dependence on the context, of
themselves, make the terminology somewhat less than precise; whilst
(b) is also open to some objections on formal grounds (as is, with even
more justification, the use of 'vinyl' for 'PVC'). Some of the objections
have influenced certain relevant standard definitions, notably those in
ISO 472, the ISO plastics vocabulary standard (its British counterpart,
BS 3502, and some ASTM specifications-e.g. ASTM D 1784-are
more inclined to acknowledge living usage). However, the fact
remains that the definitions given above under (a) and (b) do accord
with what 'PVC' means to those who deal with the material(s)
represented by the hard-worked abbreviation.
3
4 PVC Plastics-Properties, Processing, and Applications
1.1.2 The Nature and Make-Up of PVC Materials
A plastic can be defined as a polymer-based material in which the

parent polymer may be virtually the sole constituent, or may be
combined with additives of one kind or another. In PVC plastics the
parent polymers are always associated with additives, some of which
may occasionally be present in predominant proportions (e.g. the
plasticisers in certain soft PVC materials). Indeed, among plastics,
PVC is remarkable for the great variety and range of properties
realised through planned formulation of individual compositions for
particular purposes: one example is the contrast between the soft,
flexible PVC coating on an upholstery fabric (in which the hard, horny
nature of polyvinyl chloride is not apparent) and the rigid, hard
material of a PVC pipe. This scope for wide variation of properties
through appropriate formulation, which is the basis of PVC's great
applicational versatility, is unmatched by any other plastic.
In common technical usage, the intimate blend of a vinyl chloride
polymer or copolymer with the other components of a PVC formula-
tion as first made up for processing into a product, is usually referred
to as a compound or composition (the former term is sometimes
restricted to compositions produced by melt-compounding). There are
also specific terms for particular kinds of PVC compositions (see for
example Chapter 2). 'Formulation' is also sometimes used synony-
mously with 'composition' in the above sense, although there is
justification for restricting the former term to the make-up of a
composition (e.g. as recorded on paper). It is usual to refer to the
polymer constituent of PVC compositions as a PVC resin or PVC
polymer.
PVC materials incorporating significant amounts of plasticisers are
known, collectively and severally, as plasticised PVC (in this book
abbreviated to pPVC-see Section 1.1.3). Flexible PVC and soft pvc
contain plasticisers in proportions high enough to impart these
properties to the material in substantial degree. As implied by the
name, unplasticised PVC (in this book abbreviated to uPVC) contains
no plasticisers; the term is often used interchangeably with rigid PVC
(in that uPVC is indeed a rigid material): such usage is not strictly
correct however, since-whilst, in general, plasticisation reduces
rigidity-the presence of a small proportion of plasticiser (up to about
10% by weight in most cases, but occasionally even higher) can
actually increase it (see 'antiplasticisation' via the Index). Rigid and
1 General Introduction 5
semi-rigid PVC materials (the latter typically containing up to about

25% of plasticiser) exhibit the properties indicated by these terms.
Note: As used in the industry, the last two terms are adequately
descriptive and well understood, but not strictly quantitative.
In standard nomenclature, * a rigid plastic is one that has-
under stated conditions (including, subject to permitted
tolerances, 23°C and 50% RH)-a modulus of elasticity in
flexure (or, if that is not applicable, in tension) greater than
700 MPa (=105Ibf in -2). A semi-rigid plastic is similarly
defined as one having a modulus of elasticity between 70 and
700 MPa (approximately 104-1W lbf in- 2).
1.1.3 Abbreviations and Symbols for Material Names
For the sake of convenience, abbreviations of (letter symbols for) the

names of various polymeric materials, in particular many polymers and
copolymers, are freely used throughout this book. All such abbrevia-
tions are listed, with their meanings, in Appendix 3. The versions used
are in line with the recommendations of the relevant ISO standard
(ISO 1043-1978), but it should be noted that these recommendations
do not fully accord in every case either with those of the other two
relevant English-language standards (ASTM D 1600-83 and
BS 3502:Part 1:1978) or with common usage in industry. A case in
point is the abbreviation for the copolymer of ethylene and vinyl
acetate: 'EVA' is widely used in industry and also recommended by
the ASTM standard, whereas the ISO standard favours 'E/VAC', and
the BS standard 'EVAC'-quis custodiet custodes ipsos? Moreover,
none of the standards provides a truly comprehensive list of abbrevia-
tions (cf. Appendix 3).
The abbreviations uPVC (for unplasticised PVC) and pPVC (for
plasticised PVC) often seen in the technical literature, and used
throughout this book, were originally prescribed by two relevant ISO
standards-ISO 1163:Part 1 and ISO 2898:Part 1. After a subsequent,
relatively short-lived, minor modification to 'u PVC' and 'p PVC' the
two standards have again changed their abbreviations (in the current
editions issued, respectively, in 1985 and 1986) this time to 'PVC-U'
and 'PVC-P'. These latest offerings are not favoured by the present
* As put forward in the three principal English-language plastics vocabulary

standards-ISO 472-1979; BS 1755: Part 1: 1982; ASTM D 883-85.
author, who regards them as open to criticism on certain sound

grounds of logical consistency.
The abbreviation 'iPVC' has sometimes been used to designate rigid
PVC materials formulated for high impact resistance ('high-impact'
grades).
1.2 MATERIAL AND TEST STANDARDS
Standardisation of test methods and material property requirements

for plastics has now developed to the point where the standards play
an essential role in the proper running of the industry's technical
operations and quality control, as well as in product specification for
the purposes of tendering and sales.
In the Western World, the most important 'plastics' standards are
found among those developed and issued by four organisations: the
International Organisation for Standardisation* (ISO standards), the
British Standards Institution (BS standards), the American Society for
Testing and Materials (ASTM standards), and the German Institute
for Standardst (Deutsches Institut fur Normung: the DIN standards).
Note: Most other countries have their own standardisation bodies
which issue their national standard specifications. With vir-
tually no important exceptions, each national standardisation
body is a member of ISO, and each acts in its own country as
an agent of ISO, as well as of all other ISO member bodies,
for such purposes as the sale of standard specifications and
related documents and provision of information on standards.
It may be noted in passing that the official national standard-
isation body of the USA is not the ASTM, but the American
National Standards Institute (ANSI). However, a great many
ASTM standards have been adopted by the ANSI as national
standards.
Some ISO, BS, ASTM, and DIN standards are generally applicable
to many plastics (including PVC). Such standards include, for in-
stance, specifications dealing with· terminology, conditioning and test
atmospheres, and test methods for some properties (e.g. mechanical
* With headquarters in Geneva.

t With headquarters in Berlin.
properties, water absorption, etc.). Many specifications of this kind-

all with some relevance to PVC-are listed in Table 1.3 at the end of
this chapter, and others are referred to, as appropriate, throughout the
book. There are also large numbers of ISO, BS, ASTM, and DIN
standards directly relevant to PVC, and some dealing with important
constituents of PVC materials (e.g. plasticisers). Such standards are
listed at the end of each chapter to which they are relevant, and/or
mentioned in the text.
Some big industrial concerns, as well as user organisations, issue and
operate their own specifications for certain plastics materials and
products. Notable examples are the well-known US military (MIL)
specifications; those of the National Coal Board in the UK (NCB
specifications); and the specifications of major car manufacturers.
Some 'plastics' or plastics-related standards of two independent
organisations of international standing are also important: these are
the relevant specifications issued by Underwriters Laboratories Inc. *
(the UL specifications; exemplified by the much-quoted UL94-the
basis for rating the flammability of plastics materials for moulded parts
in devices and appliances), and those of the International Electrotech-
nical Commissiont (known as lEC publications; some are particularly
relevant to the electrical properties of plastics, including PVC:j:).
References to standard specifications throughout this book (both in
the tabulated lists and in the text) include in almost every case a year
of issue since this can provide a useful point of reference. Most of the
issues so quoted should be still current at the time of the book's going
to press (except where an older specification is deliberately cited) but
it will be appreciated that consecutive issues of national and ISO
standards are periodically brought out under new dates, embodying
the results of more or less regular revision. Some standards are also
being amended, some are occasionally withdrawn, and entirely new
ones are brought out.
Useful information on standard tests for plastics can be found in a
book edited by Brown. 1 Two other books are also relevant as general
reference sources on this extensive subject. 2,3 Numerous tests and
* With headquarters in Northbrook, IL, USA, and several local agencies in

the USA and abroad.
t With headquarters in Geneva.
:j: For example Publication 189-1: Low Frequency Cables and Wires with PVC
Insulation and PVC Sheath-Part 1: General test and measuring methods.
evaluation methods for PVC materials and products are cited, listed,
and discussed in a recent book by the present author. 4
1.3 ORIGINS, mSTORICAL DEVELOPMENT, AND

PRESENT POSmON OF PVC
1.3.1 Early History
The following highlights in the early history of PVC may be noted.
1835: Vinyl halides first made in the laboratory, and formation from
them of white, amorphous solids on exposure to sunlight observed (by
V. Regnault).4,5
1872: Vinyl chloride and bromide prepared (by E. Baumann) by the
action of alcoholic potash on dichloroethane, and their prolonged
exposure to sunlight in sealed tubes found to result in the formation of
white, powdery, flaky solids (polymerisation).4,5
1912-1913: Patent disclosures in Germany by Chemische Fabrik
Griesheim-Elektron,6,7 based on work led by F. Klatte,5,8 of the
reaction between acetylene and hydrogen halides as a method of
preparation of vinyl chloride and bromide, referring also to their
polymerisation (still by sunlight) and to some suggested uses for the
vinyl chloride polymer. Patent disclosures in the UK and Germany by
Ostromislensky4 of sunlight-polymerised PVC.
1916: Method suitable for technical-scale preparation of vinyl chloride
(based on the reaction of acetylene with HCI) established at I.G.
Farbenindustrie (now BASF) in Germany by Klatte and co-workers.
1928-1930: Patent disclosures of VC/V AC copolymers by Du Pont
and the Carbon and Carbide Chemicals Corp. in the USA, and I.G.
Farbenindustrie in Germany. 4 A patent obtained for 'polyvinyl hal-
ides' by Ostromislensky in the USA. 9 Vinyl chloride polymers
prepared by emulsion polymerisation by H. Fikentscher and co-
workers at I.G. Farbenindustrie (Ludwigshafen), Germany.5 Prepara-
tion of VC/VAC copolymers by E. W. Reid at the Carbon and
Carbide Chemicals Corp. in the USA,4,5 and at I.G. Farbenindustrie
in Germany (by A. Voss and E. Dickhliuser, who also pioneered
polymerisation of vinyl chloride at elevated temperatures and
pressures).5,10
The 19308: Plasticisation of PVC by phthalate esters. Introduction in

the USA of 'non-rigid vinyl chloride plastics' by B. F. Goodrich. 4
Suspension polymerisation of vinyl chloride at ICI in England and
Wacker Chemie in Germany.s Technical production of chlorinated
PVC polymer and fibres at I.G. Farbenindustrie, Germany.ll Com-
mercial production of PVC polymers in Germany and USA.4
1942-1943: Commercial production of PVC polymers in England (by
ICI and the Distillers CO.).4
Early attempts at heat-processing vinyl chloride homopolymers were

hampered by the unfortunate combination of the materials' high fusion
temperature and poor thermal stability. This difficulty promoted early
interest in vinyl chloride copolymers (in the first instance with vinyl
acetate): these, whilst in general somewhat less heat-stable than the
homopolymer, could be processed at significantly lower temperatures,
at which their stability was adequate. The role in this respect of the
co-monomer units in the polymer chains-sometimes referred to as
'internal plasticisation'-is well understood today.
The possibility of temporarily plasticising a PVC polymer by the
addition of solvents in amounts insufficient to effect solution, but
producing a dough-like mixture which might be processable (into
blocks, sheets, etc.) even without heating, was suggested in one of the
patents on Klatte's work,7 before the advent of internal plasticisation
by copolymerisation. However, true external plasticisation of the kind
practised today came after the first use of copolymers: it began with
the finding (by several workers 4) in the 1930s that compounding PVC
polymer with dibutyl phthalate (DBP) and some other phthalate esters
would yield a material processable at acceptable melt temperatures,
into products which could be permanently soft and flexible. Although
chronologically a slightly later development, it is the external and not
internal plasticisation that today provides the main route to the
formulation of flexible and most semi-rigid PVC materials. The 1930s
also saw the first use of heat stabilisers in PVC compositions. 4
The early processing of PVC before (and to some extent during)
World War II was largely carried out by methods and on machinery
originally developed for rubber and celluloid. The main processes
involved were compounding, calendering, compression moulding and
extrusion.
Thanks to the work of Kaufman, the history of PVC polymers,
compounds and processing is well recorded and documented. 12 ,13
1.3.2 Present Position
(a) PVC as a Major, Highly Versatile Thermoplastic

The original impetus for the development of PVC to its present
eminent position among plastics got under way during World War II,
partly as a result of the realisation that PVC could be an effective
replacement for rubber in some important applications, notably as
insulation and covering for electrical wires and cables.
As illustrated by the 1984 figures in Table 1.1 (and, to a first
approximation, the data should be reasonably representative for the
mid-1980s generally), PVC vies with low-density polyethylene for the
first place among the four leading polymers that jointly account for
some 50-60% of the total polymer consumption. Table 1.2 gives a
general idea, with the aid of 1984 statistics, of the main uses to which
PVC is put. The amounts taken up by a given application differ
somewhat between the two principal economic units--Western Europe
and USA-but the general usage picture (if not the detailed pattern) is
broadly similar, with pipe and conduit, profiles and cladding, and film
and sheeting accounting for the greatest rigid-product tonnages, whilst
cable coverings and flexible film and sheeting are the highest-tonnage
outlets for plasticised PVC.
Even the brief, bare outline of the range of PVC's main applications
demonstrates that this is the most versatile among thermoplastics.
(b) Some Topical Concerns

Three subjects have gained-and maintain-topicality for their social
and commercial as well as technical significance: they are, respectively,
the question of health hazards posed by vinyl chloride monomer and
by some constituents of PVC compositions, the toxicity of PVC
combustion products, and the problem of PVC waste.
VINYL CHLORIDE AS A HEALTH HAZARD

Vinyl chloride, the basic monomer of PVC polymers and copolymers, *
was found in the early 1970s to be capable of causing cancer (albeit of
rather rare kinds).t Since then, increasingly more stringent limits have
been imposed on the amounts of VC released into work-place
* In this context frequently abbreviated to 'VCM' (for 'vinyl chloride

monomer').
t Angiosarcoma (a cancer of the liver), and a form of cancer of the mouth.
TABLE 1.1
Consumption of PVC and Other Leading Polymers in 1984
(Approximate figures based on data published in the technical press.) c:J
~
Polymers PVC LDPE HDPE PP All plastics '"~
(million (% of all (million (% of all (million (% of all (million (% of all (million (%)
;;-
Area tonnes) plastics) tonnes) plastics) tonnes) plastics) tonnes) plastics) tonnes) ~
I:>..
""- ;:
:::to
'0"'
USA 3·01 15·1 3·73 18·7 2·67 13·4 2·21 11·1 19·95 100 ;0
Western Europe 3·88 25·3 3·75 24·3 1·62 10·6 1·81 11·8 15·32 100
UK 0·44 18·2 0·51 21·1 0·21 8·7 0·30 12·4 2·42 100
West Germany 1·13 15·2 0·68 9·2 0·63 8·5 0·42 5·7 7·41 100
Japan 1·21 18·9 1-16 18·1 0·85 13·3 1·23 19·2 6·40 100
-
TABLE 1.2
Consumption of PVC Polymers, by Main Application, in Western Europe and
the USA in 1984
(Approximate figures, based on data published in the technical press.)
Area Western Europe USA
(Thousand (% of grand (Thousand (% of grand

Application tonnes) total) tonnes) total)
Rigid PVC
Pipes and conduit 945 24·3 1139 37·8
Profiles and cladding 515 13·3 286 9·5
Sheeting and film 390 10·0 190 6·3
Blow-moulded bottles 315 8·1 97 3·2
Injection mouldings
(incl. pipe fittings) 73 1·9 130 4·3
Records 68 1·8 36 1·2
Miscellaneous 83 2·1 177 5·9
Total rigid 2389 61·5 2055 68·2
Plasticised PVC
Cable coverings 373 9-6 189 6·3
Sheeting and film 320 8·2 208 6·9
Flooring 197 5·1 90 3·0
Tubing and profiles 160 4·1 45 1·5
Fabric coatings 150 3·9 151 5·0
Miscellaneous 150 3-9 94 3·1
Total plasticised 1350 34·8 777 25·8
Other outlets (incl.
latex applications
and adhesives) 145 3.7 181 6.0
Grand Total 3884 100·0 3013 100·0
atmospheres, remaining in the PVC polymers after their production,

and migrating into foodstuffs and beverages packaged in PVC films or
containers. The issue of possible migration had a severely restrictive
effect on the use of rigid and semi-rigid PVC for food contact
applications in some countries, especially the USA * and Japan. In
1975, the American Food and Drug Administration (FDA) was
* Cf. e.g. the % consumption figures for blown bottles and rigid film,
respectively for the USA and Western Europe in Table 1.2.
contemplating a complete ban on such applications: the proposal was,

however, withdrawn some years later in view of the advances made by
PVC polymer manufacturers in reducing the residual VC content of
their polymers, and also because the principle was accepted that
carcinogens may be tolerated in foods if present in amounts sufficiently
low to be regarded as insignificant (the de minimis principle). Revised
FDA thinking in the late 1980s inclined to making PVC fully
acceptable as single-use or repeated-use food-packaging material
where the maximum residual VC contents do not exceed 10 ppb* in
rigid or semi-rigid PVC, and 5 ppb in flexible PVC. The technical
aspects of the presence of VC in PVC polymers and products are
discussed in Chapter 24 (Section 24.5).
SOME pvc FORMULATION CONSTITUENTS AS POTENTIAL HEALTH HAZARDS

The components of PVC formulations on which attention has been
principally focused in this connection are certain plasticisers-notably
dioctyl phthalate (DOP) and adipate (DOA)-and those stabilisers
and pigments which contain heavy metals, especially lead and cad-
mium. Several studies have been undertaken in the last few years
(some are still in progress) to determine whether some phthalate and
adipate plasticisers, in particular DOP and DOA, are carcinogenic in
man. The question is important, as these plasticisers are widely used in
PVC films for food packaging and in such medical products as
transfusion bags and tubing. This subject is discussed in Section 5.7 of
Chapter 5 (with a brief reference, inter alia, to the cling-film scare in
the UK in 1986), but it may be mentioned here that the case against
phthalate plasticisers as cancer-inducing agents is by no means
established. The intrinsic toxicity of lead and cadmium is not in doubt
(and chromium has also come under scrutiny in this regard), but the
severity of such hazards as may be posed by compounds of these
metals used as stabilisers or pigments in PVC compositions is still to
some extent controversial. One illustration of the way in which official
attitudes differ is the fact that-subject to certain restrictions on
extractability-lead stabilisers are allowed in PVC pipes for potable
water in Europe (as well as in many countries elsewhere), but not in
the USA. Possible hazards associated with heavy-metal compounds
used in PVC are referred to in connection with cadmium and lead
* Parts per American billion (i.e. per 109 ).

stabilisers in Chapter 4, and cadmium and chromium pigments in

Chapter 9.
HEALTH HAZARDS ASSOCIATED WITH COMBUSTION PRODUCTS OF PVC

This subject is particularly important in connection with fires involving
PVC products (usually wire and cable coverings, often also pipes, in
fires in such locations as buildings and mines), and also as an aspect of
incineration of PVC waste. The compounds generated in substantial
quantities by burning PVC are hydrogen chloride (HCI) , carbon
monoxide and dioxide (CO; CO2), and aromatic hydrocarbons. HCI is
normally the most plentiful; it is a strong acid corrosive to human
tissue (capable of quickly causing severe damage to the respiratory
tract and lungs) and to many materials. It is often regarded as the
principal hazard in fires in which PVC is burning, although it has been
pointed out that HCI gas or fume can 'decay' fairly quickly in fire
environments by absorption and condensation on available surfaces. 14
The nature, hazards, and assessment of PVC combustion products are
discussed in Chapter 9 (in connection with flame-retardant and
smoke-suppressant components of PVC formulations) and in Chapter
24 (Section 24.6). Anxiety, occasionally bordering on hysteria, has
been voiced from time to time concerning toxic emissions from the
incineration of PVC waste. Even the vexed problem of acid rain has
been blamed on HCI from that source! The facts, as known from the
best evidence to date, are that incineration of waste PVC is not among
the significant causes of atmospheric pollution generally (and of acid
rain in particular) and that, with suitable equipment incorporating
appropriate scrubbing and cleansing devices, it can be carried out
effectively and safely. *
DISPOSAL OF WASTE PVC PRODUCTS

This is another subject receiving continuing attention for its environ-
mental implications as well as for its economical and technical interest.
As with other plastics waste, the two general possibilities are reclama-
tion, i.e. reprocessing for re-use, or permanent elimination, in which
* Compare for example relevant statements at the European Conference on

Packaging, Brussels, 1986; those by the Society of the Plastics Industry (SPI);
and those at the 4th H. F. Mark symposium of the Austrian Plastics Institute,
Vienna 1986; also publications by the Swiss Eidgenossische Anstalt fUr
Wasserversorgnung (A. Scharsach, 1986), and the recent paper by P. Decroly
in Plastics and Rubber International (June 1987, pp. 32-35).
incineration plays an important part. However, in both these methods

of disposal PVC presents certain special problems. The toxicity and
corrosive nature of PVC combustion products have just been men-
tioned, and whilst effective and safe incineration is possible, the
special measures and equipment required make the operation rela-
tively expensive and not entirely straightforward. Reclamation in most
cases involves dealing with mixed plastics waste with a somewhat
variable PVC content. Reprocessing of such waste may, in principle,
follow one of two lines, viz. the waste may be cleaned and processed
into some useful end-product without separation, or the PVC may be
separated out to be processed into reclaimed PVC products. Industrial
systems for recycling mixed plastics waste are available (e.g. the West
German Recycloplast system, or the Italian Sorema installations), but
they are not primarily intended for PVC. Indeed, for fully effective
reprocessing, with reasonable commercial scope for the end-products,
it is necessary to separate PVC from other plastics waste, as it is not
compatible with polyethylene*-the waste's most abundant
constituent-whilst PVC's own susceptibility to thermal decomposition
can be aggravated by certain contaminants (so that effective purifica-
tion is required also for that reason) and by the presence of any PVC
polymer that has already been partly degraded in the course of past
heat treatment and/or service. Some processes have been claimed to
be effective in recovering PVC from mixed plastics waste (e.g. the
Mesco process, developed in Japan by Mitsui 16), but in general the
scale of industrial recovery of this kind remains modest. Recovered
plasticised PVC is converted into compositions used, for instance, for
cable cores (cable filling), cheap garden hose, soles for cheap
footwear, and low-grade wall skirting (e.g. for caravans).
Note: The compatibility of some PVC wastes can be limited in
certain circumstances, and practical compounding tests are
always desirable. For example, certain plasticisers have been
found to interfere in the formation of a useful blend from a
mixture of pPVC waste with scrap PVC containing an
acrylonitrile/methylacrylate copolymer .17
A fairly common source of mixed plastics waste with a high pPVC
content is provided by scrap cable and wire coverings. Perhaps the
* Although attempts have been made to promote compatibility through the

addition of chlorinated polyethylene. 15
most successful case of recovery of rigid PVC scrap is the re-use of

material from discarded PVC bottles. Reprocessing of these into
compounds for the production of certain grades of sewage and
drainage pipes and cable sheathing was initiated in France by Societe
Dorlyl. 18 Currently, in three French industrial operations (still rela-
tively small-scale), reclaimed PVC bottle material is used in composi-
tions for some mOUldings, sheeting, and extrusion of profiles and
vineyard postS. 19 Efforts to develop effective ways of recovery and use
of waste PVC are being continued both by industrial companies (e.g.
Cleveland Reclaim, Cleveland, OH, USA) and organisations promot-
ing the relevant research and development (e.g. in the USA, the
Plastics Recycling Foundation, and the Council for Plastics in Packag-
ing). Normal recirculation, in the same process, of clean PVC scrap
('rework') generated by the process, is, of course, widely practised in
most melt-processing operations.
1.3.3 The PVC Industry-Outline of General Structure
In the broadest terms, the PVC industry may be said to comprise

(a) PVC polymer producers;
(b) compounders (producers of PVC compositions for processing);
(c) processors;
(d) converters, and other companies making and selling finished
products consisting of or containing PVC.
Importers of PVC polymers and compounds are not, strictly speaking,
within the industrial set-up proper, because they do not normally
undertake any technical operations. However, together with the
polymer producers and compounders they make up the wider category
of polymer and compound suppliers.
Some companies engage in more than one of the above activities.
For example, all major polymer manufacturers produce compounds,
and some also make semi-finished products.
The number of PVC polymer producers in any country is very small
compared with that of companies in the other categories (in some
cases a polymer producer has manufacturing plants in several
countries). For many members of category (d), PVC may represent
only a relatively small part of their interests: nevertheless some-such
as motor-car manufacturers for example-can be using very large
quantities of PVc.
The principal processes used to convert PVC to finished and

semi-finished goods are extrusion, calendering, injection moulding,
and spread coating. Although some processors operate 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 (as for example with calendered PVC sheeting
to be made into inflatables).
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 may be noted that the value of the total market for some of
these materials exceeds that of many other plastics materials.
Also highly relevant-since without them the PVC industry could
not function-are manufacturers of PVC processing machinery and
auxiliary equipment, including process control devices. Many com-
panies have specialised in this field and, through their development
activities, improved processing as well as wider and also entirely new
applications for PVC have been made possible.
Some reference sources on PVC are listed in the Bibliography
below.
REFERENCES
1. Brown, R. P. (Ed.), Handbook of Plastics Test Methods, 2nd edn. George
Goodwin and the PRI, London, 1981.
2. Vishu Shah, Handbook of Plastics Testing Technology. John Wiley &
Sons, Chichester, 1984.
3. Turner, S., Mechanical Testing of Plastics, 2nd edn, George Goodwin and
the PRI, London, 1984.
4. Titow, W. V., PVC Technology, 4th edn. Elsevier Applied Science
Publishers, London and New York, 1984.
5. W. Forest et al., (Ed.) Ullmans Encyclopiidie der Technischen Chemie,
Vol. 14, p. 201 and Vol. 18, p. 87. Urban & Schwarzenberg, Munich and
Berlin, 1963.
6. DRP 278249 (1912).
7. DRP 281877 (1913).
8. Kaufman, M., Trans. J. Plastics [nst., 365-71.
9. Drukker, H. L., Proc. Symposium on Plastics, ASTM, Philadelphia, PA,
USA, pp. 165-77.
10. DRP 579048 (1928).
11. Domininghaus, H., KunststoJfe und ihre Eigenschaften. YDI-Verlag

GmbH, Dusseldorf, p. 566.
12. Kaufman, M., Plast. Polym., 37(129) (1969) 243-51.
13. Kaufman, M., The History of PVC. Elsevier, London, 1969.
14. Anon., Plast. Technol., 32(10) (1969) 135. (Summary of results of study of
the behaviour of HCl gas in fire environments, by the Southwest Research
Institute, San Antonio, Texas.)
15. Paul, D. R., Vinson, C. E. & Locke, C. E., Polym. Engng Sci., U (1972)
157; idem, ibid., 13 (1973) 202 and 308.
16. Trevitt, E. W., Polym. Paint. Col. J., 166(3918) (1976) 193-4.
17. Erwin, L. & Wilson, M. L., Plast. Rubb. Process. Appln, 2(2) (1982)
183-90.
18. Anon, Eur. Plast. News, 6(2) (1979) 3.
19. Mapleston, P., Mod. Plast. Int., 18(1) (1988) 39-41.
BIBLIOGRAPHY
SPE Vinyl Professional Activity Group, A Guide to the Literature and Patents
Concerning Polyvinyl Chloride Technology. SPE, Stamford, CN, USA,
1964.
Dux, J. P., Vinyl chloride polymers. In Encyclopedia of Polymer Science and
Technology, Vol. 14, ed. H. F. Mark & N. G. Gaylord. Wiley-Interscience,
New York, pp. 305-483.
Matthews, G., Vinyl Chloride and Vinyl Acetate Polymers. Plastics Institute
Monograph, Iliffe Books, London, 1971.
Sedlacek, B. (Ed.), Polyvinyl Chloride: Its Formation and Properties.
Proceedings of IUPAC Symposium, Prague 1970. Butterworths, London,
1971.
Sarvetnik, H. A. (Ed.), Plastisols and Organisols. Van Nostrand, New York,
1972.
Yescombe, E. R., Plastics and Rubber: World Sources of Information.
Applied Science Publishers, London, 1978, pp. 151, 177-80, 359.
Burgess, R. H. (Ed.), Manufacture and Processing of pvc. Applied Science
Publishers, London, 1981.
Brydson, J. A., Plastics Materials. 4th edn. Butterworth Scientific, London,
1982, Chapter 12.
Davidson, J. A. & Gardner, K. L., Vinyl polymers (PVC). In Kirk-Othmer
Encyclopedia of Chemical Technology, 3rd edn, Vol. 23. John Wiley &
Sons, New York, pp. 886-936.
Owen, E. D. (Ed.), Degradation and Stabilisation of pvc. Elsevier Applied
Science Publishers, London and New York, 1984.
Titow, W. V. PVC Technology. 4th edn. Elsevier Applied Science
Becker, G. W. & Braun, D. (Eds), KunststoJf Handbuch-PVC. Carl Hanser
Verlag, Munich, 1986.
Nass, L. I. (Ed.), Encyclopedia of pvc. Marcel Dekker, New York, 1986.
General Introduction 19
TABLE 1.3
Some 'Plastics' Standards Relevant to Terminology, and General Testing
Entry Standard specification

no.
Designation Subject (not necessarily the
official title)
Terms and Definitions
1 ISO 472-1979 Plastics-Vocabulary
(3 addenda: 1982; 1983;
1984)
2 ISO 194-1981 Plastics-List of equivalent terms
(four addenda: one-1981; (English, French and Russian)
three-1983 )
3 BS 1755 Glossary of terms used in the plastics
industry
Part 1: 1982 Polymer and plastics technology
Part 2: 1974 Manufacturing processes
4 BS 3558: 1980 Glossary of rubber terms
5 BS 4815: 1972 Glossary of generic names for man-
made fibres
6 BS 5168: 1975 Glossary of rheological terms
7 ASTM C 168-80 Definitions of terms relating to thermal
insulating materials
8 ASTM C 274-68 (1980) Definitions of terms relating to
structural sandwich construction
9 ASTMD 16-84 Definitions of terms relating to paint,
varnish, lacquer and related products
10 ASTM D 883-85 Definitions of terms relating to plastics
11 ASTM D 907-82 (1985) Definitions of terms relating to
adhesives
12 ASTM D 1418-85 Rubber and rubber latices-
Nomenclature
13 ASTM D 1566-86 Definitions of terms relating to rubber
14 ASTM E 6-85 Definitions of terms relating to methods
of mechanical testing
15 ASTM E 12-70 (1986) Definitions of terms relating to density
and specific gravity of solids, liquids
and gases
16 ASTME41-79 Definitions of terms relating to
conditioning
17 ASTM E 206-72 (1979) Definitions of terms relating to fatigue
testing and statistical analysis of
fatigue data
18 ASTM E 284-81 Definitions of terms relating to
appearance of material
(continued)
TABLE l.3----contd.

no.
official title)
19 ASTM F 17-76 (1982) Definitions of terms relating to flexible

barrier materials
20 ASTM F 141-85 Definitions of terms relating to resilient
floor coverings
21 ASTM F 412-84 Definitions of terms relating to plastic
piping systems
Common names and abbreviations
22 ISO 1043-1978 Plastics-Symbols
23 BS 3502 Schedule of common names and
abbreviations for plastics and rubbers
Part 1: 1978 Principal commercial plastics
Part 3: 1978 Rubber and rubber latices
24 BS 4589: 1970 Abbreviations for rubber and plastics
compounding materials
25 ASTM D 1600-83 Abbreviations of terms relating to
plastics
26 DIN 7723 (1971) Abbreviations for plasticisers
27 DIN 7728
Part 1 (1978) Symbols for terms relating to
homopolymers, copolymers and
polymer compounds
Part 2 (1980) Symbols for reinforced plastics
General test conditions and methods
(a) Conditioning and testing conditions
28 ISO 291-1977 Plastics-Standard atmospheres for
conditioning and testing
29 ISO /R 483-1966 Plastics-Methods for maintaining
constant relative humidity in small
enclosures by means of aqueous
solutions
30 ISO 554-1976 Standard atmospheres for conditioning
and/ or testing-specifications
31 ISO 558-1980 Conditioning and testing-Standard
atmospheres-definitions
32 ASTM D 618-61 (1981) Conditioning plastics and electrical
insulating materials for testing
33 DIN 50013 (1979) Climatic testing-Preferred test
temperatures
34 DIN 50014 (1985) Standard atmospheres
TABLE l.3-contd.

no.
official title)
35 DIN 50015 (1975) Constant test atmospheres
36 DIN 50016 (1962) Testing of materials, components, and
equipment in damp alternating
atmospheres
37 DIN 50017 (1982) Climatic testing-Stress in
environments containing condensed
water
38 DIN 50018 (1978) Corrosion test methods in alternating
atmosphere containing condensation
water and sulphur dioxide
39 DIN 50019
Part 1 (1979) Climates (outdoor)---Graphical and
other data
Part 2 (1963) Testing of materials, structural
components and equipment-Data on
climates (outdoor) (Withdrawn in
1986)
Part 3 (1979) with Climatic patterns: statistically-based
supplement data
(b) Some general test methods

40 ISO 62-1980 Plastics-Determination of water
absorption
41 ISO 171-1980 Plastics-Determination of bulk factor
of moulding materials
42 ISO 3451/1-1981 Plastics-Determination of ash: general
methods
CHAPTER 2
Constitution and Formulation of pvc Materials
2.1 PVC COMPOSmONS (COMPOUNDS) AND

THEIR FORMULATION
2.1.1 General Features and Main Categories
PVC polymers 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 polymer is first
combined with the necessary additives, and the operations involved in
making a compound (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 is usually
applied either to the blending together of the appropriate
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 composi-
tion, 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).
22
2 Constitution and Formulation 23
A compound 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. 2.1.
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.
Nowadays, ready-made PVC compounds are available in great
variety and profusion, formulated to meet the needs not only of the
main processes and applications, but also of individual process and
application variants, as well as particular standard specifications.
Commercial PVC compounds are discussed in Chapter 10.
As mentioned in Chapter 1, PVC materials and products fall into
two broad categories: unplasticised (uPVC) and plasticised (pPVC).
The former group is also often referred to as rigid PVC (but see
1 - - - - - - ---------1
Compounding I Ph . I f I
1 YSlca orms: I
...--_....L.._! _ _ _ _ _ _ _ _ JSolid: (al Frae-flowing powder or I
Composition powder agglomerate I
'----..---'- - ------1 (prebland; dry blend) I
1 (bl Pellets; granulate I
Processing
: Liquid: (al Paste I
IPcOd~ I
1 (bl Latex I
1 (cl Solution
1_ _ _ _ _ _ - - - - - - - - -
i
I
I
Further processing
1
1
1----*-------,
i Secondary product I
~ - - - ------.1
Fig. 2.1 Stages in the manufacture of PVC products-general outline.
Section 1.1.2 of Chapter 1 for the strict definition of this term). pPVC
materials with low plasticiser contents-up to about 20% (i.e. about
30 phr)-are known as semi-rigid; the softest plasticised materials may
contain well over 100 phr of plasticiser(s).
2.1.2 Constituents of PVC Compositions (Formulation

Components)
With the partial exception, not important in the present context, of

some PVC latex and solution compositions (see Chapters 19 and 20),
virtually all PVC compounds undergo heat treatment-as well as, in
most cases, mechanical shearing which also generates heat-in the
course of processing (including the initial compounding). Many
end-uses also entail exposure to heat in service, albeit at temperatures
generally lower than those encountered in processing. As PVC
polymers are inherently prone to heat degradation (see Chapter 4)
they must be protected by the incorporation of stabilisers. A stabiliser
(very often a composite one, and hence frequently referred to as the
'stabiliser system) is thus, next to the polymer, the second most
important constituent of virtually every PVC composition.
A basic formulation for a uPVC composition will also normally
contain a lubricant: this may be a single compound, but is frequently a
composite (and often formulated jointly with the stabiliser system).
The lubricant counteracts sticking of the melt to hot equipment
surfaces in processing ('external' lubrication) and/or reduces frictional
effects within the melt ('internal' lubrication). A processing aid may
also be included (typically a polymeric additive) to improve melt
properties and fusion characteristics. If the product is required to be
resistant to knocks and impacts in service, then an impact modifier will
be incorporated in the composition to impart toughness to the
relatively brittle PVC polymer: impact modifiers are normally poly-
meric additives (although some toughening effect is claimed also for
certain fine-particle calcium carbonate fillers; see Chapter 6).
In a basic formulation for a pPVC composition a piasticiser (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 by reducing melt viscosity and providing lubricant
action of the internal kind (see Chapter 7, Section 7.1). Certain
plasticisers, and especially plasticiser extenders, can also occasionally

provide some external lubrication; otherwise this function may be
discharged by lubricants which are sometimes specially incorporated in
pPVC compositions.
In addition to the basic constituents, other components are often
included in PVC formulations, mainly for particular end-use pro-
perties. Colourants and fillers are common additives. The latter are
often incorporated, in substantial proportions, as cheapening exten-
ders, but even in such cases the attendant effects on some properties
may be useful, e.g. reduced shrinkage, increased hardness and
stiffness. Some fillers have a principally functional role; for example,
glass or asbestos fibres provide reinforcement. Fillers and their effects
are discussed in Chapter 6.
Other formulation components with specific end-use functions in
PVC materials are the following (discussed in Chapter 9, unless
otherwise indicated): flame retardants and smoke suppressants;
antistatic agents; biostatic additives, odour control agents, matting
('flatting') and anti-blocking agents (cf. also Chapter 20); antioxidants
and UV absorbers (see Chapter 4).
Functional components with a processing role include viscosity
control agents for liquid PVC compositions (viscosity depressants,
thickeners, diluents), and blowing agents and cell-control agents for
PVC foam compositions.
2.2 THE BASICS OF FORMULATING

PVC COMPOSITIONS
2.2.1 General Considerations
The basic general principles of formulating a PVC composition (Le.

deciding on the nature and proportion of its constituents) are relatively
straightforward. However, successful practice calls for a great deal of
specialist knowledge and experience.
Note: Nowadays many PVC processors buy-in compositions from
the wide ranges of compounds formulated and produced for
various processes and applications by commercial compoun-
ders. Many compounders will also custom-make compositions
for specific requirements (see also Chapter 10).
A formulator normally designs a composition in response to a stated

need for a product, i.e. 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 proportion, viz. the
requirements of processing and service, and cost economy
considerations.
(a) Processing Requirements
To meet these requirements the composition must be in the right form
for use as feed-stock (e.g. dry blend or pellets for extrusion; paste for
spread-coating of fabrics), have the necessary heat stability under the
processing conditions, and other properties appropriate for the par-
ticular process (e.g. the right fusion characteristics and melt rheology
for extrusion or injection moulding; paste rheology and gelation
properties appropriate to a given spread-coating operation; correct
melt cohesion and lubricity in calendering).
(b) Service Requirements
These are dictated by the nature and conditions of the proposed
end-use and must include, inter alia, stability to the service environ-
ment. Some end-uses impose special requirements. The following
application areas are important examples.
FOOD-CONTACT AND MEDICAL APPLICATIONS (e.g. films for food packaging,
beverage bottles, bags and tubing for blood transfusions and drips)
Non-toxicity of all composition constituents is a cardinal requirement
here; there are also restrictions on extractability and migration of
constituents (especially plasticisers and stabilisers). Stabiliser choice is
essentially restricted to a limited number of individual representatives
of four stabiliser classes: a few approved organotin stabilisers; some
stabiliser systems based on compounds of calcium, zinc, and mag-
nesium; some derivatives of aminocrotonic acid; and some epoxy
compounds (notably epoxidised soyabean oil) used as co-stabilisers in
many formulations. The suitability and selection of plasticisers for
food-contact and medical applications are considered in Section 5.7 of
Chapter 5. In general, all formulation components for such applica-
tions should be checked for acceptability against lists of approved or
recommended materials published by organisations concerned with the
health and safety aspects of plastics products (cf. Chapter 5, Section
5.7, and Chapter 24, Section 24.5). In cases of doubt, the organisa-
tions should be consulted directly. It may be noted that each of the

materials on the lists is a specific product of a particular manufacturer,
i.e. there are no blanket recommendations for material types. In some
cases a limit is stipulated on the proportion of the material that may be
incorporated in a PVC composition. There are also procedures
prescribed by some relevant authorities (e.g. the Council of Europe l )
for obtaining approval for new non-toxic components in plastics.
OUTDOOR APPLICATIONS (e.g. window frames, rainwater goods, cladding,

flexible sheeting for reservoir or swimming-pool liners)
These applications call for particularly effective stabilisation against
photochemical degradation of the PVC polymer, selection of other
components (especially polymeric modifiers) for resistance to such
degradation, and-in plasticised compositions-use of non-migratory,
low-volatility plasticisers. UV absorbers and stabilising pigments
(carbon black, titanium dioxide) are also often included in PVC
compositions for outdoor use.
ELECfRICAL INSULATION
Compositions formulated for this purpose should contain no conduc-
tive constituents or impurities: emulsion PVC polymers are not used in
such compositions, as they usually contain trace residues of additives
from the polymerisation process (especially emulsifying agents). The
general requirement also affects stabiliser choice: the stabiliser should
not include conductive compounds, or form such compounds in the
course of discharging its stabilising function. Lead stabilisers, which
meet this condition and are also relatively inexpensive, are normally
the first choice for electrical applications. Plasticiser selection is
influenced, inter alia, by any need to cater for the composition's
stability at elevated temperatures.
(c) Material and Process Cost Economy

Except in certain special cases (e.g. some military applications) this is
always a highly important consideration in the formulation of PVC
compositions.
2.2.2 Selection of the Principal Individual Constituents of a PVC

Composition
(a) PVC Polymer

The main properties considered by the formulator in selecting the
PVC polymer for a particular composition are the chemical nature
(i.e. whether homopolymer or copolymer), molecular weight, particle

characteristics (which can be of a special importance in processing),
and quality (purity)-a significant factor in many applications. These
properties and their significance are discussed further in Section 3.3.1
of Chapter 3. The type of polymer (i.e. whether suspension, mass, or
emulsion) is also considered in selection, partly in connection with its
influence on particle characteristics. For PVC paste compositions,
paste grades of emulsion polymers are used, although suspension
polymers are sometimes added as extender ('filler') resins: the use of
PVC polymers in pastes is discussed in Chapter 18. Solid compositions
for extrusion, moulding, and calendering are commonly formulated
with suspension or (less frequently) mass polymers, although mixtures
of one of these with an emulsion resin, or even emulsion resins alone,
are occasionally used, especially in Europe, in some uPVC composi-
tions for better melt flow.
Broadly speaking, suspension and mass polymers may be regarded
as equivalent from the point of view of the ultimate product
properties, although a mass polymer may contain fewer impurities
than an otherwise equivalent suspension grade, and hence give better
clarity in transparent compounds. 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 cir-
cumstances and operations; however, the fact should not be over-
looked that-whilst the processing conditions for best results in a
particular process may not be the same for a mass polymer as for a
suspension one-if they are properly optimised for the type used,
each of the two types can be processed satisfactorily.
With regard to the chemical nature of the polymer component of a
PVC formulation, in broad terms homopolymers have better thermal
stability and impart better mechanical properties to a composition than
copolymers, whilst the latter make for easier melt processing and
greater extensibility and filler acceptance in some compositions.
Copolymers are also normally used in PVC-based solution formula-
tions for surface coatings (d. Chapter 19). The melt-processing
advantages of copolymers, like those of lower- versus higher-

molecular-weight homopolymers, are more important in rigid com-
positions, as in adequately plasticised ones the fusion and melt
rheology characteristics are governed principally by the plasticiser.
VC/VAC copolymers form the basis of uPVC compounds for
gramophone records and certain types of sheeting; they are also used
in flooring compositions. They are sometimes included (as in some
formulations in Europe) with a homopolymer to improve the ease of
processing of some rigid formulations. VC/VDC copolymers are
employed, alone or in admixture to homopolymer, in some specialised
compounds for calendering, and also as viscosity-reducing extenders in
some paste formulations.
Some formulations call for high-quality polymer, i.e. one of good
colour, free from coarse particles, fish eyes', * and particulate con-
tamination (low 'speck count').
Note: The number and size of fish-eyes in PVC polymer may be
determined by the method of ASTM D 3596-77(1983). Gels*
in a PVC film (which may be synonymous with fish eyes) can
be determined by the standard gel-count method of ASTM
D3351-74 (1980). ISO 1265 provides a method for the
determination of foreign particles in particulate PVC
polymer.
Low grade polymer can be used, in admixture with standard grades or
even alone, in formulations for the cheaper kinds of injection-
moulding compositions, usually fairly heavily filled, used for the
production of cheap moulded footwear (sandals, slipper soles) and
toys.
(b) Heat Stabilisers

Although much has been learnt over the years about the degradation
of PVC and the effects of stabilisers, the stabilisation of PVC
materials 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
* For definitions see Section 3.3.1( d) in Chapter 3.

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 0·5 and
8 phr~epending 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; for example, the completeness of
dispersion achievable with modern compounding machinery reduces
the stabiliser requirement). Heat stabilisers, their uses and effects are
discussed in some detail in Chapter 4; only the most basic points of
general relevance to formulating are mentioned here. The type of
stabiliser to be considered will be determined by the kind of PVC
composition contemplated (always subject to any special require-
ments). Within the general type, the choice of the particular
compound-or today more usually the composite system-will be
dictated by detailed requirement considerations. For flexible PVC
materials, such as sheeting and film, extrusions (profiles, hose),
mouldings, and paste products, the most widely used stabilisers are of
the barium/cadmium, or barium/cadmium/zinc type (predominantly
liquid systems, but also some solid, or mixed liquid/solid). Flexible
cable coverings and insulation compounds are most commonly stabil-
ised with lead stabilisers (in some cases barium/lead systems). Liquid
barium/cadmium or barium/cadmium/zinc stabilisers are occasionally
used in clear insulation compositions. Rigid compounds (e.g. for
pipes) are widely stabilised with lead stabilisers (especially in Europe)
and organotin or antimony stabilisers (especially in the USA). Solid
barium/cadmium stabilisers with phosphite chelators are also some-
times used. Epoxy co-stabilisers are included in many compositions to
improve heat and light stability.
(c) Plasticisers
Plasticisers convert the inherently hard PVC polymer into composi-
tions of varying degrees of softness and flexibility, processable into a
variety of products with diverse 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 Chapter 5, and
mentioned at various places in this book. Only a few salient points,
therefore, are indicated here.
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 require-
ments which may dictate the choice (see below) the formulator will
normally consider first a relatively inexpensive, general-purpose plas-
ticiser. In most cases this will be a phthalate, commonly di-2-ethylhexyl
phthalate ('dioctyl phthalate'; DOP) which offers reasonably good
all-round material properties.
The cost of phthalate-plasticised formulations (and some containing
other plasticisers) can often be reduced by replacing part of the main
plasticiser by a cheaper secondary plasticiser, e.g. a chlorinated
paraffin (which may also reduce the flammability of the plasticised
composition; cf. Chapters 5 and 24), or a hydrocarbon extender (cf.
Chapter 5). Triaryl phosphate plasticisers (which also reduce flam-
mability) are the second most important group of common plasticisers.
However, a member of this group is not often used as the sole
plasticiser, because of the cost (higher than that of general-purpose
phthalates) and the comparatively poor low-temperature properties
(e.g. cold bend, cold flex, toughness) of compositions so plasticised.
For strong enhancement of good low-temperature properties, aliphatic
diester plasticisers are included in the formulation. Some plasticisers
are particularly associated with special properties they promote in the
composition: for example, butyl benzyl phthalate (BBP) is one of the
best-solvating, quickest-fusion plasticisers for PVC, and thus promotes
rapid and easy processing of its compositions; it also imparts particu-
larly good stain resistance to PVC films and surfaces. Ditridecyl
phthalate (DTDP) 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. An outline
summary of plasticiser effects is given in Table 2.1.
Where more than one plasticiser is used in a pPVC composition, the
resulting properties 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.
TABLE 2.1
Some General Features of Plasticise.. Usage W
tv
Characteristics required Typically relevant plasticiser type(s) Examples of application
Price economy Selected phthalates, extenders Wide range of cheaper-grade compositions

for various purposes
Important features of behaviour of plas-
'"tl
ticiser in composition:
(a) High compatability with PVC resin Many phthalates, triaryl phosphates Very soft, flexible products, including paste ~
(i.e. suitability for use in high pro- mouldings and coatings ;:!;!
portions in a composition) e::to
(b) Permanence (low volatility, resis- Polymeric plasticisers; for some purposes, Shower curtains, upholstery, gaskets [;l
tance to extraction and migration in trimellitates, high-molecular-weight
compositions) phthalates, solid blending resins (e.g. ~
(:l
chlorinated PE, EVA copolymers,
nitrile rubber) ~::to
Processing properties: ~
(a) Ease of solvation, fusion and BBP, DBP, triaryl phosphates, phthalates Foamed coatings '"tl
gelation (:l
(b) Effect on viscosity of pastes: '~"'
Low viscosity Aliphatic diesters and extenders '"
~.
High viscosity BBP, DBP, triaryl phosphates, polymeric
plasticisers
End-use properties imparted to compositions: l
).
(a) Good colour Phthalates Clear compositions
(b) Good chemical resistance Polymeric plasticisers Protective clothing ~
(c) Good low-temperature properties Aliphatic diesters (sebacates, adipates, Tarpaulins, flexible tubing for use in cold ~
AGS esters) conditions ~.
(d) Electrical properties:
High resistivity Triaryl phosphates
Low resistivity Sebacates
(e) Food-contact applications Individual plasticisers (high-purity grade) Packaging films
as permitted by relevant authorities
(f) Mechanical properties:
High tensile strength Triaryl phosphates
High extensibility Sebacates
(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 pro-
cessing (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 fairly compatible, with the polymer. In selecting a lubricant,
or lubricant system, for a particular formulation, its mutual suitability
and joint effects with the stabiliser(s) must be carefully considered.
This aspect is discussed further in Chapter 7.
(e) Polymeric Modifiers

These fall into two broad categories: processing aids and impact
modifiers (which improve the toughness of uPVC compositions). The
nature and uses of these additives are discussed in Chapter 8.
(f) Fillers
Various fillers, and their applications in PVC compositions, are
considered in detail in Chapter 6. However, two general points
relevant to formulating with fillers may be mentioned here. In many
compositions a filler is included, often at very high loading levels, as a
cheapening extender. Calcium carbonate fillers are commonly
employed for this purpose. When present in substantial amounts, such
fillers 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, 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 2.3), the overall material cost saving may drop progressively
(in some cases quite rapidly) with increased filler loading.
Note: For example, if a given volume of product (say a moulding)

weighs 1 kg when produced from a compound of density
1·1gcm-3 , the weight of compound of density 1·4gcm-3
needed to produce it will be 1·4/1·1 = 1·27 kg (to the second
decimal place).
It is useful to remember that-to the extent to which the generalisa-

tion can validly be made-with particulate mineral fillers, the larger
the particle size, the greater the reduction of surface gloss of the
composition, and the higher the water absorption and the tendency to
'stress whitening' (see Chapter 6). However, the finer the filler, the
greater the plasticiser demand in pPVC compositions and the tendency
to absorb lubricants in uPVC compositions, except where the particles
are effectively surface-coated (see Chapters 6 and 7).
(g) Colourants
A colourant must be able to impart the desired colour, in adequate
strength, to a PVC composition when present in a relatively low
proportion (normally up to a few phr at most). Completeness of
colourant dispersion is of paramount importance for optimum colour
effect in a PVC material, whilst ease of handling and dispersibility of
the colourant in compounding are equally important from the point of
view of operational efficiency and economy. Colourants are available
in forms particularly suited to these requirements, viz. as pre-
compounded colour concentrates of various kinds, or as integral
components of multicomponent 'single-pack' additive systems in which
they are intimately interdispersed with other additives for direct, joint
incorporation in a PVC composition in the course of its compounding.
The aspects of colourants relevant to formulating are among those
covered in Section 9.2 of Chapter 9. Colourant manufacturers are, as a
rule, very technically minded and their advice and recommendations in
connection with specific formulation problems are readily available
and worth having.
(h) Other Components of pvc Formulations

Discussion of the other formulation components in the various
relevant chapters and chapter sections includes, inter alia, the points
of direct concern to the formulator.
2.2.3 Some Aids to Formulating
(a) Computer-Aided Formulating

Relevant laboratory data can be processed by computer to provide
reasonably accurate predictions of the likely performance of a PVC
formulation when several of its features are treated as variables. This
approach can be applied to the selection of a formulation which, at the
lowest cost, can meet a particular specification. 2 ,3 Such predictions can
be especially useful at times of price and availability fluctuations.
However, the development of the appropriate programs calls for
considerable expertise, and a large body of reliable data on the effects
of the amounts and nature of the relevant formulation components
upon the composition's properties relevant to the requirements of the
specification concerned.
(b) 'Desirability Function' in Plasticiser Selection for pPVC

Formulations
This concept was first put forward 4 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 considera-
tion. 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 com-
pounds within the (properly calculated) range of desirability values
between 0·65 and 0·90 (1·00 represents maximum desirability) are
virtually certain to be suitable for the purpose for which they are being
formulated.
2.2.4 Some Interactions and Mutual Effects of Principal

Components of PVC Formulations
Some of the interactions between the constituents of a PVC composi-

tion arise in normal consequence of the constituents' exercise of their
intended functions, e.g. plasticisation of the PVC polymer by the
plasticiser(s) in pPVC, reactions of stabilisers with polymer decom-
position products, lubrication of the composition by the lubricant(s).
However, other interactions can also occur, and should be taken into
account by the formulator. The kinds of such secondary interactions
are indicated briefly in this section: 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 7, Section 7.2). 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 6, Section 6.2, and Chapter
7, Section 7.2).
(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 (see
Chapters 4 and 24), and the synergism of glycerol ester lubricants with
sulphur-containing tin stabilisers, or that of calcium stearate lubricant
with antimony mercaptide stabilisers (see Chapter 7, Section 7.2).
(c) Other Mutual Effects

Noteworthy examples are the activating effect of some stabilisers on
blowing agents in the production of cellular PVC materials, and the
discolouration which may result through interaction of some lead
stabilisers with impurities in lubricants of the glycerol ester type (cf.
Chapter 7, Section 7.2), or through the interaction of sulphur-
containing organotin stabilisers with lead-containing pigments (due to
formation of coloured sulphides).
2.2.5 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) Stabilising action of some lubricants and lubrication action of
certain stabilisers (both permitting the use of the other com-
ponent in proportions lower than would otherwise be
necessary-see Chapter 7, Section 7.2).
(ii) Flow-promoting action (i.e. processing aid effect) of some
polymeric impact modifiers (see Chapter 8, Section 8.2).
(iii) Internal lubrication by plasticisers and their impact-modifying
effects.
(iv) External-lubricant effect of some plasticisers (see Chapter 7,
Section 7.2).
(v) Flame-retardant effects of phosphate plasticisers and
chlorinated-paraffin secondary plasticisers [cf. Section 2.2.2(c)
above; Chapter 5, Section 5.6.5, and Chapter 9, Section 9.2].
(vi) Stabilising action of epoxy plasticisers (cf. Chapter 4, Section
4.3; Chapter 5, Section 5.5.3).
(vii) Light-stabilising effect of carbon black, the common black

pigment used in plastics compositions including PVc.
(b) Undesirable Side-Effects

Examples of such side-effects include
(i) Opacifying effects of fillers, many impact modifiers and other
formulation components, which must be considered when
formulating clear compositions.
(ii) 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 Chapter 4, Section 4.8).
(iii) Detrimental effect of emulsion PVC polymer on the electrical
resistance of compositions based on this type of polymer [cf.
Section 2.2.1(b) above, and Chapter 3, Section 3.3.1(d)].
(iv) Lowering of heat stability of PVC compositions by most
antistatic agents (cf. Chapter 9, Section 9.2.3).
(v) Tendency to 'stress whitening' promoted by the presence of
some fillers (see Chapter 6, Section 6.2) and polymeric modi-
fiers (see Chapter 8, Section 8.3.3).
2.2.6 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 1.2, Chapter 1.
(a) Pipes and Tubing
(i) Rigid pipe (lead-stabilised):

PVC polymer (S* or M, t K value 65-68) 100
Stabiliser/lubricant (co-precipitate):
Tetrabasic lead sulphate 1·2 phr
calcium stearate 1·2 phr
polyethylene wax 0·1 phr
Filler: CaC0 3 (fine-particle-size grade: precipitated, 2-4phr
or ultrafine ground whiting; surface-coated)
* Suspension type.
tMass type.
Absence of impact modifier makes this a 'non-impact-resistant'

formulation.
(ii) Clear, flexible tubing (non-toxic-1or medical use):
PVC polymer (S or M, K value 65-70) 100
Stabiliser: Ca/Zn type 1·5-2·0 phr
Co-stabiliser: epoxidised soya bean 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 G 10) 0·0-0·6 phr
(b) Extruded Profiles
(i) High impact uPVC:

PVC polymer (S or M, K value 60) 100
Stabilisers: tribasic lead sulphate 6phr
dibasic lead stearate 1 phr
Lubricants (internal/external): fatty acid ester type 1·9-2·0phr
calcium stearate 0·4-0·8phr
Impact modifier: ABS type 6-1Ophr
Processing aid: acrylic type 1·8-2·2 phr
(ii) Flexible composition:
Stabiliser: a Ba/Cd soap complex (e.g. Irgastab BC 1·2-1·5 phr
247)
Co-stabiliser: an organic phosphite (e.g. decyl 0·4-0·5 phr
diphenyl phosphite, Irgastab CH 301)
epoxidised soyabean oil 5 phr
Plasticiser: DOP 47 phr
External lubricant: stearic acid 0·1-0·4 phr
This is a non-transparent composition which may be pigmented. The
BalCd stabiliser provides some lubrication, reinforced as necessary by
the stearic acid.
(c) Sheeting and Film
(i) Calendered clear uPVC-1ood packaging grade:
Stabiliser: a di-n-octyl tin (e.g. Irgastab 17 MOL- 1·1-1·5 phr
Ciba-Geigy)
Lubricants:
Internal: fatty alcohol type (e.g. Irgawax 365- 1·2-2·0phr
Ciba-Geigy)
Internal/external: fatty acid ester type (e.g. 0·2-0·5phr
Irgawax 370)
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 pPVC with good stability to light-general-

purpose and horiticultural applications:
PVC polymer (S or M, K values 69-72) 100
Stabiliser: Ba/Cd liquid (e.g. Irgastab BC 26) 1·3-1·6phr
Co-stabilisers: epoxidised soyabean oil 5phr
an organic phosphite (chelator) 0·4-0·5 phr
Plasticisers: DOP 55phr
triaryl phosphate lOphr
UV absorber: (light stabiliser, e.g. Tinuvin P) 0·2-0·3phr
External lubricant: stearic acid 0·2-0·4phr
(iii) Extruded (blown) filled pPVC film-industrial grade:

Stabiliser: a Ba/Cd soap complex (e.g. Irgastab BC 0·9-1·8 phr
247)
Co-stabiliser: an organic phosphite (e.g. Irgastab CH 0·3-0·6phr
301)
Plasticiser: DOP 42phr
Plasticiser extender: chlorinated paraffin 13phr
(50-52% CI)
Filler: whiting (a coated grade) 40phr
The barium/cadmium soap stabiliser has some external lubricant

action in this composition, so additional external lubrication may not
be necessary. Otherwise about 0·3 phr of stearic acid may be added. It
is good practice to use a chelating co-stabiliser with solid
barium/cadmium stabilisers (in the respective proportions of 1 to 3) to
improve the initial colour and light stability of the composition.
(d) Calendered PVC/Asbestos Flooring (Tiles)

Vinyl chloride/acetate copolymer (K value 55, 13- 100
15% VA)
Stabiliser: A Ca/Zn complex powder (e.g. Irgastab 2·0-4·0phr
CZ 45M)
Co-stabiliser: epoxidised soya bean oil 6·0-8·0phr
External lubricant: stearic acid 1·0-2·0phr
Pigment: titanium dioxide 10-15 phr
Fillers: asbestos (chrysotile) 100phr
whiting 160phr
Special grades of solid calcium/zinc complex stabilisers are produced
by most manufacturers for vinyl/asbestos fiooring compositions. These
stabilisers combine good compatibility with VC/VA 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 fiooring 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): 0·1 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 7, Section 7.2).
(e) Cable Covering and Insulation
(i) High-temperature cable compound:

Stabiliser: dibasic lead phthalate 7phr
Plasticiser: tri-Linevol 79 trimellitate (e.g. Reomol 70phr
LTM-Ciba-Geigy)
External lubricant: calcium stearate 1phr
Flame retardant: antimony trioxide 6phr
In this composition calcium stearate contributes to heat stabilisation
whilst acting as lubricant. Ditridecyl 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 composi-
tions 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 0·2% of an effective
antioxidant (Irganox 1010).
(ii) General-purpose insulation:
Stabiliser: basic lead carbonate 7phr
Plasticiser: di-iso-octyl phthalate (DIOP) 30phr
Plasticiser extender: chlorinated paraffin 30phr
(50-52% CI)
External lubricant (with stabilising action): 1·3 phr
calcium stearate
Filler: whiting (a coated grade) 70phr
(f) Injection Mouldings

(i) Clear, plasticised compound:
PVC polymer (S or M, K value 65~67) 100
Stabiliser: liquid Ba/Cd/Zn (e.g. Irgastab Be 206) 1·5-2·5 phr
Co-stabiliser: epoxidised soyabean oil 5phr
External lubricant: liquid, non-polar type (e.g. 0·3-0·5phr
Irgawax 360)
The lubricant used should be chosen, inter alia, for its suitability in a
clear formulation.
(ii) Oil-resistant soling compound:
PVC polymer (S, K value 66-70) 100
Stabiliser: solid Ba/Cd 4phr
Co-stabiliser: epoxidised soyabean oil 5phr
Plasticiser: DIOP 80phr
Polymeric modifier: nitrile rubber 33phr
(g) Blow-Moulded Bottles
(i) For mineral water:
Stabilisers: zinc octoate 0·15-0·20 phr
calcium stearate 0·05-0·10 phr
Co-stabilisers: distearyl pentaerythrityl diphosphite 0·4-0·5 phr

epoxidised soyabean oil 3·0phr
Impact modifier: MBS type 1O·0phr
Processing aid: acrylic type 0·5-1·0phr
All additives in a formulation for this purpose 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:
Stabiliser: liquid thiotin 1·4-1·6 phr
Impact modifier: MBS type 10-12 phr
Processing aid: acrylic type 1-2phr
Lubricant (internal/external): fatty-acid ester type 1·0-1·5 phr
(h) Paste Formulations

(i) Cold dipping paste:
PVC polymer (E, * K value 69-72) 100
Stabiliser: basic lead carbonate 2phr
Plasticisers: DOP 65phr
DOS 17phr
(ii) Conveyor belting:
PVC polymer (E, K value 69-72) 100
Stabiliser: tribasic lead sulphate 2·0-3·0pbr
Plasticiser: triaryl phosphate 40phr
Plasticiser extender: chlorinated paraffin (45% CI) 35phr
Flame retardant: antimony trioxide 5phr
Antistatic agent: e.g. Lankrostat LA3 (Lankro 10phr
Chemicals)
(iii) Composite coating for upholstery fabric:
Base coat
PVC polymer (E, K value 70) 100
Stabiliser: liquid Ca/Zn (e.g. Irgastab CZ 57) 1·5-3·0phr
* Emulsion type.
Co-stabiliser: epoxidised soyabean oil 5·0phr

Plasticiser: OOP 85phr
Filler: Whiting 20phr
Intermediate (expanded) coat

Stabiliser/activator: liquid, zinc-containing (e.g. 1·5-2·5phr
Irgastab ABC2)
Co-stabiliser: epoxidised soyabean oil 6·0-8·0phr
Plasticisers: OOP 45phr
BBP 30phr
Blowing agent: azodicarbonamide (paste, 1: 1 in 2·5-4·5 phr
OOP)
Filler: fine-ground whiting 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
Stabiliser: liquid Ba/Cd/Zn complex (e.g. Irgastab 1·5-2·5 phr
BC 206)
Co-stabiliser: epoxidised soyabean oil 5·0phr
Plasticiser: OOP 52phr
Pigment: titanium dioxide 0·0-3·0phr
Filler: whiting 0·0-10·0 phr
Colourant: as required
The stabiliser is one suitable for clear PVC to enable the formulation
to be used for unpigmented, unfilled compositions.
2.3 MATERIALS COST OF A FORMULATION
It is usual to express the formulation of a PVC composition in terms

of 100 parts by weight of the PVC resin, using the abbreviation 'phr'
(parts per hundred resin) for the content of each component so
expressed.
A EXTRACT Evaporate ether .® SOLVENT -FREE

EXTRACT
1 Org.anic st.bilisers (including
most organotins and
epoxidised soyabean oil).
2 Monomeric plasticisers and
plasticiser extenders
(chlorin.ated paraffins;
hydrocarbons) .
3 Most org.anic lubricants
(e.g- glycerol esters; stearyl
, - , - , - - - - - , Extract (SoxhleO esters).
4 Light stabilisers
with
{UV-absorbers}.
Precipitate
gradually
with
ethanol
C EXTRACT Evaporate.~SOLVENT_
methanol FREE
~
.3
B.7
EXTRACT
B RESIDUE Extract (Soxhlet) B.8
ExtractCSoxhlet) E EXTRACT
wIth methanol (36h)
with 8.1
[J
1 PVC resin(s). D RESIDUEtetrahydro1uran 8.4
2 Most inorg.mic stabilisers
'1 (24h)
(based on e.a,Ca,Cd,Pb, B.2
Sb,Zn) .and phosphorus- 64-66
containing chelators).
3 Polymeric plasticisers.
4 Polymeric modifers
5 Metal-soap lubricants
(e.g. Ca and Pb stearates).
6 Inorgoiilnic fillers and
pigments.
7 Antistatic agents.
S Polymerisation residues
(suspending agents;
emulsifiers) .
Fig. 2.2 Analysis of a PVC material: a general separation scheme.

Relevant final identification methods are as follows.
Components of extract A I : gas chromatography (GC); thin-layer chromat-
ography (this can also serve as a final separation method for individual
components): infrared spectrophotometry (IR). Light stabilisers can be
identified by UV-absorption spectroscopy. 24
Components of extract C: GC; IR.
Components of residue F: IR; chemical analysis.
Components of first precipitate G and solution H: IR.
Whilst it is convenient to formulate a PVC composition on the

weight basis, the material when made into products will ultimately be
sold effectively on a volume basis (e.g. as lengths of pipe or profile of
particular dimensions, numbers of mouldings, etc.). Thus it is relevant
to know both the weight-cost and the volume-cost of the components
of a formulation. Moreover, given two basically similar compositions
which, however, differ in density (say because the denser one contains
a heavy mineral filler used as a cheapening extender), although the
materials cost of the denser compound may be lower on a weight basis

it can be more expensive on a volume basis.
2.4 COMPOSmONAL ANALYSIS OF PVC MATERIALS
As indicated in Sections 2.2.1 and 2.2.2 above, and made evident by

other relevant parts of this book, the composition of PVC materials
can be quite complex: in consequence, so is the analysis of a PVC
material whose formulation is not known. After a preliminary visual
inspection, which will normally show whether the material is uPVC or
pPVC and can also indicate possible presence of colourants and fillers,
the analysis proper will comprise separation of components (or at least
groups of components), followed by identification of the components
(or their characteristic part-constituents-e.g. the metals in stabilisers
and pigments). Two useful separation schemes are shown, in broad
outline, in Figs 2.2 and 2.3: both relate to plasticised compositions
since the analysis of these encompasses also uPVC, in that the first
step is the removal of plasticisers whereupon the remainder becomes,
in effect, a uPVC composition. The scheme of Fig. 2.2 has evolved on
the basis of the early methods of plasticiser extraction from pPVC
materials. 5 That of Fig. 2.3 is currently the subject of an ASTM
standard,6 whose formal scope is restricted specifically to the separa-
tion, identification, and determination in a PVC composition, of only
those components named in the figure's caption. For the separation
treatments of Figs 2.2 and 2.3 the material should be comminuted (if
not already in powder form, e.g. a dry blend) for intimate contact with
the reagents. Comminution may be effected for example by grinding
after cooling in liquid nitrogen or solid CO2 , slicing with a microtome
or buffing on a coarse grinding wheel.
The techniques most widely used (often jointly) to identify the
constituents of a PVC composition after separation are IR spectropho-
tometry and gas or gas/liquid chromatography. Thin-layer chromatog-
raphy is also used (both as a final separation method for individual
liquid or solvent-soluble components, and for their identification).
Nuclear magnetic resonance is employed in some cases as a final
identification technique, as is-somewhat less widely nowadays--'wet'
chemical analysis. Examination under the microscope can be helpful in
identifying some fillers, notably asbestos fibres, glass fibres, and some
grades of calcium carbonate; crystals of some crystallisable com-
-~-----..
~ @SOLVENT-FREEEXTRACT
Extract
PVC
MATERIAL (Soxhlet) with
diethyl ether ©SUPERNATANT LIQUID
(comminuted:
(BATCHED THF EXTRACTS)
approx.lg) (6h) N
~
~
(a) Heat with tetrachloroethane ~'
until all solubles dissolved g.
,.-_:=---, (b) Add tetrahydrofuran, shake
for 30 min ~
(cJ Centrifuge for 30min
~
L----=-_----' (d) Decant supernatant liquid
(e) Repeat (b)-(d)twice(to
~
extract all PVC resin)
~
@RESIDUE Dry. ~ @ DRY RESIDUE
§"
and weigh
Fig. 2.3 Separation procedure for identification (by infrared spectrophotometry) of some components of a PVC
material,6 viz.
In Extract AI: dioctyl phthalate, tricresyl phosphate, and epoxidised soyabean oil.
In supernatant liquid C: PVC resin.
In Residue D1: lead stabilisers (basic lead carbonate, tribasic lead sulphate, diabasic lead phthalate); inorganic fillers
(calcium carbonate, chalk, antimony trioxide). ~
ponents (e.g. stearic acid where used as a lubricant) can sometimes be

identified under high magnification.
Several publications can serve as sources of further, detailed
relevant information on the following subjects.
Analysis of plastics materials (including PVC): Books by Haslam et

al. 7 Crompton8 and Hummel & Scholl;9 papers by Arnold & Willis, 10
Kagarise & Weinberger l l (IR spectra), and Tryon & Horowitz 12 (IR
spectra).
Analysis of pVC: Papers by Haslam & Newlands,13 Burley &

Bennett 14 (spectroscopic analysis), and Haslam & Soppett15 (deter-
mination of chlorine in PVC resins).
Analysis and identification of plasticisers: ASTM D 3421-75 16 (total

plasticising additives and DOP); publications by Kendall et al. 17 (IR
spectra), and Haslam et al. 18
Analysis and identification of other components of pvc

compositions: Books by Crompton/ 9 Scholl,2° and Lawson;21 papers
by Miller & Wilkins,22 and Hunt et af. 23
REFERENCES
1. Anon., Substances Used in Plastics Materials Coming into Contact with

Food, 2nd edn. Council of Europe Publications Section, Strasbourg, 1982.
2. Tang, Y. P. & Harris, E. B., SPE ]., 23(11) (1967) 91-5.
3. Pugh, D. M. & Wilson, A. S., Eur. Plast. News, 3(9) (1976) 37-42.
4. Harrington, C. E., Ind. Qual. Control, 21 (1965) 494-8.
5. Kainer, F., Polyvinylchlorid und Vinylchlorid Mischpolimerisate, Springer
Verlag, Berlin, 1951, p. 245.
6. ASTM D 2124-70 (1984). Analysis of Components in Poly(vinyl chloride)
Compounds Using an Infrared Spectrophotometric Technique.
7. Haslam, J., Willis, H. A. & Squirrell, D. C. M., Identification and
Analysis of Plastics, 2nd edn. Iliffe Books, London, 1973.
8. Crompton, T. R., The Analysis of Plastics, Pergamon Press, Oxford,
1984.
9. The Hummel/Scholl Atlas of Polymer and Plastics Analysis. Vols 1-3.
Current edition. Carl Hanser Verlag, Munich, Vienna and VCH Pub-
lishers, New York, Weinheim, Basel, Cambridge. NB. The latest edition
of Vol. 2 is 1988.
10. Arnold, P. & Willis, H. In Polymer Science, ed. A. D. Jenkins.

Northern-Holland Publishing Co., Amsterdam and London, 1972, Ch. 24.
11. Kagarise, R E. & Weinberger L. A., Infrared Spectra of Plastics and
Resins. OTS Publication PB 11438, US Dept of Commerce, 1960.
12. Tryon, M. & Horowitz, E. In Analytical Chemistry of Polymers, Part 2,
ed. G. M. Kline. Interscience Publishers, New York, 1962, Ch. 8.
13. Haslam J. & Newlands, G., 1. Soc. Chem. Ind., 69 (1950) 103-12.
14. Burley, R A. & Bennett, W. J., Applied Spectroscopy, 14 (1960) 32-41.
15. Haslam, J. & Soppett, W. W., 1. Soc. Chem. Ind., 67 (1948) 33-42.
16. ASTM D 3421-75. Extraction and Analysis of Plasticiser Mixtures from
Vinyl Chloride Plastics. (Discontinued in 1989.)
17. Kendall, D. N., Hampton, R. R, Hausdorff, H. & Pistera, F., Applied
Spectroscopy, 7 (1953) 179-88.
18. Haslam, J., Soppett, W. W. & Willis, H. A., 1. Appl. Chem., 1 (1951)
112-19.
19. Crompton, T. R., Chemical Analysis of Additives in Plastics, 2nd edn.
Pergamon Press, Oxford, 1977.
20. Scholl, F., Additives and Processing Aids: Spectra and Methods of
Identification, Vol. 3 of Ref. 9 above.
21. Lawson, K. E., Infrared Absorption of Inorganic Substances. Reinhold,
New York, 1961.
22. Miller, F. A. & Wilkins, C. H., Analytical Chemistry, 24 (1952) 1253-8.
23. Hunt, J. M. Wishert, M. P. & Bonham, L. C., Anal. Chemistry, 22 (1950)
1478-89.
24. Ruddle, H. L. & Wilson, J. R., Analyst, 94 (1969) 105-15.
Section 2
CONSTITUENTS OF PVC
COMPOSITIONS
51
CHAPTER 3
PVC Polymers
3.1 HOMOPOL YMERS OF VINYL CHLORIDE
3.1.1 Chemical Structure and Molecular Weight
The basic repeat unit of the PVC polymer chain is [-CH2-CHCI-].

The units are linked essentially 'head-to-tail' (Le. -CH2-CHCI-
CH2-CHCI-), with very few head-to-head junctions (see Table 3.3).
In commercial PVC polymers the average number of repeat units in
the molecular chain (Le. the degree of polymerisation) can range
between about 500 and 1500; this corresponds to a theoretical
molecular weight range of about 31000-94000.
Note: As with other polymers, the numerical values from deter-
minations of weight-average (Mw), number-average (Mo), and
viscosity-average (My) molecular weight of the same sample
of polyvinyl chloride are in the sequence Mw> My > Mo, with
My closer to Mw than to Mo.
In industrial practice, dilute-solution viscosity of PVC polymers is
normally determined (by direct measurement of solution and solvent
flow times) as an index of the molecular weight. The results are
commonly expressed in terms of the K value or viscosity number, but
sometimes also as specific viscosity or inherent viscosity (logarithmic
viscosity number). Where the actual value of My is required, it can be
calculated, under certain assumptions, from the Mark-Houwink
equation (also known as the Staudinger-Kiihn equation):l,2
[17] = K(My )'''
where K and Cl' are constants for a given polymer/solvent system at a

53
given temperature, and [1'/] is the limiting viscosity number (intrinsic

viscosity) determined by extrapolating to zero-concentration a plot of
the viscosity number (reduced viscosity), or of the inherent viscosity,
versus dissolved polymer concentration. The relationships between the
various viscosity terms are set out in Table 3.1.
The version of the K value in widest use is the Fikentscher K value:
its relation to other K values also sometimes quoted, and to the
various viscosity expressions in common use for PVC polymers, is
shown in Table 3.2; Fig. 3.1 shows the relationship between this K
value and molecular weight. The Fikentscher K value was first
introduced as an index of the molecular weight of cellulose polymers. 3
It is dependent on the nature of the solvent, but little influenced by the
concentration (in generally dilute solutions) and the temperature of
determination. For PVC polymers it is related to the viscosity ratio
1'/11'/0 (see Table 3.2) by the expression
cK (75K )
In (1'/11'/0) = 1000 1.5 cK + 1000 + 1
Most commercial PVC polymers have Fikentscher K values within the
range 50-80. Polymers with much higher values have also been made.
Like those of other thermoplastics, the properties of PVC polymers
are influenced by the average molecular weight and also by the
molecular weight distribution. The ratio Mwl MD (known as the
'dispersion of distribution') is a function of the latter (giving an
indication of the width of the distribution curve but not greatly
influenced by its shape). Commercial PVC polymers usually have a
relatively narrow molecular weight distribution, with Mwl MD values of
suspension polymers typically within the range 2-2·5 (reducing with
increasing polymerisation temperature). The best method for obtain-
ing complete molecular weight distribution curves of PVC polymers is
gel-permeation chromatography (GPC): the data produced by this
technique can also be used to calculate Mw and MD values (shown to be
in good agreement with direct determinations by other methods7,8). A
review of the evaluation of the molecular weight characteristics of
polymers and copolymers of vinyl chloride by GPC has been published
by Janca and Kolinsky.9 ASTM D 3593-80 (1986) gives CPC proce-
dures and Mark-Houwink constants for PVC (inter alia).
Polymerisation temperature is the most important factor governing
the molecular weight of PVC polymers: molecular weight increases
with decreasing temperature, both within the normal temperature
TABLE 3.1
Polymer Solution Viscosity: Terms and Expressions
Terms and symbols Mathematical Remarks
expressionb,c
Original Now recommendeda
Term Symbol Term Symbol
Relative viscosity "r or "rel Viscosity ratio ,,1"0 ,,1 "0

Specific viscosity "sp (" - "0)/"0 Also known as viscosity
increment: represents viscosity
increase attributable to the
dissolved polymer
Reduced viscosity RV Viscosity number (" - "o)/"oc Provides a measure of the specific
....
capacity of the polymer to
increase the viscosity ratio ~
Inherent viscosity IV Logarithmic viscosity [In (" 1"0)]1c ~
number '<'
:I
Intrinsic viscosity [,,] Limiting viscosity [,,] limc-+o [(" - "o)/"oc] The reduced and inherent '"
t:l
number = limc~o [(In" 1"0)1 c] viscosities tend to the same
limit as the dissolved polymer
concentration tends to zero.
The value of the limit (intrinsic
viscosity) is different for the
same polymer in different
solvents because of
polymer 1solvent interactions
a By the International Union of Pure and Applied Chemistry (IUPAC).

b The relationships expressed are valid for practical determinations only when the relevant viscosities are determined under the same
standard conditions.
C Key to symbols used in the expressions: viscosity of dilute polymer solution (or its time of flow in standard conditions); ~
,,=
flo = viscosity of the solvent alone (or its time of flow in the same standard conditions); c = concentration of the polymer, in g per ml of
solution.
Vl
0-
TABLE 3.2
Interrelationship between Some Common Standard Indices of Molecular Weight of PVC Polymers4 .5
(Based in part on a table compiled by Matthews and Pearson of leI, first reproduced, with permission, in the 3rd edition)
\0'
~ ~
'I) 'I)
,eo ,eo
£.l~ '<')
I:: ~ I:: ~
ilr)lr) i£.l • I:> •I:>
~ I:: ~ I::
... ... E: 8~ ..... 'l)l:! ~
8~~ c-<::S c-<::S '1)001;:
'I) 10 ~~ ~~ _~ - ..... <::st:::l f::! El
I "_ I
~
8~", ~~ ... E:..9
001;:
8'1)
'-I::
''I)
~I:: '.
'-'5
eo'l) ~ooI;:
.-
~ooI;:
~ §IO ~.~
- ~.~ ::to
Q
'I) .~~
E~.~ eo I:> '<') I:> Iil "'..9 l:'I) ~ ~ ~
::to,t;l .~C"l~ "r~
'.~- -§~
1:: ..... ;,..... .~~~
..... 8·~
..... '1::1 ..... ~ ~N ;, ;>... .!:;l '"
;,;>... .!:;l f:::Z ;, ... 'is ... I
-t:::l'<::s ;'t:::l'<::s ~;, 6~~ 'is..s! ... ..s! ;t'
.~t:t ~ 'I) ~ 'Il~!:/ ~ ~ Iil"'" 'I) ::t .g
I::~ I:> '" I:> ~ ~ £.l .::! 001;: I:: '" '" E: 'I) - ::t -c",
~ ..... t:::l ~ Eo-< -S $~-S ";'l~1r) ~ ~ooI;: <::Sl:>~ - $ilr)
"''''£.l $i~
;:..,.~ 001;
.~~
: '" E:~
~ ;:..,.~ ;,-§ ~ t:s 0_ is -ce ~8t<') '"~.
"'O'<::s
.!:;l t') I:: ~~~ ~~~ ~8~ 15~
. . -5 ~ ~.~ ~ ..... '5 Q,,'1;:! ~~ ~ ~ ,?l
$:"'I)<::S ~ ..... '5
::.: ..... <::s ~~~ ~~~ t3....... ~C- ~ c-es
;t'
c
50 0·42 0·155 1·216 42 45·3 49 0·25 0·08 275 40000 20000 '"~
52 0·44 0·165 1·227 43 46·2 50 0·26 0·09 310 ~.
54 0·47 0·175 1·237 44 47·1 51 0·27 0·10 350
57 0·49 0·185 1·247 45 47 48·4 52 0·28 0·105 380 54000 26000 §
I:>..
59 0·52 0·195 1·258 46 49 49·3 53 0·29 0·11 415
61 0·55 0·206 1·269 47 51 50·1 54 0·31 0·115 450 30000 ~
"5
:::-:
64 0·57 0·217 1·280 48 52 51·3 55 0·32 0·120 495 ~
1·292 49 53 52·4 56·5 0·34 0·125 525 ::to
67 0·60 0·228 c
70 0·62 0·239 1·304 50 54 53·6 57·5 0·35 0·13 560 70000 36000 ~
73 0·65 0·25 1·316 51 55 54·7 58·5 0·37 0·14 600
77 0·67 0·264 1·329 52 57 56·1 59·5 0·38 0·145 640 40000
80 0·70 0·275 1·342 53 58 57·2 60·5 0·40 0·15 680
83 0·73 0·285 1·355 54 59 58·2 61·5 0·42 0·155 720
87 0·75 0·3 1·369 55 60 59·5 62·5 0·44 0·16 760 100000 45500
90 0·78 0·31 1·383 56 61 60·5 63·5 0·45 0·17 800
94 0·80 0·32 1·397 57 62 61·7 64·5 0·47 0·175 840 50000
98 0·83 0·33 1·412 58 63 62·9 66 0·49 0·18 885
102 0·85 0·34 1·427 59 64 64·1 67·5 0·51 0·19 930
105 0·88 0·36 1·443 60 65 64·9 68 0·53 0·195 975 140000 55000
109 0·91 0·37 1·458 61 66 66·1 69 0·55 0·20 1025
113 0·92 0·38 1·474 62 67 67·1 70 0·57 0·205 1070
117 0·95 0·39 1·491 63 68 68·2 71 0·59 0·21 1120 60000
121 0·98 0·40 1·508 64 69 69·2 72 0·61 0·22 1175
125 1·01 0·41 1·525 65 70 70·2 73 0·63 0·225 1230 200000 64000
130 1·03 0·43 1·543 66 70·5 71·5 74 0·65 0·23 1300
134 1·06 0·44 1·562 67 71 72·4 75 0·67 0·235 1350
138 1·08 0·45 1·581 68 72 73·3 76 0·69 0·24 1420 70000
142 1·11 0·46 1·60 69 73 74·3 77 0·71 0·25 1490 .....
145 1·13 0·47 1·62 70 74 74·9 78 0·73 0·255 1570 260000 73000
~
149 1·16 0·49 1·64 71 75·8 0·75 0·26 1650
153 1·18 0·50 1·661 72 76·7 0·77 0·27 1720 ~
157 1·21 0·51 1·682 73 77·5 0·79 0·275 1810 cl'
~
161 1·23 0·53 1·704 74 78·3 0·81 0·28 1900 80000 ;!
165 1·26 0·54 1·726 75 79·1 0·83 0·29 1980 340000 82000 '"<::l
169 1·28 0·56 1·749 76 79·9 0·85 0·295 2070
173 1·30 0·57 1·772 77 SO·7 0·87 0·30 2170
177 1·33 0·58 1·796 78 81·5 0·89 0·31 2260
181 1·35 0·6 1·821 79 82·2 0·90 0·315 2360 90000
185 1·38 0·61 1·847 80 83·0 0·93 0·32 2460 480000 91500
a The recommended term is logarithmic viscosity number (cf. Table 3.1).
b This method involves measurement of the viscosity of 0·2 g/l00 ml solution of PVC polymer in cyclohexanone at 30°C.
C This is the viscosity ratio less unity (rJlTJo) = (TJ - TJo)/TJo (see Table 3.1).
d In this method specific viscosity is calculated from the results of determination on a dilute solution of PVC polymer in
nitrobenzene (0·4 g/l00 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 0·2 g/l00 ml VI
-.J
solution of PVC polymer in cyclohexanone is determined at 30°C, and the logarithmic viscosity number calculated from
the results.
100000 5·8
90000
80000
70000
1'1 60000 52
C1
o
...J
50
5·0.·100000
40000
30000 4·8
--50000
20000
4·6
10000
K ValU4
Fig.3.1 Relationship between the Fikentscher K value (DIN 53726-1983) and

the molecular weight of PVC polymers.
range for industrial production (about 40-75°C) and outside it.

Polymers of very high molecular weight (such as may be produced, for
special purposes, at near-zero temperatures) may require intensive
heating in the solvent for complete dissolution when solutions are
being prepared, e.g. for viscosity measurements or GPC
determinations.lO The effect of polymerisation temperature within the
range 0-70°C on the molecular weight of PVC polymers was examined
by Ravey & Waterman. l l The temperature also affects the degree of
stereoregularity which is present, in relatively low degree, in commer-
cial PVC polymers, in the form of rather short syndiotactic sequences:
the degree of syndiotacticity is higher in polymers produced at lower
temperatures. 12
3 PVC Polymers 59
The chemical structure of the molecules of commercial PVC

polymers deviates from the theoretical ideal of linear chains of vinyl
chloride units joined head-to-tail and terminating in -CH2-CH2CI
and -CHCI-CH3 end groups. The structural irregularities which
have been reliably identified in commercial polyvinyl chloride are
listed in Table 3.3, with the best current estimates of their respective
contents. Two of these irregularities, viz. chain-branch junctions
containing a tertiary chlorine atom, and mid-chain chloroallyl groups,
are thought to be largely responsible for the low thermal stability of
PVC [ef. Chapter 4, Section 4.1.2(b)].
3.1.2 Polymer Morphology and Some Related Properties
Commercial PVC polymers may be regarded as essentially amor-

phous in nature,13 although they do contain small crystallites in
proportions amounting to about 8-10% crystallinity as determined by
X-ray diffraction. 14 Other techniques, viz. thermal analysis (differential
thermal analysis, differential scanning calorimetry, thermomechanical
analysis (DTA, DSC, TMA» and density measurements, give similar
crystalline content values (albeit in some cases with a lower limit of
only about 2%).15-17 The crystallinity is associated with the stereo-
regular (syndiotactic) polymer fraction: 18.19 the crystalline habit of
such material was first characterised in the mid-1950s by Natta &
Corradini. 20
Note: It is also possible that microcrystallites can actually form in
plasticised PVC, where the free-volume increase caused by
plasticisation can facilitate local chain alignment (see Chapter
5, Section 5.2).
There is good evidence that, in addition to fully crystalline material,
a two-dimensionally ordered nematic phase is also present in commer-
cial PVC polymers, in proportions dependent on the processing
history. 21
The glass transition temperatures (Tg) of commercial homopolymers
lie in the range 80-84°C (as determined by DTA, DSC and TMA).13,15
Annealing above the Tg increases crystallinity and also the crystalline
melting temperature (as given by the endothermic peak on DTA
curves).15,17 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 1337 kg m- 3 (1·337 g cm- 3)Y
TABLE 3.3 ~
Irregularities in the Molecular Chain Structure of Commercial PVC Polymers
(Based on data from Refs 4 and 6.)
Irregular grouping Content a Remarks
Head-to·head monomer junctions

(-eHzCHCt-CHCt-CH 2- ) Less than 0·2 per 1000 monomer units ~
Chain branches: [
Chloromethyl (-CHzCI) 4 per 1000 monomer units Associated predominantly with
tertiary hydrogens (-eH-)
I
CHzO i
2-Chloroethyl (-CHz-CHzCl) Less than 0·5 per 1000 monomer Units} .g
2,4·Dichlorobutyl (-CH2-CHCl---CHz-CHzCl) 1 per 1000 monomer units Associated largely with tertiary ~
::to
Longer chain branches Less than 0·5 per 1000 monomer units chlorine (-eCl-) -~
Tertiary chlorine (-eO-) 0·5-1·5 per 1000 monomer units ~
~ g~
Internal allylic chlorine (-eH=CH-CHCl-) 0·1-0·3 per 1000 monomer units .,~
U nsaturation: ~.
Total 1 per molecule } Conjugated double bonds (polyene sequences)
internal double bonds 0·1-0·3 per 1000 monomer units virtually absent: less than 5 x 10- 4 per 1000
monomer units (below limit of detection) l
).
End·groups:
1,2·Dichloroalkane (-eHz-CHCl---CHzCl) 0·8-0·9 per molecule Other end-groups also possible, e.g. ~
1-Chloro-2·alkene (-eHz-CH=CH-CHzCl) Approx. 0·7 per molecule -eH=CHCl; -eHz-CHOz; ~
-eHz-CHzO; -eHCl---CH=CHz ~.
Initiator residues Approx. 0·2 per molecule May be embodied in such end-groups as
-eHZ-OC-C6 H 5 ; -eHz--O-SOz-OR,
and -eHz-OH (where R is an alkyl
group)
a Best estimates from reliable determinations to date.

3 PVC Polymers 61
As would be expected, annealing below the 1'g 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 structureY
Relatively highly crystalline PVC polymers (up to about 50%
crystallinity) with high syndiotactic material content have also been
prepared, by polymerisation at low temperatures and in the presence
of chain-transfer agents (including solvents acting in that
capacity).16,18,2I-24 The preparation of fibres and films from such
polymers has been reported,25 as well as of plasticised compounds
(with about 50 phr DOp).18,25 The melting points of the highly
crystalline polymers can be as high as 265_273°C22 ,24 (cf. commercial
PVC polymer-about 210°C in the absence of decomposition).
The plasticised compounds just mentioned had higher modulus and
hardness and lower tensile creep at room temperature (but also lower
tensile strength and extension at break), than a similar compound of
ordinary commercial PVC polymer. Below - 25°C the modulus and
hardness were lower (i.e. the flexibility and softness greater) than
those of the ordinary PVC compound. 18
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. 26 Biaxial orientation of the polymer
in PVC bottles and films increases impact resistance (cf., for example,
Chapter 15) and reduces permeability. The tensile strength and
retraction on heating of extruded products is strongly influenced by
longitudinal molecular orientation imparted by stretching in produc-
tion, whilst the 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
1). The yield and fracture behaviour of PVC polymers and uPVC
compositions is strongly influenced by the nature and extent of
molecular orientation. Investigational work in these areas has been
reported by several authors. 27-30
3.1.3 Production of PVC Polymers
Commercial PVC polymers are the products of polymerisation of vinyl
chloride (monochloroethene; chloroethylene), CHz-CHCl.
(a) Vinyl Chloride Monomer (VC)

Two main routes are used in the industrial production of this
monomer: see Fig. 3.2. The ethylene route via dichloroethane, which
is the most widely utilised, is commonly operated in the form of the
so-called balanced process. This combines the chlorination and oxy-
chlorination of ethylene to dichloroethane, followed by the latter's
pyrolytic dehydrochlorination to vinyl chloride. The HCI formed as a
by-product 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==CH2 + 4HCI + O2 - 2CH2 CI-CH2 CI + 2H2 0
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. The process in which petroleum-derived ethylene is used
affords the greatest economy when run on a large scale, at or near the
full capacity of the plant.
The acetylene route was of prime industrial importance until the
early 1960s, and especially favoured in Europe. Although in com-
parison with the ethylene route it offers the advantages of lower plant
cost and effective operation on a smaller scale (where required), it is
more energy-intensive, and acetylene produced from oil feedstocks is
more expensive than ethylene from that source. However, as acetylene
can also be readily made from coal, this route-which can thus be
completely independent of petrochemicals-remains relevant where
Ethylene route (balanced process)
Cl/catalyst
/ ~
pyrolysis~ CHz-CHCl + HCl
CHz-CH2, high temperature, CH2Cl-CH2Cl ,
O,/catalyst + HCI
t,
,,
~----------------------------------------------I
Acetylene route
catalyst
CH==CH + HCl BO-2SO"C' CH2=CHCl
(excess)
Fig. 3.2 Main reaction routes in industrial production of vinyl chloride.
3 PVC Polymers 63
coal is freely available andl or, as just mentioned, where production is

on a relatively small scale. In the coal-based process, acetylene is
produced from coke and quicklime via calcium carbide:
3C + CaO~ CaCz + CO
(coke)
CaCz + 2H20~ HC==CH + Ca(OHh
The chlorine and hydrogen to make the HCI used in the subsequent
hydrochlorination of the acetylene (see Fig. 3.2) can be produced by
electrolysis of brine (with caustic soda as a saleable by-product).
Integrated plants producing VC from coal by the acetylene route, and
PVC polymer from the monomer, have been successfully operated for
many years (e.g. the AECI 'Coalplex' plant at Sasolburg, RSA).
Vinyl chloride is a colourless gas at room temperature and normal
pressure (boiling point, -13·9°q, 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 1.3.2(b)], VC 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 VC in PVC polymers are similarly laid down, as are limits
for amounts extractable from PVC products [ef. Chapter 1, Section
1.3.2(b)].
(b) Polymerisation Processes

The polymerisation techniques used to produce PVC polymers are, in
order of commercial importance, suspension polymerisation (about
80% of total commercial polymer production), emulsion polymerisa-
lion (about 10-15%), bulk polymerisation, also called mass polymeri-
sation (about 10%), and solution polymerisation.
The commercial application of the solution process is almost entirely
confined to the manufacture of PVC copolymers for use in surface
coatings (see Chapter 19). The total production probably represents
about 1% of PVC polymer sold in the Western World.
Polymerisation is carried out in a liquid which may 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.
SUSPENSION POLYMERISATlON
In a typical suspension polymerisation process, a suspension of
monomer droplets (some 50-150 Ilm in size) is formed by vigorous
agitation in a sealed pressure reactor (autoclave), and the monomer of
the droplets, which contains a monomer-soluble free-radical initiator,
is polymerised at a temperature within the range 40-75°C, under the
autogenous VC vapour pressure corresponding to the reaction tem-
perature (up to 1·5 MPa at 80°C). The reaction is exothermic and
excessive temperature rise is prevented by use of chilled water, and
operation under reflux. Protective colloids (dispersants), nowadays
typically polyvinyl alcohol or soluble cellulose derivatives, are included
in the aqueous phase (typically 0·05-0·06% by weight) to stabilise the
suspension throughout the process, and also buffers to counteract
development of acidity. When some 80-90% of the monomer has
been converted to polymer (the widest conversion range in practice is
75-95%) 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 operation is known as stripping: to
secure an effective high degree of removal of residual VC, stripping is
assisted and completed by steam 'sparging'. Different variants, both
batchwise 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 VC 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
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
3 PVC Polymers 65
takes place inside the droplets-the processing is essentially

as in emulsion polymerisation.
MASS (BULK) POLYMERISATION

The 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 VC liquid)
and normally at 40-70°C. The process has two distinct stages, run
respectively and consecutively in a vertical reactor (prepolymeriser),
and a larger reactor, the autoclave (originally horizontal, but in the
most recent plants often vertical), each equipped with agitators and
condensers. In the first stage, polymer particles form in, and separate
from, the liquid VC phase (polyvinyl chloride is virtually insoluble in
its monomer), thus forming a heterogeneous system. This stage is
carried out under strong agitation (with a turbine-type stirrer) to
ensure uniformity and correct morphology of the PVC grains. At a
relatively low degree of conversion (around 10%) much of the VC
liquid is absorbed onto the porous polymer grains, and the viscosity of
the slurry becomes too high for effective rapid stirring, whereas the
grains develop enough strength to withstand transfer to the second-
stage reactor. Here further polymerisation and growth of the polymer
particles proceed to completion-under relatively gentle stirring with a
ribbon-blender type of stirrer-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 venting-off unreacted Vc. Residual monomer
is stripped from the polymer by degassing (in the reactor or a separate
vessel) assisted by introduction of steam or an inert gas to act as
carrier. The resulting polymer powder is then classified to remove the
small percentage of large particles usually present.
The mass polymerisation process was developed and perfected by
the French company Pechiney-Saint Gobain: subsequently, in conse-
quence of mergers and take-overs, it became the property of Rhone-
Poulenc Industries, which is now part of the nationalised French
chemical industry conglomerate.
EMULSION POLYMERISATION
In emulsion polymerisation the system consists of the monomer and
water containing emulsifier(s) (typically anionic) in substantial con-
centration (typically 2-3%) and a water-soluble initiator.
In batchwise operation, polymerisation is carried out in an autoclave
designed for operation at the VC vapour pressure generated at the
reaction temperature (typically 40-60°C), 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 O·lllm). The initiator (commonly potassium persulphate or
ammonium persulphate alone or with a reducing agent, or a more
complex redox system, e.g. HzOz/FeS04/ascorbic acid) produces free
radicals in the aqueous phase, where initiation takes place, at the
boundary with the monomer phase. The polymer particles formed
grow progressively in size throughout the process run: this may
necessitate controlled addition of further emulsifier to maintain
emulsion stability. The degree of conversion is normally about 90%,
the reaction being terminated by venting-off excess monomer. The
final stripping of VC 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. 31 The polymer particles
are normally separated out and dried by spray-drying, followed by
grinding to modify agglomerate size distribution (and break down
outsize or fused ones), and finally by size classification.
Continuous emulsion polymerisation processes are also operated.
Emulsion polymerisation was the first process to be used for large-
scale commercial production of PVC polymers.
A final product of elementary particle size somewhat larger than
that normally resulting from 'straight' emulsion polymerisation may be
obtained by 'seeding' the initial emulsion system, i.e. by introduction
of a PVC polymer latex on whose particles the new polymer then
forms. Controlled, progressive addition of emulsifier will normally be
necessary to secure such growth of the seed particles without forma-
tion of entirely new, smaller ones.
Microsuspension polymerisation, too, can yield similarly larger
particles; it also affords some control over the elementary particle size
of the final product by virtue of the fact that-since in this process
polymerisation takes place within the original monomer droplets-the
size of the polymer particles ultimately formed is much the same as
that of the droplets.
3 PVC Polymers 67
3.1.4 Physical Forms of PVC Polymers
As indicated in the preceding section, PVC polymers are produced in

particulate (powder) form.
The structure of suspension and mass PVC polymer particles is
complex, and closely similar for the two types. A schematic repre-
sentation is given in Fig. 3.3, with the nomenclature for the various
structural elements which has now been widely adopted. Some of the
main structural features are also briefly mentioned below.
Note: 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.34 It is these
variations that make individual polymer grades suitable for
particular formulations and processing methods. The numeri-
cal sizes of the structural elements given in Fig. 3.3 are fairly
representative averages: actual values may vary in practice
""" "
-0---
~ i
Stagem particle "
( polymer powder graIn) '; I
'}I
. . ;. "~/stage II particle
.... ,/"" ./ /'./ (microgranule)
...,/ ,/
/
Eo«
/
. . /",/
/ /
~ 9CQ/s;ageI particle
~ @ - \", (primary particle)
" ,, , \
,, , ,
, \
\," \
\8 Crystallite
~ ~
4nm
(40'&')
approx
Fig. 3.3 Schematic representation (after Hori 32 and Faulkner3) of the

structure of a PVC polymer particle (suspension- or mass-polymerised).
depending on polymerisation conditions (cf. Table 3.5 be-

low). Some examples from the literature are given in Table
3.4.
(a) Suspension Polymer Particles

The powder grains (Stage III particles) of a typical suspension polymer
have a fair degree of sphericity. Under the microscope in reflected
light they exhibit a characteristic puckered surface. Viewed in trans-
mitted light (especially when partly transparentised, e.g. by absorption
of plasticiser) the grain is seen to be surrounded by a dense skin
('pericellular membrane'), enclosing a partly porous interior made up
of clusters of small, near-spherical or oblong Stage II particles and the
associated interstitial voids. The skin, which has been likened to a bag
enveloping the Stage II particle clusters,35 is formed at the boundary
between the original monomer droplet (to which the Stage III particle
corresponds) and the aqueous suspending medium in the polymerisa-
tion 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 0·5 to 5 .urn), 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
TABLE 3.4
Some Examples of Stage nf and n Particle Sizes of PVC Suspension and Mass
Polymers
Grain Microgranule Type of Reference

(Stage III (Stage II polymer
particle) particle)
size (11m) size (11m)
About 100-500" 'Approaching' l a Mass Marks 35

50-250 'Submicron' Suspension Chartoff37
100-150 'About 2' Suspension Summers et al. 38
100 0·2-1·5 Unspecified Parey & Menges39
100 0·5 Suspension Menges et al. 40
Approx. 200-300 Approx.l Suspension Benjamin41
70-250 Suspension/ mass Clark42
aValues cited as generally representative of those obtainable at high conversion rates in

polymerisation. Stage III particle-size distribution graphs also given-as typical
examples-in this reference indicate a total range of about 30-200 11m (with a mean of
about 130l1m) for a mass polymer, and about 40-260 11m (with a mean of about
160 11m) for a suspension polymer.
3 PVC Polymers 69
excellent photographs of both kinds have been published by Marks. 35

An interesting method for determination of the internal particle
structure of suspension PVC polymers by analysis of the desorption
rate of vinyl chloride has been described by Daniels & Longeway.36
The Stage I microparticles which make up a Stage II particle (see
Fig. 3.3) are the basic polymer elements that are formed in the course
of polymerisation.
(b) Mass Polymer Particles

These are similar in general shape to suspension polymer particles,
although they often have a higher degree of overall sphericity, coupled
with a characteristic 'flat-sided' appearance under the microscope.
Their internal structure is also closely similar, but, as they have no
continuous outer skin, their internal pores are more directly
accessible.
(c) Emulsion Polymer Particles

Viewed under high magnification, and in electron-scan micrographs,
the primary particles of a typical emulsion or microsuspension polymer
appear as solid, smooth-surfaced spheres. They are roughly com-
parable in size with the Stage II particles of suspension or mass
polymers, to which they may be regarded as corresponding: however,
their size range is rather wider-typically about 0·1-3 Ilm for seeded
O·1f.1m - 3·Of.lm
\ I
\ I
\ I
\ I
\ I
\ I
\ I
\ I
\
\
\
Fig. 3.4 Emulsion polymer: primary

particles in an aggregate-schematic
40-50fJ.m representation.
TABLE 3.5 ~
Effects of Some Process Factors on the Characteristics of PVC Polymers Produced by the Three Principal Industrial
Polymerisation Processes
Factor Polymerisation Polymer property Effect Remarks

process affected
Nature Magnitude
Polymerisation Suspension Molecular weight Increases with Very large Cf. Section 3.1.1
~'"tI
temperature decreasing (in absence
~
::to
temperature of chain
modifiers) !:l
Particle porosity Increases with Substantial ~
decreasing ~
temperature ~
Mass Molecular weight Increases with Substantial Temperature in the first stage has ~.
decreasing little effect on the molecular :-
temperature in the weight ~
second stage ~
Particle porosity Increases with Significant If required, particle porosity can ~
decreasing be varied (without affecting the ~.
temperature (in both molecular weight) by varying
stages) the first -stage temperature
§
!:>...
Bulk density of Increases with increasing Significant
polymer powder temperature ~
~
(especially in the first
stage) £
Emulsion and Relatively little effect within the comparatively narrow temperature range used in industrial polymerisation ~.
microsuspension [see Section 3.1. 4(b ) I
Degree of Suspension Particle size Increases with increasing Significant
convergence degree of conversion
Particle porosity Decreases with Moderate Polymerisation rate low above
increasing degree of 95% conversion
conversion within the
normal range
Mass Particle porosity Decreases with Significant Degree of conversion in the first
increasing degree of stage has little effect (but
conversion in the transfer to second stage at low
second stage conversion level promotes
formation of fines)
Bulk density of Increases with increasing Significant
polymer powder degree of conversion
in the second stage
Dispersant Suspension Particle size and Affected by the nature Significant
system size distribution of dispersant (and/or
composition of
dispersant system)
Particle porosity Influenced by the Substantial Low surface activity of dispersant
Bulk density of surface activity of (single or composite) makes for
polymer powder the dispersant(s) low porosity and high bulk
w
density
Emulsifier Emulsion and Particle size and Affected by the nature Substantial Addition of small amounts of ~
system microsuspension size distribution and composition of electrolytes often reduces the
..:::
("')
emulsifier system size and increases the number
of particles (with the same
~
~
emulsifier system) :I
Agitation Suspension Particle size Decreases with Substantial '"
t:l
increasing stirrer
speed, passes through
a minimum, then
increases (due to
droplet coalescence)
Particle porosity Usually increases with Significant
increasing stirrer
speed
Agitation Bulk density of Influenced by stirrer Significant
polymer powder speed
Mass Particle size Decreases with agitator Substantial Little effect of the relatively
tip speed in the first gentle agitation in the second
stage: also influenced stage -.I
by agitator type
(continued)
-
;j
TABLE 3.5-contd.
Factor Polymerisation Polymer property Effect Remarks

process affected
Nature Magnitude
Agitation Microsuspension Particle size Influenced by the Substantial .."

The reaction system (monomer
(continued) homogenising with initiator; emulsifier; ~
pressure water) is pre-mixed then ::E
homogenised (in an ultrasonic ~
:::to
homogeniser, high-speed !:l
pump, or colloid mill), and fed
into the polymerisation reactor ~
Presence of Suspension Particle size Decreases with Large These effects are manifested ~
oxygen increasing oxygen even with very low oxygen ::\.
'"
~.
content contents (of the order of
100 ppm on the VC)
Porosity Decreases with Significant The air space in the charged ~
increasing oxygen reactor is normally ev'acuated ~
content just before final VC addition, '"
~.
to remove all oxygen
Chemical properties A1Iected Significant §
~
and stability
~
~
~
~.
3 PVC Polymers 73
emulsion or microsuspension polymers, down to as low as 0·01-0·2 Jlm

for ordinary unseeded emulsion polymers. In commercial emulsion
PVC powders the primary particles are not separate, but clustered into
somewhat irregularly shaped aggregates which form in the course of
spray-drying after polymerisation, and undergo some size modification
in the subsequent grinding [see Section 3.1.3(b) above]. The aggre-
gates can range considerably in size; however, a mean value of about
40-50 Jlm is fairly representative. Thus both on this score, and as
coherent assemblies of primary, pseudo-Stage II particles, they may be
considered as roughly equivalent to Stage III particles of suspension
and mass polymers. Figure 3.4 shows schematically the features of
emulsion polymers just mentioned.
3.1.5 Effects of Some Polymerisation Process Factors on Polymer

Characteristics
The main effects are summarised in Table 3.5.
3.2 COPOLYMERS OF VINYL CHLORIDE

3.2.1 Kinds and Applications
The oldest, and still most widely used, copolymer of vinyl chloride is
that with vinyl acetate (VC/VAC).
In most of the vinyl chloride copolymers of commercial interest the
co-monomer units are in a minor proportion (and randomly distrib-
uted) in the polymer chain, i.e. most are internal, random copolymers,
with the VC units predominating. Copolymers with vinylidene chloride
(VC/VDC) 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 self-supporting, low-
permeability films) it is the VC co-monomer which is the minor
constituent (usually to-15 % ).
Vinyl chloride is also the minority co-monomer in some types of
acrylic copolymer fibres, although the material of the original Dynel
modacrylic* fibre was a 60/40 copolymer of vinyl chloride and
acrylonitrile.
* Modacrylic fibre is defined [ISO 2076-1977 (E)] as consisting of linear

macromolecules having in the chain at least 35% and less than 85% (by mass)
of the recurring unit -CH2-CH(CN}-.
Some terpolymers of vinyl chloride are used in surface coatings (see

Chapters 19 and 20), whilst certain graft polymers and terpolymers
serve as base polymers or polymeric modifiers in weathering-resistant
PVC compositions; there is also a graft-terpolymer fibre (see Table
3.6). Graft copolymers are, as a rule, more expensive than main-chain
ones.
As has been mentioned, most copolymers exhibit behaviour as-
sociated with 'internal plasticising' effects of the co-monomer units: in
comparison with homopolymers, the processing temperature is re-
duced, as is the Tg (and hence the softening temperature, and the
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 43 ,44
have 1'g values and Vicat softening points significantly higher
than those of vinyl chloride homopolymer: cf., for example,
Hostalit LP HT 5060 (Hoechst), a copolymer containing 5%
of N -cyclohexylmaleinimide. 43
Copolymers are normally more readily soluble than homopolymers:

those used as binders in surface coatings tend to adhere better to
substrates (suitable third co-monomers are often incorporated in the
chain to promote adhesion-see Chapters 19 and 20).
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 is the case with
VDC/VC copolymers: the chain structure of PVDC is favourable to
crystallisation and the crystallinity of the homopolymer is normally
high;45,46 however, the structural regularity and hence ease of crystal-
lisation 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 VDC/VC 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 homopOly-
mer associated with its crystallinity (crystalline regions in polymers are
normally impenetrable to diffusant molecules).
TABLE 3.6
Some Vmyl Chloride Copolymers
Copolymer Some typical applications a Relevant chapter(s)/Remarks References
(...)
Vinyl chloride/vinyl 1. Unplasticised mouldings Chapters 10, 17; passim in "tl

acetate (VC/VAC) (including gramophone records) others (see Index) ~
and sheeting (including flooring cl'
and sheets for ~
;:
thermoforming)-S
2. Surface coatings-E or SL Chapters 19, 20. The Literature on VC/VAC
'"~
copolymers for some of the copolymers and
applications may contain a terpolymers is extensive;
third component, or the see for example the
VAC may be partly Bibliography at the end
saponified to produce some of Chapter 1
vinyl alcohol residues
3. Adhesives; finishing agents (for
paper; textiles; leather)-E
4. Fibres, e.g. Vinyon HH (FMC
Corp., American Viscose Div.);
Wacker MP (Wacker Chemie)
-.I
(continued) Ul
~
TABLE 3.6----contd.
Copolymer Some typical applications" Relevant chapter(s)/Remarks References

~"tJ
Vinyl chloride/vinyl Fibres-Cordelan (Kohjin, G., Part of the acetate groups
acetate/vinyl alcohol Japan); graft copolymer saponified to --OH ir
~.
Vinyl chloride/vinylidene 1. Unplasticised calendered Chapters 10, 14
chloride (VC/VDC) sheets; mouldings-S
2. Extruded films (packaging}-S Chapter 23 a~
"0:5
3. Viscosity-reducing polymer in Chapter 18 Ref. 25----general nature !ll
::to
pastes-S and preparation of the
~
4. Coatings and finishes-E For some applications copolymers
"tJ
terpolymers are used, with Ref. 46---general review ..,a
a third component in (with 92 references) ~
addition to VC and VDC Ref. 47-packaging films '"
~.
(see Chapter 20)
5. Fibres, e.g. Saran (National Saran is also the generic name ~
Plastics Products Co.) for all VDC copolymer
fibres containing at least ~
"0:5
85%VDC ~
;:,
Vinyl chloride/propylene Extruded film (packaging); Commercially available from Refs 48 and 49--polymer g.
(VC/P) injection mouldings-S Air Products and Chemicals production, structure and i;!
Inc. (USA)-Airco 400 properties
series Ref. 5~olymer
composition and density
Ref. 51---packaging film
Vinyl· chloride/ethylene Similar to VC/P copolymers-S Developed by Union Carbide Ref. 52
(VC/E) Chemical Co.
Vinyl chloride/ethylene/ 1. Extrusions (profiles, esp. See Index Refs 25, 44 and 53---polymer
vinyl acetate window frames); injection preparation, structure and
(VC/E/VAC) mouldings--graft copolymer, properties
e.g. Vinnol K510 (Wacker- Refs 44 and 54--applications
Chemie) or Baymod L (Bayer)
2. Surface coatings; finishing Chapter 20
agents; adhesives--E
Vinyl chloride/ Mainly surface coatings--E Heat after-treatment required Ref. 55
trifluorochloroethylene for good adhesion. In melt
(VC/lFCE) processing, processability
and heat stability improve
with increasing lFCE
content
Vinyl chloride/vinyl cetyl Calendered sheet-S Originally available from the
....
ether Allied Chemical Co. (USA) "1:J
and some Japanese sources ~
Vinyl chloride/acrylic 1. Modifiers--graft copolymers Refs 25, 56 and 57 cl'
ester (a) for outdoor compositions '<'
(esp. window frame §
extrusionsHraft copolymers,
e.g. Vestolit P1982K (Hills)
(b) for uPVC film and bottles
(for clarity, heat weldability
and impact strength)
Vinyl chloride/fumaric 1. For pastes fusible at relatively
ester low temperatures, e.g. Pliovic
Vinyl chloride/maleic
ester
1 AD (Goodyear)--E
2. Extruded products; injection
Vinyl chloride/itaconic mOUldings
ester
l~~~~
aThe usual method of copolymer production for each application is indicated as follows: S = suspension polymerisation; E = emulsion :::i
polymerisation; SL = solution polymerisation.
3.2.2 Production
In principle, subject to suitability of co-monomer reactivities, all the

four types of polymerisation process mentioned in Section 3.1.3(b)
may be used for the production of PVC copolymers (although in the
case of bulk polymerisation it is also necessary for the copolymer to be
substantially insoluble in the monomers). The processes commonly
used in practice are indicated in Table 3.6. Incorporation of the
required proportion of a co-monomer into the final 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 58), and suitably controlling the poly-
merisation conditions.
The graft copolymers of vinyl chloride and E/VAC, used in
compositions for outdoor applications, are typically made by grafting
polyvinyl chloride chains onto E/VAC backbone chains in a solution
of the E/VAC polymer in vinyl chloride monomer. 44
3.3 COMMERCIAL PVC POLYMERS
3.3.1 Polymer Properties Cardinal to Processing and/or Service
The properties that may be listed under this heading are: chemical
composition (i.e. whether homopolymer or copolymer); molecular
weight; polymer particle characteristics (shape, structure, size and size
distribution), and those bulk properties of polymer powder which are
influenced by the particle characteristics and are important in storage,
conveying, and processing, viz. bulk density, packed density, and
powder flow. Polymer quality, in the sense of freedom from gels (fish
eyes) and impurities, is also important in a number of applications.
(a) Chemical Composition

In broad terms, the formulator's general choice is between a homo-
polymer and a copolymer (in certain specialised formulations the latter
may be included with the former in a modifying role). The
copolymers-of which polyvinyl chloride/acetate is the most important
in the commercial sense-are used in certain cases in preference to
homopolymers largely for ease of melt processing of rigid composi-
3 PVC Polymers 79
tions, or where (as in coating, finishing or adhesive compositions) their

ease of fusion, adhesion properties and-where relevant-their easier
solubility characteristics, are beneficial. In rigid compositions based on
VC/VAC copolymers, the ease of melt flow increases with increasing
VAC content (for the same molecular weight), but the softening point,
hardness, and-to some extent-the heat stability of the products are
also progressively reduced. The commercial VC/VAC copolymers
typically contain 10-16% V AC, although the proportion may be as
low as 2% in some coating copolymers modified with a third
component (see Chapter 19).
Of the three main melt-processing outlets for VC/VAC copolymers,
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 below 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 Table 3.6), the presence of the olefin component
affects the melt viscosity in the same way as that of the vinyl acetate in
VC/VAC copolymers. However, there is comparatively little adverse
effect on heat stability and strength properties. Nevertheless, the use
of these copolymers is very limited, largely because they are con-
siderably more expensive than VC/VAC copolymers. The uses of
other VC copolymers are indicated in Table 3.6.
(b) Molecular Weight (Viscosity Number; K Value)
The molecular weight of the PVC polymer has a substantial influence
on the ease of processing of uPVC compositions, whose melt viscosity
at a given processing temperature rises considerably with increasing
molecular weight of the polymer (the effect is relatively unimportant
with pPVC where it is outweighed by the overall reduction of melt
viscosity promoted by the plasticiser). Polymer molecular weight also
influences the mechanical properties of PVC products (in pPVC rather
less than in uPVC). Both these effects are considered in discussion of
particular processes and applications at a number of places in the
book.
(c) Polymer Particle Characteristics

The shape, structure, size, and size distribution of PVC polymer
particles affect the particle packing behaviour and hence the bulk
density and settling (packing) characteristics of polymer powder and
powder compounds, as well as their dry flow in the course of
conveying, metering, hopper-feeding, and processing. Particle mor-
phology is an important factor in the rate and uniformity of absorption
of liquid additives (plasticisers; some stabilisers) in the course of
production and processing of powder blends, and in the rate and
uniformity of fusion in melt processing: the presence of substantial
proportions of fine particles can impair these functions, and adversely
affect dry flow. Rheological properties of PVC pastes are strongly
influenced by the particle size and size distribution of the paste
polymer particles (see Chapter 18).
The main reason for the very large variety of PVC polymer grades
offered by manufacturers is that each represents an attempt to gear
and harmonise the above properties for maximum suitability in a
particular combination of process (or even a process variant) and
ultimate application.
Several standard characterisation tests in wide use (see Section
3.3.2) are directly relevant to the handling and processing behaviour of
commercial PVC polymer powders. Thus, the results of bulk density
and compacted bulk density determinations 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). These
two properties as determined in the tests were shown (by Ravey &
Waterman59) to correlate linearly with one another, and hyperbolically
with the specific surface of the polymer powder. The results of the
ASTM dry-flow test in conjunction with those of the test for plasticiser
absorption are significant as a guide to hopper-feeding characteristics
of plasticised dry blends (cf. ASTM D 1755-81, Subsection 16.2).
(d) Quality (Purity)

Whilst not of such basic significance as the characteristics considered in
(a)-(c) above, polymer purity is important in some applications, e.g.
high-clarity compositions for blow-moulded bottles or packaging films.
In such compositions purity is essentially a matter of freedom from fish
eyes and external contamination.
3 PVC Polymers 81
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, fish eyes (also called gels) are
hard specks of polymer which are not dispersed in processing
and thus persist in the finished product. They can originate in
polymer production, but may also be formed in melt process-
ing as a consequence of non-uniform fusion. In opaque PVC
materials they can show up as 'nibs' in the surface.
In the general context, purity may also be impaired by the presence in
the polymer of processing residues (e.g. residual protective colloids,
emulsifiers, etc.) in significant amounts; inter alia, such impurities can
affect electrical properties. Adventitious external contaminants may
reduce heat and light stability and strength properties, apart from any
adverse effects on appearance and electrical properties.
3.3.2 Characterisation and Designation of Commercial PVC
Polymers
Certain polymer properties are very widely and commonly determined
by the manufacturers and processors, and their values quoted for the
purposes of characterisation, quality control, and technical specific-
tions. The principal standards relevant to the properties and testing of
PVC polymers are listed in Table 3.7. Designation systems for
commercial polymer grades normally include code indications of at
least some of these properties, as well as an indication of the
applicational purpose (e.g. whether a 'general-purpose' grade for
melt-processing, or a paste polymer, etc.). Three major standards
provide designation systems, with the relevant characterisation tests,
for PVC polymers: ISO 1060, DIN 7746, and (jointly) ASTM D1755
and D2474. The DIN system is in substantial technical agreement with
the ISO one. The latter and the ASTM designation system both follow
the principle of indicating the selected designatory polymer charac-
teristics by code references to the relevant groups of data (called 'data
blocks' in the ISO system). However, the two systems differ in the
actual coding, and the contents and arrangement of the blocks. The
following two examples illustrate something of the ISO designation
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).
~
TABLE 3.7
Standards Relevant to the Properties and Testing of PVC Polymers and Copolymers

no.
Designation Subject (not necessarily the official title) ~."
General (Designation, coding, characterisation) [
~.
1 ISO 1060/1-1982 Plastics-Homopolymer and copolymer resins of vinyl chloride
Part 1: Designation
2 ISO 1060/2-1985 Part 2: Determination of properties ~
~
3 ISO 6186-1980 (1985) Plastics-Determination of pourability ~
4 ASTM D 1755-81 Specification for poly( vinyl chloride) resins
'"
'"~.
Note: this standard refers to several of the ASTM test methods
listed below
5 ASTM D 2474-81 Specification for vinyl chloride copolymer resins
~
~
6 ASTM D 2873-70 (1982) Interior porosity of PVC resins by mercury intrusion porosimetry '"
~.
7 DIN 7746 s::.
Part 1 (1986) Vinyl chloride homopolymers: classification and designation 5.
Part 2 (1979) Vinyl chloride homo- and co-polymers: determination of properties )..
Viscosity and molecular weight

:g
[
8 ISO 174-1974 Determination of viscosity number of PVC resins in dilute solution g.
9 ISO 1628/1-1984 Guidelines for the standardization of methods for the determination ~
of viscosity number and limiting viscosity number of polymers in
dilute solution
Part 1: General conditions
10 ISO 3219-1977 Polymers in the liquid, emulsified or dispersed state-Determination
of viscosity with a rotational viscometer working at a defined shear
rate
11 BS 2782: Part 7
Method 730 A: 1979 (*- ISO 1628/1) Determination of reduced viscosity (viscosity number) and intrinsic
viscosity of plastics in dilute solution
Method 730 B: 1978 (== ISO 3219) Determination of the viscosity of polymers in the liquid, emulsified
or dispersed state using a rotational viscometer at a defined shear
rate
12 ASTM D 1243-79 (1984) Test for dilute viscosity of vinyl chloride polymers
13 ASTM D 3591-77 (1985) Determining logarithmic viscosity number of poly(vinyl chloride) in
formulated compounds
14 ASTM D 3592-77 Determining molecular weight (Aln) by vapour-pressure osmometry
15 DIN 53726 (1983) Determination of viscosity number and K value of vinyl chloride
polymers
I..>
Chlorine content
16 ISO 1158-1984 Determination of chlorine in vinyl chloride homopolymers and ~
copolymers
17 ASTM D 1303-55 (1979) Test for total chlorine in vinyl chloride polymers and copolymers cl'
~
(Discontinued in 1986) ~
18 DIN 53474 (1976) Plastics-Determination of the chlorine content <:!
Vinyl acetate content of vc /VAC copolymers
19 ISO 1159-1978 Determination of V AC in VC/VAC copolymers
Ash and/or sulphated ash content
20 ISO 1270-1975 PVC resins-Determination of ash and sulphated ash
[N.B. Revision document (ISO/DIS 3451-5) in 1987]
21 BS 2782: Part 4
Method 454 A: 1978 (1983) Determination of ash
Method 454 B: 1978 (1983) Determination of sulphated ash
(== ISO 1270)
(continued) ~
~
TABLE 3.7-contd.

no.
Designation Subject (not necessarily the official title)
~
Volatile matter
22 ISO 1269-1980 (1985) Determination of volatile matter (including water) in PVC r5'
homopolymers and copolymers
23 BS 2782: Part 4
Method 454 D: 1978 (1983) Determination of volatile matter (including water) in PVC resins a~
(=ISO 1269)
1
24 ASTM D 3030-84 Test for volatile matter (including water) in vinyl chloride resins j-
Impurities and foreign matter ~
~
25 .ISO 1265-1979 (1986) PVC resins--Determination of number of impurities and foreign ~
particles s·
Test for methanol extract of vinyl chloride resins ~
26 ASTM D 2222-66 (1984)
Bulk density ~
)..
27 ISO 60-1977 (1985) Determination of the apparent density of material that can be :g
poured from a specified funnel ir
28 ISO 61-1976 Determination of the apparent density of moulding material that g.
cannot be poured from a specified funnel ~
29 ISO 1068-1975 Determination of compacted apparent bulk density of PVC resins
30 BS 2782: Part 6
Method 621 A: 1978 (1983) Essentially as ISO 60 (entry no. 27 above)
(=IS060)
Method 621 B: 1978 (1983) Essentially as ISO 61 (entry no. 28 above)
(=IS061)
Method 621 D: 1978 (1983) Essentially as ISO 1068 (entry no. 29 above)
( == ISO 1068)
31 ASTM D 1895-69 (1979) Test for apparent density, bulk factor, and pourability of plastic
materials
N.B. Method A == ISO 60
Method C == ISO 61
Particle size
32 ISO 1624-1978 Vinyl chloride homopolymer and copolymer resins-Sieve analysis in
water
33 ISO 4576-1978 (1984) Plastics-Aqueous dispersions of homopolymers and copolymers-
Determination of gross particle content by sieve analysis
34 ISO 4610-1977 Vinyl chloride homopolymer and copolymer resins-sieve analysis .....
using air-jet sieve apparatus
35 BS 2782: Part 4
Method 454 F: (1978) (1983) Essentially as ISO 4610 (entry no. 34 above) ~
( == ISO 4610) :;p
~
36 ASTM D 1705-82 Particle size analysis of powdered polymers and copolymers of vinyl ~
chloride <:!
Bromine number
37 ISO 3499-1976 Aqueous dispersions of homopolymers and copolymers of vinyl
acetate--Determination of bromine number
pH of aqueous extract
38 ISO 1264-1980 (1985) Homopolymer and copolymer resins of vinyl chloride-Determination
of pH of aqueous extract
39 BS 2782: Part 4
Method 454 C: 1978 (1983) Determination of pH of aqueous extract of PVC resins
(== ISO 1264)
(continued) ~
TABLE 3.7-contd. ~

no.
~
Miscellaneous properties relevant to processing ~
40 ISO/R 182-1970 Determination of thermal stability of PVC polymers and copolymers :::s:!
and their compounds, by splitting off HCI El
PVC resins for general use-Hot plasticiser absorption
R·
41 ISO 4574-1978
42 ASTM D 2396-79 (1985) Powder-mix time of PVC resins using a torque rheometer 'f
43 ASTM D 2538-79 (1985) Fusion test of PVC resins using a torque rheometer .g~
44 ASTM D 3367-75 (1986) Test for plasticiser sorption of PVC resins under applied centrifugal '"3-.
force -~
45 ASTM D 3596-77 (1983) Determination of gels (fish eyes) in general-purpose PVC resins
46 ASTM D 4202-82 Thermal stability of PVC resins g~
~
VC monomer content '"
s·
47 ISO 6401-1985 PVC homopolymers and copolymers-Determination of residual VC ~
monomer-Gas-chromatographic method
48 ASTM D 3680-78 Residual VC monomer content by solution injection method (for PVC i).
homopolymers, copolymers and compounds) ~
49 ASTM D 3749-78 Determination of residual VC monomer content of vinyl chloride ~
homopolymers by gas chromatography (head-space method) '5'".
50 ASTM D 3834-80 Determination of the purity of VC by gas chromatography ~
51 ASTM D 4434-84 Determination of residual VC monomer content in parts per billion in
vinyl chloride polymers and copolymers
52 DIN 53743 (1979) Determination of VC in polyvinyl chloride by gas chromatography
3 PVC Polymers 87
Homopolymer for melt processing:

ISO 1060---PVC-S G, 121-56
homopolymer j~
suspension-produced
general-purpose
(i.e. not for paste)
viscosity number------'
bulk density of 0·56 g ml- 1- -.. . .
Copolymer for melt processing:
ISO lO60-VC/VAC 88-S, G, 080-75, 17 X
vinyl chloride/acetate
88% vinyl chloride-derived
j JJ 1
suspension-produced
general purpose - - - - - - - - - - '
viscosity number ( 8 0 ) - - - - - - - - '
bulk density 0·75 gml- 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)
A fairly typical set of standard characterisation tests is shown in
Table 3.8. The standard tests are widely used although some manufac-
turers have their own versions of certain tests (e.g. the ICI compaction
test for compacted bulk density; the Coulter counter test for particle
size analysis), and/or a wider range of tests that they apply.
Apart from the common test procedures used regularly for routine
purposes, other methods are also available for use in more fundamen-
tal investigations and research. Some of these are listed below.
Chemical structure characterisation: Infrared spectrophotometry;21
nuclear magnetic resonance;21 various chemical methods, and study of
model compounds. 4 ,21
Determination of molecular weight: 1 Osmometry (£10 ) ; light-
scattering methods (Mw) which also provide information on molecular
configuration in solution (dissymmetric scattering); fractional sedi-
mentation (£1w).
gg
"tI
;::;
::s!
El
~.
TABLE 3.8
PVC Polymer Properties: Common Standard Characterisation Tests
Property Test methods

1
-%
::I.
'"
'"~.
ISO ASTM
~
Dilute solution viscosity ISO 174 (viscosity number) D 1243 (inherent viscosity) g
~
Apparent (bulk) density ISO 60 (determined in g cm -3) D 1895 (test also gives bulk factor and '"
~.
pourability)
Compacted bulk density ISO 1068 (determined in gem -3)
Particle size and size ISO 1624 (sieve analysis of wet D 1921 (sieve analysis: general methods ~
).
distribution slurry) standard); ~
D 1705 (sieve analysis of wet PVC powder
slurry)
Powder mix time D2396
ISO 6168 (time of flow through D 1755 (time of flow through standard funnel)
Flowability (dry flow)
standard funnel)
r
Plasticiser absorption at room ISO 4608 (phr of DOP sorbed in test D 1755 (phr of DOP sorbed in test conditions)
temperature conditions)
Hot plasticiser absorption ISO 4574 (phr min- 1 of DOP
sorbed in test conditions)
Chlorine content (virtually ISO 1158 (determined as % by D1303
never determined on weight)
commercial polymers)
Porosity D 2873 (determined in cm3 g-l by Hg intrusion)
Volatile matter ISO 1269 D3030
pH of aqueous extract ISO 1264 D 1755 (determination of electrical
conductivity)
Thermal stability ISO/R 182 D793; D2115
Vinyl acetate contene (of ISO 1159 (hydrolysis of the acetate Designation requirements for comonomer
copolymers) groups, and back-titration) (vinyl acetate and others) content stated in
D 1755, but no test method given
Specific gravity (of D792
copolymers) '-'>
Ash and sulphated ash ISO 1270
Preparation of a paste ISO 4612 ~
Apparent viscosity of a paste ISO 4575 (Severs rheometer) ~
ISO 2555 (rotating viscometer) ~
'Fish eyes' Mentioned in ISO 1060/2 but no D3596 ::I
ISO method yet available <.:!
'"
aSome 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. 60
~
Determination of molecular weight distribution: 1 GPC; fractional

precipitation; fractional sedimentation; fractional dissolution.
Particle size and size distribution: Sedimentation methods;42,61,62
optical-microscope methods: 61 ,62 electrical sensing zone method (Coul-
ter counter);61,62 centrifugal liquid sedimentation methods;61,62 laser
diffraction;42 light blockage. 42
Particle morphology: Electron-scan microscopy;35 optical
microscopy;42 specific surface area (gas sorption) determinations. 42 ,62
Bulk powder flow: Angle of repose determination;42 shear-cell
tests. 42
3.3.3 Some Commercial Sources and Materials
Some large producers of PVC polymers operate in more than one
country; some also provide technical know-how and backing (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 3.9.
Table 3.10 gives an indication of polymer types suitable for various
applications. Further illustrations will be found in various formulations
cited in this book.
3.4 CHLORINATED POLYVINYL CHLORIDE (CPVC*)

3.4.1 Origins and Production Methods
CPVC was first produced commercially in the mid-1930s in Germany
by chlorination of PVC polymer in solution (in a chlorinated hydro-
* The abbreviation currently favoured by ISO is 'PVC-C'. However, its logical
consistency with accepted letter symbols for other polymers is questionable.
Virtually all such symbols are groups of capital letters, without hyphens, each
group reflecting the chemical nature of the actual molecular species of the
polymer, in some cases in a very general way (e.g. PA for polyamide; UF for
urea formaldehyde; UP for unsaturated polyester-cf. ISO 1043-1978). Chlor-
inated PVC is a chemically distinct molecular species and should, by the same
token, be abbreviated to CPVc. The congruity is highly suspect-to say the
least-of constructing the abbreviation on the same pattern as the present ISO
letter symbol for PVC compositions (Le. no longer the polymer itself)
containing externally added plasticisers (PVC-P), or the one indicating what is
essentially simply the absence of external plasticisation, i.e. PVC-U for
unplasticised polyvinyl chloride compositions.
TABLE 3.9
Some Major PVC Polymer Manufacturers
(Sources: Ref. 4; published technical press data.)
Manufacturer Country Trade name Production Remarks

capacity (1984)
(thousand
tonnes/year)
AECI Republic of South Corvic 135 ICI associate

Africa
Air Products and Chemicals USA Airco 225
\.,;,
Inc.
ATO Chimie (Atochem) France Lacqvyl; Lucovyl 500 Approx. half the PVC capacity in .."
France. First in copolymers. Big ~
producer of paste polymers cl'
BASF West Germany Vinoflex; Vinidur; 235 ~
Lutofan ~
B. F. Goodrich USA Geon; Dalvin (B. F. 1000 Ranked world first before the formation Zl
Goodrich, Canada) of European Vinyls Corporation (see
below)
Borden Chemical Div., USA 300
Borden Inc.
Certain Teed Corp. USA 100
Chemische Werke Hiils West Germany Vestolit 380
Chemopetrol Czechoslovakia Neralit
Chisso Corp. Japan Nipolit
Conoco Chemicals Co. USA Conoco PVC polymer and feed-stock business
acquired by Vista Polymers (see
below)
(continued) -.0
-
TABLE 3.9-contd.
~
Manufacturer Country Trade name Production Remarks
capacity (1984)
(thousand
tonnes /year)
Denki Kagaku Japan Denkavinyl "a

Dutch State Mines (DSM) Netherlands Varian 335 Joint capacity with SAV shown (see ~
below)
Electro Chem. Israel Epivyl l
Electroclor Argentina Corvic ICI associate B'
EniChem Italy Ravinil; Vipla; 775 Ranked world fifth before joining ICI in
Viplavil European Vinyls Corporation (see
~
.g.,.
(copolymer) below). The EniChem group was
formed in 1983 incorporating all l
business of Anic, Societa Italiana
Resine, Liquichirnica, Enoxy, and
Montedison
l~
European Vinyls Belgium Corvic; Ravinil; Not yet operating Formed in 1986, combining the PVC S·
~
Corporation (EVC) (headquarters) Vipla; Viplavil in 1984 business of Enichem and ICI: gained s::o
world first ranking as a result E.
Formosa Plastics Formosa and USA 940 Ranked world second in 1984
USA 398 Formed in 1985 to acquire PVC business ~
'1::i
Georgia Gulf
of Georgia-Pacific Corp. (whose 1984 ~
s::o
capacity is shown in the preceding g.
column) ill
Goodyear Tire & Rubber USA Pliovic 45 Producer of paste polymers only
Co., Chemical Division
Hoechst West Germany Hostalit 235
ICI UK (headquarters) Corvic 860 With associates ranked world third in
1984. Now partner with Enichem in
European Vinyls Corporation (see
above)
Kanegafuchi Chemical Japan Kaneka
Industry
Mitsui Toatsu Chemicals Inc. Japan Vinychlon
Norsk Hydro Norway and UK Norvinyl 315
Occidental Chemical Corp. USA Tenneco 290 In 1986 purchased all PVC business of
Tenneco Polymers Inc. (see below).
As a result now next to B. F.
Goodrich in PVC polymer production
capacity
Produit Chimiques Ugine France Ekavyi Subsidiary of Elf Aquitaine
Kuhlman
Rhone-Poulenc Ind. France Lucovyl Subsidiary of Enterprise Miniere et
Chimique I.>
Saudi Basic Industries Corp. Saudi Arabia 200 ~
(SABIC) (in 1986)
Shell Netherlands Carina
~
280
Shinetsu Chemical Industry Japan Shinetsu ~
-?
Co. l!
Shin tech Inc. USA Shintech 450 ~
Singapore Polymer Corp. Singapore SPC
Societe Artesienne du France Artevyl 335 Joint capacity with DSM shown (see
Vinyle (SAV) above)
Solvayet Cie. Belgium Solvic 800 Ranked world fourth in 1984
Stauffer Chemical Co. USA SCC
Tenneco Polymers Inc. USA Tenneco 425 (See note for Occidental Chemical Corp.
above)
Union Carbide Corp. USA Bakelite; Ucar 65
(solution
copolymers)
Vista Polymers USA Conoco Formed at end of 1984 (see note for
Conoco above) -0
Wacker Chemie West Germany Vinnol

....
~
"'tI
TABLE 3.10 ~
Polymer Types for Some AppHcations ~
Sl
~.
Application Rigid inj. or Rigid pipes Battery Plasticised Rigid sheeting, Gramophone Paste (Gen.
blow moulding; and profiles separators profiles; extruded or records; purpose spread ~
calendered (incl. window cables calendered (jor flooring coating) .g
Polymer type ~ sheeting profiles) thermoforming) ~
~.
Nature· H H H H C(ll) C(14) H
Kindb SorM SorM E S S S E (paste "'tI
grade) <:!
(')
K value 57-58 65-68 69-72 67-80 57 46-48 70-72 ~

""
~.
Examples of grades· that Corvic S57/116 Corvic S68/173 Corvic E72/660 Corvic S67/105 Corvic C57/350 Corvic C47/488 Corvic 72/755
may be considered Ravinil S230CT Ravinil S2265 Ravinil S575 Ravinil C57 Ravinil C48 Vipla P700 §
!:l..
• H, homopolymer; C, VA/VAC copolymer (% VAC content in brackets). )..
b S, suspension polymer; M, mass polymer; E, emulsion polymer. ~
C European Vinyls Corporation polymers. [
5"
i:;
3 PVC Polymers 95
carbon solvent, typically tetrachloroethane or chloroform) at elevated

temperatures (50 to about 100°C). 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.
Around 1960 the dispersion process came into use. In the originally
patented version of this process,25,45 PVC polymer in aqueous disper-
sion is treated with a large excess of chlorine at relatively low
temperatures (up to 60°C) in the presence of a swelling agent (a
chlorinated hydrocarbon, e.g. chloroform) under UV light. The early
commercial polymers produced on this way are exemplified by·
Trovidur HT (Dynamit Nobel) and Geon HT (Goodrich).
3.4.2 Chemical Structure
In both processes chlorination takes place mainly at the -CH2-
groups of the PVC polymer chain (i.e. the 1,2-chlorinated configura-
tion, -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. 3.5], rather than that of a vinyl
chloride/vinylidene chloride copolymer [(b) in Fig. 3.5] which would
be given by preferential 1, I-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. 4
Complete chlorination of polyvinyl chloride would give a pOlymer
very similar to the symmetrical polydichloroethylene [(c) in Fig. 3.5];
however, the degree of chlorination of commercial CPVC polymers
is considerably lower than this (cf. Table 3.11).
Dispersion-chlorinated CPVC polymers are less soluble than those
produced by the solution process, and their thermal stability is better.
These differences are thought to be associated with differences in the
distribution of the additional chlorine atoms among the -CH2-
groups of the original PVC molecular chains,4 arising as a result of
differences in accessibility of the molecules respectively in the dis-
solved and dispersed states. 25
* Production by direct polymerisation of the monomer is impracticable,

although some brittle, low-molecular-weight products have been obtained in
attempts to prepare the homopolymer.45
t In the dispersion process the tendency to 1, I-chlorination can be increased at
high temperatures if the chlorine concentration is allowed to fall. 45
-CHCl-CHCl-CHz-CHCI-CHCI-CHCI-CHCl-CHCI-
(a) Vinyl chloride/l,2-dichloroethylene copolymer or a chlorinated
PVC
-CHz-CClz-CHz-CHCl-CHz-CClz-CHz-CClz-
(b) Vinyl chloride/vinylidene chloride copolymer
-CHCI-CHCl-CHCI-CHCl-CHCl-CHCI-CHCl-CHCI-
(c) Homopolymer of 1,2-dichloroethlene
Fig. 3.5 Simplified representation of polymer segment structures.
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 •63 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 per-
meability to CO2 of CPVC sheet was found to increase with biaxial
orientation, in contrast with the reverse effect observed with UpVC: 63
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. 63 ,64 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.
3.4.3 Material Properties
The two most important points of difference between PVC polymers

and CPVC are the latter's higher melt viscosity in processing, and its
higher Tg (and hence the Vicat softening point and temperature of
deflection under load). Like the 1'g, the density of CPVC increases
with increasing chlorine content. Some properties of CPVC polymers
are shown in Table 3.11, and those of a number of commercial CPVC
3 PVC Polymers 97
TABLE 3.11
Some Properties of Commercial CPVC Polymers, PVC, and FuUy Chlorin-
ated PVC
Polymer CPVC PVC Fully chlorinated

Property polymer homopolymer PVC homopolymer
Chlorine content, weight % 65·67 56·8 73·2 a

Density, gcm- 3 1·52-1·59b 1-40 1·70
Tg,oC 99-123 80-84 175
Maximum service temperatureC
(for commercial
compounds), °C
Continuous exposure 90 65
Intermittent exposure 110 80
a Theoretical figure for polymer of 1,2-dichloroethylene.

b Density of commercial CPVC compounds: 1·47-1·62. This coincides almost exactly
with the density range specified for CPVC pipes and fittings in ISO 3514-1976.
C In non-aggressive environments.
compounds in Table 3.12. Among the properties, the high continuous-

service temperature is particularly important: it is the property
instrumental in the main application of CPVC, viz. as the material of
pipes and fittings for the conveyance of water and other liquids at
elevated temperatures (in some cases also under pressure).
The chemical resistance of CPVC compositions is generally similar
to that of uPVC, except for somewhat greater susceptibility of CPVC
to a number of organic solvents (ketones, chlorinated hydrocarbons,
esters, higher alcohols, aromatic hydrocarbons).
Its higher chlorine content makes CPVC less readily flammable than
PVC (oxygen index typically about 60).
3.4.4 Formulation and Processing of CPVC Compositions

CPVC compositions are formulated on the same general lines as
uPVC, but both their formulation and processing are influenced by
the much higher melt viscosity of the polymer at processing tempera-
tures, and the lower sensitivity of melt viscosity to temperature.
Note: For example, at relatively low shear rates, an increase of the
temperature of a PVC melt from 195 to 205°C may reduce the
melt viscosity by about half: with a CPVC melt the cor-
responding reduction may be only about 15%.
TABLE 3.12
Some Properties of Commercial CPVC Compounds
(Based on manufacturer's published data.)
Compound type Extrusion and Extrusion: Profile

injection pipes and coextrusion
mouldinga profiles b with pPVC:
high -ductility
Property compound c
Tensile strength, lbf in- 2 8200 8400 7300
(ASTMD 1708)
Flexural strength, lbf in- 2 14500 15600 13600
(ASTMD790)
Flexural modulus, lbf in- 2 387000 395000 396000
(ASTMD790)
Izod (notched) impact 2·3 2·0 3·2
resistance, ft lbf in- 1
(ASTMD256)
Deflection temperature 100 102 82
under load (264lb in- 2),
°C
(ASTMD648)
Specific gravity 1·52 1·57 1·47
(ASTMD792)
a Geon 88933.
b Geon 88934.
c Geon 88935.
The higher melt viscosity of CPVC makes effective lubrication (and

hence proper selection of the lubricant system) especially important.
The advice of the polymer or compound suppliers on both the
formulations and equipment requirements should always be sought
(and verified in pre-production trials) when first setting up to process
CPVC. The following few general points may also usefully be borne in
mind.
Unless used directly from freshly opened moisture-proof packages,
CPVC compounds should preferably be dried before processing
(tray-drying in layers 2-3 cm deep for 2 h at 103-105°C, or hopper-
drying for the same period at the same inlet temperature). Accurate
stock temperature control within narrow limits is important in process-
ing. The stock temperature should not be below 215°C; higher
temperatures, up to about 230°C, are in fact preferable for ease of
3 PVC Polymers 99
melt flow. The residence time should be kept to the practicable

minimum, and points of possible material hold-up eliminated: to this
end, all flow channels should be stream-lined, and breaker plates and
screen packs should not be used in extrusion. As in PVC processing,
all working surfaces should be resistant to acid corrosion: polished,
multilayer hard chrome plating is suitable; 420 stainless steel (marten-
sitic 13% chrome stainless steel, grade 420 S37 of BS 970) has been
successfully used as mould material.
3.4.5 Commercial CPVC Compounds and Their Applications
Apart from the Geon CPVC compounds (B. F. Goodrich) shown in

Table 3.12, other examples of commercial CPVC compounds are those
of the Lucalor range (Rhone-Poulenc, France) which includes
Lucalor RB 1266 specially developed for domestic central heating
systems, and the Dekadur compounds (Deutsche Kapillar Plastik,
FRG). The commercial compounds are used mainly 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), pipework and associated products (fittings, valves, tanks) for
chemical plant, extruded profiles, sheets (including co-extruded
CPVC/pPVC sheets), some electrical appliances, and constructional
applications.
REFERENCES
1. Billingham, N. C. & Jenkins, A. D. In Polymer Science, Vol. 1, ed. A. D.
Jenkins. North-Holland Publishing Co., Amsterdam and London, 1972,
Ch. 1.
2. Addleman, R. L. & Yearsley, F., Plastics and Rubber, 1(2) (1976) 81-2.
3. Fikentscher, H., Cellulosechemie, 13, (1932) 58.
5. Matthews, G. A. R. & Pearson, R. B., Plastics, 28(307) (1963) 98-9.
6. Hjertberg, T. & Sorvik, E. M. In Degradation and Stabilisation of PVC,
ed. E. D. Owen. Elsevier Applied Science Publishers, London and New
York, 1984, Ch. 2.
7. Kolinsky, M. & Janca, J., J. Polym. Sci., Polym. Chem. Ed., U (1974)
1181-91.
8. Sorvik, E. M., J. Appl. Polym. Sci., 21 (1977) 2769-90.
9. Janca, J. & Kolinsky, M., Plasty. u. Kaucuk, 13(5) (1976) 138-41.
10. Tavan, M., Palma, G. & Carenza, M., J. Appl. Polym. Sci., 19(9) (1975)
2625-7.
11. Ravey, M. & Waterman, J. A., J. Polym. Sci., Polym. Chem. Ed., 13(6)
(1975) 1475-8.
12. Liu, N. I., Tong, S. N. & Koenig, J. L., J. Appl. Polym. Sci., 2S (1980)
2205-12.
13. Haward, R. N. (Ed.), The Physics of Glassy Polymers. Applied Science
Publishers, London, 1973, pp. 201-6.
14. Baker, c., Maddams, W. F. & Preedy, J. E., J. Polym. Sci., Polym.
Phys. Ed., 15, (1977) 1041-51.
15. Gray, A. & Gilbert, M., Polymer, 17(1) (1976) 44-50.
16. D'Amato, R. J. & Strella, S., Applied Polymer Symposia, 8, Wiley-
Interscience, New York (1969) 275-86.
17. Ohta, S., Kajiyama, T. & Takayanagi, M., Polym. Engng Sci., 16(7)
(1976) 465-72.
18. Gugelmetto, P., Pezzin, G., Cerri, E. & Zinelli, G., Plast. Polym.,
39(144) (1971) 398-402.
19. Abdel-Alim, A. H., J. Appl. Polym. Sci., 19(8) (1975) 2179-85.
20. Natta, G. & Corradini, P., J. Polym. Sci., 20 (1956) 251-67.
21. Maddams, W. F. In Particulate Nature of PVC, ed. G. Butters. Applied
Science Publishers, London, 1982, Ch. 3.
22. Pezzin, G., Plast. Polym., 37(130) (1969) 295-301.
23. Bockman, O. c., Brit. Plast., 38(6) (1965) 364-5.
24. Guinlock, E. V., J. Polym. Sci., Polym. Phys.Ed., 13(5) (1975) 961-70;
idem, ibid., 13(8) (1975) 1533-42.
25. Bier, G., Kunststojfe, 55(9) (1965) 694-700.
26. Gilbert, M., Marshall, D. E., Voyvoda, J. C. & Copsey, C. J., Plast. Rub.
Process, 3 (1979) 96-108.
27. Rider, J. G. & Hargreaves, E., J. Polym. Sci. A-2, 7 (1969) 829-44.
28. Miller, L. E., Puttick, K. E. & Rider, J. G., J. Polym. Sci. C, 33 (1971)
13-22.
29. Smith, K., Hall, M, G. & Hay, J. N., J. Polym. Sci., Polym. Lett. Ed.
14(12) (1976) 751-5.
30. Brady, T. E., Polym. Engng Sci., 16(9) (1976) 638-44.
31. (a) ICI, British Patent 1553829; (b) Hoechst, US Patent 4158092.
32. Hori, Y., Japan Plastics, 3(2) (1969) 48-53.
33. Faulkner, P. G., J. Macromol. Sci. Phys., B11(2) (1975) 251-79.
34. Allsopp, M. W. In Manufacture and Processing of PVC, ed. R. H.
Burgess. Applied Science Publishers, London, 1982, Ch. 7.
35. Marks, G. C. In Developments in PVC Technology, ed. J. H. L. Henson
& A. Whelan. Applied Science Publishers, London, 1973, Ch. 2.
36. Daniels, C. A. & Longeway, G. D., Polym. Engng Sci., 19(3) (1979)
181-9.
37. Chartoff, R. P., 34th ANTEC SPE, Proceedings (1976) pp. 347-9.
3 PVC Polymers 101
38. Summers, J. W., Isner, J. D. & Rabinovitch, E. B., 36th ANTEC SPE,
Proceedings (1978) pp. 757-9.
39. Parey, J. & Menges, G., J. Vinyl Technol., 3(3) (1981) 152-6.
40. Menges, G., Berndtsen, N. & Opfermann, J., Kunststojfe, 69(9) (1979)
562-9.
41. Benjamin, P., Plast. Rubb. Mat. Appln (Nov. 1980) 151-60.
42. Clark, M. In Particulate Nature of PVC, ed. G. Butters. Applied Science
Publishers, London, 1982, Ch. 1 and 2.
43. Kiihne, G., Andrascheck, H. J. & Huber, H., Kunststojfe, 63(3) (1973)
139-42.
44. Domininghaus, H., Die Kunststojfe und ihre Eigenschaften, VDI-Verlag
GmbH, Dusseldorf, 1976, p. 566.
45. Brighton, C. A. In Advances in PVC Compounding and Processing, ed.
M. Kaufman. Maclaren and Sons Ltd, London, 1962, Ch. 1.
46. Sauntson, B. J. & Brown, G., Reports on the Progress of Applied
Chemistry: Plastics, LVI (1971) 66-76 (Society of Chemical Industry).
47. Oswin, C. R, Plastic Films and Packaging. Applied Science Publishers,
London, 1975.
48. Cantow, M. J. R, Cline, C. W., Heiberger, C. A., Huibers, D. Th. A. &
Phillips, R., Mod. Plast., 46(6) (1969) 126-38.
49. Heiberger, C. A., Phillips, R & Cantow, M. J. R, Polym. Engng Sci.,
9(6) (1969) 445-51.
50. Ravey, M., J. Polym. Sci., Chern. Ed., 13(11) (1975) 2635-7.
51. Briston, J., Packag. Rev., 96(3) (1976) 71-2.
52. Sarvetnik, H. A., Polyvinyl Chloride. Van Nostrand, New York, 1969.
53. Goebel, W., Bartl, H., Hardt, D. & Reischl, A., Kunststojfe, 55 (1965)
329-32.
54. Edser, M. H. & Bulezuik, B. W., Polym. Paint Col. J. (4 December
1974), 1051-6.
55. Ulbricht, J. & Rassler, K., Plaste u. Kaut., 23(7) (1976) 487-90.
56. Albert, W., Kunststojfe, 53(2) (1963) 86-93.
57. Bohn, L., Kunststojfe, 53(2) (1963) 93-9.
58. Burgess, R H. In Manufacture and Properties of PVC, ed. R H. Burgess.
Applied Science Publishers, London, 1982, Ch. 1.
59. Ravey, M. & Waterman, J. A., J. Appl. Polym. Sci., 18 (1974) 2927-33.
60. Grisenthwaite, R J., Plastics, 27 (January 1962) 117-9.
61. BS 3406: Determination of Particle Size Distribution (Relevant part,
current issue).
62. Particle Size Analysis, Proc. Society for Analytical Chemistry; Lough-
borough, England, September 1970. Soc. Analytical Chemistry, London,
1970.
63. De Vries, A. J. & Bonnebat, C., Polym. Engng Sci., 16(2) (1976) 93-100.
64. Hopfenberg, H. B. & Stannett, V., Ch. 9 in Ref. 13.
CHAPTER 4
Stabilisers
4.1 DEGRADATION AND STABILISATION OF PVC

4.1.1 General
It is a fact known since the earliest days of PVC processing and
application, that PVC polymers-unless suitably protected-are strong-
ly susceptible to thermal and photochemical degradation. Indeed, in
contrast with other polymers in wide industrial use, the vinyl chloride
polymers are subject to unacceptable degradation at the temperatures
necessary to bring about the degree of fusion and homogenisation
without which melt-processing into useful products is not practicable.
This is what is meant by the statement, often seen in the literature,
that PVC polymers are thermally unstable 'at normal processing
temperatures' .
This inherent thermal instability is reflected in the low energy of
activation for heat degradation of polyvinyl chloride, which has been
variously quoted as 'approximately 20 kcal per mol',1 and 25·9 kcal per
mol 2 (cf. 55, 46, and 65 kcal per mol similarly quoted! for, respec-
tively, polystyrene, polyethylene, and polypropylene). Also, the
specific energy for the generation of a homogeneous melt of polyvinyl
chloride is considerably higher than the activation energy for heat
degradation.
For the above reasons, PVC polymers cannot be heat-processed
without suitable stabilisers. Heat stabilisation is also necessary for
PVC products that may encounter elevated temperatures in service,
whilst outdoor applications additionally call for stabilisation against
degradation by light.
The original discovery (in the 1930s) that certain lead salts and tin
compounds, as well as some metal soaps, could counteract thermal
102
4 Stabilisers 103
degradation when compounded with PVC polymers, marked the

beginning of practical heat-stabilisation of PVC compositions which
opened the way to successful heat-processing. Nowadays a host of heat
stabilisers is available: most of those supplied commercially are
specialised composite systems (in many cases incorporating also
lubricant additives) developed for particular types of PVC materials,
processing methods, and service conditions. The stabiliser systems
used in PVC compositions for outdoor applications normally provide
dual heat/light-stabilising action.
The modes and mechanisms of PVC degradation and of the action
of stabilisers have been extensively studied since stabilisation first
came to be practised. The findings have resulted in considerable
insight into (but not yet full understanding of) the main aspects of the
entire, extremely complex subject, viz.
(a) the reasons for the instability of vinyl chloride polymers (this is
the best-understood aspect of the three);
(b) the ways in which degradation proceeds, and the resulting
changes in the polymer;
(c) the ways in which stabilisers act, and their relation to (a) and
(b).
However, there is still much to be elucidated before the science of
stabilisation of PVC compositions draws abreast of the highly de-
veloped art. It may be noted in passing that PVC polymers are not the
only constituents of these compositions that can suffer degradation, or
benefit from stabilisation: some others are chlorinated polyethylene
modifiers, chlorinated paraffins (used as plasticiser extenders), and
certain rubbery modifiers (e.g. some ABS types). The first two can be
degraded by heating (undergoing dehydrochlorination with formation
of double bonds and oxidation3,4), whilst the rubbery copolymers may
be photodegraded through the disruption and oxidation of the double
bonds present in their molecules.
4.1.2 Thermal Degradation
(a) Outward Manifestations

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 evolu-
tion 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.
(b) Chemical Aspects
DEHYDROCHLORINATION AND COLOUR DEVELOPMENT
It is known that the evolution of HCI is due to progressive de-
hydrochlorination of the polymer chains, which can occur at only
moderately elevated temperatures (from about 100°C). It can be
initiated, and is thereafter catalysed, by the presence of HCI (auto-
catalysis) as well as other strong acids.
Conjugated double bond systems (polyene sequences) are formed
in a polymer chain as the hydrogen and chlorine atoms are 'unzipped'
from it. The general effect is illustrated by the summary scheme (1),
without any assumption as to the nature of the actual mechanism
involved (which is still under debate).
H H H H H H H H H
I I I I I I I I I
~C-C-C-C-C-C~-C-~
I ;-1----t-; I I I I I I
H:O H:O H a H a H
l
1_ _ _ _ _ _ _ _ 1
energy;
HCI
H H H H H H H H H
I I I I I I I I I
~C-C=C-C-C-C~~-~
I ~+--h I I I I
H : CI H: CI H CI H
1________ 1
i energy;
HCI
(1)
H H H H H H H H H
I I I I I I I I I
~C-C=C-C=C-C~~~~
I .--I----h I I
H :OH:OH
i
I______ --~
energy;
Hel
H H H H H H H H H
I I I I I I I I I
~C-C=C-C=C-C=C~~~
I ,--~---~--,
H : Cl H:
I . _______ ~
and so on
4 Stabilisers 105
The illustration shows random initiation, i.e. elimination of HCI from

two ordinary neighbouring monomer residues in the polymer chain:
there is good evidence that such initiation does occur in practice,
although much less frequently than initiation at certain more vul-
nerable sites in the chain (see below). As can be seen, the first
elimination of HCI by random initiation and the subsequent steps
generate the grouping """CH=CH-CHCI""", i.e. an intra-chain aUylic
group, whose CI atom should be strongly activated by the neighbour-
ing double bond,5 facilitating further unzipping of HCl under the
catalytic influence of that already formed.
It is fairly generally assumed that the polyene sequences are
primarily responsible for the development of colour* in PVC undergo-
ing degradation. However, the possible contribution must also be
recognised from coloured carbonium salt complexes (polyenyl chloride
ion pairs) which should be formed under an ionic mechanism of
dehydrochlorination [see for example the illustrative scheme (2)]6-8
thought by some recent reviewers9 to be more likely to be operative
than the free-radical mechanism favoured by many earlier
investigators. 5,10 The formation of carbonium-type complexes in PVC
polymer degraded by heat was demonstrated by Schlimper .11,12
Cl-
"""--fCH=CHtCHCl-CHr ;::=::::! """--fCH=CH-tCH-CHr

(I)
(II) 1
-HC)
(2)
'''T
AAA rCH=CH-tCH-CHr
n+l
;::=::::! ~CH=CH-tCHCI-CHr
n+l
(IV) 1- HC) (III)
and so on
On good grounds,9 the stability of the ion pairs D and IV (i.e. their
reluctance to split off HCI) may be expected to increase with the
* Colour appears with as few as seven conjugated double bonds in a polyene

sequence, whilst sequences of up to 30 such bonds can arise in de-
hydrochlorinated pVC,1O with a sequence length of 10 being regarded by
some as a likely average. 9
length of the polyene sequence in the cation, to the point where the
polyene propagation ceases after a certain sequence length has been
reached: this is a possible explanation for the limited length of polyene
sequences in degraded PVc.
CHEMICAL BASIS OF OTHER PROPERTY CHANGES

The deterioration of various material properties that accompanies
thermal degradation of PVC is the joint, complex effect of changes
occurring in the polymer, in other susceptible constituents of the PVC
composition concerned, and in the composition as a whole (by way of
inter-reaction of its constituents or their loss by exudation, migration
or volatilisation, and through developing contamination by the
products of degradation of the constituents and of their reactions).
In addition to the dehydrochlorination and polyene formation
already mentioned, the PVC polymer undergoes chain-scission, oxida-
tion (in the presence of air) at vulnerable points in the chain (cleaved
bonds, double bonds, activated sites), cross-linking (with some conse-
quent gel formation), and some cyclisation.
Although the relevant mechanisms is by no means fully established,
there is plausible evidence that a Diels-Alder reaction between
polyene sequences of neighbouring chains [cf. illustrative scheme (3)]
is responsible for much of the cross-linking. 9
-CH=CH~H=CH-CH=CH-CH=CH
+
-CH=CH-CH=CH-CH=CH-CH=CH-
~H=CH~
1
/CH=CH~ /CH=CH-
(3)
CH' CH
~CH-CH/
/ ~ .
-CH=CH CH=CH-CH=CH-
The mechanism of cyclisation in thermal degradation of PVC

polymer is still in dispute, but the cyclisation is thought to take place
within (rather than between) chains, and benzene and cyclohexadiene
are known to be among the products.
Possible degradative changes in some other constituents of PVC
4 Stabilisers 107
compositions have been mentioned previously. Apart from those,

stabilisers are also used up as they react with some polymer degrada-
tion products, and compounds formed in these reactions appear in the
PVC material (cf. Section 4.3). In plasticised compositions, volatilisa-
tion, exudation or migration of the plasticisers under heating, as well
as their partial breakdown (with oxidation in the presence of air) can
contribute to the overall effect of thermal degradation.
VULNERABLE SITES IN THE PVC POLYMER CHAIN

Theoretical considerations, and the study of model compounds, have
established that, in the absence of sites of reduced stability in the
chain, polyvinyl chloride with the ideal, purely linear head-to-tail
monomer unit arrangement should be much more resistant to de-
hydrochlorination than the commercial PVC polymers in fact are. It is
known that the structure of the molecular chains of these polymers
does deviate in a number of ways from the simple ideal: the structural
irregularities are discussed in Chapter 3 (Section 3.1.1). It is,
therefore, a reasonable assumption-not contradicted by any of the
results of the very numerous investigations to date-that in, or near,
some of these structural features the carbon-chlorine bond is activ-
ated, constituting a favourable site for initiation of dehydro-
chlorination.
Up to the early 1980s, in consequence of much careful investigative
work--on model compounds, exchange reactions of commercial PVC
polymers, and involving evaluation by chemical and IR techniques-
the view was fairly well grounded that the structural features
principally responsible for activated, labile chlorine atoms were
chloroallyl groups, both in, and at the ends of, the molecular chains. S
Whilst it was realised that mid-chain tertiary chlorine atoms (see
Chapter 3, Section 3.1.1) should be as labile as an allylic chlorine,s
available evidence indicated that tertiary chlorines were too scarce to
playa significant role. s However, some of the most recent results,
including those of investigations by very sensitive NMR techniques,
radiochemical methods, and UV spectroscopy, now strongly support
the converse conclusion, viz. that tertiary chlorine is much more
abundant (possibly by a factor of about five) than mid-chain allylic
chlorine, and that it is mainly responsible for the relative ease of
dehydrochlorination of commercial PVC polymers. A recent review9
estimates the respective contributions to the initiation of de-
hydrochlorination as 70-80% by tertiary chlorine* at branch points in

the molecular chains (I\N\CClI\N\) and 10-15% each by mid chain allylic
~
chlorine (I\N\CH==CH-CHCII\N\), and regular monomer units serving
as random initiation sites (see illustrative scheme (1) above). This
estimate indirectly brings out the fact that the current balance of
relevant evidence on which it is based points away from the likelihood
that any of the other structural irregularities listed in Table 3.3 of
Chapter 3 playa significant role in the dehydrochlorination of ordinary
PVC polymers.
(c) Thermal Degradation in Melt Processing and Static Exposure to

Heat
The melt processing in which thermal degradation can occur is that
experienced by a PVC composition in compounding and production
operations or in dynamic stability tests (see Section 4.9). Static
exposure to heat may occur in the course of service of a PVC product
or in static stability tests (see Section 4.9).
There is as yet no complete agreement on the mechanisms in-
strumental in the thermal degradation of PVC during melt processing,
and no clear explanation of the role in this complex phenomenon of
the known instability sites in the polymer chains, although such
internal double bonds as are originally present (cf. Table 3.3 in
Chapter 3) are thought to playa significant part. Thermally activated
dehydrochlorination (with the consequent formation -of polyene se-
quences), and its autocatalysis by the HCI formed, are recognised as
major factors. There is some chain scission (partly heat-induced and
partly caused by the mechanical shear experienced by the stock), and
some peroxide and carbonyl formation at the cleaved bond sites; but
the oxygen content of a PVC melt in ordinary processing is normally
low, so that this kind of thermo-mechanical oxidative degradation is
not thought to be extensive.
Considerable similarities have been noted 14 between the IR and UV
spectra of PVC compositions degraded, respectively, in processing and
* Compare Berens' conclusion 13 (drawn as early as 1974 from the results of

degradation experiments on model copolymers) that 1-2 tertiary chlorines per
1000 monomer units would alone adequately account for the thermal
instability of commercial PVC polymers. This may also be compared with the
best current estimate of 0·5-1·5 tertiary chlorine atoms per 1000 monomer
units in such polymers (see Chapter 3, Table 3.3).
4 Stabilisers 109
by static heating in air, although the static degradation produced more

carbonyl groupS.14 Progressive dehydrochlorination autocatalysed by
the HCI evolved is a principal feature also in the degradation under
static conditions.
(d) Effects of Polymer Molecular Weight, and Some Impurities and

Additives
In general, PVC polymers of lower molecular weight are less
heat-stable than the higher-molecular-weight ones. This was originally
attributed to the increase in the end-group content with decreasing
molecular weight (since until recently some end-groups were thought
to have a significant destabilising effect4). However, the more likely
explanation now seems to be the greater 'heat history' (cf. Section 4.9)
associated with the higher polymerisation temperatures used in the
production of lower-molecular-weight PVC polymers (see Chapter 3,
Section 3.1.1 and Table 3.5).
Note: In melt-processing, the tendency to lower heat stability of the
lower-molecular-weight polymers is compensated to some
extent by the fact that their lower melt viscosity entails less
shear heating and permits somewhat lower stock tempera-
tures to be used.
The presence of impurities, both external and internal (e.g. suspend-
ing or emulsifying agents from the polymerisation process), reduces
thermal stability of PVC polymers. It is mainly for this reason that,
other factors being equal, susceptibility to thermal degradation in-
creases in the sequence
mass polymer~ suspension polymer~ emulsion polymer
4.1.3 Photochemical Degradation
The chemical bonds in an ideal PVC polymer chain with no structural

imperfections would all be saturated covalent linkages of three kinds:
C-Cl, C-C, and C-H. The dissociation energies of these bonds are
respectively 78, 81, and 98 kcal mol- 1 (to the nearest unit). In relation
to the photon energies of the radiation making up the spectrum of
sunlight, these dissociation energies are high: they are encompassed
only by those associated with the shortest wavelengths in the UV band
of the sunlight spectrum (viz. the 290-400 nm band) which itself
constitutes the spectrum's most energetic portion.
Note: The wavelengths (A) carrying photon energies (E) cor-

responding to the three bond dissociation energies quoted
above are (to the nearest unit):
A, nm 368 351 . 291
E, kcal mol- 1 78 81 98
Thus, in theory (and solely on the basis of the simplest energetic
considerations) the UV component of sunlight received at the earth's
surface should be capable of degrading the notional ideal PVC
polymer. However, the chemical bonds of such a polymer would also
not absorb radiation above about 200 nm, 15 and since without absorp-
tion no interaction can take place between a polymer and the radiation
it receives, no degradation would occur.
In practice, commercial PVC polymers are susceptible to degrada-
tion by UV light. This is attributable to the sensitising effect of some
of the structural irregularities in their molecular chains: the strongest
sensitisation is believed to be due to the unsaturation (double bonds)
that are always present, and to such carbonyl and peroxide groups as
may be present originally, or formed during photodegradation. In
PVC compositions the base polymer can be further sensitised by the
presence of degradation products originating in thermal processing, as
well as by sensitive sites in some of the other formulation components
(e.g. plasticisers I6 ), by some impurities, residual solvents, and the like.
Suitable, effective stabilisation and attention to processing conditions
are therefore especially important in the production of PVC materials
for outdoor applications.
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), embrittiement, 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-exposure to light is associated
with weathering: this introduces a number of further destructive
factors such as thermal expansion and contraction with temperature
changes, solar heating, water absorption, and possible effects of
atmospheric pollutants.
4 Stabilisers 111
PVC undergoes photodegradation on exposure to light in the

absence of oxygen as well as in its presence. The latter mode is one
more directly relevant to practical service situations, in which air will
almost invariably be present.
Photodegradation of PVC is widely believed to proceed through a
free-radical mechanism. 5,15 The chemical processes involved are com-
plex and still not completely understood, but some general features
are fairly well established. Thus, as has been mentioned, for both
non-oxidative and oxidative photodegradation, the most likely initia-
tion sites in the polymer are double bonds (mid-chain unsaturation,
and possibly also that in some end-groups17), and any adventitious
oxygen-bearing groups that may be present originally (having arisen in
the course of polymer production) or be formed through photo-
oxidation.
The main processes occurring in non-oxidative photodegradation of
PVC polymers are progressive ('unzipping') dehydrochlorination with
polyene formation, chain scission, and cross-linking. The same main
processes are observed in oxidative photodegradation in which, how-
ever, new carbonyl and hydroperoxide groups are formed (whose
presence further sensitises the polymer) through reactions with oxygen
at sensitised or cleaved-bond sites. Polyene sequences forming in the
course of dehydrochlorination may also be interrupted by reaction
with oxygen: this kind of disruption ('photobleaching') of these
colour-inducing formations may be responsible for retarded or
arrested development of colour in PVC undergoing weathering. 18,19
Oxygen-bearing groups arising in photo-oxidation are hydrophilic-
their presence is thought to play a part in the disruptive effects of
atmospheric water in weathering of PVC materials. 20
The rate and extent of dehydrochlorination in photodegradation (in
both the presence and the absence of oxygen) increase with the
intensity of the incident radiation, with its decreasing wavelength
(increasing energy), and with increasing temperature. 19
Exudation of plasticisers from PVC on weathering has been
attributed to their partial exclusion from the areas where some
cross-linking of the polymer has taken place. s
4.2 PURPOSES AND FUNCTIONS OF

STABILISERS IN PVC
Like the mechanisms of degradation of PVC, those of stabiliser action
are still not fully understood. However, it is clear even from quite
general considerations that-whatever the mechanisms of its

operation-a good stabiliser should prevent or disrupt the reactions
instrumental in thermal degradation of PVc. To this end it should, in
particular, rapidly bind and inactivate any reaction products which
may further impair stability (especially free HCI generated by de-
hydrochlorination), deactivate potential initiation sites in the PVC
polymer (e.g. by substituting stable groups for labile Cl atoms and
reacting to saturate double bonds), disrupt polyene sequences (without
damaging the polymer chain), react with free radicals, deactivate
oxygen-bearing groups (which would otherwise act as instability sites),
and neutralise the destabilising effects of impurities. A good light
stabiliser should be similarly functional with respect to photodegrada-
tion, as well as preferably, having a screening action against UV
radiation of the sunlight spectrum.
As is largely self-evident, important general requirements that
should also be met by the stabiliser include ease of intimate dispersion
in the PVC composition concerned and compatibility with all its
constituents in processing and service conditions, no adverse effect on
processing behaviour and properties, effectivity at low levels of
addition, and general cost economy. For some applications the
stabiliser may also have to be non-toxic, and/or odourless, and/or
without effect on the clarity, colour or other characteristics of the PVC
material.
When all the above requirements are considered vis-a-vis the great
variety of PVC compositions, their processing conditions and applica-
tions, each of which may (and usually does) impose some special
demands, it is not difficult to see why there are so many commercial
stabilisers for PVC, and why most of these are not single compounds
but composite, multicomponent systems. It is often said that every
PVC composition presents an individual stabilisation problem,
and-from the practical standpoint-this is hardly an exaggeration. In
the absence of prior directly relevant experience, the choice of a
stabiliser or stabiliser system for a particular formulation should be
made in consultation with the stabiliser manufacturer, and should be
verified in practical tests.
4.3 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
4 Stabilisers 113
incorporated in the PVC polymer by physical admixing. * Permanent

'internal' stabilisation of the polymer should, in principle, be possible,
either by operating the polymerisation conditions so as to eliminate (or
at least substantially reduce) the formation of the irregular structures
that constitute sites of instability in the PVC polymer chains, or by
chemically modifying these structures to neutralise their destabilising
effects.
Along the first of these lines, some possibilities have been explored
of counteracting the formation of labile-chlorine groupings (intra-chain
chloroallyl groups and tertiary chlorine) which are known to arise as a
result of chain transfer to polymer during polymerisation. Possible
means of reducing such transfer include increasing the monomer
content of the polymer gel (by raising the polymerisation pressure
and/or temperature),9 use of additives which can temporarily retain
the VC monomer (e.g. tetrahydrofuran9), or employing an anionic
polymerisation system. 9,21 However, none of these possible methods is
free from difficulties, and none has led to an industrially viable
process.
Stabilising modification of the PVC polymer by chemical reaction is
also still of largely academic interest rather than practical significance.
The following exemplify some of the main lines of approach explored
by various investigators.
(i) Substitution of labile chlorine atoms by stable groups: through
reactions with triphenyl aluminium,22 triethylaluminium,23,24
with dibutyltin mercaptide salts (reported25 ,26 to improve ther-
mal stability by factors of 6 and 9, or with alcohol/water
mixtures27 (said to have produced some promising results in
industrial-scale trials9).
(ii) Saturation of double bonds: through limited chlorination,9 or
addition of hydrogen fluoride. 9
Heat stability superior to that of commercial PVC polymers has also
been claimed for a copolymer of vinyl chloride and lead
undecylenate. 28
* Even if a stabiliser is added to the polymerisation mixture in the reactor

('in-kettle' stabilisation-usually with an organotin stabiliser-practised by
some US pipe manufacturers who produce their own PVC polymers) it still
functions as an additive, although its effectivity is maximised by the very
intimate degree of dispersion attained: its presence also protects the polymer
formed against heat degradation in the drying operations which conclude the
production cycle.
4.3.1 General Classification of Heat Stabilisers
There is no official, 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 their chemical nature and partly to the types and areas of
application. The classification adopted here is based mainly on
chemical type. On this basis, the compounds used as heat stabilisers
for PVC may be divided into the following general groups:
(i) lead compounds:
(ii) organotin compounds;
(iii) compounds of other metals;
(iv) organic stabilisers.
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, often with a view to utilising synergis-
tic effects between the components and avoiding undesirable interac-
tions. Stabilisers and stabiliser systems are also available in combina-
tion 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 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 7, Section
7.2).
Other things being equal, the effectivity of a stabiliser increases with
the thoroughness of its dispersion in a PVC composition.
The first step in selecting a stabiliser for a particular application is to
consider which of the above general types is likely to be the most
appropriate. In this connection it is also particularly important to
consider the total compound and manufacturing costs, with proper
regard to the fact that the cheapest possible stabiliser is not necessarily
the wisest choice. For example, such factors as the recycling of rejects
and general rework can involve extra demands on the stabiliser's
effectivity, and large hidden costs that may overshadow differences in
stabiliser prices.
4 Stabilisers 115
4.3.2 Lead Compounds
These are either lead salts or lead 'soaps' (salts with stearic acid). The
main technical advantages of these old-established stabilisers are 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 Hel). However, they are not suitable for
clear compositions (although some may be used in translucent ones),
where freedom from sulphur staining is necessary, or where their
toxicity presents a hazard, as, for example, in food-contact applica-
tions (e.g. packaging films, containers), products for medical use, or
children's toys. Lead stabilisers are comparatively cheap. Although
they are the heaviest (costing is often on a volume basis), and are
generally used at relatively high-loadings, they can frequently prove
most cost-effective. Subject to their above-mentioned limitations they
are, therefore, always worth considering first. Typical application
areas include pipes, pipe fittings, rainwater goods, interior and
exterior profiles, cable coverings, conveyor belting and electrical
insulation tape.
Lead compounds represent a health hazard, and exposure must be
minimised. In most Western countries stringent limits are laid down by
the appropriate regulatory bodies for maximum lead concentrations to
which people may be exposed in particular circumstances and
conditions.
In the handling and processing of lead stabilisers there are two
general, mutually complementary routes to reducing exposure. Firstly,
the stabilisers are available in forms which do not contain, or give rise
to, dust that may be inhaled. These forms are: 'dustless' powders
(stabiliser powder damped down with a small proportion-varying
with absorptivity, but in general about 1%-{)f plasticiser or mineral
oil, or treated with PTFE); liquid dispersions (pastes) in a suitable
plasticiser; agglomerated forms (granules, flakes, or 'pearls'); and
'strands' (thin miniature rods, typically 5-10 mm long and 0·5-1·5 mm
in diameter). The agglomerates and strands have the additional
advantage (over powders) of better dry flow. Finally, the stabiliser can
be supplied packaged within a sealed polyethylene bag (the pack may
also contain lubricants and other additives) for addition direct and
whole into a high-speed mixer. The mixer shreds the bag, and the
small amount of polyethylene may contribute a little external lubrica-
,...
,...
0\
TABLE 4.1 ~
Lead Stabilisers for PVC ~

~
Lead compound Main applicational features Advantages and limitations Remarks !:l
R·
Basic lead carbonate ('white Low-cost, general-purpose Not suitable for compositions melt-processed at Oldest lead stabiliser; still
'"I
lead') stabiliser. Special high- high rates and temperatures (decomposes at popular for some non- .g~
purity grades available. about 200°C, with CO2 and water-vapour critical applications.
gassing). '"~
'"~.
Non-lubricating. Opacifying.
Tribasic lead sulphate Very common component Strong heat-stabilising action. Non-lubricating. Often used with dibasic ~
of composite lead stabili- Opacifying. lead phosphite in com- ~
sers; widely used in lead- posite heat/light lead ~
~.
stabilised PVC composi- stabilisers.
tions for melt-processing.
Tetrabasic lead sulphate As tribasic lead sulphate, but still more powerful stabilising action (highest proportion of available PbO
~
~
among lead stabilisers); some UV absorption. ~
Dibasic lead phosphite Virtually standard com- Good heat stabiliser with pronounced UV- Virtually standard light-
ponent of composite lead screening and antioxidant functionality. Non- stabilising component
~
stabilisers for outdoor- lubricating. Opacifying. of composite heat/light
~.
service PVc. lead stabilisers.
Lead stearate Main use as lubricating Only moderate heat-stabilising power, but May be used with other
component of composite strong lubricant action. Will not give clear metal-stearate stabili-
lead stabilisers (espe- compounds above about 0·75 phr (general sers, e.g. calcium and
cially ones based on lead use level 0·5-1·5 phr). strontium stearates.
sulphates) .
Dibasic lead stearate Main use as high- Moderately good heat stabiliser with strong
temperature lubricant in lubricant action. More suitable for clear com-
composite lead positions than lead stearate.
stabilisers.
Lead salicylate Used in composite lead Heat stabiliser with some light -stabilising ac-
stabilisers for PVC com- tion. Chelator for iron (prevents iron-
positions containing iron- promoted colour deVelopment). Non-
bearing constituents (e.g. lubricating.
asbestos-filled PVC
flooring).
Lead silicate Used as component of Effective heat stabiliser (high PbO yield). Suit- Main applications in
composite lead able for translucent compositions (refractive pPVC including some
stabilisers. index approximates that of PVC polymer). paste products.
Non-lubricating. .j>"
Dibasic lead phthalate Used in lead stabilisers in Good heat stabiliser with some light-stabilising c;"
accordance with its func- action. Good dispersibility in PVC resins. S
<:0-
tional characteristics (see Activator ('kicker') for chemical blowing
~
next column). agents in PVC foam compositions. Non- '"<;!
lubricating. Opacifying.
Tribasic lead maleate Used in lead stabilisers for Effective heat stabiliser with some light-
pipe and sheeting, and in stabilising action. Useful stabiliser for CPVC.
some translucent
compositions.
Tetrabasic lead fumarate Main use in gramophone Good heat stabiliser, highly compatible with
records and cable PVC resin.
coverings.
- .I
-
tion in subsequent processing. Secondly, automatic or semi-automatic

handling systems are operated in many PVC compounding plants
(especially large-scale ones) so that the stabiliser can be delivered in
bulk and conveyed to weighing and mixing stations with no direct
contact with any operatives.
Methods of monitoring such parameters as 'lead in air' and 'blood
lead' levels are available, so that, provided that proper precautions are
observed, it is possible to handle lead stabilisers and other hazardous
materials with safety. Relevant information is readily available from
stabiliser suppliers. 29
The lead compounds used as stabilisers (nowadays most commonly
as constituents of composite stabilisers) for PVC are listed in Table
4.1.
Stabiliser suppliers invariably provide recommendations on the
amount of any of their stabilisers to be used in a particular kind of
PVC composition, as well as specific formulations incorporating the
stabilisers. However, on the rare occasions when a completely new
formulation may have to be devised without such assistance, two
points should be borne in mind, viz. that the stabilising action of a lead
stabiliser (i.e. the effectiveness and duration of protection afforded) is
dependent on the amount of lead monoxide (PbO) potentially
available in the compound, and that only a part of that amount should
be counted as the actual stabilising agent. This part is sometimes
referred to as 'safe PbO', because if it is exhausted (as the stabiliser is
being used up in the course of discharging its function) and further
PbO is drawn upon, the consequent further decomposition of the
stabiliser may result in 'gassing'* or in liberation of residues which may
disturb the stabiliser/lubricant balance, e.g. excess stearic acid liber-
ated from lead stearate.
Note: With a basic lead stabiliser, only the PbO from the base part
of the compound should be regarded as available for stabili-
sation, and the total amount of stabiliser to be used calcu-
lated accordingly. For example, in white lead-basic lead
carbonate, 2PbC0 3 ·Pb(OH)z- the total PbO available (ex-
pressed as a fraction) is 3PbO/2PbC03 = 0·863, whereas the
* Release of gas, normally CO2 during hot processing can be promoted or

aggravated by acidity of plasticisers in plasticised compositions.
4 Stabilisers 119
'safe' proportion may be taken as about 0·31. The respective

'safe' PbO figures for tribasic lead sulphate and dibasic lead
phosphite are 0·65 and 0·60.
The main mechanism whereby the lead stabilisers exert their effect
is thought to be neutralisation of nascent hydrogen chloride. 5 This
view accords with their basic nature, their mode and rates of reaction
with HCI,30 and the fact that lead chloride is formed in lead-stabilised
PVC materials in the course of their heat treatment and service.
Unlike the chlorides of some other stabiliser metals, lead chloride does
not promote degradation of PVC polymer. Its inactivity in this regard
is most probably the main reason why, as is well known, 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), * in that deactivation of
stabiliser decomposition products and impurities is believed to be one
of the main functions of such additives.
4.3.3 Organotin Stabilisers
(a) Chemical Nature and Types

Commercial organotin stabilisers are mainly compounds of the general
formula V, with some of those represented by formulae VI and VII
also in use (commonly in mixtures with formula V compounds, the
respective proportions being adjusted for particular effects).
In the three formulae, R can be an alkyl or an ester group (see below),

and A is normally derived either from
(i) mercapto compounds (mercaptoacids and their esters; mercap-
tides), or
(ii) carboxylic acids and their esters (e.g. maleic or lauric acids;
maleic esters and half-esters).
* But addition of cadmium/barium stabilisers to lead stabilisers can improve

both heat- and light-stability.
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, USA:
dibutyl laurate-maleate). Alkyltin stabilisers in which the A sub-
stituents 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 carboxylates: the most numerous members of this latter group
among commercial stabilisers are dibutyltin carboxylates. However,
the nomenclature commonly employed in the industry for organotin
stabilisers is predominantly associated with the nature of the sub-
stituent groups R, as shown schematically in Fig. 4.1, so that the
compounds V, VI and VII may be referred to as di-substituted,
mono-substituted and tri-substituted respectively.
Note: Recent work31 indicates that organotellurium compounds
have a stabilising action similar to that of the organotins.
Dialkyltellurium maleates were found to be the most effective
(but still inferior to the corresponding tin compounds).
The alkyltin compounds most effective individually as heat stabili-
sers for PVC are those of type V, closely followed by type VI
compounds. However, a great many commercial alkyltin stabilisers are
composite systems in which the presence of type VI compounds and,
in some cases also type VII ones, jointly with type V compounds,
confers considerable synergistic benefits. The tri-substituted alkyltins
(R3SnA), formed alongside the other two kinds in the course of
production of organotin stabilisers by the industrial processes,5 are
more toxic, and less effective in their stabilising action, than the
compounds of types V and VI.
Organotin stabilisers
I
I I
Alkyltin compounds Estertin compounds
(R = an alkyl group) (R = an ester group:
I R'·OOC·CH2 ·CH2- )
~I----~I--~--~I------~I
Methyltin Butyltin Octyltin Lauryltin
compounds compounds compounds compounds
(R = -CH3 ) (R = -C4H9) (R = -CRH 17 ) (R = -C 12H 2S )
Fig. 4.1 General nomenclature of organotin stabilisers in relation to the
substitute group R (see formulae V, VI).
4 Stabilisers 121
The estertin stabilisers are relatively new, having been first intro-
duced (by Akzo Chemie) in the mid-1970s. Since then several
commercial representatives have been available, e.g. in the Stanclere
(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 has been described by Yassin &
Sabaa,32 who claim a high degree of stabilising action in PVC for these
compounds.
(b) Characteristics and applications
The organotins are powerful heat stabilisers, imparting excellent short-
and 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 competi-
tive 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 food-contact approval.
The stabilising effectivity of organotin compounds is primarily
influenced by the nature of their A substituent groups (cf. formulae
V, VI, VII). In general, the thiotins-and especially dialkylthiotins-
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 modify-
ing polymers.
A partial restriction on the use of thiotins is that, as mercapto
compounds, they can impart an unpleasant odour to PVC composi-
* For example di-n-octyltin maleate; or di-n-octyltin bis(iso-octyl thioglyco-

late), listed in the US Federal Register as di-n-octyl-tin-S,S'-bis-iso-octyl-
Dlercaptoacetate.
tions, perceptible in processing and tending to persist in products

(more so in pPVC ones). Also, the divalent sulphur in thiotins can
form coloured sulphides with the metals of cadmium and lead
stabilisers of pigments ('cross-staining').
The thiotins have relatively little UV-stabilising action. Where a
thiotin-stabilised composition may be called upon to undergo outdoor
exposure, the stabiliser system should be augmented by a tin carboxy-
late or other light-stabilising component (e.g. an epoxy stabiliser).
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 thioglyco-
late) with epoxidised soyabean oil].
Incorporation in the composition of titanium dioxide (12-14 phr)

also improves resistance to UV, and weathering generally. In transpa-
rent compositions for outdoor use, organic UV stabilisers are normally
included.
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 appropri-
ate cases; pastes are not widely stabilised with organotins), they do not
greatly affect the paste viscosity.
The first-generation estertins (all of the liquid thiotin type) are
comparable in performance with the established non-lubricating
alkylthiotins in the major applications (calendering, extrusion, injec-
tion moulding, blow moulding). They are also somewhat better than
alkylthiotin 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, and especially the liquid ones, are non-lubricating. Suitable
lubricants may either be obtained with the stabiliser in a multicom-
ponent 'single-pack' additive system, or selected separately by the
formulator in the light of relevant criteria. As mentioned in Section
4.3.6, the stabiliser/lubricant balance must always be carefully con-
4 Stabilisers 123
sidered and, inter alia, use can be made in some formulations 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 group of 'reverse-ester' alkyltin mercaptides de-
veloped 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 influenced also by the
nature of the A substituent. In estertins significant lubricant effects can
be obtained by the appropriate choice of the R' substituent in the ester
groups.
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 alkyltin stabiliser sys-
tems effective in rigid PVC pipe compositions at very low incorpora-
tion levels (down to about 0·3 phr). Among the main trends in such
systems have been increased use of monoalkyl tins, exploitation of
synergists (e.g. some organotin sulphides), and introduction of the
lubricating tin stabilisers.
Note: An analogy may be drawn between the practical effect of the
monoalkyl compounds in composite tin stabiliser systems, and
that of zinc in barium/cadmium/zinc stabilisers (cf. Section
4.3.4): both promote good initial colour and enhance long-
term stability. In some blown-bottle and rigid-film formula-
tions, an increased proportion of mono alkyl compound in
the alkyltin stabiliser system, coupled with suitable lubricant
choice, can reduce the stabiliser requirement to below 1 phr.
In addition to the references already cited, a publication edited by
Wilkinson33 and a paper by Ayrey & Poller34 are noteworthy sources
of information on the production and chemistry of organotin com-

pounds, and their stabilising effects in PVC, respectively.
Gamma-ray sterilisation-as practised in hospital~f medical-use
PVC products stabilised with organotins, can cause the development
of colour, ranging from light yellow to deep amber. Special 'gamma-
shielding' grades of tin stabilisers* (as well as calcium/zinc stabilisers
for flexible PVC compositionst) should be used to avoid this effect.:j:
PVC products stabilised in this way are commercially available,
including medical-grade sheeting (e.g. Krene sheeting; Dynamit
Nobel, FRG).
(c) Mode of Action

On good evidence from work with model compounds and with actual
PVC compositions stabilised with organotins, it is widely accepted that
these stabilisers function in a number of ways to prevent and
counteract degradation of PVC polymers. These modes of action are
thought to be: deactivation of labile chlorine atoms (tertiary and
allylic) in the polymer chain (including their replacement by the ligand
groups of the stabiliser); binding the HCI evolved in the course of
incipient degradation; reaction with the double bonds of polyene
sequences and with other chromophoric groups; scavenging of free
radicals; and decomposition of peroxide groups in the polymer chain.
The most likely mechanisms whereby these functions are discharged
have been investigated, but not yet conclusively and finally estab-
lished. Some of the mechanisms have been reviewed in 1984 by Titow5
and Owen. 35
4.3.4 Other Metal-Based Stabilisers
(a) Nature, and Some General Applicational Features

Apart from those of lead and tin, certain compounds of other metals
act as heat stabilisers in PVC. Those in widest use are compounds of
* For example Gammashield 401 and 801 (M&T Chemicals); Mark 1955, 2242
A and 2244 (Argus Chemical).
t For example Interstab GS 4562, GS 4563 and GS 4571 (Interstab Chemicals).
:j: A typical gamma-radiation dose for sterilisation would be 2·5 Mrad, (=
25 kGy). PVC materials properly formulated with 'gamma-shielding' stabilisers
should withstand this without any discolouration. For conversion of rad to Gy
see footnote in Section 22.4.1 of Chapter 22.
4 Stabilisers 125
cadmium, barium, zinc, calcium, and antimony; strontium and mag-

nesium compounds are also used in certain stabiliser systems; finally
those of sodium, potassium, lithium, and aluminium are also
occasionally included as constituents of some composite stabilisers,
sometimes partly for their lubricant action.
The antimony compounds used in commercial stabilisers are nor-
mally antimony mercaptides. The other metal compounds are virtually
all carboxylates. In line with the rather loose, unsystematic terminol-
ogy still found in the industry, they may be divided into the three
general groups (not very clearly demarcated) of 'soaps', 'salts' and
'complexes' (the 'salts' are sometimes grouped with the 'complexes'
under the latter name). The 'soaps' are metal compounds of higher
aliphatic carboxylic acids, typically stearic and lauric (occasionally also
others, e.g. myristic or palmitic); they are normally solids with some
lubricant action in PVC compositions (but liquid composite stabiliser
systems, in which the metal soaps are dissolved or pasted-up in a liquid
carrier, are strongly represented among commercial stabilisers). The
'salts' are compounds of relatively lower aliphatic acids, such as metal
hexoates, heptoates or octoates, occasionally also caprates and unde-
cylates. The 'complexes' are the least well defined group, * which
includes compounds of the stabiliser metals with some organic acids
(e.g. benzoic), substituted phenols, and petroleum-derived acid and
phenolic mixtures (naphthenic and cresylic acids).
In some PVC compositions an individual antimony mercaptide may
constitute the sole stabiliser. Occasionally a calcium soap may also be
used alone, especially calcium stearate (as for example in certain paste
compositions, or compounds for potable-water pipes). But otherwise
all the metal compounds of this section are normally employed in
mixtures, constituting composite stabiliser systems. In such a system,
compounds of two or three different metals mutually supplement, and
sometimes synergistically enhance, one another's stabilising effects. In
many cases the mixture is further augmented by epoxy and phosphite
('chelator') co-stabilisers, which are present as regular constituents of
some proprietary mixed-metal stabiliser systems, or may be added
separately as required.
* Clarity is not aided by the fact that a combination of metal compounds in a

commercial stabiliser is sometimes referred to as a 'complex stabiliser' or
'stabiliser complex', or simply a 'complex' (especially if synergistic additives
are also present), even if the main components are metal soaps.
(b) Antimony Stabilisers

Liquid grades, based on antimony trimercaptide, were the first to be
introduced commercially (in the mid-1970s, after some early, explora-
tory use in the 1950s). Since then the range, available from a number
of suppliers, has been widened. The usage and effects of antimony
mercaptide stabilisers are, in general, similar to those of conventional
thiotins. Some proprietary versions, and uPVC compounds in which
they are used, have the approval of the American National Sanitary
Foundation (NSF) for application in potable-water pipes (with some
restrictions on the maximum content levels). At low levels of
incorporation, up to about 0·8 phr, the antimony mercaptides can be
more efficient than the thiotins; they can also be more effective in
compounds subjected to 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 ade-
quate 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 calcium stearate. 36
Stabilisers based on antimony/tin combinations have also been de-
veloped for rigid pipe compounds for single-screw extrusion and for
thick-walled, large-diameter pipe. 37 In Europe antimony-based stabili-
sers are recommended, inter alia, for some VC/VA copolymer
gramophone record compositions.
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).
(c) Calcium Stearate

Although other calcium compounds (e.g. calcium laurate) are also
available individually from stabiliser suppliers, calcium stearate is the
only one that is used as the sole stabiliser in some PVC compositions;
in others it may serve as a lubricating co-stabiliser (with synergistic
effects in some cases) in conjunction with organotin and antimony
compounds, or as a synergist with certain lead stabilisers (e.g. Irgastab
L600 or L601; Ciba-Geigy). The other calcium compounds find
4 Stabilisers 127
application as regular constituents of mixed-metal stabiliser systems in

which they are variously combined with zinc, barium or magnesium.
Whilst it is not a highly powerful stabiliser, calcium stearate has a
reasonable heat-stabilising action. It is useful with emulsion-type PVC
polymers and finds application in certain paste formulations (especially
in the UK), including some that are required to be non-toxic (e.g. for
toy production). Its non-toxic character in also utilised in uPVC
compositions for potable-water pipes in France, which widely are
stabilised with calcium stearate, often in conjunction with organic
co-stabilisers (not epoxy compounds, as these are susceptible to
microbiological attack).
(d) Mixed-Metal Stabilisers

It is in certain advantageous combinations with one another that some
of the metal compounds mentioned in Section 4.3.4(a) enjoy a
prominent position as stabilisers for Pvc. In such combinations the
effects of the individual components are mutually complementary, to
the overall benefit of the system. A characteristic example is the
barium/cadmium system, in which the cadmium compounds contribute
good initial colour hold, whilst their unsatisfactory long-term stabilis-
ing performance is compensated by the good properties in this respect
of the barium component (whose own initial colour hold is poor).
Synergistic effects also arise in this system, as they do in some other
mixed-metal stabilisers.
Versions of the principal types of mixed-metal stabiliser systems are
available in solid (e.g. 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 1 part of PVC
polymer omitted from the composition for every 2 phr of concentrate.
These developments parallel the forms in which some lubricants and
lead stabilisers are being offered, and involve similar advantages (cf.,
respectively, Section 7.5 in Chapter 7 and Section 4.3.2 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, with particularly wide application in flexible and
semi-rigid formulations, both opaque and clear.
In the barium/cadmium/zinc combinations the zinc compound
improves the initial colour hold of the PVC composition, its long-term
stability, and resistance to cross-staining with sulphur compounds to
which cadmium stabilisers are prone. Zinc compounds (e.g. the
octo ate ) are effective as activators ('kickers') for chemical blowing
agents used in the production of PVC foams. The amounts of zinc
compounds in barium/cadmium/zinc stabilisers can vary (typically
within the range 0·1-0·5 phr) depending on the other components of
the particular system and the zinc sensitivity of the PVC polymer in
the composition in which the stabiliser is to be used.
Note: The degree of sensitivity to zinc varies with the type and
grade of the PVC polymer, and also in different compositions
(e.g. plasticised, filled compositions of VC/VAC copolymers
are among the least sensitive). The variations in response of
emulsion PVC polymers to zinc compounds are well known
to occur, but the actual effects in individual cases normally
have to be checked by test. Where the sensitivity is substan-
tial, degradative discolouration ('zinc burn') can occur at
elevated temperatures.
Both liquid and solid barium/cadmium and barium/ cadmium/zinc
systems are available. The latter are combinations of the metal soaps.
Liquid systems are dispersions of the components in solvent-type
carriers. A typical basic composition of a system of this kind as
evolved over the years might be: 38
Barium nonyl phenolate 30-50%

Cadmium octo ate 10-30%
Zinc octoate 5-15%
Alkyl aryl phosphite 10-30%
White spirit 5-15%
The actual proportions would be governed by the specific application.

Subsequent, fairly recent developments gave rise to a new gener-
ation of 'high-efficiency' liquid systems with higher metal concentra-
tions and lower solvent contents, the solvents being less volatile. Such
4 Stabilisers 129
systems can be used in somewhat lower proportions than the orthodox

ones; many are self-lubricating, with less tendency to plate-out.
The barium/cadmium and barium/cadmium/zinc systems (as well as
some of the newer, high-efficiency barium/ zinc stabilisers) 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':
these synergists are normally included either by the formulator or ab
initio as constituents of the composite proprietary system. Weathering
properties can be further improved by addition of UV-absorbers.
Liquid barium/cadmium and barium/cadmium/zinc systems are par-
ticularly widely used in flexible PVC materials, typically at levels of
1-2 phr (with about 0·5-1·0 phr of a chelator and up to about 5 phr of
an epoxy co-stabiliser where appropriate).
Whilst appropriate solid systems can be used in both rigid and
flexible compositions, in some of the former, the lubricant action they
can provide in some degree may be of particular interest; they also
affect the softening temperature of the product less than do the liquid
systems. However, some of the latter have-by virtue of their solvent
carrier-a solvating effect on PVC resin, contributing to effective, fast
fusion in processing. One example is the barium/cadmium liquid
Interstab BC-4528 (mainly for melt-compounded compositions) or
BC-4531 (for dry blends).
The incorporation levels for solid systems are, as a general
guideline, 2-3 phr of the mixed-metal composition, with about 0·7-
1·0 phr (i.e. 1: 3 on the main stabiliser) of a phosphite chelator if
included (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 also 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 barium/cadmium and
barium/cadmium/zinc 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 barium and cadmium com-
ponents, the amount of zinc component if present, and the nature of
* Generally unsuitable for alkali-prestabilised emulsion grades.

the organic parts of the compounds); variable tendency to plate-out in

processing; and susceptibility to sulphur-staining (minimised in zinc-
containing systems).
CALCIUM/ZINC STABILISERS
Representatives 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 different countries). Stearates
and octoates* of the two metals, and many of their proprietary
combinations, are permitted in most countries for use in rigid and
plasticised compositions for the production of food-packaging materials
and containers, medical goods, and toys.
Calcium/zinc combinations are not among the most powerful
stabilisers, although some newly developed versions, intended as
non-toxic replacements for the more effective barium/cadmium/zinc
systems, represent considerable improvements (cf. for example
Lankromark LZ 847, LZ 935 and DP 6401; see also below).
Wherever practicable (and this is permitted for many 'non-toxic'
applications) they are used in conjunction with epoxy co-stabilisers
(which are components of many proprietary calcium/zinc systems) to
improve the stabilising effects against both heat and light, and with
organic phosphite synergists (which improve the initial colour, and
transparency in clear compositions). Other synergists available for use
(alone or in conjunction with organic phosphites) to improve the
stabilising action and efficiency of calcium/zinc systems include
stearoylbenzoylmethane (Rhodiastab 50; Rhone-Poulenc, France)
and some proprietary polyol compounds (mostly based on mannitol or-
sorbitol). These compounds, used in proportions of 0·02-0·5% with
solid calcium/zinc systems, are claimed to improve the stability of
some PVC compositions by factors of up to x2. The composite
calcium/zinc polyol systems are sometimes prone to plate-out, but the
newer proprietary versions (e.g. some marketed by Swedstab AB,
Sweden) are designed to be free from this tendency.
The calcium/zinc stabilisers are available in both solid and liquid
forms. In addition to the conventional powders, the solid versions now
include particulate concentrates in PVC polymer (e.g. Ferro-Chek
NT-3; Ferro Chemical Corp.). Where a liquid system consisting of
calcium and zinc soaps in a liquid carrier is to be used for a 'non-toxic'
* Salts of C8 carboxylic acids (often 2-ethylhexanoic or caprylic).

4 Stabilisers 131
application it is necessary to ascertain that the carrier is acceptable for

the purpose. For flexible, medical-use PVC products (e.g. tubing,
components of open-heart surgery kits) that may have to be sterilised
by gamma radiation, special 'gamma-shielding' grades of calcium/zinc
stabilisers are available to make the products resistant to discoloura-
tion under irradiation [see Section 4.3.3(b)].
Typical incorporation levels may be illustrated by the following
figures: liquid calcium/zinc system for paste compositions 1·5-3 phr
(with up to 5 phr epoxy co-stabiliser); solid (powder) system for
sheeting compositions 1-2 phr (rigid sheeting), O· 5-1· 5 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
calcium/zinc stabiliser systems is in asbestos-filled PVC flooring. Such
compositions are subject to discolouration during heat processing, due
to the catalytic action of iron present in the asbestos. In compositions
otherwise adequately stabilised with barium/cadmium or lead systems
the discolouration can be severe, but it can be effectively prevented by
the use of an appropriate calcium/zinc stabiliser [see also Chapter 2,
Section 2.2.6(d)].
Apart from the special applicability of the non-toxic grades, the
advantages of calcium/zinc 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; and limited suitability for crystal-clear
compositions. *
OTHER MIXED-METAL STABILISERS

Since the late 1970s increasing attention has been directed to the
potential hazards of cadmium in its own processing and as a
component of pigments and stabilisers. Studies and discussions have
been proceeding in several countries, and in some (such as Sweden,
Denmark and Switzerland) restrictions-statutory or voluntary-are
already in operation. These events have, inter alia, stimulated efforts
by many stabiliser manufacturers to develop alternatives to the
cadmium-containing stabilisers that would be free of that heavy metal
* Haze may develop in transparent compositions in contact with sulphur

compounds: see Section 4.8.1.
(and preferably also of lead). The task is difficult, because of the very
good stabilising performance of mixed-metal stabilisers incorporating
cadmium compounds, and their consequent wide, long-established
usage. However, considerable progress has been made, and the
alternatives now offered, some of which are claimed to approach the
cadmium-containing stabilisers in performance, include-apart from
the new calcium/zinc compositions already mentioned (characterised
by improved heat-and also light-stabilising performance )-also
barium/zinc, barium/calcium/zinc, and magnesium/zinc compositions.
References to some of these stabilisers are included among the
following examples intended to illustrate something of the nature and
applications of various mixed-metal stabilisers.
Barium/zinc: Commercial versions of this kind of stabiliser

system-several of which are offered as replacements for
barium/cadmium stabilisers-are exemplified by those cited below:
(i) Synpron 1531 (Synthetic Products Co., USA), a liquid, low-
barium, high-zinc 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 barium/zinc
combinations, for use in paste-produced PVC flooring (at
1·S-2·Sphr, 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) Naftovin BZ stabiliser series (Chemetall, FRG), self-lubricating
and with little tendency to plate-out;
(iv) Stavinor BZ 329 (Ceca SA,* France), for paste-produced
flooring compositions;
(v) Irgastab BZ 590 series (Ciba-Geigy), claimed to combine good
long-term stability with freedom from plate-out;
(vi) Lastab DC 45, 48 and 49 (Lagor SpA, Italy), another group of
barium/zinc stabilisers offered as replacements for cadmium
(and also lead) systems.
Magnesium/zinc: Selected combinations of this type may be used

(in conjunction with phosphite chelators) for stabilising flexible and
* Which took over the Stavinor stabiliser line from Rousselot in 1985.
4 Stabilisers 133
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
some proprietary veisions of this system. Its solid-soap variants (e.g.
Synpron 1534; Synthetic Products Co., USA) also have some lubricant
action.
Strontium/zinc/tin: This is another of the combinations offered as

replacements for barium/cadmium 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.
Strontium/zinc: The commercial strontium/zinc systems are ex-

emplified by strontium/zinc laurate co-precipitates* (e.g. Lankromark
M; Lankro Chemicals, 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.
Calcium/antimony: The already-mentioned combination of anti-

mony mercaptide with calcium stearate effected by some formulators
for its synergistic and lubricant features is also embodied in some
proprietary stabilisers. An example is Stavinor SB-739 (Ceca), 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).
Calcium/aluminium/zinc: Commercial versions of this system, e.g.

Lankromark LA 105 and Lankromet LA 175, are used in paste
compositions for rotational moulding where, inter alia, they promote
good mould-release.
Cadmium/zinc: 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 stabilisers (alone or in conjunction with other stabilisers,
* 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 (cf. Section 4.3.2).
usually barium/cadmium systems) and activators ('kickers') for the

blowing agent (normally azodicarbonamide). Typically (for example
with a Ciba-Geigy commercial version-Irgastab ABC 2) about
0·5 phr would be required for the activator function, and up to about
2·5 phr for stabilising effects.
Cadmium/lead: Such systems have been used in PVC window

profile compositions. An example of a single-pack version is Haro-
Mix YJ-l09 (Haagen Chemie BV, The Netherlands).
Barium/cadmium/lead: This is another example of the kind of

mixed, lead-containing plasticiser system for window profiles. Some
commercial versions, like Stavinor BCP 866, include lubricants.
These systems can offer very good performance in processing, and
weathering protection.
MODE OF ACTION OF MIXED-METAL STABILISERS

These stabilisers have long been known to act as HCI acceptors, and
also believed to remove labile CI atoms from PVC molecules,
substituting their own carboxyl residue to form a relatively stable
grouping. The current understanding of their general mode of
operation is in line with these ideas, and there is a substantial body of
evidence, largely from studies of model compounds, supporting also
the general explanation of the co-action and synergistic effects
between the individual components of the composite systems. The
detailed mechanisms and individual reaction steps involved have not
been entirely worked out.
Taking the barium/cadmium and cadmium/zinc carboxylate systems
as typical examples, the stabilisation process may be summarised by
the following scheme:
Ml(OOCR)z + 2(Pol·Cl)- M1Cl2 + 2(Pol·OOCR) (4)
M2(OOCR)z + M1C12_ Ml(OOCR)z + M2Ch (5)
M2(OOCR)z + 2HCI- M2Ch + 2RCOOH (6)
where R is a straight- or branched-chain alkyl radical, and Pol is a
PVC polymer chain. Ml is a metal which is an effective stabiliser in the
sense that it readily exchanges its carboxylating group for a labile
chlorine atom in PVC, thereby 'esterifying' the site involved to a
stable condition [eqn (4)], but whose chloride, formed in the process,
is a strong catalyst for dehydrochlorination of PVC. Zinc and cadmium
are such metals, ZnCh being even more effective than CdCh in
4 Stabilisers 135
promoting dehydrochlorination. M2 is a metal (such as barium or

calcium) whose chloride is relatively inactive in this detrimental sense,
but whose carboxylate is capable of regenerating that of the MI metal
from its chloride [eqn (5)]. The M2 metal carboxylate also disposes
safely of HCI generated by dehydrochlorination [by converting it to
harmless M2C12 : see eqn (6)]; whereas the reaction of eqn (6) involving
an M2 metal carboxylate would generate the destructive M1C12. It may
be noted that increasing concentrations of ZnClz and stearic acid were
detected and monitored in the course of a dynamic heating experiment
on PVC compositions stabilised with a zinc/calcium stearate system?9
It is when the regenerative component (the M2 carboxylate) is
used-up to the point where its concentration drops below the effective
level, that the destructive catalytic effect of the now accumulating
M1Cl2 speeds up degradation, which becomes catastrophic. The latter
factor is also responsible for the unsuitability of cadmium and zinc
compounds as sole stabilisers.
The main functions of an epoxy compound when used as a
co-stabiliser with mixed-metal systems are direct binding of nascent
HCI and assistance in the transfer of labile CI atoms to the main
stabiliser [see Section 4.3.5(c)].
4.3.5 Organic and Miscellaneous Stabilisers
None of the organic, non-metal compounds used in the stabilisation of

PVC compositions can be described as a powerful primary stabiliser.
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 barium/cadmium and
other mixed-metal systems). 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
NH2 H 0
I I "
H3 C-C=C-C-OR
Many commercial stabilisers based on these compounds are approved

for food-packaging applications in several European countries, includ-
ing the UK, West Germany, France and Italy. They are used mainly in
uPVC compositions, based on suspension and emulsion polymers of
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; or example, Irgastab Gl* is recommended for use mainly as
a co-stabiliser in plasticised compositions, at up to 0·4 phr to avoid
exudation, whereas Irgastab A 70t causes no difficulties at normal
incorporation levels.
In most cases, uPVC compositions stabilised with the aminocroton-
ates, require lubricants, although some proprietary versions may have
lubricant action.
(b) Urea Derivatives

Representatives of this group in common use are
H 0 H
I \I I
phenylurea (C6H5)-N-C-N-H;
0 H H
\I I I
diphenylurea (C6H5)-N-C-N-( C6H 5);
H S H
I \I I
diphenylthiourea (C6H5)-N-C-N-(C6H5)·
These compounds may be used as heat stabilisers (with little light-

stabilising effect) for compositions based on alkali-prestabilised emul-
sion polymers, and especially in plasticised compositions of this kind
(yellow discolouration may occur in semi-rigid and rigid PVC).
Typical incorporation levels are relatively low, around 0·3-0·5 phr,
because of the low compatibility of these stabilisers with plasticised
PVc. Long-term stability can be substantially improved by the
* Ciba-Geigy: a solid (waxy flakes) mixture of esters of aminocrotonic acid

with 1,4-butylene glycol and some fatty alcohols (C 16-C18).
t Thiodiethylene glycol bis(p-aminocrotonate), sold as a free-flowing powder.
4 Stabilisers 137
presence of an epoxy co-stabiliser (up to about 3 phr). At tempera-

tures above IS0 aC some commercial urea stabilisers may start decom-
posing 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

Many epoxy compounds, including the epoxy plasticisers, have a
stabilising effect in PVC compositions. Whilst this is not strong enough
to enable their general use as main or sole stabilisers, such epoxy
compounds as epoxidised soyabean oil (ESO) and some epoxy esters
are very important and widely used as strongly synergistic co-
stabilisers for metal-based stabiliser systems, as well as for some
organic stabilisers (see above). Their uses and benefits are referred to
at various places throughout this book (see Index), the main effects
being substantial improvements in heat and light stability. Further-
more, 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), 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 stabilisers/
plasticisers are resistant to extraction and migration: several (but not
normally epoxidised soyabean oil) improve the low-temperature flexi-
bility 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 3 phr-do not affect the clarity of transparent PVC composi-
tions. 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
compounds in PVC compositions are their susceptibility to microbio-
logical attack, 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
component of the plasticiser system should perferably not be higher
than 25% of the total 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. Thus was the
cause of development of surface tack in, for example,
calendered sheeting when, in the early days, the barium
component of barium/cadmium stabiliser systems then
coming into use was frequently barium ricinoleate.
The main mode of action of epoxy stabilisers is widely thought to
be5 the binding of HCl through reaction with their oxirane groups:
-CH-CH- + HCl- -CH-CH-
""'/ I I
o OH CI
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,40
and the exchange of the PVC polymer's labile chlorine atoms for
stabiliser groupS.41
(d) Organic Phosphites

These are not primary stabilisers, but valuable co-stabilisers, used
mainly with mixed-metal stabiliser systems (and widely with the
principal types based on barium/cadmium and calcium/zinc combina-
tions). Many proprietary phosphite co-stabilisers are acceptable, in
conjunction with suitable calcium/zinc 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
4 Stabilisers 139
phosphite as one of the components, and in many cases also a

permitted epoxy-co-stabiliser.
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 gene-
rally, as well as heat stability (especially in pPVC). Although the
mechanisms of their action are not fully elucidated, they are believed
to be numerous and complex, and to include reactions of the stabiliser
(or in some cases the products of its transformations) with the
following: 5 ,35 HCI, hydroperoxides, free radicals, metal salts, and
ketoallyl groups. The clarity improvements often effected by phosph-
ites have been attributed to the formation, in the course of stabilising
reactions, of PVC-soluble complexes with the normally insoluble
chlorides of the stabiliser metals, which are themselves formed as
these stabilisers exercise their functions. It is because of this that the
phosphite stabilisers are often referred to as 'chelators'.
Commercial organic phosphite co-stabilisers (typically liquids, with
no appreciable lubricant effect in PVC) are either individual com-
pounds, or mixtures of compounds of the general formula:
RO OR
"-/
P
I
OR
in which R can be a simple (but relatively long-chain) alkyl, or aryl
(usually phenyl), or alkyl-aryl, group or a polyhydric alcohol deriva-
tive (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
phosphite,42 distearyl pentaerythrityl 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. Irgastab 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
* Used in some formulations for PVC bottles in place of the common

combination of tris(nonylphenyl) phosphite and 2-phenylindole.
t Commercial versions (e.g. Irgastab CH 55-Ciba-Geigy; Phosclere P315-
Interstab Chemicals Inc.) are approved in many countries for food-contact
applications.
barium/cadmium systems it is fairly usual to add 1 part of the chelator

per 3 parts of the metal stabiliser combination; but, in general, the
optimum amount should be verified by tests.
(e) Other Organic Stabilisers

Stearoylbenzoylmethane and certain polyols have already been men-
tioned [in Section 4.3.4(d)] as synergistic co-stabilisers for use with
calcium/zinc stabiliser systems. Their modes of action are believed to
be similar to those of the phosphites. However, as mannitol and
sorbitol-their frequent constituents-would be expected to decom-
pose to a considerable extent at processing temperatures, it appears
possible that their stabilising effects may in fact be exerted by their
decomposition products. Another organic co-stabiliser of industrial
interest is 2-phenylindole:
~~
~NH~
One use of this additive is as a co-stabiliser (at a level of about
0·3-0·5 phr) in uPVC bottle compositions, frequently non-toxic ones,
stabilised with a calcium/zinc 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.
4.3.6 Stabiliser/Lubricant Balance and Interactions
When choosing a stabiliser, single or composite, for a particular type

of PVC formulation and processing conditions (e.g. a uPVC pipe
composition for twin-screw extrusion, a semi-rigid sheet composition
for calendering, etc.), careful thought must be given also to the proper
selection of the lubricant or lubricant system, to secure what is usually
known as correct stabiliser/lubricant balance. This is important for a
number of cogent reasons which are significant technical factors, viz.
because some lubricants have a stabilising action and some stabilisers
a lubricant action; because synergistic effects can arise between some
stabilisers and lubricants; and because, whilst lubricants reduce the
frictional and work heat experienced by PVC stock in processing (see
Chapter 7, Section 7.1), they do not all do so equally effectively.
Undesirable interactions which can occur between some stabilisers and
4 Stabilisers 141
lubricants, leading for example to plate-out or (less frequently) to

cross-staining, must also be considered.
Note: The mutual effects and interactions of lubricants and stabili-
sers are discussed in some detail in Section 7.2 of Chapter 7.
In any given case, the achievement of proper stabiliser/lubricant
balance will in effect yield a harmonised, composite stabiliser/lubricant
system, in which the beneficial factors among those just mentioned are
utilised through mutual adjustment, and negative effects such as
over-lubrication, plate-out, or cross-staining are avoided. This in turn
should promote the optimum practicable ease and effectivity of
processing, whilst minimising the danger of heat degradation (and
generally the heat history) of the material and securing the maximum
sensibly attainable cost savings. Most stabiliser suppliers provide
single-pack stabiliser /lubricant systems for various combinations of
PVC composition and processing method.
Where, for whatever reason, a formulator sets out to devise his own
stabiliser/lubricant system, he should always seek recommendations
from the suppliers of the stabilisers and lubricants he is considering.
In the course of developing the system it is necessary to carry out
laboratory tests (in a suitably equipped torque rheometer, e.g. a
Brabender Plasti-Corder, or on a laboratory-scale extruder, calender,
or two-roll mill, as appropriate) and then, in the final stage, also to
perform in-plant trials, as the laboratory-test results may not always
correlate sufficiently well with those obtained on production
equipment.
4.4 ANTIOXIDANTS AND LIGHT STABILISERS
4.4.1 Antioxidants
The oxidative breakdown mentioned in passing in Section 4.1.3,

involving a free-radical chain reaction (sometimes referred to as
'autoxidation,)43 is one of the modes of degradation of PVC polymers
by both heat and light. Some heat stabilisers (notably those that also
exhibit light-stabilising effects) have an antioxidant action in PVC.
Special antioxidant additives are also often incorporated, either
individually or as constituents of composite commercial stabiliser
systems.
Antioxidants used in plastics may be divided into two general

groups: primary antioxidants, which act as free-radical scavengers to
interrupt or prevent oxidation reactions (which are believed to
proceed by free-radical mechanisms43 •44-see also Section 4.1.3); and
secondary antioxidants, which react with hydroperoxide groups-
whose formation is a stage in the oxidation reaction chain-to convert
them to non-radical products. 5 The primary antioxidants employed in
PVC compositions are typically compounds containing sterically hin-
dered phenolic OR groups: they are popularly known as 'hindered
phenols'. An example is Ciba-Geigy's Irganox 1076. * This additive was
for many years its supplier's main antioxidant for PVc. Irganox 245, a
bisphenolic hindered phenol compound of somewhat higher molecular
weight, which is less labile, is also applicable, and can be more
cost-effective in some formulations. The other main class of compound
in the primary antioxidant group comprises secondary aromatic
amines: with a few exceptions [see 4.4.2(c) below] these are not,
however, important in the PVC context, being mainly used in rubber
compositions (especially dark-coloured ones, as they can cause strong
discolouration) .
The secondary antioxidant group consists of certain phosphites
[including organophosphite chelators and dibasic lead phosphite: see
Section 4.3.5(d) and Table 4.1 respectively], phosphites, and
thioethers. Useful synergistic effects can sometimes be obtained by the
joint use of some primary and secondary antioxidants.
Note: One route through which oxidative degradation of some

polymers can proceed, even at room temperature, is a
redox-type breakdown of hydroperoxide groups in the pre-
sence of metal ions (introduced-sometimes as impurities-
with fillers, pigments, and other additives). Metal-deactivator
additives which are sometimes employed to counteract this
* Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate:
t-Bu 0
HO <Q>-cH2.CH2.~.O.C18H37.
t-Bu
Since the relevant Ciba-Geigy patents expired in 1984 this compound is also
available as Ultranox 276 (Borg-Warner Chemicals) and Naugard 76 (Uni-
royal Chemical).
4 Stabilisers 143
process could therefore be classified among secondary anti-

oxidants, although some are hindered phenols (e.g. Irganox
MD 1024).
In PVC, autoxidation is both a degradation mechanism in its own
right and a factor increasing the rate of dehydrochlorination (cf.
Section 4.1.3). Thus incorporation of antioxidants can improve the
heat stability of many PVC compositions. Where they are added
individually, and not introduced as constituents of composite
proprietary stabiliser systems, primary antioxidants may typically be
used at levels of the order of 0·1 phr (in compositions such as some
cable sheathing and high-temperature insulation compounds, some
injection-moulding compounds, and plasticised compounds for chain-
link wire covering).
Some antioxidants, e.g. Irganox 1010 (Ciba-Geigy)-a tetrakis-
phenolic compound~an be used (generally in very low proportions,
e.g. 200 ppm) as additives to the polymerisation mixture in the
production of PVC polymers, to improve the polymer's resistance to
the relatively intense heat treatment necessary to strip off residual VC
monomer down to acceptably low levels.
4.4.2 Light Stabilisers
The UV component of the sunlight reaching the earth's surface

(waveband 280-400 nm), and especially its more energetic part (wave-
lengths up to about 320 nm*), as well as any UV radiation of
wavelengths below 290 nm, can cause photodegradation of PVC
polymers.
The light stabilisers used in polymeric compositions may be grouped
into four main general functional types: organic UV absorbers;
inorganic (particulate) UV-screening agents: free-radical scavengers;
and chromophore quenchers. This classification is not strict or formal,
and there can be a certain functionality overlap between some of the
* Wavelengths of 310-320 nm are regarded as particularly damaging to

polyvinyl chloride, and 327 nm (sometimes also 364 nm) is often quoted as a
wavelength to which VC/VAC copolymers are sensitive.
Principally in the medical context (from the point of view of scope for
damage to skin and other tissue) the UV spectrum is sometimes divided into
three bands: A (least harmful), 320-380 nm; B (medium severity), 280-
320 nm; C (most harmful) < 280 nm.
types. Primary antioxidants acting as free-radical scavengers, and

secondary antioxidants functional as hydroperoxide decomposers, can
also contribute to light stabilisation.
(a) Organic UV Absorbers

These stabilisers operate by absorbing the damaging UV radiation and
re-emitting the energy thus acquired at a lower level (longer wave-
length) as infrared radiation (Le. heat) which is relatively harmless to
the polymeric material. The ideal UV absorber should absorb com-
pletely the wavelengths between 280 and 400 nm, but none in the
visible region, so as not to impart colour to transparent or white
compositions: although many commercial UV absorbers are good in
these respects, none meets completely both these ideal requirements
(especially with regard to 100% absorption of the entire UV band).
The types of organic compound in widest commercial use as UV
absorbers for PVC compositions are modified benzophenones (espe-
cially certain alkoxy derivatives of 2-hydroxy- or 2,2-dihydroxy-
benzophenone), and benzotriazole derivatives. Proprietary additives
of the first type are exemplified by Cyasorb UV9, UV 24, and UV 531
(American Cyanamid Co, Polymers and Chemicals Dept, and Cyana-
mid of Great Britain Ltd); Uvinul D 408 (BASF); UV-Chek 541 A and
AM-300 (Ferro Corp., Chemical Div.); and Carstab 700 (Carstab
Corp.). Benzotriazole compounds figure prominently in the Ciba-
Geigy Tinuvin light-stabiliser range (e.g. Tinuvin P, 320, 326 and
327). Another commercial example is Vanox UV-1 (R. T. Vanderbilt
Co.). Normal use levels of both types are in fractional phr (typically
0·1-0·8).
Other organic compounds represented among proprietary UV
stabilisers available for PVC include substituted cyanoacrylates (e.g.
ethyl 2-cyano-3,3-diphenylacrylate-cf. also Uvinul N-35 and N-559;
BASF) , phenyl salicylate (Salol; Dow Chemical Co.), oxalic anilide
(Sanduvor; Sandoz), and phenyl formamidine (Givsorb UV-2;
Givaudan Corp., USA).
Polymeric UV stabilisers are exemplified by a polymer of 2,4-
dihydroxybenzophenone, originally applied45 with a view to reducing
the ease of diffusional migration of the stabiliser to the surface of the
PVC material (and subsequent loss by volatilisation, leaching and
wear) to which non-polymeric benzophenone UV absorbers are more
prone.
In most cases the degree of UV protection afforded increases with
4 Stabilisers 145
the additive's 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 46
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
(Le. the probability that one or more particles or molecules will lie
directly in the path) should increase fairly sharply with distance into
the material: interaction of the radiation with the PVC material itself
must also be a factor progressively reducing the amount of radiation
with distance of penetration. *
It may be noted that, because of the purely physical nature of its
mode of operation, a typical UV absorber of the kind discussed in this
section does not undergo any chemical changes, so that it is not used
up in the course of discharging its function.
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 some cases. 47 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 colouration (overall or in spots) can develop, in the

presence of alkali, in compositions (especially flexible com-
* In all polymeric 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).
pounds) stabilised with barium/cadmium or barium/cadmium/zinc

systems in conjunction with certain benzophenone or ben-
zotriazole UV absorbers (normally only those containing pheno-
lic 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 barium/cadmium stabilisers, although neutral versions
are widely available), or where the PVC polymer is an alkali-
prestabilised emulsion resin, or adventitiously from 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. 5 However, the alkoxybenzophenones, ben-
zotriazoles, and salicylates used as UV absorbers in PVC are not
normally susceptible. Some UV absorbers can interfere with fluores-
cent colorant 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.
(b) Inorganic (Particulate) UV -Screening Agents

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 absor-
bers, emits the energy in the IR region: it is also capable of capturing
free radicals: the appropriate, fine-particle grades should be used,
typically at a few phr (not less than 2 phr). 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
4 Stabilisers 147
loadings are needed (typically 5-15 phr) of 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 4.3.4 above): it can 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. Some proprietary zinc oxide/synergist
compositions have been claimed * to nearly double the light-
degradation resistance of such PVC articles as car crash-pads.
(c) Free-Radical Scavengers

As in the case of thermo-oxidative degradation, photo degradation can
be counteracted, or at least retarded, by inclusion in the polymer
composition of additives which can effectively scavenge the free
radicals formed as intermediates in the degradation process. Apart
from the hindered-phenol antioxidants used in PVC, the other
important group of free-radical scavenging additives employed as light
stabilisers in plastics comprises hindered amine light stabilisers
(HALS). Some of these compounds are highly effective, especially in
polyolefins and ABS, but they are not widely used in PVC, because
most impair heat stability in precessing. However, a few have been
used, e.g. Tinuvin 770t and Chimasorb 944.t Both these compounds
are solid, hindered secondary amines (the second is polymeric, with a
number-average molecular weight in excess of 25(0). They have been
used in compositions stabilised with some barium/ cadmiumlzinc and
barium/cadmium stabiliser systems, but not with sulphur-containing
stabilisers, such as the thiotins, because of cross-staining.
(d) Chromophore Quenchers

These are compounds able to deactivate, evidently by resonant energy
transfer, energy-absorbing (chromophoric) groups (e.g. carbonyl)
either originally present, or formed in the polymer chain in the course
of photodegradation, and 'excited'-i.e. raised to a higher energy
level-by absorption of UV radiation (and thereby primed to promote
* For example by Santech Inc., Canada.

t Ciba-Geigy.
chain-scission with the formation of free radicals). The mode of action

of quenching additives may be schematically represented as follows:
~+ UV photons - - ~
~+Q--~+Q*
Q* - - Q+heat
where © is a chromophoric group, and * indicates an excited state.
Quenchers are particularly useful in some stabiliser systems for
polyolefins, but are not much used in PVC.
(e) Some General Features of the Action of Light Stabilisers and

Antioxidants
The most general difference in the operation of UV absorbers and
screening agents on one hand and the other kinds of light stabilisers
and antioxidants on the other, is that the UV absorber's task is to
intercept as much as possible of the damaging radiation before it
interacts with the polymer. In contrast, the free-radical scavengers,
quenchers, and peroxide decomposers deactivate in various ways the
intermediate products of the antioxidation reactions (thus counteract-
ing further, more drastic, effects) after these reactions have been
initiated. However, it is also because the products are formed
anywhere in the polymer where initiation has occurred, that the
effectivity of the three last-named types of stabiliser is not limited (as
is that of UV absorbers) by the polymeric material's thickness,
although (as also in the case of UV absorbers) it is influenced by the
concentration and distribution of the stabiliser in the material.
The schematic summary (by Scott43 ) shown in Fig. 4.2 indicates the
functional mechanisms (points of intervention before or in the chain of
autoxidation reactions) of five kinds of stabiliser: free-radical scaven-
gers operating as reaction-chain-breaking electron acceptors (CB-A)
or donors (CB-O); peroxide decomposers (PO); metal deactivators
(MO) and UV absorbers (UVA).
Since UV absorbers are less effective in thin layers, this is so also in
the outermost layer of PVC products; yet it is there that the most
protection is needed, as the surface is the most directly and extensively
exposed to photochemical attack. The problem is particularly relevant
in transparent compositions for outdoor service, in which UV absor-
bers are widely used; surface application, rather than internal incor-
4 Stabilisers 149
°2
RH CB-~
~R ROO
CB-D_~ ~CB-D
MD. ttl
UVA-- - :
PO
ROOH RH
hv. Fig. 4.2 Modes of action of light

M+/M2+ stabilisers: schematic outline. 43
poration of the stabiliser, can be a useful solution in some cases. PVC

sheeting, for example, may be surface-coated with a lacquer contain-
ing a relatively high concentration (say 1-3%) of the stabiliser; such
lacquers, based on vinyl copolymer resins, acrylic resins, or other
binders are available from commercial sources. This approach can
offer cost and protection-efficiency advantages in suitable
circumstances. 48 Surface absorption from solution of a UV stabiliser
(MPB *) into PVC has also been claimed to give good results. 48
Such physical factors as the degree and uniformity of dispersion,
ease of migration through the composition, extractability, and volati-
lity, 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 AHara. 25
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
custom-compounded concentrates in PVC polymer or other appropri-
ate carriers.
4.5 STABILISERS IN SINGLE-PACK

ADDITIVE SYSTEMS
The PVC processor buying-in stabilisers as, or as part of, single-pack

products secures several advantages. The number of weighing opera-
* 2(2' -Hydroxy-5' -methylphenyl)benzotriazole.

tions preparatory to compounding is reduced substantially, and the

need to dose-in such low-level additives as antioxidants (which have to
be accurately weighed in small amounts) is avoided. The formulation
of the stabiliser, and stabiliser/lubricant, systems is carried out by the
stabiliser supplier, so that the processor is relieved of the need to
undertake this highly skilled and often costly development work. The
disadvantages are somewhat reduced formulation flexibility and rela-
tively high stabiliser price.
With mixed-metal stabilisers the use of single-pack systems is a
virtual necessity, as the systems are carefully designed (and optimised
in the course of their development) to make the best use of the
frequently complex synergistic effects. The proprietary systems often
incorporate, where appropriate, such co-stabilisers as organophos-
phites, epoxy compounds, antioxidants (most usually the suitable
hindered phenols), and polyol chelators. The solid metal-soap prod-
ucts, by virtue of the lubricant action of the soaps, can be formulated
to provide their own lubrication as required in the applications for
which they are suitable. The single-pack lead stabiliser systems, either
co-precipitated 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.
Solid stabilisers, and many one-pack combinations, are available in
various forms, such as dustless powders, flakes, prills and tablets
(about the size of an aspirin tablet).
However, dust is a major inconvenience in handling a solid,
particularly when it can be harmful if inhaled. For this reason,
considerable development work has been carried out by the manufac-
turers of solid stabilisers on forms with low dusting tendencies, and
good handle ability on dosing and conveying equipment (see individual
stabiliser sections in this chapter, and also Chapter 11).
4 Stabilisers 151
4.6 SOME COMMERCIAL STABILISERS
Many proprietary stabilisers have been mentioned or cited by way of

specific examples in this chapter, as well as in some of the other
chapters. Some commercial stabiliser manufacturers are also listed in
Table 4.2, with their product trade names.
4.7 SOME GENERAL EFFECTS OF STABILISERS ON

VARIOUS PROPERTIES OF PVC COMPOSITIONS
These are outlined in Table 4.3.
4.8 SOME STABILISER-RELATED PROBLEMS
The main problems classifiable under this heading are sulphide

staining and plate-out, which may-in some circumstances-be pro-
moted or contributed to by certain stabilisers. Discolouration of some
PVC products for medical use when sterilised by gamma radiation is
also associated with the functionality of the stabiliser system; this topic
has already been discussed in Sections 4.3.3(b) and 4.3.4(d).
4.8.1 Sulphide Staining
PVC compositions containing 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). Composi-
tions incorporating lead compounds may turn 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 barium/cadmium/zinc stabiliser may retard
colour development. However, turbidity may develop in clear
compositions if enough ZnS is formed (see also Table 4.4).
TABLE 4.2 ....
Ul
N
Some Western Stabiliser Manufacturers and Their Product Trade Names
Manufacturer a Trade names Remarks
UK and Western Europe

Akzo Chemie (Netherlands) Interstab, Stanclere "tI
BASF (W. Germany) Sicostab, Uvinul b ~
Biiropan "tI
Otto Biirlocher (W. Germany)
Ceca SA (France) Stavinor This stabiliser line taken over from Rouss-
e-
~.
elot in 1985
Ciba-Geigy (Switzerland) lrgastab, Tinuvin, b Chimassorb b Also Ciba-Geigy Industrial Chemicals, I
~
C
lrganox UK .§
Chemetall Division of Metallgesellschaft (W. Listab, Naftomix, Naftovin ~
::to
Germany) .01
Chemson (UK and Europe) See 'remarks' column Owned jointly by Cookson America and
Metallgesellschaft. Absorbed the stabili- ~
ser lines of the former Associated Lead 0:
Manufacturers Ltd (UK). ~.
Durham Chemicals (UK) Durostabe Own stabiliser line (single-pack, mixed-
metal) ~
Nuostabe Manufactured under licence from Tenneco ~
Chemicals Inc. (USA) ~
Haagen Chemie (Netherlands) Haro ~
Henkel (W. Germany) 5'
Hoechst (W. Germany) Hostastab, Hostanox i:l
Lagor (Italy) Lastab
Lankro Chemicals Lankromark Company became independent in 1986
after management buy-out from Dia-
mond Shamrock Corp. (USA)
Rhone-Poulenc (France) Rhodiastab
Swedstab (Sweden)
Victor Wolf (UK) Vinco Bought by NL Industries (USA) in 1985
USA
American Cyanamid Co., Polymer Additives Dept. Cyastab, Cyasorb, Cyanox C The Cyastab lead stabiliser line sold to
Anzon Inc. in 1986
American Hoechst Corp. Hostastab
Anzon Inc. Dythal, Dyphos, Leadstar, Lectro, Company formed by merger of Anzon
Tribase America and Associated Lead Inc. in
1985
Argus Chemical Div. of Witco Chemical Corp. Mark
Borg-Warner Chemicals Weston, Ultranox
Cardinal Chemical Co. Cardinal
Carstab/Thiokol Carstab, Advastab
Ciba-Geigy Plastics and Additives Div. Irgastab
-"'-
Eagle-Picher Industries Inc. EPIstatic
Ferro Corp., Bedford Chemical Div. Therm-Chek, Ferro-Chek, Oxy-Chek Also Ferro (GB) Ltd in the UK '"S
0-
Guardian Chemical Div., United-Guardian Inc. Voidox
~
Halstab Div., Hammond Lead Products Inc. Halstab, Halbase, Halcarb, Halphos, '"<.:!
Halthal
Interstab Chemicals, Akzo Chemie America Stanclere, Interstab, Estabex d Plastoflex d
M-R-S Chemicals Inc. MiRaStab
M&TChemicals Inc. Thermolite
Mobay Chemical Corp.
Mobil Chemical Co.
New Jersey Zinc Co. Inc. Zinstabe
a Many of the manufacturers are big international companies: for those based in Europe only the headquarters country is indicated.
b Light stabilisers.
C Antioxidants.
d Epoxy stabilisers.
Vl
t...l
-
TABLE 4.3 ~
-
Some General ElI'ects on PVC Compositions Associated with Various Stabiliser Types
Property Significant Relevant stabiliser types, Remarks

in: factors, and effects
Softening point (uPVC) Service In general, liquid stabilisers tend to This consideration can be important with
lower the softening point of the many rigid PVC products. ~
composition.
Lubrication Processing and service Suitable choice and balance of the cf. Chapter 7, Section 7.2. N.B. Surface- ~
stabiliserllubricant system very im- decoration and heat-sealing properties ~.
portant, especially in uPVC. may be affected by stabiliser exudation.
Electrical properties Service (electrical Lead stabilisers are the first choice (cf. Properties important in this connection are ~
....
insulation) Section 4.3.2). high resistivity, low power factor (esp. .g
for high-frequency cables) and high ~
::1'.
electric strength. .~
Non-toxicity Service Selected octyltin compounds. Ca/Zn
systems (with permitted co- ~
stabilisers) .
Clarity Service Organotin stabilisers. Selected BalCd Clarity is influenced by the refractive indices 5.~
systems (with epoxy and phosphite and mutual compatibility of all com- ~
co-stabilisers). Selected Ca/Zn ponents of the PVC composition con-
system (for non-toxic, clear cerned. N.B. In damp conditions cloudi- ~
compositions). ness can develop in some Ba/Cd- ~
stabilised clear compositions. ~
Weldability Heat welding Organotin stabilisers give best results. ~
Some metal soaps can cause ~.
problems.
Paste viscosity Processing In general, stabilisers should be cf. Chapter 18.
checked for effect on viscosity.
Liquid stabilisers should be used
for reduction (or least increase).
The pH of the stabiliser may have
an effect.
4 Stabilisers 155
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 PVC composition itself as its
regular components (or impurities in such components); in this case
the internally induced sulphide staining that may result is sometimes
referred to as cross-staining.
Although simultaneous use of sulphur-containing additives with
cadmium or lead compounds (say, for example, thiotin or antimony
mercaptide stabilisers in conjuction 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
cross-staining should be checked beforehand (even for black material).
A simple compounding test, e.g. on the mill for about 10 min at 180°C,
should be adequate in most cases in practice, and is simpler 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 discolouration 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 4.4). 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·9H2 0) in distilled water (1 litre), acidified with
concentrated hydrochloric acid (30 ml). In the method of ASTM
Dl712-83, thin sheet specimens (preferably about 100 mm x 13 mm)
are half-immersed (for 15 min) in a saturated solution of hydrogen
sulphide prepared by rapidly bubbling freshly produced H 2S gas
through 100-150 ml of water for about 5 min. The method of DIN
u.
0\
TABLE 4.4 -
Visible Manifestations of Sulphide-Forming Interactions of the Main Types of Stabiliser in PVC Compositions
Organic Tin
sulphur- free Ca/Zn Ba/Cd/(Zn) carboxylate Lead
"'I:l
Lead ~
::l:!
~
~.
Thiotin
.,~
.g
Tin carboxylate ~.
~
"'I:l
;:l
Ba/Cd/(Zn)
'~"'
'"
~.
Ca/Zn
~
).
Organic ~
sulphur- ctg e~.
Organic No effect
sulphur - free D
Sulphide formation,
with visible effects
~ as indicated
4 Stabilisers 157
53378-1965 involves exposure of film specimens to gaseous HzS

(continuously generated by reaction of sodium sulphide with sulphuric
acid). In all three methods any staining is detected visually, and its
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 1006:A03;
DIN 54001).
Note: The standard ASTM test method for the staining of PVC by
rubber-compounding ingredients, ASTM D 2151-68 (1982),
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 composi-
tion incorporating zinc in the stabiliser system is in contact with some
sulphur-containing gases or materials (see above, and Table 4.4), can
cause varying degrees of loss of transparency. This effect can be
quantitatively assessed, e.g. with the aid of the standard method of
ASTM D 1746. For a rough, qualitative assessment, a simple
comparison may be made by viewing, in good light, a thin-sheet
specimen of the clouded compound, 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.
4.8.2 Plate-()ut
Plate-out is a persistent sticky deposit which may sometimes appear,

and build up, on the working surfaces of PVC-processing equipment.
It can occur in any of such principal processes as extrusion, calender-
ing, and moulding, as well as in ancillary operations (e.g. milling,
embossing). Plate-out deposits are a nuisance in the equipment-
necessitating cleaning-up operations involving loss of time and
output-and detrimental to product quality. When present, for ex-
ample in extrusion dies, pipe-sizing sleeves, or on calender rolls, they
impair product surface finish and dimensional conformity; plate-out on
embossing rolls may blur the emboss, or even obliterate it in severe
cases. The deposit may also be transferred to the product, causing
marks, blemishes or stains on its surface. There is still no complete,
detailed understanding of the mechanism of plate-out formation,
which appears to be complex and probably varies somewhat with the

nature of the PVC formulation concerned and the method and actual
conditions of processing. It is known, however, that plate-out deposits
are formed by material exuding from the hot ,PVC stock in
consequence of incompatibility-which may become manifested only
in certain processing conditions~f some constituents of the PVC
composition with one another and with the PVC resin. The exudate
moves out to the surface of the hot stock or melt and thence to the
working surfaces of the processing equipment. The process factor
which can promote plate-out are local changes in temperature,
pressure, and the rate and direction of flow of the stock (melt) in the
equipment. The formulation components particularly implicated in
plate-out formation are some lubricants (especially metal soaps) and
stabilisers; incorrect stabiliser/lubricant balance is often a factor. It is
known that lubricants and stabilisers are normally the predominant
components of a plate-out deposit, which may also contain some of
the other additives, notably fillers and pigments (if those are present
in the PVC composition) occluded by the exudate.
These compositional features are well brought out in a study by
Lippoldt,49,50 who put forward a comprehensive explanation of the
nature and mode of formation of plate-out produced in the course of
extrusion of a PVC compound containing an organotin stabiliser, a
composite lubricant incorporating calcium stearate, a calcium
carbonate filler, and titanium dioxide pigment. Lippoldt's explanation
postulated a fairly complex mechanism, involving a number of
sequential steps. According to this, the hot melt exudes a gel formed
by components of the lubricant and stabiliser system, one of the
components-a hydrocarbon in that particular study-acting as a
temporary solvent while the gel is above its 'critical solution tempera-
ture' (CTS). The gel, which occludes particles of the filler and
pigment, deposits on any working surface whose temperature is below
the critical value (estimated by Lippoldt as 175°C for his particular
system). Loss of the temporary solvent and cooling after deposition
transform the deposited gel into a solid film, resistant to re-dispersion
in the PVC composition and providing a receptive surface for further
deposit build-up. Lippoldt suggested50 the following measures for the
prevention of plate-out: reduction of the CTS by suitable selection of
stabilisers and lubricants; 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 selecting a stabiliser with low capacity for
4 Stabilisers 159
solubilising fatty-acid salts (calcium stearate and others); and main-

taining the temperature in any pressure-change zones in the equipment
well above the CTS.
The first two of the above suggestions are matters of formulation;
and indeed correct initial formulation, or re-formulation at need, are
the best ways of avoiding plate-out problems. The advice of the
stabiliser, lubricant, and polymer suppliers is always well worth having
in this connection. In some cases, especially where the plate-out is
only slight, it can be cured by including in the composition low
proportions of anti-plate-out additives, like the appropriate grades of
ultra-fine pyrogenic silica or some silicates, e.g. Aerosil 200 or 300
(Oegussa) or Gasil 35 (Joseph Crosfield and Sons). Fine-particle
pigments or fillers, e.g. titanium dioxide or precipitated calcium
carbonate, incorporated at 2-5 phr, can also be helpful on occasion.
The beneficial effect of all such fine particulate additives has been
attributed51 to retention, through adsorption, of the material respon-
sible for plate-out deposits, and to the additive's direct 'scrubbing'
action on the working surfaces.
A laboratory test can sometimes be useful for checking the
tendency of a PVC composition to plate-out, and gauging the effects
on that of formulation modifications. The principle of such tests is that
a test compound, made up to the formulation concerned and contain-
ing additionally a small amount of an appropriate colourant, is run in
suitable laboratory-scale equipment (e.g. a roll-mill, or a Brabender
Plasti-Corder) 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 compound is
completely removed and a white scavenging compound run in the
equipment. The plate-out from the test compound is assessed on the
amount of colour picked up by the scavenging composition.
One variant of this procedure is exemplified by the following
recommendations. 10
Colourant for test compound Sico Red WRC* (0·1 weight % on the
total compound): Run the test compound for 7 min at 165°C
(without friction); sheet and remove from the mixer. Run the
scavenging compound for 3 min: remove and judge the degree of red
* BASF (formerly a trade name of the Siegle Company, FRG).

staining (related to the amount of plate-out) by comparison with the

unused portion of this compound. For increased accuracy of
assessment, the comparison specimens may be moulded into sheets
of identical size. Constant, uniform conditions are essential; in
particular the equipment 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.
PVC polymer: Solvic 239 (Solvay) 100
Stabiliser: dibutyltin maleate (Irgastab OM 18-Ciba- 0·5 phr
Geigy)
Epoxy co-stabiliser: Reoplast 39 (Ciba-Geigy) 5·0phr
Lubricants: stearic acid (Irgawax 330-Ciba-Geigy) O·Sphr
Irgawax 331 O·Sphr
Pigment: Ti02-anatase (Kronos A-Titangesellschaft 1·5 phr
MbH,FRG)
4.9 TESTING AND EVALUATION OF

STABILISATION EFFECTS
4.9.1 The Concept of Stability in Processing, Service, and Tests
The ease and rate of degradation of PVC by heat and light vary with
the composition, and the conditions of treatment or exposure.
Therefore, in the practical context, the stability of a PVC material may
be thought of, and assessed, in terms of the length of time elapsing
before perceptible and/or measurable signs of degradation develop (or
reach a stated level) under the relevant conditions. This approach
provides a basis for quantitative expression and comparison of the
stability of PVC polymers and compositions by reference to the
stability time and/or induction time for degradation, determined in a
suitable way. The way in which these two concepts are defined is
illustrated by Fig. 4.3: the 'degradation index' in the figure can be any
one of the various manifestations of degradation selected as relevant,
and monitored, in the particular conditions or treatment to which the
4 Stabilisers 161
x
CiI
"0
£
c
o
:;:;
C\J
"0
C\J
L.
01
CiI
Cl
Tima ~
Fig. 4.3 Induction time (t j ) and stability time (ts) of a PVC material exposed
to heat or light: schematic representation.
PVC material is exposed. The effects most often used as such indices
in practice are the intensity of colour developed in, or the HCI evolved
by, the PVC material (see also Table 4.5).
Note: In stability tests in which colour development is used as an
index of degradation it is sometimes relevant to make a
distinction between 'time to colour' and 'time to black'.
Blackening of the PVC material-indicating extensive
degradation-may develop progressively, or it may occur
rapidly as a result of accumulation of chlorides of stabiliser
metals which can catalyse decomposition of the PVC polymer
[e.g. zinc or cadmium chloride-d. Section 4.3.4(d)).
Two other concepts of practical significance in connection with the
stability of PVC in processing (and to some extent also in service,
especially at elevated temperatures) are the heat life and heat history of
a PVC composition. The heat life is the total period during which,
under given conditions (or successive sets of different conditions, as
for example in hot compounding followed by heat-processing into a
product and any subsequent heating experienced by the product) the
composition can remain 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 degrada-
tion' is defined) in comparable conditions, and like the stability (or
the induction) time it will be shorter the more severe the heat
treatment(s) experienced, or the less effective the stabilisation (see
Figs 4.4 and 4.5). Implicit in the concept of heat life is recognition of
the fact, highly important in practice, that heat treatment-or the
number of consecutive heat treatments-of a given nature, intensity
and duration, i.e. 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 history determines how close a PVC composition is to
the point of significant degradation, i.e. to the limit of its total heat
life.
4.9.2 Stability Testing
Various procedures and instrumental techniques used in the study of

PVC degradation have been referred to in the preceding sections. The
present section is concerned specifically with test methods of particular
relevance to the practical assessment of stability of PVC materials for
such purposes as formulation development, product specification,
quality control, fault investigation, and the like.
Note: It may be noted in passing, however, that where very low
levels of dehydrochlorination or cross-linking of PVC poly-
mers in the course of degradation need to be detected or
monitored for whatever purpose, laser-Raman spectroscopy
is an applicable, highly sensitive technique. 52,53
(a) Heat-Stability Tests

A heat-stability test normally comprises a suitable treatment of the
PVC material to induce degradation under controlled conditions,
followed by detection, or quantitative determination, of significant
level(s) of the manifestation of degradation which is being used as the
degradation index in the test. Some of 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 neces-
sary to characterise the extent of any degradation detected.
Heat-stability tests are of two general types: dynamic and static. The
test methods often used in the investigation and evaluation of
stabiliser effects are summarised in Table 4.5.
4 Stabilisers 163
A B c
~ -+ _ _ _ _~a~i~u~ ~::e~t~b~e -.!.e~e~o!...d~g.r!~~on
'0
c:
c:
.Q
+'
111
'0
111
'-
01
~
o
Time •
Fig. 4.4 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
2·3 2·2 2·1 2·0

1/EI , K- 1 x 103
Fig. 4.5 Arrhenius plot of log stability time (t .. minutes) as a function of the
reciprocal of absolute temperature (1/ (J) for three PVC compositions of
increasing stability (1) 2 > 3): schematic representation (but values roughly
representative of some uPVC compositions, with HCI emission as the
degradation index).
~
TABLE 4.5
Heat-Stability Tests Relevant to Practical Assessment of the Effects of Stabilisers in PVC ~
~
Manifestation Determination of degradation effects Test treatment References and remarks Ff

of degradation for which
detected or General means Method, and/or determination
measured stability criteria method t
.g
is suitable ~
::t.
Development of Visual Inspection after set time, or at in- Both static and Static: ISO 305;Q ASTM D
.~
colour in PVC tervals, and comparison with dynamic 2115; DIN 53 381 Part 2
material standards. Dynamic: Refs. 10, 54, 55
Evolution of HCl Colour change Colour change (to blue) of a Congo Static ISO/R 182;Q BS 2782, Method
Red paper, or universal indicator 130A: 1986; DIN 53 381
r
~.
sensitive at about pH 3, in contact Part 1, Procedure A §

~
with volatiles evolved during the
test. ~
'1:5
Evolution of HCl Colour change Reduction of colour of Ultra-marine Static Nelson's test: Ref. 57
Blue incorporated in the test
2
specimens, continuously moni-
~.
tored (by photo cell) during heat
treatment in oven. Onset of sig-
nificant degradation (end of sta-
bility time) indicated by sharp
drop in blue-light reflectance
curve-cf. Fig. 4.8.
Evolution of HCI pH Volatiles evolved by specimens in Static ISO/R 182;D BS 2782, Method
determination test treatment passed through a 130B: 1986; DIN 53 381 Part
standard KCI solution. Time pH 1, Procedure C
(continuously monitored) to drop
from about 6 to about 3·9
measured as stability time. b
Evolution of HCI Titration Volatiles evolved by specimens in Static ASTM D 793 (discontinued in
test treatment absorbed in NaOH 1983)
solution, and HCI determined by
back titration. Stability expressed
as mg of HCI evolved per g of
sample during heating period
(30 min).
Evolution of HCI Conductivity Absorption in water of volatiles Static Introduction of test of this
determination evolved by specimens in test kind under consideration for ""'"
c;"
treatment. Stability time meas- a revised version of ISO/R s:;
Q-
ured as time for water conduc- 182;D DIN 53 381, Part 1, ~

<II
tivity to rise by a specified figure. b Procedure B t::!
Melt viscosity rise Torque-time Stability time determined as time to Dynamic Ref. 54
with onset of de- plot reach point of torque rise ('de-
gradation of composition point') on the
composition in torque-time graph.
torque rheometer
D Under revision in 1988.

b Volatile alkyltin chlorides are formed on heating of PVC compositions containing alkyltin stabilisers. These can dissociate in aqueous
solution, and may thus interfere with HCI determination by conductivity and pH methods.
8i
-
DYNAMIC STABILITY TESTS

In dynamic tests an appropriate weight of the PVC composition is
worked at an elevated temperature in suitable equipment, typically a
torque rheometer, internal mixer, extruder, or mill. Stability is
assessed by periodically checking the effect used as the degradation
index. This is often the development of colour in the material or-in
instrumented torque-measuring equipment-4ietermination of the sta-
bility time as the period from the commencement of test processing to
'decomposition point', marked by an ultimate, sharp rise in melt
viscosity (and hence the torque) associated with a substantial amount
of cross-linking and incipient carbonisation in the material, occurring
as some of the manifestations of extensive degradation (see Fig. 4.6).
By their nature, dynamic tests are primarily relevant to the stability of
PVC compositions in processing. Indeed, the test equipment, tem-
perature and running conditions are often chosen with a view to
relating the test results t,o a particular process. Because PVC cannot be
processed without stabilisers, dynamic methods are not generally
suitable for the determination of the heat stability of PVC polymers
alone. It is a feature of properly designed dynamic stability tests, in
particular those employing equipment like the Brabender Plasti-
Corder, 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 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 lubricants54 (unless these are synergistic with the stabiliser, or
are of the stabiliser-Iubricant type: cf. Chapter 7, Section 7.2.1).
In a typical procedure for a dynamic stability test in a Brabender
Plasti-Corder, the appropriate mixing head is selected, and the mixer
preheated to the required temperature. A weighed quantity of PVC
composition is quickly introduced into the 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 intervals (say every two minutes). Otherwise the time is
4 Stabilisers 167
Test-Conditions
Order BRABENDER Mixer-Temp. 200 ·C
Operator EICKMEIER Speed 75 l/min
Check-Date 16. MAY 'B8 Meas. Range 5111 Nm
PL-Type 2000-3 Zero-Suppr. III Yo
Mixer-Type W 50 Dampin~ 3
Load. Chute MANUAL + 5 KG Test-Tl.me 15.111 min
Sample PVC Sample-Weight 57.111111 g
Additive Coden umber 2
Start-Temp. 196 "C
Torquelltlll) Telllp [OC]

58 238
45 t·m; ......... ( j . . . .j. 228

. ' ,--:,j, 218
48
35 . . . i......ii . 288
38 ......................... 198
25 188
28 178
15 . . . . ;.... .........L...................................... Llt 168
18 ······t 158
" ~--4----I~'---+---4i----~--+i---4----~i---+~-4t
5
ABX
~ II ::
8.8 3.8 b.8 9.8 12.8 15.8
Tillie [,lin]
Value Time [sJ Torque [NmJ Stocktemp.["C]

Load.Peak 4 48.5 168
Minimum 16 19.7 173
Maximum 32 37.5 188
Decomposition 838 24.3 214
Integration
- Load.Peak to Minimum Wl 2.5 E3 [NmJ
- Minimum to Maximum W2 3.7 E3 CNmJ
--Load.Peak to End W3
W4
159.5
2.7
E3
E3
CNmJ
CNm/gJ
Specific Energ~ (W3/Wei~ht)
-Decomposition nergy (T to TO 152.5 E3 CNmJ
Fig. 4.6 A Brabender Plasti-Corder plot from a dynamic stability test on a

PVC composition illustrating the main process stages, including ultimate
torque rise at decomposition point (D), B, start of gelation; X, completion of
gelation. Courtesy of Brabender® OHG, Duisburg, FRG.
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 examples may be mentioned of
combinations which have been used in investigations of stability of
PVC compositions in relation to their behaviour in industrial process-
ing: roller speeds of 35, 45, 55 and 65 r min- 1 at temperatures of 165,
180 and 185°C;55 or 50 and 100 r min -1 at 140 and 1800C. 54
Note: An interesting study by Collins et al. 55 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
correspondence between the 'time to black' of PVC composi-
tions and a pronounced increase in melt viscosity (reflected
by the commencement of an upward sweep in a plot of the
extrusion load versus time).
The effects of calendering are among the most difficult to relate to the
results of laboratory tests: in-plant trials are the only complete answer
wherever they are practicable and not precluded by cost considera-
tions. Milling tests are sometimes used to give some indications of the
likely stability in calendering of a PVC composition,5 but the results of
such tests can only be regarded as rough, general guidance. Correla-
tion with results of static tests is less close.
STATIC STABILITY TESTS

In static methods the test treatment essentially consists of heating
specimens of PVC material at the relevant test temperature. The
specimens are most often pieces of sheet, but may also be suitable
amounts of powder or pellets of PVC polymer or composition.
Temperatures of 175-180°C are most commonly used in the tests,
although higher ones are sometimes recommended, e.g. 200°C by the
French Centre Scientifique du Biitiment. 56
Note: For the same PVC composition and test method, stability
times (t s) at different elevated temperatures within a reason-
able range may be expected to conform to an Arrhenius-type
relationship: In ts = -(E / RT) + constant, where E is the
activation energy for the thermal degradation of the PVC
composition in the test, R is the universal gas constant, and T
is the absolute temperature (d. also Fig. 4.5).
4 Stabilisers 169
The sheet from which specimens are cut for a static stability test may
be moulded as described in Sections 17.1.3 and 17.1.4 of Chapter 17.
The relevant standard test specifications (cf. Table 4.5) also usually
include directions for the method and conditions of specimen prepara-
tion. With solid PVC compounds simple milling on a laboratory mill
into a sheet about 0·3 mm thick (uPVC) or about 0·5 mm (pPVC) may
be adequate. 5 In all cases the specimen preparation should be carefully
standardised, so that variations in heat history do not arise to affect
the results of the stability test itself.
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 (i.e. stability
time in those terms). This level may be that marked by the
appearance, or attainment of a certain degree, or discolouration in the
composition (cf. the example below), colour change of an indicator in
continuous contact with volatiles evolved by a specimen, or the other
effects mentioned in Table 4.5.
An oven used for static heating tests must be reliable, with good
control, and even distribution, of temperature. ASTM D2115 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. The carriers may take the form of self-levelling
shelves carried in a horizontally mounted cylindrical frame after the
manner of a 'big-dipper', or a turntable 57 with the specimens placed
around the periphery.
The following recommendations lO are fairly representative of condi-
tions and procedure for a press-heating test. A sheet is prepared under
standard conditions from the PVC composition to be tested. Speci-
mens of suitable size are cut from the sheet and placed in a press
(preferably a multi-daylight one) preheated to the test temperature
(typically 180°C), between chromium-plated metal plates, and within
moulding frames to prevent thickness reduction. Pressures of about
200 MPa (29000 lb in- 2 ) and 100 MPa (14500 lbf in- 2 ) may be used,
respectively, for uPVC and pPVC compositions.
In an oven or press test, the extent of discolouration of the
specimens, graded on a convenient scale, may be used as a semi-
quantitative degradation index. For example, when specimens of the
11 A
10
9
01 8
.!::: 7
~6
u
L.. 5
54
°3
U
2
o 10 20 30 40 50 60 70 80 90 100 110
HlZating timlZ, minutlZs
Fig. 4.7 Colour changes in four PVC compositions on heating at 180°C.
four basic compositions listed below were heated in an oven at 180°C,

the results, plotted in terms of degree of discolouration on a scale from
o to 11 versus heating time, gave the curves of Fig. 4.7. 5 The
discolouration scale was: 0, clear; 1, barely detectable change; 2, very
slight change; 3, slight yellow tinge; 4, pale yellow; 5, yellow; 6, faint
tinge of red; 7, pale red; 8, red; 9, deep red; 10, very deep red/black;
11, black. As can be seen, the four plots of Fig. 4.7 reflect the trend
illustrated by their idealised, schematic counterparts in Fig. 4.4. They
also demonstrate the stability improvement promoted by an epoxy
co-stabiliser added to a PVC composition stabilised with a barium/zinc
stabiliser. The compositions used in the determinations are listed in
Table 4.6 (parts by weight).
An oven test developed by Nelson57 (originally for plastisol mate-
rials) 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
TABLE 4.6
Compositions used in the Oven Stability Tests (Parts by Weight)
Formulation PVC DOP Barium Zinc Epoxidised Dibutyltin
resin stearate stearate oil dilaurate
A 100 50
B 100 50 2·5 0·5
C 100 50 2·5 0·5 5·0
D 100 50 2·0
4 Stabilisers 171
used, in which a heated air-stream is directed, from above, onto a

turntable (revolving at 1 rmin- 1) 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 RS 1, com-
pounded into the composition to act as indicator, in an amount
sufficient to make the colour change (reduction of the blue colour)
distinct when free HCl 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 (Evans Electroselenium Co. Ltd, UK) selenium cell: the
reflectance is continuously measured and recorded from the start of
the test (see Fig. 4.8).
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
.,!
o
ts
Time) minutes
Fig. 4.8 Reflectance of blue light as a function of heating time in Nelson's

stability test with Ultramarine Blue RSI indicator: 57 schematic representation.
t s , stability time.
flat portion of the curve, and a subsequent drop marks the end of that
period. 58
The results of static tests are more directly 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 correla-
tions 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. 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 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 somewhat more relevant (within
the generally limited degree of correlation) to the stability of the
material in injection moulding or extrusion.
(b) Light-Stability Tests

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 24, Section 24.3): 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 specifica-
tion requirementS, and in quality control. The usual test treatments
consist of exposure of suitable specimens to 'natural' sunlight (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 24.3 of Chapter 24, in connection with weathering
4 Stabilisers 173
resistance of PVC. As mentioned in that section, laboratory tests

which involve exposure to 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 sunlight-concentrating devices, or UV radiation
(for example the QUV apparatus), and/or running tests at elevated
temperatures or higher ambient oxygen concentrations.
The accelerated test treatments may be 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 an 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.
An accelerated test for photochemical stability of polymers and
plastics, including PVC, useful in some circumstances, has been
developed by the Plastics and Rubber Research Institute TNO (Delft,
The Netherlands). In the test, 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 other wall of a cooling tube, of Duran SO glass, which
surrounds an inner tube housing a high-pressure mercury lamp
(TQ-1S0, Quartzlampen GmbH, Hanau, FRG). 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 the temperatures of the cooling tube and the
glass vessel. Test temperatures up to about 90°C can be used, with UV
radiation intensities between about 200 and 1100 W m -2. The progress
of photo-oxidation of the specimens is followed by continuous
measurement of the uptake of oxygen from a nitrogen/oxygen
mixture filling the glass vessel. The concentration in this mixture may
be used as a test variable to examine its effect on the degradation of

the material tested. In tests on PVC, the HCl evolved is also
continuously determined by absorption in water and conductivity
measurement.
Determinations of stability to photo-oxidative degradation of plas-
tics by the TNO test can be up to ten times faster than those in some
types of standard equipment (e.g. the Xenotest). They have also been
claimed to correlate well with Xenotest results, as well as with those of
long-term outdoor exposure.
The effects of the test treatments in ordinary light-stability tests (as
distinct from more fundamental research investigations) are assessed
in ways similar to those employed in heat-stability determinations.
However, because, in general, these effects take longer to appear,
evaluation by before-and-after determination of selected physical
properties (most often tensile strength and elongation; with uPVC also
impact resistance) is more conveniently applicable and common than in
heat-stability tests. Also as-in consequence of the mode of
exposure-the surface of the material is the most directly and strongly
effected, inspection for manifestations of degradation such as surface
cracks, discolouration, and development of tackiness, almost in-
variably forms part of the assessment procedure. Determination of
changes in surface contour on the micro scale* is a useful technique, as
is scanning electron microscopy (SEM) in some cases.
REFERENCES
1. Rice, P. & Adam, H. In Developments in PVC Production and

Processing-i, ed. A. Whelan & J. L. Craft, Applied Science Publishers,
London, 1977, Ch. 5.
2. Chauffoureaux, J. c., Dehennau, C. & van Rijckevorsel, J., 1. Rheology,
23(1) (1979) 1-24.
3. Abu-Isa, I. A., Polym. Engng Sci., 15(4) (1975) 299-307.
4. Sosa, J. M., 1. Polym. Sci., Polym. Chem. Ed., 13(10) (1975) 2397-405.
5. Titow, V. W. PVC Technology, 4th edn Elsevier Applied Science
6. Starnes, W. H. & Edelson, D. (1976). Am. Chem. Soc. Div. Org. Coat.
Plast. Chem. Pap., 41, 505-16. And Starnes, W. H. In Developments in
Polymer Degradation-3, ed. N. Grassie, Applied Science Publishers,
London, 1981, p. 135.
* With computerised equipment such as, for example, the Hommel Tester
TIO. (Hommelwerke GmbH, FRG, and Osterwalder Werkzeugmaschinen
AG, Switzerland). Compare also Section 24.3.1(b) of Chapter 24.
4 Stabilisers 175
7. Starnes, W. H. & Edelson, D., Marcromolecules, U (1979) 797.

8. Starnes, W. H. In Developments in Polymer Degradation-3, ed. N.
Grassie. Applied Science Publishers, London, 1981, p. 135.
9. Hjertberg, T. & Sorvik, E. M. In Degradation and Stabilisation of PVC,
ed. E. D. Owen. Elsevier Applied Science Publishers, London and New
York, 1984, Ch. 2.
10. Manual of PVC: Additives (1971). Ciba-Geigy Marienberg GmbH,
Section 2.
11. Schlimper, R., Plaste u. Kautschuk, 13(4) (1966) 196-207.
12. Schlimper, R., Plaste u. Kautschuk, 14(5) (1967) 657-60.
13. Berens, A. R., Polym. Engng Sci., 14 (1974) 318-28.
14. Pukanszky, B., Nagy, T. T., Kelen, T. & Tiidos, F., l. Appl. Polym. Sci.,
27 (1982) 2615-21.
15. Decker, C. In Degradation and Stabilisation of PVC, ed. E. D. Owen.
Elsevier Applied Science Publishers, London and New York, 1984, Ch. 3.
16. Gerrard, D. L., Bowley, H. J., Biggin, I. S. & Williams, G. E., Plast.
Rubb. Mat. Appl., 6(2) (1986) 97-100.
17. Gooden, R. & Hellman, Y., 28th Macro. IUPAC Symposium
Proceedings, Amherst, 1982, p. 303.
18. Marks, G. C. & Butters, G. J., l. Macromol. Sci. Chem., AU (1978)
569-74.
19. Braun, D. In Degradation and Stabilisation of Polymers, ed. G. Geuskens.
Applied Science Publishers, London, 1975, Ch. 2.
20. Summers, J. W., 34th ANTEC SPE Proceedings, 1976, pp. 333-5.
21. Suzuki, T. & Nakumura, M., lap. Plast., 4 (1970) 16-18.
22. Kennedy, J. P. (1972) & Ichikawa, M. (1974), Polym. Engng Sci. 14,
322-6.
23. Thame, N. G., Lundberg, R. D. & Kennedy, J. P., l. Polym. Sci., AI, 10
(1972) 2507-11.
24. Mitani, K., Ogata, T., Nakatsukasa, M. & Mizutani, Y., Polymer, 21
(1980) 1463-66.
25. Allara, D. L., 34th ANTEC SPE Proceedings, 1976 pp. 245-7.
26. Starnes, W. H. & PIitz, I. M., Macromolecules, 9(4) (1976) 633-9.
27. Suzuki, T. Pure Appl. Chem., 49 (1977) 539-4l.
28. Braun, D., Kunststoffe, 54(3) (1964) 147-52.
29. The Safe Handling of Lead Chemicals, Associated Lead Manufacturers
(now Chemson), 1979.
30. Wypych, J., l. Appl. Polym. Sci., 20(2) (1976) 557-60.
31. Abed-Ali, S. S., Polym. Degrad. Stabil., 21(3) (1988) 211-25.
32. Yassin, A. A. & Sabaa, M. W., l. Polym. Sci., Polym. Chem. Ed., 18
(1980) 2513-21 and 2523-33.
33. Wilkinson, G. (Ed.), Comprehensive Organometallic Chemistry,
Pergamon Press, New York, 1982.
34. Ayrey, G. & Poller, R. C. In Developments in Polymer Stabilisation-2
ed. G. Scott, Applied Science Publishers, London, 1980, Ch. l.
35. Owen, E. D. In Degradation and Stabilisation of PVC, ed. E. D. Owen.
36. Dieckmann, D. 34th ANTEC SPE Proceedings, 1976, pp. 507-1l.
37. Hartung, M., Plast. Technol. 25(8) (1979) 67-70.
38. Dunne, J., Plast. Rubb. Process. Applns 3(4) (1983) 337-42.
39. Guyot, A. & Michel, A. In Developments in Polymer Stabilisation-2,
Ed. G. Scott. Applied Science Publishers, London, 1980, p. 89.
40. Wypych, J., J. Appl. Polym. Sci., 19(12) (1975) 3387-9.
41. Mascia, L., The Role of Additives in Plastics. Edward Arnold (Publishers)
London, 1974.
42. Hybart, F. J. & Rowley, G. N., J. Appl. Polym. Sci., 16 (1972) 715-23.
43. Scott, G., Chemistry in Britain, 21(7) (1985) 648-53.
44. Hageman, H. J. & De Jonge, C. R. H. I., Kunststojfe, 62(10) (1972)
681-3.
45. Bailey, D., Tirrell, D. Pinazzi, C. & Vogl, 0., Macromolecules, 11(2)
(1978) 312-20.
46. Anon., Eur. Plast. News. 3(3) (1976) 28.
47. Szabo, E. & Lally, R. E., Polym. Engng Sci., 15(4) 277-84 (1975).
48. Katz, M., Shkolnik, S. & Ron, I., 34th ANTEC SPE Proceedings, 1976,
pp.511-12.
49. Lippoldt, R. F., 36th ANTEC SPE Proceedings, 1978 pp. 737-9.
50. Lippoldt, R. F., Plast. Engng, 34(9) (1978) 37-9.
51. Gleissner, A., Kunststojfe-Plastics, 22(1) (1975) 11-12.
52. Gerrard, D. L., Biggin, I. S. & Bowley, H. J. PRI Conference PVC '87,
1987, Paper No.3.
53. Wilson, A. S., Bowley, H. J. & Gerrard, D. L., Plast. Rubb. Int., 13(1)
(1988) 23-6.
54. Menzel, G. & Polte, A., Kunststojfe, 65(3) (1975) 149-55.
55. Collins, E. A., Metzger, A. P. & Furgason, R. R., Polym. Engng Sci.,
16(4) (1976) 240-5.
56. Fougea, D., Cahiers Centre Sci. Tech. Biltiment, 124 (1971) p. 1070.
57. Nelson, J. H., A novel method of assessing heat stability. Paper presented
at the PRI International Conference on PVC Processing, Egham Hill,
Surrey, UK, 6-7 April 1978.
58. Casel, B. & Gray, A. P., Plast. Engng 33(5) (1977) 56-8.
CHAPTER 5
Plasticisers
5.1 GENERAL DEFINITION AND NATURE

OF PLASTICISERS
The current formal definitions of a plasticiser (those of IUPAC 1,* and

the ISO,2 ASTM,3 and BS4 terminology standards) are neither
mutually identical nor fully comprehensive. Their essential elements
may be combined and augmented to formulate the following general
working definition relevant in the PVC context.
A plasticiser is a substance of low or negligible volatility, suitably
compatible with the polymer in which it is incorporated. Whilst it
improves the processability of the resulting composition, its principal
role is to impart to the ultimate product-in degrees dependent upon
the plasticiser's nature and proportion-the properties of flexibility,
extensibility and softness. Among the usual, technically significant
concomitants of plasticisation are the lowering of the glass-transition
temperature (and softening temperature generally), reduction of
strength, and increased impact resistance.
In the practical context, a distinction is commonly made (although it
does not constitute a rigid, well defined classification) between primary
and secondary plasticisers. The former are those which are highly
compatible with PVC polymers (up to at least 150 phr) , whilst the
latter, less compatible, are generally used in mixtures with primary
plasticisers to confer some special balance of properties on the PVC
composition. The extenders, a group of least compatible secondary
plasticisers, are used in some compositions as cheaper part-
replacements for other plasticisers.
* International Union of Pure and Applied Chemistry.

177
Some of the effects resulting from the introduction of certain

co-monomer units (e.g. vinyl acetate, vinylidene chloride, propylene,
alkyl vinyl esters) into the vinyl chloride polymer chain-and thus
imparting more flexibility to the chains, as well as creating a less
morphologically uniform and hence less cohesive structure-are simi-
lar to those produced by admixing external plasticisers to the polymer.
These effects (and the incorporation of the co-monomers that produce
them) are commonly termed internal plasticisation. The ISO and BS
vocabulary standards2 •4 go so far as to define 'internal plasticiser' as 'a
chemical group incorporated by chemical reaction in a polymer to
plasticise it'. 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 sys-
tems in strength and low-temperature properties.
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 Ce C8 alcohols. The C8 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 plas-
ticisers in common use are chlorinated paraffins, or hydrocarbons.
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 molecu-
lar 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
molecular weights up to 8000) are certainly included under this
heading. However, the designation is sometimes also applied to
5 Plasticisers 179
plasticisers of high molecular weight which are not polymers, e.g.

some complex esters, or epoxidised oils.
5.2 PLASTICISATION MECHANISM, AND SOME

RELEVANT FEATURES OF PLASTICISER STRUCTURE
Two major basic explanations of the mode of action of external

plasticisers in PVC are embodied in the alternative theories of
plasticisation usually referred to as the Lubricity Theory and the Gel
Theory.
In the former, older theory, originated by Kirkpatrick,S Clark,6 and
Barron, 7 the plasticiser is thought to act as a lubricant reducing
intermolecular friction of the polymer chains between which it is
interposed, and thus making the bulk material less resistant to
deformation.
The Gel Theory, developed through the work of Doolittle ,8,9 ascribes
the deformation resistance of amorphous polymers to the existence of
a quasi cross-linked structure, likened to a loose, three-dimensional
honeycomb, with the cross-links operating between 'active centres'
along the polymer chains. The structure is envisaged as not static, but
existing in a state of an aggregation-disaggregation equilibrium, with
the cross-links continually breaking down and re-forming. When a
plasticiser is introduced into the polymer, it takes part in the
interactions within the resulting two-component system, so that
temporary links are now formed also between the plasticiser molecules
and the polymer's 'active centres'. In consequence, at any given time,
a proportion of the centres is engaged ('masked' or 'solvated') by the
plasticiser (i.e. a solvation-desolvation equilibrium is set up) and
hence it is not available for polymer-to-polymer linking, the polymer
structure being correspondingly loosened. The suggestion that in PVC
the 'active centres' are dipoles in the polymer chain has been coupled,
in a paper by Leuchs,lO with one that they can be masked by plasticiser
via either a 'screen' or a 'hinge' action (cf. Fig. 5.1), hinge-type
plasticisers being represented by the readily polarisable aromatic
compounds, and the screen types by polar, aliphatic esters.
In the light of more recent work it would appear! that the role of the
quasi cross-links is in fact played by areas of ordered structure
(micro-aggregates or crystallites) in the polymer, and that aggregation
of polymer chains (possibly along lengths of some 11-20 repeat units)
Screen type Hinge type
Fig. 5.1 Screen and hinge mechanisms of piasticiser action (after Leuchs). 10
is promoted by the presence of plasticisers and solvents, resulting in

the formation of polymer/plasticiser on polymer/solvent gels. Such
gels appear to have a significant part in determining the physical
properties of plasticised PVC, which can however also exhibit other
structural regularities not directly related to crystalline order. 1 As
remarked by Buszard, 1 it would appear that the mechanism of
polymer-plasticiser interaction in pPVC is complex and that it
operates at a number of levels, involving 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.
Certain regularities have been noted by several workers, which may
be considered to amount to significant correlations, between the
chemical structure of plasticisers and their plasticising properties in
PVC. The following features of this kind may be mentioned. 1
Molecular weight: Volatility, migration and softening efficiency all

decrease with increasing molecular weight of the plasticiser.
Polarity: Increasing polarity by 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 of
the plasticised compounds, improves solvation, and reduces extrac-
tability by aliphatic solvents.
5 Plasticisers 181
Alkyl chain length: Increasing alkyl chain length improves the

efficiency of aliphatic and phthalic diesters at equimolar concentra-
tions. Efficiency at equal weight concentration is largely independent
of chain length.
Alkyl chain linearity: Increasing linearity improves the efficiency of

the plasticiser and low-temperature flexibility of the plasticised com-
pound, but tends to reduce its electrical resistivity.
Separation of ester grouping: Increasing the distance between ester

groups at a constant Ap/Po ratio [see Section 5.4.1(e)] increases
solvation, softening efficiency, and effectiveness.
I
,.1
'00
..0
100
~~- r--- --'~-"~,.-t--

--t--
.0 ~
,DpP\
~\ ~ TTP "',t--
~-f-\.~~-
U
~
>0
O~CIYIIPOXY • ,,,,,<J.r.
~Q ~
f/1;,.,.~ ~ ...
'"
"'(l~lri\. \
N
~p t~
slearale
~
~
0 \
u 30 Ifo..,
Di n heplyl lOIS."
."
~
DOS phthalate \.
t-
~' \
• Octyl diphonyl PhD'Phltel
"PIS,of. DBP
<-~" it,,,,... I
,----
ri oClyl phosphate
0· -I-- - --
.
:nR.~.' ~~
---~~4"
~
t-
~~
- ------- f-
..~.;-~ ,"" ~
. .~~ ....~{ ...~...
, 1-------- ----'\: ~ 1\ \'I.~ ~
of! ~ "i,,'. ~"c. ,.\.\($ t,'
..
"'b- ..0", ~ ..~-~~l>'4e\ o~..~'I.e~
"'o~"?~;. '1' ' ' ' ~~~..e~
, ~.~
~
~
~i,
,'()
40. ",.
" ;P-:f,
I
I"
0-85 0-9 0-95 1-0 1-05 1-15 1-20
Relative densily 25/25'C
Fig. 5.2 Relationships between the viscosity and relative density of plas-
ticisers in bulk and their plasticising properties in PVc. 1
Reversal of ester grouping: 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 (e.g. di-n-octyl adipate is a
better plasticiser than 1,4-butylene glycol dipelargonate).
The above parameters also influence the relative density and viscosity
of plasticisers: thus a plot on this basis segregates plasticisers into
groups which are related to their plasticising properties: see Fig. 5.2.
5.3 MAIN OUTWARD MANIFESTATIONS

OF PLASTICISATION
5.3.1 Eft'ects of the Level of Plasticisation
The incorporation of a small proportion of plasticiser (up to about

10-17% depending on its nature) in a PVC compound leads to an
increase in modulus and tensile strength and a reduction in impact
strength (i.e. embrittlement) and in elongation at break (cf. Figs 5.3
and 5.4). This is the opposite behaviour to what might be expected,
and the phenomenon has been termed 'antiplasticisation'. Although its
manifestations are well known, the mechanism of antiplasticisation is
not yet fully understood. Some tentative explanations have been put
3'0 ~-
:;
f
80 "0
'"E 0",
2·5 E ~
Z i: Z
~ 60 2.0 g, (9
c
~
400
o
o
c -
200 :3ro
01
c
.Q
+--""'T'""-----r---r---+ O w
o 10 20 30 40
PlasticislZr conc. 010
Fig. 5.3 Some effects of low concentrations of DOP on the physical

properties of PVC (after Ghersa).l1
5 Plasticisers 183
120
110
DBS
100 DOA
u
0 90
~
-
:5OJ50
c
...en~40
... 30
u
E20
I1J
10
o 10 20 30
PlasticislZr contlZnt) phr
Fig. 5.4 Effect of some plasticisers, at low content levels, on the impact
strength of a PVC composition.
forward by various investigators in terms of the following: structural

ordering12 (not necessarily amounting to development of
crystallinity 13.14) made possible by increased freedom of movement of
the molecular chains in the presence of the relatively small amount of
plasticiser; the almost diametrically opposed suggestion that-in the
limited quantity present-the plasticiser just fills the original free
volume in the polymer and thus restricts the motion of the molecular
chains;15.16 phenomena associated with suppression of the viscoelastic
beta-relaxation process. 17-21
Because of the antiplasticisation effects (and in particular that of
embrittlement), PVC compositions containing less than about 20 phr
plasticiser are rarely encountered. It is also for this reason that
copolymers, or polymeric modifiers with homopolymer, are used
rather than low concentrations of conventional plasticisers in rigid
PVC formulations. 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.
Plasticisation at a moderately higher level, typically about 20-33 phr
(17-25%) with primary plasticisers, produces semi-rigid PVC com-

positions. In these, whilst the normal softening and flexibilising effects
of the plasticiser become perceptible (cf. Section 1.1.2 of Chapter 1),
the relationships between plasticiser content and degree of modifica-
tion of mechanical properties are often relatively complex and
non-linear. An early discussion of some of these effects was published
by Jacobson.14
At further increasing levels of plasticisation the PVC materials
become progressively softer, more flexible and extensible. These and
other effects are discussed in Section 5.6 below.
5.3.2 Stages of Plasticiser-Polymer Interaction
Various sequential interactions take place between a plasticiser and

PVC polymer from the time of first contact to the formation of the
ultimate, homogeneous, completely fused material: some mutual
effects can also continue for some time thereafter (see Section 5.3.3
below). The exact form of the interactions, and the steps that may be
distinguished in their progress, depend to some extent upon the nature
of the polymer/plasticiser system concerned, i.e. whether it is a paste,
or a composition undergoing dry blending, or one being melt-
compounded. However, the following summary of the main stages of
plasticisation (after Sears, Darby and Touchette22 ,23) is generally
applicable.
(i) Irreversible uptake of plasticiser into the PVC resin particles.
(ii) Absorption of the plasticiser, during which the total
resin/plasticiser volume may decrease although the resin par-
ticles 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 proceed through only the first two
5 Plasticisers 185
steps at room temperature. Steps (iii) and (iv) have high activation
energies, thus requiring a threshold temperature to be reached.
The plasticiser-polymer interactions during powder blending are
mentioned in Section 11.4.2(b) of Chapter 11. Interactions in the
course of melt-compounding are referred to in Section 13.4 of Chapter
13, and those during the gelation and fusion of a PVC paste are
discussed in Section 18.4 of Chapter 18.
Van Veersen & Dijkers24 compared published data from different
sources,25-29 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 5.1).
5.3.3 Ageing of Plasticised PVC after Processing
As has been well known for a long time,I,30 the modulus and hardness
of a plasticised PVC compound increase measurably during the period
immediately following processing. For this reason pPVC test speci-
mens are usually kept at room temperature for approximately seven
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.
TABLE 5.1
Comparison of Plasticiser Absorption of PVC by DitJerent Methods
Plasticiser Dry point25 Solvation Solid-gel Maximum Relative

eC) point26 transition swelling melting
eC) temperature1:7 temperature 28 temperature 29
eC) (0C) eC)
Diethyl 56 92 88 65 58
phthalate
Dibutyl 60 97 86 75 62
phthalate
Dihexyl 72 104 75 84
phthalate
Dioctyl 80 127 118 80 84
phthalate
Di-isodecyl 86 138 132 85 94
phthalate
Several workers31 •32 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.
5.4 PRINCIPAL FUNCTIONAL PARAMETERS

OF PLASTICISER ACTION
These parameters are the main criteria on the basis of which a
plasticiser may be classified as 'good' (or otherwise). They are:
(i) compatibility and ease of mixing with the PVC polymer;
(ii) effectivity in imparting a desirable property or properties
(usually softness and flexibility) to the plasticised polymer;
(iii) permanence.
Unfortunately, some properties of a plasticiser that make for ex-
cellence in one of the above respects may also reduce performance in
another. For example, a plasticiser which by virtue of its molecular
structure and chemical make-up is easily miscible and highly com-
patible with the polymer will also, due to the same factors, normally
tend to diffuse easily through the plasticised material, with resulting
easier loss and hence not very high permanence. A good plasticiser is
therefore one which meets simultaneously all the above three main
criteria (and any others that may be relevant) to the extent necessary
in 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 considera-
tions. Combinations of two or more plasticisers are often used for the
best overall result in particular cases. However, it is obviously
desirable to be able to assess and compare the merits of plasticisers,
especially in relation to the above three criteria. The methods of
interest in this connection are outlined in Sections 5.4.1 to 5.4.3
below.
5.4.1 Compatibility and Miscibility
Several theoretical treatments and more practical technological tests
are available, whereby a plasticiser may be assessed for compatibility
and/or miscibility with PVC.
5 Plasticisers 187
(a) The I-l Value

This is a numerical index of the degree of interaction between polymer
and plasticiser, and can be determined from the swelling equilibria of
lightly cross-linked polymer immersed in the plasticiser. The relation-
ship used to calculate I-l from such data is
TT 113
2 P2 YI V2
I-lV2 = -In (1- V2) - 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, developed by Gee,33 was used by Doty & Zable34 to evaluate
the miscibility of dialkyl phthalate plasticisers with PVc. Values of I-l
below O· 55 indicate high miscibility, and those above O· 55 limited
miscibility, reducing with increasing I-l value. The I-l values obtained by
Doty & Zable for some of the phthalate plasticisers were: dihexyl
phthalate -0.14; dibutyl phthalate and dioctyl phthalate -0.07;
diethyl phthalate +0.38; dilauryl phthalate + 1· 79.
(b) Solubility Parameter tJ

The Hildebrand solubility parameter tJ is related directly to a
compound's cohesive energy density, and is a constant for any given
compound. It can be shown35 ,36 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. 37
The solubility parameter can be calculated from the structural
formula and density of the compound involved36 ,38--40 or determined
experimentally. Table 5.2 lists the solubility parameters of some
common plasticisers, calculated by the method of Small. 38
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 of these, which is often disregarded, is
highlighted by the plasticising effect of pure isomers of TXP (trixylyl
TABLE 5.2
Solubility Parameters of Common Plasticisers
Plasticiser Molecular weight Solubility parameter
~(calll2ml-ll2)
Dimethyl phthalate 194 10.5

Dibutyl phthalate 278 9.4
Di-isobutyl phthalate 278 9.2
Dihexyl phthalate 362 9.0
Dioctyl phthalate 390 8.85
Di-iso-octyl phthalate 390 8.85
Dinonyl phthalate 418 8.5
Di-isodecyl phthalate 446 8.5
Benzyl butyl phthalate 312 9.9
Tritolyl phosphate 326 9.8
Trixylyl phosphate 410 9.75
Dioctyl sebacate 426 8.4
Ceredor S52 (ICI) 9.3
Polyvinyl chloridea 9.7
a Solubility parameter given for PVC for comparison.
phosphate), all of which have the same calculated solubility parameter

of 9.75 1 but widely differing compatibility and plasticising effects
(Table 5.3).
The solubility parameter of the chlorinated paraffin, Ceredor S52,
suggests that it should be much more compatible than is found in
practice.
TABLE 5.3
Compatibility and Plasticising Effect of Isomers of TXP
Xylenol isomer Melting point of Plasticising effect

TXP CC)
2,6 137 Stiffest composition

2,5 78 Most incompatible
3,4 71 Not compatible
2,3 58 Borderline compatibility
3,5 40 Compatible
2,4 Liquid at room Compatible
temperature
5 Plasticisers 189
(c) Clear-Point Temperature (Solid-Gel Transition Temperature)

This has been variously termed 'clear point', 'solid-gel transition',
'fusion point', 'solution temperature' and 'apparent melting tempera-
ture', but basically it is the temperature at which a mixture of PVC
and plasticiser becomes clear or undergoes an apparent phase
change. 26-28,4t-43 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 that of 4% suspensions as
described by Van Veersen & Meulenberg,27 or 5% suspensions as in
the German Standard,44 or even of virtually single particles in excess
plasticiser. 43 ,45
Although there is a 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 5.4.
(d) Interaction Parameters: Flory-Huggins (X), and 'Bigg (a)'

It has been shown that the Flory theory of melting in the presence of a
diluent could be applied to PVC-plasticiser interaction,43,46 and that
the X values correlated well with observed compatibilities.
Anagnostopoulos et al. 43 ,46 correlated the values of X with the clear
point, using the equation
1
- = 0·002226 + 0,3151«1 - X)/Vt ) (1)
Tm
where Yt is the molar volume of the plasticiser at the clear point
temperature, Tm.
Plasticisers with X values of 0·55 or above are generally regarded as
incompatible, values between 0·55 and 0·3 show moderate to poor
compatibility, and values below O· 3 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 para-
meter, and that (particularly in the case of Ceredor S52) the value
bears more relation to the observed compatibility (Table 5.5).
Unfortunately, the molar volume of the plasticiser at the clear-point
temperature is not a readily determinable factor. Bigg45 proposed that
since 1/Tm is proportional to (1- X)/Vt in eqn (1), Vt could be
TABLE 5.4
Clear-Point Temperatures of Commercial PIasticisers
Plasticiser Clear-point
temperature
CC)
Phthalates Dioctyl phthalate 117

Di-iso-octyl phthalate 116
Di-Linevol 79 phthalate 114
Di-isodecyl phthalate 139
Ditridecyl phthalate 150
Benzyl butyl phthalate 102
Low-temperature Dioctyl adipate 138
plasticisers Di-isodecyl adipate 156
Dioctyl azelate 154
Dioctyl sebacate 151
Phosphates Tritolyl phosphate 98
Trixylyl phosphate 101
Reofos 50 (Ciba-Geigy) 100
Santiciser 148 (Monsanto) 98
Trioctyl phosphate 118
Trimellitates Trioctyl trimellitate 142
Reomol LTM (Ciba-Geigy) 132
Morflex 525 (Pfizer) 147
Polymerics Crestapol 538 (Scott Bader) 138
Diolpate 150 (Briggs & Townsend) 164
Diolpate 171 137
Palamoll 644 (BASF) 155
Plastolein 9503 (Unilever-Emery) 141
Plastolein 9506 144
Plastolein 9765 151
Reopfex 430 (Ciba-Geigy) 163
Reoplex GL 123
Reoplex 903 153
Ultramoll I (Bayer) 155
Ultramoll II 165
replaced by the molecular weight, MW, of the plasticiser to give an

interaction parameter, £1', as defined in eqn (2):
(1- X) x 103
£1'= (2)
MW
The values of £1' are also shown in Table 5.5. These correlate
reasonably well with Flory-Huggins X values calculated by both
Anagnostopoulos43 ,46 and Bigg,45 as well as with observed com-
5 Plasticisers 191
TABLE 5.5
Flory-Huggins and Bigg Interaction Parameters
(X and «)
Plasticiser Xa Xb erc
Dioctyl sebacate 0.53 0.62 0.8

Ceredor S52 (ICI) 0.52 1.0
Dioctyl adipate 0.28 0.48 1.4
Trioctyl trimellitate 0.32 1.2
Benzyl butyl phthalate 0.10 0.17 2.6
Masamoll (Bayer) 0.07 2.5
Dioctyl phthalate -0.03 0.05 2.4
Dibutyl phthalate -0.05 0.04 3.4
Dctyl diphenyl phopshate -0.35 -0.02 3.3
aCalculated by Anagnostopoulos. 43 ,45

b Calculated by Bigg,45
CCalculated by Bigg45 from eqn (2).
patibility of plasticisers. Bigg and Hill47 also demonstrated that the

interaction parameter, cr, related well to the viscosity ageing charac-
teristics of PVC plastisols.
(e) Api Po Ratio

This was devised by Van Veersen & Meulenberg27 ,48,49 as a very
simplistic w~y of representing the polar-non-polar balance of a
plasticiser by a single figure. It is calculated by dividing the numbers of
C atoms in aliphatic chains in a plasticiser molecule by the number of
ester groups present. Aromatic or carboxylic C atoms are not counted.
For example, dioctyl azelate has two chains containing eight C
atoms and one chain with seven C atoms (the dibasic acid). The Api Po
ratio is therefore
(2 x 8) + 7 = 11.5
2
Similarly, the dioctyl phthalates have an Api Po ratio of 8 since
aromatic C atoms are ignored.
The Api Po ratio of a wide range of plasticisers correlates well with a
number of properties, including melting point, specific gravity, mod-
ulus, water absorption, etc.
The Api Po ratio also correlates well with the clear-point tempera-
ture, termed 'solid-gel transition temperature' by Van Veersen &
Meulenberi7 (Table 5.6). In the same paper they also show clear
relationships with the data of Anagnostopoulos et aI., 43 Graham &
Darby,26 Wiirstlin & Klein,50 Jasse,51 and Doty & Zable,34 as well as
very distinct trends relating to efficiency (by 100% modulus), low-
temperature properties of compounds (Clash and Berg), extraction
resistance, volatility, and plastisol ageing characteristics. 1
(f) Loop and 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 test strip is cut from a sheet compression-moulded from the
compound concerned [cf. Section 17.1.3(b) of Chapter 17], and rolled
into a fairly tight ro1l27 or bent into a loop,52 which is then stored
under controlled conditions for a specified time. Absence of any
evidence of plasticiser exudation after this treatment confirms
compatibility.
One version of the loop tese2 is run as follows. A strip of the PVC
material 1 in x 6 in, and 0·05 in thick, is bent through 180° into a loop
and fastened with a strong bulldog clip at a distance of 0·75 in from
the top of the loop. The test is passed if after 24 h at 25°C and
TABLE 5.6
Parallel Trends in the Solid-Gel Transition Temperatures and
ApiPo Ratios of Some Plasticisers
Plasticiser SGTTeC) AplPo ratio

Dimethyl phthalate 93 1
Diethyl phthalate 88 2
Dibutyl phthalate 86 4
Dibutyl succinate 96 5
Dihexyl phthalate 104 6
Dibutyl adipate 98 6
Dioctyl adipate 118 8
Dibutyl sebacate 117 8
Trioctyl phosphate 121 8
Dihexyl azelate 127 9·5
Dioctyl adipate 137 10
Di-isodecyl phthalate 139 10
Dioctyl azelate 142 11·5
Dioctyl sebacate 150 12
Ditridecyl phthalate 151 13
5 Plasticisers 193
60% RH the inside of the loop bend shows no droplets of exuded

plasticiser; and is not oily or sticky.
(g) Maximum-Torque Temperature (Fusion Point) in Controlled
Mixing
This is one of the significant points on the torque-versus-time curve
obtained in the course of an assessment of plasticiser/PVC polymer
interaction in a Brabender Plasti-Corder or Plastograph [see also
Chapter 11, Section 11.4.2(b)). Early descriptions of the determination
of this value have been published by Touchette et al. 29 and
McKinney53 (see also Section 5.3.2 above).
Generally, either time to maximum torque at a fixed temperature or
temperature of maximum torque (with an increasing chamber tem-
perature at, for example, 2°C min-i) is 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,53 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. 54 An extensive, regularly
updated bibliography of papers relating to this test method is available
from Brabender. 55
5.4.2 Effectivity (Efficiency) of Plasticisers
In fundamental studies, the extent to which the glass transition
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. 56 Changes in certain dynamic
mechanical properties (modulus and damping) are also used. 23 ,56
In the technological context, plasticiser effectivity is usually ex-
pressed 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 al. 57 calculated composite or average effective
quantity values for several plasticisers from room-temperature flexibi-
lity, 100% modulus, hardness, and tensile creep determinations. The
results are given in Table 5.7.
TABLE 5.7
Effectivity Quantities and Efficiencies (Relative to DOP) of Some
Common Plasticisers
Plasticiser A verage effectivity Efficiency

quantity 57 relative to
Dop1,a
Tritolyl phosphate 35·0 1-13

(ordinary commercial)
Tri-ortho-tolyl phosphate 37·2
Tri-meta-tolyl phosphate 34·4
Tri-para-tolyl phosphate 38·1
Trixylyl phosphate 36·6 1·20
Dibutyl phthalate 27·7 0·86
Di-isobutyl phthalate 29·7 1·00
Dioctyl phthalate 34·0 1·00
Di-isooctyl phthalate 35·3 1·02
Di-Alphanol-79 phthalate 0·94
Diheptyl phthalate 34·9
Dinonyl phthalate 37·5 1-10
Di-isodecyl phthalate 1·06
Ditridecyl phthalate 1-18
Dibutyl sebacate 27·5 0·72
Di-isobutyl sebacate 28·9
Dioctyl sebacate 33·7
Dicyclohexyl sebacate 33·2-
Di-iso-octyl adipate 0·84
Di-iso-octyl azelate 0·89
Paraplex G25b 39·2
Paraplex G 50b 38·7
a phr of the plasticiser required to give a compound with a 100%

modulus (at 23°C) of 1100 lbf in- 2 (7·6MPa), divided by 62·8-the
corresponding value for dioctyl phthalate.
b Rohm & Haas, USA and Europe; UK distributors Croxton & Garry
Ltd.
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 hard-
ness or modulus and perhaps related to the performance of a common
plasticisersuch as dioctyl phthalate (DOP~f. Table 5.7.
It may be thought that high effectivity is desirable in a plasticiser
and in many cases this is so. However, on occasion the converse is
5 Plasticisers 195
true. For example, if 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.)
5.4.3 Permanence 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
plasticised PVC material. These are:
(i) volatilisation, in which plasticiser is lost at a surface into air;
(ii) extraction, in which plasticiser is lost at a surface into a liquid;
(iii) migration, in which plasticiser is lost by transference into a solid
or semi-solid material in intimate surface contact with the
pPVC material.
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. 58 However, it is the critical
stage of this phenomenon which is utilised in the loop and roll
compatibility tests [see Section 5.4.1(f)).
It has been suggested by Reed59 that, for a plasticiser to be
satisfactory in general use, it should have a boiling point of at least
225°C at 4 torr, so that no appreciable volatility losses occur under
room-temperature conditions.
Studies of factors affecting loss by volatility of the plasticiser from
PVC compositions have shown that it is proportional to surface area,59
sample thickness59 time, 60,61 and increasing air flow 62 ,63 [see also
Section 24.3.2(b) on heat resistance in Chapter 24].
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. 61 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 Knappe64--66 on diffusion of plasticisers in PVC and
their migration to other substrates. The logarithms of diffusion
coefficient values obtained by Knappe for a number of plasticisers
have been shown to decrease linearly with increasing bulk viscosities
of the plasticisers. 67
5.5 PLASTICISER TYPES, THEIR

CHARACTERISTICS AND COMMERCIAL VERSIONS
5.5.1 General Type Classification
There is no standard classification scheme for plasticisers used in PVC.

The one adopted in this chapter, which is based mainly on chemical
nature, is more convenient and systematic than most other possible
schemes. It divides the plasticisers into the following six general
groups.
(a) Phthalate plasticisers.

(b) Phosphate plasticisers.
(c) Trimellitate plasticisers.
(d) 'Low-temperature' plasticisers, i.e. those used 10 PVC com-
pounds for low-temperature applications.
(e) Polymeric plasticisers.
(f) Miscellaneous other plasticisers: (i) epoxy plasticisers; (ii)
chlorinated paraffins; (iii) monoesters; (iv) glycol esters; (v)
hydrocarbons; (vi) others.
The principal applicational features of the major types of plasticiser

are indicated in Table 5.8.
TABLE 5.8
Characteristics of the Major Types of Plasticisers
Plasticiser type Particular advantages or areas of usage Disadvantages
C4 phthalates Rapid gelation, ease of processing Very high volatility normally limits their
application
C g phthalates Used in the majority of applications not
requiring special properties
Linear phthalates Improved low-temperature properties Poorer electrical properties
DNP, DIDP Lower volatility, improved aqueous extraction Less efficient-but may be an advantage in
resistance some applications
DTDP Very low volatility Poor efficiency, expensive
BBP Rapid gelation, stain resistance
Triaryl phosphates Excellent flame retardant and gelation Poor low-temperature properties V.
properties, good resistance to microbial '1:1
attack ~
Alkyl diaryl Moderate flame retardancy with improved Expensive ~.
E:;'
phosphates low-temperature properties
Trialkyl phosphates Good low-temperature properties Poor compatibility and processing '"t:l
Trimellitates Very low volatility, excellent resistance to
aqueous extractants
Adipates Good low-temperature properties Generally poorer volatility and extraction
resistance
Azelates and sebacates Very good low-temperature properties and Expensive
permanence
AGS acid esters Good low-temperature properties---cheaper Generally poor volatility and efficiency
than other low-temperature plasticisers
Polymeric plasticisers Good extraction and migration resistance, low May exhibit poor compatibility and poor low-
volatility temperature properties, high viscosity
Epoxy esters and oils Improved heat stability, oils have reasonable Can have compatibility problems, particularly
extraction resistance on ageing
Chlorinated paraffins Low cost, reduced flammability Poor efficiency and compatibility; care needed
on stabilisation ~
-
5.5.2 Plasticiser Nomenclature: Names, Synonyms, and

Abbreviations
With the very large number of plasticisers available, confusion can

sometimes arise due to the use of different synonyms for one and the
same plasticiser, or of abbreviations whose meaning may not be
directly apparent. The list in Table 5.9 may be useful as a reference in
this connection. The preferred names and abbreviations included in
TABLE 5.9
Plasticiser Names, Abbreviations, and Synonyms
Preferred chemical name" Pr.eferred Other names and abbreviations

abbreviations"
AGS esters Mixed esters of adipic, glutaric and

succinic acids also known as
nylonates
Alkyl sulphonic ester ASE n-Alkyl sulphonate
Butyl-o-acetylricinolate BAR
Benzyl butyl phthalate BBP Butyl benzyl phthalate
Butyl cyclohexyl phthalate BCHP
Butyl isodecyl phthalate BIDP
Butyl nonyl phthalate BNP
Butyl octyl phthalate BOP Butyl 2-ethylhexyl phthalate
Benzyl octyl adipate BOA Benzyl 2-ethylhexyl adipate
Dialkyl (~-~) adipate DA79A Di-Alphanolb adipate, D79A
Dialkyl (~-~) phthalate DA79P DAP, di-Alphanol b phthalate,
D 79P
Dialkyl (~-~) sebacate DA79S Di-Alphanol b sebacate, D79S
Dialkyl (~-~) azelate DA79Z Di-Alphanolb azelate
Dibutyl phthalate DBP
Dibutyl sebacate DBS
Dicapryl phthalate DCP
Dicyclohexyl phthalate DCHP
Didecyl phthalate DDP
Diethyl phthalate DEP Diethylene glycol dibenzoate
Digol benzoate DGDP
Diheptyl phthalate DHP
Dihexyl phthalate DHXP
Di-isobutyl adipate DIBA
Oi-isobutyl phthalate OIBP
Di-isodecyl adipate OIDA
Di-isodecyl phthalate DIDP
Di-Linevot< 79 phthalate D~9P
5 Plasticisers 199
TABLE 5.9-contd.
Preferred chemical name" Preferred Other names and abbreviations

abbreviations"
Di-Linevolc 911 phthalate D~llP

Di-isoheptyl phthalate DIHP
Di-isohexyl phthalate DIHXP
Di-isononyl adipate DINA
Di-isononyl phthalate DINP
Di-iso-octyl adipate DIOA
Di-iso-octyl azelate DIOZ
Di-iso-octyl phthalate DIOP
Di-iso-octyl sebacate DIOS
Di-isotridecyl phthalate DITDP DITP, ditridecyl phthalate
DTDP
Di(2-methoxyethyl)phthalate DMEP Di( ethylene glycol monomethyl
ether) phthalate
Dimethyl phthalate DMP
Dibutyl adipate DNBA
Di-n-decyl phthalate DNDP
Di-n-octyl adipate DNOA
Di-n-octyl phthalate DNOP
Dinonyl phthalate DNP Di(3,5,5-trimethylhexyl)
phthalate
Dinonyl sebacate DNS Di(3,5,5-trimethylhexyl)
sebacate
Dioctyl adipate DOA DEHA, di(2-ethylhexyl)
adipate
Dioctyl isophthalate DOIP
Dioctyl maleate DOM
Dioctyl phthalate DOP D EHP, di(2-ethylhexyl)
phthalate
Dioctyl sebacate DOS:DEHS Di(2-ethylhexyl) sebacate
Dioctyl terephthalate DOTP Di(2-ethylhexyl) terephthalate
Dioctyl azelate DOZ Di(2-ethylhexyl) azelate
Diphenyl cresyl phosphate DPCP CDP, cresyl diphenyl
DPCF phosphate; tolyl diphenyl
phosphate
Dipropylene glycol dibenzoate DPDB
Diphenyl octyl phosphate DPOP ODP, octyl diphenyl
DPOF phosphate
Diundecyl phthalate DUP
Epoxidised linseed oil ELO
Epoxidised soyabean oil ESO ESBO
Octyl decyl phthalate ODP Di-Alfold BJOphthalate
Poly(propylene adipate) PPA
Poly(propylene sebacate) PPS (continued)
TABLE 5.9--contd.
Preferred chemical name a Preferred Other names and abbreviations

abbreviations a
Tributyl a-acetyl citrate TBAC

Tri(2-butoxyethyi) TBEP
phosphate
Tibutyl phosphate TBP
Tri(2-chlorethyl) phosphate TCEP
Tricresyl phosphate TCP, TCF, Tritolyl phosphate (particularly
TIP in UK)
Tri(2,3-dibromopropyl) TDBP 'Tris', T23P
phosphate
Tri(2,3-dichloropropyl) TDCP
phosphate
Triethyl o-acetylcitrate TEAC
Tri-isononyl trimellitate TINTM
Tri-iso-octyl trimellitate TIOTM
Trioctyl phosphate TOF Tri(2-ethylhexyl) phosphate
Trioctyl trimellitate TOTM Tri(2-ethylhexyl) trimellitate
Triphenyl phosphate TPF
Tetraoctyl pyromellitate TOPM Tetra(2-ethylhexyl) pyromellitate
Trixylyl phosphate TXP, TXF Trixylenyl phosphate
3,3,5-Trimethylpentane-l,4- TXIB e Texanolf isobutyrate
diol di-isobutyrate
Undecyl dodecyl phthalate UDP
a The preferred chemical names and abbreviations are those recommended in ISO
1043-1988(E) or BS 4589: 1970, or those widely accepted in the PVC industry.
b Trade name of ICI-branched chain ~-~ alcohols.
C Trade name of Shell Chemicals-predominantly linear ~-~ and ~-Cl1 alcohols.
d Trade name of Continental Oil Co.-Mixture of linear Cs and C IO alcohols.

e The same abbreviation also for 2,2,4-trimethylpentane-l,3-diol di-isobutyrate.
f Trade name of Eastman Kodak.
the list are those recommended by ISO 1043-1988 (E) or, if not
covered by this standard, by BS 4589: 1970. It should, however, be
noted that in some cases the preferred names or abbreviations differ
between the two standards: in particular, the prefix 'mixo' used by
BS 4589: 1970 to denote commercial mixtures of primary branched-
chain alcohols and ester plasticisers derived therefrom (as in for
example dimixodecyl adipate for di-iso-decyl adipate), has never been
adopted by the ISO standard (nor by anyone concerned with the use
or technology of plasticisers).
5 Plasticisers 201
Note: The following mixed-ester plasticisers are not included in

Table 5.9:
heptyl nonyl undecyl phthalate and adipate-HNUP and
HNUA (=711 P and 711 A);
hexyl octyl decyl phthalate and adipate-HXODP and
HXODA (=610 P and 610 A);
nonyl undecyl phthalate and adipate-NUP and NUA (=911
P and 911 A).
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.
5.5.3 Properties of Individual Plasticiser Types, and Their Main

Effects in PVC
(a) Phthalate Plasticisers

These are compounds of the general formula
o
II
C-O-R
0::e--O-RII
o
where R is the esterifying alcohol residue. The phthalates constitute
the biggest and the most widely used single chemical group of
plasticisers, the majority being general-purpose Cg phthalates, of
which DOP is particularly important. However, numerous other
phthalates are available, with properties of interest in particular
formulations.
Phthalate plasticisers can conveniently be divided into the following
groups: lower phthalates; general-purpose phthalates; linear phtha-
lates. A comparison of the properties of PVC compounds plasticised
with 54 phr (35%) of the more important phthalates is shown in Table
5.10. Most of the alcohols used in the production of phthalates and
s
r:s
~
TABLE 5.10 Sll::".
Properties of Phthalate Plasticisers in PVC Compounds at 54 phr !;;
Name Abbrevi- Liquid properties IRHD a BSS no. Cold Vola- Extraction resistance (% mass loss) ~
.g
ation at 25°C flex tile ~
eC) loss 3-.

Visco- Density (%) Petrol Min- Olive Soap Deter- .~
sity (gmrl) eral oil gent ~
(cSt) oil '"~
~.
Dibutyl phthalate DBP 16 1·035 72 48 -19 17 23 18 19 18 15
;:,
Di-isobutyl ;::0
;:,.
phthalate DIBP 29 1·042 74 45 -5 13 20 12 12 11 14
~
Dioctyl phthalate DOP 56 0·980 78 37 -19 1·0 24 19 18 4 3 :g
Di-iso-octyl ;::.,
phthalate DIOP 53 0·981 77 39 -16 1·0 24 17 17 4 3 £

g.
Di-Alphanol 1;;
79 phthalate DA79P 48 0·983 80 36 -18 1·0 23 18 17 4 4
Dicapryl
phthalate DCP 55 0·968 79 36 -17 1·3 23 16 15 2·5 2·4
Di-n-octyl
phthalate DNOP 31 0·975 77 38 -25 0·7 25 19 23 2·1 2·0
Dinonyl phthalate DNP 80 0·970 86 26 -8 0·2 24 17 18 2·0 2·0
Oi-isononyl
phthalate DINP 0-976 80 35 -14 0-3 16 16 15 0-6 0-9
Oi-Linevol
79 phthalate O~9P 33 0-985 76 42 -26 0-8 24 21 21 6 3
Oi-Linevol
911 phthalate OL.,llP 49 0-962 87 27 -27 0-1 26 23 30 1-7 +0-8
Oi-Alfol610
phthalate (OHOP) 33 0-971 77 38 -27 0-7 21 20 19 3 1-8
Oi-Alfol 810
phthalate OOP 37 0-964 81 34 -25 0-2 20 18 18 1-2 0-8
Oi-isodecyl
phthalate DIOP 85 0-962 84 26 -16 0-1 25 22 25 0-3 0-1
Oiundecyl
phthalate OUP 54 0-947 91 20 -26 0-2 21 18 22 0 +0-2 v,
Oi-isotridecyl
~
phthalate OTDP 243 0-950 95 13 -16 0 26 25 25 +1 +0-2 El
Benzyl butyl ~.
!:;-
phthalate BBP 45 1-124 79 35 -7 3-8 12 16 18 14 8
Oi(2-meth-
'"<::l
oxyethyl)
phthalate OMEP 32 1-167 76 40 -12 10 8 14 15 16 17
a International Rubber Hardness degrees_
8
other alkyl-alcohol diesters are manufactured by the 'OXO process'

or carbonylation reaction. 1
LOWER PHTHALATES
The two members of this group most significant in the PVC context
are DBP and DIBP. Originally widely used (in the early 1950s) for
their good efficiency and rapid gelation in pPVC, they are now
restricted to compositions where these properties are particularly
important, whilst their high volatility and poor aqueous extraction
resistance can be tolerated. Otherwise they have been replaced by
phthalates of higher molecular weight. Like other high-volatility
plasticisers, DBP and DIBP can adversely affect the growth of plants. 1
It is particularly important, therefore, that they should not be used in
compositions for films, hoses, glazing strips, etc., for glasshouses, or
other horticultural applications.
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 iso-octanol). DA79P, which was based on mixed ~, Cs and C9
branched-chain alchols is no longer manufactured. DOP, DIOP and
DA79P have very similar properties and are generally regarded as
interchangeable, the choice being dependent on the current supply
position.
More recently, DINP, di-isononyl phthalate, based predominantly
on dimethyl-1-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 mark-
edly less efficient and finds particular application where low plastisol
viscosities are desirable--especially for semi-rigid dip coatings, slush
mouldings, and rotational castings (cf. Section 5.4.2).
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 Cs 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
5 Plasticisers 205
alcohols by fat hydrogenation, e.g. straight-chain C6-C lO alcohols from

coconut oil. The majority are now manufactured from synthetic
hydrocarbon feedstocks. 1
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 considerably lower volatile losses than their branched-
chain counterparts at elevated temperatures: the differences can be
particularly pronounced on prolonged processing at temperatures of
190°C and above, l and are also reflected in loss of low-temperature
flexibility on ageing at 90°C (see Fig. 5.5).
However, compounds plasticised with linear phthalates do exhibit
poorer electrical properties (i.e. lower volume resistivities), which are
undesirable in cable insulation compositions.
DOP/DOA
to 50:50
DOP/DOA
Ij 60:40
Ij
f
-10
DOP/DOA
70:30
U
e....
~
1i
'j( (I
f,//
:l DOP
!
.a
..
-20
1",/
I!
Q.
E
.!
~
610P
°
---.--
..J
_ _ _ 810P
t -3D
2 3 4 5 6
- Time [days]
Fig. 5.5 Change of low-temperature flexibility of pPVC compounds on

ageing at 90°C. 1 The compounds were formulated to give equal Clash & Berg
temperatures (341Okgfcm- 2 ) of -30°C.
HIGHER PHTHALATES
In general, these are less efficient than DOP and other Cs phthalates,
but also less volatile and more resistant to aqueous extraction: see the
relevant data for DIDP, DTDP and DUP in Table 5.10, in comparison
with those for DOP, DIOP and DNOP. Before the advent of
trimellitate plasticisers, DTDP (di-isotridecyl phthalate) was widely
used in applications requiring low volatility, e.g. high-temperature
cable coverings, low-fogging leathercloth. DUP (diundecyl phthalate)
and UDP (undecyl dodecyl phthalate) are also used for low-volatility
applications, sometimes in blends with a trimellitate, but more
commonly in North America than in Europe.
MISCELLANEOUS PHTHALATES
Benzyl butyl phthalate is widely used where ease and rapidity of fusion
of the pPVC composition is important. Due to these properties it
allows regular production rates at lower temperatures or increased
rates at normal processing temperatures. It also imparts good resis-
tance to staining to pPVC films and sheeting, and hence is frequently
used in clear wear-layer compositions for vinyl flooring.
Dioctyl terephthalate (DOTP), originally introduced commercially
in the USA by Eastman Kodak, is claimed to offer reduced volatility
and generally better permanence, as well as greater lacquer mar
resistance, in comparison with DOP.
Modified phthalates, such as Hexaplas OPN (ICI), are also available
from some companies. These have similar low-temperature properties
to the straight-chain phthalates, but greater volatility. However, their
plastisol rheology and storage stability are superior, and they are
claimed to promote volume cost savings over most other phthalates.
(b) Phosphate Plasticisers

RJ
I
o
I
R 2 -O-P=O
I
o
I
R3
[R = alkyl, aryl, or substituted aryl group]
Phosphate plasticisers may be divided into four classes: triaryl phos-
phates; trialkyl phosphates; mixed alkyl aryl phosphates; and halogen-
ated alkyl phosphates.
5 Plasticisers 207
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 the phosphate plasticisers has been
published by Buszard. 68
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 Re%s range of synthetic triaryl phosphates based on isopropy-
lated phenol and introduced by Geigy (now Ciba-Geigy) in 1968.
The isopropylated phenyl phosphates are applicational equivalents
to the older TIP (TCP) , TXP and COP, 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 Re%s 95, Re%s 65, and Re%s 50,
and from Albright and Wilson Ltd as Pliabrac 524, Pliabrac 521, and
Pliabrac 519. They are also available in the United States from FMC
as Kronitex 100 and Kronitex 50.
A comparison of these phosphates is shown in Table 5.11. As a
TABLE 5.11
Comparative Perfonnance of Triaryl Phosphates
(Formulation: PVC 100, plasticiser 54, white lead paste 4, calcium stearate 1.)
Re%s TXP Re%s TTP Re%s

95 65 50
Viscosity at 25°C, cSt 95 95 60 60 50
Density at 25°C, g ml- I 1·131 1·134 1·161 1·158 1·170
IRHD, Shore A 87 87 85 82 83
BS softness no. 25 24 27 31 30
Cold-flex temperature
(BS 2782 method
104B),OC +5 +8 +4 +6 +3
Volatile loss, % 0·5 0·3 0·5 0·6 1·0
Extraction resistance
weight loss, %
Petrol 15 15 15 15 15
Mineral oil 11 11 13 11 13
Olive oil 11 11 12 12 13
Soap 9 9 11 11 12
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
illustrated in Fig. 5.6.
Oxygen index (%)

46
Fig. 5.6 Effect of phosphate plasticisers at various concentrations on the

Oxygen Index of pPVC. 69
5 Plasticisers 209
TRIALKYL PHOSPHATES
Trioctyl phosphate (e.g. Disflamoll TOF; Mobay Chemical Corp.,
USA) is the most popular of this group for PVC formulations (e.g. for
industrial-fabric coatings; wall-coverings), but in general trialkyl
phosphates are relatively little used in PVC today. They have poor
compatibility and, although somewhat flame-retardant, they offer only
moderate advantage over phthalates in this respect. However, they do
confer excellent low-temperature properties, this being the main
reason for their use in those PVC formulations in which they are
incorporated.
MIXED ALKYL ARYL PHOSPHATES
Octyl diphenyl phosphate (e.g. Santicizer 141-Monsanto; Disflamoll
DPO-Mobay Chemical Corp.) and isodecyl diphenyl phosphate (e.g.
Santicizer 148) are two mixed alkyl aryl phosphates available commer-
cially. Three other commercial alkyl diaryl phosphates are Phosflex
362, 370 and 390 (Stauffer Chemical Co., USA). The properties
imparted to pPVC by these mixed-ester phosphate plasticisers are
intermediate between those conferred by trialkyl and triaryl phos-
phates, thus offering a compromise in flame retardance and low-
temperature properties. The physical and flammability properties
imparted by octyl diphenyl phosphate and isodecyl diphenyl phosphate
are comparable with those produced by a blend of 60% triaryl
phosphate and 40% dioctyl adipate (Table 5.12).
HALOGENATED ALKYL PHOSPHATES
These additives, for example tri(2-chloroethyl) phosphate (TCEP) and
tri(monochloropropyl) phosphate, are effective flame retardants but
exhibit poor compatibility with PVC. They are more of interest as
flame retardants in other polymers (e.g. polyurethanes), and are only
occasionally used as supplementary flame-retardant additives in PVc.
(c) Trimellitate Plasticisers
o
II
C-O-R
R-O-C
II
U C-O-R
II
o 0
Esters based on trimellitic anhydride have become very popular
primary plasticisers for PVC compounds, for use at high temperatures
N
0
-
TABLE 5.12
Performance of Dift'erent Phosphate Plasticiser Types in PVC Compounds at 54 phr
"'tl
Re%s 50 TOF Santicizer Santicizer Phosphate DOP ri
(isopropylated (trioctyl 141 148 blend (dioctyl "'tl
phenyl phosphate) (octyl (isodecyl (60% Re%s 50/ phthalate) [
::to
phosphate) diphenyl diphenyl 40% DOA) f:l
phosphate) phosphate)
.,~
{5
IRHD 83 78 76 78 76 78
BS softness no. 30 38 41 37 41 37 '"3-.
Cold-flex temperature ~
"'tl
(BS 2782 method 2l
l04B),OC 3 -50 -19 -17 -18 -19 lil
Volatile loss at 82°C, % 1·0 1·7 1·7 0·7 2·0 1·1 !:l
~.
Extraction resistance
weight loss, % ;:s
Petrol 15 17 22 20 20 24
""
""-
~
Mineral oil 13 16 21 17 17 19 :g
Olive oil 13 18 21 16 18 18
Soap 12 12 19 17 12 4 e
5'
Oxygen index, % 34 27 29 29 29 24 ~
5 Plasticisers 211
or for applications requiring excellent resistance to aqueous extrac-

tants, e.g. washing machine parts. Table 5.13 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
cable applications, whilst straight-chain trimellitates, as with phtha-
lates, give better low-temperature properties.
(d) Aliphatic Diester Plasticisers

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 ROOQCH2)n COOR.
The most popular dibasic acids are adipic (n = 4), azelaic (n = 7)
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 iso-octanol, 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 5.14.
(e) Polymeric plasticisers

The majority 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
N
N
-
."
TABLE 5.13 ~
Properties of Trimellitate Plasticisers in PVC Compounds at 54 phr
[
Plasticiser Viscosity Density IRHD BSS Clash Volatile Extraction resistance (% mass loss) ~.
at 25°C at 25°C no. and loss
(cSt) (gmrl) Berg (%) Petrol Mineral Olive Soap Deter-
eC) oil oil gent
.g~
::1-.
.,'"
Tri-Alphanol 79 ~
trimellitate 181 0·995 84 30 -10 0·1 21 14 14 +0·1 +0·3 ::p
Tri-Linevol 79 c(")
trimellitate 107 0·993 83 30 -15 0·1 21 14 15 +0·2 +0·3 ~
Tri-iso-octyl ~.
trimellitate 250 0·988 91 20 -7 0·2 22 19 14 +0·4 +0·7 ;:,
;:,
Tri(2-ethylhexyl) ;:,..
trimellitate 205 0·985 88 24 -10 0·2 22 ~
12 14 +0·4 +0·8
Tri-Alfol 810 ~
trimellitate 92·5 0·971 93 17 -20 0·1 26 26 22 +1 +0·8 £
5·
i:l
TABLE 5.14
Properties of Linear Diester Plasticisers in PVC Compounds at 54 pbr
Plasticisers Viscosity Density IRHD BSS Clash Volatile Extraction (%)

at 25°C at 25°C no. and loss
(cSt) (gmrl) Berg (%) Petrol Mineral Olive Soap Deter-
("C) oil oil gent
Di-isodecyl succinate 22·4 0·919 85 26 -38 1·8 25 24 24 4·5 1·9 v.

Iso-octyl ester ~
of AGS acids 13·5 0·928 79 37 -47 7·5 26 23 24 15 8 ~
Isodecyl ester i';.
1;;.
of AGS acids 23·3 0·917 86 25 -38 1·0 23 23 24 3·5 1
Dioctyl adipate 12·3 0·924 74 46 -45 2·4 26 22 26 7·5 4·5
'"t:!
Di-iso-octyl adipate 13·5 0·926 81 33 -48 1·7 25 21 21 8 4
Di-isodecyl adipate 22 0·912 85 27 -39 0·4 27 26 25 1·3 0·8
Benzyl octyl adipate 14·2 0·916 74 45 -36 3·2 23 23 23 17 7·5
Di-iso-octyl azelate 18 0·913 78 37 -47 0·6 24 22 25 1·4 1·0
Dibutyl sebacate 8·7 0·933 72 48 -52 9 26 26 27 18 6
Dioctyl sebacate 19·5 0·911 80 35 -51 0·5 24 24 25 0·4 0
Di-iso-octyl sebacate 22·4 0·911 80 34 -46 0·4 26 27 26 1 1
tv
V>
-
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:
H-oiR-O-C-RI-C-otH non-terminated
II II
o 0 n
RII-c-iR-O-C-RI_C-iR-O-C-RII acid-terminated
II II II II
o 0 0 n 0
RII-O-C-RI_C-iR-O-C-RI_C-iRII alcohol-
II II II" terminated
o 0 0 0 n
There are therefore two main parameters which can be varied in

polymeric plasticisers-their constituents, including chain stoppers,
and their degree of polymerisation, i.e. molecular weight-and since
both these factors are important in determining the resultant pro-
perties, it can be seen that there is considerable scope for variation. It
also follows that polymeric plasticisers are not simple, readily de-
finable 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-iso-octanol, 2 ethylhexanol, isodecanol,
Linevol 79 and 911 (Shell Chemicals)
The effect of molecular weight on the properties of a non-
ends topped polypropylene adipate has been demonstrated by Moseley
& DawkinslO-Table 5.15. From these results it can be seen that
5 Plasticisers 215
TABLE 5.15
The Effect of Molecular Weight on the Properties of Polypropylene
Adipate
Molecular weight 2000 3000 4000 9000

Viscosity at 25°C, P 150 250 350 850
Hydroxyl value, mg KOH g-l 55 45 30 25
Compound properties
BS softness no. 27 24 23 20
Cold-flex temperature, °C -1·7 -1·5 +2 +5·8
Volatile loss, % 3·2 2·7 2·4 2·3
Tensile strength, MN m- 2 17·8 19·8 19·9 20·8
Extraction loss, %
Hexane 0·4 0·3 0·1 0·1
Mineral oil 1·0 0·4 0·1 0
Soap solution (1 %) 9·0 6·8 4·7 3·8
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 addi-
tion, higher-molecular-weight products are more difficult to process
and often exhibit reduced compatibility with pvc.
Moseley & Dawkins also demonstrated the effect of varying the
reactants as well as molecular weight in typical commercially available
polymeric plasticisers (Table 5.16).
Endstopping will reduce the liquid viscosity of a polymeric plas-
ticiser 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 5.16 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 = 1 and 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. 1 These modified polyester plasticisers have the idealised
tv
0 -.
TABLE 5.16
The Etrect of Composition on the Properties of Commercially Available Polymeric Plasticisers
-
1 2 3 4 5 6 7 8 9 10
"1::1
Acid Adipic Adipic Adipic Adipic Adipic Adipic/ Adipic/ Phthalic Phthalic mop
phthalic phthalic anhydride anhydride ~
anhydride anhydride ~
El
:::-.
Diola 1,2-Pr 1,3-Bu Ne 1,3-Bu 1,2-Pr 1,2-Pr 1,2-Pr Dieth 1,2-Pr
!:l
glycol glycol glycol glycol glycol glycol glycol glycol glycol
Chain-stopper Alcohol Alcohol Alcohol None None Alcohol Alcohol Alcohol Alcohol ~
~
Viscosity at 25°C, ~
cP 2300 3400 5500 22000 24000 800 32000 700 900 72 ....
'"
BS softness no. 32 34 30 25 24 36 29 33 34 45 ~.
Cold flex, °C -6 -7·5 0 -0·5 -1·5 -5 2 -2 1·5 -20
Tensile strength, ~
kgfcm- 2 205 211 198 210 202 210 223 191 210 147 '"~
Volatile loss, % 4·1 3·7 3·9 2·9 3·2 4·0 2·9 6·7 12·0 22·4 ""
~.
Volume resistance,
;:s
Qcm- I 1 x 1012 8 X 1011 6 X 1013 1 X 1012 5 X 1012 2 X 1013 5 X 1013 3 X 1012 6 X 1013 2 X 1013 '"
I:>..
Extraction loss, % ~
Hexane 4·2 3·9 2·7 0·7 0·7 5·7 2·8 10·1 15·1 35·0 ~
Mineral oil 3·9 3·1 1·8 0·1 0·7 5·5 3·4 6·0 4·3 16·0 [
Water 0·2 0·3 0·1 2·1 2·3 0·6 0·6 1·2 0·3 0
g.
~
Soap solution
1% 6·1 5·4 4·7 3·7 4·8 9·3 6·9 11·6 11·4 13·0
Humidity (com- Moder- Moder- Moder-
patibility) ate ate ate Poor Poor Very good Moderate Excellent Very good Excellent
a Abbreviations: Pr, propylene; Bu, butylene; Ne, neopentyl; Diet, diethylene.

5 Plasticisers 217
structure:
The commercially available examples of this type of structure, based

on caprolactone, give plasticisers which have excellent compatibility
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
(Unilever-Emery).
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
more truly regarded as blending resins (polymeric modifiers) rather
than as plasticisers (see Chapter 8).
However, they have recently penetrated areas previously considered
to be the preserve of more conventional polymeric plasticisers and
blending grades of nitrile rubber 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; polyurethane elas-
tomers such as Baymod PU* (Bayer, and Mobay in the USA) and
Durelast 100 (Briggs and Townsend); appropriate grades of Baymond
EVA; and Uresin B (Hoechst), a carbamate resin for blending with
PVC.
* Formerly Ultramoll PU.

(f) Miscellaneous Plasticisers
EPOXY PLASTICISERS
The characteristic functional group of these compounds is the epoxy
group (oxirane ring)
o
1\
-C-C-
They are usually derived from the reaction of unsaturated compounds

with peracids. The unsaturated compounds used are generally natu-
rally occurring oils or the alkyl esters of natural unsaturated fatty
acids, although some 'synthetic' trigy1cerides and esters are manufac-
tured. The resulting commercial epoxy products are primary or
secondary plasticisers for PVC and also exhibit an effective stabilising
action (see also Chapters 2 and 4).
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 redissolves on heating to 30-40°C for a short
period, with no detrimental effect on the plasticising or stabilising
properties.
Alkyl epoxy esters are generally manufactured from tall-oil acids (a
by-product of paper manufacture), which contain a significant propor-
tion 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
stabilising reaction, their compatibility is greatly reduced. Care should
therefore be taken to ensure that the appropriate ultimate com-
patibility limits are not exceeded.
5 Plasticisers 219
Typical commercial products are:

Epoxidised soyabean oil: Edenol D81 (Henkel)
Lankroftex GE (Lankro Chemicals)
Paraplex G62 (Rohm & Haas)
Reoplast 39 (Ciba-Geigy)
Epoxy-alkyl esters: Edenol D72, B74, B35, HS235
Lankroftex ED3, ED6
Monoplex S-71 (Rohm & Haas)
Reoplast 38, 42
CHLORINATED PARAFFINS AND OLEFINS

The effects of chlorinated paraffins, when used within their com-
patibility limits in PVC compositions, are comparable with those of the
octylphthalates. The modern versions-produced by chlorination of
straight-chain liquid paraffin feedstocks-no longer suffer from the
poor colour and thermal stability problems which were experienced in
the early days.
Modern chlorinated paraffin plasticisers are exemplified by the
well-known Clereclor (ICI) range. Withing this range, two grades
(Cereclor S52 and S45) 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 usually
employed as partial replacements for phthalate or phosphate 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 flame retardance may be improved when Ceredor is
included in a vinyl composition.
The important properties of these Ceredor grades are given in Table
5.17. Ceredor S52 is the general-purpose grade, suitable for most
applications, while the 45% chlorinate, Ceredor S45, was specifically
developed for use in PVC plastisols, where its lower viscosity is an
advantage, and for compounds having good low-temperature pro-
perties. The slightly higher volatility of Ceredor S45 still allows
compounds containing this grade to pass most international ageing loss
specifications.
The use of chlorinated paraffin secondary plasticisers is straightfor-
ward 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.
TABLE 5.17
Properties of tbe Cereclor Grades
Cereclor S45 Cereclor S52

Chlorine content, % 43-45 50-52
Average chain length C I5 C I5
Density, gml- 1 at 25°C 1·16 1·25
Viscosity, Pa s 0·15-0·25 1-2
Volatility, % weight loss on
heating 4 h at 180°C 2·8 1·4
Thermal stability, % HCl after
4h at 175°C 0·06-0·1 0·07-0·12
Toxicity Very low Very low
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, 1·5 phr of Ceredor have to be included for each part of the
replaced octyl phthalate. Table 5.18 shows that the physical properties
are relatively unaffected in compounds reformulated to contain either
Ceredor S45 or S52.
In addition to leI, chlorinated products are also available from,
amongst others, the following manufacturers: Hoechst, Hiils, Dynamit
Nobel, and Caffaro in Europe; Diamond Shamrock, Keil, Dover, and
Witco (Pearsall Div.) in the USA; and Toya Soda, Asahi Denka, and
Ajinomoto in Japan.
The Witco Pearsall Div. Flexchlor products exemplify chlorinated
olefins, offered as alternatives to chlorinated paraffins. Derived from
straight-chain alpha-ole fins , they are claimed to be more stable to
dehydrochlorination in processing at elevated temperatures. Several
grades are available, with different viscosities and chlorine contents.
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 tetrahy-
drofurfuryl oleate. They are claimed to be good low-temperature
secondary plasticisers with advantages in some plastisol applications.
Two sulphonic acid esters may be included as a sub-group under the
TABLE 5.18
Properties of Compounds4 Containing Cereclor
Plasticiser
DIOP 54 38 35
DIDP 62 51 48
Reofos 95 66 30
Cereclor S45 25 15 35
Cereclor S52 30 20
v.
BS Softness no. 40 40 40 40 40 40 40 40 "tl
Shore A 75 75 75 75 75 75 75 75 ~
Tensile strength, ~.
c;.
MNm- 2 17·3 17·8 17.2 15·6 17·6 16·2 20·1 19·3
Elongation at break, % 300 315 320 315 325 330 245 290 '"<:!
Cold flex, DC -16 -20 -16 -16 -18 -16 -6 -10
Ageing loss (24 h
at lOODq, % 0·75 0·95 0·85 0·36 0·74 0·52 0·15 0·6
Volume resistivity,
Qcm x 1013 2 2 2 0·6 0·5 0·6 6 3
aFormulated for constant BS softness by varying the plasticisers (amounts given in phr) in otherwise
the same formulation.
~
-
present heading: Mesamoll (an alkyl sulphonic acid ester) and the
newer Mesamoll II (an alkyl sulphonic acid/phenol ester), both
manufactured by Bayer. Mesamoll has for some time been popular in
Germany as a good primary plasticiser resembling the general-purpose
phthalates in its effects.
GLYCOL AND POLYGLYCOL ESTERS
Like most of the monoesters, the glycol esters are also of relatively
limited interest and application. They include aromatic esters of
glycol, such as diethylene glycol dibenzoate (BenzoJlex 2-45; Velsicol
Chemical Corp.), propylene glycol dibenzoate (BenzoJlex 284), and
dipropylene glycol dibenzoate (BenzoJlex 9-88): these are popular in
the United States. They are rapidly solvating plasticisers, which also
offer low fusion temperatures and good resistance to staining and oil
and solvent extraction (compared with many other monomeric plas-
ticisers). Polypropylene glycol benzoate (BenzoJlex 4(0) is offered as a
low-volatility, high-solvating, moderate-cost alternative to alkyl benzyl
phthalates.
The unsaturated acrylic and methacrylic esters of glycols, such as
diethylene glycol dimethacrylate, may also be included in this general
group. These esters, together with other cross-linkable plasticising
additives, are of interest for the speciality uses discussed in Section
22.4.2 of Chapter 22. Other applications include addition to plastisols
and rigisols as adhesion promoters for coatings, e.g. on steel.
OTHER MISCELLANEOUS PLASTICISERS
Citrate plasticisers, such as triethyl citrate (CitroJlex C-2; Morflex
Chemical Co.), acetyltriethyl citrate (CitroJlex A-2), tri-n-butyl citrate
(CitroJlex C-4) and acetyl-n-butyl citrate (CitroJlex A-4) are primary
plasticisers with good low-temperature properties and a low order of
toxicity, but not particularly good resistance to extraction by aqueous
extractants, especially soapy water. They are of particular interest in
products for food contact and medical use: a discussion of the
application of these plasticisers in medical-grade PVC has been
published by Hull & Mathur. 71
A plasticiser of international importance not readily classifiable into
the previous categories is Texanol isobutyrate (KodaJlex TX/B),
manufactured by Eastman Chemicals Inc. This product is the di-
isobutyrate of 2,2,4-trimethyl-l,3-pentanediol. It is of a particular
interest in non-stain flooring and plastisol applications such as rota-
tional casting, where low plastisol viscosities and good viscosity
5 Plasticisers 223
stability are required. The high volatility of TXIB limits its use in some
applications. Other esters of Texanol (e.g. Nuoplaz 1406; Tenneco)
are available but are much less popular.
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 (Hiils);
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.
5.5.4 Transport, Handling, and Storage of Plasticisers
This topic is considered in Section 11.2.1(a) of Chapter 11. However,

it may be additionally mentioned here that storage tanks and transfer
lines for plasticisers can 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 polymeric and elastomeric
materials for use in contact with plasticisers, e.g. in hoses, flexible
couplings, O-rings and seals. Table 5.19 summarises the effect of liquid
plasticisers on many materials from which such products are made.
Note: In this context the term 'compatibility' is often employed in
the sense of suitability for use (satisfactory resistance on
contact) with the liquid in question. As can be seen, in this
particular application of the term its meaning is almost
directly opposite to that discussed in Section 5.4.1 above.
If any doubt exists regarding the suitability of a material for contact
with plasticisers, advice should be sought from the manufacturer of the
material or the plasticiser (and preferably both).
TABLE 5.19
Suitability of Polymeric Materials for Use as
Flexible Seals, etc., in Contact with Plasticisers
Material Rating a
Butyl rubber 1
Ethylene propylene rubber 2
Chlorosulphonated polyethylene 4
Natural rubber 4
Nitrile rubber 3
Polyamide 1
Polychloroprene 4
Polyethylene 2
Polypropylene 2
Polytetrafiuoroethylene 1
Polyurethane 3
Silicone 2
Viton 2
a Rating: 1 = generally recommended; 2 =
acceptable; 3 = possibly suitable under certain
conditions; 4 = unsuitable.
5.5.5 Some Commercial Sources and Trade Names of Plasticisers
The listing in Table 5.20 is not meant to be comprehensive, but it

should provide a reasonable indication of the major Western manufac-
turers and their products.
5.6 PLASTICISER-INFLUENCED PROPERTIES OF PVC
5.6.1 Formulating Considerations-General Points
The general principles of formulating PVC compositions indicated in

Chapter 2 apply fully to plasticiser selection: that is, for each particular
formulation the selection should be made to suit the requirements
imposed by the processing method, the end-use performance, and cost
economy. The following points are also applicable specifically to
choosing plasticisers for a formulation.
It is often advantageous on technical grounds (and can actually be
cheaper in some cases) to use more than one plasticiser-i.e. to
formulate a plasticiser system-to secure the optimum balance of
5 Plasticisers 225
TABLE 5.20
Commercial Plasticisers: Some Western Manufacturers
and Trade Names
Company Classes manufactureda Trade names
United Kingdom
Albright & Wilson 1,2,4 Pliabrac
B. P. Chemicals 1,3,4,6E Bisoftex, Enerftex
Briggs & Townsend Diolpate, Dolplas
Ciba-Geigy 1,2,3,4,5, 6A, 6F Reofos, Reomol,
Reoplast, Reoplex
Courtaulds 2
Lankro Chemicals 1,3,4,6A Lankroftex
ICI 1,4,6B Cerecior, Hexaplas
Robinson Bros 5 Arbeflex
Scott Bader 1,3,5 Crestapol
Shell Chemicals 1,6E Linevol, Dobane,
Dutrex
Tenneco 2
Victor Wolf 5,6C Wolftex
Austria
Chemie Linz 1 Mollan
Belgium
Argus Chemicals 6A Drapex
Essochem Europe 1 layftex
Monsanto Europe 1,2,4,5,6F Santicizer
UCB-FfAL 1,3,4,6F
Denmark
Scandiftex 1,3,4 Scandinol
France
CdF Chemie 1 Gedeflex
D'Electrofine-Chemie 6E
ICI Europa 1,3,4 Hexaplas
Nyco S.A. 6D,6F Nycoftex
Produits Chemie Ugine
Kuhlman Plastifiant K
Rhone-Poulenc Polymeres 1,2,4,5,6B Garbeflex, Garbefos,
Alaiftex
Italy
Akzo Italia 4,5,6C,6F Estaftex
Distillerie Italiane 1,4,5, 6A, 6F Diplast, Diepox,
Staftex (continued)
TABLE 5.2O--contd.
Montedison 1,4 Sicol

Sisas 1
Sprea 5 Spreaflex
The Netherlands
Akzo Chemie 6A Estabex
Unilever-Emery 4,5, 6A, 6C, 6F Emery, Plastolein,
Unem
Uraplast 1,4,5 Uraplast (formerly
Scadoplast)
Sweden
Berol Kerni 1,4
Switzerland
Reichhold Chemie 1,4,5, 6A, 6E, 6F Ricatyl, Contrastat
USA
ACS Technical Products 6A Epoxol
Armak 4, 6C,6F Kesscoftex
Ashland Chemicals 5
BASF Wyandotte 1,3 Plastomoll, Palatinol
Continental Oil 1
Crowley Chemical Co. 6E Viplex
Diamond Shamrock 6B Chlorowax
Dover Chemical 6B Chlorez
Eastman Chemical
International 1,3,4,5,6F Kodaftex, Texanol
Emery Industries 4,5, 6A, 6C, 6F Emery, Plastolein
Exxon Chemical 1,3 layftex
FMC 2, 6A, 6C Kronitex
C. P. Hall Co. 4,5,6F Paraplex, Plasthall
Harwick 1,4,6F Polycizer
Hercules 1,5, 6B, 6F Clorajin, Hercoftex,
Hercolyn
ICI Americas 6B,6F Cerecior, Hexplas
Keil 6B,6D
Mobay Corp. 2 Disftamoll
Monsanto 12,3,4,5, Arocior, Santicizer
6A, 6D, 6E, 6F
Morflex Chemical Co. 1,3,4,6F Citroftex, Morftex
Nuodex Inc. 1,3,4,6F Nuoplaz
Reichold 1,3,4,5, 6A, 6C, 6F Peroxidol, Staftex
Rohm & Haas 4,5, 6A, 6C, 6F Monoplex, Paraplex
Sherex 5,6A Admex b
5 Plasticisers 227
TABLE 5.2O-contd.

Stauffer Chemical Co. 2 Phosjiex
Swift 6A Epoxol
Tenneco 1,2,3,4,5 Nuoplaz
Union Carbide 2, 6A,6D F1exol
Union Camp 1,3,4,5,6C Unijiex
USS 1,3,4, 6A, 6C PX
Velsicol 6D Benzojiex
Witco Corp
Argus Chemical Div. 6A Drapex
Pearsall Chemical Div. 6B Flexchlor
West Germany
BASF 1,4,5,6F Palatinol, Plastomoll,
Palamoll
Bayer 1,2,4,5, 6E, 6F Adimoll, Disjiamoll.
Mesamoll, Vltra-
moll, Unimoll
Chemische Werke Hills 1,4, 6B, 6C, 6E Vestinol, Lipinol
Deutsche Texaco 1,3 Reproxal
Dynamit Nobel 1,3,4,5,6B,6C Witamol, Witador
Henkel & Cie 1,4,5, 6A, 6C Edenol
Hoechst 1,6B
Wacker-Chemie 1,4 Wacker
a 1, Phthalates; 2 phosphates; 3, trimellitates; 4, low-temperature plasticisers; 5,

polymerics; 6A, epoxies; 6B, chlorinated paraffins; 6C, monoesters; 6D, glycol esters;
6E, hydrocarbons; 6F, others.
b This plasticiser line bought by Nuodex Inc. in 1985.
processability, service performance and cost in a particular PVC

composition. The processing aspect is especially important in plas-
ticiser selection for PVC paste formulations, where the formulator
must take account of the need for suitable paste rheology, for a certain
(fairly high) minimum plasticiser content (dictated by the liquid nature
of the composition), and-in many cases--also for particular gelation
and fusion characteristics: these requirements will be evident from the
relevant discussion in Chapter 18. With other kinds of PVC composi-
tion, special considerations may include for example possible
difficulties presented by highly viscous polymeric plasticisers in powder
blending, or volatility of some plasticisers in calendering, where, for a
substantial portion of the processing time, the material is in the form
of a relatively thin, hot sheet.
The end-use criterion usually applied first in formulating is the
required softness and/or 100% modulus of the product, and the

overall plasticiser content is decided in relation to that, commonly
initially in terms of a general-purpose Cs phthalate. Partial substitution
or addition of any speciality plasticisers that may be needed for such
properties as improved low- or high-temperature performance, flame
retardance, stain resistance, rapid gelation, migration resistance, etc.,
is then planned, and the amounts calculated on the basis of equivalent
efficiency factors (cf. Section 5.4.2, and below). The properties of
various plasticiser types relevant to such further adjustment of a
formulation are indicated in Table 5.8. Depending on the nature of the
product, it may not be necessary to use a speciality plasticiser, but
merely to 'shade' the properties a little by using a related phthalate
from a different alcohol.
The desirability of a plasticiser extender (a chlorinated paraffin or a
hydrocarbon) and/or a filler would normally be considered next.
Once the above general points have been settled, more detailed
consideration must be given to the required balance of the various
relevant properties, so that the actual plasticiser levels and ratios can
be finalised. In general, the properties imparted to a pPVC composi-
tion by a mixed plasticiser system will normally tend to represent a
combination of the individual contributions by the system's com-
ponents in accordance with the proportions present. For highest
accuracy, the plasticiser ratios in a composite system should be
determined by volume (not weight).
As has been mentioned, comparisons of the effects of different
plasticisers in a formulation, and hence also decisions regarding
plasticiser replacement or part-substitution, are commonly made on
the basis of appropriate efficiency (effectivity) quantities (see Section
5.4.2 and Tables 5.7 and 5.21). The corollary, which should not be
overlooked, is that comparisons of different plasticisers at equal
efficiencies may yield results considerably different from those ob-
tained at equal plasticisation levels. This is illustrated by the data of
Table 5.21. Compare particularly DA79 P and DNP: at equal levels
(60 phr) the former plasticiser appears to provide much better low-
temperature properties; but at equal efficiency quantities the
difference is minimal.
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
5 Plasticisers 229
TABLE 5.21
Comparison of Plasticisers at Equal Concentration and Equal Efficiency
Plasticiser Efficiency Efficiency Properties at Properties at
concen- factor b 60phr efficiency
tration a concentration
Tensile Cold Tensile Cold

strength flex strength flex
(MNm-~ eC) (MNm-~ eC)
Dibutyl phthalate 54·0 0·85 17·0 -25 17·9 -21

Dioctyl phthalate 63·5 1·0 17-4 -23 15-9 -27·5
Di-iso-octyl phthalate 65·5 1-03 18·4 -22 17·1 -30
Di-Alphanol 79
phthalate 61·2 0·97 16·5 -25 15-9 -28
Dinonyl phthalate 74·2 1·17 19-4 -12·5 16·0 -24·5
Tritolyl phosphate 79·3 1·25 23-1 -1·5 17-6 -13
Trixylyl phosphate 83-1 1·31 23·5 +1 17·2 -12·5
Dibutyl sebacate 49·5 0·78 14·7 -56 16·9 -39
Dioctyl sebacate 58·8 0·93 16·1 -47 16·3 -46
Dioctyl adipate 59·9 0·94 16·6 -49 16·5 -49
a phr to give a 100% modulus of 6·9 MN m- 2 (1000 Ibfin- 2).

b Efficiency concentration divided by the efficiency concentration of DOP (63·5).
20 phr of it with DOA and yet retain the same modulus, then the
20 phr of TIP should be replaced by (see Table 5.21):
0·94
20 x - = 15·0 phr DOA
1·25
Even for the experienced PVC formulator the design of a compound

to perform a critical task can be difficult, because of the conflict in the
necessary properties that so often occurs. For example, plasticisers
which impart good low-temperature properties' will inevitably have
inferior oil-extraction resistance, and will lower the volume resistivity
of the composition: this obviously complicates the formulation of an
oil-resistant cable covering for use at low temperatures. Some 'theor-
etical' aids to formulating have been mentioned in Section 2.2.3 of
Chapter 2.
5.6.2 Softness and Tensile Properties
As has been mentioned the softness of a pPVC composition is an

important criterion in assessing plasticiser efficiency. The tensile
modulus at 100% elongation is also widely used in such assessments.
The tensile strength and elongation at break are sensitive to plasticiser
content (the first reducing and the second increasing with increasing
plasticisation) and-at equal plasticisation levels-also in some degree
to the nature of the plasticiser.
(a) Softness
In the rubber industry it is the hardness of a material that has been
traditionally measured, either on the BS scale (in the UK) or the
Shore Durometer scales* (especially in the USA), or more recently in
terms of the International Rubber Hardness scale (Method N of BS
903, Part A26: 1969, in technical agreement with ISO 48-1979; ASTM
D 1415-83). Each of these scales ranges from 0 to 100: the harder the
material the higher the number. However, in the case of PVC,
particularly in the UK, it is normal to employ the BS softness (BSS)
number scale, where the higher numbers represent greater softness
(cf. BS 2782, Part 3, Method 365A:1983-formerly Method 307A of
BS 2782: 1970). In practice the BS softness number may be deter-
mined either with a standard 'dead-load' precision laboratory instru-
ment (as in BS 2782, Method 365A: 1983) or with a spring-loaded
pocket instrument. The use, calibration, and limitations of pocket-type
instruments (BSS, IRH and Shore durometer) are covered by BS
2719: 1975. Such instruments, if properly used, are suitable for routine
checks of BS softness values of PVC materials, but not for standard
tests or strict 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. 5.7.
* ISO 868-1985 (identical with BS 2782: Part 3: Method 365 B:1981); ASTM
D 2240-85.
Two Shore durometer scales, are in use, A and D (respectively for softer and
harder materials), associated with two durometers of the same designations.
Scale A is applicable to most of the flexible PVC materials. Measurements
with Type D durometer should be made where values above 90 are obtained
with the Type A durometer, and Type A should be used for materials that
register less than 20 with the Type D instrument.
5 Plasticisers 231
50
40
30
BS softness number
(Depth of indentation'D' in Table 3 of BS903: part A26: 1969)
Fig.5.7 International Rubber Hardness and Shore A hardness at 20°C versus

BS softness number. e, International rubber hardness degrees (IRHD~BS
903: PART A26: 1969 (Table 3); x, Shore A duro meter hardness at 20°C.
Note: In the standard determinations of IRH, the relationship

between the depth of indentor penetration (P, mm) and the
Young's modulus of the material (M, MPa) is represented by
the expression (precise for substantially elastic, isotropic
materials):72,73
F/M = 1·9R 2 (P/R)1.35
where F is the indenting force in newtons and R the indentor
radius in mm.
Figures 5.8 and 5.9 show the variation of softness at room temperature
(23°C) with plasticiser level for nine common plasticisers, in terms of
BS softness number and Shore A hardness value respectively. As
100 4
80
'-
CI
.c 3
E
::l
60
C
I/)
I/)
CI
.5 40
g
III
III 20
0 20 40 60 80 100
Plasticis~r l~vQI, phr
100
80
'-
CI
.c
E 60
::l
C
I/)
I/)
CI 8
....c 40
'0
I/)
III
III 20
o 20 40 60 80 100
Plasticis~r l~v~l, phr
Fig. 5.8 Effect of plasticiser level on BS softness number. 1, DOP; 2, DIDP;

3, DTDP; 4, DOA: 5, Re%s 65 (Ciba-Geigy); 6, TOTM; 7, ESO; 8, PPA; 9,
PPA alcohol-endstopped.
5 Plasticisers 233
100
90
« 80
l:!0
.s::
III 70
3
60
2
50
0 20 40 60 80
Plasticis~r l~v~l, phr
100
90
« 80
ClI
'-
0
.s::
III 70
60
9
50
0 20 40 60 80 100
Plasticis~r I~V~I, phr
Fig.5.9 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.
softness varies considerably with temperature, the degree of variation

depending on the plasticiser type and content, it is possible to
formulate for a desired softness at a particular temperature. Figure
5.10 shows the effect of increasing temperature on the softness of a
PVC composition plasticised with DOP at three concentrations.
Compounds based on different plasticisers, if formulated for equal
softness at one temperature, may differ at another.
(b) Tensile Strength and Elongation at Break

The effects of plasticiser type and concentration on tensile strength
and elongation at break are shown in Figs 5.11 and 5.12 respectively.
These properties also vary with temperature.
IS
130
120
110
100
L
Of
.0
E
...
z"
Of
70l
I
5
0
U)
60~
I
I
U)
ID I
SO:
40j
i
I
30~
201
10
1
, I I ,
20 30 40 SO 60 70 80
Temp«raturc. °c
Fig. 5.10 BS softness of a PVC composition versus temperature, at three

DOP content levels.
5 Plasticisers 235
25
20
-
N
E
z
l:
15
....01
.c
c:
CI
!..
'lii 10
~
'iii
c:
{!.
5
o 20 40 60 BO 100
Plasticiser level, phr
25
20
-
N
E
z
~
~15
....
.s::
01
c:
~
'lii 10
~
'iii
c:
{!.
5
o 20 40 60 BO 100
Plasticiser level, phr
Fig. 5.11 Effect of plasticiser level on tensile strength. 1, DOP; 2, mDP; 3,

DTDP; 4, DOA; 5, Reolos 65; 6, TOTM; 7, ESO; 8, PPA; 9, PPA
alcohol-endstopped.
500
4
1
.-
.,e
400 2
3
.>L.
ra
~ 300
.0
1ii
c
0
~200
01
c
.2
w
100
o 20 40 60 80 100
Plasticisar laval, phr
500
400
.>L.
ra
~ 300
.0 5
1ii 6
~~
c
o
:;:; 200
ra
01
c 8
o
W
100
o 20 40 60 80 100
Plasticisar laval» phr
Fig. 5.12 Effect of plasticiser level on elongation at break. 1, DOP; 2, DIDP;

3, DTDP; 4, DOA; 5, Re%s 65; 6, TOTM; 7, ESO; 8, PPA; 9, PPA
alcohol-endstopped.
5 Plasticisers 237
5.6.3 Low-Temperature Properties

Plasticisation improves the low-temperature performance of PVC, but
the degree of improvement depends on both the concentration and the
nature of the plasticiser (cf. Fig. 5.13 and Table 5.22). As an example
of the concentration effect, if the level of plasticisation of the
compositions represented in Fig. 5.13 was increased, the curves would
be displaced to the left without substantial change in their shapes and
gradients (the latter two features being governed primarily by the
nature of the plasticisers).
It follows that a particular low-temperature performance of a pPVC
material can be formulated for by appropriately selecting, and where
necessary combining, the plasticisers (cf. for example Table 5.22). The
low-temperature properties of pPVC are very often assessed by tests
which essentially determine the stiffness in torsion at low (and usually
progressively reducing) temperatures. A test widely used in the UK is
the cold-flex test (Clash and Berg) of BS 2782: Method 150B: 1796. * In
,,
..... ......
- 50 -~o -30 - 20 -10 o 10 20 30 ~o so

TEMPERA TURE (·el
Fig. 5.13 Log rigidity modulus versus temperature for pPVC compositions
containing four common plasticisers at 54 phr. 1
* A revised version of the original specification BS 2782: 1970 Method 104B.

In the original method the deflection through 200 was regarded as equivalent
0
to a modulus of rigidity of 1655 kgf cm- 2 •

~
00
~
~
TABLE 5.22
Effect of Linevol Phthalates and Adipates on Low-Temperature Properties of Identical PVC Formulations4 ~.
Linevol 79 adipate/ Linevol 911 adipate/ 2-EH-adipate/ ~
Linevol 79 phthalate Linevol 911 phthalate 2-EH -phthalate .g
(phr) (phr) (phr) '"
::!-.
.~
50/0 30/20 20/30 0/50 50/0 30/20 20/30 0/50 50/0 30/20 20/30 0/50
Cold-flex temperature g~
(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 100°C §
(BS 2782: 1970 M 104 B), °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.
:g
r
5 Plasticisers 239
terms of this test, the cold-flex temperature is that temperature at

which, under a specified torque, the test specimen is deflected through
an arc of 200°. The closely related test of Method 150A is also in use.
These, and other relevant test methods are discussed in Section 24.3
of Chapter 24. Figure 5.14 illustrates the effects of plasticiser nature
and concentration upon the results of the cold-flex test.
5.6.4 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. 5.15.
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 fre-
quencies are successfully utilised in the high-frequency welding of PVC
sheet (see Chapter 21, Section 21.2.6).
Outside the area of electrical insulation, low values of resistivity,
particularly surface resistivity, are often beneficial in reducing prob-
lems of static build-up (cf. Chapter 9, Section 9.2.3). A good review of
the electrical properties of polymers and the effect of plasticisers has
been made by Coulson. 74
5.6.5 Flammmmabitity
Many plasticisers (e.g. phthalates, trimellitates, polymerics, and
others) increase the flammability of the pPVC compounds by
effectively diluting the PVC polymer, which is inherently not readily
flammable. Others, like phosphates and chlorinated paraffins and
olefins, do not have this effect. This subject is covered-among other
related topics-in the discussions of flammability of PVC materials in
Chapters 9 and 24.
5.6.6 Permmanence Properties
Plasticiser(s) of unsatisfactory permanence may be lost in substantial
amounts from a pPVC material-to the detriment of its properties-
through volatilisation (volatile loss), extraction, or migration.
20
10
.
lJ
t:J~
0
...ro
'-
::J -10
'-
t:J
a. -20
E
...
t:J
x -30
.£!
....
"U -40 3
"0 2
lJ
-50
-60
0 20
Plasticiser level,
20
10
.
lJ
~
o
~ -10
...ro
::J
; -20
a.
E
2 -30
x
t:J
;;:: -40
"U
"0
lJ -50
-60~----~----.-----.-----r----'
o 20 40 60 80 100
Plasticisllr level, phr
Fig. 5.14 Effect of plasticiser level on 'Clash and Berg' low-temperature

flexibility (BS 2782: 1970, Method 104B: N. B. Current revised version, BS
2782, Method 150B: 1976). 1, DOP; 2, mDP; 3, DTDP; 4, DOA; 5, Re%s
65; 6, TOTM; 7, ESO; 8, PPA alcohol-endstopped; 10, ~9P,
5 Plasticisers 241
E
u
a
;: 10'3
>
....
I/)
I/)
~
~ 10'2
;:)
-'
~
10'O .......~_ _--L_ _ _- ' -_ _ _..L..._

40 50 60 70
PLASTICISER CONTENT (phr)
Fig. 5.15 Effect of plasticiser type and level on volume resistivity at 23°C. 1
(a) Volatile Loss

The rate of plasticiser loss by volatilisatioJ,1 is controlled by its rate of
evaporation at the surface, which normally leads (i.e. is faster than)
the rate of diffusion through the solid material to reach the surface.
Although at room temperature the volatilisation of even the general-
purpose plasticisers is relatively slow, over long periods of service their
volatile loss from, for example, PVC upholstery or other kinds of
leathercloth (which, by their nature have a high surface-to-volume
ratio) can be quite high, leading to such undesirable manifestations of
'ageing' as hardening and cracking. For best results, low-volatility
plasticisers should be used in formulations that are to be resistant to
volatile loss: such plasticisers are the polymerics, trimellitates, and
pentaerythritol esters.
Figure 5.16 illustrates the well-known fact that with monomeric
plasticisers volatile loss tends to be reasonably linear with time up to
fairly high loss levels, whereas with polymeric plasticisers the tendency
40
30
200 400 600 800 1000

Hours at 100 0
Fig. 5.16 Volatile loss of some monomeric and polymeric plasticisers from
pPVC compositions.
is for the loss to stabilise at a relatively low value (after the

low-molecular-weight 'tails' have been lost) and remain at this level for
an extended period.
Laboratory determinations of volatile losses by oven tests at
elevated temperatures, and their assessment by determination of the
resultant physical property changes (ageing), are discussed in Chapter
24.
Note: The apparently characteristic changes in physical properties

may not necessarily indicate just loss of plasticiser; particu-
larly when the ageing tests are carried out at high tempera-
tures, oxidation of plasticiser and cross-linking and/or chain
scission of the polymer molecules can also be involved. In
such cases, the inclusion of an antioxidant in the composition
may appear to reduce plasticiser volatility.
Two important practical cases exemplifying some consequences of

volatile loss of plasticisers are automotive fogging and the ageing of
cable coverings.
5 Plasticisers 243
AUTOMOTIVE FOGGING
This is the build-up of an oily condensation or fog on car windscreens
and other parts of the car interior. The problem was originally
attributed entirely to volatile plasticisers, but later numerous analyses
of the deposits by a number of laboratories implicated substances of
other origin, in addition to plasticisers from PVC crash-pads and
leathercloth. These include plasticisers from adhesives, certain
pigment-dispersing media, catalyst residues and other components of
polyurethanes, some antioxidants, components of some stabiliser
systems, * and even airborne hydrocarbons, as well as minor impurities
such as residual emulsifiers in the polymer, or free-alcohol residues in
plasticisers.
There are several fogging tests in use, and a number of different test
temperatures, e.g. 60, 75 and 90°C, depending on the car
manufacturer's quality control policy and on the part of the car and
the conditions for which the material's are destined. t The test
requirements are normally in terms of a stated, high light reflectance
from a surface exposed to possible fogging in the test treatment (a
fogging deposit reduces reflectance).
The most stringent tests-as carried out for example on crash-pad
and window-visor components-involve temperatures as high as 90°C,
with a minimum reflectance requirement of 90%. To pass these tests
the PVC composition must be formulated 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. Ordinary polymeric plasticisers are not generally
suitable 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 Cs alcohol from the finished
product than C lO-C 14 alcohols.
Some typical basic formulations designed to pass the Volvo fogging
test at 60, 75 and 90°C have been cited by Buszard. 1
* Some manufacturers offer special grades of low-fogging stabilisers. For

example, Sicostab B241 (BASF) liquid barium/zinc stabiliser is claimed to
meet all test requirements, even at 90°C.
t For example, the so-called 'Arizona Parking Lot Test' is intended to simulate
conditions inside a closed car in a sunny car park, with interior temperature
reaching 60°C.
PLASTICISATION OF CABLE COVERINGS

The choice of plasticiser for cable coverings is dependent upon the
service conditions to be catered for. General-purpose insulation and
sheathing compounds based on Cs phthalates, often with chlorinated
paraffin extenders, are normally limited to a maximum continuous
service temperature of 60-65°C. For continuous operation at higher
temperatures, low-volatility plasticisers must be used, e.g. DIDP or
perhaps a selected phosphate plasticiser for a maximum rating of 75°C.
For 90°C cables DTDP is preferred. Trimellitates, polymerics, or
pentaerythritol esters are required for 105°C rated cables. The tem-
perature resistance of cable coverings and some of the tests for its
determination are discussed further in Chapter 24.
(b) Extraction Resistance

This is possessed in the highest degree by polymeric plasticisers (whose
efficiency is, however, generally somewhat lower than that of the
monometrics). Some of the most relevant points are brought out by
the data of Table 5.23. Inter alia, the figures illustrate the particularly
good resistance to non-polar extractants (hexane and oils) of a
high-molecular-weight, non-endstopped polymeric plasticiser (Diolpate
150). The endstopped polymerics Diolpate 214 and 217 show less
resistance to non-polar solvents, but better resistance to aqueous
extractants and also superior compatibility, especially at high humi-
dity, and greater efficiency. The endstopped, mixed adipate/phthalate
polymeric Diolpate 171 exhibits reasonable extraction resistance and
improved processing behaviour, both with respect to lower plastisol
viscosities and faster gelation.
It should be noted that complete gelation (fusion) of the PVC
composition in processing is essential to securing the good resistance
to extraction and migration of which polymeric plasticisers are
capable. The high-molecular-weight non-endstopped products are
particularly dependent on completeness of fusion in this respect: if the
achievement of full gelation cannot be guaranteed in a particular
compounding/processing operation, then it is preferable either to use
an endstopped polymeric plasticiser of lower molecular weight, or to
include in the formulation a proportion of a rapid-gelling plasticiser,
such as triaryl phosphate. As can be seen from Table 5.23, the
replacement of an alkyl by an aryl group in a dialkyl phthalate reduces
the non-polar extraction resistance of the plasticiser. Triaryl phos-
phates and epoxidised soya bean oil exhibit extraction resistance
TABLE 5.23
Properties and Extraction Resistance of Plasticisers at 60 phr
DOP BBP TXP ESO Diolpate Diolpate Diolpate Diolpate
150 171 214 917
Viscosity at 25°C, St 0·5 0·6 0·9 5 130 9 35 41 v.

BS softness no. 45 43 41 41 28 42 41 44 "tj
Cold-flex temperature, °C -20 -12 +2 -12 -3 -6 -7 -4
Tensile strength, MN m- 2 11·5 20·3 16·5 18·0 17·4
If
1';.
17·8 18·7 16·9
!.O.
Elongation at break, % 335 195 280 365 320 315 330 350
Volatile loss, % 22·5 16·3 6·9 9·0 2·9 3·6 3·4 3·3
'"t:I
Extraction loss, %
Hexane 35 14·0 15·5 18·6 1·2 7·6 2·9 2·4
Mineral oil 15·8 12·4 6·7 10·7 +0·5 7·3 2·1 1·9
Olive oil 23·5 15·4 9·6 14·5 3·1 9·8 5·8 3·8
Water 0·1 0·5 +0·3 0·1 1·6 0·4 0·3 0·1
Soap (1%) 12·8 19·6 21·2 4·1 7·2 8·2 2·7 2·9
~
phates and epoxidised soyabean oil exhibit extraction resistance

intermediate between the dialkyl phthalates and the polymeric
plasticisers.
Solid polymeric modifiers can successfully replace high-molecular-
weight polymeric plasticisers in some applications for maximum
extraction resistance, but it should be remembered that their efficiency
is considerably lower (cf. Table 5.24).
Specimen thickness is a factor significantly influencing the results of
extraction tests: the results are higher with (i.e. more plasticiser is
extracted from) thick specimens than thin ones. This effect is
associated with the way diffusion proceeds under the concentration
gradient set up in the specimen undergoing extraction (in a thick
specimen the gradient is relatively steep, with a greater reservoir of
plasticiser in the interior). Where test results are expressed in terms of
weight of plasticiser extracted per area of specimen, with related
maximum requirements formulated on this basis, * a particular PVC
TABLE 5.24
Physical Properties of a PVC Compound Con-
taining a Solid Polyurethane Elastomer-
Durelast l00a
BS softness no. 45
Cold-flex temperature, °C -22·5
100% modulus, MN m- 2 5·6
Tensile strength, MN m- 2 15
Elongation at break, % 530
Tear strength, kN m- 1 59
Volatile loss, % 0;2
Extraction loss, %
Hexane +0·3
Mineral oil +0·1
Olive oil -0·1
Water +0·7
Soap (1%) +0·4
Formulation: PVC 100
Durelast 100 100
ESO 10
Cd stearate 6
a Trade name of Briggs & Townsend.
* Compare for example the upper limit of 10 mg dm -2 in the original EEC
Draft Directive75 on overall migration of additives from plastics food-
packaging materials when tested in contact with the range of food simulants
(distilled water, aqueous citric acid, aqueous alcohol, and olive oil).
5 Plasticisers 247
composition may meet the requirements when tested in one thickness,

but may fail at a higher specimen thickness.
Note: In practice it may be necessary to reformulate if the

practicable material thickness is limited, as was done in the
case of a thin PVC cling film which-before the introduction
of a polymeric plasticiser on reformulation (see Table 5.25)--
failed the EEC test in respect of extractability with olive oil.
(c) Migration Resistance

Migration is the transfer of plasticiser from a PVC material into
another material (which may occasionally also be PVC, of a different
composition) when the two materials are in surface contact. The
transfer takes place by diffusion, and thus the main factors governing
its rate and final extent will be the chemical make-up and molecular
size and shape of the plasticiser, its concentration gradient, the
temperature, the chemical nature and morphology of the recipient
material, and the intimacy of its surface contact with the PVC donor
material. The effects of some of these factors are illustrated by the
data of Table 5.26.
In many applications of pPVC materials, the migration resistance of
their constituent plasticisers is an important consideration. For ex-
ample, 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 its adhering to the gasket. Other examples include PVC
TABLE 5.25
Reformulation of Stretch Wrap PVC Food-Packaging Films to Include a
Polymeric Plasticiser
Old New
formulation formulation
PVC suspension polymer 100 100

DOA 25 10
Reoplex 430 (Ciba-Geigy) 20
ESO 5 5
Ca/Zn stabiliser 3 3
Antifogging agents 1 1
Overall migration resistance into
olive oil (10 days at 40°C), mg dm- 2 32 9
TABLE 5.26
Migration Resistance of Plasticisers"
Cellulose Natural Polyethylene

nitrate rubber
PPS 2·7 2·9 0·1

PPA 2·2 1·0 0·34
PPS/ acid-endstopped 9·1 o 0·3
PPA/ acid-endstopped 10·7 2·5 0·7
PPA/ alcohol-endstopped 6·4 0·7 0·1
Epoxidised oil 9·1 1·3 0·25
DOP 14·1 11·0 2·2
a Method according to DIN 53 405-1981.
cables in contact with plastics electrical appliance cases, self-adhesive

PVC films, insulation tapes and the adhesion of print and lacquer to
PVC films.
For practical test purposes, migration resistance is usually deter-
mined by the method of DIN 53405-1981 or the closely similar ISO
177-1976. In both methods, pre-weighed discs of the pPVC composi-
tion to be tested are sandwiched between similar discs of the relevant
plastics material, and the sandwich-placed between glass plates with
a weight on top-is heated for a prescribed period in an oven at 70°C
(the revision document for the ISO specification-ISO/DIS 177·2-
currently in train allows two other temperatures if relevant: viz. 50°C
or 85°C). The loss of weight by the PVC discs and the gain by the
recipient material are then determined.
(d) High-Humidity Compatibility

Many plasticisers which have good compatibility under normal condi-
tions of usage can exhibit severe incompatibility under conditions of
high humidity, e.g. in refrigerators or in tropical climates. Non-
ends topped polymeric plasticisers such as polypropylene adipate are
particularly bad in this respect. Phosphate plasticisers exhibit very
good compatibility at high humidity.
5.6.7 Stain Resistance
Flexible PVC is susceptible to staining by many different substances

and compositions, but particularly those that are based on oils or
oleophilic solvents (e.g. ball-point pen ink, shoe polish, tar, etc.). It
5 Plasticisers 249
has been shown that the degree of staining increases with the
plasticiser content, and that at equal levels of softness the type of
plasticiser is also important. 1 Plasticisers which give reduced levels of
staining are 2,2,4-trimethyl-l,3-pentanediol di-isobutyrate (e.g.
Kodafiex TXIB; Eastman Chemicals), the monoisobutyrate monoben-
zoate ester of the above diol (e.g. Nuoplaz 1046; Tenneco), benzyl-
butyl phthalate (e.g. Santicizer 160; Monsanto), and triaryl phosphates
(e.g. Reofos 50). The major applications where stain resistance is
important are in PVC flooring, and, to a lesser extent, in wall
coverings and claddings.
5.6.8 Resistance to Weathering and Photodegradation
Although these properties of PVC materials depend primarily upon

the stabiliser system (see Chapter 4), they are also influenced by the
plasticisers in pPVc. The following are among the manifestations of
weathering in which plasticisers playa part.
(i) Discolouration (which may be accelerated by photo-oxidation
of a plasticiser).
(ii) Loss of fiexibility-due to loss of plasticiser by volatilisation,
extraction or photo-oxidation.
(iii) Surface tackiness. This is usually due to plasticiser exuding to
the surface, frequently as a result of its partial exclusion from
the polymer undergoing some cross-linking in the course of
photodegradation-see Section 4.1.3 of Chapter 4. The exuda-
tion is most frequent with plasticisers containing carbon-carbon
double bonds, chlorinated paraffins or high levels of epoxy
compounds [which may also partly lose their compatibility with
PVC as their oxirane groups are used up while discharging the
stabilising action of which they are capable: see Chapter 4,
Section 4.3.5(c)].
(iv) Dirt pick-up. This is often promoted by (iii), and is particularly
a problem with PVC-coated steel used in outdoor cladding.
(v) Sensitisation of the PVC polymer and promotion of its
dehydrochlorination, by transfer to the polymer of free radicals
first formed in the plasticiser. 76 For compositions plasticised
with DOP, DOA and BBP it has been confirmed77 that this
promotion of dehydrochlorination depends on the extent of
sorption of solar-radiation photons by the plasticiser (and hence
on the nature and amount of plasticiser present).
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.
Aromatic phthalates such as BBP have markedly poorer light stability
than dialkyl phthalates.
Some aspects of the weathering resistance of PVC, and its evalua-
tion, are also discussed in Chapter 24.
5.6.9 Resistance to Biological Attack
The resistance of PVC materials, including plasticised compositions, to

microbiological attack (by fungi and bacteria) and to insect and animal
depredations is discussed in Chapter 24.
5.7 TOXICITY AND HEALTH ASPECTS
5.7.1 Plasticisers in Food-Contact and Medical Applications
It is particularly important that all formulation constituents used in

PVC materials for these applications should be non-toxic and non-
carcinogenic. Regulatory measures exist in most countries, but they
are by no means identical. In the USA, for example, only those
additives may be used which are specifically permitted by the Food
and Drugs Administration (FDA). In the UK and West Germany
there is currently no list of specifically, legally approved materials, but
voluntary observance is assumed of recommendations issued by the
British Plastics Federation (BPF) and the Kunststoff-Kommission des
Bundesgesundheitsamtes (BGA) respectively. These recommenda-
tions are in line with the relevant Council of Europe or EEC directives
that are coming into being. It is essential that, for detailed up-to-date
relevant information, the user of plasticisers should consult the
plasticiser manufacturer or the national or international organisation
concerned.
The possible carcinogenic effects of the most common plasticisers
5 Plasticisers 251
have been the subject of several investigations. 1 Whilst the question is

not yet completely settled, the balance of all currently available
evidence strongly supports the conclusion that the two plasticisers-
DOP and DOA-most closely investigated because of their wide use,
present no demonstrable direct carcinogenic or toxic risk to man in the
quantities in which they are likely to migrate into foodstuffs packed in
pPVC materials. This view is embodied also in the informed response
by the BPF78 and the UK Ministry of Agriculture, Fisheries and Food79
to certain fairly recent sensationalist claims about the alleged cancer or
toxic risks supposedly presented by the migration of plasticisers-
especially DOA-from PVC cling film into foods.
5.7.2 Plasticiser Handling and Processing
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
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 5.27 indicates the
concentration of plasticiser vapour which could occur in saturated air
at 160°C. Laboratory experiments80 and actual measurements on
industrial plastisol coating plants indicate that 25-50 kg h- 1 of plas-
ticiser could be lost by volatilisation alone. This indicates the need for
good ventilation if the threshold limit value (TL V) of 5 mg m -3 is to be
met; this is considered to be the safe maximum concentration by the
American Conference of Governmental Industrial Hygienists81 and
adopted by the US Health and Safety Administration (OHSA).
TABLE 5.27
Vapour Pressure of Dialkyl Phthalates
Plasticiser Molecular Vapour Concentration in

weight pressure saturated air
(mmHg) at 160°C (g m- 3 )
DBP 278 1·2 12

DOP 390 0·121 1·75
DIDP 447 0·029 0·48
TABLE 5.28
Standards Relevant to the Properties and Testing of Plasticisers and Their
Etfects in PVC

no.
Designation Subject (not necessarily
the official title)
Bulk properties
1 ISO 1385-1977 Parts 1-5 Phthalate esters for industrial use
Method of test: (1) general; (2)
colour after heating; (3) ash
determination; (4)
determination of acidity; (5)
determination of ester content.
2 ISO 2520-1974 Tritolyl Phosphate for Industrial
Use-List of test methods
Use-Determination of acidity
Use-Determination of
apparent free phenol content
5 ISO 2523-1974 Adipate Esters for Industrial
use-Methods of test
Use-Measurement of colour
after heating
Use-Determination of acidity
Use-Determination of ash
Use-Determination of ester
content
10 BS 573: 1973 (1987) Dibutyl phthalate
11 BS 574: 1973 (1987) Diethyl phthalate
12 BS 1995: 1973 (1987) Di-(2-ethylhexyl) phthalate
13 BS 1996: 1973 (1987) Dimethyl phthalate
14 BS 1997: 1973 (1987) Glycerol triacetate (triacetin)
15 BS 1998: 1970 (1987) Triphenyl phosphate
16 BS 1999: 1964 Tritolyl phosphate
(±ISO 2520/2)
17 BS 2535: 1973 (1987) Dibutyl sebacate
18 BS 2536: 1973 (1987) Di-(2-ethylphenyl) sebacate
19 BS 3647: 1973 (1987) Dimethoxyethyl phthalate
20 BS 4835: 1973 (1987) Methods of Test for Plasticiser
Esters (±ISO 1385 and 2524)
5 Plasticisers 253
TABLE 5.28--contd.

no.
the official title)
21 BS 4968: 1973 Di-isobutyl phthalate, di-iso-octyl

phthalate and di-iso-octyl
sebacate
22 ASTM D 1045-86 Sampling and Testing Plasticisers
Used in Plastics
23 ASTM D 1249-81 Specification for Octyl
Orthophthalate Plasticisers
24 ASTM D 2288-69 (1980) Test for Weight Loss of
Plasticisers on Heating
25 DIN 53 400 (1970) Testing of Plasticisers:
(under revision since 1985) Determination of Density,
Refractive Index, Flash Point
and Viscosity
26 DIN 53 401 (1985) Plasticisers: Determination of
saponification value
acid value
saponification rate (Withdrawn
in 1984)
29 DIN 53 409 (1967) Plasticisers and Solvents:
Determination of Hazen colour
(platinum cobalt colour,
APHA method)
Properties in association with PVC (Compatibility; Volatility; Migration)

30 ISO 176-1976 Plasticiser Loss from Plastics
(Activated Carbon Method)
31 ISO 177-1977 Plastics-Determination of
migration of plasticisers
32 BS 2782: Part 4 Plasticiser Loss (Activated
Methods 465 A Carbon Method) (=ISO 176)
and B: 1979 (1986)
33 BS 2782: Part 5 Effect of PVC Compound on the
Method 511 A: 1970 Loss Tangent of Polyethylene
34 ASTM D 1203-67 (1981) Volatile Loss of Plasticisers from
Plastics (Activated Carbon
Methods)
(continued)
TABLE 5.28-contd.

no.
the official title)
35 ASTM D 2134-66 (1980) Test for Softening of Organic

Coatings by Plastic
Compositions (e.g. effect of
plasticisers from pPVC on
nitrocellulose lacquers)
36 ASTM D 2383 88 Standard Practice for Testing
Plasticiser Compatibility in
pPVC under Humid Conditions
37 ASTM D 3291-74 (1980) Test for Compatibility of
Plasticisers in PVC Plastics
under Compression
38 ASTM D 3421-75 Extraction and Analysis of
Plasticiser Mixtures from Vinyl
Chloride Plastics
39 DIN 53 405 (1981) Determination of Migration of
Plasticisers
40 DIN 53 407 (1971) Determination of Loss of Weight
of Plasticised Plastics by the
Activated Carbon Method
41 DIN 53 408 (1967) Determination of Solubility
Temperature of PVC in
Plasticisers
Effects on PVC
42 ISO 4574-1978 PVC Resins-Determination of
Hot Plasticiser Absorption
43 ISO 4608-1084 Vinyl Chloride Homopolymers
and Copolymers: Determination
of Plasticiser Absorption at
Room Temperature
44 BS 2782: Part 4 Determination of Plasticiser
Method 454 E: Absorption at Room
1978 (1984) Temperature by PVC Resins
(""ISO 4608)
45 ASTM D 2396-79 (1985) Powder-Mix Test for PVC Resins
in a Torque Rheometer
46 ASTM D 3367-75 (1986) Test for Plasticiser Sorption by
PVC Resins under Applied
Centrifugal Force
47 DIN 53408 (1967) Determination of the Solubility
Temperature of PVC in
Plasticisers
5 Plasticisers 2'55
5.8 STANDARDS RELEVANT TO PLASTICISERS
The standards (some of which have already been mentioned in this

chapter) are listed in Table 5.28. The extraction of plasticisers from
PVC compositions, and their determination, are dealt with in Section
2.4 of Chapter 2.
REFERENCES
1. Buszard, D. L. In PVC Technology, 4th edn, W. V. Titow. Elsevier

Applied Science Publishers, London and New York, 1984, Ch. 5, 6 and 7.
2. ISO 472-1979. Plastics-Vocabulary.
3. ASTM D 883-86b. Standard Terms and Definitions Relating to Plastics.
4. BS 1755. Glossary of Terms Used in the Plastics Industry. Part I: 1982,
Polymer and Plastics Technology.
5. Kirkpatrick, A., J. Appl. Phys., 11 (1940) 255.
6. Clark, F. W., Chem. Ind., 60 (1941) 255.
7. Barron, H., Plastics (London), 7 (1943) 449.
8. Doolittle, A. K., The Technology of Solvents and Plasticisers. John Wiley,
New York, 1954, Ch. 14 and 15.
9. Doolittle, A. K., Plasticiser Technology, ed. P. F. Bruins. Reinhold, New
York, 1965, Ch. 1.
10. Leuchs, D., Kunststoffe, 46 (1956) 547.
11. Ghersa, P., Mod Plast. 36(2) (1958) 135.
12. Horsley, R. A. In Progress in Plastics, ed. P. Morgan. Iliffe, London,
1957, p. 77.
13. Tabb, D. L. & Koenig, J. L., Macromolecules, 8 (1975) 929.
14. Jacobson, U., Brit. Plast., 32(4) (1959) 152.
15. Robeson, L. M., Polym. Engng Sci., 9 (1969) 277.
16. Robeson, L. M. & Faucher, J. A., J. Polym. Sci. B, 7 (1969) 59.
17. Bohn, L., Kunststoffe, S3 (1963) 826.
18. Nakamura, K., Hashimoto, F., Nakanishi, M., Kinjo, N., Komatsu, T. &
Nakagawa, T., Proc. 5th Int. Congo Rheol., 1970, p. 409.
19. Kinjo, N. & Nakagawa, T., Polym. J. 4(2) (1973) 143.
20. Pezzin, G., Ajroldi, G. & Garbuglio, D. M., J. Appl. Polym. Sci., 11
(1967) 2553.
21. Pezzin, G., Ajroldi, G., Casiraghi, T., Garbuglio, C. & Vittadini, J., J.
Appl. Polym. Sci., 16 (1972) 1839.
22. Sears, J. K., Darby, J. R. & Touchette, N. W. Paper presented at the
12th Ann. It. Tech. Meeting of Sabine Area AICHE and the Texas-
Louisiana Gulf ACs, Orange, Texas, 1965.
23: Darby, J. R. & Sears, J. K. In Encyclopedia of Polymer Science and
Technology, Vol. 10, ed. H. F. Mark et al. Interscience, New York, 1969.
24. Van Veersen, G. J. & Dijkers, J. L. c., Kunststoffe, 64 (1974) 292.
25. Mazzur, R. P., SPE Tech. Papers, 13 (1967) 177.
26. Graham, P. R & Darby, J. R, SPE J., 17 (1961) 91.

27. Van Veersen, G. J. & Meulenberg, A. J., SPE Tech. Papers, 18 (1972)
314.
28. Luther, H., Glander, F. O. & Schleese, E., Kunststojfe, 29 (1963) 409.
29. Touchette, N. W., Seppala, H. J. & Darby, J. R, SPE 20th Ann. Tech.
Con/., January 1964.
30. Bessant, K. H. c., Dilke, M. G., Hollis, C. E. & Millane, J. J., J. Appl.
Chem., 2(9) (1952) 501.
31. Juijn, J. A., Crystallinity in Atactic Polyvinyl Chloride. J. A. Pasmans,
s'Gravenhage, 1972, Ch. 4, p. 42.
32. Lehame, S. A., Park, G. S. & Norman, R. H., Brit. Polym. J., 11 (March
1979) 7.
33. Gee, G., Trans. Faraday Soc., 42B (1946) 33; 42 (1946) 585.
34. Doty, P. & Zable, H. S., J. Polym. Sci., 1 (1946) 90.
35. Burrell, H., Interchem. Rev., (Spring 1955) 3.
36. Brydson, J. A., Plastics, 26 (1961) 107.
37. Gardon, J. L. In Encyclopedia of Polymer Science and Technology,
Volume 3, ed. H. F. Mark et al. Interscience, New York, 1969, p. 833.
38. Small, P. A., J. Appl. Chem., 3 (1953) 71.
39. Fedors, R F., Polym. Engng Sci., 14 (1974) 147.
40. Koenhen, D. M. & Smoulders, C. A., J. Appl. Polym. Sci., 19 (1975)
1163.
41. Severs, F. T. & Smitmans, G., Paint Varnish Prod., 47 (1957) 54.
42. Thinius, K., Plaste u. Kaut., 5 (1958) 52.
43. Anagnostopoulos, C. E., Coran, A. Y. & Gamrath, H. R. J. Appl.
Polym. Sci., 4(11) (1960) 181.
44. DIN 53408-1967 Determination of solubility temperature of polyvinyl
chloride (PVC) in plasticisers.
45. Bigg, D. C. H., J. Appl. Polym. Sci., 19 (1975) 3119.
46. Anagnostopoulos, C. E., Coran, A. Y. & Gamrath, H. R., Mod. Plast.,
43 (1965) 141.
47. Bigg, D. C. H. & Hill, R. J., J. Appl. Polym. Sci., 20 (1976) 565.
48. Van Veersen, G. J. & Meulenberg, A. J., Kunststojfe, 57 (1967) 561.
49. Van Veersen, G. J. & Meulenberg, A. J., Kunststojfe, 56 (1966) 23.
50. Wiirstlin, F. & Klein, H., Kunststojfe, 46 (1956) 23.
51. Jasse, B., RGCP Plastiques, 5(6) (1968) 393.
52. Bell, K. M. & McAdam, B. W., Kunststojfe, 57 (1967) 26.
53. McKinney, P. V., J. Appl. Polym. Sci., 9 (1965) 3359.
54. Paul, K. T., RAPRA Members J., (November 1973) 273.
55. Chemical Industry Bibliography. Published annually by Brabender OHG,
Duisburg, FRG.
56. Immergut, E. H. & Mark, H. F., ACS Adv. Chem. Series, 48 (1965)
Ch. 1.
57. Jones, H., Hill, A. & Williamson, I., Plast. Inst. Trans., (1950) 18.
58. Frey, H. E., Kunststojfe, 46 (1956) 81.
59. Reed, M. c., J. Polym. Sci., 2 (1947) 115.
60. Reed, M. C. & Connor, L., Ind. Engng Chem., 40 (1948) 1414.
61. Quackenbos, H. M., Ind. Engng Chem., 46 (1954) 1335.
5 Plasticisers 257
62. Small, P. A., J. Soc. Chern. Ind. Lond., 66 (1947) 17.

63. Royen, M., Bull. Am. Soc. Test. Mat., 243 (1960) 43.
64. Knappe, W., Kunststoffe, 52 (1962) 387.
65. Knappe, W., Z. Angew. Phys., 6 (1954) 97.
66. Hellwege, K. H., Knappe, W. & Lohe, P., Koll. Zeit., 179(1) (1961)
40-9.
67. Titow, W. V. In Penn's PVC Technology, 3rd edn, ed. W. V. Titow & B.
J. Lanham. Applied Science Publishers, London, 1971, pp. 85-8.
68. Buszard, D. L., Chern. Ind., 16 (1978) 610.
69. Sherwood, M., Chern. Ind., 24 (1982) 994.
70. Moseley, J. & Dawkins, P., Chern. Ind., 16 (1978) 620.
71. Hull, E. H. & Mathur, K. K., Mod. Plast. Int., 14(6) (1984) 42-5.
72. ASTM D 1415-83, Standard test method for rubber property-
International hardness.
73. BS 903 (Methods of testing vulcanised rubber): Part A26 (Determination
of hardness): 1969, Appendix A (Relation between IRHD and Young's
modulus).
74. Coulson, S. H. In Plasticisers, Stabilisers and Fillers, ed. P. Ritchie.
Iliffe/PRI, London, 1972, Ch. 8.
75. 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/1444/78.
76. Biggin, I. S., Gerrard, D. L. & Williams, G. E., J. Vinyl Tech. 4 (1982)
150-6.
77. Gerrard, D. L., Bowley, H. J., Biggin, I. S. Williams, G. E. Plast. Rubb.
Process. Applns, 6(2) (1986) 97-100.
78. Your Questions Answered About Plasticised PVC Cling Film, British
Plastics Federation, 1986.
79. Surveillance Report on Plasticiser Levels in Food Contact Materials and
Foods, UK Ministry of Agriculture Fisheries and Food, 1987.
80. Poppe, A. C., Kunststo!fe, 70(1) (1980) 38-40.
81. Threshold Limit Values for Chemical Substances in Workroom Air for
1978, American Conf. of Govt. Ind. Hygienists, Cincinnati, Ohio.
82. Threshold Limit Values 1980 Health and Safety Executive, Guidance Note
EH15/80.
CHAPTER 6
Fillers
6.1 DEFINITION AND GENERAL

FUNCTIONS OF FILLERS
Fillers may be broadly defined as solid particulate or fibrous

materials, substantially inert chemically, incorporated in plastics com-
positions (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 the significant quantities in which they
are normally used affect in some measure the material and/or
processing properties of the plastic: 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 (cf. 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 some technical advantages in the properties and
service performance of the product, possibly improvement in ap-
pearance, product cost reduction, and improved or easier processing
at no higher cost. 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 a filler system in any particular case is usually a
compromise dictated by the balance of technical requirements and cost
considerations. For example, whilst such low-cost fillers as ground
limestone and coarse ground whitings offer the highest material cost
258
6 Fillers 259
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 mechani-
cal properties but increases the cost and affects the processing
behaviour of the material.
Whilst many fillers find application in PVC, the greatest industrial
and commercial importance has been attained by calcium carbonate,
chrysotile (white) asbestos, and certain types of clay.
6.2 PARTICULATE MINERAL FILLERS
On the basis of their chemical structure these fillers may be classified

into three broad groups: silicates and silicas; sulphates of the alkaline-
earth metals; and various kinds of calcium carbonate.
6.2.1 Silicates and Silicas
The silicate mineral fillers most widely used in PVC are clay and
asbestos. Others, with a relatively minor scale of application, are talc,
wollastonite, and mica; slate flour has occasionally been used as a
cheapening extender (slate is a complex of muscovite mica, chlorite,
and quartz, i.e. a composite hydrated potassium/magnesium/
aluminium silicate combined with silica); a proprietary form of
magnesium silicate has been evaluated as a lubricant additive
(i.e. not as a filler) in some uPVC compositions (see Chapter 7,
Section 7.1).
The common mineral silica fillers (sand, diatomaceoQ.s silica, quartz)
are of little interest for PVC compositions. Some special froms of
fine-particle silica are used, not as fillers but-at relatively low levels
of addition-as matting or anti-blocking agents in some pPVC
compositions, and as thickening agents in pastes (see the appropriate
chapters via the Index).
Some material property data for silicate fillers are given in Table
6.1.
(a) Clay
There are several varieties of clay, all essentially forms of complex,
hydrated alumino-silicates, with varying amounts of other, minor,
constituents (including oxides of iron, potassium, and titanium). Of
~
TABLE 6.1
Some Material Properties of Silicate Fillers Used in PVC·
."
Filler material Specific Refractive Oil Mohs Particle Remarks
gravity index absorption a hardness shape ~
."
~
Clay ~.
Kaolinite 2·60 1·56 36 2·5 Platelets Speswhite: b pH 5·0; brightness (ISO)
85·5; particle size 80% below 21lm ~
Hexafil: pH 9·0; brightness (ISO) 65; i::l
~
particle size 80% below 2 Ilm ...'"
Calcined 2·63 1·62 25 2·5 Platelets (some Pole Star 501: b pH 5·0; brightness ~.
fused into (ISO) 84·5; particle size 50% below
aggregates) 2 Ilm, 10% about 10 Ilm c~
Asbestos (chrysotile) 2·55 1·55 34 2·5-4·0 Fibres "~
Talc (Carotalc C ) 2·80 1·59 27-40 1·0-1·5 Platy '"
~.
Calcium silicate
;:
Wollastonite 2·90 1·59 26 5·0 Crystalline '"'-"
Precipitated 2·23 1·40 160 5·0 Crystalline Average particle size <lllm ).
Mica (muscovite) 2·75 1·59 47 3·0 Platelets ~

Nepheline syenite 2·60 1·60 20 6·0 Crystalline [
g.
a Most of the data relate to the rub-out test of ASTM D281-31 (1974). ill
b English China Clays International (data from Plast. Rubb. Int., 10(1) (Feb. 1985), 17).
C Croxton & Garry Ltd, UK (subsidiary of Pliiss-Staufer AG, Switzerland).
6 Fillers 261
the various clays only kaolinite ('kaolin', 'china clay'*) is significant as

a filler for PVC, used either directly (after grinding and some
purification) or in the calcined form (in which it is usually known as
calcined clay). Calcination refines the clay (by removing some im-
purities, including iron compounds, which significantly improves
electrical resistivity and enhances whiteness), removes the water of
hydration, and improves the processing performance. The main uses
of china clay in PVC are as a filler in some plasticised compositions for
extrusion and calendering, and in pastes (especially for certain coating
TABLE 6.2
Effects of Some men at Increasing Loading Levels upon Three Properties of a
Simple pPVC Compound"
Filler Properties of compound
Nature Content Tensile strength Cold flex temp. Water absorption

(phr) (lbfin- 2) eC) (% wt increase
ASTM D638 BS 2782 after 48 h immersion
at 60°c)
None 0 1700 -21 0·6

Hard china 20 1700 -18 2·8
clay 30 1400 3·7
40 1210 -15 4·9
50 890 5·1
60 1090 -9 6·5
Precipitated 20 1300 -20 1·5
calcium 30 1210 1·5
carbonate 40 920 -19 1·5
50 750 1·2
60 500 -18 1·2
Wollastonite 20 1450 -17 11·3
30 1150 8·3
40 780 -16·5 6·8
50 820 6·5
60 1100 -16 7·1
Carbon black 20 1920 -14·5 1·2
(MPC) 30 1710 -11 0·9
40 1760 -7 0·9
a PVC polymer 100 pbw; DOP 50 phr; basic lead carbonate 7 phr; filler as shown.
* Strictly speaking, although kaolinite-AI2(Si20s)(OH)4-is the principal

component of china clay, the two are not entirely identical.
applications). It is also used in some formulations for pPVC hose,

wellington boots, floor tiles, and rigid PVC pipes and fittings.
Note: Bentonite clay has also been used (as well as china clay) in
some carpet-backing compositions based on PVC latices.!
In all its applications in PVC, china clay has been yielding ground to
calcium carbonate fillers, which are normally cheaper grade-for-grade
whilst otherwise fairly comparable in their effects (except for their
somewhat greater opacifying action, and some of the differences
brought out in Table 6.2 and Fig. 6.1). Calcined clay is used mainly in
pPVC cable insulation compounds where-although calcium carbonate
fillers (notably ground whiting) also compete-it is superior by virtue
of its better electrical properties; in some cases it is used in addition to
300
c 200
.2
1G Carbon black ,/.
'"o
C
100
o 10 20 30 40 50 60 70
./. By WQight of filler
Fig. 6.1 Effect of some fillers on the elongation of a pPVC compound (PCC,
precipitated calcium carbonate).
6 Fillers 263
a calcium carbonate filler, to improve insulation resistance (especially

in high-temperature insulation). Some effects of a calcined clay filler in
a pPVC composition are shown in Table 6.3. Much industrial
information on china clay is contained in a publication by Highley. 2
(b) 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·2H20). It is a fibrous material (fibre length 1-40mm,
fibre diameter 0·01-1 ,urn) with a very high fusion point (1500°C) and
100% strength retention at temperatures up to 400°C. 3 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.
Dura/orm; 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. Despite the
increasing stranglehold on the use of asbestos by restrictive and
prohibitory regulations, its safe handling and incorporation in plastics
TABLE 6.3
Some Eft'ects of a Calcined Clay Filler" in a pPVC Compositionb
Filler content, phr 0 5 10 15 20 30 40 50

Composition
propertyc
Tensile strength, Ibf in- 2 2500 2500 2500 2500 2400 2500 2400 2400
Modulus at 100% extension, Ibf 1500 1700 1800 1900 2000 2200 2300 2400
. -2
In
Tear strength, Ib in -1 1200 1300 1400 1400 1400 1400 1500 1500
BS softness no. 38 32 32 30 29 28 26 23
Volume resistivity, ohm em x 1014
After conditioning at 23°C, 0·3 11 13 15 13 12 8 6
65%RH
After immersion in water for 0·2 3 6 7 7 6 4 2
24h at 6O"C 0·006 0·5 0·9 1-1 9 7 6
• Pole Star 501, English China Clays International.

b PVC polymer 100 pbw; DOP 50 phr; triabasic lead sulphate 7 phr; paraffin wax 1 phr; filler as
shown.
C Compounding and testing in accordance with BS 2571:1955.
is technically practicable, if appropriate precautions are observed. 4 For

several years past much effort has been devoted to developing
mineral-fibre replacements for asbestos, so far without real success,
although optimistic claims in that regard have been made from time to
time. The possibility that the stability and colour of asbestos-
containing PVC compositions may be affected by the iron compounds
present as minor chemical constituents in chrysotile, is a factor in their
formulation in processing [ef. entry for lead salicilate in Table 4.1 in
Chapter 4, and Chapter 2, Section 2.2.6(d)].
(c) Talc
This material also consists of hydrated magnesium and silicon oxides
(with admixtures of other minerals and impurities, never 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 needle-shaped, with
sizes in the range 1-50 .um.3 Talc is used in some calendered PVC
floor-tile compounds to increase melt cohesion and the stiffness and
hardness of the finished product: 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.
(d) Other Silicate Fillers
WOLLASTONITE
This is a calcium metasilicate/ sometimes employed as a filler in floor
tiles and plastisol products.
MICA
The name is a general one for a group of complex
potassium/aluminium silicates with plate-like particles. Mica is of
some interest in certain electrical insulation formulations. Fibrous
calcium silicate has been suggested as a low-cost alternative to both
mica and wollastonite.
NEPHELINE SYENITE
This is a form of anhydrous sodium/potassium/aluminium silicate. It
has been used in some semi-transparent PVC compositions (e.g. for
filled sheet) because of its low opacifying effect.
6 Fillers 265
6.2.2 Alkaline-Earth Metal Sulphates
Only two of these have some relevance as fillers for PVC, viz. barium
sulphate and anhydrous calcium sulphate.
(a) Barium Sulphate

The two grades of barium sulphate (BaS04) in use as fillers are both
produced from its naturally occurring form, the mineral barytes. The
grades are: the mineral itself, ground and purified; and precipitated
BaS04, known as 'blanc fixe'. Except where a high-density filled
compound may be required for some special reason (as for example in
backings for heavy floor coverings), the high specific gravity of BaS04
(4·5 in the crystalline form) is a disadvantage as it makes the filler
expensive on a volume cost basis. Its advantages are high brightness
(up to 99·5% reflectance) and low oil absorption (9-14gg- 1). Flexible
PVC compositions incorporating this filler find use in specialised
applications where high resistance to acids or opacity to X-rays is
required.
Note: A·typical basic formulation for an X-ray opaque film-coating

solution for surface application to PVC articles would be:
PVC polymer 100 pbw; cyclohexanone 63 phr; tetrahydrofu-
ran 63 phr; BaS04 40 phr.
(b) Anhydrous Calcium Sulphate

Anhydrous calcium sulphate (CaS04) is commercially available as a
filler in two forms: particulate and fibrous. An example of the former
is Snow White (US Gypsum Co.) a filler of 7 J.lm average particle size
now offered for PVC pastes and some solid pPVC compositions, inter
alia; other relevant grades are CS20 (for pastes) and CA-5 for PVC
pipes, conduit, and cladding. The commercial fibrous CaS0 4 (from the
same producer) is Franklin Fiber. This filler consists of single-crystal
fibres (in which the calcium sulphate is said to be in the hemihydrate
form*) of 60 J.lm average length and 2 J.lm average diameter. 5 It is
among those that have been suggested as possible substitutes for
asbestos. 6
* Truly anhydrous fibres are also available for plastics compositions for
high-temperature applications.
6.2.3 Calcium Carbonate FUlers
(a) General: Types and Characteristics

The calcium carbonate (CaC03) fillers may be classified into the
following general types.
Mineral CaCOJ fillers: Whiting; ground limestone, marble and

calcite; ground dolomite.
Precipitated CaCOJ : 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 crystal-
lisation, 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.
Many grades of the various types of calcium carbonate fillers are

available in surface-coated versions (see Section 6.4).
(b) Whiting
This is a fine, white powder, produced by grinding and classifying
chalk,7 which is fairly pure natural calcium carbonate found in the
form of deposits of aggregated, fossilised skeletons of microscopic
marine organisms collectively known as nanofossils, and comprising
mainly the groups foraminifera and 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 Ilm in size:
under suitable magnification some can be seen to have a fine granular
structure, with the granules (in most cases about 0·2-0·6Ilm) recog-
nisable as elements of a coccolith skeleton; some of the particles are
actually complete, ring-shaped skeletons roughly 4-8 Ilm in diameter,
or parts of such rings.
6 Fillers 267
Basic dry grinding of chalk leads to an end-product with the

majority of particles between 1 and 5 J.tm 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,
and freedom from iron compounds).
(c) Ground Limestone, Marble, and Calcite

Limestone is a very widely occurring natural calcium carbonate formed
from deposits of calcified foraminifera, originally sedimented and later
consolidated by heat and pressure. Marble and calcite are hard,
compact crystalline varieties of limestone. 7 ,8 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.
(d) 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.
(e) 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 J.tm, and the average size
is well below this level. * For this reason the precipitated calcium
* For example the typical primary particle size of Winnofil (leI) precipitated
calcium carbonate (calcium-stearate-coated) is 0·06-0·09 ,urn. Although there
is some aggregation into larger secondary particles, the aggregates tend to
disperse in plastics compositions on incorporation and in processing.
carbonates are normally supplied in the coated form (see Section 6.4
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 manufac-
ture (and not as an additional processing step). The process also
affords good control over the quality, particle size, and purity of the
product, 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 nomencla-
ture is incorrect (see the description of whiting above).
(f) Filler Properties and Selection Criteria
The features especially important in the selection of CaC03 (and
other) fillers for particular applications are: (i) maximum particle size;
(ii) particle size distribution and mean particle size; (iii) colour
(whiteness)-dry brightness; (iv) refractive index (important to opac-
ifying effects); (v) oil (plasticiser) absorption; (vi) dispersion charac-
teristics; (vii) cost.
MAXIMUM PARTICLE SIZE
Coarse filler particles can spoil the surface appearance of the product,
and impair mechanical properties (by providing points of local stress
concentration). For most pPVC compositions for extrusion, fine-gauge
calendering, and injection moulding, a maximum particle size of
10 J.lm is normally acceptable. In plastisols for spread-coating still
larger particles can be tolerated due to a higher plasticiser content and
less need for particularly good mechanical properties (but in low-
viscosity plastisols coarse filler particles may tend to sediment-out).
For rigid PVC compositions it had long been accepted that the
maximum filler particle size should be under 1 J.lm for the desirable
level of mechanical properties and surface appearance. This effectively
restricted this usage area to precipitated calcium carbonates. However,
ground natural CaC0 3 fillers-which are cheaper~an now be used
(with maximum particle size of about 5 J.lm), thanks to improvements
in selection and milling techniques, compounding equipment, and
formulations.
PARTICLE SIZE DISTRIBUTION AND MEAN PARTICLE SIZE
The particle size distribution influences the way in which the filler
particles pack together. This in turn affects the highest tolerable filler
6 Fillers 269
loading that is still compatible with acceptable rheological properties

of heavily filled PVC melts and pastes. For example, with PVC pastes
for car-body undersealing, the use as filler of a blend of fine-ground
whiting and a coarser-ground calcite permits high loading levels, whilst
the paste is still sufficiently fluid for spray application, and the sprayed
coating has good non-sag characteristics.
In general, the finer the mean particle size, the better the physical
properties and surface appearance of the filled material (for the same
content and size of the coarsest particles). In PVC pastes for slush or
rotational moulding, fillers of mean particle size no greater than
1-31lm should be used to avoid filler settlement problems in
processing.
A standard method suitable for the determination of the particle
size distribution in the sub-sieve range of such fillers as clay, talc,
mica, and the calcium carbonates (as well as titanium dioxide and
other mineral pigments) is the sedimentation method of ASTM D
3360. 9
DRY BRIGlITNESS
This is normally measured and expressed in terms of percentage of
light of a stated wavelength reflected from the smoothed surface of the
white filler powder specimen in comparison with a stated standard
material.
Note: The method of ISO 2470 10 (originally established for white
paper and board) is commonly used, with a magnesium oxide
powder standard, or an absolute standard. 10
REFRACTIVE INDEX (OPACIFYING EFFECT)

The main factor governing the opacifying effect ('hiding power') of a
white filler or pigment in a given medium is the extent to which incident
light is refracted and reflected (scattered) by the particles. * Both the
refraction and reflection depend on the refractive indext of the filler or
pigment material in the medium (reflection also to some extent on the
* In a dispersion of filler particles in a medium the incident light will undergo

multiple refractions and reflections.
t For practical purposes the refractive index of a filler material may be
regarded as constant: however, as with any other material, it normally
increases somewhat with decreasing wavelength of the incident light ('normal
dispersion'). For materials that actually absorb light in any part of the
wavelength region concerned, the refractive index also changes within the
absorption band ('anomalous dispersion,).12
particle configuration and size), and both increase with its value.
Thus---other factors (such as particle size and shape, size distribution,
level of loading, and dispersion) being equal-the higher its refractive
index, the greater the opacifying effect of a filler or pigment in a given
plastics composition.
Note: For light incident normally (i.e. at zero angle of incidence) on
the surface of a substantially transparent dielectric material
(such as that of one of the fillers discussed in this section) of
refractive index n, the proportion reflected is given by the
Fresnel relationshipll r = (n - 1)2/(n + 1)2. This proportion
increases with increasing angle of incidence (i.e. as the light
strikes the surface more obliquely) in accordance with a
function more complex than the simple Fresnel equation. At
grazing incidence a phase change also occurs.
The opacifying capabilities of a few common fillers-in comparison
with that of titanium dioxide-in air, PVC polymer, and a common
general-purpose plasticiser (DOP), are illustrated by the data of Table
6.4. As can be seen, all the filler materials listed are strongly opaque in
air, as their refractive indices are much higher than unity and the
proportions of light reflected (even in the ideal, lower-limit case of
normal incidence to which the Fresnel relationship applies) are quite
substantial, ranging from 4·8% for kaolinite to 6% for barium
sulphate. However, the table also brings out clearly the difference in
opacifying power in PVC and DOP between white fillers on one hand
and a true pigment like titanium dioxide on the other. Thus, the
refractive indices of even anatase (the less opaque of the two Ti0 2
pigments) in the two media are comparable with that of barium
sulphate (the most opaque of the fillers) in air, as are the percentages
of light reflected. At the same time, the refractive indices of barium
sulphate in PVC and DOP are both near unity (indicating relatively
little opacification by refraction) and the corresponding light reflection
values are only 0·096% and 0·26% respectively.
Note: Thus if reflection was due only to normally incident light the
filler would appear almost transparent even in DOP. In
practice various degrees of optical translucence are achiev-
able in PVC compositions.
Another point brought out by the data of Table 6.4 is that whilst the
refractive indices of two fillers in a medium may differ by a factor of
TABLE 6.4
Refractive Indices of Some White Fillers, and Proportions of Light Re8ected at Normal Incidence in
Three Media, in Comparison with Titanium Dioxide Pigments
Refractive index values Fraction of light reflected
at normal incidenceo
In air, In PVC polymer InDOP In air In PVC polymer In DOP
n. np = n./npb n. = n./n L c ra rp r.
0\
Kaolinite 1·56 1·006 1·047 0·048 0·000009 0·00053 :!l
Whiting 1·57 1·013 1·054 0·049 0·000042 0·00069 ~
-
Talc 1·59 1·026 1·067 0·052 0·00016 0·0011 t:!
Calcined clay 1·62 1·045 1·087 0·056 0·00048 0·0017
Precipitated CaC03 1·63 1·052 1·094 0·057 0·00064 0·0020
Barium sulphate 1·65 1·064 1·107 0·060 0·00096 0·0026
Titanium dioxide
Anatase 2·52 1·626 1·691 0·186 0·057 0·066
Rutile 2·76 1·781 1·852 0·219 0·079 0·089
r r. = (n. -1)2/(n. + 1)2; rp = (np -l?l(n p + 1)2; rl = (n. -l?/(n. + 1f.
b np = refractive index of PVC polymer: taken as 1·55 for the purpose of the calculation.
C nL = refractive index of DOP: taken as 1·49 for the purpose of the calculation.
!:j
....
only 1·057, the fractions of normally incident light they will respec-
tively reflect can differ by a factor of nearly 5 (compare the relevant
data for kaolinite and barium sulphate in DOP).
Differences between the refractive indices of a filler in air and in a
PVC composition play a cardinal role in the phenomenon of 'stress
whitening' ('crease whitening'). This can be brought about by strong
local stressing (as for example by sharp bending or creasing) of a filled
PVC material in which the interfacial adhesion between the filler
particles and the polymer matrix is relatively poor (e.g. as a result of
incomplete 'wetting-out' of the former by the latter in compounding
and processing). The 'whitening' is strong local opacification caused by
the formation of microvoids between the filler particles and the PVC
matrix: in these voids the local refraction and reflection of light by the
particles is governed by their refractive index relative to air (or even
partial vacuum), which is much higher than that relative to the PVC
composition (with or without plasticisers-cf. Table 6.4).
OIL (PLASTICISER) ABSORPTION

The standard tests for this property originally evolved for use with
pigments for paints, and many specify the use of an oil (commonly
linseed oil). However, they are also applicable to pigments and fillers
for plastics: in the context of PVC this kind of test is normally run with
DOP (or sometimes with another plasticiser that is relevant to a
particular formulation). In terms of the standard tests, oil (or
plasticiser) absorption is defined as the weight in grams of the
appropriate oil (or plasticiser) required to 'wet-out' completely (so
that a paste of stipulated consistency is formed) 100 g of the pigment
or filler. The main relevant standard specifications are: ISO 787:Part
5-1980 (palette-knife rub-out on a glass plate of 100 g of pigment or
filler with oil added dropwise) identical with BS 3483:Part 7:1982;
ASTM D 281-84 (spatula rub-out of 100 g of pigment with linseed oil
or another liquid, to a stiff, putty-like paste); ASTM D 1483-84
(Gardner-Coleman method, involving dropwise addition, with gentle
stirring, of specified linseed oil to 100 g of pigment).
Note: DIN 53199 originally operated in Germany has been aban-
doned in favour of ISO 787 Part 5.
The plasticiser absorption of pigments and fillers for PVC composi-
tions is related to, but is not a direct measure of, the actual 'plasticiser
demand', i.e. the extent to which the filler will absorb plasticiser when
6 Fillers 273
incorporated in a plasticised composition. It is an important considera-

tion in deciding on fillers for such compositions, including pastes.
The plasticiser demand and oil absorption both tend to increase with
the surface area of the filler, and hence to decrease with increasing
particle size. Fillers with good particle packing characteristics exhibit
lower oil absorptions, and the more crystalline the particles the less
they absorb internally. The presence of a coating on a filler (see
Section 6.4) reduces oil absorption in tests and the actual plasticiser
demand in PVC compositions. Thus the use of coated fillers can save
costs by permitting either increased filler loading for the same amount
of plasticiser, or a reduction in plasticiser for the same filler loading.
The filler's plasticiser absorption can be related to the softness of a
filled flexible compound, and the viscosity of a filled plastisol. Fillers
with high oil absorptions (over 20 g per 100 g) will normally necessitate
the use of substantially more plasticiser when formulating for a
particular BS softness, than will low-absorption fillers. 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.
DISPERSION CHARACrERISTICS
It is important that any filler used should be thoroughly and uniformly
dispersed in the PVC composition. Non-uniform dispersion can
adversely affect the physical properties, whilst undispersed aggregates
have the same effect as large particles (see above). Different kinds of
filler can differ in ease of dispersion in a given composition;
fine-particle versions of a filler are generally more difficult to disperse
than coarse ones. The presence of a stearate coating on a filler
facilitates and speeds up dispersion in PVC compositions.
COST
With the partial exception of some functional fillers, filler addition is
commonly a means of reducing formulation cost. However, it is always
important to consider in this context not just the price of the filler, but
also its nett cost-effectiveness in the composition and in processing.
A substantial loading of a low-price filler may appear attractive, but
the apparent price advantage could easily be offset by a consequent
reduction in processing rate (with lower output), cost of any extra
pigment that might be required to improve whiteness, increased
plasticiser level, poorer physical properties and/or surface finish. For
example, whilst the cheapest CaC03 fillers-ground coarse whitings
and limestone-are widely used, at high loadings, in low-cost flooring
compositions, they are not normally suitable for applications in which
good physical properties and appearance of the product are important.
Moreover, their high plasticiser demand, relatively poor whiteness and
dispersibility will-in comparison with a finer, more uniform CaC0 3
filler grade-necessitate more plasticiser and pigment, with longer and
harder mixing. Fusion times in melt-processing could also be longer. A
coated filler, although more expensive than an uncoated grade, can
give up to 50% higher extrusion outputs, as well as allowing reductions
in the lubricant and/or plasticiser contents. Fine fillers can be used at a
higher loading for the same physical property level as that 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.
The relatively highly-priced precipitated, surface-coated calcium
carbonate fillers can-by virtue of their very small particle size,
uniformity and good dispersibility~ffer advantages that favourably
affect the ultimate product cost and quality. The advantages are:
shorter fusion times and the counteraction of plate-out in processing,
and (in the product) improved surface smoothness and gloss, and
prevention of such surface defects as 'sharkskin' that can sometimes
arise under high shear gradients in processing (e.g. in some injection
mOUldings). Impact resistance improvements are also effected [see
Section 6.3.1(e)iii].
In considering the effective cost of a filler for a formulation, an
important element is the volume cost (cf. Section 2.3 of Chapter 2).
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
6 Fillers 275
example, for calcium carbonate, with a relative density of 2·7, the cost
of 1 ml will be 2·7 times the cost of 1 g; for barium sulphate the factor
is about 4·5, and so on.
(g) Applications, and Some Effects of Filler Loading
The main applications of CaC0 3 fillers are indicated in Table 6.5. The
following points may be mentioned by way of amplification.
FLOORING
This is a big usage area for fillers, especially asbestos and CaC03 in
PVC. Calcium carbonate fillers are incorporated in flooring composi-
tions not merely to save cost, but also because substantial filler
loadings increase weight, reduce shrinkage, and improve impact
identation resistance. Crystalline types (calcite) and finely ground
limestone are widely used in plastisol compositions for backed
flooring, produced by spreading the plastisol on a substrate (fabric or
paper). Filler loadings may range between 200 and 500phr, subject to
considerations of the required plastisol rheology. Figure 6.2 presents
some relevant data l for a plastisol composition highly filled with
Calibrite (special ground calcite grade; Pliiss-Staufer AG). As indi-
cated by the figure, it is possible, by running the spreading process at
suitably high shear rates (i.e. high spreading speeds, which also result
in high output), to operate at very high loadings of this particular filler
whilst keeping the viscosity reasonably low.
PLASTICISED COMPOUNDS
Fine-ground whitings and calcites are the most suitable CaC0 3 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 6.6. 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 6.7 shows the effects of increasing loading level of a
coated whiting (Omya BSH). The coated whitings have good disper-
sion characteristics and improve the process ability 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 for
bulk-handling systems. In cable compounds, coated whiting offers
some advantages (including lower plasticiser demand) over cor-
responding uncoated grades, even at relatively low loading levels-d.
Table 6.8.
TABLE 6.5
Applications of CaC03 Fillers in PVC
Application Relevant filler Filler features and advantages / Examples

Remarks of
Type a Typical particle commercial
size (1'"1) products
Mean Nominal
maximum
1. Plastisols
Fabric coatings; foams Ground calcite 13-15 60-75 Low plasticiser demand, good Calibrite b
rheological properties (for
fast spreading)
Ground calcite (s) 3-5 10-20 The finer filler gives good sur- Millicarb;b Omya
face finish; obviates possible BLHb
settlement problems
Spread-coated flooring Ground calcite (some 30 200 Good physical properties are Omya D40b
(base coats) grades of ground lime- not normally critical in this
stone also suitable) application, hence relatively
coarse filler can be used for
high loading and fast
spreading rates
Rotational moulding; dip- Ground calcite (s) 3 10 Filler fineness and crystalline Millicarb;b Omya
coating structure (and coating if pre- D2b
sent) give, respectively free-
dom from settlement and re-
latively moderate thickening
2. Extrusion compounds
(a) flexible:
General Ground whiting, s 2 10 Fine particle size gives good Britomya BSH;b
Ground calcite 3 10 surface finish and physical Millicarb b
properties
Dry blends Precipitated, s <1 <4 Good dispersion, low equip- Day/Cal;C
ment abrasion, good flow, Hakuenka b
relatively low plasticiser
demand
Ground calcite 1-3 7-10 Good dispersion and physical Millicarb ;b
properties Hydrocarb b
Cable sheathing and Ground whiting (s) Up to 2 10 Good physical properties and Britomya M or
insulation fast output promoted by BSHb
filler fineness (fastest pro-
duction with coated grades).
Special 'electrical' grades
available
(b) Rigid:
Pipe, cladding, profiles Precipitated, s <5 About 7 Small particle size and good Super-Pflex 200;d
Ground whiting, s 1-2 5 dispersion are particularly Omyalite 9srb
important (for good physical
properties and processability,
respectively)
Soil pipe, rainwater goods Ground whiting, s 2 10 Somewhat coarser particles ac- Britomya BSHb
ceptable here
3. Injection-moulding compounds
(a) Flexible:
General Ground calcite 3 These fine-particle grades give Millicarb b
10} good balance of physical
Ground whiting, s 2 10 properties, ease of dispersion Britomya BSHb
and pro<:e~sability
Shoe-sole compounds Ground calcite Finest particle grades required for good wear Hydrocarb b
Ground whiting (s) properties, resistance to flex cracking, cut growth Omyalite b
Precipitated, s and other effects of damage in service
(b) Rigid:
Pipe fittings 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 low K value) (continued)
TABLE 6.5-contd. ~
Application Relevant filler Filler features and advantages / Examples
Remarks of
Type" Typical particle commercial
size (11m) products
"tI
Mean Nominal ~
"tI
maximum
~
General Generally as for extruded soil pipe and rain-water goods

4. Calendering compounds t
~
(a) Flexible: ~
Thin sheeting Ground calcite (s) 3 10 Good dispersion, physical pro- Millicarb;b Pfinyl ~.
Ground limestone (s) <5 10 perties, surface finish, and 402;d Britomya ....
Ground whiting, s 2 10 low plasticiser demand are BSH·, b ~
<::>
the main requirements to be
met
"~
'"
~.
Thick sheeting Ground whiting (s) 2-3 10- Physical properties usually less MordenR;b
100 critical, hence less refined Britomya
filler may be used. Coarse V/L;b ~
).
ground calcite may be in- Britomya
~
cluded in some compositions BSHb ~
I:>
to counteract blister 5'.
formation !:l
(b) Rigid sheeting Ground whiting, s 1-2 5-10 Fine grades (coated for good Britomya BSH;b
dispersion) required, to give Omyalite 95Tb
good physical properties.
Finest particle size for high
impact strength sheeting
"s = Stearate or other suitable surface treatment (desirable but optional if shown in brackets).
b Croxton & Garry Ltd, UK.
C H"rnsnn Fnternnses_ lJSA_
6 Fillers 279
10 4
9
B
c.. 7
u
6
>:
..... 5
'iii
0 4
U
III
:> 3
103
300 400 500 600
Calibrite loading, phr
Fig. 6.2 Viscosity of a Calibrite-filled plastisol composition for spread-coating

as a function of filler loading and shear rate.
RIGID COMPOUNDS
In these, the more expensive CaC0 3 fillers are used-viz. surface-
treated precipitated grades and ultrafine ground, surface-treated chalk
whitings-not as cheapening extenders but, at relatively low loading
levels, to improve processing and/or product properties. In the
whitings, even a small proportion of particles coarser than about 2 Ilm
can have a detrimental effect on the mechanical properties of the
compound.
Even when present in a relatively low proportion, fine CaC0 3 filler
can increase the internal friction in the stock during, compounding and
TABLE 6.6
Some Elfects of FiBer (3 pm Whiting) Loading on Plasticised Compound"
Filler, phr 0 10 20 30 40
Tensile strength, lbf in- 2 2585 2605 2500 2465 2410
Elongation at break, % 325 335 325 315 305
Hardness, Shore A 79 80 81 82 83
Relative density 1·234 1·271 1·312 1·350 1·384
Brittle temperature, °C -50 -40 -35 -30 -30
aPVC resin 100 phr; plasticiser (DOP) 55 phr; stabiliser (Ba/Cd) 2 phr; lubricant (stearic
acid) 0·5 phr; filler 0-40 phr.
TABLE 6.7
Some Effects of Increased Loadings of a Coated Whiting (Omya BSH) on a
Plasticised Compound"
Filler, phr 0 10 12 15 20 35 50 150

Tensile strength, lbf in- 2 2700 2500 2475 2425 2425 2225 2035 1925
Modulus at 100%
elongation, lbf in - 2 2225 1985 1970 1965 1925 1850 1775 1950
Tear resistance, lb in- 1 81 81 80 78 76 75 67 47
Brittle temperature, °C -20 -19 -19 -18 -18 -17 -14 -5
a PVC resin 100 phr; plasticiser (DOP) 50 phr; stabiliser (dibasic lead phthalate) 3 phr;
lubricant (dibasic lead stearate) 1 phr; filler 0-150 phr.
processing: this improves the dispersion of the other additives (pig-

ments, lubricants, stabilisers, etc.).
With precipitated, surface-treated calcium carbonates-typically
characterised by very fine particle size (about O·lllm) and narrow size
distribution-the filler's own dispersibility, and its effect on that of
other additives in the uPVC compound, are very good at the usual
relatively low incorporation levels (up to about 10 phr); the dispersed
filler also promotes uniform frictional heating and shear throughout
the stock, and thus reduces fusion time. In some formulations it is
possible to reduce or even eliminate the polymeric processing-aid
additive by substituting an only slightly higher proportion (in terms of
phr) of precipitated CaC0 3 filler. At loadings significantly above
TABLE 6.8
Effect of Surface-Treated Whiting on Some Pro-
perties of a Cable Compound
PVC resin 100 100

nop 45 43·3
Lead stabiliser 3 3
Lubricant 1 o
Uncoated whiting 15 o
Coated whiting o 15
Tensile strength, kg cm- 2 190 195
Elongation at break, % 200 210
Brittle temperature, °C -17 -18
Relative density 1·33 1·33
Volume resistivity 1.7 x 1014 5·5 x 1014
at 20°C, Oem
6 Fillers 281
10 phr, the internal shear increase in the stock can become excessive,
due to the thickening effect of the very fine filler particles.
These effects are much less drastic with the so-called ultra-fine
ground whitings which-despite the name-are coarser by an order of
magnitude 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 CaC0 3 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 production trials.
6.3 FUNCTIONAL FILLERS
These are the fillers that impart or modify a particular property or

group of properties in a PVC composition: their presence most often
increases the formulation cost, and may also make processing more
difficult or expensive.
6.3.1 Reinforcing F~ers
Most of these are fibrous, although glass spheres (and even precipi-
tated 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 in particularly wide industrial use in PVC: however,
several merit a mention for the sake of their general technological
interest.
(a) Asbestos (Chrysotile) Fibres

The application of chrysotile asbestos as a reinforcing filler for PVC
has already been mentioned [in Section 6.2.1(b)]. 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 poly-
ethylene glycol) applied to the asbestos fibre were found 13 to improve
the impact strength and flexural modulus of the filled PVC compound.
The practical and commercial repercussions of the concern about
health hazards believed to be associated with the handling of asbestos
in processes and products have made themselves strongly felt on both
sides of the Atlantic.
(b) Miscellaneous Inorganic Microfibres

None of these is of major current importance as a reinforcement for
PVC. However, the following materials may be briefly mentioned to
illustrate what is generally available in the way of possible asbestos
substitutes.
(i) Hydrated sodium/aluminium fibre (Dawsonite; ALCOA). *
(ii) Potassium titanate fibre (Tismo;t developed by the Otsuka
Chemical Co., Japan, and marketed by the Biddle Sawyer
Corp., USA).
(iii) 'Processed Mineral Fibre' (PMF; Jim Walter Resources Inc.,
USA), produced from blast-furnace slag.
(iv) Polymeric calcium sodium metaphosphate fibre (Phosphate
Fiber; Monsanto). This high-strength fibre is claimed to de-
grade naturally (by hydrolysis to orthophosphate ions) if
ingested, inhaled, or exposed for prolonged periods to the
environment.
(v) A low-cost slag fibre (Thermafiber FRF; USG Acoustical
Products, USA). This is offered mainly as a cheaper alternative
to milled glass.
(c) Glass Fibres

As in the case of other thermoplastics, the incorporation of glass fibres
in a rigid PVC compound can substantially upgrade some mechanical
* Aluminium Company of America.

t This fibre may be regarded as the technical successor to the Du Pont Fybex
potassium titanate fibre, which was discontinued in 1974. Until that time some
Fybex-reinforced rigid PVC compositions were also available from certain
suppliers. 1,3,4
6 Fillers 283
properties (especially the flexural modulus and tensile strength), as

well as resistance to creep and fatigue. As with other thermoplastics
reinforced with short glass fibres, the degree of improvement in these
properties depends on the orientation of the fibres in relation to the
direction of imposed stress, and-given that-also on the fibre length,
amount present, and the interfacial adhesion between the fibres and
the PVC matrix. The temperature of deflection under load is also
normally increased by glass-fibre reinforcement of uPVC, but the
increase is only relatively moderate (cf. Tables 6.9 and 6.10 and
Appendix 1).
After their original introduction, towards the end of the 1960s/ the
industrial demand for glass-fibre-reinforced uPVC compositions was
not particularly high. In the late 1970s it declined further, to the point
where the compositions ceased to be produced, partly as a result of
two unfavourable features of these materials: the adverse effect of
moisture on their mechanical properties (attributable to disruption by
moisture of the matrix-glass interfacial bond), and the further
complication by the presence of the glass fibres of the melt rheology in
processing (already fairly difficult due to the high melt viscosity of
uPVC and its susceptibility to thermal degradation). In 1986, the
second generation of glass-fibre-reinforced uPVC compositions for
injection moulding and extrusion was launched by B. F. Goodrich in
the shape of the various grades* of their Fiberloc compounds. These
incorporate a specially developed surface treatment for the glass fibres
to promote effective adhesion to the PVC matrix. The easy-flow
grades also benefit from the know-how accumulated by B. F.
Goodrich in this area. All grades are said to be produced by a special
compounding procedure. Some properties of one original producer's
first-generation reinforced uPVC compounds (as moulded, i.e. not
after prolonged exposure to moisture), and those of some Fiberloc
grades are shown, respectively, in Tables 6.9 and 6.10.
(d) Microspheres
Hollow microspheres (glass or ceramic) are occasionally used in some
PVC pastes, where they increase viscosity in processing, as well as the
hardness and abrasion resistance of the products, with less effect upon
the density than would be exerted by solid microspheres. Slag
* Over 20 basic grades are available, plus special additional grades repre-
senting variants adjusted for particular purposes.
TABLE 6.9
Effect of Glass-Fibre Reinforcement on Some Properties of Rigid PVC
Property Method Units Unreinforced Reinforced

of (Ethyl 7042 (Ethyl 7042 compoundt
determination compoundt
10% glass 20% glass 30% glass
Specific gravity ASTM 0 792 1·40 ± 0·02 1·45 1·53 1·61

. -1
Mould shrinkage in In
or
-1
mmmm 0·003-0·004 0·002 0·001 0·001
Tensile strength ASTM 0·638 lbf in -2 (MN m -2) 6400(44·1) 9000 (62·0) 14000 (96·5) 16000 (110·3)
Tensile modulus ASTM 0 638 lbf in -2 (MN m -2) 420000 (2 896) 650000 (4481) 1200 000 (8273) 1300000 (8963)
flexural modulus ASTM 0 790 lbf in -2 (MN m -2) 375 000 (2 585) 600 000 (4 136) 950000 (6550) 1100 000 (7584)
~ in (3·175 mm) bar ASTM 0 256 ft lbf in -1 (J m -1) 15 (800·20) 6 (320·08) 3·5 (186·71) 2 (106·69)
Heat distortion at
264 lbf in -2 (1.82 MN m -2) ASTM 0 648 °C 70·6 81·7 86·7 87·8
• Ethyl Corporation, USA (the PVC business of this company was taken over in the early 1980s by Georgia-Pacific Chemicals Inc., which in tum was
incorporated in the Georgia Gulf Corp. in 1985: ct. Table 3.8 in Chapter 3).
TABLE 6.10
Some Properties of New-Generation Glass-Fibre-Reinforced UPVC Compounds"
(Table based on manufacturer's published data)
Extrusion Injection moulding
b b
Single- Twin· Nomrol High·fIow, Nomrol High-jlow, b Nomrol High·fIow, High-flow
screw screw flow high-Dr' flow high-DT flow high-DT high-impact
Glass fibre content % by weight 10 10 10 10 20 20 30 30 30
Specific gravity 1·39 1-40 1·43 1·37 1·50 1-43 1·57 1·53
Tensile properties
Strength lit x (lbf in -2) 7-8 g·3 10·5 g·O 12·g 10·0 13·9 11·5 15·0
Elongation at break % 7·2 5·0 6·0 6·6 2·7 4·4 2·0 3·5
Flexural properties
Strength lit x (Ibf in -2) 11·7 12·6 17·6 12·2 22·5 15·g 22·g 17·9 21·0
Modulus 1(i' x (Ibf in -2) 4·5 5·1 6·4 4·6 9·7 6·g 11·9 9·5 12·0
Impact resistance (Izod) ft-Ib in-I
Notched 1-6 l·g O·g l·g 1·0 1·9 1-1 l·g O·g
Unnotched g·5 9·0 6·0 g.g g·O 9·3 g·4 g.g 9·0
Deflection temperature under load OC 77 7g 75 73 75 74 76 75 76
(264lbf in - 2)
Coefficient of linear thermal 10- 5 x (OC)-1
4-1 4·3 3·6 3·g 2·3 3·6 2·2 2·5 2·0
expansion
Flow in spiral mould in 32 36 28 33 25 28 30
a Fiberloc (F. G. Goodrich).
b Special bigh-flow compounds, with still bigher flow lengths in the spiral mould also available (the 802 series).
C Deflection temperature under load.
microspheres have also been reportedly incorporated 14-apparently as

a cheapening filler/extender, in loadings up to 50%-in formulations
for pipes, profiles and sheeting developed by the Institute of Plastics
Processing and Application, Chinese People's Republic.
(e) Fine-Particle Calcium Carbonate

The functional role of the finest-particle grades of CaC03 fillers at low
loading levels in uPVC compositions has been mentioned in Section
6.2.3(g) above. By way of a more complete summary, the following
effects may be noted (mainly-some exclusively-{)btainable with
precipitated calcium carbonate fillers of the surface-coated type).
(i) Processing-aid and melt-stabilising function in melt-processing,
with improved surface smoothness and gloss in products.
(ii) Improved cell-size control in some PVC foam compositions.
(iii) Improved impact strength (especially at low temperatures).
(iv) Improved resistance to weathering (through enabling milder
melt-processing conditions and hence reduced degradation; inhibition
of dehydrochlorination by absorption of HCI; improved light reflection
from the smooth, glossy surface of products).
(v) Improved whiteness, allowing reductions in the amounts of
titanium dioxide pigment necessary in some compositions.
6.3.2 Flame-Retardant and Smoke-Suppressant Fillers
Functional fillers of this kind are discussed in Chapter 9, Section 9.2.2.
6.3.3 MisceUaneous Functional Fillers
(a) Carbon Black

As a constituent of PVC and other plastics compositions, carbon black
may have one of three main functions. It may be incorporated to im-
part black colour, or to improve resistance to photochemical degrada-
tion, or to reduce electrical resistivity (in some cases to the point of
imparting conductivity). Different grades of carbon black are used for
these three purposes. The first two functional applications-i.e. as a
pigment or stabiliser-are discussed respectively in Chapters 9 and 4:
in both, the carbon black is used at loadings of only a few phr, i.e. well
below the levels typical for fillers proper. It is only in its application as
a conductive filler that the loading levels required for optimum effect
become substantial. This application is discussed in Section 9.2.3(c) of
Chapter 9.
6 Fillers 287
Two general points may be noted in passing, viz. that the kind of
reinforcing effect that carbon black exerts in natural rubber composi-
tions does not arise in PVC, and that improvements in the
processability as well as electrical conductivity of carbon-black-filled
PVC compounds have been reported to result when the carbon filler
was pretreated by grafting vinyl chloride polymer onto its surface. 15
(b) Metal, or Metallised Particles and Fibres

These two are sometimes used as conductive fillers, for antistatic and
conductivity effects (see Chapter 9, Section 9.2).
(c) Wood Flour

Although the incorporation of wood flour in uPVC 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. Such products (some in cellular, structural-foam versions,
with densities down to about 0·9 gcm- 3 ), the compounds for their
manufacture, and the wood fillers for incorporation in the compounds,
are all available from commercial sources. The filler loadings can be
substantial (several tens of phr): as would be expected, these can
result in a reduction of some mechanical properties (in particular,
extensibility can be severely reduced) vis-ii-vis similar but unfilled
compositions. However the effects need not be drastic overall, as
evidenced by the following values quoted 16 for a commercial wood-
filled uPVC compound (Nordxyl; Nordchem SpA, Martignacco,
Italy); tensile strength at yield 350 kg cm- 2 (34 MPa), and 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
wood filler in the compound is an increased tendency to take up
moisture: drying before processing is good practice (several hours at
80°C is sometimes recommended). Some modifications to the heads
and dies of standard extrusion equipment may be necessary for
optimum processing.
(d) Cellulose Fibres

Short cellulose fibres have been used in pPVC compositions as a
filler/extender. A commercial example is Santo web WB (Monsanto)
wood-pulp fibre, surface-treated to promote ease of dispersion in, and

adhesion to, the PVC matrix in fiooring compositions.
(e) Starch
An early technically significant use of starch in PVC compositions was
as an extractable, fine-particle filler in the production of rigid porous
sheeting with applications in filtration and for battery separation plates
(cf. Section 17.3.2 of Chapter 17). Later, plasticised and semi-rigid
compositions with a starch filler were formulated and examined 17 for
biodegradability and general properties (which were found to be fairly
similar to those of comparable compositions containing mineral fillers
at the same loading levels). In burial tests, the starch-filled composi-
tions were readily attacked by a mixture of micro-organisms commonly
present in soil.
6.4 SURFACE TREATMENTS FOR FILLERS
Some grades of calcium carbonate fillers, as well as certain other

particulate and fibrous fillers, are treated with substances which coat
the filler surface and thereby modify its chemical nature. The
modification promotes affinity between the filler and the polymeric
host material, typically by making the originally hydrophilic filler
surface hydrophobic and oleophilic. The treatments are aimed at one
or both of the following two general practical advantages (some other
consequential benefits also arise-see below).
(i) The treated filler is more easily and thoroughly dispersible in

the polymeric matrix during compounding and processing.
(ii) In melt-compounded compositions and melt-processed final
products, the treatment promotes intimate interfacial contact
between the filler and the matrix at the interface. Where the
substance used to treat the filler can act as a coupling agent, the
resulting positive interfacial bonding improves any reinforcing
action (by aiding in affective stress transfer from the matrix to
the filler) and prevents any 'wicking' of moisture along he
interface-compare for example the 'new generation' of
glass-fibre-reinforced uPVC compounds mentioned in Section
6.3.1(c) above.
6 Fillers 289
The amount of treatment substance required to bring about the

improvement is generally relatively low, e.g. with stearate treatments
on calcium carbonate filler (see below) up to about 3% on the weight
of the filler.
A review of surface treatments, with some discussion of their
effects, has been published by Morrell. 18
By reference to the reagents used in surface treatments of fillers
employed in PVC compositions, the treatments may be considered
under the headings of stearate, silane, organotitanate, and mis-
cellaneous and proprietary treatments.
6.4.1 Stearate Treatments
These treatments are the longest-established, and still most widely

used, especially on calcium carbonate fillers. Stearic acid and some
stearates are the usual treatment reagents. In treatment of CaC03
fillers with stearic acid (other fatty acids are also sometimes used) the
acid bonds positively to the filler particle surface through calcium salt
formation: this is demonstrated inter alia by the fact that such
coatings are not removed by solvent extraction. Examples of commer-
cial CaC03 fillers with such surface-bonded coatings are Winnofil S
(lCI) , Polcarb S (ECC) , Omya BLR/3 and Omyalite 95T (Pliiss-
Staufer), Gama-Sperse CS 11 (Georgia Marble Co.), Super-Fil
(Pfizer). Some of the fillers are marketed as 'double-coated' grades,
e.g. Britomya BSH 30 (Croxton & Garry): in comparison with the
corresponding uncoated material (Britomya M), the coating reduces
oil absorption by about 25% and DOP absorption by about 35%.1
6.4.2 Treatment with Silane Coupling Agents
Until fairly recently, silane treatments were not applied to glass fibres
or other fillers for PVc.
Note: Silane coupling agents are widely used on glass fibres
incorporated as reinforcement in other plastics. 3
However, silanes of interest for such applications have now ap-
peared, e.g. the amino-functional silane blend Xl-6100 (Dow Corning
Corp.), and the mercapto-functional dialkoxysilane D 3403 (Kaye-
Fries Inc., USA).
Silane-treated perlite filler grades (from Grefco Inc., USA) have
also been used in some PVC pipe compositions.
6.4.3 Organotitanate Treatments
Alkoxy organotitanates, introduced in 1974/1975 in the USA as

coupling agents for fillers in thermoplastics (as well as in some
thermoset systems4 ,19), are now established in the commercial field,
inter alia as surface treatments for calcium carbonate fillers and
alumina trihydrate flame retardants for PVC. Use of a suitable
organotitanate (e.g. Ken React LICA 38;* Kenrich Petrochemicals
Inc., USA) can make possible increased filler loadings in flexible PVC
compositions (including those for the production of cellular materials),
with no detriment to-and in some cases with improvement of-
ultimate mechanical and wear properties. In uPVC improvements can
be effected in processability (with significantly lower processing
temperatures possible in some cases, and consequent savings on
stabilisers and lubricants), and in the impact strength of the products,
even at increased filler loadings. It has also been suggested20 that the
presence of an organotitanate coating on the CaC0 3 filler can have
some flame-retardant effect in a compound. Among commercial
calcium carbonate fillers surface-treated with organotitanates are some
of the grades supplied (in the USA) by the Sylacauga Calcium
Products Co., and the Solemite calcium carbonates from Solem
Industries Inc.
6.4.4 Proprietary and Miscellaneous Treatments
The nature of proprietary surface treatments applied to some com-

mercial fillers is not generally disclosed, although they are often of the
stearate type. Others include the so-called 'calcium resinate' treat-
ment (as for example on Gama-Sperse CR-12; George Marble Co.,
USA), and treatments involving certain proprietary surface-active
agents of Byk-Mallinckrodt (FRG and USA). Opacifying surface
treatments may also be mentioned (for example as represented by
Omya BLR 2 and BLR 3; Pliiss-Staufer AG), although their function
is not to promote the effects discussed above, but to increase the
refractive index of the CaC03 filler and hence its whitening power in a
compound.
* This reagent can also be included in plastisol formulations to reduce viscosity

and promote adhesion to various substrates (including metal, glass, fabrics,
and paper).
6 Fillers 291
Note: Organometallic coupling agents of the zirco-aluminate type

have also become available commercially in recent years (the
Caveo Mod reagents supplied by Cavedon Chemical Co. Inc.,
USA). In the PVC context these are at present of interest
primarily as additives for plastisols, in which they can
substantially reduce viscosity (with possible plasticiser sav-
ing), permit higher filler loadings, and improve adhesion to
metal and other substrates.
TABLE 6.11
Trade Names and Commercial Sources of Some Fillers
Trade name Nature a Source
Aerosil SS Degussab
Alfrimal AT Fiilstaff GmbH, FRG
Amical CC T AC Industries Inc., USA
Atomite CC(C/D) Cyprus Industrial Minerals, USA
Baco FRF AT B.A. Chemicals Ltd, UK
Bennite CC(L) Ben Bennet Jr Ltd, UK
Britomya CC(W) Croxton & Garry Ltd, UK
Cab-O-Sil SS Cabot Corp., Cab-O-Sil Div., USA
Calciplast CH and CC Folstoff GmbH, FRG
ACH
Calibrite CC(C/D) Ploss-Staufer AG, Switzerland
Calmote CC(L) Derbyshire (Div. Tarmac) Ltd, UK
Caloftl }
Calopake PCC John & E. Sturge Ltd, UK
Cal%rt
Camel-Cal } CC Genstar Stone Products Co., USA
Camel-White
Devolite CL ECCb,c
Eccospheres MS W. R. Grace & Co. b
Fillite MS Fillite Inc., USA
Fordcal CC(C/D) ECC
Gama-Sperse CC Georgia Marble Co., USA
Gasil SS Joseph Crosfield & Sons Ltd, UK
Glomax CL Georgia Kaolin Co., USA
Hakuenka PCC Croxton & Garry Ltd, UK
Hexafil CL ECC
Hi-Sil SS PPG Industries Inc., USA
Hydral AT ALCOAb
Iceberg} CL Burgess Pigment Co., USA (continued)
Icecap
TABLE 6. 11-contd.
Trade name NatureD Source

Micaftex M Eagle Quality Products Co., USA
Micawhite M Mineral Industrial Commodities of
America Inc.
Micral AT Solem Industries Inc., USA
Microcarb CC(W) Microfine Minerals & Chemicals Ltd, UK
Microdol CC(C/D) Norwegian Talc (UK) Ltd
Micro-White CC Sylacauga Calcium, USA
Millicarb CC(C/D) Pliiss-Stauffer AGb
Monykup AO Malvern Minerals Co., USA
Ny tal T R. T. Vanderbilt Co. Inc. USA
Omya CC(C/D) Pliiss-Staufer AG and Omya Inc., USA
Omyalite CC Pliiss-Staufer AG and Omya Inc., USA
Polarite CL ECC
Polcarb CC(C/D) ECC
Pole Star CL ECC
Q-Cell MS PQ Corp., USA
Queensil CC(C/D) ECC
Satintone CL Englehard Corp., USA
Seahorse CC(W) Swedish Whiting Co. Ltd
Snowcal CC(W) Blue Circle Industries Ltd, UK
Sochalu AT Atochemb
Speswhite CL ECC
Sturcal PCC John & E. Sturge Ltd, UK
Super-fil CC(L) Pfizer Inc. ,USA
Superlon CC(L) Longcliffe Quarries Ltd, UK
Suzorite M Suzorite Mica Products Inc., USA
Syloid SS W. R. Grace & Co.
Texchem 11 CC(L) Franklin Limestone Co., USA
Timonox AO Anzon Inc., USA
Tisyn CL Burgess Pigment Co., USA
Trihyde AT Croxton & Garry Ltd, UK
Translink CL Englehard Corp., USA
Vansil WO R. T. Vanderbilt Co. Inc., USA
Vantalc T R. T. Vanderbilt Co. Inc., USA
Vertal T Vermont Talc Inc., USA
Winnofil S PCC ICI b
Wolastokup WO Malvern Minerals Co., USA
D Key: AO, antimony oxide; AT, alumina trihydrate; CC, calcium carbonate;
C/D, calcite or dolomite; CL, clay (kaolin or calcined); L, limestone; M,
mica; MS, hollow microspheres (glass or ceramic); PCC, precipitated calcium
carbonate; SS, synthetic silica; T, talc; W, whiting; WO, wollastonite.
b Wide geographical coverage (including supply through subsidiaries and
agents).
C English China Clays International Ltd, and ECC America.
6 Fillers 293
6.5 COMMERCIAL FILLERS
Some commercial filler trade names and sources are listed in Table
6.11.
REFERENCES

2. Highley, D. E., Mineral Dossier No. 26: China Clay. HM Stationery
Office, London, 1984.
3. Titow, W. V. & Lanham, B. J., Reinforced Thermoplastics. Applied
Science Publishers, London, 1975.
4. Titow, W. V. In Developments in PVC Production and Processing-i, ed.
A. Whelan & J. L. Craft. Applied Science Publishers, London, 1977, Ch.
4.
5. Skurauskis, M. & Tripathi, V., Plastics Compounding, 7 (1984) 25-8.
6. Rogan, J., Plast. Technol., 25(8) (1979) 100.
7. Whiting: Notes on Origin, Manufacture, Properties and Uses. Research
Council of the British Whiting Federation, April 1962.
8. Lowry, T. M., Inorganic Chemistry, 2nd edn. Macmillan & Co., London,
1946, pp. 732-3.
9. ASTM D 3360-80. Particle size distribution by hydrometer of the
common white extender pigments.
10. ISO 2470-1977. Paper and board-Measurement of diffuse blue reflec-
tance factor (ISO brightness).
11. Jenkins, F. A. & White, H. E., Fundamentals of Optics. McGraw Hill
Publishing Co., New York, London, Toronto, 1953, Ch. 28.
12. Jenkins, F. A. & White, H. E., Fundamentals of Optics. McGraw Hill
Publishing Co., New York, London, Toronto, 1953, Ch. 23.
13. Axelson, J. W. & Kietzman, J. H., 34th ANTEC SPE Proceedings (1976)
601-5.
14. Anon., Mod. Plast. Int., 16(10) (1986) 19.
15. Anon., Plast. Techno!., 25(7) (1979) 95.
16. Anon., Mod. Plast. Int., 6(10) (1976) 14, 15.
17. Westhoff, R. P., Otey, F. H., Mehltretter, C. L. & Russell, C. R., Ind.
Eng. Chem. Prod. Res. Develop., 13(2) (1974) 123-5.
18. Morrell, S. H. Plast. Rubb. Process. Applns 1(2) (1981) 179-86.
19. Monte, S. J., Sugerman, G. & Seeman, D. J., 34th ANTEC SPE
Proceedings, 1976, 27-39.
20. Naitove, M. H. & Evans, L., Plast. Technol., 22(8) (1976) 71-4.
CHAPTER 7
Lubricants
7.1 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 ex-
ample, in the extrusion of a rigid PVC composition effective lubrica-
tion 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
(either directly, or through interaction with other components of the
formulation; see below), impact strength of some uPVC compositions,
surface finish and printability (which may be impaired by the presence
of a lubricant). The lubricating action and effects may be divided into
external and internal, but the lubricants themselves cannot be so
classified with complete accuracy, since many can combine both
functions in varying degrees, depending on the proportion used and
the particular processing conditions. Moreover, other components of a
PVC formulation can have lubricant effects, and influence the perfor-
mance of, or requirements for, the lubricant proper.
The principal external lubrication effect is the reduction of friction
and sticking between the hot PVC composition and the working
surfaces of processing machinery due to the presence of a layer of
lubricant at the interface. The direct operational benefits are easier
movement of the stock through the machinery, and prevention of its
294
7 Lubricants 295
adhesion to the hot metal that would quickly result in local formation
of stagnant layers, their overheating and degradation ('burn-up').
Note: Avoidance of stagnant deposits is important in all melt-

processing of PVC, as-apart from its own deterioration-the
degraded material contaminates the stock and promotes
further decomposition of the polymer.
The basic internal lubrication effect is the lowering of internal (Le.

intermolecular) friction in the polymer, as the composition is being
hot-sheared, fused into a melt, and processed in that form. Reduction
of interparticle friction before and during melt formation is also
sometimes included as an aspect of internal lubrication (because the
compatibility of a lubricant with a basically internal action may be
relatively low at the comparatively low temperature and pressure
obtaining at that stage, say in the feed zone of an extruder; see below
for the role of lubricant compatibility). The main outward manifesta-
tions of effective internal lubrication are reduction of frictional heat
build-up under shear, and lowering of the melt viscosity. Among the
resulting practical benefits in processing are: reduced risk of heat
degradation and reduction of heat history of the material; easier and
faster flow of the melt through the equipment (including channels and
gates in moulding); easier and better mould filling (including reduced
tendency to sink marks, better part-size control and surface finish);
reduced die swell in extrusion; and reduced tendency to stress
whitening in products.
An additive, especially one of relatively low molecular weight,
which is dispersible in the PVC polymer at the molecular level (i.e. at
least to some extent 'soluble' in it), may be expected to have some
lubricant action. If, at the level of addition appropriate to the
formulation, the additive's compatibility with the palymer at the
processing temperature is complete, then the additive may function as
an internal lubricant (i.e. it should reduce work-heat build-up and
lower melt viscosity).
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
polymeric processing aid) and polymeric plasticisers do have

an internal lubricant action in that they lower the melt
viscosity of PVC compositions.
If the compatibility is not complete, the excess additive will form a
boundary layer between the PVC composition and the hot metal
working surfaces: the layer will provide external lubrication if the
relevant chemical and physical properties of the additive make it a
sufficiently effective 'slip agent'.
In broad terms, the compatibility of common additives capable of
lubricant action, and their usual level of addition in PVC composi-
tions, both decrease in the sequence:
primary plasticisers > secondary plasticisers and extenders>
impact modifiers* and processing aidst > stabilisers and
lubricants
The important general actions and characteristics to be looked for in
an effective lubricant for PVC may be summarised (with Marshale) as
follows.
For internal lubrication: Reduction of internal friction; improve-

ment of melt flow (lowering of melt viscosity); fairly low affinity for,
but some compatibility with, PVC polymer, little or no affinity for the
metal working surfaces; no chemical interaction with PVC; solid at
room temperature, preferably liquid at the processing temperature.
For external lubrication: Reduction of external friction; formation

of a parting layer, easily sheared or peeled, at the PVC-metal
interface; very low compatibility with PVC; little or no affinity for
PVC but some affinity for the metal working surfaces; no chemical
interaction with PVC; solid at room temperature but preferably liquid
at the processhlg temperature.
Since the mode of a lubricant's action, and to some extent its

effectivity, are closely linked to its compatibility with PVC, con-
* Some polymeric impact modifiers (e.g. highly chlorinated polyethylene,

nitrile rubber, some VC/E/VAC graft copolymers) are highly compatible with
PVC polymer-see Chapter 8.
t Some processing aids are occasionally used in high proportions to increase
the resistance of uPVC to deformation at elevated temperatures-see Chapter
8.
7 Lubricants 297
siderable attention has been directed to ways of assessing com-

patibility, and studies have been made of the relationship between the
compatibility and chemical structure of lubricants. Some of the
methods used to assess compatibility of plasticisers with PVC (see
Section 5.4 of Chapter 5) have been applied to the same end with
lubricants, viz. determination of the reduction of the Tg of PVC by a
lubricane (greatest reduction with highest compatibility), and com-
parison of solubility parameters. 1 Determination (visual, by micro-
scopic examination, or by instrumental measurement--e.g. with an
integrating sphere photometer3 ) on the onset of haze in a clear PVC
composition with increasing content of lubricant is another method of
compatibility assessment: the first appearance of haze indicates that
the limit of compatibility is being exceeded, with the lubricant
molecules, previously accommodated between the polymer chains,
now aggregating to form particles of a separate phase large enough to
scatter light. In some cases, e.g. with stearic acid, the particles of the
excluded lubricant are seen under the microscope to have the form of
dendritic crystals.
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,4 are
consistent with the theoretical expectation that the aliphatic 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 7.1:
among those, typical examples of low compatibility and external
lubrication effects are provided by, say, the polyethylene and synthetic
paraffin waxes, whilst relatively high compatibility and associated
internal lubricant action are exemplified by monoesters of glycerol
with fatty acids of relatively short aliphatic chain length.
Two materials may additionally be mentioned which, although not
conventional lubricants, have a substantial lubricant action in PVC
compositions. These are certain processing aids of the acrylic polymer
type, and a special grade of synthetic magnesium silicate.
Some all-acrylic processing aids combine their primary function (see
TABLE 7.1
Compounds used as Lubricants in PVC
General type Class of compound Typical Typical useb Some commercial versions e
functionalityQ
Natural hydrocarbons Paraffins and paraffin e (a few also i) u Hostalub XL-200; Veba C60;
(generally petroleum- waxes Advawax ML 2516;
derived)
Synthetic paraffins e u Sasolwax
Low-molecular-weight e (some also i) u (some p) Epolene E-14P, Hoechst Wax
polyolefins P E 130 (polyethylene
waxes); Hostalub PP 230
(atactic polypropylene)
Fatty alcohols (Iong- Various (commonly C 16- u Irgawax 365; Hostalub Al
chain) C 1S alcohols)
Fatty acids Various (most commonly Mainlye Mainly u, some p Hostalub FI; Glycan S-90;
stearic) Hystrene 9718
Fatty acid salts (soaps) Predominantly stearates e (some i d ) uandp Hostalub CaFI, Interstab Ca-
(mainly of calcium, lead 18-1 (Ca stearates);
and zinc; also lithium, Hostalub PbFI (Pb stearate)
aluminium, magnesium
and some othersC )
Esters Simple fatty acid esters Mainly i (some i and e) Some u, some u and p Loxiol G30; Hostalub ARE-1
Complex esters Mainlye u and p Loxiol G 71; Glycolube P
Glycerol esters and partial Mainly i u, some p Loxiol G 10; Irgawax 361 and
esters 369; Atmer 1010 (glycerol
mono-oleate)
Glycol esters i u Loxiol G13
Ester waxes (including e and i u andp Hoechst Wax E and OP;
montan acid esters) Hostalub CA W-1 (montan
wax)
Amides Amide waxes e and i Mainly u Hostalub FA1; Interstab G8257
a e, External lubrication; i, internal lubrication.

b u, Unplasticised and rigid compositions; p, plasticised compositions.
C Several of these soaps also have a stabilising action (see Section 7.2.1).
d Depending on the metal of the soap, the two functions may be combined, or e may predominate (e.g. calcium stearate--e with some i;
lead stearate essentially e.
e Advawax, Carstab/Morton-Thiokol, USA; Atmer, ICI Europa Ltd, Belgium; Epolene, Eastman Chemical Products, USA; Glycolube,
Glycon, Glyco Inc., USA (Subsidiary of Lonza, Switzerland); Hostalub, Hoechst, FRG and USA; Hystrene, Humko Chemical Div.,
Witco, USA; Interstab, Interstab Chemicals, USA; Loxiol, Henkel, FRG and USA; Sasolwax, Sasol Marketing Co., RSA; Veba,
Durachem Corp., USA.
Chapter 8) with an external lubricant effect in PVC compositions. An

example is Acryloid* K175: whilst of limited compatibility in PVC at
processing temperatures (and thus providing external lubrication for
the melt), it is non-migrating in the product at room temperature
(unlike some conventional external lubricants). Its other functional
features contrasting with those of many conventional lubricants are: no
appreciable effect on the fusion characteristics of PVC compositions;
no contribution to plate-out; no impairment (and often improvement)
of clarity of transparent compositions; no adverse effect on product
strength.
A pronounced lubricant effect in uPVC is claimed for a synthetic,
particulate magnesium silicate (spherical particles of 5 tJ,m average
size) marketed under the trade name Magnesol (Reagent Chemical &
Research Inc., USA). In-plant extrusion trials with a uPVC pipe
composition have been reported5 showing that incorporation of the
additive reduces the drive power requirement and back-pressure even
at a somewhat reduced melt temperature: these findings are consistent
with effective lubrication. The lubrication is thought to be provided by
finely divided amorphous silica gel formed in the PVC composition
from the Magnesol as it reacts with nascent HCI (thereby also
exercising a stabilising function).
Certain performance traits tend to be exhibited by representatives of
particular lubricant types. Some examples are: synergism with certain
stabilisers (a feature of glycerol partial esters and some metal soaps;
see also Section 7.2); tolerance of differences in processing conditions
(good-fatty acid esters; relatively poor-paraffins, polyethylene
waxes); contribution to plate-out (some metal soaps); tendency to
migration or exudation in products (fatty alcohols; fatty acids).
Whereas rigid PVC compositions normally require both internal and
external lubrication, only externally functional lubricants are normally
considered for flexible compositions, as in those the plasticiser will
normally provide internal lubrication (some external lubrication may
also be effected by certain plasticiser extenders, if present, in
consequence of their lower compatibility). However, an external
lubricant may be useful, or necessary, even in some highly plasticised
paste compositions, especially for intricate mOUldings.
* Rohm & Haas Co., USA: the trade name Acry/oid is used in the USA, and
Para/oid in the UK and Europe, but the product coding is universal, i.e.
Aery/oid K175 is the same product as Para/oid K175.
7 Lubricants 301
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 (especially the stabilisers), more than one lubricant
(i.e. a lubricant system) is commonly employed in rigid PVC formula-
tions (where up to four lubricants may be combined in some cases)
and sometimes also in pPVc. The mutual effects of the lubricants with
the stabilisers and some other formulation components are important
considerations, affecting both the choice of the lubricant system and
the design of the formulation as a whole. The effects are not
predictable theoretically, and whilst many are now known from
accumulated practical experience, the formulation of lubricant systems
for particular PVC compositions is still very much a practical art. As
one example of some of the complexities facing the formulator, it may
be mentioned that, in a basic study,6 the effectiveness of calcium
stearate and stearic acid-two lubricants in wide industrial use-in
external lubrication of simple uPVC powder blends was found to be
critically dependent on such factors as the nature of the stabiliser in
the PVC composition, and whether the lubricants were used singly or
together: changes in these factors could actually reverse the
effectiveness ranking of the lubricants in otherwise identical
conditions.
7.2 INTERACTION AND CO-ACTION OF LUBRICANTS

WITH OTHER PVC FORMULATION COMPONENTS
7.2.1 Lubricant/Stabiliser Effects
(a) Stabilising Effects of Lubricants
DIRECT STABILISING ACTION

Most lubricants of the metal soap type (see Table 7.1) 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. In particular 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 stabilisa-
tion 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

The best known effects include: improvements in heat stability (mainly
long-term) in compositions stabilised with sulphur-containing tin
stabilisers when partial esters of glycerol are used as lubricants* (liquid
versions, e.g. glycerol monoricinoleate, are appropriate for transpar-
ent compositions); enhancement by these esters of the stability of
compositions containing some lead stabiliser systems (but discoloura-
tion can arise, especially on outdoor exposure, where inorganic lead
stabilisers are present, e.g. lead phosphite or sulphatet); synergistic
improvement of the long- and short-term stability of some lead-
stabilised uPVC compositions by pentaerythritol/fatty-acid partial
ester lubricants (allowing significant reductions in the amount of
stabiliser in many cases7); beneficial synergism between calcium
stearate lubricant and antimony mercaptide stabilisers;8 stability im-
provement in rigid PVC compositions stabilised solely with calcium
stearate (e.g. some pipe compositions for potable water in Europe)
that can be produced by many lubricants, whether synergistic or
'neutral' with other stabilisers. 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).
INDIRECT STABILISING ACTION

In discharging their primary functions, the lubricants can also affect
the thermal stability of PVC compositions. Because they lower
work-heat build-up and melt viscosity (and hence the effective
processing temperature), and limit direct contact between the stock
and the hot metal of processing surfaces, whilst simultaneously
preventing the formation of stagnant deposits, lubricants reduce the
* The extent of improvement depends in a complex way on several factors,

including the type and grade of the PVC polymer, the nature of the stabiliser
system, and the respective amounts of stabiliser and lubricant.
t This has been attributed to a reaction of these compounds, in the presence of
light, with residual amounts of free glycerol often present in commercial
glycerol esters. 7
7 Lubricants 303
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 is
a factor in enhancing the long-term stability of the composition. In
these ways an effective system can reduce functional demands on the
stabiliser.
(b) 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 Chapter 4). Some tin stabilisers also exert lubricant effects
(e.g. dibutyltin dilaurate), as do barium/cadmium 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 itself.
7.2.2 Mutual Etfects of Lubricants and Plasticisers
(a) Primary Plasticisers

The internal lubricating action of primary plasticisers has been
mentioned (see Section 7.1 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.
(b) Secondary Plasticisers and Extenders

Some of these may exert external lubricant effects in addition to their
internal lubricant functionality. However, the occurrence (and, if
occurring, the extent) of external lubrication will depend on the
compatibility of the additive concerned at the processing temperature
(which will be a function of the chemical nature and the amount
present), and to some extent also on the nature of 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.
7.2.3 Effects of Polymeric Modifiers
The polymeric additives incorporated in PVC compositions, in rela-

tively minor proportions, as impact modifiers and processing aids, can,
in individual cases, affect the total lubricant requirement and/or that
for the internal/external lubricant balance. Such effects are associated
with the extent of the modifier's compatibility with the composition as
a whole, or-as in the already-mentioned case of some acrylic
processing aids-with its own lubricant action.
(a) Impact 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, VC/E/VAC 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.
(b) Processing Aids

Most 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, the relatively
low-molecular-weight grade of poly-a-methylstyrene used as a proces-
sing aid (see Chapter 8) does lower the melt viscosity, and-as
mentioned above-some all-acrylic processing aids provide effective
external lubrication.
7.2.4 Effects of Fillers and Pigments
Fillers and pigments (especially fine-particle grades) can bind lubric-

ants by adsorption (cf. plasticiser demand-Chapters 5 and 6) 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 6), as this can not only reduce adsorption of
lubricants at the particle surface, but also actually contribute to
external lubrication.
7 Lubricants 305
7.3 ASSESSMENT OF LUBRICANT PERFORMANCE
7.3.1 Test Methods
Several methods are available for the assessment and comparison of

lubricant effects in PVC compositions. The associated equipment
ranges from relatively simple to quite sophisticated. In-plant trials are
also necessary but, in view of the expense and possible disruption of
regular production, they should preferably be undertaken as a final
step after a preliminary laboratory-scale evaluation.
Some of the test methods mentioned in this section can, in addition
to indicating the presence and extent of lubrication, also distinguish
between internal and external lubricant effects.
(a) Sheet 'Fluidity' Test

This is a simple, practical test, originated by Jacobson9 and Marshall ,1
whereby the effects may be roughly gauged of different lubricants, or
different amounts of the same lubricant, in a PVC composition.
A pressed sheet is made from each variant of the composition
(representing lubricant variation), and one control sheet without
lubricant. The sheets may be made by the method described in Section
17.1.3 of Chapter 17, to a final thickness of 2-4 mm, each from four to
six cross-laid mill sheets about 1 mm thick. A square specimen about
50 mm x 50 mm is cut from each sheet. Each specimen, heated to a
temperature relevant to the processing temperature concerned, is then
pressed between metal plates in controlled conditions of pressure and
time. The metal of the plates may be the same as that of the working
surfaces of any production equipment to be used ultimately. The hot
specimen will flow out under pressure, losing its square shape and
forming a thinner disc. The 'fluidity' (F) of the material is then
calculated from the relationship F = (AL - As)/As, where AL is the
area of the disc formed by the lubricated material and As the area of
the standard material disc. A plot of fluidity against lubricant content
can sometimes be interpreted to obtain indications of the compatibility
limit of the lubricant and (very approximately) the respective internal
and external lubrication effects. 1
(b) Two-Roll Milling

Running a composition on a two-roll mill in standard conditions in
comparison with a non-lubricated control (or a control with a standard
lubricant system) can give an indication of the effect of lubricants in
the test composition in terms of ease of formation of a mill hide, and

'time to tack'. The latter is the time taken for the stock to begin
sticking to the rolls, and is a function of the effectiveness of external
lubrication (however, it is also influenced by that of stabilisation).
(c) Flow in Moulds and Dies

The performance of lubricants or lubricant systems in a PVC moulding
composition may be gauged and compared in terms of flow behaviour
in a spiral mould, in the Rossi-Peakes flow tester, or through
plastometer dies.
FLOW IN A SPIRAL MOULD 10 ,l1

The mould, typically of platen size about 30 cm x 23 cm (12 in x 9 in),
spiral length 199 cm, and half-round channel section of 4·7 mm
diameter,lO,11 with means of accurate temperature control, is used with
a small injection-moulding machine of adequate shot capacity, capable
of accurate adjustment of melt temperature, injection pressure, feed,
and time cycle. In the absence of over-lubrication with the attendant
abnormal effects, the flow of the molten composition in the mould will
be assisted by effective lubrication. Under standardised test condi-
tions, the better the lubrication the greater the 'flow length', i.e. the
length of the spiral filled by the melt. Graphs of flow lengths versus
temperature may be plotted to obtain quantitative data over a range of
conditions. 11
FLOW IN A ROSSI-PEAKES FLOW TESTER

In a standard test for thermoplastics employing this apparatus,12 either
the degree of flow is measured-under controlled conditions of
temperature, pressure, and time-in what the relevant standard terms
as 'extrusion mould', or the temperature is determined at which the
material attains a certain degree of flow in the conditions of the test.
In a test for lubricant effects in a PVC composition, the results in
either variant of the method are influenced mainly by internal
lubrication. Apart from the special flow apparatus, equipment is also
needed for moulding the test specimens (cylindrical pellets of height
and diameter 9·5 mm).
FLOW IN A PISTON PLASTOMETER

A standard plastometer test method, intended specifically for PVC
compositions (and other rheologically unstable thermoplastics),13 can
7 Lubricants 307
be used inter alia to compare the effectiveness of lubricants (especially

those with internal functionality) in basically similar PVC composi-
tions. In some cases the results correlate with those obtainable in
processing conditions (see also Section 16.2 of Chapter 16).
THE ASTM CAPILLARY RHEOMETER TEST 1•

This is sensitive to the effects of additives-including lubricants-in
plastics compositions (including PVC ones, which are tested in the
temperature range 170-205°C), and is operated under conditions that
can be related to those obtaining in some industrial processes.
(d) Tests Using the Brabender Plasti-Corder

Determinations in this equipment can indicate the type of lubricant
action, and the magnitude of the effects.
FUSION TEST IN A ROLLER MIXER ATTACHMENT

In the fusion test outlined in Section 11.4.2(b) of Chapter 11, the most
characteristic effects of lubricants are manifested as follows. With
typical external lubrication, fusion time is increased and the torque
value may be reduced (because of decrease of external friction).
Effective internal lubrication reduces torque significantly (in conse-
quence of the drop in melt viscosity), with little or no effect on fusion
time. Typical conditions for initial ranging tests (which may later be
modified according to the preliminary results) would be: 15 torque-
measuring range around 50 Nm (but generally adapted to the type of
composition); processing temperature within the range 140-160°C,
depending on the composition; rotor speed 30 r min -\. The fusion time
found can provide guidance on such processing parameters as the
combination of extruder screw speed and length required, and the
likely output at particular screw lengths and speeds. The maximum
torque in the test can be similarly related to the drive power
requirements in the production extruder. 15 Such interpretation of the
test results is based on a working assumption of similarity between the
torque curve ('plastogram') obtained from the test and an analogous
torque profile in an extruder in relation to the screw length, as shown
schematically in Fig. 7.1. However, the way in which lubricant effects
are reflected in the results of the fusion test may not always correlate
with performance in a production extruder, because the functionality
of some internal lubricants may be different at the generally higher
shear rates experienced in the latter.
~
H
III
o{)
III
H
:>
......
OJ
go
E<
TORQUE/VISCOSITY
STOCK TEMPERATURE
FIXED TEMPERATURE
LEVEL
1/3 TIME
\ .'. -.
LENGTH OF BARREL
Fig. 7.1 Torque distribution along the screw of a processing machine, in relation to the results of a Brabender fusion
test (After Liiben 15-courtesy of Brabender® OHG, Duisburg, FRG).
7 Lubricants 309
PROCESSABILITY TEST IN A BRABENDER EXTRUSIOGRAPH WITH A RHEOMETRIC

HEAD
In essence, this combination of an instrumented extruder with a
capillary rheometer provides data on torque and pressure experienced
by the stock in its progress along the barrel, the stock temperature,
and melt flow: hence information is also obtained on the shear rate
and melt viscosity. Interpreted on the basis illustrated by the graphs in
Fig. 7.1, the results of a suitable series of comparative tests enable
evaluations to be made of lubricant action, since melt viscosity and
torque are reduced in proportion to the effectiveness of internal
lubrication, and the pressure profile is similarly influenced by external
lubrication.
7.3.2 Some Research Equipment and Methods
Highly sophisticated equipment has been described by Chauffoureaux

and co-workers,16 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. Inter alia, these investigators observed directly an
increase in the melt velocity at the wall face of an extruder die (slip
effect) in the case of a PVC composition containing a lubricant with
effective external action: this effect was absent when the lubricant used
was one with typically internal functionality.
Apparatus-the lateral friction tester-has been devised6 for the
investigation of the effect of lubricants with external functionality on
the frictional properties (particle/particle and particle/working-surface
friction) of particulate PVC compositions at temperatures below the
fusion temperature.
Reviews of some studies directed to characterising and classifying
lubricant effects have been published by Gale 17 and by Logan &
Chung. 18
7.3.3 'Lubricant Value'
The concept of 'lubricant value' (LV) has been put forward 19 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 the mixing attachment of a Brabender Plasti-Corder

are used in the formula:
LV= l000E/T. md
where E is the total weight of lubricant additive (phr); T is the stock
temperature in the mixing compartment (oq; 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 19 to lie between 6 and
14.
7.4 SOME EFFECTS OF INCORRECT LUBRICATION
These are indicated in Table 7.2.
7.5 COMMERCIAL LUBRICANTS
Most 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 physical forms in which lubricants, lubricant/stabiliser systems,
and one-pack systems are supplied include liquids, powders, flakes,
and prills (free-running granules). Also available are lubricant con-
centrates in a PVC carrier, in the form of PVC particles heavily loaded
(about 50% and over) with normally solid lubricants (especially metal
stearates). The principal advantages of such concentrates are that they
are virtually dust-free, can be pneumatically conveyed, and have
dry-flow properties similar to those of PVC resins.
Some lubricant trade names and sources are indicated in Table 7.1.
The following may also be mentioned by way of further examples:
Biiropan (Otto Barlocher, FRG); Ceroxin (Henkel); Coad (Mathe
Div., Norac Co., USA); Comboloob (Durachem Corp., USA);
Irgawax (Ciba-Geigy); Kemamide (Humko Chemical Div., Witco,
TABLE 7.2
Some Typical Manifestations of Incorrect Lubricatiou
Lubrication Lubrication Effects
type fault
In processing In product
External Overlubrication Excessive slippage (causing lower output, or Weak weld lines, and tendency to delamination
(or wrong balance) disruption of production in extreme cases); in mouldings and extrusion products.
impaired melt homogenisation; plate-out Increased tendency to stress-whitening.
'01
Possible impairment of impact resistance.
Surface bloom (with impaired printability). l:"-
I::
<::7"
Haze in clear products ~.
Underlubrication Increased frictional effects, heat build-up and Impaired heat stability (through increased heat
(or wrong balance) sticking, with increased risk of degradation history). Possible deterioration in physical ~
and 'bum-up' (scorching) in extreme cases properties and appearance in extreme cases
(because of degradation)
Internal Overlubrication Contribution to plate-out in some cases Possible reduction of softening point and
(or wrong balance) (especially by any impurities in the lubricant) deflection temperature under load
Underlubrication Increased melt-shear effects (with increased Increased tendency to sink marks in mOUldings.
(or wrong balance) work-heat and risk of degradation). Reduced Impaired heat stability (through increased
moulding speed. Increased die swell and heat history). Possible heat degradation in
possibility of melt fracture in extrusion some extreme cases
t..>
-
USA); Lobowax (Durachem Corp., USA); Metablen* (M & T Chemi-

cals, USA): Metaglide and Metawax (Acima, Switzerland): Petrac
(Petrochemicals Co. Inc., USA); Realube (Reagens SpA, Italy);
Stenol (Henkel); Unislip (Unichema Chemicals, USA); Vestowax
(Hiils).
REFERENCES
1. Marshall, B.I., Brit. Plast., 42(8) (1969) 70-8.

2. King, L. F. & Noel, F., Polym. Engng Sci., U(2) (1972) 112.
3. ASTM D 1003-61 (1977). Haze and Luminous Transmittance of Transpar-
ent Plastics.
4. Illmann, G., SPE 1., 23 (1967) 71-8.
5. Anon., Plast. Technol., 32(7) (1986) 74-5.
6. Portingell, G. C. In Particulate Nature of PVC, ed. G. Butters. Applied
Science Publishers, London, 1982, Ch. 4.
7. Worschech, K. F., 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.
8. Titow, W. V. In Developments in PVC Production and Processing-l ed.
A. Whelan & J. L. Craft. Applied Science Publishers, London, 1978, Ch.
4.
9. Jacobson, U., Brit. Plast., 34(6) (1961) 328-33.
10. Campbell, G. & Griffiths, L. I., Plastics Progress, Iliffe Books, Butter-
worth, London, 1956, p. 259.
11. Anon., The Principles of Injection MOUlding. ICI Technical Service Note
Gl03, 1965, p. 13.
12. ASTM D 569-82. Measuring the Flow Properties of Thermoplastic Mould-
ing Materials.
13. ASTM D 3364-74 (1983). Flow Rates for Poly(vinyl chloride) and Rheolo-
gically Unstable Thermoplastics.
14. ASTM D 3835-79 (1983). Rheological Properties of Thermoplastics-With
a Capillary Rheometer.
15. Uiben, H. E., CAR-Computer-Aided Rheometry. Brabender OHG,
Duisburg, 1986.
16. Chauffoureaux, J. c., Dehennau, C. & van Rijkevorsel, J., 1. Rheol.,
23(1) (1979) 1-24.
17. Gale, G. M. In Developments in PVC Technology, ed. J. H. L. Henson &
A. Whelan. Applied Science Publishers, London, 1973, Ch. 3.
18. Logan, M. S. & Chung, C. I., Polym. Engng Sci., 19(15) (1979) 1110-16.
19. Bottner, E. F. & Rosenthal, C., Kunststoffe, 62(10) (1972) 685-7.
* Metablen P-700 is an acrylic processing aid with some lubricant effect.

CHAPTER 8
Polymeric Modifiers
8.1 NATURE AND FUNCTIONS-GENERAL
The polymeric additives incorporated into PVC compositions are of

two main functional kinds: processing aids and impact modifiers. The
prominent differences between these two groups lie in the nature of
the polymers, and usual level of addition (normally substantially
lower with the processing aids), and in the type of effect: processing
aids-as their name implies-improve some hot-processing charac-
teristics of PVC compounds (but have no fundamental effect on the
properties 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 at
temperatures somewhat higher than those at which typical processing
aids exert their effects); processing aids can significantly affect some
product properties. Some of the polymeric additives may also be used
in exceptionally high proportions to upgrade the heat-distortion
properties of uPVC compositions or to combine a toughening effect
with plasticisation of virtually ideal permanence. All these points are
discussed in the following sections.
In the production of PVC powder blends, the order of addition of
the formulation components, in conjunction with the temperature at
the various mixing stages, can affect the ease and effectiveness of
dispersion of polymeric modifiers. The following guidelines for a
particular sequence and conditions in hot high-speed mixing of a
313
powder blend to be used as extrusion feedstock illustrate one

recommended procedure. 1
--charge the PVC polymer powder to the mixer and mix at the
appropriate (high) speed;
-add colourant and stabilisers at 45°C, then impact modifier at
60°C;
-add lubricant(s) at 80°C;
-when the temperature reaches lOO°C add acrylic processing aid;
--continue mixing, and at 110-112°C discharge the batch into a
cold mixer (e.g. a water-jacketed ribbon blender); run till cooled
to 40°C and discharge.
For further, general, features of hot-mixing procedures see Section
11.2.2(b) of Chapter 11.
8.2 PROCESSING AIDS
Polymers of the following types are used as processing aids in PVc.

(a) acrylates and methacrylates (acrylic or 'all-acrylic' processing
aids);
(b) styrene/methacrylate copolymers;
(c) acrylonitrile/butadiene/styrene (ABS) polymers;
(d) styrene/acrylonitrile (SAN) copolymers;
(e) poly-a-methylstyrene (PAMS).
The molecular weight of the PAMS grades marketed as processing
aids for PVC (e.g. Amoco Resin 18; Amoco Chemicals Corp., USA)
is low compared with that of other processing aids. The associated
possibility of volatilisation is the reason for the occasional appearance
of voids in PAMS-containing PVC compounds processed at extreme
temperatures.
Some ABS polymers are used also as impact modifiers (as are some
acrylic polymers; see Section 8.3). Their modulus of elasticity, which
depends on the composition of the terpolymer, can provide a rough
indication of suitability for one or the other application. ABS
modifiers with good processing-aid action have the highest moduli,
whilst the moduli of those useful as impact modifiers are relatively
low (typically less than about 1·4 GPa).
8 Polymeric Modifiers 315
Processing aids are employed mainly in rigid PVC compositions, in

relatively low proportions (about 1-6 phr) , to facilitate melt process-
ing. The following effects are typical of their presence in the hot stock.
(i) Faster fusion and homogenisation, except in the case of
lubricating processing aids (cf. Chapter 7, Section 7.1) which
extend fusion time [but reduce torque and back-pressure in
extrusion; cf. (v) below].
(ii) Improved melt cohesion (strength and extensibility): in the case
of acrylic modifiers this has been attributed2 to a kind of local
reinforcement through entanglement of their longer, more
flexible molecules with the shorter, stiffer ones of the PVC
polymer.
(iii) Reduction of melt modulus, die swell, and tendency to melt
fracture.
(iv) In some cases, increased melt viscosity (not with PAMS, by
which it is reduced in most uPVC compositions, or with
acrylics, which do not greatly affect it).
(v) Promotion of complete fusion at a lower temperature, or
improved fusion at a given temperature (up to about 190°C).
(vi) Increased torque during the fusing (fluxing) stage in melt-
compounding and extrusion (with increased back-pressure in
the latter): attributed to the faster, higher-shear character of
the fusion process2 ,3 [i.e. effect (i) above] in conjunction with
effect (v), and not primarily to a general increase in melt
viscosity that might be caused simply by the presence of the
processing aid.
Effects (i) and (vi) can be sensitive to the nature and amounts of the
lubricants present in the PVC composition (especially where the
processing aid is PAMS4).
Effect (ii) is the main reason why processing aids (especially the
acrylic ones) can make possible faster processing rates in extrusion and
calendering, and deeper draw in thermoforming.
Although used primarily in uPVC compositions, and relatively less
important in pPVC (which is processed at substantially lower tempera-
tures), some processing aids-notably the acrylics-can have a bene-
ficial effect in semi-rigid and flexible compositions where, too, they
improve the fusion rate and melt cohesion. Lubricating acrylics (e.g.
Aery/oid K175; Rohm & Haas, USA) can also improve output rate
and product quality (surface finish and uniformity), e.g. in extrusion,
and counteract plate-out (where they are used in a formulation instead

of ordinary lubricants).
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.
Some improvement in impact resistance (or further improvement if an
impact modifier is also present) may be effected by acrylic processing
aids in uPVC compositions.
Incorporation in uPVC compositions of high proportions (up to
about 50phr) 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 Sahajpal5 ) 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
85°C and impact strength (ASTM D 256) of 32·4 kgf cm cm- 2 .
Suspension PVC polymer, K value 58 100
Stabiliser: Irgastab 17 MOK (Ciba-Geigy) 1·2 phr
Polymeric modifiers: SAN 20 phr
MBS lOphr
Lubricants: Sapchim Lubricant 4150 0·7 phr
Sapchim Lubricant 6164 0·5 phr
8.3 IMPACT MODIFIERS

8.3.1 Impact Resistance-Definition, Significance, and
measurement
In the functional sense, impact modifiers for PVC are formulation
components incorporated in rigid compositions to increase the impact
resistance of the PVC polymer (and hence of the entire composition).

In the context of tests and service, impact resistance is determined
and expressed in terms of the impact energy required to break (i.e.
cause to fail by fracture) a plastics test specimen or product (e.g. a
moulding, extruded pipe, etc.).
Note: Strength-another highly important mechanical property of
plastics-is determined (in the appropriate mode, i.e. ten-
sion, compression, flexure or shear) via the breaking force or
load, and expressed as the corresponding stress (i.e. force
per unit cross-sectional area). It is for this reason that the
term 'impact resistance' is now favoured over the previously
widely used 'impact strength'.
'Toughness' is sometimes used as simply another name for impact
resistance. However, strictly speaking, toughness is a wider concept, in
that it is a material's resistance to breaking under any applied force,
not just by impact. As such, this property (which may be regarded as
the opposite of brittleness) is evaluated in terms of the total energy
required to break the material in any mode (as given in tests by the
area under the relevant stress-strain curve).
Impacts in tests and service involve rates of deformation comparable
with those that may be experienced by objects free-falling onto a hard
surface from a height, and thus very much higher than those
encountered in tensile strength tests on plastics. Some illustrative
values for the deformation rates are: in free drop 2-7 m S-1; in a
standard tensile strength test6 0·75-550 mm min- 1 (=1·67 X
10-5 m S-1); in a standard tensile impact tese 2·5-250 m min- 1
(=0·042-4·2 m S-1).
The dissimilarities just mentioned, although highly significant in all
relevant respects, do not mean that impact tests are fundamentally
different from strength tests. Although not measured directly in the
latter, the total energy to break the specimen 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 shown8 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 is the same in the two tests.
As is known, the mode of failure of a plastics material under impact
is strongly influenced by two external factors: the temperature and the
rate of deformation. The failure mode may be ductile or brittle (or

sometimes intermediate between the two). Low temperatures and high
deformation rates are conducive to brittle fractures: it has been
suggested9 that in this regard, with thermoplastics, a ten-fold increase
in the rate of deformation is roughly equivalent to a 10°C temperature
drop.
Lowering the temperature and/or increasing the speed of impact can
bring about a transition from ductile to brittle failure (with consequent
reduction in the energy to break, i.e. in impact resistance). Where the
change occurs as a result of a drop in temperature, the temperature at
which it takes place is known as the ductile/brittle transition tempera-
ture (Tb ), sometimes also referred to as 'brittle point', 'brittleness
temperature' or 'brittle temperature'.
Note: In some cases the transition may be so gradual that no
definite Tb can be established.
If the conditions of a particular test or service situation do not span
the Tb , the impact resistance of a plastic may remain constant over a
wide temperature range: compare the curves for PMMA and PS in
Fig. 8.l.
Note: In contrast with the impact resistance, the tensile strength of
thermoplastics increases with decreasing temperature. For
example, the tensile strength of a rigid PVC composition
tested by Dyment & Ziebland lO was found to increase from
7·7 X 103 lbf in -2 at 20°C to 19·7 x 103 lbf in -2 at -196°C,
with a corresponding increase-by a factor of 2·13-in
Young's modulus.
Other 'external' factors which can influence the impact resistance of
a plastics material or product include the shape and hardness of the
impacting object; the point of impact; and such environmental effects
as the presence of stress-cracking agents.
The main 'internal' factors of particular significance to the impact
resistance of uPVC are:
(a) local stress concentrators-gels, nibs, particulate impurities,
un dispersed aggregates of filler or pigment particles;
(b) local weakness sites-local heat degradation, surface damage
through photodegradation (or weathering generally), incom-
plete gelation (fusion), incomplete interdispersion of formula-
tion components.
PC
20
r.
b.
<:
~ 10
1;;
...
u
"
§
Il.
OL-____ ~ ____ ~ ______ ~ ____ ~ ______ ~ ____ ~ ____ ~
-200 -150 -100 -50 0 50 100 150

Tut tllmpllraturll, -C
Fig. 8.1 Impact resistance (in a Charpy-type test on notched specimens with
0·25 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 Fig. 11.3 of PVC Technology, 4th Edn,
Elsevier Applied Science Publishers, London, 1984).
These, and other features, are discussed more fully in Chapter 11 of

Ref. II.
In some standard impact tests (e.g. Izod, Charpy) the specimens
may be notched, the notch acting as a stress-concentrating feature. A
notch of 0·25 mm tip radius-specified in several standard tests-may
be regarded as approximating to the most severe defect likely to be
encountered in practice, whilst, at the same time, its use in
multipoine z tests permits coverage of a wider range of temperatures
than does that of blunter notches which may approximate better to the
most common defects. In most standard tests the notches are
V-shaped, but some Charpy methods and method variants prescribe
square (flat-bottomed) notches (cf. e.g. ISO 179; BS 2782:Method
359; DIN 53453).
Note: 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.
The standard specifications for impact resistance tests on plastics are

listed in Appendix 1. The flexural impact tests on standard specimens
(Izod, Charpy, Dynstat) are still the most common for material testing
and evaluation, partly because they provide for the use of variously
notched specimens where required. Table 8.1 shows the relationship
between the units in terms of which the results of such tests are
normally expressed.
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 instrumental falling-weight impact
testers* in conjunction with similar tests on suitable material speci-
mens, can provide a great deal of information on the effects of design
and processing, as well as basic data on the fracture mechanism. But it
TABLE 8.1
Conversion Factors for Common Units of Flexural Impact
Resistance
Sf unit Other units

kJ m- 2
kgfcmcm- 2 ftlbfin- 2 ftlbf
[per inch of specimen
(notch) width a ]
1 1·02 0·476 0·191

0·981 1 0·467 0·187
2·10 2·14 1 0·401
5·24 5·36 2·50 1
a Conversion factors for these units applicable only to rectangular

specimens with notch-tip radius of 0·25 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. 15
* For example the 'Dynatup' impact tester (Effects Technology Inc., USA) or
the CEAST Advanced Fractoscope System (CEAST SpA, Italy).
should be remembered that specimen features influence the test

results: each specimen type of each material has its own impact-
response characteristics, and the concepts appropriate for one material
may not necessarily apply to a different one.13
Impact testing of PVC pressure pipes with the aid of explosive
charges 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).
The following standards give impact tests (all of the falling weight
type) for extruded PVC products.
ISO 3127-1980. Unplasticised polyvinyl chloride (PVC) pipes for

the transport of fluids-Determination and specification of resistance
to external blows.
BS 5255:1976. Plastics waste pipe and fittings.

ASTM D 2444-84. Impact resistance of thermoplastic pipe and
fittings by means of a tup (falling weight).
ASTM D 4226-85. Impact resistance of rigid poly(vinyl

chloride )(PVC) building products. *
ASTM D 3679-86. Rigid poly(vinyl chloride) (PVC) siding. This is a

product specification, prescribing inter alia the impact test of ASTM 0
4226.
Useful impact test data, illustrating the influence of molecular
weight (Mw) on the critical strain-energy release rate (Gc ') in uPVC
have been published by Jones et al. 14 A plot of Gc ' against Mw
indicates a critical value (at about Mw = 100 0(0) below which (but not
above) the toughness is Mw-dependent. The likely mechanism (prob-
ably operative also in other polymers) is that below the critical Mw
increasing chain length enables increasingly greater chain entangle-
ments (which promote toughness), whereas above the critical value the
chains may be 'fully entangled', with fracture of the polymer occurring
by chain scission rather than slippage.
* Impact resistance of rigid PVC sheeting, and profile, as well as extruded or

moulded test specimens, determined on a variable-height falling-weight tester
(Gardner type).
8.3.2 The Impact Resistance of PVC

Flexible PVC compositions are tough materials, resistant to failure
under impact at room temperature and down to the lowest tempera-
ture at which they still retain their flexibility; the actual value of this
temperature in each case is determined by the particular formulation,
and is especially dependent on the nature and proportion of
plasticiser(s) present-see Chapter 5.
Rigid PVC is not intrinsically a brittle material at ordinary tempera-
tures: the brittle point of properly made un-notched uPVC specimens
in a flexural impact test can be as low as - 50°C. 16 However, the
material is sensitive to the presence of stress-concentrating features (as
evidenced by its notch-sensitivity in impact tests; see Fig. 8.2), and
also to the rate of deformation, in the sense that these factors-when
operative at levels encountered in service conditions and in tests--can,
singly or jointly, bring about a ductile/brittle transition and thereby
cause brittle failure to occur in impact situations even at room
30
60
N
~~ 20°C
;Q20
40
-
~
.>f.
cu N
C>I
.0
L
'E
--,
E ~
~10 20
L
C>I
C
W
o 0·04 0·06 008

Notch radius I in
(05) (lO) (l5) (20)
(mm, approx)
Fig. 8.2 Impact resistance of a uPVC composition as a function of notch-tip

radius in a Charpy-type test at various temperatures.
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. 8.1: the
rapid drop in the impact strength of notched specimens within a
relatively narrow range of common service temperatures is attributable
to the onset of brittle fracture brought about by the relatively severe
effect of 0·25 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: the latter effect is due to a modification of the
stress field at the incipient crack tip (transition from plane-
stress to plane-strain conditions 1?).
Incorporation of impact modifiers in PVC compositions is a practical
way of increasing their impact resistance. The room-temperature
impact strength (notched Izod, ASTM 256) of an unmodified PVC
based on a relatively low-molecular-weight polymer may be as low as
0·4 ft lbf in -1, 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 29 ft lbf in -1 or even higher in
some cases, with considerable improvement also in low-temperature
impact resistance. In terms of the PVC graph in Fig. 8.1 such
upgrading amounts to a displacement of the curve upwards and to the
left.
Some impact modifiers (e.g. MBS and acrylic ones) are useful also
in plasticised PVC, where they can improve low-temperature tough-
ness and flexibility, help to maintain mechanical properties at high
filler loadings, improve drape and texture, promote sag resistance at
elevated temperatures, and improve surface properties (including
emboss retention).
8.3.3 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:
(a) acrylonitrile/butadiene/styrene (ABS) graft terpolymers;*

(b) methacrylate/butadiene/styrene (MBS) terpolymers;t
(c) all-acrylic and modified acrylic modifiers;
(d) proprietary rubber-modified styrene/maleic-anhydride copoly-
mers-the Elix 300 series:!: (Monsanto);
(e) acrylonitrile/butadiene copolymers (nitrile rubber);
(f) ethylene/vinyl acetate (E/VAC) copolymers and E/VAC/VC
graft terpolymers;
(g) chlorinated polyethylene (CPE);
(h) polyurethane (PUR) elastomers.
Other polymers, generally of an elastomeric nature, have been
patented, examined, or used as impact modifiers for PVC, including
butadiene/2-vinylpyridine, butadiene/methyl isopropenyl ketone ,18
butadiene/fumaric ester copolymers/8 ,19 and Hytrel 3495 (a copoly-
ester thermoplastic elastomer produced by Du Pont).20
Typical levels of incorporation of most commercial modifiers in
uPVC compositions range between 5 and 20phr, although some (e.g.
Elix; some ABS grades) are used in higher proportions to produce
PVC blends with special properties (see below).
Some fine-particle fillers [especially calcium carbonate-see Chapter
6, Section 6.3.1(e)] and pigments (e.g. titanium dioxide) can, when
properly dispersed, also improve the impact resistance of uPVc.
The mechanism of operation of impact modifiers is not fully
understood, although it is plainly associated with the way in which the
presence of these additives modifies the morphology of PVC composi-
tions. The kind of modification that can occur is largely known, as is
the fact that it can vary with different modifiers, presumably involving
corresponding variation in the toughening mechanism. In some cases
the morphological change produced by the same modifier can vary
with the amount of the additive present and the character of its
dispersion in the PVC matrix, both these factors being influenced by
the processing method and conditions. The state of the matrix itself,
with regard to the degree of PVC polymer particle breakdown and
completeness of fusion (cf. Chapter 13, Section 13.4) is also thought to
be an important factor: results and comments have been published
* Normally of relatively high butadiene content (and hence comparatively low

modulus-see Section 8.2).
t In some cases incorporating also an acrylonitrile component.
:j: Formerly Cadon 300.
indicating that, with many impact modifiers, the toughening effect

should be greatest in compositions where the PVC polymer still retains
something of its primary particle structure. 21 ,22 However, this claim
may simply reflect the dependence of the morphological effects upon
the kind of modifier concerned, as may the apparently contrary view
that complete fusion of the PVC is necessary to attain maximum
toughness in an impact-modified composition. 23 ,24
Many impact modifiers, in particular the rubbery ones, are known to
form a microparticulate disperse phase in the PVC matrix, with the
particle size and shape characteristic of the modifier concerned, but
largely independent of the amount of shear and heat-processing
undergone (above the minimum necessary to produce the dispersion).
Modifiers of this kind are characterised by a somewhat restricted
compatibility with PVC (that may be reflected inter alia in their
solubility parameter values 18): they have been classified as of 'pre-
determined elastomer particle size,.2,25 The group includes MBS (and
acrylic-modified MBS), all-acrylic and modified acrylic modifiers. The
mechanism of action of these additives is complex: it probably
involves, at least as an element, the utilisation of some of the impact
energy to generate heat and lower the Tg of the PVC matrix near the
interface with a modifier particle (so that ductile deformation rather
than brittle failure can occur26 ,27): the concept of modifier particles as
stress-concentrating and crack-arresting centres (in analogy with simi-
lar explanations for the function of the rubbery disperse phase in
rubber-toughened polystyrene) may also have some applicability.
There is substantial evidence that, in contrast with the rubbery
modifiers, the modifying effect of those which have significant
compatibility with PVC is associated with a different kind of dispersion
and resulting morphology. The modifiers in this group are CPE,
appropriate grades of EIVAC, and modified EIVAC. Depending on
the chemical make-up (e.g. the degree of chlorination of the CPE
used) and the processing conditions (especially the amount of shear-
working experienced at the appropriate processing temperature), the
form of dispersion of a modifier of this kind may range from a
continuous network interpenetrating the PVC matrix, to a virtually
complete molecular blend. Modifiers which exhibit such behaviour
have been described-rather elaborately-as of 'not predetermined
elastomer particle size'. 2,25 The impact-modifying performance of such
an additive can vary considerably with the kind of dispersion attained
(and hence with the nature and severity of processing undergone).
Many ABS impact modifiers are considered to form a separate

group, intermediate between the other two.
Side-effects on the properties of uPVC materials, exerted-in
varying degrees-by many polymeric impact modifiers at their normal
levels of addition, include the following: some reduction of hardness,
modulus and strength (tensile and flexural); reduction of deflection
temperature under load (the Etix 300 modifiers are a notable
exception here-see below); decrease of chemical resistance; increase
of permeability to some permeants. Rubbery modifiers with unsatura-
tion in the molecule can impair the weathering resistance. Some
impact modifiers promote stress whitening in uPvc. This phenomenon
is attributed to the formation of microscopic voids or crazes through
local separation of the disperse phase [including fillers~f. Section
6.2.3(f) of Chapter 6] from the PVC 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 MBS modifiers are suitable.
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!). 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 minimum
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 propor-
tions. 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. EVA/VC graft polymers rich in the VC
component; highly chlorinated polyethylene). Others, like, for ex-
ample, nitrile rubber and some ABS polymers, also modify con-
siderably the properties of the blends they form with PVC at the high
levels of loading.
(a) ARS 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 moderate effect on heat-distortion temperature and soften-
ing point. Commercial compounds containing ABS modifiers in
substantial proportions are sometimes referred to as PVC/ ABS alloys
or blends.
The blends are of particular interest for the production of housings
for business machines, computers, and other electronic equipment.
Several commercial versions are available (e.g. the Ron/aloy V
range-DSM, The Netherlands; Comalloy 8321000-Comalloy Inter-
national Corp., USA).
Very high proportions of suitable ABS polymers can be incorpor-
ated in flexible PVC compositions (e.g. 65/35 ABS/PVC in some
cases) if the plasticisers are chosen for compatibility 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.
ABS modifiers suitable for clear compositions have made their
appearance in the last few years. A commercial representative is
Blendex 27967 (Borg-Warner Chemicals).
(b) MRS 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 in a notched Izod-type test. The
Blendex modifiers, like the Acryloid (Paraloid) KM 600 and BTA

series (Rohm & Haas) are among the best-known MBS modifiers, for
PVC.
(c) Acrylic Modifiers
In addition to their principal function in PVC compositions, these
modifiers can also have some processing-aid effect, and promote low
die-swell in extrusion. Suitable formulations (especially ones stabilised
with appropriate barium/cadmium or lead-containing systems) incor-
porating 5-lOphr of a good acrylic impact modifier, e.g. Acryloid
KM-323 B, or KM-330 (for improved low-temperature toughness),
have very good weathering resistance and are much used for outdoor
applications (in particular PVC window frames and siding). Other
positive features of such formulations are that the acrylic modifier has
relatively little effect on the physical properties of the composition and
on its temperature of deflection under load, whilst the ease of
processing (melt characteristics and latitude in processing conditions)
is greater than with compositions modified with EIVAC or CPE. The
tendency to high surface gloss, which acrylic-modified formulations
may exhibit, can be controlled by the addition of a suitable matting
agent: this may itself be an acrylic polymer, e.g. Acryloid KF 708 or
710 (d. also Section 9.2.5 of Chapter 9).
(d) Rubber-Modified Styrene I Maleic Anhydride Copolymers
These are commercially available in the Monsanto Elix 300 range.
Although the improvement in impact strength they impart to PVC
compositions is only moderate, they do not lower, and in fact they
substantially increase, the softening point, temperature of deflection
under load, and hot-sag resistance. Even at the high incorporation
levels recommended, the reduction in strength and modulus values (an
effect usual with impact modifiers) is relatively minor (see below).
Each of the Elix grades is intended to confer a different balance
between resistance to impact and to heat distortion.
For normal purposes, the incorporation level is about 30 phr, but up
to about 50 phr may be used. Even at the upper end of this range the
modifier does not eliminate uPVC's normal low flammability, and V-O
ratings can be achieved by specimens 1/16-1/8 inch thick in the test
to UL 94.
Monsanto recommend the use of organotin stabilisers in pre-
ference to lead systems in Elix-modified compositions, as the modifier
interacts with lead compounds.
The manufacturer's published data indicate the following property

values for a rigid PVC composition modified with 30 phr of Elix 330
(in comparison with an unmodified version): density 1·3gcm- 3 (down
from 1·4); Vicat softening point (1 kg) 97°C (up from 81°e); tensile
strength at yield 7395lbf in -2 (down from 7830); elongation at break
85% (down from 95); flexural strength 123001bfin- 2 (down from
13 500); flexural modulus 420600 Ibfin- 2 (down from 435100);
notched Izod impact strength, t inch specimen, 0·92 ft lb in- l (up from
0·43); spiral flow, at 210°C and 1785Ibfin-t, 1·8 inches (down from
2·2).
(e) Nitrile Rubbers * (Acrylonitrile / Butadiene Copolymers)

These act as rubbery modifiers of the 'predetermined particle size
type': the fine structure of the most intimate blends with PVC has
been reported to be heterogeneous, with rubbery domains of sub-
micrometre size revealed by electron microscopy. 28
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
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,29 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 resistance to oils, fuels, and
ozone, strength (tensile and tear), and stiffness, as well as weather-
ability (with proper stabilisation), abrasion resistance, flame resis-
tance (which may be enhanced by the presence of phosphate plas-
ticisers 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.
* Designated NBR rubbers in standard nomenclature (ct. e.g. ASTM D 1418).

Note: PVC was originally introduced as a blending additive to

nitrile rubber to improve the ozone resistance. 3o NBR
rubber/PVC blends are also more resistant than NBR rubber
alone to fuels with increased aromatic content. 31
The properties of PVC mainly upgraded by incorporation of nitrile

rubber are toughness (impact resistance), flex-crack resistance, low-
temperature flexibility, and resilience.
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 all-proportions miscibility with PVC polymer, and
its principal effects on the properties of PVC compositions. However,
this modifier is not a plasticiser in the strict sense of the term, because
it is not dispersible in PVC down to the molecular state of division (see
above), and because it does not affect the 1'g of the composition in the
way characteristic of true plasticisers. l l
Nitrile-rubber modifiers for PVC are available in three physical
forms: as crumb, powder, or liquid. Crumb is usually suitable where
blending is to be carried out in equipment providing intensive mixing
action. The liquid form is often recommended for flexible PVC
compositions processed in calendering, extrusion, or injection mould-
ing, and for plastisols. The powder is supplied in linear or cross-linked
polymer grades. There are many commercial versions of nitrile
rubbers for blending with PVC. Three examples are the appropriate
grades in the Hycar (B. F. Goodrich) and Krynac (Polysar) ranges,
and Chemigum NX 775 (Goodyear, France)-a carboxyl-modified
nitrile rubber.
PVC/NBR blends are also available commercially: the main ad-
vantages claimed for their use (as against own compounding) are a
particularly high degree of homogenisation, better properties, and
reduced need for high-temperature mixing. Some commercial blends
are formulated for specific applications, such as for example Norsk
Hydro Polymers' compounds XG 75364 and VG 1402 for window
glazing: others have a broader spectrum of applications (cf. e.g. the
Europrene N 0 ZO compounds-EniChem, Italy and UK, or Denka
LCS compounds-Denki Kagaku Kogyo, Japan). Blends containing a
metal to provide ionic cross-linking of functional groups have been
developed for oil-resistant hoses and gaskets. 32
The use of PVC/NBR blends for cable sheaths was an early
development in the cable industry, as was the vulcanisation of the

rubber component in such blends. Other common applications include
conveyor belt covers and rollers, and footwear soles.
(f) E/VAC Modifiers

This group comprises ethylene/vinyl acetate copolymers, and their
graft terpolymers with vinyl chloride (E/VAC/VC). In general, the
impact-modifying effect of E/VAC in PVC increases with increasing
vinyl acetate content: in commercial E/V AC modifiers that content is
typically in the range 55-70% by weight of VAC.
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 modifier loadings.
The vinyl chloride component in E/VAC/VC copolymers promotes
compatibility with PVc. Some graft terpolymers of this kind can be
used as solid plasticisers in amounts as high as 80 phr.
The E/VAC modifiers (as represented e.g. by Baymod L *-Bayer;
Hostalit H-Hoechst; and the Du Pont Elvaloy grades) do not impair
the weathering resistance in appropriately stabilised compositions for
outdoor service: they are therefore applicable in such products as
window frames, cladding, siding, and rainwater goods.
(g) Chlorinated Polyethylene (CPE)

The chlorinated polyethylenes used as modifiers in PVC are produced
by chlorination of HDPE. Of the chlorination methods available,33
chlorination in solution gives the greatest uniformity of distribution of
chlorine (CI) atoms in the HDPE polymer chains. 34 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. 35 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). Room-temperature 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-
* Previously Levapren 2450. Baymod is the new name for the entire former
Levapren range.
temperature toughness: the modifier also has some processing-aid

action, and lubricant effects have been reported. 36
Note: Some published evidence37 suggests that, when compounded-
in under relatively moderate heat and shear-working condi-
tions (which do not disrupt the primary particles of PVC
polymer), the modifier grades of CPE remain as a separate,
micro-disperse phase in the PVC composition; and that it is
this morphology that secures the highest improvement in
impact resistance.
Property retention of PVC compositions on weathering is not
substantially impaired by modification with CPE (given proper general
formulating for weathering resistance).
CPE with chlorine contents higher than those of the PVC-modifier
grades 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 chlorine contents). The highly chlorinated CPEs
can be used at very high incorporation levels in PVC compositions to
function as plasticisers of excellent permanence.
In such products as, for example rigid profiles for outdoor use (and
especially in cellular versions), a CPE modifier can promote filler
acceptance. The use of more highly chlorinated grades as solid
plasticisers for flexible PVC sheeting has been growing in such
application areas as seepage barriers and horticultural sheeting.
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. 38
(h) Polyurethane (PUR) Elastomers

Like nitrile rubbers, the appropriate grades of these elastomers are
widely compatible with PVc. They are effective impact modifiers,
imparting in addition good abrasion resistance and low-temperature
flexibility (cf. e.g. Table 5.24 in Chapter 5). Commercial PUR
modifiers for PVC include those in the Storey Chemical Corp. (USA)
range, Baymod PU (Bayer, and Mobay Corp.), and Durelast 100
(Briggs & Townsend, UK). Blends with PVC are also available
commercially, and used in such applications as moulded industrial
boots and shoe soles, as well as for some construction applications,

e.g. window gasketing (d. Uravin compounds, Vinchem Corp.,
USA).
REFERENCES
1. Sahajpal, V. In Developments in PVC Technology, ed. J. H. L. Henson

& A. Whelan). Applied Science Publishers, London, 1973, Ch. 4.
2. Lutz, J. T. In Degradation and Stabilisation of PVC, ed. E. D. Owen.
3. Petrich, R. P., Effect of processing aids and impact modifiers on
processing characteristics of rigid PVc. Paper presented at the PRI
International Conference on PVC Processing, Egham Hill, Surrey, UK
6-7 April 1978.
4. Wilson, A. & Raimondi, V. V., Poly-cy-methylstyrene as a process aid for
rigid polyvinyl chloride. Paper presented at the PRI International Con-
ference on PVC Processing, Egham Hill, Surrey, UK, 6-7 April 1978.
5. Sahajpal, V., Kunststoffe, 66(1) (1976) 18-20.
6. ASTM D 638 M-87b. Tensile Properties of Plastics.
7. ASTM D 2289-84. Tensile Properties of Plastics at High Speeds.
8. Vincent, P. I., Plastics, 27(291) (1962) 115-17.
9. BS 4618:Section 1.2:1972. Impact Behaviour.
10. Dyment, J. & Ziebland, H., J. Appl. Chem., 8 (1958) 203-6.
11. Titow, W. V., PVC Technology, 4th edn, Elsevier Applied Science
Publishers, London and New York, 1984, Chapter 11.
12. BS 7008. Acquisition and Presentation of Comparable Data for Basic
Properties of Plastics. Part 1:1988. Method for single-point data. Part
2:1988. Method for multipoint data.
13. Turner, S., Read, P. E. & Money, M., Plast. Rubb. Proc. Applns., 4(4)
(1984) 369-78.
14. Jones, D. P., Leach, D. C. & Moore, D. R., Plast. Rubb. Proc. Applns.,
6(1) (1986) 67-79.
15. Vincent, P. I., Impact Tests and Service Performance of Thermoplastics.
Plastics Institute Monograph, London, 1971.
16. Vincent, P. I. In Thermoplastics: Properties and Design, ed. E. M.
Ogorkiewicz. John Wiley & Sons, London, 1974, Ch. 5 and 6.
17. Bucknall, c., Gotham, K. V. & Vincent, P. I. In Polymer Science, Vol. 1,
ed. A. D. Jenkins. North Holland Publishing Co., Amsterdam, 1972, Ch.
10.
18. Bramfitt, J. E. & Heaps, J. M. In Advances in PVC Compounding and
Processing, ed. M. Kaufman. Maclaren & Sons, London, 1962, Ch. 4.
19. Bier, G. Kunststoffe, 55(9) (1965) 694-700.
20. Nishi, T. & Kwei, T. K., J. Appl. Polym. Sci., 20(5) (1976) 1331-7.
21. Bysted, J. & Lundquist, J., J. Vinyl Technol., 2 (1980) 209-12.
22. Rabinovitch, E. B., J. Vinyl Technol., 4 (1982) 62-7.
23. Summers, J. W., Isner, J. D. & Rabinovitch, E. B., 36th ANTEC SPE
Proceedings, 1978, p. 757.
24. Faulkner, P. G., J. Macromol Sci.-Phys., B11 (1975) 961-7.
25. R6hrl, E., KunststoJfe, 70(1) (1980) 41-5.
26. Newman, S. & Strella, S., J. Appl. Polym. Sci., 9 (1965) 2297-301.
27. Strella, S., J. Polym. Sci., 4 (1966) 527-32.
28. Landi, V. R., Acrylonitrile in Macromolecules, Applied Polymer Sympo-
sium 25 (1974) 223-31.
29. Schwarz, H. F. & Edwards, W. S., Acrylonitrile in Macromolecules,
Applied Polymer Symposium 25 (1974) 243-59.
30. Dunn, J. R., Plast. Rubb. Proc. Applns, 2(2) (1982) 161-8.
31. Pfisterer, H. A. & Dunn, J. R., Rubb. Chem. Technol., 53 (1980) 357-67.
32. Anon., Mod. Plast. Int., 15(12) (1985) 40-2.
33. Domininghaus, H., Die KunststoJfe und Ihre Eigenschaften, YDI-Verlag
GmbH, Dusseldorf, FRG 1976, p. 29.
34. Frey, H. H., Abgehandelte Polyolefine. In KunststoJf Hq,ndbuch, Bd. IV,
Polyolefine. Carl Hanser Verlag, Munich, FRG, 1969, pp. 148-54.
35. Blanchard, R. R. & Burnell, C. N., SPE J., 24(1) (1968) 74-8.
36. O'Toole, I. L., Reventas, A. A. & von Toerne, T. R., Mod. Plastics,
41(7) (1964) 149-52.
37. Siegmann, A. & Hiltner, A., Polym. Engng Sci., 24 (Mid-Aug. 1984)
869-76.
38. Nass, L. I. (Ed.), Encyclopedia of PVC, Marcel Dekker, New York,
1978.
CHAPTER 9
Miscellaneous Additives
This chapter deals briefly with those additives for PVC which are used,
mainly in relatively small proportions, for particular effects. Several of
these (both the additives and their effects) are also discussed or
mentioned elsewhere in the book.
9.1 ADDITIVES ACTIVE IN PROCESSING
9.1.1 Chemical Blowing Agents for PVC Foams
Blowing agents are compounds which decompose on heating within a

defined temperature range, to generate a large volume of gas. The
range, and the rate of gas release, must be suited to the processing
conditions of the PVC composition concerned. The blowing agent can
be solid or liquid, and inorganic or organic in nature.
Although organic blowing agents (especially the azodicar-
bonamides-see below) remain paramount in the production of PVC
foams by 'chemical' blowing, some inorganic agents have also been
coming into use, notably those based on the combination sodium
bicarbonate/citric acid (SB/CA).
Note: An example of a commercial version is the 70% concentrate
Hydrocerol BIH 70 (Boehringer Ingelheim KG, FRG, and
Henley & Co., USA).
The use of such concentrates in suitable carriers overcomes the earlier
difficulties of achieving a dispersion of the blowing agent in a PVC
composition sufficiently intimate for effective, uniform blowing. The
SB/CA agents offer shorter cycles and outgassing times, as well as
335
lower pressures in processing. The last-named feature is of particular

interest in tbe counterpressure process for structural foam moulding (in
which mould pressurisation at about 1·7 MPa is required with an azo
blowing agent, but only some 0·7-1 MPa with Hydrocero/ BIH 70).
By contrast with the exothermal decomposition of the azo agents, that
of SB/CA is endothermal; the gas generated is carbon dioxide; some
water is also evolved.
The advantages of the organic blowing agents used with PVC
include generally good compatibility with PVC compositions, availabi-
lity of the solid ones in uniform particle sizes (including some very
fine-particle grades) which promotes uniformity and fineness of the
cells in the ultimate foam, and relatively narrow decomposition-
temperature ranges (cf. Fig. 9.1.) Many organic blowing agents also
tend to be self-nucleating during decomposition, another feature
making for cell uniformity in the foam.
The blowing agent most widely used with PVC compositions,
including pastes, is azodicarbonamide (ADA), sometimes also called
azobisformamide (ABFA). It comes close to meeting all the principal
general requirements for a successful blowing agent,l and, in addition,
is not flammable in ordinary conditions. The general operational
temperature range (in terms of the plastics stock temperature in
processing) for which unmodified ADA is suitable is about 200-250°C
(cf. Fig. 9.1). This would be rather high for PVC processing (especially
pastes), but the range can readily be extended downwards to about
165°C (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 165-230°C can be regarded as the typical
operational range in PVC of most commercial ADA blowing agents
(see Table 9.1).
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 decom-
position (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 face is widely
utilised in formulating compositions for chemically blown PVC foams:
as little as 0·5 phr of a kicker can be sufficient for activation (i.e. much
9 Miscellaneous Additives 337
250
A
........
200
I XXX
0> X
E 150 X
- ...:--
X
"0 /,.. :
....ro
Cj
:
/ X
L /
g 100 I :
Cj
0> I X
CIl I ;
ro I x
(!) I x
50
I
I
/
;/
0
Temperature, ·C
250
..............................
!
B 170·C
215·C
200
'0>
.
E 150
"0
....ro
Cj
185·C
L
-----
Cj
170·C
; 100
0>
CIl
ro
(!)
50
o
Time, minutes
Fig. 9.1 Volume of gas generated by some blowing agents, as a function of

temperature (A), and time at a constant temperature (B). - - , Azodicar-
bonamide (ADA); x x x, ADA non-plate-out, grade; "', ADA activated
with a liquid Cd/Ba/Zn stabiliser system; - - . - - , ADA activated with a
liquid Pb stabiliser system; - - - - - -, a commercial hydrazide-based blowing
agent; - - , 4,4'-oxybis(benzene sulphonylhydrazide) (OBBS).
w
w
00
"t)
r:i
"t)
if
~.
...~
{l
~
::l'.
~
TABLE 9·1 "t)
Operational Temperatures and Applications of Some Commercial Azodicarbonamide Blowing Agents, with Special ~
<">
Reference to the Celogen Range (Uniroyal Chemical)" ~
'"
~.
General type Celogen grade Approximate Application areas Examples of other similar
operational commercial products b §
!:I..
range ("C)
Materials Sources ~
"::l
Regular AZ130 165-230 ERC (profile, pipe, Genitron 2

sheeting) (or Ficel) ~.
AC
EF (sheeting,C wire and Azocel
cabled) PoroforADC
SR;c c;e p" Kempore Fisons Industrial
Chemicals, UK
(Genitron)
Modified
Non-plate-out AZNP 130 165-230 EF (profile,' sheeting: Genitron (or Haake Inc., USA
wire and cable'') Fieel) EP (Fieel)
Kempore Me Fairmount Chemical
Non-plate-out AZ760 165-180 EF (profile,' sheeting: Co., USA (Azoeel)
(compounding) wire and cable') Bayer, FRG,
grade) and Mobay Chemical,
Flow-treated AZ3990 165-230 EF (profile/ wire and Kempore 125N USA (Porofor)
cable'); Stepan Chemical Co.,
SF;d R;e p;e C" USA (Kempore)
Activated AZ754 From 145 EP (film and sheeting; Kempore FF '-0
wire and cable)
Activated AZRV 160-200 ERd (profile, pipe, ~
1:;.
sheeting); SR d ~
[
a Based in part on data from Uniroyal Chemical technical literature. ~
b Not necessarily directly equivalent. !li
C Some application, with suitable activation. ~
d A main application.
e A main application, with suitable activation.
f Some application.
f
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.
w
W
>D
less than required for stabilisation, in normal circumstances, with lead,

zinc and cadmium 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 (cf., for
example, Irgastab L600, ABC 2, or CZ 11; 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 lead, zinc or cadmium, or even certain
carbon blacks)-in case of doubt, practical trials should be
carried out.
The effect of the concentration of a lead activator (dibasic lead
phthalate-Dythal; National Lead Co.) on the density of extruded
PVC foam is illustrated in a paper by Wells. 3 The use of isocyanates as
retarders (i.e. deactivators) in certain foams blown with borohydride
blowing agents was patented in the USA some time ago. 4 Isocyanates
have also been considered as indirect blowing agents (generating CO2
and water in processing).
The principal gaseous products evolved-in a high yield (cf. Fig.
9.1)-by ADA at its 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 AC/2, 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 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 9.l.
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 deposi-
tion 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, ap-
pearing 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 decom-
position 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 130-170°C, 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 80°C and 110°C 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
AZDN (Fisons, UK), Porofor N (Bayer, UK and Europe), Poly-Zole

AZDN (Stepan Chemical, USA).
Blowing 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-130°C 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'-dinitrosotere-
phthalamide (DMDNT). This compound decomposes at about 100°C,
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 50°C.
A technique has also been developed 4 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-tert-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, s soluble in many plasticisers.
Decomposition into nitrogen gas and entirely liquid residues which are
colourless, non-toxic, non-staining, non-blooming, and odourless is a
further feature of interest. 5
Incorporation levels of blowing agents range fairly widely, from
about 0·5-0·8 phr in structural foam compositions for injection
moulding to 2-10 phr in foamable paste coatings on substrates for

flooring with some 'chemical emboss' effects (see Section 22.1.4 of
Chapter 22). The form in which the blowing agent is introduced, and
the method of incorporation depend 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 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.
9.1.2 Cell-Control Agents for PVC Foams
In the production of cellular PVC by injection moulding and extru-

sion, the quality of the product depends, inter alia, 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,5 the melt viscosity of the plastics material,6,7 and 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 unifor-
mity and eliminating 'overblow', even in foaming composi-
tions heavily filled with mineral fillers (d. for example,
product VS-103; Air Products & Chemicals Inc., USA).
Cell-control (cell-stabilising) agents are cardinally important in the

production of flexible foams by mechanical frothing. The agents
included in foam formulations to stabilise the 'wet' foam and control
its cell size, also assist in the mixing-in of the air: they are surfactants,
normally non-ionic or anionic (and usually mixtures). To discharge
properly both the functions just mentioned, a cell-control agent must
have the right chemical structure, to combine the requisite degree of

solubility in the plasticiser system of the PVC paste being foamed,
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
functions characterised by Acton & Debal8 as:
(i) lowering the interfacial tension between paste and air (to
reduce the energy required for frothing, and to promote
stability of the bubbles formed);
(ii) increasing surface elasticity;
(iii) promoting surface plasticity.
The effect of (ii) is seen by these authors as reduction of the
tendency of the 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 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).
9.1.3 Minor Additives for PVC Pastes
These additives are discussed in Section 18.5.2 of Chapter 18.
* 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.
9.2 ADDITIVES INCORPORATED FOR

END-USE PROPERTIES
9.2.1 Colourants
(a) General
As mentioned in Chapter 2 [Section 2.2.2(g)], a colourant's basic
function (subject also to certain additional requirements, including
stability in processing and service) is to impart to the plastics (in this
context the PVC) material, the desired colour in adequate intensity:
this must be achieved when the colourant is present in a low
proportion (up to a few phr in normal circumstances). The colourants
used in PVC may be broadly divided into pigments and dyes. The
pigments are fine-particle materials, intimately dispersible-but 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 (i.e. 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 precipitated onto
inorganic compounds, which act as bases or carriers in this combina-
tion); and organic compounds. In addition carbon black may be
regarded as forming a 'group' on its own. Many colourants used in
PVC materials are tabulated (by chemical composition) in Ref. 1.
Special-effect pigments include the following.
(i) Metallic colourants: these may be either metal flakes (usually
aluminium for silver effects and copper or bronze for gold)
which may also be tinted with organic colourants for metallic
colour effects, or non-metallic pigments which give metal effects
(but are non-arcing, non-tarnishing and non-toxic, e.g. Mearlin
Super Russet, Super Bronze, and Super Copper; Mearl Corp.,
USA *). Noteworthy in this connection are also Denka Metallic
* World's largest manufacturer also of pearlescent lustre pigments and

irridescent colourants. European Office: Haarlem, The Netherlands.
Compounds (Denki Kagaku Kogyo KK, Japan), metal-free

PVC compositions with metallic appearance (including stainless
steel and aluminium effects).
(ii) Pearlescent colourants
(iii) Glossy and nacreous colour pigments (as represented e.g. by
the [riodin range of E. Merck, FRG, or the Afflair range; EM
Industries, USA): typical pigments of this kind consist of mica
platelets carrying a thick layer of precipitated Ti02 (or a
conjoint coating of Ti02 and iron or chromium oxide for
coloured lustre effects).
(iv) Fluorescent pigments
Colourants of the inorganic pigment type are widely used in PVC:
many of these combine good all-round stability and high colour value
with relatively moderate cost. The group includes also the highly
important 'titanium whites' (the appropriate pigment grades of tita-
nium dioxide-the pigments universally employed in good-quality
white PVC compositions, and included in coloured compositions to
brighten or to reduce the shade.
Note: It should be noted that, in general (and with only a few
exceptions, e.g. Nickel Titanium Yellow and Chrome Oxide
Green), inorganic pigments are not suitable for application in
white reductions.
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 important from the point of view of operational facility,
efficiency and economy. Apart from straightforward 'dry colourants'
(nowadays normally supplied as non-dusting powders or granules),
forms are also available that are particularly suited to the above
requirements: these are solid or liquid concentrates of various kinds,
and single-pack multi-additive systems incorporating a suitably dis-
persed colourant.
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, for example, the Siscoversal
concentrates (BASF) which are suitable for use in PVC, inter alia, at
up to 3 phr loading, and of the Spectrum Universal Masterbatch
granules (Regent Chemicals Ltd, UK) recommended for use at 1-2%
levels. Another example of a proprietary universal carrier is Resin 18
(Amoco Chemicals Co., USA).
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 hand-
ling, 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 typically
dispersions of colourants in plasticisers, often referred to as paste
concentrates; liquid polymeric carriers are also used in some concen-
trates (e.g. those of the Bee Chemical Co., USA).
(b) Choice of Colourant

The principal considerations in choosing a colourant for a given PVC
composition are briefly summarised below. It is also worth remember-
ing that colourant manufacturers are, as a rule, very technically
minded, and their advice and recommendations are both readily
available and worth having.
COLOUR
It is self-evident that the colourant(s) chosen for a particular formula-
tion must be capable of producing the required colour and shade (or
special effect such as pearlescence, gloss, etc.).
Note: Shade changes can sometimes occur with variation in the
concentration of some commercial pigments in PVC com-
positions: such changes have been attributed to dichroic
effects. 9
PROCESSABILITY
This includes ease of handling, conveying and metering in the process
concerned, ease of dispersion in, and compatibility with, the PVC
composition, and stability of the colourant in processing conditions.
STABILITY AND PERFORMANCE IN SERVICE

The main points relevant under this heading 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.
Progressively increasing use of the rigid PVC in outdoor applications
(window frames, siding, soffit and fascia boards, rainwater goods) has
been paralleled by additions to the manufacturers' ranges of col-
ourants suitable for particular types of formulations whilst also
combining fastness to light with IR reflectivity (to limit heat build-up
in the PVC material when exposed to sunlight).
Formulation compatibility considerations include in particular the
nature of the stabiliser system and any impact modifier present. The
following few examples are mentioned purely by way of illustrative
indication.
Carbon black is not desirable as a sole pigment or a dark-shading
component in uPVC materials for outdoor service, because of its high
IR absorption: a strong phthalocyanine blue (e.g. Microlith Blue
4G-KP; Ciba-Geigy) is preferable for shading. However, phthalo-
cyanine green is not recommended for dark green shades in view of its
substantial absorption in the IR and visible-light regions of the
spectrum (combinations of more suitable individual blue and yellow

colourants are preferable). Some inorganic blacks have good weath-
erability and IR reflectance: two examples are V 777 and V 7000
blacks of the Ferro Corp. Colour Division. In the Ciba-Geigy range,
Chromophtal Brown 5R is known for its low IR absorption. The BASF
pigments Sicatan Brown K 2611 and K 2711 (incorporating a stabilised
grade of rutile Ti0 2) are recognised for their weathering fastness and
hiding power in barium/cadmium stabilised PVC, whilst Sicopal Brown
K 2795 (a chrome iron brown) is more suitable for lead-stabilised
formulations; Poliogen Brown K 2683 (an organic pigment) is an
example of a colourant suitable for dark-toning weather-resistant
formulations. Further examples of BASF colour ants for PVC generally
are the Sicovinyl powder and granule colours, and the Sicodop colour
pastes (for pPVC). The Drakenfeld 10000 series of mixed-metal oxide
inorganic pigments (Hercules Pigment Co., USA, purchased in the
mid 1980s by Ciba-Geigy) have been used in the USA for PVC siding
since the early 1970s.
HEALTH AND SAFETY CONSIDERATIONS

In this area, particular attention has been increasingly focusing on
inorganic pigments containing heavy metals (especially lead, cadmium
and chromium) which can act as cumulative poisons. Other colourant-
associated health hazards are polychlorinated biphenyls, present as
impurities in some colourants of the phthalocyanine and diarylide type
and regarded as carcinogenic, and organic colour ants based on
benzidine (now widely recognised as a carcinogen).
As with other PVC formulation components, information and
guidance on the latest thinking, and any specific regulations, concern-
ing the possible health hazards associated with colourants are available
from the various official and professional bodies mentioned in Chapter
24, Section 24.5.2. Organisations directly concerned with colourants
include the USA Dry Color Manufacturers Association, the UK
Society of Dyers and Colourists and the Oil and Colour Chemists
Association, and the German Mineralfarben-Industrie eV.
(c) Some Practical Tests

The following practical tests may be used to assess some important
aspects of the processing and service suitability of a colourant in a
PVC composition. The composition should preferably be the one for
which the colourant is intended, with the colourant included at the
appropriate level. Otherwise a general-purpose test compound may be

used, plasticised or unplasticised, as appropriate.
HEAT STABILITY
A portion of sheet, produced from the composition on a two-roll mill
as described in Section 17.1. 3 of Chapter 17, is compression-moulded
between polished steel plates for 30 min at a temperature appropriate
to the composition type (see Section 17.1.3). The resulting sheet is
compared with one similarly pressed for 5 min. Alternatively, portions
of sheet pressed for 5 min may be further heated in an air-circulation
oven with good temperature control, for 30 min at 170°C or for 10 min
at 200°C. Any colour differences not attributable to polymer degrada-
tion (which may be verified by inspection of similarly treated,
uncoloured specimens of the same composition) are assessed by
reference to the Grey Scale [see Chapter 24, Section 24.3.1(b)].
A useful test method for heat stability in processing of colourants
(with or without a Ti02 pigment), with special reference (but not
exclusive) to injection moulding, is given in DIN 53772 (1988).
STABILITY TO LIGHT AND WEATHERING
Specimens (plaques), moulded under standard conditions from the
coloured composition concerned, are exposed in laboratory apparatus
or outdoors, as appropriate, under relevant conditions. Any colour
fading is assessed by reference to standard dyeings of the Blue Wool
Scale [cf. Section 24.3.1(b) of Chapter 24] exposed alongside the
specimens.
COLOUR MIGRATION
A sheet specimen of the coloured PVC composition is sandwiched
between two similar white sheets, between two glass plates, under a
weight producing a pressure of 1lbf in -2 on the sheets. The assembly is
placed in an oven at 70°C for 24 h, and the degree of any staining of
the white sheets is thereafter assessed by reference to the Grey Scale.
With plasticised compositions, the basic procedure for testing pi as-
ticiser migration may be followed [cf. Section 5.6.6(c) of Chapter 5].
Information respectively on the nature of organic pigments, extrac-
tability of colourants (and some other additives) from PVC composi-
tions, and on important aspects of the colouring of plastics (including
PVC) is contained in publications by Inman,lO Brighton,l1 and
Webber. 12
A monograph by Donnet & Voet,13 and a paper by Ferch 14 are
useful sources of information on carbon black (respectively, the main

technical aspects, and the surface chemistry of pigment grades).
9.2.2 Flame Retardants and Smoke Suppressants
The presence of chlorine in a substantial proportion in a PVC polymer

constitutes built-in flame-retardance, in that the hydrogen chloride
which is generated in the pyrolysis part of the burning process (cf.
Section 24.6.1 of Chapter 24) hinders that process in two ways: whilst
itself incombustible, the HC1 prevents-or at least reduces-access of
oxygen to the combustion zone; it also reacts with free radicals
(especially HO·), thus acting as terminator for important combustion-
propagation reactions.
The inherent flame retardance of the polymer is counteracted in
pPVC compositions by the 'diluting' effect of the plasticiser(s).
Note: Chlorinated extenders, and phosphate ester plasticisers
(which can act as flame retardants in their own righe) are the
exceptions here. It is interesting to note in this connection
that a significant flame-retardant action has been claimed for
tris( dibromopropyl) phosphate at the incorporation level of
1 phr! Usual levels for this purpose range-depending on the
phosphate plasticiser-between 5 and 15 phr (normally intro-
duced as part-replacement for the cheaper general-purpose
phthalate plasticisers).
It is therefore normally necessary to include special flame-retardant
additives in plasticised PVC compositions required to possess some
resistance to burning (e.g. cable coverings). The additives most widely
used for this purpose are antimony oxides and alumina trihydrate
[AI(OHh or Al 2 0 3 • 3H2 0].
Antimony trioxide (Sb 2 0 3 ) has, for a long time, been the oxide
universally employed (and is still often referred to simply as 'antimony
oxide' in this context) but more recently antimony pentoxide (Sb 20 s)
has also become commercially available (e.g. Nyacol ZTA colloidal
Sb20 5 powder; Nyacol Products Inc., USA). Antimony oxides need
the presence of a halogen compound to exert their fire-retardant effect
(chiefly by way of a reaction in the vapour phase with the hydrogen
halide-HCI in the case of PVC-formed in the course of burning; 1 in
polymers which do not contain a halogen, the antimony oxides are
incorporated jointly with a halogenated organic compound.
The flame-retardant and smoke-suppressing action of alumina trihy-

drate in pPVC compositions is thought to comprise a number of effects.
The water of hydration, present in the compound in a substantial
proportion, is rapidly split off at the high temperature of burning, and
the vapour (steam) evolved obstructs the access of oxygen to the
polymer, thus hindering the combustion process. The decomposition
reaction
is endothermic; the heat absorption lowers the temperature and

suppresses pyrolysis, thus reducing smoke generation: the alumina
(Ah03) formed may also aid this effect by acting as a heat barrier.
Moreover, in its finely divided nascent state it probably absorbs some
of the smoke constituents (especially HCI), thus further contributing
to smoke reduction.
Although antimony oxides are used in moderate proportions in
pPVC compositions (typically between about 4 and 10 phr cf. Table
9.2), they are still relatively expensive. Alumina trihydrate must be
used at high loading levels for its effects on flammability to be properly
realised: this not only represents a significant cost consideration, but
can also entail some of the undesirable effects of high particulate filler
loading upon the processing and the physical properties of the PVC
composition (cf. Chapter 6). Another effect can be a lowering of the
electrical insulation resistance, although this can often be compensated
by replacing about 20% of the alumina trihydrate with the appropriate
electrical grade of calcined clay (e.g. Pole Star 501; ECC~f. Table
6.3 in Chapter 6).
Partly for some of the above reasons, several of the commercial
flame retardants for PVC are mixtures of antimony oxide or alumina
trihydrate with other materials, some of which also have a synergistic
effect. Examples are combinations of Sbz0 3 with molybdic oxide
(Mo03)' in which the latter enhances the smoke-suppressing effect.1
Note: The action of zinc oxide is similar to that of Sbz0 3 , but less
effective. Zinc oxide also functions as a smoke suppressant,
but it tends to impair the thermal stability of PVc.
Examples of commercial flame retardants and/or smoke suppres-
sants not based on antimony oxides or AI(OHh include the following:
proprietary tin/zinc compositions (some believed to be based on zinc
TABLE 9.2
Effects of Antimony Oxide and a Smoke Suppressant in some PVC
Compositions
Table based on data of Fletcher & Walker15
Formulation components Flame-retarded formulations Formulations for
(pbw) reduced smoke
emission (pbw)
PVC polymer 100 100 100 100 100 100 100

Plasticisers ;
DOP 15 75 30
DIDP 25 40
Trimellitate 60
Polyester (medium mol. wt) 50
Cereclor S 52 30
Expoxidised soyabean oil 5
Antimony oxide 5 6 6 10 3 6 2
Ongard 2" 5 3 2
China clay 10 5 4 5
Calcium carbonate 30 25 20 21
Stabiliser or 5·25 4·5 4·5 5·7 7·2 5 7
stabiliser /lubricant
Oxygen Index 29·0 32·6 32·6 38·0

Reduction in
smoke emission, % 33 43 45
" A proprietary metal complex (Anzon Ltd).
stannate or zinc hydroxystannate, e.g. those of the Flamtard range of

Alcan Chemicals); magnesium hydroxide (various grades, e.g. the
Versamag range of the Ventron Division of Morton Thiokol, USA;
magnesium carbonate either alone (e.g. the subhydrate developed for
this application by ICI Mond Division, or in combinations (e.g. with
a phosphate ester plasticiser as in Monsanto's Phosgard LSV; and
magnesium-zinc complexes (e.g. Ongard 2, Anzon). PVC com-
pounds, flame-retardant and/or with low smoke-emission levels, are
also commercially available. One example of cable compounds with
very low HCl emission (achieved through incorporation of HCl
absorbers) is the Sicron X range (EVe).
A CIA pUblication16 lists some 200 fire retardants, with some
information on chemical nature and applications.
9.2.3 Additives for Antistatic and Conductivity EtI'ects
Static electricity charges of up to several tens of thousands of volts

can build up in a dry atmosphere on high-resistivity plastics like
PVC. Once present, electrostatic charges may constitute a nuisance
or a serious hazard, depending on their magnitude and the particular
circumstances. For example, in mines where PVC conveyor belts are
used, discharge in the form of a spark can cause a fire or possibly a
dust explosion. Electronic circuits can be damaged by discharge of
accumulated 'static', whilst the presence of high charges close to
electronic equipment (e.g. on equipment housings, microelectronic
packaging, chip carriers) can give rise to electromagnetic interference
(EMI). 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
may affect the bulk density and handling properties (even though they
often dissipate later in storage). Dust attracted to a charged surface of
a PVC record can interfere with sound reproduction, or even damage
the grooves; on light-coloured upholstery, for example, it can cause
dirty marks.
Build-up of static electricity charges on plastics surfaces can be
prevented, or charges already present can be dissipated, by ionising
the air near the surface (with the aid of a radioactive source, or
high-voltage electrical discharge equipment). Such 'external' treat-
ments are most appropriate for continuous sheet materials, which may
be passed under the ionising device; but the effect is of limited
duration.
More permanent results are obtained by incorporating in the plastics
material an additive which lowers the material's electrical resistance to
the point where accumulation of static charges on the surface is
prevented, or even further, so that the material becomes conductive.
It is not possible to define absolute resistance-value limits respectively
for conductive, antistatic, and static-prone PVC compositions: in
practice such limits will vary somewhat, depending on the nature of
the product, its application, and service conditions (especially atmos-
pheric humidity). A very approximate general indication in round
figures is given by the following values (volume resistivities in Q cm,
at room temperature and 60% relative humidity), with the effects
named increasing in the direction of the arrows in each case:
conductive PVC 5 antistatic PVC 8 Static-prone PVC
( 10( 10 )
The additives incorporated in PVC (as well as other plastics) for the
above effects may be conveniently considered under three headings:
surface-active agents, (in this context also often referred to as
'antistatic agents'), polymeric antistatic additives, and conductive
fillers.
(a) Antistatic Surface-Active Agents

These are selected surface-active agents incorporated in the composi-
tion (typically at 0·5-5 phr but up to about 1 phr in some cases) and
intended to migrate gradually to the surface of the finished product,
there to attract and hold atmospheric moisture. The microscopic
moisture layer thus formed conducts away incipient electrostatic
charges (the conductivity may be enhanced by the hydrophilic polar
groups of the surface-active agent). It is because of their dependence
on this mechanism that the effectiveness of the antistatic action of
surface-active agents drops at low relative humidity.
The surface-active agents can also, in some cases, be applied to the
surface of the product (e.g. film, sheeting, mouldings) by spraying,
wiping with or dipping in, an aqueous solution. However, the effect is
less permanent than that obtainable by internal incorporation.
The following examples illustrate the chemical types to which the
surface-active antistatic agents for PVC belong, and indicate some
commercial products.
(i) Quarternary ammonium compounds, e.g. Markstat AI-26, AL-
44, and AL-48 (Argus Division of Witco Corp., USA); Cyastat
LS (American Cyanamid); Lankrostat QAT (Lankro Chemicals
Ltd., UK).
(ii) Non-ionic compounds, e.g. Atmer 129 (ICI); Lankrostat NP6;
Gafac RE.
(iii) Anionic compounds, e.g. Hostastat HSI (Hoechst); Bevaloid
4300 M3 (Bevaloid Ltd., UK).
(iv) Miscellaneous proprietary agents: Sandin VU (Sandoz), Interstat
50 (Interstab); Hostastat FE 20; Bevaloid 4360.
Most antistatic agents-in particular those of the quaternary am-
monium type-reduce the thermal stability of PVC compositions in
which they are incorporated. This undesirable effect can be minimised
by careful selection of the antistatic agent (some are much less harmful
than others in this respect) and using an appropriate stabiliser system
(on which the stabiliser and antistatic-agent producers will always
advise).
(b) Polymeric Antistatic Additives

These are intrinsically conductive polymers which may be blended
with the polymer whose electrical resistivity is to be reduced. An early
example was Resin QX2611 (Dow)-a copolymer of a quaternary
ammonium compound with styrene. More recent offerings are repre-
sented by conductive polymers developed by Zipperling Kessler &
Co., some of which are claimed to be suitable for use in pVC. 17
(c) Conductive Fillers

Plastics materials, including PVC compositions, can be made per-
manently antistatic by the incorporation of conductive fillers (cf. Table
9.3) in relatively minor proportions. At increased loadings the effect
can progress to electrical conductivity. Carbon black was the original
conductive filler, and is still in common use today. The various carbon
blacks differ in their own intrinsic conductivity: in general this
increases with decreasing particle size, and with increasing 'structure',
surface purity, crystallite size and orientation. High-structure furnace
blacks can therefore be particularly suitable 18 (compare, as commercial
examples, Conductex 975 or Corax-see Table 9.3).
For substantially spherical filler particles, a theoretical treatment
involving the probability of particle alignment into conductive chains
within the composition 19 suggests a relationship between the filler
loading and the composition's electrical resistance represented by
curve (1) in Fig. 9.2. The relationships actually found in practice are
more in keeping with curve (2) of the figure. Some of the reasons for
this discrepancy between theory and practice are considered in a paper
by Ajayi & Hepburn.20 Depending on the nature of the filler and the
plastic, the steep drop in resistivity exhibited by curve (2) of Fig. 9.2
may occur anywhere between about 5 and 25% filler content (cf. also
Table 9.3) over a resistivity range of the order of ten decades.
Conductive and antistatic plastics compounds, including PVC ones,
are commercially available (e.g. in the Cabelec range-Cabot Corp.,
USA, and Cabot Plastics, UK and Europe).
(d) Some Relevant Test Methods and Specifications

Whilst a plastic's tendency to develop static electricity charges is
indicated by its resistivity, the build-up, magnitude, and decay of
charge can be measured directly on plastics surfaces with the aid of
field meters and electrometers of various kinds. These instruments can
also be used qualitatively, to detect the presence (or points of greatest
density) of a static electricity charge.
TABLE 9.3
Some Commercial Conductive fillers
Filler Typical loading Examples of proprietary materials
to achieve
Physical Chemical nature conductivity a in Trade name Source
form compound (%)
Powder Carbon 20-35 b Conductex Columbian Chemical Co., USA

Corax Degussa, FRG
Vulcan P Cabot Corp., Carbon Black Div., USA
Phi/black XE 2 c Phillis Commercial Co., USA '0
5-15 Ketjenblack EC 6()(Y'- Akzo Chemie, The Netherlands
Aluminium -30 ~
!:;.
Copper 30-35 ~
Nickel 20-30 Inco HDNP Inco Europe Ltd, UK
Flake Aluminium
Mica (Ni-coated)
-20
-20
Transmet
Suzorite E-Mica
Transmet Corp., USA
Lacana Mining, Suzorite Mica Div.,
r
Si
).
USA ~
Fibres Carbon 5-20 Various brands and
i·
Suppliers
Aluminium 20-30
Al-coated glass 20-30 Aluglass Palindent, Israel
Ni-coated carbon 10-15 Cycom NCG American Cyanamid Co., USA
Stainless steel 5-15 Bekaert Steel Wire Corp., USA
a Less for antistatic effects.

b 5-15 claimed for some special grades, e.g. Phillips EC Carbon.
a 'Superconductive' grade. In Europe rights were secured by Degussa in 1986, and the material was renamed Printex
XE2. ...,
~
d Very high-efficiency conductive carbon black.
I
\
\
\
\
\
\
1\
\
\
"-
"
Filler loading (vol. 0 / o } - - - - -...
Fig. 9.2 Effect of conductive filler content on the volume resistivity of filled
plastics compositions. Generalised schematic representation. Curve (1), shape
as computed from theoretical considerations: 19 •20 curve (2), typical shape
obtained in practice.
Note: Microprocessor-controlled field scanners are available for the

measurement of static charges in the range 1-100 ()()() V with
a claimed accuracy of about 0·1 % (e.g. the Model2C scanner
of Scientific Enterprises Inc., USA).
A British Standard code of practice21 provides much useful basic
information on the generation of static electricity, its measurement
and control. Three other publications, respectively by Ferraris,22
Quackenbos,23 and Gale & Pacitti,24 albeit older, are also of interest in
this connection.
Measurement of the rate of charge decay in laboratory or factory
conditions can provide an indication of the effectiveness of antistatic
agents and treatments: the results of such determinations are often

quoted in terms of the 'half-time', i.e. the time required for the charge
to be reduced by a factor of 2. A US Federal Standard (Test Method
Standard lOlB, Method 4046) gives a method for the measurement of
static charge decay rates (with the aid of a static decay meter: Electro
Tech Systems Model SDM 406B.
Two qualitative tests give visual indication of the presence of
electrostatic charges on a plastics surface (and also of the ease of their
acquisition by rubbing). In one, the pick-up is observed of cigarette
ash by the surface concerned. In the other-the so-called 'soot (or
smoke) chamber' test-the attraction to the surface of a polyethylene
bottle of smoke from burning toluene is assessed under standard
conditions (ASTM D2741-84).
The antistatic or conductivity requirements to be met by PVC
products are normally stated in terms of maximum electrical resistance
or volume resistivity as determined in specified tests. The following are
some illustrative examples: the maximum resistivity 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 relevant National Coal Board specification
(NCB 158/1971); the upper limit set by BS 2050: 1978 for many
antistatic products for use in hospitals (e. g. anaesthetic tubing,
furniture buffers, mattresses and pads) is 106 Q, for flooring for
explosive-handling areas it is 5 x 104 Q, and for conducting footwear
(soles and heels) for use in such areas, 1·5 x 105 Q; the limit for small
antistatic mouldings is 106 Q. Apart from BS 2050, methods suitable
for the determination of electrical resistance or resistivity of antistatic
or conductive plastics and rubbers are given in ISO 3915-1981, BS
2044: 1984 and BS 3187: 1978. The determination of antistatic pro-
perties of plastics films is covered by BS 2782: Methods 250A Band
C: 1976.
9.2.4 Odour Control Agents
Additives of this kind are used in some formulations to impart a smell

(e.g. a leather-like odour to PVC handbags or upholstery), or to mask
an undesirable one. According to its function in a particular composi-
tion, such an additive may be described as an odorant, reodorant or
deodorant.
Odorants and reodorants are in most cases essential oils and
'fragrances' as used by the scent and perfume producers. Those
available specifically for incorporation in plastics are mainly

proprietary mixtures. In the matter of choice and incorporation level,
the manufacturer's advice provides the best starting point, but in
general the addition levels are low: the typical range (within which
they will vary with the agent and the product's application) is
0·1-1·5phr. Concentrates (masterbatches) are widely used, for con-
venience of dispersion and minimum loss of the agent in the course of
addition. Two examples are Poly trap (Wickhen Products Inc., USA),
a group of concentrates of odorants in an acrylic resin carrier
compatible with thermoplastics, including PVC; and the Emeressence
aroma chemicals (Emery Chemicals, USA; European distributor,
Chemtech).
In a PVC composition, odours-which may require masking-may
arise from the following causes: plasticisers, or their impurities, or
reaction products (e.g. resulting from oxidation in processing); some
stabilisers (especially tin mercaptides); certain lubricants; impurities in
fillers; trace impurities in printing inks; products of microbial decom-
position of plasticisers and some stabilisers. Additives which have been
proposed as deodorants chemically active in the sense that they may
react with odour-causing substances include perborates, persulphates,
and benzoyl peroxide.
9.2.5 Matting ('Flatting') and Anti-blocking Agents
As the name implies, matting agents are additives incorporated in

PVC compositions to produce a matt ('silk') surface finish. Whilst this
is commonly done to meet a requirement for that particular surface
appearance, most matting agents also have some anti-blocking effect,
and vice versa [ct. also Section 20.4.3(e) of Chapter 20].
Note: Among the exceptions are certain waxes used as anti-
blocking agents. Some of these (e.g. Syntewax; Plastichem,
UK-a high-melting synthetic amide wax) can actually im-
prove surface gloss whilst reducing the blocking tendency of a
pPVC surface.
Matting agents for PVC are of two general kinds: fine-particle
inorganic powders (commonly amorphous silica), and polymeric addi-
tives, which are mainly acrylic resins. Some commercial repre-
sentatives of the first group are: Syloid precipitated silica (W. R.
Grace & Co.), and Degussa's precipitated silica TS 100 and Flatting
Agent OP 278. The polymeric matting agents include the well-known

Aeryloid KF 708 and 710 (Rohm & Haas, USA) and the same
Paraloid grade in Europe, and all-acrylic gloss control agents, Maltex
(Mercury Plastics, UK)-an acrylic resin of high molecular weight-
and Vinnol P90 (Wacker Chemie).
The two kinds of matting agent differ in the way in which they
produce the matt effect. The particulate mineral agents form micro-
scopic protrusions on the PVC surface: these increase the scattering of
light reflected by the surface [ef. also Section 6.2.3(f) of Chapter 6].
Features sometimes cited as disadvantages of this matting mechanism
are that the protrusions can act as points of stress concentration in the
surface and thus reduce the impact resistance of uPVC (cf. Section
8.3.1 of Chapter 8) or the tear resistance of soft PVC, and that the
micro-unevenness of the surface can promote dirt pick-up and
retention.
Surface gloss reduction by an effective acrylic additive (such as for
example Aeryloid KF 710), which blends into the PVC composition
(rigid or plasticised), is a function mainly of the degree of its
compatibility with the PVC matrix: it is also thought that an
acrylic-rich layer is formed on the surface,25 and that this may playa
part in the preservation of the general clarity (as distinct from surface
gloss) of transparent PVC materials surface-matted with additives of
this kind-a feature useful in such applications as non-glare coverings
for documents and maps.
Typical incorporation levels of both the inorganic and the polymeric
agents in PVC compositions are in the range 0·5-3 phI.
REFERENCES
1. Titow, W. V. PVC Technology, 4th edn. Elsevier Applied Science

2. Nass, L. I. Mod. Plast., 40(7) (1963) 151-65.
3. Wells, J. N. J. Cell. Plast., 4(3) (1968) 109-12.
4. Gallagher, R. B., Kamens, E. R., Lanse, F. W. & Kamath, V. E. 36th
ANTEC SPE Proceedings, 1978, pp. 777-9.
5. Sheppard, C. S., Schack, H. N. & Mageli, O. L. J. Cell. Plast., 2(2)
(1966) 97-111.
6. Shea, F. C., 36th ANTEC SPE Proceedings, 1978, pp. 205-7.
7. Nakajima, N., Ward, D. W. & Collins, E. A., J. Appl. Polym. Sci., 20(4)
(1976) 1187-98.
8. Acton, J. & Debal, F., Plast. Rubb. Wkly, (18 June 1976) 22-3.
9. D'Amico, J. N., 28th ANTEC SPE Proceedings, 1970, pp. 678-95.
10. Inman, E. R., Organic Pigments, RIC 1967 Lecture Series, No. 1. The
Royal Institute of Chemistry, London, 1967.
11. Brighton, C. A., Plast. Polym. (Dec. 1968),549-54.
12. Webber, T. G. (Ed.), Coloring of Plastics. Wiley-Interscience, New
York,1979.
13. Donnet, J. B. & Voet, A., Carbon Black. Marcel Dekker, New York,
1976.
14. Ferch, H. (1974), Pigment Resin Technol., (Nov. 1974) 4-20.
15. Fletcher, F. J. & Walker, A. G., Plastics SA, (4) (April 1985), 19-24.
16. Anon., Fire Retardant Products and Their Uses. Chemical Industries
Association, London, 1986.
17. Wessling, B., Mod. Plast. Int., 16(10) (1986) 118-20.
18. Garret, M. D., Kunststojfe, 67(1) (1977) 38-40.
19. Holm, R., Electrical Contacts. Hugo Gebers Publishers, Stockholm, 1946,
p.43.
20. Ajayi, J. D. & Hepburn, C., Plast. Rubb. Process. Applns, 1 (1981),
317-26.
21. BS 5958. Code of Practice for Control of Undesirable Static Electricity.
Part 1: 1980. General considerations. Part 2: 1983. Recommendations for
particular industrial situations.
22. Ferraris, E., Materie Plastiche, 21(1) (1955) 53-61.
23. Quackenbos, H. M., Polym. Engng Sci., 8(1) (1968) 24-31.
24. Gale, G. M. & Pacitti, J., Antistatic Agents: A Critical Review of the
Literature. RAPRA Technical Review No. 43, 1968.
25. Rabinovic, I. S., 32nd ANTEC SPE Proceedings, 1974, pp. 522-6.
Section 3
PRODUCTION (COMPOUNDING) OF
SOLID PVC COMPOSITIONS
363
CHAPTER 10
Solid ('Dry') PVC Compositions
10.1 GENERAL
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 batchwise production
of powder pre-mixes and dry blends. Continuous production of
powder compounds, in special equipment which can be integrated with
an extrusion line, is also being increasingly practised. This kind of
arrangement can offer a number of advantages, both technical and
economic, including suitability for small-scale operations with rela-
tively low outputs. 1 The industrial compounding of solid compositions
is discussed in detail in Chapter 11. A paper by Adams2 provides a
useful summary of the advantages of in-house compounding of such
compositions.
However, many small and medium-sized processors use purchased
compounds: this brings the benefits of the commercial compounder's
special equipment and expertise without own-capital and staff commit-
ments. Even large processors, who are equipped to produce their own
compounds, usually have some short runs on compositions that they
find it more economical to buy-in. They may also occasionally need to
supplement their own internal compound supply, even for regularly
produced, large-volume lines. The use of externally produced master-
batches is also quite widespread.
365
TABLE 10.1
Trade Names and Sources of Some Commercial PVC Compounds
Trade name Source Remarks
Benvic Solvay & Cie, Belgium

Cabelac Cabot Plastics Belgium SA Masterbatches for conductive
compounds. Cabot is the
biggest specialist masterbatch
producer in Europe
Carloy Cary Chemicals Inc., USA Range includes grades (e.g.
6190) for fibre-optics
applications
Doeflex Doeftex Vinyl, UK The only remaining major
independent PVC
compounder in the UK
Dorlyl Dorlyl, France A subsidiary of Shell and
Atochem. Big range of blow-
moulding compounds.
Factories in France, Italy and
Brazil; licensees in Portugal,
Morocco and Argentina
Dural Alpha Div. of Dexter Plastics, USA
Fiberloc B. F. Goodrich, USA Glass-fibre-reinforced PVC
compounds
Geon B. F. Goodrich, USA
Hostalit Hoechst, FRG
Hy-Vin Norsk Hydro, Norway and UK
Kohinor Compound/Packaging Div. of Pantasote Inc.,
USA
Kunstonyl PVC Plastochem, FRG Marketed by Kunstoplast-
Chemie, FRG
Ladene Saudi Basic Industries Corp. (SABIC),
Saudi Arabia
Lucalor Rhone-Poulenc Ind., France
Novablend Novatec Plastics & Chemicals, USA
Oxyblend PVC Resins and Compounds Div. of
Occidental Chemical Corp., USA
Pantalast Compound/Packaging Div. of Pantasote PVC/EVA blends
Inc., USA
Plasblak Cabot Plastics Universal black masterbatches
Plaswite Cabot Plastics Universal white masterbatches
(Ti02 pigment)
Polydon Industrial Polymers (UK) Ltd
TempRite B. F. Goodrich, USA CPVC compounds
Trosiplast Dynamit Nobel, FRG W. Germany's biggest producer
of moulding compounds
Unichem Colorite Plastics Co., USA
Vinidur BASF,FRG
Vinite Alpha Div. of Dexter Plastics, USA
Vip/ast European Vinyls Corporation, Italy
Vitron European Vinyls Corporation, Italy
Vyflex Plascoat Systems Ltd, UK Powder-coating compounds
Vythene Alpha Div. of Dexter Plastics, USA
Welvic European Vinyls Corporation, UK and
Switzerland; AECI, RSA
10 Solid PVC Compositions 367
Masterbatches and direct-use compounds are the two kinds of

composition either self-compounded by PVC product manufacturers,
or supplied commercially. It has been estimated3 that of the 300 or so*
commercial plastics compound suppliers in Western Europe, about
65% provide only direct-use compounds, about 15% only master-
batches, and about 20% compounds of both kinds. The same source
reported the Western European production of PVC compounds in
1986 as 970000 tonnes.
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 inde-
pendent compounders. The latter group includes some processors with
space compounding capacity, who produce compounds to order and
for general sale.
In addition, imported compounds are available in most countries
(normally ones produced by foreign polymer producers and marketed
by their local subsidiaries or agents).
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 codes) for both their
polymers and compounds: in some cases the manufacturer's name is
also the product trade name. Many other compound trade names have
no connections of this kind. Some example are given in Table 10.1.
10.2 TYPES AND FORMS OF PVC COMPOUNDS
The general applicational types of commercial PVC compounds are

outlined in Table 10.2. The solid compounds are available in powder
form (dry blends; compositions for powder-coating applications) or as
melt-compounded pellets (often the same compound in both forms).
The respective advantages of powder and pellet feedstocks, and
reasons for using compounds in one or the other of these forms as
feeds in the melt-processing of PVC compositions into products, are
discussed in some detail in Chapter 11 [Sections 11.2.2(a) and (c)]. An
indication of the physical forms of PVC compound feedstocks com-
* The latest (1986) edition of the Directory of Thermoplastic Compounders in

Western Europe (published by BIS Marketing Research Ltd, London) details
440 compounders in 16 European countries (with particulars of production by
polymer and compound or masterbatch type).
TABLE 10.2
Commercial So6d PVC Compounds: General OutHne of Main App6cational
Types
General type Common applicational types a
Extrusion compounds
Rigid Pipes (various); electrical conduit; rainwater
goods (downpipe and guttering); profiles
(various, including window-frame lineals);
cladding; sheeting; general-purpose
Flexible Electrical wire and cable coverings (various);
other wire coverings (e.g. chain-link
fencing); sheeting; tubing (various); profiles
(various); waterstops; seals and gaskets;
general-purpose
Calendering compounds
Rigid Sheeting
Flexible Sheeting; flooring
Moulding compounds
Rigid (injection) Pipe fittings; electrical components (including
junction boxes); industrial mouldings;
technical parts; general-purpose
Rigid (compression) Gramophone records
Flexible (injection) Footwear; gaskets, bushes, grommets;
electrical components; car trim and bellows
for cars; medical-application components
(e.g. transfusion set parts); bottle-cap liners;
general-purpose
Blow-moulding compounds
Rigid Bottles (various); jars (various); other
containers
Flexible Sachets (for toiletries, etc.)
Powder coating compoundsb
Mainly flexible Wire coating (fencing); dishwasher baskets;
weather- and wear-resistant (railings,
outdoor furniture); general-purpose
Masterbatches
Rigid and flexible Colours; fillers; other additives (including
single-pack additive combinations)
a Various grades available within each type. See also Tables 10.3-10.5, and
relevant information on the processing and applications of PVC compositions
in other chapters.
b Primers required for application of the coating compositions to metal
surfaces are usually available from the compound suppliers.
monly used in the manufacture of some products by the major

melt-processing methods is given in Tables 10.3 and 10.4 here (and
also in Table 11.3 in Chapter 11).
Note: Certain advantages are claimed for particular pellet shape in
pelleted compounds. Thus oval pellets have been said to melt
faster than the conventional cylindrical or square pellets, by
virtue of greater specific surface, and closer packing in the
screw flights of extruders and injection-moulding machines.
Faster melting should reduce PVC polymer degradation in
melt processing-a consideration particularly significant in
connection with PVC products for food-contact and medical
applications (for which oval-pellet compounds are primarily
offered by some suppliers).
Commercial compounds offered for applications where certain
property standards are desirable or obligatory, are normally formu-
lated to meet the relevant standard specifications (e.g. BS, ASTM,
DIN, IEC, etc.). 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 variety of grades is available within the individual
applicational types in most cases, e.g. clear or opaque grades,
coloured or natural compositions formulated for different surface
finish (including 'controlled gloss' compositions ranging from satin
finish to full matt, for such applications as various cable coverings,
steering-wheel covers, etc.). Special grades include compositions for
cellular products (e.g. shoe soles, floats); products for medical use, for
applications involving contact with food (e.g. packaging films), bever-
ages (e.g. tubing for milk transfer, bottles for fruit squashes), or
potable water; and compositions resistant to chemicals and particular
environments (e.g. for hoses resistant to fuels and oils, for wire and
cable coverings resistant to seawater), to marring by contact with
various materials, to elevated temperatures, and to outdoor exposure.
Hot-melt compounds (in the UK originally supplied by Vinatex Ltd*
under the trade name Vinamold) are a special kind of composition,
* Taken over by Norsk-Hydro in the early 1980s.

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
130-170°C. 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 80°C without
serious distortion.
10.3 SOME MATERIAL PROPERTIES OF

PVC COMPOUNDS
Typical values, and/or value ranges, for a substantial number of

material properties of uPVC and pPVC are quoted in Appendix 1.
Other figures are cited, as appropriate, at various places in this book.
Some further relevant data are given below.
10.3.1 Physical and Short-Term Mechanical Properties
Some of these are shown for a number of compounds in Tables

10.3-10.5.
10.3.2 Creep and Fatigue in Rigid Compositions
Products made from rigid PVC are used in some applications where
they have to bear and sustain stress, continuous or intermittent
(cyclic), which may cause creep or fatigue.
(a) Creep
Creep, to which all thermoplastics are subject, is the increase of strain
(deformation) with time under continued stress. For a given thermo-
plastic the creep strain will normally be higher, the greater the applied
stress, and the higher the temperature. The creep rate, i.e. the slope at
a given time of a plot of creep strain versus time (c.f. e.g. Fig. 10.1), is
also subject to these factors. 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.
Creep modulus and creep rupture strength are often referred to in
connection with the creep properties of thermoplastics. Creep modulus
TABLE 10.3
Examples of Some Typical Properties of Commercial Rigid PVC Compounds for a Few Common Applications
(Based in part on manufacturers' published data.)
Application Extrusion injection moulding Blow moulding
Property~ Pipes and Special pipes Profiles Blown Electrical Parts for Detergent Edible-oil
profiles (for household {high· film components household bottles bottles
(food grade) appliances) impact) (junction appliances (v. high- (medium-
boxes) impact) impact) ......
0
Physical form Pellets or Pellets Pellets Pellets or Pellets Pellets Pellets or Pellets or
powder powder powder powder ~
Optical nature Opaque Opaque Opaque Clear Opaque Opaque Crystal Clear s:
~
clear
-3
Density, g cm 1·39 1-44 1·33 1·35 1·48 1·43 1·32 1·33 ~
g
Vicat softening 77 78 72 80 71
point,OC
~
~
Young's modulus, GPa 3·0 3·2 2·5 3·4 3·0 3·1 2·7 3·0 ~:
Impact strength ~
-2
(Charpy), kJ m
At 23°C 9·0 2·0 50 1·0 9·0 4·0 32·0 15·0
At -100C 1·0 7·0 5·0
Example of a suitable
commercial compound
(Welvic b ) HE 0508 HE 0514 HE 3554 HE 0516 HS 1055 HS0510 HF3570 HF 1575
a Numerical properties determined mainly by DIN standard methods.

b ICI (Switzerland) AG: now part of the European Vinyls Corporation (cf. Table 10.1, and Table 3.8 in Chapter 3).
VJ
-.I
-
t;.>
~
TABLE 10.4
Examples of Some Typical Properties of Commercial Plasticised PVC Compounds for a Few Common
Applications
(Based in part on manufacturers' published data.)
'"1::1
~
Application Extrusion Injection moulding <"'l
::!:!
Propertya~ Food-grade Profiles Trans- Wire Waterstops Electrical Gaskets Medical- I:;
tubing (general- parent covering ~.
components grade
(milk purpose) tubing components
conveyance) (for trans-
~
~
"5
fusion sets) '"3-.
Physical form Pellets Pellets Pellets Pellets Pellets Pellets Pellets Pellets
.~
Optical nature Clear Opaque Gear Opaque Opaque Opaque Opaque Gear ~
<::>
Density, g cm -3 1·20 1·39 1·24 1·27 1·32 1·25 1·27 1·18-1·29
Hardness (Shore A) 65 95 82 88 70 70 63 63-96
"~
S·
'"
Tensile properties ~
Strength, MPa 14 33 18 24 16 16 12 13-25 s::.
;:,
Elongation, % 380 240 260 270 340 345 425 430-200 ""-
Cold-bend temperature, -40 -20 -25 -13 -26 -35 -40 ::t-
°C ~
Example of a suitable £g,
commercial compound WE 6554 WE 9505 WEBOO1 WE 8551 WE 7053 WS7008 WS6005 WS6078-
(We/vic b ) WS 9578 (with ~
other grades
between)
a Numerical properties determined mainly by DIN standard methods.

b ICI (Switzerland) AG: now part of the European Vinyls Corporation (ct. Table 10.1, and Table 3.8 in Chapter 3).
TABLE to.5
uPVC and Other Plastics Materials with Some Overlapping Apptications (Especially in Pipes and Pipe Fittings)-A
General Comparison of Some Typical Properties4
Property and units Method of upvc cpvc LDPE HDPE PP ABS
determination
Ordinary High-impact
Specific gravity ASTM D 792 1·37-1·45 1·34-1·36 1·52-1·57 0·91-0·93 0·941-0'965 0·90-0·91 1·03-1,07
Tensile strength, lbf in -2 x 10 3 ASTMD638 7·0-8·5 6·0-7·0 8·2-8·5 1·0-2·0 3·0-5·0 3·0-5·0 5·5-8·0
Elongation at break, % ASTM D 638 2-10 2-30 8-15 90-650 20-800 20-600 5-80 .....
Tensile modulus, lbf in -2 x 105 ASTM D 638 3·5-5·5 3·2-3·9 4·0-5·5 0·2-0·4 0·6-1·8 1·0-2·2 2·0-1·0 c
Flexural strength, lbf in -2 x 103 ASTM D 790 13.50 11.00 14·5-16·0 1·0-2·0 3·0-3·5 5·0-8·0 6·0-12·0
4.00 3.20
~
Flexural modulus, lbf in -2 x 105 ASTM D 790 3·8-4·3 0·1-0·6 1·0-2·0 1·7-2·5 2·0-3·5
Creep modulus at 1000 h,o lbf in- 2 235 188 40 60 172
E:
"tI
(copolymer)
Impact resistance, Izod (notched), ~
ft lbfin- I ASTM D 256 0'7-3'0 8-18 2-3 no break 3-20 2_ 10b 2·5-12·0 g
Deflection temperature under load ~
(264lbfin -2 stress), °C ASTMD648 75 0 700 100-105 32-40 43-55 55-60 85-105 Sl
Coefficient of linear thermal expansion, 7·7-8·3 ~:
mm mm -1 0C - I x 10- 5 ASTM696 6·0-6·5 3·8-6·5 12-17 11-13 6'8-11·0 6·0-11·0 &l
Thermal conductivity, Wm- I K- 1 ASTMC177 0·1~ 0'1~ 0·14 0·33-0·35 0·33-0·47 0·10-0·22 0·19-0·34
Maximum temperature for continuous
service,oC 60-65 60 90 70 80 110 100
Hardness, Rockwell ASTM D 785 R115° RI02-R113 R118-R120 RIO-R20 R1O-R20 R80-RllO R3O-R118
Water absorption at equilibrium,
% at 200C (100°C) 0·10 (0·20) 0·05e 0·00 (0·01) 0·00 (0·01) 1·05 (1·40)
Oxygen Index ASTM D 2863 400 380 500 17-18 -18 -20
o Representative values (particular compounds).

b Homopolymer-copolymer.
e Absorption after 24 h (ASTM D 570). w
-.:t
W
At 51°C
~
6·0 e.·o
5·01 5·0 ~
~
~
r
4' 4·01 5'
'3230 psI
~
~
'I:j
c
o ~
.. 3·0 ::t.
c jll
~
)C
IIJ ~
~
o~ ~
2" '"
~.
~
:g~
~
5"'
i;l
0'1 10 100 1000 0'1 10 100 1000
Time in Hours
Fig. 10.1 Creep of a high-impact uPVC composition (Breon RA 170) at two temperatures.
is the ratio of applied stress to creep strain in a creep situation,

formally defined (by ISO 899-1981) as 'the ratio of initial stress to
creep strain ... given by the equation Ee, = of Et , where 0 is the initial
stress in megapascals, and Et is the creep strain at time t'. Creep
rupture strength (sometimes also called 'stress rupture strength') has
been defined 5 as 'the stress that will cause fracture in a creep test at a
given time, in a specified constant environment'.
Early work by Turner6 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
on the heat history of the uPVC composition concerned. Later work
by Ogorkiewicz & Bowyer7 compared the tensile creep of rigid PVC
with that of some other thermoplastics: the findings indicated that at
low stresses and for relative 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 poly-
acetal. Some creep characteristics of uPVC are illustrated in Figs
10.1-10.3.
(b) Fatigue
A useful working definition of fatigue is8 'The process of progressive
localised permanent structural change occurring in a material sub-
300kg/cm 2 (42661bf iri2 )
__------==----------- 200kg/cm
2 2
(26441bf Iri )
100 kg I cm 2 (1422 Ibf iri2 )
Tim., under load, h
Fig. 10.2 Creep curves for a uPVC pipe composition at room temperature
under different loads. 4
40.---------,---------.---------,---------,
10 10 2
Timcz,h
Fig. 10.3 Creep of a uPVC pipe composition: stress/time relationship for a

given strain. A, 3% strain; B, 2% strain; C, 1% strain; D, 0.5% strain.
jected 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'. The associated
concept of fatigue life, in the context of fatigue testing, is defined (by
the same source) as 'the number of cycles of stress or strain of a
specified character that a given specimen sustains before failure of a
specified nature occurs'. The important practical point about fatigue of
plastics in service situations is that loads which are satisfactorily
accommodated at short times can produce failure at long times. In the
plastics context 'fatigue' usually means dynamic fatigue, i.e. 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. In plastics, fatigue can be
aggravated by temperature rises occurring under cyclic stressing 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 molecular weight of the polymer is a significant factor in the
fatigue resistance of a PVC (especially uPVC) composition, the
resistance increasing with 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 faults in a PVC product (or notches in a test specimen) also
reduces fatigue resistance. Whilst the resistance to flexural fatigue of
such plasticised PVC materials as coatings on fabrics is a property
significant in the relevant applicational areas, the greatest attention
has been centered on the fatigue resistance of rigid PVC compositions,
notably those used in the production of pipes. 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, for
example as fluids are pumped through the pipes, or in consequence of
repeated opening and shutting of valves.
Results of fatigue endurance evaluation for plastics materials
(including uPVC) are usually presented in the form of an 'S-N' curve
(called the Wohler curve in German technical literature): this is a plot
of maximum stress versus the logarithm of the number of cycles to
failure. The fatigue limit, a theoretical value of maximum stress below
which no amount of cyclic loading should produce failure, can be
estimated from such plots. A 'fatigue modulus' has also been defined,
as the quotient of applied stress and total strain after the nth cycle: a
model (the Hwang-Han model) based on the underlying concepts is
claimed to provide a better fit for the experimentally determined mean
number of cycles to failure than the S-N curve. 9
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,1O,l1 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: these 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. 10.4. The range
of stress or stress amplitude values (ordinates) and the number of
Number of cycles to failure
Fig. 10.4 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.
cycles to failure (abscissae) within which the curve might typically lie
would be, respectively, about 10-60 MPa and 10-106 cycles.
With a square-wave form of loading (rather than the sinusoid-wave
form widely employed in experiments) the data can also be repre-
sented on a stress-time basis, * for direct comparison with creep failure
('static fatigue') curves obtained for the same material under con-
tinuous 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 lO for calendered uPVC sheet, and by Gotham &
Hitch l l for rigid pipe material. Two further general points (made by
Gotham lO) 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.
* 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. \0
The role of plastic deformation in the failure of PVC under stress has
been considered by Gotham & Turner;12 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 & Hitch,l1 and Moore et al.13
10.3.3 Thermal Properties
A number of these are featured in Appendix 1, and some are

instanced in Table 10.5. The following values have also been quoted 14
for Welvic (lCI, UK) rigid PVC moulding material:
Specific heat at 20°C 110 J kg- 1°C- 1
Thermal conductivity at 20°C 0·17 W m -1 °C- 1
Approximate total heat (moulding) 270 x 106 J m- 3
See Appendix 1 and various specific references elsewhere in this book

(via the Index).
10.3.5 Chemical Properties
The chemical resistance of PVC homopolymer at ordinary tempera-

tures is generally good, except to solvents of the following groups:
ketones, chlorinated hydrocarbons, esters of acetic acid, aromatic
hydrocarbons, and ethers. Some of these actually dissolve the polymer
(tetrahydrofuran, cyclohexanone, isophorone) and others swell it
strongly. More detailed indications are provided by the data for uPVC
compositions in Tables 10.6 and 10.7, in that the resistance of some of
these compositions is closely similar to that of the parent polymer.
Copolymers are somewhat less resistant than the homopolymer,
especially to organic solvents (cf. PVC solutions-Chapter 19). How-
ever, their general resistance characteristics are broadly comparable
with those of the homopolymer.
As is usual with thermoplastic polymers, the susceptibility of PVC
polymers and copolymers to chemical attack increases with rising
temperature: the same behaviour is exhibited by PVC compounds,
whose resistance is also affected by the presence of the various
formulation components. Thus, for example, some impact modifiers
may reduce the solvent resistance of uPVC compounds, whilst
TABLE 10.6 ...,
General Chemical Resistance Characteristics of PVC at Room Temperatnre ~
Reagents Rigid PVC Plasticised PVC

General Remarks General Remarks
resistance resistance '"'tI
ratingQ ratingQ ~
Inorganic acids r
Dilute sl No attack up to 60°C, but S No significant attack up to ~.
max. allowable design 20°C; plasticisers and
stress should be lowered some fillers may be ~
~
affected at higher ~
::to
.,'"
temperatures
Concentrated SI M Plasticiser and some fillers ~
may be affected '"'tI
~
Oxidising M Attacked above 20°C; U Short-term contact may be
(concentrated) max. allowable design acceptable in some cases
'"~
s·
stress should be reduced ~
substantially I:>
:.
Organic acids M M s:...
Alkalis ~
~
Dilute No attack up to 60°C; Some plasticisers and fillers ~
I:>
allowable design stress may be affected
Concentrated should be substantially 5·
:} reduced
:} a
Oxidising agents S Allowable design stresses S Some fillers may be
should be substantially affected
reduced
Reducing agents S No attack up to 60°C S No attack up to 60°C
Detergent solutions S S
Inorganic salt solutions S S
Halogens
Chlorine M Little attack in the absence U
of moisture
Bromine U U
Fluorine U U
Iodine U U
Aliphatic alcohols S Allowable design stresses M
should be substantially
reduced
Water S Some softening possible at S Softening, and some effects ....c
elevated temperatures on certain fillers at
elevated temperatures ~
Aliphatic hydrocarbons S M Extraction of plasticisers s:
and some effects on ."
'<:::
other components ~
Aromatic hydrocarbons U U possible g

Chlorinated U U ~
hydrocarbons ~
Esters U U ~:
Ethers U U ~
Ketones U U
Aldehydes M M
Amines M M
Liquid fuels S-M See also Table 10.7 M-U
Turpentine U U
Oils:
Mineral S M-U
Vegetable and animal S M-U
Fats S M-U w
00
....
a Rating key: S = satisfactory; M = moderate (dependent on formulation and conditions); U = unsatisfactory.
TABLE 10.7
Chemical Resistance of Rigid PVC (Long Contact),
Chemical Temperature Chemical Temperature
("C) ("C)
20 60 20 60
Acetaldehyde
40% S M Citric acid, sat. S S
100% U U Copper fluoride, 2% S S
Acetone U U Copper cyanide S S
Acetic acid Cottonseed oil S S
20% S S-M Cresol M U
80% M M-U Cresylic acid S S
Glacial M-U U Cupric fluoride S S
Aluminium fluoride S S Cyclohexanol U U
Ammonia liquid, 100% M M-U Cyclohexanone U U
Ammonium fluoride, 20% S S Dibutyl phthalate S-M M
Ammonium hydroxide, 0·88 S S Diethylene glycol S S
Ammonium sulphide S S Diglycolic acid S S
Amyl acetate, 100% U U Dioctyl phthalate U U
Aniline, 100% U U Ethanol S-M M-U
Barium chloride S S Ethyl acetate U U
Barium sulphide (sat. soln) S S Ethyl butyrate M U
Benzaldehyde M U Ethyl chloride S S
Benzene S-M U Ethyl ether U U
Bleach lye, 10% S S Ethylene chloride U U
Bromic acid, 10% S Ethylene dichloride U U
Bromine gas, weak S Ethylene glycol S-M U
Bromine liquid U U Ethylene oxide U U
Butyl acetate U U Fatty acids S S-M
Butyric acid Ferric chloride, sat. soln. S S-M
20% S M Ferric sulphate S S
Conc. U U Ferrous chloride S S
Butanol Ferrous sulphate S S
Primary S-M M-U Fluosilicic acid S S
Secondary S-M U Formaldehyde, 40% S S-M
Calcium chlorate S S Formic acid
Calcium hypochlorite, S S 50% S M
soln Conc. S U
Carbon disulphide M U Fruit juices S S
Carbon tetrachloride U U Fuel oils S S
Castor oil S S-M Furfural U U
Chloroacetic acid, 100% S S Glucose soln S S
Chloric acid, 1-20% soln S S Glycerine S S
Chlorine gas S S Heptane M M-U
Moist gas S Hexane M-U U
Liquid U U Hydrochloric acid, 30% S S-M
Chlorobenzene U U Hydrocyanic acid S S
Chloroform U U Hydrobromic acid
Chlorosulphonic acid M U 50% S S-M
Chromic acid S S-M Conc. M M-U
TABLE 1O.7-contd.
('C) ("C)
20 60 20 60
Hydrogen bromide, 10% S

Hydrogen peroxide S-M M Potassium chloride, S S-M
Hydrogen sulphide S S sat. soln.
Hypochlorous acid S S Potassium dichromate S S-M
Kerosene S S Potassium chromate, 40% S U
Ketones U U Potassium hydroxide, cone. S S
Lactic acid Propanol S S-M
10% S M Propylene dichloride U U
90% U U Silver cyanide S S
Linseed oil S M Soap solution S S
Magnesium chloride S S Sodium acetate S S
Magnesium hydroxide S S Sodium bisulphite S S
Maleic acid, sat. S M Sodium bromide S S
Mercuric chloride S S Sodium chlorate, S S
Mercuric cyanide S S sat. soln
Mercurous nitrate S S Sodium chromate S S
Methanol S S Sodium cyanide S S
Methyl bromide M U Sodium dichromate, S S
Methyl chloride, 100% M sat. soln
Methyl ethyl ketone U U Sodium ferrocyanide S S
Methyl isobutyl ketone U U Sodium fluoride S S
Methylene chloride, 100% U U Sodium hydroxide
Milk S S 10% S S
Mineral oils S S 30% S S
Molasses, commercial S S 50% S S
Naphtha S S Sodium hypochlorite S S
Naphthalene U U Sodium sulphide, sat. soln S S
Nickel chloride S S Stannous chloride S S
Nitric acid Stannic chloride S S
1-30% S M Stearic acid, 100% S S-M
70% S M Sulphur dioxide
98% U U Dry S S
Nitrobenzene U U Wet S S
Octylcresol M M Liquid M U
Oleic acid S S Sulphuric acid
Oxalic acid, sat. soln. S M 20% S S
Perchloric acid, up to 70% S S 50% S S
Petrol, aliphatic S S 90% S S-M
Petrol/benzene, 80/20 U U fuming U
Phenol,90% S-M M-U Tanning extracts S
Phenylhydrazine, 100% U Tartaric acid, sat. S S
Phosgene, liquid S U TetraethyUead S
Phosphoric acid, 75% S S Tetrahydrofuran U U
Phosphorus pentoxide S Thionyl chloride U U
Phosphorus trichloride U
Picric acid, 1% S (continued)
TABLE lO.7-contd.

("C) ("C)
20 60 20 60
Toluene U U Urea up to 30% S S

Transformer oil S S Vinegar S S-M
Trichloroethylene U U Water, distilled S S
Triethanolamine S S Xylene U
Trisodium phosphate S S-M Zinc chloride sat. soln S S
Turpentine M-U U Zinc sulphate S S
a Key: S = satisfactory; M = moderate (dependent on formulation and conditions); U = unsatis-

factory.
susceptibility to acids and alkalis may be affected by substantial

contents of such fillers as calcium carbonate, or wood flour. As
indicated in Table 10.6, the presence of plasticisers in pPVC composi-
tions affects their chemical resistance adversely (as well as the rate of
attack in many cases).
Apart from any direct chemical action, or distortion and mechanical
weakening through swelling, some reagents (especially those which act
as swelling agents) can affect the properties of PVC materials by
leaching or dissolving out formulation components (e.g. plasticisers,
stabilisers), even if only from the surface layer. Plasticisers may also
be lost by migration into some materials in close contact with pPVC
(e.g. adhesives, lacquers): the properties of both materials may be
affected as a result.
In addition to Table to.6, further data on the chemical resistance of
uPVC are contained in Table to.7. Noteworthy among relevant
sources of reference are ISO/TR 7473-1979 (which gives data on the
resistance of uPVC pipes to many fluids at up to 60°C) and the
RAPRA chemical resistance data sheets which give quantitative data
on the effects of 48 chemicals on a number of rubbers and plastics,
including PVc.
The chemical resistance of plastics materials, including PVC, is
normally tested by determining changes in appearance, dimensions,
weight, and some mechanical properties of specimens after a period of
contact with the chemical(s) concerned. Some of the relevant stand-
ards give a list of chemicals for determining the general resistance, and
specify the properties to be used in assessment; compare for example
ISO 175 (determination of the resistance of plastics to chemicals), BS
2782:Method 830A (equivalent to ISO 175), ASTM D 543 (partly
equivalent to ISO 175), and BS 4618:Section 4.1 (chemical resistance
of plastics to liquids). Some basic requirements in respect of the
general chemical resistance of uPVC and CPVC compositions are laid
down in Table 2 of ASTM D 1784-81. Other standards of interest in
this general context include the following: ISO 3743 (effect of
sulphuric acid on uPVC pipes); BS 3506 (includes test for resistance of
uPVC pipes to sulphuric acid); BS 3260 and 3261 (which inter alia
cover resistance of PVC floor tiles and flooring to scratching after
immersion in some liquids); ASTM D 1239 (resistance of plastics films
to extraction by chemicals); DIN 53476 (testing resistance of plastics to
liquids); DIN 53756 (effects of storage of plastics in contact with
chemicals); DIN 537428 (determination of resistance of cellular plas-
tics to liquids, vapours, gases, and solids).
10.3.6 Miscellaneous Properties
(a) Optical
The light-transmission properties of transparent PVC materials are
good. The transparency of many uPVC compositions is comparable
with that of clear polymethyl methacrylate. 'Crystal' compositions of
high clarity and 'sparkle' can be formulated (e.g. for glazing sheets,
packaging films, and blow-moulded bottles). Light-transmission curves
for clear and translucent (white) pigmented uPVC films are shown in
Fig. 10.5.
(b) Water absorption

Some typical figures for the absorption of water by PVC in widely used
standard tests are quoted in Appendix 1. Such tests lay down a fixed
time for sorption in the particular test conditions. Thus the tests do not
(nor are they designed to) necessarily provide information on the
equilibrium sorption value (i.e. the saturation water take-up in the
particular test conditions), the sorption kinetics, or the diffusion
coefficient. However, such data are quite often of interest not only in
academic contexts, but also in some practical ones. The following
values, from Braden's data on the absorption of water by plastics, 15
are noteworthy in this connection.
100
A
E
'c"
....~ 40
....
.c
OJ
::J
20
°0~.3~~-0~'~4----~0~·5~--~0~.6~--~0~'7~--~0~'8
Wav<li<lngth,llm
Fig. 10.5 Light transmission through uPVC films (compositions based on

mass-polymerised resin). A, clear formulation; B, translucent formulation
(Ti0 2 -pigmented).
Diffusion coefficient, cm2 S-1 uPVC pPVC

At 20°C 4-4 X 10- 10 4-4 X 10- 10
At 37-4°C 17 X 10- 10 17 X 10- 10
Equilibrium concentration, g per g
At 20°C 0-0092 0-0092
At 37-4°C 0-0092 0-0092
As pointed out by Braden, it appears rather surprising that each of the

two parameters was found to have the same value in uPVC and pPVC:
the author thought that, at least in the case of the diffusion coefficient,
this could be explained on the grounds that the mobility of the water
molecules is the controlling property. 15 Braden also points out two
practical applications of the parameters, viz_ in the calculation of
drying times of polymer granules of various sizes, and the loss of water
by radial diffusion through walls of pipes. In the latter case, substitut-
ing his determined values for the diffusion coefficient and equilibrium
concentration of water in uPVC at 20°C into the appropriate equation
for steady-state diffusion, Braden calculated the loss as 0·009 cm3 per
metre length of pipe of unit wall thickness per week. 15
(c) Others
Other properties of PVC materials, e.g. flammability, permeability,
impact resistance, and many others, are discussed in various chapters
of this book (see the Contents List and Index).
10.4 CHARACTERISATION AND STANDARD

DESIGNATION OF COMMERCIAL PVC COMPOUNDS
As in the case of PVC polymers, there are ISO, ASTM and DIN
standards laying down property requirements and designation systems
for PVC compounds, namely for uPVC compounds ISO 1163, ASTM
D 1784 and DIN 7748, and for pPVC compounds ISO 2898, ASTM D
2287 and DIN 7749. In addition, ASTM D 3915 and D 4216 similarly
cover, respectively, compounds for PVC pipes and pipe fittings, and
for building materials.
10.4.1 Characterisation
Each of the above general quality standards specifies a number of

properties for the PVC compounds to which it relates (to be
determined in accordance with named standard specifications). These
groups of properties are widely featured in characterisation test
schemes employed by the producers and users of PVC compounds,
although some companies use more, and others fewer, tests than those
specified by the standards (as well as, in some cases, their own test
methods). A typical basic characterisation scheme may, for example,
comprise tests for the following properties.
Properties associated with the physical form of the

compound: Apparent density; bulk factor; dry flow; moisture content.
Material properties:
uPVC: melt flow (to ASTM D 3364, or by another suitable
rheometric method); density; impact resistance; tensile
strength and elongation; tensile modulus; deflection tem-
perature under load and/or Vicat softening temperature.
pPVC: melt flow (as above); density; durometer (Shore) hardness

or BS softness; tensile strength and elongation; tensile stress
at 100% elongation (often known as '100% modulus'*);
torsional stiffness as a function of temperature (ISO 458),
and/or brittleness temperature (ASTM D 746); plasticiser
loss and/or migration.
Properties important in particular applications: Weathering resis-
tance and coefficient of thermal expansion (e.g. ASTM D 4216);
resistance to chemicals (e.g. ISO 2898/2; ASTM D 1784); flammability
(ASTM D 1784 and D 2287); hydrostatic design basis (ASTM D
3915); electrical properties (e.g. of cable compounds).
10.4.2 Designation
Standard designation systems for PVC compounds are laid down in the
specifications mentioned above as sources of the characterisation tests
(d. also Table 10.8). They are based on principles similar to those
used in standard designation of PVC polymers (d. Chapter 3, Section
3.3.2). .
TABLE 10.8
Standards Relevant to the Properties and Testing of Solid PVC Compositions
(See also Appendix 1)

no.
Designation Subject (not necessarily the offiCial title)
General (Designation, coding, characterisation tests)
(a) Rigid compositions
ISO 1163 Plastics--Unplasticised compounds of
vinyl chloride homopolymers and
copolymers
1 Part 1-1985 Designation
2 Part 2-1980 Determination of properties
3 ASTM D 1784-81 Specification for rigid PVC and CPVC
compounds
4 ASTM D 3010-71 (1981) Recommended practice for preparing
compression-moulded test sample
plaques of rigid PVC compounds
* At 100% elongation in a tensile test, the strain is (2/0 -10)/10 (where 10 is the
original test length), i.e. strain = 1. With the modulus defined as stress/strain,
the modulus at this elongation is stress/I, i.e. it is equal to the stress.
TABLE 1O.8---contd

no.
Designation Subject (Not necessarily the official title)
5 ASTM 3915-80 PVC and related plastic pipe and fitting
compounds
6 ASTM D 4396-84 Rigid PVC and related plastic
compounds for non-pressure piping
products
7 ASTM D 4216-83 Rigid PVC and related plastic building
products compounds (including
CPVC)
DIN 7748 Plastic moulding materials;
unplasticised PVC
8 Part 1 (1985) Classification and designation
9 Part 2 (1988t Determination of properties
(b) Flexible compositions
ISO 2898 Plastics-Plasticised compounds of vinyl
chloride homopolymers and
copolymers
10 Part 1-1986 Designation
11 Part 2-1989" Determination of properties
12 BS 2571:1963 Q
Flexible PVC compounds
13 ASTM D 2287-81 Specification for non-rigid vinyl chloride
polymer and copolymer moulding and
extrusion compounds
DIN 7749 Plastic moulding materials; plasticised
PVC
14 Part 1 (1985) Classification and designation
15 Part 2 (1988t Preparation of specimens and
determination of their properties
Properties and tests
(a) Bulk density and pourability
16 ISO 60-1977 (1985) and BS Apparent density-see Chapter 3,
2782 Method 621 A Table 3.12, entries nos 27 and 30
17 ISO 61-1976 and BS 2782 Apparent density-see Chapter 3,
Method 621 B Table 3.12, entries nos 28 and 30
18 ISO 171-1980 (1985) Plastics-Determination of bulk factor
of moulding materials
19 ISO 6186-1980 (1985) Plastics-Determination of pourability
20 ASTM D 1895-69 (1979) Test for apparent density, bulk factor,
and pourability of plastics materials
(cf. also Chapter 3, Table 3.12, entry
no. 31)
(continued)
TABLE 10.8-contd

no.
21 DIN 53466 (1984) Determination of bulk factor and

apparent density of moulding
materials (N.B. Former DIN
specifications 53467 and 53468 were
incorporated in this standard in 1984)
(b) Water absorption (see also Appendix 1)
22 ISO 62-1980 Plastics-Determination of water
absorption
23 BS 2782:Methods 430 A-D Determination of water absorption (at
23°C and boiling)
24 ASTM D 570-81 Water absorption of plastics
25 ASTM D 2842-69 (1975) Water absorption of rigid cellular
plastics
26 DIN 53471 (1976) Superseded by DIN 53495
27 DIN 53473 (1979)
28 DIN 53495 (1984) Determination of water absorption (on
immersion at 23°C and at the boil,
and from humid air)
(c) Temperature effects
Physical
BS 2782
29 Method 122 A:1983 Determination of deformation under
heat of flexible PVC compound
30 Method 150 B:1983 Determination of cold-flex temperature
of flexible PVC compound
31 Method 150 C:1983 Determination of low-temperature
extensibility of flexible PVC sheet
Chemical
32 ISO/R 182-1970 Determination of thermal stability of
PVC, related copolymers, and their
compounds by splitting off HCI
33 ISO 305-1976 Determination of thermal stability of
PVC, related polymers and
copolymers, and their compounds-
Discolouration method
BS2782
34 Method 130 A:1986 Determination of the thermal stability
of PVC by the Congo Red method
(== ISO/R 182)
35 Method 130 B:1986 Determination of the thermal stability
of PVC by the pH method ( == ISO/R
182)
TABLE 1O.8--contd

no.
36 ASTM D 793-49 (1976) Test for short-time thermal stability of

plastics containing chlorine
(Discontinued in 1983)
37 ASTM D 2115-67 (1980) Recommended practice for oven heat
stability of PVC compositions
DIN 53381 Determination of the thermal stability
of PVC by dehydrochlorination
methods
38 Part 1 (1983) Congo Red method
39 Part 2 (1983) Discolouration method
40 DIN 53418 (1984) Draft: Determination of the efficiency
of thermal stabiliser in PVC
(d) Mechanical properties
ISO 458 Plastics-Determination of stiffness in
torsion of flexible materials
41 Part 1-1985 General method
42 Part 2-1985 Application to plasticised PVC
(homopolymer and copolymer
compounds)
(e) Miscellaneous properties and analysis
43 ASTM D 2124-70 (1984) Analysis of components in PVC
compounds, by IR method
44 ASTM D 2151-68 (1982) Test for staining of PVC compositions
by rubber compounding ingredients
45 ASTM D 2538-79 (1985) Recommended practice for fusion test
of PVC resins using a torque
rheometer
46 ASTM D 3364-74 (1983) Flow rates of PVC and rheologically
unstable thermoplastics
47 ASTM D 3421-76 Extraction and analysis of plasticiser
mixtures from vinyl chloride plastics
48 ASTM D 3591-77 (1985) Determination of the logarithmic
viscosity number of PVC resin in
formulated compounds
49 ASTM D 3596-77 (1983) Recommended practice for determining
gels (fish eyes) in general-purpose
PVC resins
a Revision under way (in 1990).

REFERENCES
1. Weber, M., Plast. Rub. Int., 8(5) (1983) 32-4.

2. Adams, H. J., 34th ANTEC SPE Proceedings, 1976,330-2.
5. ASTM E 6-81. Standard Definitions of Terms Relating to Methods of
Mechanical Testing.
6. Turner, S., Brit. Plast., 37(6) (1964) 322-4; 37(12) (1964) 682-5.
7. Ogorkiewicz, R. M. & Bowyer, M. P., Brit. Plast., 42(9) (1969) 125-8.
8. ASTM E 206-72 (1979). Standard Definitions of Terms Relating to
Fatigue Testing and Statistical Analysis of Fatigue Data.
9. Hwang, W. & Han, K. S., 1. Camp. Mater. 20(3) (1986) 154-65.
10. Gotham, K. V. In Thermoplastics Properties and Design, ed. R. M.
Ogorkiewicz. John Wiley and Sons, London, 1974, Ch. 4.
11. Gotham, K. V. & Hitch, N. J., Pipes Pipelines Int., (Feb. 1975) 10-17.
12. Gotham, K. V. & Turner, S., Polym. Engng Sci., 13(3) (1973) 113.
13. Moore, D. R., Gotham, K. V. & Hitch, M. J., The mechanical properties
of PVC and how these are influenced by changes in processing, formula-
tion and polymer type. Paper presented at PRI International Conference
of PVC Processing, Egham Hill, Surrey, UK, 6-7 April 1978.
14. Anon., Plastics; The Principles of Injection Moulding. ICI Technical
Service Note G 103, 2nd edn. ICI Plastics Division, UK.
15. Braden, M., Plast. Inst. Trans., 31(94) (1963) 83-8.
CHAPTER 11
Compounding: Operations and Equipment
11.1 GENERAL
The function of compounding is to combine the PVC polymer with the

other components of the formulation and to provide the resulting
composition (compound) in a form appropriate to the further process-
ing intended. In laboratory compounding the form may have to be
suitable for testing or experimentation.
Industrial PVC compounding operations may be grouped under the
following general headings (d. also Fig. 11.1).
(a) Preparation of powder compositions (pre-mixes and dry
blends).
(b) Melt-compounding, with production of pelletised compositions.
(c) Compounding for direct feeding of calenders.
(d) Preparation of liquid compositions--pastes, latex compositions,
and solutions.
(e) Recycling (of own-process scrap or reclaimed material).
The equipment used in industrial compounding of PVC can be divided
into the upstream section ahead of the compounder, the compounding
section, and the downstream section (Fig. 11.2). The upstream
equipment is much the same in all the five types of compounding
operation, but the compounding set-up and corresponding down-
stream equipment vary according to operation type.
By virtue of their small scale, laboratory compounding operations
do not normally require any elaborate or automated upstream
equipment. The compounding equipment is either a reduced-size
version of the corresponding industrial machinery (with two-roll mills
393
w
PVC rework
or reclaim
'e.
material
Solid-phase (powder) Liquid-phase Recycling via

compounding appropriate
/compOrding~ compounding and/or ~
processing
1 operation !r
'"
~.
1 ~
.g
Compound for
Used directly as further processing, a.
feedstock for or finished product -~
extrusion or ~
moulding ,
~
'""
------------------~
'"
~.
Melt-compounding Further (melt-)
and pelletising compounding
and direct (in-line) ~
feeding to calender )..
1 :g
[Pcllet~ I
I
Calendering into
2
~.
_________ L _________ ~
Used as feedstock:
1
for extrusion or '
moulding
Fig. 11.1 Compounding of PVC: general schematic outline.

11 Compounding 395
r--T------------------,I
I I-
1 aJ RAW MATERIAL 1
i~ STORAGE i
13
1
I W
- 1
I
1
1 ~ 1
1 <! I
I w 1
1 0:: I
i tn RAW MATERIAL i
I cL
IL _::>_
WEIGHING I
I
~ _______ _
r--T--------
I I ,...--_~ _ _...,
I I- 1
-I
zi
::>1
(!)I
~I
01
ZI
::>1
~I
~I
01 COATING
UI
1
--~-------- --------~
r~-T-------- --------,
~ 1 PRODUCT i
Iti COOLING i
51 I
@i I
i
PRODUCT
::E I CONVEYING I
I I
[ PRODUCT [
STORAGE OR
~i
I 1 I
BAGGING [
1 I
--~------------------~
Fig. 11.2 Compounding of solid PVC compositions: equipment and opera-

tions (block diagram).
in much wider use in the laboratory than they are in industry

nowadays), or special instrumented apparatus based on the torque
rheometer (as represented for example by the widely-used Brabender
equipment range). Downstream equipment is also commonly simpler
than its industrial counterparts.
11.2 INDUSTRIAL PRODUCTION OF

SOLID COMPOUNDS
11.2.1 Upstream Equipment and Operations
(a) Handling, Storage, and Conveying
POLYMER AND FILLERS

In relatively small-scale industrial operations, these powder materials
may be delivered in containers or bags, which are then kept in suitable
stores. Otherwise, delivery is by tanker (road or rail) and silos are
used for storage (typically where consumption is about 30 tonnes or
above, per month, per material, see Fig. 11.3). Silo capacities fairly
typically range between 150 and 250 m3 , although units outside this
range are also employed in some cases. 1 Common construction
materials are an aluminium/magnesium alloy (AIMg 3), or glass-fibre-
reinforced polyester (for silos near the lower end of the above capacity
range).
Pneumatic conveying systems (normally pressure- rather than
suction-operated) are used to fill silos from road- OJ rail-tankers; such
vehicles are designed to withstand the pressures involved. Screw
compressors are used to generate the required flow of oil-free air.
With the usual pipe diameters of 80-100 mm, typical conveying
capacities are in the range 15-30 tonnes per hour. Control systems are
available for silo and tank filling levels, providing visual displays and
print-outs (e.g. equipment from Keller Spezialtechnik, FRG).
For operational flexibility, and ability to handle smoothly small
batches of different formulations and qualities if required, most plants
have an additional dumping station for filling the storage silos (or
holding bins, or both) with bag-packaged goods. A manual dumping
station (hand-opening and dumping of bags), with a filling rate
of-typically-about 3 tonnes per hour, is often sufficient. Where
larger quantities of bagged materials have to be handled, a semi-
automatic or automatic bag-dumping machine may be needed (typical
capacity about 600 bags per hour). Bag-dumping stations must include
provision for drawing-off dust airborne during dumping to a filter via a
suitable exhaust system. As a rule, these stations are supplied with a
11 Compounding 397
Fig. 11.3 Silo installation for PVC polymer and fillers.
built-in filter which can be cleaned mechanically to return the collected

dust to the bulk material. An exhaust system should provide an air
flow of about 20 m3 min -1. The resulting air-withdrawal velocity during
dumping should be about O·S m S-1.
Discharge is an important operation in the functioning of a silo.
Most conical silo outlets are built with a hopper angle of 60°. Except
for pellets, virtually all fine particulate materials require discharge
aids. Fluidisation of polymer and filler powders is widely used to aid
flow (see Fig. 11.4): the powder is fluidised by blowing air (which must
be free of dust and oil) through aeration plates (covered with nylon or
polyester fabric, porous ceramic or sintered metal plates, and some-
I
I View A-A
I vent
I
I
I
I
11 f1uidisation inserts
air connection
fluidisation cone
Fig. 11.4 Storage silo for PVC polymer or fillers.
times polyethylene board). The plates are designed to produce a

pulsation effect by blowing-in the air section-wise. Another important
mechanical discharge aid is the vibration plate, particularly useful in
restraining materials that tend to 'shoot over'.
Pneumatic filling of silos results in dust-loading of the air, differing
in extent depending on silo size, filling level, and powder-particle size.
The dust is removed by suitable filter units (separate ones for each
11 Compounding 399
tank, except where a number of silos are permanently used to store

the same material).
Any two consecutive operations in the production sequence for solid
compounds are usually separated by a transport distance to be
traversed by the material concerned (solid starting components,
powder blends, finished pellets, rework or reclaimed material for
recycling). The available conveying systems are of two types: pneuma-
tic and mechanical (employing screws, bucket elevators, etc.), and the
type and its most suitable variant is selected in the light of such
considerations as the conveying distance, transport rate required,
special cleanliness requirements, material temperature (and whether it
will cool or heat up in transit), and possibility of segregation into
fractions.
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
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. The basic division in
pneumatic conveying is between suction and pressure systems. There
are also combinations, which are sometimes referred to as pull/push
systems. The main features of various types of conveying systems and
their applications are summarised in Table 11.1.
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 -1, the materials no longer
ricochet; instead, they are pushed through the pipe in the form of
lumps and plugs. Figure 11.5 illustrates the typical pneumatic convey-
ing modes. Some of their respective basic features may be listed as
follows.
Suspension and stream conveying: Relatively inexpensive system;

suitable for virtually all pneumatically conveyable materials; tolerant
8
."
~
[
~.
~
.g
ii.
TABLE 11.1 ~
Main Features of Conveying Systems
System Operating Compressor Conveying Application Material Material

l
!:l
pressure distance (m) pick-up delivery ~.
range
(mmw·g·t ~
~
High-pressure 15 000-25 000 Screw Long distances Filling of storage silos Pressure- Cyclone with ~
(generally compressor from pressure-proof resistant rotary valve, ~
employed for tankers silo silo filter ~.
high conveying
rates)
Medium-pressure 4000-8000 Piston 200 Filling of production Rotary valve Cyclone with
compressor or holding silos rotary valve,
from storage silos or filter
from bag-dumping
stations
Low-pressure <2000 Radial Up to 50 Filling of holding silos Rotary valve, Cyclone with
blower (very limited) pendulum rotary valve,
flap filter
Suction conveyor'> Vacuum of about
-5000 Piston 150 Silo filling Picked up (1) Cyclone with
(i.e. 5000 mm compressor by suction rotary valve,
w.g. absolute filter
pressure)
-1500 Radial 30 Charging pellets into (2) Vacuum pot
(i.e. 8500 mm blower bins and machines; with filter
w.g. absolute removing free-
pressure) flowing materials
from tips or .....
.....
containers
Suction/pressure Piston Short to medium Silo filling, suction Picked up Filter, ~
conveyor compressor, distances pick-up from by suction cyclone with ~c
radial grinding mills rotary valve I:
;:,
blower
~
a 10000 mm w.g. = 1 kgf cm- 2 . ""
b This system offers special advantages in conjunction with such process steps as drying and cooling.
~
-
11 Compounding 403
of material modifications; appropriate where no extreme demands

arise in terms of operating time or conveying rates.
Low-velocity conveying: Gentle treatment of material conveyed;

stable conveying mode; no excessive abrasion (generating dust or
floss); no serious problem with electrostatic charges; system wear,
energy consumption, dust removal cost, and noise level along pipes
and at separator, all low .
The conveying modes usually employed for solid, particulate materials
in PVC processing plants are summarised in Table 11.2.
PLASTICISERS
Small-scale processors normally receive plasticisers in drums (e.g.
200 kg), and large-scale ones in bulk, in road-tankers holding 10-
20 tonnes (occasionally in tanker compartments holding 5 tonnes) or in
rail-tank cars of 15-30 tonnes capacity.
TABLE 11.2
Pneumatic Conveying of So6d, Particnlate Materials in PVC Processing:
Conveying Modes and So6d Loadings
Material Conveying mode Typical solids loading

(kg h- 1 solids:
kgh- 1 air)
PVC polymer Mainly suspension conveying 20-25
(suspension-or
mass-type)
PVC polymer Mostly suspension, but also About 10
(emulsion-type) some plug conveying
(because the fine powder
cannot stick to the pipe
walls in this mode)
PVC pellets Mainly suspension, although 20-25 (suspension);
ftuidised conveying (low- about 150 (ftuidised)
velocity) more effective in
avoiding pellet abrasiona
Fillers Mostly suspension conveying. 10-25
With abrasive materials (e.g. 60-80
untreated chalk) plug
conveying possible, with
solids loading shown
a Nominal pipe diameters usually 80-125 mm. Aluminium alloys used for
straight pipe sections; stainless steel for bends (typical radii 1·0-1· 5 m).
It is usual for road-tankers to have an outlet nozzle of 80 mm

nominal size, and to be equipped with a pump or compressor for
discharging the plasticiser. The normal maximum delivery head is
10 m, providing 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. All delivery pipework should be
laid so that it can run empty into the storage tank. It is advisable to
use 80 mm nominal size piping for the transfer of plasticiser into the
holding or production tanks. Heating (especially for pipelines) may be
necessary to reduce plasticiser viscosity, and hence ease the flow
(particularly with highly viscous plasticisers, and/or in cold weather).
The viscosity-temperature relationships for a number of common
plasticisers are shown in Fig. 11.6.
A storage tank should be large enough to accommodate the entire
contents of one delivery vehicle. It is advisable to install a second
tank, to ensure continuous withdrawal and complete emptying.
Typical storage tank capacities are 6, 12, or 24 m3 • Tanks may be
constructed of corrosion-resistant steel, steel with paint finish resistant
to the plasticiser, aluminium, or a suitable grade of glass-reinforced
polyester resin (GRP). Suitable pipe and valve construction materials
include corrosion-resistant steel, aluminium, GRP (for pipes), and cast
iron (for valves). Use of tanks can become economical at consumption
levels (of each plasticiser) above about 5 tonnes per month.
OTHER FORMULATION COMPONENTS (ADDITIVES)

These 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 bag- or drum-dumping
stations into the production or holding silos with capacities between
0·5 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. The various types of conveying screws were recently
reviewed by Hoppe & Eberhardt. 2
11 Compounding 405
1\\l'\ "
10000
r-.. I\.
"'\.
5000
\ , \ 1\ r\.
,
3000
1\'
"
2000 I\.
\ 1\' "f\.
1500 \\ \ I\, f\.
'\
1000 ~
750 ~ \\. \ r-.. "-
500
\, 1\ \\ \ '\ r\.
\ \ \.
~\ ~
"'"
""
400
'1\\\
, \
\ ~
, "1\
300
~250 1\ \\ '-\ '\.. I\.
~200 :\ \~ l\ \ I\,
Ul
\ '\ f\\\ \
150 ~ '\ '\
E 100 ~ 1\ ~ l\ f\
",-
E
'\
l\.
1\ 14
"I"
~
...,~ \ \ ~ ~\\ \ I~ f\
~ r\ ~ ~1\ '~ 1\
75
'iii " 13
0
u
Ul
50
'> 1\ \' \ \ 1\ \ l\, 1\
\,
40
1\\ \ "\ \ \
1\ \ \ \.
1\ \ \ , \ \\ \ \ \
35
30 \ r-.. ~
\ \\ 1\ 1\ 1\ 1\\ \ ,1\ ~
25
20
1\ \ 1\ \ f\ i\ 1\\~ r\ \
12
'") '\ '\ \

15
12,5
'\ '\ \ 1\
1\ ~3 ~ ~6 I,} ~9 I~
11
10
-10 0 10 20 30 40 50 60 70 80 90 100110120130140
TC2mpC2raturC2, ·C
Fig. 11.6 Viscosity-temperature relationships of a range of plasticisers. 1,

DOA; 2, DBP; 3, DIDA; 4, D~9P; 5, Re%s 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).
(b) Metering
GENERAL
Where, as is normally the case, material has to be removed from
storage (e.g. silo, tank, etc.) in specified amounts (by weight or
volume) or at a specified constant rate, metering equipment is used.
Accurate metering of individual formulation components is cardinal to
the maintenance of composition constancy and hence of final product
quality. The nature of the components and the final product are the
main factors determining the metering method to be used. The
accuracy achievable is also an important consideration, especially
where relatively small batches may have to be produced to formula-
tions calling for small proportions of some of the components. The
general kinds of metering method available for choice are volumetric
metering (continuous or intermittent), or gravimetric metering (con-
tinuous or intermittent).
The accuracy of continuous volumetric metering is affected by
variation in physical properties of the materials metered (bulk density,
particle size and shape, and flow behaviour of powders; density and
viscosity changes of liquids with temperature). In weight terms (which
is the basis of the formulation and assembly of PVC compositions) this
sensitivity limits the accuracy of volumetric metering to about ±2-S%,
depending on the materials and equipment concerned.
Continuous metering by weight is not sensitive to the effect of
material properties, and accuracy (short-term deviation from set
points) within ±O·3-0·S% is achievable, e.g. with belt weighers or
metering-screw weighers.
MAJOR FORMULATION COMPONENTS

Batch weighing is the metering method widely used for these
components in modern PVC compounding plants in which batchwise
production of powder compounds (pre-mixes, dry blends) is practised.
Inter alia, batch-weighing effectively utilises the advantages offered by
the high accuracy of modern weighing equipment. The weighing
systems may be mechanical, electromechanical, or hybrid types. 1 A
weighing set-up for solids is schematically illustrated in Fig. 11.7. The
batch-weighing installation is an important section of a modern PVC
compound production line.
Most such lines have at least two installations of this kind. One, for
weighing solid components, is integrated into the automatically
11 Compounding 407
Fig. 11.7 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.
operated sequence compnslOg metering of the formulation com-

ponents in a specific order, weighing (set-point/ actual comparison),
emptying the scale into a holding container or directly into a
pre-mixer, initiation of the mix-weighing process, batch counting, and
pneumatic refilling of the production or holding bins from the storage
silos. The other main weighing installation is used for metering
plasticisers, which are circulated by gear-type pumps from the produc-
tion or holding tanks via pipeline loops through automatically con-

trolled ball valves into the weighing tank. When the plasticisers, in
amounts called for by the formulation, have been assembled in the
weighing tank, the tank is drained automatically into a holding tank,
or directly into the downstream mixer.
The general methods available for automatic metering of plasticisers
or other liquid formulation components are shown schematically in
Fig. 11.8. Of these, weighing (section A of the figure) is the most
accurate since, as previously mentioned, it is not affected by tempera-
ture fluctuations and the associated (or otherwise occasioned) liquid
density and viscosity changes.
MINOR FORMULATION COMPONENTS

For the purpose of this discussion, minor formulation components are
those additives which are used in proportions from fractional phr to
about 10 phr. The amount of such an additive required for a
formulation batch may be less than 300 g or even 100 g, the two values
which may be regarded as the practical lower limits in acceptably
accurate automatic metering respectively on-line and off-line. For the
dosing of minor components in amounts below these limits, an off-line
minor-component weighing station is normally employed. The least
sophisticated operating procedure for such a station is to have an
operative manually weighing out the required amount of each minor
component, which he then encloses in a PVC pouch; the pouches, with
their contents, are incorporated into the composition batch being
assembled: this takes place at a minor-component station in the
production line, where the mixing station calls up the additives
automatically for each batch. For faster, more stream-lined operation
a manual, multi-bin weighing station2 or a fully automatic, modular
weighing station, may be used; the latter is exemplified by the circular
carousel-type design developed by Waeschle/-3 which can automati-
cally meter out, weigh, and package in sachets up to 16 minor
formulation components.
CONTROL AND ACCURACY IN METERING INSTALLATIONS

The control loop of a weight-metering system is shown schematically
in Fig. 11.9. The main potential sources of error in such systems are:
mechanical errors in the scales; cut-off inaccuracies or errors in
metering; discharge errors (in emptying scales); errors in data input or
acquisition. The system error of a weighing installation is determined
11 Compounding 409
by comparing the difference between the set-point value and the

amount actually weighed out at the top of the weighing equipment's
nominal range. It is usual to state the accuracy as a percentage in
relation to the weighing range.
BATCH ASSEMBLY
The following procedure is fairly representative of the practice in a
compounding plant.
-Plant in general is switched on.
-All scales are set 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'.
-Punched cards are placed in the reader or the appropriate part of
computer program is activated.
-The mixer filling system is released.
-Formulation is called for by the mixer control system.
-The individual components are metered in coarse/fine stream,
with 'finished' report following the last components.
-The individual scales are emptied in predetermined order and
with predetermined timing.
-Batches (solid components, liquids, additives) are transferred to
the mixer calling for them.
-All scales move to 'zero', and the next weighing procedure can be
initiated.
The weighing installations and all operations are monitored via
displays at the control desk.
The simplest type of control system is 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. Provision for manual operation
is necessary as a back-up in case of emergency, even where fully
automatic control systems are installed.
An example of a modern batch assembly control system is a
freely-programmable type, schematically shown in Fig. 11.10. In this
kind of system all the input and output data of the weighing
installations are fed to a computer. The logical sequence of the
oj:>.
o
flowmeter -
~
."
ir
::to
!:l
~
~
C. Flow ratE" mE'asurE"mE"nt
A. Weighing ::t
'"
'"~ .
."
~
"~
~.
§
s:...
::t.
metering ~
pump e
~.
B. VolumE"tric mE'asurE'mE'nt D. VolumE'tric displacE"mE'nt
Fig. 11.8 Metering methods for liquids.

11 Compounding 411
Fig. 11.9 Control loop of a weighing installation.
~OmyUler,
b)
Freely --
~
0
0
amm 0
Real value
I rec0-1 ing I
Fig. 11.10 Freely programmable control system: schematic representation.

successive switching operations, measurements, monitoring operations

and data outputs is laid down in the form of a computer program.
With this system, the control procedure can be altered or adapted
from the central desk.
Various microprocessor-based system variants exist, offering opera-
tional versatility.
The general objectives of automation in a compounding operation
may be listed as: maximising good-quality production; minimising
scrap; securing high productivity, operational and labour cost
economies.
11.2.2 Compounding Operations and Equipment
(a) General
As indicated in Fig. 11.1, industrial production of solid PVC com-
pounds normally involves the initial preparation of a powder mix. In
some cases, a suitable powder mix may be used directly as feedstock
for processing into products (e.g. in extrusion of rigid PVC pipe;
extrusion blow moulding of some containers). Otherwise it is further
melt-compounded, cooled and pelletised to provide feedstock in this
form. In some processes-notably calendering, or production of
gramophone records-the molten compound is fed directly to the
processing machinery.
The main advantages of using a powder mix directly as feedstock
are: processing economy (as the cost of melt-compounding is saved);
reduced heat history of the material (which does not have to undergo
the heating and shearing involved in melt-compounding); and the
relative simplicity of the operation needed to make up virtually any
solid formulation.
In comparison with melt-compounded, pelletised compositions, the
principal disadvantages of powder-mix feedstocks are less easy con-
veyance and storage (poorer dry flow properties, possibility of caking);
less uniform and intimate interdispersion of formulation components
in the compound; and more need for effective removal of moisture and
other volatiles in further processing.
Properly melt-compounded pellet feedstocks offer the following
main advantages: thorough, intimate interdispersion of all formulation
components (some, e.g. stabilisers, lubricants, polymeric modifiers,
plasticisers, are blended with the PVC polymer on the molecular
level); very good, uniform and constant storage, conveyance and
11 Compounding 413
feeding characteristics; high constant bulk density (advantageous in

feeding for melt-processing); absence of the moisture and volatiles
already removed during melt-compounding (and hence reduced risk of
void formation in the ultimate product).
Most industrial PVC powder blending operations are still run
batchwise, mainly in high-speed mixers, and occasionally in slow
mixers (commonly ribbon blenders). However, continuous-production
powder mixers are being increasingly used, especially in conjunction
with extrusion lines.
Melt-compounding is also practised either on a continuous basis, for
which several types of equipment are available, or batchwise in
intensive internal mixers.
Figure 11.11 shows various types of equipment for batch-mixing
particulate PVC compositions (including one mixer for PVC paste
preparation) .
(b) Production of Powder Mixes

In a powder-blending operation the PVC polymer powder is mixed
with the other formulation components (stabilisers, lubricants, fillers,
plasticisers, etc.) so that the resulting blend is still in particulate form.
BATCH MIXING
The mixing may be run either cold or hot: each results in a somewhat
different kind of blend.
Cold mixing (below 50°C) is carried out in slow (low-intensity)
mixers, typified by the ribbon blender; it produces what is sometimes
termed 'distributive' blending; i.e. in the resulting powder mix the
components are mutually interdistributed, but each retains its original
physical form (although plasticisers are largely absorbed into the pores
of PVC polymer particles). Relatively long mixing times are required,
and the powder blend is not entirely 'dry' or completely free-flowing
(especially at high plasticiser contents). For all these reasons such 'cold
blends' are normally only used as pre-mixers for melt-compounding.
Hot mixing is typically performed in high-speed (high-intensity)
mixers (sometimes also in heated slow mixers), the material tempera-
ture being raised to about 100°C or even higher. This kind of mixing
produces 'dispersive' blending, whereby the various formulation com-
ponents not only undergo mutual interdistribution, but also merge to
some extent, so that the particle characteristics are modified. Stabili-
sers, lubricants and plasticisers are absorbed to varying extents by the
MECHANICAL MIXERS ~
PNEUMATIC MIXERS .-
~
with rotating mixer container with rotating mixer tool
Name Illustration PVCQIlIJiication Nome - lIIustrotion PVC aooiicalion Nome Illustration PVC application
cold mixer
Tumbling Helical ribbon
or
barrel mixer Pneumatic
,j£L hot mixer granulate
circulating
possibly for
~ mixer
mixing
Drum Ribbon bar
additive ~
tumbler mixer
premixing ~
:. Gyrowheel
~ ~
j El
)(
FbddIe mixer cold mixer
mixer
E ~ ~iI ~~ t
~
~ Cl
"5 Ploughshare ~
Wobble
& mixer mixer ~.
~. [~ .'"
Double cone granulate Change-can
~
PVC pastes ~
mixer mixing mixer J[E
~ ~
~.
Twin shell
High-speed
mixer "'l/ - hot mixer
tank mixer §
(vee' ""'-
)..
~ ~
Low-speed ~
cold mixer
tank mixer
~ ~
cold mixer, ~.
OrbIting vertical
granulate
screw mixer
\l mixing
Vertical screw granulate

silo mixer miXing
- ~
Fig. 11.11 Batch mixers for particulate PVC compositions.
11 Compounding 415
PVC polymer particles. The resulting powder mix is substantially 'dry'

and free-flowing. It is variously termed 'dry blend', 'dry powder', 'dry
mix', or 'powder compound', but the terminology tends to be rather
loose. If, in the course of hot mixing, the material is heated above the
softening temperature of the polymer particles (which may be in-
fluenced by the presence of liquid stabilisers and polymeric modifiers
in uPVC compositions, and plasticisers in pPVC compositions), then
the resulting blend will consist of agglomerates of the original
individual particles. Such agglomeration or 'sintering' (which does not
involve complete melt-fusion of the PVC polymer particles) is most
readily effected in mixers with high-speed mixing tools: it becomes
desirable where large proportions of filler or plasticiser have to be
incorporated, and where the possibility of component segregation
before the next process step is to be minimised.
In a high-intensity mixer the mixing process is quasi-adiabatic, the
material being heated primarily by the mechanical energy imparted by
the effective surfaces of the mixing tools and by the mutual impacts of
the particles. Other, minor, contributory heating mechanisms are:
friction between the mixing tool and the material and air; interparticle
friction; friction between the material and the tank wall; heat transfer
from heated tank wall to air and material; radiation heating. With
properly designed mixing tools, external heating (by means of a
heating jacket) is required only in certain cases, e.g. when emulsion
polymer is being mixed with a high percentage of plasticiser: for such
compositions high drive ratings are employed (about 1 kW per kg of
material). Otherwise typical ratings are in the range 0·4-0·6 kW kg-I.
Where a hot-mixed dry blend or agglomerate is to be conveyed an
appreciable distance and/or stored-i.e. unless it is fed directly to a
melt-compounder or processing extruder-it must be cooled down to a
temperature at least below 50°C, to prevent lumping or caking. In
theory the cooling could take place in the same mixer, but this would
be time-consuming and expensive in production practice, whilst the
alternating thermal stresses on the mixer in continuous use would
shorten its service life. Moreover, cooling the mix; in the shortest
possible time, is desirable both to reduce the heat history and because
cold shock is known to improve free-flowing properties. Thus, whilst
hot mixers can be used alone directly ahead of melt-compounders or
extruders, it is common practice for the hot mixer to be followed, in
series, by another, cooling ('cold') mixer, so that they jointly form a
so-called hot/cold mixer combination. Two forms of such combination
are shown in Figs 11.12 and 11.13. The former figure also gives the
mixing tool (impeller) speed ranges typical respectively for high-
intensity hot mixers and cold mixers, as well as the relative mixing-
chamber volumes. As both mixers operate within the same cycle
times, the volume of the cooling mixer chamber must be larger, to
compensate for the poor heat conductivity of PVc.
The temperature of the mix increases with the duration of the
mixing. The total mixing time (typically within the range 8-20 min) is
governed by the final maximum temperature (usually between 100 and
130°C) which is predetermined by the operator with a view to
producing a dry, free-flowing powder blend or agglomerate: the
attainment of this condition of the mix is in fact the main criterion for
the selection of the maximum temperature at which the hot mixing is
terminated. The molecular weight (K value) of the polymer, its
particle structure, and the proportion of plasticiser in the composition,
Hot mixer
Tank volume
VI
Peripheral speed of tool
Vu =20-50ms-'
Cold mixer
Fig. 11.12 Hot/cold mixer combination with hot mixer vertical and cold
mixer horizontal.
11 Compounding 417
Hot mixer
-_·..--'t--,--
( I !
I I
I
Cold mixer
I
I
Fig. 11.13 Hot/cold mixer combination with both hot mixer and cold mixer
vertical.
are also factors in the selection. Figures 11.14 and 11.15 illustrate the
temperature-time relationships in high-speed mixing of PVC powder
blends of various compositions. As for the rate of temperature rise in
hot mixing, it is a good practical guideline that this should not exceed
15°C min-I.
The simplest procedure for material addition with a uPVC composi-
tion is first to mix all components except the lubricants (or composite
stabiliser/lubricant system) at relatively low speed, then to increase
the speed and add the lubricants when the temperature has risen to a
value about 20°C below the desired final temperature. Another
sequence that is sometimes adopted is to enter the PVC polymer at
room temperature (the polymer may be pre-heated to enhance
absorption of other components), followed by any liquid stabilisers (at
about 70°C), then lubricants and solid stabilisers (at about 80°C), and
finally the other particulate components (polymeric modifiers, fillers
and pigments, at about 85-90°C). The late addition of fillers and
pigments is aimed at minimising abrasion.
With pPVC compositions, the solid components may be pre-mixed
first as above, and the plasticiser(s) then injected, at 70-80°C, at a rate
slow enough not to cause a sharp rise in the power demand (motor
O(OC)
120
110
100
90
80
70
60
50
40
30
20
10
0
0 2 345 6 7 8 9 10 11 t(min)
Fig. 11.14 Temperature rise in a high-speed mixer as a function of mixing
time.! 1, Rigid composition (suspension polymer); 2, rigid composition
(emulsion polymer); 3, 30% plasticised composition (suspension polymer); 4,
40% plasticised composition (suspension polymer); 5, 50% plasticised com-
position (suspension polymer); 6, 40% plasticised composition (emulsion
polymer).
amperage). Figure 11.16 illustrates schematically the power demand

changes accompanying the main phases in the mixing cycle of a rigid
PVC composition. The final levelling-off of the power demand shown
in the figure signals the completion of hot mixing. Power requirements
increase also with the amount of material in a mix batch. This limits
the maximum batch size to about 800 kg.
Among the best-known intensive mixers and hot/cold mixer com-
binations are those marketed by Thyssen Henschel, MTI Mischtech-
nik, Papenmeier, Moritz ('Turbosphere' mixers), Dierks & Sohne
('Diosna' mixers), Spangenberg, and Covema.
°C
130
120 - A~ - J
~\ ~B
110
/~ I\ -
100
) \ --- .. / \
90
I \ / J \
, V'
/ \ V i\. .-
80 ,/ ........
I "Ii',.
70 J ~ / \/ g
I
\ ~
V I ~
60 ,/ "-f ' §
50 J \. V i'..
/ / j'..... ....... !
40 "-
I I{
30
o 234567890 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
I" Heating time ~1 .. COOling time.1 ,.. Heating time ~ I" Cooling time .1
5 min. 4mln. 9 min. 8 min.
Fig. 11.15 Temperature-time relationships for two PVC compounds in a hot/cold mixer combination (inlet
temperature of cooling water approx. 15°C).1 A, uPVC pipe compound; B, pPVC shoe-soling compound.
~
\0
-
A
.111
f:
\
\
\
\
\
,
~
.~ \
\
1. I
I
I
I
IT ITI I IV V VI VIT :I
Blending time min.
Fig. 11.16 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.
A more detailed discussion of intensive mixers and hot I cold mixer

combinations, their design and operation will be found in Ref. 1.
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 40°C in the cold mixer. For certain purposes, e.g. the produc-
tion 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 degassed 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.
CONTINUOUS MIXING
Continuous blending of PVC powder mixes has been increasingly
coming into use since the early 1980s as an alternative to the
conventional batch blending. Industrial equipment of two different
designs is available, respectively from Buss (Buss-Condux in the
USA) and Thyssen Henschel, both companies well-known for their
plastics compounding machinery. In both cases the equipment is
11 Compounding 421
primarily intended for operation in sequence with a melt-compounding

machine producing pelleted compound, or a production extruder, to
which the hot mix is fed directly as produced (more than one machine
may be fed by a continuous compounder). However, passing the mix
to storage without a special, separate cooling operation is also a
possibility.
The Buss equipment (Fig. 11.17) is the Buss Mixing Turbine MT for
continuous powder blending, a modification of equipment of this kind
long available for the production of PVC pastes (see Chapter 18). The
advantages claimed for this machine in comparison with a conven-
tional hot/cold batch mixer combination are: short material dwell
times (about 3 s in many cases) and narrow dwell-time spreads, low
heat content of the mix and controllable mix-discharge temperature,
more uniform product quality, lower capital and running equipment
costs, smaller floor space requirements and lower energy consumption.
Powder mix outputs can reach about 2000 kg h- 1 (with some pPVC
compositions) .
Fig. 11.17 Buss MT turbine for powder blending.

The Thyssen Henschel 'Kontinuum' TK / D horizontal mixer (Fig.

11.18) is available in a number of sizes. The output rate quoted for the
TK/D 250 model is about 1500 kg-I. The general operational and cost
advantages claimed for this equipment are similar to those of the
Mixing Turbine. The mixing elements in TK/D mixers are rotating
blades of special configuration. The material is heated by friction alone
up to 110-120°C, and the completed mix is discharged first into a
heated buffer chamber equipped with a stirring device, whence it is
passed on to processing equipment. Continuous powder-blending units
suitable for direct extruder feeding are also made by Colortronic
Reinhard & Co. (FRG).
(c) Melt-compounding: Objectives and General Features

Melt-compounding, culminating in the production of pellets for use as
feedstocks for further melt-processing, is used where only limited
homogenisation is achievable in the final processing equipment (such
Fig. 11.18 Henschel TK/D horizontal mixer.

11 Compounding 423
as, for example, simple extruders, calenders, most injection moulding

machines), and where stringent quality specifications for the ultimate
product necessitate the highest degree of homogenisation of the PVC
composition. Such homogenisation, with the most intimate inter-
dispersion of the PVC polymer with the other formulation com-
ponents, can only be achieved by adequate shear-mixing in the melt.
Pellet feedstocks are also used where powder mixes are not acceptable
by reason of particular material-handling arrangements or feed
requirements.
Table 11.3 gives an approximate indication of the respective
proportions of powder mixes and melt-compounded pellets used as
feedstocks in the manufacture of main PVC products by melt-
processing techniques.
PVC is subject to heat degradation. The extent to which this may
occur in processing depends on stock temperature and residence time;
therefore both must be carefully controlled in compounding (as well as
in further melt-processing). The effects of melt-compounding tem-
perature and time on a typical, well-stabilised uPVC composition for
extrusion is illustrated in Fig. 11.19, with special reference to these
effects in a Buss Kneader compounding machine. Furthermore, the
degree of gelation of the composition effected in melt-compounding
influences the energy input required in further processing to produce
an optimal, homogeneous melt. Thus the compounding process must
TABLE 11.3
Approximate Proportions of Important PVC Product Made, Respectively,
from Pre-mix and PeUetised Compounds (Worldwide)
Products Produced from:
Pre-mix (%) Pellets (%)
Extrusions (pipes, profiles, tubes, hoses,

siding) 90 10
Injection mouldings 25 75
Cable coverings 100
Records 75 25
Blow mouldings (bottles) 70 30
Calendered sheeting 100
Extruded film and sheeting 40 60
Paste products: paste compounded from
polymer, plasticiser and additives
M.1t
T.mpl'ratu,e
(Oe)
o 5 10 25 50 ~ 100
Ultlmote Processing TIme (Minutes)
AREA OF HEAT HISTORY
IN BUSS COMPOUNDING
ANO PELLET ISING LINES TYPE KG
Fig. 11.19 Influence of compounding time and temperature on the heat

history and further processability of a melt-compounded uPVC composition.
also in this sense be matched to the conditions of the subsequent

processing (production) operation(s), whilst achieving its fundamental
objective of the maximum homogenisation of the composition with the
lowest practicable input of thermal and thermomechanical energy so
that the heat history of the polymer is kept to a minimum. In recent
years, too, greatly increased processing speeds of calenders and
extruders have added effective degassing of the PVC compound-
formerly mainly effected on roll mills and in internal mixers-to the
functions of melt-compounding.
Roll mills and internal mixers find only relatively limited application
in present-days industrial melt-compounding of PVC, which is now
largely the domain of continuous-compounding, screw-type equip-
ment. 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
capable of both supplying and removing heat. For this reason, systems
based on the circulation of liquid heat-transfer media (such as water,
HT Oil, Dowtherm, etc.) in screws and separate barrel zones have
gained wide acceptance.
11 Compounding 425
As will be clear from Table 11.3, both uPVC and pPVC composi-
tions are melt-compounded. The format of a continuous, screw-
compounding process is essentially similar in both cases: a typical flow
diagram is shown in Fig. 11.20. It is usual to pass the free-flowing
powder mix produced in the pre-mixer [(7) in Fig. 11.20] through a
holding bin (not shown in the figure), before it is charged into the feed
hopper of the compounding machine: the hopper also functions as a
product-surge container, and a volumetric metering element; it may
also be designed additionally for powder de-aeration, but this does not
obviate the need for later degassing of the fluxed stock in the
compounder. An agitator is normally mounted in the upper part of the
hopper to prevent powder bridging (cf. Fig. 11.21). Metering devices
used in conjunction with the hopper include a vertical metering screw
at the bottom of the agitator, or a separately driven twin-screw
Fig. 11.20 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 FEED HOPPER WITH

HORIZONTAL TWIN SCREW VERTICAL SINGLE SCREW
Fig. 11.21 Typical feed hopper designs.
arrangement (see Fig. 11.21). In the intake zone of the compounder

the metered powder is picked up and conveyed to the fusing and
homogenising zone, where the shear energy imparted to the material
heats up and fuses the polymer and also disperses the additives.
The plots of Fig. 11.22, although obtained with a capillary rheo-
meter, are fairly representative of the differences between the
behaviour of pPVC and uPVC compositions in continuous melt com-
pounding. With pPVC, relatively high outputs are obtained within
a comparatively narrow, and generally low, pressure range, whereas
the output of various uPVC compositions is more dependent on the
pressure (and the associated shear) and requires higher pressure
values. In screw-type compounding machines the energy conversion is
essentially a function of shear rate and system pressure: hence
regulation of the degree of gelation of a uPVC composition in
compounding calls for special means of control of these parameters,
which are provided in the equipment (see below).
Homogenisation of the composition at the desired degree of
gelation, its degassing, and conversion into pellets, are the three main
objectives catered for by modern continuous-compounding equipment.
Cylindrical pellets, of diameters 2·5-4 mm and lengths 1-4 mm, have
proved suitable for feeding final-processing machines. To produce the
pellets, it is necessary to force the homogenised PVC melt through a
multi-hole die plate. One way to do this is to incorporate in the
screw-type compounder a suitable metering/pumping zone and to
11 Compounding 427
plasticised PVC rigid PVC

[k~l Output
-+-t+~H-~~T-! -----L---~--__\_-I-t-+l--#___+___II_
I---r 1
2,0
iii
I ! I !
1,5
1 --
1,0 -----
-I- I
0,5
Extrusion
o-J-"""'~~~_+-_~~:::~~:::=L:::::'=--J-__L_-J~Pr~.~ssure
o 10 20 30 40 50 60 70 80 (~)
Fig. 11.22 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.
mount the multi-hole die directly on the end of such a machine. One
example of this approach is the new Baker-Perkins XLT compounder:
this machine employs co-rotating screws with a large-diameter, inter-
meshing section in the compounding zone and a reduced-diameter
section (in a reduced barrel bore) serving as the metering and pumping
zone. However, as-generally speaking-the optimum design and
performance parameters for the compounding and melt-metering
(extrudate-forming) operations normally tend to conflict, in several
versions of successful modern high-output, continuous-compounding
equipment they are separated into two distinct stages. Such two-stage
compounding lines normally comprise a compounding component
(which may be a single-, twin-, or multi-screw machine) followed by a
pelletising extruder (normally single-screw): the latter forms the
compounded melt into strands by pushing it out through a multi-hole
die, the strands being cut into pellets at the die face. 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 mentioned above, when compounding uPVC compositions it is
necessary to control effectively the system pressure in the compound-
ing stage, to secure and maintain the required degree of gelation in the
ultimate, pelleted compound. This control is achieved in various ways.
In some two-stage compounding equipment (e.g. the cascade ex-
truder), the homogenised PVC stock drops in lumps through a tube
connecting the outlet of the compounder with the feed opening of the
pelletising screw. Vacuum may be applied to the connecting tube to
degas the stock en route. Buss Kneader KG compounding lines
employ a regulating screw instead of a connecting tube between the
two stages (Fig. 11.23). The speed of this 2·5 L/ D 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. 11.24, shaded area) into
the outlet orifice to a greater or lesser extent, so that the back-pressure
can be varied infinitely without stopping production.
Yet another approach is the use of 'barrel valves' at two points in
the barrel of a Baker-Perkins MPC/V compounder: 1 these can be set
to build up or reduce back-pressure.
BUSS KNEADER
REGULATING SCREW
PELLETISER
Fig. 11.23 Back-pressure control by regulating screw.
11 Compounding 429
Fig. 11.24 Back-pressure control by adjustable outlet orifice.
All three systems allow the PVC composition to be degassed in

transit to the pelletising screw.
A fairly typical figure for the specific energy dissipated in the
compounding step would be about 0·06-0·08 kWh kg- 1 for uPVC
compositions and 0·04-0·06 kWh kg- 1 for pPVC compositions. In the
pelletising extruder, 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 one-tenth
to one-fifth of the energy dissipated during compounding. The
introduction of energy causes the stock temperature to rise as it moves
through the compounder. Figure 11.25 shows some typical stock
temperature profiles for various PVC formulations.
T ('C)
200
4
180
3
160
140 2
120
100
80
60
40
20
}4 12 ~ SffiEW LENGTH
(LA. tot.)
Fig. 11.25 Melt-compounding of PVC: stock temperature profiles. 1, Record
compounds; 2, pPVC; 3, uPVC; 4, uPVC (US grades).
The capacities of industrial continuous-compounding lines range

from about 100kgh- 1 to about 7th- I .
(d) Melt-Compounding Machinery: Continuous Compounding

Examples of equipment typifying screw-compounding systems are
given in Table 11.4. Some of the machines are briefly reviewed below.
THE PLASTIFIKATOR (SHEAR·CONE COMPOUNDER)
PVC applications: Compounding and pelletising of pPVC composi-

tions (cable, shoe soling, profile, tubing, flooring).
Equipment assembly: See Fig. 11.26.
Operating principle of compounder: See Fig. 11.27. The plastication

and homogenisation section 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, then to be reformed
again. Axial displacement of the shear cone in relation to the housing
varies the shear gap and therefore the amount of shear energy
dissipated.
Typical output: 150-2400 kg h -1, depending on model.
THE BUSS KNEADER

(Figs 11.17, 11.28, 11.29).
PVC applications: (i) Compounding and pelletising of plasticised

PVC compositions (cable, shoe soling, profile, records): (ii) com-
pounding of rigid, semi-rigid, and plasticised PVC for calender
feeding.
Equipment assembly: See Fig. 11.28. The powder mix moves

through a holding silo into the feed hopper of the compounder,
equipped with an agitator terminating in a vertical metering screw (see
Fig. 11.21). If pellets are being produced (cf. Fig. 11.28), the stock
homogenised in the kneader is transferred cascade-fashion to a
11 Compounding 431
Fig. 11.26 Plastifikator PK400. 1, Stirred feed hopper; 2, feed screws

(intermeshing, co-rotating); 3, compounding section (shear cone); 4, discharge
screw; 5, pellet cutting knives; 6, pellet collector casing.
pelletising extruder screw, which pushes the material through a

multi-hole die. The strands so produced are cut into pellets in a
dry-cutting operation.
Operating principle of compounder: See Fig. 11.30. The Buss
Kneader is a continuous-operation, single-screw machine of special
screw and barrel design. Whereas conventional single-screw machines
E- ..1~\\PlU~
3 2 1
_~'\\\l\~
--lIIIiiiiiiii.::d...J)' j t 1 t 1
Product flow
Fig. 11.27 Working principle of the Plastifikator. (See text for details).
TABLE 11.4 ~
W
tv
Some Well-Known Screw-Type Compounding Machines
Machine type and Supplier Computer control Typical applications Remarks

designation
Compounding Compounding Compounding
and for and direct "tI
pel/etising calender extrusion
-.:::
~
feeding
~
;:to
Single-screw Q
Plastifikator (shear cone) Werner & Pfleiderer As required j ForpPVC
GmbH,FRG compositions ...~
Buss Kneader Buss AG, Switzerland; As required j j ~
Buss-Condux Inc.,
~. '"
USA .~
Cascade extruder (1) Barmag Barmer As required j j Direct cascade
"tI
AG,FRG arrangement (Fig. ~
11.29)
(2) Berstorff j j Vertical'L'
Maschinenbau configuration J."
GmbH,FRG; of the two 1:>
;:,
Berstorff Corp., single-screw !:>...
USA components )..
Twin-screw :g
Kombiplast (with ZSK Werner & Pfleiderer EPC 11 system; j Intermeshing; co- ~
1:>
extruder, including GmbH,FRG formulation storage rotating; ;:to
0
custom-engineered memory; plug-in segmented screws a
versions) algorithms
Werner & Pfleiderer
Corp., USA
Egan compounding Egan Machinery Div., CMR system; j Intermeshing; co-
extruder John Brown Plastics formulation storage rotating;
Machinery Inc., memory (up to 100 segmented screws
USA items); assembly
language
FCM continuous mixer Farrel Corp., Emhart As required / / Non-meshing screws
Machinery Group, (customised)
USA
David Bridge Co.
Ltd, UK
Leistritz compounding Leistritz Maschinen- Micromatex 16.2 / / Some models
extruder fabrik GmbH, FRG system; interfaces bimodal, with
American Leistritz with computer for screws which can
Extruder Corp., memory storage; either counter-
USA language as rotate or co-
required rotate
MPC/V compounder, Baker-Perkins Inc., CST system; /
and MP2000 USA formulation storage
compounding extruder memory; language: ......
series BASIC ......
Bitruder BT Reifenhiiuser GmbH, As required / /
FRG ~
Reifenhiiuser- Van ~c
DornCo., USA $::
;:,
Reifenhiiuser Ltd, UK
Planetary ~
C>Q
W E Planetary gear Berstorff, FRG and As required / / Planetary section
compounder USA provides large
Planetary roller Battenfeld As required / / interface area for
compounder Ekstrusionstechnik heat transfer, and
GmbH,FRG hence good melt
Purnell Inc., USA temperature
control
<'Z
w
11 Compounding 435
Fig. 11.29 Split barrel of a Buss-Kneader.

Fig. 11.30 The screw and barrel of: a, conventional single-screw machine; b,
the Buss Kneader.
employ variants of a continuous Archimedes' screw rotating around its

axis [Fig. 1l.30(a»), in the Buss Kneader each turn of the screw helix is
interrupted by three gaps to form the screw kneading tools. Their
counterparts in the barrel, the kneading pins or teeth, are arranged in
three rows [Fig. 11.30(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. A detailed
discussion of the mode of operation of the Buss Kneader can be found
in Ref. 1.
11 Compounding 437
Typical output: pPVC (on WKG series machines), 75-7000kgh- 1

depending on model and screw. * Rigid PVC (on WKG and KG series
machines), 40-3200 kg h- 1 depending on model and screw size. *
THE CASCADE EXTRUDER
PVC applications: Compounding and pelletising pPVC and uPVC

compositions; compounding and direct extrusion of uPVC and pPVC
sheeting and film.
Equipment assembly and mode of operation: See Figs 11.31 and
11.32. 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 degassing tube [to which
vacuum as high as 80 mbar can be applied] into the intake section of
the discharge extruder. Retention time in the degassing 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.
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.
Typical output (rigid PVC): 150-1000 kg h-t, depending on
machine size.
THE KOMBIPLAST EQUIPMENT
PVC applications: Compounding and pelletising of uPVC and

pPVC compositions.
* Also on the formulation and operating conditions. On some new machine
models, improved drive systems provide greater screw speeds and higher
torques, resulting in higher outputs in comparison with larger older models.
1 cJ
:>
~
..
.s..
.....=
It)
'0
~
It)
It)
'0
ell
(,)
0 '"ell
....0
(,)
I:
bll
Or;]
It)
0
.....
~
.....
.....
oil
~
11 Compounding 439
Standard Extruder ~ ~
~1~~ln
Process Steps
IVariableland Fixed Operating Conditions
Fig. 11.32 Comparison of a standard extruder with a cascade extruder:

process steps and operating conditions.
Equipment assembly: See Fig. 11.32. The equipment consists of a

twin-screw compounding extruder (ZSK or ZDS-K model), which
feeds into the pressureless intake area of a slow-running, single-screw
discharge (pelletising) extruder. The two units are typically positioned
at right angles (see Fig. 11.33). In operation, a powder mix is
introduced into the feed section of the compounder by a vertical
forced-feed screw. The compounded stock drops cascade-fashion into
the single-screw extruder (ES-A unit), where it is conveyed to, and
through, the pelletising die (often preceded by a breaker plate).
Operating principle of the compounder: The ZSK and ZDS-K

compounding extruders are versatile twin-screw machines, with inter-
meshing, co-rotating screws whose helical-flight sections are inter-
~
~
::E
!:l::to
!:l
~
~
~::to
~
~
.,~
~.
~
~
~
[
S"
~
Fig. 11.33 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.
11 Compounding 441
rupted by sections containing special kneading disc elements (see Fig.

11.34). The discs co-act to shear and knead the stock and change the
local direction of its flow as it moves past 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 intenstiy is determined both by
the speed of the screws and the resistance offered by the kneading
discs.
The configuration and arrangement of the discs shown schematically
in Fig. 11.34 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 general design ensures that the
root of each screw is wiped by the flight tip of the other. This
self-cleaning profile eliminates dead spots and normalises the residence
time of the material. The helical-flight and kneading-disc elements are
removable and interchangeable (as bushings on the screw shafts). This
enables the length and distribution of the respective sections to be
varied to attain the correct heating and gelation levels in optimum
time and without polymer degradation.
Typical output: pPVC, 200-7500 kg h- 1 ; uPVC, 100-3800 kg h- 1 ,

depending on Kombiplast model, conditions, and PVC composition.
Fig. 11.34 Operational principle of the kneading discs of a ZSK or ZDS-K

compounding extruder.
THE FCM CONTINUOUS MIXER
PVC applications: Compounding and pelletising pPVC and uPVC

compositions; compounding of rigid, semi-rigid and plasticised PVC
for calender feeding.
Design and mode of operation: See Fig. 11.35. The FCM compoun-
der is fed not from a hopper but from a belt weigher (if the feed is a
powder pre-mix) or a number of such weighers (if-as can be done
with this machine-individual formulation components are introduced
separately). The metered material is plasticated and homogenised by
the two screws in the mixing chamber, and then discharged-in the
form of a ribbon-through a flap, adjustable to provide control over
the outlet cross-section. For feeding a calender, the ribbon is passed to
a roll mill or to a strainer extruder. For the production of pellets, a
B
"
Section A-A Section B-B
Mixing Feeding
Fig. 11.35 Working principle of the FCM compounder.
11 Compounding 443
suitable ribbon can be discharged for subsequent dicing, or the

product may be passed to a pelletising extruder.
The two screws (sometimes referred to as rotors) of the FCM
compounder are not intermeshing: the operating principle is thus
somewhat similar to that of a batch-type Banbury mixer. In the inlet
section the rotors have the form of helical screws; in the mixing zone
they are paddle-shaped for kneading action. The two shafts are
counter-rotating, and are run at variable, mutually different speeds:
this produces shearing and mixing in addition to the shear experienced
by the stock between the rotors and the chamber (barrel) wall. The
energy input and mixing effect can be controlled by adjusting the flap
to change the outlet cross-section.
Typical output: pPVC, 160-5000 kg h- 1 ; uPVC, 90-3700 kg h-l,

depending on machine model, conditions, and PVC composition.
THE MPC!V COMPOUNDER
PVC applications: Compounding and pelletising of pPVC and

uPVC compositions.
Design and mode of operation: The machine consists of a dual-

diameter twin-screw compounder, attached at right angles to a
pelletising, single-screw extruder (Fig. 11.36). Hot cutting at the die
face is used for pelletising, but, in contrast to other processes, the
pellets are cooled by being whirled into a cold-water film. Kneading
discs, similar to those of the ZSK extruder in the Kombiplast set-up,
are used to effect shearing and mixing in the compounder. A barrel
valve, positioned as shown in Fig. 11.36, is used to control the
back-pressure in the kneading zone, and hence the energy input into
the material.
Typical output: pPVC, 250-6000 kg h- 1 ; uPVC, 130-2800 kg h- 1 ,

depending on the usual relevant factors.
THE BITRUDER BT

uPVC compositions. Compounding and direct extrusion of PVC (e.g.
rigid profiles and pipes).
Discharge
Screws
Vacuum
Connection
Extruder
Fig. 11.36 MPC/V design.
Design and mode of operation: Unlike the other compounders

discussed here, the Bitruder does not employ the dual-cascade layout.
It is a twin-screw compounding extruder with intermeshing counter-
rotating screws, and all the operations of material intake, plastication,
homogenisation, discharge, strand extrusion, and pelletising are per-
formed on this machine. The PVC powder 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. The homogenis-
ation of the molten stock takes place in the compounding zone, where
the screws closely intermesh. A degassing port is provided in the
barrel-as a standard feature-ahead of the discharge zone. From this
zone the homogenised stock is forced by the screws out through a
multi-hole pelletising die plate equipped with a torpedo. The pellets
are produced by hot die-face cutting, and conveyed pneumatically to
the pellet cooler.
Typical output: Rigid PVC, 120-1200kgh- 1 •
THE PLANETARY COMPOUNDER

The designs of the two machines listed in Table 11.4 are very similar,
and no distinction need be made between them for the purpose of the
general discussion here.
11 Compounding 445
Fig. 11.37 Planetary compounder: schematic representation.

uPVC compositions; compounding such compositions for calender
feeding.
Design, and operational outline: The basic design features are
schematically indicated in Figs 11.37-11.39. In operation, a powder
pre-mix from a force-feed hopper enters the feed zone of the machine
and thence passes on to the compounding (planetary-screw) section:
this comprises four interacting elements, viz. the driving main screw
(spindle), the satellite planet screws, (which may number 6-18), the
3 2
Fig. 11.38 Basic features of a planetary compounder. 1, Feedstock inlet; 2,

barrel; 3, retention ring for planetary screws; 4, discharge gap for homogen-
ised melt.
50 30
2 1
60
4
J
Fig. 11.39 Planetary compounder with discharge extruder. 1, Feed zone; 2,
compounding zone (planetary system); 3, degassing zone; 4, discharge screw;
5, retention ring.
stationary barrel, and the retention ring. As the main screw rotates,
the planet screws rotate along with it, rolling around inside the barrel.
As a result, the PVC stock is continuously rolled out into thin layers,
being sheared and squeezed between the helix flanks and roots of the
main screw and those of the planet screws, and the barrel wall. Shear
heating, usually with some external heating also, plasticates the stock.
The removeable retention ring has two functions: it prevents the axial
movement of the planet screws (which would otherwise tend to be
'screwed out' of the barrel), and controls the level of back-pressure 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 (ct. 3. and 4. in Fig. 11.38). For calender
feeding without degassing, the machine terminates as in Fig. 11.37, the
homogenised stock emerging from the retention ring in the form of
helical strands which are fed to the calender. Where intensive
degassing is required, a short single-screw section-with degassing and
discharge zones-may be present, as an in-line extension, after the
planetary screw section. For compounding and pelletising, the con-
figuration shown in Fig. 11.39 is widely used: this is a typical cascade
arrangement, in which the planetary compounder is followed by a
single-screw discharge extruder terminating in a pelletising die. There
is normally a degassing tube between the two units.
11 Compounding 447
Typical output: Approximate ranges, kg h- l , are pPVC, 100-5000;

semi-rigid PVC, 300-3500; uPVC, 50-3000; PVC/ ABS blends, 50-1000.
MACHINE DRIVES AND CONTROLS

The driving power in modern screw-type compounding machines is
provided by variable-speed motors (dust-and splash-proof), which are
well suited to remote control of screw speeds. Power transmissions
from motor to gear-box are typically as follows: direct drive via an
elastic coupling for machines with screw speeds in excess of
200 r min- l (or where a V-belt drive is not appropriate for some
technical reason); V-belt drives for screw speeds of 50-200 rpm; drive
chains are fairly common with slow screws (e.g. for pelletising
discharge extruders in cascade arrangements).
Where temperature regulation (heating and cooling) is by means of
liquid' heat-transfer medium systems, heating zone temperatures are
adjusted via heat exchangers (one for each zone) through which the
liquid passes. In electrical heating systems the heaters are cut in or out
as required, and cooling is additionally effected by liquid circulation or
by air fans. With either type of system, each heating zone represents a
closed control loop, with the set-point temperature as command
variable.
The important factors influencing ultimate product quality are the
energy input (in terms of specific energy, i.e. energy imparted to a unit
weight of stock*), and the heat history acquired by the material. Both
have to be monitored and controlled, the former normally via the
input power, and the latter by adjusting the temperature profile of the
stock as it moves through the line (the temperature being monitored
and controlled by one of the available temperature probe systems).l
MACHINE WORKING SURFACES AND PARTS
As in all PVC-working machinery, these elements must be resistant to
acid corrosion; they should also have reasonable wear resistance. For
working parts that experience severe mechanical loading, many
designers favour martensitic steels (17% chromium) because of their
high yield point and good fatigue strength. Chromium/nickel steels,
whilst more resistant to corrosion, have much lower yield points and
thus are only suitable for elements less highly stressed in operation.
* Calculated by dividing the momentary driving power N (in kW) by the

output rate G (in kg h- I), i.e. e = N /G, where the units of e are kW h kg-I.
ON-LINE OPERATIONAL AND MELT QUALITY CONTROL

With increasing automation of compounding lines, both direct opera-
tional control, and continuous control of material quality by monitor-
ing a key property of the melt, are increasingly practised_ Automatic
operational controls are exemplified by computerised, systems for
compounding lines as offered, by Battenfeld, Maplan, and Cincinnati
Milacron inter alia: typically, such systems control the forced feed,
extruder screw speeds and torque, equipment temperatures (barrel
and die zones), melt temperature and pressure, degassing vacuum,
pelletiser operation, and subsequent pellet handling [see (e) below].
Melt quality is monitored and controlled in some systems (e.g. one
developed by Werner & Ptleiderer3 with the aid of an on-line
(side-stream) rheometer, or (as in the Rheometrics* system) with a
dynamic mechanical analyser, which can provide indications of mole-
cular weight distribution in addition to rheological data. Other systems
(e.g. the Automatikt IROS-l(0) determine melt composition (includ-
ing contaminants, degradation products, and moisture) by IR
spectrophotometry of side-stream melt, or melt samples.
(e) Further Processing
PELLETISING
Two basic arrangements are available for cutting into pellets the
strands emerging from the multi-hole die plate: central cutting and
side cutting. Both arrangements employ rotating knives at the outer
surface of the die plate (Fig. 11.40). Pellet length can be changed by
altering the speed of rotation of the knives. The die head is enolosed 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, although in hot countries the air may have to be passed
through a cooler and possibly also a drier. 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
* Rheometries Inc., USA.

t Automatik Machinery Corp., USA.
11 Compounding 449
KNIFE SHAFT AND DIE PLATE CONCENTRIC
KNIFE SHAFT NEXT TO DIE PLATE
Fig. 11.40 Basic cutting arrangements in pelletising equipment.
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. 11.41) 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
flowmeter is used to control the amount of water atomised.
PELLET COOLING
From the pelletiser head (where their temperature may be anywhere
from 130 to 190°C depending on PVC type and formulation) the
COMPRESSED AIR
WATER
PNEUMATIC PELLET CONVEYING
Fig. 11.41 Water-mist cooling of cut pellets.

pellets are conveyed pneumatically through a pipe to the pellet cooler.

En route, the pellet temperature will fall (by 40-50°C depending on air
flow, pellet loading and distance): in the cooler it is lowered further, to
about 40-60°C, 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. Several
pellet-cooling systems are available. 1
MIXING (BLENDING) OF PELLETS

This is carried out to homogenise the product by blending different
production batches of pellets of the same basic formulation, or where
a mixture of pellets with different characteristics is required. A wide
selection of mixers is available for mixing relatively small batches of
pellets (up to a total mix volume of about 10 m3): some of these are
listed in Fig. 11.11. Mixers used for larger batches include mechanical
types, such as the vertical-screw silo mixer and orbiting vertical-screw
mixer (see Fig. 11.11), and the double-cone mixer; pneumatic circulat-
ing mixers (see Fig. 11.11); and gravity mixers. The latter require no
driving power: although they cannot produce fully randomised ('ideal')
mixes, they are adequate for some purposes. In a gravity mixer a form
of mixing may be achieved by withdrawing pellets simultaneously from
different levels of the mixing silo into a common chamber; in another
version, silo cells formed by vertical partitions are filled successively
(say with different pellet batches) and then tapped simultaneously to
form mixed batches. Figure 11.42 gives an indication of the capacities
of the various types of mixer, and of their driving power requirements.
A more extensive discussion will be found in Ref. 1.
FINAL HANDLING AND DELIVERY

Homogenised batches of pellets from a mixer are delivered for
transport or processing. In most cases mixer silos are mounted on
frames, so that tankers (road or rail) or container trailers can be
driven underneath for gravity filling. If the pellets are to be bagged,
semi-automatic bagging installations are fed directly from the mixers.
Fully automatic systems normally provide automatic stacking of the
bagged goods on pallets, followed by the wrapping of each such load
with shrink-wrap or stretch-wrap 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.
11 Compounding 451
0'1
C
:g
....
(J)
·c>
o
0.1 10 100 1000 10000
Capacity m3
Fig. 11.42 Drive power rating as a function of volume capacity in pellet
mixers. A, orbiting vertical-screw mixer; B, double-cone mixer; C, vertical-
screw silo mixer; D, pneumatic mixer.
(f) Batch Compounding in Internal Mixers

The best-known early form of internal mixer (sometimes also called
intensive mixer was the Banbury, first produced by F. H. Banbury in
1916 for compounding rubber. Later, like other rubber-processing
machines (the calender, the two-roll mill, the extruder), the internal
mixer came to be used for processing PVC compositions.
In an internal mixer, the stock is mixed under conditions of high
shear and pressure. The main working elements of the machine, all of
robust construction, comprise: the mixing chamber fed through a feed
hopper (injection systems for introducing liquids in the course of a run
are also available); two non-intermeshing mixing rotors with 'winged'
profiles housed in the chamber; and a floating weight (ram) suspended
in a weight cylinder, to exert pressure on the stock being worked by
the rotors. The rotors and the chamber walls are cored or channelled
for circulation of cooling water or steam. In modern internal mixers
the rotors are computer-designed (in some equipment, e.g. the
Intermix internal mixer, they have interlocking profiles) for optimum
mixing and shearing action, and the operational variables such as rotor
speed, ram pressure, stock temperature and energy input are also
computer-controlled. Simultaneous control and synchronisation of at

least two of the three important parameters represented by the usual
set-points in the compounding of a PVC batch-viz. the operating
time (duration of run), the maximum temperature to be reached, and
the total energy input-<:an now be exercised by computerised
adjustment of rotor speed and ram pressure.
Note: Until recently, control systems usually gauged the completion
of a run by the attainment of only one of the set-points, i.e.,
say, a batch might be discharged after the set time has been
reached, irrespective of whether the set maximum tempera-
ture and energy input have also been attained.
Cycle times for PVC batches in present-day internal mixers are
short, typically about 2-5 min. In modern installations the com-
pounded melt batch is normally dropped through the machine's
discharge door directly onto a two-roll mill (for sheeting and strip-
feeding to a pelletising machine or into a calender-feed train: see
Chapter 14); alternatively the batch may be dropped into a large
discharge extruder for subsequent continuous pelletising or other
processing.
Various basic internal mixer models are available, with chamber
capacities typically within the approximate range 15-600 litres (mix
weight capacities approximately 10-400 kg), but 'stretched' mixing
chambers can be fitted to some models, and other modifications can be
made to suit particular requirements. In comparison with a continuous
melt compounder, the advantages of an internal mixer (especially in
compounding for calender feeding) have been listed l 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 rework (promoted by the large loading port and ram
operation) and its thorough redispersion; generally greater heat
transfer capacity; and comparatively moderate routine maintenance
costs. The main comparative disadvantages include more severe
working of the stock (the main factor in the primary suitability of
internal mixers for pPVC compositions and those based on more easily
processing copolymers), and the need to handle large discharged
material batches; the connected-power requirements are also relatively
high, although the total energy consumption is roughly comparable
with that of an equivalent continuous compounder. In general, the
batch mixers are best suited to operations involving relatively short
11 Compounding 453
runs on different formulations, although in modern installations they

can be integrated into continuous-production lines.
The two principal suppliers of internal mixers are Farrel* (the
Banbury mixers) and Francis Shawt (Intermix mixers).
(g) Compounding Some Recycled Materials

Direct recycling of PVC rework (in-line scrap) is widely practised: for
a typical example-the re-use of calendering scrap (edge trim and
starting scrap)-see Chapter 14, Section 14.3.1a. The practice is
similar in compounding for pelletising, where scrap may take the form
of material of the wrong composition or colour shade.
In some cases, clean scrap from one process may be recycled by
conversion to a product in another process. An example is a
development aimed at re-use of die-cutting scrap from PVC sheet
processing in the production of extruded profiles and pipes, or of
calendered sheeting.! The scrap is first ground up in a grinding mill.
Extra stabiliser (preferably that used in the original sheet formulation)
is added in the pre-mixer, where pigments may also be added to obtain
the desired colour. The pre-mix is put through a 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, to be 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. 11.43).
RIGID PVC SCRAP PLASTICISED PVC SCRAP
PlA5T1C~ ~
~v~.A~Wl
STRAINER
Fig. 11.43 Recycling of film scrap.
* Farrel Bridge Ltd., UK; Farrel Corp., USA.

t Francis Shaw & Co., UK.
Because the plasticiser cannot diffuse in the PVC regrind in the

pre-mixer 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.
The compound from the strainer may be fed at the appropriate point
into a calender feeding line (if it is to be used for calendered sheet
production), or it may be pelletised for subsequent use in extrusion.
Copper-free pPVC cable insulation and sheathing scrap are often
recycled to produce filling cores for cables or, occasionally, also such
products as low-grade pPVC profiles (e.g. for caravans) or cheap
soling compositions. If the material to be recycled comes from own
cable covering or sheathing operations, then no special pre-processing
is normally necessary. If, as is sometimes the case, it is being
reclaimed from discarded scrap cables, then a fairly complicated,
multi-step procedure may first be necessary to separate the PVC from
the metal conductors and from any other plastics insulation materials
present, clean it, and comminute to the required degree. For the
production of cable-core compounds-whose only role is to fill-in any
spaces between the functional components in a cable (and which thus
do not normally have to comply with any specifications for mechanical
or electrical properties}-the clean PVC scrap, ground to a particle
size of 5-10 mm, is often compounded with large proportions (up to
some 700 phr) of a cheapening filler, usually calcium carbonate. One
version of equipment specially designed for this purpose is shown in
Fig. 11.44. The ground scrap is fed into the first inlet, which is
PVC SCRAP FILLER
PLASTlC~ ~ v' "
Fig. 11.44 Compounding of cable filler cores.

11 Compounding 455
followed by a first kneading zone where the material is thoroughly

plasticated so that it can accept the high loading of filler metered into
the second inlet, preceding a second kneading zone. Where increased
plasticisation is required, plasticiser is injected by a pump into both
kneading zones. The equipment may also be used for compounding
virgin compositions.
11.2.3 Compounding for Direct Feeding of Calenders
This subject is discussed in Chapter 14.
11.3 COMPOUNDING OF LIQUID PVC COMPOSITIONS
The compounding of liquid compositions is discussed in the chapters

dealing with such compositions, viz.
Pastes-Chapter 18;
Solutions-Chapter 19;
Latices-Chapter 20.
11.4 SMALL-SCALE (LABORATORY) COMPOUNDING
11.4.1 General
(a) Usual Objectives

The usual objectives of laboratory-scale compounding operations are:
(i) development, comparison, and evaluation of formulations;
(ii) production of sample quantities of compositions for the deter-
mination of properties;
(iii) study of mixing characteristics and rheological properties of
compositions, and the effects on these of particular formulation
components (e.g. lubricants, polymeric modifiers) and/or for-
mulation modifications.
(b) Scope of Discussion in this Chapter

The objectives of laboratory-scale compounding listed above relate
equally to all PVC compositions, whether solid or liquid. However, as
each type of liquid composition is dealt with individually in a separate
chapter of this book, the discussion here is centered on solid

compositions.
11.4.2 Laboratory Compounding Equipment and its Uses
Virtually every manufacturer of industrial PVC compounding equip-

ment produces laboratory versions of his machines: many will also
custom-make small-scale equipment to suit a customer's particular
requirements. The items mentioned in Section (a) below are cited
purely by way of example, and to illustrate some of the available
features.
As has been mentioned, the two-roll mill is much more important in
laboratory practice than in industrial use as melt-compounding equip-
ment for PVC compositions (cf. e.g. Chapter 17, Section 17.1.3).
(a) Some Laboratory and Pilot-Scale Counterparts of Industrial

Compounding Equipment
POWDER MIXERS
A mixer for very small charges is produced by MTI-Mischtechnik.
TWO-ROLL MILLS
See Fig. 45; laboratory mills also available from Brabender inter alia
[see Section (b) below], and Erie Mills & Press Co. (USA).
KOMBIPLAST
The laboratory and pilot-scale version of this equipment is the KP
30/60, consisting of a ZSK-30 compounder and ES-A 60 mm screw-
discharge extruder. PVC output rate; 4·5-50kgh- 1 •
BUSS KNEADER
The laboratory model, intended particularly for formulation develop-
ment and trials, is the KKG 4.6-7.
COMPOUNDING EXTRUDERS
Leistritz Tri-Mode laboratory extruder: Output 5-50 Ib h- 1 • This

functions as a single-screw, or twin-screw co-rotating or counter-
rotating machine.
11 Compounding 457
Fig. 11.45 Laboratory-scale equipment for PVC processing (Farrel Bridge

Ltd.). Two-roll mill (swing-side, variable friction, rolls 6 in x 13 in).
Beetol* BTS 30 twin screw laboratory and pilot-scale extruder: With

30 mm, closely intermeshing, co-rotating screws, it has interchangeable
screw and barrel sections. All, or part of, the barrel can be slid off for
immediate access to stock for examination (or for screw cleaning).
Baker-Perkins MP 2030 30mm twin-screw compounder: With hex-
agonal screw shafts (for high torque transmission) and segmented,
clam-shell split barrel for ease of access (cf. also Table 11.4).
* Beetol Machinery Ltd, UK.

The Collin * twin-screw compounding laboratory extruder: Operable

in either co-rotating or counter-rotating mode. It has modular screws
and barrel. Output is 6·S-SSlb h- 1 •
INTERNAL MIXERS
Laboratory models are available from both Farrel and Francis Shaw.
The Farrel laboratory machine range comprises three Banbury mixer
models (the Midget, the BR and the OOC) with respective approxi-
mate nett mixing chamber volumes of 0·4, l·S and 4·3litres, and
corresponding approximate mix capacities of 0·3, 1·2, and 3 kg.
Another supplier is Haake Buchler Instruments Inc., USA (mixing
chamber volume range 30-S00 ml).
(b) Specialised Instrumented Equipment for Investigation and Study of

Compounding Behaviour and Effects
Equipment used for these purposes, originally a relatively simple form
of instrumented torque rheometer, has today reached a high degree of
sophistication and versatility. The well-known Brabender Data-
Processing Plasti-Cordert represents advanced modern equipment
embodying these features in a computerised modular system employ-
ing a number of interchangeable attachments ('measuring heads')
which enable quantitative data to be obtained on the processing and
processing-related properties of plastics compositions in dry (powder)
mixing, liquid-state mixing, melt compounding, and extrusion, see
illustration in Fig. 11.46. Other torque rheometers include the
RAPRA instrument,:j: and equipment of this kind available from
Haake Buchler Instruments Inc. (USA).
The Plasti-Corder system is particularly applicable, and widely used,
in the PVC field, inter alia for the determination of powder blending
behaviour and plasticiser absorption in powder mixing (actually
specified in ASTM D 2396-79 (198S)§), fusion characteristics in
* Dr. Collin GmbH, FRG.

t Brabender OHG Duisburg (FRG); C. W. Brabender Instruments Inc.
(USA); and agents in most industrialised countries. The predecessor of the
Plasti-Corder was known as the Brabender Plastograph.
* Developed by the Rubber and Plastics Research Association (UK).
§ The mixer attachment specified by this standard is the sigma-blade measuring
mixer, but the determination of plasticiser absorption in powder blending can
also conveniently be carried out with a planetary mixer attachment (cf. Fig.
11.48). This attachment, although not specifically prescribed, is also suitable
for similar determinations in accordance with DIN 54802, ISO 4574 and
ISO 4612.
11 Compounding 459
(A)
~ __ 'I"O_.""'.
-~
(B)
Fig. 11.46 Brabender Plasti-Corder with different attachments. (A) Mixing

chamber attachment. (B) Measuring extruder attachment. Courtesy of
Brabender® OHG, Duisburg, FRG.
melt-compounding of PVC compositions [specified in ASTM D

2538-79 (1985)], investigation of the effects of lubricants (see Chapter
7), dynamic stability studies and evaluation of stabilisers (see Chapter
4), as well as investigation of the rheology and behaviour of PVC
pastes in the course of their compounding, processing, gelation, and
fusion (see Chapter 18).
Figure 11.46 shows the Data-Processing Plasti-Corder with two
different attachments. Schematic representations of three measuring
heads are shown in Fig. 11.47.
In a mixing or compounding experiment, the equipment displays
and records a plot ('plastogram') of the torque and stock temperature
as functions of processing time. The progress, ease, and duration of
mixing are reflected by the shape of the torque vs time curve, and the
(A) (B) (C)

Fig. 11.47 Schematic representation of three measuring heads of the Plasti-
Corder system. A, planetary mixer; B, measuring extruder; C, measuring
roller mixer. Courtesy of Brabender® OHG, Duisburg, FRG.
magnitudes of the parameter values at the characteristic points. The

energy input is also calculated.
Figure 11.48 is a plot from a fairly typical powder-mixing run in a
planetary mixing head. The usual procedure is as follows. 4 The mixer
is preheated to the required temperature (88°C in ASTM D 2396), the
PVC polymer powder is poured into the mixing bowl, the mixer is
started, and run for about 5 min to warm the powder up. The
plasticiser is then added (through a distributing funnel), whereupon
the torque rises steeply as the stock becomes lumpy (the consistency
has been compared with that of wet snow).4 Completion of the
absorption of all the plasticiser into the polymer particles (the 'dry
point') is marked by a sudden drop of the torque. The torque may
then increase somewhat again, in line with the degree of any swelling
of the polymer particles by the plasticiser (dependent upon the natures
of both). The time between the moment of plasticiser addition and the
dry point is the mixing time. For the same polymer:plasticiser ratio at
the same mixing temperature, this time is dependent on the identities
of the two components, as is the extent of torque rise. Other factors
being equal, the mixing time is also a function of the components'
ratio. Varying the total amount of mix at the same ratio does not
substantially affect the mixing time, but the torque values are higher
for greater quantities of mix. The scope for evaluation and comparison
of the effects of the kinds of polymer and plasticiser used (as well as
the presence and nature of other formulation components), their
proportions, and the mixing temperature, is self-evident even from this
brief outline of the procedure.
A fusion test, relevant to the progress and general ease of
plastication and fusion of a PVC composition (rigid, semi-rigid, or
flexible) in melt-compounding or processing is typically run in a roller
mixer attachment (cf. Fig. 11.47), often in accordance with the method
of ASTM D 2538. A rapid-loading chute is normally used to introduce
11 Compounding 461
Test-Conditions
Order BRABENDER Mixer-Temp. 88 ·C
Operator JAEDTKE Speed 100 lImin
Check-Date 16. MAV '88 Meas. Range 2 Nm
PL-Type 2000-3 Zero-Suppr. o 'l.
Mixer-Type P 600 DampinC} 3
Load. Chute Test-T1me 30.0 min
Sample PVC Sample-Weight 400.00 g
Plasticizer DOP Plast.-Weight 200.00
Start-Temp. 83 ~C
Torque[",,]
2.8
1.8 98
1.6 .J" i-\ L.-- 88
1.4 V .~
• 78
·
1.2
:! --
1.8 : j....-
• 58
8.8 ! •
! : • 48
8.6
• I •
• 38
•
• • •
8.4 • 28
•
8.2 ~ ..... • • 18
.~:
8.8 ~: : , , , 8
8 6 12 18 24 38
Ti",e [",in]
Value Time [s] Torque [Nm] Stocktemp.[·C]

Maximum 326 1.4 84
Dry Point 526 0.7 85
Integration
- Energy from start to 5 min Wl 0.7 E3 [Nm]
- Energy from 5 min to Dry Point: W2 3.0 E3 [Nm]
Results
-- Dry Point
Drying Time
526 s
226 s
Fig. 11.48 Computer print-out of a PVC powder mixing (dry-blend plasticiser

absorption) test in a planetary mixer attachment of the Data-Processing
Brabender Plasti-Corder system. Courtesy of Brabender® OHG, Duisburg,
FRG.
Test-Conditions
Order BRABENDER Mixer-Temp. 180 'C
Operator EICKMEIER Speed 60 lImin
Check-Date 16. MAY 'BB Mea5. Range 50 Nm
PL-Type 2000-3 Zero-Suppr. o 'l.
Mixer-Type W 50 Damp in 9 3
Load. Chute MANUAL + 5 KG Te5t-Tl.me : 10.0 min
Sample PVC Sample-Weight: 57.00 g
Additive Coden umber : 1
Start-Temp. 178 'C
Torque [ItIII 1 Telllp [Gel

58 218
45
48
35
, ··lllilll
--tt:t-4~- ;--+--f=!'9 - 288
198
138
ft:l:nr:~ -: -_. -._. _

. . ---i -- t- -- ,- -··1
,;...---r-. (ri'" •
38 178
25 168
28 \-+-+-t -It -.- --i-· - . . _. . ___ L J .-.:j 158
\~·j;.=t.·'.·'.· ~.'·~J. .• .• . . .•. .• lj.·,•. .·•.·•.•.

15 148
18 .• '.·'.·I"·'-'·'.·:.·'.·.• .• .•,·.,•...•. :.•.. : . . . . . . .........1 138
5 j ............. J. . . . . . . . J ............... +1 128

A B x: i
8 i I I i; i i i 118
8 2 4 6 B 18
Tillie [",in]
Value Time [5] Torque [Nm] Stocktemp.[·C]

Load.Peak 2 58.0 162
Minimum 90 10.8 176
Maximum 174 32.3 185
End 600 26.1 194
Integration
Load.Peak to Minimum Wl 8.6 E3 [Nm]
- Minimum to Maximum W2 9.5 E3 [Nm]
- Load.Peak to End W3 90.9 E3 [Nm J
- Specific Energy (W3/Weight) W4 1.6 E3 [Nm/gJ
Fig. 11.49 Computer print-out of a PVC fusion test in a roller mixer

attachment of the Data-Processin£ Brabender Plasti-Corder system. Courtesy
of Brabender OHG, Duisburg, FRG.
11 Compounding 463
the composition (usually a powder blend) into the mixer as quickly as

possible (within 20 s at most) for best reproducibility and com-
parability of test results. As the loading proceeds, the torque vs time
curve first rises very steeply to a sharp peak (the loading peak); it then
drops rapidly, reflecting the decreasing resistance of the stock to shear
as it is being heated and compressed, to rise, more gradually again to a
second, lower peak marking the 'fusion point' at which all the polymer
particles are merged into a melt. The time between the loading peak
and the fusion point is the fusion (plasticating) time. Thereafter the
torque drops gradually, as less force is required to continue mixing and
homogenising the fused stock. For a particular mixing temperature,
the torque value at the fusion point can be related to the power
required for the fusion of a particular composition in a given
production machine. The fusion time can similarly serve to indicate
the conditions in a production machine (screw speed in relation to
screw length in a screw compounder, rotor speed and the pressure in
an internal mixer) to be used for satisfactory fusion of the composi-
tion. An actual fusion test curve is shown in Fig. 11.49. A full
discussion of the operation and application of the Brabender Data-
Processing Plasti-Corder will be found in Ref. 4.
REFERENCES
1. Henschel, W. & Franz, P. In PVC Technology, 4th edn, W. V. Titow.
2. Hoppe, H. & Eberhardt, N., Rubber Southern Africa (March 1986) 16-19;
(May 1986) 4-19.
3. Herrmann, H., Mod. Plast. Int., 16(10) (1986) 140-2.
4. Liiben, H. E., CAR-Computer-Aided Rheometry. Brabender OHG,
Duisburg, FRG, 1986.
Section 4
PROCESSING OF SOLID
PVC COMPOSITIONS INTO PRODUCTS
465
CHAPTER 12
Main Types of pvc Products and Methods

of Their Production
12.1 PVC PRODUCTS OF GREATEST INDUSTRIAL

IMPORTANCE-GENERAL
These are the products listed, in descending order of PVC polymer

consumption, in Table 1.2 of Chapter 1, and discussed further in the
following sections of the present chapter.
12.2 RIGID PVC PRODUCTS
12.2.1 Pipes and Conduit
The acceptance of rigid PVC pipes in a number of important

applications, coupled with their increasing utilisation, has been car-
dinally instrumental in the general growth 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.
(a) Types of pvc Pipes
PRINCIPAL GENERAL KINDS

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);
467
(iv) pressure pipes for gas supply;

(v) non-pressure pipes for sanitary pipework in buildings: dis-
charge pipes-main and branch-for soil water (toilets) and
waste water (bathrooms, showers, sinks); house drains; ven-
tilation 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 require-
ments: relevant international and national standards abound. The ISO
specifications for PVC pipes and fittings can be found among the pipe
standards which make up Volume 2 of ISO Handbook 28;1 the ASTM
ones are collected in Volume 08.04 of the Book of ASTM Standards;2
and the DIN PVC pipe and fitting specifications are contained in DIN
Handbooks 52 and 190?a,b There is no similar collection of BS
specifications for pipes and fittings: those relevant to such PVC
products are listed in Table 12.1. Various standards of special interest
to the important properties, quality, and testing of PVC pipes are
mentioned in Section (c) below (see also Section 8.3.1 of Chapter 8,
and Table 21.1 in Chapter 21).
Specifications concerned with CPVC pipes and fittings can also be
found in the above-mentioned specification collections. They include
ISO 3514-1976 (for CPVC pipes and fittings), ISO 3608 (tolerances on
external diameters and wall thicknesses of CPVC pipes), and
ASTM D 3915 (PVC and related plastics pipe and fitting compounds).
uPVC pipes can be used for town or natural gas distribution systems
operating at pressures up to about 1 bar. However, with pipe
compositions unmodified for impact resistance, there is a possibility of
brittle fracture, especially at low temperatures. Susceptibility to
environmental stress cracking promoted by some trace contaminants in
the gas (benzene, toluene, xylene, naphthalene 4 ,5) is also a considera-
tion. Pipes of impact-resistant 'ductile' uPVC (modified with chlorin-
ated polyethylene or ethylene/propylene copolymers6) have proved
12 PVC Products and Production Methods 469
TABLE 12.1
British Standards Relevant to Rigid PVC Pipes and Pipe Fittings
no.
official title)
1 BS 3505:1968 (1982) Unplasticised PVC pipe for cold water

services
2 BS 3506:1969" Unplasticised PVC pipe for industrial
purposes
3 BS 3943:1979 Plastics waste traps
BS4346 Joints and fittings for use with uPVC pressure
pipes
4 Part 1:1969 Injection-moulded PVC fittings for solvent
welding, for use with pressure pipes,
including potable water supply
5 Part 2:1970 Mechanical joints and fittings principally of
uPVC
6 Part 3:1982 Solvent cement
7 BS 4514:1983 Unplasticised soil and ventilating pipe, fittings
and accessories
BS4576 Unplasticised PVC rainwater goods
8 Part 1:1982b Half-round gutters and circular pipe
BS4607 Non-metallic conduits and fittings (electrical
use)
9 Part 1:1984 Fittings and components of insulating material
10 Part 2:1970 (1985) Rigid PVC conduit and fittings (Imperial
units)
11 Part 3:1971 (1985) Pliable corrugated, plain and reinforced
conduits of self-extinguishing plastics
material
12 Part 5:1982 Specification for rigid conduits, fittings and
components of insulating material
13 BS 4660: 1973 b Unplasticised PVC underground drainpipe
and fittings
14 BS 4962:1982 Pipes for use as light sub-soil drains
15 BS 5481:1977 Unplasticised PVC pipe and fittings for
gravity sewers
16 BS 5556:1978 (1986) General requirements for dimensions and
pressure ratings for pipes of thermoplastics
materials (metric series)
BSCP312 Plastics pipework (thermoplastics materials)
17 Part 1:1973 General principles and choice of material
18 Part 2:1973 Unplasticised PVC pipework for the
conveyance of liquids under pressure
" Revision undertaken in 1987.

b Revision undertaken in 1986.
acceptably tough and more resistant to (though not entirely immune

from S) environmental stress cracking: such pipes are used in some
countries in this application.
General advantages of uPVC pipes over non-plastics alternatives in
various application areas include the following: structural flexibility
(i.e. ability to withstand substantial deformation without breaking or
permanent distortion); resistance to furring and general ease of flow
(d. Table 12.2); resistance to corrosion, and lower weight (which
makes for ease of handling, transport and installation).
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 pipes. Particular effectivity is claimed for uPVC
drainage pipes with perforations in the form of circumferen-
tial slots (Extrudex pipes; Turner & Newall Ltd, UK).
SOME SPECIAL PIPE FORMS
Foam-core pipe: This kind of pipe has a sandwich wall structure,

with solid skin layers at the inner and outer surfaces enclosing a
cellular core. Production is by coextrusion, either with two extruders
(one for the solid skin compound and the other for the foamable core
compound, as in the Atochem Bipeau process), or with three
extruders (as in the Battenfeld system, one each for the inner and
outer skin compounds, and one for the core material). Foam-core
TABLE 12.2
Typical Ease-of-Flow Characteristics of Pipes
(All values relate to flow through a new uPVC pipe, taken as unity.)
Pipe material Relative ease of flow· Retention of

original ease of
New pipe After 30 years' flow (%)
operation
uPVC 1 0·93 93
Cast iron 0·87 0·27 31
Steel 0·93 0·29 31
Asbestos/ cement 1 0·73 73
• Based on the Hazen-Williams hydraulic roughness factors for 100-mm bore

pipes carrying water.
pipes are used as sewer, waste and vent pipes, and for drainage (in the
perforated version): their use in these applications has been expanding
in recent years both in Europe and America. In comparison with
solid-wall uPVC pipes, the advantages of foam-core pipes are lower
weight, better insulating properties, and lower material cost.
ASTM F 891-86 covers the properties and certain other aspects of
these pipes.
Corrugated single- and double-walled pipe: Pipes with corrugated

walls (including large-diameter ones for culverts and sewers) are
manufactured in uPVC (and other thermoplastics) by extrusion, with
in-line expansion of the tubular extrudate by air pressure against
corrugated sectional mould blocks. A variant of this successful
process-originated by the Corma company (Toronto, Canada}-is
also used to make double-walled pipe with a corrugated outer and
smooth inner wall, or vice versa: in either case the two wall layers are
welded together at the corrugation valleys. Another way of producing
single-walled corrugated pipe is by helically winding and side-fusing a
continuously extruded strip. Large material savings are claimed for the
double-walled pipes in comparison with equivalent conventional solid-
walled ones. The double-walled pipes are used in sewer lines, as
ducting for electric cables, and (with suitable perforations made in the
course of production) in drainage and irrigation systems. There are
two ASTM specifications for corrugated uPVC pipes and compatible
fittings. 7
Hollow-walled pipe: Sewer pipes have been produced incorporating

closely spaced longitudinal channels in the wall (Wavihol pipe; Wavin
Overseas BV, The Netherlands). Substantial weight-and hence
cost-reduction in comparison with solid pipe has been claimed, at
only moderate sacrifice of relevant mechanical properties. 8 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-wall pipe: Controlled, partly biaxial, mole-

cular orientation induced in the wall by a stretching step in production
can promote 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 (Superpolyroc
pipe; Yorkshire Imperial Plastics, UK).
Ribbed pipe: Pipes with integral circumferential ribs (flanges are

produced, in diameters up to about 1 m, by 'grow-moulding'-stepwise
injection moulding in sections (over a mandrel positioned in the
mould). Although uPVC is not an easy material to mould in this
process, especially into large-diameter pipes, the use of foaming
compositions can reduce the difficulties: uPVC pipes with cellular
(structural foam) walls of density about 1 g cm- 3 have been produced.
The main general advantage claimed for the ribbed structure is that
the pipe's ability to withstand external loads within the normal service
range can be on a par with that of a conventional plastics pipe
containing twice the amount of material per unit length. Applications
of various plastics ribbed pipes (Ribstruct-developed by Duropenta
(Pty) Ltd, RSA) include non-pressurised sewers and effluent drains,
ventilation ducting, multicore cable ducting, shuttering for concrete,
and pneumatic conveyance of materials.
(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 through
proper compound formulation. At the same time, the need to process
effectively at the fastest possible rates (for processing economy), whilst
achieving a fault-free product with good service properties, also calls
for expert, sophisticated formulation. The most economical approach
may entail the use of not the cheapest, but the most effective
formulation constituents, which can be incorporated in minimum
quantities. For example, some high-effectivity organotin and anti-
mony stabilisers can be used in American-type formulations at levels
of only 0·3-0·4 phr. Correct lubrication and stabiliser/lubricant bal-
ance are essential. This point, well understood from practical ex-
perience, was clearly brought out by the results of an experimental
study by Zechinati et al. 9 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) 100
Stabiliser: methyltin mercaptide 0·3phr
Lubricant system:
External lubricants: paraffin wax (MP 71°C) 1·2 phr
partially oxidised
polyethylene (MP 104°C) 0·2 phr
Internal lubricant: calcium stearate 0·8phr
Acrylic processing aid 1·0phr
Pigment: Ti02 1·5 phr
Filler: CaC03 2·5 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.
(c) Important Pipe Properties and Their Determination

The importance of some properties of uPVC pipes is relative to the
end-use: for example, 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 13 (Section
13.4). 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, such as 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 D2152) or dichloro-
methane (DIN 53419; 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 increas-
ingly serious under-gelation). A desirable refinement, employed in
* Keuringsinstituut voor Waterleiding Artikelen, Delft, The Netherlands.

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 homo-
geneity within the pipe wall. Examination under the microscope for
grainy appearance and inhomogeneity (frequently involving com-
parison with standard specimens or photomicrographs) 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 & Birch10 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. Application of appropriate fracture mechanics
techniques is claimed by Moore et al. 11 to yield reliable
quantitative data on the toughness of both pipe materials and
manufactured pipes.
Some aspects of the quality of extruded uPVC pipe can also be

assessed by subjecting longitudinal strip specimens cut from the pipe
wall to heat treatment, typically for 30 min at 180°C in an air-
circulation oven. Presence of moisture in the extrudate, and faults in
the cooling and vacuum control during vacuum sizing of the hot pipe
after extrusion, are usually clearly revealed by such effects of the test
treatment as layer separation in the specimen, blistering, and scale-
peeling at the outer surface. One version of this test is described in
ASTM F 1057-87: the specification also provides illustrations of the
failure manifestations just mentioned, with indications of their
significance.
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 to longer times-in
accordance with established procedures-of plots of relevant test data
(compare, for example, ASTM D 1598 and D 2837, and Refs 12 and
* Compare also the paper on fatigue failure prediction by S. H. Joseph [Plust.

Rubber Process. Applns, 4(4) (1984) 325-30].
13). Much is now also available in the way of actual results obtained in
long-term service. 12,14
Note: Evidence has been produced 12 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, and/or possibly also to some
annealing effects.
12.2.2 Profiles and Cladding (Siding)
(a) 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
mounting purposes, to very complex hollow-section multi-channel
products for use in modern uPVC window-frame systems. Cladding
(siding) is another form of extruded uPVC profile with a substantial
application in the building industry, especially in the USA. Both
cladding profiles and window-frame lineals have been produced (by
coextrusion) with a covering of an acrylate 'skin', which may be plain
or coloured, to provide surface protection against weathering, inter
alia.
Note: uPVC casings are also applied to timber profiles for use as
window- and door-frame components, where the covering
serves as a permanent protective and decorative surface
finish. Continuing development of uPVC window-frame pro-
files has resulted in effective formulations and sophisticated
extrusion technology.
Other solid (i.e. non-cellular) profiles 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
draught seal), rods, and various angle sections for general
applications.
Entirely cellular (structural foam) profiles have been used in place
of the traditional wood products in such applications as skirting boards
and architraves, furniture, boat and caravan trim, and picture frames.
Wood flour is often incorporated in uPVC compositions for these
profiles. The foam density and thickness of the integral skin are suited
to 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 0·50-0·80 g cm -3,
with thick-sectioned purely decorative beading fairly typically near the
lower limit and, say, relatively thin-section skirting board around
0·70 g cm- 3 •
Foam-cored profiles with solid outer layers are also produced, by
coextrusion, for such applications as cladding, roller-blind slats, and
window sills.
(b) 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-ii-vis the end-uses, virtually all uPVC
profile formulations must provide for some degree of impact resis-
tance: in many cases provision is also necessary for good resistance to
weathering. Both of these requirements certainly apply in the case of
compositions for window-frame profiles, which must also have good
processing characteristics and possess in adequate degree certain other
material properties normally defined in terms of the results of the
appropriate standard tests. For example, a compound with the
following performance in the relevant ASTM tests (and otherwise
acceptable with regard to processing and weathering resistance in
service) should be basically suitable: 15 tensile strength, 6200 lbf in -2;
tensile modulus, 329800 lbf in -2; impact resistance (Izod),
20 ft lbf in-I; Vicat softening point, 82°C; deflection temperature under
load (264lbf in- 2 stress), 72°C; hardness, Shore D scale, 83: water
absorption (24 h) 0·2%; property retention after weathering test, 85%.
Note: Some of the corresponding minimum requirements of the
relevant UK trade standard [see Section (c) below] are:
softening point, 72°C; apparent modulus of elasticity
2250 MPa; impact strength 6 kJ m-2; retention of impact
strength after artificial ageing, 70% of original value.
Many successful compositions are in use, geared principally to
product service in moderate climates, but development and improve-
ments are still going on, especially in formulations suitable for

geographical areas where intense solar radiation and heat are ex-
perienced (e.g. parts of Australia or South Africa).
Four general formulation routes are represented among the various
uPVC window-frame compositions in current use, all aimed at
securing the requisite combination of good impact resistance and
weathering performance coupled with adequate levels of the other
relevant properties. These approaches are reflected in the following
types of composition.
(i) Special compounds without impact modifiers but offering ac-

ceptable impact resistance. One commercial example is Benvic
S (Solvay).
(ii) Compounds modified with chlorinated polyethylene, ex-
emplified by Hostalit Z (Hoechst), and the relatively new range
from Dow (with various modifier and calcium carbonate filler
levels).
(iii) Compounds incorporating conventional acrylic impact modi-
fiers (e.g. Acryloid KM 323B, Rohm & Haas), or ones
modified with acrylate/vinyl chloride graft copolymers (often
butyl acrylate/vinyl chloride), e.g. such compounds in the
commercial Vinnol (Wacker Chemie) and Vestolit (Hiils)
ranges.
(iv) Compounds modified with EVA copolymers, commonly graft
copolymers of EVA and vinyl chloride, e.g. Baymod L *
(Bayer), or Elvaloy (Du Pont). Some of the graft copolymers
can also be used as the sole polymer component of the
formulation.
The following are other typical components of uPVC window-frame

formulations.
Stabilisers: Barium/cadmium and barium/cadmium/lead combina-

tions (with dibasic lead phosphite as the only, or the main, lead
component) are common in Europe (where some all-lead systems are
also used), and selected organotins in the USA. Commercial stabiliser
systems usually incorporate appropriate lubricants.
* Formerly Levapren.
Processing aids: The well-established acrylic processing aids are

popular (e.g. Acryloid K 120N and K125, and/or the lubricating
Acryloid 175).
Lubricants: These are normally composite systems. Combinations

of calcium stearate with a wax [e.g. paraffin wax, or ethylene
bis(stearamide)] are used, or in some cases a lubricating acrylic
processing aid (e.g. Acryloid 175).
Pigments: Titanium dioxide (rutile, a stabilised grade) is commonly

used as the white pigment with a light-stabilising action. The loading
levels may vary between 4 and 12 phr depending on the stabiliser,
lower proportions with barium/cadmium/lead and all-lead systems,
highest with organotins. Rutile-based or mixed-metal-oxide colouring
pigments are typically used for good weathering resistance and hiding
power in window-frame and cladding (siding) formulations, e.g.
Sicotan Brown K2611 and K2711 (BASF) in compositions stabilised
with barium/cadmium systems; Sicopal Brown K 2795 (a chrome iron
brown) in lead-stabilised compositions; the Drakenfeld 10000 series
(Ciba-Geigy, formerly produced by the Hercules Pigment Co.).
Fillers: Ultrafine calcium carbonate fillers are included in some

formulations, at up to about 5 phr, mainly for improved impact
resistance [cf. also Section 6.3.1(e) of Chapter 6]. Higher loadings
(around 20 phr) of the regular fine grades are also occasionally used.
The main claims made for the unmodified Benvic S composition for
window-frame profiles are that its impact resistance (in falling-weight
and tensile impact tests) is comparable with, or better than, that of
many impact-modified materials, that its stiffness is better, and its
yield strength (about 45 MPa) on a par with that of impact-modified
compositions. Acrylic-modified compositions are popular 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 rela-
tively high proportions needed for this purpose in cold climates) and
that they are inferior to the best acrylics in processing behaviour and
weathering performance. Compositions modified with chlorinated
polyethylene can be effective but-for best results-require con-
siderable care in processing. Susceptibility to yellowing of white
profiles in some circumstances has also been alleged.
(c) 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, or cut out of a profile) and product properties,
evaluated in tests on finished profiles. As has been indicated in (b)
above, the material properties frequently determined include tensile
and flexural strengths with the corresponding moduli, impact resis-
tance (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 compl-
eteness 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.).
In some cases, purely practical, non-standard tests may also be run,
e.g. for nail or screw acceptance and retention by foamed profiles used
as replacements for wooden profiles.
The major standards relevant to uPVC profiles are listed in Table
12.3.
Note: In addition, two new British draft standards for plastics

windows are in the process of completion: BS Documents
88/13834 (window types, material requirements, consfruc-
tion, and certain other aspects), and 88/12085 (white uPVC
extruded hollow profiles with fusion-welded corner joints).
Processing conditions can significantly influence the stability in

service of profiles for outdoor use. Incipient degradation caused by
TABLE 12.3
Standard Specifications of Greatest Practical Relevance to uPVC Profiles
(Including Window Frames)

no.
official title)
1 BPF/GGF Standard 1986" Specification for high-impact modified
uPVC extruded hollow profile
section, fabricated windows, and
uPVC-encapsulated unbonded
timber windows
2 Technical Schedules to
BS 5750:Part 1
TS/M/18 (1981) Hollow uPVC profiles for windows,
and window design
TS/M/19 (1981) Fabrication of uPVC-framed window
systems
3 UEA tcb
M.O.A.T. No. 17: 1981 Directive for the assessment of uPVC
windows
4 ASTM D 3678-86 Rigid PVC interior-profile extrusions
5 ASTM D 3679-86 Rigid PVC siding
6 ASTM D 4099-87 PVC prime windows
7 ASTM D 4216-87 Rigid PVC and related plastic building
products compounds
8 ASTM D 4477-85 Rigid PVC soffit
9 ASTM D 4495-85 Impact resistance of PVC rigid profiles
by means of a falling weight
10 ASTM D 4726-87 White rigid PVC exterior-profile
extrusions used for assembled
windows and doors
11 RAe-RG 716/1
Appendix 5 Plastics windows-Quality control
12 DIN 16941 (1986) Extruded profiles of thermoplastics
materials-Tolerances (for linear
dimensions, and geometrical)
13 DIN 53419 (1977) Extruded uPVC profiles-Test of
behaviour against methylene
chloride
14 NEN 7034 (1987) uPVC profiles for window and door
frames
15 41-GP-19 Ma:1978 Rigid vinyl extrusions for windows
and doors
• British Plastics Federation and Glass Glazing Federation Trade standard.

bUnion Europeenne pour l'Agrement Technique dans la Construction (Euro-
pean Union of Agrement).
C Reichsausschuss rur Lieferbedingungen (Committee for Delivery Terms and
Quality Control), Frankfurt, FRG.

overheating in processing promotes degradation on weathering. In-

complete gelation can be another cause of premature deterioriation in
service. Shrinkage or surface distortion can occur-in consequence of
recovery of production-induced stresses-at elevated temperatures
resulting from solar heating. The resultant characteristic surface
rippling and bulging, occasionally observed on siding, is sometimes
called 'oil canning': uPVC materials with high enough heat distortion
temperatures (say about 87°C or higher) are less prone to this effect.
The stress 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 contemplated. 16
12.2.3 Sheeting and Filin
(a) Terminology
Plastics sheeting and films are familiar to virtually everybody in
present-day Western society. It is, therefore, somewhat surprising that
the formal definitions of the two products in the latest issues of two of
the three relevant English-language standards of plastics terminology
(ISO and BS 17 ,18) make no clear distinction between them. General
usage in the plastics and packaging industries, and in the technical
literature, is no more precise in this respect. The fact that some
plastics films for certain applications are sometimes also referred to as
'foils' (a term now dropped altogether from the most recent issues of
plastics terminology standards, and not really well-defined in the
earlier ones 15) hardly contributes to terminological clarity. The one
general point recognised by all who deal with these products is that a
sheet is thicker than a film, so that the sequence (in ascending order of
thickness) film--thin sheet--sheet is universally applicable.
Note: The ASTM standard19 is the only one of the major three to
quantify the distinction between sheeting and film, defining
the latter as ' ... in plastics, an optional term for sheeting
having a nominal thickness not greater than o· 25 mm
(0·01 in)', whilst the cardinal part of this standard's definition
of sheeting is 'a form of plastic in which the thickness is very
small in proportion to length and width ... ', sheet being
defined as 'an individual piece of sheeting'. The very small
thickness of sheeting and film in relation to the length and
width is the principal feature of the definitions of these terms

also in the other two main standards.
It may be recalled that an attempt to define 'film', 'foil' and 'sheet' was
made by Levinstein20 as early as 1930, i.e. in the days when plastics
films in predominant use were solvent-cast nitrocellulose and cellulose
acetate ones, and the thicker sheets were commonly produced by
slicing from a block of polymer. Levinstein's proposal is schematically
represented by A in Fig. 12.1. However, as pointed out by Yarsley &
Flavell in 1956,21 neither in Levinstein's time nor in theirs could this
terminology be readily systematised, both because of rather confused
usage in industry and in view of such complicating factors as the
emergence of new materials, new methods of production, and new
applications of film and sheeting. The position is still not clarified
today, although industrial usage (as distinct from the somewhat vague
formal definitions) is in many cases roughly in line with the schematic
representation B in Fig. 12.1, at least with regard to PVC sheet and
film products.
Note: It may be noted additionally that, whereas standard defini-

tions generally place the thickness of metal foils below
Foil Film Sheet

----- A
25~m 50~m 375~m
IO.OOlin) IO.OO2in) IO.015in)
Sheet
------ B
------- Film
75~m
Foil .
750~m
(O.OO3in)* (O.030in)
Film Sheet
------- ------ C
250~m
IO.010in)
Fig. 12.1 Schematic representation of some thickness-based definitions of

film, sheet, and foil. A, Levinstein20 (1930); B, current industrial usage for
PVC products in some contexts Ref. 15, pp. 890, 901_2;15 C, ASTMD
883-86b.
* The 1967 version (now superseded; ct. Ref. 17) of BS 1755:Part 1 put the
thickness demarcation point between PVC film (unsupported) and sheeting at
0·003 in (76Ilm). It also listed 'foil' as a (discouraged) synonym for 'film'.
12 PVC Products and Production MethodY 483
0·13 mm (sometimes 0·15 mm),15 in the plastics and packag-

ing industries the thickness range for PVC 'foils' (as used for
thermoforming into insert trays or blister packs, for example)
is sometimes quoted, or implied, to be about 0·1-0·7 mm (cf.
Fig. 12.1, B).
(b) Production Types

PVC sheeting, and what-depending on terminological preferences-
may also be called thick films, are produced by calendering or
extrusion. Films (thin films) are made by the extrusion-blowing
technique. These production processes are discussed in Chapters 14
and 13, respectively. Some solution-cast films are also produced, for
applications where high clarity and/or freedom from molecular orien-
tation are important (see Chapter 19). PVC sheets with special
decorative surface effects, sheets for laboratory tests, and thick sheets
for use as panels (sometimes to be thermoformed) are made by
compression moulding (see Chapter 17, Sections 17.1 and 17.2).
(c) Some Formulation Aspects

There are a great many formulations for uPVC film and sheeting,
varying among themselves according to the nature, production method
and end-use of the product. Some basic formulations are given, by way
of example, in Chapters 2 and 14.
Use is made of some vinyl chloride copolymers in uPVC film and
sheeting for packaging applications, e.g. VC/V AC copolymers in
some thermoformable sheet compositions, VC/propylene copolymers
in films for food wrapping (especially for fresh meat) and in overwrap
films for cigarette packets, VC/VDC copolymers in low-permeability
films. Laminated sheets of polyvinyl fluoride and PVC have been used
in the production of vacuum-formed containers required to have
superior barrier properties and stability. 22
(d) Properties and Applications

Rigid PVC films and thin sheeting find their principal outlets in various
areas of packaging. Some important uses are: skin and blister (bubble)
packs; thermoformed packaging elements, e.g. tubs and lids for foods,
support containers (sectional nesting trays for chocolates, confec-
tionery, medical articles, etc.; video cassettes; press-through pill
packs; cold-formable laminates with aluminium foil. Shrink-on sleeves
and labels, and shrink-wrap film and sheeting represent a substantial
application sector: these PVC elements are stretched in production, so

that they can be made to retract on moderate heating after application
to the object to be shrink-wrapped (which thereby becomes encased in
a tight wrapping). Some typical property data for one kind of
commercial PVC film for shrink-sleeve labels and bottle tops are given
in Table 12.4.
Thicker rigid sheet is used in the production of panels of various
kinds, including thermoformed panels for walls. The main service
performance requirements applicable to external cladding panels are
analogous to those for extruded siding profiles and window frames,
and thus include resistance to weathering and impact as important
features. Similar formulating approaches are used, with acrylic and
chlorinated polyethylene modifiers popular in formulations.
As with extruded siding, some aspects of the stability in service of
external cladding panels are related to the effects of processing.
The best-known standards for uPVC films and sheeting are listed in
Table 12.5.
TABLE 12.4
Some Properties of a Quality Commercial Filma for the Production of
Shrink-Sleeve Labels and Shrink-on Tops for Bottles
Properties and units Test method Numerical values
Density, gcm- 3 ASTM D 1505-67 1·38

Thickness, /-1m Direct measurement 40 or 75
Weight per area, g m- 2 Direct weighing
40/-lm film 55·2
75 /-1m film 103·5
Tensile properties (40 /-1m film): DIN 53455
Strength (ultimate), N mm- 2
Longitudinal 6Oapprox.
Transverse 1l0approx.
Elongation at break, %
Longitudinal 180approx.
Transverse 75 approx.
Shrink capacity, % 15 min immersion in
water at 95°C
Longitudinal 6 max.
Transverse 50approx.
Temperature for commencement of Direct determination 6Oapprox.
shrinkage, °C
a Genotherm GZ 44 (Kalle, Film Division of Hoechst, FRG).

TABLE 12.5
Standards Relevant to uPVC Films and Sheeting, and Plastics Films and
Sheeting GeneraUy

no.
official title)
1 ISO 1352-1973 Plastics-Determination of electrical

properties of thin sheet and film o
2 BS 3757:1978 Rigid PVC sheet
BS4203 Extruded rigid PVC corrugated sheeting
3 Part 1:1980 (1987) Performance requirements
4 Part 2:1980 (1987) Profiles and dimensions
BS 3887 Pressure-sensitive tapes for packaging
5 Part 1:1984 Specification for polypropylene,
regenerated cellulose and uPVC tapes
6 ASTM D 1927-81 Rigid PVC plastic sheet
7 ASTM D 2123-81 Rigid poly( vinyl chloride-vinyl acetate)
plastic sheet
8 DIN 16927 Rigid PVC sheets-Technical delivery
specification
(Draft-1987) Note: The new draft combines the
former Parts 1 and 2 of the previous
(1977) issue of this specification
9 DIN 16929 (1965) Tubes and sheets of rigid PVC-
Resistance to chemicals. No longer
current
10 US Commercial
Standard CS 201-55 Rigid PVC sheets
DIN specifications for testing plastics films and sheeting
11 DIN 53353 (1971) Tear test
12 DIN 53365 (1974) Mass per unit area
13 DIN 53366 (1983) Blocking test
14 DIN 53369 (1976) Shrinking stress
15 DIN 53370 (1976) Thickness
16 DIN 53375 (1986) Coefficients of friction
17 DIN 53377 (1969) Dimensional stability
18 DIN 53378 (1965) Colour-fastness to hydrogen sulphide
19 DIN 53380 (1969) Gas transmission rate
20 DIN 53488 (1963) Hole test
oWithdrawal under consideration (in 1988) in view of the publication of IEC

Document 674-2.
12.2.4 Blow Mouldings
These are predominantly containers of various sorts. All aspects of

uPVC blow mouldings are discussed in Chapter 15.
12.2.S Injection Mouldings
Pipe fittings account for a substantial part of the uPVC injection

mouldings produced. Other products, formulations, and various re-
levant aspects of injection mouldings are mentioned or discussed in
several chapters of this book: see especially Chapters 2 [Sections
2.2.6(f) and (g)), 3 (Tables 3.9 and 3.11), 10 (Tables 10.2, 10.3 and
10.8), and 16 (Sections 16.2.2, 16.3.4 and 16.4, and Table 16.2).
In addition to comments on this subject in Chapter 16, it may be
mentioned that 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 &
Gooding23 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.
12.2.6 Gramophone Records
These are discussed in Section 17.1.2 of Chapter 17.
12.3 PLASTICISED PVC PRODUCTS

12.3.1 Electric Cable and Wire Coverings
(a) Types and Applications

Plasticised PVC compositions-applied by extrusion coating-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 rework and
reclaimed material are employed as filling core for composite cables.
pPVC has maintained its 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 electrical break-
down resistance (important in high-voltage applications).
Although the flammability of appropriately formulated PVC cable
coverings is low, and smoke emission can also be considerably reduced
by suitable formulation, concern has been growing in recent years
about the effects of hydrogen chloride-very harmful to the human
respiratory tract and corrosive to metals-which is generated in
quantity when the coverings are involved, and burn, in fires. This
concern has inspired further improvements in PVC compositions with
reduced smoke emission. However, formulating for such improve-
ments normally involves some reduction in the mechanical properties
(and not infrequently also in the electrical properties) of the composi-
tion, with a limit beyond which these penalties become unacceptable.
As a result, other kinds of cable coverings-albeit by no means free of
their own particular limitations (especially in regard to flammability}-
have made some inroads into this application that was hitherto
dominated by pPVC compositions. Materials based on polyurethanes
and E/VAC copolymers (usually fairly heavily filled with flame
retardants and smoke suppressants) have been introduced for some
applications, with emphasis on the fact that they do not contain
halogens, and thus cannot generate hydrogen halide gases and fumes
on burning. Some material combinations have also appeared: for
example, a new kind of cable sheathing for use in naval vessels,
claimed to give a better balance between flammability and the
emission of smoke and toxic gases than the PVC compositions used
hitherto. This sheathing (Zero-hal; Raychem) consists of a cross-
linked polyolefin, surrounded by a thin layer of polyvinylidene fluoride
(less flammable than PVC, but not halogen-free) with a synthetic
elastomer filled with alumina trihydrate (cf. Section 9.2 of Chapter 9).
Some applications of cross-linked PVC wire insulation are men-
tioned in Section 22.4.2 of Chapter 22.
Examples of some basic formulations for cable-covering compounds
are given in Table 12.6 [see also Chapter 2, Section 2.2.6(e)).
(b) Properties and Tests

Cable compounds are rated according to the conductor temperature to
be withstood in continuous service, inter alia, but resistance to still
higher temperatures which may be experienced sporadically (e.g. heat
~
TABLE 12.6
Some Basic Fonnulations for Cable Coverings (pbr)
Cable covering, Insulation, Insulation Sheathing

gen. purpose hard (filled) high temp high temp ""1::1
~
PVC polymer, suspension or mass (K value 65) 100 100 100 100 ""1::1
Maina stabiliser: Fr
~.
Tribasic lead sulphate 5·5 7 6
Basic lead carbonate 6 ~
Stabiliser/lubricants: ~
~
Dibasic lead stearate 3
Calcium stearate 0·5 0·7 0·7 1
'"~
'"~.
Lubricants:
Stearic acid 0·3 0·3 ~
Paraffin wax 0·3 "~
Antioxidant: Hindered phenol type 0·5 '"
~.
Plasticisers
DOP 40 36 ::s
'"""-
DUDP 54 ).
DTDP 74 ~
Filler: fine ground calcium carbonate, coated grade ~
(e.g. Omya BSH) 10 20 15 g"
Flame retardant: antimony oxide 6 i:l
Colourant (pigment) As required
• For illustration purposes the components of the stabiliser /lubricant system are set out separately. In practice an
equivalent proprietary single-pack system would normally be used.
shock resulting from a short-circuit) is also assessed by tests: d. for

example the heat-shock test of BS 6746 (at 150°C), and thermal
stability test of DIN VDE 0271. The same specifications also contain
tests for resistance to heat-ageing (as well as for the determination of
low-temperature properties).
In most cases, the continuous-service temperature limits, which the
various relevant formulations are designed to meet, range from 60°C
(for general-purpose compounds) to 105°C for special high-
temperature compounds. Susceptibility to damage by hot objects or
materials (Le. soldering irons, hot oil splashes) is also a consideration
for some applications.
Standards of particularly direct relevance to PVC cable coverings
are listed in Table 12.7.
Collections of specifications and test standards for plastics cable
coverings (including PVC) are contained in the following publications:
BS 2782 Part 2; Book of ASTM Standards, Volumes 10.01 and 10.02;
DIN VDE 0281, Parts 102, 104 (both still in draft form), 403 and 404;
and DIN Handbook 18.
Examples of some electrical properties of PVC compositions re-
levant to their use as cable coverings are given in Appendix 1.
12.3.2 Sheeting and Film
Plasticised film, sheeting and thick sheets are produced by the same
methods as their rigid counterparts.
Films and thin sheeting find applications in the packaging industry,
food-wrapping being a major outlet. An example of a popular product
in this line is PVC cling film, whose DOA content (normally about
15%) featured in the relatively recent health-hazard scare in connec-
tion with the possibility of migration of this plasticiser into foods,
especially fatty ones (e.g. cheese, ham), and its allegedly possible
carcinogenic effects on ingestion.
Note: DOP has also been put under suspicion in food-contact (as
well as medical) applications, but British-manufactured cling
film does not normally contain this plasticiser.
Although there were some plausible data to show that some
migration does take place, there was no direct evidence of any kind
that, in the amounts involved, DOA is carcinogenic in man, or poses
any other health hazard [see also Chapter 1, Section 1.3.2(b), and
TABLE 12.7
Standards Closely Concerned with the Material Properties of PVC Cable
Coverings

no.
official title)
1 IEC Publication 189 Low-frequency cables and wires with PVC
Part 1"-1986 insulation and sheath-General tests and
measuring methods
2 IEC Publication 216 Guide for the determination of thermal
Part 1-1987 endurance properties of electrical
insulating materials
General guidelines for ageing procedures
and evaluation of test results
3 IEC Publication Extruded solid-dielectric-insulated power
502-1983 cables for rated voltages 1-30 kV
4 BS 6469:1984 Methods of test for insulation and sheaths
of electric cables
5 BS 6746:1984 Specification for PVC insulation and
sheath of electric cables
6 ASTM D 1047-83 Specification for PVC jacket for wire and
cable
7 ASTM D 2219-81 Specification for PVC insulation for wire
and cable, 60°C rating
8 ASTM D 2220-80 Specification for PVC insulation for wire
and cable, 75°C rating
9 ASTM D 2405-81} Specifications for acrylonitrile-
10 ASTM D 2432-81 butadiene/PVC jackets for wire and
11 ASTM D 2708-81 cable (respectively general-purpose,
heavy-duty and extra-heavy-duty)
12 ASTM D 2633-82 Methods of testing thermoplastic insulation
and jackets for wire and cable
13 DIN VDE 0271 (1986) PVC-insulated cables with nominal
voltages up to and including 6/10 kV
14 DINVDE0281 PVC-covered cables (various kinds) (N.B.
Parts 102, 104, Some parts under revision since 1987)
403,404
a Other Parts (2-7) also relevant.

Chapter 5, Section 5.7]. The scare was eventually laid to rest, but not
before considerable damage had been done to the demand for PVC
cling film, in favour of polyethylene film alternatives, some of which
(e.g. the special LLDPE versions such as Purecling-DRG Plastics,
UK) claim to be fully effective functional replacements.
Substitution of part of the liquid plasticiser(s) in PVC film for food
wrapping with an elastomeric modifier (e.g. Chemigum PFC; Good-
year) can improve the relevant physical properties (toughness, resis-
tance to tear and puncture) and reduce any risk of plasticiser
migration; d. e.g. the Superstretch film (Protoplast AG, Switzerland).
Another notable use of pPVC film and thin sheeting is in stretch-
wrapping, where it competes with EIVAC and LLDPE: the Du Pont
Paklar polyolefin film in particular has been claimed to provide a fully
equivalent alternative. A useful brief review of stretch-wrapping (with
special reference to its comparison with shrink-wrapping and to the
properties of the films used) has been published by Johnson &
Langford. 24
A substantial application of PVC film and thin sheeting is repre-
sented by adhesive tapes (e.g. for electrical insulation, and for medical
use) and self-adhesive decorative surface coverings.
Other products typically made from pPVC sheeting include shower
curtains, * table covers, some types of rainwear and inflatables;
mattress covers for general use (camping, hostels) and medical
applications (e.g. water-beds used for patients suffering from burns or
bed sores; clear bags for enclosing wounded limbs-d. for instance
Sterishield bags; UK Department of Heath and Social Security).
Medium-thickness sheeting is used as a lining for water reservoirs,
effluent lagoons and other large-scale seepage-barrier applications,
swimming pool linings, and damp-proof coursing. *
Products fabricated from thick sheets include: safety swing doors
(transparent and opaque) for factory and storage premises (typical
sheet thicknesses about 5 mm or over); suspended-strip curtain doors
for air-conditioned premises, cold rooms, and the like (typical strip
thickness and width, respectively, about 4 mm and 200-300 mm).
Standards relevant to the nature and applications of pPVC film and
sheeting are listed in Table 12.8.
* Formulations for products serving in moist or wet conditions normally

incorporate biostat additives.
TABLE 12.8
Standards Relevant to pPVC Films and Sheeting
no.
official title)
1 ISO 6453-1985 Flexible PVC foam sheeting

2 BS 1763:1975 Thin PVC sheeting (calendered, flexible,
unsupported)
3 BS 2739:1975 Thick PVC sheeting (calendered,
flexible, unsupported)
BS 2782:Part 6
4 Method 641 A:1983 Determination of dimensional stability
at 100°C of flexible PVC sheet
5 Method 643 A:1983 Shrinkage on heating of film intended
for shrink-wrapping applications
6 BS 3872:1982 Flexible PVC sheeting for hospital use
BS3887 Pressure-sensitive tapes for packaging
7 Part 2:1985 Specification for pPVC tapes (inter alia)
8 ASTM D 1239-55 (1982) Test for resistance of plastic films to
extraction by chemicals
9 ASTM D 1593-81 Specification for non-rigid vinyl chloride
plastic sheeting
10 ASTM D 1893-67 (1985) Test for blocking of plastic film
11 ASTM D 2301-84 Specification for pressure-sensitive PVC
electrical insulating tape
12 ASTM D 3005-84 Specification for low-temperature-
resistant PVC pressure-sensitive
electrical insulating tape
13 ASTM D 3083-76 (1980) Flexible PVC sheeting for pond, canal
and reservoir lining
14 ASTM D 3354-74 (1979) Test for blocking load of plastic film
(parallel-plate method)
15 ASTM D 4551-86b Flexible PVC concealed water-
containment membrane
16 DIN 16937 (1986) Plasticised PVC waterproofing sheets
(bitumen-compatible)
17 DIN 16938 (1986) Plasticised PVC waterproofing sheets
(not compatible with bitumen)
18 DIN 53372 (1970) Determination of break at low
temperature of non-rigid PVC films
12.3.3 Flooring
Unsupported PVC flooring consists of thick, filled sheeting, tradition-

ally produced by calendering. It is discussed in Chapter 14.
Flooring produced by coating a continuous support (fabric, paper)
with PVC is, technically, a coated product. Coating operations are
12.3.4 Tubing and Profiles
Both of these products are made by extrusion or-in the case of some
tubing-modified extrusion processes.
The use of extruded (usually double-walled) flexible PVC tubing
as garden hose is widespread.
Heavy-duty versions, reinforced with polyester or nylon braid and
overcoated with another pPVC layer formulated for abrasion resis-
tance, 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 (e.g. Heliflex; A.
G. Petzetakis, Greece) is used as a conduit in many applications.
Versatile ribbed flexible tubing is produced, on special machinery
(developed by CMI International, USA),25 by helically winding an
extruded pPVC strip on a mandrel and side-welding together the
contacting coils of the resulting helix, to form a continuous tube wall.
The tube's applicational versatility is increased by the scope for
variation of the parent strip: this can be of various cross-sectional
shapes, solid or hollow, and may encapsulate an electrical conductor
(for example if the hose is to be current-carrying when used in vacuum
cleaners with powered heads).
Transparent flexible tubing is used in laboratory and plant applica-
tions, for beverage conveyance (food-grade tubing), and in various
medical applications. Examples of tubing for medical use include
drainage, infusion and endotracheal tubing, tubes in blood collection
and transfusion sets, and internally divided (bi- and multi-lumen)
tubing produced on special extrusion lines (e.g. the Model 116 Betol
line-Betol Machinery Ltd, UK; lines from Wayne Machine & Die
Co., USA). All components for medical tubing formulations must be
non-toxic, non-carcinogenic, and of suitable purity; the compositions
are also often required to be stable to sterilisation by gamma
irradiation, and some have to be opaque to X-rays, so that-when

used for example as catheters-they can be traced on X-ray photo-
graphs after insertion into the body.
pPVC shrink tubing represents another interesting application. The
tubing is used for a number of purposes: as protective coverings
(against corrosion or abrasion), handle material on some equipment,
electrical insulation, connecting sleeving and the like. There are two
general kinds of shrink tubing: one is shrinkable by heating, and the
other by simple drying in air. In both cases the tubing is supplied in
expanded form, to be applied to (drawn over) the item to be covered,
and shrunk onto it to provide a tightly gripping covering. The
heat-shrinkable tubing is made by in-line expansion of extruded tubing
followed by immediate rapid cooling to 'freeze' it in the expanded
form.
When subsequently reheated on application (typically at 140-
160°C)-with a hot air blower, by a radiant heater, or in a heating
oven or tunnel-the tubing retracts to the original, as-extruded
diameter. If the tubing is stored after production for several months,
especially in warm conditions, some relaxation may occur, reducing
the 'strain memory' and hence the ultimate shrinkage capacity. A
commercial example of heat-shrinkable tubing is Vinloc FPVC (Shrink
Tubes and Plastics, Ltd* UK). Tubing shrinkable by simple air-drying
is supplied in a 'wet' state, i.e. expanded by absorption of a swelling
agent sufficiently volatile to evaporate within a reasonable time when
the tube is exposed to air at ordinary temperatures. One advantage of
this system is that-as no heating is necessary to bring about
shrinkage-application to heat-sensitive objects presents no difficulty,
and the tubing can be used where no heating facilities are available.
Commercial tubing of this kind is exemplified by Airshrink (Airshrink
Products, RSA and Australia) and No-Heat (Insulation Systems Inc.,
USA). Products other than tubing, e.g. tape, caps, are also available
under these trade names.
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, draught
* Now Canussa.
excluders and the like, as well as application in vehicle fittings (seat

welting; decorative and protective trim strips).
Standard specifications relevant to pPVC tubing and profiles are
listed in Table 12.9.
12.3.5 Fabric Coatings
These are discussed in Chapters 14 (laminated coatings) and 18

(spread and transfer coatings).
TABLE 12.9
Standards Relevant to pPVC Tubing and Profiles

no.
official title)
1 BS 1882:1976 Specification for flexible polymeric
tubing and drainage sheeting (radio-
opaque) for medical use. Withdrawn
in 1986
2 BS 2848:1973 Specification for flexible insulating
sleeving for electrical purposes
3 BS 3746:1964 (1983) PVC garden hose
BS4607 Non-metallic conduits and fittings for
electrical installations
4 Part 3:1971 (1985) Pliable, corrugated, plain and reinforced
conduits of self-extinguishing plastics
materials
5 ASTM D 867-84 Non-rigid PVC tubing for electrical
insulation
6 ASTM D 922-84 Non-rigid PVC tubing
7 ASTM D 3150-85 Specification for cross-linked and non-
cross-linked PVC shrinkable tubing
for electrical insulation
8 DIN 16940 (1964) Extruded hoses of non-rigid PVC,
permissible ~eviations for dimensions
9 DIN 16941 (1986) Extruded profiles of thermoplastics
materials-Dimensional tolerances
10 DIN 16942 (1966) Water-hoses of non-rigid PVC-
Dimensions
REFERENCES
1. Anon., ISO Handbook 28, Vol. 2. Pipes, Fittings and Valves: Plastics
Products.
2. Anon., Book of ASTM Standards, Vol. 08.04. Plastic Pipe and Building
Products.
3. (a) Anon., DIN Handbook 52: Plastics 5. Standards on Thermoplastics
Pipes, Fittings and Pipe Joints. (b) Anon., DIN Handbook 190: Plastics 6.
Standards on Thermoplastics Pipe Components. Application Standards.
4. Wolf, J., Gas, 87 (Nov. 1967),433.
5. Wolters, M., Plast. Rubb. Process. Applns, 3(4) (1983) 323-30.
6. Benjamin, P., Plast. Rubb. Int., 4(5) (1979) 269-73.
7. (a) ASTM F 800-84. Corrugated Poly(vinyl chloride) Tubing and Com-
patible Fittings. (b) ASTM F 949-86a. Poly(vinyl chloride) (PVC) Corru-
gated Sewer Pipe with a Smooth Interior and Fittings.
9. Zechinati, J., Harvey, B. & Despain, C. R., 36th ANTEC SPE
Proceedings, 1978, pp. 740-4.
10. Marshall, G. P. & Birch, M. W., Plast. Rubb. Process. Applns, 2(4)
(1982) 369-79.
11. Moore, D. R., Prediger, R. & Stephenson, R. C., Plast. Rubb. Process.
Applns, 5(4) (1985) 335-41.
12. Hucks, R. T., Jr, AWWA J., (July 1981) 384-6.
13. Janson, L. A. & Valimaa, P., Pipes Pipelines Int., (Jan./Feb. 1973).
14. Gaube, E., Diedrich, G. & Miiller, W., Kunststojfe, 66(1) (1976) 2-8.
15. Titow, W. V., PVC Technology 4th edn. Elsevier Applied Science
16. Changfoot, J., Dickson, A. G., Noel, F. & Stark, W. M., 34th ANTEC
SPE Proceedings, 1976,42-4.
18. BS 1755:Part 1:1982. Terms Used in the Plastics Industry-Polymer and
Plastics Technology.
19. ASTM D 883-86b. Standard Definitions of Terms Relating to Plastics.
20. Levinstein, H., J. Soc. Chern. Ind., 49 (1930) 53T.
21. Yarsley, V. E. & Flavell, W., Cellulose Plastics, Part 1. Monograph No.
C6, Plastics Institute, London, 1956.
22. Briston, J., Packaging Rev., 96(3) (1976) 71-4.
23. Copsey, C. J. & Gooding, V. J., 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 Perfor-
mance of Polymers, University of Nottingham, July 1977.
24. Johnson, F. M. & Langford, A. J., Plast. Rubb. Int., 7(6) (1982) 217-20.
25. Anon., Mod. Plast. Int .., 18(9) (1988) 36.
CHAPTER 13
Extrusion
13.1 HISTORY AND SIGNIFICANCE OF EXTRUSION

IN PVC PROCESSING
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 (L/ D) 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), or 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.
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 been 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-1950s-
and 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 11).
Apart from the role of extruders in the compounding of PVC
compositions (see Chapters 11 and 14), 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.
497
The main PVC products manufactured by extrusion are discussed in

Chapter 12, and in later sections of the present chapter.
The production capacity of extrusion machinery-which increased
by a factor of 3-4 between the late 1950s and 19801-has continued to
rise through the 1980s, mainly as a result of developments in screw
design, in downstream equipment (especially that for cooling and
sizing), and in general process control, although such factors as
improvements in die design, compound formulation and-in some
cases-new developments in the physical form of feedstock, have also
played their part. Whereas around 1980 a typical maximum figure for
the production capacity of a modern twin-screw extruder line for PVC
pipe would have been about 800 lb h - \ 2 the corresponding figure in
1986 would be 1000-1400 lb h- 1 depending on compound formulation
and the calibration method employed. 3
13.2 EXTRUDERS USED IN PVC PROCESSING
13.2.1 General
In the context of the present chapter, 'processing' means extrusion of

PVC to form products. Extrusion processing in the making of PVC
compounds is dealt with in Chapter 11. The extruders used in the
processing of PVC into products are either twin-screw or single-screw
machines. The twin-screw extruders for such processing commonly
have counter-rotating, intermeshing screws, straight or conical (taper-
ing); some screw configurations feature partly intermeshing or non-
intermeshing sections. With both twin-screw and single-screw ex-
truders, screw design is a cardinal factor in the output rate and product
quality, and substantial progress has been made in this area over the
past few years.
The use of single-screw extruders for rigid PVC compositions is less
widespread in Europe than in the USA, although in recent years the
balance there has also shifted in favour of the twin-screw machine for
such products as pipes and siding. Profiles are still at present mainly
produced on single-screw extruders, in America, where such extruders
also continue to be predominantly used by small processors.
The downstream equipment of a PVC extrusion line must be
capable of handling the extruder output. In the extrusion of the
13 Extrusion 499
large-production-volume uPVC products which require sizing (pipes,

profiles), the sizing and cooling equipment plays a crucial role in this
regard. For pipes, especially with larger diameters, vacuum-tank
calibration (rather than pressure sizing) combined with water-spray
cooling, suitable haul-off and sufficiently fast cut-off equipment make
for the highest production rates. Complete downstream handling
systems for pipe or profile extrusion operations are available, compris-
ing 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. Belling
equipment for the production of a shaped socket at one end of a
length of pipe (required for making joints) is an important auxiliary.
Partly or fully automated versions are available: some of the latter
may operate in-line with the extrusion train.
13.2.2 Basic Operational Features
(a) The Screw

Continuous progress is taking place in screw design for PVC process-
ing, two of the most important objectives being increased productivity
(by increasing output per revolution) and improved homogenising
action. The screw designs involve 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 extruder. Other factors
being equal, the LID ratio of the screw plays an important role in
processing capacity, and influences the amount of heat generated as
well as heat transfer in the system screw /materiallbarrei. Strictly
defined, the L/ D ratio is the ratio (conventionally expressed in
relation to unity) 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 that
of the barrel bore).
L/ D ratios of screws in modem 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 prac-
ticable, 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). PVC processing screws should have a built-in
cooling facility.
(b) The Barrel

Venting of the barrel, standard in modem PVC extrusion, is particu-
larly important with powder feed, because of the low bulk density
(high air content) of the powder. A 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), and where
the stock may fill the screw flights incompletely, to ensure that it is not
extruded through the vent. Two venting ports spaced along the barrel
are provided in some cases.
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 incor-
poration 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 ex-
truders, 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 diameter-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.
PVC, and especially uPVC, is susceptible to thermal degradation,
and its 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
13 Extrusion 501
and gelation to be imparted under less drastic conditions of tempera-

ture 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 expression4 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):
QexD 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 0·8 for uPVC and 0·6 for
pPVC. 4 Since if vex D n then hex Dn , it follows that the output per
revolution of the screw is proportional to D2+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 fric-
tional effects on the material.
(c) The Head and Die Assembly

Most dies 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 (see Fig. 13.1), down to small dies for
profiles of simple, small cross-section. Dies for use with rigid PVC
must have 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 90° 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
Fig. 13.1 Large pipe die on a Reifenhauser extruder. Courtesy of A.

Reifenhauser Ltd.
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 die aperture). On flat-sheet dies,
the lips are normally adjustable. In microprocessor-controlled extru-
sion lines, the adjustments are made automatically on signal from
on-line production control devices.
(d) The Hopper

The feedstock may be dropped directly into the hopper and thence
into the feed throat of the extruder barrel, but is more often
introduced via a vibratory delivery chute, or a pneumatic, vacuum, or
screw-type metering device, to ensure a constant rate of feed. Feeds
may also be completely automated, the feedstock being 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 on PVC extrusion
lines. These devices raise the temperature of the material, so that the
extruder's work in producing a melt is reduced: the resulting ad-
vantages claimed include increased extruder output (by up to 50%),
and reduced wear on screw, barrel and gears, as well as maintenance
of constant feed temperature irrespective of ambient conditions.
13 Extrusion 503
(e) Main Operating Characteristics of Single-Screw and Twin-Screw

Extruders for pvc Processing
These two types of extruder differ substantially in the mode of
movement of the stock forward inside the barrel. 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: 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. Single-screw extruders are dependent for
stock mixing action on the development of substantial back-pressures.
The principal advantages of a single-screw extruder in comparison
with a twin-screw machine are economic: lower equipment capital
cost; lower maintenance costs; on the average, shorter down-time for
repairs; and lower rate of wear of screw, barrel and gearbox. The
theory of design and operation is also better developed for single-
screw machines.
An operational limitation is that the processing of uPVC on
single-screw extruders with screw diameters greater than about 4 cm
degradation can be a real risk (due to occurrence of unstable flow
patterns), unless extra stabiliser is used in the formulation, whereby
material cost is increased. Some special screw designs are claimed to
overcome this limitation (e~g. the 'Dray Concept' screw;5 Dray
Manufacturing Inc., USA).
The comparative advantages of a twin-screw extruder may be listed
as follows:
Features stemming from the positive pumping action: (i) Generally

lower melt temperature; (ii) more uniform melt flow (but cf. also gear
pumps in Section 13.3 below); (iii) less scope for product variations.
Features consequent upon the generally lower melt temperature in

processing: (iv) higher outputs with less risk of degradation; (v)
possibility of using cheaper formulations (less expensive stabilisation).
Other features: (vi) better stock temperature control; (vii) better

mixing action and removal of entrapped air (hence greater suitability
for processing bulky powder feeds); (viii) insensitivity to the cross-
sectional area of die opening in operation.
Note: Some sophisticated screw designs in single-screw extruders

are claimed to put such extruders on a par with twin-screw
machines in some of the above respects. For example, the
'double wave' screw (HPM Corp., USA) is claimed to
operate effectively with stock temperatures significantly lower
than those typical for conventional single-screw extruders,
and to make the single-screw machine competitive with a
twin-screw one in the extrusion of pipe from dry blends. 6
Some design concepts of twin-screw extruders are discussed, in a

number of papers by Prause,7-9 with references to equipment pro-
duced by several manufacturers (in the late 1960s). Some experimental
work on twin-screw machines, and its theoretical interpretation, have
been published by Jewmenow et al.lO,U 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. 12 Three recent reference books on extruders and extrusion
have been published by Stevens,13 Rauwendaal,14 and Hensen,
Knappe & Potente. 15
13.3 SOME GENERAL POINTS RELEVANT TO

PVC EXTRUSION
13.3.1 Working Surfaces
The general points made in connection with the working surfaces of

injection-moulding equipment apply also here. Specifically with regard
to the working surfaces of extrusion machines, the following further
points may be noted.
The extruder barrel is internally lined, commonly with a nitro alloy
liner.
Screws are made of steel and surface-hardened (most commonly by
nitriding) for increased resistance to wear and some corrosion protec-
tion. For protection against corrosion in PVC processing, appropriate
chromium plating should be applied (multiple hard-chrome finish for
CPVC): hard-chroming will also confer some wear resistance. Other
means of increasing resistance to abrasive wear are nitrogen-ion
13 Extrusion 505
implantation16 and coating with special proprietary alloys, e.g. Z-Core

(Z-Core Inc., USA); or Ion Bond (Scientific Coatings, Inc., USA}-a
vapour-deposited titanium nitride coating claimed to offer a high
degree of protection against abrasion and acid corrosion (including
HCI from decomposing PVC).
Note: Nitrogen-ion implantation was originally developed in the
UK, at the AERE, Harwell, and has been commercially
operated for several years (by Ionic Plating Co., UK, and
Tech-Ni-Plant, UK: the process has also recently become
available in the USA and Japan.
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 & Maddy. 17
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 &
Csongor. 18 These authors point out, inter alia, that hard facings
(applied by various welding methods) of cobalt-chromium-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 conventionally hardened steels)
combined with high resistance to corrosion, particularly by hydrogen
chloride. Such facings can be applied in relatively thick layers resistant
in service to penetration and undermining. 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.
13.3.2 Use of 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 in man-made fibre spinning (a form of
extrusion) since the early days of cellulose acetate fibre production 19
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 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,20 of extrusion of a uPVC precision profile in a 4·5-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 were caused by such an increase.
Gear pumps can benefit extrusion of sheet and blown film 2! as well as
profile and pipe.
Gear pumps are also used on twin-screw compounding extruders to
cut energy costs, as well as in lines for pipe extrusion, extrusion of
sheet for thermoforming, and blown film. Manufacturers of gear
pumps include MAAG Gear-Wheel Co. (Switzerland); Luwa Corp.
(USA)-the Polyrex and Therrnorez lines of pumps; Barmag (FRG);
Nichols Zenith Div. of Parker Hannifin Corp. (USA); and Slack &
Parr Ltd (UK).
13.3.3 Purging
Effective and rapid internal cleaning of extrusion equipment is

important for the reduction in machine down-time it can effect,
prevention of contamination of extrudates with any previously
scorched material, colour contamination between different batches,
and reduction of material waste. The general remarks on the purging
of injection-moulding machines in Sections 16.3.1(b) and 16.3.2(c) of
Chapter 16 are relevant also here. Specially developed commercial
purging compounds are available, suitable for both injection-moulding
and extrusion equipment. They include both special grades for use
with PVC (e.g. Rapid Purge-Rapid Purge Corp, USA; Chern
Purge-Engineering Chemicals BV, The Netherlands; Polyvin-A.
13 Extrusion 507
Schulman Inc., USA; Polypurge V-Hitech Polymers Inc., USA) and

general-purpose compounds intended for a wide range of plastics [but,
in some cases, graded for particular kinds of extrusion lines, e.g. Dyna
Purge PG (Shuman Plastics, USA) for cleaning film and sheet
extruders]. A liquid cleaning agent is also available for adding (at
2-5%) to the polymer being processed to make a purging batch
(Novoclean; Novosystems GmbH, FRG). Some purging agents of
American origin, available in the 1980s, have been reviewed by
Brockschmidt. 22
13.3.4 Coextrusion
PVC is hardly ever used as a component of the coextruded multi-layer

films and blown containers which have made inroads into many
packaging applications. However, the occasional use is reported, as for
example in a composite ionomer/metal/polyester/PVC film for pack-
aging fresh products. 23
In the main, coextrusion of PVC compositions is confined to the
manufacture of such products as foam-cored profiles and pipes (the
solid outer layer being formed from a composition coextruded over the
foaming composition), certain kinds of siding (with the 'inner' side
which is not exposed in service extruded from a composition cheaper
than that for the outer side), some profiles and sheets 'capped' by
coextrusion with protective or decorative layers of acrylic polymers
or-in some cases--with highly pigmented PVC compositions.
13.3.5 Extrusion of CPVC
Among the important points to be borne in",mind in connection with

equipment requirements are the following. The extruder's barrel
temperature control zones (at least three, and preferably four) should
provide temperatures up to 235°C. The machine should be capable of
exerting high torque at low rates of screw revolution, and the rated
head-pressure should not be less than 52 MPa. It is beneficial to have a
tapering screw tip with a corresponding adaptor section in the extruder
head; screen packs or breaker plates should preferably not be used.
Dies should be highly streamlined, with narrow flow channels (to
maintain compression). The ratio of die land length to wall thickness
of extrudate should preferably be between 25: 1 and 30: 1. The
adaptor, spider and die land should have separate temperature

controls, and the mandrel should be cored for circulation of tempera-
ture control liquid. It is highly important that all working surfaces
should be resistant to acid corrosion.
13.3.6 Computerisation and Automation of Extrusion Lines
Developments have been proceeding in the following three general

areas
(i) Computer modelling of the extrusion process, and the strat-

egies of its automation.
(ii) Use of computer models and programs in the design of
extruder screws, dies and other parts.
(iii) Practical computerisation of extruder lines, including micropro-
cessor controls in automatic 'no break' systems to eliminate
power supply interruptions, thermal centering of pipe and
hollow profile wall thickness on fully automatic lines, wall
thickness adjustment, and automatic control of 'downstream'
operations. Automatic programmable controllers are now
offered with many extrusion lines, with memory capacities for a
number of products and their parameters.
13.4 MATERIAL ASPECTS
13.4.1 Formulations
Formulations for various extruded products are discussed in Chapter

12, and are also referred to elsewhere in the book.
13.4.2 Feed Types
Both powder and pellets are used as feedstocks in extrusion of PVc.

Their respective advantages, and considerations behind their use in
particular processes, are discussed in Sections 11.2.2(a) and (c) of
Chapter 11 (see also Table 11.3 in that chapter, and Tables 10.3 and
10.4 in Chapter 10).
13 Extrusion 509
13.4.3 Stock Transformations in the Course of Extrusion
A uPVC powder compound may be processed by extrusion for one or

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. Chapter 11, Section 11.2.2)-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.
There is a considerable body of evidence to support the view that
the conversion of polymer powder particles (Stage III particles of
suspension or mass PVC polymer; cf. Fig. 3.3 in Chapter 3) in the
course of extrusion to a homogeneous, fully fused melt (subsequently
solidified, on cooling, into the extrudate) proceeds via the progressive
breakdown of the particles, under the action of heat and shear (cf. e.g.
review discussion in Ref. 2). The mechanism of conversion envisaged
in this way has been termed the comminution mechanism. However,
according to another view, 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* proposed a very different
mechanism, involving not breakdown but compaction, densification,
fusion and elongation of the polymer grains, followed directly by
melting (the CDFE mechanism). More recently, Gilbert et al. have
* Cf. M. W. Allsopp in Manufacture and Processing of PVC, ed. R. H.

Burgess. Applied Science Publishers, 1982, Chapter 8.
claimed further decisive evidence for the CDFE mechanism in

extrusion. 24
Whatever the mechanism, the attainment of complete gelation (as
marked by the associated optimum mechanical properties) is as-
sociated with complete disappearance of powder (Stage III) particle
boundaries in the finished product, as well as complete, or near-
complete, merging of the primary (Stage II) particles, resulting in the
formation of a network of polymer chains (containing some crystalline
domains and intimately interdispersed additives). This condition can
only be achieved after shear processing at a sufficiently high tempera-
ture (in practice just short of that which would produce appreciable
degradation of the PVC polymer). Thus, in practical terms, the ideal
result aimed at in the extrusion (as also in other melt-processing) of
PVC is the achievement of complete gelation, coupled with the
absence of degraded polymer, voids, and external contaminants (i.e.
absence of any features which can act as stress concentrators).
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 of varying degrees of severity have
been the subject of much investigation by optical and electron
microscopy.25--32 On the basis of morphological features detectable by
such techniques, 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
number of molecular chains participating in 'ties' across a perceptible
inter-granule 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.
13 Extrusion 511
This low density of molecular ties is also the main factor in the lower
weathering resistance: photochemical disruption by incident UV light
of a comparatively small number of these can, because of their relative
scarcity, cause cracking at the inter-granule boundary under 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 resort is usually made to
more straightforward, direct determination of some property of the
product, influenced (like some of those just mentioned) by the degree
of completeness of fusion. Such determinations have the merit of
relative simplicity, and the property determined may also be directly
relevant to service requirements (e.g. to the hoop strength of extruded
pipe, which is sensitive to the completeness of gelation). However, 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 quantita-
tively relatable to one another. This is well brought out in the results
obtained in a study by Benjamin27 of the degree of gelation of an
extruded pipe of a relatively simple formulation. Benjamin's data are
reproduced in Table 13.1.
For practical purposes the completeness of gelation of extruded
products (pipe, profile) is usually assessed in terms of a solvent
immersion test [cf. Chapter 12, Section 12.2.1(c»), or a strength or
impact test.
Various methods of assessing the degree of gelation of PVC after
processing are briefly reviewed in a paper by Gilbert et al. 24
13.4.4 Some Extruded-Product Faults
(a) Manifestations of Incomplete Gelation

These can take various forms. Inadequate overall gelation (see
preceding section) 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, which-
if sufficiently pronounced-can be manifested as transverse undula-
tions (in more drastic cases, lines of transverse weakness) in the
TABLE 13.1
Degree of Gelation of a PVC Pipe as Reflected in its Various Properties
(Data of Benjamin.)
Gelation lever (%) 32 44 68 90

Property
Resistance to attack by Severe Light No No
methylene chlorideb attack attack attack attack
Homogeneity Inhomo- Some Homo- Homo-
of microtome sectionC geneous inhomo- gen- gene-
geneity eous eous
Tensile strength, 20°C
Yield, N mm- 2 54 55 56 56
Elongation at break, % 108 133 115 58
Tensile impact energyd
O°C Nmmmm- 2 381 706 711 656
20°C Nmmmm- 2 624 763 733 697
Resistance to stress
cracking: 20°C
Critical strain, Ee , % 0·8 1·5 5·1 3·6
a Determined by the rheological method.

b By the method of KIWA KE 49.
C Section (approximately 10 I'm thick) taken across the pipe wall.
d Determined by the falling-weight method of KIWA KE 49.

e Determined by the steel-ball indentation test of DIN 53449.
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 are fully suited to the pipe size being made
and the production rate.
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 decomposi-
tion of the polymer (or of an additive) due to excessive shear, or
incomplete gelation (because the material moves out of the barrel
before full gelation has been attained). Reduction of screw speed,
13 Extrusion 513
and-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 modem extrusion practice.
(b) 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 sheets).
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, 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 rework) 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.
(c) Variation or Fluctuation in Dimensions

These may arise from a number of causes, such as inadequate
extrusion die setting or adjustment, sizing die problems (with pipes or
hollow profiles), take-off irregularities, poor melt uniformity, and even
operator error.
(d) Plate-Out
The nature and origin of plate-out deposits on products and equipment
are discussed in Chapter 4 (Section 4.8.2).
13.5 BASIC EXTRUSION LINES FOR IMPORTANT

EXTRUDED PVC PRODUCTS
13.5.1 Rigid Pipe Extrusion
A simple, basic pipe extrusion line is shown schematically in Fig. 13.2,

and illustrated (in part) in Fig. 13.3. It should be noted that for
Ut
.....
.j>.
~"tI
r~.
....~
.g
~
::to
I I ~ .~
~~'VL§){ I "tI
(3
~~ ~ IM JUl»4,,,f=
Co ~
=
DISCHARGE SAW MARKING HAUL WATER DIE AND EXTRUDER
SIZING
"~
TABLE MACHINE OFF BATH
DEVICE ~.
Fig. 13.2 A simple, basic extrusion line for small-diameter uPVC pipe. Schematic representation. ~
~
I~.
13 Extrusion 515
Fig. 13.3 Pipe extrusion line and extruder detail.

large-diameter pipes a number of cooling tanks may be used, starting

with a combined sizing-cooling tank.
13.5.2 Profile
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 the
hollow multi-channel profiles of complex cross-section used for mod-
ern 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 equip-
ment. Whole lines, specially designed for window-frame profile, are
available from manufacturers of this type of machinery, incorporating
advanced control systems and cutters. 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, 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. 33
13.5.3 Sheeting and FUm

A basic sheet extrusion line, employing a cascade extruder, is shown
schematically in Fig. 13.4. The essential elements of a set-up of this
8 7 6 5 4 3 2
Jf
D ~
r---
I
~dJ ........
'"
'~~
=r -.... __~~o§ _Itfl ~
~ . 1-- ~
g'
1 Extruder 5 Edge trimmer

2 Flat sheet die 6 Twin-roll haul-off unit
3 Triple-roll smoothing system 7 Length cutter
4 Roller conveyor 8 Sheet depos it
Fig. 13.4 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.
VI
......
-.I
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 1·5 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 adaptor, 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 calculated35 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.
Blown film extrusion of PVC follows the general pattern of this type
of process. The melt is extruded through a tubular die (see Fig. 13.5),
and the resulting tube is taken off vertically upwards while 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 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
* 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. 34
13 Extrusion 519
Fig. 13.5 Ring die for film production.
two sheets separately wound up), or it may be wound up directly as

'lay-flat tubing'.
13.5.4 Wire Covering
Insulation and sheathing compositions are applied to wire and cables
by extrusion coating. This involves the use of crosshead dies in which
VI
!:l
~
~
El
~-"t Jr-:'h ,I uL. H! tt-:!£~ f;.
t
C1
~:::to
.~
'"tl
f!' C1
<">
~l~i-_~ _~ ..,~
~__ 14
L--~- ll"""'~
-ktLSr- ~.
§
1 ~3 1:1..
Fig. 13.6 A typical building-wire insulation and sheathing line. 1, Dual reel flyer pay-off for insulation or earth wire :i
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. 4.)
13 Extrusion 521
the melt is turned through a 900 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. 36 and
by Fenner & Nadiri. 37
There are two basic kinds of internal die configuration, correspond-
ing to two general methods of forming the insulation around the wire
or cable: these methods 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 ad-
vantages 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 basic building-wire insulation and
sheathing line is shown in Fig. 13.6 (and a cable-covering line in Fig.
13.7).6
Good accounts of extrusion coating of wire and cable with PVC
have been published by Barnett4 and by Burton & Clarke. 38
Fig. 13.7 A cable-covering extrusion line and extruder (Maillefer).

13.6 SOME COMMERCIAL EXTRUSION EQUIPMENT
Lists of suppliers of extrusion equipment and lines for the manufacture

of PVC products by extrusion can be found in the current editions of
such sources as the Modern Plastics Encyclopedia, the Plastics
Technology Manufacturing Handbook and Buyers Guide, Plastics and
Rubber Weekly (occasional surveys), and the British Plastics
Federation's Buyers Guide for Plastics Processing Machinery and
Equipment. Recent tabulations of some major producers can also be
found in Refs 2 and 39.
REFERENCES
1. Anon., Plast. Technol. 26(13) (1980) 62-4.

2. Titow, W. V. PVC Technology, 4th edn. Elsevier Applied Science
Publishers Ltd, London and New York, 1984.
3. Kiesche, E. Plast. Technol., 32(2) (1986) 77-80.
4. Barnett, G. P. In Developments in PVC Production and Processing, ed.
A. Whelan & J. L. Craft. Applied Science Publishers, London, 1977.
7. Prause, J. J., Plast. Technol., 13(11) (1967) 41-5.
10. Jewmenow, S. D. & Kim, W. S., Plaste u. Kaut., 20 (1973) 356.
11. Kim, W. S., Statschkow, W. W. & Jewmenow, S. D., Plaste u. Kaut., 20
(1973) 696.
12. Wyman, C. E., Polym. Engng Sci., 15(8) (1975) 606-11.
13. Stevens, M. J., Extruder Principles and Operation. Elsevier Applied
Science Publishers, London and New York, 1984.
14. Rauwendaal, C., Polymer Extrusion, Carl Hanser Verlag, Munich, FRG,
1986.
15. Hensen, F., Knappe, W. & Potente, H. (Eds), Handbuch der Kunststoff-
Extrusionstechnik: Vol. 1 (1987), Grundlagen. Vol. 2 (1986),
Extrusionsanlagen. Carl Hanser Verlag, Munich, FRG.
16. Picraux, S. T. & Peercy, P. S., Scientific American, 252(3) (1985) 84-92.
17. McCandless, W. W. & Maddy, W. D., Plast. Technol., 27(2) (1981)
89-93.
18. Avery, D. H. & Csongor, D., 36th ANTEC SPE Proceedings, 1978, pp.
446-8.
19. Yarsley, V. E. & Flavell, W., Cellulosic Plastics, Part 1, Cellulose Acetate,
Cellulose Esters, and Regenerated Cellulose. Plastics Monograph No. C6,
The Plastics Institute, London, 1956.
20. Rice, W. T., Plast. Technol., 26(2) (1980) 87-91.
13 Extrusion 523
22. Brockschmidt, A., Plast. Technol., 28(3) (1982) 73-6.

24. Gilbert, M., Hemsley, D. & Miadonye, A., Plast. Rubb. Proc. Applns, 3
(1983), 343-51.
25. Chartoff, R. P., 34th ANTEC SPE Proceedings, 1976, pp. 347-9.
26. Summers, J. W., Isner, J. D. & Rabinovitch, E. B. 36th ANTEC SPE
Proceedings, 1978 pp. 757-9.
27. Benjamin, P., The influence of processing on the properties of PVC pipe.
Paper presented at PRI International Conference on PVC Processing,
Egham Hill, Surrey, UK, 6-7 April 1978; idem, Plast. Rubb. Mat.
Applns, (Nov. 1980), 151-60.
28. Hattori, T., Tanaka, K. & Matsuo, M., Polym. Engng Sci., U (1972) 199.
29. Faulkner, P. G., 1. Macromol. Sci. (Phys.), B11 (1975) 251.
30. Krzewki, R. J. & Sieglaff, C. L., Polym. Engng Sci., 18 (1978) 1174.
31. Summers, J. W. & Rabinovitch, E. B., J. Macromol. Sci. (Phys.), B20(2)
(1981) 219.
32. Summers, J. W., J. Vinyl Technol., 3 (1981) 107-9.
33. Davies, B., Plast. Rubb. Wkly, (3 Oct., 1975) 20-1.
34. Matsubara, Y., Polym. Engng Sci., 19(3) (1979) 169-72.
35. Johnson, J. E., 36th ANTEC SPE Proceedings, 197836-40.
36. Carley, J. F., Endo, T. & Krantz, W. B., 36th ANTEC SPE Proceedings,
1978, pp. 453-61.
37. Fenner, R. T. & Nadiri, F., Polym. Engng Sci., 19(3) (1979) 203-10.
38. Burton, V. A. C. & Clarke, J. J., Cable extrusion machinery for PVC.
Paper presented at the PRI International Conference on PVC Processing,
Egham Hill, Surrey, UK, 6-7 April 1978.
39. Anon., European Plastics News (March 1987) 23.
CHAPTER 14
Calendering
14.1 ORIGINS, AND CURRENT POSmON

IN THE PVC INDUSTRY
The multi-roll calender, precursor of the modern machine, was
originally developed in the mid-1800s for the processing of rubber into
sheet. Rubber sheeting is still produced by calendering, which has also
become the leading industrial process for the production of PVC
sheeting of all kinds (including flooring sheets for direct use or for
subsequent cutting into floor tiles). Other thermoplastics sometimes
calendered into sheeting include some polyurethane compositions,
thermoplastic rubbers, polyolefins (including chlorinated poly-
ethylene), and ABS plastics.
14.2 EQUIPMENT AND PROCESS: GENERAL ASPECTS

Operationally, a calender is a set of heated rolls (sometimes referred
to as 'bowls') to which hot, pre-compounded plastics stock-in the
present context a uPVC or pPVC compound-is fed, to be rolled out
into continuous sheet as it passes through the consecutive roll nips. In
a PVC calendering line, the calender is preceded by a compounding
and feed section (cf. Figs 14.3 and 14.4) and followed by the
post-calender section, comprising the sheet take-off, cooling, inspec-
tion and wind-up equipment (cf. Fig. 14.6).
Apart from straightforward production of sheeting, a calender may
be used to coat continuous substrates, such as fabric or paper, onto
which the hot sheet is rolled (cf. Fig. 14.8), or to laminate together
externally fed sheets: however, the latter operation is lamination by
calender, not calendering proper.
524
14 Calendering 525
The general thickness range for typical calendered PVC sheeting is

about 75-900 I'm, although sheet up to about 1·5 mm can be
produced.
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 opera-
tional flexibility for short runs in comparison with extrusion.
The major suppliers of calenders and calender lines include the
Berstorff Group (W. Germany and USA), BKMI Industrieanlagen
GmbH (W. Germany), the Farrel Group (USA and UK), the Bolling
Division of Intercole Bolling Corp. (USA), and the Independent
Machine Co. (USA).
14.2.1 The Calender
The machine comprises the arrangement ('stack') of rolls mounted in
bearing blocks supported by side frames ('gables') equipped with roll
drives, nip-adjusting gear, and heating arrangements.
Four-roll calenders are widely used for general production of PVC
sheeting. There is no fundamental reason for limiting the number of
rolls to this figure, but-in general-the more rolls the greater the
cost, the structural complexity, and the space requirement of the
machine, whilst the PVC material experiences longer heating times
and more shear-working. Nonetheless, five-roll machines are used
(including a recently developed, versatile type-see Fig. 14.2, B}-
especially for the production of some types of thin, rigid sheeting
(where the extra nip can substantially improve the surface finish), and
PVC calenders with up to seven rolls are available (e.g. from
Berstorff) .
At the other end of the scale, sequences of two-roll (single-nip)
units are typically used for processing flooring compositions, and
three-roll (two-nip) calenders also find use in the production of PVC
flooring. A small laboratory calender is illustrated in Fig. 14.1.
Some calender roll arrangements are shown in Fig. 14.2. The
advantages of the four-roll 'L' configuration common in PVC calen-
dering, and particularly of its inverted form [cf. Fig. 14.2, A(i)] are
usually quoted as reasonable cost; good visibility and accessibility of
all the rolls in the stack; good rigidity imparted by the vertical
Fig. 14.1 Four-roll laboratory calender ('inverted L' type, rolls 6 in x 15 in).
Courtesy of Farrel Bridge.
superposition of three of the four rolls; good range of the available

total lap ('wrap') of the material round the rolls (up to 540°C,
depending on the position 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). The 'z' type also offers a relatively wide
range of the degree of lap as well as easy access for fabric coating.
The following typical features of modern industrial calenders are
instrumental in their operational versatility and effectivity.
Working face widths up to about 3 m (120 in) are available: a large
width makes for high output rate, and provides the option of slitting
the product into any lower widths required.
Note: Calender producers will normally supply machines made to
order in virtually any dimensions. Some typical calender sizes
(in terms of, respectively, roll diameters and working face
widths) are: for production machines, 18 in x 48 in to 36 in x
120 in; and for laboratory and pilot-scale machines, 4 in x 8 in
to 14 in x 30 in (6 in X 13 in is a popular size in this range).
14 Calendering 527
(i) (ji)
(iii )
(ii)
B c
Fig. 14.2 Some roll arrangements and customary roll numbering in calenders.
A, Four- and three-roll stacks: (i) inverted 'L' type; (ii) inclined 'Z' type,
downstack; (iii) 'L' type; (iv) three-roll offset. B, Arrangement of a new
five-roll PVC calender (developed by Berstorff): (i) regular set-up, with roll 1
offsefto roll 3: this still provides the four nips of a five-roll calender (i.e. the
same shear-processing) but with hot-surface contact and dwell time of the hot
sheet reduced in comparison with those in a conventional five-roll 'L' stack
(see C). The conventional ('L' type) configuration of a five-roll PVC calender.
In modern calenders the rolls are individually driven, and heated by

circulation of the heating medium (high-pressure hot water or special
heat-exchange liquid) through drilled channels running close to the roll
surface over virtually the entire roll width. The individual drives
provide scope for wide variation in the roll speed ratios and the
corresponding available friction ratios: these two features respectively
enable the calender to cope with a range of compositions differing in
rheological behaviour, and make possible a high degree of control
over the material in the rolling nip (which, inter alia, promotes good
surface finish in the product). The heating system provides good
temperature control, with fast response to adjustments: this makes for
processing and product quality superior to those obtainable with
older-type cored rolls.
Another important feature is the provision for counteracting deflec-
tion 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 pro-
nounced in the middle where the restraining effect of the bearings is
least; it also increases with roll length (working face width).
Note: The distorting forces developed can be substantial: up to
about 1 MN per linear metre of working face width in the
production of thin rigid sheeting. With a typical plasticised
compound a representative range would be about O· 2-
0·5 MN per linear metre.
These forces actually deflect the rolls so that-if the deflection is not
suitably corrected or compensated for-the sheet produced can be
substantially thicker in the middle than at the edges. In modern
calenders the effects of roll deflection are counteracted by the
techniques known as roll bending and roll crossing (the latter is also
sometimes referred to as roll skewing or cross-axis roll adjustment).
Note: An older method, less versatile and much less common
today, is roll contouring ('crowning'), which may be as-
sociated with provision for partial nip adjustment by lateral
movement of some of the rolls in the stack. 1
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
14 Calendering 529
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 0·075 mm)l 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
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 of radius of about 0·75 mm. 1
The roll-crossing facility is usually available at least on the last nip of
the calender (the gauge-determining or 'gauging' nip).
Nip settings, roll bending and roll crossing may be automatically
controlled by sensors (normally of infrared or beta-ray type) which
also operate a profile scan display. Some systems are suitable for
retro-fitting to existing calender lines.
14.2.2 The Calendering Operation: Main Features and Their

Effects on the Structure and Properties of Calendered Sheet
The operation of a four-roll calender has been said2 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 considered to function, respectively, as the
feed, metering, and final sheet-forming and finishing stages. Whilst the
calendering operation may perhaps be viewed in this way in very
general outline, 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, 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.
The calender itself essentially only forms into sheet the homogenised
fused (gelled), hot PVC composition which it receives as feed.
Furthermore, because of the way the final product is formed by the
calender roll nips, it differs from extruded sheeting in some mor-
phological features and in certain properties associated therewith. This

is brought out by the following brief consideration of the material's
passage through a four-bowl, inverted 'L' calender.
In operation, three banks of material are maintained at the three
nips [ef. Fig. 14.2, A(i)]: a large, relatively narrow feed bank at the
first nip (between rolls nos 1 and 2), and progressively smaller but
wider banks at the subsequent two nips (with a full-width bank
between rolls nos 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 reworked 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-which affect those 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.
14.3 CALENDER LINES
14.3.1 Regular General-Purpose Lines
Arrangements fairly typical for a general-purpose PVC calendering

line are illustrated jointly by Figs 14.3 and 14.4 (pre-calender section:
compounding and feed) with Fig. 14.6 (calender and post-calender
section). The arrangements-especially those of the compounding and
feed section-can differ in some respects, depending on the kind and
range of calendering operations undertaken. Parts of a calender train
are shown in Fig. 14.5.
14 Calendering 531
Plasticiser Polymer Other additives

storage storage
~storrge/
Metering (weighing) devices
111
High-speed (hot) mixer
1
Cooling mixer
1
Feed (metering) hopper
o ( ®
Internal mixer
1
Buss
Kneader
Two-roll mill
1 j
Metering Two-roll mill
j
extruder/strainer
~ Feed conveyor
(with metal detector)
1
CALENDER
Fig. 14.3 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.
532 PVC Plastics-Properties, Processing, and Appiications
Fig. 14.4 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, butler 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.
(a) Pre-calender (Compounding and Peed) Section

The essential task of this section is to deliver to the calender hot PVC
stock in a thoroughly compounded, homogenised, degassed and fused
condition, and free from impurities and contaminants. Whilst each of
the machines comprising the section contributes to the achievement of
this objective (a more detailed discussion of the equipment and its
operation can be found in Ref. 1), the particular importance of the
melt-compounding machine is self-evident. This machine may be a
continuous compounder, e.g. a Buss Kneader, planetary extruder, or
FCM continuous mixer [see Sections 11.2.2(c) and (d) of Chapter 11]
or an internal mixer. Generally speaking, the batch mixer effects more
drastic working of the stock (a factor instrumental in.confining its use
in PVC calender lines to processing plasticised compositions): it also
requires provision for handling large batches of stock. In the arrange-
ment of Fig. 14.3, A, the two-roll mill links the batchwise operation of
....
"""
~
Fig. 14.5 An 'inverted L' calender, and the cooling rolls of a calender train. Courtesy of Farrel Bridge.
VI
W
W
the internal mixer 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 provide-
continuously and at the appropriate rate-calender feed in the form of
a flat or round strip.
Continuous compounders are equally suitable-and widely used-
for 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
Kneader.
In some pre-calender line arrangements the compounding machine
may not be followed by another compounding or metering unit, but
more usually a metering extruder/strainer is included, or sometimes a
two-roll mill (cf. Fig. 14.3, B). Where a mill is used, it makes a
convenient addition point for re-circulation of clean edge-trim,
because of easy accessibility; moreover, the heat history of such
material (which has already experienced a full heat-processing cycle) is
kept down in this way.
As indicated in Figs 14.3 and 14.4, the final member of a typical
pre-calender set-up 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 means (for example by
infrared 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 other locations may
sometimes be used).
14 Calendering 535
(b) Calender Section

Several features of the calender and its operation have already been
mentioned. The following are further relevant points.
The passage of hot PVC material from the feed to the outlet end of
the calender is actuated by two main factors; their operation also
governs the material's actual route through the machine (the 'sheet
path') in that they determine whether or not the hot sheet is
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, it is usual to have the roll temperatures (as well as the
speeds) going up with roll numbers. However, if the last roll is not
lapped by the sheet [e.g. roll no. 4 in the arrangement of Fig. 14.2,
A(ii)], then that roll will normally be run at a lower temperature, and
usually also a lower speed than its partner (roll no. 3 in the figure)
which is required to retain the sheet.
Examples of roll temperature settings in particular runs on particu-
lar compounds in a production machine are given in Table 14.1. As
can be seen, the settings for a nip-forming roll pair are close: as a
general guide, the difference should be within lOoC. If, with optimum
friction ratio, a difference of this order still does not make for
satisfactory operation, the temperature measuring and control equip-
ment should be checked, and/or the lubricant system of the compound
re-formulated. The nature of the compound, and also in particular its
lubrication, are always factors in the roll temperature settings: in
general, for typical industrial production, these may be within the
overall range of 150-195°C.
TABLE 14.1
Some Dlustrative Features of Industrial Production of PVC Sheeting on an 'L'
Type Calender with Highly PoUshed Rolls
Composition type
Rigid Flexible
(crystal clear) (opaque)
Basic formulation
pvc homopolymer resin 87 pbw (K value 57) 100 pbw (K value 71)
Stabilisers 2·5 pbw (organotin) 2·5 pbw (Ba/Cd liquid)
Lubricants 1· 5 pbw (internal! 0·5 pbw (external)
external)
Plasticiser 46 pbw (DIDP)
Processing aid 5pbw
Impact modifier 8pbw
Filler 5 pbw (coated CaC03)
Pigment 8pbw
Processing conditions
High-speed mixer
Tool tip speed 2541 m min- 1 2541 m min- 1
Mix temperature on
discharge 90°C 110°C
Cooler mixer
Tool tip speed 724 m min-l 724mmin- 1
Mix temperature on
discharge 40°C 40°C
Buss Kneader
Compound temperature
at die head 130°C
Internal mixer
Discharge temperature 180°C
Two-roll mill
Roll 1 temperature 140°C 180°C
Calender
Stripping device
General temperature 130°C 175°C
Embossing roll
Temperature (Not embossed) 15°C
Cooling train
Temperature 25°C 25°C
14 Calendering 537
TABLE 14.1-contd.
Composition type
Rigid Flexible
(crystal clear) (opaque)
Sheet properties
Tensile strength (yield)" 49-60MPa 22-29MPa
Elongation at breaka •b 206-273%
Tear strengthb (ASTM
D 1922):
In machine direction 4·5-6·9 kgfmm- I 8·7-11·3 kgfmm- I
In transverse direction 6.0-8.4 kgf mm- I 12·1-12·9 kgfmm- I
Tensile impact strength
(DIN 53448) 323-555 kgf cm cm- 2
a Dumb-bell specimens, with parallel central portion 10 mm wide.

b Sheet 251-350 !lm.
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 tempera-
tures below the material temperature aimed at). Subject to this
general consideration, and any special ones that may arise in in-
dividual cases, it is normally desirable to operate at the highest
practicable material temperature for ease of processing (lowest mate-
rial viscosity) and good ultimate sheet properties. With roll tempera-
ture 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 200°C. For material coming off the last bowl a fairly
typical range would be 170-17SoC.
(c) Post-calender Section
The post-calender section of a modern line is shown schematically in
Fig. 14.6, with the principal components clearly labelled. The figure is
largely self-explanatory, but the following additional points may be
mentioned.
2 3 4/5
(O(lJ~ RO..J
Fig. 14.6 A four-roll, 'L' type calender with post-calender section, set up for
SHEET TAKE-OFF AND STRETCHING

The hot sheet is removed from the calender bowl on which it runs
after the final nip, by a stripper (pick-off) roller. In modern practice
this is the first of a set of similar rollers (see Fig. 14.6), temperature-
controlled in groups of two or more: this makes for good control over
sheet thickness and for uniform, gradual cooling, or alternatively for
close maintenance of sheet temperature if that needs to be kept up for
in-line embossing. For the latter purpose, provision is also normally
made for an extra heat boost, by an infrared heater (as shown in Fig.
14.6) or by passage over a hot drum. Since the sheet laps the rollers,
its passage through the set brings each of its surfaces into contact with
every second roller: this is a positive factor in uniform heat transfer
and temperature control.
The running of the stripper rollers may be so regulated that the
sheet coming off the calender is stretched to a predetermined extent
while 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 advantages of 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.
14 Calendering 539
EDGE TRIIt1ING
U
(
CTION SCREEN
UALITY
L
PVC sheet production: schematic representation.
The final calender nip (the gauging nip) is set wider than would be
required for direct production of the sheet thickness that is ultimately
achieved by stretching, so that lower distorting forces on the rolls and
somewhat less drastic working (and heating) of the material are
obtained. 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.
EMBOSSING
Although calendered sheeting can be embossed away from the
calendering line in an entirely separate operation (which involves
reheating to a suitable temperature), embossing is often carried out
in-line (the embossing unit is so arranged that it can be by-passed-cf.
Fig. 14.6). 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 reheated, but
merely kept hot after leaving the calender), and minimises acquisition
of extra heat history.
A typical embossing unit consists of a pair of rollers (see Fig. 14.6):

the embossing roller and a back-up roller with a partly resilient
surface. The unit is followed by a set of take-off rollers (see Fig. 14.6).
The drive of the embossing part of the train is normally independent
of those of the other parts, but it must be suitably synchronised, to
avoid stretching the sheet.
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, high-temperature stretching off the calender; see
above), and especially avoidance of such straining at relatively low
temperature (below about 100°C), are important considerations in the
running of the train. The presence of low-temperature strain impairs
the dimensional stability of the sheeting in any subsequent heat-
processing (e.g. heat-lamination) and in service. A typical example 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 tempera-
ture inside a car can reach about 80°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 into the
sheeting at or below such temperatures.
COOLING
The object of the cooling operation is to bring the temperature of the
sheet gradually and uniformly down to that of the surroundings
(sometimes even below), without thermal shock (which can impair the
sheet properties, especially with rigid compositions), and without
introducing low-temperature strain. In typical modern practice this
object is achieved by passing the sheet around a large number of
water-cooled drums (cf. Fig. 14.6), or-in some arrangements--over a
smaller number of larger-diameter drums preceded by an air-cooling
'relaxer' section in which the sheet is supported on small rollers. The
cooling drums (also known as 'cans') run uniformly (under an
independent drive but in synchronisation with the rest of the train),
and are temperature-controlled at decreasing values: as an example, in
the cooling section of Fig. 14.6, drums 1-3 might be kept at 50°C,
drums 4-6 at 40°C, drums 7-9 at 25°C, and drums 10-12 at a
temperature about 5-lOo C below ambient.
14 Calendering 541
MEASUREMENT AND CONTROL OF SHEET THICKNESS

This is a necessary part of production control. The p-gauge is
widely-used for the purpose, although other systems are also available.
The gauge 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 is such that it yields the
gravimetric thickness value, i.e. the notional average thick-
ness (t) which, for a uniform sheet of given area, is
determined by the area (A), mass (m) and density (p) in
accordance with the relationship t = m/Ap. * For a plain
sheet, the gravimetric thickness is the same as the directly
measurable 'geometrical' thickness. A direct thickness mea-
surement on an embossed sheet is not appropriate because
of the surface contouring produced by the emboss, and the
gravimetric thickness is more meaningful. Thus the {3-gauge is
equally applicable to both plain and embossed sheeting.
In modern calender lines it is usual for the {3-gauge to be integrated
into a complete, computerised on-line control system (such as for
example the Measurex Vinyl Calender Control System; Measurex
Corp., USA), which automatically makes continuous adjustments to
the roll-crossing and roll-bending devices to keep the sheet thickness
and profile within acceptable tolerances around the appropriate set
target values. Such systems also provide multicolour visual displays,
and data print-outs, and in some cases they include a 'target adaptive
control' (TAD) facility, which automatically adjusts the sheet thick-
ness to within a specified percentage of a nominal limit, so that the
sheet area or weight in the finished roll is optimised.
EDGE TRIMMING
The edges of the sheeting are trimmed in the course of production.
More commonly, this is done after cooling ('cold trimming') towards
* Standard laboratory methods of measuring gravimetric thickness 3-normally

prescribed for embossed sheeting-involve weighing a specimen of known area
and determining, separately, the density of the material.
the end of the line (cf. Fig. 14.6). 'Hot trimming', on the calender
itself, is also sometimes practised, but this can have two disadvantages:
a bead tends to form on the hot-trimmed sheet edges (which can cause
problems in the final winding and, in any case, spoils the neatness of
edge-finish); whilst the trimming knives may mark the calender roll
surface.
WIND-UP
The wind-up unit may be a variant of one of the two general types:
centre-core winders or surface (contact) winders. Winders of the
former type are widely used for PVC sheeting (more especially for
thick, stiff sheeting, and where large sheet rolls need to be built up).
The surface winders are more suitable for flexible, thin sheeting.
Constant-torque drives, featured by modern centre-core winders,
keep the winding tension in the sheeting at a constant, set value
despite the rise in 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.
Various features of wind-up units include accumulator fittings,
squeeze rolls (for sheet-roll density control), variable-indexing and
cutting devices.
14.3.2 Other Lines and Arrangements
(a) Lines for Calendered flooring

PVC flooring compositions, which are normally heavily filled with
asbestos fibres and particulate fillers (typically calcium carbonate) 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.
One version of such a flooring line is represented schematically by the
flow diagram of Fig. 14.7. In another version, an internal mixer may
Pre-blend
storage Rework
hopper hopper
,/
~ /<.'
Batch
weighing
station
.....
-I:..
r-------' -------l ~
Internal Internal
mixer mixer
i I
I
I I
f
Mixer '" Two-roll _ _ Two-roll _ _ Two-roll _ _ Two-roll _ _ Cooling
'"
(blender) Conveyor mill calender calender calender and
cutting
Fig. 14.7 Flow diagram of a calender line for PVC flooring (basic layout). Use of two appropriately sized internal
mixers, feeding the mill alternately, provides effectively continuous supply of compound in batches conveniently
accommodated on the mill.
~
w
be followed by two two-roll mills (the dumping and sheeting mill), the
second mill feeding the first calender of the line. In the production of
the familiar mottled PVC flooring or tiles, multicoloured vinyl chips
may be added either on the first or the second mill.
The consecutive two-roll calenders progressively roll out the hot
sheet down to the required thickness.
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 homo-
geneity in the stock).
Sheets of suitable flooring compositions calendered on a three- or
four-roll calender can be laminated-by various techniques-to pro-
duce multi-layer flooring of the type conventionally, if somewhat
incongruously, styled 'homogeneous'. The individual plies may be of
the same or different compositions. 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 of sheeting
of the same reasonably wear-resistant formulation, and calendered to
the same thickness (fairly typically about 0·5 mm), may be laminated
together, the sheeting with the best-looking surface being used as the
top layer.
(b) 'Calandrette'Lines
These lines are simple, compact and small in relation to a full-size,
regular calender line. They are essentially combinations of a com-
pounding extruder (typically a planetary extruder) feeding hot
compound-directly or via a metering extruder-in the form of strands
to a small two- or three-roll calender, which is followed by the
appropriate auxiliary equipment.
Typical size ranges (as exemplified by the Battenfeld 'calandrette'
lines) are: roll diameter 16-24 in; roll width 32-64 in; line length
38-57 ft. Production rates (for PVC sheeting up to about 0·040 in
thick) might typically be 250-1500 lb h -1.
In the Kleinewefers 'calandrette' line (EKK Kleinewefers, FRG), a
planetary extruder homogenises the PVC composition, at a melt
temperature somewhat below that usual for conventional extrusion;
14 Calendering 545
the extrudate is automatically cut into lumps (to increase the specific
surface for ease of subsequent degassing) 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 sheet 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.
The Bekalex equipment (Berstorff) is another example of an
industrial 'calendrette' line.
(c) Lamination on or at the Calender
The calender can be used to laminate the hot-calendered sheeting, on
the machine or in-line, to other continuous-web materials, such as
textile fabrics, paper, felt, and other sheeting. Three basic arrange-
ments are shown schematically in Fig. 14.8. In the calender nip
A B
c
,
~
Fig. 14.8 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.
lamination arrangement illustrated in Fig. 14.8,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. 14.8,B). The
in-line lamination method (Fig. 14.8,C) is of special interest with
heat-sensitive substrates, or where a priming layer is to be applied
prior to lamination.
Calender lamination can be economically attractive where long
continuous runs with no frequent formulation changes are involved.
Otherwise, PVC paste coating provides an alternative, especially for
multi-layer coatings, subject, however, to the limitation that it is
essentially confined to non-rigid coatings.
14.4 FORMULATION OF PVC COMPOSITIONS

FOR CALENDERING
As in all PVC formulating, the principal considerations are the

requirements arising from the nature and conditions of the process,
end-use requirements, and cost.
Something of the basic make-up of calendering compositions is
indicated by the formulation examples in Sections 2.2.6(c) and (d) of
Chapter 2, and in Table 14.1 here. Successful formulation for the
calender calls for considerable skill, as well as knowledge not only of
calendering of PVC generally, but also of any special requirements
(especially with regard to PVC compound lubrication) of the particular
equipment concerned. Where compositions are purchased rather than
being formulated in-house (and there is a large selection available
from the ranges produced by PVC compound suppliers) it is particu-
larly important to carry out pre-production trials.
The following further points may be noted.
The lubricant system and its balance with the stabiliser system,
important in all melt-processing, are especially so in calendering,
particularly with regard to the extent 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
14 Calendering 547
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 7, Sections 7.1 and 7.2). The same is broadly
true of processing aids, but these-especially some of the acrylic
ones---<:an also promote the proper combination of adhesion/release
properties of the hot sheet and counteract plateout. Much calendered
sheeting is surface-printed, whilst some large-outlet applications (e.g.
reservoir linings, inflatables, luggage covering) involve welding of the
sheeting. Print adhesion, and bond formation in welding, can both be
impaired by excessive lubrication.
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 composi-
tions (as well as some pigmented ones) are widely 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 compound-
ing, and good dispersibility. However, in highly plasticised composi-
tions a solid system may be preferable to avoid lowering the melt
viscosity. 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 suitability for high-rate
processing, particularly with regard to ease of fluxing, gelation, and
fusion. Flexible compositions are normally based on high K -value
resins (cf. e.g. Table 14.1). This promotes good physical properties
important in service, whilst the associated increase in melt viscosity
and cohesion is actually helpful-especially in highly plasticised
formulations-as it compensates to some extent for the opposite effect
of plasticisers.
Note: In some formulations, the main reason for incorporating a

filler may be to bulk ('sludge') up the plasticised composition
for higher melt viscosity.
In rigid compositions, use of polymers of lower K value is dictated-

as in other melt-processing compounds (e.g. for blow moulding
or injection moulding)-by the need to ease processing. However,
K values in excess of 60 can be used in otherwise rheologically
well balanced compositions (cf. e.g. Vinoflex KR 3563-BASF),
especially for thick, rigid sheeting with high strength properties.
Easier melt-processing is also the reason for the use of VC/VAC
copolymers in heavily-filled calendered flooring compositions and
in those for some types of sheet for thermoforming (although
acrylic-modified homopolymer compositions are widely used for
such sheeting), as well as VC/VDC copolymers in some special
formulations.
The choice of plasticiser(s) for a flexible calendering composition is
primarily influenced by end-use and cost requirements, but considera-
tion 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 ap-
propriate (relatively high) chlorine content is often used as a solid
plasticising modifier in calendered PVC sheeting for outdoor use (e.g.
as seepage barriers in reservoirs and the like). The cost of PVC/CPE
blends of this kind can be reduced-without too drastic an impairment
of properties-by the incorporation of phthalate plasticisers. An
interesting study by Young4 indicated that some compositions based
on a blend of PVC resin of relatively high molecular weight (Diamond
450; Diamond Shamrock Chemical Co.) with a chlorinated HDPE
(containing 42% or 46% chlorine: respectively, XO 43.49 and 2243.51;
Dow Chemical Co) incorporating diundecyl phthalate (Monsanto) or
linear phthalate esters (Santicizer 711; Monsanto) compared favour-
ably 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
types of sheeting (e.g. supported or unsupported vinyl upholstery
material). Some useful data on the effects of particle surface area and
surface treatment of calcium carbonate fillers on the properties of
calendered flexible PVC sheeting have been published by Mathur
et al. 5
14 Calendering 549
14.5 SOME FAULTS AND DEFECTS OCCURRING IN

CALENDERED SHEETING
Several of these can also occur, in the same or similar form, 10

sheeting produced by extrusion.
14.5.1 Simple Dimensional Faults
These are rare with good modern equipment and correct operation.
However, the following may be mentioned for the sake of
completeness.
Excessive thickness 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-they
may sometimes arise as a result of, respectively, over- or under-
plasticisation, even if the setting is basically correct (for a properly
plasticised composition).
14.5.2 Structural Defects
Presence of strain imparted at relatively low temperature: The origin

and consequences of this fault are mentioned in various parts of
Section 14.3.1(c) above.
Unsatisfactory lay-flat behaviour: This can cause problems in wind-

ing 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 14.2.2
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.
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; poor
high-temperature stability (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.
14.5.3 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 3.3.1(d) of Chapter 3].
Flecking ('fleck marking'): The flecks are a characteristic manifesta-

tion 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 4 (Section 4.8.2). Some of the main
factors responsible are the same as those involved in flecking, although
plate-out is a more complex phenomenon.
14 Calendering 551
Pluck marks (tracking): These are manifestations of poor release of

the hot sheet from the calender roll surface. The release difficulty can
be caused by under-lubrication of the composition, or sometimes by
over-heating in compounding and/or too high roll temperatures in
calendering. Some acrylic processing aids are useful in counteracting
this fault.
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.
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 mate-
rial. 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 6 of the form and measurement of surface rough-
ness in pPVC extrudates, and of the processing factors instrumental in
its origin, is of some intere.st 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 emerge 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 under-
gelation (which may also be manifested in some of the ways mentioned
above).
Overall discolouration: 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 over-heating 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).
Pinholes: This fault in calendered sheeting, especially the flexible

type, is 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. 14.6).
Automatic, laser-scan inspection devices are also available for
detecting the presence and location of pinholes, as well as gauging
their size. Their use also reduces the time between detection and
remedial action.
14.6 FURlliER PROCESSING OF

CALENDERED SHEET
14.6.1 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. 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 175°C, and the actual material tempera-
ture only slightly lower.
The operation is sometimes referred to as press-surfacing or
'planishing,. 7 The hot-pressing not only imparts good surface finish to
the sheets, but also regularises sheet thickness and relieves internal
14 Calendering 553
stresses and residual strains. Press-finished sheets are used for pro-
ducts 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.
14.6.2 Press Lamination
This way of producing a thick sheet from a number of thinner ones is

discussed in Section 17.1.2(b) of Chapter 17.
14.6.3 Surface Treatments
The main kinds of treatment under this heading are printing,

embossing away from the calender, and surface coating.
Printing (see Section 22.1.1 of Chapter 22)-much of it done by the
gravure method-is the process used for decorating the surface of
sheeting for such products as vinyl shower curtains, inflatables,
self-adhesive decorative surfacing sheets (including imitation veneers),
etc.
Embossing of calendered sheeting away from the calender is
discussed in Section 22.1.4 of Chapter 22, and protective and
decorative surface coating, with special reference to lacquering, in
Section 22.3.1. Apart from coating of these two kinds, adhesive layers
are also coated onto PVC sheeting as a preliminary to lamination with
other materials, and the manufacture of self-adhesive surfacing sheets,
tapes, plasters, and the like.
14.6.4 Continuous Lamination away from the Calender
This alternative to lamination on or at the calender [cf. Section

14.3.2(c) above] in many cases offers greater convenience and opera-
tional 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 itself is by hot-pressing. 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 transpar-
ent 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. The subsequent handling of the hot sheet and its conveyance to
the lamination point without distortion is cardinally important (but not
easy in practice). The pre-heated sheet is next brought into contact-
under suitable tension and/or pressure-with the base sheet, on the
surface of a drum kept at about 170°C. 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 expandable calendered sheeting! (as an alternative to the
paste-coating methods).
An example of calendered PVC sheeting faced, by adhesive
lamination, with a PVF-sheet layer is mentioned in Section 22.3.3 of
Chapter 22.
14.7 CALENDERED-SHEET PRODUCTS:

PROPERTIES AND APPLICATIONS
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 14.1-14.3 together
with numerical values that are either fairly typical of the product to
which they relate (Table 14.1) or representative of minimum require-
ments laid down in relevant standards (Tables 14.2 and 14.3).
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
TABLE 14.2
Some Standard Property Requirements for Calendered Flexible PVC Sheeting
Standard BS 1763:1975 BS 2739-1975 BS 3878: 1982c ASTM D 1593-81
(Type 103 (Type 1
sheeting b) sheeting d )
Thickness, 11m Up to 400 (inclusive) 250-900 Up to 900 (inclusive) 75-250

Tensile strength, MPa (minimum) 13 14 13 14·5-15·9
Elongation at break, % (minimum) 160 180 160 150
Tear strength, N mm- 1 (minimum) 21 21 21 35
Dimensional stability: change in a 9 (plain-surfaced 8 9 (single sheeting) 7
linear dimension, % (maximum) sheet)
11 (other surfaces, or 11 (laminated sheeting)
laminated sheet)
Low-temperature extensibility,
% (minimum) 8 15 8
Extensibility after heat ageing,
% (minimum) 50 50
a Each numerical property value quoted relates to the determination method appropriate to the standard specification concerned.
b 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).
TABLE 14.3
Some Standard Property Requirements for Rigid PVC Sheeting
Standard BS 3757:1978" CS 201-55a
Units Numerical value for sheet type b Units Numerical value

for sheet
Type C1 Type C3 TypeD type b
Property Type I Type II
Tensile strength (minimum) MPa 45 38 38 Ibfin- 2 7000 5000

Flexural strength (minimum) Ibfin- 2 11000 8500
Elastic modulus in flexure c (minimum) MPa 2500 2000 2000 Ibfin- 2 400000 300000
Impact resistanced Number of Negotiable' 0 Negotiable' ft-Ib per in 0·5 3·0
failures of notch
in test (Izod)
Softening point (minimum) °C 70 60 50
Dimensional change at 120°C (maximum) % 15 15 Negotiable'
Heat deflection temperature (at
264lbfin- 2 fibre stress) (maximum) °C 70 66
Hardness (Rockwell R) (minimum) R scale units 110 100
Resistance to delamination No failure in the mechanical splitting test No delamination or disintegration in the
prescribed in the specification acetone immersion test prescribed
Property retention
After immersion in 80% sulphuric acid
Change in weight (maximum) % increase 5 15
% decrease 5 0
Change in flexural strength % increase}
(maximum) 15 25
% decrease
After immersion in 100% acetic acid % increase 10 20

Change in weight (maximum) % decrease 0 0
% increase 0 0
Change in flexural strength % decrease 55 80
(maximum)
a Both standards are directed to rigid sheeting generally, but Types C1, C3 and D of BS 3757 are specified as calendered or extruded
sheets. CS 201 is a US commercial standard.
b BS 3757: Type C1-general-purpose sheet suitable for most applications and fabricating techniques.
Type C~imilar to C1 but with specific impact strength and possibly lower chemical resistance.
Type D-particularly suitable for deep vacuum forming.
CS 201: Type I--chemical resistant, normal impact resistance.
Type II--chemical resistant, high impact resistance.
C In BS 3757 applicable to sheet of minimum nominal thickness of 0·5 mm.
d In BS 3757 applicable to sheet of minimum nominal thickness of 1·0 mm.
C Between supplier and purchaser.
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
requirement specifications (cf., for example, BS 1763, BS 2739, BS
3878, and relevant standards among those listed in Appendix 1).
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 100°C 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 180°C in some cases), are also in use where
they are relevant to particular processing or service conditions that the
embossed sheet may experience. 1
TABLE 14.4
Calendered Flexible PVC Sheeting 1 IDOl Thick, for Reservoir Lining and
Similar Applications: Typical Property Requirements
D
Property Test method Numerical value
Specific gravity ASTM D 792, Method A 1·20

Tensile properties: b ASTM 882
Tensile strength 17MPa
Elongation at break 300%
Modulus at 100% 9MPa
elongation
Tear resistance ASTM D 1004 (Die C) 50Nmm- 1
Brittleness temperature ASTM D 1790 -30°C
Dimensional stability ASTM D 1204 Linear dimensional
(15 min at 100°C) changeb not to
exceed 5%
Volatile loss ASTM D 1203 Method A Not to exceed
0·5% by weight
Water extraction ASTM D 3083 Weight loss not to
exceed 0·35%
Hydrostatic resistance ASTM D 751 Method A 690kPa
Resistance to soil burial:
original property
retention
Tensile strength 95%
Elongation at break 80%
Modulus at 100% 90%
elongation
a Cf. also ASTM D 4551-86b Flexible PVC Water-Containment.

b In both the machine and transverse directions.
14 Calendering 559
The properties which are of interest in flexible calendered sheeting

for reservoir lining are listed in Table 14.4, together with some
relevant standard test methods and typical requirements.
Major standards relevant to PVC film and sheeting are listed in
Tables 12.5 (uPVC) and 12.8 (pPVC) of Chapter 12.
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 unsup-
ported film); production of baby pants; production of adhesive tapes
and labels; motor-car trim (door panels, head-liners, crash-pads);
decorative surface coverings; facing sheet for metal and board panels
for partitioning and building applications; production of book bind-
ings, document cases, folders; shower curtains; tablecloths; mattress
covers; floor coverings (continuous or tiles); and luggage.
Rigid calendered PVC sheeting finds substantial outlets in thermo-
formed 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; and film-packaging
applications. Press-laminated sheeting is used in chemical plant
construction; wall cladding; tank lining; corrosion-resistant ducting;
and tunnel lining.
REFERENCES

2. Eighmy, G. W. In Modern Plastics Encyclopedia, 1982-1983 edn,
McGraw-Hill, New York, 1982, pp. 220-2.
3. (a) ISO 4591-1979 (1985). Plastics-Film and Sheeting-Determination of
average thickness of a sample and average thickness and yield of a roll by
gravimetric techniques (gravimetric thickness). (b) BS 2782: Part 6: Method
631A: 1982. Determination of Gravimetric Thickness and Yield of Flexible
Sheet. (Identical with ISO 4591.) (c) ASTM D 1593-81. Non-rigid vinyl
Chloride Plastic Sheeting. (d) ASTM E 252-84. Thickness of Thin Foil and
Film by Weighing.
4. Young, W. L., 36th ANTEC SPE Proceedings, 1978, pp. 750-3.
5. Mathur, K. K., Greenzweig, J. E. & Driscoll, S. B., 36th ANTEC SPE
Proceedings, 1978, pp. 732-5.
6. Bareich, G., 28th ANTEC SPE Proceedings, 1970, pp. 569-72.
7. Rusinovitch, G., Plast. Engng, 38(11) (1982) 31-3.
CHAPTER 15
Blow Moulding
15.1 BASIC FEATURES
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 charac-
teristics are also needed, e.g. sufficient thermal stability under
processing conditions.
Blow-moulded PVC bottles (produced by the extrusion-based pro-
cess) 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 1962.1
As practised today, all the numerous variants of blow moulding
include the following essential elements:
(i) 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.
560
PLASTICS extrusion
OPEN-ENDED enclose in mould MOULDED EXTRUSION BLOW
FEEDSTOCK TUBE blow, cool ARTICLE MOULDING
- (PARISON)
enclose in first PREFORM transfer to second

(preform) mould, (article) mould, ....
MOULDED EXTRUSION
(CLOSE-ENDED (ORIENTED) STRETCH-BLOW
blow TUBE WITH FULLY stretch and blow.
(possibly cool) cool ARTICLE MOULDING
FORMED NECK)
PREFORM
injection transfer to second
PLASTICS moulding.
(CLOSE-ENDED (article) mould, MOULDED INJECTION
FEEDSTOCK TUBE WITH blow, cool ARTICLE BLOW MOULDING
FULLY FORMED
NECK)
transfer to second (article)

mould.
MOULDED INJECTION
stretch and blow. cool
(ORIENTED) STRETCH-BLOW
ARTICLE MOULDING
dip mandrel into melt

PREFORM transfer to second
PLASTICS extrusion HOT MELT in cavity (CLOSE-ENDED (article) mould. MOULDED DIP (DISPLACEMENT)
FEEDSTOCK 0' injection IN CAVITY complete shaping of
TUBE WITH blow. cool ARTICLE BLOW MOULDING
preform round mandrel FULLY FORMED
by piston push on melt NECK)
Fig. 15.1 Characteristic operational elements in the main types of blow moulding process: schematic outline.
(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.
Individual processes differ in the ways in which these basic operations
are performed, and in the number of associated process steps (see
Section 15.2).
uPVC is one of the group of plastics important as blow-moulding
materials. The other members of this group are polyethylene (espe-
cially HDPE), polyethylene terephthalate (PET), polypropylene (PP),
polycarbonate (PC), and certain modified acrylonitrile polymers.
Some of these, notably HDPE and PET, compete with uPVC in many
applications (see Section 15.5.1).
Note: PVC is now used as a component of blow-moulded containers
with multilayer walls, produced from coextruded parison or
co-injection-moulded preforms, which have been gaining
ground for some time, especially in applications requiring
particularly good barrier properties.
15.2 BLOW-MOULDING PROCESSES AND

THEIR APPLICATION TO PVC
15.2.1 General Characterisation and Principal Features of Blow-

Moulding Techniques 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. 15.1. 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
15 Blow Moulding 563
which they are combined may collectively be regarded as the third

main distinguishing feature of a blow-moulding process.
(a) Extrusion Blow Moulding
GENERAL OPERATIONAL SEQUENCE

In a typical sequence of operations in simple extrusion blow moulding,
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). This 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 then 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 15.2 and 15.3, 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
Fig. 15.2 A continuous-extrusion machine (Sidel, France) for stretch-blow

moulding of bottles: 1, parison; 2, preform mould; 3, temperature condition-
ing of preforms; 4, conveyor; 5, bottle mould; 6, demoulding.
1 2 3
4 5 6
Fig. 15.3 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.
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. 15.3). The object of stretch-blowing is to produce biaxial
molecular orientation in the moulding; the effects and advantages of
this are discussed in Section 15.2.2 below. For the best results the
orientation should be imparted at a temperature below the extrusion
temperature (with uPVC at about 9O-100°C). In most industrial
equipment provision is made for temperature-conditioning of the
parison or preform during and/or after its cooling in the course of
formation in the pre-blowing mould: the conditioning may take place
at a separate station (as for example on the Sidel MSF machines).
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 modifica-
tion, e.g. for the older versions of Kautex KEB machines), a modern
extrusion blow-moulding set-up usually includes parison programming,
and in some cases also other features for parison control.
PARISON PROGRAMMING AND OTHER CONTROL

The term 'parison programming' 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 can
also include certain other ways of parison thickness control now
available.
The number of zones along a parison in which its thickness can be
varied by a parison programmer depends on the particular program-
ming system. Many are available, from a number of manufacturers.
Some of these systems are incorporated, as standard features, in
particular makes of blow-moulding equipment. The systems range
from relatively inexpensive, lO-point thickness programmers, adequate
for long-run production of simple blow mOUldings (e.g. the lO-point
Moog* system), to sophisticated computerised, fully automatic sys-
tems for control at up to 50 points (cf. e.g. the 49-point parison-
* Moog Inc., Electronics and Systems Div., USA, and Moog GmbH, FRG:
the group also supplies more advanced systems with full microprocessor
control, e.g. the Moog 4O-point analogue parison programmer.
programming facility of the MACO Vlt integrated control system for

extrusion blow-moulding equipment, and Moog 4O-point analogue
parison programmer). Other examples are the 30-point parison
programmer used on some Bekum* machines, 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 displays the resulting parison thickness
profile, and continuously, automatically computes and executes the
necessary adjustments of the movable die elements metering the
amount of material along the length of the parison.
Other programming and control capabilities include the following:
parison length control and stretch compensation; parison ovalisation;
minimisation of the amount of waste material in the pinch-off areas of
the moulding; and inclined blow pin and neck-finish calibration (for
containers with inclined necks or spouts).
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 can bring
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). Estimates from
different sources indicate potential material (moulding weight) savings
of 11-30% in the production of PVC bottles, with similar percentage
increases in the production rate? However, in any particular case, the
possibility should also not be overlooked of saving material and
securing good thickness distribution simply by suitable design of the
moulding.
Note: Computer programs exist for the design of blow mouldings
for optimum critical-area/thickness relationship, processing,
and material economy, e.g. the PITA (Parison Inflation
Thinning Analysis) program originated by the General
Electric Co. 3
t Barber-Colman Co. Industrial Instruments Div., Rockford, IL, USA, and
*
Kriftel, FRG.
Bekum Maschinenfabriek GmbH, Berlin, FRG.
§ Hunkar Laboratories Inc., Cincinnati, OH, USA.
(b) Injection Blow Moulding

In the main-stream version of this 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 variants of the process preforms are
cooled, and may be stored, to be reheated and blown in a separate
operation. In either case, the hot preform may be stretch-blown in the
blowing mould (see Section 15.2.2). Injection-moulded flat discs are
also used as preforms in some systems (e.g. the Japanese Aoki AKH
and Nissei ASB machines) for the production, by stretch-blowing, of
relatively small, wide-mouth containers.
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 control over wall
thickness and its distribution in the final product (not with simple disc
preforms). Material cost savings associated with pre-shaping of pre-
form, and generally with lack of waste. Virtually constant weight of
mouldings (but less easy to alter than in the extrusion-based process).
An accurately moulded neck finish in bottles (not with simple disc
preforms) particularly useful for crown closures. Better-quality finish
with no nip closure (pinch weld) line.
The main disadvantages are: limitations on the ratio of neck
diameter to length in containers (in practice a maximum of about 1: 12
for core-moulded preforms, due to core-rod deflection problems; even
less with disc preforms); containers with handles are not readily
produced; highly oval cross-sectional shapes are not as successful as
with extrusion blow moulding; tooling costs are normally higher.
(c) Dip Blow Moulding

Also known as displacement blow moulding, this process came into
use in the 1970s. 2 Whilst some operational features differ in different
machines, the general principles, common to all equipment, are as
follows. A predetermined amount of hot plastics melt is introduced
(by horizontal or vertical extrusion, or by injection) into a heated
cavity kept at a controlled, optimum temperature. 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-centrally-into the melt in the cavity,
displacing the melt upwards and shaping it into an annulus defined by
the mandrel and the cavity walls. The annulus becomes the body of
the ultimate preform, whose shaping is finally completed-after 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
a '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
(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: low shear stress
experienced by the melt during its flow into the mould and subsequent
shaping; 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 injec-
tion 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.
A recent variation on the dip moulding theme, which has been
called 'intrusion blow moulding', is exemplified by equipment pro-
duced in France by the ADS company. 4
15.2.2 Stretch-Blowing in Blow Moulding

Stretch-blowing can be carried out at the blowing stage of all
blow-moulding processes. The combination of longitudinal stretching
with transverse expansion [see Section 15.2.1(a) and Fig. 15.3] in this
operation imparts biaxial orientation to the walls of the resulting
moulding. The degree of stretch to be imparted in a particular case is
influenced by the geometry of both the preform and the final
moulding. In general, for uPVC typical stretch factors would be: axial
stretch x 1·3-1·5: transverse (radial) stretch x 2·2-2·7.
Note: In continuous stretch-blow moulding processes, i.e. where
the preform (or parison) is only partly cooled down (to the
stretch-blowing temperature) and then expanded directly,

the rate and duration of cooling-in relation to preform wall
thickness-are factors important to the quality of the final
product and to general productivity. As an example, cooling
times of 3·S-S s would, typically, be appropriate for uPVC
preforms with walls l-l·S mm thick. In view of its excellent
thermal conductivity, beryllium/copper alloy is a good mate-
rial for the body of a preform mould, whatever the cooling
system.
The biaxial orientation imparted by stretch-blowing improves
several properties important in containers, which constitute the vast
majority of commercially produced PVC blow mouldings. The pro-
perties 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 & Bonnebat. 5
Brady's study of the effect of biaxial stretching upon the mechanical
properties of uPVC6 (O·01S-in thick calendered sheet) indicated, inter
alia, that optimum property improvements are obtainable at a stretch
factor of x2 in each direction, and that 100°C was the optimum
stretching temperature. Some effects of uniaxial and biaxial stretching
of uPVC and pPVC are discussed in a recent paper by Gilbert & Lui. 7
Despite the somewhat higher equipment cost associated with stretch
blowing, the property improvements obtainable can make possible net
savings2 promoted by the following factors: reduction in the amount of
material (because the wall thickness of the moulding can be reduced
without sacrificing performance); reduction or elimination of impact
modifiers in the formulation; and possible reduction in processing cost
(mainly because thinner walls make for faster cooling).
15.2.3 Process and Equipment Arrangements in Blow Moulding
These arrangements comprise a number of elements: the particular

way in which the specific versions of these elements are utilised and/or
combined in a process is a distinguishing feature of the process. The
elements are: the number of main process stages (i.e. whether one- or
two-stage operation); the nature and number of process steps; the
number of stations in the equipment (more than one process step may
be carried out at one station); blowing arrangements-e.g. whether
through a mandrel (blowing pin) or a needle introduced into a
completely closed parison (as in some extrusion blow-moulding
operations, especially with containers with very narrow or very wide
neck openings,2 whether 'top blow' (with the container in the upright
position) or 'bottom blow' (with the container upside-down in the
mould); and certain other, less basic but significant features. All these
elements are discussed in some detail in Ref. 2.
In a single-stage process, all operations (process steps) are carried
out in continuous sequence on the same equipment unit (see for
example Fig. 15.2). A two-stage process employs two units: com-
monly, the first unit produces preforms, which are then blow- (or
stretch-blow-) moulded into final articles in the second unit (some-
times after a considerable time interval and/or at a different location).
Note: In the context of blow-moulding processes, the terms 'stage'

and 'step' are sometimes used interchangeably, to the detri-
ment of clarity. The usage adopted in this section is the most
common, and logically consistent.
An example of a two-stage process is the Krupp-Corpoplast system

for the production of stretch-blown bottles in PVC, PAN, and PET.
In the first stage of this process, 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): 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 chan-
nelled for subsequent stretching and blowing operations) to the
temperature optimum for stretch-blowing. Infrared heaters are used,
the pre-moulded neck of the preform being screened from the
radiation. The heated preforms are then stretch-blow-moulded into
the final products.
Note: It is an interesting operational feature of the heating step,

that the peak emission wavelengths of the heaters can be
matched to those at which the plastics material absorbs most
strongly. An early discussion of this method of increasing the

efficiency of radiant heating of polymeric materials was
published by Grant & Foster. 8
15.2.4 Cooling Methods
The importance of proper cooling of PVC preforms has been

mentioned. The cooling of the final blow mouldings before removal
from their moulds is also important: as in any moulding process, rapid
cooling of a blow-moulded article is desirable 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). 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 obtained during the cooling of a moulding when
the temperature is continually falling. Heat flow in steady-state condi-
tions is governed by thermal conductivity. The thermal diffusivity (a)
of a plastic can be calculated from the relationship:
where A is the thermal conductivity; p is the density and cp is the

specific heat capacity at constant pressure all in the appropriate,
consistent units. The following calculated average values of a (in
cm2 S-1) are fairly representative for the temperature range over which
a moulding would be cooling: uPVC, 1·2 x 10- 3 ; PP (homopolymer),
0·6 x 10- 3 ; PET, 0·8 x 10- 3 •
Note: The mould shrinkage of uPVC is substantially lower than

those of polyolefins and PET. The typical value ranges are:
0·1-0·5% for uPVC; 1·5-5% for PE (all densities); 1·0-2·5%
for PP (homo- and co-polymers); 2·0-2·5% for PET (blow-
moulding grades).
The basic method of cooling a moulding is by circulating a coolant

(heat-exchange liquid) through drilled channels or milled labyrinth
cavities in the mould block. Blowing pins in extrusion blow moulding,
and core rods in injection and dip blow moulding, are also channelled
for the circulation of heat-exchange liquid.
Note: Preform temperatures prior to stretch-blowing can be con-
trolled via the liquid circulation system, with the liquid
(normally water) temperatures suitably adjusted up to about
95°C.
Water and glycol are commonly used as heat-exchange liquids:
chilled water, at about 5°C, is most often the coolant 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.
Note: The sweating is dew formation, which takes place when the
air surrounding the mould is cooled down to its dew-point. A
relatively new development-the 'dry-air curtain' system
(available on some Krupp-Kautex extrusion blow moulding
equipment)-enables the die and mould to be surrounded
with air pre-dried to reduce its dew-point: this permits lower
coolant temperatures with consequent speeding up of the
moulding cycle.
Factors in the efficiency of cooling, more important than mould
temperature alone, are the rate and nature of the flow of coolant
through the mould channels: for effective heat transfer the flow should
be fast and turbulent. The optimum cooling conditions are achieved by
a combination of appropriately high pressures in pumping the coolant
through, with suitable design and control of the cooling circuits.
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. Injection into the moulding of liquid nitrogen (as in the

Extrublas system; MG Industries, USA), or of carbon dioxide, or
chilled air (at about -50°C); injection of compressed air and water
mist (as in the Hunkar ILC process; Hunkar Laboratories Inc.,
USA-or the Frost Air system; Ryder Associates, USA); or repeated
flushing with compressed air while maintaining the blowing pressure
(as for example in the Interval Blowing system; Battenfeld-Fischer
Blasformtechnik, FRG).
Heat-transfer analysis for the cooling of mOUldings is discussed in a
paper by Luciana. 9
A theoretical model (confirmed by experimental study) has been put
forward by Edwards et al. 10 for the prediction of temperature profiles
and heat-transfer rates relevant to the influence of operating condi-
tions on the cooling time of blow mouldings (with special reference to
the use of chilled moulds and gas circulation). A paper by Valyill
discusses the basic general relationship between the cooling time (t)
and the wall thickness (w) of a moulding (t = constant x w2 ), and
indicates a practical way of using the relationship to predict cooling-
cycle times.
15.2.S MisceUaneous Features
(a) Mould Venting
This is important in blow moulding, to avoid impairment of the
moulding's surface finish (an 'orange peel' effect in extreme cases) by
air trapped in the mould, and to promote effective cooling through
good surface contact between the moulding and the mould cavity.
(b) Removal o/Waste Material

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 ('top and tail' waste),
and-in containers with handles-handle pinch-off waste and flash. All
the waste has to be removed. The removal operations are automated
to a large extent in modern equipment, and the waste may be
automatically routed to a granulator and from there to the extruder.
(c) Part Removal (Take-Off) Systems

These too are largely automated, especially in modern blow-moulding
equipment. Typically, mOUldings trimmed of waste material are
positively deposited, in the required orientation, on a conveyor on
which they proceed to leak-testing, decorating or labelling, and

packing.
(d) Blowing Pressures

The normal blowing pressures in blow-moulding processes are typi-
cally within the range 0·5-1·0 MPa.
15.3 INDUSTRIAL BLOW MOULDING OF PVC
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 (mod-
ified 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 Section 15.4 below, and Chapter 16). Like that of
other plastics, blow moulding of PVC is benefiting from the advent of
unified control systems, now capable of providing in increasing
measure automatic control, monitoring and in-process adjustment of
equipment operation and product quality; quick mould changing is
also increasingly featured. 12
The extruders used in the extrusion blow moulding of PVC are of
the general kind suitable for PVC extrusion (cf. Chapter 13): LID
ratios around 25: 1 and compression ratios of 1·8: 1-2· 5: 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 mentioned in Chapter 13; the points made apply also to their use
in 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.
Features of equipment design and/or arrangement which reduce the
risk of stock hold-up and consequent local decomposition are particu-

larly important in the blow moulding of PVc. In some equipment the
extruder is mounted end-down, for straight-through vertical extrusion.
With the more common horizontal extrusion arrangement, axial
crossheads are usual, designed to preserve (e.g. by means of a 'swan
neck' curve) smooth melt flow at a constant rate as the flow direction
changes from the horizontal to the vertical. The general, basic
configuration of a typical die is similar to that in pipe extrusion (see
Chapter 13). The die head temperature is usually kept below that of
the entering 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-with multiple heads or one multi-parison
head-is attractive in principle as a means of increasing production
without a corresponding 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 secure
uniformity of melt temperature: because a hotter portion of the melt
will tend to flow faster, local melt-temperature variations can cause
uneven parison length, and variability in parison and moulding wall
thickness. Parison curling (outward splaying) may occur if the outside
of the tube is colder than the inside. Suitable screw temperature
control can promote good melt temperature homogenisation and flow
characteristics. 'Swinging the parison' (non-symmetrical adjustment of
the die ring to increase parison thickness on one side) is sometimes
used as an ad hoc way of compensating for the effects of non-uniform
melt temperature in a production run. A special flow-dividing device
for multi-parison extrusion (the Szentimihaly unit) is also claimed to
work well with PVc. 13 Suitable balancing of flow paths and flow
lengths is a necessary general feature. Multi-parison heads are
available on modern extrusion blow-moulding equipment for PVC,
e.g. the four-parison heads on some Bell and Plastimac models (Bell
Engineering Works Ltd, Lucerne, Switzerland, and Plastimac SpA,
Milan, Italy).
Resistance of working surfaces to acid corrosion is as important in
the 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 ap-
propriate grade of stainless steel* 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).
A more detailed discussion of industrial machines for the blow
moulding of PVC can be found in Ref. 2. Some noteworthy, relatively
recent equipment features include the following. Special provisions for
moulding containers with very thin walls (e.g. collapsible tubes) or
special neck finishes (as on the Pressblower equipment, Ossberger-
Turbinenfabrik GmbH, FRG. Equipment for blow-moulding medical
containers (liquid drug vials), on-line filling, and hermetically sealing
with integrally produced closures (e.g. the Rommelag line, Rommelag
Kunststoff Maschinen GmbH, FRG). Auxiliary parison-head support
for use with extra-heavy die head assemblies (Tahara-Shoyei Co. Ltd,
Japan). Equipment for the coating of PVC (and PET) bottles with
PVDC for improved barrier properties (e.g. the Gom Mark II
machine; Euro-Gom Ltd, Plastics Division, UK).
15.4 PVC COMPOSmONS FOR BLOW MOULDING
Bottle compounds (uPVC compositions for the production of bottles

and jars) are the most important in the industrial context.
Like any other PVC composition, a bottle compound is formulated
in the light of three key considerations: behaviour in processing,
properties for service, and costs.
15.4.1 The Processing Aspect
The basic processing-related considerations in formulating a bottle

compound are substantially the same as those applicable generally to
* A useful review of mould steels has been published by Hoffmann. 14

PVC compositions for extrusion and injection moulding, with addi-

tional emphasis on the following features: ease of processing (pro-
moted by the use of relatively low K-value polymer); need for
particularly good dynamic heat-stability in the manufacture of clear
blow mouldings; and freedom from plate-out (inter alia, to avoid
blockage of vents in blowing moulds).
The uPVC feedstocks for extrusion blow moulding may be in
powder (dry blend) form (widely used in Europe), or in the form of
melt-compounded pellets (predominant in the USA). Pellet feeds are
favoured for the injection blow moulding of good quality bottles and
jars. The respective merits of the two forms of feedstock are
considered in Sections 11.2.2(a) and (c) of Chapter 11.
It is always advisable to check the processing behaviour of any
newly acquired PVC blow-moulding compound. Some of the relevant
tests may be run on suitable laboratory equipment, e.g. the Brabender
Plastic-Corder, or an appropriately instrumented torque rheometer.
The following properties are of particular 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 4.9.2(a) of
Chapter 4. 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. *
Rate of fusion: A bottle compound should be fast-fusing for good,

rapid homogenisation and minimum acquisition of heat history in
processing. Rates of fusion can be determined in a suitable torque
rheometer, e.g. in accordance with ASTM D 2538 16 [cf. also Section
11.4.2(b) of Chapter 11].
* A concise review of melt rheometry (with 78 references) has been published

by Dealy.ls
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.
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 a
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, deter-
mining the amount produced, and identification (e.g. by IR
spectrophotometry). 17
Melt fracture: In extrusion blow moulding of PVC this can cause

varying degrees of surface roughness in the product. Tests, to check if
melt fracture can occur with the particular composition in the
processing conditions, can be carried out directly on the extrusion
equipment, or in a rheometer covering the relevant shear-rate range.
15.4.2 The End-Use Aspect
Except for applications where (as for example in 'squeeze' bottles)

softness is desirable or acceptable, rigidity is an important property in
blow-moulded bottles, jars, and other containers. This is because their
relatively thin-walled structure is better able to resist deformation in
storage, transport and service, the more rigid the walls. Moreover, the
greater the inherent rigidity of the wall material, the lower the
thickness necessary (i.e. the less material need be used) to achieve the
required degree of deformation resistance. This is one of the main

reasons why only unplasticised PVC compositions are used for
blow-moulded bottles. Other important considerations are the better
barrier properties and general chemical resistance of uPVC in com-
parison with pPVC, and its greater stability to extraction of formula-
tion constituents by the bottle's contents. Such plasticisers as are
sometimes included are there not primarily in a plasticising capacity.
Thus, epoxy compounds (usually epoxidised soyabean oil) are used, at
low phr, as components of some stabiliser systems (their presence also
eases melt flow), and small proportions of dibutyl phthalate have been
incorporated in some mineral-water-bottle compositions, to assist
fusion and later to act as preservative (sometimes in conjunction with
benzoic acid) and fungistat.
Properly formulated uPVC has a number of properties which qualify
it as a good material for bottles and other containers for a variety of
uses (see Section 15.5.1 below). These include rigidity, toughness (in
impact-modified or biaxially stretched mouldings), resistance to en-
vironmental stress cracking, high clarity and 'sparkle' of transparent
compositions, good barrier properties, and suitability (when formu-
lated 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 hydro-
carbon solvents, lower impact strength, greater susceptibility to
stress-whitening (of some impact-modified compositions), permeability
to some penetrants, lesser suitability for carbonated-drink containers,
and greater difficulty of recycling.
PVC bottle compounds for the packaging· of oil, beverages, and
pharmaceuticals must fulfil the requirements of the appropriate
regulatory authorities with regard to the acceptability of all formula-
tion components. They must also be formulated to minimise odour
and taste effects and to resist microbiological infestation.
15.4.3 Formulations
(a) Commercial Compounds
The market for PVC blow-moulding compounds is substantial, and
still expanding.
Note: Two of the biggest producers of blow-moulding compounds
in the Western world, Occidental Chemical Corp. in the USA
and Dorlyl in Europe, were each producing over 70000

tonnes a year of such compounds in the period 1986-1987.
The compounds formulated and marketed by most PVC compound
manufacturers (see for example Table 10.1 in Chapter 10) comprise
stock lines in both general-purpose and specialised grades; custom
formulation and compounding to specific requirements is also widely
practised.
Some examples of specialised-formulation compounds are: composi-
tions for food and beverage containers (including compounds for
bottles with good alcohol-blush resistance, e.g. Geon 87388; B. F.
Goodrich, USA); compounds for injection blow moulding and extru-
sion blow moulding with or without stretch blowing; high-impact-
resistance compositions; compounds for products with high surface
gloss; high-clarity transparent compositions; compounds with good
UV-barrier properties (to protect light-sensitive contents); compounds
for medical-use mouldings suitable for gamma-ray sterilisation; com-
pounds for containers suitable for hot filling, and for containers
resistant to contents that can be aggressive towards PVC. Some
compositions are formulated to combine a number of such features.
(b) Formulation Components

The following points may be mentioned concerning the components of
blow-moulding formulations.
PVC POLYMER
Suspension (sometimes mass) polymers are used, with particle struc-
ture and size characteristics suited to ease-of-processing and rapid
fusion. The K value is commonly relatively low (up to about 60) for
easy melt flow.
Note: More recently, polymers of K value 60-70 have also been
developed for blow-moulding compositions. One example is
Solvay's HTP resin ('high-technology polymer') for stretch-
blow moulding compositions, claimed to combine normal
processability with improved product properties (including
substantially reduced creep and permeability).
The polymer, should be of good quality, free from gels (which
produce 'fish eyes' and 'nibs' in mouldings), and of appropriately low
VC monomer content conforming with relevant regulations (especially
in the case of containers for foodstuffs and beverages).
Note: Whilst general standard methods for gel determination are

available,18,19 one intended specifically for bottle compounds
has been described by Latham & Mendham.17 In this, a
free-blown, thin-walled bubble is produced (on a Plasti-
Corder with an extrusion attachment and bubble die), in
which any gels should be plainly visible. In an opaque
production bottle, gels may not be readily detectable from
the outside, but they often show up as small protrusions on
the inside surface. Their presence may significantly impair
strength properties, since they can act as stress concentrators.
STABILISER SYSTEM
Liquid systems have the advantage of not increasing the melt viscosity
of a blow-moulding compound. Thiotins are widely used for their high
heat-stabilising effectivity and good compound clarity: for food-contact
applications, permitted octyltin stabilisers are available (more recently
also some methyltins, which are cheaper). Calcium/zinc systems,
whilst less effective as heat-stabilisers, are also much used in blow-
moulding compounds: many non-toxic grades are available for food-
contact and medical applications. They offer better organoleptic
properties (less odour and taste effects) than do the organotins: this is
particularly important in compounds for food, toiletry, and cosmetic
containers. Epoxy co-stabilisers are often included, sometimes with
phosphate or other synergists.
IMPACT MODIFIERS
As toughness is a highly desirable property in blow mOUldings,
especially in many kinds of blow-moulded containers, impact modifiers
are important components of uPVC compositions for such mOUldings,
particularly those produced without biaxial stretching. The nature of
impact modifiers, and their effects in uPVC, are discussed in Section
8.3 of Chapter 8. MBS impact modifiers are normally used in
formulations for clear blow mouldings, and ABS ones are popular-
though not exclusively employed-in those for opaque products.
In blow-moulded containers, the impact modifier can adversely
affect such properties as permeability; colour; softening point; and
resistance to stress whitening, chemicals, photochemical degradation,
and environmental stress cracking. The extent of a particular effect can
vary substantially among individual members of the same class of
impact modifiers: for example, some otherwise comparable MBS
modifiers differ considerably in the way they affect the resistance to

environmental stress cracking of clear PVC containers for oils (edible
and mineral), cleaning liquids, and solvent- or oil-containing composi-
tions (e.g. certain toiletries). It is, therefore, an important selection
criterion that the particular modifier chosen should combine optimum
toughening effects with the least impairment of all the relevant
properties.
LUBRICATION
The most effective lubricant systems for blow-moulding compositions
are mUlti-component ones, combining internal and external lubricating
functions. Freedom from plate-out is an important formulating con-
sideration, as is permanence in service (resistance to extraction and
migration). Impact resistance of the product can be significantly
reduced by excessive internal lubrication. Irgawax 368 (Ciba-Geigy)
and Loxiol HOB 7111 and 7112 (Henkel), are examples of proprietary
composite lubricant systems developed for blow-moulding
applications.
OTHER COMPONENTS
Processing aids (commonly acrylic) are usually included in blow-
moulding compositions. The improvements in melt strength and
elasticity promoted by the presence, at low phr, of such acrylic
processing aids as (for example) Aeryloid K120 ND can be particularly
important in blow moulding. Another beneficial effect of such process-
ing aids is a reduction of the yellowing and tendency to haze
development of clear compositions containing certain impact modi-
fiers: this improvement arises as the processing aid, when intimately
mixed with the PVC polymer, brings the refractive index of the
resulting blend closer to that of the impact modifier (the refractive
indices of many impact modifiers are appreciably lower than those of
PVC polymers).
Polymeric modifiers which increase the heat-distortion temperature
of blow mouldings are incorporated in compositions for the production
of 'hot-fill' bottles and jars, and containers which are sterilised after
filling (e.g. bottles for certain fruit juices). Some commercial com-
pound grades (e.g. those available froni Solvay), incorporating such
modifiers, can withstand filling or sterilisation temperatures of 85-
95°C.
Colourants and pigments are incorporated in some blow-moulding

compositions, as appropriate.
15.5 PVC BLOW MOULDINGS
15.5.1 Applications
The vast majority of PVC blow mouldings comprises containers, used

for the packaging of a variety of products. The containers are mostly
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.
In Europe, the largest application area for PVC bottles has long
been the packaging of consumable liquids (including fruit squashes,
edible oils, vinegar, cheaper varieties of table wine, and mineral and
natural-spring water). In the mid-1980s, the most important single
European outlet for PVC bottles has been the packaging of mineral
water (especially in France and Spain). In France, over 75% of all
liquid packaging has been in PVC bottles. 2o The packaging of
comestibles in blow-moulded containers in the USA began to gather
momentum only in 1983, when edible oils came to be packaged on a
substantial scale in uPVC bottles. This was brought about by the
partial lifting of long-standing objections by the FDA, following the
introduction, in 1981, by the Ethyl Corporation of their blow-
moulding compounds with a claimed extractable VC monomer level of
only about 5 parts per billion (109 ). Similar materials from other
manufacturers became available soon afterwards. Currently, the
packaging of wine and non-alcoholic drinks in uPVC is allowed by the
FDA, with an extension of approval to alcoholic drinks being
considered.
Liquids for household use (detergents, cleaners, disinfectants,
bleaches), cosmetics and toiletries (e.g. lotions, oils, shampoos and
other hair-care preparations, liquid soaps), and some pharmaceuticals,
are widely packaged in blow-moulded uPVC containers. In several of
these applications the competing materials are polyethylene tereph-
thalate (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 pharmaceuticals-e.g.
mouthwash), and modified polyacrylonitrile (applications in which
barrier properties are of particular importance).
Note: As mentioned in passing in Section 15.3, the barrier pro-
perties of PVC containers can be improved by a PVDC
coating (usually 8-10 Jlm thick, applied by dipping in or
spraying a dispersion of the polymer). In some cases such a
coating applied to a preform may retain its cohesion and
adhesion in the course of subsequent blowing. Coating
solutions of ethylene/vinyl alcohol copolymers have been
developed (by the US Industrial Chemicals Co., USA) for
application to finished containers blow-moulded in various
materials, including PVC.
15.5.2 Properties and Tests
The properties of a PVC blow moulding are influenced by the

material, the design and the processing of the article.
The material-related features of PVC blow mOUldings have been
mentioned in some of the preceding sections.
The most important design features are not specific to PVC
mouldings, and are thus outside the scope of this chapter. It may be
mentioned, however, that promotion of 'vertical strength' (resistance
to vertical loading) is perhaps the most important single design
consideration with blow-moulded containers: common features which
can reduce vertical strength are shallow shoulder slopes, and the
presence of horizontal corrugations in the container body: if these
latter take the form of sharp-ridged bellows, they can also aggravate
susceptibility to environmental stress cracking. A useful discussion of
the design of plastics bottles has been published by Szajna. 21
Apart from those general processing factors which influence the
quality of all PVC products manufactured by melt-processing (com-
pletenesses of homogenisation and fusion of the material, heat history,
and maximum temperature in processing), the others that affect the
properties of blow-moulded PVC containers are molecular orientation
(in particular that imparted by stretch-blowing); the temperature of
(and temperature distribution in) the parison or preform at the
blowing stage; and the rate and efficiency of cooling. The properties
most affected are strength and dimensional conformity: in extrusion
blow moulding the parison temperature is a factor 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).
Two properties normally monitored in the course of routine quality
control in production are the integrity (freedom from leaks), and wall
thickness of the containers. Modern leak detectors are microprocessor-
operated: they work by detecting the rate of pressure decay after
slightly inflating the container.
Service-related quality control tests widely performed on blow-
moulded 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 per-
meability). Another ASTM standard (D 2911) lays down dimensional
tolerances for blow-moulded containers. Compatibility with the in-
tended contents is also sometimes determined, usually by relevant
mechanical property tests on containers before and after a prescribed
period of contact: such tests are desirable for example with some oils,
whose penetration into some impact-modified uPVC materials may be
excessive over a period of several months.
As has been mentioned, resistance to environmental stress cracking
is a requirement in respect of PVC bottles for oils and certain
solvent-containing compositions [see Section 15.4.3(b)]. Such resis-
tance is often evaluated in terms of changes in the impact strength
(tensile or flexural) of specimens moulded from the container material,
after immersion, under stress, in either the actual liquid to be
packaged or in another relevant test liquid (e.g. turpentine; sunflower-
seed oil). 22
The containers used in container-property tests may be samples of
actual production, or standard container specimens of prescribed
design and size (e.g. the 4-oz bottle for Procedure A of ASTM D 2684-
84; or the 750-cm3 Lesieur test bottle23 ). Such standard containers are
also often used in comparisons or evaluation of the effects of
moulding-compound formulation and properties upon the properties
of the container.
A non-destructive dynamic compression test of a few seconds'
duration has also been proposed. 24 This yields a numerical index of the
container's resistance to flexure under 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 container's relevant mechanical properties, and to
correlate well with the results of some conventional destructive tests.
As containers for carbonated drinks, PET bottles are much more
widely used than PVC ones. This is so because even stretch-blown
PVC bottles have difficulty in meeting the leading drinks manufac-
turers' specifications for heavily carbonated soft drinks. With carb-
onated drinks, the principal requirement is for a combination of
sufficient resistance to internal pressure with a low enough per-
meability to CO2 to provide a sufficiently long shelf-life before
'carbonation loss' occurs. For a two-litre PET bottle, a typical
specification may require a shelf-life of 16 weeks (with 8-12 weeks for
a half-litre bottle) even in hot climates. Claims made for some
specially designed, heavy-weight, stretch-blown PVC bottles indicate
that they may come close to meeting this kind of requirement even for
more heavily carbonated drinks. 2
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 Sahajpa1. 2s
REFERENCES
1. Couzens, E. G. & Yarsley, V. E., Plastics in the Modern World. Penguin

Books, Harmondsworth, Middx, UK, 1968, p. 298.
4. Brownbill, D., Mod. Plast. Int., 16(9) (1986) 34, 55.
5. De Vries, A. J. & Bonnebat, C., Polym. Engng Sci., 16(2) (1976) 93-100.
6. Brady, T. E., Polym. Engng Sci., 16(9) (1976) 638-44.
7. Gilbert, M. & Lui, Z., Plast. Rubb. Process. Applns, 9(2) (1988) 67-72.
8. Grant, R. & Foster, R. Mod. Plast., 43(2) (1965) 122-9, 199.
9. Luciana, J., Plast. Engng, 37(10) (1981) 23-5.
10. Edwards, M. F., Georghiades, S. & Suvanaphen, P. K. Plast. Rubb.
Process. Applns, 1(2) (1981) 161-5.
11. Valyi, E. I., Plast. Techno/., 27(10) (1981) 133-45.
12. Sneller, J. A., Mod. Plast. Int., 18(9) (1988) 49-51.
13. Smith, A., Plast. Rubb. Wkly, (21 June 1986) 20.
14. Hoffmann, M., Plast. Technol., 28(4) (1982) 67-72.
15. Dealy, J. M., Plast. Engng, 39(3) (1983) 57-61.
16. ASTM D 2538-79 (1985). Standard Test Method for Fusion of Poly(vinyl
chloride) (PVC) Resins Using a Torque Rheometer.
17. Latham, J. R. & Mendham, W. E., 31st ANTEC SPE Proceedings, 1973,
pp.458-60.
18. ASTM D 3351-74 (1980). Standard Test Method for Gel Count of Plastic
Film.
19. ASTM D 3596-77 (1983). Standard Practice for Determination of Gels
(Fisheyes) in General-Purpose Poly(vinyl chloride) (PVC) Resins.
20. Anon., Plast. Rubb. Wkly, (12 April 1986) 8-9.
21. Szajna, J. L., Plast. Engng, 27(3) (1981) 83-7.
22. Lutz, J. T. In Degradation and Stabilisation of pvc (ed. E. D. Owen).
23. Sisson, W. B., Plast. Polym., 36(125) (1968) 453-63.
24. Hunkar, D., Plast. Rubb. Wkly, (12 Nov. 1976) 30-1.
25. Sahajpal, V. K., PVC compounding for low organoleptics and controlled
bacterial growth. Paper presented at the PRI International Conference on
PVC Processing, Egham Hill, Surrey, UK, 6-7 April 1978.
CHAPTER 16
Injection Moulding
16.1 THE PROCESS AND ITS APPLICATION

TO PVC-GENERAL
Injection moulding is one of the most important melt processes for

thermoplastics. With PVC, and especially uPVC, its operation is
complicated by two factors: the susceptibility of PVC polymers to heat
degradation, and their high melt viscosity. These factors can give rise
to problems: they necessitate particularly careful control of the
thermal input, melt temperature, and pressures in the process.
However, in recent years the difficulties have been considerably eased
by the development of effective, sophisticated electronic means of
process control, and by the advent of 'easy flow' uPVC moulding
cOQlPounds.
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; and finally emptying the
mould.
The two features mentioned above as sources of difficulty in
processing PVC are particularly significant in the stages of melt
preparation and mould filling, because it is in these stages that the
melt reaches its maximum temperature and is forced to flow through
restricting elements such as the cylinder nozzle, sprue, runners, and
gates. In the other stages of the process it is generally satisfactory to
consider PVC as one would other, 'easier' thermoplastics.
588
16 Injection Moulding 589
16.2 THE MATERIAL ASPECT
16.2.1 PVC Melt Properties and Behaviour
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: susceptibility to decomposition, in times of the order of
moulding cycles, at the levels of temperature found to be necessary;
and-in the absence of plasticisers or other flow promoters-a melt
viscosity at those temperature levels which is significantly higher than
that of many other thermoplastics.
As has been mentioned in Chapter 4, in PVC melt-processing
degradative effects can become apparent over a range of temperatures,
including levels below those typical in moulding, and within the times
for which the melt is held at these levels. This lends relevance to the
concept of residence time (often applied by moulders when setting up
a trouble-shooting programme), but this concept should not be used 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
almost always much less prominent and camouflaged by thermal
effects.
The graph of Fig. 16.1 illustrates, in a general way, with values for
specific time-temperature pairs, the ·straightforward effect of melt
temperature for three types of PVC moulding compound, and-4ln this
basis-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 significant thermal decomposition in the time concerned).
However, as has been indicated, to deal adequately with degradative
effects occurring during moulding, the broader picture of integrated
thermal input has to be considered. In this connection it should be
230
220
210
\r>.
'"
I...
::J
1;i200
I...
'"
a.
E
~ 190
180
Tlml2.S
Fig. 16.1 Time-temperature limit curves for degradation effects in the

moulding of three typical PVC compounds. A, Pipe fitting compound; B,
rigid general-purpose compound; C, flexible compound. Generalised repre-
sentation.!
realised that the degradation which may occur during moulding cannot
be attributed to one specific time-temperature value pair.
The melt reaches the mould cavity by what might be regarded as an
integration of a series of temperature-time steps varying continuously
as the plastic material proceeds from hopper to mould entry. Shear
work, dissipated as thermal energy which raises 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,
promoting non-homogeneous build-up of temperature. Poor stream-
lining 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 composition of the PVC material determines the melting and
flow behaviour during the melt preparation stage, and melt rheology
during the rest of the moulding operation. Shear work is another
feature dependent upon composition via rheology (slip and flow
behaviour--cf. also Section 7.1 of Chapter 7).
16.2.2 Moulding Compounds
(a) General Points

The plasticisers present in pPVC compositions lower the melt viscosity
and make for easier processability, generally at heat inputs and
temperatures lower than those required for uPVc. It is thus the uPVC
compounds with which the factors mentioned in Section 16.1 come
particularly strongly into play, and can give rise to processing
problems: this is the reason for uPVC's traditional unpopularity with
moulders, and has been long operative as a restrictive influence on the
scope and volume of industrial injection moulding of 'rigids'. As has
been mentioned, the situation has improved in both these respects
with the appearance of 'easy flow' rigid PVC compounds, and
sophisticated process controls.
The mould shrinkage of rigid PVC compositions is relatively low:
typically 0·1-0·7%. That of plasticised compositions is generally more
variable and considerably higher.
Note: Shrinkage of plastics mouldings is a function not only of the
coefficient of thermal expansion of the material and of part
'geometry', but also of some processing factors, notably the
processing rates and conditions (especially during the holding
phase). Useful comments on the practical aspects of mould
shrinkage calculations for optimum processing rates have
been published by Glenn? and on computer programs for
shrinkage calculations by Menges et al. 3
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 exposure to humid atmos-
pheres. Even in such cases a hopper drier on the injection machine
may be sufficiently effective. Any oven pre-drying should normally be
done in shallow layers (up to about 4 cm), with the temperature and
time of drying preferably not exceeding 65°C and 3 h respectively.
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 homogen-
ised and uniformly fused (cf. Chapter 13), and thus-unlike powder
(dry blend) feed~oes 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.
(b) 'Easy Flow' Moulding Compounds

The melt viscosity of rigid PVC compounds, and shear-heat generation
in the melt, can be significantly reduced-with little or no sacrifice of
ultimate product properties-by suitable formulation, and in particular
by the use of special PVC homopolymer resins of relatively low
molecular weight (and usually also fine particle size and medium
porosity). 'Easy flow' injection-moulding compounds commonly based
on such resins (with processing aids and impact modifiers in many
cases) are available from a number of suppliers. With good equipment
and moulding practice, they enable production of thin-walled mould-
ings of large surface area, involving complex flow-paths; deep draws,
as well as normally difficult surface detail, can also be achieved in
many cases. Typical applications are in moulding computer and
word-processor keyboard surrounds, housings and bases for personal
computers and video display unit terminals, office and electronic
equipment. Some examples of commercial 'easy flow' compounds are:
Trosiplast 3233, 3255 and 3256 (Dynamit Nobel), Geon easy flow
grades (B. F. Goodrich), and Benvic IR grades (Solvay). Data
illustrating some properties of impact-modified 'easy flow' compounds
are presented, by way of example, in Table 16.l.
Compounds based on copolymers of vinyl chloride are also some-
times used (where the ultimate product properties are acceptable), as
are ones based on blends of PVC homopolymers with certain suitable
polymers (see also Chapter 8). Some of the latter compositions
combine ease of flow with good mechanical properties and high
softening temperatures, as for example in the case of some
PVC/styrenic 'alloys' (Georgia Gulf Corp., USA) with deflection
temperatures under load (at 1·82 MPa-ASTM D 648) in the range
85-90°C.
(c) Melt Flow Tests for Moulding Compounds

The three tests most directly relevant to PVC moulding compounds
have all been mentioned in Section 7.3.1(c) of Chapter 7. They are the
determination of 'flow length' in a spiral mould (which can be carried
out under the actual processing conditions concerned), the piston
plastometer test of ASTM D 3364-74 (1985), and the capillary
rheometer test of ASTM D 3835-79 (1983).
TABLE 16.1
Properties of Some 'Easy Flow' Impact-Modified Rigid PVC Moulding
Compounds
(Table based on manufacturer's published data.)
Property Test Compounds (grade codes)"
method
(ASTM) 327 335 337 339 341
Density, g cm- 3 0792 1-43 1-41 1·33 1-45 1·40

Durometer hardness, 02240 79 77 76 77 79
Shore D
Tensile properties D638
Yield stress, MPa 50 50 45 45 46
Strength at break, MPa 40 40 34 36 37
Elongation at break, % 140 114 26 35 76
Young's modulus, MPa 2880 2990 2760 3030 2700
Impact resistance
(Izod), Jim D256b
Notched
At 23°C 67 48 61 33 114
AtO°C 43 34 36 24 41
At -20°C 36 32 21 18 30
Un-notched
At 23°C >2370 2010 520 1140 No break
AtOOC 1240 1590 546 437 1750
At -20°C 660 361 316 343 762
Vicat softening point
(50N load), °C 01525 77 81 90 86 80
Flow length in spiral
mould (15 mm x 2 mm),
mm 360 400 550 550 400
a Benvic IR grades.
b Or ISO 180.
The piston plastometer (a melt-flow index apparatus with a modified

die) provides means of comparing the melt flow of PVC compounds
with particular reference to the effects of compositional factors and
thermal and rheological stability. ASTM D 3364 claims some correla-
tion of the test results with actual behaviour in processing, but the
validity of this claim in individual cases is subject to such factors as the
differences in shear rates between the 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 results of the standard ASTM capillary rheometer test can

reflect the rheological effects of molecular weight and molecular
weight distribution of the PVC polymer, the thermal and rheological
stability of the compound, and the effects of additives. The shear rates
and temperatures (170-205°C for PVC) used in the test are com-
parable with those encountered in processing.
16.3 EQUIPMENT AND PROCESS CONSIDERATIONS
The main general factors governing the quality of a moulding are:

suitability and quality of the material (the moulding compound); the
design of moulding and mould (which are interrelated); the quality
and general suitability of the equipment; and correct processing (which
involves correct operation of the equipment in a way appropriate to
the material being processed and good control over all phases and
parameters of the moulding cycle).
The discussion in this section focuses on such aspects of injection-
moulding equipment and process as are particularly relevant to the
moulding of PVC, and especially uPVc. General aspects of machine
design, part and mould design, and common features of moulding
equipment are not covered: accounts of these subjects can be found,
inter alia, in Refs. 4-8.
16.3.1 Equipment
(a) Features and Operation

The modern injection-moulding machine is a sophisticated piece of
equipment, which may be operated with the aid of multiple-
microprocessor devices and systems affording full closed-loop control
over process parameters, the individual process steps, and their
balance and integration. This provides the means of setting up and
maintaining optimum conditions for the moulding of 'difficult', heat-
sensitive materials like uPVc. 'Intelligent' control systems are avail-
able, with sets of software programs for monitoring and instan-
taneously analysing operations in the injection-moulding machine, and
continuously optimising process parameters during production. The
process elements that must be suitably controlled for optimum
moulding quality are melt temperature (controlled via barrel and
nozzle temperatures and temperature profile, screw speed and back-

pressure); mould temperature; the rate and time-profile of injection;
injection pressure; holding pressure and time; and the suitability and
accuracy of the shot weight.
Whilst manufacturers will always advise on 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 3·5 tons (UK) per square inch of projected
area of moulding (i.e. about 55 MN m- 2 , in round figures), although
anything from about 2 UK ton in- 2 (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 of excessive heat
history when operating near the top limit of the relatively narrow
melt-temperature range (see below) 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
the balance of the effects of melt temperature, residence time, and
cycle time-always important with PVC-becomes progressively more
critical.
Several features of equipment 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 the 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-tip patterns for
different circumstances have been published by Tulley & Harris,9 and
about the moulding of rigid PVC generally by Huber. 10 The screw
should preferably be of a design intended for uPVC processing: L/ D
ratios in the range 14-24: 1, and compression ratios of 1·5-2·0: 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 1·5: 1 2·0:1 2·5:1 3·0:1

Back-pressure range, lbf in- 2 0-1000 0-400 0-100 0-50
Rotational speed range, r min- 1 20-100 20-80 20-50 20-30
It can be worthwhile to set the machine to operate under zero cushion

mode: otherwise a minimum cushion (say 2-6 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. The use
of a mould evacuation system (e.g. Mold Vac System 2000; Applic-
ation Engineering Corporation, USA) can be helpful in preventing
short shots and burns, particularly with complex moulds. The tem-
perature control system should preferably be of the PID (proportional-
integral-derived action) type.
A paper by Ganzeman 12 reviews some of the points relevant to
process control in the moulding of PVC. Two brief general summaries
of considerations important in injection moulding of uPVC have been
published by Whelan 13 and Murrey & Dito. 14
(b) 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. A useful
tabulation of steels recommended for various moulding materials and
conditions in injection, compression, blow moulding, and extrusion
has been published by Worbye. 15
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 in-
hibitors, usually in sprayable form) are available on the
market.
16.3.2 Processing
(a) Stock Temperature, and Temperature Settings

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 to the factors influencing
shear heating in the barrel (the back-pressure and rotational speed of
the screw-see above) and the frictional heating thereafter (size and
configuration of the nozzle, flow channels and gates; rate of injection).
The melt temperature should be monitored directly.
Note: In the absence of a suitable continuous control system, it may
be intermittently checked by inserting a thermocouple into
the melt flushing out of the nozzle while the barrel is
retracted from the mould.
Temperature sensors should be positioned so that they do not cause

additional friction or stagnant spots in the 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 temperatures are normally set to lag behind the
desired stock temperatures: the heat needed to make up the difference
should come from the right amount of mechanical working of the
material in the barrel, secured by the appropriate speed and back-
pressure of the screw.
The actual heater temperature settings will vary with the composi-
tion being processed, with the machine and mould set-up, and with the
screw type, speed and back-pressure, but the kind of general arrange-
ment just mentioned offers the following advantages. The final fusion
of the stock to a melt takes place well forward in the barrel, so that the
amount and the 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.
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 5°C) until the
screw is running normally.
The melt temperature should preferably not exceed 205°C, and
should never be higher than 215°C: the range 180-205°C may be
regarded as typical for most processing.
The mould (inlet water) temperatures used are normally within the
general range 20-70°C, with 20-40°C 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.
Some general recommendations on the moulding and processing
temperatures for plastics (including PVC) are contained in a publica-
tion by Regloplas. 16
In the case of stoppages of appreciable length, the heater tempera-

ture 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 emptied completely and
purged with a purging compound (see Chapter 13, Section 13.3.3), or
with a general-purpose polystyrene, ABS or HOPE moulding mate-
rial, at a relatively low temperature (about 160°C): uPVC should never
be left to solidify in the barrel.
(b) 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 through
excessive frictional heating (often first manifested by streaky discol-
ouration at and near the gate point-d. Table 16.2).
Note: If the injection rate is reduced too far, weak weld lines, sink
marks, or even short shots may result. When the characteris-
tic 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.
Injection pressure is interdependent with injection rate, and is 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 three-
quarters 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 25 000 lbf in -2 (about
172 MNm- 2).
(c) Interaction of pvc with Acetal Polymers and Copolymers

PVC and acetal resins (e.g. Delrin-Ou Pont; Hostaform-Hoechst;
Kematal-Amcel UK; Celcon-Amcel, USA) interact strongly 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, ex-
truders, melt compounding mixers, etc.). It is highly preferable that
the same machine should not be used for the processing-especially

consecutive processing-{)f these materials: at the very least, ex-
tremely thorough purging must be carried out (with a suitable purging
compound-see above) before a change-over, and/or where prac-
ticable a change of the injection unit (cylinder and screw).
16.3.3 Flow Moulding
The variant of injection moulding known under this name* enables

large mOUldings to be produced on relatively small injection machines
(e.g. a 30-lb pipe fitting on a 250-ton machine) 1 by utilising the
pressure developed by the rotation of the screw (instead of that
produced by the injection stroke). The process may be regarded as a
combination of extrusion (as the means of supplying the melt to the
mOUld) and injection moulding (in that conventional-though
modified-injection-moulding equipment is used). The modifications
include adjustment of the hydraulics to keep the screw in the forward
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 well suited to heat-sensitive materials such as PVC.
6.3.4 Moulding Quality Maintenance, and Some Common Faults
Good knowledge of the material concerned (more important with

PVC compounds than with other common thermoplastics), and
effective use of such control aids as the equipment provides, are two
general prerequisites to achieving continuous, in-balance, quality
mOUlding.
The moulder with a limited range of machines faces problems not
necessarily encountered by the one who can match more closely
machine size to moulding-shot weight and cooling time. The essential
feature to be considered in this connection is the residence time
or-more accurately-the integrated thermal input (temperature-time
integral) as discussed in Section 16.2.1.
* Originated by Durapipe Ltd, Cannock, UK.

In the absence of satisfactory automatic controls, it is important to

maintain observation of heater read-out indications during operation
(watching out, inter alia, for any persistent and increasing override),
filling rate (to spot any tendency to increase with running time), and
changes in the thickness of cushion layer.
Observation of the product provides the clues from which process
adjustments can be decided upon. Table 16.2 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). A book by
Brown17 provides some useful general comments on the origin and
nature of faults in plastics mouldings, and on remedial measures.
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.
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.
Possible useful modifications to older equipment (only screw-type
machines are suitable) may include: removal of unstreamlined non-
return valves and addition of conical extension to the screw tip;
possibly addition of proprietary control features (often not a difficult
matter); introduction of cavity pressure control and/or screw-advance
rate control (especially where streamlining of the forward zone may be
difficult) .
16.4 SOME EFFECTS OF PROCESSING ON THE

MORPHOLOGY OF INJECTION MOULDINGS
As with other thermoplastic polymers, quenching stresses and molecu-

lar orientation can and do arise in PVC (particularly in uPVC)
mouldings. 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.
TABLE 16.2
Common Faults in PVC Mouldings
Observation Significance Adjustment

1 Splay marks or Maybe due to Choice of reduction of
silvery streaks condensed moisture forward band heater
emanating from the but, more important, settings (especially
gate position could be initial signs nozzle temperature),
of decomposition due screw speed, back-
to thermal input pressure, filling rate,
increased above singly or in various
acceptable level combinations
2 Dark centre to Progressive over-heating Adjust barrel temperature
sprue or internally of material and/or reduce back-
in gate area (sometimes associated pressure, and/or screw
with hot spot at screw speed; if fault persists
tip) attend to shape or
smooth runs of screw
tip; perhaps change to
distorted tip to give an
increase of local shear
3 Dark, streaky areas Increasing over-heating Reduce band-heater
on surface of sprue of material settings, and/or back-
pressure and speed of
the screw
4 More prominent Some decomposition of Retract barrel and make a
areas of darkened material due to over- few air shots to remove
material on sprue heating overheated stock.
surface often Return barrel, reduce
extending from heater settings; increase
sprue into the cooling, lower screw
moulding speed and/or back-
pressure; consider
residence time
5 Dark streaks High shear or stagnation Better streamlining
spreading from gate in this region required: slow down
point input rate, attend to
streamlining if
necessary; consider
enlarging nozzle and/or
gate(s)
6 Dark decomposition Local 'burning' First try reducing injection
spot at the same rate; if fault persists
point in each attend to proper mould
moulding venting and radiusing of
(sometimes in weld corners
line)
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 has been published
by Haworth et al. 18
16.4.1 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 may be set up 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.
16.4.2 Orientation and Related Features
The shear involved in melt flow, and the flow pattern, give rise to
molecular orientation resulting in anisotropy of the mechanical and
other properties of the moulding. 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 normally 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
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
trouble-shooting, enabling some of the complex interrelationships
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 processing conditions on the
properties of injection-moulded rigid PVC products is due to Gilbert et
al.,19 who give a description of the behaviour of a selected rigid
composition involving typical ingredients. A low level of crystallinity
in mOUldings made from this composition was observed, as were
differences between the skin and core, a layered structure developing
during mould filling and cooling. The distinct skin layer was highly
oriented as shown by its strong birefringence (when a thin cut section
was viewed through the thickness), whereas the core was largely
unoriented. The skin layer decreased in thickness, from about 0·4 mm
down to around 0·1 mm, as moulding thickness of this oriented skin
was governed by each of the commonly varied process factors: filling
rate, mould temperature, material temperature. Unfortunately, no
reference is made in the paper to quenching stresses, which must have
developed in parallel with the oriented skin layer.
16.5 INJECTION MOULDING OF CPVC
The principal general consideration, as in all melt-processing of

CPVC, is that the melt viscosity of CPVC compounds is substantially
higher than that of uPVC ones at similar temperatures, whilst viscosity
reduction (increase in fluidity) with rising temperature is considerably
less (see Chapter 3, Section 3.4.4). Although CPVC is subject to heat
degradation, it can-and should-be processed at temperatures higher
than those appropriate for uPVc. In injection moulding the melt
temperature should not be less than 215°C; it should be typically in the
range 220-235°C, and generally the highest practicable, for the
greatest ease of flow.
The following recommendations may be mentioned as further
guidance points.
The machine: Reciprocating-screw type, with screw compression

ratio 2·0: 1-2·5: 1. Screw equipped with a smear-head tip (material
and/or machine manufacturer's recommendations should be sought for
the most suitable tip land length and clearance between tip and
barrel).
Moulds: Preferably ring or side gating, with cold-slug wells near

gates. Gates generally larger than for uPVC (actual size in particular
cases should be determined by prototype trials or computer-aided
design (CAD) methods). Too small gates can cause sink marks (short
shot), burn marks (dark streaks-see item 5 in Table 16.2), weak weld
lines, and blush marks, and promote internal stresses in mouldings.
Runners should be full round, and the shortest possible; the desirable
minimum runner diameter depends on shot weight (e.g. 9·5 mm
should be generally suitable for the shot range 170-680 g). Venting
should follow normal good practice, i.e. vents opposite the gates and
at other points (e.g. site of a weld line) where air could be trapped.
The mould's working surfaces should be protected by multiple-layer,
hard-chrome plating; suitable stainless steel moulds may also be used.
Processing: The melt temperature considerations have already been

mentioned. Operating-as is desirable-at the highest possible tem-
perature is safest (i.e. the risk of degradation is least) when the
machine capacity is closely matched to that of the mould, because the
material residence time at the high temperature is minimised. In
general, the total shot weight (including runner and sprue material)
should not be less than 75% of the machine's rated capacity: otherwise
some material will remain overlong at the high temperature and is
likely to suffer degradation, or the temperature may have to be
reduced to below the optimum. The back-pressure should be the
highest practicable without material degradation (fairly typically 700-
1380 kPa). Maximum injection pressure is normally used to ensure
proper mould filling.
REFERENCES
1. Turner, L. W. In PVC Technology, 4th edn, W. V. Titow. Elsevier

Applied Science Publishers, London and New York, 1984, Ch. 15.
2. Glenn, W. B., Plast. Technol., 26(10) (1980) 73-5.
3. Menges, G., Schmidt, T. & Potsch, G., Mod. Plast. Int., 17(9) (1987)
68-71.
4. Johannaber, F., Injection Moulding Machines-A Users Guide. Carl
Hanser Verlag, Munich, 1983.
5. Anon., The Principles of Injection Moulding. ICI Technical Service Note
G 103 (2nd edn), ICI Plastics Division, England.
6. Stokhert, K. (Ed.), Mould Making Handbook. Carl Hanser Verlag,
Munich, 1983.
7. Menges, G. & Mohren, P., How to Make Injection Moulds. Carl Hanser
Verlag, Munich, 1986.
8. Pye, R. G. W., Injection Mould Design, George Goodwin Ltd/PRI,
London, 1982.
9. Tulley, F. T. & Harris, B. C. In Encyclopedia of PVC, ed. L. I. Nass.
Marcel Dekker, New York, 1979, Ch. 24, p. 1313.
10. Huber, M., Plast. Rubb. Wkly (18 Feb, 1977) 20-3.
11. Anon., Technical Bulletins 8/73. Ethyl Corporation, Polymer Division,
Baton Rouge, LA, USA.
12. Ganzeman, A. J., Plast. Rubb. Process. Applns, 4(2) (1984) 127-33.
13. Whelan, A., Brit. Plast. Rubb., (Apr. 1981) 25.

14. Murrey, J. L. & Dito, A. L., Plast. Technol., 27(12) (1981) 79-82.
15. Worbye, J., Polym. Plast. Technol. Engng, 25 (1986) 109-26.
16. Anon., Recommended Molding and Processing Temperatures of Plastics
and Rubbers. Regloplas AG, Flurhofstrasse 158, CH-9006 St Gallen,
Switzerland.
17. Brown, J., Injection Moulding of Plastic Components-A Guide to
Efficiency, Fault Diagnosis and Cure. McGraw-Hill Book Co., London,
1979.
18. Haworth, B., Sandilands, G. J. & White, J. R., Plast. Rubb. Int., 5(3)
(1980) 109-13.
19. Gilbert, M., Marshall, D. E., Voyvoda, J. C. & Copsey, C. J., Plast.
Rubb. Process., 3 (1979) 96.
CHAPTER 17
Other Processes
17.1 COMPRESSION MOULDING OF PVC
17.1.1 General
In terms of commercial importance, compression moulding is not

among the major PVC-processing methods. Its significant industrial
applications are essentially confined to the production of gramophone
records, and the manufacture of thick PVC sheets by press lamination
of stacks of thinner ones.
Note: Press finishing of sheets is also practised (see Chapter 14,
Section 14.6). However, the object of this operation is
essentially to improve the thickness uniformity and surface
finish of the sheets (which are products already manufac-
tured, by methods other than compression moulding). Thus it
is very strongly arguable whether the operation can be
regarded as compression moulding in the proper sense of the
term.
For laboratory-scale production of samples and test specimens, com-
pression moulding is still the common (and indeed in many cases the
standard) method.
17.1.2 Industrial Applications
(a) Production of Gramophone Records

Records are compression-moulded from VC/VAC copolymer com-
positions, melt-compounded for best homogenisation. In the original,
607
early format of the process, a pelleted compound was first produced

on the set-up
Internal mixer~ Two-roll mill~ Extruder (with pelletiser)
Weighed amounts of the pellets were next heat-fused to form
coherent, hot 'slugs', and each slug was then fed into a mould where it
was pressed to form a record: the pre-weighing was so regulated that
little or no flash was produced in the moulding. The pressed record
would be cooled briefly in the mould, and the cooling completed (in an
air stream) after demoulding. Typical slug and mould temperatures
might be, respectively, 160-175°C and about 90°C. Nowadays it is
common, for best results, first to produce a dry blend in suitable
high-speed mixing equipment, then to melt-compound in a screw-type
compounder/extruder, and to feed metered portions of the hot
extrudate directly to the record moulds.
PVC compositions for record production must be highly homogen-
ised, flow easily in processing, and provide the requisite degree of
rigidity in the product. The first two features enable the composition
to take on a faithful impression of the intricate groove pattern of the
record mould, for good quality of subsequent sound reproduction. To
the same end, the polymer should be free from fish eyes and
particulate impurities, and the other formulation components (espe-
cially the carbon black generally used as a pigment) should be
thoroughly dispersed with no particle aggregates or lumps, to provide
smooth, defect-free groove surfaces. The frictional characteristics of
the composition must also be such as to promote smooth running of
the stylus and freedom from 'hiss' in playing: these considerations are
factors, additional to the processing requirements, also in the choice of
the stabiliser/lubricant system for a record formulation.
To meet this combination of requirements, record compound
formulations are based on vinyl chloride/acetate copolymer (high-
purity for best results), of low K value (typically 47-50) for good flow.
Liquid stabiliser/lubricant systems are preferable for completeness of
dispersion and good melt flow, although powders are also used.
Antimony mercaptide stabilisers are favoured in some formulations:
e.g. Stavinor SB 739 (Ceca SA, France; formerly Rousselot)-a liquid
calcium/antimony-mercaptide system-or Irgastab S110 (Ciba-Geigy);
although barium/cadmium and lead stabilisers, e.g., respectively,
Interstab M12lO (Interstab Chemicals) and Halstab 51 (Halstab Div.,
Hammond Lead Products), as well as easy-processing tin stabilisers,
17 Other Processes 609
e.g. Thermolite 3J (M and T Chemicals), have also been used. Lubri-

cating ability is one of the features normally looked for in stabiliser
systems for record compositions.
(b) Compression Moulding of Thick Sheets (Press Lamination)

uPVC sheets up to about 25 mm thick are produced by heat-laminating
under pressure stacks of thinner sheets. Thick sheets (panels) made in
this way are used for such applications as the construction of fume
scrubbers, chemical plant, covers and linings for chemical storage or
processing tanks, trunking and ducting resistant to chemical corrosion,
and glazing. Pressed sheet reinforced with a long-fibre grade of
chrysotile asbestos, e.g. Durafoam (TBA, UK), has long been 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), and for motorway signs.
Note: Sheet thicknesses almost up to the top limit for thick sheets
as commonly produced by press lamination are within the
range (0·25-24·0 mm) covered by the relevant British stand-
ard (BS 3757: 1978-Rigid PVC Sheet), but well above that
of the corresponding ASTM standard (ASTM D 1927-81,
which deals with sheets 0·25-6·35 mm thick).
The press-laminating operation resembles in general format press

finishing of thinner sheets (d. Chapter 14, Sectiori 14.6)-and, like the
latter, benefits from close control of the temperatures and times of
treatment, except that only two pressing plates are used, one each at
the bottom and the top of the stack of sheets to be laminated. The
sheets in the stack merge together under the heat and pressure in the
press, and the surfaces of the resulting thick sheet acquire the desired
high-quality finish imparted by the plates. The sheets to be combined,
including the outermost ones, need not have good surfaces or quality
finish, but uniformity of thickness is desirable for a straight, parallel-
faced final product. The pressed sheet may be produced with a plain,
glossy surface on one side and a matt or patterned one on the other-a
combination not obtainable by the main sheet-production methods
(calendering and extrusion) which, in any case, are not suitable for
very thick sheets. Sheets for special purposes (e.g. vacuum forming of
components such as office machine housings), or ones with special
decorative surface effects, are also made by compression mOUlding.
17.1.3 Sheet Moulding for Samples and Test Specimens
Compression moulding is the usual method for producing PVC sheet

from which sample plaques or specimens for tests are subsequently cut
or machined. The tests may be run for purposes of quality control, or
to evaluate the properties of a PVC composition, or to compare two or
more compositions (sometimes as a means of determining the effects
offormulation changes).
To produce the moulded sheet, the PVC composition (pre-mix, dry
blend, or pellets) is first sheeted on a two-roll mill, and portions of the
resulting sheet are then compression-moulded into sheets in a picture-
frame mould (a positive male/female mould may also be used).
(a) Unplasticised PVC Sheet

For a uPVC composition a typical procedure would be as follows.
PREPARATION OF MILL SHEET

The composition is banded, as rapidly as possible, on a two-roll mill
with hard-chrome-surfaced rolls. Whilst the size of the mill is not
critical, a convenient roll diameter and working width are, respec-
tively, 150 mm and 250-300 mm: one version of such equipment is
shown in Fig. 11.4.3 in Chapter 11. The mill should be capable of
maintaining a constant working temperature of up to 200°C. In the
absence of specific recommendations (e.g. from the composition's
supplier) or relevant prior experience, the roll temperature may first
be set at 90°C above the Vicat softening temperature of the material as
determined by Method B of ISO 306. If sticking occurs, as may
occasionally happen (e.g. with some VC/VAC copolymer composi-
tions), the temperature setting should be lowered just sufficiently to
prevent it. Actual roll temperatures at particular settings should
always be checked by measurement (e.g. with a contact pyrometer) on
stationary rolls. The surface speed of the front, working roll (the slow
roll) should be about 10 m min-I, and the speed ('friction') ratio
between the slow and the fast roll should be kept as low as convenient
within the range 1: 1·1-1 : 1·4. As the composition is fed to the mill
rolls, any material falling through the nip gap (set close, for rapid
banding) into the tray should be quickly collected and returned to the
rolls. After banding, the nip gap is set to about 1 mm. The total
amount of material should be such that, at this nip setting and with the
stock banded on the working roll, a rolling bank of 10-20 mm
diameter can be maintained on the mill. If no relevant instructions or

experience are available, milling should be continued for at least 5 min
to homogenise the stock. During this time, the sheet on the roll is
frequently cut diagonally in the usual way, allowed to roll-up, and the
roll fed back into the nip. For final removal of the sheet the nip gap is
opened out to about 2 mm and the roll speed adjusted as necessary to
enable the sheet to be taken off without stretching. The sheet is then
left to cool, sandwiched between two smooth metal plates lying on a
horizontal surface (stainless steel plates 6-7 mm thick are suitable: at
this thickness the top plate provides sufficient weight to make the
cooled sheet flat).
Note: When the sheet is taken off the mill, the mill direction should
be noted, to enable cross-laying of the milled sheet layers for
the moulding of the ultimate pressed sheet, so that directional
anisotropy can be avoided (see below).
COMPRESSION MOULDING OF FINAL SHEET IN A PICTURE-FRAME MOULD

The equipment needed for this operation is a hydraulic moulding press
of suitable platen size, a steel picture-frame mould (of frame thickness
appropriate to that required in the final sheet) with two polished,
hard-chrome-plated steel moulding plates 1-3 mm thick and of surface
area sufficient to cover the frame-mould cavity, and parting foils
(aluminium foil about 0·1 mm thick, or thin photographic ferrotype
plates). The press should be fitted for platen heating and cooling, with
ability to reach and maintain uniform platen temperatures up to about
200°C, and should exert a compressive force sufficient to give and
maintain a moulding pressure (i.e. pressure on the area of the mould
cavity) of at least 5 MPa, and preferably 10 MPa. To mould a sheet,
sections of the milled sheet are cut, slightly (say by 3-5 mm) undersize
in relation to the mould frame, and in the number calculated to enable
the material to fill the mould completely when fused (with allowance
of about 10% for moulding flash).
Note: A trial moulding may be run to check the calculation and
finalise the amount of material to be used.
The press platens are preheated to a temperature about 100°C above
the Vicat softening temperature of the material as determined by
Method B of ISO 306 (unless a different temperature has been reliably
recommended or is known from experience).
A moulding plate is covered with a parting foil or ferrotype plate,

and the mould frame is placed on this. The pre-cut milled-sheet
sections are put in the frame, with the mill direction of each one at
right angles to that of the one below. The frame is then covered with a
second parting foil and moulding plate, and the assembly is put into
the hot press. The platens are closed to give a contact pressure on the
mould of 0·1-0·5 MPa for the preheating cycle (the pressure should
not be high enough to make the material flow out of the mould during
this cycle). In the absence of reliable recommendations, prior ex-
perience, or pointer test results, the preheating cycle should be run for
7-10 min. After this, the pressure is increased to 5-10 MPa for the
moulding cycle which should last for some 2-4 min: during this time
the material should become sufficiently fluid for a small amount of
moulding flash to appear between the parting foils and the edges of the
mould frame. At the end of the moulding cycle the heating is turned
off and the cooling system turned full on, while the moulding pressure
is maintained. Cooling is allowed to proceed in these conditions till the
mould temperature drops to about 40°C (this may take up to
10-20 min, depending on the press and the thickness of the moulding);
the moulded sheet is then removed from the mould.
Variants of this kind of milling-cum-moulding procedure for uPVC
sheet, fairly similar mutually, form the bases of two existing standard
methods and one draft method (ASTM D 3010-71 (1981): DIN 7748:
Part 2-1979; ISO/DP 1163/2-1986). An ISO standard for the compres-
sion moulding of test specimens of thermoplastic materials (ISO
293-1986) is also of some general relevance.
(b) Plasticised PVC Sheet

The equipment and general procedure for pPVC sheet are the same as
just described for uPVC, but the temperatures used in milling and
pressing are lower, as is the moulding pressure.
Thus, where no reliable recommendations or prior experience are
available relevant to the composition to be processed, the surface
temperature of the rolls may be set according to the Shore hardness of
the pPVC material (with such adjustments as may be necessary to
ensure that the material can be banded in 1-2 min). The following
figures can be used as a guide: 135-160°C for materials of Shore A
hardness values up to 90; 145-170°C for Shore D values up to 50; and
160-175°C for Shore D values above 50.
Note: Compositions plasticised with poorly solvating plasticisers

may require processing temperatures near the top of the
ranges indicated.
Similarly, the guideline values for press platen temperatures in
compression moulding are: 140-16SoC for materials of Shore A
hardness up to 90; 1S0-17SoC for Shore D values up to SO; and
170-180°C for Shore D values above SO. The moulding cycle may also
be somewhat shorter (say 2-3 min), and a typical moulding pressure
would be in the range 2-6 MPa. Very soft (highly plasticised)
materials may have to be cooled down to room temperature in the
mould before removal.
A method on the above lines has been standardised in DIN
7749:Part 2-1979, and an ISO draft method is currently under
consideration (ISO/DIS 2898/2-1987).
17.1.4 Compression Moulding of PVC Paste
This is not a method of any substantial significance in PVC paste

processing. However, it can be used to make, from a paste, moulded
sheet samples in a wider range of thicknesses, and with rather better
thickness control, than is afforded by the alternative method of casting
a paste layer on a metal plate, hot bench or gel block. The
compression-moulded sheets are usually made to serve as sources of
specimens for evaluating paste formulations, checking the effects of
formulation changes, and determining and monitoring the properties
of paste products. A typical compression-moulded sheet sample would
be a disc or square 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 the
following steps and conditions: preheating the mould to about 80°C
and filling with paste (which should preferably have been de-aerated,
although the large specific surface of the paste layer in the sheet mould
promotes rapid heating and this, with the associated drop in viscosity,
facilitates release of entrapped air before the mould is closed); closing
the mould and heating in the press under contact pressure to about
170°C (or such higher temperature as may be needed for complete
fusion, during the moulding cycle time, of the paste layer of the
particular formulation and thickness); moulding at that temperature
for about 10 min under a moulding pressure of about 2-5 MPa; cooling
under slightly increased pressure (to counteract shrinkage); and
demoulding when the temperature has dropped to about 50°C.
17.2 THERMOFORMING
17.2.1 General Features
In thermoforming, a pre-manufactured plastics element, normally a

sheet or foil (although laminates and pre-formed shape~.g. tubes-
are also thermoformed in some variants of the process), is softened by
heating, formed in or against a mould by vacuum or relatively low
pressure, and set by cooling in the shape so imposed. In certain special
versions of the process, e.g. the Topformer system,I,2 a sheet preform
is first moulded from polymer granules, and then thermoformed into
an article. Otherwise, calendered or extruded sheet is normally used
(the extrusion may be followed directly by an in-line forming section),
or sometimes cast sheet, as for example in the production of plastics
baths by vacuum-forming of lightly cross-linked polymethyl methacry-
late sheet.
The general economic advantages of thermoforming in comparison
with other moulding processes are the use of lighter and cheaper plant
and moulds, rapidity of production, and relative simplicity and ease of
changing designs. There are also technical advantages: large articles
can be made simply, from relatively thin sheet materials; design details
which do not involve sharp thickness changes can be closely re-
produced; pre-printing of the sheet is possible as a means of achieving
surface decoration of the finished product more simply than by
in-mould decoration as practised in blow moulding or injection
moulding, or by post-production decoration.
Disadvantages include the presence in the mOUldings of imposed
strain, imparted in the course of stretching of the heated sheet
material and its subsequent cooling. This makes thermoformed articles
prone to distortion if exposed to elevated temperatures at which
injection mouldings of the same materials would not yet deform.
Excessive orientation, as well as uneven thickness distribution and
local thinning, can occur in thermoformed articles, impairing their
strength and/or stiffness. Quenching stresses may also be present in
some mOUldings, arising from the rapid cooling of the hot sheet.
However, with sensible article and mould design, correct choice of

thermoforming technique, and with good equipment employing sound
process monitoring and control, effective operation with high yield of
good-quality products is possible.
17.2.2 Plastics Materials Used in Thermoforming
To be suitable for thermoforming, a thermoplastic material should

preferably be available in sheet form. It must also (i) not degrade at
the processing temperatures; (ii) have a suitable stretchability (attain
an appropriately 'rubbery' state) within the processing temperature
range; (iii) possess the service properties required in the intended
application.
The thermoplastics used in industrial thermoforming differ among
themselves in their responses to, and behaviour under, the processing
conditions. ABS and high-impact polystyrene have the best proces-
sability. Other widely used materials are PVC, polymethyl methacry-
late, polyethylene, polyethylene terephthalate, and polypropylene.
PVC sheet compositions for thermoforming are usually specially
formulate<i--<;ommonly as rigid compounds incorporating selected
acrylic modifiers-with a view to providing good working elasticity
over the widest practicable processing temperature range (and hence
good tolerance of temperature fluctuation during processing and/or
possible temperature differences over the heated area of the sheet).
Whilst VC/VAC copolymer-based PVC compositions can also be
used, their working elasticity is not generally up to that of the best
acrylic-modified ones, and the lower softening points of copolymers
vis-a-vis homopolymers is a relevant consideration in connection with
some end-uses.
Note: In otherwise comparable compositions, chlorinated PVC is a

better thermoforming material than PVC homopolymer,
because of the greater extensibility, uniaxial and biaxial, of
CPVC over a relatively wide range of temperatures above the
Tg. 3 This difference is consonant with the lowering of inter-
chain attraction by the presence of additional chlorine atoms
in CPVc.
The following are examples of commercial PVC sheeting used in

thermoforming: Kydex;* Penta/orm 172t (working elasticity range
130-170°C); Pentalan, t the Fromopack* range of clear, rigid PVC
sheeting; Genolon N§ clear, coloured rigid PVC sheeting and some
other members of the Genolon§ range, as well as of the Genopak§ and
Genotherm § sheeting ranges. Sheets of antistatic (carbon-loaded) PVC
compositions are also thermoformed into mOUldings used as equip-
ment housings or casings for electromagnetic interference (EMI)
screening and in packaging applications. Typical products thermo-
formed in quantity from PVC thin sheeting and foil are blister packs,
skin packs, food trays, nesting (insert) trays for confectionery and
medical kits, and tubs and lids (including tubs for some hot-fill foods,
such as jams or processed cheese spreads, for which heat-resistant
sheet grades are used~.g. Genotherm ZH 53, ZH 54, ZH 55 or ZH
65).
Thicker PVC sheets, as well as laminate and sandwich sheets
incorporating a PVC component, are also thermoformed. Examples
are ABS/PVC solid-sheet laminates of the Royalitell range, and
sandwich sheets with a PVC foam core and ABS facings used for the
production of window and door surrounds, side-panels and side-liners
for aircraft interiors. Some inner fuselage trim panels may be up to
1 cm thick and 1-2 m2 in area, with draw depths of up to 60 cm.
17.2.3 Assessment of the Thermoforming Characteristics of

Materials
In any version of the thermoforming process, it is important that the

sheet should be heated to, and uniformly attain, the optimum
temperature for processing. For practical purposes, this optimum can
be regarded as (and determined in terms of) the sheet temperature at
which the material's elongation at high levels of extension or at break
in a creep-type test (with uniaxial or biaxial stretching) is at its
maximum. As would be expected, the optimum temperature is
strongly dependent on the nature and composition of the material.
* Acrylic-modified uPVC sheeting (Rohm and Haas, USA-European

licensee: Mazzucchelli Celluloide, Italy).
t Klockner Pentaplast GmbH, West Germany.
:I: Weston Hyde Products Ltd., UK.
§ Kalle Films Division of Hoechst A.G., West Germany.
II Uniroyal, Plastics Division, USA.
Some relatively simple techniques may be used to compare mate-

rials, and to a degree assess their thermoforming characteristics. In
Ref. 5 rapid creep tests are described, comparing the extensibility at
elevated temperatures of two PVC sheet materials as a guide to their
thermoforming behaviour. The tests consisted of applying a predeter-
mined dead load to strips of the sheet material at different tempera-
tures, the load being such that extension to high strains-in the range
of 4-5 or up to breaking point---<:ould be achieved in about 1·4 s. As
described in the reference, the tests involved optical observation of
strains for plotting the creep curves, but other recording means can
also be employed to provide a useful evaluatory procedure. In tests of
this kind, the strain (elongation) peaks at a certain temperature, the
peak indicating the operating temperature region for thermoforming
(cf. Fig. 17.1). The manner in which the data curve falls away above
and below the peak provides useful guidance as to the behaviour of
the test material. The peak's position on the temperature scale, its
sharpness, and the overall shape of the curve can be correlated with
actual forming experiments.
For the uPVC sheet used in the strain-to-break test represented by
Fig. 17.2, the curve shows a rather narrow optimum temperature
range (approximately 129-135°C). A broad peak is preferable as it
reflects a greater processing tolerance, and this is what is aimed for by
formulators of PVC compositions for thermoforming sheet.
It has also been shown (by Turner6 ) that, in a rupture test similar.to
those just mentioned, rapid uniaxial creep can be resolved into stress
Optimum
Strain
level Area of
rupture
~ fi'i
~~a:~d
';me
Increasing strain
rate under fixed load
Temperature
Fig. 17.1 Effect of temperature on rapid strain.
700
600
*'
isoo
!!?
CD
....
(II
c:
o
.~ 400'
01
c:
o
ijj
200~----~----~------~----~----~
100 110
120 130 140 150
Temperature, °C
Fig. 17.2 Elongation at break of a high-impact calendered uPVC sheet as a
function of temperature.
and time factors, and a fracture envelope can be readily derived.

Correlation between such creep data and actual thermoforming
behaviour of the material can be established5 ,7 and used as a guide to
processing performance. For this purpose the draw ratio* is the
significant process variable to observe at various temperatures for
correlation with creep-test data.
Small laboratory-scale thermoforming units are available, suitable
for direct practical testing of the thermoformability of plastics sheet-
ing. Typically, such equipment works with sheet areas between about
25 cm x 25 cm and 60 cm x 60 cm, offering draw depths of about
10-15 cm, and automatic, semi-automatic or manual controls. Some
examples are: Unit R12 (Atlas-Vac, USA); Pro-Test (T. M. Plastics,
* Defined as the ratio of the cross-sectional area of the undrawn plastic to that
of the drawn plastic (see e.g. BS 1755:Part 1:1982).
USA); Lab/orm 1620 (Hydro-Trim Corp., USA); and the laboratory

models produced by John Brown Plastics Machinery (USA and UK),
Leesona Plastics Machinery (USA and UK), and Gloenco Ltd (UK).
17.2.4 Thermoforming Methods
(a) Main Types and Variants

Thermoforming methods may be classified into three groups, accord-
ing to the way in which the forming pressure is applied to hot plastics
sheet: (a) vacuum forming; (b) pressure forming; (c) matched-mould
forming. In addition, a technique often referred to as 'ridge forming',
in which the forming is effected by what amounts to localised
mechanical pull (of a skeleton frame mould moving into the hot
sheet), may be regarded as a fourth kind of method.
The main operational elements of a relatively simple, basic equip-
ment for vacuum or pressure forming are shown in Fig. 17.3, and the
common variants of these two methods are illustrated schematically in
Figs 17.4 and 17.5 respectively. A schematic representation of
matched-mould forming is given in Fig. 17.6, and one of ridge forming
in Fig. 17.7. The sheet profiles in the figures give an indication of the
thickness distribution during processing and in the product in each of
Fig. 17.3 Main operational elements

of a simple vacuum or pressure form-
H ing set-up. C, chamber ('box'); M/P,
male mould, or plug (mould shown);
M, mould (male or female-female
M shown); S, plastics sheet; CL, clamps;
C
H, heaters (movable; brought in only
for the initial heating stage). Not
o
Ii
I~c: _AIR IN shown: bubble control devices
C -AIR OUT (usually optical or electrical); cooling
VAC +- - -=::!) --- -VAC air fans; internal mould cooling.
Fig. 17.4 Vacuum forming techniques: schematic outline of main method features. ~
Key to designations of individual stages in methods 1-10 (equipment elements essentially as in Fig. 17.3).
(a) Heated sheet in position.
(b) Bubble formed from heated sheet by vacuum ( ... ~ ) or air pressure (~ ) applied to chamber.
(c) Vacuum or pressure maintained in chamber.
(d) Forming ring moved into contact with sheet.
(e) Mould moved up to or into sheet. ~
(f) Plug moved up to or into sheet. ~
(g) Mould or plug in fully advanced position. ~.
(h) Sheet allowed to slip by slip-ring damping arrangement.
(i) Vacuum ( ... ~ ) or air pressure ( ~ ) applied to mould or plug. ~
(j) Vacuum or air pressure maintained in mould or plug. .g
(k) Sheet sucked or pressed into conformity with mould. ~
::l'.
(I) Vacuum or pressure released from chamber. ~
(m) Vacuum or pressure released from mould or plug.
(n) Cooling applied.
(0) Cooling completed. ~
..~
(p) Mould and/or plug and/or forming ring withdrawn. ~.
§
I:>...
~
~
~
(a) (e)(i) (j)(k)(n) (m)(o)(p) ~.
----.. ----.. ----..
~ ,
r¥1 M
Direct ('negative') forming
~
t t Cl
::I
"is.
I:
0
t
I:
0
:E
~E
en
::I
t)
...
~
! Cl
t
I:
'E...
t
Cl
I:
'E... .2
.2 CD
Q.
~
o
t t
1+Q0 ~+
Fig. 17.4--<:ontd. t§
(a)(d) (eW) (g)(j)(k) (n)(m)(o)(p)
"tI
---.. ----.. ---.. ~
~
, !;
~.
+~ I:
~ ~
5 Ring-assist drape forming
c,J I
• ::,t'
.g
(n)(m)(o)(p)
.,'"
(a)(b) (c)(e) (g)(I)(i)(k) :::.
~
c~
+ "..,~
~.
+ ~ ---.. ---..
§
M s::...
~
N ~6 Vacuum-bubble, snap-back forming
rY1 ~
~
(a)(b) (c)(e) (g)(l)(illkl (n)(m)(o)(p) 5'
i:l
---.. ---.. ---..

L;J
=1= f'1 rf1
7 Pressure-bubble, snap-back forming
c;J
(a)(b) (c)(e)(i) (g)(j)(I)(k) (n)(m)(o)(p)
---. ---. ---..

M'1 • rt1 t;J
~ 8 Vacuum-bubble, reverse-draw forming
(a)(b) (c)(e)(i) (g)(j)(l)(k) (n)(m)(o)(p)
....
'I
+ o
So
+ ---. ·t
---.. ---.. ~
1 I
(] rfl i ~
9 Pressure-bubble, reverse-draw forming
M l~
~
(a) (e)(h) (g)(i)(j)(n) (m)(o)(p)
---.. ---. ---..

ttJ f'f ~
10 Drape forming with slip-ring. NB A slip-ring may be used with other techniques, notably plug-assist forming.
§
~
....- ~ ....-
\ I
~ lin
1
, r
~
1itr
iTIJ
I "tI
u\1= I I
"litt ~
(1 ) (2) (3) (4) "tI
Fr
~.
t=\ ~~
"
~ ~ , .-,"
"
&- --.. (}==
-. - --.. 0 l
::to
-~ jll
~
(1 ) (4) "tI
(2) (3) ~
~
"
Fig. 17.5 Pressure forming:schematic outline of the techniques. '"
~.
Upper sequence: Direct ('trapped sheet') forming. §
(1) Sheet in position over mould, under heated blowing plate (porous or finely channelled for air passage). (2) Sheet in ~
air-tight contact with mould and plate (in some versions air is initially blown through the mould, or vacuum applied to ~
the plate, to secure intimate contact between sheet and plate: the plate may also not be heated. but the sheet preheated 1'r
as in other methods). (3) Air pressure through plate pushes sheet into conformity with mould (the mould is channelled ~.
for venting, or for vacuum-assist during the forming step). (4) Pressure released. Cooling applied. Plate and mould ~
withdrawn.
Lower sequence: Twin-sheet forming.
(1) Heated sheets in position between mould halves. (2) Mould closed, with sheet sections forming peripherally
nip-sealed envelope penetrated by blowing pin. Air-pressure application through pin commencing (the mould is
channelled for venting or vacuum-assist). (3) Envelope expanded into conformity with mould. (4) Mould opened and
withdrawn to release article after cooling.
f1 D
~
~Y U~
~
~~ ~ ~
~
(3)
(1 )
.. (2)
Fig. 17.6 Matched-mould forming:schematic outline.
(1) Heated sheet in position between male and female halves. (2) Mould halves in full agreement, forming article from .....
sheet. (3) Mould halves separated to release article after cooling. 'I
o
So
~
.."
~
"~
~ ~ ~
nr '~"'
+ (1 )
~ (2)
~ (3) QI4J
Fig. 17.7 Ridge-forming (ring-assisted):schematic outline.
(1) Heated sheet in position over skeleton (open-frame) mould, with assist-ring in contact above. (2) Mould fully raised
into sheet against ring (the ring having assisted in evenly pushing the sheet over the mould). (3) Sheet fully formed over
the mould: ring withdrawn: cooling commenced. (4) Mould withdrawn after completion of cooling.
~
the techniques illustrated. As can be seen, the bubble and plug-assist

versions give the best (most uniform) final thickness distribution.
(b) Some Processing Considerations

It is important that, in the forming step, full vacuum or pressure
should be applied to the hot sheet as rapidly as possible. To avoid the
very high expense of pumps of sufficiently high self-capacity, it is usual
for the equipment to incorporate an accumulator tank, which-since
the vacuum (or pressure) is only required intermittently-<:an be kept
'topped up' by a smaller pump.
The use of a slip ring for clamping the sheet in some variants of the
vacuum-forming process enables extra material to slip in during the
forming step. This counteracts possible tendencies to edge-tearing and
buckling of the sheet, and reduces thinning-out at corners and edges.
Although shown in the illustrations in connection with drape forming
(Fig. 17.4, panel 10), slip-ring clamping is useful also in plug-assisted
forming, especially of large parts. In this arrangement, as indeed in all
other vacuum-forming techniques, it is important that the clamping
means should ensure a good seal between the sheet and the edge of
the mould.
The methods promoting maintenance of material thickness uni-
formity in the moulding, such as bubble forming and plug-assist
forming, are particularly useful when the design of the moulding in-
volves sharp edges or corners, and intricate features. In bubble methods,
the extent of expansion of the bubble is controlled by a photoelectric
cell.
Whilst, as has been mentioned, PVC compositions for thermoform-
ing are formulated with a view to the widest possible processing
temperature range, good heating control is very important in the
process, to ensure that the sheet attains the optimum forming
temperature uniformly, and in a suitably short time. Some modern
production machines provide selective heating, whereby-as is some-
times necessary in the production of large, intricate parts from thick
sheets-particular areas of the sheet can be selectively heated,
occasionally to different temperatures. Radiant heaters are almost
universally employed, although in some non-automatic operations
convection heating may be used in certain cases with thick PVC or
composite sheets, in view of the poor thermal conductivity of the
material.
17.2.5 Thermoforming Equipment
(a) Machinery
Thermoforming machines range from simple, single-cycle equipment
to continuous-operation automatic lines with multi-station arrange-
ments involving turntables or straight-line sequential processing.
The forming cycle in a vacuum or pressure forming process will
normally comprise the following main stages (see also Figs 17.4 and
17.5). The sheet, securely held round the edges, is heated. In a
single-cycle machine this will be done by radiant heaters, moved into
position either above the sheet or both above and below. In a
continuous process, the sheet (or section of web off a roll) may be
passed through one or more oven stations with heaters in place. When
the sheet has reached the appropriate temperature (commonly gauged
via the heater temperature and sheet exposure time, but in some most
recent computer-controlled systems measured directly on the sheet),
the heaters are removed (in a single-cycle machine) or the sheet is
passed to a forming station (in a continuous process). The mould is
then presented, and the forming step carried out. Cooling takes place,
or at least commences, with the formed article still in contact with the
mould. After cooling, the moulding is removed from the mould: this
may be assisted by an air blast through the vents or vacuum channels.
Any finishing operations are then carried out (in automated lines
trimming may be done before demoulding).
The main features of modern industrial thermoforming equipment
may be very briefly summarised under the following headings.
Feed type: Individual sheets (fed manually or by an automatic sheet

loader), or continuous sheeting ('web') fed from a roll.
Depth of draw: Generally within the approximate range 8-140 cm

(many machines offer a range of draw depths).
Forming area: wide range of different length/width combinations,

typically from about 20 cm x 25 cm to about 450 cm x 500 em.
Operational arrangements: Single station; or multi-station, sequen-

tial or rotary; or integrated lines (nowadays often with modular
lay-out) as used for example for high-volume production of blister
packs, cups, packaging trays and skin packaging-the modules may,

typically, be ones for loading from a sheet stack, sheet transfer system
(with automatic centering), heating, forming, cooling, lateral punch-
ing, edge-trimming, vertical punching, unloading of mouldings, and
transfer of scrap.
Heating: Predominantly radiant elements (one or both sides of the

sheet); direct or oven. In some modern in-line equipment arrange-
ments, extruded sheet is fed directly to the thermoformer at forming
temperatures.
Cooling: Air (direct fan blowing or forced draught), with or

without mould cooling (by water circulation); in some cases a water
spray may be used.
Controls: Manual, semi-automatic, or fully automatic (or any

combination of these).
In-line sheet extrusion as a feature of integrated thermoforming
lines is becoming increasingly popular: the main advantages it can
offer include energy saving, improved product quality, reduced 'heat
history' of the material (desirable with PVC), and reduction in scrap.
The modern integrated lines-which may include also a packaging
section (e.g. presses and blister-sealing machines for the production of
blister packs}-utilise computerisation in operation monitoring sys-
tems, sheet loading, sheet heating (including selective patterned
heating) and temperature control, forming sequences, trimming, scrap
handling, product packaging, process data storage and analysis, and
memory storage of equipment settings for particular jobs. Quick-
mould-change systems are also being introduced.
(b) Moulds
MOULD MATERIALS
Tooling for thermoforming is comparatively inexpensive. For con-
tinuous production involving long runs at high speeds, aluminium or
light alloy moulds (cast or machined) are required, for durability and
resistance to damage. Copper, and copper-containing metals (e.g.
brass), should be avoided with PVc. For moulds to be used in
low-volume production with short, intermittent runs many materials

may be considered, including plaster of Paris in some cases. Cast
epoxy resin moulds (made from wood or plaster master patterns) are
acceptable, as are wooden moulds (produced by machining); both
these materials are also used for prototype work. Shrinkage considera-
tions are important in mould material selection-both the mould's own
shrinkage and that of the moulding must be taken into account. In
comparison with metal moulds, those made from epoxy resin or wood
are more vulnerable to damage, even when sprayed with metal or-in
the case of cast resin---containing metal fillers. In plug-assist moulding,
where the plug is not operated with an air cushion (see Fig. 17.4,3), its
surface should be wood, leather, or another poor heat conductor
which will not cause chill marks on the moulding.
APPLICATIONAL FEATURES OF MAIN MOULD TYPES

Male moulds are, in general, cheaper to make than female moulds: on
that score they are preferable for short runs. They also permit deeper
forming, and are more suitable where accurate internal dimensions of
the moulding are important. Female moulds provide better surface-
feature definition in the moulding. They are also used for low depths
of draw, and are more suitable where, in large-scale production, a
number of cavities have to be placed close together, or where very
little draft can be allowed. Plug- or ring-assist, or matched-mould
forming, is rarely used for low-volume production or for short runs, in
view of the higher cost.
MOULD CONSTRUCTION
As regards general mould dimensions in relation to the depth of draw,
in a female mould the depth of draw should preferably not exceed half
the minimum moulding width; in a male mould the height can be equal
to the narrowest dimension, and even greater. All moulds must be
vented (annular grooves are also occasionally incorporated) for
vacuum application in vacuum forming, and to prevent air entrapment
in pressure forming. The closer the detail-or intimate conformity to
the mould-required, the greater the number of vents necessary. On
the side that comes in contact with the sheet, the hole diameter should
preferably not exceed 0·75 mm: with relatively thin sheeting, half the
thickness of the material may sometimes be used as a guide. On the
other side, the holes may be opened much wider and tapered to give
more rapid evacuation. With metal moulds, sand-blasting, vapour-

blasting or polishing of the surfaces is desirable, to avoid trapping air
between the mould surface and the hot sheet, and so to prevent
surface blemishes on the moulding whilst promoting good thermal
contact for effective heat transfer. Large moulds (especially male), and
those used in large production runs, should be cored for water cooling.
Walls should never be completely upright. It is highly preferable that
the draft angle, which facilitates removal of the moulding, should be at
least 30 , although in some cases as little as 10 may be acceptable. In
general, a generous draft will always make for a better product. Radii
should be as large as possible, certainly at least the thickness of the
material being moulded (and in any case not less than 0·75 mm).
17.2.6 Finisbing Operations
The first finishing operation, almost invariably necessary, is trimming

(with removal of scrap). Depending on the kind and scale of the
thermoforming process concerned, as well as the nature and size of the
mouldings, trimming may be performed in-line in the mould, or after
removal of the part. Other, subsequent finishing may involve cutting
shapes out of the moulding, joining parts together by welding or
adhesive bonding, and surface decoration.
17.2.7 Thermoformed Parts
(a) General Design Considerations

The main ones are:
(a) economy of material and production costs-this is promoted by
gradual transitions in any changes of profile or thickness,
smoothly curved rather than angular profiles, and large radii;
(b) structural stability of the moulding-stiffening beads and sec-
tions included in the design make for greater stability of large
flat and/or thin areas, and .counteract warping;
(c) avoidance of excessive thinning and orientation-as by sufficient
sheet thickness allowance;
(d) ease and simplicity of trimming and suitability for any sub-
sequent decorative treatment;
(e) avoidance of any need for such post-moulding operations as
welding (e.g. by designing for moulding in one piece an article

that might otherwise have to be made up by bonding two
thermoformed parts).
(b) Dimensional Stability, and Effects of Temperature and Draw Ratio

on Part Quality
When heated to a sufficiently high temperature, a thermoformed
article tends to retract, and may even revert to a flat sheet in an
extreme case. The amount of distortion suffered in particular condi-
tions (of duration and temperature of exposure) is a function of the
degree of extension imparted in the original forming: thus shallow-
formed articles will tend to distort less than deep-drawn ones. For
applications where high temperatures may be encountered in service
(e.g. through exposure to strong, direct sunlight, or proximity to
heaters), the risk of possible distortion must be borne in mind:
selection of thermoforming material with a high softening-temperature
range, and carrying out the forming at the highest practicable
temperature within that range, are two ways of reducing the suscep-
tibility of the resulting moulding to heat distortion. It can also be
beneficial to keep the formed article at the high forming temperature
as long as sensibly practicable, to promote relaxation of strains in the
material through the thermal agitation experienced by the polymer
chains. However, such measures are subject to limitations: operating
at higher temperatures and longer cycle times reduces the production
rate, whilst keeping the material at a high temperature may affect
surface finish of the sheet, or possibly even cause discolouration. As
has been mentioned, one aim in formulating PVC sheet material for
thermoforming is to provide for a wide processing temperature range.
However, quite apart from the possible special considerations just
referred to, the choice of the actual forming temperature within the
range will be influenced by such factors as the process rate, energy
consumption, ease of manipulation of the sheet, and detrimental
temperature effects. Thus in practice the processor would aim to
operate close to the shaded portion of the area within the heavy-line
curve in Fig. 17.8. This area represents the relationship between
acceptable product quality on one hand, and the forming temperature
and draw ratio on the other, the heavy line being the boundary
between good and bad forming. The general representation of Fig.
17.8 can be quantified for any particular process by means of the kind
(Cold)
rupture
......
0
«II
I:
Discoloration
~ degradation
0
...«II
reproduced
Temperature
Fig. 17.8 Product quality aspects of correlations between draw ratio and
temperature.
of determinations mentioned in Section 17.2.3 and/or practical form-

ing trials.
17.3 POWDER SINTERING AND 'LOST FILLER'

METHODS IN THE PRODUCTION OF
POROUS PVC SHEETS
17.3.1 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,8,9 intercommunicating cell structures are
usually obtained.
Powder sintering has been in use for a long time lO as the method of
production of porous PVC sheets for the manufacture of battery
separators. The process comprises the following main stages. (a) For-
mation of a layer of PVC powder (up to about 1 mm thick, with a
spaced-rib profile) on a moving belt (usually of stainless steel). The
layer is either deposited by a special powder-feed device (as in the
original Sandvik processl l ), or formed on the belt by a roller (as in the

Jungfer roll-coating process). (b) Consolidation of the powder layer by
heat-sintering the particles under radiation or convection heating. (c)
Cooling the continuous, porous sheet formed. (d) Removal of the
sheet and cutting up into separator plates.
Many PVC manufacturers supply a suitable polymer grade, viz. an
emulsion-produced homopolymer with particle size range and dis-
tribution 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.
17.3.2 The 'Lost FUler' 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 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. The earliest removable fillers used in practice
were mineral salts (especially common salt), dissolved out by immer-
sion of the filled material in water.
In the PVC context an early practical embodiment of the method
was the original Porvic process8 for the production of porous sheeting.
The method was also used in the manufacture of PVC battery
separators,10 although nowadays these are normally made by sintering
of powder). In both cases the removable filler was starch: this was
leached out of the formed products by hydrolysis and dissolution with
dilute sulphuric acid.
An unusual variation on the general theme-with finely dispersed

droplets of water constituting the 'filler'-is disclosed in a US Patent
for the production of porous pPVC film from a plastisol. 12 The paste
may contain up to 50 phr of water, 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, the majority of the voids arising simply
as a result of the disappearance of the dispersed water from the
composition.
REFERENCES
1. 'Topformer' literature form Bone Craven Daniels, Stroud, Glos., UK.

2. Anon., Plast. Rubb. Wk/y (23 Nov 1979) 17-26.
3. De Vries, A. J. & Bonnebat, c., Polym. Engng Sci., 16(2) (1976) 93-100.
5. Harris, B. L. & Bruins, P. F. In Basic Principles of Thermoforming, ed.
P. F. Bruins. Gordon & Breach, New York, 1973, p. 81.
6. Turner, L. W., Society of Chemical Industry Monograph No. 17. SCI,
London, 1958.
7. Malpass, V. E. & White, C. H. (1973). In Basic Principles of
Thermoforming, ed. P. F. Bruins. Gordon & Breach, New York, 1973, p.
103.
8. Titow, W. V., J. Plast. Inst. (Dec. 1961) 186-93.
9. Laskowski, W. & Skowronski, T., Polim. Tworz. Wielk. 14(8) (1969)
389-94.
10. Collins, D. H. (Ed.), Batteries. Macmillan, New York, 1963, pp. 16-17.
11. Anon., Brit. Plast., (Aug. 1969) 80.
12. Greenhoe, J. A. (to Monsanto Chemical Co.), US Patent 2864 777.
Section 5
LIQUID PVC COMPOSITIONS: NATURE,

PREPARATION, PROCESSING,
AND APPLICATIONS
635
CHAPTER 18
PVC Pastes
18.1 THE NATURE AND TERMINOLOGY OF

PVC PASTE~ENERAL
PVC pastes are liquid or semi-liquid suspensions, comprising-as the

essential components-PVC polymers (paste grades, made by the
emulsion or microsuspension process) and plasticisers: various addi-
tives are also usually present in a paste, as required for processing and
product properties. Suspension-produced PVC polymers are some-
times incorporated in pastes for special effects (see Section 18.5.2
below).
The term plastisol (formally defined as a suspension of finely divided
PVC polymer in a plasticiser) is very often used as a synonym for
'paste' in the PVC context: in fact, of the two, only 'plastisol' is
included in the main relevant English-language terminology standards
(although 'paste' is common usage in the UK, and is freely used in
some standards, e.g. ISO 4612 1). Three special kinds of PVC paste are
denoted by the following terms.
Organosol: A paste in which the liquid suspending medium is a

mixture of plasticiser(s) with some solvent(s). Organosols are useful in
applications where low initial paste 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.
Plastigel: A paste thickened (by the addition of a thickening agent)

to a gel-like consistency (one resembling butter or putty in some
cases). Plastigels are used where such consistency is a desirable
637
applicational feature, e.g. in some spread-coating operations, or in

paste moulding.
Rigisols: This term was coined to denote plastisols formulated to

combine relatively low plasticiser contents (for comparatively hard
ultimate products) with fluidity still sufficiently high for normal
processing (see Section 18.5.3 below).
The end-use considerations in formulating pastes are substantially

the same as those applicable in the case of solid pPVC compounds, but
the processing requirements the formulations have to meet are, of
course, quite different. Paste rheology appropriate to the particular
process is the most important single factor.
18.2 THE ROLE AND BASICS OF

PASTE RHEOLOGY
PVC is unique among industrially significant polymers in its suitability

for being made into pastes, and conveniently processed in this special
liquid form to yield products whose material is normal pPVC, but
which it is not in most cases practicable to make from other kinds of
PVC composition. Paste-produced pPVC coatings on fabrics and other
substrates are notable examples of such products.
It is necessary for successful processing that the paste should have
the right rheological properties, and that these should not alter
substantially during any periods of storage before use.
18.2.1 Viscosity of PVC Pastes
(a) Features Relevant to Behaviour in Processing

Paste viscosity, and the way in which that may be affected by the
relevant processing conditions (especially the shearing experienced by
the paste) are cardinal rheological considerations. Viscosity stability is
also of practical importance: there should be no thickening in storage
and transport. Such thickening, sometimes referred to as 'ageing',
occurs as the polymer particles become appreciably swollen by the
plasticiser (so that the effective volume fraction of the solids in the
paste increases), whilst the viscosity of the plasticiser phase increases
18 PVC Pastes 639
due to the dissolution of some of the finest polymer particles. At

ordinary temperatures, properly formulated pastes should remain
stable in this respect for at least 2-3 weeks.
The viscosity of a paste, and its susceptibility to changes under
shear, are functions of the respective proportions and the properties of
the two main components of the system-the plasticiser(s) and PVC
polymer (although they may also be substantially modified by the
presence of additives incorporated in the paste). The properties mainly
concerned are the viscosity of the plasticiser and its solvating power
for the polymer, and the polymer's particle size and size distribution.
These various features are jointly responsible for the fact that PVC
pastes behave as non-Newtonian liquids, i.e. that their viscosity varies
(in a number of ways depending on the formulation) with the rate of
shear being undergone, and sometimes also with time under constant
shear.
(b) Basic Modes of Rheological Behaviour: Effects of Shear Rate, and

of Time under Constant Shear
In the conditions of laminar flow in a thin liquid layer undergoing
simple shear, the shear rate (i.e. the lateral change of shape of
the layer under the shearing force) may be assumed to be equal to the
velocity gradient (dV /dx) arising across the thickness (dx) of the
liquid layer. That is,
y=dV/dx
where y is the shear rate. Under the same simple assumptions, with
the shearing force (F) acting over an area (A), the shear stress ('r) is
given by
r:=F/A
Liquids in which the shear stress is directly proportional to the shear

rate (r: = y x a constant) are called 'Newtonian': for such liquids, the
proportionality constant (the ratio of shear stress to shear rate) is often
termed 'Newtonian viscosity'. That is, for Newtonian liquids
r:/y= 11
where 11 is the viscosity, and a graph of r: versus y is a straight line of

slope 11, passing through the origin (Fig. 18.1).
Shear
stress
(7)
Shear rate (')')

Fig. 18.1 Viscosity relationship for Newtonian liquids.
Those liquids for which the shear stress is some other, more
complex, function of the shear rate, i.e. whose viscosity is not
constant, are called non-Newtonian. PVC pastes belong to this group.
Note: The viscosity value obtained for a non-Newtonian liquid in a

determination at a particular shear rate (Le. corresponding to
a single point on the plot of one of the Figs 18.2-18.4) is
usually called apparent viscosity. Thus, by definition, the
apparent viscosity will depend on the shear rate (or in some
cases on time at a constant shear rate-d. Figs 18.5 and
18.6). In the practical context of PVC pastes this means that a
paste may flow (or spread, or drain) differently, depending on
the amount of shear experienced in, or time taken by, the
particular processing.
The following modes of non-Newtonian behaviour may be encoun-

tered in PVC pastes.
'Bingham body' behaviour: This is illustrated by Fig. 18.2 and

described by the expression T = TJY + K. With this kind of rheology, a
certain stress must be reached (the 'yield point' or 'yield value') before
appreciable flow will start, but Newtonian behaviour is observed
thereafter. An appropriate yield value is important in pastes (which
should be formulated accordingly) for application to vertical surfaces,
e.g. by spraying or dipping.
18 PVC Pastes 641
Shear
stresys
(T)
Yield
value
Shear rate <-y)

Fig. 18.2 Bingham body behaviour.
Dilatancy and pseudoplasticity (also known respectively as shear

thickening and shear thinning): These modes of rheological behaviour
are illustrated by the graphs of Figs 18.3 and 18.4. They may be
represented by the power function TJa = Kyn-l, where K is a constant,
and the power index n =1= 1 (if n = 1, the apparent viscosity TJa will be
constant, i.e. the behaviour Newtonian). For dilatancy, n > 1 (shear
stress and viscosity increase with increasing shear rate-d. Fig. 18.3),
whilst 1 > n > 0 characterises the opposite, pseudoplastic behaviour.
Pastes with high polymer: plasticiser ratios tend to be dilatant,
especially in processing conditions involving high rates of shear. This
may, for example, make them difficult to spread in a coating process,
but will also counteract excessive penetration into a substrate.
Pseudoplastic pastes give good spreadability and ultimate surface finish
in coating operations involving high shear rates.
Apparent
viscosity
(7]a)
Shear rate (-y)

Fig. 18.3 Dilatant behaviour: viscosity increasing with shear rate.
Apparent
viscosity
(1)a)
Shear rate (oy)
Fig. 18.4 Pseudoplastic behaviour: viscosity decreasing with shear rate.
Thixotropy and rheopexy: The latter is also known as negative

thixotropy or antithixotropy. These are manifestations of variation of
apparent viscosity and shear stress with time at a constant shear rate,
as illustrated by Figs 18.5 and 18.6. 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.
As has been mentioned, the above modes of rheological behaviour
may be affected (or in some cases induced) by incorporation in PVC
pastes of certain additives (e.g. fillers, pigments, thickening agents,
viscosity depressants, diluents-see Section 18.5.2).
Shear
(T)
stress
or
Apparent
(1)a)
viscosity
Time
Fig. 18.5 Thixotropic behaviour: shear stress and apparent viscosity decrease
with time.
18 PVC Pastes 643
Shear
(T)
stress
or
Apparent
(7la)
viscosity
Time
Fig. 18.6 Rheopectic behaviour: shear stress and apparent viscosity increase
with time.
18.2.2 Rheological Effects of the Polymer Component in a PVC

Paste
(a) Polymer Particle Content ('Polymer Fraction')

The volume fraction of PVC polymer in a plastisol can be quite high
(well over 0·2); it will be particularly high in rigisols, and in plastisols
to which 'extender' polymers have been added. The latter are
suspension-type (non-paste-making) PVC polymers of relatively large
particle size (see Section 18.5.2 for their role in pastes).
A number of equations have been proposed to describe the relation-
ship between the apparent viscosity of a simple plastisol and its
polymer fraction. 2 Of these the most widely applicable and practically
useful is the expression due to Johnston & Brower: 3
10glO 1f, = (1'33 - 0'84~)

C{Jc
(~)
C{Jc C{J
where C{J is the volume fraction of the polymer (which is the suspensoid
in the system), C{Jc is the 'critical' polymer volume fraction, and 1f, is
the relative viscosity, i.e. the ratio of the viscosity of the suspension
(the plastisol) to that of the suspending liquid (the plasticiser). The
critical volume fraction is defined as the polymer volume fraction at
the stage when (as in a fairly advanced phase of the final gelation of
the paste by heating-see Section 18.4) the polymer particles have
absorbed the plasticiser to the point where it no longer fills the
interstices between them, and consequently the paste viscosity be-
comes extremely high. The Johnston & Brower equation provides
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, and the extent of the volume increase of
polymer particles as a result of plasticiser absorption can be
estimated. 3 The authors' own estimates indicate volume increases on
ageing from about 0·13% for stable resins to 1·76% for less stable
ones.
(b) Polymer Particle Characteristics
PARTICLE SIZE AND SIZE DISTRIBUTION

Even the simplest PVC pastes-plastisols with no solid, particulate
additives-are not simple, monodisperse suspensions. When prepared
by one of the usual methods, such a basic plastisol will normally
contain some primary particles. The primary particles of paste-making
PVC resins range in size between about 0·1 and 3 I'm: aggregate sizes
(including partly broken-down aggregates) of 1·8-70 I'm have been
found in pastes prepared from typical representatives of such resins4
(cf. also Fig. 3.4 in Chapter 3).
Whilst some commercial paste-making resins have particle-size
distributions so narrow that the resulting pastes approach monodisper-
sity, a broad particle-size distribution is a feature of others. Substan-
tially bimodal size distributions are also encountered,4,5 whereas pastes
containing added extender polymers (of particle size roughly in the
range 80-150 I'm) are certainly grossly bimodal or polydisperse
systems. The particle size and size distribution of the polymer strongly
influence the viscosity and flow behaviour of pastes.
PARTICLE INTERACTIONS
In the type of suspension exemplified by a basic form of PVC plastisol
[dispersion of resin in plasticiser(s)], non-Newtonian flow behaviour is
principally 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 mechani-
cal linkages, increased or reduced under various rates and durations of
shear. 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 a
18 PVC Pastes 645
breakdown of structure already present,6 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 phenom-
ena. 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. 7 ,8 As pointed out by Rangnes &
Palmgren,9 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
concentration and characteristics of the other constituents. These
effects are discussed in later 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.
18.3 MEASUREMENT OF PVC PASTE VISCOSITY
The viscosity of PVC pastes is measured for the purposes of quality

control (including the determination of ageing characteristics), for-
mulation development and adjustment, verification of applicational
suitability, and some trouble-shooting investigations. Viscosity changes
are also followed in determinations of viscosity stability (commonly by
measurements directly after paste preparation, and then after ageing
for 1, 7, and 14 days), and in the course of studies of the gelation and
fusion of pastes (see Section 18.4).
The viscometers most widely used for the determination of paste
viscosities are the Brookfield spindle viscometer (for measurements at
relatively low rates of shear, typically in the viscosity range 0·02-
5000 N s m-2 relevant to rotational and slush moulding, and dipping
processes, in practice), and the Castor-Severs extrusion rheometer (for
measurements at high shear rates comparable with those encountered

in paste-spreading operations). Both instruments are specified (with
good descriptions of the apparatus and methods) in the relevant ISO
standards. 10,11
Note: Other related standards are: for Brookfield viscometry,
ASTM D 1824-87; for Castor-Severs viscometry, ASTM
D 1823-87 and DIN 54 801 (1979); for general informa-
tion on rotational viscometers, ISO 3219-1977 (viscosity de-
termination on polymer liquids, emulsions and dispersions)
BS 2782 Method 730B (identical with ISO 3219), DIN 53 019
Part 1 (1980).
For the monitoring of paste viscosity in routine industrial operations,
simpler equipment, providing viscosity values in relative terms, can be
quite adequate. One example, suitable for reasonably free-flowing
pastes, is the No. 4 Ford cup (ASTM D 1200-82) with the outlet
enlarged to 5·6 mm: with this, the viscosity can be measured in terms
of the time for 50 cm3 of paste (pre-stirred for about 20 s) to run out of
the cup. If desired, some idea of the corresponding absolute viscosity
values may be obtained by calibrating the apparatus with Newtonian
liquids of known viscosity. Another example is a weighted-plunger-
type viscometer (with symmetrical holes cut in the plunger, as
required, for thicker pastes): with such apparatus the time is measured
for the plunger to fall through the paste filling its containing cylinder.
18.4 GELATION/FUSION OF PVC PASTES
18.4.1 General Features of the Transformation of a Paste into a

pPVC Material
A PVC paste is transformed into a 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
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 homoge-
neous plasticised PVC melt: on cooling this solidifies into the familiar
plasticised PVC material. Overall, the transformation may be regarded
18 PVC Pastes 647
as a phase inversion: a change from a suspension of particulate

polymer in the continuous phase of liquid plasticiser, to a molecular-
level dispersion (solution) of plasticiser in a continuous polymer
matrix, solid at room temperature. Thus the transformation is con-
cluded by the fusion of polymer and plasticiser into a homogeneous
plasticised PVC material. This has led to the use of 'fusion' as the
general term for the entire transformation process. 'Gelation' is also
sometimes used, interchangeably with 'fusion' in this general sense,
especially in the context of production operations (and also in some
relevant publications). However, strictly speaking, gelation is a
relatively early consequence of the heating of a paste, when-as a
result of absorption of the plasticiser(s) by the polymer particles-the
originally liquid paste becomes a comparatively weak (but already
cohesive) gel.
18.4.2 Polymer-Plasticiser Interactions during the Gelation/Fusion
of a PVC Paste
The process of transformation of a paste into the final, fused pPVC

material has been extensively studied, mainly in terms of progressive
changes in the viscosity, appearance and morphology, and physical
properties of the system. Rheometers capable of following changes
over a wide range of viscosities and temperatures have been
employed, whilst the temperature gradient bar 12• 13 and its development
the Geigy Gel Block 14 have served as means of rapidly inducing
progressively more advanced stages of the transformation along the
same specimen of paste.
Note: In equipment of this kind (another version is known as the
'hot bench'), a metal element (bar, block, etc.) is
differentially heated, to produce several zones kept at in-
creasingly higher, closely controlled temperatures. A thin
layer of paste is cast on the surface of the element, so that it
spans the heating zones. After an appropriate time (which
may also be one of the variables investigated), the PVC
layer-now solidified in varying degrees along its length-is
removed, and the degree of transformation in the consecutive
sections is investigated by the appropriate methods (e.g.
examination under the microscope, tensile tests, etc.).
In outline, the following main consecutive stages may be distinguished
in the transformation process as reflected in the changes in the
viscosity of a paste with increasing temperature (cf. Fig. 18.7). A more

detailed discussion can be found in Ref. 2.
The first effect of rising temperature in the heat treatment of a PVC
paste is a short-term reduction in viscosity [slope (a) in Fig. 18.7]. 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. For a given paste resin, the magnitude of the effect [steepness
of slope (a)] depends primarily on the nature of the plasticiser, and
can vary by as much as a factor of about 20 (cf. Fig. 18:8). The
viscosity then rises sharply [slope (b) in Fig. 18.7] as a result of
progressive absorption of the plasticiser into the polymer particles
(with some, relatively minor, contribution from the viscosity increase
of the 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 is
(d)
Temperature
Fig. 18.7 Principal changes in the viscosity of a PVC paste (as measured
directly, e.g. in a balance rheometer, or in terms of torque in a torque
rheometer) reflecting the transformations with increasing temperature in the
gelation/fusion process. Schematic representation. For the significance of
features (a)-(e), see text.
18 PVC Pastes 649
DNP
80
70
60
50
I/)
u
~ 40
'iii
o
.~
> 30
20
10
Temperature (OC)
Fig. 18.8 Plasticiser viscosity as a function of chemical nature and
temperature.
often referred to as 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. 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
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
* The region of slope (b) of the curve in Fig. 18.7 has also been called (by
Alter 15 ) the 'gel region', whilst Newton & Cronin 16 refer to the temperature at
which the paste viscosity reaches 1000 P as the 'setting temperature'.
triaryl phosphate) if other processing requirements (e.g. paste rheol-

ogy, which is also affected by plasticiser compatibility), cost considera-
tions, and ultimate service performance requirements do not preclude
such substitution.
The steep rise of the viscosity curve terminates in a shoulder with,
sometimes, a small peak [cf. (c) in Fig. 18.7]. The rise and shoulder,
and-in some cases-the peak, are also seen on corresponding plots of
modulus versus temperature. The shoulder (or peak) is regarded by
some authors 17 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,18 who has distinguished and named a number of sub-stages
in the gelation/fusion process (see below), suggest that it is more likely
to be the 'gel point' or even possibly the 'haze point' or even the
'elastomeric point' (in Greenhoe's nomenclature).
The next point of interest, and of major importance in the process,
is the fusion temperature, marked by the main final peak (d) of the
curve in Fig. 18.7. The drop in viscosity at still higher temperature
[negative slope (e) to the right of peak (d)] has been ascribed to the
disruption (melting) of centres of ordered structure (microcrystallites)
believed to be formed in plasticised PVC polymer (cf. Section 5.3.3 of
Chapter 5), and thought to act in the same way as microcrystalline
regions in naturally crystalline polymers, i.e. as quasi cross-linking
points stiffening the structure.
Note: It should also be noted in this connection that the fusion
point indicated by peak (d) of the curve in Fig. 18.7 does not
necessarily in practice correspond to the development of the
highest room-temperature tensile strength. In many cases that
ultimate strength level is attained only after heating at a
somewhat higher temperature for an appropriate time, to
effect complete fusion.
In its morphological aspect, complete fusion (as marked also by the
development of the optimum mechanical properties) may be defined
as the state attained when the PVC polymer and the plasticiser(s) have
been fully interdispersed to form a physically homogeneous pPVC
material.
The actual temperature and viscosity (or torque) values with which
the features (a)-(e) in Fig. 18.7 are associated can vary substantially,
18 PVC Pastes 651
depending on the formulation of the paste, and especially the nature

of the plasticiser(s) and the polymer(s). By way of an approximate
illustration, for a simple plastisol consisting of a general-purpose
phthalate plasticiser and a regular general-purpose paste polymer, the
values may be (assuming a heating rate of about 3°C min -1):
The minimum
(trough) between
(a) and (b) (c) (d) (e)
Temperature,oC 50 80 140 180
Paste viscosity, log P 1·8 4·9 5·1 4·5
On the basis of his work with the temperature gradient bar,

Greenhoe 13 ,18 postulated six transition points between the original
liquid paste and the final fused product, each point being differentiated
by the appearance and/or some structural features of the material.
The points were (with increasing temperature): the fluid point (where
the paste becomes dry and putty-like), dry point (where it changes to a
somewhat crumbly solid), gel point (where the material begins to
acquire physical strength), haze point (where clarity increases),
elastomeric point (where tensile strength and significant elongation at
break develop), and fusion point (where optimum tensile strength is
attained).
18.4.3 Practical Detennination of the Completeness of Fusion in

Paste Products
The mechanical and other properties of a paste product reach their

optimum levels when fusion is complete. It follows that, for the
purposes of quality control, product evaluation and characterisation,
etc., test methods are needed to determine completeness of fusion.
Where practicable, determination of the tensile properties (tensile
strength and elongation at break, 100% modulus) is used for the
purpose. However, such tests are not applicable to PVC coatings on
fabrics and other substrates, which represent a large proportion of
paste-derived products.
Note: With such products, the surface appearance of the coating
can often provide a useful indication of whether the material
has been completely fused. If it has, the surface will normally
be glossy and shiny (providing no matting agents are pre-

sent). A dull, matt surface is a strong clue that fusion has not
been complete.
A solvent-immersion test can be particularly useful as a means of

determining the completeness of gelation of a pPVC coating on a
fabric. Early versions of such tests include the ethyl acetate immersion
methods of Kling 19 and Schimke,z° and the acetone immersion tests
widely used with PVC-coated gloves2 and prescribed by some stand-
ards for PVC-coated fabrics. 21 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
cracking or 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 cracking or 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
of imposed strain in the specimen.
Some solvent-immersion tests, notably the acetone test for PVC-
coated gloves, can be used not merely to obtain an indication of the
completeness of fusion on a pass or fail basis, but also-through a
suitable series of determinations2-to gauge the extent to which the
state of the PVC material falls short of complete fusion. Such use of
the test can also indicate the minimum temperature required for
complete fusion of a particular paste composition, and the minimum
time of treatment required at this, or any higher temperature. 2
The 'clear-point' test discussed in Section 5.4.1(c) of Chapter 5 can
provide an a priori indication of the relative ease (and, especially in
the light of relevant prior experience, sometimes also the likely
temperature) of fusion of a paste based on a particular
polymer/plasticiser combination.
18 PVC Pastes 653
18.5 THE COMPOSmON OF PVC PASTES
18.5.1 Paste Fonnulatio~eneral Points
The PVC paste is a special physical form, adapted to certain kinds of

processing, of a PVC composition which will ultimately become a
normal plasticised PVC material. Therefore, all those formulation
constituents required for the intended end-use are found in a PVC
paste (although some, such as for example the paste-grade PVC
polymers, may have to be of a nature suitable for use in the paste).
However, because of its liquid state and special processing require-
ments, a paste will also often contain ingredients never required in
solid PVC compositions, such as viscosity modifiers of various kinds.
18.5.2 Components of PVC Pastes
(a) Paste Polymers

The regular paste-making polymers are produced by the emulsion or
microsuspension processes. Their particles have a degree of resistance
to penetration by plasticisers at room temperature (which makes for
paste stability), but at suitably elevated temperature the rate of
penetration increases sufficiently for the rapid attack and ultimate
dissolution required for satisfactory gelation and fusion. The particle
size and size distribution of different paste polymer grades are also
suited to particular rheological requirements, such as the production of
high-, medium-, or low-viscosity pastes,2 with shear-response charac-
teristics appropriate to specific applications. For example, paste
polymers are available which promote high paste viscosity (and thus
are particularly suitable for pastes of high plasticiser content) and.
pseudoplastic behaviour. Such polymers (e.g. Hostalit PX 1219;
Hoechst) are suitable for plastisols for such applications as very soft
foams, coating of open-structure fabrics, application by screen print-
ing, and undersealing of motor-cars. A feature of pastes based on
Hostalit PX 1219 and similar polymer grades is that they adhere well
to electrophoretically treated steel surfaces, even in humid atmos-
pheres. By contrast, another special grade-Hostalit PX 1215-
exemplifies a paste polymer of high K value producing pastes of low
viscosity suitable, inter alia, for high filler loading.
New developments in paste polymers include a 'copolymer alloy'
resin (Goodtouch 250x 100, B. F. Goodrich), claimed to impart a
rubbery feel to paste-moulded gloves, and to provide pastes of good

rheology and viscosity stability.
Certain grades of suspension-produced PVC resins are occasionally
included as extender polymers replacing part of the paste polymer in
pastes. Their function is to reduce paste viscosity whilst preserving or
increasing the polymer content of the finished product. The viscosity
reduction arises because the paste becomes a system in which the
relatively coarse extender particles (typical size range 80-140,um) are
loosely suspended in a 'liquid' consisting of the dispersion of the much
finer paste resin particles in the plasticiser(s). 22,23
With appropriate extender polymer grades, the viscosity-lowering
effect is reasonably permanent.
Occasionally, homopolymers with more absorbent particles, or
copolymers with high co-monomer contents, are used as extenders. In
such cases the paste viscosity increases, and ageing properties de-
teriorate. Viscosity-lowering extender polymers are employed in
pastes for spraying, rotational casting, and some coating applications.
The selection and use of extender polymers are discussed in a paper by
Park. 24
(b) Plasticisers
In addition to the properties important vis-a-vis the end-use (see
Chapter 5), the choice of plasticisers for pastes is governed by
considerations of the required paste rheology, including the
gelation/fusion properties.
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 considera-
tions 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.
Solvating power of plasticisers as a factor in paste ageing is discussed
in a paper by Bigg & Hill. 25
As has been mentioned in Chapter 5, a mixture of plasticisers will
normally impart to a pPVC material physical properties and end-use
characteristics intermediate between those imparted by its individual
18 PVC Pastes 655
components. This is so also in paste products. Moreover, the principle

also extends to plasticisers' effects upon the flow properties and ageing
characteristics of the liquid pastes themselves. A more detailed
discussion of these effects can be found in Ref. 2. The following salient
points may be noted here.
In general, the phthalate plasticisers tend to give medium-viscosity
pastes, with low to medium setting (gelation) temperatures. Many
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 shear (as for example in coating operations).
However, some plasticisers thixotropic in their effect at moderate
shear rates (e.g. DOP, DOS) may promote dilatant behaviour at rates
of shear that are substantially higher. Plasticisers whose own viscosity
is high, and those with good solvating power (e.g. BBP, DBP), tend to
make viscous pastes. Dilatancy, even at low shear rates, may be
promoted by triaryl phosphates and some aromatic esters of glycols
(e.g. diethylene glycol dibenzoate). The phosphates tend to improve
the rate of gelation and fusion, and their tolerance for plasticiser
extenders is good. Neither high viscosity (unrelieved by thixotropy)
nor dilatancy is normally desirable in a paste, as these properties make
the paste difficult to stir, de-aerate, and spread. They can be
counteracted by replacing part of the plasticiser system with an
aliphatic diester 'low-temperature' plasticiser (e.g. DIDA; some 'nylon
acid' esters). Some higher phthalates, notably DINP, can also be
useful in this connection. Other phthalates promoting advantageous
paste rheology and viscosity stability in storage are dicapryl phthalate
and Hexaplas OPN [a proprietary product of ICI, cf. Section 5.5.3(a)
of Chapter 5]. 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.
In pastes containing aliphatic diesters (normally as a part of the
plasticiser system), several of these plasticisers can promote a large
initial drop in paste viscosity with increasing temperature (a feature
useful in rotational casting), and good ageing resistance, along with
relatively high setting temperatures.
Polymeric plasticisers tend to impart fairly high viscosity, and may
promote dilatancy, but they may at the same time improve the paste's
ageing properties. They are included in pastes principally for their
permanence properties in the final product.
(c) Stabilisers
With regard to stabilisers, the service-suitability aspect of paste
formulation is very similar to that of other plasticised PVC composi-
tions. The effects on paste rheology are associated partly with the
stabiliser's chemical nature (see below) and partly with its physical
state: liquid stabiliser systems are used where any viscosity increase is
to be kept to a minimum.
Barium/cadmium and barium/cadmium/zinc systems are more
widely used in pastes than any other type of stabiliser. Liquid
calcium/zinc and magnesium/zinc systems can be useful 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 calcium/zinc and cadmium/zinc 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 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 silicate 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.
(d) Fillers
Fillers are included in pastes for the same end-use purposes as in solid
compounds, but their effects on paste rheology and ageing characteris-
tics must be considered, as most can increase the viscosity and reduce
the shelf life of the paste, or modify the response to shear. 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 lifelike appearance to paste-moulded PVC
dolls.
18 PVC Pastes 657
Other factors being equal, paste viscosity tends to rise with

increasing filler loading and with decreasing particle size. Inter alia, the
latter factor increases adsorption of plasticiser by the filler, because
the specific surface (surface/volume ratio) of the filler increases. The
surface adsorption can be considerably reduced if a coated grade of
filler is used. Some of the effects of organic coatings on fillers upon the
viscosity and other properties of filled PVC pastes are discussed in a
paper by Monte & Sugerman. 26
The rheological effects of two commercial grades of calcium
carbonate (CaC03) filler are shown in Fig. 18.9; 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
1500
Sturcat L
- - - - - - - - 3 3 phr
_ _- - - - - - - - - C a l o f i l A.4
a. 33phr
~
·iii
ou
:>'"
._ - - - - - - - - - S t u r c at L
Bphr
-=_-----------CatofilAA
Bphr
_ _- - - - - - - - - - - No fillar
o 5 10 15
Tima, days
Fig. 18.9 Effects of two commercial CaC03 fillers (from John E. Sturge Ltd,
UK) on PVC paste viscosity. Sturcal L: medium-oil-absorption filler. Calofil
A4: resin-coated, low-oil-absorption filler. Paste formulation: PVC paste-
grade polymer 100 phr; DOP 33 phr; TIP 33 phr; stabiliser (white lead paste)
1· 7 phr; filler as shown.
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 both the formulator and the processor.
Note: The viscosity stability of a paste is often expressed in terms of

the ageing index (sometimes called the viscosity stability
index) calculated as a ratio VL : Vs , where VL is the viscosity
measured after an appropriate, long period (say 14 days) and
Vs is the viscosity value obtained in an earlier measurement
(say the 24-h or 48-h viscosity).
(e) Additives Modifying Paste Rheology
THICKENING AGENTS
These additives increase paste viscosity, and usually also impart
thixotropy, so that the viscosity increase (which can reach the plastigel
state) does not hamper such operations as coating, spreading, etc.,
whilst there is also an anti-sag and anti-run effect in processing.
Certain grades of fumed or precipitated silica serve as thickening
agents, mostly with thixotropic effects, for PVC pastes: cf. e.g. Gasil
23 and Neosyl (Joseph Crosfield & Sons Ltd, UK); Aerosil 200
(Degussa); Sylox (W. R. Grace & Co., Davison Chemical Div.,
USA); and some grades in the Wacker HDK range. Some proprietary
grades of particulate inorganic thickening agents are based on fine-
particle bentonite. Aluminium stearate has been used for a long time
(e.g. the original Higel No.1; Albright & Wilson Ltd, UK), and more
recently a range of proprietary organic compounds of calcium has
become available (the Ircogel 900 series, Lubrizol Corp., USA): this
includes gel or liquid grades, incorporating plasticisers and solvents for
easy dispersion, by simple addition (at levels between 2 and 10 phr), in
PVC pastes.
With particulate thickening agents and aluminium stearate (both
typically used at levels from one to a few phr, but higher where silicas
are used to produce stiff plastigels for modelling) it is usual to pre-gel
the plasticiser with the agent, and use the resulting product for
preparing the paste. This procedure ensures ultimate complete disper-
sion of the agent. With aluminium stearate in particular, the prelimi-
nary dispersion in the plasticiser(s) is warmed, until a clear solution is
obtained, which may gel on cooling.
18 PVC Pastes 659
Note: As aluminium stearate is not readily soluble in triaryl

phosphate plasticisers, DOP or DOS should be used for the
pre-gelling for pastes containing this plasticiser.
VISCOSITY DEPRESSANTS
These are liquid additives, used to reduce paste viscosity (so as to e.g.,
keep it down to workable levels in polymer-rich pastes for near-rigid
products). Many viscosity depressants are selected surface-active
agents, typically condensates of polyethylene glycols with fatty al-
cohols (e.g. Lubrol MOA; ICI) or acids (e.g. polyethylene glycol
mono-oleate). Examples of proprietary commercial products are: the
Lipinol VR range (Hiils, FRG) and the Byk 'polycarbonic oligomers'
4015 and 4010 (the respective grades for unfilled and filled pastes).
Such proprietary additives may contain air-release agents or special
wetting agents for fillers. Viscosity depressants of the secondary
plasticiser type are exemplified by TXIB (cf. Table 5.9 of Chapter 5)
and dodecylbenzene: their addition levels may range up to about
20phr (cf. about 3-7phr for Byk 4010).
DILUENTS
These are organic solvents incorporated to reduce viscosity: their
presence makes the paste an organosol-d. Sections 18.1 above and
18.5.3(a) below.
(f) Miscellaneous Additives

Those with processing functionality include moisture scavengers some-
times used, at about 1 phr, in pastes for rotational moulding (cf. e.g.
Byk NP 2610, a proprietary dispersion of calcium oxide), and
mould-release agents. Other additives used in pastes are among the
formulation components discussed in Chapter 9.
18.5.3 Pastes for Rigid Products
Although it is possible in some cases to incorporate cross-linkable

plasticisers in a paste (and subsequently to irradiate the final product-
cf. Section 22.4.2 of Chapter 22) to meet the combined requirements
of rigidity in the product and reasonably low viscosity of the parent
paste, such requirements are more commonly catered for by the
special versions of PVC pastes known as organosols and rigisols.
(a) Organosols
These are pastes containing volatile liquids as diluents. The diluents
with the least effect on viscosity stability are aliphatic hydrocarbons
(e.g. white spirit, solvent naphtha). An aromatic hydrocarbon (e.g.
toluene, xylene) and some ketones (e.g. methyl isobutyl ketone, or
methyl ethyl ketone) may produce a similar initial viscosity decrease,
but their swelling action on the PVC resin will also impair viscosity
stability. This effect can be limited by their use in mixtures with
aliphatic hydrocarbons. The level of incorporation of diluents may
vary widely depending on the paste formulation and the degree of
viscosity reduction required (which will in turn depend upon the
process to be used, e.g. spreading, spraying, etc.). Inclusion, at about
1-phr level, of a liquid surface-active agent of the polyethylene glycol
type can substantially improve the initial viscosity reduction and the
maintenance of viscosity stability. Polyethylene glycol mono-oleate of
molecular weight 400 was one of the early successful additives of this
kind. 27
(b) Rigisols
As mentioned in Section 18.1, rigisols are plastisols formulated to
provide a combination of suitably low viscosity for processing with
high polymer content (and hence considerable rigidity of the final
product). The following formulation factors are instrumental in this
result.
(i) Use of the appropriate grade of paste polymer (or, if necessary,
a blend of such polymers) recommended by the polymer
manufacturer. This may be combined with the use of a suitable
extender polymer (suspension homopolymer or selected
VC/VDC copolymer).
(ii) Selection of plasticisers. which promote low paste viscosity.
Several aliphatic diester plasticisers, especially the 'nylon acid'
esters, are particularly suitable [cf. Section 18.5.2(b) above].
(iii) Use of liquid stabilisers with no thickening effects.
(iv) Restriction on any filler loading (to not more than 15 phr,
preferably) .
(v) Use of viscosity depressants: polyethylene glycol (400 MW)
monolaurate has been particularly recommended. 28
(vi) Use of aromatic-free diluents, such as white spirit or aliphatic
naphtha, if and as required.
18 PVC Pastes 661
TABLE 18.1
Examples of Rigisol Formulations
(Parts by weight)
PVC resins: Paste-grade polymer, low viscosity
(K value 65 a ) 50 50 100
Suspension polymer (K value 5Y) 50 50
Stabiliser system: BalCd liquid 2 2 2
Epoxy co-stabiliser 2 2 2
Plasticisers ('nylon acid' esters):
Reomol MDb 25 30
Reomol MNb 25
Viscosity depressant: Lubrol MOA 2 2 2
Apparent viscosity of paste,C P
After 1 day 18 22 42
After 7 days 18 20 98
BS softness no. of ultimate product 6 7 9
a 0.5 g polymer in 100 cm3 dichloroethane at 25°C.
b Ciba-Geigy.
C At low shear rate.
In the preparation (mixing) of rigisol pastes it is particularly

important to ensure that the paste is completely homogenised.
Useful advice on basic rigisol formulations for specific purposes is
available from manufacturers of paste resins and plasticisers. The
general examples29 in Table 18.1 illustrate the nature of such formula-
tions, and some of the points made above.
18.6 PREPARATION OF PVC PASTES
18.6.1 Some General Points
Modem paste resins are well adapted to rapid, thorough dispersion in

the plasticiser during paste preparation, and simple mixing in a batch
mixer with an effective action can produce a satisfactory paste. Batch
mixing is practised both in laboratory preparations and on the
industrial scale. Continuous mixing is normally a plant-scale operation,
carried out in special equipment (see Section 18.6.3 below).
Two-stage batch preparation, involving a first 'thick' mixing stage, is
also sometimes practised, especially with pastes which are more
difficult to homogenise (e.g. rigisols, or highly filled paste composi-

tions), or low-viscosity pastes. In the 'thick stage', the polymer and
any solid formulation components (fillers, pigments, solid
stabilisers)-the latter thoroughly pre-wetted with some plasticiser-
are first mixed with part of the total plasticiser(s). This makes for
high-shear mixing, which promotes effective interdispersion. The
mixer may have to be cooled at this stage to prevent shear heating and
the consequent gratuitous thickening of the paste as the plasticiser
begins to swell the polymer at the elevated temperature. When the
'thick' mix has been homogenised, the remaining plasticiser(s) and any
other liquid formulation components (e.g. diluents) are added gra-
dually over a period of time while the mixing continues. At the end of
this second ('thin') stage, the paste attains its proper viscosity.
With any mixing method, unless carried out under effective vacuum,
some air is entrapped in the paste. This must be removed, to prevent
bubbles in the final product. With a thin paste, de-aeration can
sometimes be effected by leaving the paste to stand for, say, 24 h.
Otherwise, a de-aeration treatment is necessary (see Sections 18.6.2
and Fig. 18.10 below).
A properly formulated and prepared paste should keep satisfactorily
for some weeks, providing it is stored in a cool place. The material of
the container may also play a part: iron and zinc should be avoided,
unless covered by an acceptable surface finish (e.g. a lacquer inert to
the paste). Glass, aluminium, tinplate, and enamel are satisfactory.
18.6.2 Small-Scale (Laboratory) Paste Preparation
A planetary mixer of sufficient power, with stainless steel bowl and

blades, and bowl-cooling facility, is the most convenient equipment
(for studying mixing characteristics, instrumented equipment like the
Brabender Plasti-Corder, with the appropriate mixing attachment,
may be used). In such equipment, a small batch of paste of the order
of 1 kg can be simply prepared by placing the polymer and other solid
components in the mixer bowl, pouring the plasticiser evenly over
them, and mixing, at first slowly until the composition has been pasted
up, and then at a fast rate, until the paste has been completely
homogenised. The total preparation may take some 20-30 min. If the
mixer is not equipped for vacuum application during mixing, the paste
must be de-aerated subsequently. Standard versions of this kind of
method are laid down in specifications [e.g. ISO 4612-1979 (1986) and
BATCH CONTINUOUS
RAW PVC FILLER PLASTICISER PVC
MATERIAL
STORAGE
METERING
.....
00
PREPARATION ~
~
FIL TERING ..~'"
-{;}-,-
I
DE-AERATION I
I
I
AGEING
(PASTE
BUFFER
TANK)
Fig. 18.10 Flow diagram for industrial preparation of PVC paste. ~

DIN 54800 (1979)] for the control and evaluation of paste formulation
factors.
Note: The standard conditions for measuring the viscosity of a paste
prepared in accordance with ISO 4612 are given in
ISO 1060/1-1982 E. They are: measurement 24 h after pre-
paration of the paste (and storage at 23°C); a Brookfield RV
viscometer with No. 6 spindle operated at the rotational
frequency of 20 r min- 1 ; viscosity read after 1 minute's
rotation.
18.6.3 Industrial Production of Pastes
The production may be continuous or batchwise, depending on the

type of paste, its application, volume required, and other considera-
tions. A typical operational sequence for each of the two kinds of
procedure is shown schematically in Fig. 18.10. The most versatile
mixer for the batch method is a dissolver (see Fig. 18.11)-a mixer
with a disc agitator operable at infinitely variable speed, and pre-
ferably equipped with removable bowls and a vacuum facility. Other
types of mixers used are planetary mixers, horseshoe (anchor) stirrer
mixers, ribbon, roll and paddle blenders. Ball-milling or triple-roll
milling may be resorted to where fine, intimate homogenisation is
required (e.g. in the production of colour pastes). An effective
b
a
Fig. 18.11 Dissolver. a, Disc agitator; b, scraper.

18 PVC Pastes 665
3---+-+-
5--I~
Fig. 18.12 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.
continuous-mixing machine is the Buss MT mixing turbine (cf. Figs

18.10 and 18.12). Certain versions of the dissolver may also be
adapted to continuous running. The equipment and operations in-
volved in the industrial production of PVC pastes are discussed in
some detail in Ref. 2.
18.7 APPLICATION OF PVC PASTES:

PROCESSES AND PRODUCTS
18.7.1 Moulding Processes
(a) Rotational Casting

This process-also known as rotary casting, roto-casting, or rotational
moulding-is the main way of producing hollow moulded pPVC
articles (playing balls, 'squeaky' toys, dolls' heads and body parts;
PVC skins for foam-filled products-e.g. arm rests for car interiors,
etc.); it enables such products to be manufactured from pre-metered
amounts of paste with uniform thickness and good surface detail.
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-carried 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 of the filling step of the next cycle.
Modern rotomoulders are programmable for various cycles: other
typical features include multiple-step heating and cooling, multiple
forward and reverse rotation timing, and automatic fault alarm.
18 PVC Pastes 667
(b) Slush Moulding

This process also produces hollow articles from paste deposited on the
interior surface of a mould. The paste is poured into the light, open
mould and then poured out, leaving a layer coating the inside mould
surface. The layer thickness may be governed entirely by the paste
rheology and process timing, or it may be increased by using a hot
mould to effect some gelation. In either case fusion is subsequently
completed by a final heat treatment. A greater layer thickness may be
built up by filling and emptying the mould a number of times, each
consecutive layer being partially gelled. At the end the mould is
cooled sufficiently to enable the moulding to be removed without
damage or permanent distortion. Several variants of the basic tech-
nique are practised. 2 The hollow mouldings may be filled in situ with
flexible polyurethane foam (as in the production of some motor-car
dashboards and trim components), or the foaming may be performed
in a separate retainer mould.
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 to 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 mould-
ings). 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.
(c) Dip Moulding

In this process a hollow moulding is formed in a way which may be
regarded as the reverse of rotational or slush moulding. A suitably
shaped metal former is pre-heated, and dipped into the paste in a
dipping tank: it is then withdrawn at a controlled rate, inverted to let
any drips merge back into the paste layer adhering to the former's
surface, and transferred to a heating station where the paste layer is
finally fused. The resulting hollow moulding is stripped from the
former after cooling.
Disposable, unsupported pPVC gloves (typically produced from a
basic plastisol composition containing about 100 phr DOP), and covers
for cable terminals are two examples of dip mouldings.
18.7.2 Coating of Objects and Articles
(a) Dip Coating
HOT-DIP COATING
This process is very similar to dip moulding, and useful for producing
pPVC coatings on metal objects suitable for dipping in paste. The
main difference is that the fused paste layer is not stripped, but
remains as a permanent coating. Positive interfacial adhesion, de-
sirable in any coating, is usually secured by applying to the metal
surface a thin priming coat (deposited from solvent solution). Articles
substantially below 3 mm in thickness will not normally be suitable for
coating by this process, because low heat capacity hampers satisfactory
fusion. On thicker wire, coatings 0·5-0·8 mm thick can usually be
obtained in one dip. In all cases the final fusion of the coating is
effected in a separate heating step. The metal surface temperature
(which may be between 90°C and 130°C), rate of entry into and
withdrawal from the paste, and the dwell period in the paste are
important factors in the coating process. Articles coated by the process
include fence posts and fittings, thick wire baskets and trays, mounting
brackets, and the like.
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.
18 PVC Pastes 669
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 Fig. 11.46.
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
between the two, are household clothes lines and some types of cords
and ropes.
(b) 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.
The spraying method and equipment may be of the air-spray or
airless variety, with appropriate arrangements for charge generation.
After spraying, the coating is fused by a heat treatment; pre-heating
may be necessary to remove any solvent used in the paste: in this step
the heating should be so controlled as to prevent bubble formation by
the departing solvent. Other problems occasionally experienced in
spray-coating with PVC pastes are generally similar to those encoun-
tered 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.
18.7.3 Coating of Fabrics and Paper
These are the continuous substrates most widely coated with PVC
pastes, in the manufacture of such important large-volume products as
tarpaulins, tent fabrics, awnings, upholstery materials, wall-coverings,
book-binding fabrics and papers, leathercloth for travel and fancy
goods and garments (protective and fashion), floor coverings, con-
veyor and drive belts, and adhesive tapes.
The subject is extensive, and only some of the most important
general features of continuous coating operations can be indicated
here. A more thorough discussion will be found in Ref. 2.
(a) Coating Processes and Methods

The paste-coating methods 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
products.
The common basic arrangements for applying a coat of PVC paste
directly to a continuous sheet material are schematically illustrated in
Figs 18.13 and 18.14. 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.
The suitability of each basic type of industrial coating arrangement
in a particular situation will depend on several mutually interacting
* Not to be confused with reverse roller coating-d. Fig. 18.13.

18 PVC Pastes 671
Fig. 18.13 A reverse-roller coating arrangement (nip feed): schematic

representation; only basic components shown.
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 protective-
garment fabrics), complete impregnation of the substrate may
be required. With most true coatings on fabrics a depth of
penetration of one-third to one-half 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 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
coating 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
Fig. 18.14 Knife coating (spreading) arrangements: schematic representation.

A, Knife over roller; B, air knife; C, knife over plate; D, knife over blanket.
substantial extensibility will be more prone to penetration by a given

paste in a given 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.
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 arran-
gements for the substrate, and paste reservoir and feed, may constitute
the entire set-up for simple 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
18 PVC Pastes 673
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. With organosol coatings, a
pre-heating zone should preferably precede the fusion oven: the
pre-heating, at a relatively low temperature, is practised to prevent
skinning of the paste layer, which can lead to blistering by the
temporarily trapped volatiles. Some ovens are provided with inte-
grated exhaust incineration (to prevent air pollution), and with
heat-recovery systems.
Tensioning control and drive systems for the substrate, incorporat-
ing unwinding, compensating, rewinding and wind-up gear, are typical
features of good industrial equipment, 'as are measuring devices (e.g.
beta-ray gauges) for the monitoring of coating thickness and its
running adjustment via a link-up to the coating station(s).
The modern versions of the transfer (reverse) coating process are
capable of close control producing good-quality, uniform, multilayer
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
deposit-by direct application-a layer of paste (or a number of layers
to form a composite coating), on the smooth surface of a continuous
support, laminate the substrate to be coated to the paste layer(s), and
remove the laminate so formed. 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.
The production of a typical leathercloth (e.g. for 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 by the transfer method).
Where appropriate, adhesion between the coating and the substrate
may be promoted by a bonding (tie, priming, or keying) coat. 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 coats on
paper or fabric substrates may be thin latex-deposited PVC layers.
Adhesion-promoting additives may be incorporated in the coating
paste. For example, a special liquid isocyanurate (Vulcabond VP; ICI)
has been used in this way in PVC pastes for coating nylon and
polyester fabrics in the production of tarpaulins and materials for
protective clothing.
The embossing and surface-protection treatments applied to paste-
coated materials are discussed in Sections 22.1.4 and 22.3.1 of Chapter
22.
(b) Quality and Testing of Paste-Coated Materials
SOME COATING FAULTS
The main general effects of incorrect selection or setting in the matter
of such basic process parameters as roller arrangement and setting, or
knife profile and positioning, fabric tension and rate of advance, and
paste rheology, are broadly predictable; and conversely, their man-
ifestations 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 particular operation~f 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 at-
tributable 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-
tions the compatibility of constituents may be affected by the
18 PVC Pastes 675
high-shear conditions under the blade to the point where separation

and agglomeration can occur-this particular problem can be pre-
vented 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 defin-
itely 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 expansible 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 ap-
pearance 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 (i.e. apply the coating in
two consecutive layers) so that the number of pinholes penetrating the
total coating thickness is reduced in proportion to the chance that a
pinhole in the first layer will coincide with one in the second.
TESTING
Completeness of fusion of coatings on fabrics can be determined by
solvent tests (see Section 18.4.3). In some cases a test of the strength
properties of the coating may be practicable (as when the coating can
be removed from the substrate, e.g. with the aid of a leather-splitting
machine).
Most of the other property requirements and tests applicable to
coated fabrics and such products as conveyor belting are contained in
the standard specifications listed in Table 18.2. Some actual require-
ments are quoted, by way of example, in Table 18.3.
Note: A conveyor belt of the PVC variety (rubber ones are also
made) may be of one of two types: a solid woven core
impregnated with a PVC paste and covered with a coating of
a different paste formulation, or a laminate of plies of fabric
each coated with a PVC paste, the laminate again covered
with a coating of a different paste formulation. In both cases
the PVC is fully fused together throughout the structure. All
paste formulations must be fire-retardant (phosphate plas-
ticisers and fire-retardant additives are commonly used), and
the cover composition is also formulated inter alia for
antistatic properties and abrasion resistance (PVC/NBR
blends are used in some formulations).
Apart from those represented in Table 18.3, the coated-fabric pro-

perties of frequent interest include (as appropriate to the service
conditions) low-temperature properties of the coating (cf. Section
24.3.2 of Chapter 24), flammability [for burning tests on conveyor
belts see Section 24.6.4(b) of Chapter 24], volatiles content, and
weathering resistance. A useful test for resistance to soiling (employ-
ing an abrasion tester) has been described by Kratschmann. 3o
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. 31
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. 32
18 PVC Pastes 677
TABLE 18.2
Standards Relevant to tbe Properties and Testing of Coated Fabrics and
Conveyor Belting

no.
official title)
Coated fabrics
1 ISO 1419-1977 Accelerated ageing and simulated
service tests for rubber- or plastic-
coated fabrics
2 ISO 1420-1987 Determination of resistance to
penetration by water (of fabrics as in
ISO 1419)
3 ISO 1421-1977 Determination of breaking strength and
elongation (of fabrics as in ISO 1419)
4 BS 3424:1982 Multi-part specification for various tests
for coated fabrics
5 BS 3546:Part 2:1981 Specification for PVC-coated fabrics
BS 5790 Coated fabrics for upholstery
6 Part 1:1979 PVC-coated knitted fabrics (replaces
BS 4216)
7 Part 2:1979 PVC-coated woven fabrics (replaces
BS 2601)
8 ASTM D 751-79 Standard methods of testing coated
fabrics
9 ASTM D 815-81 Coated fabrics-Hydrogen permeability
10 ASTM D 2136-84 Coated fabrics-Low-temperature bend
test
11 ASTM D 2137-83 Brittleness point of flexible polymers
and coated fabrics
12 ASTM D 3389-87 Coated fabrics-Abrasion resistance
13 ASTM D 3393-75 Coated fabrics-Waterproofness
14 ASTM D 3690-78 Standard performance specification for
vinyl-coated and urethane-coated
indoor upholstery fabrics
15 ASTM D 3959-86 Rubber- and plastic-coated fabrics-Test
for sensitivity to discolouration by
tobacco smoke
16 DIN specifications: Relating to various properties of coated
DIN 53352-53354; fabrics (not specifically PVC-coated)
DIN 53 356-53 362
Conveyor belting
17 ISO 284-1982 Conveyor belts-Electrical conductivity:
Specification and test method
(continued)
TABLE 18.2--contd.

no.
official title)
18 ISO 1813-1979 Similar to ISO 284, but for V-belts
19 ISO 4195-Part 1:1987 Conveyor belts-Test method for heat
resistance
20 BS 351:1976 (1985) Transmission belting for general use
(rubber or plastics)
21 BS490 Conveyor and elevator belting
Part 1:1985 Rubber and plastics conveyor belting of
textile construction for general use
Part 2:1975 Rubber and plastics conveyor belting of
textile construction for use on bucket
elevators
22 BS 3289:1982 Conveyor belting primarily for use
underground (including fire
performance)
18.7.4 Paste Casting
This is a relatively straightforward technique, employing compara-

tively 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, antislip undermats 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 hotplate 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 the paste is cast into a cylindrical mould
around an axially placed metal core, surface-primed for ultimate
positive adhesion (typically with an epoxy or acrylic thin priming
layer). Mats and like products are produced by open casting into
shallow dish moulds: excess paste may be removed by passing a doctor
blade across the top, and the cast paste should then be de-aerated.
TABLE 18.3
Some Standard Property Requirements for PVC-coated Upholstery Fabrics
Standard BS 5790:Part 1:1979 BS 5790:Part 2:1979
(for PVC-coated knitted fabrics) (for PVC-coated woven
fabrics)
Type 1 Type 2 Grade A Grade B
(with solid PVC (with PVC coating
coating) incorporating an ....
Qc
expanded layer) ~
Property" Grade V Grade X ~

~ ~
Total mass per unit area, g m- 2 (minimum) 590 760 795 550 420 ~
Base cloth mass per unit area, g m- 2 110 75 110
(minimum)
Coating mass per unit area, g m- 2 (minimum) 480 685 685 300 240
Tear strength, N per 50 mm (minimum)
Lengthways 40 29
Transverse 40 29
Bursting strength, kPa (minimum) 690 380 690
Breaking strength, N (minimum)b 580 450
Coating adhesion, N per 50 mm (minimum) 26 26 26 26 26
Elongation, % (minimum)
Lengthways 10 15 10
Transverse 40 50 40 ~
(continued) \0
~
TABLE 18.3---(contd.)
Standard BS 5790:Part 1:1979 BS 5790:Part 2:1979

(for PVC-coated knitted fabrics) (for PVC-coated woven
fabrics) ."
Type 1 Type 2 Grade A Grade B

~
(with solid PVC (with PVC coating
::s!
coating) incorporating an ~.
!:l
expanded layer)
~~
Property a Grade V Grade X ~
~
:::to
Tension set, % of actual elongation (maximum) 33 33 33 ~
Flex cracking, cycles (minimum) 400000 400000 400000 400000 300000 ."
~
(")
Surface drag angle, degrees (maximum) 30 30 30 30 30
Heat-ageing, % coating mass loss (maximum) 5 5 5 5 5 ~
~.
Print wear, change of appearance, grey scale 3 3 3 3 3
rating (minimum)
Thickness, mm (minimum) i
~
Mean 1·09 1·27
~
Individual reading 0·97 1·14 0·4 0·4
~brasion resistance, cycles,C (minimum) 700 700 B
~.
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.
18 PVC Pastes 681
In all cases the cast paste is fused in the mould at a temperature and
for a time appropriate to the formulation and the layer thickness.
IS.7.S Other Paste-Processing Methods of Minor Significance
These are: low-pressure injection moulding; compression moulding;

and extrusion of pastes. Some information on their applications can be
found in Ref. 2.
REFERENCES
1. ISO 4612-1979 (confirmed 1986). Plastics-PVC paste resins-Preparation

of a paste.
3. Johnston, C. W. & Brower, C. H., SPE J., 26(9) (1970) 31-5.
4. Underdal, L., Lange, S., Palmgren, O. & Thorshaug, N. P., PVC paste
technology and polymer characteristics. Paper presented at the PRI
International Conference on PVC Processing, Egham Hill, Surrey, UK,
6-7 April 1978.
5. Bjerke, 0., Relation between the distribution of size of the primary
particles and the rheological properties of PVC plastisols. SCI Monograph
No. 26, pp. 370-80.
6. Gillespie, T., J. Colloid Interface Sci., 22 (1966) 554-9.
7. Hoffman, R. L., J. Colloid Interface Sci., 46 (1974) 491-7.
8. Strivens, T. A., J. Colloid Interface Sci., 57 (1976) 476-80.
9. Rangnes, P. & Palmgren, 0., J. Polym. Sci.-Part C, 33 (1971) 181-7.
10. ISO 2555-1989. Plastics-Resins in the liquid state or as emulsions or
dispersions-Determination of apparent viscosity by the Brookfield
method.
11. ISO 4575-1985. Plastics-Polyvinyl chloride pastes-Determination of ap-
parent viscosity using a Severs rheometer.
12. McKenna, L. A., Mod. Plast., (June 1958) 142.
13. Greenhoe, J. A., Plast. Techno!., 6(10) (1960) 43-7.
14. Wheeler, A. & Clifton, B. V., Brit. Plast., (Dec. 1962) 640.
15. Alter, H., J. Appl. Polym. Sci., 6 (1959) 312.
16. Newton, D. S. & Cronin, J. A., Brit. Plast., (Oct. 1958) 426.
17. Cayrol, B., Klason, C. & Kubat, J., Polym. Engng Sci., 14(12) (1974)
968-72.
18. Greenhoe, J. A., Plast. Techno!., 7(2) (1961) 35-8.
19. Kling, A., Kunststojfe, 41(8) (1951) 240-2.
20. Schimke, F., Kunststojfe, 46(11) (1956) 537-9.
21. (a) BS 3424: Part 22: 1983. Methods of Determination of Fusion of PVC
Coatings and the State of Cure of Vulcanised Rubber Coatings. Method
25 A. Determination of fusion of PVC coatings. (b) ASTM D 4005-81
(1986). Plastic-Coated Fabrics-Degree of fusion of PVC dispersion
coatings.
22. Lewis, T. B. & Nielson, L. E., Trans. Soc. Rheo/., U(3) (1968) 421-4.
23. Farris, R. J., Trans. Soc. Rheol., U(2) (1968) 281-93.
24. Park, R. A., Plast. World, 33(1) (1975) 48.
25. Bigg, D. C. H. & Hill, R. J., J. Appl. Polym. Sci., 20(2) (1976) 265-8.
26. Monte, S. J. & Sugerman, G., 3fXh ANTEC SPE Proceedings, 1978, pp.
781-4.
27. Werner, A. c., Mod. Plast., 36 (July 1959) 126-73.
28. Goodier, K., Proceedings of the International Congress on the Technology
of Plastics Processing, Amsterdam 17th-19th October. N.C. V't Raed-
thuys, Amsterdam, 1960.
29. Ciba-Geigy Technical Service Bulletin PL 3.3, 1975.
30. Kratschmann, F., Kunststojfe, 50(9) (1960) 534-5.
31. Ciba-Geigy Technical Service Bulletin PL 1.1.1, 1976.
32. Blumberg, H., Krummheuer, W. & Nebe, J., Kunststojfe, 66(2) (1976),
97-103.
CHAPTER 19
Solutions
19.1 GENERAL
The applications of solutions of vinyl chloride polymers and copoly-

mers, though well established, are much less extensive than those of
solid compounds or pastes. The main usage areas are: surface coatings
(including certain paints, anti-corrosion coatings, and over-lacquers for
pPVC products); some printing inks; adhesives (solvent cements) for
PVC; and solutions for the production of PVC fibres and solvent-cast
films. Vinyl chloride copolymers and terpolymers are used in many of
these applications, to meet best such special requirements as wider
solubility tolerance for diluents in the solution system, compatibility
with other polymeric solutes, acceptably low solution viscosities at
substantial polymer concentrations and pigment loadings, and good
adhesion of solution-deposited films to substrates (especially metals).
Most of the PVC copolymers used in solution compositions are
actually also made by solution polymerisation, which gives uniform
molecular weight controllable at the desired level, and high purity of
the polymer-all features particularly desirable for solution use.
19.2 COMPOSITION 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 are often multi-
component compositions. The components of PVC solutions are
briefly discussed below.
683
19.2.1 The PVC Polymers
The polymer type (homopolymer, copolymer or terpolymer) and the

molecular weight are the two main considerations in the choice of
polymer for a PVC solution. The choice is made in relation to the
solution properties desirable for processing, and the service require-
ments to be met by the final product. The significance and role of the
polymer type are indicated below. The molecular weight influences the
product properties (high molecular weight for good strength and other
mechanical characteristics), ease of solution and maximum polymer
content at manageable solution viscosities (both of these features
improving with lower molecular weight). The two sets of effects have
to be reconciled, so that in practice the choice of polymer molecular
weight is always a compromise in this respect.
(a) Homopolymers
In broad terms, these offer better service properties (especially greater
strength and higher softening temperatures), but their solubility and
tolerance for solvent diluents is lower than that of copolymers and
terpolymers, as is the flexibility imparted to the final products, which
also exhibit poor 'air-dried' adhesion to non-PVC substrates (espe-
cially metals). For these reasons the use of homopolymers is largely
confined to solutions for the production of cast films, solution-spinning
of some PVC fibres, and solvent cements for uPVC.
(b) Copolymers and Terpolymers

These are used in solution compositions for various surface coatings
and adhesives, for which they are more suitable than homopolymers,
principally by virtue of easier solubility in a greater range of solvents,
as well as the other characteristics mentioned in Section 19.1.
The copolymers are, typically, those of vinyl chloride with vinyl
acetate. The terpolymers contain additionally either hydroxyl groups
(introduced in the usual way, by in-situ hydrolysis of some of the
acetyl groups in a VC/VAC copolymer), or carboxyl groups (supplied
by inclusion of maleic anhydride as the third monomer in copolymeri-
sation). Typical compositions of PVC solution copolymers and ter-
polymers are illustrated in Table 19.1, by reference to the Ucar (Union
Carbide) commercial range. Another example of a commercial resin
range for solution applications is provided by some Vinnol II grades
TABLE 19.1
Ucar" Solution Resins
Desig- Composition (%) Molecular Solution Solubility Some typical uses Remarks
nation weight viscosityb characteristics
Vinyl Vinyl Other (cP)
chloride acetate
VYHH 85-86 14-15 Medium 57 Soluble in some General coating Acceptable in several
ketones, esters, uses food-contact
chlorinated (especially applications
hydrocarbons, where high
alone or in toughness and
combination with durability
aromatic required)
hydrocarbons
VYHD 84-87 13-16 Medium 36 As VYHH (higher General coating Acceptable in some
(lower solids content uses (where food-contact
than solutions possible) highest applications
VYHH) toughness and
durability not
essential)
VYLF 87-88 12-13 Medium- 16 Soluble in some Blending with
low ketones and esters VYHHto
increase solids
content, gloss
and 'build' in
paints
(continued)
TABLE 19.1-contd.
Desig- Composition (%) Molecular Solution Solubility Some typical uses Remarks
nation weight viscosityb characteristics
Vinyl Vinyl Other (cP)
chloride acetate
VYNS Approx. Approx. Medium- 82 Best solvents include Overlacquers for Poor air-dry adhesion
90 10 high some ketones, PVC coatings; of coatings to
especially MEK strippable unprimed metal
and MIBK; coatings; surfaces (improved
relatively low protective by baking)
tolerance for coatings
aromatic
hydrocarbons
VMCH 85-88 11·8- 0·8-1·2 Medium 60 Similar to VYHH General coating Good air-dry adhesion
14·2 maleic uses (alone or of coatings to metal,
acid in paper and other
combination substrates; tough,
with other durable coatings
resins)
VMCC 81·5- 14·4- 0·8-1-1 Medium 37 Similar to VMCH, Similar to Acceptable in several
84·5 17·7 maleic (lower but higher VMCH(but food-contact
acid than tolerance for where applications
VMCH) aromatic toughness and
hydrocarbons and durability
higher solids requirements
content solutions lower)
possible
YMCA 79-82 15·5- 2·1-2·5 Similar to 20 Good solubility in Coating and Recommended for use
18·9 maleic VMCC ketone/aromatic adhesive in conjunction with
acid solvent mixtures applications cross-linking systems
(esp. VERR d )
VAGH 89·5- 2·0-5·3 5·2-6·5 Medium 87 Soluble in some Coatings (alone Acceptable in several
91·5 vinyl ketones, esters and orin food-contact
alcohol c chlorinated combination applications; cross-
hydrocarbons; with other linkable by virtue of
tolerance for resins) hydroxyl content
alcohols in the
solvent systems
VAGD 89·5- 2·0-5·3 5·2-6·5 Medium 43 Similar to VAGH, Similar to Acceptable in several
91·5 vinyl (lower but higher VAGH food-contact
alcoholc than solubility and applications; cross-
VAGH) maximum solids linkable by virtue of
contents in hydroxyl content
solutions
VROH 79-83 Approx. Approx. Low 17 Similar to VAGD, Similar to As VAGH, but lower
5 vinyl but still easier and VAGH costs in coatings as
12- alcohol greater solubility higher applied solids
16 and cheaper solvent
systems can be used
a 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 25°C.
C Formed by hydrolysing part of the vinyl acetate component.
d See Note in Section 19.3.

(VC/VAC copolymers; Wacker-Chemie) and Vinnol Y57 M and THF

(homopolymer resins for PVC solvent cements).
Note: Other types of solution copolymers are those of vinyl chloride
with triftuorochloroethylene, with vinyl isobutyl ethers, and
with vinylidene chloride. The first two are used in some
surface coatings, and the last as solution-applied barrier
layers on certain packaging films.
In the terpolymers, the hydroxyl groups provide reactive sites
through which cross-linking can be effected by reaction with amino
resins (urea- or melamine-formaldehyde) or isocyanates. They also
improve compatibility with some other polymers (e.g. nitrocellulose
and alkyd resins) in surface-coating formulations. The carboxyl groups
in acid-modified VC/VAC 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 (cf. Table 19.1).
19.2.2 Solvents and DUuents
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 10, Section 10.3.5), the
homopolymer will give solutions of reasonable concentrations and
workable viscosities in only relatively few solvents. Of those, tetrahy-
drofuran and cyclohexanone are the most important in the technologi-
cal 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-monomers present and activity of functional groups
brought thereby into the polymer chain. Several ketones, some
aliphatic esters (especially acetates), chlorinated hydrocarbons and
nitro compounds become solvents at room temperature. Some cello-
solves (ethylene glycol monoalkyl ethers) also act as solvents or
co-solvents, and benzene, toluene and xylene have a marked swelling
action (in some cases a mild solvent effect-solubility of about 1%).
The solubility of some VC/V AC copolymers in ketone solvents
19 Solutions 689
[acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclo-

hexanone, methylcyclohexanone, mesityl oxide, isophorone] ranges
between 20 and 30 g per 100 g of solution; some solutions in acetone
and MEK can tolerate about 50% dilution with the aromatic hydro-
carbons (although tolerance for these diluents varies from one PVC
copolymer to another). Some of these points are illustrated by the
formulation examples given in Tables 19.2 and 19.3. The examples
also demonstrate that the choice of solvent or solvent/diluent system
in a 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. 19.1), and-for
many systems, but not invariably-with increasing 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.
19.2.3 Other Constituents of PVC Solutions
In any particular case, the nature and amounts of additional com-

ponents of a PVC solution depend primarily on the intended applica-
tion: the formulation examples given in Tables 19.2 and 19.3 illustrate
this point. The following general features of solution formulations are
also relevant in this connection.
Heat stabilisers, essential in heat-processed PVC compositions, may
be omitted from many solution formulations except where the solution
or the final product (normally a film of some sort) will experience
significant heating in processing (e. g. forced drying of coatings, heat
treatment of stoving finishes) or in service. The generally lower heat
stability of copolymer and terpolymer PVC resins in comparison with
homopolymer should also be borne in mind in this connection. For
10000.---------------------------------~
I
i
, I
I I.
.: .
:' /.
a.. 1000
u !
, :: /
: /,/
: /
/ "/
.
:>,
.~
,i
'o"
u
:'j :
,'/
'"
>
/ ••/ ,c'-'
.
c ,;- ~
/
Q
....::J
//
o 100
•
~
(/)
"
10+---~----,_--_r,----._--_r--_,r_--~,
o 5 10 15 20 25 30 35
"10 Polymer
Fig. 19.1 Solution viscosity (Brookfield) versus concentration for some
commercial copolymers. - - , Ucar VYNS/MIBK; - ' - , Ucar
VYNS/MEK; ...... , Ucar VAGH/MIBK; + + + + Ucar VAGD/MIBK;
- - - - , VC/VAC copolymer (15% VAC) in MEK/xylene, 1: 1.
formulations requiring stabilisation, the choice of stabiliser(s) should

be made in the light of advice from suppliers (of both stabilisers and
solution resins) and its suitability verified by tests.
In general, barium/calcium stabiliser systems, preferably augmented
by an epoxy co-stabiliser, are suitable in many cases, but not normally
in solutions of hydroxyl-containing terpolymers. A tin mercaptide, in
conjunction with an epoxy resin, has been used as a typical stabiliser
system for a baked surface coating. 1 Selected lead stabilisers may be
used, where non-toxicity and clarity are not required in the final
product. Clarity is also impaired by many metal-soap stabilisers, which
may additionally cause blooming in some cases. Other potential
stabiliser-associated problems to be considered are the possible
development of alkalinity with some lead stabilisers (this may be
troublesome with terpolymer resins containing acid groups), and
possible discolouration on heating of compositions based on VC/VAC
19 Solutions 691
polymers (including hydroxyl-containing grades) especially if unplas-

ticised or of low plasticiser content.
Stabilisation against photochemical degradation may be effected by
suitable pigmentation: with carbon black (up to about 6 phr), where
black colour is acceptable; titanium dioxide (in still higher
proportions-d. e.g. Table 19.3); and, where appropriate, with such
other pigments as have light-screening functionality (and are otherwise
appropriate to the application). In the absence of protective pigments
the resistance to light of solution resins---especially the copolymers
and terpolymers-is relatively poor. A significant improvement may
be obtained by incorporating in a clear composition an effective
UV-stabiliser system, e.g. 0·3% (by weight on the total non-solvent
content of the formulation) of the combination, in equal parts, of
Tinuvin* 326 and Chimassorb* 944 LD. Use of a suitable epoxy
co-stabiliser (e.g. Bakelite Resin ERL 4221; Union Carbide) in
conjunction with an organic UV-stabiliser can also be beneficial. It is
relevant to note that the stability to light of PVC films and coatings
produced from solution systems can be adversely affected by the
presence of residual solvents and/or of trace impurities which may be
introduced by the solvents.
Plasticisers may be incorporated in PVC solutions, for increased
flexibility of the ultimate products. The compatibility of the usual PVC
plasticisers both with the solutions and the PVC polymers or copoly-
mers 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 incorpor-
ated 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 copoly-
mers. The amounts used in solution-deposited coatings based on
hydroxyl-modified 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 70°C.
Apart from the UV-protective action of pigments already men-
tioned, they are included in PVC solution formulations for the usual
* Ciba-Geigy.
reasons: to impart colour to the final product, and to increase covering

power where the final product is a coating. Selected solvent-soluble
colourants can also be used, in rather lower concentrations, in
solutions for the production of clear, coloured coatings and films.
Occasionally use is made of a special-purpose pigment/filler-e.g.
cuprous oxide in marine antifouling paints (cf. Table 19.3). The
loadings of some pigments, especially in high-cover surface-coating
solutions, can be so substantial that they act also as fillers in the final
product. Matting fillers, used at low phr levels, are at the other end of
the scale. Fillers with a purely extender (cheapening) function are used
much less in PVC solutions than they are in other kinds of PVC
compositions. The pigment supplier's advice should always be sought
when formulating pigmented PVC solution compositions, inter alia to
avoid problems that can occasionally arise, e.g. promotion of polymer
degradation by some zinc and iron pigments in solutions which are
heat-processed (e.g. baked finishes), or problems caused by pigment-
originated alkalinity in compositions based on terpolymers containing
acid groups.
19.3 PREPARATION OF PVC SOLUTIONS
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 the
industrial scale. The mixer should preferably be jacketed for heating,
and covered (with a reflux facility) to reduce solvent loss. Mild heating
(at up to about 35°C) can be helpful to facilitate dissolution of the
polymer and keep solution viscosity down for ease of stirring. The
preferred materials for all working surfaces of the mixer are stainless
steel, glass, or enamel.
A useful technique for dissolving a PVC resin in a solvent or solvent
mixture 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
19 Solutions 693
preventing lump and gel formation. Where the proportions of

solvent(s) and diluent(s) in the formulation are sufficiently high, the
resin may first be dispersed in the diluent(s) , and the solvent(s) then
added gradually, with vigorous stirring, to the 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,
fibrer-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 (formerly
Bakelite) vinyl resin solution VYNC (a clear, 40% solution of
a hydroxyl-modified vinyl chloride/acetate copolymer in
isopropyl acetate) and Ucar vinyl resin solution VERR-402 (a
40% solution of an epoxy-modified vinyl chloride/acetate
copolymer of low molecular weight in MEK/toluene). Ex-
amples of another kind of commercial PVC solutions are
proprietary solvent cements for bonding pipes and fittings
(see Chapter 21, Section 2l.3.1).
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 compositions (for use as paints
and the like), which may also contain other constituents, e.g.
plasticisers (d. Section 19.4), may be carried out in more than one
way, depending on the equipment available. Advice is readily ob-
tainable 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), with-
preferably-some grinding aid, in a 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 the latter in).
Where 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 (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, and urethane prepolymers
(which can react with the hydroxyl groups of such terpolymers as Ucar
VAGH or VAGD, to give tough coatings with good adhesion to
substrates) .
19.4 APPLICATIONS
The general application areas of copolymer and terpolymer solution

resins are indicated in Table 19.1. Some further examples of specific
applications are: spray-applied cocooning compositions for equipment
protection; moisture-resistant coatings for concrete, wood, and metal
in the building industry; and heat-activated adhesives (e.g. some
successful commercial versions based on Vinnol II40/55 and H15/45 M
VC/VAC copolymers). Two basic formulations are illustrated by way
of example in Table 19.2.
Modified copolymers (whose carboxyl or hydroxyl groups variously
improve adhesion to substrates and reactivity with other resins) alone
or in combination with one another and/or with the unmodified
copolymers, are used in a variety of solution-coating applications on
19 Solutions 695
TABLE 19.2
VC/VAC Copolymer Solutions: Examples of Basic Formulations for Some
Coating Applications
(Based on data from technical literature of Union Carbide Corp.)
Solution component Formulation (Pbw)
Strippable coating Cocooning solution
Ucar VYNS resin 10

Ucar VYHH resin 5
Plasticiser 4 8
Aluminium powder 6
Methyl ethyl ketone (MEK) 27 70
Methyl isobutyl ketone (MIBK) 27
Toluene 27
a For bridging large gaps (say about 40 cm) 2 parts of the resin should be
replaced with polyvinyJidene chloride resin of high molecular weight.
paper, fibreboard, and wood substrates, where good adhesion, coating

toughness and gloss, and resistance to water, oils, fats, and aqueous
acids and alkalis are desirable features.
Industrial-maintenance and marine paints for steel and other sub-
strates constitute a long-established area of application of solution
systems based on VC/VAC copolymers and terpolymers. High-build
paint versions of such systems offer some advantages over each of the
rival types of coating (alkyl, epoxy, or chlorinated rubber) in handling,
performance (especially corrosion and weathering resistance), or costs.
Some examples of basic formulations are given in Table 19.3.
Baked finishes (solution-applied by roller or spray) for tinplate or
sheet iron, based on hydroxyl-containing VC/VAC copolymers in
conjunction with co-reactive resins (urea-formaldehyde, melamine-
formaldehyde, epoxy, urethane prepolymer) combine protective pro-
perties with adhesion which can be strong enough to withstand
forming operations (drawing, stamping) whereby the coated metal
sheet is converted into containers, closures, and the like.
Note: The Steel Structures Painting Manual (Steel Structures Paint-

ing Council, Pittsburg, PA, USA) contains specifications and
requirements for various PVC-solution paint formulations
(inter alia).
Solutions of vinyl chloride homopolymer resins (of relatively high
TABLE 19.3
High-Build Vinyl Marine and Maintenance Paints: Examples of Basic
Formulations!
Component Formulation (Pbw)

Red lead Shipbottom White anti- White
primer antifouling corrosive topcoat
primer
Cellosolve acetate 44·45 13·15 36·76 38·20
Methyl butyl ketone 6·35 1·88 5·25 5·46
Toluene 6·98 2·07 5·78 6·00
Xylene 4·44 1·32 3·67 3·82
YM & P naphtha 1·27 0·38 1·05 1·09
Ucar resin VAGH 13·18
Ucar resin VYHH 2·49
Ucar resin YMCA 21·90
Ucar resin VYHD 15·66
Tricresyl phosphate 1·36 2·27
Didecyl phthalate 3·92 3·90
Thixotropic agent 1·96 1·39 0·92 1·05
Red lead 20·01
Rosin 9·75
Cuprous oxide 65·30
Dispersant 0·27
Titanium dioxide 11·53 10·95
Clay extender 13·60
Zinc phosphate 9·22
molecular weight for good mechanical properties) are used, at

polymer-solids contents of up to 30%, for the production of PVC
films. The films, which can be of very high clarity, are used for special
packaging applications (including some film laminates suitable for
thermoforming) and for lamination as protective layers on documents
and artwork. Two commercial examples are Prime wrap (Goodyear
Films Division, USA) and HI-S Cast (Nippon Carbide Industries Co.,
Japan). In production, the de-aerated, filtered solution is cast from a
spreader ('hopper') onto a stainless steel band (a large-diameter
casting wheel-also called a drum-is an alternative to the band) in
the way originally developed for casting cellulose acetate films,3,4 and
the solvent is removed from the cast solution layer as the band passes
through a heating enclosure. The casting process, when properly run,
affords very good control over film thickness and thickness uniformity
19 Solutions 697
even with very thin films (of the order of 1Ilm). Lack of molecular
orientation, and hence freedom from mechanical and optical ani-
sotropy (which, inter alia, virtually eliminates retraction on heating
and affects optical properties) is a special feature of cast polymer films.
A brief outline of the mechanical format of the film-casting process has
been published by Ricklin. 5
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,6 or the actual compositions of the mouldings, etc., to be
bonded. Solvent cements for PVC are mentioned in Section 21.3.1 of
Chapter 21, where some relevant standard specifications are listed in
Table 21.1. A similar solvent cement (a solution of at least 10% of a
PVC compound in a mixture of tetrahydrofuran with cyclohexanone or
methyl ethyl ketone), used for transition joints between PVC and ABS
piping components, is the subject of ASTM D 3138-83.
PVC fibres are spun from solutions of suitable copolymers.
REFERENCES

2. Anon., Bakelite Vinyl Chloride-Acetate Resin Solution VERR-40, Union
Carbide Corp. Technicalleaftet, 1978.
3. Yarsley, V. E. & Flavell, W., Cellulosic Plastics, Part 1. Cellulose Acetate,
Cellulose Ethers, and Regenerated Cellulose. Plastics Monograph No. C6,
Plastics Institute, London, 1956.
4. Couzens, E. G. & Yarsley, V. E., Plastics in the Modern World. Penguin
Books Ltd, Harmondsworth, Middlesex, UK, 1968.
5. Ricklin, S., Plastics Engng, 39(5) (1983) 29-33.
6. ASTM D 2564-84 Specification for solvent cements for poly(vinyl chloride)
(PVC) plastic pipe and fittings.
CHAPTER 20
PVC Latices
20.1 mE NATURE AND PVC VERSIONS OF A LATEX
20.1.1 Definition and General Characteristics
A latex may be defined as a stable dispersion of fine polymer particles

in water, containing also some non-polymeric constituents* (emulsi-
fiers and others-see later sections in 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 significant single difference
being the nature of the liquid dispersion medium-water in a 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.
All three types of liquid PVC composition are processed to yield a
solid PVC material as the ultimate product. With solutions and latices
this is obtained by evaporation of the liquid component of the
compositions [solvent(s) and water respectively in the two systems]. A
paste undergoes a phase inversion in processing, without substantial
loss of plasticiser, which remains as an important constituent of the
final solid product (see Chapter 18).
The main advantageous features of a PVC latex in comparison with
* The ISO definition is 'a colloidal, aqueous dispersion of a polymeric

material' (ISO 472-1979).
698
20 PVC Latices 699
a solution may be listed as follows (not necessarily in order of

technical importance).
(1) The liquid component of the latex system is innocuous and

cheap.
(2) Higher polymer contents are obtained at comparable or even
lower viscosities.
(3) The viscosity of the system is independent of the molecular
weight of the polymer (hence polymers of relatively high
molecular weight may be used if required for better mechanical
properties of the ultimate solid product).
Similarly, the main favourable features of PVC latices vlS-a-vis

pastes are the following. (1) The liquid component of the latex system
is (a) cheap and of relatively low viscosity, and (b) not capable of
interacting to any significant extent with the polymer (cf. ageing
of pastes; Chapter 18). (2) Virtually any combination of
polymer/plasticiser(s) can be used. (3) There is a relatively wider
tolerance for the kind and amount of fillers incorporated. (4) There is
scope for varying viscosity of the system within wide limits by simple
dilution. (5) The viscosity is not greatly sensitive to the kind and
amount of plasticiser present. (6) PVC latices can be processed into
unplasticised solid PVC products.
The following significant disadvantages of the latex system may be
noted. (1) The stability is limited in certain conditions (it is sensitive to
cold and pH, inter alia). (2) Its processing behaviour and ability to
wet substrates is less good and more variable than that of suitable PVC
solutions in comparable circumstances. Ultimate solid products have
relatively low softening points and only moderate mechanical pro-
perties. (3) Ultimate solid products may contain residual emulsifiers
(to the detriment of some properties). (4) The system is not readily
processable into solid unplasticised homopolymer products (as is
possible with PVC solutions).
PVC latices are produced by emulsion polymerisation. The particle
size of the solid (polymer) disperse phase is typically 0·1-0·25 flm in
most cases, and generally within the range 0·1-2·5 flm.
The latices constitute a relatively small proportion of all composi-
tions processed in industry, and in this sense they are of minor
importance in comparison with pastes, or the solid compositions for
extrusion, calendering and mOUlding.
20.1.2 Basic Processing Features
All industrially significant uses of PVC latices involve their application

to some kind of substrate to form a deposit, first of the latex, and then
the solid polymer (with any permanent additives) after the water phase
has been removed (by evaporation, with or without some intermediate
absorption into the substrate). In most latex applications the deposit is
finally consolidated into a continuous film through the coalescence of
the polymer particles.
The general mechanism of deposit/film formation is virtually the
same for many polymer latices,I,2 including PVC. 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 water component. 2 The layer of latex
originally deposited on the substrate [cf. Fig. 20.1(A)] loses water
fairly rapidly by evaporation at a rate comparable with that of pure
water (some water may also be absorbed by the substrate). As the
A B
c D
Fig. 20.1 Formation of a polymer film from a latex layer: schematic

representation (after Vanderhoff et al. 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.
20 PVC Latices 701
water is lost to the extent roughly represented in Fig. 20.1(B), the

particle content of the deposit is effectively increased to about 70%
(for the common latex particle size range of 0·1-0·25/lm), the
interparticle spaces being still filled by water. At this stage the
interfacial area between the water and the ambient air is substantially
reduced, which causes a corresponding drop in the rate of further
evaporation. As this proceeds, the particles are packing ever more
closely together, although intimate overall surface contact is ham-
pered, 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 together. The capillary forces eventually
exceed the electrostatic repulsion and the particles 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, exten-
sive surface contact.
Note: Differences in particle softness between some PVC homo-

polymer and copolymer latices have been demonstrated in
electron micrographs, showing the copolymer particles de-
formed from the original spherical shape by the impact of the
electron beam, while the harder homopolymer particles
remain unaffected. 4
In this state the deposit is a granular polymeric layer, with little free
liquid water remaining [Fig. 20.1(C)]. The rate of loss of this residual
water now becomes relatively very slow, being governed by that of its
movement to the surface through the capillary channels between
deformed polymer particles, or diffusion through the polymer sub-
stance. The quality of softness which makes particle deformation and
resultant intimate packing possible is usually associated with relative
freedom of movement of the polymer chains. The combination of
intimate interparticle contact and chain mobility plays a cardinal role
in the ease of ultimate coalescence of the particles into a cohesive,
homogeneous polymer film [Fig. 20.1(D)]. The term 'autohesion' has

been coined for this kind of effect. 9
With harder particles, coalescence sufficient for the ultimate
formation of a continuous film may occur only at suitably elevated
temperatures at which the free-volume content and thermal agitation
of the polymer are suitably increased. Particles of a homopolymer
latex usually require the presence of plasticisers for satisfactory fusion
even at high temperatures.
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 (which is lowered by plasticisation), whilst above Tg the
process is accelerated by heating and enhanced by pressure?
20.2 TYPES OF PVC LATICES
20.2.1 General
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 form of vinyl chloride copolymer material or
product, the particles of a copolymer latex may be regarded as
'internally' plasticised by the presence of co-monomer units in their
molecular chains. In the practical context of latex technology, the
main effects of this chemical modification are similarly to those of
inclusion of external plasticiser(s) in a homopolymer latex, in that the
temperature needed to fuse the particles of a latex deposit on a
substrate is lowered, and the resulting fused film is softer and more
flexible than a uPVC homopolymer film.
Some latex copolymers are carboxylated to promote good adhesion
to, and bonding ability for, many substrates. Some are chemically
20 PVC Latices 703
modified to permit cross-linking in processing (cf. e.g. Geon Latex

590X4 or Vinamul R 35025): latices containing polymers so modified
are often referred to as heat-reactive. Films produced from such latices
have improved mechanical properties and resistance to some solvents
and water. Some heat-reactive latices require only relatively low
temperatures for cross-linking. This is advantageous in their applica-
tion to heat-sensitive substrates. The polymers of some latices are both
carboxylated and heat-reactive (e.g. Geon Latex 46OX6; Polysar Latex
7560).
External plasticisation, usually necessary for satisfactory film
formation by vinyl chloride homopolymer latices, is often practised
also with copolymer latices, to increase still further the effects of
internal plasticisation. Plasticised PVC latices, whether homopolymer
or copolymer, are either supplied with the plasticiser already incorpor-
ated, or prepared by the user from the appropriate unplasticised
versions [cf. Section 20.4.3(b)].
20.2.2 Homopolymer Latices
Most of these are not normally film-forming in the absence of

plasticisers, tending to give rather powdery deposits on drying at even
quite high temperatures. External plasticisation promotes particle
coalescence after water removal in processing, but temperatures of
about 160°C or over are needed for satisfactory fusion, assisted by
pressure in some cases.
20.2.3 Copolymer Latices
As indicated by the data of Table 20.1, the film-forming temperatures

of copolymer latices depend on the composition of the copolymer and
the presence or absence of plasticisers. Even the relatively low-fusing
copolymer latices may be externally plasticised, however, to modify
the ultimate film properties (to increase softness and flexibility; in
some cases to improve resistance to yellowing on heating or exposure
to light).
In general, processing temperatures substantially in excess of the
minimum film-forming temperature (MFFf) reduce the time for full
TABLE 20.1
Some Properties of Commercial PVC Latices
(Based on suppliers' published data current circa 1985-1986.)
Latex type Homopolymer; unplasticised Copolymer; unplosticised Copolymer; plasticised

Properties ~
Non-jilm Film·forming b Textile Special Cross· Textile Adhesive Genera/·
h
forming" binderC paints bosed linking' binde! bose" purpose
Polymer
Chemical nature Polyvinyl chloride Polyvinyl VC/VAC VC/VDC/Ai VC/VAC/E VC/VAC VC/VAC/VI!
(Fikentscher K chloride
value 70)
Predominant particle
size, I'm 0·1 0·15 0·2 0·1-0·5 0·15 0·5-2
'Cor
(Tg),""'."
"'" 76- 14
-'} Not film-fonning
Minimum film-fonning
temp., 'C 60 15-17 48-54 13 0
Latex
Non·volatile content,
wt% 6O± I 57- 50± I 56-58 49-51 50± I 56± I 56-
Density, kg I-I 1-16 1-19 1-12
Viscosity
Value SOOmPa s 0·03 Pas 80 ±6OmPas 68mPas 0·5-2·0P lOO±30mPas 12±4Pas 43cP
Viscometer E.STV(C/III)' B.LVF(2/30)Bm B.RVT(I/20) B.RVT(2/6O) B.RVT(2/50) B.RVT(I/20) B.RVT(5/20) B
Plasticiser
Type DBP DOP Alkyl
phthalate
Content 25 15 About 30
Emulsifier system Anionic Anionic Surfactant Anionic Anionic Surfactant PVAL Anionic
surfactant surfactant surfactant surfactant surfactant
pH 9·0-9·5 10·0 5·0 1·0-2·0 6·5-7·5 5·0 4·5 9·8
Fina/film Not film-forming Tough film
Tensile strength, MPa 6·7 (ultimate) 4 2
Low (brittle film) 3·2 (yield stress)
Elongation at break, % 300 700

}
: Vestolit-Dispersion M (Hills).
Polysar Latex 7177(Polysar).
c Winnol-Dispersion 50(Wacker-Chemie).
d Haloflex 208 (ICl).
e Vinamul R 35025(Vinyl Products).
f Vinnol-Dispersion 50/25 C (Wacker-Chemie).
g Vinnapas-Dispersion T 56/34 VL (Wacker-Chemie).
h Geon Latex 576 (B. F. Goodrich).
" A, Acrylate.
I VL, Vinyllaurate.
k Determined by DSC.
I Epprecht rheometer STY, conditions C/IIl.
m Brookfield viscometer. Model (e.g. LVF, RVT, etc.), spindle no. and r min -\ shown in parentheses.
particle fusion and attainment of ultimate mechanical properties of the

resulting film. Providing that the heating time is long enough for
complete fusion, the ultimate film properties of an unplasticised latex
do not greatly benefit from processing at high temperatures. Those of
a film from an externally plasticised latex of basically similar MFFf
may appear to benefit at short processing times, as complete and
uniform penetration of the polymer by the plasticiser is necessary, in
addition to complete particle fusion, and the rate and effectivity of
penetration increases with temperature.
20.3 COMMERCIAL PVC LATICES
PVC latices are obtainable from a number of manufacturers of PVC

polymers. Several Western sources are indicated, by reference to some
of the latices they supply, in the notes to Table 20.1.
Examples of the properties of some commercial PVC latices
representing the various latex types and certain particular versions, are
given in Table 20.1.
20.4 FORMULATION AND COMPOUNDING

of PVC LATICES
20.4.1 General Considerations
PVC latices are formulated with a view to meeting three general

technical requirements, viz.
(a) stability of the latex in storage and transport;

(b) suitability for, and stability in, processing;
(c) suitability of the ultimate product for the intended end-use.
As ever with all PVC formulations, cost is also an important

consideration, as is the mutual compatibility of all constituents. The
formulation components necessary to meet requirements (a) and (b)
jointly form the group of constituents controlling latex stability and
properties: the group includes emulsifier systems acting as emulsion
stabilisers, wetting agents, thickeners, anti-foaming agents, and pH
modifiers.
20 PVC Latices 707
Selection of the formulation components to satisfy requirement (c)

is governed by much the same considerations as apply with any kind of
PVC composition (cf. Chapter 2, and Section 20.4.3 below): in the
present chapter these components will be grouped under the heading
of additives incorporated for end-product properties. The members of
this group most common in PVC latices are heat-stabilisers, plas-
ticisers, fillers, opacifying pigments, and anti-blocking agents.
For some applications a commercial PVC latex may be used as
formulated and supplied by the manufacturer, without further mod-
ification (apart, possibly, from dilution). Others (e.g. the preparation
and use of latex-based paints) may call for extensive compounding.
Latex stability must be preserved in all compounding operations. To
this end, manufacturers' recommendations on the preparation and
incorporation of compounding additives should be sought and
followed. The physical form and pH of any additive should be such as
to promote compatibility with the basic latex. As a general rule,
additives should normally be pre-dissolved or dispersed in water for
compounding into the latex. Mixing must not involve unacceptably
high shear (i.e. it must be carried out below the critical shear level),
whilst ensuring thorough blending of all components. Slow, even-
speed paddle or turbine mixers are recommended and, with any
apparatus, excessive incorporation of air (e.g. through 'vortexing' or
cavitation) must be avoided. Excessive mechanical agitation can cause
flocculation.
20.4.2 Constituents ControlHng Latex Stability and Properties
(a) Latex Stabilisers (Emulsifiers)

These are constituents of the latex system incorporated to impart and
preserve chemical and mechanical stability in storage, handling,
compounding and processing. Depending on the type and nature of
the latex, the stabiliser may be a surface-active agent, or a protective
colloid, or a system combining both. Protective colloids (e.g. polyvinyl
alcohol; some water-soluble cellulose derivatives) can be particularly
effective in counteracting destabilisation by mechanical shear. Selected
surfactants offer the greatest degree of protection against chemical
destabilisation.
When choosing a stabiliser it is necessary to consider, inter alia, its
effect on the wetting properties of the latex for the substrates it will
encounter, and on the water sensitivity of the ultimate product (in
which some stabiliser will be retained). Enhanced wetting power,

associated with reduction of surface tension by surfactant stabilisers,
can be advantageous in promoting intimate contact between latex and
substrate. However, reduced surface tension can also promote unde-
sirable foaming in processing, whilst the more effective and/or
abundant the surfactant in the stabiliser the greater the sensitivity of
the ultimate film to water in service.
Certain factors and conditions which affect adversely the stability of
PVC latices should be avoided; they are
(i) exposure to freezing conditions or to excessively high
temperatures;
(ii) subjecting the latex to very high shear (for example as
experienced in pumping through close-clearance gear pumps);
(iii) addition of electrolytes of pH substantially different from that
of the latex:
(iv) addition of monovalent ionic salts in high concentrations;
(v) addition of water-soluble solvents, such as ketones or alcohols.
(b) Wetting Agents

Where it is necessary to modify the wetting characteristics that a latex
exhibits for a given substrate [and these will be particularly influenced
by the surfactant(s) of its emulsifier system], the modification can be
plade by addition of further surface-active agent(s). In the absence of
relevant experience, the latex user should obtain his supplier's advice
on the nature and amount of agent to be added, as these will vary
according to the particular circumstances and the latex used. In
general, for PVC latices, selected anionic and non-anionic surfactants
can be used to reduce surface tension and thus improve the wetting
characteristics. Wetting agents may also be used to aid the dispersion
in a latex of fillers and pigments that may need to be incorporated (see
also Section 20.4.3 below).
(c) Thickeners
These are agents added to latices to increase the viscosity of the
aqueous phase, and hence of the latex as a whole. Water-soluble
polymers of several kinds have provided thickeners for PVC latices,
viz. polyvinyl alcohol, cellulose derivatives (e.g. methyl cellulose,
sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose,
hydroxyethyl cellulose), polyacrylates, polyacrylamides, and others.
20 PVC Latices 7W
Such thickeners are normally added in relatively small proportions,

typically up to about 2% by weight of the dry PVC polymer content
of the latex. However, it should be remembered that different types of
thickener, and even individual thickeners within the same type, can
differ considerably in their effects on a given PVC latex. Some latices
can be destabilised by certain thickeners to the point of coagulation or
sedimentation in extreme cases.
Note: Sedimentation of PVC latices is analogous to 'creaming' of
rubber latices. In both cases the polymer particles cease to
form a stable dispersion in the aqueous phase, but the heavy
PVC particles (SG> 1) settle downwards, whereas the rela-
tively light rubber particles rise to the surface to form a
'cream'.
Certain specially processed grades of bentonite clays (e.g. Bentone
LT-NL Industries Inc., USA; Ben-A-Gel EW-F. W. Berk & Co.
Ltd, UK) can have effective thickening action, at addition levels of
around 1%.
Even with a basically suitable thickener, some viscosity change may
occur over a period of time before the value becomes steady: for
thickeners which exhibit such behaviour in PVC latices this 'maturing
time' may typically be about a week at room temperature. Specific
advice on thickening agents most suitable for use in a particular latex
(and its given application) is available from latex manufacturers: its
implementation should also be checked in practical trials.
It may be noted in passing that some additives incorporated in a
latex for end-product properties (e.g. fillers, pigments, certain plas-
ticisers) can have a thickening effect.
The basic rules for incorporating a soluble thickener in a PVC latex
are the same as for other latices. The best, most efficient dispersion is
achieved when the latex is added slowly, under constant, slow
agitation to a solution of the thickener. Alternatively, a master batch
technique may be used. The masterbatch is prepared by thoroughly
mixing the thickener solution for a large batch of ultimate compound
with a minor proportion of the latex, in an efficient mixer of
appropriate size. This mix, when added gradually to the remaining
major part of the latex, will blend well under efficient stirring. 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.
With bentonite, the initial wetting-out by water of this particulate

thickener in the course of preparing an aqueous dispersion for
blending with the latex, can be aided by pre-wetting with a small
amount of alcohol.
(d) Anti-foaming (Defoaming) Agents

Various defoaming agents, both silicone-based and non-silicone, can
be used to increase the surface tension of PVC latices and thus reduce
or suppress foaming in processing. It is important that the most
suitable and effective defoaming agent should be chosen for a given
latex, and here again the advice of the latex producer should be
obtained (and checked by a practical trial). Examples of some agents
used with PVC latices are:
Bevaloid 566, 642 or 6250 (Bevaloid Ltd, UK);
Byk 035 (Byk Chemie GmbH, FRG);
Hercules 1052 (Hercules Inc., USA);
Nopco DNH-l, NDW, NXZ, or 8034E (Diamond Shamrock
Chemicals Co., USA and UK);
Surfynoll04 H (Air Products and Chemicals Inc., USA);
Wacker Silicone Antifoam Agents S882 or SL, or Emulsion SLE
(Wacker-Chemie, FRG)
Typical addition levels are in the range 0·05-0·3% by weight of the
latex.
(e) pH-Modifiers and Buffers

As can be seen from Table 20.1, commercial PVC latices differ widely
in pH, depending on their nature and applications. Where pH
modification or stabilisation is necessary (e.g. in connection with the
addition of some of the formulation components required for particu-
lar end-product properties, or for other compounding or processing
purposes), the latex manufacturer's advice should be obtained on the
appropriate reagents and procedures, and practical tests carried out to
verify their efficacy.
As a general principle, and in the absence of special considerations,
it is normally desirable to adjust the pH of any suspension, emulsion
or solution of an additive to be compounded with a PVC latex (these
being the forms in which additives should preferably be introduced-
see Section 20.4.3) to a value as close as possible to that of the latex
itself. Alternatively, it may be possible to adjust and buffer the latex's
20 PVC Latices 711
own pH to prevent destabilisation by an additive. In normal cir-

cumstances, strongly acid substances should not be added to anionic
latices.
With neutral or slightly alkaline latices (pH 7-8), additives should
be adjusted to pH at least 7, or 7-8. A pH-modifier suitable for the
purpose is ammonium hydroxide, which may be added in fairly
concentrated solution without causing flocculation, and is not retained
in the ultimate film after processing. Alkali phosphates and sodium
bicarbonate also act as pH-modifiers. Common buffering agents are
phosphates such as trisodium phosphate or sodium hexametaphos-
phate (Calgon; Albright & Wilson, UK). Phosphate addition to a latex
system can partially counteract the effects of sharp pH changes, aid
dispersion of solid ingredients and, to a certain extent, sequester the
harmful cations of calcium, zinc, and magnesium. A more powerful
sequestering agent is ethylenediamine tetra-acetic acid. This material
does not have the economic or buffering advantages of phosphate, but
used carefully in small quantities it may help prevent the insolubilisa-
tion of stabiliser soaps by calcium, zinc, and magnesium.
20.4.3 Additives Incorporated for End·Product Properties
(a) Heat-Stabilisers
The vinyl chloride polymer or copolymer of a PVC latex is prone to
heat degradation when exposed to elevated temperatures in processing
and/or subsequent service. Even those latices which are film-forming
at room temperature are commonly heat-processed to remove the
water phase and to ensure and speed-up the attainment of full
end-product properties. To minimise detrimental heating, the water
of a latex layer on a substrate should first be dried-off at around 100°C,
the temperature then raised to the optimum for fusion, held for the
minimum necessary time, and the material finally cooled. In many
processes PVC latices are applied in thin layers, which dry readily and
need fusion times of only a few seconds: heat stabilisation may not be
necessary in such cases, if high temperatures will not be experienced
by the product in service. In general it will be required where high
temperatures or prolonged treatment times at about 150°C or above
occur in processing. The choice of stabiliser will be made-preferably
in the light of advice from the latex and/or stabiliser manufacturer-
with appropriate regard to effectivity of heat-stabilising action, the
processing and service conditions envisaged, 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 may be
comminuted (commonly by ball-milling) to a fine aqueous suspension,
and a liquid one emulsified in water, in both cases with the aid of
dispersing or emulsifying agents. The dispersions should be compatible
with the latex, with no detrimental effects on its stability.
These requirements impose considerable restrictions on the choice
of stabiliser. Moreover, the stabilising performance in a latex may be
different from that in a solid, 'dry' composition. Explanations ad-
vanced for this occasional disparity relate to the influence of water and
emulsifiers present in a latex. Selected organotin stabilisers with epoxy
co-stabilisers have provided systems successful in many latices.
The aqueous dispersion of the heat-stabiliser system (or of its
solution) is usually added to the latex early in the compounding cycle,
under constant, slow stirring.
(b) Plasticisers
As with any PVC composition, a plasticiser incorporated in a PVC
latex confers softness and flexibility on the final product. In a
homopolymer it can promote film formation in processing where
otherwise a hard, discontinuous deposit would result. In general, the
presence of plasticiser(s) in a PVC latex, and hence in the ultimate
deposit, facilitates fusion as its penetration into the polymer increases
the free volume and reduces the Tg , thus effectively increasing the
chain mobility (as well as particle softness; cf. also Section 20.1.2
above).
In practice the common phthalates are often used in latex
formulations, but any liquid plasticiser that can be made into an
aqueous dispersion sufficiently stable for addition to the latex, and
compatible with it, is potentially suitable for use where the properties
it can impart to the final product are of sufficient interest. Fairly
typically, about 25 phr DOP in a homopolymer latex may be expected
to give a hard and stiff (but generally cohesive) film after the drying
and heat fusion (at about 150-160°C) of a deposit; 50phr DOP should
impart appreciable flexibility and extensibility to the fused film; 75 phr
should give a soft, flexible film; and with 100 phr DOP the fused film
may be expected to be very soft, flexible, and slightly tacky.
Note: The plasticiser compounded with a latex is not normally

absorbed to any substantial extent by the polymer particles
20 PVC Latices 713
with which it is co-suspended in the aqueous phase. Plas-

ticisation is only effected when the water has been driven off
from a latex deposit, and the residue heated to an appropri-
ate temperature.
For some applications, appropriate nitrile rubber latices may be

blended with PVC latices to impart to the final product the properties
conferred by the nitrile rubber as a plasticising modifier in PVC (cf.
Chapter 8). The latex supplier's advice should be sought on suitable
blending combinations of this kind; ready-made blends are also
available (e.g. Geon Latex 552).
Where it is desired to have, as the final product, a very hard film
that would not normally be formed by an otherwise suitable,
unplasticised latex, a temporary 'fugitive' plasticiser may be used. An
example is propylene glycol, which evaporates from a latex-deposited
PVC layer at fusion temperatures around 160°C, but assists film
formation at about 100°C in the earlier stages of processing.
The main factors to be taken into account when selecting plasticisers
for latex formulations include all those relevant in the formulation of
solid PVC compositions (cf. Chapters 2 and 5) with-additionally-
suitability for producing an aqueous dispersion and its compatibility
with the latex concerned. The likely effects of a plasticiser in the
ultimate latex-derived product may be estimated from a knowledge of
the effects in solid PVC compositions. However, where other com-
position features are comparable, less plasticiser (in terms of phr)
may be needed in a latex formulation because of the inherent
structural flexibility of thin films (the most common form of the
end-product in PVC latex processing).
Several plasticised types and grades of PVC latices (i.e. latices
containing plasticisers compounded-in during manufacture) are avail-
able commercially. However, it may also be necessary for the latex
processor to incorporate plasticiser(s) in an unplasticised commercial
latex (or additional plasticisers in a factory-plasticised one) for a
particular application. Other factors being comparable, factory-
plasticised latices may yield somewhat more effectively plasticised
end-products: this is indicated by the data of Table 20.2, which also
illustrate some of the effects of different plasticisers at similar
incorporation levels in two different PVC latices.
Compounding a plasticiser into a PVC latex should be performed so
that a uniform, stable co-dispersion is achieved. Where some dilution
TABLE 20.2
Physical Properties of Films" from Breon PVC Laticesb after the addition of
Some Plasticisers
(Data from Ref. 4.)
Latex Plasticiser (35 phr) Tensile strength Elongation at
(lbf in- 2 ) break (%)
Breon 151 (unplas- DAP 1800 150
ticised TIP 3200 150
homopolymer Breon 1562c 2780 150
latex) Acetyl tributyl citrate (ATBC)
2000 210
Breon 352 (unplas- DAP 1850 300
ticised copolymer TIP 2400 210
latex) Breon 1562c 2700 100
ATBC 1750 250
Breon 599 (plas- Alkyl phthalate plasticiser,
ticised version of factory-incorporated 1700 350
Breon 352)
a Thick films cast on glass plates, dried at 23°C and fused at 16O"C.
b The Breon PVC latex range, originally supplied by BP Chemicals (UK) Ltd, was
Iliscontinued in the early 1980s.
c A nitrile rubber latex (medium-nitrile content).
of the latex is acceptable, the best approach (especially with

common phthalates) is to pre-emulsify the plasticiser in water (with
the aid of emulsifier(s) advised by the latex manufacturer) and then
add the emulsion to the latex gradually, under slow constant stirring.
Where dilution must be kept to a minimum, the plasticiser may be
emulsified directly into the latex. If the latex's own emulsifier system
can provide sufficient emulsifying action to disperse the plasticiser
effectively (as is the case with some latices which-like e.g.
Vestolit-Dispersion M-are deliberately formulated with extra emulsi-
fier) the plasticiser can be added to the latex gradually, with stirring
slow enough not to impose excessive shear on the relatively viscous
system. Where additional emulsifier is required, this should preferably
first be dissolved or dispersed in the appropriate amount of water (in
many cases 3-5 parts by weight of emulsifier per 100 parts of latex may
be suitable, dispersed in its own weight of water). The solution or
dispersion should then be slowly blended with the latex, and the
plasticiser finally added as above. Alternatively, where the emulsifier
is suitable for such a procedure, it may be dissolved or dispersed in the
plasticiser first and the plasticiser so treated then stirred into a latex.
When direct emulsification of plasticiser in a latex is contemplated, it
20 PVC Latices 715
is desirable to check (in the absence of past experience, or an

assurance from the latex manufacturer) that the mode and rate of
stirring necessary to disperse the plasticiser effectively do not result in
a shear rate so high that it will break the emulsion. The presence in
the latex system of such components as fillers and thickeners can aid
stabilisation during and after plasticiser addition.
Blending an unplasticised latex with a similar, compatible, plas-
ticised one can provide another route to plasticisation.
(c) Fillers
The main functions of fillers in PVC latices are essentially the same as
in other kinds of PVC composition, viz. to cheapen the ultimate
product and/or to modify some of its properties. The fillers most
widely used are calcium carbonate (especially whiting) and some clays;
talc, mica, and barytes are also incorporated for some applications
(notably in certain surface coatings). All fillers increase the hardness,
stiffness, and density of latex-produced deposits and films. Even at
relatively moderate loadings they also reduce gloss, and counteract
tackiness: in these respects they can therefore act as matting or
antiblocking agents, even if not incorporated specifically or mainly for
that purpose.
In general, whitings produce the least hardening and stiffening in
latex-derived products, with the effects of clays and mica respectively
intermediate and highest in these regards. Barytes increases substan-
tially the density and weight per unit area of latex products, even at
low loading levels: when using this high-density filler, the compounder
may have to include extra thickeners or otherwise adjust latex viscosity
to prevent sedimentation, which can produce a compact, hard-to-
disperse layer of the filler at the bottom of the container.
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 for a given
application 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 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
measuring a physical property, such as strength and/or elongation at
various filler (or pigment) loadings, and plotting the results against
percentage of filler (or pigment) content by volume. Although the
actual property values will depend on several factors (and especially
the nature of the polymer and its binding power for the filler in the
particular system), the general form of the plot is fairly universal: it is
typified by the curve of Fig. 20.2, in which the cpvc is marked by the
change of the slope.
A water-sorption method has also been described lO for determining
the cpvc of a latex-produced film.
Even with low filler loadings, well below cpvc, it is important that
the filler should be in fine-particle form and well dispersed (free of
aggregates or agglomerates). Coarse aggregates or large particles can
form points of stress concentration or weakness in the final product.
It is normal to pre-disperse fillers in water in the presence of a
700
600
500
;: 400
~
><
~ 300
.c
11
c
o
~200
'"oc
W
100~2-----3~--4~~5~~6~7~e~9~1~0-------+-2~0----~--~40~~50~
PigmQnt concQntration, vol. .,.
Critical pigment volumQ

concClntration (cpvc)
Fig. 20.2 Elongation at break of a latex-produced, pigmented PVC film

versus pigment loading.
20 PVC Latices 717
dispersing agent, and pass the resulting slurry through a cone mill or
high-speed colloid mill to de-aggregate the particles. When small
amounts of very fine dispersions are needed, ball mills may be used,
but they are too slow and uneconomical for large scale production.
At loadings around cpvc, when the polymer in the latex-produced
film acts as a binder for the filler, the choice of filler becomes more
critical. Other factors being equal, fine particles have a large surface
area and hence a greater binder demand, but can give increased
covering power. They may be preferable where binding and covering
power is the prime requirement (as, say, in a quality surface coating)
but, where economy is the main consideration, a coarser filler may be
tolerated in a greater amount. China clay is commonly used for dense,
high-hardness coatings (where the more expensive talc, mica and/or
barytes are not necessary), and coarse whitings for maximum filler
loadings and economy.
(d) Pigments
Pigments are used to impart opacity and whiteness or colour to
latex-produced films. Although fillers can also have opacifying and
whitening effects, pigments are-by definition-more effective in these
functions, and are employed in lower concentrations.
Titanium dioxide is the preferred pigment for a white base, but
lithopone (barium sulphate/zinc sulphide) and blanc fixe can also be
used. It is advisable to incorporate a white base in filled and unfilled
stocks required in pastel shades.
A choice of colouring pigments, both inorganic and organic, is
commercially available. The form most appropriate for incorporation
in a latex is a fine 'micronised' aqueous dispersion or paste: grades of
such dispersions suitable for PVC latex compositions are supplied by
colourant manufacturers. If the pigment to be used is in a dry form, it
should be dispersed in water with a suitable wetting agent, and the
dispersion milled to homogenise and de-aggregate it before addition to
the latex.
In general, the colourants used are ones which do not contain ionic
or ionisable iron, copper, or zinc, as these can catalyse decomposition
of PVC, especially at elevated temperatures.
(e) Miscellaneous Additives

For some applications special properties may be required in a
latex-derived product, e.g. absence of gloss (in an essentially unpig-
mented, unfilled film), resistance to blocking, enhanced flame retar-

dance, or resistance to microbiological attack. Additives incorporated
in latex compositions for these end-effects are briefly mentioned
below.
MATTING AGENTS
Most of the matting agents discussed in Chapter 9 can be added to
PVC latices (in the form of aqueous dispersions) to reduce the gloss
of films ultimately formed. The addition levels required (best con-
firmed in preliminary tests) are generally low-up to a few phr.
ANTI-BLOCKING AGENTS
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 substrate. * Blocking occurs most commonly between con-
tinuous, 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 12) is a
function of the pressure and the degree of tackiness. Unfilled films
produced from latices of soft PVC copolymers, or ones containing high
proportions of external plasticiser(s), are prone to blocking in cir-
cumstances favourable to this effect. The presence of common fillers at
their usual, fairly substantial, loading levels reduces surface tack, so
that filled latex-derived films do not normally block. In essentially
unfilled compositions the same function can be discharged by anti-
blocking agents compounded into the latex in proportions much lower
than those normal for fillers. Among the most effective are some
fine-particle silicas and certain silicates, which may be incorporated at
up to about 10phr (considerably less in some cases). Some examples
are: Syloid precipitated amorphous silica (W. R. Grace & Co.,
Davison Chemical Div., USA); Micro-Cel calcium silicate (Manville
Products Corp., USA): Sipernat precipitated silicas (Degussa). Most
matting agents also have some anti-blocking action at their normal
incorporation levels. Aqueous dispersions of some paraffin and amide
waxes can be blended with PVC latices, in proportions of a few phr of
solid wax, for anti-blocking effect: this arises because the wax, which
has poor compatibility with PVC polymer, exudes to the surface of
the latex-produced film, where it suppresses the inherent tackiness.
* This definition is slightly more comprehensive than those given in relevant

standards. 11,12
20 PVC Latices 719
Blending a latex which produces blocking-prone films with a com-

patible one of a harder PVC polymer can be helpful, if the increased
hardness and stiffness of the resulting film are acceptable.
Note: The blocking tendency of a latex-produced film can
sometimes be reduced by external measures, such as emboss-
ing (which breaks up the smooth surface and reduces the
effective area of contact with other surfaces), or increasing
the heat treatment (temperature and/or duration) in proces-
sing beyond that normally required for rapid, complete
fusion.
FLAME RETARDANTS
For maximum flame retardance a VC/VDC latex should be used if
practicable, or a homopolymer latex, compounded-where plasticisa-
tion is required-with a phosphate plasticiser. Antimony oxide is also
widely used as a flame-retardant additive, in quantities up to about
15 phr. Colloidal aqueous dispersions of antimony pentoxide are now
available (e.g. from Nyacol Products Inc., USA) that are not only very
stable (for effective blending with a latex) but can also have a
stabilising effect on latices with which they are compatible.
BIOSTATS
Several antibacterial and antifungal agents, effective in PVC latex
products which may encounter warm and humid service conditions,
are available. The advice of latex suppliers and/or suppliers of the
biostats (e.g. ICI, UK and USA; Abbott Laboratories, USA: Bode
Laboratories, UK; Acima Chemical Industries Ltd, Switzerland)
should be sought in individual cases, Microbiological attack on the
latex itself, or a latex-based composition, may also have to be
counteracted ('in-can' protection): fungal attack is often the more
likely, as PVC latices, especially those of a low pH, tend to be more
resistant to bacteria.
20.5 APPLICATIONS OF PVC LATICES
20.5.1 Typical Uses-General
Some typical uses of commercial PVC latices are indicated in Table

20.3. Depending on the application, a latex may be used virtually as
~
TABLE 20.3
Some Applications of Commen:ial PVC Latices
General area and type of application Examples ~
Specific application Type of latex Some relevant commerciallatices G ~

~
Surface coatings III
~.
Emulsion paints Exterior and interior Copolymer (VC/VAC/E) Vinamul3401, 3405, 3409
Silk-finish; high pigment Copolymer (VC/VAC/E) Vinamul 3459
Textured finishes Copolymer (VC!VAC/E) Vinnapas-Dispersion CEZ 16
~
a
General paint base Copolymer, plasticised Polysar Latex 7303 ~
Coatings for:
Masonry Exterior coatings plain l
and textured Copolymer (VC/VAC/E) Vinamul R 34151 ~
Concrete Facade paints Copolymer Haloflex 208 lil
(VC/VDct!VA b ) ~
Floor paints Copolymer Haloflex 208 ~.
(VC!VDC/VA)
Barrier coatings (incl. Copolymer Haloflex 202 and 202 S §
Q..
transparent) (VC/VDC/VA)
Metal surfaces Steel paint primers Copolymer Haloflex 202 and 202 S ~
'l;j
(VC/VDC/VA) ::::
Wood Fire-retardant paint Copolymer Haloflex 202 2
(VC/VDC/VA)
g.
Textile treatments and finishes ~
Bonding agents (for non-wovens) Heat-sealable binders Copolymer, plasticised Polysar Latex 7303
Copolymer, phosphate- Geon Latex 575X43
plasticised
Low-flammability binders Copolymer (modified Vinamul R35025
VC!VAC/E)
Needle-felt binders Copolymer, heat-reactive Polysar Latex 7560
Coatings or impregnats for fabrics General-purpose (heat- Copolymer, phthalate- Geon Latex 576
sealable) plasticised
Flock-coating adhesives Copolymer, heat-reactive Polysar Latex 7560
Fire-retardant coating for Copolymer Haloflex 202
canvas (VC/VDC/VA b )
Sizing agents (fibres, yarns or Fibre and fabric sizes Copolymer Geon Latex 351 and 352
fabrics)
Fibre and fabric sizes Copolymer VC/VAC/E Vinnapas-Dispersion CEF 18
Fibre and fabric sizes Copolymer, plasticised Polysar Latex 7303
Paper coatings Wear-resistant coatings Copolymer Geon Latex 460 (various grades)
(carboxylated; heat-
reactive)
Washable and wear- Copolymer Geon Latex 351 and 352; Polysar
resistant coatings Latex 7151
Wall-paper coatings Copolymer (VC/VAC/E) Vinamul 3452 !:5
Grease-proof carton Copolymer, plasticised Polysar Latex 7351
coatings "1:1
Heat-sealable coatings Copolymer (VC/VAC) Vinnol-Dispersion 50 ~
(suitable for food Copolymer (VC/VAC/E) Vinnol-Dispersion CE35 t-o
c:.
packaging) 1';-
Release coatings Copolymer, plasticised Geon Latex 552 ~
(by factory-blending
with nitrile rubber
latex)
Copolymer Polysar Latex 7151 and 7152
Leather treatments Leather finishes Copolymer (VC/VDC) Geon Latex 650X17
Copolymer Polysar Latex 7151
Leather adhesive base Copolymer Vinnapas-Dispersion T53/22 VL
(VC/VAC/VU)
Copolymer Vinnapas-Dispersion T56/34 VL
(VC/V AC/VL)
phthalate-plasticised
Adhesives Laminating and heat- Copolymer Geon Latex 460 (various grades)
sealing (carboxylated; heat- -...I
(continued) tv
reactive) ......
TABLE 20.3----contd. ;:j
N
General area and type of application Examples
Specific application Type of latex Some relevant commercial latices a
Adhesives for plastics Copolymer Vinnapas-Dispersion T53/22 TL

films (VC/VAC/VU) ~
Copolymer Vinnapas-Dispersion T56/34 VL ::l:!
(VC/VAC/VL), ~
::to
phthalate-plasticised Q
Tile adhesives Copolymer (VC/VAC/E) Vinnapas-Dispersion CEZ 16
Priming coats for PVC on Copolymer, phthalate- Geon Latex 576 ~
fabrics and paper plasticised ;:!
Miscellaneous ~
Flame-retardant coatings For fabrics and decorative Homopolymer (plasticiser Vestolit-Dispersion M ~.
impregnations sheets should be added by .'"
user) ~
Coatings and saturants Homopolymer (high film- Polysar Latex 7177 ~
for paper and textiles forming temperature) ~
S·
Water-based inks Ink binders Copolymer (self-cross- Geon Latex 590X4 ~
linking, phosphate-
plasticised) i
Copolymer, plasticised Polysar Latex 7303 )..
:g
a For suppliers see notes to Table 20.1.
b VA, vinyl acrylate.
a~.
C VL, vinyllaurate.
d VDC, vinylidene chloride.

20 PVC Latices 723
supplied (perhaps after a minor modification such as addition of

plasticiser and/or dilution), or as the basic constituent of a more
complex composition. A few illustrations are provided by the
examples below. Advice on the formulation and compounding of latex
compositions for particular applications is available from latex sup-
pliers. The suitability and performance of a latex composition should
be checked by application trials and appropriate tests on the final
product obtained in such trials.
20.5.2 Examples of Basic Formulations for Particular Applications
(a) Simple flame-retardant treatment (by impregnation or coating)

for paper or light fabric:
Homopolymer latex (e.g. Vestolit-Dispersion M) 100 pbw, wet
Phosphate plasticiser (Reofos 65) 24 pbw (=40 phr)
To be diluted as appropriate to the method of application. May also
be modified with extra plasticisers if softer finish or low-temperature
flexibility is required.
(b) Binder for non-woven textiles:

Copolymer latex (Geon 351) 60 pbw, dry solids
Nitrile rubber latex (Geon 1562) 40 pbw, dry solids
Wetting agent 0·25 pbw
Antifoaming agent 0·10 pbw
To be diluted if and as necessary depending on the method of
application and the required properties of the finished product. These
factors also determine the admissibility of fillers and pigments. The
application methods include l 3-16 full saturation by immersion (with
removal of excess latex by squeezing or suction), impregnation with
foam latex (in which case no defoaming agents are used in the
composition), spraying, printing, and others.
(c) Fire-retardant paint (ICI Haloflex formulation M90) for another

application of a Haloflex-based coating, see Fig. 20.3:
Premix (% by wt)
Water 12·29
Defoamer (Bevaloid 642; Bevaloid Ltd, UK) 0·20
Anionic dispersant (Poly wet ND2; Uniroyal 0·20
Inc., USA)
Fig. 20.3 Tennis court coated with Haloflex paint. Courtesy of ICI.
Non-ionic surfactant (Synperonic PE 39/70, 4·80

30% solution; ICI)
Cellulose thickener (Methocel J12MS; Dow 0·10
Chemical Co., USA)
Ammonia to pH 8 (to solubilise Methocel)
Pigments (% by wt)
Tale (Luzenac 20MOOS; Tales de Luzenac, 15-28
France)
Titanium dioxide (Tioxide RC42; Tioxide 10-39
Group Ltd, UK)
Antimony oxide 4-09
Let-down (% by wt)
Haloflex 202 (lCI) 49-65
Completion (% by wt)
Fungicide 0-10*
Coalescent (Texanol; Eastman Chemical Pro- 3-00
ducts Inc., USA)
* Addition of the order of 0·1 % by weight, but actual amount dependent on

the choice of fungicide.
20 PVC Latices 725
20.6 SOME STANDARD TEST METHODS FOR

POLYMER LATICES
Test methods developed for rubber latices were the earliest chrono-
logically. Some of these are applicable also to other polymer latices.
There are no major standards specifically for PVC latices: the general
standards of interest in this connection are listed in Table 20.4.
TABLE 20.4
Some Standards Relevant to Polymer Latex Properties
No.
ISO 1147-1975 Aqueous dispersions of polymers and
copolymers-Freeze-thaw cycle stability test
2 ISO 1148-1980 Aqueous dispersions of polymers and
copolymers-Determination of pH
copolymers-Determination of residue at 105°C
copolymers-Determination of white point tem-
perature and minimum film-forming temperature
5 ISO 3219-1977 Liquid, emulsified or dispersed polymers: Deter-
mination of viscosity with a rotational viscometer
6 ISO 3499-1976 Aqueous dispersions of homopolymers and co-
polymers of vinyl acetate-Determination of
bromine number
BS 6057 Rubber latices (including synthetic rubber)
7 Part 1 : Section 1.3: 1982 Coding system for rubber latices
8 Part 3: Section 3.2: 1981 Determination of the total solids content
9 Part 3 : Section 3.7: 1982 Determination of density
10 Part 3: Section 3.9: 1981 Determination of pH
11 Part 3: Section 3.11: 1984 Determination of viscosity
12 Part 3: Section 3.14: 1984 Determination of high-speed mechanical stability
13 . DIN 53567-1983 Determination of mechanical stability of natural
rubber latex
REFERENCES
1. Blackley, D. C., High Polymer Latices, Vol. 1. Applied Science Pub-
lishers, London, 1966, Ch. 1.
2. Vanderhoff, J. W., Bradford, E. B. & Carrington, W. K., J. Polym. Sci.,
Part C (Polymer Symposia), 41 (1973) 155-74.
3. Titow, W. V. In Adhesion 2 ed. K. W. Allen. Applied Science

Publishers, London 1978, Ch. 12.
4. Anon., Breon Latices. Technical Manual No.5, BP Chemicals (UK) Ltd,
London, 1969.
5. Glasstone, S., Textbook of Physical Chemistry, 2nd edn. Macmillan and
Co. Ltd, London, 1948, p. 1220.
6. Brown, G. L., 1. Polym. Sci., 22 (1956) 423.
7. Vanderhoff, J. W., Tarkowski, H. L., Jenkins, M. C. & Bradford, E. B.,
1. Macromol. Chem., 1 (1966) 361.
8. Dillon, R. E., Matheson, L. A. & Bradfrod, E. B., 1. Colloid Sci., 6
(1951) 108.
9. Voyutskii, S. S., Polymer Reviews, Vol. 4. Autohesion and Adhesion of
High Polymers, Wiley-Interscience, New York, 1963.
10. Humbert, L. & Humbert, P. Official Digest, 181 (1959) 413, 736.
11. (a) ISO 472-1979. Plastics-Vocabulary. (b) ASTM D 883-78a. Standard
Definitions of Terms Relating to Plastics.
12. (a) ASTM D 1893-67 (Reapproved 1978). Blocking of Plastic Film. (b)
ASTM D 3354-74 (Reapproved 1979). Blocking Load of Plastic Film by
the Parallel Plate Method. (c) BS 2782: 1970: Method 31OA. Blocking of
Flexible PVC Sheet.
13. Krcma, R., Manual of Nonwovens. Textile Trade Press, Manchester, UK,
and W. R. C. Smith Publishing Co., Atlanta, GA, USA, 1971.
14. Gillies, M. T. Nonwoven Materials. Noyes Data Corp., NJ, USA, 1979.
15. Whitehead, D. A., Tex. Ind. SA, (Feb. 1980) 5-11.
16. Schlauch, W. F. & Caimi, R. J. (Feb. 1980) Text. Chem. Color., 6(10)
(1974) 223-9.
Section 6
POST-PRODUCTION PROCESSING
OF PVC PRODUCTS
727
CHAPTER 21
Fabrication, Conversion and Related

Processing of pvc Sheet and Parts
21.1 FABRICATION AND RELATED

OPERATION~GENERAL
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 commonly 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); welding of PVC flooring
or reservoir linings (of flexible PVC sheeting); and production of
tubular-frame garden furniture from rigid PVC pipes.
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 sheet; sheet laminates;
flooring, etc.).
The main general types of PVC sheeting involved in fabrication,
conversion and surface processing operations are: rigid homopolymer
sheet and film; rigid copolymer sheet and film; plasticised sheet and
729
film; plasticised/rigid sheet laminates;* PVC sheet laminates with

other materials. 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 co-extrusion-with relatively thin
decorative or protective layers (e.g. of acrylic polymers, for weather-
ing resistance) are also on the market.
The following are some examples of commercial sheet products
relevant in the present context. See also Fig. 21.1.
Linings for chemical or food-storage tanks and reactors: Vybak
(Wardle Storeys, UK)-pressed PVC sheet for GRP-clad installations
(service temperatures up to 95°C claimed); Darvic (Weston Hyde
Products Ltd, UK)-industrial grade sheet, and uPVC/pPVC sheet
laminate for tank and chemical plant lining; Armodur (Societe la
Cellophane, France)-rigid PVC sheet (thick, press-laminated from
calendered sheeting based on mass-polymerised resin grade).
Roofing and wall<ladding sheet: Sinticlad (Hepworth Allied Prod-
ucts, UK)-rigid corrugated sheet for roofing applicationst 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., Belgium:j: (based on their Benvic emulsion resin grades
claimed particularly suitable for outdoor applications )----offers im-
proved impact resistance imparted by the orientation, coupled with
retention of this property down to very low temperatures (-40°C is
* This type of laminate was originally developed for lining metal tanks for
heavy chemical duty. Bonding large areas of rigid PVC sheet to mild steel can
present considerable 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 can be achieved, coupled with the overall effect of an all-uPVC
internal tank surface. 1
t 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. 2
:j: cf. also Oriex, biaxially stretched PVC sheeting of Tenneco Chemicals Inc.,
USA.
21 Fabrication, Conversion and Related Processing 731
claimed). Cobex 1350 (Wardle Storeys, UK~heet for internal

cladding of food factories, bottling plants and the like (meets the
requirements of BS 3757, Part 1, and BPF/BIBRA code for food-
contact materials); Duraform (TBA Industrial Products Ltd, UK}-
pressed sheet reinforced with a long-fibre grade of chrysotile asbestos.
Glazing, including safety glazing: Darvic-clear, and clear wire-

laminate grades; Pentalon (Klockner Pentaplast GmbH, FRG); PVC-
Glas (Simona GmbH, FRG}-high-clarity natural and coloured sheets
(in 1-20 mm thickness).
Fig. 21.1 Applications of rigid PVC sheet. Processing-solution tanks in an

automatic colour film processor. Tanks fabricated from Daroic by Refrema
A/S, Roskilde, Denmark. Daroic 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.)
Fig. 21.1 (contd). 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~urtesy of TBA Industrial Products
Ltd.)
Safety doors: Astraglass (Dynamit Nobel, FRG and UK)-ftexible,

thick sheet.
Sign boards: Pacton SQ (ICI)-impact-resistant rigid sheet for

road-signs; Pentaprint (Klockner Pentaplast GmbH, FRG)-rigid
sheet (replaced aluminium as material of destination sign boards on
West German state railways).
Miscellaneous: Simona-PVC-EL (Simona GmbH FRG)-antistatic

sheeting (surface resistivity down to 106 Q); Krene (Dynamit Nobel):
medical-grade sheeting (sterilisable by gamma rays); 'laser-friendly'
sheeting for credit cards (ICI-Staufen).
21.2 WELDING OF PVC PRODUCTS
21.2.1 General
The international standard for plastics nomenclature3 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 21.3) of PVC involve the applica-
tion 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, 180-21O°C4 and 250-300°C. 5 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.
The welding methods used with PVC products are: hot gas welding
(including extrusion welding); heated-tool (hot-plate) welding; indirect
heated-element welding; friction welding (comprising spin welding and
vibration welding); high-frequency welding; and ultrasonic welding.
Useful summaries of most welding methods applicable to PVC are
given in Refs 4 and 5. 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 draw-
ings and brief explanations) respectively the processes for the welding
of plastics (named in German, English and French)6 and their
technical principles. 7 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.
Reviews have been published of welding methods for
thermoplastics. 8 ,9 An EEUA handbook provides some relevant infor-
mation on several aspects of heat welding of plastics. 10
Analyses of some welding processes for thermoplastics in terms of
their principal parameters are given in papers by Frankel & Wang H
(ultrasonic welding), and Potente & Reinke 12 (heated-tool, ultrasonic,
and friction welding).
21.2.2 Hot-Gas Welding
In the main embodiment of this method, the edges of the parts to be

joined (very often these will be sheets of substantial thickness) are
chamfered, so that jointly they form a V-shaped groove. They are then
softened by a stream of hot gas (air or nitrogen) delivered by the
nozzle of a hand-held blow gun ('torch'). Simultaneously, a filler rod
(of the same or similar PVC material) is laid into the groove whilst
also being softened by the hot gas stream. The rod material fills the
groove and fuses with the sides to form a solid joint on cooling. If, as
is most often the case (e.g. in PVC floor welding), the material of the
original welding rod (or 'cable' as it is often called in the context of
floor welding) forming the ultimate seam protrudes above the adjoin-
ing surfaces, it is finally trimmed level, with a sharp knife or a special
trimming tool.
In a variant of the technique, known as hot-gas overlap welding, the
welding nozzle is passed between the faces of the 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
preheat 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 the appropriate method for batch production
(especially where the ultimate jointed products are large or compli-

cated) where fully mechanised or automated techniques are not
suitable, for many on-site operations (particularly where those involve
the jointing of sheet materials to form continuous layers of large area),
and for butt-welding of relatively thick sheets. The welding of pipes by
the hot-gas technique is also practised in the construction of pipe lines.
Other examples are seam welding of PVC flooring, liners for refriger-
ated vans, chemical or food-storage tank linings, wall linings in
hospital operating theatres, industrial clean rooms, food halls, etc.
In the lining of metal tanks with PVC sheeting (in which the
sheeting is normally attached to the metal by means of a suitable
adhesive), all the sheet joints (butt and corner) are usually hot-gas-
welded. Use of thermoplastic sheeting for this kind of application is
covered by a recent British Standard. 13 For the production of PVC
linings for reinforced plastics tanks, a British Standard covering the
construction of such vessels 14 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 correspond-
ing figure, given in DIN 169304 as the general minimum 'valence ratio'
for hot-gas-welded joints between rigid PVC sheets, is 0·6 (i.e. tensile
strength across the weld at least 60% that of the sheet), whilst ASTM
D 178915 stipulates a general minimum of 75%. The latter specification
lists, and illustrates, the main causes of poor welds.
21.2.3 Heated-Tool (Hot-Plate) Welding
In this method the surfaces to be welded are first heated by direct

contact with a heated metal element and then brought together under
pressure. The element (variously termed 'hot-plate', 'heating plate',
'heated tool', or 'heating mirror'), which is electrically heated, is
generally plate-like, but may also be wedge-shaped, or have a surface
appropriately contoured for particular, intricate joints. The surface of
the heated tool is normally coated with PTFE. In some variants of the
method the plastics surfaces to be joined are brought close to, but not
quite into contact with, the hot tool surface, so that the heating
proceeds by radiation. 16
In outline, a typical welding cycle comprises the following opera-
tions. The parts to be welded are clamped so that the surfaces to be
joined are appropriately aligned, at some distance apart. The tool,
heated to the appropriate temperature (8 T ), is positioned between the
surfaces, which are moved up to and pressed against the tool's faces
(at a predetermined pressure PT ). As the surfaces soften, the pressure
PT makes the parts advance further 'into' the tool's faces. The advance
is limited to a distance (fairly typically about 1 mm) set beforehand in
accordance with the nature of the plastics material, the tool tempera-
ture, and other relevant conditions; the rate of advance (and hence the
time it takes, t A ) is similarly pre-set. The pressure contact so effected
between the plastics surfaces and the tool faces is then maintained for
a predetermined 'static' heating period (time t s ). At the end of this,
the heated tool is removed, and the fused plastics surfaces are brought
together under the appropriate welding pressure (Pw ), which is then
maintained for a suitable time (tw)' The distance by which the two
parts are allowed to move 'into' each other as their hot surfaces flow
under the pressure Pw is also set beforehand.
Apart from the properties of the material itself, the parameters
influencing the quality and strength of the weld are: the tool
temperature «(IT) and surface condition, the times of the various stages
(tA' ts> and tw) including the time taked' in removing the tool
('change-over time'), the pressures employed (PT and Pw-in practice
these are often set to the same value), and the final cooling rate.
Haworth's investigation of the corner welding of PVC window frames
by the heated-tool method 17 demonstrated inter alia that-for a given
material formulation-the strength of weld is mainly influenced by the
temperature of the tool and the static heating time (ts). With properly
designed heating tools and close tool temperature control, suitably
formulated rigid PVC products can be effectively welded to weld
strengths approaching the original material strength. This known fact
was well brought out by the results of another recent study18 in which
hot-gas welded joints produced, under controlled conditions, between
Darvic rigid PVC sheets, attained between 28 and 85% of the original
sheet strength, whereas welds produced by the heated-tool method
reached 94% of the original strength.
In addition to the weld quality achievable, the advantages of
heated-tool welding include applicability to a wide range of products,
speed and economy in production, and suitability for automation
where that is warranted by the scale of operations. Inter alia, this
welding method is used in the production of PVC window frames from
extruded profiles (in most cases of complex, multi-cavity structure)--a
fairly substantial outlet for uPVC (annual UK consumption expected
to reach 75000 tonnes by 199019).
Useful outlines of heated-tool welding and its applications 16 ,2o have

been published by members of staff of Bielomatik Leuze GmbH
(FRG), a big, old-established producer of equipment for this process.
21.2.4 Indirect Heated-Element Welding
This method is normally confined to the heat-welding (heat-sealing) of

thermoplastic films and thin sheets. In essence, the procedure involves
applying insulated* heating elements (with simultaneous application of
suitable pressure, either by the elements themselves or by some other
means) to the outer surfaces of the workpieces to be joined, so that
the corresponding inner surfaces in the area 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).
21.2.S Friction Welding
There are two variants of this method: spin welding and vibration
welding. 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 used with suitable rigid PVC parts.
(a) Spin Welding

This is a very effective method for making circular joints in parts of
which at least one is rotatable. In the absence of specially made
equipment, a simple drill press may be used, with means of securely
and firmly clamping the parts to be joined. Normally one part is held
stationary and the other rotated in pressure-contact with it, to give a
relative velocity at the joint site of 3-10 m s-1, with a pressure of
3·5-4·8 MPa. Typical figures for the welding time and subsequent
holding (cooling) time are, respectively, 0·25-0·5 sand 0·5-1·5 s; i.e. a
total time for joint production of 0·75-2 s. Proper joint design is
important. The joint area also limits the maximum part size that may
be handled.
* The insulation (commonly PTFE) serves as a parting layer preventing

disruption (through sticking) or marking of the plastics surface by the hot
element.
(b) Vibration Welding

Here too the weld is effected by frictional heat, but the method is not
limited by joint geometry. However, the joint and part design must be
such as to permit lateral displacement, linear or angular, of about
±0.8 mm. The two parts to be joined are fixed in form-fitting
fastenings on the platens of the welding machine. One part is held
stationary and the other reciprocated against it at a frequency of
100-300 Hz, under a pressure of 1·4-2·8 MPa (the joint plane must
always be parallel to the plane of movement). The joint is normally
made between two flat flanges, and the design may include flash traps.
Large and relatively intricate parts may be welded by this method
(up to about 0·5 m x 0·5 m).
21.2.6 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 sandwiched
between two electrodes. The electrodes form the plates of a capacitor,
with the material to be welded as the dielectric. A high-frequency
voltage is applied to the electrodes: the polarity of this voltage will
undergo reversals according to the frequency: e.g. at a frequency of
50 MHz the polarity will reverse 50 million times a second. Polar
molecules in the material between the electrodes attempt to align
themselves in the electric field, and so are set into rapid vibration as
the field polarity undergoes its reversals. The mechanical work
involved in the vibration generates heat in the material, in accordance
with the relationship
Heat generated = V 2 wC tan {)
where V is the root-mean-square value of the applied voltage, in
volts;
w is 2:Jr x voltage frequency;
C is the dielectric capacitance, in farads;
tan {) is the tangent of the dielectric loss angle.
Pressure applied via the electrodes makes heat-softened parts of the
joint fuse together. The electrodes may be flat or three-dimensionally
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. Various arrangements
and electrode designs are used. Thermal insulation on the electrodes
(PTFE, or other heat-resistant, low-stick insulant) reduces heat loss

from the hot plastics material to the relatively cooler electrode metal.
Note: For effective dielectric heating, and hence suitability for
high-frequency welding, a thermoplastic should have a rela-
tively high loss tangent (dissipation factor). Hence among
PVC materials the method is primarily applicable to those
based on flexible compositions (cf. loss tangent values in
Appendix 1). It may thus be regarded as mutually com-
plementary with ultrasonic welding, which is normally suit-
able only for rigid PVC materials (see Section 21.2.7).
As can be seen from the formula above, the higher the frequency
the greater the heat generation. The internationally recognised stand-
ard operating frequency for industrial welding equipment is
27 ·12 MHz, with a tolerance limit of only ±O·6%. 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 elec-
trodes as fusion takes place in the course of welding, does not result in
frequency drift beyond the prescribed limits. 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. Even with thermally insulated electrodes, effective welding
of very thin films may not be possible for this reason even with long
cycle times. Otherwise, the optimum welding time increases with
material thickness. However, for best results, the shortest practicable
time cycle should be used (to minimise possible plasticiser loss and
consequent material embrittlement) with relatively light pressure, and
electrodes with radiused edges (sharp edges can cause field concentra-
tion and overheating).
The nature of the PVC material influences the quality of the welds.
With thin sheets in particular, the presence of furnace carbon blacks or
metallic particles may result in conductive paths within the material,
and hence serious troubles in welding, unless the particles are very
effectively dispersed and the loading level relatively low. In general,
the lower the pigment or filler content of the composition the better
the welds. Highly filled cheap pPVC materials should therefore be
used with caution, particularly in the production of inflatable goods
where good seams are vital.
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; up-
holstery; inflatables; baby wear; pram covers; quilted goods; tar-
paulins; large welded sheets; car trim.
The welding press platen sizes range from, say, about 25 mm x
3 mm (for welding blood-transfusion equipment) to 3 m 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.
It has been estimated21 that over half of all the welding in industrial
conversion of flexible PVC film and sheeting into products 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 up of
pPVc.
21.2.7 Ultrasonic Welding
With regard to the bond-formation mechanism this may be considered

as a special case of friction 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 tip of the tool component of the
ultrasonic system (known as the 'horn', or 'sonotrode', or occasionally
'velocity transformer'). The configuration of the horn differs according
to the particular application. Depending on the equipment and the
application, the frequency of vibration applied by the horn varies
between 20 and 70 kHz, and the amplitude is typically 50-100 Ilm.
Frictional heat produced at the joint interface softens the surfaces,
which merge under the static pressure applied; this is normally
maintained both during the welding and the cooling phases of the
operation (each typically lasting about 0·1-1·5 s). The main ad-
vantages of ultrasonic welding are the short time required to complete
the weld, and the weld strength attainable (over 90% of the material
strength). The process also lends itself well to microprocessor control
and automation. Joint design is an important consideration: the
so-called 'energy director' type of joint is particularly suitable for
non-crystalline plastics, including rigid PVc. The main limiting factors
are the sound transmission characteristics of the plastics 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 and semi-rigid than for flexible PVC (in
general, the softer the plastics material the more difficult it is to weld
ultrasonically: soft pPVC can suffer degradation and 'burning').
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); Telsonic (Switzerland and UK);
Mecasonic (France) and its sister company Forward Ultrasonics Ltd
(UK); Herfurth GmbH (FRG).
21.3 BONDING OF PVC WITH SOLVENTS, SOLVENT

CEMENTS, AND ADHESIVES
The distinction made in this chapter between welding and bonding of

plastics is that in the former type of process heat is the principal agent
promoting the union between the two parts of a joint, whereas in
bonding the union is brought about with the aid of solvents (solvent
bonding), solvent cements (cementing), or adhesives (adhesive bond-
ing). This terminology is broadly in line (but not in full conformity)
with the relevant IS0 22 and ASTM23 definitions.
21.3.1 Solvent and Solvent-Cement 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
technique is not normally applicable to butt joints where these are
likely to experience significant bending stresses in service.
As normally practised, the operation of solvent or solvent-cement

bonding 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. It may be
noted that solvent cements are not gap-filling (even a 'strong'
cement, containing, say, 30% polymer solids, can ultimately fill
only 30% of the gap volume when the solvent is eventually
lost). It is therefore essential for good results that the surfaces
of parts to be joined should fit closely together.
Note: In some cases a 'primer' (often tetrahydrofuran, or another
good solvent, single or mixed) is applied to the surfaces
before the application of the cement.
(iii) The joint is left 'open' for a short time. In this period the
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.
The main function of the pressure is to promote intimate
surface contact between the components. Where-as, for ex-
ample, in the cylindrical joints between 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 con-
centration in the bond zone (mainly by diffusion into the
material away from the original interface, and to a small extent
also by evaporation from the exposed 'edges' of the bond
zone 24).
Where practicable--e.g. with an essentially planar joint
between parts which can be held in a pressure jig---closing
pressure may be usefully maintained during this period. Suit-
able heating can accelerate the development of full strength.
The ultimate shear strength of a properly made solvent or solvent-
cement joint can approach that of the bulk material of the com-
ponents, but the initial 'green' strength is low.
A discussion of the mechanism of bond formation in solvent-bonded
joints has been published by the present author. 24 Some practical
aspects of solvent bonding of plastics are featured in papers by
Mittrop,25 and Trauernicht. 26 Detailed instructions for bonding proce-
dures 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 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
* For pressure-pipe joints (pipe-to-pipe or fitting-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 1·5 hour's ageing for each
atmosphere of service pressure (within the rated limit for the pipe).
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.
Many commercial solvent cements have been marketed for a large
number of years. The original Tensol Cement No. 53 (lCI, UK) and
Tangit (Henkel International, FRG) may be mentioned by way of
example.
Some standard specifications of direct interest in connection with
solvent cements for PVC products and their application are listed in
Table 21.1.
TABLE 21.1
Some Standards Relevant to Solvent and Solvent-Cement Bonding of PVC
Pipes and Fittings
BS 4346 Joints and fittings for uPVC pressure pipes

Part 1:1969 Injection-moulded PVC fittings for solvent welding
Part 3:1982 Solvent cement
ASTM D 2564-84 Solvent cements for PVC pipe and fittings
ASTM D 2855-83 Making solvent cement joints with 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 PVC
pipe and fittings
ASTM F 545-80 (1985) PVC and ABS injected solvent-cemented pipe
joints
ASTM D 2846-86 CPVC hot- and cold-water distribution systems
(Section 7 contains requirements for solvent
cements and adhesive jOints)
ASTM F 493~g5 Solvent cements for CPVC pipe and fittings
21.3.2 Adhesive Bonding

In general, adhesive bonding of uPVC-whether to itself or other
substrates-is easier than that of pPVc. In the latter case the presence
of the plasticisers can interfere with initial bond formation, or the
formed bond may be weakened by their subsequent migration into the
adhesive layer. However, a selection of commercial adhesives is
available for both pPVC and uPvc. Table 21.2 gives a general
indication of the main types of suitable adhesive systems, together
with some specific examples.
Advice is available, and should be sought, from adhesive manufac-
turers, regarding adhesives suitable for particular PVC materials and
applications. A general principle, applicable in all cases, is that the
PVC surfaces to be joined should be cleaned (usually by wiping with a
suitable solvent which is not a strong swelling agent for the material)
and dry, and that they should be roughened (e.g. with emery paper)
for better mechanical keying. Application of pressure once the joint
has been closed is always beneficial (and mandatory in bonding soft
PVC with solvent-based adhesives).
Two directories provide information, respectively, on industrial
bonding technology (including a glossary of relevant terms in English,
German, French, Russian and Chinese),27 and on classification of
adhesives by end-use, trade names, commercial sources, and
selection.28
21.4 CUTTING AND MACIDNING

Although many plastics, including PVC, can often be machined with
ordinary engineering workshop equipment, certain tool characteristics,
speeds and settings may be used to advantage. A useful brief early
review of the subject has been published by Koranj29 Special tools,
including automated equipment, are available for cutting and machin-
ing plastics sheeting and parts. 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 a service.
21.4.1 Cutting
Ordinary (sharp) scissors or shears can be used for cutting thin
material. Electrically operated nibbling shears are useful for sheets up
TABLE 21.2
Main Types of Adhesives fOI" PVC
Type General applicability Examples of commercial products Remarks
Adhesive Some typical use areas
Polyurethane (two- Both pPVC and Bostik a 3250 Footwear ("'PecialIY} PU resin solutions
component systems, uPVC can be bonded soles-to-uppers) typically used for these
or PU resin (with suitable Film laminates applications
solutions) versions) Coated fabrics
Acrylic (acrylate Both pPVC and uPVC Selected members Acrylic-based, pressure-
copolymers) can be bonded (with of the Permabond b sensitive adhesives
suitable versions) C and F ranges widely used on
4141 ""d 4142 ~ Recommended 1m
Bo,.' adhesive tapes
(aqueous emulsion bonding uPVC to
type) itself and some
Bostik M 890 (a substrates
modified two-part
acrylic system)
Adhesive L-52c Bonding films to
porous substrates
Hot-melt (polyester, Both pPVC and Synthacryl ranged For bonding pPVC Synthacryl range based
acrylic, or elastomer- uPVCcan be on Hoechst
based) bonded (with technology. Includes
suitable versions) solvent-based, contact
adhesives for self-
adhesive products
Hi-Floe
Instaweldf
E/VAC copolymers PVC films and Vinnapas Eg
sheeting aqueous emulsions
(adhesive base)
Epoxy resin/hardener uPVC Aralditeh A W 136 H
systems or N with Hardener
HY994
Cyanoacrylate Both uPVC and Loctite i IS 414 Various rapid-bond With pPVC
pPVCcan be Cyanoliti 611 applications cyanoacrylate bonds
bonded (with Eastman k 910 are weaker than with
suitable versions) uPVC and time to
handling strength is
longer
Nitrile rubber For pPVC and uPVC Bonding pPVC to PU
bonding foam (e.g. in motor-
car upholstery)
Flooring adhesives
a Bostik companies in most Western countries. Hager & Kassner (FRG).

b Permabond Adhesives (UK), and associated companies.
C Rohm GmbH (FRG).
d Resinous Chemicals (UK).
e DRG Kwikseal (UK).
f National Adhesives & Resins (UK).
g Wacker Chemie GmbH (FRG, UK, and Europe).
h Ciba-Geigy (world-wide).
i Loctite (USA and UK).
i Industrial Science Ltd (UK).
k Eastman Kodak (world-wide).
TABLE 21.3
Macbining of uPVC-Some Typical Features
Operation Tool features Typical operation speed Feed rate Other features Remarks
(r min ~1) (ft min ~1)
Drilling Included point angle = E.g. Peripheral: Lubricant desirable

1400 l-in drill: 6 000 100-200 towards top of
Quick spiral !-in drill: 1 000 speed range
I-in drill:500
Turning Included cutting angle = 300-1000 0·01-0·03 With a straight Possible faults: Top
60" in rev~l turning tool: rake too low-
Tip radius: about 0·025 in Top rake = 100 chipping, and
(side cutter) or higher Front clearance shattering;
(round-nosed cutter) =200 Front rake too
Tool material:high-speed low--overheating
steel or carbide tip (for Feed too fast-
filled PVC) dripping and/or
rough surfaces
Milling Generally similar to turning
Routering Tool Z-shaped; of high- Highest Smooth Fixed-head router
speed steel; preferably practicable preferable; material
l-~ in diameter temperature
preferably above
20°C
Sawing:
General Typically Slight negative Lubricants not
about 4 ft rake with no normally necessary
min-I bevel
Band saw 5-10 teeth per inch } 4000-
Circular saw 4-9 teeth per inch 8000
Engraving Included angle of cutter About 5 000 Low Material should be
about 50-60° (spindle speed) pre-chilled for
working
Coolant/lubricanta : a
soluble oil or
silicone emulsion
a If none used, the material may be wiped over with an antistatic agent to prevent sticking of swarf.
to about 0·080 in thick. Guillotining is also suitable: the blade bevel

angles should be 60-80° (with bevels of blades that are not often
sharpened in the upper part of the range). For normal sheet
thicknesses the cutting temperatures should be 20-30°C; for thicker
sheets, say 0·25 in, higher temperatures can be helpful (say up to
about 50°C). Cutting machines are available with microprocessor-
controlled, automated cycles.
21.4.2 Machining
Some relevant features of the machining of uPVC by a number of

common techniques are indicated in Table 21.3.
21.5 MANIPULATION AND CONVERSION OF PVC FILM

AND SHEETING FOR PACKAGING
There is a variety of techniques and equipment for these purposes, but

few are unique to PVC sheet materials, and the subject generally falls
within the sphere of packaging technology rather than PVC plastics as
such. The results of some of the processing concerned are represented
among the PVC products mentioned in Chapter 23.
An early review by Bippus & Ackerman (Mechanical Processing of
pvc Foils in the Packaging Sector)30 is still of interest. Other sources
of information include books by Briston & Katan,31 Oswin,32 and
Bruins,33 the relevant RAPRA Abstracts, and the current edition of
Modern Packaging Encyclopedia (McGraw-Hill).
REFERENCES
1. Bateman, G. T., Brit. Plast., 43(5) (1970) 96-9.

2. Gamski, K. M., 3fxh ANTEC SPE Proceedings, 1978, pp. 20-2.
4. DIN 16930:1964. Welding of Rigid PVC (Rigid Polyvinyl Chloride):
Directions. (Note: although this specification was withdrawn as an official
standard in 1984, the technical guidance it provides remains relevant.)
5. DIN 16931:1959. Welding of Flexible PVC (Flexible Polyvinyl
Chloride) :Directions.
6. DIN 1910-Part 3:1977. Welding:Welding of Plastics: Processes.
7. DIN 16960-Sheet 1:1974. Welding of Thermoplastics: Principles.
8. Streese, G., Kunststoffe, 59(11) (1969) 679-84.
9. Anon., Eur. Plast. News, 6(3) (1979) 11-28.

10. Anon., Thermal and Chemical Welding of Plastics Materials. Handbook
No. 35, Engineering Equipment Users Association, London, 1976.
11. Frankel, E. J. & Wang, K. K., 36th ANTEC SPE Proceedings, 1978, pp.
57-60.
12. Potente, H. & Reinke, M., Plast. Rubb. Process. Applns, 1(2) (1981)
149-60.
13. BS 6374:Part 1:1985. Lining of Equipment with Polymeric Materials for
the Process Industries-Lining with Sheet Thermoplastics.
14. BS 4994:1973. Vessels and Tanks in Reinforced Plastics.
15. ASTM 0 1789-65 (1977). Welding Performance of Poly(vinyl chloride)
Structures. (Note: this specification was discontinued as an official stand-
ard in 1984. However, the technical guidance it provides remains relevant.
16. Pecha, E., Kunststojfe. 76(4) (1986) 318-23.
17. Haworth, B., Eur. Plast. News, 13(11) (1986) 95-6.
18. Abram, J., Clegg, D. W. & Quale, D. V., Plast. Rubb. Int., 7(2) (1982)
58-60.
19. Anon., Plast. Rubb. Int., 12(2) (1987) 30.
20. Neubert, W., Welding Machines for Assembling Plastic Parts. Technical
publication, Bielomatik Louze GmbH (Bielomatik London Ltd).
21. Anon., Eur. Plast. News, 6(3) (1979) 11-28.
22. ISO 6354-1982 (ElF). Adhesives-Vocabulary.
23. Anon., Compilation of ASTM Standard Definitions, 3rd edn, 1976.
24. Titow, W. V. In Adhesion 2, ed. K. W. Allen. Applied Science
Publishers, London, 1978, Ch. 12.
25. Mittrop, F., Kunststojfe, 59(10) (1969) 685-7.
26. Trauernicht, J. O'R., Plast. Technol., 16(8) (1970) 43-9.
27. W. Winter (Ed.), Adhesive Technology. Verlag Winter GmbH, Hausenst-
amm, FRG, 1986.
28. Adhesives Directory. A. S. O'Connor & Co. Ltd., Richmond, Surrey,
UK,1978.
29. Korani, R., Kunststojfe, 59(10) (1969) 688-9.
30. Bippus, W. & Ackermann, H., Kunststojfe, 58(3) (1968) 197-206.
31. Briston, J. H. & Katan, L. L., Plastic Films. Butterworth, London, 1974.
32. Oswin, C. R., Plastic Films and Packaging. Applied Science Publishers,
London, 1975.
33. Bruins, P. F., Packaging with Plastics. Gordon & Breach, New York,
1975.
CHAPTER 22
External Treatments of pvc Products
22.1 DECORATIVE SURFACE TREATMENTS
In terms of surface area processed, film and sheeting (including their

supported forms, i.e. PVC coatings on textiles and paper) are the most
important group among PVC products to which decorative surface
treatments are applied. However, the surface decoration of other
products (e.g. PVC containers, mouldings, extruded profiles) is also
significant in its commercial and technical aspects.
Two publications, by Satas1 and Margolis,2 provide information on
the decoration of plastics.
22.1.1 Printing
The rotogravure process-popular for continuous sheet materials

('webs' in printers' parlance) in both plastics and textiles-is widely
used for printing PVC sheeting and PVC coatings on paper (e.g. vinyl
wall-coverings) and fabrics, on machines usually specially designed for
these products. Solvent-based inks are commonly 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 may also contain 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-e.g. the
cross-linkable Vinaprint GV inks (Claremont Polychemical
Corp., USA) for PVC-coated fabrics and wall-coverings.
752
22 External Treatments 753
PVC sheeting and packaging films are also printed by the

jiexographic process, often in-line, directly after production. Machines
are also available for printing separate, individually fed items. An
example of flexographically printed products is PVC shrink-sleeving;
like many kinds of PVC labels, this is normally printed on the inner side,
so that the print is protected in service by the thickness of the material.
Some PVC articles, mouldings and containers (especially bottles)
are printed by the silk-screen and offset techniques. Pad-printing 3 is
also employed: this can be particularly useful for thin-walled parts,
and for convex, concave, textured or irregular surfaces. Various
specialised versions of the basic equipment are available, including
rotary pad-printers for in-line printing of extruded products (as, for
example, in the application of wood-grain printed pattern to profiles).
Inks for pad-printing on PVC are commonly based on PVC resins and
acrylic binders. Solventless inks, cured by exposure to UV radiation
after application, are available for pad, screen, and offset printing:
some machines operating with such ink systems incorporate also
stations where protective lacquer is applied over the printed surface.
Credit cards-a highly specialised vinyl sheet product-are printed
with special inks by a hot-printing technique. The computerised
equipment used in this process also carries out magnetic encoding.
One example is the Digicard PCP 180 machine (Digicard Plastikkarten
Druck-u. Codiersysteme GmbH, Austria).
Some methods and techniques may be regarded as spanning the
borderline between printing and marking. Two such are ink-jet
printing and laser printing (as distinct from laser marking through
stencils, which is definitely a marking method).
Laser printing4 (introduced in West Germany by Siemens, Laser
Optronics, Lasitron, and Carl Baasel Lasertechnik Gmbtl) has been
increasingly coming into use for such items as computer and business
machine housings, keyboard key caps, small electrical parts, and
blow-moulded bottles. The main advantages of the method are its
no-contact operation, electronic control with wide scope for program-
ming and automation, relatively high printing speed, and applicability
to areas too small for mechanical printing methods. The principal
limitations are the high equipment and operation costs, unsuitability
for colour printing, * and disturbance of surface texture in some
* However, coloured prints can be made by a combination of laser and

sublimation printing technique. 4
materials (because of surface heating by the laser beam). Complex

images cannot be produced, so that in practice the method is confined
to relatively simple digits, letters, and emblems.
The print quality and contrast achieved depend on the nature of the
substrate (the formulation in case of PVC).
Ink jet printing is another no-contact method, which-whilst it can
produce coloured prints-is also primarily suitable for simple marks,
symbols, letters, and digits. Solvent-based inks are used, available in
compositions suitable for most plastics substrates. Curved and small-
area surfaces may be printed (e.g. PVC insulation on electric cables).
In typical equipment, printing heads eject ink in accordance with the
printing program, in appropriate (drop-wise) amounts.
22.1.2 Heat Transfers
In this method, a pre-printed image (which may be multicoloured)

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).5,6 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 (espe-
cially blown bottles and containers) in that it allows multicolour
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
DI-NA-CAL process (Diamond International Corp., USA and UK),
and the DRI-CAL process (Dri-Print Foils Inc., USA). In general the
heat-transfer method of surface decoration is more economical for
large volumes of production.
Holograms are incorporated in vinyl credit cards by the heat transfer
of pre-produced hologram images from a carrier film. Know-how and
equipment (standard models or custom-made) are available from
companies specialising in this technology (e.g. Leonhard Kurz GmbH,
FRG).
Foils for in-mould decoration of injection mouldings, although they
are not heat transfers in the strict sense, operate on a similar principle.
This method of decoration is not much used with PVC mouldings.
22.1.3 Hot Foil Stamping
This method is also known as 'hot foil marking', and sometimes

referred to as 'hot stamping', 'gold blocking' or 'gold stamping' (as it is
frequently used to produce metallic gold effects), 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 (commonly
a polyester film, typically some 0·5-0·75 mm thick) and in the course
of application is fused onto the surface of the plastics article in the
image area under heat and pressure exerted by a hot die. In most
cases-and invariably where the image is a letter, number, symbol or
the like-it is actually impressed into the surface, after the manner of
an inlay-emboss print. However, other modes of application are also
practised, viz. 'tipping' (in which only a raised pattern on the surface is
marked, to provide a decorative trim), overall 'roll-on' application
(e.g. to provide a simulated patterned-metal or wood-grain finish over
the entire top surface of an extruded profile, a plastics casing, etc.), or
reverse application (to the back of a transparent plastics object or
sheet, for a stereo effect and/or abrasion resistance---e.g. for key
rings, badges, labels, etc.). The image-forming material is carried on
the release tape in the form of a film or foil: * this has given rise to the
common name for the process, although the terminology is rather
loose, and the whole composite tape (see Fig. 22.1) is often referred to
as 'foil'. This material is either an appropriate plastic suitably coloured
A
F
S
R
Fig. 22.1 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.
* For strict definitions of these two terms see Chapter 12, Section 12.2.3(a).
(with heat-resistant and generally fast colourants) or a metal foil

(normally of a mirror-finish aluminium). With metal foils a hot-melt
adhesive layer must be used, appropriate to the surface to be marked,
and a protective layer (often called the 'lacquer'): this is always
transparent, but may be coloured to modify the colour of the
image-forming material~.g. a yellow colouration will produce a gold
effect over an aluminium layer. For hot foil stamping of plasticised
PVC, non-metal image-forming layers and the protective layer must be
formulated to be unaffected by plasticiser migration. The make-up of
tapes for hot foil stamping is shown schematically in Fig. 22.1
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 multicolour 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
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 (plastics bottles are often
inflated to provide support to the wall undergoing decoration by hot
foil stamping). The main advantages of the process are that it is the
only method of true metallic printing on plastics, that inlay-emboss
print effects can be produced on both smooth and irregular surfaces
(and that thus, even if the metal or coloured image should be
removed, a permanent impression remains), that the process is 'dry'
and allows instantaneous colour changes, and that high-quality images
are obtainable without any after-treatment. Microprocessor controls
on the modern equipment regulate dwell times, temperature of
application, and foil feed rate, can effect running adjustments, and
provide displays of error indication and fault diagnosis.
22.1.4 Embossing
(a) General
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 em-
bossed in the hot state (fairly typically at 140°C 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 14). Separate embossing is
also practised with calendered or extruded sheeting, e.g. where only
short runs are involved. The sheeting must be uniformly preheated to
the required temperature, and subsequently cooled evenly with
minimum strain. Other factors being equal, lower surface gloss will be
obtained with a heated embossing roller than with a cool one.
Local surface embossing of PVC products (e.g. for marking pur-
poses) may be carried out, sometimes with a special version of
high-frequency heating equipment incorporating suitably shaped dies.
(b) Embossing of Foamed Sheet Products

Embossing is a major decorating technique for such commercially
important vinyl sheet products incorporating foam layers as ftoor- and
wall-coverings ('cushioned' by virtue of the presence of such layers),
and leathercloths for various kinds of fancy goods, bags, etc. 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 on a substrate (fabric
or paper) and then heating to expand and fuse the printed paste
deposits: however, this technique is a production method, not an
external decorative treatment for a PVC product. Even the other two
main emboss-producing techniques may be considered to span the
borderline between production proper and external surface treat-
ments; however, as they certainly constitute processing for surface
decoration, they have been included in the present section.
MECHANICAL EMBOSSING
Relatively coarse embossing or quilting of PVC foam sheets by the
application of heat and patterned pressure came into practice in the
manufacture of soft upholstery linings. However the object of such
treatment is to structure the material rather than to improve or
decorate its surface (PVC upholstery foam has also been largely
displaced by the cheaper polyurethane). Soft cellular PVC products
with a decorative surface emboss, including paste-produced coatings
on fabrics and paper, are normally embossed by rollers, although in
transfer coating with PVC pastes (see Chapter 18, Section 18.7.3(a»
the paste composition that will form the surface layer of the final
product may be cast onto embossed release paper, ultimately to take
up the emboss pattern. Depending upon the nature of the material and
the emboss, the rollers may be set to a fixed gap, and both be
water-cooled, the surface of the PVC layer being pre-softened by
heating. The conditions must be so regulated that the heat and
pressure do not cause excessive collapse of the cell structure in the
foam layer. The roller-embossing operation may form part of the
production line, and be directly followed by the application of a
surface lacquer coat.
CHEMICAL EMBOSSING
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 action of an activator present in the layer (but
not for its heat-stabilising action if the activator is also the stabiliser),
or for the blowing agent itself, in the sense of reducing its suscep-
tibility to activation: 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
azodicarbonamide (ADA) and-as is normal-a suitable activator is
also present in the PVC composition, trimellitic anhydride or fumaric
acid may, for example, be employed as inhibitors for the activator's
action. Alternatively, the ADA itself may be inhibited against
activation in the printed areas if the print contains a suitable reagent,
e.g. 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
multilevel 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
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. Some variants of the chemical emboss
method were originally patented by Congoleum-Nairn Inc. 7 and
Fisons Industrial Chemicals. 8
22.2 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). Typical examples
are the in-line marking operations on PVC pipes, electrical conduit,
cable coverings, and blow-moulded containers.
Virtually any printing method technically suitable in the particular
conditions may be used for surface marking (including laser and
ink-jet printing) and most methods are in fact represented by the
marking equipment available from commercial suppliers. Spray ap-
plication of an ink or paint via a stencil is also practised, as is laser
marking with the pulsed laser beam impinging on the cut-out of a
suitable stencil (as in the Lasermark system* whereby marks of area
0·010-1 in 2 can be produced). One advantage of this kind of laser
marking is that the method is not sensitive to any surface contamina-
tion in the area of the mark. Local embossing with a heated die is
another marking method.
22.3 PROTECTIVE TREATMENTS
22.3.1 Lacquering
A thin top coat of a lacquer is commonly applied to paste-produced

PVC coatings (e.g. of wall coverings, leathercloth), some calendered
pPVC sheeting, and to other pPVC products, such as articles
rotationally cast or slush-moulded from paste (e.g. toys, PVC skins on
* Lumonics Inc., Kanata, Ontario, Canada.

7(JJ PVC Plastics-Properties, Processing, and Applications
motor-car dashboards or arm-rests). The lacquer may have, or

combine, any of the following functions: increasing resistance to
abrasion and soiling; prevention of plasticiser exudation and/or
volatile loss (manifested, respectively, in surface tackiness and hard-
ening); imparting or reducing surface gloss; modifying surface colour;
imparting special decorative effects (especially when applied over an
emboss-see below). Many commercial lacquers for PVC are dilute
solvent solutions of acrylic or methacrylic polymers, frequently in
conjunction with a vinyl chloride copolymer, e.g. some of the Deckor
lacquers (Scott Bader, UK), or Argutop LG (Argus Chemical, USA
and FRG). Some processors make up their own lacquers: an example
of a basic formulation would be:
VC/VAC copolymer (Ucar VYNS*) 5·O-7·5pbw
Methyl methacrylate polymer 2·5-5.0pbw
Cellulose acetate-butyrate O·2-0·4pbw
Methyl ethyl ketone (MEK) 40pbw
Methyl isobutyl ketone (MIBK) 60pbw
In this formulation, increasing the vinyl copolymer content within the
indicated range will increase the toughness, flexibility and adhesion of
the lacquer coat. The amount of the solvent system in relation to the
polymers may be varied according to the viscosity required for
application and the desired solids content, but the ratio (4: 6) of MEK
to MIBK should be preserved. The cellulose acetate-butyrate imparts
surface slip and counteracts blocking.
Heat- and light-stabilisers may be incorporated in lacquers to
protect the polymer (especially the PVC) components of the lacquer
itself,and also-where required-the PVC substrate. In the latter case
the lacquer may carry extra UV stabiliser if the service conditions of
the product put it at particular risk of photodegradation. Colourants
are also common constituents of the lacquers, as are matting agents
where a matt finish is required. The polymeric components of lacquers
may also be (or include) polymers other than those already men-
tioned, such as polyamides or polyurethanes (cf. e.g. respectively
Argutop LN l060-a high-gloss commercial lacquer, and Argutop
LU).
Keying solvents (e.g. cyclohexanone, tetrahydrofuran) may be
included in the lacquer formulation for better ultimate adhesion to the
* See Chapter 19, Table 19.1.

PVC substrate, but care must be taken that they do not disfigure the
surface or any print that may be present.
Whilst the lacquers have traditionally been solvent-based, aqueous
polyurethane and acrylate systems (colloidal dispersions) are also
available. Two examples are Neo-Rez R-900 (Polyvinyl Chemical
Industries Inc., USA) and Laqua WB 240 (Bee Chemical Co., USA).
Lacquers are usually applied to individual articles (e.g. mOUldings)
by spraying, and to continuous sheet materials by an engraved
(gravure) roller or by doctor knife. Special effects may be achieved on
embossed surfaces if the colour of the lacquer is different from that of
the substrate. 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 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) 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 'antique-
ing' or 'antique finish'.
It may be noted that the 'breathability' of a cellular leathercloth
may be impaired by the lacquer coating.
22.3.2 Other Protective Coatings
The barrier properties of PVC (as well as PET) blow-moulded bottles
can be upgraded by the application of a thin coating of PVDC or VDC
copolymer grades supplied for this purpose by several producers of
these polymers and/or of PVC compounds for blow moulding (e.g. the
Ixan* VDC copolymer for treating bottles produced from Benvic*
PVC compounds). Equipment is commercially available for carrying
out the treatment at rates conformable with bottle production rates
(e.g. up to 4000 bottles, of up to 3-litre capacity, can be treated per
hour by the GOM Mark llt machine).
* Solvay.
t Euro-Gom Ltd.
In another kind of protective treatment (not specific to PVC), high

gloss and protection against weathering and aggressive environments
are imparted to plastics surfaces by the application of fluororesins*
from solution; the resulting protective film is subsequently cured by
heating, or at room temperature over a longer time.
22.3.3 Filin and Sheet Lamination
A common example of PVC surface protection by lamination is the

application to flooring-or to a base layer of calendered sheeting in
the production of PVC facing sheets for furniture and panels-of clear
or decorated, tough, top ('wear') layers (see Chapter 14, Sections 14.3
and 14.6).
Calendered PVC sheeting for certain applications, especially out-
doors, can be provided with an adhesive-bonded facing layer of thin
polyvinyl fluoride sheet (e.g. Tedlar). t Good-quality laminates of this
kind have particularly effective resistance to soiling and weathering
when used as, for example, wall coverings or greenhouse sheeting.
22.4 TREATMENT WITH HIGH-ENERGY IONISING

RADIATION (IRRADIATION FOR CROSS-LINKING)
High-energy ionising radiation consists of photons, or of sub-atomic

particles, possessing energies high in comparison with the binding
energy of orbital electrons in atoms. In the context of industrial
irradiation of polymers, the term normally denotes either gamma
radiation from a radioactive source (usually cobalt-60) or a beam of
electrons (beta radiation) produced by an electron accelerator.
22.4.1 Effects of High-Energy Radiation on Essentially Saturated,

Linear Polymers
The principal changes occurring in such polymers, of which PVC is

one, on exposure to high-energy radiation are degradation (through
chain scission), and cross-linking. At moderate (Le. non-destructive)
radiation dose levels, these effects are proportional to the dose. At
such dose levels, a polymer may tend to undergo mainly chain scission
* Lumiflon (leI), originally developed by Asahi Glass Ltd in Japan.

tDu Pont.
or mainly cross-linking, depending on its chemical structure.

Polypropylene, polyethylene terephthalate, andPTFE are examples of
polymers substantially degraded by high-energy radiation. Others,
such as polyethylene or polystyrene, undergo mainly cross-linking.
Polyvinyl chloride is a borderline case: either effect can predominate,
depending on the formulation of the PVC composition concerned, and
on the conditions of treatment. The presence of oxygen can influence
the rate and mode of degradation of a polymer exposed to high-energy
radiation.
For practical industrial purposes, PVC materials (as well as those
based on other polymers) are irradiated with a view to cross-linking as
this upgrades properties important in certain applications.
The degree of cross-linking achieved in a suitable polymer or
polymer-based composition depends on the radiation dose. At rela-
tively low doses, the cross-links formed increase the average size of the
polymer chains, their degree of branching, and hence also the
intermolecular entanglements: this is reflected in improvements in
some bulk properties, as well as in an increase in the viscosity (melt
and solution) of the polymer. With increasing dose level, cross-links
are formed between the enlarged but initially still separate molecules,
resulting in the formation here and there within the material of closed
'meshes' of a three-dimensional network. The portion of the polymer
involved in such networks becomes insoluble in solvents which dissolve
the polymer in normal circumstances. This portion is usually referred
to as the 'gel fraction' (and the remaining, still soluble, portion as the
'sol fraction'). In practical tests, the gel fraction is determined by
solvent extraction of the sol fraction: with PVC the solvent is normally
tetrahydrofuran. 9 ,10 As irradiation is continued to higher dose levels,
the gel fraction can reach unity, i.e. all the polymer will be involved in
the three-dimensional network.
Note: For a linear polymer with no large pendant groups, the

radiation dose theoretically required for first appearance of
gelation (in the absence of cross-linking aids) can be calcu-
lated (under a few reasonable assumptions). The figure
obtained in the calculation ll is approximately 5 Mrad. *
* 1 rad = 100 ergs of energy absorbed per gram of material. In terms of the
Gray (the SI unit of absorbed radiation-see Appendix 2),1 rad = 0·01 Gy and
hence 5 Mrad = 50 kGy.
22.4.2 Irradiation of PVC Products
The radiation treatment is applied to otherwise finished PVC products,

for direct upgrading of their properties.
(a) PVC Compositions for Products Cross-Linkable by High-Energy

Radiation
Ordinary PVC compositions suffer unacceptable degradation on ex-
posure to high-energy radiation: in order to achieve satisfactory
cross-linking (with the attendant improvement in properties) it is
necessary to incorporate in the formulation special additives which
participate in the cross-linking process. These additives are unsatur-
ated compounds capable of polymerising under irradiation, and
believed to knit simultaneously into a three-dimensional network with
the chains of the PVC polymer. 9,10
Note: The presence of such additives reduces the radiation dose

necessary for the desired level of cross-linking both in PVC
and in those polymers in which-as for example in
polyethylene-cross-linking is normally the dominant effect
of irradiation.
A cross-linking additive often used in PVC compositions is tri-

methylolpropane trimethacrylate:
CH3 ·CH2·QCH2·O·C·C = CH2h·

II I
OCH3
Others include other polyfunctional acrylates and methacrylates (e.g.

1,4-butanediol diacrylate), diallyl phthalate (e.g. Bisomer DALP, BP
Chemicals International), triallyl cyanurate, and some proprietary
additives (e.g. Santoset, Monsanto; Sartomer, Ancomer Ltd).
The radiation cross-linking treatment is applied to plasticised PVC
products. The special additives also have some plasticising action
during the production and processing of the composition, and in the
product before irradiation. For this reason they are sometimes
referred to as cross-linkable plasticisers.
The two outline formulations shown in Table 22.1, used by workers
in this field I2 ,13 in developing cross-linkable compositions, illustrate the
make-up of such compositions.
TABLE 22.1
Outline (Development) Formulations for Cross-Linkable Compositions for
Two App6cations
Application Composition Composition
for for
cross-linked cross-linked
PVC shoe PVC cable
soles 12 (phr) insulation 13
Formulation components (phr)
PVC polymer 100 100

Stabiliser system
Main stabiliser 3-6
Epoxidised soyabean oil 3-6
Plasticiser (a phthalate) 70-90b 20-28
Polymeric modifi!!r (nitrile rubber) 25-35
Lubricant system 1-2 1
Cross-linking aide 5-12 17-30
Flame retardant (antimony trioxide) 3
Pigment -0·8
a Lead type.
b A trimellitate substituted for phthalate for applications involving con-
tinuous exposure to elevated temperatures.
e Initially also functioning as secondary plasticiser in processing; may contain
small proportions of inhibitors to prevent polymerisation at processing
temperatures.
(b) Property Improvements in Irradiated PVC Products

The main effects of irradiation treatment of pPVC products are:
increased resistance to heat distortion and abrasion; increased tensile
strength and modulus (and reduced sensitivity of both to temperature
increase); reduced elongation at break; increased hardness; increased
impact resistance (if the cross-linking has not been excessive); reduced
creep; increased resistance to solvents; reduced tear propagation. The
following figures illustrate the general order of modification in some
properties (cross-linked PVC insulation on electric wires, in com-
parison with ordinary PVC insulation of generally similar grade).
Tensile modulus Increased by factors of 2 to 3

Tensile strength Increased by factors of 1·3 to 1· 5
Resistance to abrasive
wear Increased by factors of up to 10
Elongation at break Reduced by factors of 1·5 to 1·8
BS softness Reduced by factors of up to 7
The main application of cross-linked pPVC so far has been in

electric wire insulation. Other uses that have been explored include
flooring, (cross-linked PVC floor tiles have significantly better service
properties l4 ) industrial footwear soling, and heat-shrink tubing.
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)Y Some cross-linked
wire coverings suffer no cut-through after application for 5 min of a
weighted soldering iron at 350°C, and their tensile strength at 150°C
can be about 3 MPa (i.e. matching a Type 5 hard insulation to BS
6747).15
The dose requirement for substantial degrees of property improve-
ment depends on the formulation of the PVC, and in particular on the
nature and the proportion of the cross-linking additive. Other factors
being equal, the extent of cross-linking-as indicated by the mechani-
cal properties and the gel fraction-also increases (for the same
radiation dose) with increasing original molecular weight of the PVC
polymer. 9 As a general illustration, about 6 Mrad may be required to
attain about 0·8 gel fraction in a PVC composition with 15 phr of
trimethylolpropane trimethacrylate.
Note: Two theoretical relationships, pointed out by Charlesby, 11

may be mentioned. Thus, for a random distribution of
molecular weight and the cross-links formed, the dose r (in
Mrads) required for a given reduction of the solubility (s) can
be estimated from a plot of (s + Vs) versus r-l, which should
be a straight line from (s + Vs) = 2 (corresponding to the
dose value rg for commencement of gelation), to (s + Vs) = 0
(at r- 1 = 0). Secondly, the Young's modulus (E) of a
cross-linked polymer is given by the relationship
E, dynes per cm2 = 3pRT(r - ro)G /0·48
where ro is a correction factor (for chain-ends and for the

dose needed to form an incipient network), G is the number
of cross-links formed per 100 eV absorbed, p is the density, R
the gas constant (both in appropriate units), and T the
absolute temperature.
(c) The Irradiation Treatment

The PVC products to be cross-linked by high-energy radiation are
made by the appropriate process (e.g. extrusion coating of a wire) and
then irradiated in the finished form. The radiation source, and the
arrangements for exposing the product, must be such as to ensure the
required depth of penetration and degree of cross-linking. Of the two
kinds of high-energy radiation mentioned at the beginning of this
section, although the radiation from a gamma-ray source like cobalt-60
is more penetrating, an accelerated electron beam is more effective in
terms of dosing rate and energy transfer to the polymeric material
(and hence the overall product throughput). Moreover, with a
radioactive source, more extensive shielding is needed and the
emission is continuous, presenting a constant potential hazard,
whereas with an electron accelerator emission ceases when the
equipment is not in operation. For these reasons the electron beam is
commonly used for industrial cross-linking of polymeric products. In
this treatment, the depth of penetration depends on the accelerator
voltage: with a polymer of unit density it is roughly linear up to about
5 MeV (the highest voltage in common use), as indicated by Fig. 22.2.
Individual plastics articles are usually presented to the beam on a
conveyor. Insulation on a wire, and other continuous-length products
(like tubing or film), are passed through the beam-if necessary
20
E
~ 15
c
.Q
~
~GI 10
a.
....o
Accelerator voltage (MeV)

Fig. 22.2 Electron beam penetration into a polymer of unit density versus
accelerator voltage in the range 0·5-4·5 MeV.
repeatedly, back and forth-by means of a suitable on-and-off winding

arrangement.
A cross-linked 'skin' can be produced on products (such as films for
some packaging and medical applications) by low-penetration treat-
ment with the electron beam, or by contact with plasma.
REFERENCES
1. Satas, D. (Ed.), Plastics Finishing and Decoration. Van Nostrand Rhein-

hold, Wokingham, 1986.
2. Margolis, J. M. (ed.), Decorating Plastics. Carl Hanser Verlag, Munich,
1987.
3. Rogers, M., Plast. Technol., 25(10) (1979) 73-7.
4. Anon, Plast. Technol., 33(5) (1987) 31-5.
5. Titow, W. V., Plast. Technol., 12(8) (1966) 38-40.
6. Frazier, J. F., 36th ANTEC SPE Proceedings, 1978, pp. 212-14.
7. Congoleum-Nairn Inc., US Patents 3293094 and 3293108.
8. Fisons Industrial Chemicals, US Patent 3464 934.
9. Schuler, M. Th., Kunststoffe-Plastics, 22(11) (1975) 13-21.
10. Bowmer, T. N., Hellman, M. Y. & Vroom, W. I., J. Appl. Polym. Sci.,
28 (1983) 2083-92.
11. Charlesby, A. In Polymer Science, Vol. 2, ed. A. D. Jenkins. North-
Holland Publishing Co., Amsterdam and London, 1972, Ch. 23.
12. Bloom, L., Plast. Rubb. News, (June 1984) 9-12.
13. Scalco, E. & Moore, W. F., Radiat. Phys. Chem., 21(4) (1983) 389-96.
14. Du Plesis, T. A. & Badenhorst, F., Improvement of PVC floor tiles by
gamma radiation. Paper presented at the 6th International Meeting on
Radiation Processing, Ottawa, Canada, 1987.
15. Matheson, A. F., Electrical Times (5 June 1981).
Section 7
APPLICATIONS OF PVC PRODUCTS, AND

SOME IMPORTANT
APPLICATION-RELATED PROPERTIES
769
CHAPTER 23
Miscellaneous PVC Products and

Their Applications
The main types of PVC products, representing substantial production

volumes, are discussed in Chapter 12. Many such products are also
mentioned in other parts of the book. It is the purpose of the present
chapter to indicate briefly something of the diversity of PVC applica-
tions, by reference to various other products which represent them,
including some less widely known.
23.1 CELLULAR PVC PRODUCTS
With the relatively minor exception of porous sheets used for example
as battery separators (cf. Section 17.3 of Chapter 17), the bulk of
cellular PVC products is produced by foaming techniques: the three
principal ones are 'chemical' blowing by means of blowing agents
incorporated in the PVC composition (cf. Chapter 9, Section 9.1),
dispersed-gas blowing and mechanical frothing. In dispersed-gas blow-
ing, an inert gas is dispersed in a plastisol (usually at reduced
temperature and increased pressure) and then allowed to expand at
the appropriate stage in processing to produce uniform cells in the
finally fused and cooled pPVC composition. In mechanical frothing
(gas entrainment), a plastisol is expanded into a stable 'wet' foam
(froth) by vigorous mechanical agitation. The gas so entrained is
normally air. The foam is usually spread on a support (release paper,
or fabric for a permanent cellular PVC coating), then the foamed
plastisol is heat-fused, and solidified by cooling. In both the gas-
entrainment and mechanical frothing processes, surface-active agents
771
are incorporated in the plastisol to act as foaming aids, foam

stabilisers, and cell-control agents.
Density is an important characteristic of expanded PVC (as well as
other plastics) materials, partly because it correlates with several of
their mechanical and other properties. Three density ranges are
commonly distinguished: although they are not rigidly defined, the
following figures can serve as a rough general guide:
Mgm- 3
or
kgm- 3 gcm- 3 lb /1- 3
Low-density range 10-50 0·01-0·05 0·6-3
Medium-density range 50-350 0·05-0·35 3-21
High-density range 350-900 0·35-0·90 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.
Various typical expanded products are listed in Table 23.1. There
are numerous methods and processes for the industrial production of
PVC foams and cellular mouldings. 1
A detailed discussion of formulations for expanded PVC products,
of some industrial processes, and of product properties can be found in
Ref. 1. An unusual development is represented by Divinycell Rep
(Diab-Barracuda, Sweden): this is a rigid, fine-cell foam based on
very high-molecular-weight PVC polymer, and reinforced with a
cross-linked aromatic polyamide. Uses include load-bearing sandwich
structures and buoyancy parts in underwater engineering applications.
Major standards concerned specifically with expanded pVC mate-
23 Miscellaneous PVC Products 773
TABLE 23.1
Some Expanded PVC products
Method type Starting Typical Examples

composition characteristics
of cellular
material
produced
Chemically blown foams a
Free blowing:
Direct Plastisol Largely closed- Carpet and
expansion cell at flooring
medium underlays;
densities, embossed wall
largely open- coverings;
cell at low cellular
densities leathercloth;
upholstery;
cushioning
Cavity filling Plastisol Soft. Low-to- Foam filling for
medium arm rests,
density, handlebar
mainly open- grips, dolls and
cell, but soft toys
mixed
open/ closed
in some
products
Sheet blowing Sheet Largely closed- Foam flooring;
(calendered cell at cellular
or extruded) medium leathercloth.
incorporating densities, Foamed sheets
blowing agent largely open- maybe
(not activated cell at low laminated with
in sheet densities fabric and
production) topped with
dense skin layer
Pressure blowing Plastisol Semi-rigid or Shock-absorbent
(in closed soft, low-to- material for
mouldsb ) medium crash-pads and
density, helmets, life-
mainly closed- jackets,
cell packaging
Plastisol Rigid, low or Buoyancy blocks;
incorporating medium fishing floats;
volatile or density, sandwich panel
cross-linking closed-cell cores (thermal
plasticisers or acoustic
insulation
layer)
(continued)
TABLE 23.1-contd.
Method type Starting Typical Examples

composition characteristics
of cellular
material
produced
Blowing in Extrusion Medium density, Porous irrigation
extrusion compounds mainly open- tubing; filtration
cell (tubes and
sheets)
Medium-to-high Electrical cable
density, mainly sheathing;
closed-cell pipes; foamed
profiles
Blowing in Moulding Rigid or Shoe, sandal, and
injection compounds flexible, slipper soles;
moulding medium-to- rigid structural
high density, foam mouldings
mixed (largely
closed) cell
structure
Foams produced by gas entrainment
Dispersion of Plastisol Typically low-to- Some kinds of
gas in PVC medium foam-backed
composition density, mainly clothing; travel
open cell in and fancy
most cases goods;
embossed
quilting
Foams produced by mechanical frothing
Entrainment of Plastisol Wide density Cellular
air by range; soft, leathercloth;
mechanical mainly open- carpet backings;
agitation cell, but mixed garment
open/ closed padding
structure in
some products
a Starting composition incorporates a chemical blowing agent.
b Expansion may be completed by post-heating in some cases.
rials are not very numerous. They include the following (most titles
shortened).
Rigid PVC:
BS 3869:1965. Rigid expanded PVC for thermal insulation purposes
and building applications.
ASTM F891-88a. Coextruded PVC pipe with a cellular core.
TABLE 23.2
Standard Specifications for Some Properties of CeUuIar Plastics
Test or property specified Relevant standard
ISO BS ASTM DIN
Rigid cellular materials

Apparent density 845-1977" 4370:Part 1:1988:Method 2 D 1622-88 53420 (1978)
Compression properties 844-1978" 4370:Part 1:1988:Method 3 D 1621-73 (1979) 53421 (1984)
N.B. Compressive creep: N.B. Creep of package N.B. Compressive creep
7616-1986 and 7850-1986 cushioning:D 2221-68 under heat: 53425 (1965)
(1984)
Shear properties 1922-1981 4370:Part 2:1973:Method 6 C 273-61 (1980) 53427 (1986)
(Sandwich panels)
Tensile properties 1926-1979 (1986) 4370:Part 2: 1973: Method 9 D 1623-78 53430 (1975)
Bending or flexure 1209-1976" 4370:Part 1: 1988:Method 4 C 393-62 (1980) 53423 (1975)
(Cross-breaking strength) (Sandwich panels)
Linear dimensions 1923-1981 . 4370:Part 1:1988:Method 1
Water absorption 2896-1974 D 2842-69 (1975) 53433 (1983)
Thermal conductivity 2581-1975 4370:Part 2:1973:Method 7 C 177-76 18 164--Part 1 (1979)
(Thermal insulation spec.)
Friability 4370:Part 3:1988:Method 12 C421-83
(Tumbling test)
Dimensional stability 2796-1986 4370:Part 1:1988:Method 5 53424 (1978)
(Cf. also TR 2799-1978)
Closed-ceU content 4590-1981 4370:Part 2: 1973:Method 10 D 2856-87 (Air
pyknometer method)
Flexible cellular materials
Apparent density 4443:Part 1: 1988:Method 2
Compression set 1856-1980 4443:Part 1:1988:Method 6 53572 (1986)
Compression stress/strain 3386/1-1986 (Low- 4443:Part 1:1988:Method 5 53577 (1986)b
characteristics density materials)
3386/2-1984 (High
(continued)
density materials)
TABLE 23.2-contd.
Tensile properties 1798-1983 4443:Part 1:1988:Method 3 53571 (1986)

Indentation hardness 2439-1981 (1986) 4443:Part 2:1988:Method 7 53576 (1984)'
Dynamic fatigue (by constant
load pounding) 3385-1972 4443:Part 5:1980 53574 (1977)
Dynamic cushioning 4651-1988 4443:Part 3:1988:Method 9 D 1596-78 (1983) DIN ISO 4651 (1986)
performance (Package cushioning
materials)
Ageing tests 2440-1983 4443:Part 4:1987:Method 12 53578 (1985)
4443:Part 4:1987:Method 11
(Humidity/heat ageing)
Air flow value 7231-1984 4443:Part 6:1980:Method 16
Measurement of dimensions 4443:Part 1:1988:Method 1 53570 (1981)
Tear strength 4443:Part 6:1980:Method 15
Creep 4443:Part 3:1988:Method 8
Cell count 4443:Part 1:1988:Method 4
Preparation of water 4443:Part 6:1980:Method 14
extract
a Currently under revision.

b Compressibility test on profiles: DIN 53 579 Part 2 (1985).
C Indentation hardness test on shaped parts: DIN 53579 Part 1 (1985).
Flexible PVC (not including cellular coatings on fabrics):

ISO 6453-1985. Specification for PVC foam sheeting.
BS 4023:1975 (1984). Flexible cellular PVC sheeting.
ASTM D 1565-81 (1986). Specification for flexible open-cell foam of
vinyl chloride polymers and copolymers.
ASTM D 1667-76 (1986). Specification for flexible closed-cell foam
of vinyl chloride polymers and copolymers.
Many of the national and international test and material specifica-

tions for cellular plastics in general are also applicable-where
relevant-to cellular PVC. Most such specifications are indicated in
Table 23.2.
23.2 PVC FIBRES AND FIBRE PRODUCTS
Apart from the vinyl chloride copolymer fibres mentioned in Chapter

3, homopolymer fibres are also produced. Some examples of commer-
cial products are: Rhovylon (continuous filament and staple fibre,
originally produced by Societe Rhovyl SA, * France) and other fibres
from the same makers, e.g. Thermovyl, Fibravyl, Rectractyl; Movil
(Montecatini, Italy); and the Wacker MP VC/VAC fibre (for the
paper, textile, and non-woven industries).
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. Some of the fibres (e.g. Rhovylon) are used in
certain kinds of thermal underwear and sportswear.
Blends with other fibres are also used: one example is the use of
shrinkable Rectractyl fibre yarns in cloque fabrics, where retraction
under heating of this PVC yarn produces special effects. The use of
fibres of VC/VAC copolymer modified with maleic acid has also been
proposed2 in heat-sealable thermoplastic papers to improve fibrilla-
tion, sheet formation and sealing. PVC fabrics find application inter
alia in fire-resistant upholstery (used for example in the Erasme Hall
of the Council of Europe, Strasbourg, in the liner QE2, and the
French TGV high-speed train).
* Now part of Rhone-Poulenc Textiles (state-owned since the early 1980s).

23.3 LAMINATES OR LAMINATE-LIKE PRODUCTS

INVOLVING PVC LAYERS
Noteworthy among products of this kind are the following examples.
(i) PVC-sheet-faced sandwich panels with insulant (non-PVC)

cores for some constructional and partitioning applications.
(ii) PVC/PE/fluoropolymer film for some types of medical blister
packs.
(iii) PVC/PE laminate sheet for vacuum forming (inter alia into
containers-topped with metal foil-for tea-bags: developed
by Borden (UK) Thermoforming group).
(iv) Reinforced or laminated pPVC sheeting for signs, including
translucent sheeting reinforced with polyester-fibre scrim (e.g.
Panaflex, 3M Co., USA) which can also be used for canopies
and awnings; and flexible sheeting laminated each side with
thin PVF (Tedlar, Du Pont) film (e.g. SignOflex-Plus, ABC
Extrusion Co., USA).
(v) Vacuum-metallised PVC films (e.g. as produced by Deuvac
Metallisierung, FRG).
(vi) Wire for the production of chain-link fencing, and for gabions,
extrusion-coated with PVC compounds.
(vii) PVC-coated non-woven fabric made of lead fibres, for use as
acoustic insulation (Toray, Japan, and Snia Fibre, Italy).
(viii) PVC/metal sheet laminates. As with 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
(examples, respectively, are Hishi-metal-Mitsubishi Plastics
Industries Ltd, Japan, and Bondene-Storey Brothers, UK).
Applications of the former include electronic equipment cas-
ings, electric cookers, refrigerators, lighting apparatus and
show cases: the PVC/aluminium sheeting is also used for
electronic equipment casings, interior and exterior signs and
display panels, and road-tunnel linings.
23.4 SHEET·TYPE INTERIOR WALL·COVERINGS

The salient features of PVC wall-coverings-whether of the panel type
(including various thermoformed panels) or wallpapers-are distinc-
tive appearance (with a variety of possible decorative effects), durabi-
lity and washability (in all but a few cases, such as flocked or
metallised finishes on some PVC wallpapers).
PVC sheeting and panels for interior wall cladding and decoration
are mentioned in Chapters 17 and 21 (Sections 17.2.2 and 21.1
respectively) .
Most PVC wallpapers consist of clear vinyl coatings on paper and
cotton fabric bases, but base materials such as woven acrylics, hessian,
and even silk, are also occasionally encountered. Further variants
include wallpapers with embossed PVC layers, which mayor may not
be cellular. Top coatings are often applied over the main PVC layer.
23.5 POWDER COATINGS AND MOULDINGS

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)3.4 and electrostatic deposi-
tion (electrostatic spraying), 3--5 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
normally used, commonly in the form of dry-blends, but melt-
compounded compositions-comminuted 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 coatings
techniques.
The main considerations in the two techniques, brought out well in
Newton's summary,3 may be listed as shown in Table 23.3.
* For example in the UK, Vyfiex 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 220-260°C to fuse the
powder deposit.
TABLE 23.3
Comparison of Electrostatic Deposition and F1uidised-Bed Dipping
Techniques
Electrostatic Fluidised-bed
deposition dipping
Typical coating 0·075-0·2 0·25-0·75
thickness, mm (Tends to be self- (Not self-limiting)
limiting)
Preferred particle 30-80 Over 100
size of powder, (Oversize particles (Some oversize particles
11 m tend to accumulate on acceptable)
recirculation)
Pre-heating of part Not normally necessary Required
to be coated (powder coating held
by electrostatic
attraction until
sintered)
Automation Readily effected with Possible, but needs careful
suitable equipment design
The useful features of powder coating in comparison with other

methods are the 'dry' nature of the process (absence of liquid media
such as 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 deter-
gent solutions, for coating dishwasher baskets), metal furniture and
vehicle seat frames, metal pipework, road signs, railings and posts of
balustrading (including those required to withstand heavy marine
weathering conditions, as in lighthouses l ). An interesting application is
a clear coating on laboratory glassware6 to retain 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 ftuidised-bed technique.
Mouldings can be produced with PVC powders by methods analo-
gous to those used with PVC pastes (see Chapter 18, Section 18.7),
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' when practised with a powder composition)
employing a fluidised bed.
23.6 MEDICAL APPLICATIONS
Medical grades of PVC, and polystyrene, are the two plastics most
widely used in medical devices.
Plasticised PVC compositions are the materials of many kinds of
tubing for medical uses (cf. Section 12.3.4 of Chapter 12), blood
collection and transfusion sets (as well as bags and tubing for saline
drips), stopcocks, aprons, and sheeting. Whilst general-purpose plas-
ticisers are used in many of these products, non-migratory, extraction-
resistant ones are preferable where contact with blood is involved, as
cases are on record of DOP being leached out (e.g. from PVC
blood-storage containers7) and subsequently detected in patients'
bodies after repeated, extensive transfusions. Recent developments
include pPVC compositions with improved resistance to body fluids,
and ones opaque to X-rays (to enable catheters and tubing to be
traced after insertion into the body).
Bags fabricated from clear, flexible PVC sheeting have been used
for enclosing wounded limbs to provide an environment controlled in
terms of bacterial content, humidity, temperature and pressure, thus
creating suitable conditions for healing without ordinary dressing so
that the wound can be observed directly through the transparent bag
(cf. the Sterishield bags, developed in the UK by the Biomedical
Research and Development Unit of the Department of Health and
Social Security).
Thermoformed PVC trays, designed specially to accommodate the
contents (which may be sealed-in with a transparent PVC film), are
available with single-use medical devices, e.g. anaesthetic hand-
ventilation circuit assemblies for chest operations.
Rigid, transparent compositions based on vinyl chloride/propylene
copolymers have been used for moulding and extrusion of components
for medical applications.
Flexible PVC film tapes with a pressure-sensitive adhesive layer are
widely used as water-resistant sticking plasters.
23.7 APPLICATIONS IN MOTOR-CARS
Apart from the wide general use of pPVC as insulation on electrical

wiring, the usage of PVC in motor-cars tends to vary somewhat from
country to country and with different makes and different models of
the same make.
Note: As an example, circa 1986 the VW Golf had a total plastics
content of about 59 kg, in which PVC accounted for the
highest proportion (about 18%). The other plastics present in
substantial amounts were: polyurethane (15%), poly-
propylene (13%), polyethylene (13%), ABS (12%) and
modified polyphenylene oxide (9%).
With the decline in popularity of PVC leathercloth upholstery for
motor vehicles (although it is still used in many 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 material), 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 (cf. Chapter 18, Section 18.7.1). In some models the steering
wheel and gear-lever knob may also be PVC-covered.
In some of the products just mentioned, in which a layer of PVC is
in intimate contact with flexible or semi-flexible polyurethane foam,
the PVC can sometimes suffer discolouration or staining, and hard-
ening and distortion accompanied by embrittlement in severe cases.
Development of these faults may be promoted by exposure to high
temperatures (such as arise in car interiors in hot, sunny climates).
Products such as crash-pads, in which the polyurethane composition
has been foamed in situ against a PVC skin, tend to be particularly
prone to the faults. The hardening and any associated distortion can
be due to migration of plasticiser from the PVC into the foam
(although this should not occur with PVC compositions properly
formulated with migration-resistant plasticisers). The staining can be
caused, and the embrittlement promoted, by penetration into the PVC
of certain components of the foam composition: thus some of the
amine catalysts used in these compositions can act as staining agents,
especially at elevated temperatures, and can also promote degradation
of the PVC material by catalysing dehydrochlorination of the PVC
polymer. Useful discussions of these phenomena have been published
by Wilson et al. 8 and by Zimmerman & Austin. 9
PVC paste compositions are used as underseals and for corrosion

protection in wheel arches and other vulnerable areas.
23.8 FOOTWEAR APPLICATIONS
Microcellular soles moulded from pPVC or-for more exacting

applications-from PVC blends (especially with nitrile rubber, but also
with polyurethane and E/VAC compositions) have been in use for a
considerable time,lO as have PVC shoe linings (expanded PVC-coated
non-wovens and solid non-wovens l l ), and PVC uppers12 in some types
of footwear. PVC's main competitors in some soling applications
(albeit at a cost premium in most cases) are polyurethane, some
thermoplastic rubbers, natural rubber, and E/VAC. Complete units
(boots, shoes, sandals) are produced from PVC compositions by
injection moulding. Some relevant standards (for PVC industrial
boots) are: ISO 4643, BS 6159:Part 1 and DIN 4843 (general); ISO
6110 (chemical-resistant); ISO 6112 (resistant to oils and fats).
23.9 SOME SPECIAL, UNUSUAL OR MINOR

PRODUCTS AND APPLICATIONS
Furniture frames: Mainly for outdoor use; produced from rigid PVC
pipe, specially formulated for impact and weathering resistance
(commercial compounds available, e.g. Conoeo RP 100; Geon
BOx 3).
Baby pants: Some still produced from thin pPVC sheeting formu-
lated for resistance to hardening by loss of plasticiser (especially by
migration in wear, and leaching in washing), staining resistance, tear
resistance, and good weldability.
Simulated skin: Originally developed (by the Stores and Clothing

R&D Establishment of the UK Ministry of Defence) for the
evaluation of protection afforded by clothing against molten metal. 13
The formulation is given as (phr): PVC resin 100; di-a-naphthyl
phthalate 26; TIP 13·75; chlorinated paraffin 12·5; white pigment 10;
lead tartrate 1·75; lead stearate 1·0; calcium stearate 0·75.
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 .14,15
Ball valves: All-PVC (for use in food and chemical industries);

PVC/polyacetal combinations (for use with water and other non-
corrosive liquids); PVC/PTFE combination (housing, threaded bushes
and body ends injection-moulded in uPVC; ball seal, PTFE-Georg
Fischer, FRG).
Industrial duckboards: Embossed or smooth heavy duckboards for

industrial premises, trucks for animal transport, milking sheds and the
like (e.g. the Heron duckboard, Plastic Extruders Ltd, UK). Softer,
hollow-section version also produced (for cushioning effect on
worktops).
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-to provide a robust,
wear-resistant surface with playing characteristics similar to a medium-
to-fast grass pitch. 1
Self-adhesive marking film, lettering, symbols, and decorative

designs: e.g. Scotch-Cal (3M Co., USA); Scotch Light (reflective vinyl
sheeting) (3M Co., USA);16 Fascal 900 (Fasson, UK).
Packing materials for cooling towers: Claimed to offer substantial

savings over conventional materials. Two examples are: Munter C1019
modular PVC packing material (Davenport Engineering, UK) and
uPVC honeycomb packs bonded with adhesive (Hamon Sobelco,
UK).
Protective sheath for hydrophones: Specially formulated PVC tub-

ing 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. 1 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 seawater, and retain its properties at near-zero temperatures (for
use in the North Sea and other cold waters).
Various minor applications and products: 1 These include the

following.
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 radioactivity, poison, flammable material, and other
hazards.
Rug and mat underlays, including special surface-grip and dust-
capturing kinds.
Moulded tyres for model cars.
Ear-protection pads covered with flexible PVc.
Decoy dummy aircraft fabricated in PVC (some equipped with radar
reflectors for correct response).
Safety goggles, moulded in high-clarity PVC compound (Welvic
X16/909; ICI).
Composting bins for garden-use, made of interlocking, perforated
rigid PVC profiles.
Extruded, fluted PVC curtain rods covered (by an in-line operation
during production) with vacuum-metallised polyethylene terephthalate
sheet.
Erasers (for pencil and ink-a successful application of suitably
formulated, filled pPVC compositions).
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 thermoplastics, including PVC (Nor-Core;
Norfield Corp., Conn., USA).
Cellular PVC monofilament has been used as the bristles in
rough-duty brushes.
PVC gasket, moulded in situ around a sidelight (the window being
subsequently bonded directly to the body of the car) is a feature of the
Rover 800 motor-car model.
REFERENCES

2. Morse, E. A., (Assignor to Personal Products Corp.), US Patent 2 899
351.
3. Newton, D. S., Plast. Rubb. Int., 3(5) (1978) 203-6.

5. Cross, U., Chern. Britain, 17(1)(1981) 24-6.
6. Anon., Eur. Plast. News, 9(7) (1982) 29.
7. McHattie, G. V., General aspects of use of polymers in biomedical
applications. Paper presented at the Symposium on Polymers in Biomedi-
cal Applications, Brunei University, 2 May 1974.
8. Wilson, A. S., Bowley, H. J. & Gerrard, D. L., Plast. Rubb. Int., 13(1)
(1988) 23-6.
9. Zimmerman, R L. & Austin, T. H., J. Cell. Plast., 24(5) (1988) 256-65.
10. Bloom, L. I., BBSI J., (Jan./Feb. 1977) 214-20.
11. Anon., Text. Horizons, 5(12) (1985) 45-7.
12. Pettit, D., Plast. Rubb. Int., 6(5) (1981) 205-10.
13. Metha, P. N. & Willerton, K., Text. Inst. Ind., 15(10) (1977) 334-7.
14. Bloch, R, Finkelstein, A., Kedem, O. & Vofsi, D., Ind. Engng Chern.:
Process Design Develop., 6 (1967) 231.
15. Vofsi, D., Kedem, 0., Bloch, R & Marian, S., J. Inorg. Nucl. Chern., 31
(1969) 2631-4.
16. Smoluk, G., Mod. Plast. int., 16(5) (1986) 37-8.
CHAPTER 24
PVC Properties of Special Significance in Some

Important Usage Contexts
The properties briefly reviewed in this chapter are the principal

mechanical properties, resistance to environmental stress cracking and
crazing, some electrical properties, properties of special interest for
outdoor service, properties relevant to barrier applications, some
health-hazard aspects of PVC, and those aspects of flammability and
smoke emission which are not dealt with in Chapter 9.
24.1 MECHANICAL AND RELATED PROPERTIES
24.1.1 Principal Mechanical Properties
The practical importance of a particular property or group of

properties falling under this heading depends in a very substantial
measure upon the application for which the given PVC material is
intended. To the extent to which valid generalisations can be made,
tensile strength and extensibility may perhaps be singled out as the
mechanical properties most widely significant in all kinds of PVC
compositions, both in regard to service performance, and as impor-
tant indicators of material quality in tests and evaluations (including
those involved in formulation development and in investigations of
material deterioration or faults). The relevant elastic moduli are also
significant not only in rigid compositions but in many flexible ones in
which the value of the secant modulus at 100% extension-commonly
known as the '100% modulus'-is a property widely measured and
quoted as a quality index.
Impact resistance and flexural strength are properties significant in
engineering and related applications of rigid PVC, along with
787
resistance to creep and fatigue-the two long-term properties most

important in many such applications. Fatigue resistance is also
required in some plasticised PVC materials, especially those that, like
for example coatings on fabrics, may regularly experience repeated
flexing in service. Other properties particularly significant in many
pPVC compositions are the degree of hardness, tear resistance, and
bursting strength (which is often used as the main index of the strength
of flexible-PVC coatings on fabrics).
The principal mechanical properties of PVC materials are strongly
featured, in their various aspects, in the relevant parts of a number of
chapters in this book. Most are also listed, defined, and illustrated by
typical values, in Appendix 1. As is well known, the properties of PVC
products-in common with those made from other plastics-are not
solely dependent on the material properties, but can also be strongly
influenced by the product design and the processing conditions. In the
latter respect, factors particularly detrimental to PVC include any
shortcomings in the interdispersion of formulation components, in-
complete homogenisation and fusion of the composition, and any
excessive heat history or actual incipient degradation induced by
processing.
24.1.2 Environmental Stress Cracking and Crazing
The abbreviation 'ESC' is very often used for either of these closely
related kinds of failure. Plasticised PVC is not normally susceptible to
ESC. Unplasticised PVC can be, albeit that cases are not very
common or frequent: two kinds of uPVC products which may
occasionally suffer environmental stress cracking or crazing in regular
service are gas-distribution pipes, and blow-moulded bottles for
packaging certain oils (d. Section 15.5.2 of Chapter 15).
Cracking of various materials, and the typical appearance of a crack,
are matters familiar to virtually everyone. Cracks typically resulting
from the environmental stress cracking of plastics are wedge-shaped,
and may range in size from hair-cracks to large discontinuities,
depending on the material and conditions.
Crazing may be thought of as a form of incomplete cracking in
which the local stress does not produce an open crack, but attenuates
the polymeric material in the stressed region with the resulting
formation of microvoids. Hence a craze may be defined (after
Kambour l ) as a thin, plate-like region containing apparently con-
24 PVC Properties of Special Significance 789
tinuous but in fact microcellular material, usually oriented, intercon-

nected 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. 1,2 Thus crazes constitute regions of comparative weakness in
a plastic. Because of their microcellular structure they usually appear
opaque, especially in a transparent material.
The cardinal feature of ESC is that it is promoted by contact with an
'active environment', i.e. a cracking or crazing agent (which may be a
gas, vapour, liquid or semi-liquid, e.g. a grease), either entirely in the
absence of an externally imposed stress, or at external stress levels
substantially below the normal short-term yield strength of the
material in air. In practice, the stresses responsible-jointly with an
'active environment'-for the onset of ESC may be internal, or
external, or a combination of the two.
Internal stress may arise from any of the following causes.
(i) differential cooling of the plastic in the final stages of moulding
(thermally-induced moulding stresses);
(ii) molecular orientation, with or without crystallization, 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 ESC 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 liquids), strongly active as
cracking agents for certain glassy polymers, can promote ESC under a
stress two orders lower than the minimum cracking or crazing stress in
air at the same temperature. 2
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
defined3 as that minimum strain at which under a particular set of

conditions stress cracking or crazing is known to start (i.e. below
which it will not normally take place, even after several days in the
particular conditions). The main factors making up the 'set of
conditions' are the 'active environment', the stress, the rate of
straining, and the temperature. Most of the methods used in systema-
tic study of ESC are ultimately concerned with the determination of
critical strain and the associated (critical) stress in the relevant
environments. 4 Practical tests, applied in product quality assessment
or in trouble-shooting investigations, are usually aimed either at
detecting the presence in mOUldings of internal stresses, or at assessing
susceptibility of plastics materials to ESC in particular environments.
In the former case, the moulding is immersed in a liquid known to be a
cracking agent for the plastic concerned: development of cracks or
crazes within a prescribed period shows up the presence of unaccep-
tably high internal stress. 4 In standard methods of the second kind,
plastics specimens are placed under known external stress, and
exposed in this state to the reagent(s) or environments concerned.
Such methods are given in the following major standards (which are
applicable to PVC inter alia, but not specific to it).
ISO 4599-1986. Plastics-Determination of resistance to environ-
mental stress cracking (ESC}-Bent strip method.
mental stress cracking (ESC}-Ball or pin impression method.
Currently under revision.
mental stress cracking (ESC}-Constant tensile stress method.
Currently under revision.
DIN 53449 (1984), Parts 1, 2 and 3, respectively corresponding to
ISO 4600, ISO 6252 and ISO 4599.
A brief discussion of ESC, with some reference to testing and the
presentation of test data, is contained in Subsection 1.3.3: 1976 of BS
4618. Other references relevant to this subject include a brief review
by Titow4 of a large number of methods of determination and study of
ESC, a paper by Wales5 on surface crazing of PVC and other
polymers, and one by Deanin & Hauser6 on ESC phenomena in some
plastics.
The mechanism of ESC in essentially non-crystalline polymers like
PVC is not fully established. The explanation most likely on evidence
available to date is that the cracking agent penetrates to the tips of

microcracks (microvoids) in the surface of the polymeric material
causing local plasticisation sufficient to reduce substantially the
material's stress-resistance at these sites, but not adequate also to
increase significantly the critical strain (which would enable the
material at a crack tip to accommodate the local stress concentration
without crazing or fracture propagation). Another, possibly contribu-
tory, factor may be reduction of the surface energy for craze or crack
formation (whether on the micro or macro scale) when the cracking
agent contacts (wets) the surface.
Flexible PVC is in the rubbery state (i.e. above its effective Tg) at
room temperature: it is thus able to relax sufficiently readily for rapid
dissipation of any internal stresses. It is also relatively highly exten-
sible under external stress, so that its critical strain is correspondingly
high. These are the main reasons why significant plasticised PVC is not
normally subject to ESC.
Under suitable conditions (including sufficiently high contact con-
centration 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 demon-
strated in the laboratory, e.g. for n-hexane and toluene. 7 In an earlier
investigation (by Wolf,8 in The Netherlands) the appearance of
hair-cracks in uPVC pipe conveying natural gas was identified as
environmental stress cracking promoted by naphthalene found to be
present, in appreciable concentration, in the gas concerned. Another
Dutch study, by Wolters,9 showed that ESC can occur in unmodified
uPVC as well as in PVC/CPE pipe materials in contact with
high-calorific gas (or air) containing relatively low volume percentages
of benzene, toluene or xylene. The effect was manifested after contact
periods between 300 and 400 h, at strains of 0·73%.0·95% and 1·15%.
Wolters' paper lists many relevant references and describes a
'strained-ring' test method for the determination of ESC resistance of
pipes. A case is also recorded 1o of local cracking (and subsequent
bursting) in service of a section of a 90-mm uPVC high-pressure water
pipe which had been in temporary contact with toluene (through
accidental spillage).
ESC may occasionally occur in PVC bottles containing some oils, or
liquids incorporating certain organic constituents (e.g. turpentine).
The resistance of a bottle compound to such ESC may be tested (on
suitable moulded specimens) by any convenient standard method of
the ISO or DIN specifications mentioned previously, or by some of the

methods listed in Ref. 4. In such tests, the test reagent ('active
environment') should ideally be the actual liquid to be packaged in
the bottles. Otherwise sunflower-seed oil or turpentine may be
standardised on as test reagents. A laboratory test method employing
these reagents is also outlined in Ref. 22 of Chapter 15. In the test,
rods or tapes (0·5-1 cm thick) extruded from the bottle compound
concerned are stressed by bending round a metal mandrel of 15-30 cm
diameter, immersed in this state in the reagent(s), and thereafter
inspected for signs of ESC and tested for any significant drop in impact
resistance.
Some information from early studies of ESC phenomena in uPVC is
contained in a number of papers published up to the early 1970s. 11
24.2 PROPERTIES RELEVANT TO

ELECTRICAL APPLICATIONS
The properties under this heading comprise principally those com-

monly referred to as 'electrical' properties, but certain others are also
relevant: of these the most important are some aspects of resistance to
high temperature, flammability, and smoke evolution in burning.

In the context of common, wide-use plastics like PVC, these are the
properties which determine the plastic's performance as an insulant
and/or dielectric. In both these respects the performance is the result
of the combined effects of several material characteristics, each of
which is fairly readily assessed, in quantitative terms, by a practical,
standard test. Thus a plastic's electrical properties are not, strictly
speaking, basic properties of the·material, but rather manifestations of
the material's reactions to externally applied electrical forces. How-
ever, these manifestations are ultimately dependent on the electronic,
atomic and molecular make-up of the material. Because of this, the
electrical properties are also influenced by the presence, nature,
amount, and distribution of additives, impurities, or contaminants
(including absorbed moisture).
The following properties are instrumental in the electrical perfor-
mance of a plastics material (see Appendix 1 for relevant standards,
and property values typical for PVC).
(i) Resistivity (volume and surface). This is highly important in

insulation for conductors carrying direct current.
(ii) Electrical strength, closely related to dielectric strength.
(iii) Permittivity, also known as dielectric constant.
(iv) Loss tangent (dissipation factor, power factor). Together with
permittivity this is of prime importance in insulation for
conductors carrying alternating current.
(v) Tracking, are, and surface-discharge resistance.
To perform well in insulant/dielectric applications, a plastics material
should have high resistivity and electric strength, low permittivity and
power factor, and high resistance to tracking, arcing and surface
discharge. Moreover, these properties should remain substantially
constant over a wide range of temperatures, humidities, and current
frequencies.
Table 24.1 shows a comparison of some electrical properties of four
plastics widely used in electrical applications. A fifth (polyamide 6.6)
has been included in the table to indicate, by contrast, the property
differences which limit its applicability in this field.
pPVC compositions are extensively used as electric wire and cable
coverings. Some of the main application areas are mentioned in
Section 12.3.1 of Chapter 12. As also mentioned in that section,
polyethylene is preferred for very-high-voltage cables (above 10 kV)
where high electric-breakdown resistance is required, and high-
frequency cables for which insulation with low dielectric loss is
cardinally important.
Several major standards relevant to the use of PVC in cables are
listed in Table 12.7 of Chapter 12. Some others concerned with
electrical applications of PVC are given in Table 24.2 here. Some
useful general information on the properties of plastics which, like
PVC, are insulant/dielectrics can be found in Ref. 12.
24.2.2 Other Relevant Properties
Flammability and smoke emission are important considerations in

many applications of electric wires and cables. Whilst the flammability
of PVC polymer is inherently low (cf. Chapter 9, Section 9.2, and
Section 24.6 below), the fact that even 'smoke-retarded' PVC
compositions release some hydrogen chloride on burning has been an
important factor in an increasing swing to other, halogen-free cable
~
TABLE 24.1 '"tI

Some Typical Electrical Property Values of Plastics Materials Widely Used in Electrical Applications" ~
'"tI
Property Test specification uPVC pPVC LDPE PTFE Polyamide Fi
~.
and units 6·6a
I
Resistivity ~
_10 16
.g
Volume DIN 53482, ohm cm 1012_10 15 >10 17 >1018 -1012
~.
1013_1014 101!_1O12 _10 14
...'"
Surface DIN 53482, ohm _10 17 _10 10
Dielectric strength ASTM D149, kV mil-I 200-400 150-300 >700 -500 -400
.~
Permittivity ~
<:>
At 50Hz DIN 53483 3·3-3·6 4·5-8·5 -2·4 <2·1 -8 '~"'
At 106 Hz DIN 53483 2·9-3·1 3·5-4·5 -2·4 <2·1 -4 ~.
Loss tangent (tan b)
I:>
At 50Hz DIN 53483 -0·011 -0·08 2·4 x 10- 4 <2 X 10- 4 -0·14 ;0
I:>..
At 106 Hz DIN 53483 -0·015 -0·12 2·0 x 10- 4 <2 X 10- 4 -0·08 ~
Tracking resistance DIN 53480, Levels KB and KC -600 >600 >600 >600 ~
a Data for polyamide 6.6 (a plastic not in wide use for electrical insulation) have been included to illustrate the
e5·
significant differences in the relevant properties. i:l
TABLE 24.2
Standards Relevant to Some Electrical Applications of PVCa

no. -----------------------------------------------
the official title)
1 BS 6004:1984 PVC-insulated, non-armoured cables

for electric power and lighting
2 BS 6231:1981 Specification for PVC-insulated cables
for switchgear and controlgear
wiring
3 BS 6346:1987 PVC-insulated cables for electricity
supply
4 BS 6485:1971(77) PVC-covered conductors for overhead
power lines
5 BS 6746C:1969(79) Colour chart for PVC insulation and
sheath of electric cables
6 ASTM D 149-81 Tests for dielectric breakdown voltage
and dielectric strength of electrical
insulating materials at commercial
power frequencies
7 ASTM D 257-78(1983) Tests for DC resistance or conductance
of insulating materials
8 ASTM D 876-84 Testing non-rigid PVC tubing used for
electrical insulation
9 ASTM D 1755-81 Specification for PVC resins-Section
4: Electrical conductivity of water
extract (this test distinguishes be-
tween electrical and non-electrical
grades of PVC resins)
10 ASTM D 3150-85 Specification for heat-shrinkable PVC
tubing (cross-linked and non-cross-
linked) for electrical insulation
11 BS 2782:Part 2 Test methods for the electrical pro-
perties of plastics
12 DIN Handbook 18 Plastics I-Mechanical, thermal and
electrical properties
a Some specifications concerned with the material properties of PVC

cable coverings are listed in Table 12.7 of Chapter 12.
coverings in recent years (cf. also Section 12.3.1 of Chapter 12).

Flammability tests relevant to PVC cable and wire coverings are
referred to in Section 24.6 of this Chapter.
Various aspects of resistance to heat and to damage or distortion in
the hot state, jointly make up a set of requirements important in
connection with many service circumstances of cable and wire

coverings. Apart from the regular maximum operating temperature of
the conductor, for which a covering is normally rated [cf. Section
12.3.1(b) of Chapter 12], excessive heat may be encountered as a
result of such events as conductor overheating, short-circuits, or
contact with hot objects (e.g. soldering irons), and the covering may
experience distorting forces while in the hot state. An appropriate
degree of resistance to deterioration, damage, deformation or
penetration (e.g. local outward penetration of the conductor) is
required and needs to be specified. Standard tests are available to
assess these properties, and requirements can be laid down in terms of
the test results. The results also provide some guidance (though not
absolute assurance) on the likely behaviour of the coverings in the
kind of service circumstances to which the tests are relevant.
The following thermal properties of PVC coverings for electric wires
and cables are featured in the major relevant standards, which are
listed in the key below. *
Resistance to accelerated (oven) ageing [1, 2, 3, 4]: Typically for 7

days at 80°C [1,2]' or at still higher temperatures [2,3], with
requirements in terms of maximum permitted weight loss [2] or/and
minimum retention of tensile strength and elongation [1,2,3,4].
Resistance to cracking under heat shock: Test conditions and

requirements-no visible cracks in specimens wound on prescribed
mandrels, after 1 h at 150°C [1,2].
Resistance to hot deformation [2) or distortion [3): At 120°C for 1 h,

under pressure of flat-ended indentor of 9·5 mm [3) or 3·15 mm [2) end
diameter, loaded according to material thickness; requirements-a
maximum permitted percentage difference between the original and
indented material thickness.
* Key: [1] IEC Pub!. 189-1: 1986.

[2] BS 6746:1984 (referring to BS 6469:1984 for all test methods).
[3] ASTM D 1047-87, D 2219-87, D 2220-87.
[4] ASTM D 876-84.
[5] IEC Pub!. 811-1-4 1985.
Resistance to pressure at high temperature [1,2]: At a temperature

appropriate to material rating-e.g. [2] 60, 80, 90 or 95°C-for 4 or
6 h under the edge of an indentor blade loaded according to material
thickness and conductor cross-section; requirement-indentation not
deeper than 50% or original thickness.
Resistance to insulation shrinkage after oven-heating of conductor,

[1]: Shrinkage after 15 min at 150°C should not exceed maximum
appropriate to the insulation material.
Tensile properties after oil immersion [3,4]: Prescribed mlmmum

percentage retention of tensile strength and elongation after immer-
sion in prescribed oil for 4 h at 70°C, or-for Grade C material of
ASTM D 876-at lO5°C).
Cold-bend resistance [1, 2, 3]: No cracking on winding on prescribed

mandrel after at least 4 h at -15°C [1,2], or after 1 h at -lOoC, or
-30°C, or -35°C [3).
Low-temperature elongation [2]: At least 20% elongation of speci-

mens cooled to a test temperature of -15, -20, or -40°C, depending
on material type.
Low-temperature impact resistance [2, 5]: No cracks when specimens

cooled to prescribed temperature are impacted with a falling hammer
of weight increasing with specimen diameter.
Note: It may be noted that the only major standard thermal

stability test for PVC cable and wire coverings is that
prescribed by DIN VDE 0271 (1986), by reference to the
method of DIN VDE 0472, Part 614 (1985) and the require-
ments of DIN VDE 0207, Part 4 (1986). The method is
similar to the Congo Red method (cf. Table 4.5 in Chapter
4), but a universal indicator paper is used. The test tempera-
ture is 200 ± 0·5°C, and the prescribed 'stability times'
(periods elapsing to the time when the indicator colour
change corresponds to pH 3) are 40, 100, or 120 min,
depending on the type of PVC composition.
24.3 PROPERTIES RELEVANT TO SOME EFFECTS

OF THE ENVIRONMENT IN SERVICE
24.3.1 Properties for Outdoor Applications
(a) Stability to Light (UV Resistance)

Various aspects of this subject are discussed in Chapter 4 [Sections
4.1.3, 4.4.2, and 4.9.2(b)]. Those pertaining to weathering are dealt
with in (b) below.
(b) Resistance to Weathering
DEFINmON OF WEATHERING
The term 'weathering' may be used in one of two related senses.
(i) To denote the action on a plastics material of the agents (see
Table 24.3) operating when the material is exposed out of
doors (natural weathering), or in other conditions designed to
have similar effects (artificial weathering, laboratory
weathering), possibly in a shorter time (accelerated weathering).
This meaning is implicit in phrases like 'resistance to weather-
ing' or 'three years' weathering'.
(ii) To designate the effects on the material of the weathering
actions, i.e. the changes produced thereby in the material (as
illustrated for example by the phrase 'weathering in the form of
surface cracking').
FACfORS INSTRUMENTAL IN THE WEATHERING OF PVC

In PVC, the changes symptomatic of natural weathering may result
from the action of a number of factors (d. Table 24.3), the most
important single factor being degradation of the polymer by the UV
component of incident sunlight.
MANIFESTATIONS OF WEATHERING OF PVC

Typical manifestations of significant weathering of PVC (cf. also Table
24.3) are, for uPVC, loss of surface gloss, chalking, * surface cracking
* Defined as 'a dry, chalk-like appearance or deposit on the surface of a

plastic' (ISO 472-1979; BS 1755:Part 1:1982) or 'a powdery residue on the
surface of a material resulting from degradation, or migration of an ingredient,
or both' (ASTM D 883-86b).
TABLE 24.3
Some Factors Instnunental in the Natural Weathering of PVC, and Examples of Their Main Effects
Factor Typical action on PVC material Main observable Remarks

(environmental effects a
agent)
Sunlight Degradation of PVC polymer by UV 1, 2, 3, 4, 5, 6, Direct sunlight is also a source
component of the radiation 7,8 of heat and hence can pro- ~
Fading of colourants mote temperature effects
(see below) ."
~
Temperature Mainly effects of heat and temperature Temperature effects can pro- ~
fluctuation, including: mote and enhance those of ~
(i) Heat degradation 1,2,3,4,5,6,8 other agents .§
(ii) Exudation and volatilisation of '"~.
components (especially plasticisers)
(iii) Physical disruption by local and .::a,
general stresses caused by tempera- ~
~
ture changes §:
Water (including (i) Mechanical erosion of surface 1,3 Effects aggravated by the ac- ~
atmospheric pre- (especially by wind-borne tion of other factors (e.g. aQ'
;:
cipitation, i.e. rain, precipitation) chemical reactions, UV, '5;
snow, hail, vapour, (ii) Leaching out of components (espe- 1,8,9 heat) 2
;:
and condensate) cially plasticisers) "'"
(iii) Mechanical disruption (especially of 1,5,7,8
surface) by repeated absorption and
desorption (which may be aggrav-
ated by presence of absorbent fillers
in the material)
(iv) Chemical effects of pollutants (e.g. 1,2,4,9
acids) dissolved in rain -..J
(continued) ~
8
TABLE 24.3-contd.
~
Factor Typical action on PVC material Main observable Remarks ~

(environmental effects a ::!i!
agent) El
::to
Q
Air Oxidation of reactive sites in PVC poly- 1,2,4,5,6 Effects promoted and en- ~
mer and some other components hanced by those of UV Cl
radiation (instrumental in ~
~.
creating reactive sites, espe- .~
cially double bonds) ~
Atmospheric pollutants (i) Leaching out of components 1,2,3,4,5,6, Effects can be accelerated by Cl
(in vapour, liquid (ii) Chemical reactions with the PVC 8,9,10 heat and sunlight '~"'
and solid particle polymer and possibly other com- '"
~.
form) ponents of the material
(iii) Surface erosion (by wind-borne par- i
ticulate pollutants) ~
~
a 1, Dulling, marring and pitting of surface; 6, reduced extensibility; Q
2, cracking (in severe or advanced cases); 7, surface buckling or rippling; ~.
3, stiffening; 8, distortion (various degrees and kinds);
4, discolouration (e.g. yellowing or darkening); 9, development of microporosity;
5, reduced strength; 10, environmental stress cracking or crazing.
and/or blistering, and deterioration of mechanical properties (in

particular tensile strength and elongation, and impact strength), and
for pPVC the effects mentioned in Section 5.6.8 of Chapter 5, as well
as (especially in the more severe cases), surface cracking and drop in
the tensile strength and elongation.
WAYS OF PROMOTING WEATHERING RESISTANCE OF PVC

The main ways (which should be combined for best results) of
promoting weathering resistance of PVC compositions are: appropri-
ate formulation; care in processing; and avoidance of adventitious
residues and contaminants. In addition, suitably formulated protective
surface layers, usually based on acrylic polymers, may be applied-in
appropriate cases-by coating or co-extrusion (as for example in
co-extrusion 'capping' of PVC profiles for outdoor use). Application of
UV absorbers to the surface of PVC sheeting-by absorption, or in
surface coatings-has also been explored 13 as a way of providing more
cheaply a degree of weathering protection comparable with that
afforded by the conventional dispersion of a greater amount of the
stabiliser throughout the composition.
The role of formulation as a factor in weathering resistance of PVC
compositions is discussed, in its various aspects, in the chapters
dealing with individual formulation components, and it is also con-
sidered in passing elsewhere in the book [cf. e.g. Section 12.2.2(b) of
Chapter 12]. In summary, the following salient points may be recalled.
The PVC polymer should normally be a homopolymer of the highest
practicable molecular weight, although in some compositions graft
copolymers (with EVA) are used for impact resistance. The stabiliser
system plays a crucial part. Depending on the type and service purpose
of the composition, it may be one of the following four types: a
barium/cadmium soap combination (commonly laurates, with high
cadmium content) including an epoxy co-stabiliser and phosphite
chelator (use of this system predominant in Europe, but declining,
partly because of objections to cadmium); a system combining
barium/cadmium and dibasic lead phosphite (successful in Europe;
increasingly preferred to barium/cadmium systems); a tin carboxylate
(notably dibutyltin maleate) system (used mainly in the USA, espe-
cially in siding formulations); a lead system based on dibasic lead
phosphite (used in Europe). UV absorbers (with, in some cases,
selected antioxidants) are beneficial, particularly in transparent com-
positions, when incorporated in addition to the primary stabilisers
(especially with barium/cadmium systems). Impact modifiers for

uPVC compositions should be selected from among the chlorinated
polyethylene, acrylic, and EVA types. Rubbery modifiers, with
unsaturation in the molecule (ABS, MBS), should be avoided, as they
are more prone to photochemical degradation.
Note: PVC/CPE blends incorporating acrylonitrile/styrene/acrylic
ester (ASA) modifiers (e.g. the Stauffer Chemical SCC-l000
series resins) can have softening points of nearly 90°C, which
is high enough to resist 'oil canning' in dark-coloured house
cladding.
The weathering resistance of plasticised compositions is promoted by
using the purest possible plasticiser grades, keeping the plasticiser
content well within the compatibility limits and generally as low as
possible, and using selected high-permanence plasticisers.
The stabilising effects of some pigments are mentioned in Sections
4.4.2(b) of Chapter 4, and 9.2.1 of Chapter 9. Carbon black and
titanium dioxide in particular both contribute to UV stability, and
hence to resistance to weathering, but black PVC materials (and many
dark-coloured ones) can heat up to an undesirable extent on pro-
longed exposure to sunlight. Some colourants can also have a
UV-stabilising effect: two examples are Indanthrene Blue and Car-
bazole Violet. 14 Pigments with low infrared absorption are also
available (see Section 9.2.1 of Chapter 9).
The aspects of heat-processing particularly important in promoting
resistance of PVC materials to weathering are: completeness of
dispersion in the PVC resin of all stabilising additives; completeness of
fusion of the composition; and preservation (by attention to the
temperatures in processing) of the maximum possible stability time,
with no incipient degradation.
The presence of small amounts of adventitious materials, such as
solvent residues (e.g. in solvent-cast films, or in originally solvent-
expanded shrink tubing-d. Section 12.3.4 of Chapter 12), or of trace
impurities that may be introduced with solvents or with some of the
regular formulation components (e.g. plasticisers), can have a marked
destabilising effect in the weathering of PVC products.
EVALUATION OF THE RESISTANCE OF PVC TO WEATHERING (Table 24.4)

As in the case of many other properties of various PVC materials, the
weathering resistance of those intended for outdoor use needs to be
tested for such purposes as prediction of service performance and

development or comparison of formulations. Any test applied in this
connection must comprise two elements: first a test treatment, i.e.
exposure of the material to conditions capable of producing changes
identical with, or equivalent to, those caused by natural weathering,
and then assessment of such changes resulting from the test treatment.
The most relevant and reliable test treatment is obviously actual
exposure of the material at the appropriate geographical location and
for the time over which it is desired to ascertain the extent of the
material's resistance to weathering (providing that the time is long
enough to equalise the effects of year-to-year weather variations).
However, the useful service life ideally aimed at with most PVC
products for outdoor use is counted in tens of years: it is thus not
practicable to test by actual full-time exposure for such purposes as
material comparison or formulation development. Long-term natural
weathering tests are normally carried out to collect reference data for
eventual use in the future (especially for determining the degree of
correlation with other, more rapid, test treatments).
Note: The time scale of exposure in natural weathering may be
shortened if very thin 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.
The faster weathering treatments are of the following three kinds.
(i) Outdoor exposure, with artificial concentration of sunlight: This
is the closest practical approach to accelerated natural weathering, but
the degree of acceleration is limited by equipment and procedure
factors. A typical apparatus (heliostat) employs mirrors to direct extra
sunlight onto the specimens, which are cooled by an air stream to
prevent overheating, and may be periodically sprayed with water (as in
the EMMAQUA equipment, a development of the original EMMA *
* Equatorial Mount with Mirrors for Acceleration.

TABLE 24.4 ~
Major Standards Relevant to Various Aspects of Weathering Resistance of Plastics
no.
Outdoor weathering: general ~
1 ISO 4607-1978 Plastics-Methods of exposure to natural weathering (Revision commenced in 1986)
2 BS 4618:Section 4.2:1972 Resistance of plastics to natural weathering ~
~.
3 ASTM D 1435-85 Standard practice for outdoor weathering of plastics
4 ASTMG7-83 Environmental outdoor exposure testing of non-metallic materials ~
5 DIN 53 386 (1982) Outdoor weathering of plastics Cl
~
Outdoor weathering: accelerated ~.
6 ASTM D 4141-82 (1987) Standard practice for conducting accelerated outdoor exposure tests for coatings- !"
procedure C: Fresnel reflector rack exposure ."
7 ASTM E 838-81 Performing accelerated outdoor weathering using concentrated natural sunlight ~
8 ASTM G 90-85 Accelerated outdoor weathering of non-metallic materials using concentrated ~
.,.,
natural sunlight ~.
Outdoor exposure under glass
9 ISO 877-1976 Plastics-Determination of resistance to change upon exposure under glass to ~
daylight (Revision commenced in 1986) ~
10 BS 2782:Part 5: "='
Identical to ISO 877 ~
Method 540A:1977
11 ASTM G 24-73(1980) Conducting natural-light exposures under glass
""
~.
12 DIN 53 388 (1984) Testing of plastics and elastomers-Exposure to daylight under glass
Laboratory weathering tests
13 ISO 4892-1981 Plastics-Methods of exposure to laboratory light sources (incorporates and
supersedes former ISO 878 and 879)
14 BS 2782:Part 5:
Method 540B:1982 Identical to ISO 4892
15 BS 3900: Part F3; 1986 Resistance (of paints) to artificial weathering (exposure to enclosed carbon-arc
radiation)
16 ASTM D 1499-84 Operating light- and water-exposure apparatus (carbon-arc type) for exposure of
plastics
17 ASTM D 1920-69 (1976) Determining light dosage in carbon-arc light-ageing apparatus (Discontinued in
1983)
18 ASTM D 2565-85 Operating xenon-arc-type light- and water-exposure apparatus for plastics
19 ASTM G 23-81 Operating light-exposure (carbon-arc-type) apparatus for non-metallic materials
(Incorporates and replaces former ASTM G25) ~
20 ASTMG26-84 Similar to G23, but for xenon-arc-type apparatus
21 ASTM G53-84 Similar to G23, but for fluorescent UV /condensation-type apparatus ~
22 DIN/ENT 53387 (1987) As ISO 4892-1981 (supersedes DIN 53389) '"tl
~
Laboratory exposure tests relevant to marine and coastal-type environments ~
23 ISO 3768-1976 Neutral salt-spray test ~.
24 ISO 3769-1976 Acetic acid salt-spray test
..sa,
25 ISO 4611-1987 Exposure to damp heat, water spray, and salt mist
26 BS 3900:Part F4: 1968(1985)Resistance (of paints) to salt spray ~
27 BS 4618:Section 4.4:1973 Effects on plastics of marine exposure ~
BS 5466 c",
0;;'
28 Part 1:1977 Neutral salt-spray test ;:s
'$;
29 Part 2:1977 Acetic acid salt-spray test
30 ASTM B 117-85 Salt spray (salt fog) testing §
~
31 ASTM B 287-74 (1980) Acetic acid salt-spray test (Intent to withdraw published in 1988)
Assessment and evaluation of weathering effects
32 ISO 4582-1980 (1986) Plastics-Determination of changes in colour and other properties after exposure to
daylight under glass, natural weathering, or artificial light
33 BS 4618:Section 4.3:1974 Resistance of plastics to colour change on exposure to light
34 ASTM G 45-75 Standard recommended practice for specifying limits for fading and discolouration of
non-metallic materials
~
apparatus,15-17 first used at the Desert Sunshine Exposure Test Station

in Arizona). A heliostat can produce up to ten-fold concentration of
the total incident sunlight (although the incident energy in the UV
region may be concentrated by factors of only three to five 18 ,19), with
up to nine-fold increase in the rate of degradation of some PVC
materials. 20
(ii) Relatively short-term exposure in hot, sunny climates: Two

favourite locations, known to offer severe weathering conditions, are
sites in Arizona (sunny, hot, dry conditions) and Florida (sunny, hot,
humid conditions). The weathering effects developed for periods of up
to about three years at such sites are used to make predictions-on the
basis of the necessary information on relevant correlations-of the
likely resistance of the materials concerned to longer-term weathering
either in similarly severe conditions or in more moderate climates.
Clearly, the validity of the predictions is cardinally dependent upon
that of the correlations assumed. Unfortunately the accuracy of the
latter (never 100%) can vary quite widely, inter alia according to the
projected duration of long-term exposure, the material concerned, and
the actual locations for long-term service. Nonetheless, a reasonable
degree of predictive confidence is possible in some cases. It may be
noted in this connection that a world-wide study of weathering of
PVC21 has been claimed to show that a substantial degree of
correlation can be attained between results from widely differing
geographical areas.
In any natural-weathering test exposures, whether long- or short-
term, the mounting and positioning of the test specimens are sig-
nificant factors. Thus, backing a specimen with a good insulator (e.g.
plywood) helps to bring out the effect of temperature, and the
orientation of specimens also plays a part. Exposure racks are
normally south-facing (north-facing in the Southern Hemisphere), and
the specimens may be positioned vertically, horizontally, or tilted at
45°C, depending on the standard method used. In some methods the
specimens are exposed under glass, so that the effects of UV radiation
are unimpeded, whilst those of some other factors (wind, rain) are
excluded.
(iii) Exposure in laboratory weathering equipment: Such equip-

ment typically comprises a source of light for irradiating the speci-
mens, means of periodically spraying and/or condensing water onto
the specimens, and means of controlling the humidity and temperature

in the test enclosure.
Note: The temperature is usually measured and expressed as the

black-panel temperature. This is the temperature of a black-
coloured metal plate (whose radiation absorption characteris-
tics approximate those of an ideal black body) as measured
by a thermometer or thermocouple in good thermal contact
with the plate. With proper positioning of the plate, the
black-panel temperature corresponds reasonably closely to
the maximum surface temperature of the specimens (except
where those are very thin or light-coloured, when their
surface temperature may be significantly lower).
The radiation sources used in laboratory weathering equipment are

of two general kinds: those producing radiation whose spectral energy
distribution in the UV region (up to about 350 nm-see Fig. 24.1)
approximates fairly closely to the average distribution in sunlight
reaching the earth's surface ('global radiation'), and those with strong
principal emission in the UV region (cf. Fig. 24.1). Two sources of the
first kind widely used for standard laboratory weathering tests are a
xenon arc with borosilicate glass filters (as for example in the
Xenotest* equipment-d. DIN 53387; or xenon-arc Weather-
Ometert-<f. ASTM D 2565 and G 26), or a carbon arc with similar
filters (as for example in the 'sunshine' carbon-arc Weather-Ometer*
with Corex D filter-<f. ASTM G23). The UV emitters are fluorescent
lamps of various kinds: lO the QUV:j: apparatus is an example of
standard equipment employing this kind of source (cf. ASTM G 53).
The laboratory weathering tests are commonly referred to as
'accelerated weathering'. Whilst the description is accurate in the
literal sense (see below) the tests are by no means of short duration:
some thousands of exposure hours are still required to provide a
reasonable level of confidence in predicting likely long-term weather-
ing resistance in service.
Two factors make for acceleration of weathering effects in labora-
tory equipment in comparison with natural exposure outdoors: the
* Quartz-Lampen GmbH, Hanau, FRG.

t Atlas Electric Devices Co., Chicago, USA.
:j: The Q-Panel Co., Cleveland, OH, USA.
1c:: 2·0
'"E
~
.....cOl 1·6
c::
III
1 1·2
....~
'c:l
I...
III
a.
~ 0·8
c::
",
'0
",
I...
.!:
0·4
OOI~~L-~~~~~~~~~~~~=d~==~==b=~
250 300 350 400 450 500 550 600 650 700 750 800
Wavelength (nm)
Fig. 24.1 Spectral energy distribution of light sources widely used in

weathering tests on plastics. Partly schematic representation based on a chart
published by Ciba-Geigy. - - , Sunlight (direct global radiation, 'average
optimum', Miami, measured at 45°S, 20 March 1984; - - -, 'Sunshine' carbon
are, Corex-D filtered (as used in Atlas Weather-Ometer); .... , 6500-W
xenon-arc lamp with borosilicate inner and outer filters (as used in Atlas
Weather-Ometer); - - FS-40 fluorescent sunlamp (as used in the Atlas
UVCON™ and QUV Accelerated Weathering Tester).
amount of radiant energy received by a specimen per unit overall

exposure time is considerably higher (since even in the sunniest
climates the average duration of sunlight will normally be under 10 h
in a 24-h day); and the equipment can be operated virtually
continuously.
In apparatus employing fluorescent UV light sources, the presence
of the highly energetic UV radiation in the 270-290 nm region, which
is virtually absent from the incident sunlight and from the xenon-arc
and carbon-arc spectra (cf. Fig. 24.1), also additionally accelerates
degradative effects in plastics, but such degradation may not neces-
sarily be identical with the photochemical effects in natural weather-
ing. This factor should not be overlooked, as it can affect the accuracy
of predictions of weathering resistance in actual service made on the

basis of laboratory exposures to UV sources (although close correla-
tions have been claimed in some cases,1O especially for the QUV
apparatus 19 ,22).
Modern laboratory weathering equipment (e.g. some versions of the
Atlas Weather-Ometer) can be programmed to deliver set amounts of
radiant energy within particular wavelength bands, as well as to
provide particular temperature and relative humidity combinations,
wet/ dry cycling, and-where required-also contact with gaseous
atmospheric pollutants or degradative agents (e.g. sulphur dioxide;
nitrogen oxides; ozone).
In the plastics industry it has for a long time been common to use
the number of hours of exposure in a particular laboratory equipment
both as a measure of a material's resistance to this kind of artificial
weathering and as a basis for predicting long-term service perfor-
mance. Occasionally, those unaware of the complexities and limita-
tions involved in such predictions might even attempt to equate a
particular number of hours to a specific number of years at an outdoor
location. Such correlations cannot be formulated with any great degree
of reliability. As has been increasingly recognised in recent years, it is
more meaningful to consider the total amount of radiant energy
(especially the total in the UV region of the spectrum) received by the
material in test and service exposures: some relevant illustrative data
are given in Tables 24.5 and 24.6.
Note: It is noteworthy that the amount of total UV energy (in the
region below 400 nm) received by a specimen per unit area in
unit time from a fluorescent UV source of a laboratory
apparatus (such as the QUV) can actually be less than that
experienced in some equipment with xenon-arc or carbon-arc
sources (cf. for example Table 24.6).
As regards the predictive value of laboratory weathering tests on
PVC, it may be mentioned that, for some impact-modified composi-
tions, good correlations have been claimed between exposure in a
Xenotest 450 (at 50°C black-panel temperature) and natural weather-
ing in central Europe. 23 In another study, uPVC materials with various
light stabilisers were ranked in the same order on the basis, respec-
tively, of exposure in a Xenotest 1200 and outdoors in Arizona. 24
Instruments (radiometers, pyranometers) are available for the
measurement-in both laboratory and outdoor exposure~f radia-
00
o
-
TABLE 24.5
~
'"1::1
Incident Solar Energy in Various Climates [
(Based in part on data from Refs 26 and 27.)
Climate type Geographical location Incident solar energy Hours of

?
~
sunshine in .g
UV, 290-385 nm Total Total in 1972 1972 ~
::l".
(average kLy year-1t (average kLy year-1t (kLy) -~
'"1::1
Dry, desert Phoenix, Arizona, USA 8·5 187 190 4 ()()() ~
Sub-tropical, humid Miami, Florida, USA 7·1 140 150 3 ()()() "~
Sub-tropical, coastal, humid Durban, RSA 6·6 135 133 2280 '"
~.
Sub-tropical, continental, Johannesburg, RSA 8·7 175 164 3290
high altitude
Temperate, coastal Melbourne, Australia 120 2060 ~
Temperate, marine Brixham, UK 101 1680
:g~
aLy=Langley (a unit of incident radiant energy). 1 Ly=1 cal cm- 2 = 4·1855 Jcm- 2 (the calorie used in this definition is the 15°C !if
calorie--see Appendix 2). g.
i;
TABLE 24.6
Irradiation Energy in Various Weathering Test Conditions
(Based on data from Refs 19 and 28.)
Test exposure Irradiation energy received by specimens

~
Conditions Duration Total (full spectrum) UV band (below 400nm) only
(MJ m- 2 )
(kJ m- 2 h- 1 ) (kJ m- 2 d- 1 ) (MJ m- 2 ) ~
::,0
Xenon-arc weathering apparatus .§
Conditions A a 500h 711 ;,.
'"
~.
1000h 1422 144
144 .Q.,
2000 h 2844 { 288
4000 h 5688 576 ~
Conditions Bb Per hour 137·2 r a~
c;..,
QUV weathering tester aQ.
C ;:,
Conditions A 500h 53 'S;
1000h 106 103
103
2000 h 213 { 206 s ~
4000 h 425 413
Conditions Bd Per hour 57·3 r
Sunlight-concentrating apparatus
Arizona 44d 8000 242
93d 16273 451
132d 20 ()()() 462
00
-
00
N
-
TABLE 24.6-(contd).
Test exposure Irradiation energy received by specimens ~
Conditions Duration Total (full spectrum) UV band (below 400 nm) only e~
(Ml m- 2 ) ~.
2
(kJ m- h- 1) 2
(kJ m- d- 1) (Ml m- 2)
...~
.g
Transvaal (Pretoria) Per day 1722·7 ~
.~.
Natural outdoor exposure
Florida 6 months 4290 144 ~
12 months 6276 282 ~
24 months 12505 562 ~
~.
Transvaal (Pretoria) Per day 961·6
a Xenon-arc Weather-Ometer. Cycle: 690 minutes light, 30 minutes light and water spray. Black-panel ~
)..
temperature: 80 ± 3°C. 28
b Atlas 6500 xenon-arc Weather-Ometer. Cycle: 120 minutes light, 18 minutes light and water spray.
~
~
c:.
White-panel temperature 50°C. 29
C Fluorescent UV-condensation apparatus. Lamp: fluorescent UVB-313. Cycle: 20 hours UV at 80°C, 4 5·
i.:!
hours condensation at 50°C. 28
d QUV tester. Cycle: 4 hours UV at 50°C white-panel temperature, 2 hours condensation at the same
temperature. 28
tion energy received (irradiance either over the whole range of

incident wavelengths, or within individual wavelength bands, espe-
cially UV). Such instruments and their use are discussed in two ISO
publications. 25 Some of the relevant terms are defined in ASTM
772-87 (Standard terminology relating to solar energy conversion).
Any of the typical manifestations of weathering may be used-as
appropriate-to assess the effect on PVC materials of exposure in tests
or in service. For quantitative determinations, measurement of
changes in the mechanical properties-especially tensile strength and
elongation, and impact strength (for uPVC~r of colour change, are
most often used. Detailed examination of surface changes, where
required, may be by microscopy (optical and/or electron) or by
micro-contour measurement (see Fig. 24.2). In assessing colour
development (yellowing, darkening), colour changes, or resistance to
colour fading, use is often made of the relevant standards. Thus the
degree of yellowing may be determined in terms of the Yellowness
Index [BS 2782: Part 5:Method 530 A:1976 (1983), or ASTM D
1925-70 (1977)], change of colour in terms of the Grey Scale [ISO
105-A02-1978; BS 1006:A02:1978;* ASTM D 2616-67 (1979)], and
colour-fastness in terms of the Blue Wool Standards, originally set up
for textiles (ISO 105-BOl-1978; BS 1006:B01:1980; BS 4618:Section
4.3:1974).
Thermal and thermomechanical analysis (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. 29
24.3.2 Behaviour at Low and High Temperatures
(a) Low-Temperature Properties

Many PVC products, both rigid (e.g. pipes, containers, panels) and
flexible (e.g. cable and wire coverings, tarpaulins, inflatables), are
used in conditions in which they may experience low (sub-zero)
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-within the general limits
* For colour change on staining, BS l006:A03:1973.

E
.e- A '; A
....
-1mm-t
B B
E D
~ C
-Imm-
2
Fig. 24.2 Effects of outdoor exposure on the surface micro-profile of some
rigid PVC compositions. Illustrations extracted from Ciba-Geigy data ref. A
5·5:1987. (Reproduced with permission of Ciba-Geigy Ltd). 1, Unpigmented,
EIV AC-modified, Ba/Cd-stabilised composition. Outdoor exposures in Flor-
ida: radiant energy dose 450 kLy. 2, Compositon generally as in 1, but
pigmented with 4 phr rutile TiO z. Outdoor exposures in Arizona: radiant
energy dose 600 kLy. A, Unexposed controls; B, no light stabilisers; C,
0·15 phr Tinuvin 320 (UV stabiliser) and 0·15 phr Tinuvin 770 (hindered
amine light stabiliser); D, 0·3 phr Chimassorb 944 FL (light stabiliser).
of PVC's capabilities-is essentially a matter of formulation, supple-

mented by proper compounding (to ensure good interblending 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 requisite degree of
impact resistance: in the absence of appropriate impact-modifiers,
uPVC can reach its 'brittle point' (transition from ductile to brittle
failure on impact), with corresponding substantial reduction in impact
resistance, at only slightly lowered temperatures (see also Section
8.3.1 of Chapter 8). It is for this reason that compositions for uPVC
pipes to be used at low temperatures are always suitably impact-

modified [cf. Section 12.2.1(a) of Chapter 12].
The main effects of cooling of flexible PVC are stiffening, hard-
ening, 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.
Correct formulation (and especially the proper choice of
plasticiser(s}---see Chapter 5) is again the key factor in ensuring good
low-temperature performance.
Some tests for behaviour at low temperatures of wire and cable
coverings have been mentioned in Section 24.2.2 above. The low-
temperature characteristics of other PVC products (especially pPVC
ones) are also often determined and described in terms of the
following concepts.
Brittleness temperature: In the context of the relevant tests, this is

usually defined as the temperature at which 50% of the specimens
(film, sheet, or mouldings, according to the standard concerned)
break or shatter on impact under the test conditions [ISO 974-1080;
ASTM D 746-79 (1987); ASTM D 1790-83].
Cold crack temperature (of film, sheeting or coatings): This is the

temperature at which cracks first appear when a loop of film or sheet is
flattened by a blow of a standard hammer under prescribed test
conditions (BS 2782:Part 1:Method 150D:1976; the method of this
standard is not always satisfactory with thin, polished pPVC sheeting,
or pPVC sheeting of low plasticiser content).
Cold flex temperature (of flexible PVC in thin-strip form): This is

the lowest temperature at which, in the test of BS 2782:Part 1:Method
150B:1976, a specimen deflects through an angle of 2000 under a fixed
torque. The torque apparatus used is a modification of one originated
by Clash & Berg.30
The effect of temperature, over a wide range, upon the stiffness in
torsion (apparent modulus of rigidity) of non-rigid plastics generally
(in the thickness range 1-5 mm) may be determined by methods which
form the basis of the following standards: ISO 458-1985; BS 2782:Part
1:Method 150A:1976; ASTM D1043-87; DIN 53 447 (1981).
Cold bend temperature: This is the lowest temperature (measured in

multiples of 5°C) at which a sheet specimen of flexible PVC remains
uncracked when wound onto a standard mandrel (BS
2782:Part 1:Method 151A:1984). For the same pPVC material the cold
bend temperature is normally lower than the cold flex temperature.
Three other specifications are of direct interest: BS 2782: Part

1:Method 150 C:1983 (low-temperature extensibility of flexible PVC
sheet); BS 3424:Part 8:1983 (test methods for low-temperature perfor-
mance of coated fabrics); ASTM D 759 (although now withdrawn as a
standard, this specification gives useful guidance on the testing of
plastics at subnormal and supernormal temperatures).
The tests for low-temperature properties of PVC are useful prin-
cipally in monitoring production quality, 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 (although
they do give useful indications in that direction).
(b) High-Temperature Effects
GENERAL
In relation to the applications of PVC materials, the effects of elevated
temperatures may be considered under three general headings: (i)
thermal degradation, with serious deterioration of material properties
and appearance; (ii) less drastic but generally undesirable permanent
effects of exposure to relatively moderately elevated temperature,
including those collectively known as 'heat ageing'; (iii) temporary,
mainly reversible, changes in properties (e.g. lowering of modulus and
strength, increased extensibility) arising from the thermoplastic nature
of PVC.
The causes, manifestations, and other aspects of thermal degrada-
tion are discussed in some depth elsewhere in this book (see especially
Chapter 4).
As regards the effects of moderately elevated temperatures, the
following considerations merit particular mention for their importance
in connection with the prediction and evaluation of service behaviour
of PVC materials: maximum temperature for continuous service, i.e.
the highest temperature at which no unacceptable heat ageing and
deterioration will take place during the service life; the temperature of
deflection under load of rigid PVC; and volatile loss from flexible
PVC (especially coatings on fabrics). The deterioration of mechanical
properties (one of the main symptoms of heat ageing) on prolonged
moderate heating, and effects of brief exposure to high temperatures
(cf. the thermal tests on PVC wire and cable coverings in Section 24.2.2
above), are also significant in many applications.
MAXIMUM 'SAFE' TEMPERATURE FOR CONTINUOUS SERVICE (IN THE ABSENCE OF

MECHANICAL STRESS)
This temperature can be estimated for a given PVC material (as for
other plastics) on the basis of determinations of thermal endurance in
a series of tests at various elevated temperatures. The procedure,
described in several standard specifications,31-33 is based on a number
of assumptions, the main one being that the thermal degeneration
responsible for heat ageing of a plastics material proceeds essentially
in a homogeneous phase, and thus obeys an Arrhenius-type relation-
ship. The service-temperature guidance figure obtained from such
determinations for the material concerned is often referred to as the
temperature index (TI), or relative temperature index (RTI) if the tests
have been run on a comparative basis against a reference material.
The actual value of a TI depends on the material (in the case of PVC
on the particular formulation), and to some extent also on the
property whose changes on heating are evaluated in the tests. The
earliest TI figure published for PVC (of unidentified composition)34
was 70°C. Since then, TI values for continually increasing numbers of
plastics materials (including many proprietary ones) have been deter-
mined by Underwriters Laboratories Inc., and published inter alia in
some editions of the Modern Plastics Encyclopedia (McGraw-Hill).
Standards, not so far mentioned, of general relevance to heat ageing
include ISO 1137 and the corresponding ASTM D 1870 (Ageing test in
a tubular oven), and ASTM D 2115 (Oven-heat stability of PVC).
HEAT AGEING OF FLEXIBLE PVC

The main feature of heat ageing of flexible PVC at moderately
elevated temperatures is the loss of a proportion of volatile formulation
components such as non-permanent plasticisers. Depending on the
temperature, this may also be accompanied by some degradation. The
reduction of plasticiser content may, in the initial stages of heat
ageing, produce a degree of improvement in such properties as tensile
strength and modulus. However, this apparent benefit is most often

eventually cancelled by progressive degradation, whilst the undesirable
effects of partial plasticiser loss (reduction of flexibility, extensibility
and softness) remain, and may increase. Moreover, stresses can be set
up in the material's surface (especially where plasticiser loss is locally
non-uniform), and these-either alone or in conjunction with any
imposed external stress-<:an promote cracking of the stiffened,
hardened surface material.
The performance of PVC coatings on fabrics (upholstery, clothing,
tarpaulins), as well as of flexible sheeting, in tests for loss of volatiles
at elevated temperatures is of practical interest, in that it is often used
as an indication of the likely long-term durability of the material in
service at ordinary temperatures. Although the correlations between
such predictions and service performance are variable, several
standard methods are in use, and some of the specifications also lay
down permitted loss limits. The following standards may be men-
tioned: ISO 176-1976; BS 2782:Part 4:Methods 465 A and B:1979; BS
3424:Method 14 A:1973* (this method is specified by both parts of BS
5790:1979, which cover, respectively, PVC-coated knitted and woven
fabrics and replace the original BS 4216:1970 and BS 2601:1973):
ASTM D 1203-86.
For a given formulation, the volatile loss, in standard conditions,
from a plasticised PVC sheet or coating on a fabric, is a function
primarily of the specific surface (surface per unit volume) and hence
the thickness.1O Volatilisation of plasticisers from pPVC is discussed in
Sections 5.4.3 and 5.6.6 of Chapter 5.
EFFECTS ASSOCIATED WITH THE THERMAL SOFfENING OF PVC AT ELEVATED

TEMPERATURES
These effects are generally in line with those exhibited by other
thermoplastics. Thus, for example, the modulus and strength decrease,
whilst extensibility and creep increase, as do permeability and suscep-
tibility to some chemicals.
'Oil canning' [see Section 12.2.2(c) of Chapter 12] of PVC siding,
and recovery of strain imparted in production to calendered sheeting
[see Section 14.3.1(c) of Chapter 14] are two examples of practical
problems that may be caused by elevated temperatures experienced in
service by some PVC products.
* Currently under review.

24.3.3 Resistance to Biological Attack
(a) Microbiological Attack (Biodegradation)

In the plastics context this normally means attack by fungi (mould,
mildew) or bacteria. Infestation by algae is not a major problem even
with such PVC products as linings for swimming pools, reservoirs and
canals.
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 charac-
teristic pink stain35 ) 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 PVC), or
surface cracking. The resistance of PVC materials can vary widely
depending on the formulation. However, even resistant compositions
can be affected indirectly if in contact with a material susceptible to
attack: thus, for example, bacteria and fungi can thrive in the cotton
fabric lining of a pPVC-coated protective glove (especially if the lining
is kept moist for appreciable periods by perspiration or condensation),
or in a slightly moist adhesive (paste) layer of a PVC wall-covering, or
in surface contaminants (grease, dirt) on uPVC cladding.
Of the main PVC formulation components, those vulnerable to
microbiological attack are: most plasticisers (in varying degrees,
depending on the chemical nature, with epoxy compounds most highly
susceptible and aryl phosphates and chlorinated extenders the least);
some stabilisers and lubricants (especially epoxy compounds, some
stearates and waxes), although others (e.g. some organotins and
phosphite co-stabilisers) can inhibit microbiological growth; and some
organic fillers, i.e. wood flour. PVC polymers are resistant to attack by
micro-organisms, but some emulsifier and suspending-agent residues
left in after polymer production can be susceptible.
Thus, in general, any PVC composition may be subject to micro-
biological attack if it contains one or more of the vulnerable
constituents. Plasticisation promotes susceptibility, which also in-
creases with increasing plasticiser content (as demonstrated inter alia
by Decoste's extensive soil-burial test series36). Plasticised PVC

products at greatest risk are those experiencing warm, humid
environments and/or contact with soil or water outdoors (e.g. shower
curtains, wall coverings, foul-weather clothing, swimming-pool liners
and covers, coverings of buried cables).
Special additives are available for inclusion in PVC compositions to
protect against microbiological attack. Those with a positive ability to
destroy fungi and bacteria are often referred to, respectively, as
fungicides and bacteriocides (and collectively as biocides). The terms
'fungistat', 'bacteriostat', and 'biostat' are applied to substances which
deter micro-organism growth by whatever mechanism. In a study circa
1970, Kaplan et al. 37 evaluated the protective effects in PVC film of 32
biostats then available. Many biostatic additives now current provide
protection against a range of micro-organisms. Some examples are:
Estabex ABF (Akzo Chemicals); Mikro-Chek 12 (Ferro Corp., Chemi-
cal Div.); some bioMet additives (M&T Chemicals). An arsenic
compound (lO,lO'-oxybisphenoxarsine) is claimed to be among the
most widely used broad-spectrum biostats for plastics (cf. e.g.
Vinyzene; Morton Thiokol Inc., Ventron Div.). A bacteriostat of
lower-than-average toxicity, 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/PA; Ciba-Geigy): it is also active against certain
fungi which grow on the skin, e.g. that causing 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.
Some organomercury compounds are the only biostats of proven
effectiveness against Pseudomonas aeruginosa, which can cause prob-
lems in flexible PVc. However, the use of such additives has been
discontinued as a precaution against their toxic effects, direct and
environmental.
The incorporation levels of biostats used in PVC vary considerably
(fairly typically within the range 0·1-1 % by weight of the composi-
tion), depending on the nature of the additive and the PVC
formulation.
Testing the resistance of a plastics material to microbiological attack
typically involves soil burial, or controlled contact with stock cultures
of representative micro-organisms, followed by an assessment of any
changes in visual appearance and in one or more selected properties.
Some relevant 'plastics' standards are: ISO 846-1978 (1986) (Evalua-
tion of the effects of fungal and bacterial action); BS 4618:Section

4.5:1974 (Effects of soil burial and biological attack); ASTM G 21-70
(1985) (Determination of resistance to fungi); ASTM G 22-76 (1985)
(Determination of resistance to bacteria). Of these, BS 4618 gives a
short bibliography, and ASTM G21 lists in an appendix several
standard (ASTM) methods for determining changes in the properties
which may be monitored in the tests.
(b) Attack by Insects and Rodents

The insects concerned are almost invariably termites, so that in
practice the insect attack problem is confined to tropical or sub-
tropical countries. Termites appear to prefer plasticised to rigid PVC
(and, generally, soft plastics to hard). Products that may be attacked
include electrical insulation and cable coverings, PVC-coated up-
holstery fabrics, and PVC foam. There is some evidence that
phosphate-plasticised PVC compositions may be more resistant than
other kinds of pPVc. 38,39 Incorporation of insect repellents in the
PVC, or their external application in coatings, has been suggested, but
the effectiveness of such measures has not been established. In some
countries, the use of a metal barrier (wrapping tape) is prescribed by
regulations to prevent termite and animal attack on the PVC
coverings on electrical cables, and this is an effective measure.
Rodent attacks on PVC are sporadic. Rats and mice, the animals
most commonly involved, do not appear to regard even plasticised
PVC as food, and seem to attack PVC materials mainly if those
obstruct their way to proper food or to water. Some less purposeful
gnawing has also been suffered, however, by such PVC products as
electrical insulation and conduit, water pipes, and reservoir linings.
Rodent-repellent additives incorporated in some PVC compositions
have not achieved any outstanding success.
24.4 PROPERTIES RELEVANT TO BARRIER

AND PROTECTIVE APPLICATIONS
24.4.1 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 permeant
(such as gas, vapour, or liquid). In line with this concept, the
permeability of a polymeric material is normally measured by deter-

mining the amount of permeant passing through the material in
specified conditions. Low permeability is advantageous in plastics
used for various barrier applications (e.g. PVC films and coatings
employed in rainwear, inflatables, tarpaulins, protective gloves).
It can readily be seen, largely as a matter of common sense, that
the permeability of a plastic towards a given permeant 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) (1)
In this expression J is the flux of the permeant, 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 (~O)
or chemical potentials (~Jl), of the permeant 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
permeant/barrier material.
As can be seen, F / L is the driving force gradient within the barrier
(which, for a given value of F, will increase with decreasing barrier
thickness). The various quantities in eqn (1) 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 practical testing of permeability of plastics materials (see Table
24.7), it is the flux of the permeant that is actually measured, but the
test results are expressed in various ways, depending inter alia on the
context in which they are to be used. The expressions of permeability
most widely used for practical purposes are transmission rate,
permeance, and permeability.
Note: The adoption of the last-named term for one particular kind
of numerical expression of permeability is rather unfortunate,
as it can be a gratuitous source of confusion. It is also
unnecessary, since what is termed 'permeability' in that

narrow sense is in fact the coefficient P of eqn (1), and could
thus have been called-more accurately and less
confusingly-'permeability coefficient' or 'permeability factor'
(see 'permeability' below).
Transmission rate: This way of expressing permeability is particu-
larly widely used in quantitative statements of permeability of plastics
to water vapour. It is the rate of transfer of the permeant per unit area
of the material (i.e. J /A in terms of eqn (1». The units most
commonly employed are g m- 2 d- 1, but versions involving multiples
and sub-multiples are also encountered, e.g. g m- 2 h- 1 or
Ilgm-2s-1--<:f. Table 24.7. The SI unit is molm- 2s- 1. As can be
seen, for a numerical statement of transmission rate to be capable of
direct comparison with other expressions of permeability (for the
same or another plastics material) it is necessary to know also the
value of the driving force and the barrier thickness, as well as the
temperature. In connection with determinations of water vapour
transmission rate through plastics materials, it is usual to state the
driving force (which is the water vapour pressure difference) in terms
of the difference in relative humidity on the two sides of the barrier.
Where necessary, the corresponding pressure difference can be found
in the appropriate published tables (cf. e.g. Ref. 40).
Permeance: This is the rate of transmission per unit driving force

(the driving force being most often a pressure difference), i.e.
J /(A. F) in terms of eqn (1). The expression does not include the
barrier thickness: thus in the context of most practical tests on
plastics, permeance is the flow of permeant per unit time and unit area
under a specified pressure difference through the entire thickness of
a specimen. This way of expressing the test result is useful if
the specimen is heterogeneous (e.g. foam with solid skins). In SI
units permeance is oft~n expressed in ng N- 1 S-1; perm or metric
perm are also employed, being, respectively, 1 grain/(ff h inHg) and
1 g/(m2 d mmHg).
Permeability: In most standard specifications 'permeability' is the

permeability coefficient of eqn (1), i.e. P = (J/A)/(F/L) , or
(J. L)/(A . 6.p) where-as is very often the case-the driving force is
a difference in the vapour pressure of the permeant on the two sides of
the barrier. In such a case the SI units of permeability often used in
~
TABLE 24.7
Principal Standards Relevant to the Detennination of Permeability of Plastics Materials (Including PVC)
Entry Standard specification ."

no. ~
Designation Subject Method Units ::s!
El
Type Main conditions ~.
Water vapour transmission (WVT) ~

1 ISO 1663-1981 Determination of WVT Dish (with Temp./RH
a
~
WVT:
rate through rigid desiccant) combinations :" Ilg(m2 S)-l '"~.
cellular plastics 38°Cj88·5%, or Permeance: .'"
23°C/85%, or ng(Pa s m 2)-1
23°C/50% Permeability :
~
ng(Pa s m)-l
'"~
S·
2 ISO 2528-1974 b Determination of WVT Dish (with Temp./RH ~
rate through sheet desiccant) combinations : WVT: g(m2 d)-l §
materials (including 38°C/90%, or s:...
).
specially creased, i.e. 25°C/90%, or ~
fluted, sheets) 25°C/75% [
3 BS 2782:Part 5:1970
Method 513 N Determination of WVT Dish (with Temp.: 25°C
5'
~
rate through sheet or desiccant) RH:75%
moulded disc:
'temperate'
conditions
Method 513 Be As 513A, but 'tropical' Dish (with Temp.: 38°C WVT: g(m2 d)-l
conditions desiccant) RH:90%
4 BS 3177:1959 Determination of Dish (with Temp./RH 'Permeability ,
permeability to water desiccant) combinations : (in fact
vapour of flexible 25°C/75%, WVT):
sheet materials (esp. ('temperate' g(m3 d)-1
packaging sheeting) conditions) or
38°C/90% ('tropical'
conditi~ns )
5 BS 3837:Part 1:1986 Expanded polystyrene Dish (with Temp.: 38°C Permeability :
boards (inter alia desiccant) RH: 88% ng(Pasm)-1 ~
prescribes a wvr Permeance: ."
test for these cellular ng(N S)-1 ~
products: a modified ."
version of Method 8 ~
'1:j
of BS 4370:Part 2) '"
...::l".
6 BS 4370:Part 2:1973 Methods of test for Dish or Temp./RH Permeability : ~
Method 8 cellular materials: beaker combinations : (Ilg m)(N h)-1 .Q..
Methods 6-10 (with 25°C/75% or Permeance: ~
Measurement of water desiccant) 38°C/88% Ilg(N h)-1 ~
vapour transmission §.:
7 ASTME96-80 Standard test methods Dish, either Temperatures: 23°C for WVT: QQ'
;:s
""
for water vapour (1) desiccant- Procedures A, Band d g (m2 h)-1 'S;
transmission of filled or BW; 32·2°C for Permeance: d £
;:s
materials Procedures C and D; g(Pasm2 )-1 ~
37'8°C for Procedure Permeability :d
E g(Pa sm)-1
(2) water- RH: 90% for Procedure
filled E, otherwise 50%
8 DIN 53122 Determination of wvr
rate through plastics
films and other sheet 00
materials N
(continued) Vl
00
TABLE 24.7-(contd) ~

no.
Designation Subject Method Units
Type Main conditions "'tI
~
Part m974) Gravimetric method Dish (with Temp./RH
1 ::s!
desiccant) combinations: WVT: g(m2 d)-l El
:::to
Condition A: 25°C/90% !:l
Condition B: 38°C/90%
Part 2 (1982) Electrolysis method Electrolytic Condition C: 25°C/75% a~
":5
I
hygrometer Condition D: 23°C/85%
Condition E: 20°C/85%
'"~
'"~.
Gas transmission rate (GTR)
"'tI
9 ISO 2556-1974 Determination of gas Manometric Temp.: 23°C (other GTR: e a
transmission rates temperatures cm3 (m 2 d atm) "~
through films and thin permissible) '"
~.
sheets under
atmospheric pressure §
10 BS 2782:Part Identical to ISO 2556 ""-
~
8: Method ~
821A:1979 e
(confirmed 1986) g.
11 ASTM D 1434-82 Determining gas (1) Mano- Temp.: 23°C; specific 1 ~
permeability metric conditions for each of
characteristics of (2) Volume- the two alternative
plastics film and tric methods GTR: e
sheeting cm3 (m2 d atm)-l
12 ASTM D 3985-81 Determination of Coulometric Prescribed conditioning Also permeance
oxygen transmission procedure l and permeability
through plastics film in both metric
and sheeting, and inch-pound
laminates, co- units'
extrusions, and
plastics-coated papers
or fabrics
13 DIN 53 380(1969) Determination of the Coulometric Temp.: 23°C; other GTR: e
(new draft 1982) gas transmission rate temperatures, and use cm3 (m 2 d bar)-1
through plastics films of moist gases ~
permissible
."
Transmission of other permeants
14 DIN 53 536(1985) Testing of rubber and Volumetric Constant temperature Permeability ~
."
elastomers: coefficient m 2 Cl
determination of Pa- 1 S-1 or
permeability to gases m 2 s- 1 Bar- 1
l::to
~
15 ASTM D 2684-84 Standard test method Gravimetric Temperatures as relevant Rate of average s.,
for permeability of to purpose of test weight change
plastics containers to
~
of/illed
packaged reagents container: g !
and proprietary d- 1 c"
<>'0.
products Permeability ;:s
'5;
factor:
(g cm)(d m 2 )-1
§
~
a All RH figures quoted are differences between the RH values on each side of the specimen.
b Partly replaces ISO/R 1195-1970 (withdrawn in 1980).
C These methods will eventually be replaced by new methods 820 (BS 2782:Part 8) at present still in draft form.
d Values in inch-pound units are regarded as standard in this specification, viz. WVT:g;~i~S Permeance: Perm (inch-pound).
Permeability: Perm inch. Conversion factors are given. t
e Volume at STP, i.e. at 273·15 K and 1·013 bar.
f Many unit conversions are given in an appendix to ASTM D 1434. ~
practice are g Pa -1 s-1 m -1 or ng m N- 1 s- \ but other units are also

employed (see Table 24.7 and Ref. 10).
The basic mechanism of transmission of a permeant through a
continuous plastics barrier (including closed-cell foams, in which the
cell walls constitute individual barriers) is diffusion. In effect, the
permeant dissolves in the barrier material on the side where its
pressure (or concentration, or chemical activity) is higher, and its
molecules travel through the material down the driving-force gradient
(clustering can occasionally occur) and come out at the opposite
surface. As diffusion is a thermally activated process, the permeability
in any plastic/permeant system depends on the temperature in this
sense, and also, secondarily, because the free volume content of the
plastic will increase with temperature (regularly outside the glass
transition temperature, and sharply at the Tg). The chemical structures
of the system's components--and hence chemical interactions between
them~onstitute another important factor, as does the fine structure
and morphology of the plastics material. For many plastics materials,
including PVC compositions, the rate of diffusion may also increase
with the sorbed permeant concentration, especially if the permeant
interacts strongly with (i.e. is a good plasticiser, swelling agent or
solvent for) the polymer.
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 the permeability coefficient P of eqn (1) may
also be defined by the expression
P=DS (2)
where D is the diffusion coefficient (assumed to be constant or
dependent only on permeant concentration), and S is a solubility
factor expressing the equilibrium content of the permeant in the
plastics barrier material at the relevant temperature. If S is expressed
as a ratio (of the equilibrium concentration of the permeant in the
barrier material to the permeant concentration 'upstream' of the
barrier, with both concentrations in the same units), it becomes a
dimensionless partition coefficient, and P will have the same dimen-
sions and units as the diffusion coefficient (length2 • time-I).
The permeability of porous plastics materials i.e. ones in which the
voids are intercommunicating, is governed by the rate of flow of the

bulk permeant through the pores. lO In such a case the chemical and
other intrinsic properties of the barrier material are not of primary
importance.
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.41
Two useful, earlier publications by Lebovits42 and Hennessy et al. 43
review the permeability of polymers and plastics to fluids. The latter
work deals in considerable detail with practical methods of
determination.
Permeabilities of uPVC and other polymers to water vapour, carbon
dioxide and oxygen are compared in Table 24.8.
To the extent to which it is valid to generalise over a broad range of
conditions and potential permeants, the following points may also be
made. Other things being equal, PVC compositions based on homo-
polymers are less permeable than those based on copolymers with
vinyl acetate, but more permeable than vinyl chloride/vinylidene
chloride copolymer compositions. Blending with other polymers tends
to increase permeability, but the opposite effect can occur: even with
the same compounds in a blend the permeability can increase or
TABLE 24.8
Typical Permeabilities of Some Polymer Films at Room Tem-
perature on a Comparative Basis (Permeability of Unstretched
uPVC Film Taken as Unity)
Permeant Water Carbon Oxygen

Polymer vapour dioxide
Polyvinylidene chloride 0·10 0·01 0·06
High-density polyethylene 0·18 25 22
Polypropylene 0·29 20 26
Low-density polyethylene 0·50 120 55
uPVC 1·00 1·00 1·00
Polyethylene terephthalate 1-15 0·67 0·60
Polyethylene terephthalate (S)" 0·67 0·40 0·50
uPVC (S)" 0·61 0·50 0·70
Polyamide 6.6 2·00 0·50 0·60
Polystyrene 3·00 27 40
Polycarbonate 4·00 25 48
* Stretched film.
1000
600
600
400
200
~
~
s:
~
(\J
Cl'
E
en
$
~
c:
0
'iii
II)
'E 10
II) 8
c:
...
C1I 6
'-
r..
::J 4
0
a.
ra
>
...'-
Q/
2
~
08
06
04
0 ·2
01
10
Sheet thickness (~m)
Fig. 24.3 Typical value ranges for water vapour transmission rates through
PVC sheets. (Determinations at 23°C and 85% relative humidity difference.)
'OE 2000
1il
J-..
~ 1000
N
":" 800
'"'E 600
a. 400
l-
...
I/)
~
1'1 200
E
u
cu
.....
tu
100
<- 80
c
0 60
.;n
III
·E 40
III
c:::
...<-
tu
III
tu
<D
20 40 60 eo 200 400 600 BOO

10 100 1000
Sheet thickness (lJ-m)
Fig. 24.4 Transmission of some gases through uPVC sheets: typical value
ranges. (Determinations by the method of DIN 53 380.)
10000
8000
6000
4000
2000
~
~
"
N
"j 400
E
a:::
~ 200
....".
Vl
M
E 100
u 80
....".GI 60
... 40
c
0
'iii
<II
'E
<II
20
C
.......
".
<II 10
".
(!) 8
6
10
Sheet thickness (~m)
Fig. 24.5 Transmission of some gases through pPVC sheets: typical value
ranges. (Determinations by the method of DIN 53 380.)
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 (E/VAC):44 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 per-
meability of uPVC film by factors of up to about 2.
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,
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 compatibility and hydrophobic nature of this type of
additive.
The respective permeabilities of PVC packaging films and sheets to
moisture, air, oxygen, and carbon dioxide offer the right combination
for preserving, for an appreciable time, the freshness and colour of
such foodstuffs as meat, and fresh fruit and vegetables. The ranges of
permeability values for some typical PVC sheeting are shown in Figs
24.3-24.5.
24.4.2 Chemical Resistance
The chemical resistance of PVC materials is discussed in Section 10.3.5

of Chapter 10.
24.5 HEALTH HAZARD ASPECTS
Certain health hazards arise in the production, processing, use, and

disposal of many plastics materials. PVC is by no means exceptional in
this respect, but-as is the case with other plastics--some hazards are
834 PVC Plastics-Properties, Processing,. and Applications
specifically associated with the chemical nature and the make-up of

PVC compositions. These are briefly considered in the present section;
a few peripheral hazards are also mentioned.
24.5.1 Vinyl Chloride Monomer
The risk of certain cancers involved in exposure to VC monomer, and

the associated severe regulatory restrictions on its residual content in
PVC polymers as produced, and on its migration from PVC com-
pounds, have been mentioned in Section 1.3.2(b) of Chapter 1. Most
industrial countries also impose corresponding regulations relating to
the amounts of VC monomer in workplace atmospheres. The
maximum permitted limits are very low: commonly about 1 ppm VC in
air, and-in the USA-low parts per (American) billion migrating
from various PVC products used in contact with foodstuffs* (e.g.
packaging films). These stringent regulatory limits, and the general
concern with the potential hazard, have created a need for highly
sensitive methods of detection and determination of vinyl chloride.
The major standards relating to procedures for quantitative deter-
mination of residual VC monomer are listed in Table 3.12 of Chapter
3. There is also a relevant directive of the Commission of the
European Communities (Commission Directive 81/432/EEC: Com-
munity method of analysis for the official control of vinyl chloride
released by materials and articles into foodstuffs). In these, and in
general use, gas-chromatographic methods predominate.
Note: One example of the specialist apparatus employed is the

HNU 301 D photoionisation gas chromatograph (Analysis
Automation Ltd, UK), which rapidly measures the residual
monomer in small PVC specimens by the Gaeke head-space
method to a detection limit of 5 ppb (109 ).
Clip-on badges have been developed for monitoring exposure levels to

VC in air. 45 Among methods for assessing the severity of exposure to
VC undergone by the human body, one reported as highly sensitive is
based on determination of alkylation by this compound of some of the
amino-acids of haemoglobin. 46
* Current EEC regulations lay down a migration limit of 0·01 mg per kg of

food.
24.5.2 PVC Compositions and Their Regular Constituents
Here, the principal hazard is possible toxicity or carcinogenic effect in

food-contact or medical applications (e.g. transfusion or infusion
equipment). A relatively minor but relevant consideration is
also the possibility of dermatitis arising from skin contact (e.g.
with PVC-coated clothing, protective gloves, etc.): albeit by no
means common, this can occasionally occur in particular sensitive
individuals.
Hazards of this kind are usually considered from the point of view of
the properties of individual components of a formulation. It is normal
to 'clear' each of these before the formulation is finalised. The
clearance may be based on own previous experience, or on reliable
information from the suppliers concerned, or on the relevant rules and
recommendations of the appropriate authorities or organisations. In
the USA the organisations most directly concerned are the Food and
Drugs Administration (FDA), the Occupational Health and Safety
Administration (OHSA), the US Department of Health Education
and Welfare (HEW), and-in some connections-the Environmental
Protection Agency (EPA). In the EEC as a whole, the relevant
regulatory body is the CEC. * Information can also in many cases be
obtained from the European Council of the Chemical Manufacturers
Federation (CEFIC). The main sources of information in the UK are
the Health and Safety Executive (HSE), the Health and Safety
Commission (HSC) , the British Plastics Federation (BPF) , and the
Chemical Industries Association (CIA), whilst in West Germany the
best source of official information is the Kunststoff Kommission des
Bundesgesundheitsamtes (BGA), i.e. the Commission for Plastics
of the Federal Health Office. Some of these organisations (e.g.
FDA, BPF) issue lists of substances (e.g. plasticisers, colourants,
stabilisers) approved (or forbidden) for food-contact applications.
In the UK the BPF publishes a code of practice for safety in use of
plastics for such applications, based in part on extensive evaluation
tests undertaken by the British Industrial Biological Research Associa-
tion (BIBRA).
Given an appropriately low residual VC monomer content, PVC
resins (homopolymers and copolymers) present no known health
hazard in PVC compounds.
* Commission of the European Communities.

24.5.3 Peripheral Hazards in Production, Processing, and Bulk

Conveyance
Most of these are common to many thermoplastics. They comprise the

fire and explosion hazards, respiratory hazards (where vapours and
fumes are evolved, or fine powders released into the atmosphere), and
toxic hazards. The appropriate precautions are nowadays reasonably
well known and observed in the industry.
The following points specific to PVC may be mentioned.
Under certain conditions, the presence of fine PVC resin dust can
lower the explosive limit of VCI air mixtures. Potentially ignitable
levels of gaseous VC may arise in high-speed mixing equipment.
Guidance on safe operation of high-speed mixers is provided in a
booklet published jointly by the BPF and the CIA (Vinyl Chloride
Monomer. Guide to the High Speed Mixing of pvc Resins and
Compounds ).
As reported by Butters,47 pure PVC dust of mean particle size
125 ~m has a minimum explosible concentration of 8·5 gm- 3, and a
minimum ignition energy of about 100 J (this is a high value, unlikely
to be encountered in a PVC processing plant). There is no history of
explosions with such materials. A guidance note published by the HSE
gives advice on the control of exposure to PVC dust: inter alia
methods are described of sampling and measurement of both total and
respirable contents of PVC dust in air (in accordance with HSC's
recommendations these concentrations should not exceed respectively
10 mg m- 3 and 5 mg m- 3). The note also mentions the health risks
involved in exposure to PVC dust and indicates the operations in
which exposure may occur.
24.6 BURNING BEHAVIOUR, FLAMMABILITY,

AND COMBUSTION PRODUCTS
The meanings (whether explained or implied) of the technical terms

used in this section are generally in line with the relevant standard
terminology4&--53 (but it should be noted that different standards'
definitions of one and the same term are not identical in all cases).
In particular, for the purposes of this section, the following
definitions are assumed.
Burning behaviour: All the physical and/or chemical changes that

take place when a material or product is exposed to a specified ignition
source. 48 ,51
Combustion: A chemical process of oxidation that occurs at a rate

fast enough to produce heat and usually light either as a glow or a
flame, and that may be accompanied by emission of smoke. 48,51
Flammability: A material's relative ease of ignition and relative

ability to sustain combustion (under specified or otherwise known
conditions) .
Flammable: Subject to relatively easy ignition and sustained flaming

combustion (under specified or otherwise known conditions).
Ignition: Initiation of combustion. 48
It is also worth noting that such apparently definitive terms as

'self-extinguishing', 'non-flammable', 'flame resistant', 'slow-burning'
can only have meaning in relation to a well-defined or specified set of
relevant conditions (e.g. those of a particular standard test). It is for
this reason-and the related possibility of serious consequences in the
event of a misunderstanding-that the first of these terms is depre-
cated, and its use discouraged, by the principal terminology standards.
24.6.1 General Burning Mechanisms
As in the case of other polymers and their derivative plastics, the

burning of PVC comprises two main processes: pyrolysis and
combustion. Pyrolysis is the heat-actuated breakdown of the polymer
(and any other pyrolysable formulation components) into products of
lower molecular weight, including simple, volatile, hydrogen-rich
carbon compounds, linear and cyclic. It is these pyrolysis products
that undergo and support the combustion. Both processes involve,
inter alia, the formation and recombination of free radicals: the ease
and rate of formation of these-and in particular of the OH'
radicals54 ,55-are thought to be significant factors in the flammability of
a plastics material. Both processes need suitably elevated temperatures
to initiate and sustain them: combustion additionally requires oxygen
(pyrolysis can proceed without it, although its absence may influence
the temperatures for commencement and maintenance of the process,

as well as the nature of degradation products formed). Pyrolysis starts
first: with a number of organic polymers the rate may be substantial at
about 300°C, as is the case for example with many PVC compositions,
even under nitrogen. 56 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 pyroly-
sis, which in turn provides more degradation products for the
combustion process (cf. Fig. 24.6).
The pyrolysis products may be initially 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~lectric 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. Some typical temperature values for PVC are: flash
ignition (in the test of ASTM 1929-78) 450°C (uPVC normal impact
strength gradelO); 420°C (a uPVC composition57 ); 391°C (PVC
polyme~8): spontaneous ignition of PVC polymer 454°C. 58 An ISO
standard is in preparation (cf. ISO/DIS 10093-1989), specifying
laboratory sources of ignition for use in fire tests on plastics.
24.6.2 Flammability of PVC
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 24.6.3). The low
flammability is due to the large chlorine content: like the other
halogens (cf., for example, PTFE in Table 24.9) chlorine acts as a
retardant in the process of combustion (see Chapter 9, Section 9.2).
The performance of PVC compositions in flammability tests falls
with increasing 'dilution' of the polymer by the other formulation
components (which decreases the overall chlorine content). This is the
main reason for the well-known fact that plasticisation increases
POLYMER
(or its derivative
plastic)
Pyrolysis +- - - - - - - - - - - --
I
I
I
I
I
Liquid or Gaseous (vapour Solid or I
semi-liquid phase)degradat~n semi-solid
degradation products degradation I
products
('tar')
products
(primary 'char')
I
I
I
I
I
Further pyrOlysis+---1
I
I
I
Solid I
carbonaceous I
Combustion residue I
(secondary 'char')
\
\
I
\
\
I
\ I
\
\
I
) I
Combustion
I
< /Heat" ,
products (including
CO, CO2 ,HP and / " II
/---------~
"" /
various oxides)
/
'V
Fig. 24.6 Simple, schematic representation of the general mechanism of

burning of polymeric materials.
flammability (d. e.g. Fig. 5.6 in Chapter 5), albeit this effect is
reduced in the case of chlorinated extenders and phosphate plas-
ticisers, since the former introduce their own chlorine, and the latter
can have some flame-retardant action. The flammability of 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
24.6.3 Products Generated by Burning PVC
These are often referred to simply as combustion products, but this is

not strictly accurate, as in fact they always include also compounds
generated by the pyrolysis of PVC polymer and of any other organic
constituents of the particular PVC composition.
(a) Chemical Nature

The products arising when PVC burns always include a substantial
proportion of hydrogen chloride (usually appearing as an acid, highly
irritant white fume), which is the principal product of thermal
breakdown of polyvinyl chloride and of copolymers in which the
VC-derived component predominates. Another substantial product of
drastic pyrolysis of PVC is benzene. 56 ,59 Other aromatic hydrocarbons
(notably toluene, xylene, naphthalene and some of their derivatives)
also appear, in· relatively minor proportions, and small amounts of
somealkenes and alkanes may also be formed. 56 ,59,61,62 The principal
products of the combustion part of the burning process are carbon
monoxide and carbon dioxide58 ,60 (the respective proportions depend-
ing on the oxygen supply and the temperature); some water is also
normally formed. 59 ,60 Methyl chloride and vinyl chloride have been
reported in trace quantities,56,59 but not free chlorine. The literature
on the products of burning PVC is extensive: several of the references
cited here themselves contain lists of earlier references.
Apart from other, more soundly grounded concerns about some
irritant and toxic substances generated by burning PVC, there crops
up from time to time-occasionally in a somewhat sensationalised
form-the allegation that, inter alia, dangerous quantities of phosgene
are evolved. To place this allegation in proper perspective, the

following questions must be considered in the light of the most reliable
factual evidence available to date. (i) Has phosgene indeed ever been
found among the products generated by burning PVC? (ii) If found
present, is this gas evolved in quantities substantial enough to
constitute a definite toxic hazard? (iii) Can any respiratory injuries or
any fatalities suffered by people in fires involving PVC be reliably
attributed to inhalation of phosgene? Regarding the first point, it
appears to have been established that some phosgene can be formed
when PVC is burning in certain conditions in laboratory experiments: 63
that it is not invariably generated is evidenced by some investigators'
flat statements that it was not detected in their experiments even
where sensitive detection methods were used. 56 In what was probably
the most thorough relevant study reported to date, Brown & Birky63
have found that, out of the four different sets of burning conditions
they investigated, only one resulted in the formation of significant
(albeit rather low) quantities (of the order of 10 ppm) of phosgene
(some fractional or low ppm were apparently produced under some of
the other conditions). The conditions in which the more significant
amounts of phosgene were generated in Brown & Birky's experiments
were somewhat exotic: electrical arcing between electrodes partly
covered with PVC, and flaming combustion in a cup furnace, initiated
by an electric arc: on the other hand, electrical overloading of a
PVC-clad wire appears to have produced very little phosgene. As
regards the third of the above-mentioned cardinal points, there is no
documented evidence of any casualties or fatalities directly at-
tributable to the effects of phosgene in connection with fires involving
PVC materials. At most, some speculations have been voiced regard-
ing a possible toxic hazard from this source. 64 ,65
Irrespective of the problematical and largely speculative question of
the presence and alleged hazards of any phosgene in actual fires
involving PVC materials, it is well known that the most harmful
PVC-derived constituents of the volatile products of such fires--and
the ones responsible for virtually all clearly documented casualties--
are hydrogen chloride and carbon monoxide (CO). The presence of
carbon dioxide can aggravate the harmful effects of CO, 66 whilst-in
any fire-<>xygen depletion is a major respiratory danger.
It may also be mentioned that the evolution of trace quantities of
toxic dioxins and dibenzofurans, sometimes alleged to be directly
generated when PVC burns, is more likely to be the indirect result of a

series of reactions initiated by an interaction of HCl from burning
PVC with some organic materials involved in the same fire. 67 ,68
(b) Smoke Emission

Any of the products of both pyrolysis and combustion may be found in
smoke emitted by a burning plastic. As regards its physical nature,
smoke is a suspension of particles in a mixture of air and the gases
and vapours generated in the burning process. 69 ,70 The particles may
be solid or liquid (or some of each), and-in some cases-may carry
condensed or adsorbed layers of the volatile smoke constituents.
Occasionally a particle may have a carbon 'skeleton,.71 Smoke from
burning PVC always contains the whitish fume of HCl condensed into
droplets (which may also contain some water). Some dark smoke is
usually generated by any phthalate plasticisers in burning pPVc.
Gases and vapours are invisible: hence, in any given case, for a
particular total amount of matter in the smoke, the smoke density
(usually defined in terms of obscuration of light in standard conditions)
will be a function of the proportion of smoke constituents present in
the particulate phase, and to some extent also of the particle size and
size distribution. In general, the higher the proportion of pyrolysis
products in the smoke (i.e. the less complete the combustion), the
greater the visible smoke density (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 tempera-
ture and the supply of oxygen); the same factors also influence the
parameters governing smoke density.
24.6.4 Burning Tests

No single laboratory test, or even a group of such tests, can fully
evaluate or predict the likely behaviour of a plastics material or
product in a large-scale fire. This is in part due to the fact that
conditions in fires can vary widely. However, providing that the
purposes and limitations of the available tests are properly under-
stood, and the most appropriate testes) applied in any given case, it is
TABLE 24.9
Oxygen Index Values of Some Plastics Materials
Material Oxygen index

(typical or
representative value)
PVC resin (homopolymer) 45

uPVC compound (medium impact strength) 40
uPVC compound containing 15% glass fibre 40
PVC floor tile (asbestos-filled) 30
pPVC compounds 21-26
PVDC 60
PTFE 95
Polyamide (nylon 6.6) 23
Polycarbonate 23-27
Polymethyl methacrylate 17-18
Polyethylene 17-18
Polypropylene 17-18
Polypropylene with flame retardant 22
Polypropylene asbestos-filled 21
Polystyrene 18
uPVC foam 25
pPVC foam 22
Polystyrene foam 18
Polystyrene foam with flame retardant 24
Polyurethane foam 19
Polyurethane foam with flame retardant 22
Polyisocyanurate foam 26
usually possible to obtain useful indications from the test results,

especially with regard to the fire-resistance ranking of a plastics
material in comparison with others.
Most of the standard burning tests to which PVC materials are
commonly subjected are applicable also to other plastics. In the brief
discussion in the present section only a few tests or groups of tests
have been singled out for a mention, either because of their general
importance, or their special interest in connection with some impor-
tant applications of PVC. Reference 10, 72, 73, 74, and 75 list various
burning test methods.
(a) Small-Scale Laboratory Tests

These are intended mainly as a means of preliminary comparison of
materials (e.g. in formulation modifications or quality control), and
can in some cases provide an indication of ease of ignition (by a small,

temporarily applied source) and self-maintenance of burning. They
cannot yield reliable information on the likely behaviour of a plastics
material in a large-scale fire. However, two such tests are widely
employed to characterise a plastic's propensity for burning. In many
cases their results are used in qualifying plastics products for certain
applications. The tests are: the Underwriters Laboratories' flam-
mability tese6 (the '94 V-O' rating in this test is widely accepted as
evidence of substantial resistance to burning), and the oxygen index
(limiting oxygen index) test (ISO 4589; BS 2782:Part 1:Methods A-D;
ASTM D 2863). The oxygen index figure is the minimum concentra-
tion of oxygen required to support-in the test conditions-the
burning (candle-fashion) of a standard specimen: thus the higher the
figure, the greater the resistance to burning. Some typical oxygen
index values are shown in Table 24.9. The flammability of PVC-coated
fabrics may be assessed in accordance with BS 5790 (actual test by
Method 17 of BS 3424); ISO 3795 (originally based on US Federal
Motor Vehicle Safety Standard 302) is also widely used for PVC-
coated upholstery fabrics.
(b) Larger-Scale Tests

Some of these tests are individually concerned with the key aspects of
a plastic's burning behaviour, viz. ignitability, surface spread of flame,
rate of heat release, and smoke emission.
Note: The determination of heat-release rate can be of particular
interest in material evaluations or investigations, in that it is a
material-related parameter: for a sufficiently high radiant
flux, the heat produced per unit mass of a polymeric
material depends virtually exclusively on the material's chem-
ical composition and the degree of ventilation. 77
Other tests are designed to cater for particular products or/and
service situations. In this category, three groups of tests may be
instanced for their relevance to important PVC applications, viz. fire
tests for cables, for building materials, and for conveyor belting. IEC
Publication 332 deals-in its various parts-with many cable tests,
including (in Part 3) large-scale tests for bunched cables important in
connection with a variety of installations. A test of this kind was first
developed at CESI (Centro Elettrico Sperimentale Italiano Giacinto
Motta SPA, Milan, Italy): a useful review of subsequent developments
and relevant considerations has been published by that organisation. 78

The stringent tunnel flame test for cable coverings provided by UL 910
specification may also be mentioned.
Fire tests for building materials are comprehensively covered by
multipart British and German Standards (BS 476 and DIN 4102), and
some relevant tests are also contained in such important American
specifications as ASTM E 119 (Heat endurance of materials), the
Steiner (25-ft) tunnel test specifications (ASTM E 84; UL 723; NFPA
255), the 8-ft tunnel test (ASTM D 286) and ASTM E 162 (the radiant
panel test). EEC Document 111-744-85 (the 'Blachere Report') and the
EUR 8750 are similar to, but less comprehensive than, Parts 20-22 of
BS 476 which are currently being finalised. The relevant ISO specifica-
tion is ISO 834 (Fire resistance of building elements).
Various fire tests for conveyor belting are provided in ISO 340; US
Code of Federal Regulations, Schedule 2G,Title 30; BS 3289 (similar
to NCB Specification 158-1980); DIN 22118; and the EEC standard
for the 'Gallery Test'. A review of the subject has been published
by Anderson. 79
24.6.5 Tests for Smoke Emission and Properties
(a) Smoke Density

None of the standard methods of test for emission of smoke by a
burning plastic can provide an accurate, absolute prediction of the
amount of smoke the material will evolve in an actual fire, just as the
composition of the smoke cannot be expected to be exactly the same
in the two cases. This is so because no two large-scale fires are
identical with respect to all factors influencing smoke emission and
composition, and because these factors in such fires do not generally
correlate closely with those in laboratory tests [a partial exception is
the good correlation claimed for the composition of smoke generated
in an NBS calorimeter-see (c) below]. Burning conditions also differ
between different laboratory tests. However, any established standard
laboratory test can be successfully used for direct comparison or
ranking of generally similar plastics materials, including PVC
compositions.
It is the 'optical density' of the smoke generated by a standard
specimen burning under specified conditions that is measured in a
typical laboratory test (in terms of the degree of obscuration of a light
beam passing through a smoke-collection chamber). In some tests the
smoke matter may also be collected on a filter and weighed. Of the

major standards concerned with smoke generation by plastics
materials, only one-ASTM 0 2843 (employing the XP-2 smoke
chamber originated by Rohm & Haas)-is entirely confined to a
smoke-density test. The others include determination of smoke
emission as one of the number of aspects of burning behaviour being
tested. Some of these standards are: ASTM E 662 (using the NBS
smoke chamber) and its derivative ASTM F 814 (specific to solid
materials for aerospace applications); standards for the Steiner tunnel
test [see 24.6.4(b) above]; BS 6401 (also employing the NBS cham-
ber), and the European Airbus specification AST 1000.001. An ISO
document (ISO/DTR 5924) also describes a dual-chamber test.
(b) Acid Index

As has been mentioned, the products of burning PVC (Le. in practice
the smoke generated) always contain a substantial proportion of
hydrogen chloride. The generation by plastics materials of acid
substances on burning, including the evaluation of HCl from PVC
compositions, is often measured and expressed in terms of the acid
index. This is defined as the number of milliequivalents of acid
(pH < 4) evolved per cubic centimeter of the original polymer when
burned in pure oxygen. so Properly interpreted, the acid index can
indicate the order of respiratory and corrosion hazards presented by
acid(s) in the smoke from a burning polymeric material. Some
illustrative examples of acid index values are: PVC polymer, 22;
'low-HCr PVC cable compound, 2; general-purpose PVC cable
insulation, 12; TFE/FEP copolymer, 52; flame-retarded E/VAC, 8;
polyethylene, O.
(c) Toxicity
As remarked by Brabauskas et aI., 66 the toxicology of combustion
products is still a young and growing science, and there is no
universally applicable method of fully evaluating the toxic hazards
presented by the volatile products of burning. Variants of two general
approaches are used: animal experiments, and what has been called
the 'N gas method': the latter assumes that a relatively limited number
of gases is responsible for the toxicity of the volatile products of
burning, so that hazards can be assessed by determining the con-
centrations of these gases in a suitable experiment. Sometimes a
'toxicity index' is then calculated by combining the individual results.
In any experiment, however, the conditions can strongly influence the

composition of the products of burning, and these conditions can vary
between different experiments and different large-scale fires. Two
fairly popular arrangements for burning specimens in a standard test,
with a view to susbsequent analysis (most often by gas chromatog-
raphy) of a sample of the atmosphere of the enclosure into which the
products of burning are released, are those of the British Naval
Engineering Standard 713, * and the NBS cone calorimeter. 81 The
latter has been designed to match, on a laboratory scale, the burning
conditions of a large-scale fire. A British draft standard currently
under discussion is also of interest in this general connection (87/36704
DC: The assessment of toxic hazards in fires in buildings).
24.6.6 Some Relevant Publications
In addition to the various references already cited, the following

further sources of information may be noted.
Troitzsch, J., International Plastics Flammability Handbook:
Principles, Regulations, Testing and Approval. Carl Hanser Verlag,
Munich, 1984.
Report on the Behaviour of pvc in Fires. British Plastics Federation
Fire Committee,t March 1987.
Fire Safety Aspects of Polymeric Materials (10 volumes). National
Materials Advisory Board of the USA Academy of Sciences, London,
1979.
REFERENCES
1. Kambour, R. P., Polym. Engng Sci., 8(4) (1968) 281-5.

2. Haward, R. N. (Ed.). The Physics of Glassy Polymers, Applied Science
Publishers, London, 1973.
3. Dempsey, L. T. Polym. Engng Sci., 7(2) (1967) 86.
4. Titow, W. V., Plast. Polym., 43(165) (1975) 98-101.
5. Wales, J. L. S., Polymer, 21 (1980) 684-90.
* Determination of the toxicity index of the products of combustion from small

specimens of materials.
t Lists 26 references.
6. Deanin, R. D. & Hauser, D. I., Polym. Plast. Technol. Eng., 17(2) (1981)
123-37.
7. Faulkner, P. G. & Atkinson, J. R., Plast. Polym., 40(147) (1972) 109-17.
8. Wolf, J., Gas, 87 (Nov. 1967),433.
9. Wolters, M., Plast. Rubb. Process. Applns, 3(4) (1983) 323-30.
11. (a) Bergen, R. L., Jr, SPE J., 20 (1964) 630-3. (b) Cheija, K., Werkstoffe
u. Korrosion, 19 (1968) 316-20. (c) Haslett, W. H., Jr & Cohen, L. A.,
SPE J., 20 (1964) 246-51. (d) Hubeny, H., Mitt. d. Chem. Forschungs-
inst. Sonderheft, (Feb. 1972) 54-9. (e) Menges, G. & Schmidt, H.,
Kunststoffe, 57 (1967) 881-5. (f) Richard, K. & Ewald, R., Kunststoffe,
49 (1959) 116-20. (g) Richard, K., Diedrich, D. & Gaube, E.,
Kunststoffe, 49 (1959) 616-21. (h) Henning, A. H., Krekeler, K.,
Menges, G. & Mittrop, F., Die Spannungsrisskorrosion bei Kunststoffen:
Zusammenstellung von Priifverfahren und Untersuchungen an PE und
PVC. Forschungsbericht des Landes Nordrhein-Westfalen, No. 1747.
KOln-Opladen, 1966.
12. Kroschwitz J. I. (Ed.), Electrical and Electronic Properties of Polymers.
John Wiley and Sons, New York, 1988.
13. Katz, M., Shkolnik, S. & Ron, I., 34th ANTEC SPE Proceedings, 1976,
p.511.
14. De Coste, J. B. & Hansen, R. H., SPE J., 18(4) (1962) 431-9.
15. Gamer, B. L. & Papillo, P. J., Atlantic City Meeting, 9-14 Sept. ACS
Organic Coatings and Plastics Chemistry Div., 22(2) (1962) 110-13.
16. Caryl, C. R. & Helmick, W. E., US Patent 2 945 417 (1960).
17. Caryl, C. R. SPE J., 23(1) (1967) 49.
18. Davis, A. & Sims, D., Weathering of Polymers. Elsevier Applied Science
19. Gish, B. D. & Jablonowski, T. L., Weathering Tests for EPDM Rubber
Sheets for Use in Roofing Applications. Paper presented at the 8th
NBS/NRCA Conference on Roofing Technology, Gaithersburg, USA, 16
April 1987,
20. Ives, G. c., Mead, J. A. & Riley, M. M., Handbook of Plastics Test
Methods, Iliffe Books, London, 1971.
21. Szabo, E. & Lally, R. E. Polym. Engng Sci., 15(4) (1975) 277-84.
22. Grossman, G. W., J. Coatings Technol., 49(633) (1977) 45-54.
23. Gliick, L. & Poschet, G., Kunststoffe, 72 (1982) 353-8.
24. Gugumus, F. In Plastics Additives, ed. R. Gachter & H. Miiller. Hanser
Verlag, Munich, Vienna and New York, 1984, p. 97.
25. (a) ISO/DP 9370.2-1986. Guide to the Instrumental Determination of
Radiant Exposure in Weathering Tests. (b) ISO/DTR 9673-1987. Solar
Radiation and its Measurement for Determining Outdoor Exposure
Levels.
26. Scrivener, A. J., Weathering of rigid PVC. Paper presented at the PISA
conference, 28/29 May 1986, Durban, RSA.
27. Scott, J. L., J. Oil Col. Chem. Assoc., 65 (1982) 182-90.
28. Zahradnik, B. & Jurriaanse, A., 42nd ANTEC Proceedings, 1984, pp.
397-400.
29. Cassel, B. & Gray, A. P., Plast. Engng, 33(5) (1977) 56-8.
30. Clash, R. F., Jr & Berg, R. M., ASTM Symposium on Plastics,
Proceedings, 1944, p. 54.
31. ISO 2578-1974. Plastics-Determination of time-temperature limits after
prolonged action of heat.
32. Anon., Guide for the Determination of Thermal Endurance Properties of
Electrical Insulating Materials. IEC Publication 216-1987.
33. ASTM D 3045-74 (1984). Standard Practice for Heat Aging of Plastics
without Load.
34. Reymers, H., Mod. Plast., 47(9) (1970) 78-81.
35. Scullin, J. P., Girard, T. A. & Koda, C. F., Rubb. Plast. Age, 46(3)
(1965) 267-8.
36. Decoste, J. B., Ind. Engng Chem., 7(4) (1968) 238-47.
37. Kaplan, A. M., Greenberger, M. & Wendt, T. M., Polym. Engng Sci.,
10(4) (1970) 241-6.
38. Wessel, C. J., SPE Trans., 4 (1964) 193-207.
39. Bultman, J. D., Southwell, C. R. & Beal, R. H., Naval Res. Lab. Report
No. 7417, Washington, DC, 1972.
40. Weast, R. C. & Astle, M. J. (Eds) CRC Handbook of Chemistry and
Physics, 60th edn. CRC Press Inc., Boca Raton, FL, 1979-1980, pp.
D-195 and 196.
41. Hopfenberg, H. B. (Ed.), Permeability of Plastics Films and Coatings.
Plenum Press, New York, 1974.
42. Lebovits, A., Mod. Plast., 43 (March 1966), 139-46, 150, 194-213.
43. Hennessy, B. J., Mead, J. A. & Stenning, T. C., The Permeability of
Plastics Films. Plastics Institute, London, 1966.
44. Shur, Y. J. & Ranby, B., J. Appl. Polym. Sci., 19(7) (1975) 1337-46.
45. Anon., Chem. Engng News, (8 March 1976), p. 6.
46. Anon., New Scientist, 183 (19 April 1979), No 1151, 185.
47. Butters, G., Plast. Rubb. Process. Applns, 5(1) (1985) 27-33.
48. ISO/TAG 5 N50 (1987). Unified Glossary of Terms-Fire Tests (Draft
ISO /IEC Guide).
49. ISO 3261-1975. Fire Tests-Vocabulary.
50. ISO 472-1979/Add. 2-1983 (E/F). Terms Relating to Burning Behaviour.
51. Anon., Compilation of ASTM Standard Definitions, 6th edn, 1986.
52. IEC Publication 695 Part 4 (1986). Terminology Concerning Fire Tests.
53. ASTM E 176-88a. Standard Terminology Relating to Fire Standards.
54. Mascia, L., The Role of Additives in Plastics. Edward Arnold, London,
1974.
55. Collington, K. T., Plast. Polym., 41(151) (1973) 24-9.
56. Clark, C. A., SPE J., 28 (July 1972) 30-4.
57. Paul, K. T., Plast. Rubb. Proc. Applns, 4(3) (1984) 221-8.
58. Cullis, C. F. & Hirschler, M. M., The Combustion of Organic Polymers.
Clarendon Press, Oxford, 1981, p. 47.
59. Hurst, N. W. & Jones, T. A., Fire and Materials, 9(1) (1985) 1-8.
60. Edgerley, P. G. & Pettett, K., Plast. Rubb. Proc. Applns, 1(2) (1981)
133-7.
61. !ida, T., Nakanishi, M. & Goto, K., J. Polym. Sci., Polym. Chem. Ed.,
13(6) (1975) 1381-92.
62. Mitera, J. & Michal, J., Chem. Prum., 26(8) (1976) 417-20.
63. Brown, J. E. & Birky, M. M., J. Anal. Toxicol., 4 (Jul./Aug. 1980)
166-74.
64. Donovan, L., R.N., 41(2) (1978) 58-63.
65. Durant, R. B., Navy Lifeline, Occup. Safety and Health J., (Jan/Feb.
1978) 10-11.
66. Babrauskas, V., Levin, B. C. & Gann, R. G., Standardization News,
14(9) (1986) 28-33.
67. Eduljee, G. H., Chemistry in Britain, 25(5) (1989) 467.
68. Choudhry, G. G. & Hutzinger, 0., Mechanistic Aspects of the Thermal
Formation of Halogenated Organic Compounds, Including Polychlorinated
Dibenzo-p-dioxins. Gordon & Breach Science Publishers, London, 1983.
69. Titow, W. V., Trans. Plast. Inst., 29(84) (1961) 186-95.
70. Gaskill, J. R., ASTM Standardization News, 7(12) (1979) 23-4.
71. Tadihisa, J., Res. Inst. Japan, 33 (1971) 40-4.
72. Anon., Flammability Test Methods for Plastics: An International List.
Chemical Industries Association Ltd, London, 19
73. Anon., Flammability Standards and Flammability Test Methods (2 vol-
umes). Technomic Publishing Co. Inc., Lancaster, PA, USA, 1982.
74. PD 6520: 1988. BSI Guide to Fire Test Methods for Building Materials and
Elements of Construction.
75. Brown, R. P. (Ed.), Handbook of Plastics Test Methods, 2nd edn. George
Goodwin/PRI, London, 1981.
76. ANSI/UL 94-1985. Tests for Flammability of Plastics Materials for Parts
in Devices and Appliances.
77. Tewarson, A., Polym. Phys. Group Bulletin, 24 (July 1985) 14.
78. Farneti, F., Gasparini, G. & Ostano, P., Fire Propagation along Cable
Bundles: Influencing Factors, Test Methods and State of the Art of the
Relevant Standards. CESI Publication 85/44, 1985.
79. Anderson, A. E., Plast. Rubb. Proc. Applns, 4(4) (1984) 355-63.
80. Warren, P., The acid index-a property of polymer combustion. Paper
presented at the 33rd Wire and Cable Symposium, Reno, Nevada, USA,
November 1984.
81. Babrauskas, V., Fire and Materials, 8 (1984) 81-95.
APPENDIX 1
Some Material Properties of pvc

Products and Compounds
851
Property and Brief definition Common units Some standards relevant Typical values or value ranges
usual symbol to determination for PVca
in plastics
Rigid PVC Flexible PVC
Density Mass of unit volume. For kgm- 3 ; ISO/R 1183-1970;e M; S: 1·30- M: H0-1·35g
p practical purposes numer- gcm- 3 ; BS 2782: Part 6: Methods 1·45gcm- 3 cm- 3
ically equal to relative Ibin- 3 ; 620A-D: 1980; M(G): approx.
density (also sometimes lb ft- 3 BS 4618: Section 5.1: 1970; 1·5gcm- 3
called specific gravity), ASTM D 792-66 (1979) (Dis- F: approx. 1·4
which is the ratio of the placement method); gcm- 3
density of a material to ASTM D 1505-85 (Density PVC
that of water at the same gradient tube); homopolymer:
temperature DIN 53 479-1976 1·4gcm- 3
Tensile Maximum stress which the Nm- 2 (=Pa); ISO/R 527-1966; M: 31-60MPa M (and other
strength material will withstand Ibfin- 2 (psi); ISO/R 1184-1983 (For films); (BS2782 or compounds):
aTb before failure (yield or kgfcm- 2 ISO 6239-1987 (For small ASTMD638t 10-25MPa
break) For fibres: g per specimens) ; M(G): approx. (BS 2782)
N.B. Comments on denier, or g per BS 2782: Part 3: 1l0MPa S: 15-21MPa
common types of tex Methods 320 A to F: (ASTM D 638) (ASTMD882)
failure in strength 1986 S: 38-45MPa
tests are given Methods 326 A to C: F: 2·7-3·0 g per
in BS4618: 1983 (for films); denier (=330-
Section 1.3: 1975 ASTM D 638-84; 370MPa
ASTM D 882-83 (For thin sheet approx.)
and films);
ASTM D 1708-84 (Microtensile
specimens) ;
DIN 53 455-1981
Elongation at The increase in the length of Normally % of As for tensile strength M: 2-40% M: 150-400%
break (or a test specimen caused by the original (measured in the same M(G): 1-2% S: 120-250%
yield) the tensile stress at the length; oc- tests) S: 5-35%
eT d moment of rupture (or casionally units F: 10-20%
yield) of length
Flexural Maximum stress in the outer As for tensile ISO 178-1976;e M: 62-100 MPa Very low values
strength fibre of a specimen at the strength BS 2782: Part 3: Method (ASTM 0 790) for normally
a/ moment of break in bend- 335A:1983; M(G): approx. plasticised PVC
ing (in specified ASTM 0 790-84; 138MPa materials
conditions) DIN 53 452-1977 (ASTMD 790)
N.B. Flexural strength
at yield is the
analogous stress at
yield (calculated
from a formula ap-
propriate to the
test method)
Tear resist- Force or load (stated di- N; kgf; lbf; ISO 6383-1983: Parts 1 and 2 S: 20-100Nmm- 1
ance (tear rectly or per unit speci- or BS 1763: 1975 (Thin sheeting:
strength) of men thickness) required g; oz; lb; Elmendorf test);
sheeting and to initiate tearing or/and or BS 2739: 1975 (Thick sheeting);
film propagate a tear in spec- Nmm- 1 ; BS 2782: Part 3: Method 360B:
ified test conditions kgfmm- 1 1980 (Trouser-tear test);
aM = mouldings; M(G) = mouldings with 25% glass fibre; S = sheeting and/or film; F = fibre.
b,d Symbol not in wide general use.
e 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).
e Under revision.
(continued)
usual symbol to determination for pvca
in plastics
Tear ASTM D 1004-66 (1981);

resistance ASTM D 1922-67 (1978)
(contd) (Elmendorf test);
ASTM D 1938-67 (1978);
ASTM D 2582-67 (1978) (snag
resistance) ;
DIN 53 363-1979
Impact Energy required to break a Nm (=J); Flexural impact tests M:0·5- With small
resistance standard test piece by kgfcm: Izod: 25lbf ft in- l amounts of plas-
(Impact impact in a standard test. lbf ft; ISO 180-1982; (ASTM D 256) ticiser impact
strength) N.B. A useful outline of per unit length BS 2782: Part 3: M(G): approx. strength can be
impact behaviour of of notch (for Method 350: 1984; 1lbfftin- 1 very low «
plastics is given in BS notched ASTM D 256-84, (ASTMD 256) 0·5lbfft in-I),
4618: Section specimens) or Methods A and C the embrittle-
1.2: 1972 (with special per unit area of Charpy: ment being
reference to design the cross- ISO 179-182: caused by the
data) section of the BS 2782: Part 3: so-called 'anti-
unnotched part, Method 359: 1984; plasticisation'
or (for un- ASTM D 256-84, effect. Very
notched Method B; high at normal
specimens) per DIN 53 453-1975 plasticiser
unit specimen Dynstat: contents
width or cross- DIN 53435-1977
sectional area
Falling weight or dart
ISO 6603: Part 1-1985 (for rigid
plastics);
BS 2782: Part 3: Method
352D: 1979 (for thin film);
ASTM D 3029-84 (for sheeting
or parts);
ASTM D 4272-85 (instrumented
dart);
DIN 53 443-1975
Tensile impact
ISO/DIS 8256-1987:
ASTM D 1822-84;
DIN 53 448-1977
Miscellaneous
ASTM D 3998-81 (test carried
out on plastometer
extrudates);
ASTM D 45088 (test on 'chips',
i.e. small, fiat specimens')
Hardness Ability of material to resist Completely arbi- Durometer (shore) hardness M (and other M (and other
indentation under rigidly trary, related to ISO 868-1985; compounds): compounds):
specified conditions (in- arbitary hard- BS 2782: Part 3: Method Durometer BS softness no.
cluding particular, spec- ness scales used 365B:1981; (Shore D 15-90
ified combinations of in- in particular test BS 2719: 1975 (pocket-type sca1e)65-85 Durometer (Shore
dentor and stress) methods (e.g. instrument); Rockwell (R A scale) 50-95
N .B. Determination of hard- Shore, ASTM D 2240-85; scale) 110-120 Rockwell (R
ness by scratch resis- Rockwell, Bar- DIN 53 505-1985 Ball indentation scale) 5-80
tance is not relevant to col specified (DIN 53456):
PVC scale units) BS softness numbe,s 75-155
365A:1983
f Readily machined from products or exposure-test specimens (e.g. weathering). Test very sensitive to presence of microcracks.
g Applicable mainly to pPVC. (colllinued)
usual symbol to determination for PVC"
in plastics
Ball-indentation hardness
ISO 2039: Part 1-1987;
BS 2782: Part 3 : Method
365D:1983:
DIN 53 456-1973
Rockwell hardness
ISO 2039:Part 2-1981;
365C: 1986;
ASTM D 785-65 (1981)
Barcol Hardness h
1001:1983
(identical with European stand-
ard EN 59)
ASTM D 2583-87
Elastic moduli:
(a) in tensioni Ratio of tensile stress to As for tensile ISO/R 527-1966; M (and other Very low at nor-
E tensile strain in revers- strength BS 2782: Part 3: Methods 320A compounds): mal plasticiser
ible conditions to F: 1986; 2·5-3·5GPa contents
N.B. Secant modulus: The ASTM D 638-84; (ISO, BS,
ratio of stress to cor- ASTM D 882-83 (For thin sheet ASTM or DIN
responding strain at and films); methods)
any given point on the DIN 53 457-1968
stress-strain curve
(b) in shear 'Modulus of rigidity': ratio As for tensile (or ISO 458-1985 M (and other Very low at nor-
G of shear stress to shear shear) strength Part 1 (General compounds) : mal plasticiser
strain in reversible method--flexible 1·0-1·8GPa contents
conditions materials) ;
N.B. In practice usually de- Part 2 (Stiffness in
termined by torsional torsion of pPVC);
methods ISO 537-1980 (Torsion pen-
dulum method);
ASTM D 1043-84 (Torsion
test);
ASTM D 4065-82 (Inter alia
replacing ASTM D 2236
withdrawn in 1985);
DIN 53 447-1981 (Torsion
pulley method)
(c) in flexure Ratio of stress to cor- As for tensile (or ISO 178-1975;e M: 2·0-3·5 GPa Very low at nor-
EB responding strain in bend- flexural) ISO/TR 4137-1978 (Alternating (ASTMD 790) mal plasticiser
ing, in reversible strength flexure method); M(G): approx. contents
conditions ISO 6721-1983 (Complex mod- 8·5GPa
ulus by bending vibration); (ASTMD 790)
BS 2782: Part 3: Method 332A: S: 2·0-3·0 GPa
1983 (Stiffness of film): (BS 2782:
Method 335A: 1983; Method 335A)
ASTM D 747-84 (Cantilever
beam method);
ASTM D 790-84;
DIN 53 457-1968
~ Relevant to glass-reinforceo plastics.

i Also known as Young's modulus, elastic modulus, or modulus of elastiCity.
(continued)
in plastics
(d) in COffi- 'Bulk modulus': ratio of As for tensile (or ISO 604-1973;e M: 2·2-3·5 GPa Low at normal
pression K change in external pres- compressive) ASTM D 695-85; (ASTMD 695) plasticiser
sure to fractional change strength DIN 53 457-1968 contents
in volume, in reversible
conditions
Vicat The temperature at which a °C or of ISO 306-1974;' M (and other M (and other
softening flat-ended needle of spec- BS 2782; Part 1: Methods 120A compounds) : compounds):
point ified dimensions pene- to E: 1983; 65-1000C (ISO General-purpose
trates a specimen to a ASTM D 1525-82: 306: 5 kg load) plasticised
prescribed depth under a DIN 53 460-1976 compound typi-
prescribed load (usually cally about
1 kg or 5 kg), in standard 4OOC, but the
test conditions range is wide
(ASTMD 1525
does not recom-
mend the test
for pPVC for
that reason)
Thermal con- The quantity of heat which See relevant con- BS 874: 1973 (1980); M (and other M (and other
ductivity passes in unit time version table in BS 4618:Section 3.3: 1973; compounds): compounds):
k;'A through unit area of a Appendix 2 ASTM C 177-85; 0·14-0·28 0·14-0·17
slab of uniform material DIN 52 612-1979 Wm-1K- 1 Wm-1K- 1
of infinite extent and unit (ASTMC 177) (ASTMC 177)
thickness, when unit differ-
ence of temperature is
established between its
parallel faces
Coefficient of Change in length per unit K-\ °C- 1 ; °F- 1 BS 4618: Section 3.1: 1970; M (and other M (and other
linear thermal original (reference) length ASTM D 696-79; compounds) : compounds):
expansion (l' per degree temperature ASTM E 228-85 (Dilatometer); (5 -15) (10- 25)
change; i.e. ASTM E 831-81 (By thermo- x 1O- 5 K- 1 x 10- 5 K- 1
mechanical analysis); (ASTMD 696) (ASTMD 696)
(l' = llL/(Lo . llT) VDE 0304: Parts 1 and 4 M(G): 2·7 x 10- 5
N.B. For cubical (ASTMD 696)
thermal expan-
sion:ASTMD
864-52 (1978)
Deflection The temperature at which, °C; of ISO 75-1987; M (and other Very low at nor-
temperature in specified conditions, a BS 2782: Methods 121A and compounds) : mal plasticiser
underload test specimen (bar of B:1983; 6O-800 d (ISO, contents (pPVC
prescribed dimensions) ASTM D 648-82; BS, ASTMor not normally
undergoes a specified de- DIN 53 461-1969 DIN) tested for this
flection under a flexural M(G): 70-90od property)
load causing a maximum (ISO, BS,
fibre stress in the speci- ASTMor
men of either 1·82 MPa DIN)
(264lbf in -2) or
0·455 MPa (66lbfin- 2)
Deformation Percentage deformation of a % BS 2782: Part 1: Method M (and other
under heat of sheet specimen of pre- 122A:1983 compounds):
flexible PVC scribed dimensions by a 15-65%
compoundsk specified load at 70°C, (BS2782)
under stated test
conditions
j At 254Ibfin- 2 •
k The temperature of heat distortion (extension or shrinkage), under tensile load, of 0·0025-1·5 mm thick, relatively stiff plastics sheeting
(room-temperature elastic modulus >69 MPa) may be determined by the method of ASTM D 1637-83.
(continued)
in plastics
Specific heat Amount of heat required to Jg- 1 K-\ BS 4618: Section 3.2: 1973; M (and other M (and other
c raise the temperature of a leal g-1 .C- 1; ASTM C 351-82 compounds): compounds):
unit mass of material by lBtu Ib- 1 "F- 1 0.8-0.9 J g-1 K- 1 1.0-2.0 J g-1 K- 1
one degree (within a spec-
ified temperature range)
Permittivity'" Ratio of the capacitance None ISO 1325-1973 (Electrical pro- M (and other M (and other
(dielectric (Cx ) of a given configura- (a ratio) perties of thin sheet and compounds): compounds) :
constant) tion of electrodes with the film); 3·3-3·6 at 4·5-8·5 at
k'; e' particular material as the BS 2782: Part 2: Methods 240 A 50 Hz; 2·9-3·1 50 Hz; 3·5-4·5
dielectric, to the capacit- and B: 1982: at 1 MHz at 1 MHz
ance (Cv ) of the same BS 4618: Section 2.1: 1970; (ASTMor (ASTMor
electrode configuration ASTM D 150-81; DIN) DIN)
with vacuum (or air) as DIN 53 483-1969, 1970:
dielectric; i.e. k' = Cx/Cv IEC Publ. 250-1969
Loss tangent" The ratio of true power None ISO 1325-1973 M (and other M (and other
(dissipation dissipated to the apparent (a ratio) BS 2782: Part 2: Methods 240 A compounds): compounds):
factor)O power absorbed during and B:1982 0·007-0·017 at 0·08-0·15 at
tan c5 the passage of an alternat- BS 4618: Section 2.2: 1970 60 Hz; 0·006- 60Hz; 0·04-
ing current through a ASTM D 150-81 0·019 at 1 MHz 0·14 at 1 MHz
dielectric DIN 53 483-1969, 70 (ASTMD 150) (ASTMD 150)
Resistivity Volume resistivity: The el- Om BS 4618: Section 2.3: 1975; M (and other M (and other
p;s ectrical resistance between 0 cm BS 2782: Part 2: Methods 230A compounds): compounds):
opposite faces of a unit- and B:1982; About 1016 1012_lOIS 0 em
side cube of the material ASTM D 257-78 (1983); o em or higher at 60% RH;
N.B. May also be defined in DIN 53 482-1967; at 60% RH; room tempera-
terms of potential gra- IEC Publ. 93-1980 room temperature (ASTM;
dient and current den- ture (ASTM; DIN)
sity (see, e.g., ASTM DIN)
D 257 or BS 4618:
Section 2.3)
Surface resistivity: The resis- g BS 4618: Section 2.4: 1975; M (and other M (and other
tance between surface- BS 2782: Method 231A: 1982; compounds): compounds):
mounted electrodes of ASTM D 257-78 (1983); 1013 _10 14 g at 1011 _10 12 gat
unit width, at unit spacing DIN 53 482-1967; 60% RH; 60% RH;room
N.B. May also be defined in IEC Publ. 93-1980 room tempera- temperature
terms of potential gra- ture (DIN) (DIN)
dient and current per
unit width of surface
(see, e.g. ASTM D
257 or BS 4618 Sec-
tion 2.4)
Insulation For a set-up of two elec- g BS 2782: Part 2: Method Example (core of
resistance trodes in contact with, or 232:1983; 600-1000 V
(dependent embedded in, a IE Publ. 167-1964 cable):
upon both specimen-the ratio of the N.B. Dielectric resistance of 50MQ km- 1
volume and direct voltage applied to cables (cores or
surface the electrodes to the total coverings) also
resistivity current flowing between sometimes determined
of specimen) them directly (in MQ km- 1 )
Electric The maximum potential gra- kVmm- 1 BS 2782: Part 2: Methods 220
strength dient that the material can and 221 : 1983
withstand without rupture
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)
usual symbol to determination for pvca
in plastics
Dielectric Field strength (ratio of ap- Vm- l ; Vcm- l ; BS 2782: 1970: Methods 201; M (and other M (and other
strength plied voltage to thickness) V mm- l ; V mil- l ASTM D 149-81; compounds): compounds):
required to produce (1 mil = 0·001 in) DIN 53 481-1974 400-500 250-400
breakdown of the material V mil-l V Mil-l
under specified test (ASTM- (ASTM-
conditions specimen specimen
125 mil thick) 125 mil thick)
Water The amount of water ab- g; mg;mass % ISO 62-1980P ,q (Cold water M (and other M (and other
absorption sorbed by a standard (volume % for absorption; boiling water compounds): compounds):
specimen in prescribed cellular plastics) absorption) ; 8-50mg 30-150mg
test conditions BS 2782: Part 4: Methods 430 A (48h);(BS (48 h); (BS
to D: 1983 (B and D allow for 2782: Method 2782: Method
water-soluble matter) 5OlC) 0·07- 5OlC) 0·15-
ASTM D 570-81;Q 0·4O%r (ASTM 1·0%r(ASTM
ASTM D 2842-69 (1975) (for D57~24h D57~24h
cellular plastics); specimen specimen 0·125
DIN 53 495-1984 (Superseding 0·125 in thick) in thick)
DIN 53 471 AND 53 473)
Abrasion Resistance to surface da- No conventional ASTM D 1044-78 (Taber Abrasion resistance of PVC materials
resistance mage or wear caused by units. Measured abraser); and products varies widely depend-
rubbing by prescribed in terms of mass ASTM D 1242-56 (1981); ing, inter alia, on formulation and
abrasives in strictly spec- loss by speci- ASTM D 673-70 (1982) (Mar test conditions. As an example, loss
ified conditions men, or visual resistance) ; by calendered sheeting in a version
N. B. Abrasion resistance effects, e.g. DIN 53 754754-1977 of the Taber test may be 10-8Q mg
(adhesion) of print on marring of sur" per 1000 cycles under a 1 ~g load
thin PVC sheeting face, loss of (with a CS-10 wheel)
prescribed in BS transparency
1763:1975 (measured
according to BS
2782: 1970: Method
,lOR)
Coefficients The two coefficients of fric- None (a ratio) ISO 8295-1986 (fAs and fAD of The values of friction coefficients
of friction tion, static" (fAs) and film and sheet); of PVC depend cardinally on the
fA dynamic' (fAD) are defined BS 2782: Part 8: Method formulation, and generally decrease
by the expressions: 824:1984; with increasing rigidity
BS 4618: Section 5.6: 1975; M (and other M (and other
fAs=FslL fAD = FOIL compounds); compounds);
ASTM D 1894-78 (fAs and ltD of
where Fs = the minimum film and sheet); Also S: normally Also S:
force required to initiate ASTM D 3028-83 (ltD of solid <0·2 about
sliding; FO = minimum plastics and sheet); 0·2-2·0
force required to maintain IEC Pub!. 648-1979
it (at a particular speed);
and L = the force (usually
gravitational) acting nor-
mally to the surfaces to
maintain their contact
Refractive Ratio of the velocity of light None (a ratio) ISO 489-1983; PVC resin: ap- The refractive in-
index in vacuo to the velocity in BS 4618: Section 5.3: 1972; prox.1·55 dex is often
fA;n the particular material ASTM D 542-50 (1977); M: 1·52-1·55 lowered by
DIN 53 491-1955 plasticisation,
but the effect
(like compound
clarity) depends
on the plasti-
ciser (and the
formulation
generally).
P Identical with ISO 62.

q Methods close technically to those of ISO 62.
, Highest absorption is exhibited by some filled compounds.
• Also known as the starting coefficient of friction.
, Also known as the kinetic or sliding coefficient of friction.
APPENDIX 2
Quantities and Units: The SI System:

Unit Conversion Tables
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 for their general relevance in this
context to the material presented in the book.
Sources of further information include the following standards and
publications.
ISO 31, Parts 0-13

This mUlti-part specification (British equivalent BS 5775) deals with
quantities, units and symbols in the following aspects and fields:
general principles (Part 0); space and time (Part 1); periodic and
related phenomena (Part 2); mechanics (Part 3); heat (Part 4);
electricity and magnetism (Part 5); light, and related electromag-
netic radiations (Part 6); acoustics (Part 7); physical chemistry and
molecular physics (Part 8); atomic and nuclear physics (Part 9);
nuclear reactions and ionising radiations (Part 10); physical sciences
and technology (Part 11); dimensionless parameters (Part 12);
solid-state physics (Part 13).
ISO 1000. SI units and recommendations for the use of their multiples
and of certain other units (British equivalent BS 5555).
BS 350. Conversion factors and tables
(Part 1: 1983, and Supplement No.1: 1982 to Part 2). *
* Part 2 itself now withdrawn.

864
A2 Material Properties of pvc Products and Compounds 865
The International System of Units. HMSO, London, 1973.

Quantities, Units and Symbols. The Royal Society, London, 1975.
Quantities and Units of Measurement: A Dictionary and Handbook,
Drazil, J. V. Mansell, New York, 1983.
A Dictionary of Scientific Units, Including Dimensionless Numbers and
Scales, Jerrard, H. G. & McNeill, D. B. Chapman & Hall, London,
1986
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.
Named Units of the SI System
Quantity (usual symbol(s) Unit Common Equivalent in

in brackets) equivalent base (and
Name Symbol in SI supplementary)
units SI units
Base units Length (L, I) metre m

Mass (M, m) kilogram kg
Time (T, I) second
Electric current (/) ampere A
Thermodynamic temperature
(8, T) kelvin K
Luminous intensity (J, J) candela cd
Amount of substance (N, n) mole mol
Supplementary Plane angle (ll', (3, y, e, <p, etc.) radian rad
units Solid angle (Q, w) steradian sr
Derived units Absorbed dose (ionising
wilh special radiation) gray Gy J kg-I m2s '-2
names Electric capacitance (C) farad F Cyl S4 A 2 m- 2 kg- 1
Electric conductance (G) siemens S Ay-I s-' A 2 m- 2 kg- 1
Electric potential,
tension (V, U) volt Y WA I m 2 kgs--' A-I
Electric resistance (R) ohm Q YA- I m 2 kgs--'A- 2
Energy (E), Work (W, w),
Quantity of heat (Q, q) joule J Nm m2 kg S-2
Force (F) newton N m kg S-2
Frequency (v, f) hertz Hz S-I
Illuminance (E) lux Ix cd sr m- 2

Inductance (L, M) henry H m 2 kg S·2 A- 2
Luminous flux (<I» lumen 1m cd sr
Magnetic flux (<I» weber Wb m2 kgs- 2 A- I
Magnetic flux density (B) tesla T kgs- 2 A-I
Power (P), Energy flux (E q,) watt W m 2 kg s--'
Pressure (p), Stress (G, r) pascal Pa kgm- I S-2
Quantity of electricity,
Electric charge (Q, q) coulomb c As
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.
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.
Multiple X 1018 X 1015 X1012 X 109 X 106 xlW xlOZ xlO

Prefix exa peta tera giga mega kilo (hecto) (deca)
Symbol E P T G M k h da
Sub-
multiple xlO- 1 X 10- 2 xlo- 3 X 10-6 X 10-9 X 10- 12 X 10- 15 xlo- 18
Prefix (deci) (centi) milli micro nano pico femto atto
Symbol d c m I' n P f a
Unit Conversions: Time
SI unit Other common units
s year dD hD minD
(solar day)b (hour) (minute)
1 3·169 x 10-8 1-157 X 10- 5 2·778 X 10- 4 1·667 X 10- 2

3·155 6926 x 107 1 365·24 8·766 x 103 5·259 X 105
8·640 X 104 2·738 X 10- 3 1 24 1440
3600 1-141 X 10- 4 4·167 X 10- 2 1 60
60 1·901 X 10-6 6·944 X 10- 4 1·667 X 10- 2 1
D Units recognised for use with the International System.
b 1 sidereal day = 86164·090 6 seconds; 1 year = 366·25 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.
A2 Material Properties of pvc Products and Compounds 867
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.
Unit Conversions: Area
Sf units Other common units
1 1 X 104 1 X 106 1·196 10·764 1·550 x 103

1 X 10- 4 1 100 1.196x 10- 4 1·076 x 10- 3 0·1550
1 x 10- 6 0·01 1 1·196 x 10- 6 1·076 x 10- 5 1.550x 10- 3
0·8361 8.361 x 103 8·36127 X 105 1 9 1·296 X 103
0·09290 929 9·2903 x 104 0·1111 1 144
6·452 x 10- 4 6·4516 645·16 7·716 x 10- 4 6·944 x 10- 3 1
Unit Conversions: Density

SI units Other common units
kgm- 3 gcm- 3 kg litre- 1 lb in- 3 lbfr 3 lb UK gar 1
1 1 x 10- 3 1 X 10- 3 3·6127 x 10- 5 0·062428 0·010022

1x103 1 1 0·036127 62-4280 10·0224
1x103 1 1 0·036127 62·4280 10·0224
2·767 99x 104 27-6799 27-6799 1 1·728 x 103 277-419
16·0185 0·0160185 0·0160185 5·787 Ox 10-4 1 0·160544
99·776 0·099776 0·099776 3·604 6 x 10- 3 6·22884
Unit Conversions: Mass Flux
Sf unit Other common units
1 3600 6 737·34
2·777 6x 10- 4 1 1·6666 x 10- 3 0·20481
0·16666 600·00 1 122·89
1·3561 x 10- 3 4·88243 8·137 Ox 10- 3 1
~
"tl
Unit Conversions: Length
~
::s!
E;
:::.
Sf units Other common units Q
m cm mm p,mQ A yd ft in ~~
(angstrom) (yard) ~
(foot) (inch)
:::
!ll .
1 100 1000 1 X 106 1 X 1010 1·093610 3·28084 39·3701 •1ll
0·01 1 10 1 X 104 1 X 108 0·010936 0·032808 0·393701 "tl
1 X 10- 3 ~
0·1 1 1 X 103 1 X 107 1·093 6 X 10- 3 3·2808 X 10- 3 0.039370 '"
1 X 10- 6 1 X 10- 4 1 X 10- 3 1ll
1 1 X 104 '"
1 X 10- 10 1 X 10-8 1 X 10- 7 1 X 10- 4 ~.
1
0·9144 91·44 914·4 1 3 36 I':>
;s
0·304 8 30·48 304·8 0·333333 1 12 $:l.
0·0254 2·54 25·4 2·54 X 104 0·027778 0·083333 1 ~

~
i;'
QThe name 'micron' for this unit (micrometre) is discouraged. I':>
g.
~
~
N
Unit Conversions: Volume ~

~
i
Sf units Other common units ~
~
m 3 cm 3 mm 3 UK gal US gal I ft 3 in 3
(UK gallon) (US gallon) (litret

1Oi
.Q.,
1 lxl06 Ix 109 220·0 264·2 Ix 103 35·32 6·1024x104
lxl0- 6 1 lxl~ 2.2x 10- 4 2·642 x 10- 4 1 X 10- 3 3.532x 10- 5 0·061024 ~
Ix 10- 9 lxlO- 3 2.2x 10- 7 2·642 x 10- 7 Ix 10- 6 3·532 X 10-8 6·102 4 x 10- 5 ~
1 ~
4·546 x 10- 3 4·546 x 103 4·546 x 106 1 1·201 4·546 0·1605 277·4
3·785 x 10- 3 3·785xl~ 3·785xl06 0·8327 1 3·785 0·1337 231·0 ~
Ix 10- 3 lxl~ lxl06 0·2200 0·2642 1 0·03532 61·024 §
0·02832 2·832x104 2·832 x 107 6·229 7·4805 28·32 1 1·728xl03 I':>..
1·6387 x 10-5 16·39 1·6387xl04 3·605 x 10- 3 4·329 x 10- 3 0·01639 5·787 x 10- 4 1 ~
~<::>
a Unit recognised for use with the International System.
~
$
~
Unit Conversions: Mass

~
~
SI units Other common units ::2
El
~.
kg g ta UK ton b US tonC cwt lb oz
(gram) (tonne) (hundred- (pound) (ounce) ~
weight) ~
~
lxlO-3
::!.
1 lxlW 9·8421 x 10- 4 1·1023x1O-3 0·019684 2·20462 35·2740 ~
1 X 10-3 1 lxl06 2·20462 x 10-3 0·035274 ~
lxlW lxlW 1 0·984207 H02310 19·6841 2·20462xlW 3·52739xlif ~
1-01605xlW 1·01605 1 H2 20 2·24x 103 3·584 x 104 ~
"
907-185 0·907185 0·892857 1 17·8571 2xlW 3·2xlif '"
~.
50·8023 5·08023xlif 0·05080 0·05 0·056 1 112 1.792x 103
0·453592 453·592 4· 535 9 x 10- 4 4·464 3 x 10- 4 5·00x 10- 4 8.9286x 10-3 1 16 ~
0·028350 28·3495 0·0625 1 ).
:g
a 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). 5'.
b The 'long' ton. i:!
C The 'short' ton.
A2 Quantities and Units: The Sf System: Unit Conversion Tables 871
Unit Conversions: Force
N kgf dyn UK tonf lbf pdl

(kilogram- (dyne) (UK ton- (pound- (poundal)
forcet force) force)
1 0·1020 1xHf 1·004 x 10- 4 0·2248 7·233

9·807 1 9·842 x 10- 4 2·2046 70·93
Ix 10- 5 1.02x 10- 6 1 2·248 x 10- 6 7·233 X 10- 5
9·964xHr 1·016x103 1 2·240 x 103 7·207 X 104
4·448 0·4536 4·464 x 10- 4 1 32·174
0·1383 0·0141 1·390xlO-5 0·0311 1
4 Called 'kilopond' (kp) in Germany.

Unit Conversions: Power
W metric kgfms- 1 cal S-1 hpb Btuh- 1

horsepower 4
(horse-
power)
1 1·360 X 10- 3 0·10197 0·2388 1·341 x 10- 3 3·4128
735·5 1 75·00 175·7 0·98632 2·510 x 1~
9·807 0·01333 1 2·343 0·01315 33·47
4·187 5·692 x 10- 3 0·4268 1 5·613 x 10- 3 14·29
745·7 1·013 9 76·04 178·1 1 2·545 x 1~
0·29307 3·984 x 10-4 0·02988 0·06999 3·929 x 10-4 1
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 SI unit Other units
Periodic frequency hertz (Hz) cycle per second (c s- l t

Rotational frequency reciprocal second revolutions per
(i.e. number of rotations (S-I) second; minute, etc.
in unit time) (i.e. r S-I, r min-I;
etc.)b
Angular frequency reciprocal second (S-I)
4 Equivalent to Hz but discouraged (both equivalent to S-I).

b The notation 'rev' for 'revolution' (as in rev/min) is now discouraged.
~
Unit Conversions: Pressure, Stress

~
~
SI unit Other common units ~
~
kgfcm- 2 <fbfin-2 in H2fr C dyncm- 2 ~"
Pa a atm bar mmHg
(standard (inches of (millimetres
atmosphere )b water) of mercury) a~
9·869 X 10-6 Ix 10- 5 1·020 x 10-5 1·450xlO- 4 4·015 x 10- 3 7·501 X 10- 3 10
~:::to
1
1·013x1W 1 1·013 1·033b 14·70 406·8 760 1·013 x 106 ~
~
1x1W 0·9869 1 1·020 14·50 401·5 750·1 Ix 106 a
9·807x1~ 0·96708 0·9807 1 14·22 393·7 735·6 9·807x1W '~"'
6·895 x 103 0·06805 0·06895 0·07031 1 27·68 51·71 6·895x1~
~"
249·1 2·458 x 10- 3 2·491 x 10- 3 2·540 x 10- 3 0·03613 1 1·868 2·491 X 103
133·3 1·316x10- 3 1·333xlO-3 1·36Ox10- 3 0·01934 0·5352 1 1·333x1~
0·100 9·869 x 10- 7 Ix 10- 6 1·020 x 10- 6 1·450xlO-5 4·015xlO- 4 7·501 X 10- 4 1 i
~
a 1 Pa= 1Nm-2 ; 1 MPa= 1 MNm- 2 = 1 Nmm2 • '"a.
b atm = 1·033228 technical atmosphere (at); 1 at = 1 kgfcm- 2 • ,,"
C Often denoted by 'psi'.
'~""
d Often referred to as 'inches water gauge' (in w.g.) .
• 1 mm Hg = 1 torr (to within one part in seven million); 1 torr = 1/760 atm.
Unit Conversions: Energy, Work, Heat
)..
N
SI unit Other common units 10

§
J kWh kgfm cal therm Btu ftlbf s:~
(kilowatt (calorie)" (British
hour) thermal unit)" t
1 2·778 x 10-7 0·1020 0·2388 9·478 x 10- 9 9·478 X 10- 4 0·7376 ~
0·03412
a'
3·600 x Ht 1 3·671 x Hf 8·5985 x Hf 3·4121 x 103 2·6552 x 106
9·8066 2·724 X 10- 6 1 2·3420 9·294 x 10- 8 9·294 X 10- 3 7·2330 ~
4·1868 1·163 x 10- 6 0·4270 1 3·968 x 10-8 3·968 X 10- 3 3·0880 ~
1·055 06 x lOS 29·307 1·0759 x 107 2·5200 x 107 1 1 x Hf 7·7817 x 107 ~
1·05506 x 1~ 2·931 X 10- 4 107·59 252·00 1 x 10- 5 1 778·17
1·3558 3·766 x 10- 7 0·1383 0·3238 1·285 x 10-8 1·285 X 10- 3 1 ~
~
" In this table these units have their International Table values, now in general use (1 cal == 4·186 8 J; 1 Btu == 1055·06 J). ~:
These values are always implied when the unit is written without a specifying subscript (i.e. simply 'cal' or 'Btu') but the ~
notation 'cal1T' and 'BtulT' is still sometimes employed. Other values occasionally used are: ~
~
~
The 4"C calorie, cal4 == 4·2045 J. g'
The 15"C calorie, cal15 == 4·1855 J.
~
The mean (0"-100"C) calorie, cal (mean) == 4·1897 J. I:J"'
The thermochemical calorie, cal (thermochem) == 4·1840 J. if
The mean (32°-212°F) Btu, Btu (mean) == 1055·79 J.
::sw
Unit Conversions: Temperature
As a unit of temperature (temperature interval) 1 Ka = 1°C = l·goR =

1·8°F
is KQ °cb OR of
equivalent (kelvin) (degrees (degrees (degrees

A to Celsius) Rankine) Fahrenheit)
temperature
reading of
yKQ y y-273015 1·8y 1·8y - 459·67
xOC x+273015 x 1·8(x + 273·15) 1-8x +32
uOR u/l·8 (u/l·8) - 273015 u u -459·67
z"F (z + 459·67)/1·8 (z - 32)/1·8 z +459·67 z
Q The SI unit of temperature.

b Unit recognised for use with the International System.
Unit Conversions: Thermal Resistivity
This is the reciprocal of thermal conductivity, and the unit conversions

can be found by us(ng the reciprocals of the appropriate units and
values in the thermal conductivity table, e.g. for the thermal conduc-
tivity of 1 W m- 1 K- 1 the corresponding thermal resistivity is
1 K m W- 1 == l/6·933°F ft2 h in- 1 Btu- 1
== 0·144 23°F fe h in- 1 Btu- 1
Unit Conversions: Thermal Conductance (Heat Transfer Coefficient)
Sf unit Other common units

Wm- 2 K- 1 Qkcal h- I m- 2 K- 1 °cals- 1 cm- 2 K- 1 °Btu h- I ft- 2 of-I
1 0·85984 2·388 46 x 10- 5 0·17611

1-16301 1 2·7777 x 10- 5 0·20481
4-1868 x 10" 3-600 1 x 10" 1 7·3729 x 103
5-67827 4·88240 1·3562 x 10-4 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).
)..
N
Ie
§
Unit Conversions: Thermal Conductivity ::t.
~.
~
SI unit Other common units ~
~o
Wm- 1 K- 1 Wcm- 1 K- 1 acal S-l cm- 1 K- 1 kcal h- 1 m- 1 K- 1 aBtu h- 1 ft- 1 0p-l 1
Btu in h- fr 20 p - l
~
1 1 X 10- 2 2.388 X 10-3 0·8598 0·5778 6·933 '"~
100 1 0·2388 85·98 57·78 693·3 ~
418·7 4·187 1 360·0 241·9 2·903 x 103 '"~
1·163 0·01163 2·778 x 10-3 1 0·6720 8·064 ~
1·731 0·017 31 4·134 x 10-3 1·488 1 12·00
1·442 x 10-3 3·445 X 10- 4 0·1240
~
::;'0
0·1442 0·083·33 1
~
;:s
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). ~
goO!
~
~
ir
~
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 conduc-
tance of 1 W m- 2 K- 1 the corresponding thermal resistance is
1 Km2 W- 1 == 1/0·17611°Pft2h Btu- 1
= 5·678 27°P ft2 h Btu- 1
Unit Conversions: Viscosity
DYTUlmic viscosity Kinematic viscosity

Sf unit Other common units Sf unit Other common units
Nsm- 2 p" cP St b cSt

(poise) (centipoise) (stokes) (centistokes)
1 10 1 X 103 1 1 X 106
0·1 1 100 1 X 10-4 100
1 X 10-3 0·01 1 1 X 10- 6 1
agcm-ls-l.
b cm2s-1.
APPENDIX 3
Abbreviations (Letter Symbols) Used in the Book

for Some Polymers, Their Derivative Plastics,
and Certain Monomers
877
00
0Cl
Abbreviation Substance Common abbreviation Abbreviations currently recommended by
used in this and/or name the relevant English-language standards
book
ISO 1043/1-1987 BS 3502: ASTM D 1600-860
Part 1: 1978
""~
ABS Acrylonitrile/butadiene- ABS ABS ABS ABS
/styrene terpolymer a~
Chlorinated polyethylene CPE PE-C ~.
CPE CPE
CPVC Chlorinated polyvinyl CPVC; chlorinated PVC CPVC ~
chloride PVC c:!
"5
E/VAC Ethylene/vinyl acetate EVA E/VAC EVAC EVA "-
copolymer ....~.
HOPE High-density polyethylene HOPE PE-HD HOPE
LOPE Low-density polyethylene LOPE PE-LO LOPE
::p
~
LLOPE Linear low-density LLOPE PE-LLO
~
polyethylene ~.
MBS Methacrylate/butadi- MBS MBS
c:.
;:
ene/styrene ter-
~
polymer
PAMS Poly( a-methylstyrene) PAMS ~
"5
PAN Polyacrylonitrile PAN PAN PAN ~
c:.
PC Polycarbonate PC PC PC PC
~.
PE Polyethylene PE PE PE PE
PET Polyethylene PET PET PETP PET
terephthalate
PMMA Polymethyl methacrylate PMMA; acrylic PMMA PMMA PMMA
PP Polypropylene PP PP PP PP
PPO Modified polyphenylene PPO PPE PPE
oxide
PS Polystyrene PS PS PS PS
PTFE Polytetraftuoroethylene PTFE PTFE PTFE PTFE
PUR Polyurethane PU;PUR PUR PUR PUR
PVAL Polyvinyl alcohol PYA PVAL PVAL PVAL
PVC Polyvinyl chloride (poly- PVC; vinyl PVC PVC PVC
mer or plastic)
Plasticised PVC; flex- PVC-P ~
pPVC Plasticised PVC w
ible PVC (or vinyl)
~
uPVC Unplasticised PVC Unplasticised PVC (or PVC-U 0-
0-
vinyl); rigid PVC (or ~
c::
vinyl) S·
PVDC Polyvinylidene chloride PVDC PVDC PVDC PVDC ~.
PVF Polyvinyl fluoride PVF PVF PVF PVF
SAN Styrene/acrylonitrile SAN; AS (in USA and SAN SAN SAN ~
.,.
copolymer Japan in commercial .,~
contexts)
~
VAC Vinyl acetate Vinyl acetate mono- VAC;VA VAC ::l
0-
mer; VA c
VC Vinyl chloride Vinyl chloride mono- VC VC ~
mer; VCM
.,.~
VDC Vinylidene chloride Vinylidene chloride VDC ~
monomer S·
VL Vinyl laurate .,.So
ttl
NOTE: Those abbreviations which are explained each time they appear in the text are not included in this Appendix. 8;>:00
~
INDEX
Acid index, 846 'AGS' acid ester plasticisers (see also

Acrylic under Aliphatic diester
impact modifiers, 324, 325, 328-9 plasticisers), 197,211,213
lacquers, 760-1 Alcohols for plasticiser production,
light-protective coatings, 801 200,201,204
lubricant, 297, 300 Aliphatic diester plasticisers, 31, 32,
matting agents, 360-1 188,190,192,194,197,198-9,
processing aids, 297, 300, 314-16 211,213,252
thickeners for PVC latices, 708 adipates, possible health hazard,
Acryloid modifiers, equivalence to 13,251
Paraloid, 300 performance in PVC, 194, 197,
Acrylonitrile/butadiene/ styrene 205,213,233,235,236,237,
(ABS) copolymers 240,241
blends with PVC, 327 plastisol rheology, effects on, 655
impact modifiers, as, 324, 326-7 Alumina trihydrate
processing aids, as, 314 effect on general PVC properties,
sheet laminates with PVC, 616 352
Activators ('kickers'). See under flame and smoke retardant, as,
Blowing agents 351-2
Additives (see also under individual trade names, 291-2
names) Analysis of PVC compositions, 44-47
analysis for, 45-48 Anti-blocking (see also Blocking)
health aspects of, 13, 26, 250, 835 agents, 25 (passim); 360 (passim);
asbestos, 263, 282 718-19
pigments, 349 techniques, 719
plasticisers, 13, 250-1 Anti-foaming agents, 710
stabilisers, 115, 121, 127, 130-2, Antimony oxides, 351-3
136,137,139,140 Antimony stabilisers, 126
Adhesion comparison with organotin
promoters for PVC coatings, 368, stabilisers, 126
668,674, 779 synergism with calcium stearate,
of solution-deposited PVC 126
copolymers, 686, 688, 694 Antioxidants, 141-143
Adhesive bonding of PVc. See under Antiplasticisation, 4, 182, 183
Bonding of PVC Antique finish ('Antiqueing'), 761
Ageing Antistatic agents,
heat 796, 816-18 nature and use, 354-9
of pPVC after processing, 185-6 thermal stability of PVC, effect on,
of PVC pastes, 638, 654, 655, 656 38,355
Bigg's parameter, and, 191,654 Ap/Poratio(ofplasticisers), 191, 192
881
882 Index
Apparent melting temperature. see Biaxial stretching--contd.

Clear-point temperature uPVC products, property
(definition) improvements by, 569
Asbestos Bigg's parameter, 189-91
filler, as, 259 (passim), 260, 263-4, 'Bingham body' behaviour, 640-1
281-2 Biodegradation, see Microbiological
hazards of, 263 attack.
heat stability of PVC, effect on, 41, Biostats, 25 (passim); 719, 820
117,264 Blanc fixe, 265
properties, 263 Blends of PVC with
PVC flooring, in, 41, 263, 542, 548 ABS,327
PVC sheet, reinforced with, 263 chlorinated polyethylene, 331-2
Autoignition, 838 nitrile rubber, 329-31
AZDN,341 other polymers, 316, 324-33
Azobisformamide (ABFA) alias polyurethane, 332
Azodicarbonamide (ADA), SAN polymers, 314-16
336-41 Blocking, 718
Blow moulding
basic elements, 560, 562
Bakelite PVC solution resins, see "bottom blow", 570
Ucar dip (displacement) process, 567-8
Banbury internal mixers, 451-31, 458 equipment and process
Barium arrangements, 561, 569-71
stabilisers containing, 30, 39, 40, extrusion process, 563-5, 574-6
42,44,125,127-9,132,134, parison control in, 565-6
151,154,156,170,477,536, injection process, 561, 567, 574
547,656,661 product
sulphate, 265, 271 cooling, 571-3
Barrier properties of removal systems, 574
blow-moulded containers, 569, 576, PVC compositions for
584,585,586,761,827 end-use aspect, 579-80
PVC compositions, see formulation aspect, 42, 580-3
Permeability processing aspect, 576-8
PVC/PVF sheet laminates, 483 single stage processes, 570
stretched films, 61, 96, 829 stretch-blow methods, 561, 563-5,
Barytes, 265, 715 568-9
Battery separators "top blow", 570
production, 632-3 two-stage processes, 570-1
PVC polymer for, 91-93, 633 Blow mOUldings
Baymod applications, 583-4
L (formerly Levapren), 331,477 properties, 584-5
PU (formerly Ultramoll PU), 217, property tests, 585-6
332 Blowing agents, 335-43
Beta (p) gauge, 541, 673 activators ('kickers') for, 128, 134,
Biaxial stretching 336,340,656
impact resistance and permeability, decomposition
effects on, 61, 96, 569 products of, 340, 341
stretch-blow moulding, in, 569 rates of, 337
Index 883
Blowing agents----contd. Bulk (mass}-<:ontd.

decomposition-<:ontd. polymer particle characteristics,
temperatures, 336-7, 338-9, 341 67-8, 70-2, 80
incorporation levels, 342-3 polymers, 28, 38, 39, 40, 41, 42, 43,
operational temperature ranges of, 109,488,580
336-9 Burning (see also Flammability)
retarders for, 340, 758 plastics, of (general), 837-8, 839
volumes of gas generated by, 337 PVC, of, 838, 840-2
Blue wool standards, 350, 813 effect of plasticisers, 209, 351
Blueing (colour reversal), 326 products of, 840-2
Bonding of PVC role of chlorine content in, 351
adhesive, 745,746-7 terminology, 836-7
definition, 741 tests, 842-6
solvents and solvent cements, by, Buss
cement compositions, 697, 741, Kneader, 430-1, 433-7, 456, 531-2
744 mixing turbine, 421, 663, 665-6
mechanism, 743
procedures, 742-3
specifications relevant to, 697, 744 Cable and wire insulation and
Brabender Plasti-Corder coverings (see also under
compounding tests, use in, 457-62 Compounding) ,
dynamic stability tests, use in, application (by extrusion), 519-21
166-8 compounds,
lubricant performance assessment, formulation, 41, 42, 244, 275,
use in, 307-9 277,280,488
melt fusion test in, 461, 462 PVC/nitrile rubber, 330, 490
system, 193, 458-63 cross-linked, 765, 766
Brabender Plastograph, 193, 458 standards and tests for, 489-90,
Brittle-ductile transition, 318, 322-3, 795-7,844
378,814 types and applications, 486-7
Brittle fracture, 318, 322-3, 378 Cadmium compounds
Brittle point, 318, 814 interaction with UV absorbers, 146
Brittle temperature, 318 pigments, as, 349
Brittleness temperature, 318, 815 stabilisers, as, 30, 39, 40, 125,
Brookfield viscometer, 645-6, 704-5 127-30,133-4,477
BS softness, 230-1 stabilising action of, 134
fillers, effect on, 263 sulphide staining with, 151, 155,
measurement of, 230 156
number scale, 230-1 toxic hazard of, 10, 131,349
plasticisers effect on, 202-3, 207, Cadon 300 modifiers
210,212-13,215-16,221, effects in PVC, 328-9
232-3,234,245,246 name change to Elix 300, 324
rubber hardness, and, 230-1 Calandrette system, 544-5
Shore hardness and, 230-1 Calcium carbonate fillers
temperature, effect on, 234 applications, 33, 275-8, 280-1, 548
values of, for pPVC, 855 cost considerations, 273-5
Bulk (mass) dispersion characteristics, 273, 275,
polymerisation, 63, 65 280
884 Index
Calcium carbonate fillers-contd. Calendered sheeting--contd.

fine particle, functional effects of, thickness
277,279,286,324,478 gravimetric, 541
latices, in, 715 stretch-down effect, 538
loading, effects of, 261, 262, 275, typical range, 525
279-81 Calendering,
plastisols, in, 275, 276, 279, 657 advantages over extrusion, 525
precipitated, 261, 262, 267-8, 271, formulation aspects, 536, 546-8
277,280,286 general features, 529-30
properties, 266-73 material temperature in, 537
surface treated, 276-8, 288-90, 657 materials processed by, 524
types, 266-8 roll
"Calcium resinate", 290 speed (friction) ratios in, 528,535
Calcium stearate stabilisers/ temperature settings in, 535-6
lubricants, 38, 41, 42, 43, scrap reprocessing, in, 453, 534
125-7,298,301 sheet path in, 535
Calcium sulphate, 265 sheet production aspects in,
Calcium/zinc stabilisers (see also Zinc cooling, 540
containing stabilisers), 26, 39, edge trimming, 541-2
41, 130-1, 132, 134-5, 154, embossing, 539-40
156,581,656 lamination, see under
Calender, 524-9, 533, 535, 537,538 Calendered sheeting
compounding and feed for, 430-2, stretch-down, 538
442,445,531-2,534 wind-up, 542
lines, 530-9, 542-5 'Capping' (coextrusion), see under
main components of, 524 Weathering resistance
roll (bowl) Carbon black
arrangements, 525-7 colourant, as, 286, 345, 348, 351
bending, 528-9 conductive filler, as, 286, 356-7
crossing, 529 light stabiliser, as, 38, 146
crowning, 528 pPVC compounds, in, 261, 286-7
deflection, 528 Castor-Severs viscometer, 645-6
number in stack, 525 Cell stabilisers (for foam production),
numbering, 527 343-4
operational features, 525-9 Cellular PVC (see also Foams)
Calendered sheeting applications, 632, 633, 772-4
applications, 483-4, 489, 491, 554, evaluation and testing, 774-7
558,559 production methods
defects and faults in, 549-52 'chemical' blowing, 335-43
flooring, for, 41, 493, 524,542-4 dispersed-gas blowing, 771
formulations, 536, 546-8 mechanical frothing, 343, 771
lamination of, 545-6, 553-4, 609 "lost-filler" method, 633-4
low-temperature strain in, 530, 540 sintering of powder, 632-3
morphology of, 530, 549-50 Chalking, 798
press finished, 552-3, Chemical blowing agents, see
properties and tests, 485, 492, Blowing agents, and under
536-7,554-8 Cellular PVC
surface treatments applied to, 533 Chemical embossing, 758-9
Index 885
Chemical properties of PVC, 53, 54, Cling film ('Cling-wrap'), 13,251,

59,78-9,87,379-85,684-9 489,491
tests for, 384-5, 390-1 Coated fabrics
Chlorinated olefins, 219-20 applications and products, 12, 43-4
Chlorinated paraffins production, 524, 545-6, 553-4, 655
degradation of, 103 (passim), 668, 670-4, 752
flame retardancy, see under Flame (passim), 756-9
retardants. properties and tests, 243, 652, 676-
plasticiser extenders, as, 31 8,679-80,718,721,723,815,
(passim), 196 (passim), 816,826-7,844,845
219-21 Coating, see under Lacquers, Latices,
Chlorinated polyethylene, 324, 331-2 Pastes, Solutions, and Surface
chemical structure of, 331 Coatings
degradation susceptibility of, 103 PVC-based 720-1,723
(passim) latex, 779-81
impact modifier, as, 324, 331-2, powder, 368
477,548 solution, 683 (passim), 685-7,
Chlorinated PVC (CPVC), 9 694-6
(passim); 90, 95-9 PVC, on
applications, 99, 468 barrier properties, for, 576, 584,
chemical structure of, 95-6, 97 761-2
commercial versions, 97, 99, 366 decorative, 760-1
fibres from, 9, 95 protective, 760-2, 801
pipes and fittings, 468 Coextruded pipes and profiles, 470,
processing of, 507-8, 604-5 475,476,507,772,774
production of, 9 (passim), 90, 95 Coextrusion, 470, 475, 476, 507, 518,
properties of, 96-8, 569 774,801
solvent cements for, 744 Cold-bend temperature, 816
thermoformability of, 615 Cold-crack temperature (of film,
Chromium pigments, 14 (passim); sheet, or coating), 815
346 (passim), 349,478 Cold-dip coating, 668-9
Citrate plasticisers, 222 Cold-flex temperature (Clash and
Cladding, 475, 480, 484, 616, 730 Berg)
Clash and Berg, see Cold-flex definition, 239, 815
temperature. determination of, 237, 815
Clay effect of plasticisers on, 202-3, 207,
Bentonite 210,212-13,215,216,229,
PVC latices, in, 709 237-8,240
PVC pastes, in, 658 Colour reversal, see Blueing
filler, as, 259-63, 271, 291-2, 352, Colourants, 34, 345-51, 478, 691,
715 717,802
oil absorption of, 260 choice considerations, 347-9
Clear-point temperature of commercial, 345-7, 348-9
plasticisers general types, 345-6
definition, 189 metallic, 345-6
paste fusion temperature, and, 652 nacreous, 346
test techniques, 189 physical forms, 346
values, 190 Compounding, 393-463, 531-2, 534,
886 Index
Compounding--contd. Compounds--contd.
543,544,661-6,692-4, conductive, 356-9, 366
706-19 definitions, 22-3
continuous melt-compounded, feedstocks as,
Buss Turbine, by, 421, 665-6 371-2,412-13,423,508-9,
'Kontinuum' mixer, by, 422 577,591
paste dissolvers, by, 664 physical forms, 371-2
powder blends, of, 420-2 standard designations of, 387-9
'downstream' equipment associated Compression moulding, 607-14
with,393-395 gramophone records, of, 607-9
ingredients (PVC formulation pastes, of, 613-14
components) sheet samples, of, 610-13
conveyance of, 396-404, 415 thick sheets, of, 609
metering and weighing of, Congo Red test, 164, 390, 797
406-12 Conveyor belts,
storage of, 494-7 antistatic property requirements
in-line for, 359, 677
calendering, for, 430-2, 442, construction, 671, 676
445,531-2,534,543-4 specifications and tests,
extrusion, for, 421 flammability, 678, 845
latex compositions, of, 706-19 others, 677-8
melt, 422-48, 451-5 Cooling of PVC mouldings, 571-3
equipment for, 424-47, 451-5 Copolymers of vinyl chloride,
pellet production and handling, commercial, 8, 75-7
in, 448-51 early appearance, 8, 9
mixing and fusion tests, 458-63 emulsions (latices) of, 701, 703-6,
operations, general nature and 714, 720-2, 723
objectives of, 22, 393-5 graft, 74, 77, 78, 477, 801
pastes, of, 661-6 morphologyof,74
continuous, 665-6 production, 75-8
equipment for, 662-6 properties of (general), 28-9, 73,
laboratory-scale, 662, 664 74,78,79
standards for, 662, 664 solution type, 684-8, 695, 696
powder blends, of, 313-14, 412-22 VC/acrylic ester, 77, 477
cold, 413, 416-17 VC/ acrylonitrile (fibres), 73
continuous, 420-2 VC/ethylene, 76, 79
hot, 413, 415-20 VC/E/V AC, 77, 78, 477, 801
mixers used, 413-22 VC/fumaric ester, 77
high-speed (intensive), 413-20 VC/itaconic ester, 77
hot/cold combination, 414-20 VC/maleic ester, 77
recycled material, of, 453-5 VC/maleinimide (N-substituted),
schematic outline, 393-5 74
solution compositions, of, 692-4 VC/propylene, 76, 79, 483, 781
'upstream' equipment associated VC/trifluorochloroethylene
with,395-412 (TFCE),77
Compounds (see also under PVC) VC/vinyl acetate, 8, 9, 41, 73, 75,
580,592 78-9,83-86,94,477,483,548,
commercial, 366, 368, 371, 372, 607,615,685-6,695,696
580,592 VC/vinyl alkyl ether, 77
Index 887
Copolymers of vinyl chloride-contd. 'Dead load' hardness tester, 230

VC/vinylidene chloride, 73, 74, 76, Defoaming agents, see under Anti-
483,548,660,704,719,720-1 foaming agents
Co-precipitates, 38, 133 Degradation of PVC, see under
nature, 133 Photochemical degradation
Sr/Zn laurate, 133 and Thermal degradation
Cordelan, 76 Desirability function, 35-6
Corpoplast process, 570 Dilatancy, 641-2
Co-stabilisers Dip coating, 668-9, 779-80
epoxy (see under Epoxy stabilisers) Dip moulding, 667, 781
organic, 135-8, 140 Draw ratio, 618
phosphites, 30, 37, 39, 40, 43, Dry blends (see also Powder
128-9,135,138-40,581,801 compounds, and powder
polyols, 130, 140 blends under Compounding)
Coupling agents (for reinforcing feeds, as, 412, 423, 577
fillers), 282, 283, 288-91 blow moulding, in, 412, 577
CPVC (see Chlorinated PVC) dip-coating, in, 779
cpvc (critical pigment volume extrusion, in, 412, 508-9
concentration),715-16 injection moulding, in, 591
Creep, 370, 374-5 nature, 22-3, 413, 415
coated fabrics, resistance to, 676 passim, 394-5
data for uPVC, 373-5, 375 production of, 313-4, 413-22
definitions, 370, 375 Dry colourants, 346
modulus, 373, 375 Dry point (in gelation of pastes), 650
rate, 370 Durometer (Shore) hardness,
PVC pipe, resistance to, 377, 474 scales, 230-1
rupture, 370, 375, 474 tests, 230
strain, 375
temperature, effect of, 617, 818 Efficiency factor, see under
tests on Plasticisers
PVC pipes, 474 Electrical
thermoforming sheet, 617-18 insulation see Cable and wire
'Critical solution temperature' (in insulation
plate-out), 158 properties of PVC, 27, 32,115,
Cross-linked PVC 239,241,262-3,352,354,359,
cable or wire insulation, as, 765, 487,489,490,738-9,792-3,
766 794-7, 864-6
cross-linking additives for, 764-5 Electrically conducting PVC
gel fraction in, 763 compositions, 354, 356-9
properties of, 765-6 Elix 300, see Cadon 300
Cross-staining, see under Sulphide Embossing, 539-40, 756-9
staining calendering, in, 539-40
Crystallinity cellular sheet materials, of, 757
plasticised PVC, in, 179-80, 183, 'chemical', 758-9
186,650 PVC paste coatings, of, 673
PVC polymers, in, see under screen printing, by, 757
Polyvinyl chloride Emboss-retention tests, 558
VC/VDC copolymers, in, 74 EMMA and EMMAQUA apparatus,
Cutting of PVC sheet, 745, 749-50 803
888 Index
Emulsion Extruders--contd.
polymerisation, 66, 70-1, 75-7 single screw, 430, 431, 435-6,
polymers 437-41,499-500,503,505
applications, 28, 43-4 twin screw, 439-41, 443, 498
particle characteristics of, 69-71, mode of oper..ation:
73, 80, 704-5 differences from single screw,
purity of, 28, 109 503-4
PVC latices, in, 700 screw arrangements, 428,
PVC pastes, in, 28, 637, 644-5, 439-41,444,498,499-500,504
653-4, 660, 661 venting of, 437, 444, 500
Environmental stress cracking and ZSK (in Kombiplast set-up), 428,
crazing, 788-92 431,439-41
cracking agents for PVC, 791 Extrusion
definitions, 788-9 ancilliary equipment in, 421-2,
mechanism, 790-1 498-9,505-6,514-17,520
PVC bottles, of, 788, 791-2 blow moulding, 560, 561, 562-6
PVC pipes, of, 468, 791 compounding, see under
resistance to, tests for, 790, 792 Compounding and Extruders
Epoxy plasticisers, 137-8, 218-9 (compounding).
Epoxy stabilisers, 30, 37,125,127, compounds for, 368, 371-2
129, 130, 131, 137-8 CPVC, of, 507-8
formulations, in, 39-44, 133, 136, dies
137-8,579,581,691,801 blown film, for, 518-19
interaction with unsaturated cross-head, 501, 519-21
additives, 138 pipe, for, 501-2, 514-15
mode of action, 138 sheet, for, 517-18
Estertin stabilisers, 120-1 variable-thickness (adjustable),
Extenders 501-2,518,566
fillers, as, 258, 273, 275 feedstocks for, 367, 369, 371-2,
for plasticisers, 219-21, 223 412-13,423,508-9,577
chlorinated olefins, 219-20 formulation aspects, 38, 39,41,42,
chlorinated paraffins, 219-21 123,472-3,476-8,487-8,489,
hydrocarbons, 223 491
Extruders fusion and gelation in
Bitruder, 432, 443-4 completeness, 473-4, 510-12
blow moulding, in, 574-5 mechanism, 510-11
cascade, 431, 437-9, 517 gear pumps, use in, 505-6
compounding, 431-2, 433-41, head and die assemblies, in, 501-2
443-7 historical development of, 497
heating and cooling arrangements lines
in, 447 cable and wire coating, 519-22
LID ratio of, 497, 499-500, 574 pipe, 502, 513-15
output, 498 sheet, 516-19
factors affecting, 500-1 pipes, of, 497-9, 502, 513-15
PVC compositions, 437, 441, products, common faults in,
444,447,498 511-13
planetary, 432, 444-7 profile, of, 475, 479, 481, 498,
screw design in, 433, 435-6, 499 516
Index 889
Extrusion-contd. Fillers-contd.
sheet, of (see also under Sheet), surface treated, 36, 276-8, 279,
516-19,525 (comp. with 280,288-91
calendering) trade names, 260, 263, 265, 267,
window-frame profiles, of, 475, 275,276-8,282,283,285,
479,516 289-92
wood flour, 287
Fatigue Film
definition, 375-6 applications of, 483-4, 489, 491
dynamic, 376 cling, see Cling film
life, 376 definition, 481-3
pipes, of, 377-8, 474 extruded, 483 (passim); 518-19
resistance of PVC, 376-8, 788 latex, from, 700-2, 703, 704-5,
temperature, effect in, 376 706,715-17
Feedstocks for PVC processing, see shrink-wrap, 483-4
under Compounds, Powder solution-cast, 483 (passim); 695-7
compounds, Dry blends, and standards for, 485, 492
Extrusion stretch-wrap, 247, 491-2
Fibres 'Fish Eyes'
copolymer, 73, 75-6, 777 count, specification for, 29, 86, 89,
fillers, as, see under Fillers 391
PVC, 75-6, 777 definition, 81
Fillers (see also under individual passim, 550, 581
names and types) Flame retardants
clay, 259-63 alumina trihydrate, 351-2
conductive, 355, 356-8 antimony oxides, 351-3
cost considerations, 33, 273-5 chlorinated paraffins, as, 219, 351,
definition, 258 840
fibrous, 259,260,281-5 fillers, as, 840
flame retardant, see under Flame modes of action, 351-2
retardants phosphate plasticisers, as, 208-10,
functional, 281-3, 286-8, 478 239,351,353,840
general, 25, 33-4 Flammability (see also Burning)
glass, 282-6 definition, 837
latices, in, 715-17 PVC, of, 351, 838
loading, effects of, 261-3, 275, terminology, 836-7
279-80,285,356,358 Flash ignition, 838
microfibre, 282 Flatting, see Matting
mineral, 259-81 Flooring (see also under Asbestos and
oil (plasticiser) absorption Calendered sheet)
(demand), see Oil absorption antistatic, 359
pastes, in, 656-8 asbestos filled, stabilisers for, 41,
reinforcing, 263-4, 281-5 119,131
silicaceous, 259-64 calendered, 525, 542-4
smoke suppressant, see under chemical resistance of, 385
Smoke coated, 275, 276, 493 (passim);
starch,288 670, 759
suppliers, 291-2 cross-linked, 766
890 Index
Flooring-contd. Formulation-contd.
embossed, 757, 759 examples-contd.
fillers in, 41, 263, 264, 275, 276, 542 sheet and film, 39-40, 247, 536
formulation, 41, 119, 131,275 solutions, 695, 696, 760
stain resistance of, 547, 676 wire and cable coverings, 41-2
unsupported, 493 (passim); 543-4 general considerations, 25-35,
Flory-Huggins parameter (X), 189, 191 301-4
Flow moulding, 600 process-related considerations,
Fluoropolymer surface protection for 472-3,546-8,580-3,591-2,
PVC sheet products 653-61,683-92,706-19
by lamination with PVF film, 483, weathering resistance, for, (see
(Tedlar); 554, 762, 778 under Weathering).
(Tedlar) window-frame compositions, of,
by solution coating (Lumiflon), 762 477-8
Foam (see also Cellular PVC and Fracture,
Sections 9.1.1 and 9.1.2 of impact-caused, 318
Chapter 9). modes of, 318-19
composite, cross-linked, 772 uPVC, of, 323
density, 772 Fusion, see Gelation/fusion
production, see under Cellular PVC Fusion point (fusion temperature)
products, 772-4 pastes, of, 650, 651
standards relevant to, 775-6 PVC compositions, of, 460, 462
'Fogging' (automotive), 206, 243 PVC polymer/plasticiser
Foil interaction, in (see also Clear-
applications, 483 point temperature), 193,460
definition, 482-3
stamping, see Hot-foil stamping
Footwear, 42, 765, 766, 772, 783 Gamma-ray sterilisation
Ford cup, 646 commercial PVC sheeting stable
Formulation to, 732
components (see also under heat stabilisers for PVC
individual names). compositions stable to, 124,
kinds, 24-5, 27-35 131
mutual effects, 36-7, 272-3, 'Gassing', 116
302-4 Gear pumps, 505-6
nature and functions (general), 'Gel block', 647
27-35 Gel fraction (in cross-linked PVC),
side effects (general), 37-8 763
costing, 46 Gel theory of plasticisation, 179
examples Gelation/fusion
blow mouldings, 42-3, 316 melt processing, in, 193,307,460,
flooring, 41 462,473-4,481,509-12
foam compositions, 43-4 pastes, of, 510, 511, 647-51
injection mouldings, 42 stages in, 648-51
latex-based, 723-4 solvent tests for degree of,
pastes, 43-4, 661 paste products, in, 652
pipes and tubing, 38-9, 473 pipes and profiles, in, 473-4,
profiles. 39 511,512
Index 891
Gels, Health hazards-contd.

blow-moulding compositions, in, PVC resins and compositions, of,
581 835
definition, 81 regulatory bodies concerned with,
relevant tests, 29, 89, 391, 581 12, 250-1, 835
stress-concentrators, as, 318 VC monomer, of, 10, 12, 13, 583,
Glass transition temperature (Tg) 834
PVC polymer and compounds, of, Heat (see also under Stability)
59,297,330 ageing of pPVC, 817-18
plasticisation, effect on, 177, 330, degradation (see Thermal
702,791 degradation of PVC)
role in. history, 161-2
film formation from latex, 702 life, 161-2
mode of fracture, 325 non-degradative effects of, 88-9,
Glazing compositions, 330 195,241-2,379,387-8,390,
Global radiation, 807 481,540,796-7,817-18
Gloves (PVC) Heat shrinkable
coated(fabric-lined) film ('shrink-wrap'), 483, 492
dip coating (of fabric liners), 668 labels and sleeves, 484
solvent tests on, 652 tubing, 493-5, 766, 795
unsupported, 667 Heat stabilisers (see also under
Gramophone records, 607-9 individual and type names)
compounds for, 368, 448, 608 activators for blowing agents, as,
formulations, 133, 608 see under Blowing agents
polymers for, 75, 79, 94, 607 blow mouldings, in, 581
production, 608 calendering, in, 132-3, 536, 547
stabilisers for, 608-9 chelator, 30, 125, 139
Gravimetric thickness (of sheeting commercial, 119, 122, 124, 126,
and film), 541 127,129, 130, 132-4, 136, 139,
Gray (SI unit of absorbed ionising 152-3
radiation) cadmium replacement systems,
definitions, 870 132-3
relationship to the rad, 763 suppliers and trade names, 152-3
Grey scale, 350, 813 complexes, 125
'Grow moulding' , 472 cross-staining by, 122, 128, 155
detection and analysis of, 46-8
evaluation and testing, 162-72, 390
Hardness (see also BS softness) general, 29-30, 154
data for PVC, 855-6 latices, in, 711-12
Durometer (Shore), 230-1 lubricants, and or as, 37, 116-17,
International Rubber Scale, 230-1 125,126,129,140-1,301-3,
plasticisers, effect on, 233 310
tests, 230-1 lubricants, balance with, 140-1,
Health hazards 302-3,310-11
additives, of, 13-14,26-7,115-16, mixed-metal, 30, 127-35
121,126,131,548-9,263,349 mode of action, 117, 124, 134-5,
combustion products of PVC, of, 137,138,139,140
14,840-2 non-metallic, 135-40
892 Index
Heat stabilisers-contd. Impact resistance--contd.

non-toxic, 26,121,126-7,130-1, temperature, effect of, 318, 322,
135-6,137, 138, 140 797,814,815
one-pack systems, in, 149-50 tests, 319-21, 585
organic, 135-40 units, 320
pastes, in, 132, 154, 656 uPVC, of, 319, 322-3, 371, 373,
physical forms, 115, 127, 149-50, 579,854
310 Injection moulding, 588-606
polymeric, 121 colourant stability in, 350
selection criteria, 29-30, 114 compounds
single-metal compounds, 115-27 commercial, 366, 368-9, 371-2,
types, 30, 114 592-3
window-frame formulations, in, CPVC, 97-9, 366, 373
134,478 'easy flow', 592-3
Hose, see Tubing formulation, 42,591-2
'Hot bench', see Gel block melt flow tests for, 592-4
Hot-dip coating and moulding time-temperature behaviour of,
pastes, with, 667-8 589-90,600
powders, with, 779-81 CPVC, of, 604-5
Hot foil stamping, 755-6 equipment, 594-7
'Hundred percent modulus', see faults, 601, 602
under Modulus feedstocks, 367-9, 371-2, 394,
Hydrocarbons, plastiser extenders, 422-3,591
as,223 process, 595, 597-600
temperature
effects, 588, 589-90,595, 597-8
Impact modifiers (see also under settings, 597-9, 602
individual type names) thermal input in, 589, 602
effects in pPVC, 323 trouble shooting in, 600-1, 602
fillers as, 278, 286, 324, 478 Injection mouldings
mode of action, 324-6 examples of, 472, 486, 772, 774,
polymeric, 324-33 781, 783, 785
window-frame compositions, in, faults in, 601-2
328,331-2,477 formulations for, 42, 94
Impact resistance (impact strength), morphology of, 61, 486, 601, 603-4
316-23,322-3,854-5 orientation in, 61, 486, 603-4
biaxial stretching, effect of, 61, 96, property data, 371-2, 852-63
569,582 quenching stresses in, 601, 603
blow mouldings, of, 569, 579, shrinkage of, 591
581-2 Intensive mixers, see under Mixers
definition, 316-17 Internal mixers, 451-3, 458, 531, 532,
factors affecting, 317-20, 322-3, 543
473 International Rubber Hardness
mode of failure, and, 317-20 (IRH), 230-1
notches, effect of, 319-20, 322-3 'Interval blowing' cooling system, 573
PVC polymer, effect of (in Ion implantation, see Nitrogen ion
compositions), 321, 478, 580-1 implantation
Index 893
K value Leathercloth
concept, 53-4 applications, 673, 773
effect on properties and processing, 'fogging', role in, 206, 243
79,94,547-8,577,581,608, production, 673, 757, 759, 772
653,661 Lesieur test bottle, 586
Fikentscher, 54, 56, 58 Levapren, see Baymod
ICI,56 Light stability, see under Stability
molecular weight, and, 53-4, 56-8 Limiting Oxygen Index (LOI), see
specific viscosity, and, 53, 56 Oxygen Index
viscosity number, and, 53, 56 Lithium stabilisers (passim), 125
'Kickers', see under Blowing agents Lithopone,717
(activators for) Loop test, 192
Kombiplast equipment, 431, 437, Low-temperature plasticisers see
439-41 Aliphatic diester plasticisers
'Kontinuum' mixer, 422 Low-temperature properties of PVC,
31,32,197,202-3,205,207,
210,212-13,216,221,229,
Labile chlorine, 60, 107 237-9,240,245,246,318-19,
Lacquer coating 322,331,797,813-16
compositions, 686, 760-1 'Lubricant value', 309-10
methods, 673, 758, 761 Lubricants, 24, 33, 294-312
objectives of, 760 acrylic modifiers, as, 297, 300
various PVC products of, 759, 761 blow mOUldings, for, 582
Laminates, calendering, role in, 546-7
PVF film, with, 554, 762, 778 chemical structure, 297-300
sheet, various, 616, 730, 778 commercial, 310, 312
Langley, 810 compatibility with PVC, 295-6
Latices, 698-726 compounds used as, 298-9
definition, 698 concentrates, 310
film formation by, 699-702, 706 functions and effects, 24, 33, 296,
vinyl (PVC) 298-300,309,311
anti-foaming agents for, 710 general, 33
applications, 719-24 magnesium silicate, as, 300
compounding ingredients and mutual effects with
techniques for, 706-19 fillers and pigments, 304
sedimentation in, 709 plasticisers, 303
stability of, 707-8 polymeric modifiers, 304
types, 702-6, 720-2 stabilisers, 36-7,114,122,126,
Lead stabilisers, 115-19 134,140-1,150,302-3
applications, 27, 30, 38, 41, 42-3, one-pack systems, in, 114, 122,
477, 488, 656 134, 149-50,310
chemical nature, 115, 116-17 stabilisers, balance with, see
hazards, 115 Stabiliser/lubricant balance
limitations, 38, 115, 690 stabilising effects of, 37, 301-2
mode of action, 119, 302, 303 tests (performance), 305-9
physical forms, 115 Lubrication, 24, 33, 294-6, 298-9,
Leak detectors, 585 311
894 Index
Lubrication-contd. Mixers (see also relevant entries under

effects of Compounding)
magnesium silicate, 300 continuous, 419-21, 663, 664-6
plasticisers, 37, 296, 303 dissolver, 664
polymeric modifiers, 295-6, 300, general types, 413-18, 450
304 horseshoe (anchor) stirrer type,
stabilisers, 37,118, 123, 126, 664
129,131-3,303 hot/cold,413-19
evaluation of effects, 305-9 intensive (high speed), 413-20
external, 33, 294-6 internal, 451-3, 458
internal, 33, 294-6 laboratory, 456-8
paddle, 414, 664
Machining of rigid PVC, 748-9 planetary, 460-1, 662, 664
Magnesium compounds pneumatic, 414, 450
flame/smoke retardants, as, 353 ribbon blender, 413, 414, 664
lubricant application of, 300 Modacrylic fibres, 73
Marine exposure tests, 805 Modifiers (see Polymeric modifiers)
Mass polymerisation and polymers, Modulus
see under Bulk as basis for distinction between
Matting (flating) agents, 25 (passim), rigid and semi-rigid plastics, 5
360-1,718,760 definitions, and typical values for
Maximum swelling temperature, 185 PVC, 856-8
Maximum torque temperature (melt '100%' (ofpPVC)
fusion point), 193,460 definition, 368, 787
MBS impact modifiers, 43, 316, 324, values, 246, 280
325,326,327-8,582 Moisture content, 84
Melt-flow tests, 305-7, 391, 592-4 Molecular weight (mass)
Microbiological attack determination by GPC, 54
definition, 819 distribution, 54
manifestations and mechanism, 819 fatigue resistance, and, 376
protective additives, 719, 820 polymeric plasticisers, of, 178,
resistance to 214-15
plasticisers, of, 819 PVC, of, 53-4, 56-7
PVC, of, 819, 820-1 K value, and, 53-4, 56-7, 58
testing of resistance to, 820-1 f-l value, and, 187
Microporous PVC sheet, 632-3 polymerisation temperature,
Migration of and,54,58,70
additives into foodstuffs, 13, 247, processing and properties, effect
251,489,835 on, (see also under K value),
colourants, 345, 350 28,79,376,592,684-7,699
plasticisers, 13, 32, 195-7, 224, Molybdenum trioxide, 352
228,247-8,251,253,489 Mould shrinkage of PVC and other
VC monomer, 12,834 polymers, 572, 591
Mills f-l value, 187
ball, 664, 693, 712 Multi-layer extrusion, 507
2-roll, 155, 168,456,457,531,532,
534,543,544,608,610,612 NBS Smoke chamber, 846
3-roll,664 Newtonian viscosity, 639-40
Index 895
'Nibs', 81, 318 (passim); 550, 581 Pastes (see also Organosols,
Nitrile rubber, 217, 224 (passim); Plastigels, Plastisols, and
329-31 Rigisols)
Nitrogen ion implantation, 505 casting of, 678
Novodur A, see Baymod coating of sheet materials with,
'Nylon ate' ('nylon acid') plasticisers, 670-6
see AGS acid ester plasticisers components and formulation of,
643-5, 653-61
compression moulding of, 613-14
definition, 637
Octoates, 42, 125, 128 dip coating with, 668-9
Odour control agents, 25, 359-60 dip moulding of, 667
Oil absorption, 34, 36, 272-3, 289, extrusion of, 681 (passim)
657 foam production from, 344, 771,
'Oil canning', 481, 802, 818 773-4
'One Pack' additive systems, 34, 114, gelation/fusion of, see under
115,122, 134, 141, 149-50, Gelation/fusion
310,346 (passim) preparation, 661-6
Opacifying effect of fillers and rheological properties of, 638-44,
pigments, 269-72 648-51,657,658-9
Organosols, 637, 660, 669, 675 rotational casting of, 666
Organotin stabilisers, 30, 39, 43, 113, slush moulding of, 667
117-124,133,154,156,170, spray coating with, 669-70
472-3,477,536,547,581,656, standard specification for
690 preparation, 89, 662, 664
antimony stabilisers, comparison viscosity determination, 89,
with,126 645-6,664
characteristics and applications, terminology, 637-8
121-4 viscosity of, see under Viscosity
chemical nature and types, 119, Permeability, 821-33
120-21 blow mouldings, of, 568-9, 585,
mode of action, 124 586,827
polymeric, 121 definitions, 821-3
'reverse ester', 123 determination of, 822, 824-7
Oxo process, 204 mechanism of, 828
Oxygen index porous materials, of, 828-9
definition, 844 PVC, data for, 829-32
plasticisers, effects of, 208, 838 units, 823-7
plastics, values for, 373, 840 stretch-orientation, effects on, 96,
test methods, 844 569,829,833
Phosphate plasticisers, 31, 32, 188,
190,191,194,197,206-9
flammability, effect on, 37,197,
Paraloid, see Aeryloid modifiers 208-9,351
Particle characteristics of PVC PVC compounds, performance in,
polymers, see under PVC 32,181,183,188,194,197,
Paste polymers, 28, 653-4, 660, 661, 206-9,210,229,232-3,235-7,
844-5 240,241,242,245,252
896 Index
Phosphite stabilisers, see under Plasticisation--contd.

Costabilisers theories of, 179-80
Photochemical degradation, 109-11 Plasticised PVC (pPVC),
additives protective against, see ageing of (after processing), 185-6
UV stabilisers; Antioxidants; chemical resistance of, 380-1, 384
Carbon black; Titanium compression moulding of, 612-13
dioxide filler loading, effects in, 261, 262,
impurities, effects of, 110, 142, 802 263, 279, 280
mechanism, 111, 141-3, 147-9,249 properties of (see also under
relevant tests, 172-4, 802-13 individual plasticiser and
weathering, in, 110, 111, 249, 798,799 property names), 224-50
phr (abbreviation), 44 stain resistance of, 206, 248-9
Phthalate plasticisers, 31, 32, 39-44, weathering of, 110-11,249-50,
201-6 801-802
flammability, effect on, 208, 239 Plasticiser absorption.
pastes, in, 655 fillers, by, see under Oil absorption
possible health hazard, 13,251, PVC polymer particles, by, 80, 86,
489,491, 781. 88,185,254
PVC compositions, performance Plasticiser content of PVC,
in, 181, 182, 183, 185, 194, determination of, 44-7, 254
197,202-6,229,232-8,240-1, Plasticiser demand (see Oil
242,245,248 absorption)
Pigments (see also Colourants) Plasticisers (see also under individual
latices, in, 717 or type names)
outdoor formulations, for, 27 abbreviations (letter symbols) for,
(passim), 122,146-7,691 198-201
solutions, in, 691-2, 696 bulk properties of, 181,252-3
weathering, effects in, 146-7, chemical nature of, 178, 180-2,
348-9,478, 802 198-223
Pipes citrate, 222
applications, 467-8 commercial, 225-7
compositions for, 38, 368, 371, 373 compatibility
formulation aspects, 38, 472-3 external materials, with, 223-4
production of, 502, 513-16 PVC, with, 186-93, 248
properties and tests, 321, 473-4 cross-linkable, 659, 764, 773
special forms of, 470-2 definition, 177
specifications relevant to, 321, effectivity (efficiency), 188, 193-5,
468-9,473,474,744 228-9
types, 467-8 efficiency factor, 194,228-9
Piston plastometer (ASTM), see extraction
under Rheometers PVC materials, from (for
Planetary extruder (compounder), analysis, etc), 44-7
444-7,532,544 resistance to, 244-7
Plasticisation exudation, tests for, 192, 195
external, 9, 178 flexible seals, in contact with,
internal, 9, 74,178,702 223-4
PVC latices, of, 703, 704, 713-15, food contact considerations, 13, 26,
720-2 246-7,250-1,489,835
Index 897
Plasticisers-contd. Plate-out-contd.
fusing (gelation) rapid, see strongly blowing agents, with, 341
solvating (below) calendering, in, 157, 550
general, 30-2, 197 deposits, nature of, 158-9
glycol ester, 222 extrusion, in, 157, 516
handling and storage, 251, 403-4 test for, 159-60
hazards, 13, 204, 250-1, 489, 825 Polymeric modifiers (see also Impact
interaction parameters, 186-93 modifiers and Processing aids)
'low temperature' , see Aliphatic heat-distortion resistance, for, 328,
diester plasticisers 583
migration of, 32, 195-6, 247-8 lubricants, as, 300, 304
miscellaneous, 218-23 matting agents, as, 328, 360-1
monoester, 220, 222 Polymerisation processes, 63-6, 70-2
monomeric, definition, 178 Polyols, see under Co-stabilisers
names and abbreviations, 198-201 Polyurethane
pastes, in, 637, 647,654-6, 660-1 lacquers, 760, 761
permanence of, 195-6 modifiers, 217, 246, 324, 332
polymeric, 211, 214-7 Polyvinyl chloride (homopolymer)
compositions, in, 215-16, 247, chemical structure of, 53, 59-60
855 crystallinity in, 59-61
definition, 178,211,214 fine structure (morphology) of,
primary, definition, 177 59-61
producers of, 225-7 molecular orientation in, 61
PVC latices, in, 704, 712-15, syndiotactic, 59-61
720-2 Porous materials
secondary, definition, 177 permeability of, 828
selection of, 30-2, 197, 224, 227-9 production methods for, 288, 632-4
solubility parameters of, 187-8 Porvic process, 633
strongly solvating, 31, 32, 44,197, Powder
204,206,208,222,654,655 coating and moulding, 368, 779-81
synonyms, 198-201 compounds,
threshold limit values for, 251 feedstocks, as, 371, 412-13, 423,
trade names, 225-7 508,509,577
types (genera!), 30-2, 196-7 production, see under
usage features (general), 32, 197 Compounding
viscosity-temperature relationship sintering of, 632-3
of,404-5,648,649 types of, 412, 415
volatilisation of, 195,241-3,251, pPVC, as abbreviation for plasticised
817 PVC (q.v.), 5
Plasti-Corder, see under Brabender Prills, 150, 310
Plastigels, 637-8, 658 Printing, see Surface decoration of
Plastisols (see also Pastes) PVC
basic form of, 644-5 Processing aids, 314-6
synonymity with pastes, 637 blow moulding compositions, in,
Plastograph, see under Brabender 42-3,582-3
Plate-out, 157-60 calendering compositions, in, 536,
additives, effects on, 129, 130, 132, 547
158 extrusion compositions, in, 39
898 Index
Processing aids-contd. PVC-contd.

lubricant action of, 297, 300, 304 window frames, see under Profiles
Profiles PVDC
applications, 475-6, 494-5 barrier coatings, 576, 584, 761
cellular, 475-6,516 polymers and copolymers, 73, 74,
compositions for, 39, 368, 371-2 76,483,548,660,704,719,
formulation aspects, 39, 134,332, 720-1
476-9 PVF (surface protection for PVC),
production of, 475, 493 (passim); see under Fluoropolymer, and
502,516 Weathering resistance
specifications and tests, 320-1, Pyrolysis, 837-8, 839, 840, 842
479-80,495
window frame, 134,328,332,368,
475,476-80,516 QUV apparatus, 807, 808, 811
Pseudoplasticity, 641-2
Purging
extruders, of, 506 Rad (unit of absorbed ionising
injection machines, of, 599, 600 radiation), 124, 763
materials for, 507 Radiation darkening of medical
PVC products, 124
acetal polymers, interaction with at RAPRA torque rheometer, 458
elevated temperatures, 599 Recycling of PVC
cellular, see Cellular PVC compounding, and, 453-5
compounds (see also under general problems, 14-16
Compounding and possible sulphide staining in, 155,
Compounds) 156
characterisation, 387-9 Refractive index, 269-72
commercial, 366-70, 371-2, 580, Regulatory bodies, see under Health
592-3 hazards
standard designation, 387 Relative melting temperature, 185
definitions, 3 Retractyl PVC fibre, 777
fibres and fibre products, 9, 73, Rheometers
75-6,777 capillary, 168, 307, 427, 592, 594,
health hazards associated with, see Castor-Severs, 89, 645, 646
Health hazards melt rheometry, for, review of
historical development, 8-9 (passim), 577
polymers (resins) piston plastometer (ASTM),
characterisation, 80-2, 87-90 306-7,592,593
characteristics, 27-9, 53-61, torque, 458
70-2, 74, 78-81, Rheopexy,642,643
commercial, 78, 81, 87, 91-3 Rhovylon PVC filament, 777
general kinds, 27-9, 94 Ribstruct pipe, 472
particles, 67-73, 80, 644-5, Rigid PVC
653-4,698,701-2,709 chemical resistance of, 380-5
production, 61-6 definition, 4-5
standard designation, 81, 87 properties, 4-5, 370-88
usage statistics, 11, 12 Rigisols, 638, 660-1
waste, disposal of, 14-16 Roll test, 192
Index 899
Rossi-Peakes flow tester, 306 Smoke--contd.

Rotational casting, 666 evolution-contd.
tests for, 845-7
nature, 842
Salt spray tests, 805 PVC, generated by, 842
Selective membranes, 783 suppressants, 352-3
Semi-rigid PVC S-N curve, 377
definition, 4-5 Softness (see also BS softness),
properties, 5, 184 measurement, 230
Sheet and sheeting plasticiser demand by fillers, effect
antistatic, 355, 359, 616, 732 on,273
applications of, 483-5, 489, 491, plasticisers, effect on, 230-3
556-9, 730-2, 753, 778 Solid-gel transition temperature, see
calendered, see Calendered sheet Clear-point temperature
commercial, 676, 730-2 (definition)
definition and characteristics, Solubility parameter (b)
481-3,525,729-30 concept, 187
embossing, see Embossing plasticisers, of, 187-8
extruded 516-18 PVC polymer, of, 188
"planishing" (press finishing) of, Solution polymerisation, 63-4, 683
552 Solution polymers, 684-8, 690
press-laminated, 609 Solution temperature, see Clear-point
properties, 483, 537, 554-8, 730-2 temperature (definition)
tank lining with, 729, 735 Solutions, PVC of, 683-97
tests and standards, 485, 492, films cast from, 483 (passim); 696-7
555-8,852,853,857-8 ready made, 693
thickness solvent cements, as, 697, 742, 744
measurement and control, 541 Solvation point, 185
values and ranges, 482-3, 518, Solvent bonding of PVC, see under
525 Bonding of PVC
types, 483,491, 518,524,536-7, Solvent cements, see under Bonding
555-9, 609, 616 of PVC, and Chlorinated PVC
Shore (Durometer) hardness 'Soot Chamber' (,Smoke Chamber')
BS softness, and, 230-1 test, 359
determination of, 230 Spiral mould, melt 'flow length' test,
effect of fillers on, 279 for, 306, 592, 593
typical value ranges for PVC, Spontaneous ignition, see
232-3 Autoignition
Shrink sleeves, 483-4 Stabilisation (see also Heat
Siding, 321, 328 stabilisers, UV stabilisers, and
Simulated skin, 475, 480-1, 818 Antioxidants)
Single-pack additive systems, see effects, evaluation of, 160-74, 797
'One-pack' additive systems external, 112
Slush moulding, 667 general, 102-3
Smoke 'in kettle', 113
density, 842, 845-6 internal, 112-13
evolution mechanisms, 119, 124, 134-5, 137,
burning plastics, by, 842 138, 139, 140, 144, 146-9
900 Index
Stabiliser/lubricant balance, 114, 122, Suspension-contd.

140-1,301-3,310,472,546 67-9,70-2,80
Stabilisers, see under functional types polymerisation, 64, 70-2
(e.g. Heat stabilisers, UV polymers, 28, 38-43, 488, 580, 644,
stabilisers, Antioxidants) 654, 660, 661
Stability Syndiotactic PVC polymer, 59, 61
heat, to, Synergism
adverse effects of formulation co-stabilisation, in, 126, 127, 129,
components on, 38, 128, 348, 130,140
352,355 lubricant/stabiliser, between, 302,
concept, 160-2 310
induction time, and, 160-1, 162 calcium stearate and antimony
polymer nature, effect on, 59, mercaptide, between, 126,302
60,107-9 glycerol esters and thiotins,
stability time, and, 160-1, 163, between, 123, 302
168
testing, 86,162-72,390-1,796,
797,817-18
light, to, 109-11, 143-9 Taber abraser, 862
testing, 172-4,804-5,810-11 Talc, 259, 260, 264, 271, 292
Stain resistance of pPVC, 222, 248-9 Tangit solvent cement, 744
Standards institutions, 6 Tank lining with PVC sheet, 729, 735
Static electricity charges Tedlar (Du Pont), see under
electrical resistivity, and, 354, 356, Fluoropolymer
358-9 Tellurium-based heat stabilisers,
measurement, 356, 358 (passim); 120
Stress Temperature-gradient bar, 647
concentrating features, 268, 318, Temperature index, 817
323 Tensile properties
cracking, see Environmental stress paste products, of, 650, 651
cracking plasticisation, effects on, 532-4,
rupture strength, 375 852-3
whitening temperature, effect on, 318, 817,
filled compositions, in, 34, 38, 272 818
impact modified compositions, typical values for PVC, 852-3
in, 38, 326, 582 Tensol solvent cement, 744
mechanism, 272, 326 Termites, resistance of PVC to, 821
Strontium stabilisers, 125, 133 Tertiary chlorine, 59, 60, 107-8
Sulphide staining 'fg, see Glass transition temperature
as cross-staining, 122, 128, 155 Thermal decomposition products
occurrence, 38, 126, 128, 151, 155- plastics of, (general), 837, 839
7 PVC, of, 103,841,846
tests for, 155, 157 Thermal degradation of PVC
Surface treatment of fillers, see under activation energy for, 102, 168
Fillers and Calcium carbonate and specific energy for melt
fillers generation, 102
Suspension heat-processing conditions, effects
polymer particle characteristics, on, 102, 108,424,588-91
Index 901
Thermal degradation of PVC-contd. uPVC

impurities and residues, effect on, 109 as abbreviation for unplasticised
manifestations of, 103-4 PVC, 5
measurements of, 162, 164-72 use as abbreviation for rigid PVC
mechanisms of, 104-9 (q.v.),4
Thermal diffusivity, 571-2 Urea derivatives as heat stabilisers,
Thermal properties of PVC materials, 136-7
283-5,318-19,322,328,330, UV stabilisers, 144-9
332,373,379,390-1,592,594,
796-7,813-18,858-60
Thermoforming, 614-32
Thermovyl fibre, 777 Vacuum forming, see Thermoforming
Thickening agents Venting
latices, in, 708-10 extruders, of, 437, 444, 500
pastes, in, 658-9 moulds, of, 573, 577
Thixotropy, 642 Vinyl chloride,
Time/temperature effects in melt copolymers, see under Copolymers
processing, see under Thermal homopolymer, see under Polyvinyl
degradation chloride
"Time to black", 161, 168 Vinyl chloride monomer (VC or
"Time to colour", 161 VCM)
Tin stabilisers, see Organotin detection and determination, 86,
stabilisers 834
Titanium dioxide explosive limits, 63
clay, in, 259 hazards of, 10, 12-13, 834
light stabiliser, as, 27,146-7,478, polymerisation of, 63-6
691, 802 production of, 62-3
white pigment, as, 346, 478 properties, 63
Torque rheometers, see under regulatory measures concerning,
Rheometers 583,834
Toughness, 317 'stripping' from PVC polymer, 64,
Toxicity, see Health hazards 65,66
Transfers (surface decoration), 754 Viscometers (see also Rheometers)
Trialkyl phosphate plasticisers, 197, Brookfield, 645-6, 664
200,208,209,210 Castor-Severs, 89, 645-6
Triaryl phosphate plasticisers, 197, Ford cup, 646
200,207-8,210,252 Viscosity
Trimellitate plasticisers, 197, 200, depressants for pastes, 659
209,211,212,243,244 expressions and terms, 53-7
Tubing (flexible), 368, 372, 493-5, melts, of, 295-6, 306-9, 427,
781 577-8,589,592-4
number, see under K value
pastes, of, 89, 638-44, 653-4, 655,
656
ageing index, 658
Ucar PVC solution polymers, 684-7, diluent, effects of, 637, 659, 660
690, 695, 696 extender polymers, effect of, 654
Ultramoll PU, see Baymod fillers, effect of, 656-8
902 Index
Viscosity---contd. Weathering---contd.
pastes, of---contd. resistance---contd.
measurement of, 89, 645-6 processing, effect of, 802
plasticisers, effect of, 654-6 solvent residues and impurities,
thickening agents, effect of, effect on, 110, 802
658-9 ways of promoting, 801-2
PVC polymers, of (in solution-see tests, 172, 802-13
also under K value), 53-7, Weather-Ometer, 807, 808, 811
82-3,88 Welding of PVC (see also Bonding),
solutions, of, 53-7, 88, 685-7, 690 733-41
specific (see also under K value), flooring, 734
53-7 recommended temperatures for,
stability (pastes), 638, 657-8 733
standards and definitions, 53-7, specifications relevant to, 733-4,
82-3,88 735
Volatile loss, 89, 195,241-3,388,817 tank linings, 735
window frames, 736
White lead, 116
Wacker MP fibre, 777 Whiting, see Calcium carbonate fillers
Water (types)
absorption, 34, 385-6, 390, 862 Window frames, see under Profiles
fillers, effect on, 34, 261 Wohler curve, 377
diffusion in PVC, and, 385-7 Working surfaces (in PVC melt
equilibrium concentration in PVC, processing), 447, 504-5, 576,
386 596-7
Weathering (see also under
Photochemical degradation)
definition, 798 Xenon-arc radiation, 805, 807, 808,
effects, 110-11,249-50,798-801, 811
814 Xenotest apparatus, 807, 809
factors instrumental in, 109-11, XP-2 smoke chamber, 846
249, 798-801
plasticisers, effects in, 11,249-50,
801
resistance Yellowness index, 813
assessment, 172
formulating for, 27, 116, 122,
134,137,139,143-9,328,331, Zinc-containing stabilisers, 26, 30, 39,
332,477-9,691,801-2 41,42,43,44,125,128-35,
improvement of, 147,151,154,156,170,547,
coextrusion 'capping', by, 581,656
475,507,518,730,801 Zinc oxide, 147, 352
lamination with PVF film, by, Zinc sensitivity of PVC resins, 128,
554, 762, 778 147 (passim); 352 (passim).
protective coating, by, 760, ZSK compounding extruder, 428,
762,801 431,439-41,499 (passim)

W. V. Titow M. Phil., PH.D., C. Chem., F. R. S. C., F. P. R. I., C. Text., A.T.I. (Auth.) - PVC Plastics - Properties, Processing, and Applications-Springer Netherlands (1990) PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

W. V. Titow M. Phil., PH.D., C. Chem., F. R. S. C., F. P. R. I., C. Text., A.T.I. (Auth.) - PVC Plastics - Properties, Processing, and Applications-Springer Netherlands (1990) PDF

Uploaded by

Copyright:

Available Formats

PVC PLASTICS

Properties, Processing, and Applications

ELSEVIER APPLIED SCIENCE

Sale distributor in the USA and Canada

WITII 120 TABLES AND 149 ILLUSTRATIONS

© 1990 ELSEVIER SCIENCE PUBLISHERS LTD

British Library Cataloguing in Publication Data

Titow, W. V. (Witold Victor) 1926-

Library of Congress Cataloging in Publication Data

Special repletions for readen in the USA

This book originated from my Publisher's request for anew, concise

additional information I needed for Chapter 20. I am most grateful for

2.1.1 General Features and Main Categories . . . . . 22

Section 2-Constituents of PVC Compositions 51

3.1.2 Polymer Morphology and Some Related Properties 59

exposure to heat; (d) effects of polymer molecular

stability tests; static stability tests; (b) light-stability

5.5.4 Transport, Handling, and Storage of Plasticisers 223

ticiser) absorption; dispersion characteristics; cost;

flow in a piston plastometer; the ASTM capillary

practical tests-heat stability; stability to light and

Section 3-Production (Compounding) of Solid PVC Composi-

11.2 Industrial Production of Solid Compounds . . . . . . . 396

Section 4---Processing of Solid PVC Compositions into Products 465

Chapter 13 . . . . . . . . . . . . . . . . . . . . . " 497

13.3 Some General Points Relevant to PVC Extrusion 504

14.3.2 Other Lines and Arrangements: (a) lines for

(b) formulation components-PVC polymer; sta-

phone records; (b) compression moulding of thick

Section 5---Liquid PVC Compositions: Nature, Preparation,

18.2.2 Rheological Effects of the Polymer Component in

Section 6----Post-production Processing of PVC Products . . . . 727

22.3.2 Other Protective Coatings. . . . . . . . . . 761

Section 7-Applications of PVC Products, and Some Important

24.2.1 Electrical Properties 792

24.6.6 Some Relevant Publications 847

1.1 SOME KEY TERMS, DEFINITIONS,

(a) 'polyvinyl chloride', i.e. the homopolymer of vinyl chloride, or

1.1.2 The Nature and Make-Up of PVC Materials

A plastic can be defined as a polymer-based material in which the

semi-rigid PVC materials (the latter typically containing up to about

1.1.3 Abbreviations and Symbols for Material Names

For the sake of convenience, abbreviations of (letter symbols for) the

* As put forward in the three principal English-language plastics vocabulary

author, who regards them as open to criticism on certain sound

1.2 MATERIAL AND TEST STANDARDS

Standardisation of test methods and material property requirements

* With headquarters in Geneva.

properties, water absorption, etc.). Many specifications of this kind-

* With headquarters in Northbrook, IL, USA, and several local agencies in

1.3 ORIGINS, mSTORICAL DEVELOPMENT, AND

1.3.1 Early History

The following highlights in the early history of PVC may be noted.

The 19308: Plasticisation of PVC by phthalate esters. Introduction in

Early attempts at heat-processing vinyl chloride homopolymers were

1.3.2 Present Position

(a) PVC as a Major, Highly Versatile Thermoplastic

(b) Some Topical Concerns

VINYL CHLORIDE AS A HEALTH HAZARD

* In this context frequently abbreviated to 'VCM' (for 'vinyl chloride

Area Western Europe USA

(Thousand (% of grand (Thousand (% of grand

atmospheres, remaining in the PVC polymers after their production,