PVC TECHNOLOGY

Fourth Edition

PVCTECHNOLOGY

Fourth Edition

W. V. TITOWM. Phil., Ph.D., C.Chem., F.R.S.C., F.P.R.I., C. Text., A. T.!.

Formerly of the Yarsley Research Laboratories Ltd,Ashtead, Surrey, England

ELSEVIER APPLIED SCIENCE PUBLISHERSLONDON and NEW YORK

ELSEVIER APPLIED SCIENCE PUBLISHERS LTDRipple Road, Barking, Essex, England

Sole Distributor in the USA and CanadaELSEVIER SCIENCE PUBLISHING CO., INC.52 Vanderbilt Avenue, New York, NY 10017, USA

First edition 1962

Second edition 1966

Reprinted 1967

Third edition 1971Fourth edition 1984

Reprinted 1986

British Library Cataloguing in Publication Data

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

ISBN-13: 978-94-010-8976-0 e-ISBN-13: 978-94-009-5614-8DOl: 10.1007/978-94-009-5614-8

WITH 171 TABLES AND 230 ILLUSTRATIONS

© ELSEVIER APPLIED SCIENCE PUBLISHERS LTD 1984Softcover reprint of the hardcover 1st edition 1984

Special regulations for readers in the USAThis publicatiQ1l .has been registered with the Copyright ClearanceCenter Inc, (G;~c), Salem, Massachusetts. Information can be obtainedfrom the CCC 'about conditions under which photocopies of parts of thispubliCatio~ may be made in the USA. All other copyright questions,including photocopying outside of the USA, should be referred to the

publisher.

The selection and presentation of material and the opinions expressedin this publication are the sole responsibility of the authors concerned

All rights reserved. No part of this publication may be reproduced,stored in a retrieval system, or transmitted in any form or by anymeans, electronic, mechanical, photocopying, recording, or otherwise,

without the prior written permission of the publisher.

Preface to the Fourth Edition

This book continues the tradition of the first two editions of the lateW. S. Penn's original PVC Technology, and the extensively revisedthird (1971) edition prepared by myself and B. J. Lanham.

In the present edition the original general format, and the arrange­ment of chapters, have been largely preserved, but virtually nothingnow remains of Penn's own text: a part of the contents is based onmaterial from the 1971 TitowlLanham version (revised, updated andmainly rewritten): the rest is new, including, inter alia, several chaptersspecially contributed by experts from the plastics industry in the UKand Europe. The section listing international (ISO) and national (BS,ASTM and DIN) standards relevant to PVC, which was first intro­duced (as Appendix 1) in the 1971 edition, proved a popular feature: ithas now been brought up to date and considerably extended. Twofurther appendices provide, respectively, comprehensive unit conver­sion" tables (with additional information on some of the most frequentlyencountered units, and the SI units), and a list of many properties ofinterest in PVC materials, with definitions, typical numerical values,and references~to relevant standard test methods.For various reasons, work on this edition involved more than theusual quota of problems: I am truly grateful to the Publisher's Manag­ing Editor, Mr G. B. Olley, for his understanding, patience, unfailingcourtesy and friendly encouragement. I am also most appreciative ofthe helpful attitude of all other members of the Publisher's staff whowere concerned with the various aspects of processing the manuscriptand bringing the book out.

If my own contribution to the book has any merit, then I would liketo dedicate it-respectfully and affectionately-to all my friends of theYarsley Laboratories with whom I was priviledged to share manyhappy years, participating in the worthwhile work of a good team.

W.V.T.

v

Acknowledgements

I am much indebted to Messrs W. B. Duncker, F. J. Olivier and D. J.Sieberhagen of Vynide Ltd for their most helpful comments on thedraft of Chapter 18 and for the trouble they took-individually andseverally-to provide the drawing for Fig. 18.3, data for Table 18.1,and a few items of information on certain practical aspects of calender­ing. I am also grateful to Mr J. M. Hofmeyr of Union Carbide for theinformation he kindly supplied on the Ucar range of copolymer resins,and for his permission to use it in Chapter 24.

It is a pleasure to record my thanks to Mr R. Coates of AECIIChlor-Alkali and Plastics Ltd for a most useful discussion of the scriptsof Chapters 2 and 3, for items of information I have used in Tables 2.5and 2.6, and for arranging his Company's permission-which I verymuch appreciate-to reproduce from their technical literature thecontents of Tables 3.4-3.7.For the illustrations contained in the Plates my thanks are due to thecompanies and/or individuals identified in each caption, who kindlyprovided the original photographs.A small number of graphs and drawings, and one table (Table 14.1),are straight reproductions from other publications: the copyright hol­ders' and authors' permissions to use these items-which are men­tioned in each individual case-are much appreciated.A few definitions and sets of numerical data have been directlyquoted (with sources clearly identified) from ISO, British and ASTMStandards. Such material from ISO specifications is reproduced bypermission of the British Standards Institution granted on behalf of theInternational Organisation for Standardisation. The extracts from Brit-

vii

viii Acknowledgements

ish Standards are reproduced by permission of the British StandardsInstitution, 2 Park Street, London W1A 2BS, from whom completecopies of the standards concerned can be obtained. The material fromASTM Standards is copyright the American Society for Testing andMaterials, 1916 Race Street, Philadelphia, PA 19103, and is reprintedwith permission.I am particularly grateful to Mrs Rene Chizlett-whose invaluablesecretarial contribution to the previous edition was greatly missed withthe present one-for timely help with last-minute verification of severalitems of information on suppliers of commercial PVC materials.Mrs Connie von Gernet typed most of the manuscript-it is apleasure to acknowledge her professional assistance. I am also mostappreciative of Mrs Micky Kruger's secretarial help with two of thechapters and urgent correspondence.No aid on the technical side could be more important than thesupport and patience of my wife, Margaret Ley-Titow, during the longperiod, not lacking in stress, when the book was being put together.For all she has done she has my truly appreciative thanks.

W.V.T.

Preface

Contents

v

Acknowledgements vii

List of Contributing Authors xxix

Chapter 1Introduction-W. V. TITOW . . . . . . . . . . . . . 11.1 PVC: General Terminology and Relevant Definitions 11.2 Early History and Development of PVC . . . . . 41.3 General Statistics 101.4 Outline of the PVC Sector of the Plastics Industry 121.5 Vinyl CWoride Polymers and Copolymers . . . . 13

1.5.1 PVC Homopolymers: chemical structure; mor-phology 13

1.5.2 Vinyl CWoride Copolymers . . . . . . . 191.5.3 'External' Modification of PVC by Other Polym-

ers 211.5.4 Properties of PVC Compositions 24

1.6 CWorinated Polyvinyl Chloride (CPVC) 241.7 Material and Test Standards 29References . . . . . . . . . . . . . . . 30

Chapter 2Commercial PVC Polymers-W. V. TITOW

ix

37

x Contents

2.1 Introduction-Production and Main Types .2.2 Polymer Characteristics Cardinal to Behaviour in Process-

ing and/or Service Performance .2.2.1 Composition . . . . . . . . . . . . . .2.2.2 Molecular Weight (Viscosity Number and K

Value) .2.2.3 Polymer Particle Characteristics: particle size and

size distribution; particle shape and morphology .2.2.4 Purity . . . . . . . . . . . . . . . .

2.3 Characterisation and Designation of Commercial PVCPolymers .

2.4 Examples of Basic Properties of Commercial Polymers asUsed for Some Major Applications . .

2.5 Commercial Sources of PVC PolymersReferences. . . . . . . . . . . . . . . .

Chapter 3Commercial PVC Compounds-W. V. TITOW3.1 Introduction .3.2 Commercial Sources of PVC Compounds3.3 Types and Applications of Commercial PVC Com-

pounds .3.4 Properties and Designation of Commercial PVC Com-

pounds .3.4.1 Designation .3.4.2 Properties Used in Characterisation of PVC Com-

pounds ' .3.4.3 Some Typical Properties of Commercial PVC

CompoundsReferences

Chapter 4Elementary Principles of PVC Formnlation-W. V. TITOW4.1 Introduction . . . . . . . . . . . . . . . . . . .4.2 The Components, and Basic Types, of a PVC Formula-

tion .4.3 Formulation Costing-Basic Points . . . . . . . . . .4.4 Main General Considerations in the Selection of Principal

Formulation Components . . . . . . . . . . . . . .

37

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7979

8183

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Contents xi

4.4.1 Nature and Characteristics of Individual Compo­nents of a Formulation: PVC polymer; heatstabilisers; plasticisers; lubricants; polymeric mod-ifiers; fillers; colourants 86

4.4.2 Interactions and Mutual Effects of FormulationComponents: compatibility effects; synergism;other mutual effects 103

4.4.3 Side Effects of Formulation Components: 'secon-dary functionality' effects; undesirable side-effects 105

4.5 Some Special End-use Requirements 1064.5.1 Food-contact Applications 1064.5.2 Resistance to Weathering 1074.5.3 Electrical Insulation 107

4.6 Examples of Basic Formulations 1074.6.1 Film and Sheeting 1074.6.2 Calendered Plasticised Vinyl/Asbestos Flooring

(Tile~ 1094.6.3 Pipe and Tubing 1104.6.4 Cable Covering and Insulation 1114.6.5 Gramophone Records 1124.6.6 Blow-moulded Bottles 1124.6.7 Injection Mouldings 1134.6.8 Extruded Profile 1144.6.9 Paste Formulations 114

Chapter 5Theoretical Aspects of PlasticisatiOD'--D. L. BUSZARD 1175.1 General Introduction . . . . . . . . . 1175.2 Definition of Plasticisers and Plasticisation 1175.3 Chemical Nature of Plasticisers 1195.4 Theories of Plasticisation 1205.5 Stages of Plasticiser Interaction with PVC Polymer 1225.6 Requirements for PVC Plasticisers 124

5.6.1 Compatibility and Miscibility: the IL value; solubil­ity parameter 8; clear point temperature;Flory-Huggins interaction parameter x; Ap/Poratio; loop or roll compatibility tests; maximumtorque temperature 125

xii Contents

5.6.2 Effectivity of Plasticisers 1325.6.3 Permanence of Plasticisers 134

5.7 General Relationships between the Structure of Plasticis-ers and their Behaviour in PVC 136

5.8 Ageing of Plasticised PVC 1385.9 Antiplasticisation 142References . . . . . . . . . 143

Chapter 6Commercial Plasticisers-D. L. BUSZARD 1476.1 Introduction . . . . . . . . . . . . 1476.2 Classification of Commercially Available Plasticisers 1476.3 Group Characteristics of Major Plasticiser Gasses 1486.4 Synonyms and Abbreviations 1486.5 Group 1 Plasticisers-Phthalates . 152

6.5.1 Lower Phthalates .... 1526.5.2 General-purpose Phthalates 1536.5.3 Linear Phthalates 1536.5.4 Higher Phthalates 1566.5.5 Miscellaneous Phthalates 158

6.6 Group 2 Plasticisers-Phosphates 1596.6.1 Triaryl Phosphates . . . 1596.6.2 Trialkyl Phosphates 1606.6.3 Mixed Alkyl Aryl Phosphates 1616.6.4 Halogenated Alkyl Phosphates 163

6.7 Group 3 Plasticisers-Trimellitates . 1636.8 Group 4 Plasticisers-Aliphatic Diesters 1636.9 Group 5 Plasticisers-Polymeric Plasticisers 1656.10 Group 6 Plasticisers-Miscellaneous Plasticisers 170

6.10.1 Epoxy Plasticisers 1706.10.2 Chlorinated Paraffins 1716.10.3 Monoesters . . . . 1736.10.4 Glycol Esters 1736.10.5 Hydrocarbon Extenders 1746.10.6 Other Miscellaneous Plasticisers 174

6.11 Storage and Handling of Plasticisers 1756.12 Plasticiser Manufacturers 180References . . . . . . . . . . . . . . 180

Conren~ xili

Chapter 7Properties of Plasticised PVC-D. L. BUSZARD 1817.1 Introduction . . . . . . . . . . . . . . 1817.2 Formulation of a Plasticised PVC Compound 181

7.2.1 The 'Desirability Function' 1837.2.2 Computer-assisted Formulating 183

7.3 Softness and Tensile Properties 1847.3.1 Effect of Plasticiser ..... 1857.3.2 Compounding at Equal Efficiency 185

7.4 Low-temperature Properties 1927.5 Permanence Properties 195

7.5.1 Extraction Resistance 1967.5.2 Migration Resistance 1997.5.3 Volatile Loss 2007.5.4 Automotive Fogging 2027.5.5 High-humidity Compatibility 204

7.6 Flame-retardant Properties 2047.7 Electrical Properties 2067.8 Weathering and Light Stability . . . 2067.9 Resistance to Microbiological Attack 2087.10 Resistance to Insect and Rodent Attack 2097.11 Stain Resistance . . . . . . . . . . 2097.12 Toxicity and Health Aspects of Plasticisers 210

7.12.1 Plasticisers for Food-contact Application 2107.12.2 Health and Safety 211

References . . . . . . . . . . . . . . . . . . . 212

Chapter 8FiDers in PVC-I. D. HOUNSHAM and W. V. TITOW 2158.1 Introduction . . . . . . . . . . . . . . . 2158.2 Mineral Fillers . . . . . . . . . . . . . . 216

8.2.1 Silicates and Silicas: asbestos; talc; clay 2168.2.2 Alkaline-earth Metal Sulphates 2198.2.3 Calcium Carbonates 221

8.3 Calcium Carbonate Fillers-Nature, Properties and Ap­plications . . . . . . . . . . . . . . . . . . . .. 2248.3.1 General Types: whiting; ground limestone, marble

and calcite; ground dolomite; precipitated calciumcarbonates 224

xiv Contents

8.3.2 Surface Treatments: stearate treatments; or­ganotitanate treatments; proprietary and miscel-laneous treatments 225

8.3.3 Filler Properties and Selection Criteria: maximumparticle size; particle size distribution and meanparticle size; colour (dry brightness); refractiveindex; oil (or plasticiser) absorption; dispersioncharacteristics; cost. 228

8.3.4 Applications, and Effects of Filler Loading: floor-ing; plasticised compounds; rigid PVC 232

8.4 Functional Fillers 2408.4.1 Reinforcing Fillers: asbestos (chrysotile) fibres; in­

organic microfibres; glass fibres; carbon fibres;glass spheres; fine-particle calcium carbonate 240

8.4.2 Flame-retardant and Smoke-suppressant Fillers 2478.4.3 Miscellaneous Functional Fillers: carbon black;

metal powders; wood flour; starch; syntheticsilicas 248

8.5 Some Filler Suppliers and Trade Names 251References . . . . . . . . . . . . . . . 253

Chapter 9Stabilisers: General Aspeds-W. V. TITOW 2559.1 Introduction . . . . . . . . 2559.2 Degradation of PVC Polymer 256

9.2.1 Thermal Degradation 2569.2.2 Photochemical Degradation 260

9.3 Ideal Requirements for a Stabiliser, and General FactorsAffecting Stabiliser Selection 261

9.4 Heat Stabilisers 2639.4.1 Lead Compounds 2659.4.2 Organotin Stabilisers: chemical nature and types;

characteristics and applications 2709.4.3 Compounds of Other Metals: metal compounds

with stabilising effects in PVC; composite metalstabilisers 275

9.4.4 Organic (Miscellaneous) Stabilisers: esters ofaminocrotonic acid; urea derivatives; epoxy com­pounds; organic phosphites; miscellaneous organicco-stabilisers 286

Conren~ xv

9.5 Antioxidants and UV Absorbers 2929.5.1 Antioxidants 2929.5.2 UV Absorbers 294

9.6 Main Modes of Stabiliser Action 2999.6.1 Lead Stabilisers . . . . 2999.6.2 Organotin Stabilisers . . 3009.6.3 Other Metal-based Stabilisers 3029.6.4 Organic Stabilisers, Antioxidants, UV Stabilisers 304

9.7 Some General Features and Common Faults of StabilisedCompositions ..... 3059.7.1 Plate-out . . . . . . . . . . . . 3059.7.2 Sulphide Staining 308

9.8 Testing and Evaluation of Stabiliser Effects 3119.8.1 Concept of Stability in Processing, Service and

Tests 3119.8.2 Heat Stability Testing 3159.8.3 Light Stability Testing 328

9.9 Detection and Analysis of Stabilisers 330References . . . . . . . . . . . . . . 330

Chapter 10Commercial Stabillser Practice-P. S. COFFIN 33510.1 Introduction 33510.2 Choosing a Commercial Stabiliser . . . 33710.3 The Importance of a Well-balanced Lubricant System 33910.4 One-pack Systems and the Physical Form of Stabiliser

Products . . . . . . . . . . . . . . . . . . . .. 34010.5 Hygiene and Environmental Considerations ..... 34110.6 UK Stabiliser Manufacturers-Product Ranges and Ap-

plications 34210.6.1 Associated Lead Manufacturers Ltd 34210.6.2 Ciba-Geigy Ltd . . . . . . . . . 34610.6.3 Durham Chemicals Ltd ..... 34810.6.4 Diamond Shamrock Polymer Additives Division 35110.6.5 Victor Wolf Ltd 356

References . . . . . . . . . . . . . . . . . . . . . " 356

Chapter 11Some MisceUaneous Components of PVC Formulations-W.V. TITOW . . . 35911.1 Lubricants . . . . . . . . . . . . . . . . . . .. 359

xvi Contents

11.1.1 Functions, Nature and Effects 35911.1.2 Interaction and Co-action of Lubricants with

Other PVC Formulation Components:lubricant/stabiliser effects; mutual effects oflubricants and plasticisers; effects of polymericmodifiers; effects of fillers and pigments 364

11.1.3 Assessment of Lubricant Effects 36711.1.4 Sources of Information on Lubricants and their

Commercial Suppliers 37011.2 Polymeric Modifiers 371

11.2.1 Processing Aids 37211.2.2 Impact Modifiers: impact resistance-its nature,

significance and measurement; the impact resis-tance of PVC; the nature, effects and applica-tions of polymeric impact modifiers for PVC 375

11.3 Colourants 40111.3.1 General Nature and Functioning 40111.3.2 General Classification 40311.3.3 Forms in which Colourants are Available 40511.3.4 Choice of Colourant-Main Considerations:

general appearance and colour requirements;processability and stability in processing; stabil­ity and permanence in service; health andsafety considerations 407

11.3.5 Some Commercial Pigments 41011.4 Antistatic Agents 419

11.4.1 Static Electricity Charges on PVC: Phenomenaand Tests 420

11.4.2 Nature and Use of Antistatic Agents 42211.5 Flame and Smoke Retardants 424

11.5.1 General Mechanism of Burning of Polymers andPlastics 424

11.5.2 Flame Retardance and Smoke Suppression inPVC Compositions 427

References 435

Chapter 12MisceUaneous Properties of Special Interest in PVC Materialsand Products-W. V. TITOW 43912.1 Introduction 439

CQnren~ xvli

12.2 Low-temperature Properties 43912.2.1 Cold Flex Temperature (Clash and Berg) 44212.2.2 Cold Bend Temperature 44212.2.3 Low Temperature Extensibility of Flexible PVC

Sheet 44212.3 Heat Resistance . . . . . . . . . . . . 44312.4 Permeability 45212.5 Environmental Stress Cracking and Crazing 46612.6 Weathering Resistance . . . . . . . . . 46912.7 Resistance to Biological Attack . . . . . 483

12.7.1 Microbiological Attack (Biodegradation) 48312.7.2 Insect and Animal Depredations: attack by ter-

mites; attack by rodents 48612.8 Chemical Resistance . . . . . . 48712.9 Health Hazards . . . . . . . . 495

12.9.1 Vinyl Chloride Monomer 49612.9.2 PVC Compounds and their Regular Con-

stituents 49812.9.3 PVC Decomposition Products 49912.9.4 Peripheral Hazards 500

12.10 Burning Behaviour 501References . . . . . . . . . . 509

Chapter 13Industrial Compounding Technology of Rigid and PlasticisedPVC-W. HENSCHEL and P. FRANZ 51313.1 Introduction 51313.2 Raw Materials. . . . . . . . . 514

13.2.1 PVC Polymer and Fillers 51413.2.2 Plasticisers 51913.2.3 Other Additives . . . . 519

13.3 Upstream Equipment (Silo Storage to Weighing) 51913.3.1 Silo Storage of PVC Polymer and Fillers: silo

sizes; materials of silo construction; raw mater­ial intake (silo filling); raw material discharge;dust removal system . . . . . . . . . . .. 519

13.3.2 Conveying of PVC Polymer and Fillers:pneumatic conveying . . . . . . . . . . .. 525

13.3.3 Storage of Plasticisers: tank sizes; suitable con-

xviii Contents

struction materials; plasticiser delivery; pointerson pipe laying 530

13.3.4 Storage of Additives. . . . . . . . . .. 53213.3.5 Metering and Weighing: fundamentals of meter-

ing and weighing technology; control andmonitoring equipment . . . . . . . . 532

13.4 Mixing . . . . . . . . . . . . . . . . . . . . .. 54713.4.1 Blending of Bulk Materials in Overall Solid

Phase: introduction; theoretical aspects of mix­ing, with special reference to dry blending ofPVC compositions; mixers for plastics proces-sing; tank-type or intensive mixer . . . . .. 547

13.4.2 Melt Compounding: compounding and pelletis­ing; compounding of PVC for feeding calen­ders; extrusion of film, sheet and board; recycl-ing 577

13.4.3 Preparation of PVC Pastes: silo storage; meter­ing; pasting-up and dispersion; filtering; de-gassing; ageing; colouring 603

13.4.4 Machinery: screw-type machines; machinedrives; control and instrumentation; interlocks;materials of construction; machines for the pro-duction of pastes 609

13.5 Pellet Cooling and Storage . . . . . . . . . . . .. 66013.5.1 Pellet Cooling: nature and outline of the opera-

tion; pellet cooler systems 66013.5.2 Pellet Mixing and Storage: pellet mixer designs;

handling of PVC pellets 664

Chapter 14Extrusion of PVC-General Aspeds--B. J. LANHAM and W.V. TITOW . . . . 67314.1 Introduction 67314.2 The Extruder . . . . . . . . . . . . . . . . . .. 674

14.2.1 Main Components and Their Functions, withSpecial Reference to Extrusion of PVC: thescrew; the barrel; the head and die assembly;heating and cooling; the hopper . . . . . .. 674

14.2.2 Some General Points Relevant to Extrusion ofPVC: machine outputs and energy efficiency in

Contents

modem extrusion practice; some features of,and aids to, modem extrusion; use of compu­ters; some material aspects; some features andcommon faults of extruded products . . . . .

14.3 PVC Material Flow, Homogenisation and Gelation (Fu-sion) in the Extrusion Process

14.4 Single-screw Extruders ...14.5 Twin-screw Extruders . . .14.6 Some Commercial Machines14.7 Ancillary Equipment14.8 Extrusion of Plasticised PVC

14.8.1 Normal (Relatively Slow) Extrusion14.8.2 High-speed Extrusion .14.8.3 Examples of Industrial Extrusion of Plasticised

PVC: PVC coating of wire and cable; produc­tion of pPVC hose with braid reinforcement

References

Chapter 15Injection Moulding of PVC-The late L. W. TURNER15.1 Introduction .15.2 Melt Properties of Particular Significance, Melt Be­

haviour in Relation to Moulding Conditions, and Mould­ing Compounds . . . . . . . . . . . . . . . .15.2.1 Moulding compounds .

15.3 Effect of Processing Factors upon Product Properties15.3.1 Quenching Stresses .15.3.2 Orientation and Related Features .

15.4 The Moulding Process: Available Equipment; ProcessControl; Some Features of uPVC Moulding15.4.1 Rate of Injection and Injection Pressure15.4.2 Working Surfaces .15.4.3 Interaction of PVC with Acetal Polymers and

Copolymers15.5 Materials and Applications15.6 Trouble-shooting ....

15.6.1 Machine Selection15.6.2 Processing Features Specific to PVC15.6.3 General Considerations.

References . . . . . . . . . . . . . . . . . .

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xx Contents

Chapter 16Sheet 'Thermoforming and Related Techniques for PVC-Thelate L. W. TURNER 74316.1 Introduction 74316.2 Materials Used . . . . . 74516.3 Vacuum Forming of Sheet 745

16.3.1 Principal Methods: negative forming; plug­assisted forming; drape forming; bubble form-ing; snap-back forming 745

16.3.2 Details of Methods 75116.3.3 The Moulds .... 75316.3.4 Finishing . . . . . . 754

16.4 Matched-mould and Related Methods 75516.5 Tolerances in Dimensions and Dimensional Stability of

Formed Parts . . . . . . . . . . . . . 75616.6 Equipment Suppliers 75716.7 Materials Assessment and Design Aspects 757

16.7.1 Effect on Quality of Draw Ratio and Tempera-ture . . . . . . . . . . . 759

16.7.2 Thermoformability of CPVC 761References . . . . . . . . . . . . . . . 761

Chapter 17Blow Moulding of PVC-W. V. TITOW . . . . . . . . .. 76317.1 Basic Features and Historical Development of Blow

Moulding 76317.2 Blow-moulding Processes and Their Application to

PVC 76517.2.1 General Characterisation and Main Features of

Processes and Systems: main characteristics ofextrusion; injection, and dip blow moulding; therole and effects of stretching in stretch-blowmoulding; processing and equipment arrange-ments; cooling methods 765

17.2.2 Industrial Blow Moulding of PVC: some processand equipment considerations; extrusion blow­moulding equipment; injection blow-mouldingequipment; dip blow-moulding equipment;sources of information on blow-moulding

Contents xxi

equipment . . . . . . . . 78417.3 PVC Compositions for Blow Moulding 789

17.3.1 The Processing Aspect . . . 78917.3.2 The End-use Aspect . . . . 79217.3.3 PVC Bottle Formulations: PVC polymer; stabil-

iser system; impact modifiers; lubrication; otheradditives . . 793

17.4 PVC Blow Mouldings 79517.4.1 Applications 79517.4.2 Properties and Tests 797

References . . . . . . . . . . . 800

Chapter 18Calendering of PVC-W. V. TITOW 80318.1 Introduction 80318.2 The Calender . . . . . . . . 80418.3 The Calendering Operation: General Features and Their

Effects on the Structure and Properties of CalenderedSheet 808

18.4 Calender Lines . . . . . . . . . . . . . . . . .. 80918.4.1 General-purpose Line: pre-calender (com­

pounding and feed) section; calendering; thepost-calender train 809

18.4.2 Special Lines and Arrangements: calenderedflooring lines; lamination on or at the calan-der 828

18.5 The Formulation Aspect . . . . . . . . . . . 83018.6 Some Faults and Defects of Calendered Sheeting 833

18.6.1 Simple Dimensional Faults 83318.6.2 Structural Defects . . . . . . . 83418.6.3 Faults Manifested in Appearance 835

18.7 Further Processing of Calendered Sheet 83718.7.1 Press Finishing 83718.7.2 Press Lamination 83718.7.3 Surface Treatments: printing; coating; embos-

sing . . . . . . . . . . . . . . . . . 83818.7.4 Continuous Lamination 839

18.8 Properties and Applications of Calendered Materials 840References . . . . . . . . . . . . . . . . . . . . . 847

xxii Contents

Chapter 19Rigid PVC: Main Products-Production, Properties andApplications-B. J. LANHAM and W. V. TITOW 84919.1 Introduction 84919.2 Some Material Properties of uPVC 85619.3 uPVC Pipes 866

19.3.1 Types of uPVC Pipe . . . 86719.3.2 Production of uPVC Pipe: equipment and pro-

cess; some formulation aspects .... 86919.3.3 Pipe Properties and Their Determination 87819.3.4 Some Special Pipe Products . 879

19.4 uPVC Profiles 88319.4.1 Main Types and Applications 88319.4.2 Production . . . . . . . 88419.4.3 Some Formulation Aspects 88619.4.4 Testing and Specifications 889

19.5 uPVC Sheet and Film 89019.5.1 Terminology ..... 89019.5.2 Production . . . . . . 89119.5.3 Applications and Properties 893

19.6 Gramophone Records . . . . . 89619.7 Injection-Moulded uPVC Articles 897References . . . . . . . . . . . . . 898

Chapter 20PVC Sheet and its Fabrication-W. V. TITOW 90120.1 Introduction 90120.2 Unsupported PVC Sheet Materials 90420.3 Main Fabrication Techniques Applicable to PVC Sheet

Materials and Parts 91020.3.1 Welding: hot-gas welding; extrusion welding;

high-frequency welding; heated-tool welding 91020.3.2 Bonding: solvent bonding; adhesive bonding 92320.3.3 Machining 93020.3.4 Conversion and Manipulation of PVC Film and

Sheeting for Packaging . . . . . . . . . ., 93220.3.5 Surface Decoration, Marking, and Other Sur-

face Processing of PVC Materials and Products:surface decoration; surface marking; surface

Referencesprocessing

Contents xxiii

932936

Chapter 21PVC Pastes: Properties and Formolation-W. V. TITOW 93921.1 Introduction 93921.2 PVC Pastes: Rheological Properties and Theory . . 940

21.2.1 Viscosity of a Simple Suspension .... 94121.2.2 Main Compositional Factors Influencing the

Apparent Viscosity of PVC Pastes . . . . 94221.2.3 Expressions for the Apparent Viscosity of

Pastes . . . . . . . . . . . . . . . . .. 94321.2.4 Variation of Paste Viscosity with Rate of Shear,

or with Time at Constant Shear Rate 94521.2.5 Gelation and Fusion of PVC Pastes .... 95121.2.6 The Measurement of Viscosity of PVC Pastes 960

21.3 Paste Components and Formulation . . . . . . .. 96221.3.1 The Polymer: paste polymers; extender polym-

ers %221.3.2 Plasticisers 96521.3.3 Stabilisers 96921.3.4 Fillers 97021.3.5 Thickening Agents (for Thixotropic Plastisols

and Plastigels) 97321.3.6 Miscellaneous Paste Components: viscosity de-

pressants; diluents; other minor additives . 97521.4 Pastes for Rigid Products: Organosols and Rigisols . 975

21.4.1 Organosols 97521.4.2 Rigisols 976

References 978

Chapter 22Preparation, Processing and Applications of Pastes-W. V.TITOW . . . . . . . . 98122.1 Introduction 981

22.1.1 Preparation . . . . . 98122.1.2 Conversion to Products 982

22.2 Applications 98622.2.1 Rotational Casting . . 986

xxiv Contents

22.2.2 Slush Moulding 98822.2.3 Paste Casting 99122.2.4 Dip Coating and Moulding: hot-dip coating;

hot-dip moulding; cold-dip coating 99222.2.5 Spray Coating 99622.2.6 Coating of Sheet Materials (Fabrics and Paper):

paste coating (spreading) by doctor knife; pastecoating by roller; direct-coating process; trans-fer (reverse) coating process; promotion ofadhesion between coating and substrate; sur-face decoration and finishing of PVC pastecoatings; testing of coated materials 998

22.2.7 Miscellaneous Paste Processing Methods ofMinor Significance: low-pressure injectionmoulding; compression moulding; extrusion 1010

References 1012

Chapter 23PVC Latices-Revised and edited by W. V. TITOW 101323.1 Introduction 101323.2 Types of PVC Latices 1016

23.2.1 Homopolymer Latices 101723.2.2 Unplasticised Copolymer Latices 101723.2.3 Plasticised Copolymer Latices . 1018

23.3 Some Properties of Polymeric Products from PVCLatices 101823.3.1 Mechanical Properties 101823.3.2 Toxicity Considerations 1019

23.4 Compounding 101923.4.1 Latex Property Modifiers: latex stability; wet-

ting agents; thickeners; antifoaming agents; pHmodifiers and buffers . . . . . . . . 1020

23.4.2 Polymer Property Modifiers: heat stabilisers;plasticisers; fillers; pigments 1029

23.5 Anti-blocking Techniques 103923.6 Applications 1040

23.6.1 Textile Applications: as bonding agents in non-woven fabrics; for coating or impregnation offabrics . . . . . . . . . . . . . . . . . . 1040

23.6.223.6.323.6.4

References

Contents

Paper Treatments . .Leather FinishesAdhesive Applications

xxv

1042104410441045

Chapter 24PVC Solutions and their AppUcations--W. V. TITOW 104724.1 Introduction 104724.2 Components of PVC Solutions 1048

24.2.1 The PVC Polymer: homopolymers; copolymers;terpolymers 1048

24.2.2 Solvents and Diluents 104924.2.3 Other Solution Constituents 1054

24.3 Preparation of PVC Solutions, and Solution Composi-tions for Particular Applications 1057

24.4 Applications 106024.5 Adhesion of Solution-applied Coatings to Substrates 1063References . . . . . . . . . . . . . . . . . . . . . 1065

Chapter 25CeUuIar PVC Materials and Products-W. V. TITOW 106725.1 Introduction 106725.2 Production Methods and Processes 1069

25.2.1 Foams: dispersed-gas blowing: 'chemical' blow­ing; gas entrainment (mechanical frothing); in­situ gas evolution and cross-linking; solvent(monomer) blowing 1069

25.2.2 Other Cellular PVC Materials: the 'lost filler'method; sintering of powder 1078

25.3 Formulation and Process Factors in Foam Production 108025.3.1 Effects of Formulation and Processing Variables

on Foam Properties . . . . . . . . . . . . 108025.3.2 Chemical Blowing Agents-Nature and Opera-

tion . . . . . . . . . . . . . . . . . . . 108525.4 Some Surface Treatments-Embossing and Lacquer

Coating of Flexible Cellular Sheet Materials 109225.4.1 Mechankal Embossing . . . . . . . . . 109225.4.2 Chemical Emboss . . . . . . . . . . . 109325.4.3 Emboss Effects by Screen Printing of Paste 1094

xxvi Contents

25.4.4 Lacquer Coating 109425.5 Examples of Basic Formulations 109525.6 Evaluation and Testing 1095References . . . . . . . . . . . . 1101

Chapter 26Applications of PVC-W. V. TITOW . . . . . . . . . . . 110326.1 Main Applications of Primary PVC Products ..... 1104

26.1.1 Pipes and Tubing: rigid (uPVC) pipes; flexibletubing . . . . . . . . . . . . . . . . . . 1104

26.1.2 Extruded Profiles and Channels . . . . . . . 110626.1.3 Unsupported Sheeting and Film: rigid sheet;

flexible sheet; foil and film . . . . 110726.1.4 Foam: rigid foam; flexible foam . . . . . 1110

26.2 Composite Products (Coated, Laminated, or Filled) 111126.2.1 Coated Fabrics 111126.2.2 Conveyor Belting 111226.2.3 Sheet-type PVC Interior Wall-coverings 111326.2.4 PVC Coatings and Coverings on Metal Sub-

strates: wire and cable insulation and coverings;PVC/metal sheet laminates; 1114

26.2.5 Laminates of PVC with Non-metallic Materials:sandwich panels; PVC/polystyrene sheet lami-nate; PVC/polyacetallaminated sheeting. 1115

26.2.6 Unsupported PVC Flooring and Floor Tiles 111626.3 PVC Fibres and Fibre Products . . . . 111726.4 Miscellaneous Products and Applications 1117

26.4.1 Gramophone Records 111726.4.2 Blown Bottles and Containers 111826.4.3 Footwear . . . . . . . . . 111826.4.4 Battery Separators . . . . . 111826.4.5 Powder-coated Products and Mouldings Pro-

duced by Powder-coating Methods 111826.4.6 Medical Applications 112026.4.7 Applications in Motor Cars . . . . . . . . . 112126.4.8 Tubular-frame Furniture and Related Applica-

tions 112126.5 Some Special, Unusual, or Minor Products and Applica-

tions 1122References . . . . . . . . . . . . . . . . . . . . . . . 1125

Contents xxvii

Appendix 1Standards Relevant to PVC Materials and Products-Compiledby N. HERBERT and W. V. TITOW 11271. Plastics Terminology, Properties and Testing: General 11311.1 Terminology: general; common names and abbrevia-

tions; equivalent terms in various languages . . . . 11311.2 General Test Conditions and Methods: conditioning

and testing conditions; some general test methods . 11342. Vinyl Polymers and Copolymers . . . . . . . . 11352.1 General (Designation, Coding, Characterisation

Tests) . . . . . 11352.2 Viscosity . . . . . . . . . . 11362.3 Chlorine Content . . . . . . . . . . 11372.4 Vinyl Acetate Content in VCNA Copolymers 11372.5 Ash and/or Sulphated Ash Content . 11372.6 Volatile Matter (including Water) 11372.7 Impurities and Foreign Matter 11382.8 Bulk Density 11382.9 Particle Size .... 11382.10 Bromine Number 11392.11 pH of Aqueous Extract 11392.12 Miscellaneous Properties Relevant to Processing 11392.13 Methanol Extract 11402.14 VCM Content 1140

3. Vinyl Compounds 11403.1 General (Designation, Coding, Characterisation

Tests): rigid compounds; flexible compounds, pastes;miscellaneous 1140

3.2 Properties and Tests: bulk density and pourability;water absorption; temperature effects; mechanicalproperties; miscellaneous properties and analysis 1142

4. Plasticisers 11444.1 Bulk Properties . . . . . . . . . . . . . . . . 11444.2 Properties in Association with PVC (Compatibility,

Volatility, Migration) 11464.3 Effects on PVC . 1147

5. PVC Sheeting and Films 11485.1 Rigid 11485.2 Flexible 11485.3 Sheet and Film Fabrication and Products 1149

xxviii Contents

6. PVC Pipes, Tubing, and Pipe Fittings 11506.1 Rigid Pipes and Fittings, Including Pressure Pipes 11506.2 Flexible Tubing 11566.3 Miscellaneous Standards R~evant to Pipes 1157

7. PVC-coated Materials and Products 11587.1 Coated Fabrics, including Conveyor and Transmis-

sion Belting . 11587.2 Other Coated Materials and Products 1160

8. Cellular Vinyls 11608.1 Rigid Cellular Materials 11608.2 Flexible Cellular Materials 11628.3 Miscellaneous Standards: definition and classifica-

tion; physical properties-general; thermal prop­erties-general; flammability and burning; chemicalresistance and permeability; insulation materials:cushioning materials, sandwich structures 1163

9. PVC Wire and Cable Insulation, Cable Sheathing andJacketing 1165

10. PVC Flooring 116711. Various Product Standards and Tests 1167

11.1 Colour Bleeding and Staining 116711.2 Miscellaneous 1167

Appendix 2Quantities and Units: The SI System: Unit ConversionTables--Compiled by W. V. TITOW 1169

Appendix 3Some Material Properties of PVCComponnds-Compiled by W. V. TITOW

Products and1185

Index 1General ., . . . . . . . . . . . . . . . . . . . . . . 1199

Index 2Material and Product Trade Names . . . . . . . . . . . . 1223

Index 3Named Equipment and Processes . . . . . . . . . . . . . 1231

List of Contributing Authors

W. V. Trrow

Formerly Manager (Special Projects), Yarsley ResearchLaboratories Ltd, Ashtead, Surrey, England

D. L. BUSZARD

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

P. S. COFFIN

General Manager-Technical, Roeol Ltd, Rocol House, Swilling­ton, Leeds, LS26 2BS, England

P. FRANZ

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

W. HENSCHEL

Manager of the Design and Construction Department, Buss Ltd,CH-4133 Pratteln, Switzerland

Miss N. HERBERT

Head, Standards Information Centre, South African Bureau· ofStandards, Private Bag X191, Pretoria 0001, Republic ofSouth Africa

xxix

xxx List of Contributing Authors

I. D. HOUNSHAM

Sales Manager, PVC Division, Croxton and Garry Ltd, CurtisRoad, Dorking, Surrey, RH4 lXA, England

B. J. LANHAM

European Marketing Manager, LNP Plastics Nederland BV., POBox 13, Ottergeerde 24, Raamsdonksveer, The Netherlands

The late L. W. TuRNER

Formerly Senior Research Associate, Yarsley Technical Centre Ltd,Redhill, Surrey, England