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PLASTICS
MATERIALS
SEVENTH EDITION
J.
A.
Brydson
Former Head
of
the Department
of
Physical Sciences
and
Technology,
Polytechnic
of
North London
(now
known
as the University
of
North London)
f
EINEMANN
OXFORD AUCKLAND BOSTON JOHANNESBURG MELBOURNE NEW DELHI
Butterworth-Heinemann
Linacre House, Jordan Hill, Oxford OX2 8DP
225 Wildwood Avenue, Wobum, MA 01801-2041
A
division of Reed Educational and Professional Publishing Ltd
A
member
of
the Reed Elsevier plc group
First published by Iliffe Books Ltd 1966
Second edition 1969
Reprinted 1970
Third edition 1975
Reprinted with revisions 1977
Reprinted 1979
Fourth
edition published by Butterworth-Heinemann 1982
Reprinted 1985
Fifth edition 1989
Reprinted 1991, 1993
Sixth edition 1995
Reprinted 1995, 1996, 1998
Seventh edition 1999
0
J. A. Brydson 1995, 1999
All
rights reserved.
No
part
of
this publication
may
be reproduced in any material form (including
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or
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means and whether
or
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of
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Designs and Patents Act 1988
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Applications
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to reproduce any part
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addressed
to the publisher
British Library Cataloguing in Publication Data
Brydson, J. A. (John Andrew), 1932-
Plastics materials.
-
7th ed.
1. Plastics
I.
Title
668.4
ISBN
0
7506 4132
0
Library
of
Congress Cataloguing in Publication Data
Brydson,
J.
A.
Plastics materia1slJ.A. Brydson.
-
7th ed.
p. cm.
Includes bibliographical references and index.
ISBN
0
7506 4132
0
(hbk.)
1. Plastics.
I.
Title.
TP1120 B7 99-30623
668.4-dc21 CIP
Composition by Genesis Typesetting, Laser Quay, Rochester, Kent
Printed and bound in Great Britain by Biddles Lt4 Guildford and King’s Lynn
Contents
Preface to the Seventh Edition
Preface
to
the First Edition
Acknowledgements for the Seventh Edition
Abbreviations for Plastics and Rubbers
1
The Historical Development of Plastics Materials
1.1 Natural Plastics
1.2 Parkesine and Celluloid
1.4
1.5 Developments since 1939
1.6 Raw Materials for Plastics
1.7 The Market for Plastics
1.8
The Future for Plastics
1.3 1900-1930
The Evolution
of
the Vinyl Plastics
2 The Chemical Nature
of
Plastics
2.1 Introduction
2.2 Thermoplastic and Thermosetting Behaviour
2.3
Further Consideration
of
Addition Polymerisation
2.3.1
2.3.2 Ionic polymerisation
2.3.3 Ziegler-Natta and metallocene polymerisation
Elementary kinetics of free-radical addition polymerisation
2.4 Condensation Polymerisation
3
States
of
Aggregation in Polymers
3.1 Introduction
3.2 Linear Amorphous Polymers
3.2.1
3.3 Crystalline Polymers
3.3.1 Orientation and crystallisation
3.3.2 Liquid crystal polymers
Orientation
in
linear amorphous polymers
3.4
Cross-linked Structures
3.5 Polyblends
3.6 Summary
xvii
xix
xxi
xxiii
1
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V
vi
Contents
4
Relation of Structure to Thermal and Mechanical Properties
4.1 Introduction
4.2 Factors Affecting the Glass Transition Temperature
4.3 Factors Affecting the Ability to Crystallise
4.4 Factors Affecting the Crystalline Melting Point
4.5 Some Individual Properties
4.5.1 Melt viscosity
4.5.2 Yield strength and modulus
4.5.3 Density
4.5.4 Impact strength
5
Relation of Structure to Chemical Properties
5.1
Introduction
5.2 Chemical Bonds
5.3 Polymer Solubility
5.3.1 Plasticisers
5.3.2 Extenders
5.3.3 Determination
of
solubility parameter
5.3.4 Thermodynamics and solubility
Effects
of
Thermal, Photochemical and High-energy Radiation
5.4 Chemical Reactivity
5.5
5.6 Aging and Weathering
5.7 Diffusion and Permeability
5.8 Toxicity
5.9 Fire and Plastics
6
Relation of Structure to Electrical and Optical Properties
6.1 Introduction
6.2
6.3
6.4 Electronic Applications of Polymers
6.5 Electrically Conductive Polymers
6.6 Optical Properties
Appendix-Electrical Testing
Dielectric Constant, Power Factor and Structure
Some Quantitative Relationships of Dielectrics
7 Additives for Plastics
7.1 Introduction
7.2 Fillers
7.2.1 Coupling agents
7.3 Plasticisers and Softeners
7.4 Lubricants and Flow Promoters
7.5 Anti-aging Additives
7.5.1 Antioxidants
7.5.2 Antiozonants
7.5.3 Stabilisers against dehydrochlorination
7.5.4
Ultraviolet absorbers and related materials
7.6 Flame Retarders
7.7 Colorants
7.8 Blowing Agents
7.9 Cross-linking Agents
7.10 Photodegradants
7.11 2-Oxazolines
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134
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150
153
154
155
Contents
vii
8
Principles
of
the Processing of Plastics
8.1 Introduction
8.2 Melt Processing of Thermoplastics
8.2.1 Hygroscopic behaviour
8.2.2 Granule characteristics
8.2.3
8.2.4 Thermal stability
8.2.5 Flow properties
8.2.5.1 Terminology
8.2.5.2 Effect of environmental and molecular factors
on
viscous flow properties
8.2.5.3 Flow in
an
injection mould
8.2.5.4 Elastic effects in polymer melts
8.2.6 Thermal properties affecting cooling
8.2.7 Crystallisation
8.2.8 Orientation and shrinkage
Melt Processing of Thermosetting Plastics
Processing
in
the Rubbery State
Solution, Suspension
and
Casting Processes
Thermal properties influencing polymer melting
8.3
8.4
8.5
8.6 Summary
9 Principles of Product Design
9.1 Introduction
9.2 Rigidity of Plastics Materials
9.2.1
The assessment of maximum service temperature
9.2.1.1 Assessment of thermal stability
9.2.1.2 Assessment of softening point
The assessment of impact strength
9.3 Toughness
9.3.1
9.4 Stress-Strain-Time Behaviour
9.4.1 The
WLF
equations
9.4.2 Creep curves
9.4.3
9.5 Recovery from Deformation
9.6 Distortion, Voids and Frozen-in Stress
9.7 Conclusions
Practical assessment
of
long-term behaviour
10 Polyethylene
10.1 Introduction
10.2 Preparation of Monomer
10.3 Polymerisation
10.3.1 High-pressure polymerisation
10.3.2 Ziegler processes
10.3.3 The Phillips process
10.3.4 Standard Oil Company (Indiana) process
10.3.5 Processes for making linear low-density polyethylene and
metallocene polyethylene
Structure
and
Properties
of
Polyethylene
10.5.1 Mechanical properties
10.5.2 Thermal properties
10.5.3 Chemical properties
10.5.4 Electrical properties
10.5.5
10.5.6 Properties of metallocene-catalysed polyethylenes
10.4
10.5 Properties of Polyethylene
Properties of LLDPE and VLDPE
158
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159
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174
17.5
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226
227
227
viii
Contents
10.6 Additives
10.7 Processing
10.8
10.9 Cross-linked Polyethylene
10.10 Chlorinated Polyethylene
10.11 Applications
Polyethylenes of
Low
and High Molecular Weight
11
Aliphatic Polyolefins other than Polyethylene, and Diene Rubbers
11.1 Polypropylene
11.1.1 Preparation of polypropylene
11.1.2
11.1.3 Properties of isotactic polypropylene
11.1.4 Additives for isotactic polypropylene
11.1.5 Processing characteristics
11.1.6 Applications
11.1.7 Atactic and syndiotactic polypropylene
11.1.8 Chlorinated polypropylene
11.2.1 Atactic polybut- 1-ene
Structure and properties of polypropylene
11.2 Polybut-1-ene
11.3 Polyisobutylene
11.4
Poly-(4-methylpent-l-ene)
11.4.1 Structure and properties
11.4.2 General properties
11.4.3 Processing
11.4.4 Applications
11.5 Other Aliphatic Olefin Homopolymers
11.6 Copolymers Containing Ethylene
1
1.6.1
1 1.6.2 Ethylene-cyclo-olefin copolymers
11.7 Diene Rubbers
Ethylene-carbon monoxide copolymers (ECO)
11.7.1 Natural rubber
11.7.2 Synthetic polyisoprene (IR)
11.7.3 Polybutadiene
11.7.4 Styrene-butadiene rubber(SBR)
11.7.4.1 ‘High styrene resins’
11.7.5 Nitrile rubber (NBR)
11.7.6 Chloroprene rubbers (CR)
11.7.7 Butadiene-pentadiene rubbers
11.8 Thermoplastic Diene Rubbers
11.9 Aliphatic Olefin Rubbers
11.10 Rubbery Cyclo-olefin (Cyclo-alkene) Polymers
11.9.1 Thermoplastic polyolefin rubbers
1
1.10.1 Aliphatic polyalkenamers
11.10.2 Polynorbomene
11.10.3 Chlorine-containing copolymers
11.11 1,2-Polybutadiene
11 .I2 Ethylene-styrene copolymers
11.13 Other elastomers
12 Vinyl Chloride Polymers
12.1 Introduction
12.2 Preparation
of
Vinyl Chloride
12.3 Polymerisation
12.4 Structure
of
Poly(viny1 chloride)
12.4.1 Characterisation
of
commercial polymers
228
232
238
239
240
24 1
247
247
248
25 1
253
260
262
265
267
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289
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306
307
307
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309
311
311
313
315
317
320
12.5
12.6
12.7
12.8
12.9
Compounding Ingredients
12.5.1 Stabilisers
12.5.2 Plasticisers
12.5.3 Extenders
12.5.4 Lubricants
12.5.5 Fillers
12.5.6 Pigments
12.5.7
12.5.8 Miscellaneous additives
12.5.9 Formulations
Properties
of
PVC Compounds
Processing
12.7.1 Plasticised PVC
12.7.2 Unplasticised PVC
12.7.3 Pastes
12.7.4 Copolymers
12.7.5 Latices
Applications
Miscellaneous Products
12.9.1 Crystalline PVC
12.9.2 Chlorinated PVC
12.9.3 Graft polymers based on PVC
12.9.4 Vinyl chloride-propylene copolymers
12.9.5 Vinyl
chloride-N-cyclohexylmaleimide
copolymers
Polymeric impact modifiers and processing aids
13 Fluorine-containing Polymers
13.1 Introduction
13.2 Polytetrafluoroethylene
13.2.
I
Preparation
of
monomer
13.2.2 Polymerisation
13.2.3 Structure and properties
13.2.4 General properties
13.2.5 Processing
13.2.6 Additives
13.2.7 Applications
13.3
Tetrafluoroethylene-Hexafluoropropylene
Copolymers
1
3.4
Tetrafluoroethylene-Ethylene
Copolymers (ETFE)
13.5
Polychlorotrifluoroethylene
Polymers (PCTFE)
13.6 Poly(viny1 fluoride) (PVF)
13.7 Poly(viny1idene fluoride)
13.8
1
3.9
Hexafluoroisobutylene-Vinylidene
Fluoride Copolymers
13.10 Fluorine-containing Rubbers
13.11 Thermoplastic fluoroelastomers
13.12 Miscellaneous Fluoropolymers
Poly(viny1 acetate) and its Derivatives
14.1 Introduction
14.2 Poly(viny1 acetate)
and Copolymers with Ethylene (ECTFE)
Other Plastics Materials Containing Tetrafluoroethylene
14
14.2.1 Preparation
of
the monomer
1
4.2.2 Polymerisation
14.2.3 Properties and uses
14.3.1 Structure and properties
14.3.2 Applications
14.3 Poly(viny1 alcohol)
Contents
ix
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390
39 1
x
Contents
14.4 The Poly(viny1 acetals)
14.4.1 Poly(viny1 formal)
14.4.2 Poly(viny1 acetal)
14.4.3 Poly(viny1 butyral)
14.5 Ethylene-Vinyl Alcohol Copolymers
14.6 Poly(viny1 cinnamate)
14.7 Other Organic Vinyl Ester Polymers
15 Acrylic Plastics
15.i
15.2
15.3
15.4
15.5
15.6
15.7
15.8
15.9
15.10
15.11
Introduction
Poly(methy1 methacrylate)
15.2.1 Preparation of monomer
15.2.2 Polymerisation
15.2.3 Structure and properties
15.2.4
15.2.5 Additives
15.2.6 Processing
15.2.7 Applications
Methyl Methacrylate Polymers with Enhanced Impact
Resistance and Softening Point
Nitrile Resins
Acrylate Rubbers
Thermosetting Acrylic Polymers
Acrylic Adhesives
Hydrophilic Polymers
Poly(methacry1imide)
Miscellaneous Methacrylate and Chloroacrylate Polymers
and Copolymers
Other Acrylic Polymers
General properties
of
poly(methy1 methacrylate)
16 Plastics Based on Styrene
16.1
16.2
16.3
16.4
16.5
16.6
16.7
16.8
16.9
16.10
16.11
16.12
16.13
Introduction
Preparation of the Monomer
16.2.1 Laboratory preparation
16.2.2 Commercial preparation
Polymerisation
16.3.1 Mass polymerisation
16.3.2 Solution polymerisation
16.3.3 Suspension polymerisation
16.3.4 Emulsion polymerisation
16.3.5 Grades available
Properties and Structure of Polystyrene
General Properties
High-impact Polystyrenes (HIPS) (Toughened Polystyrenes (TPS))
Styrene-Acrylonitrile Copolymers
ABS Plastics
16.8.1 Production of ABS materials
16.8.2
Processing
of
ABS
materials
16.8.3
Miscellaneous Rubber-modified Styrene- Acrylonitrile
and Related Copolymers
Styrene-Maleic Anhydride Copolymers
Butadiene-Styrene Block Copolymers
Miscellaneous Polymers and Copolymers
Stereoregular Polystyrene
16.13.1 Syndiotactic polystyrene
Properties and applications of ABS plastics
39
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452
454
454
Contents
xi
16.14 Processing
of
Polystyrene
16.15 Expanded Polystyrene
16.15.1 Structural foams
16.16 Oriented Polystyrene
16.17 Applications
17 Miscellaneous Vinyl Thermoplastics
17.1 Introduction
17.2
Vinylidene Chloride Polymers and Copolymers
17.2.1
17.2.2 Vinylidene chloride-acrylonitrile copolymers
Properties and applications
of
vinylidene chloride-vinyl
chloride copolymers
17.3 Coumarone-Indene resins
17.4 Poly(viny1 carbazole)
17.5 Poly(viny1 pyrrolidone)
17.6 Poly(viny1 ethers)
17.7 Other Vinyl Polymers
18 Polyamides and Polyimides
18.1
18.2
18.3
18.4
18.5
18.6
18.7
18.8
18.9
18.10
18.1
1
18.12
18.13
18.14
18.15
18.16
Polyamides: Introduction
Intermediates
for Aliphatic Polyamides
18.2.1 Adipic acid
18.2.2 Hexamethylenediamine
18.2.3
18.2.4 Caprolactam
18.2.5 w-Aminoundecanoic acid
18.2.6 w-Aminoenanthic acid
18.2.7 Dodecanelactam
Polymerisation of Aliphatic Polyamides
18.3.1
18.3.2 Nylon 6
18.3.3 Nylon 11
18.3.4 Nylon 12
18.3.5 Nylon 7
Structure and Properties
of
Aliphatic Polyamides
General Properties
of
the Nylons
Additives
Glass-filled Nylons
18.7.1
Processing
of
the Nylons
Applications
Polyamides of Enhanced Solubility
Other Aliphatic Polyamides
Aromatic Polyamides
18.12.1 Glass-clear polyamides
18.12.2 Crystalline aromatic polyamides
Sebacic acid and Azelaic acid
Nylons 46, 66, 69, 610 and 612
Comparison
of
nylons 6 and 66 in glass-filled compositions
18.12.2.1 Poly-rn-xylylene adipamide
18.12.2.2 Aromatic polyamide fibres
18.12.2.3 Polyphthalamide plastics
Polyimides
Modified Polyimides
18.14.1 Polyamide-imides
18.14.2 Polyetherimides
Elastomeric Polyamides
455
457
4.59
46 1
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48 1
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52 1
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526
Polyesteramides- 528
xii
Contents
19
Polyacetals and Related Materials
19.1
Introduction
19.2
Preparation of Formaldehyde
19.3
Acetal Resins
19.3.1
Polymerisation of formaldehyde
19.3.2
19.3.3
Properties of acetal resins
19.3.4
Processing
19.3.5
Additives
19.3.6
Acetal-polyurethane alloys
19.3.7
Polyethers from Glycols and Alkylene Oxides
19.5.1 Elastomeric polyethers
Structure and properties of acetal resins
Applications of the acetal polymers and copolymers
19.4
Miscellaneous Aldehyde Polymers
19.5
19.6
Oxetane Polymers
19.7
Polysulphides
20.1
Introduction
20.2
Production
of
Intermediates
20.3
Polymer Preparation
20
Polycarbonates
20.3.1
Ester exchange
20.3.2
Phosgenation process
Relation
of
Structure and Properties
20.4.1
Variations in commercial grades
20.4
20.5
General Properties
20.6
Processing Characteristics
20.7
20.8
20.9
20.10
Miscellaneous Carbonic Ester Polymers
Other Thermoplastics Containing p-Phenylene Groups
Applications of Bis-phenol
A
Polycarbonates
Alloys based on Bis-phenol A Polycarbonates
Polyester Carbonates and Block Copolymers
2
1
21.1
21.2
21.3
21.4
21.5
21.6
21.7
21.8
21.9
21.10
Introduction
Polyphenylenes
Pol y-p-xylylene
Poly(pheny1ene oxides) and Halogenated Derivatives
Alkyl Substituted Poly(pheny1ene oxides) including PPO
21.5.1
Structure and properties of
21.5.2
21.5.3
21.5.4
Styrenic PPOs
21.5.5
Processing of styrenic PPOs
21.5.6
Polyamide PPOs
21 57
Poly(2,6-dibromo-l,4-phenylene
oxide)
Polyphenylene Sulphides
21.6.1
Amorphous polyarylene sulphides
Pol ysulphones
21.7.1
21.7.2
General properties of polysulphones
21.7.3
Processing
of
polysulphones
21.7.4
Applications
21.7.5
Blends based on polysulphones
Polyarylether Ketones
Phenoxy Resins
Linear Aromatic Polyesters
poly-(2,6-dimethyl-p-phenylene
oxide) (PPO)
Processing and application of PPO
Blends based in polyphenylene oxides
Properties and structure of polysulphones
531
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533
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538
542
543
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[...]... for much of our married life xxi Abbreviations for Plastics and Rubbers Many abbreviations for plastics materials are in common use Some of these have now been incorporated into national and international standards, including: IS0 1043 (1978) Plastics- Symbols BS 3502 Common Names and Abbreviations for Plastics and Rubbers Part 1 Principal commercial plastics (1978) (The 1978 revision was carried out... the light of the merits and the demerits of the material The title of the book requires that a definition of plastics materials be given This is however very difficult For the purpose of this book I eventually used as a working definition ‘Those materials which are considered to be plastics materials by common acceptance’ Not a positive definition but one which is probably less capable of being criticised... the light of the merits and the demerits of the material The title of the book requires that a definition of plastics materials be given This is however very difficult For the purpose of this book I eventually used as a working definition ‘Those materials which are considered to be plastics materials by common acceptance’ Not a positive definition but one which is probably less capable of being criticised... the light of the merits and the demerits of the material The title of the book requires that a definition of plastics materials be given This is however very difficult For the purpose of this book I eventually used as a working definition ‘Those materials which are considered to be plastics materials by common acceptance’ Not a positive definition but one which is probably less capable of being criticised... 842 846 847 848 850 85 1 xvi Contents 30 Miscellaneous Plastics Materials 30.1 Introduction 30.2 Casein 30.2.1 Chemical nature 30.2.2 Isolation of casein from milk 30.2.3 Production of casein plastics 30.2.4 Properties of casein 30.2.5 Applications 30.3 Miscellaneous Protein Plastics 30.4 Derivatives of Natural Rubber Gutta Percha and Related Materials 30.5 30.6 Shellac 30.6.1 Occurrence and preparation... Rapra Technology Ltd, Peter Lewis of the Open University, Simon Robinson of European Plastics News, Christopher Sutcliffe of Crystal Polymers Ltd and Graham Bonner of BP Chemicals Once again I should acknowledge that I have drawn heavily from the journals European Plastics News, Kunstoffe, Modern Plastics International and Plastics and Rubber Weekly for data on production and consumption statistics My thanks... different materials arise, to discuss their properties and to show how these properties can to a large extent be explained by consideration of the composition of a plastics material and in particular the molecular structure of the base polymer employed After a brief historical review in Chapter 1 the following five chapters provide a short summary of the general methods of preparation of plastics materials. .. different materials arise, to discuss their properties and to show how these properties can to a large extent be explained by consideration of the composition of a plastics material and in particular the molecular structure of the base polymer employed After a brief historical review in Chapter 1 the following five chapters provide a short summary of the general methods of preparation of plastics materials. .. Edition Plastics materials are processable compositions based on macromolecules’ In most cases (certainly with all synthetic materials) the macromolecules are polymers, large molecules made by the joining together of many smaller ones Such a definition does however include rubbers, surface coatings, fibres and glasses and these, largely for historical reasons, are not generally regarded as plastics. .. polyurethane foams-as rubbers or as plastics? What about nylon tennis racquet filament?or polyethylene dip coatings? Without being tied by definition I have for convenience included such materials in this book but have given only brief mention to coatings, fibres and glasses generally The rubbers I have treated as rather a special case considering them as plastics materials that show reversible high . Development of Plastics Materials
1.1 Natural Plastics
1.2 Parkesine and Celluloid
1.4
1.5 Developments since 1939
1.6 Raw Materials for Plastics
1.7. The Market for Plastics
1.8
The Future for Plastics
1.3 1900-1930
The Evolution
of
the Vinyl Plastics
2 The Chemical Nature
of
Plastics
2.1 Introduction
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Xem thêm: Tài liệu PLASTICS MATERIALS SEVENTH EDITIONJ pdf, Tài liệu PLASTICS MATERIALS SEVENTH EDITIONJ pdf, 5 Effects of Thermal, Photochemical and High-Energy Radiation, 2 Dielelectric Constant, Power Factor and Structure, 5 Solution, Suspension and Casting Processes, 6 Distortion, Voids and Frozen-in Stress, 5 Polychlorotrifluoroethylene Polymers (PCTFE) and Copolymers with Ethylene (ECTFE), 6 High-Impact Polystyrene (HIPS) (Toughened Polystryenes (TPS)), 5 Alkyl Substituted Poly (Phenylene Oxides) Including PPO, 5 Poly(Ethylene Terephthalate) Moulding Materials, 13 Surface Coatings, Plasticisers and Rubbers, 5 Diluents, Flexibilisers and Other Additives