(Analytical Techniques in the Sciences AnTs _) Barbara H. Stuart-Polymer Analysis-Wiley (2002) (1)

POLYMER ANALYSIS Analytical Techniques in the Sciences (AnTS) Series Editor: David J Ando, Consultant, Dartford, Kent, UK A series of open learning/distance learning books which covers all of the major analytical techniques and their application in the most important areas of physical, life and materials sciences Titles Available in the Series Analytical Instrumentation: Performance Characteristics and Quality Graham Currell, University of the West of England, Bristol, UK Fundamentals of Electroanalytical Chemistry Paul M S Monk, Manchester Metropolitan University, Manchester, UK Introduction to Environmental Analysis Roger N Reeve, University of Sunderland, UK Polymer Analysis Barbara H Stuart, University of Technology, Sydney, Australia Forthcoming Titles Chemical Sensors and Biosensors Brain R Eggins, University of Ulster at Jordanstown, Northern Ireland, UK Analysis of Controlled Substances Michael D Cole, Anglia Polytechnic University, Cambridge, UK POLYMER ANALYSIS Barbara H Stuart University of Technology, Sydney, Australia JOHN WILEY & SONS, LTD Copyright 2002 by John Wiley & Sons, Ltd, The Atrium, Southern Gate, Chichester, West Sussex PO19 SSQ, England Telephone (+44)1243 779777 Email (for orders and customer service enquiries): cs-books@wiley.co.uk Reprinted with corrections September 2003 All Rights Reserved No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except under the terms of the Copyright, Designs and Patents Act 1988 or under the terms of a licence issued by the Copyright Licensing Agency Ltd, 90 Tottenham Court Road, London WIT 4LP, UK,without the permission in writing of the Publisher, with the exception of any material supplied specifically for the purpose of being entered and executed on a computer system, for exclusive use by the purchaser of the publication Neither the author@)nor John Wiley & Sons, Ltd accept any responsibility or liability for loss or damage occasioned to any person or property through using the material, instructions, methods or ideas contained herein, or acting or refraining from acting as a result of such use The author(s) and Publisher expressly disclaim all implied warranties, including merchantability of fitness for any particular purpose Designations used by companies to distinguish their products are often claimed as trademarks In all instances where John Wiley & Sons is aware of a claim, the product names appear in initial capital or all capital letters Readers, however, should contact the appropriate companies for more complete information regarding trademarks and registration Other Wiley Editorial Ofices John Wiley & Sons Inc., I River Street, Hoboken, NJ 07030, USA Jossey-Bass, 989 Market Street, San Francisco, CA 94103-1741, USA Wiley-VCH Verlag GmbH, Boschstr 12, D-69469 Weinheim, Germany John Wiley & Sons Australia Ltd, 33 Park Road, Milton, Queensland 4064, Australia John Wiley & Sons (Asia) Pte Ltd, Clement1 Loop #02-01, Jin Xing Distripark, Singapore 129809 John Wiley & Sons (Canada) Ltd, 22 Worcester Road, Etobicoke Ontario M9W 1L1 Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronic books British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN 047 1899267 (Hb) ISBN 047 18 1363X (Pb) Typeset in 10/12pt Times by Laserwords, Private Limited, Chennai, India Printed and bound in Great Britain by Biddles Ltd, Guildford and King’s Lynn This book is printed on acid-free paper responsibly manufactured from sustainable forestry, in which at least two trees are planted for each one used for paper production Contents Series Preface xi Preface xiii Acronyms, Abbreviations and Symbols xv About the Author Introduction 1.1 Introduction 1.2 History 1.3 Thermoplastics 1.4 Thermosets 1.5 Elastomers 1.6 High-Performance Polymers 1.7 Copolymers 1.8 Blends 1.9 Composites 1.10 Additives 1.11 Speciality Polymers 1.11.1 Liquid Crystalline Polymers 1.11.2 Conducting Polymers 1.11.3 Thermoplastic Elastomers 1.11.4 Biomedical Polymers 1.1 1.5 Biodegradable Polymers References Xxi 1 11 15 17 20 22 23 24 24 25 25 26 27 28 28 Polymer Analysis vi Identification 2.1 Introduction 2.2 Preliminary Identification Methods 2.2.1 Solubility 2.2.2 Density 2.2.3 Behaviour on Heating Infrared Spectroscopy 2.3 2.4 Raman Spectroscopy 2.5 Nuclear Magnetic Resonance Spectroscopy 2.6 Ultraviolet-Visible Spectroscopy 2.7 Differential Scanning Calorimetry 2.8 Mass Spectrometry 2.9 Chromatography 2.10 Emission Spectroscopy References Polymerization 3.1 Introduction 3.2 Chain Polymerization 3.2.1 Free-Radical Chain Polymerization 3.2.2 Ionic Chain Polymerization 3.2.3 Coordination Polymerization 3.2.4 Ring-Opening Polymerization 3.2.5 Practical Methods of Chain Polymerization 3.3 Step Polymerization 3.3.1 Statistics 3.3.2 Kinetics 3.4 Copolymerization 3.5 Cross-Linking 3.6 Dilatometry 3.7 Infrared Spectroscopy 3.8 Raman Spectroscopy 3.9 Nuclear Magnetic Resonance Spectroscopy 3.10 Differential Scanning Calorimetry 3.11 Electron Spin Resonance Spectroscopy 3.12 Refractometry References 31 31 31 32 33 33 37 41 46 52 55 58 60 64 68 71 71 72 72 75 78 79 80 83 83 84 87 89 90 92 92 95 95 95 98 100 Contents vii Molecular Weight 103 Introduction Molecular Weight Calculations Viscometry Chromatography Ultracentrifugation Osmometry Light Scattering End-Group Analysis Turbidimetric Titration References 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 Structure I Introduction 5.2 Isomerism 5.3 Chain Dimensions 5.4 Crystallinity 5.5 Orientation 5.6 Blends 5.7 Thermal Behaviour 5.8 Dilatometry 5.9 Infrared Spectroscopy 5.10 Raman Spectroscopy 5.1 Nuclear Magnetic Resonance Spectroscopy 5.12 Thermal Analysis 5.12.1 Differential Scanning Calorimetry 5.12.2 Thermal Mechanical Analysis 5.12.3 Dynamic Mechanical Analysis I3 Optical Microscopy 5.14 Transmission Electron Microscopy 5.15 X-Ray Diffraction 5.16 Neutron Scattering References Surface Properties 6.1 6.2 Introduction Infrared Spectroscopy 103 104 106 108 112 113 115 116 118 119 121 121 122 124 126 132 134 135 140 141 148 149 152 152 155 157 161 163 164 169 170 173 173 174 Polymer Analysis Vlll 6.2.1 Attenuated Total Reflectance Spectroscopy 6.2.2 Specular Reflectance Spectroscopy 6.2.3 Diffuse Reflectance Spectroscopy 6.2.4 Photoacoustic Spectroscopy 6.3 Raman Spectroscopy 6.4 Photoelectron Spectroscopy 6.5 Secondary-Ion Mass Spectrometry 6.6 Inverse Gas Chromatography 6.7 Scanning Electron Microscopy 6.8 Surface Tension 6.9 Atomic Force Microscopy 6.10 Tribology References Degradation 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 7.10 Introduction Oxidative Degradation Thermal Degradation Radiation Degradation Combustion Dissolution Infrared Spectroscopy Raman Spectroscopy Electron Spin Resonance Spectroscopy Thermal Analysis 7.10.1 Thermogravimetic Analysis 7.10.2 Differential Scanning Calorimetry 7.10.3 Thermal Mechanical Analysis 7.1 Pyrolysis Gas Chromatography References Mechanical Properties 8.1 Introduction 8.2 Stress-Strain Behaviour 8.3 Viscous Flow 8.4 Viscoelasticity 8.4.1 Creep 8.4.2 Models 8.4.3 Stress Relaxation 8.5 Elasticity 8.6 Processing Methods 8.7 Tensile Testing 174 176 176 178 178 178 182 183 185 186 187 188 189 191 191 192 193 195 195 196 198 199 199 20 20 205 205 207 208 209 209 210 213 215 215 217 220 222 224 227 Contents ix 8.8 Flexural Testing 8.9 Tear-Strength Testing 8.10 Fatigue Testing 8.1 Impact Testing 8.I2 Hardness Testing 8.13 Viscometry 8.14 Dynamic Mechanical Analysis References 229 229 230 23 231 232 233 235 Responses to Self-Assessment Questions 237 Bibliography 263 Glossary of Terms 265 Units of Measurement and Physical Constants 269 Periodic Table 273 Index 275 ... been introduced with the aim of providing a broader coverage of the many areas of science in which analytical techniques and methods are now increasingly applied With this in mind, the AnTS series... analysis and other significant topics In addition, books in the series will include the application of analytical techniques in areas such as environmental science, the life sciences, clinical analysis,... Following upon the success of the ACOL series, which by its very name is predominately concerned with Analytical Chemistry, the Analytical Techniques in the Sciences (AnTS) series of open learning texts