Polymer Physics

301 Pages·1999·16.357 MB·English

by  Ulf W. Gedde (auth.)

POLYMER PHYSICS
POLYMER PHYSICS
Ulf W Gedde
Associate Professor of Polymer Technology
Department of Polymer Technology
Royal Institute of Technology
Stockholm, Sweden
Springer-Science+Business Media, B.V.
Library of Congress Cataloging-in-Publication Data
ISBN 978-0-412-62640-1 ISBN 978-94-011-0543-9 (eBook)
DOI 10.1007/978-94-011-0543-9
Printed on acid-free paper
First edition 1995
Reprinted 1996
Reprinted 1999
Reprinted 2001
All Rights Reserved
© 1999 Springer Science+Business Media Dordrecht
Originally published by Kluwer Academic Publishers in 1999
No part of the material protected by this copyright notice may be reproduced or
utilized in any form or by any means, electronic or mechanical,
including photocopying, recording or by any information storage and
retrieval system, without written permission from the copyright owner.
To Maria, Alexander and Raija
CONTENTS
Preface xi
1 A brief introduction to polymer science 1
1.1 Fundamental definitions 1
1.2 Configurational states 2
1.3 Homopolymers and copolymers 5
1.4 Molecular architecture 6
1.5 Common polymers 6
1.6 Molar mass 6
1.7 Polymerization 12
1.8 Thermal transitions and physical structures 13
1.9 Polymer materials 15
1.10 A short history of polymers 15
1.11 Summary 18
1.12 Exercises 18
1.13 References 18
1.14 Suggested further reading 18
2 Chain conformations in polymers 19
2.1 Introduction 19
2.2 Experimental determination of dimensions of chain molecules 21
2.3 Characteristic dimensions of 'random coil' polymers 23
2.4 Models for calculating the average end-to-end distance for an ensemble of statistical chains 24
2.5 Random-flight analysis 33
2.6 Chains with preferred conformation 35
2.7 Summary 36
2.8 Exercises 3 7
2.9 References 38
3 The rubber elastic state 39
3.1 Introduction 39
3.2 Thermo-elastic behaviour and thermodynamics: energetic and en tropic elastic forces 41
3.3 The statistical mechanical theory of rubber elasticity 44
3.4 Swelling of rubbers in solvents 48
3.5 Deviations from classical statistical theories 48
3.6 Small-angle neutron scattering data 51
3.7 The theory of Mooney and Rivlin 51
3.8 Summary 51
3. 9 Exercises 52
3.10 References 53
3.11 Suggested further reading 53
viii Contents
4 Polymer solutions 55
4.1 Introduction 55
4.2 Regular solutions 55
4.3 The Flory-Huggins theory 58
4.4 Concentration regimes in polymer solutions 65
4.5 The solubility parameter concept 66
4.6 Equation-of-state theories 68
4.7 Polymer-polymer blends 70
4.8 Summary 73
4.9 Exercises 74
4.10 References 75
4.11 Suggested further reading 75
5 The glassy amorphous state 77
5.1 Introduction to amorphous polymers 77
5.2 The glass transition temperature 78
5.3 Non-equilibrium features of glassy polymers and physical ageing 82
5.4 Theories for the glass transition 87
5.5 Mechanical behaviour of glassy, amorphous polymers 89
5.6 Structure of glassy, amorphous polymers 95
5.7 Summary 96
5.8 Exercises 97
5.9 References 97
5.10 Suggested further reading 98
6 The molten state 99
6.1 Introduction 99
6.2 Fundamental concepts in rheology 99
6.3 Measurement of rheological properties of molten polymers 104
6.4 Flexible-chain polymers 105
6.5 Liquid-crystalline polymers 109
6.6 Summary 127
6.7 Exercises 128
6.8 References 129
6.9 Suggested further reading 129
7 Crystalline polymers 131
7.1 Background and a brief survey of polymer crystallography 131
7.2 The crystal lamella 137
7.3 Crystals grown from the melt and the crystal lamella stack 147
7.4 Supermolecular structure 151
7.5 Methods of assessing supermolecular structure 155
7.6 Degree of crystallinity 157
7.7 Relaxation processes in semicrystalline polymers 162
7.8 Summary 164
7.9 Exercises 165
7.10 References 166
7.11 Suggested further reading 167
Contents ix
8 Crystallization kinetics 169
8. I Background 169
8.2 The equilibrium melting temperature 171
8.3 The general Avrami equation 175
8.4 Growth theories 178
8.5 Molecular fractionation 189
8.6 Orientation-induced crystallization 194
8.7 Summary 195
8.8 Exercises 197
8.9 References 198
8.10 Suggested further reading 198
9 Chain orientation 199
9.1 Introduction 199
9.2 Definition of chain orientation 199
9.3 Methods for assessment of uniaxial chain orientation 203
9.4 Methods for assessment of biaxial chain orientation 208
9.5 How chain orientation is created 208
9.6 Properties of oriented polymers 21I
9.7 Summary 214
9.8 Exercises 215
9.9 References 216
9.10 Suggested further reading 216
10 Thermal analysis of polymers 217
10.1 Introduction 217
10.2 Thermo-analytical methods 218
10.3 Thermal behaviour of polymers 226
10.4 Summary 234
10.5 Exercises 234
10.6 References 236
10.7 Suggested further reading 237
11 Microscopy of polymers 239
11.1 Introduction 239
11.2 Optical microscopy (OM) 241
11.3 Electron microscopy 244
11.4 Preparation of specimens for microscopy 247
11.5 Applications of polymer microscopy 252
11.6 Summary 256
II. 7 Exercises 256
11.8 References 257
11.9 Suggested further reading 257
X Contents
12 Spectroscopy and scattering of polymers 259
12.1 Introduction 259
12.2 Spectroscopy 260
12.3 Scattering and diffraction methods 269
12.4 Summary 273
12.5 Exercises 273
12.6 References 273
12.7 Suggested further reading 273
13 Solutions to problems given in exercises 275
Chapter 1 275
Chapter 2 275
Chapter 3 278
Chapter 4 279
Chapter 5 281
Chapter 6 282
Chapter 7 283
Chapter 8 286
Chapter 9 287
Chapter 10 289
Chapter 11 291
Chapter 12 291
References 292
Index 293
PREFACE
This book is the result of my teaching efforts during the last ten years at the Royal Institute of Technology.
The purpose is to present the subject of polymer physics for undergraduate and graduate students, to focus
the fundamental aspects of the subject and to show the link between experiments and theory. The intention
is not to present a compilation of the currently available literature on the subject. Very few reference citations
have thus been made. Each chapter has essentially the same structure: starling with an introduction, continuing
with the actual subject, summarizing the chapter in 30D-500 words, and finally presenting problems and a
list of relevant references for the reader. The solutions to the problems presented in Chapters 1-12 are given
in Chapter 13. The theme of the book is essentially polymer science, with the exclusion of that part dealing
directly with chemical reactions. The fundamentals in polymer science, including some basic polymer chemistry,
are presented as an introduction in the first chapter. The next eight chapters deal with different phenomena
(processes) and states of polymers. The last three chapters were written with the intention of making the
reader think practically about polymer physics. How can a certain type of problem be solved? What kinds
of experiment should be conducted?
This book would never have been written without the help of my friend and adviser, Dr Anthony Bristow,
who has spent many hours reading through the manuscript. criticizing the content. the form and the
presentation. I also wish to thank my colleagues at the Department, Maria Conde Braiia, Kristian Engberg,
Anders Gustafsson, Mikael Hedenqvist, Anders Hult, Jan-Fredrik Jansson, Hakan Jonsson, Joanna Kiesler, Sari
Laihonen, Bengt Ranby, Patrik Roseen, Fredrik Sahlen, Marie-Louise Skyff, Bengt Stenberg, Bjorn Terselius,
Toma Trankner, Goran Wiberg and Jens Viebke, who have provided help of different kinds, ranging from
criticism of the manuscript to the provision of micrographs, etc. Special thanks are due to Dr Richard Jones,
Cavendish Laboratory, University of Cambridge, UK, who read through all the chapters and made some very
constructive criticisms. I also want to thank friends and collaborators from other departments/companies:
Profs Richard Boyd, University of Utah, USA; Andrew Keller, University of Bristol. UK; David Bassett,
University of Reading, UK; Clas Blomberg, Royal Institute of Technology, Sweden; Josef Kubat. Chalmers
University of Technology, Sweden; Torbjom Lagerwall, Chalmers University of Technology, Sweden, and
Mats Ifwarson, Studsvik Material AB, Sweden. I wish to emphasize, however, that I alone have responsibility
for the book's shortcomings.
I am also indebted to Chapman & Hall for patience in waiting for the manuscript to arrive and for performing
such an excellent job in transforming the manuscript to this pleasant shape. More than anything, I am grateful
to my family for their support during the almost endless thinking and writing process.
UlfW. Gedde
Stockholm