Polymer Characterization: Physical Techniques, 2nd Edition

492 Pages·2000·42.698 MB·English

by  Dan Campbell, Richard A. Pethrick, Jim R. White

Polymer Characterization

Polymer
Characterization
Physical techniques
Second Edition
D. Campbell
School of Engineering
University of Northumbria, UK
R.A. Pethrick
Department of Pure and Applied Chemistry
University of Strathclyde, UK
and
J.R. White
Department of Mechanical, Materials and Manufacturing
Engineering
University of Newcastle-upon-Tyne, UK
Taylor & Francis
Taylor & Francis Group
Boca Raton London New York
A CRC title, part of the Taylor & Francis imprint, a member of the
Taylor & Francis Group, the academic division of T&F Informa pic.
Published in 2000 by
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2000 by D. Campbell, R.A. Pethrick and J. R. White
CRC Press is an imprint of Taylor & Francis Group
First edition published by Chapman & Hall 1989
H
No claim to original U.S. Government works
International Standard Book Number-10: 0-7487-4005-8 (Softcover)
International Standard Book Number-13: 978-0-7487-4005-5 (Softcover)
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Contents
Preface ix
1 Introduction: Preliminary survey 1
1.1 The purpose of characterization 1
1.2 Molecular architecture 6
1.3 Amorphous polymers 7
1.4 Crystallizing polymers 8
1.5 Survey of characterization techniques 11
References 14
Further reading 14
2 Molecular mass determination 15
2.1 Introduction 15
2.2 Primary methods 19
2.3 Secondary methods 34
2.4 Other methods 48
2.5 Conclusions 49
Further reading 49
Exercises 50
3 Introduction to spectroscopic techniques 51
3.1 General remarks 51
3.2 Strategy in spectroscopic studies 52
3.3 Energy level calculations 53
3.4 Properties of electromagnetic radiation 53
3.5 Double beam optics 54
3.6 Fourier transform spectroscopy 55
References 57
vi Contents
4 Ultraviolet-visible spectroscopy 58
4.1 Introduction 58
4.2 Instrumentation 59
4.3 Theoretical estimation of electronic energy levels 61
4.4 Application to polymers 64
Reference 66
5 Vibrational spectroscopy: infrared and Raman
spectroscopy 67
5.1 Fundamentals of vibrational spectroscopy 67
5.2 Experimental techniques 75
5.3 Applications to polymers 85
5.4 Raman analysis 96
5.5 Near-infrared (MR) 106
Conclusions 106
References 107
6 Nuclear magnetic resonance spectroscopy 108
6.1 Introduction 108
6.2 Principles of magnetic resonance 109
6.3 Experimental techniques 124
6.4 Applications of NMR to polymers 133
6.5 NMR of polymers in the solid state 145
6.6 Two-dimensional NMR 150
6.7 NMR imaging 153
6.8 Conclusions 153
References 153
Exercises 154
7 Electron spin resonance spectroscopy 155
7.1 Introduction 155
7.2 Basic theory 156
7.3 Experimental considerations 168
7.4 Polymerization studies 174
7.5 Radiation effects in polymers 178
7.6 Mechanical degradation 186
7.7 Thermal degradation 188
7.8 Relaxation studies 188
7.9 ESR imaging 191
7.10 Conclusions 191
Further reading 192
Exercises 192
Contents vii
8 X-ray diffraction 194
8.1 Introduction 194
8.2 Generation and properties of X-rays 194
8.3 Diffraction theory 195
8.4 Practical aspects 210
8.5 Applications to polymer characterization 217
8.6 Conclusions 235
References 235
Further reading 236
Exercises 236
9 Transmission electron microscopy and diffraction 237
9.1 Introduction 237
9.2 Layout of the TEM 238
9.3 Resolution limitation 242
9.4 Electron diffraction 244
9.5 Image contrast 248
9.6 Operating conditions and procedures for
beam-sensitive materials 262
9.7 Polymer studies in TEM 266
9.8 Multiple dark field imaging 287
9.9 Scanning transmission electron microscopy (STEM) 289
References 291
Further reading 291
Exercises 292
10 Scanning electron microscopy 293
10.1 Introduction 293
10.2 Design and operation of the SEM 293
10.3 Observation of polymers in the SEM 301
10.4 Examples of SEM applications with polymers 313
10.5 Conclusions 323
Further reading 325
Exercise 325
11 Light optical techniques 326
11.1 Introduction 326
11.2 Refractive index 326
11.3 Birefringence 328
11.4 Light microscopy 344
11.5 Small angle light scattering 357
Reference 360
Further reading 360
Advanced reading 360
Exercises 360
viii Contents
12 Thermal analysis 362
12.1 Introduction 362
12.2 Differential thermal analysis (DTA) and
differential scanning calorimetry (DSC) 362
12.3 Thermomechanical analysis 376
12.4 Thermogravimetric analysis 381
12.5 Dynamic mechanical thermal analysis 382
12.6 Dielectric thermal analysis (DETA) 399
References 407
13 Density, surface properties and neutron diffraction 408
13.1 Density 408
13.2 Surface analysis of polymeric materials 412
13.3 Chemical analysis of the polymer surface 416
13.4 Surface probe or scanning tip microscopy 427
13.5 Neutron scattering studies 432
References 435
Further reading 436
Exercise 436
14 Multiple characterization applications 438
14.1 The structure of a spherulite 438
14.2 Skin-core characterization in moulded polymers 440
14.3 Weathering of polymers 442
14.4 Particular studies 443
14.5 Conclusions 450
References 451
15 Theoretical predictions of the physical properties of
polymeric materials 452
15.1 Introduction 452
15.2 Types of approach available for modelling
polymer physical properties 452
15.3 Molecular based structural additivity calculations 453
15.4 Ab initio calculations of polymeric properties 455
References 464
Appendix: Solutions to exercises 465
Index 472
Preface
The spectacular growth in the number and variety of polymers, has
generated materials with a wide range of physical properties and appli-
cations. Being able to identify and characterize these materials is not just
of academic interest but also of commercial and environmental concern.
Many of the important structural and microstructural features of poly-
mers have no counterparts in other classes of materials. For instance,
molecular mass has little or no significance for metals or ceramics
whereas it has a major influence on the properties of polymers.
Furthermore a characterization method may need to be considerably
modified when it is applied to polymers. An example of this is trans-
mission electron microscopy, where the electron beam sensitivity of poly-
mers has necessitated the development of procedures that are
unnecessary with metals and ceramics. This book concentrates on those
techniques peculiar to polymers and on those aspects which are of partic-
ular value in polymer studies. In recent years there has been an
increasing interest in the characterization of surfaces which can have a
significant effect on the physical properties and technological applica-
tions of these materials.
The book is intended for use as the basis of a course offered to second
or third year undergraduate students in Materials Science, Polymer
Technology and Chemistry, and it is hoped that it will be of value to
many scientists and technologists working in the polymer industry.
Although the book is meant to be self-contained, a certain knowledge
of physics, chemistry and of polymeric materials is assumed. The
emphasis of this book is on illustrating applications of the methods and
the basic theory behind the various techniques is introduced only spar-
ingly. A bibliography is provided at the end of each chapter to help the
interested reader to find out more about both the background theory
and practical aspects of the techniques. The scope of this book has been
enlarged to include polymer composites whenever there are good exam-
ples of applications with these methods.
D. Campbell
R.A. Pethrick
J.R. White