Polymer Microscopy

416 Pages·1996·17.296 MB·English

by  Linda C. Sawyer, David T. Grubb (auth.)

Polymer
Microscopy
Polymer
Microscopy
Second edition
LINDA C. SAWYER
Hoechst Celanese Corporation
Summit, NJ
USA
and
DAVID T. GRUBB
Cornell University
Ithaca, NY
USA
Springer-Science+Business Media, B.V.
First edition 1987
Second edition 1996
© 1987, 1996 Springer Science+Business Media Dordrecht
Originally published by L. C. Sawyer and D. T. Grubb in 1996
Softcover reprint of the hardcover 2nd edition 1996
Typeset in 10/12 pt Palatino by Techset Composition Ltd., Salisbury,
Wiltshire.
ISBN 978-94-015-8597-2 ISBN 978-94-015-8595-8 (eBook)
DOI 10.1007/978-94-015-8595-8
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Contents
Color plates appear between pages 274 and 275
Preface to the second edition xi
Acknowledgements xüi
1 Introduction to polymer morphology 1
1.1 Polymer materials 1
1.1.1 Introduction 1
1.1.2 Definitions 2
1.2 Polymer morphology 3
1.2.1 Amorphous polymers 4
1.2.2 Semicrystalline polymers 4
1.2.3 Liquid crystalline polymers 7
1.3 Polymer processes 7
1.3.1 Extrusion of fibers and films 8
1.3.2 Extrusion and molding 10
1.4 Polymer characterization 12
1.4.1 General techniques 12
1.4.2 Microscopy techniques 12
1.4.3 Specimen preparation methods 13
1.4.4 Applications of microscopy to polymers 14
1.4.5 New microscopy techniques 14
2 Fundamentals of microscopy 17
2.1 Introduction 17
2.1.1 Lens-imaging microscopes 18
2.1.2 Scanning-imaging microscopes 20
2.2 Optical microscopy (OM) 21
2.2.1 Introduction 21
2.2.2 Objective lenses 21
2.2.3 Imaging modes 22
vi Contents
2.2.4 Measurement of refractive index 23
2.2.5 Polarized light 24
2.3 Scanning electron mieroscopy (SEM) 25
2.3.1 Introduction 25
2.3.2 Imaging signals 28
2.3.3 SEM optimization 29
2.3.4 Special SEM types 30
2.4 Transmission electron microscopy (TEM) 30
2.4.1 Imaging in the TEM 30
2.4.2 Diffraction techniques 32
2.4.3 Phase contrast and lattiee imaging 33
2.5 Scanning probe mieroscopy (SPM) 33
2.6 Mieroscopy of radiation sensitive materials 36
2.6.1 SEM operation 36
2.6.2 Low dose TEM operation 37
2.7 Analytieal mieroscopy 39
2.7.1 X-ray microanalysis 39
2.7.2 X-ray analysis in the SEM vs. AEM 40
2.7.3 Elemental mapping 41
2.8 Quantitative microscopy 41
2.8.1 Stereology and image analysis 41
2.8.2 Calibration 42
2.8.3 Image processing 42
2.9 Dynamie mieroscopy 43
2.9.1 Stages for dynamie microscopy 43
3 Imaging theory 48
3.1 Imaging with lenses 48
3.1.1 Basie opties 48
3.1.2 Resolution 50
3.1.3 Electron diffraction 54
3.1.4 Contrast mechanisms 56
3.1.5 Illumination systems 58
3.2 Imaging by scanning electron beam 60
3.2.1 Scanning opties 60
3.2.2 Beam - specimen interactions 61
3.2.3 Image formation 63
3.3 Imaging by scanning a solid probe 64
3.4 Polarizing mieroscopy 65
3.4.1 Polarized light 65
3.4.2 Anisotropie materials 65
3.4.3 Polarizing microscopy 68
3.5 Radiation effects 70
3.5.1 Effect of radiation on polymers 70
3.5.2 Radiation doses and specimen heating 73
3.5.3 Effects of radiation damage on the image 74
Contents
VII
3.5.4 Noise limited resolution 77
3.5.5 Image processing 78
4 Specimen preparation methods 83
4.1 Simple preparation methods 83
4.1.1 Optical preparations 83
4.1.2 SEM preparations 84
4.1.3 TEM preparations 84
4.1.4 SPM preparations 89
4.2 Polishing 91
4.2.1 Polishing artifacts 91
4.2.2 Polishing specimen surfaces 91
4.3 Microtomy 94
4.3.1 Peelback of fibers / films for SEM 94
4.3.2 Seetions for OM 95
4.3.3 Seetions for SEM 98
4.3.4 Ultrathin sectioning 99
4.3.5 Ultrathin cryosectioning 100
4.4 Staining 102
4.4.1 Introduction 102
4.4.2 Osmium tetroxide 103
4.4.3 Ebonite 108
4.4.4 Chlorosulfonic acid 110
4.4.5 Phosphotungstic acid 111
4.4.6 Ruthenium tetroxide 112
4.4.7 Silver sulfide 119
4.4.8 Mercuric trifluoroacetate 119
4.4.9 Iodine 120
4.4.10 Summary 122
4.5 Etching 122
4.5.1 Introduction 122
4.5.2 Plasma and ion etching 122
4.5.3 Solvent and chemical etching 125
4.5.4 Acid etching 127
4.5.5 Summary 130
4.6 Replication 130
4.6.1 Simple replicas 131
4.6.2 Replication for TEM 132
4.7 Conductive coatings 136
4.7.1 Coating devices 136
4.7.2 Coatings for TEM 137
4.7.3 Coatings for SEM and STM 138
4.7.4 Artifacts 141
4.7.5 Gold decoration 146
4.8 Yielding and fracture 147
4.8.1 Fractography 147
viii Contents
4.8.2 Fracture: standard physical testing 148
4.8.3 In situ deformation 152
4.8.4 Crazing 154
4.9 Freezing and drying methods 157
4.9.1 Simple freezing methods 158
4.9.2 Freeze drying 158
4.9.3 Critical point drying 161
4.9.4 Freeze fracture-etching 163
5 Polymer applications 174
5.1 Fibers 174
5.1.1 Introduction 174
5.1.2 Textile fibers 175
5.1.3 Problem solving applications 183
5.1.4 Industrial fibers 192
5.2 Films and membranes 197
5.2.1 Introduction 197
5.2.2 Model studies 198
5.2.3 Industrial films 202
5.2.4 Flat film membranes 208
5.2.5 Hollow fiber membranes 218
5.3 Engineering resins and plastics 219
5.3.1 Introduction 219
5.3.2 Extrudates and molded parts 221
5.3.3 Multiphase polymers 229
5.3.4 Failure analysis 244
5.4 Composites 247
5.4.1 Introduction 247
5.4.2 Composite characterization 248
5.4.3 Fiber composites 251
5.4.4 Particle filled composites 257
5.4.5 Carbon black filled rubber 261
5.5 Emulsions and adhesives 264
5.5.1 Introduction 264
5.5.2 Latexes 264
5.5.3 Wettability 271
5.5.4 Adhesives and adhesion 272
5.6 Liquid crystalline polymers 275
5.6.1 Introduction 275
5.6.2 Optical textures 277
5.6.3 Solid state structures 280
5.6.4 High modulus fibers 287
5.6.5 Structure-property relations in LCPs 293
Contents ix
6 New techniques in polymer microscopy 315
6.1 Introduction 315
6.2 Optical microscopy 315
6.2.1 Confocal scanning microscopy 315
6.2.2 N ear field optical microscopy 318
6.3 Scanning electron microscopy (SEM) 319
6.3.1 Low voltage SEM 319
6.3.2 High resolution SEM 325
6.3.3 High pressure (environmentaD SEM 326
6.4 Transmission electron microscopy (TEM) 327
6.4.1 High resolution TEM 327
6.4.2 Structure determination by electron diffraction 331
6.5 Scanning tunneling microscopy (STM) 332
6.5.1 Principles of STM 332
6.5.2 Instrumentation and operation of the STM 334
6.5.3 STM of insulators 336
6.5.4 Adsorbed organic molecules 337
6.5.5 Other polymer applications 339
6.6 Scanning force microscopy (SFM) 339
6.6.1 Principles of atomic force microscopy (AFM) 340
6.6.2 Atomic resolution in the AFM 343
6.6.3 Metrology using scanning probe microscopy 346
6.6.4 Frictional force microscopy 350
7 Problem solving summary 357
7.1 Where to start 357
7.1.1 Problem solving protocol 358
7.1.2 Polymer structures 358
7.2 Instrumental techniques 359
7.2.1 Comparison of techniques 360
7.2.2 Optical techniques 362
7.2.3 SEM techniques 363
7.2.4 TEM techniques 364
7.2.5 SPM techniques 365
7.2.6 Technique selection 365
7.3 Interpretation 365
7.3.1 Artifacts 366
7.3.2 Summary 368
7.4 Supporting characterizations 369
7.4.1 X-ray diffraction 369
7.4.2 Thermal analysis 371
7.4.3 Spectroscopy 372
7.4.4 Small angle scattering 374
7.4.5 Summary 375
x Contents
Appendices 379
Appendix I Abbreviations of polymer names 379
Appendix 11 List of acronyms - techniques 380
Appendix III Manmade polymer fibres 381
Appendix IV Common commercial polymers and tradenames for plastics,
films and engineering resins 382
Appendix V General suppliers of microscopy accessories 384
Appendix VI Suppliers of optical and electron microseopes 385
Appendix VII Suppliers of x-ray microanalysis equipment 385
Appendix VIII Suppliers of scanning probe microscopes 386
Index 387
Preface to the second edition
The major objective of this text is to provide information on the basic microscopy
techniques and specimen preparation methods applicable to polymers. This book will
attempt to provide enough detail so that the methods described can be applied, and will
also reference appropriate publications for the investigator interested in more detail.
Some discussion will consider polymer structure and properties, but only as this is
needed to put the microscopy into context.
We recognize that scientists from a wide range of backgrounds may be interested in
polymer microscopy. Some may be experienced in the field, and this text should provide
a reference work and resource whenever a new material or a new problem comes to
their attention. The scientist, engineer or graduate student new to the field needs more
explanation and help. Some may need to know more about the intrinsic capabilities of
different microscopes, others may know all about microscopes and little about polymer
fibers. This text inc1udes sections designed for all of these groups, so that some portions
of the text are not for every reader. The organization of chapters and section headings
should lead the reader to the information needed, and an extensive index is provided
for the same purpose.
The first edition of this book was published in 1987. In the past eight years there have
been major changes in microscopy that have had an effect on research into many
materials, inc1uding polymers. It was no surprise when Chapman & Hall invited us to
provide a second edition which would inc1ude the new techniques, as we were already
applying them to our own research. This second edition follows the same basic
principles as the first, with the addition of new material throughout the text as well as in
a new chapter.
Chapter 1 provides abrief introduction to polymer materials, processes, morphology
and characterization. Chapter 2 is a concise review of the fundamentals of microscopy,
where many important terms are defined. Chapter 3 reviews imaging theory for the
reader who wants to understand the nature of image formation in the various types of
microscopes, with particular reference to imaging polymers. All of these chapters are
mere summaries of large fields of science, to make this text complete. They contain
many references to more specialized texts and reviews. Chapters 4 and 5 contain the
major thrust of the book. Chapter 4 covers specimen preparation, organized by method,