Polymers, Part B: Crystal Structure and Morphology. Methods of Experimental Physics, 16B.

449 Pages·1980·19.238 MB·English

by  Author Unknown

Methods of
Experimental Physics
VOLUME 16
POLYMERS
PART 6: Crystal Structure and Morphology
METHODS OF
EXPERIMENTAL PHYSICS:
L. Marton and C. Marton, Editors-in-Chief
Volume 16
Polymers
PART B: Crystal Structure and Morphology
Edited by
R. A. FAVA
ARC0 Polymers, Inc.
Monroeville, Pennsylvania
@
I980
ACADEMIC PRESS
A Subsidiary of Horcourt Brace jovanovrch, Publishers
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COPYRIGH@T 1 980, BY ACADEMIPCR ESSI,N C.
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ACADEMIC PRESS, INC.
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United Kingdom Ediiion published by
ACADEMIC PRESS, INC. (LONDON) LTD.
24/28 Oval Road, London NWI 7DX
Library of Congress Cataloging in Publication Data
Main entry under title:
Polymer physics.
(Methods of experimental physics ;v. 16)
Includes bibliographical references and index.
CONTENTS: pt. A. Molecular structure and
dynamics. pt. B. Crystal structure and morphology.
1. Polymers and polymerization. I. Fava, Ronald
A. 11. Series.
QD381 .P612 547’.84 79-26343
ISBN 0-12-475957-2
PRINTED IN THE UNITED STATES OF AMERICA
80818283 9 8 7 6 5 4 3 2 1
CONTENTS
CONTRIBUTOR.S. . . . . . . . . . . . . . . . . xi
...
FOREWOR. D. . . . . . . . . . . . . . . . . .
XI11
PREFAC.E . . . . . . . . . . . . . . . . . . . xv
CONTENTOSF VOLUME1 6, PARTSA AND C . . . . . . . x vii
CONTRIBUTOTROS VOLUME1 6, PARTSA AND C . . . . . xxi
VOLUMESI N SERIES. . . . . . . . . . . . . . . . x xiii
6. X-Ray Diffraction
6.1. Unit Cell and Crystallinity
by JOSEPHE . SPRUIELALN D EDWARDS. CLARK
6.1 .l. Introduction . . . . . . . . . . . . 1
6.1.2. Basic Crystallography . . . . . . . . . 2
6.1.3. Diffraction Theory . . . . . . . . . . 25
6.1.4. Experimental Techniques . . . . . . . . 39
6.1.5. Crystal Structure Determination . . . . . . 68
6.1.6. Disorder in Crystalline Polymers . . . . . 98
6.1.7. Measurement of Crystallinity by
X-Ray Diffraction . . . . . . . . . . 114
6.2. Crystallite Size and Lamellar Thickness
by X-Ray Methods
by JING-IW ANGA ND IANR . HARRISON
6.2.1. Introduction . . . . . . . . . . . . 1 28
6.2.2. Crystallite Size by Wide-Angle Techniques . . 129
6.2.3. Lamellar Thickness Using Small-Angle X-Ray
Scattering (SAXS) . . . . . . . . . . 1 53
6.2.4. Summary . . . . . . . . . . . . . 184
V
vi CONTENTS
7. Electron Microscopy
by RICHARDG . VADIMSKY
7.1. Introduction . . . . . . . . . . . . . . . 185
7.2. Fundamentals . . . . . . . . . . . . . . . 1 86
7.2.1. Particle-Wave Concept . . . . . . . . . 186
7.2.2. Image Formation . . . . . . . . . . . 187
7.2.3. Image Interpretation . . . . . . . . . . 190
7.3. Electron Optics . . . . . . . . . . . . . . 1 95
7.3.1. Lens Theory . . . . . . . . . . . . 1 96
7.3.2. The Ideal Lens . . . . . . . . . . . 1 97
7.3.3. Image-Degrading Factors . . . . . . . . 199
7.4. The Instrument . . . . . . . . . . . . . . 2 06
7.4.1. The Illuminating System . . . . . . . . 2 06
7.4.2. The Specimen Holder . . . . . . . . . 2 08
7.4.3. The Objective Lens . . . . . . . . . . 208
7.4.4. The Projection System . . . . . . . . . 2 11
7.5. Operational Considerations . . . . . . . . . . 2 12
7.5.1. Specimen Preparation . . . . . . . . . 2 12
7.5.2. Focusing . . . . . . . . . . . . . 2 17
7.5.3. Resolution . . . . . . . . . . . . . 2 20
7.5.4. Magnification Calibration . . . . . . . . 2 21
7.6. Other Microscopy Techniques . . . . . . . . . 221
7.6.1. Small-Angle Electron Diffraction . . . . . 2 22
7.6.2. Stereomicrography . . . . . . . . . . 2 22
7.6.3. Topographical Contrast Imaging . . . . . . 2 22
7.6.4. Scanning Electron Microscopy . . . . . . 2 24
7.6.5. Scanning-Transmission Electron Microscopy . 227
7.6.6. Low-Loss Electron Microscopy . . . . . . 2 27
CONTENTS vii
7.7. Applications . . . . . . . . . . . . . . . 2 28
7.7.1. Single Molecules . . . . . . . . . . . 2 28
7.7.2. Polymer Single Crystals . . . . . . . . 2 29
7.7.3. Melt-Crystallized Polymers . . . . . . . 2 30
7.7.4. Oriented Polymers . . . . . . . . . . 2 33
8 . Chemical Methods in Polymer Physics
by G . N . PATEL
8.1. Disorder in Polymer Crystals and Chemical Methods . 237
8.2. Solvent-Etching . . . . . . . . . . . . . . 239
8.3. Plasma-Etching . . . . . . . . . . . . . . 2 41
8.4. The Surface Modification Techniques . . . . . . . 2 45
8.4.1. Halogenation . . . . . . . . . . . . 2 45
8.4.2. Dehydrohalogenation of Poly(viny1idene
Chloride) . . . . . . . . . . . . . 252
8.4.3. Methoxymethylation of Polyamides . . . . . 2 53
8.4.4. Acylation of Polystyrene . . . . . . . . 2 55
8.5. The Surface Degradation Techniques
8.5.1. Selective Degradation Reagents . . . . . . 2 55
8 S.2. Nitric Acid Degradation . . . . . . . . 2 56
8.5.3. Ozone Degradation . . . . . . . . . . 2 57
8.5.4. Deduction of Crystal Morphology . . . . . 2 61
8.5.5. Location of Unsaturation and Branches . . . 2 66
8.5.6. A Test for Random Attack . . . . . . . 2 67
8.5.7. Preparation of Low-Molecular-Weight
Fractions for GPC . . . . . . . . . . 2 68
8.5.8. Hydrolysis . . . . . . . . . . . . . 2 69
8.5.9. Degradation by a Mixture of Potassium
Permanganate and Sulfuric Acid . . . . . . 2 77
8.5.10. Hydrazinolysis of Polyamides . . . . . . 2 77
8.6. Irradiation and Selective Degradation . . . . . . . 2 78
8.6.1. Radiation-Induced Chemical Changes . . . . 2 78
8.6.2. Location of the Chemical Changes . . . . . 2 81
viii CONTENTS
9 . Thermal Analysis of Polymers
by JAMESR UNTA ND IANR . HARRISON
9.1. Introduction . . . . . . . . . . . . . . . 287
9.2. Instrumentation and Method . . . . . . . . . . 287
9.3. Theory . . . . . . . . . . . . . . . . . 2 91
9.4. Basic Factors Affecting the DTA/DSC Curve . . . . 293
9.4.1. Instrumental Factors . . . . . . . . . 2 93
9.4.2. Sample Factors . . . . . . . . . . . 2 93
9.4.3. Reference Material . . . . . . . . . . 2 94
9.5. Melting Behavior of Polymers . . . . . . . . . 294
9.5.1. Introduction . . . . . . . . . . . . 294
9.5.2. Dependence of Melting on Crystallization
Conditions . . . . . . . . . . . . . 297
9.5.3. Dependence of Melting on Molecular Weight
and Molecular-Weight Distribution . . . . . 298
9.5.4. Annealing . . . . . . . . . . . . . 299
9.5.5. Effect of Heating Rate on Polymer Melting . . 300
9.5.6. Multiple Melting Peaks . . . . . . . . . 303
9.5.7. Dried and Suspension Crystals . . . . . . 308
9.5.8. The “True” Melting Point . . . . . . . . 313
9.6. Quantitative Methods . . . . . . . . . . . . 3 16
9.7. Other Applications . . . . . . . . . . . . . 3 27
9.7.1. Phase Changes . . . . . . . . . . . 3 27
9.7.2. Glass Transition . . . . . . . . . . . 3 27
9.7.3. Polymerization . . . . . . . . . . . 3 31
9.7.4. Identification . . . . . . . . . . . . 3 34
9.7.5. Polymer Reactions . . . . . . . . . . 3 35
9.7.6. Crystallization . . . . . . . . . . . . 3 36
. . . . . . . . . . . . . . . .
9.8. Summary 337
CONTENTS ix
10. Nucleation and Crystallization
by GAYLONS . Ross AND LOISJ . FROLEN
10.1 Introduction . . . . . . . . . . . . . . . 339
10.1 .1 . Aims and Objectives . . . . . . . . . . 339
10.2 General Background on Semicrystalline Polymers . . . 3 40
10.2.1. Requirements for Crystallization . . . . . . 3 40
10.2.2. Historical Development . . . . . . . . . 3 41
10.3 Experimental Methods for Measuring
Crystallization Rates . . . . . . . . . . . . . 3 52
10.3.1. General Considerations . . . . . . . . . 352
10.3.2. Methods Using a Thin-Film-Type Specimen . . 354
10.3.3. Methods Using a Bulk-Type Specimen . . . 3 69
10.3.4. Differential Thermal Analysis (DTA) as
Applied to the Determination of Tm0. . . . . 3 75
10.3.5. Crystallization from Solution . . . . . . . 3 81
10.4 Nucleation . . . . . . . . . . . . . . . . 3 85
10.4.1. Homogeneous Nucleation . . . . . . . . 3 85
10.4.2. Heterogeneous Nucleation . . . . . . . . 3 96
AUTHORIN DEX FOR PARTB . . . . . . . . . . . . . 3 99
SUBJECITN DEX FOR PARTB . . . . . . . . . . . . . 4 11