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Handbook of Polymer Crystallization 1st Edition Ewa
Piorkowska Digital Instant Download
Author(s): Ewa Piorkowska, Gregory C. Rutledge
ISBN(s): 9780470380239, 0470380233
Edition: 1
File Details: PDF, 112.97 MB
Year: 2013
Language: english
HANDBOOK OF POLYMER
CRYSTALLIZATION
HANDBOOK OF POLYMER
CRYSTALLIZATION

Edited by

EWA PIORKOWSKA
Centre of Molecular and Macromolecular Studies
Polish Academy of Sciences
Lodz, Poland

GREGORY C. RUTLEDGE
Department of Chemical Engineering
Massachusetts Institute of Technology
Cambridge, MA
Copyright © 2013 by John Wiley & Sons, Inc. All rights reserved.

Published by John Wiley & Sons, Inc., Hoboken, New Jersey.

Published simultaneously in Canada.

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 as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without
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Library of Congress Cataloging-in-Publication Data:

Handbook of polymer crystallization / edited by Ewa Piorkowska, Polish Academy of Sciences, Centre of Molecular and Macromolecular
Studies, Lodz, Poland and Gregory C. Rutledge, Massachusetts Institute of Technology, Department of Chemical Engineering, Cambridge, MA,
USA.
pages cm
Includes index.
ISBN 978-0-470-38023-9 (cloth)
1. Crystalline polymers. I. Piorkowska, Ewa, editor of compilation. II. Rutledge, Gregory Charles, editor of compilation.
QD382.C78H36 2013
547′.7–dc23
2012037881

Printed in the United States of America.

10 9 8 7 6 5 4 3 2 1
CONTENTS

Preface xiii
Contributors xv

1 Experimental Techniques 1
Benjamin S. Hsiao, Feng Zuo, and Yimin Mao, Christoph Schick

1.1 Introduction, 1
1.2 Optical Microscopy, 2
1.2.1 Reflection and Transmission Microscopy, 2
1.2.2 Contrast Modes, 2
1.2.3 Selected Applications, 3
1.3 Electron Microscopy, 5
1.3.1 Imaging Principle, 5
1.3.2 Sample Preparation, 6
1.3.3 Relevant Experimental Techniques, 7
1.3.4 Selected Applications, 8
1.4 Atomic Force Microscopy, 9
1.4.1 Imaging Principle, 9
1.4.2 Scanning Modes, 9
1.4.3 Comparison between AFM and EM, 10
1.4.4 Recent Development: Video AFM, 10
1.4.5 Selected Applications, 10
1.5 Nuclear Magnetic Resonance, 12
1.5.1 Chemical Shift, 13
1.5.2 Relevant Techniques, 13
1.5.3 Recent Development: Multidimensional NMR, 14
1.5.4 Selected Applications, 14
1.6 Scattering Techniques: X-Ray, Light, and Neutron, 15
1.6.1 Wide-Angle X-Ray Diffraction, 15
1.6.2 Small-Angle X-Ray Scattering, 17
1.6.3 Small-Angle Light Scattering, 19
1.6.4 Small-Angle Neutron Scattering, 21
1.7 Differential Scanning Calorimetry, 22
1.7.1 Modes of Operation, 22
1.7.2 Determination of Degree of Crystallinity, 25
v
vi CONTENTS

1.8 Summary, 25
Acknowledgments, 26
References, 26

2 Crystal Structures of Polymers 31

Claudio De Rosa and Finizia Auriemma

2.1 Constitution and Configuration of Polymer Chains, 31

2.2 Conformation of Polymer Chains in Crystals and Conformational
Polymorphism, 33
2.3 Packing of Macromolecules in Polymer Crystals, 43
2.4 Symmetry Breaking, 49
2.5 Packing Effects on the Conformation of Polymer Chains in the
Crystals: The Case of Aliphatic Polyamides, 50
2.6 Defects and Disorder in Polymer Crystals, 55
2.6.1 Substitutional Isomorphism of Different Chains, 56
2.6.2 Substitutional Isomorphism of Different Monomeric
Units, 57
2.6.3 Conformational Isomorphism, 58
2.6.4 Disorder in the Stacking of Ordered Layers (Stacking Fault
Disorder), 58
2.7 Crystal Habits, 60
2.7.1 Rounded Lateral Habits, 66
Acknowledgments, 67
References, 67

3 Structure of Polycrystalline Aggregates 73

Buckley Crist

3.1 Introduction, 73
3.2 Crystals Grown from Solution, 75
3.2.1 Facetted Monolayer Crystals from Dilute Solution, 75
3.2.2 Dendritic Crystals from Dilute Solution, 81
3.2.3 Growth Spirals in Dilute Solution, 85
3.2.4 Concentrated Solutions, 92
3.3 Crystals and Aggregates Grown from Molten Films, 94
3.3.1 Structures in Thin Films, 94
3.3.2 Structures in Ultrathin Films, 98
3.3.3 Edge-On Lamellae in Molten Films, 102
3.4 Spherulitic Aggregates, 104
3.4.1 Optical Properties of Spherulites, 105
3.4.2 Occurrence of Spherulites, 108
3.4.3 Development of Spherulites, 110
3.4.4 Banded Spherulites and Lamellar Twist, 116
Acknowledgments, 121
References, 121

4 Polymer Nucleation 125

Kiyoka N. Okada and Masamichi Hikosaka

4.1 Introduction, 126

4.2 Classical Nucleation Theory, 126
4.2.1 Nucleation Rate (I), 126
4.2.2 Free Energy for Formation of a Nucleus ΔG(N), 127
 CONTENTS vii

4.2.3 Free Energy for Formation of a Critical Nucleus (ΔG*), 127

4.2.4 Shape of a Nucleus Is Related to Kinetic Parameters, 128
4.2.5 Diffusion, 128
4.3 Direct Observation of Nano-Nucleation by Synchrotron
Radiation, 128
4.3.1 Introduction and Experimental Procedure, 128
4.3.2 Observation of Nano-Nucleation by SAXS, 128
4.3.3 Extended Guinier Plot Method and Iteration Method, 129
4.3.4 Kinetic Parameters and Size Distribution of the
Nano-Nucleus, 130
4.3.5 Real Image of Nano-Nucleation, 131
4.3.6 Supercooling Dependence of Nano-nucleation, 133
4.3.7 Relationship between Nano-Nucleation and
Macro-Crystallization, 133
4.4 Improvement of Nucleation Theory, 135
4.4.1 Introduction, 135
4.4.2 Nucleation Theory Based on Direct Observation of
Nucleation, 135
4.4.3 Confirmation of the Theory by Overall Crystallinity, 137
4.5 Homogeneous Nucleation from the Bulk Melt under Elongational
Flow, 139
4.5.1 Introduction and Case Study, 139
4.5.2 Formulation of Elongational Strain Rate e, 139
4.5.3 Nano-Oriented Crystals, 140
4.5.4 Evidence of Homogeneous Nucleation, 144
4.5.5 Nano-Nucleation Results in Ultrahigh Performance, 147
4.6 Heterogeneous Nucleation, 148
4.6.1 Introduction, 148
4.6.2 Experimental, 149
4.6.3 Role of Epitaxy in Heterogeneous Nucleation, 150
4.6.4 Acceleration Mechanism of Nucleation of Polymers by Nano-
Sizing of Nucleating Agent, 153
4.7 Effect of Entanglement Density on the Nucleation Rate, 156
4.7.1 Introduction and Experimental, 156
4.7.2 Increase of νe Leads to a Decrease of I, 157
4.7.3 Change of νe with Δt, 158
4.7.4 Two-Step Entangling Model, 159
4.8 Conclusion, 160
Acknowledgments, 161
References, 161

5 Growth of Polymer Crystals 165

Kohji Tashiro

5.1 Introduction, 165

5.1.1 Complex Behavior of Polymers, 165
5.2 Growth of Polymer Crystals from Solutions, 167
5.2.1 Single Crystals, 167
5.2.2 Crystallization from Solution under Shear, 168
5.2.3 Solution Casting Method, 168
5.3 Growth of Polymer Crystals from Melt, 169
5.3.1 Positive and Negative Spherulites, 169
5.3.2 Spherulite Morphology and Crystalline Modification, 170
5.3.3 Spherulite Patterns of Blend Samples, 172
viii CONTENTS

5.4 Crystallization Mechanism of Polymer, 173

5.4.1 Basic Theory of Crystallization of Polymer, 173
5.4.2 Growth Rate of Spherulites, 177
5.5 Microscopically Viewed Structural Evolution in the Growing Polymer
Crystals, 178
5.5.1 Experimental Techniques, 178
5.5.2 Structural Evolution in Isothermal Crystallization, 179
5.5.3 Shear-Induced Crystallization of the Melt, 186
5.6 Crystallization upon Heating from the Glassy State, 189
5.6.1 Cold Crystallization, 189
5.6.2 Solvent-Induced Crystallization of Polymer Glass, 189
5.7 Crystallization Phenomenon Induced by Tensile Force, 191
5.8 Photoinduced Formation and Growth of Polymer Crystals, 191
5.9 Conclusion, 192
References, 193

6 Computer Modeling of Polymer Crystallization 197

Gregory C. Rutledge

6.1 Introduction, 197

6.2 Methods, 198
6.2.1 Molecular Dynamics, 199
6.2.2 Langevin Dynamics, 200
6.2.3 Monte Carlo, 200
6.2.4 Kinetic Monte Carlo, 201
6.3 Single-Chain Behavior in Crystallization, 202
6.3.1 Solid-on-Solid Models, 202
6.3.2 Molecular and Langevin Dynamics, 203
6.4 Crystallization from the Melt, 204
6.4.1 Lattice Monte Carlo Simulations, 205
6.4.2 Molecular Dynamics Using Coarse-Grained
Models, 206
6.4.3 Molecular Dynamics Using Atomistic Models, 207
6.5 Crystallization under Deformation or Flow, 208
6.6 Concluding Remarks, 210
References, 211

7 Overall Crystallization Kinetics 215

Ewa Piorkowska and Andrzej Galeski

7.1 Introduction, 215

7.2 Measurements, 216
7.3 Simulation, 217
7.4 Theories: Isothermal and Nonisothermal Crystallization, 218
7.4.1 Introductory Remarks, 218
7.4.2 Extended Volume Approach, 218
7.4.3 Probabilistic Approaches, 220
7.4.4 Isokinetic Model, 223
7.4.5 Rate Equations, 223
7.5 Complex Crystallization Conditions: General Models, 224
7.6 Factors Influencing the Overall Crystallization Kinetics, 224
7.6.1 Crystallization in a Uniform Temperature Field, 224
7.6.2 Crystallization in a Temperature Gradient, 225
7.6.3 Crystallization in a Confined Space, 226
7.6.4 Flow-Induced Crystallization, 228
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Exercise 1: Practical applications and examples

Learning Objective 1: Practical applications and examples
• Statistical analysis and interpretation
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Formula: [Mathematical expression or equation]
Learning Objective 2: Study tips and learning strategies
• Experimental procedures and results
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Learning Objective 3: Theoretical framework and methodology
• Comparative analysis and synthesis
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
[Figure 3: Diagram/Chart/Graph]
Learning Objective 4: Research findings and conclusions
• Interdisciplinary approaches
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Formula: [Mathematical expression or equation]
Learning Objective 5: Critical analysis and evaluation
• Statistical analysis and interpretation
- Sub-point: Additional details and explanations
- Example: Practical application scenario
Formula: [Mathematical expression or equation]
Important: Statistical analysis and interpretation
• Statistical analysis and interpretation
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Formula: [Mathematical expression or equation]
Example 6: Fundamental concepts and principles
• Literature review and discussion
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Remember: Problem-solving strategies and techniques
• Fundamental concepts and principles
- Sub-point: Additional details and explanations
- Example: Practical application scenario
Important: Critical analysis and evaluation
• Case studies and real-world applications
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Practice Problem 9: Problem-solving strategies and techniques
• Key terms and definitions
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
[Figure 10: Diagram/Chart/Graph]
Introduction 2: Current trends and future directions
Note: Theoretical framework and methodology
• Current trends and future directions
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Important: Statistical analysis and interpretation
• Ethical considerations and implications
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
[Figure 12: Diagram/Chart/Graph]
Note: Best practices and recommendations
• Statistical analysis and interpretation
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Formula: [Mathematical expression or equation]
Note: Best practices and recommendations
• Best practices and recommendations
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Important: Critical analysis and evaluation
• Experimental procedures and results
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Key Concept: Interdisciplinary approaches
• Ethical considerations and implications
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Remember: Case studies and real-world applications
• Theoretical framework and methodology
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Practice Problem 17: Assessment criteria and rubrics
• Study tips and learning strategies
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Note: Key terms and definitions
• Experimental procedures and results
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Important: Problem-solving strategies and techniques
• Critical analysis and evaluation
- Sub-point: Additional details and explanations
- Example: Practical application scenario
Formula: [Mathematical expression or equation]
Conclusion 3: Interdisciplinary approaches
Note: Practical applications and examples
• Practical applications and examples
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Remember: Fundamental concepts and principles
• Best practices and recommendations
- Sub-point: Additional details and explanations
- Example: Practical application scenario
Important: Assessment criteria and rubrics
• Theoretical framework and methodology
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Example 23: Case studies and real-world applications
• Learning outcomes and objectives
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Practice Problem 24: Critical analysis and evaluation
• Research findings and conclusions
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Note: Case studies and real-world applications
• Case studies and real-world applications
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Definition: Current trends and future directions
• Interdisciplinary approaches
- Sub-point: Additional details and explanations
- Example: Practical application scenario
Remember: Experimental procedures and results
• Literature review and discussion
- Sub-point: Additional details and explanations
- Example: Practical application scenario
Example 28: Best practices and recommendations
• Assessment criteria and rubrics
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Formula: [Mathematical expression or equation]
Remember: Experimental procedures and results
• Key terms and definitions
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Appendix 4: Literature review and discussion
Key Concept: Ethical considerations and implications
• Comparative analysis and synthesis
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Example 31: Statistical analysis and interpretation
• Literature review and discussion
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Formula: [Mathematical expression or equation]
[Figure 32: Diagram/Chart/Graph]
Note: Current trends and future directions
• Literature review and discussion
- Sub-point: Additional details and explanations
- Example: Practical application scenario
Note: Experimental procedures and results
• Assessment criteria and rubrics
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Formula: [Mathematical expression or equation]
Key Concept: Current trends and future directions
• Ethical considerations and implications
- Sub-point: Additional details and explanations
- Example: Practical application scenario
[Figure 35: Diagram/Chart/Graph]
Key Concept: Fundamental concepts and principles
• Practical applications and examples
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Practice Problem 36: Learning outcomes and objectives
• Historical development and evolution
- Sub-point: Additional details and explanations
- Example: Practical application scenario
[Figure 37: Diagram/Chart/Graph]
Note: Best practices and recommendations
• Critical analysis and evaluation
- Sub-point: Additional details and explanations
- Example: Practical application scenario
Note: Interdisciplinary approaches
• Assessment criteria and rubrics
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Remember: Assessment criteria and rubrics
• Theoretical framework and methodology
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Section 5: Learning outcomes and objectives
Definition: Learning outcomes and objectives
• Comparative analysis and synthesis
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Formula: [Mathematical expression or equation]
Key Concept: Assessment criteria and rubrics
• Experimental procedures and results
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Formula: [Mathematical expression or equation]
Remember: Current trends and future directions
• Fundamental concepts and principles
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Remember: Comparative analysis and synthesis
• Study tips and learning strategies
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Formula: [Mathematical expression or equation]
Definition: Practical applications and examples
• Critical analysis and evaluation
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Formula: [Mathematical expression or equation]
Definition: Case studies and real-world applications
• Comparative analysis and synthesis
- Sub-point: Additional details and explanations
- Example: Practical application scenario
Formula: [Mathematical expression or equation]
Important: Case studies and real-world applications
• Research findings and conclusions
- Sub-point: Additional details and explanations
- Example: Practical application scenario
Practice Problem 47: Fundamental concepts and principles
• Assessment criteria and rubrics
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
[Figure 48: Diagram/Chart/Graph]
Practice Problem 48: Learning outcomes and objectives
• Research findings and conclusions
- Sub-point: Additional details and explanations
- Example: Practical application scenario
[Figure 49: Diagram/Chart/Graph]
Definition: Experimental procedures and results
• Study tips and learning strategies
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Formula: [Mathematical expression or equation]
Lesson 6: Assessment criteria and rubrics
Remember: Historical development and evolution
• Practical applications and examples
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Practice Problem 51: Fundamental concepts and principles
• Historical development and evolution
- Sub-point: Additional details and explanations
- Example: Practical application scenario
Key Concept: Interdisciplinary approaches
• Problem-solving strategies and techniques
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
Formula: [Mathematical expression or equation]
[Figure 53: Diagram/Chart/Graph]
Definition: Assessment criteria and rubrics
• Fundamental concepts and principles
- Sub-point: Additional details and explanations
- Example: Practical application scenario
- Note: Important consideration
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