Introduction to Physical Polymer Science

866 Pages·2005·8.61 MB·English

INTRODUCTION TO
PHYSICAL POLYMER
SCIENCE
FOURTH EDITION
L.H. Sperling
Lehigh University
Bethlehem,Pennsylvania
A JOHN WILEY & SONS, INC. PUBLICATION
Copyright © 2006 by John Wiley & Sons,Inc.All rights reserved
Published by John Wiley & Sons,Inc.,.Hoboken,New Jersey
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Library of Congress Cataloging-in-Publication Data:
Sperling,L.H.(Leslie Howard),1932–
Introduction to physical polymer science / L.H.Sperling.—4th ed.
p. cm.
Includes index.
ISBN-13 978-0-471-70606-9 (cloth)
ISBN-10 0-471-70606-X (cloth)
1. Polymers. 2. Polymerization. I. Title.
QD381.S635 2006
668.9—dc22
2005021351
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
This book is dedicated to the many wonderful graduate and
undergraduate students, post-doctoral research associates, and visiting
scientists who carried out research in my laboratory, and to the very many
more students across America and around the world who studied out of
earlier editions of this book. Without them, this edition surely would not
have been possible. I take this opportunity to wish all of them continued
good luck and good fortune in their careers.
CONTENTS
Preface to the Fourth Edition xv
Preface to the First Edition xvii
Symbols and Definitions xix
1 Introduction to Polymer Science 1
1.1 From Little Molecules to Big Molecules / 2
1.2 Molecular Weight and Molecular Weight Distributions / 4
1.3 Major Polymer Transitions / 8
1.4 Polymer Synthesis and Structure / 10
1.5 Cross-Linking,Plasticizers,and Fillers / 18
1.6 The Macromolecular Hypothesis / 19
1.7 Historical Development of Industrial Polymers / 20
1.8 Molecular Engineering / 21
References / 22
General Reading / 22
Handbooks,Encyclopedias,and Dictionaries / 24
Web Sites / 24
Study Problems / 25
Appendix 1.1 Names for Polymers / 26
2 Chain Structure and Configuration 29
2.1 Examples of Configurations and Conformations / 30
2.2 Theory and Instruments / 31
2.3 Stereochemistry of Repeating Units / 36
2.4 Repeating Unit Isomerism / 42
vii
viii CONTENTS
2.5 Common Types of Copolymers / 45
2.6 NMR in Modern Research / 47
2.7 Multicomponent Polymers / 51
2.8 Conformational States in Polymers / 55
2.9 Analysis of Polymers during Mechanical Strain / 56
2.10 Photophysics of Polymers / 58
2.11 Configuration and Conformation / 63
References / 63
General Reading / 65
Study Problems / 65
Appendix 2.1 Assorted Isomeric and Copolymer
Macromolecules / 67
3 Dilute Solution Thermodynamics, Molecular Weights,
and Sizes 71
3.1 Introduction / 71
3.2 The Solubility Parameter / 73
3.3 Thermodynamics of Mixing / 79
3.4 Molecular Weight Averages / 85
3.5 Determination of the Number-Average Molecular Weight / 87
3.6 Weight-Average Molecular Weights and Radii of Gyration / 91
3.7 Molecular Weights of Polymers / 103
3.8 Intrinsic Viscosity / 110
3.9 Gel Permeation Chromatography / 117
3.10 Mass Spectrometry / 130
3.11 Instrumentation for Molecular Weight Determination / 134
3.12 Solution Thermodynamics and Molecular Weights / 135
References / 136
General Reading / 139
Study Problems / 140
Appendix 3.1 Calibration and Application of Light-Scattering
Instrumentation for the Case Where P(q) =1 / 142
4 Concentrated Solutions, Phase Separation Behavior,
and Diffusion 145
4.1 Phase Separation and Fractionation / 145
4.2 Regions of the Polymer–Solvent Phase Diagram / 150
CONTENTS ix
4.3 Polymer–Polymer Phase Separation / 153
4.4 Diffusion and Permeability in Polymers / 172
4.5 Latexes and Suspensions / 184
4.6 Multicomponent and Multiphase Materials / 186
References / 186
General Reading / 190
Study Problems / 190
Appendix 4.1 Scaling Law Theories and Applications / 192
5 The Amorphous State 197
5.1 The Amorphous Polymer State / 198
5.2 Experimental Evidence Regarding Amorphous Polymers / 199
5.3 Conformation of the Polymer Chain / 211
5.4 Macromolecular Dynamics / 217
5.5 Concluding Remarks / 227
References / 227
General Reading / 230
Study Problems / 230
Appendix 5.1 History of the Random Coil Model for Polymer
Chains / 232
Appendix 5.2 Calculations Using the Diffusion Coefficient / 236
Appendix 5.3 Nobel Prize Winners in Polymer Science and
Engineering / 237
6 The Crystalline State 239
6.1 General Considerations / 239
6.2 Methods of Determining Crystal Structure / 245
6.3 The Unit Cell of Crystalline Polymers / 248
6.4 Structure of Crystalline Polymers / 256
6.5 Crystallization from the Melt / 260
6.6 Kinetics of Crystallization / 271
6.7 The Reentry Problem in Lamellae / 290
6.8 Thermodynamics of Fusion / 299
6.9 Effect of Chemical Structure on the Melting Temperature / 305
6.10 Fiber Formation and Structure / 307
6.11 The Hierarchical Structure of Polymeric Materials / 311
6.12 How Do You Know It’s a Polymer? / 312
References / 314
General Reading / 320
Study Problems / 320
x CONTENTS
7 Polymers in the Liquid Crystalline State 325
7.1 Definition of a Liquid Crystal / 325
7.2 Rod-Shaped Chemical Structures / 326
7.3 Liquid Crystalline Mesophases / 326
7.4 Liquid Crystal Classification / 331
7.5 Thermodynamics and Phase Diagrams / 338
7.6 Mesophase Identification in Thermotropic Polymers / 341
7.7 Fiber Formation / 342
7.8 Comparison of Major Polymer Types / 344
7.9 Basic Requirements for Liquid Crystal Formation / 345
References / 346
General Reading / 347
Study Problems / 348
8 Glass–Rubber Transition Behavior 349
8.1 Simple Mechanical Relationships / 350
8.2 Five Regions of Viscoelastic Behavior / 355
8.3 Methods of Measuring Transitions in Polymers / 366
8.4 Other Transitions and Relaxations / 375
8.5 Time and Frequency Effects on Relaxation Processes / 377
8.6 Theories of the Glass Transition / 381
8.7 Effect of Molecular Weight on T / 397
g
8.8 Effect of Copolymerization on T / 399
g
8.9 Effect of Crystallinity on T / 404
g
8.10 Dependence of T on Chemical Structure / 408
g
8.11 Effect of Pressure on T / 410
g
8.12 Damping and Dynamic Mechanical Behavior / 412
8.13 Definitions of Elastomers,Plastics,Adhesives,and Fibers / 415
References / 415
General Reading / 420
Study Problems / 420
Appendix 8.1 Molecular Motion near the Glass Transition / 423
9 Cross-linked Polymers and Rubber Elasticity 427
9.1 Cross-links and Networks / 427
9.2 Historical Development of Rubber / 430
9.3 Rubber Network Structure / 432
9.4 Rubber Elasticity Concepts / 434
CONTENTS xi
9.5 Thermodynamic Equation of State / 437
9.6 Equation of State for Gases / 439
9.7 Statistical Thermodynamics of Rubber Elasticity / 442
9.8 The “Carnot Cycle”for Elastomers / 450
9.9 Continuum Theories of Rubber Elasticity / 453
9.10 Some Refinements to Rubber Elasticity / 459
9.11 Internal Energy Effects / 469
9.12 The Flory–Rehner Equation / 472
9.13 Gelation Phenomena in Polymers / 473
9.14 Gels and Gelation / 478
9.15 Effects of Strain on the Melting Temperature / 479
9.16 Elastomers in Current Use / 480
9.17 Summary of Rubber Elasticity Behavior / 488
References / 489
General Reading / 494
Study Problems / 495
Appendix 9.1 Gelatin as a Physically Cross-linked Elastomer / 497
Appendix 9.2 Elastic Behavior of a Rubber Band / 501
Appendix 9.3 Determination of the Cross-link Density of Rubber by
Swelling to Equilibrium / 503
10 Polymer Viscoelasticity and Rheology 507
10.1 Stress Relaxation and Creep / 507
10.2 Relaxation and Retardation Times / 515
10.3 The Time–Temperature Superposition Principle / 529
10.4 Polymer Melt Viscosity / 533
10.5 Polymer Rheology / 538
10.6 Overview of Viscoelasticity and Rheology / 547
References / 548
General Reading / 550
Study Problems / 550
Appendix 10.1 Energy of Activation from Chemical Stress Relaxation
Times / 552
Appendix 10.2 Viscoelasticity of Cheese / 553
11 Mechanical Behavior of Polymers 557
11.1 An Energy Balance for Deformation and Fracture / 557
11.2 Deformation and Fracture in Polymers / 560
11.3 Crack Growth / 585
11.4 Cyclic Deformations / 588
xii CONTENTS
11.5 Molecular Aspects of Fracture and Healing in Polymers / 593
11.6 Friction and Wear in Polymers / 601
11.7 Mechanical Behavior of Biomedical Polymers / 603
11.8 Summary / 606
References / 607
General Reading / 610
Study Problems / 611
12 Polymer Surfaces and Interfaces 613
12.1 Polymer Surfaces / 614
12.2 Thermodynamics of Surfaces and Interfaces / 615
12.3 Instrumental Methods of Characterization / 619
12.4 Conformation of Polymer Chains in a Polymer Blend
Interphase / 644
12.5 The Dilute Solution–Solid Interface / 646
12.6 Instrumental Methods for Analyzing Polymer
Solution Interfaces / 652
12.7 Theoretical Aspects of the Organization of Chains at Walls / 659
12.8 Adhesion at Interfaces / 667
12.9 Interfaces of Polymeric Biomaterials with Living
Organisms / 675
12.10 Overview of Polymer Surface and Interface Science / 677
References / 679
General Reading / 683
Study Problems / 684
Appendix 12.1 Estimation of Fractal Dimensions / 686
13 Multicomponent Polymeric Materials 687
13.1 Classification Schemes for Multicomponent Polymeric
Materials / 688
13.2 Miscible and Immiscible Polymer Pairs / 692
13.3 The Glass Transition Behavior of Multicomponent Polymer
Materials / 693
13.4 The Modulus of Multicomponent Polymeric Materials / 698
13.5 The Morphology of Multiphase Polymeric Materials / 706
13.6 Phase Diagrams in Polymer Blends (Broad Definition) / 710
13.7 Morphology of Composite Materials / 721
13.8 Nanotechnology-Based Materials / 723
13.9 Montmorillonite Clays / 728