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FUNDAMENTALS OF
Second EditionRevised and Expanded
Anil KumarIndian Institute of TechnologyKanpur, India
Rakesh K. GuptaWest Virginia UniversityMorgantown, West Virginia, U.S.A.
M A R C E L
MARCEL DEKKER, INC. NEW YORK • BASEL
Copyright © 2003 Marcel Dekker, Inc.
Library of Congress Cataloging-in-Publication Data
A catalog record for this book is available from the Library of Congress.
ISBN: 0-8247-0867-9
The first edition was published as Fundamentals of Polymers by McGraw-Hill, 1997.
This book is printed on acid-free paper.
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Current printing (last digit):
10 9 8 7 6 5 4 3 2 1
PRINTED IN THE UNITED STATES OF AMERICA
Copyright © 2003 Marcel Dekker, Inc.
PLASTICS ENGINEERING
Founding Editor
Donald E. HudginProfessor
Clemson UniversityClemson, South Carolina
1. Plastics Waste Recovery of Economic Value, Jacob Letdner2 Polyester Molding Compounds, Robert Burns3 Carbon Black-Polymer Composites The Physics of Electrically Conducting
Composites, edited by Enid Keil Sichel4 The Strength and Stiffness of Polymers, edited byAnagnostis £ Zachanades
and RogerS Porter5 Selecting Thermoplastics for Engineering Applications, Charles P Mac-
Dermott6 Engineering with Rigid PVC Processabihty and Applications, edited by I Luis
Gomez7 Computer-Aided Design of Polymers and Composites, D H Kaelble8 Engineering Thermoplastics Properties and Applications, edited by James
M Margolis9 Structural Foam A Purchasing and Design Guide, Bruce C Wendle
10 Plastics in Architecture A Guide to Acrylic and Polycarbonate, RalphMontella
11 Metal-Filled Polymers Properties and Applications, edited by Swapan KBhattacharya
12 Plastics Technology Handbook, Manas Chanda and Salil K Roy13 Reaction Injection Molding Machinery and Processes, F Melvin Sweeney14 Practical Thermoforming Principles and Applications, John Flonan15 Injection and Compression Molding Fundamentals, edited by Avraam I
Isayev16 Polymer Mixing and Extrusion Technology, Nicholas P Cheremismoff17 High Modulus Polymers Approaches to Design and Development, edited by
Anagnostis E Zachanades and Roger S Porter18 Corrosion-Resistant Plastic Composites in Chemical Plant Design, John H
Mallinson19 Handbook of Elastomers New Developments and Technology, edited by Anil
K Bhowmick and Howard L Stephens20 Rubber Compounding Principles, Materials, and Techniques, Fred W
Barlow21 Thermoplastic Polymer Additives Theory and Practice, edited by John T
Lutz, Jr22 Emulsion Polymer Technology, Robert D Athey, Jr23 Mixing in Polymer Processing, edited by Chns Rauwendaal24 Handbook of Polymer Synthesis, Parts A and B, edited by Hans R
Kncheldorf
Copyright © 2003 Marcel Dekker, Inc.
25. Computational Modeling of Polymers, edited by Jozef Bicerano26. Plastics Technology Handbook: Second Edition, Revised and Expanded,
Manas Chanda and Salil K. Roy27. Prediction of Polymer Properties, Jozef Bicerano28. Ferroelectric Polymers: Chemistry, Physics, and Applications, edited by Hari
Singh Nalwa29. Degradable Polymers, Recycling, and Plastics Waste Management, edited
by Ann-Christine Albertsson and Samuel J. Huang30. Polymer Toughening, edited by Charles B. Arends31. Handbook of Applied Polymer Processing Technology, edited by Nicholas P.
Cheremisinoff and Paul N. Cheremisinoff32. Diffusion in Polymers, edited by P. Neogi33. Polymer Devolatilization, edited by Ramon J. Albalak34. Anionic Polymerization: Principles and Practical Applications, Henry L. Hsieh
and Roderic P. Quirk35. Cationic Polymerizations: Mechanisms, Synthesis, and Applications, edited
by Krzysztof Matyjaszewski36. Polyimides: Fundamentals and Applications, edited by Malay K. Ghosh and
K. L. Mittal37. Thermoplastic Melt Rheology and Processing, A. V. Shenoy and D. R. Saini38. Prediction of Polymer Properties: Second Edition, Revised and Expanded,
Jozef Bicerano39. Practical Thermoforming: Principles and Applications, Second Edition,
Revised and Expanded, John Florian40. Macromolecular Design of Polymeric Materials, edited by Koichi Hatada,
Tatsuki Kitayama, and Otto Vogl41. Handbook of Thermoplastics, edited by Olagoke Olabisi42. Selecting Thermoplastics for Engineering Applications: Second Edition,
Revised and Expanded, Charles P. MacDermott and Aroon V. Shenoy43. Metallized Plastics: Fundamentals and Applications, edited by K. L Mittal44. Oligomer Technology and Applications, Constantin V. Uglea45. Electrical and Optical Polymer Systems: Fundamentals, Methods, and
Applications, edited by Donald L. Wise, Gary E. Wnek, Debra J. Trantolo,Thomas M. Cooper, and Joseph D. Gresser
46. Structure and Properties of Multiphase Polymeric Materials, edited by TakeoAraki, Qui Tran-Cong, and Mitsuhiro Shibayama
47. Plastics Technology Handbook: Third Edition, Revised and Expanded,Manas Chanda and Salil K. Roy
48. Handbook of Radical Vinyl Polymerization, Munmaya K. Mishra and YusufYagci
49. Photonic Polymer Systems: Fundamentals, Methods, and Applications,edited by Donald L Wise, Gary E. Wnek, Debra J. Trantolo, Thomas M.Cooper, and Joseph D. Gresser
50. Handbook of Polymer Testing: Physical Methods, edited by Roger Brown51. Handbook of Polypropylene and Polypropylene Composites, edited by Har-
utun G. Karian52. Polymer Blends and Alloys, edited by Gabriel O. Shonaike and George P.
Simon53. Star and Hyperbranched Polymers, edited by Munmaya K. Mishra and Shi-
ro Kobayashi54. Practical Extrusion Blow Molding, edited by Samuel L. Belcher
Copyright © 2003 Marcel Dekker, Inc.
55 Polymer Viscoelasticity Stress and Strain in Practice, Evaristo Riande,Ricardo Diaz-Calleja, Margarita G Prolongo, Rosa M Masegosa, and Cat-alma Salom
56 Handbook of Polycarbonate Science and Technology, edited by Donald GLeGrand and John T Bendler
57 Handbook of Polyethylene Structures, Properties, and Applications, AndrewJ Peacock
58 Polymer and Composite Rheology Second Edition, Revised and Expanded,Rakesh K Gupta
59 Handbook of Polyolefms Second Edition Revised and Expanded, editedby Cornelia Vasile
60 Polymer Modification Principles, Techniques, and Applications, edited byJohn J Meister
61 Handbook of Elastomers Second Edition, Revised and Expanded, editedby Anil K Bhowmick and Howard L Stephens
62 Polymer Modifiers and Additives, edited by John T Lutz, Jr, and Richard FGrossman
63 Practical Injection Molding, Bernie A Olmstea and Martin E Davis64 Thermosetting Polymers, Jean-Pierre Pascault, Henry Sautereau, Jacques
Verdu, and Roberto J J Williams65 Prediction of Polymer Properties Third Edition, Revised and Expanded, Jozef
Bicerano66 Fundamentals of Polymer Engineering Second Edition, Revised and
Expanded, Anil Kumar and Rakesh K Gupta
Additional Volumes in Preparation
Handbook of Plastics Analysis, edited by Hubert Lobo and Jose Bonilla
Metallocene Catalysts in Plastics Technology, Anand Kumar Kulshreshtha
Copyright © 2003 Marcel Dekker, Inc.
To the memory of my father.
Anil Kumar
To the memory of my father.
Rakesh Gupta
Copyright © 2003 Marcel Dekker, Inc.
Preface to the Second Edition
The objectives and organization of the second edition remain essentially
unchanged. The major difference from the first edition is the inclusion of
new material on topics such as dendrimers, polymer recycling, Hansen
solubility parameters, nanocomposites, creep in glassy polymers, and twin-
screw extrusion. New examples have been introduced throughout the book,
additional problems appear at the end of each chapter, and references to the
literature have been updated. Additional text and figures have also been added.
The first edition has been successfully used in universities around the
world, and we have received many encouraging comments. We hope the
second edition will also find favor with our colleagues, and be useful to future
generations of students of polymer science and engineering.
Anil Kumar
Rakesh K. Gupta
v
Copyright © 2003 Marcel Dekker, Inc.
Preface to the First Edition
Synthetic polymers have considerable commercial importance and are known
by several common names, such as plastics, macromolecules, and resins.
These materials have become such an integral part of our daily existence that
an introductory polymer course is now included in the curriculum of most
students of science and engineering. We have written this book as the main
text for an introductory course on polymers for advanced undergraduates and
graduate students. The intent is to provide a systematic coverage of the
essentials of polymers.
After an introduction to polymers as materials in the first two chapters,
the mechanisms of polymerization and their effect on the engineering design
of reactors are elucidated. The succeeding chapters consider polymer char-
acterization, polymer thermodynamics, and the behavior of polymers as
melts, solutions, and solids both above and below the glass transition
temperature. Also examined are crystallization, diffusion of and through
polymers, and polymer processing. Each chapter can, for the most part, be
vii
Copyright © 2003 Marcel Dekker, Inc.
read independently of the others, and this should allow an instructor to design
the course to his or her own liking. Note that the problems given at the end of
each chapter also serve to complement the main text. Some of these problems
cite references to the literature where alternative viewpoints are introduced. We
have been teaching polymer science for a long time, and we have changed the
course content from year to year by adopting and expanding on ideas of the
kind embodied in these problems.
Since polymer science is an extremely vast area, the decision to include
or exclude a given subject matter in the text has been a difficult one. In this
endeavor, although our own biases will show in places, we have been guided
by how indispensable a particular topic is to proper understanding. We have
attempted to keep the treatment simple without losing the essential features;
for depth of coverage, the reader is referred to the pertinent technical literature.
Keeping the student in mind, we have provided intermediate steps in most
derivations. For the instructor, lecturing becomes easy since all that is
contained in the book can be put on the board. The future will tell to what
extent we have succeeded in our chosen objectives.
We have benefited from the comments of several friends and colleagues
who read different parts of the book in draft form. Our special thanks go to
Ashok Khanna, Raj Chhabra, Deepak Doraiswamy, Hota V. S. GangaRao,
Dave Kofke, Mike Ryan, and Joe Shaeiwitz. Professor Khanna has used the
problem sets of the first seven chapters in his class for several years.
After finishing my Ph.D. from Carnegie-Mellon University, I (Anil
Kumar) joined the Department of Chemical Engineering at the Indian Institute
of Technology, Kanpur, India, in 1972. My experience at this place has been
rich and complete, and I decided to stay here for the rest of my life. I am
fortunate to have a good set of students from year to year with whom I have
been able to experiment in teaching various facets of polymer science and
modify portions of this book continuously.
Rakesh Gupta would like to thank Professor Santosh Gupta for introdu-
cing polymer science to him when he was an undergraduate student. This
interest in polymers was nurtured by Professor Art Metzner and Dr. K. F.
Wissbrun, who were his Ph.D. thesis advisors. Rakesh learned even more from
the many graduate students who chose to work with him, and their contribu-
tions to this book are obvious. Kurt Wissbrun reviewed the entire manuscript
and provided invaluable help and encouragement during the final phases of
writing. Progress on the book was also aided by the enthusiastic support of
Gene Cilento, the Department Chairman at West Virginia University. Rakesh
adds that these efforts would have come to nought without the determined help
of his wife, Gunjan, who guarded his spare time and allowed him to devote it
viii Preface to the First Edition
Copyright © 2003 Marcel Dekker, Inc.
entirely to this project. According to Rakesh, ‘‘She believed me when I told
her it would take two years; seven years later she still believes me!’’
I doubt that this book would ever have been completed without the
constant support of my wife, Renu. During this time there have been several
anxious moments, primarily because our children, Chetna and Pushkar, were
trying to choose their careers and settle down. In taking care of them, my role
was merely helping her, and she allowed me to divide my attention between
home and work. Thank you, Renu.
Anil Kumar
Rakesh Gupta
Preface to the First Edition ix
Copyright © 2003 Marcel Dekker, Inc.
Contents
Preface to the Second Edition v
Preface to the First Edition vii
1. Introduction 1
1.1 Defining Polymers 1
1.2 Classification of Polymers and Some Fundamental
Concepts 4
1.3 Chemical Classification of Polymers Based on
Polymerization Mechanisms 16
1.4 Molecular-Weight Distributions 19
1.5 Configurations and Crystallinity of Polymeric Materials 22
1.6 Conformation of Polymer Molecules 27
1.7 Polymeric Supports in Organic Synthesis 29
1.8 Conclusion 38
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References 39
Problems 39
2. Effect of Chemical Structure on Polymer Properties 45
2.1 Introduction 45
2.2 Effect of Temperature on Polymers 45
2.3 Additives for Plastics 50
2.4 Rubbers 61
2.5 Cellulose Plastics 66
2.6 Copolymers and Blends 68
2.7 Cross-Linking Reactions 72
2.8 Ion-Exchange Resins 80
2.9 Conclusion 89
References 90
Problems 91
3. Step-Growth Polymerization 103
3.1 Introduction 103
3.2 Esterification of Homologous Series and the Equal
Reactivity Hypothesis 105
3.3 Kinetics of A–R–B Polymerization Using Equal
Reactivity Hypothesis 107
3.4 Average Molecular Weight in Step-Growth Polymerization
of ARB Monomers 111
3.5 Equilibrium Step-Growth Polymerization 116
3.6 Molecular-Weight Distribution in Step-Growth
Polymerization 118
3.7 Experimental Results 125
3.8 Conclusion 140
Appendix 3.1: The Solution of MWD Through the
Generating Function Technique in Step-Growth
Polymerization 140
References 143
Problems 145
4. Reaction Engineering of Step-Growth Polymerization 153
4.1 Introduction 153
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4.2 Analysis of Semibatch Reactors 156
4.3 MWD of ARB Polymerization in Homogeneous
Continuous-Flow Stirred-Tank Reactors 166
4.4 Advanced Stage of Polymerization 169
4.5 Conclusion 174
Appendix 4.1: Similarity Solution of Step-Growth
Polymerization in Films with Finite Mass Transfer 175
References 181
Problems 181
5. Chain-Growth Polymerization 188
5.1 Introduction 188
5.2 Radical Polymerization 192
5.3 Kinetic Model of Radical Polymerization 197
5.4 Average Molecular Weight in Radical Polymerization 199
5.5 Verification of the Kinetic Model and the Gel Effect
in Radical Polymerization 201
5.6 Equilibrium of Radical Polymerization 210
5.7 Temperature Effects in Radical Polymerization 215
5.8 Ionic Polymerization 216
5.9 Anionic Polymerization 222
5.10 Ziegler-Natta Catalysts in Stereoregular Polymerization 226
5.11 Kinetic Mechanism in Heterogeneous Stereoregular
Polymerization 230
5.12 Stereoregulation by Ziegler-Natta Catalyst 232
5.13 Rates of Ziegler-Natta Polymerization 233
5.14 Average Chain Length of the Polymer in Stereoregular
Polymerization 238
5.15 Diffusional Effect in Ziegler-Natta Polymerization 240
5.16 Newer Metallocene Catalysts for Olefin Polymerization 242
5.17 Conclusion 244
References 244
Problems 248
6. Reaction Engineering of Chain-Growth Polymerization 255
6.1 Introduction 255
6.2 Design of Tubular Reactors 256
6.3 Copolymerization 273
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6.4 Recycling and Degradation of Polymers 285
6.5 Conclusion 287
Appendix 6.1: Solution of Equations Describing
Isothermal Radical Polymerization 287
References 293
Problems 294
7. Emulsion Polymerization 299
7.1 Introduction 299
7.2 Aqueous Emulsifier Solutions 300
7.3 Smith and Ewart Theory for State II of Emulsion
Polymerization 304
7.4 Estimation of the Total Number of Particles, Nt 313
7.5 Monomer Concentration in Polymer Particles, [M] 315
7.6 Determination of Molecular Weight in Emulsion
Polymerization 319
7.7 Emulsion Polymerization in Homogeneous
Continuous-Flow Stirred-Tank Reactors 324
7.8 Time-Dependent Emulsion Polymerization 326
7.9 Conclusions 334
References 335
Problems 336
8. Measurement of Molecular Weight and Its Distribution 340
8.1 Introduction 340
8.2 End-Group Analysis 342
8.3 Colligative Properties 343
8.4 Light Scattering 350
8.5 Ultracentrifugation 354
8.6 Intrinsic Viscosity 358
8.7 Gel Permeation Chromatography 364
8.8 Conclusion 369
References 369
Problems 371
9. Thermodynamics of Polymer Mixtures 374
9.1 Introduction 374
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9.2 Criteria for Polymer Solubility 376
9.3 The Flory-Huggins Theory 379
9.4 Free-Volume Theories 396
9.5 The Solubility Parameter 398
9.6 Polymer Blends 401
9.7 Conclusion 403
References 403
Problems 405
10. Theory of Rubber Elasticity 407
10.1 Introduction 407
10.2 Probability Distribution for the Freely Jointed Chain 408
10.3 Elastic Force Between Chain Ends 415
10.4 Stress-Strain Behavior 418
10.5 The Stress Tensor (Matrix) 420
10.6 Measures of Finite Strain 423
10.7 The Stress Constitutive Equation 427
10.8 Vulcanization of Rubber and Swelling Equilibrium 429
10.9 Conclusion 432
References 433
Problems 434
11. Polymer Crystallization 437
11.1 Introduction 437
11.2 Energetics of Phase Change 443
11.3 Overall Crystallization Rate 447
11.4 Empirical Rate Expressions: The Avrami Equation 450
11.5 Polymer Crystallization in Blends and Composites 456
11.6 Melting of Crystals 459
11.7 Influence of Polymer Chain Extension and Orientation 462
11.8 Polymers with Liquid-Crystalline Order 464
11.9 Structure Determination 467
11.10 Working with Semicrystalline Polymers 479
11.11 Conclusion 480
References 481
Problems 484
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12. Mechanical Properties 487
12.1 Introduction 487
12.2 Stress-Strain Behavior 488
12.3 The Glass Transition Temperature 497
12.4 Dynamic Mechanical Experiments 501
12.5 Time-Temperature Superposition 504
12.6 Polymer Fracture 508
12.7 Crazing and Shear Yielding 511
12.8 Fatigue Failure 516
12.9 Improving Mechanical Properties 518
References 520
Problems 523
13. Polymer Diffusion 526
13.1 Introduction 526
13.2 Fundamentals of Mass Transfer 527
13.3 Diffusion Coefficient Measurement 531
13.4 Diffusivity of Spheres at Infinite Dilution 542
13.5 Diffusion Coefficient for Non-Theta Solutions 546
13.6 Free-Volume Theory of Diffusion in Rubbery Polymers 547
13.7 Gas Diffusion in Glassy Polymers 552
13.8 Organic Vapor Diffusion in Glassy Polymers:
Case II Diffusion 557
13.9 Polymer-Polymer Diffusion 560
13.10 Conclusion 564
References 565
Problems 569
14. Flow Behavior of Polymeric Fluids 573
14.1 Introduction 573
14.2 Viscometric Flows 576
14.3 Cone-and-Plate Viscometer 578
14.4 The Capillary Viscometer 584
14.5 Extensional Viscometers 589
14.6 Boltzmann Superposition Principle 592
14.7 Dynamic Mechanical Properties 595
14.8 Theories of Shear Viscosity 598
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14.9 Constitutive Behavior of Dilute Polymer Solutions 605
14.10 Constitutive Behavior of Concentrated Solutions and
Melts 615
14.11 Conclusion 622
References 622
Problems 626
15. Polymer Processing 630
15.1 Introduction 630
15.2 Extrusion 631
15.3 Injection Molding 651
15.4 Fiber Spinning 667
15.5 Conclusion 680
References 680
Problems 684
Contents xvii
Copyright © 2003 Marcel Dekker, Inc.