FUNDAMENTALS OF Second Edition Revised and Expanded Anil Kumar Indian Institute of Technology Kanpur, India Rakesh K. Gupta West Virginia University Morgantown, West Virginia, U.S.A. MARCEL 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. Headquarters Marcel Dekker, Inc. 270 Madison Avenue, New York, NY 10016 tel: 212-696-9000; fax: 212-685-4540 Eastern Hemisphere Distribution Marcel Dekker AG Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland tel: 41-61-260-6300; fax: 41-61-260-6333 World Wide Web http:==www.dekker.com The publisher offers discounts on this book when ordered in bulk quantities. For more information, write to Special Sales=Professional Marketing at the headquarters address above. Copyright # 2003 by Marcel Dekker, Inc. All Rights Reserved. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher. Current printing (last digit): 10987654321 PRINTED IN THE UNITED STATES OF AMERICA Copyright © 2003 Marcel Dekker, Inc. PLASTICS ENGINEERING Founding Editor Donald E. Hudgin Professor Clemson University Clemson, South Carolina 1. Plastics Waste Recovery of Economic Value, Jacob Letdner 2 Polyester Molding Compounds, Robert Burns 3 Carbon Black-Polymer Composites The Physics of Electrically Conducting Composites, edited by Enid Keil Sichel 4 The Strength and Stiffness of Polymers, edited byAnagnostis £ Zachanades and RogerS Porter 5 Selecting Thermoplastics for Engineering Applications, Charles P Mac- Dermott 6 Engineering with Rigid PVC Processabihty and Applications, edited by I Luis Gomez 7 Computer-Aided Design of Polymers and Composites, D H Kaelble 8 Engineering Thermoplastics Properties and Applications, edited by James M Margolis 9 Structural Foam A Purchasing and Design Guide, Bruce C Wendle 10 Plastics in Architecture A Guide to Acrylic and Polycarbonate, Ralph Montella 11 Metal-Filled Polymers Properties and Applications, edited by Swapan K Bhattacharya 12 Plastics Technology Handbook, Manas Chanda and Salil K Roy 13 Reaction Injection Molding Machinery and Processes, F Melvin Sweeney 14 Practical Thermoforming Principles and Applications, John Flonan 15 Injection and Compression Molding Fundamentals, edited by Avraam I Isayev 16 Polymer Mixing and Extrusion Technology, Nicholas P Cheremismoff 17 High Modulus Polymers Approaches to Design and Development, edited by Anagnostis E Zachanades and Roger S Porter 18 Corrosion-Resistant Plastic Composites in Chemical Plant Design, John H Mallinson 19 Handbook of Elastomers New Developments and Technology, edited by Anil K Bhowmick and Howard L Stephens 20 Rubber Compounding Principles, Materials, and Techniques, Fred W Barlow 21 Thermoplastic Polymer Additives Theory and Practice, edited by John T Lutz, Jr 22 Emulsion Polymer Technology, Robert D Athey, Jr 23 Mixing in Polymer Processing, edited by Chns Rauwendaal 24 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 Bicerano 26. Plastics Technology Handbook: Second Edition, Revised and Expanded, Manas Chanda and Salil K. Roy 27. Prediction of Polymer Properties, Jozef Bicerano 28. Ferroelectric Polymers: Chemistry, Physics, and Applications, edited by Hari Singh Nalwa 29. Degradable Polymers, Recycling, and Plastics Waste Management, edited by Ann-Christine Albertsson and Samuel J. Huang 30. Polymer Toughening, edited by Charles B. Arends 31. Handbook of Applied Polymer Processing Technology, edited by Nicholas P. Cheremisinoff and Paul N. Cheremisinoff 32. Diffusion in Polymers, edited by P. Neogi 33. Polymer Devolatilization, edited by Ramon J. Albalak 34. Anionic Polymerization: Principles and Practical Applications, Henry L. Hsieh and Roderic P. Quirk 35. Cationic Polymerizations: Mechanisms, Synthesis, and Applications, edited by Krzysztof Matyjaszewski 36. Polyimides: Fundamentals and Applications, edited by Malay K. Ghosh and K. L. Mittal 37. Thermoplastic Melt Rheology and Processing, A. V. Shenoy and D. R. Saini 38. Prediction of Polymer Properties: Second Edition, Revised and Expanded, Jozef Bicerano 39. Practical Thermoforming: Principles and Applications, Second Edition, Revised and Expanded, John Florian 40. Macromolecular Design of Polymeric Materials, edited by Koichi Hatada, Tatsuki Kitayama, and Otto Vogl 41. Handbook of Thermoplastics, edited by Olagoke Olabisi 42. Selecting Thermoplastics for Engineering Applications: Second Edition, Revised and Expanded, Charles P. MacDermott and Aroon V. Shenoy 43. Metallized Plastics: Fundamentals and Applications, edited by K. L Mittal 44. Oligomer Technology and Applications, Constantin V. Uglea 45. 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 Takeo Araki, 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 Yusuf Yagci 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 Brown 51. Handbook of Polypropylene and Polypropylene Composites, edited by Har- utun G. Karian 52. Polymer Blends and Alloys, edited by Gabriel O. Shonaike and George P. Simon 53. Star and Hyperbranched Polymers, edited by Munmaya K. Mishra and Shi- ro Kobayashi 54. 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 G LeGrand and John T Bendler 57 Handbook of Polyethylene Structures, Properties, and Applications, Andrew J Peacock 58 Polymer and Composite Rheology Second Edition, Revised and Expanded, Rakesh K Gupta 59 Handbook of Polyolefms Second Edition Revised and Expanded, edited by Cornelia Vasile 60 Polymer Modification Principles, Techniques, and Applications, edited by John J Meister 61 Handbook of Elastomers Second Edition, Revised and Expanded, edited by Anil K Bhowmick and Howard L Stephens 62 Polymer Modifiers and Additives, edited by John T Lutz, Jr, and Richard F Grossman 63 Practical Injection Molding, Bernie A Olmstea and Martin E Davis 64 Thermosetting Polymers, Jean-Pierre Pascault, Henry Sautereau, Jacques Verdu, and Roberto J J Williams 65 Prediction of Polymer Properties Third Edition, Revised and Expanded, Jozef Bicerano 66 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 memor y of my father. Anil Kumar To the memor y 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 thermodyn amics, and the behavior of polymers as melts, solution s, 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 indispens able 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. [...]... Measures of Finite Strain The Stress Constitutive Equation Vulcanization of Rubber and Swelling Equilibrium Conclusion References Problems Polymer Crystallization 437 11 .1 11. 2 11 .3 11 .4 11 .5 11 .6 11 .7 11 .8 11 .9 11 .10 11 .11 437 443 447 450 456 459 462 464 467 479 480 4 81 484 Introduction Energetics of Phase Change Overall Crystallization Rate Empirical Rate Expressions: The Avrami Equation Polymer Crystallization... References Problems 17 5 18 1 18 1 Chain-Growth Polymerization 18 8 5 .1 5.2 5.3 5.4 5.5 5 18 8 19 2 19 7 19 9 5.6 5.7 5.8 5.9 5 .10 5 .11 5 .12 5 .13 5 .14 5 .15 5 .16 5 .17 6 Introduction Radical Polymerization Kinetic Model of Radical Polymerization Average Molecular Weight in Radical Polymerization Verification of the Kinetic Model and the Gel Effect in Radical Polymerization Equilibrium of Radical Polymerization Temperature... Problems 4 10 5 10 7 11 1 11 6 11 8 12 5 14 0 14 0 14 3 14 5 Reaction Engineering of Step-Growth Polymerization 15 3 4 .1 153 Introduction Copyright © 2003 Marcel Dekker, Inc Contents xiii 4.2 4.3 Analysis of Semibatch Reactors MWD of ARB Polymerization in Homogeneous Continuous-Flow Stirred-Tank Reactors 4.4 Advanced Stage of Polymerization 4.5 Conclusion Appendix 4 .1: Similarity Solution of Step-Growth Polymerization... Edition v vii Introduction 1 1 .1 1.2 1 1 1. 3 1. 4 1. 5 1. 6 1. 7 1. 8 Defining Polymers Classification of Polymers and Some Fundamental Concepts Chemical Classification of Polymers Based on Polymerization Mechanisms Molecular-Weight Distributions Configurations and Crystallinity of Polymeric Materials Conformation of Polymer Molecules Polymeric Supports in Organic Synthesis Conclusion 4 16 19 22 27 29 38 xi Copyright... Thermodynamics of Polymer Mixtures 374 9 .1 374 Introduction Copyright © 2003 Marcel Dekker, Inc Contents 9.2 9.3 9.4 9.5 9.6 9.7 10 xv Criteria for Polymer Solubility The Flory-Huggins Theory Free-Volume Theories The Solubility Parameter Polymer Blends Conclusion References Problems 376 379 396 398 4 01 403 403 405 407 10 .1 10.2 10 .3 10 .4 10 .5 10 .6 10 .7 10 .8 10 .9 11 Theory of Rubber Elasticity 407 408 415 418 ... and Composites Melting of Crystals Influence of Polymer Chain Extension and Orientation Polymers with Liquid-Crystalline Order Structure Determination Working with Semicrystalline Polymers Conclusion References Problems Copyright © 2003 Marcel Dekker, Inc xvi 12 Contents 487 12 .1 12.2 12 .3 12 .4 12 .5 12 .6 12 .7 12 .8 12 .9 13 Mechanical Properties 487 488 497 5 01 504 508 511 516 518 520 523 Introduction... Principle Dynamic Mechanical Properties Theories of Shear Viscosity Copyright © 2003 Marcel Dekker, Inc Contents 14 .9 14 .10 14 .11 15 xvii Constitutive Behavior of Dilute Polymer Solutions Constitutive Behavior of Concentrated Solutions and Melts Conclusion References Problems 605 615 622 622 626 Polymer Processing 630 15 .1 15.2 15 .3 15 .4 15 .5 630 6 31 6 51 667 680 680 684 Introduction Extrusion Injection... Superposition Polymer Fracture Crazing and Shear Yielding Fatigue Failure Improving Mechanical Properties References Problems Polymer Diffusion 526 13 .1 13.2 13 .3 13 .4 13 .5 13 .6 13 .7 13 .8 526 527 5 31 542 546 547 552 13 .9 13 .10 14 Introduction Fundamentals of Mass Transfer Diffusion Coefficient Measurement Diffusivity of Spheres at Infinite Dilution Diffusion Coefficient for Non-Theta Solutions Free-Volume Theory of. .. Olefin Polymerization Conclusion References Problems 15 6 16 6 16 9 17 4 2 01 210 215 216 222 226 230 232 233 238 240 242 244 244 248 Reaction Engineering of Chain-Growth Polymerization 255 6 .1 6.2 6.3 255 256 273 Introduction Design of Tubular Reactors Copolymerization Copyright © 2003 Marcel Dekker, Inc xiv Contents 6.4 Recycling and Degradation of Polymers 6.5 Conclusion Appendix 6 .1: Solution of Equations... Coefficient for Non-Theta Solutions Free-Volume Theory of Diffusion in Rubbery Polymers Gas Diffusion in Glassy Polymers Organic Vapor Diffusion in Glassy Polymers: Case II Diffusion Polymer- Polymer Diffusion Conclusion References Problems 557 560 564 565 569 Flow Behavior of Polymeric Fluids 573 14 .1 14.2 14 .3 14 .4 14 .5 14 .6 14 .7 14 .8 573 576 578 584 589 592 595 598 Introduction Viscometric Flows Cone-and-Plate . Inc. 9.2CriteriaforPolymerSolubility376 9.3TheFlory-HugginsTheory379 9.4Free-VolumeTheories396 9.5TheSolubilityParameter398 9.6PolymerBlends4 01 9.7Conclusion403 References403 Problems405 10 .TheoryofRubberElasticity407 10 .1Introduction407 10 .2ProbabilityDistributionfortheFreelyJointedChain408 10 .3ElasticForceBetweenChainEnds 415 10 .4Stress-StrainBehavior 418 10 .5TheStressTensor(Matrix)420 10 .6MeasuresofFiniteStrain423 10 .7TheStressConstitutiveEquation427 10 .8VulcanizationofRubberandSwellingEquilibrium429 10 .9Conclusion432 References433 Problems434 11 .PolymerCrystallization437 11 .1Introduction437 11 .2EnergeticsofPhaseChange443 11 .3OverallCrystallizationRate447 11 .4EmpiricalRateExpressions:TheAvramiEquation450 11 .5PolymerCrystallizationinBlendsandComposites456 11 .6MeltingofCrystals459 11 .7InfluenceofPolymerChainExtensionandOrientation462 11 .8PolymerswithLiquid-CrystallineOrder464 11 .9StructureDetermination467 11 .10 WorkingwithSemicrystallinePolymers479 11 .11 Conclusion480 References4 81 Problems484 Contentsxv Copyright. Inc. 9.2CriteriaforPolymerSolubility376 9.3TheFlory-HugginsTheory379 9.4Free-VolumeTheories396 9.5TheSolubilityParameter398 9.6PolymerBlends4 01 9.7Conclusion403 References403 Problems405 10 .TheoryofRubberElasticity407 10 .1Introduction407 10 .2ProbabilityDistributionfortheFreelyJointedChain408 10 .3ElasticForceBetweenChainEnds 415 10 .4Stress-StrainBehavior 418 10 .5TheStressTensor(Matrix)420 10 .6MeasuresofFiniteStrain423 10 .7TheStressConstitutiveEquation427 10 .8VulcanizationofRubberandSwellingEquilibrium429 10 .9Conclusion432 References433 Problems434 11 .PolymerCrystallization437 11 .1Introduction437 11 .2EnergeticsofPhaseChange443 11 .3OverallCrystallizationRate447 11 .4EmpiricalRateExpressions:TheAvramiEquation450 11 .5PolymerCrystallizationinBlendsandComposites456 11 .6MeltingofCrystals459 11 .7InfluenceofPolymerChainExtensionandOrientation462 11 .8PolymerswithLiquid-CrystallineOrder464 11 .9StructureDetermination467 11 .10 WorkingwithSemicrystallinePolymers479 11 .11 Conclusion480 References4 81 Problems484 Contentsxv Copyright. Inc. Contents PrefacetotheSecondEditionv PrefacetotheFirstEditionvii 1. Introduction1 1. 1DefiningPolymers1 1. 2ClassificationofPolymersandSomeFundamental Concepts4 1. 3ChemicalClassificationofPolymersBasedon PolymerizationMechanisms16 1. 4Molecular-WeightDistributions19 1. 5ConfigurationsandCrystallinityofPolymericMaterials22 1. 6ConformationofPolymerMolecules27 1. 7PolymericSupportsinOrganicSynthesis29 1. 8Conclusion38 xi Copyright