The Elements of Polymer Science and Engineering - 3rd Edition - ISBN: 9780123821782, 9780123821799

The Elements of Polymer Science and Engineering

3rd Edition

Authors: Alfred Rudin Phillip Choi
Hardcover ISBN: 9780123821782
eBook ISBN: 9780123821799
Imprint: Academic Press
Published Date: 14th December 2012
Page Count: 584
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The Elements of Polymer Science and Engineering, Third Edition, is a textbook for one- or two-semester introductory courses in polymer science and engineering taught primarily to senior undergraduate and first-year graduate students in a variety of disciplines, but primarily chemical engineering and materials science. Since the publication of the second edition in 1999, the field of polymers has advanced considerably. A key feature of this new edition is the inclusion of new concepts such as polymer nanocomposites and metallocene catalysts in existing chapters as well as new chapters covering selected contemporary topics such as behavior of natural polymers, polymer dynamics, and diffusion in polymers.

This book has been completely reorganized to become more aligned with how instructors currently teach the course. There are now several enhancements to the book’s pedagogy, including the addition of numerous worked examples and new figures to better illustrate key concepts and the addition of a large number of end-of-chapter exercises, many of which are based on recently published research and relevant industrial data.

This third edition will appeal to advanced undergraduate and graduate students in the physics, chemistry, and chemical engineering departments who are taking courses related to polymer science and engineering, as well as engineers new to the field of polymers.

Key Features

  • Focuses on applications of polymer chemistry, engineering, and technology
  • Explains terminology, applications, and versatility of synthetic polymers
  • Connects polymerization chemistry with engineering applications
  • Contains practical lead-ins to emulsion polymerization, viscoelasticity, and polymer rheology


Advanced undergraduate and graduate students in the physics, chemistry, and chemical engineering departments who are taking courses related to polymer science and engineering

Table of Contents



In Memoriam for Alfred Rudin (1924–2011)

Chapter 1. Introductory Concepts and Definitions

1.1 Some Definitions

1.2 Degree of Polymerization

1.3 Polymerization and Functionality

1.4 Why Are Synthetic Polymers Useful? [3]

1.5 Copolymers

1.6 Molecular Architecture

1.7 Thermoplastics and Thermosets

1.8 Elastomers, Fibers, and Plastics

1.9 Miscellaneous Terms

1.10 Polymer Nomenclature

1.11 Constitutional Isomerism

1.12 Configurational Isomerism

1.13 Polymer Conformation

1.14 Molecular Dimensions in the Amorphous State


Chapter 2. Basic Principles of Polymer Molecular Weights

2.1 Importance of Molecular Weight Control

2.2 Plan of This Chapter

2.3 Arithmetic Mean

2.4 Molecular Weight Averages as Ratios of Moments

2.5 Breadth of the Distribution

2.6 Summarizing the Molecular Weight Distribution


2.8 Integral and Summative Expressions

2.9 Typical Molecular Weight Distributions

Appendix 2A


Chapter 3. Practical Aspects of Molecular Weight Measurements

3.1 Methods

3.2 Light Scattering

3.3 Dilute Solution Viscometry

3.4 Size Exclusion Chromatography

Appendix 3A Multigrade Motor Oils [29]


Chapter 4. Mechanical Properties of Polymer Solids and Liquids

4.1 Introduction

4.2 Thermal Transitions

4.3 Crystallization of Polymers

4.4 The Glass Transition

4.5 Rubber Elasticity

4.6 Rodlike Macromolecules

4.7 Polymer Viscoelasticity

4.8 Dynamic Mechanical Behavior at Thermal Transitions

4.9 Stress–Strain Tests

4.10 Crazing in Glassy Polymers

4.11 Fracture Mechanics

4.12 Toughness and Brittleness

4.13 Rheology

4.14 Effects of Fabrication Processes


Chapter 5. Polymer Mixtures

5.1 Compatibility

5.2 Thermodynamic Theories

5.3 Solvents and Plasticizers

5.4 Fractionation

5.5 Practical Aspects of Polymer Blending [19]

5.6 Reinforced Elastomers

5.7 Reinforced Plastics


Chapter 6. Diffusion in Polymers

6.1 Introduction

6.2 Fick’s Laws

6.3 Diffusion Coefficients

6.4 Mutual Diffusion

6.5 Self-Diffusion of Polymer Chains in Dilute Polymer Solutions

6.6 Self-Diffusion of Solvent in Polymers


Chapter 7. Step-Growth Polymerizations

7.1 Condensation and Addition Polymers

7.2 Step-Growth and Chain-Growth Polymerizations

7.3 Requirements for Step-Growth Polymerization

7.4 Polymer Size and Extent of Conversion of Functional Groups in Equilibrium Step-Growth Polymerizations

7.5 Interfacial and Solution Polymerizations of Acid Chlorides and Other Reactive Monomers

7.6 Step-Growth Copolymerizations


Chapter 8. Free-Radical Polymerization

8.1 Scope

8.2 Polymerizability of Monomers

8.3 Overall Kinetics of Radical Polymerization

8.4 A Note on Termination Rate Constants

8.5 Methods of Producing Radicals

8.6 Length of the Kinetic Chain and Number Average Degree of Polymerization of the Polymer

8.7 Modes of Termination

8.8 Chain Transfer

8.9 Inhibition and Retardation

8.10 Readily Observable Features of Free-Radical Polymerizations

8.11 Radical Lifetimes and Concentrations

8.12 Determination of kp and kt

8.13 Deviations from Ideal Kinetics

8.14 Molecular Weight Distribution

8.15 Free-Radical Techniques for Polymers with Narrower Molecular Weight Distributions

8.16 Effects of Temperature

8.17 Free-Radical Polymerization Processes


Chapter 9. Copolymerization

9.1 Chain-Growth Copolymerization

9.2 Simple Copolymer Equation

9.3 Copolymer Structure Inferences from Reactivity Ratios

9.4 Azeotropic Compositions

9.5 Integrated Binary Copolymer Equation

9.6 Determination of Reactivity Ratios

9.7 Multicomponent Copolymerizations

9.8 Sequence Distribution in Copolymers

9.9 Gel Formation During Copolymerization and Cross-Linking [22]

9.10 Reactivities of Radicals and Monomers

9.11 Analysis of Reactivity Data

9.12 Effect of Reaction Conditions

9.13 Rates of Free-Radical Copolymerizations

9.14 Alternative Copolymerization Models


Chapter 10. Dispersion and Emulsion Polymerizations

10.1 Dispersion Polymerization

10.2 Emulsion Polymerization

10.3 Other Ingredients in Emulsion Recipes

10.4 Emulsion Polymerization Processes


Chapter 11. Ionic and Coordinated Polymerizations

11.1 Comparison of Ionic and Free-Radical Polymerizations

11.2 Anionic Polymerization

11.3 Group Transfer Polymerization

11.4 Cationic Polymerization

11.5 Coordination Polymerization

11.6 Olefin Metathesis Catalysts


Chapter 12. Polymer Reaction Engineering

12.1 Scope

12.2 Step-Growth Polymerizations

12.3 Chain-Growth Polymerizations

12.4 Homogeneous and Heterogeneous Polymerization Processes

12.5 Batch, Semibatch, and Continuous Processes

12.6 Polymerization Reactors


Chapter 13. Biopolymers

13.1 Introduction

13.2 Natural Polymers

13.3 Bio-Based Polymers (Bioplastics)

13.4 Biopolymer Blends and Biocomposites

13.5 Future of Bioplastic Products


Appendix A. Conversion of Units

Appendix B. List of Symbols



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About the Author

Alfred Rudin

Alfred Rudin is a member of the Professional Engineers of Ontario. Professor Rudin spent 14 years with a large Canadian chemical company in research, development, and production. He joined the University of Waterloo chemistry department where he is now a Distinguished Professor Emeritus. He is the author or co-author of 295 research papers and 25 patents. Dr. Rudin is also a fellow of the Chemical Institute of Canada, the Royal Society of Canada, and the Federation of Societies for Coatings Technology.

Affiliations and Expertise

University of Waterloo, Ontario, Canada

Phillip Choi

Prof. Phillip Choi received his B.A.Sc. in chemical engineering in 1988 from the University of British Columbia and his M.A.Sc. and Ph.D., also in chemical engineering, in 1992 and 1995, respectively, from the University of Waterloo. While pursuing his graduate studies, he received scholarships from the Federation of Societies for Coatings Technology and the Natural Sciences and Engineering Research Council of Canada to study solubility properties of non-ionic surfactants and polyolefin blends under the guidance of Professor Alfred Rudin and Dr. Tom Kavassalis of Xerox Corporation, currently VP – Strategy Planning.

Upon completion of his Ph.D., Prof. Choi worked in the coating industry as a development chemist developing high solids urethane and water-borne epoxy coating formulations. He then joined the Department of Chemical and Materials Engineering at the University of Alberta as a sessional instructor in 1996 and at the same time, carried out research in the area of polymer rheology in Prof. Michael Williams’ lab. In 1997, he became an assistant professor and was promoted to the rank of full professor in 2006. In the 2003/2004 academic year, Prof. Choi spent a one year sabbatical in Prof. Wayne L. Mattice’s lab of the Maurice Morton Institute of Polymer Science at the University of Akron studying crystallization behavior of polypropylene blends using the rotational isomeric state theory. Prof. Choi has supervised 9 postdoctoral fellows as well as 6 Ph.D., 8 M.Sc. and 30 B.Sc. theses over the past ten years.

Prof. Choi’s current research interests lie in the areas of molecular simulation of polymers, statistical thermodynamics of polymer solutions and blends, structure-property relationships of branched polyethylene and of block copolymers used in nanoscopic drug delivery systems and adsorption behaviour of polymer on inorganic surfaces. He has published over 100 book chapters, referred journal articles and conference proceedings and is constantly in demand as manuscript reviewer for major polymer and physical science journals and proposal reviewer for various Canadian and American funding agencies. Prof. Choi is also an active consultant to various multinational organizations on issues related to polymer product development. He is currently the chair of the Edmonton section of the Canadian Society for Chemical Engineering and a board of director of the Canadian Society for Chemical Engineering. He is a registered professional engineer in the province of Alberta.

Prof. Phillip Choi won the Faculty of Engineering Undergraduate Teaching Award and was named the McCalla Professorship in 2007 at the University of Alberta recognizing his dedication to undergraduate education. In particular, he has accumulated 13 years of experience teaching introductory polymer courses to senior undergraduate and first year graduate students. He received an international IUPAC Travel Award in 2002 and a National Young Innovator Award from Petro Canada Inc. in 2002 and 2001, respectively, recognizing his work on molecular simulation of polymers.

Affiliations and Expertise

Professor of Chemical Engineering, Department of Chemical & Materials Engineering, University of Alberta, Edmonton, AB, Canada


"The textbook has been a solid teaching text for introductory polymer science and engineering courses....It remains a very good textbook for many introductory concepts and is thought out and developed well for teaching purposes." --Eli Pearce, Polytechnicnic University, Brooklyn, NY, Polymer News, 1999