Introduction to Physical Polymer Science

by Leslie H. Sperling

Overview

An Updated Edition of the Classic Text

Polymers constitute the basis for the plastics, rubber, adhesives, fiber, and coating industries. The Fourth Edition of Introduction to Physical Polymer Science acknowledges the industrial success of polymers and the advancements made in the field while continuing to deliver the comprehensive introduction to polymer science that made its predecessors classic texts.

The Fourth Edition continues its coverage of amorphous and crystalline materials, glass transitions, rubber elasticity, and mechanical behavior, and offers updated discussions of polymer blends, composites, and interfaces, as well as such basics as molecular weight determination. Thus, interrelationships among molecular structure, morphology, and mechanical behavior of polymers continue to provide much of the value of the book.

Newly introduced topics include:

• Nanocomposites, including carbon nanotubes and exfoliated montmorillonite clays
• The structure, motions, and functions of DNA and proteins, as well as the interfaces of polymeric biomaterials with living organisms
• The glass transition behavior of nano-thin plastic films

In addition, new sections have been included on fire retardancy, friction and wear, optical tweezers, and more.

Introduction to Physical Polymer Science, Fourth Edition provides both an essential introduction to the field as well as an entry point to the latest research and developments in polymer science and engineering, making it an indispensable text for chemistry, chemical engineering, materials science and engineering, and polymer science and engineering students and professionals.

Product Details

ISBN-13:	9781119103745
Publisher:	Wiley
Publication date:	02/02/2015
Sold by:	JOHN WILEY & SONS
Format:	eBook
Pages:	880
File size:	22 MB
Note:	This product may take a few minutes to download.

About the Author

Trained as a chemist, L. H. SPERLING is Professor Emeritus of both Chemical Engineering and Materials Science and Engineering at Lehigh University in Bethlehem, Pennsylvania. He remains active in consulting, speaking, and writing.

Read an Excerpt

Today, there are two main divisions in polymer science: polymer synthesis and polymer physics. While these are often integrated in one textbook to make a one-semester course, more and more colleges and universities are teaching polymer science in two semesters, making textbooks devoted to one-half or the other highly desirable. From another point of view, students interested primarily in chemical engineering, materials science and engineering, mechanical engineering, or physics often have little preparation or interest in synthesis, but a course emphasizing theory and properties is their meat. This book is dedicated to all of those students and faculty who are interested in the physical side of polymer science.

For a long time now, between one-third and one-half of the chemists, chemical engineers, and materials science and engineers graduates of all degree levels have been engaged in some aspects of polymer science and engineering. While this has been commented on many times, the reader is directed to C&EN, 77 (26), 57 (1999) for recent statistics. The question of who is really specializing in polymers hinges on who asks and who answers. Take a chemical engineer in charge of a certain factory. The question is asked, ``What do you consider your professional specialty? They may answer, ``I'm a process engineer.'' The questioner continues, ``And what do you manufacture?'' ``Why, we make polyester fibers, of course!'' Is such an individual actually a process engineer, a polymer engineer, or some of both? Similar questions and responses could involve a physical chemist researching the interfacial bonding forces in polymer blends. I have become conceited enough to believe that such individuals would benefit professionally by at least a course or two in polymer science and engineering.

Actually a new breed of scientist/engineer is emerging: those individuals who are being degreed directly in polymer science and engineering. There are now several departments around America offering this program. In addition there are over 30 inter-disciplinary polymer degree programs in America, focused on various centers and institutes. For example, at Lehigh University, we have the Center for Polymer Science and Engineering, offering the M.S., M.E., and Ph.D. degrees, with five departments participating: chemical engineering, chemistry, materials science and engineering, mechanical engineering, and physics. The departments of chemical engineering, chemistry, and materials science and engineering also offer an undergraduate minor in polymer science and engineering. Now, approximately one-half of all of the chemical engineering, chemistry, and materials departments around America offer at least one polymer course. Those interested in further statistics should contact the POLYED committee of the American Chemical Society.

A significant amount of new polymer research has been published since the second edition was finished in 1990, reflecting many key advances. The third edition has been given a general overhaul to incorporate these new findings, while deleting some outdated material. Many new example problems have been added throughout. Two new chapters have been added, polymer surfaces and interfaces, and multicomponent polymeric materials. With the added material, the instructor has several options. While it still is possible to teach substantially the whole book in one regular semester, the instructor may opt to emphasize one portion or the other to suit the student's interests and needs. Alternately, there is now ample material to provide two quarters worth of instruction.

Chapters 1 to 3 continue to be basic polymer science. Chapters 4 to 11 provide the bulk of physical polymer science fundamentals. Chapters 12 and 13, entirely new material, emphasize the new topics of polymer interfaces and multicomponent polymer materials. Chapter 14, about two-thirds new material, focuses on a range of modern topics, with some emphasis on applications. While this book emphasizes the subject of polymer physics, it is broader in outlook, covering aspects of polymer engineering and processing, materials science, and polymer history, while holding synthesis and kinetics to a minimum.

I want to take this opportunity to thank the many students who helped in proof-reading the various manuscripts. If I had to pay them even a nickel a correction, I would be a poor man! The result in each case, of course, is one fewer error that future students will have to endure. Many thanks must also be given to the Department of Chemical Engineering and the Department of Materials Science and Engineering, as well as the Materials Research Center and the Center for Polymer Science and Engineering. Special thanks must be given to Ms. Andrea Pressler, photographer par excellence, who provided many of the figures for the book. Special thanks are also due Ms. Gail Kriebel and her staff at the E. W. Fairchild--Martindale Library, who helped with literature searching, and provided me with a carrel.

L. H. Sperling
Bethlehem, Pennsylvania

Table of Contents

Preface to the Fourth Edition.

Preface to the First Edition.

Symbols and Definitions.

1. Introduction to Polymer Science.

1.1. From Little Molecules to Big Molecules.

1.2. Molecular Weight and Molecular Weight Distributions.

1.3. Major Polymer Transitions.

1.4. Polymer Synthesis and Structure.

1.5. Cross-Linking, Plasticizers, and Fillers.

1.6. The Macromolecular Hypothesis.

1.7. Historical Development of Industrial Polymers.

1.8. Molecular Engineering.

References.

General Reading.

Handbooks, Encyclopedias, and Dictionaries.

Web Sites.

Study Problems.

Appendix 1.1. Names for Polymers.

2. Chain Structure and Configuration.

2.1. Examples of Configurations and Conformations.

2.2. Theory and Instruments.

2.3. Stereochemistry of Repeating Units.

2.4. Repeating Unit Isomerism.

2.5. Common Types of Copolymers.

2.6. NMR in Modern Research.

2.7. Multicomponent Polymers.

2.8. Conformational States in Polymers.

2.9. Analysis of Polymers during Mechanical Strain.

2.10. Photophysics of Polymers.

2.11. Configuration and Conformation.

References.

General Reading.

Study Problems.

Appendix 2.1. Assorted Isomeric and Copolymer Macromolecules.

3. Dilute Solution Thermodynamics, Molecular Weights, and Sizes.

3.1. Introduction.

3.2. The Solubility Parameter.

3.3. Thermodynamics of Mixing.

3.4. Molecular Weight Averages.

3.5. Determination of the Number-Average Molecular Weight.

3.6. Weight-Average Molecular Weights and Radii of Gyration.

3.7. Molecular Weights of Polymers.

3.8. Intrinsic Viscosity.

3.9. Gel Permeation Chromatography.

3.10. Mass Spectrometry.

3.11. Instrumentation for Molecular Weight Determination.

3.12. Solution Thermodynamics and Molecular Weights.

References.

General Reading.

Study Problems.

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.

4.1. Phase Separation and Fractionation.

4.2. Regions of the Polymer-Solvent Phase Diagram.

4.3. Polymer-Polymer Phase Separation.

4.4. Diffusion and Permeability in Polymers.

4.5. Latexes and Suspensions.

4.6. Multicomponent and Multiphase Materials.

References.

General Reading.

Study Problems.

Appendix 4.1. Scaling Law Theories and Applications.

5. The Amorphous State.

5.1. The Amorphous Polymer State.

5.2. Experimental Evidence Regarding Amorphous Polymers.

5.3. Conformation of the Polymer Chain.

5.4. Macromolecular Dynamics.

5.5. Concluding Remarks.

References.

General Reading.

Study Problems.

Appendix 5.1. History of the Random Coil Model for Polymer Chains.

Appendix 5.2. Calculations Using the Diffusion Coefficient.

Appendix 5.3. Nobel Prize Winners in Polymer Science and Engineering.

6. The Crystalline State.

6.1. General Considerations.

6.2. Methods of Determining Crystal Structure.

6.3. The Unit Cell of Crystalline Polymers.

6.4. Structure of Crystalline Polymers.

6.5. Crystallization from the Melt.

6.6. Kinetics of Crystallization.

6.7. The Reentry Problem in Lamellae.

6.8. Thermodynamics of Fusion.

6.9. Effect of Chemical Structure on the Melting Temperature.

6.10. Fiber Formation and Structure.

6.11. The Hierarchical Structure of Polymeric Materials.

6.12. How Do You Know It's a Polymer?.

References.

General Reading.

Study Problems.

7. Polymers in the Liquid Crystalline State.

7.1. Definition of a Liquid Crystal.

7.2. Rod-Shaped Chemical Structures.

7.3. Liquid Crystalline Mesophases.

7.4. Liquid Crystal Classification.

7.5. Thermodynamics and Phase Diagrams.

7.6. Mesophase Identification in Thermotropic Polymers.

7.7. Fiber Formation.

7.8. Comparison of Major Polymer Types.

7.9. Basic Requirements for Liquid Crystal Formation.

References.

General Reading.

Study Problems.

8. Glass-Rubber Transition Behavior.

8.1. Simple Mechanical Relationships.

8.2. Five Regions of Viscoelastic Behavior.

8.3. Methods of Measuring Transitions in Polymers.

8.4. Other Transitions and Relaxations.

8.5. Time and Frequency Effects on Relaxation Processes.

8.6. Theories of the Glass Transition.

8.7. Effect of Molecular Weight on TG.

8.8. Effect of Copolymerization on TG.

8.9. Effect of Crystallinity on TG.

8.10. Dependence of TG on Chemical Structure.

8.11. Effect of Pressure on TG.

8.12. Damping and Dynamic Mechanical Behavior.

8.13. Definitions of Elastomers, Plastics, Adhesives, and Fibers.

References.

General Reading.

Study Problems.

Appendix 8.1. Molecular Motion near the Glass Transition.

9. Cross-linked Polymers and Rubber Elasticity.

9.1. Cross-links and Networks.

9.2. Historical Development of Rubber.

9.3. Rubber Network Structure.

9.4. Rubber Elasticity Concepts.

9.5. Thermodynamic Equation of State.

9.6. Equation of State for Gases.

9.7. Statistical Thermodynamics of Rubber Elasticity.

9.8. The "Carnot Cycle" for Elastomers.

9.9. Continuum Theories of Rubber Elasticity.

9.10. Some Refinements to Rubber Elasticity.

9.11. Internal Energy Effects.

9.12. The Flory-Rehner Equation.

9.13. Gelation Phenomena in Polymers.

9.14. Gels and Gelation.

9.15. Effects of Strain on the Melting Temperature.

9.16. Elastomers in Current Use.

9.17. Summary of Rubber Elasticity Behavior.

References.

General Reading.

Study Problems.

Appendix 9.1. Gelatin as a Physically Cross-linked Elastomer.

Appendix 9.2. Elastic Behavior of a Rubber Band.

Appendix 9.3. Determination of the Cross-link Density of Rubber by Swelling to Equilibrium.

10. Polymer Viscoelasticity and Rheology.

10.1. Stress Relaxation and Creep.

10.2. Relaxation and Retardation Times.

10.3. The Time-Temperature Superposition Principle.

10.4. Polymer Melt Viscosity.

10.5. Polymer Rheology.

10.6. Overview of Viscoelasticity and Rheology.

References.

General Reading.

Study Problems.

Appendix 10.1. Energy of Activation from Chemical Stress Relaxation Times.

Appendix 10.2. Viscoelasticity of Cheese.

11. Mechanical Behavior of Polymers.

11.1. An Energy Balance for Deformation and Fracture.

11.2. Deformation and Fracture in Polymers.

11.3. Crack Growth.

11.4. Cyclic Deformations.

11.5. Molecular Aspects of Fracture and Healing in Polymers.

11.6. Friction and Wear in Polymers.

11.7. Mechanical Behavior of Biomedical Polymers.

11.8. Summary.

References.

General Reading.

Study Problems.

12. Polymer Surfaces and Interfaces.

12.1. Polymer Surfaces.

12.2. Thermodynamics of Surfaces and Interfaces.

12.3. Instrumental Methods of Characterization.

12.4. Conformation of Polymer Chains in a Polymer Blend Interphase.

12.5. The Dilute Solution-Solid Interface.

12.6. Instrumental Methods for Analyzing Polymer Solution Interfaces.

12.7. Theoretical aspects of the Organization of Chains at Walls.

12.8. Adhesion at Interfaces.

12.9. Interfaces of Polymeric Biomaterials with Living Organisms.

12.10. Overview of Polymer Surface and Interface Science.

References.

General Reading.

Study Problems.

Appendix 12.1. Estimation of Fractal Dimensions.

13. Multicomponent Polymeric Materials.

13.1. Classification Schemes for Multicomponent Polymeric Materials.

13.2. Miscible and Immiscible Polymer Pairs.

13.3. The Glass Transition Behavior of Multicomponent Polymer Materials.

13.4. The Modulus of Multicomponent Polymeric Materials.

13.5. The Morphology of Multiphase Polymeric Materials.

13.6. Phase Diagrams in Polymer Blends (Broad Definition).

13.7. Morphology of Composite Materials.

13.8. Nanotechnology-Based Materials.

13.9. Montmorillonite Clays.

13.10. Fracture Behavior of Multiphase Polymeric Materials.

13.11. Processing and Applications of Polymer Blends and Composites.

References.

General Reading.

Study Problems.

14. Modern Polymer Topics.

14.1. Polyolefins.

14.2. Thermoset Polymer Materials.

14.3. Polymer and Polymer Blend Aspects of Bread Doughs.

14.4. Natural Product Polymers.

14.5. Dendritic Polymers and Other Novel Polymeric Structures.

14.6. Polymers in Supercritical Fluids.

14.7. Electrical Behavior of Polymers.

14.8. Polymers for Nonlinear Optics.

14.9. Light-Emitting Polymers and Electroactive Materials.

14.10. Optical Tweezers in Biopolymer Research.

14.11. The 3-D Structure and Function of Biopolymers.

14.12. Fire Retardancy in Polymers.

14.13. Polymer Solution-Induced Drag Reduction.

14.14. Modern engineering Plastics.

14.15. Major Advances in Polymer Science and Engineering.

References.

General Reading.

Study Problems.

Index.

Editorial Reviews

This third edition of a text and reference for students and professional chemists, chemical engineers, materials scientists, and polymer researchers emphasizes the interrelationships between molecular structure and the morphology and mechanical behavior of polymers, and incorporates new findings in processing and characterizing polymers. There are new chapters on polymer surfaces and polymer blends, and new discussions of solid-state nuclear magnetic resonance methods, self-assembled polymers, scaling law basics, and hyperbranched dendrimers. This new edition reflects current research in polyolefins, thermoset plastics, pyroelectric and piezoelectric polymers, and supercritical fluids. Many new worked examples and study problems have been added for this edition. Sperling teaches chemical engineering and materials science and engineering, and directs the Polymer Laboratory, Lehigh University. Annotation c. Book News, Inc., Portland, OR (booknews.com)

New edition of a textbook, with three new chapters plus additions to old ones bringing up-to-date information on polymers. Annotation c. Book News, Inc., Portland, OR (booknews.com)

Booknews

"Anyone in need of a basic text on polymer science would find this to be a very good choice, and it is highly recommended." (IEEE Electrical Insulation Magazine, January/February 2007)

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