Polymer Thermodynamics : Blends, Copolymers and Reversible Polymerization book cover
1st Edition

Polymer Thermodynamics
Blends, Copolymers and Reversible Polymerization

ISBN 9781138113497
Published June 14, 2017 by CRC Press
371 Pages 62 B/W Illustrations

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Book Description

Polymer Thermodynamics: Blends, Copolymers and Reversible Polymerization describes the thermodynamic basis for miscibility as well as the mathematical models used to predict the compositional window of miscibility and construct temperature versus volume-fraction phase diagrams. The book covers the binary interaction model, the solubility parameter approach, and the entropic difference model. Using equation of state (EOS) theories, thermodynamic models, and information from physical properties, it illustrates the construction of phase envelopes.

The book presents nine EOS theories, including some that take into account molecular weight effects. Characteristic values are given in tables. It uses the binary interaction model to predict the compositional window of miscibility for copolymer/homopolymer blends and blends of copolymers and terpolymers with common monomers. It discusses Hansen fractional solubility parameter values, six phase diagram types, the role of polymer architecture in phase behavior, and the mathematical framework for multiple glass transition temperatures found in partially miscible polymer blends. The author also illustrates biomedical and commercial applications of nanocomposites, the properties of various polymer alloys, Fick’s laws of diffusion and their implications during transient events, and the use of the dynamic programming method in the sequence alignment of DNA and proteins. The final chapter reviews the thermodynamics of reversible polymerization and copolymerization.

Polymer blends offer improved performance/cost ratios and the flexibility to tailor products to suit customers’ needs. Exploring physical phenomena, such as phase separation, this book provides readers with methods to design polymer blends and predict the phase behavior of binary polymer blends using desktop computers.

Table of Contents

Introduction to Polymer Blends
History of Polymer Blends
Flory–Huggin’s Solution Theory—and Beyond
Miscible Polymer Blends
Partially Miscible Polymer Blends
Natural Polymers
Polymer Alloy

Equation of State Theories for Polymers
Small Molecules and Large Molecules
PVT Relations for Polymeric Liquids
Tait Equation
Flory, Orwoll, and Vrij Model
Prigogine Square-Well Cell Model
Lattice Fluid Model of Sanchez and Lacombe
Negative Coefficient of Thermal Expansion

Binary Interaction Model
Compositional Window of Miscibility: Copolymer–Homopolymer
Compositional Window of Miscibility: Copolymers with Common Monomers
Compositional Window of Miscibility: Terpolymer System with Common Monomers
Compositional Window of Miscibility: Terpolymer and Homopolymer System without Common Monomers
Spinodal Curve from B Values and EOS
Copolymer/Homopolymer Blends of AMS–AN/PVC
Copolymer/Homopolymer Blends of AMS–AN with Other Copolymers
Intramolecular Repulsion as Driving Force for Miscibility–Mean Field Approach

Keesom Forces and Group Solubility Parameter Approach
Hildebrandt Solubility Parameter
Hansen Three-Dimensional Solubility Parameter
Specific Interactions

Phase Behavior
Circular Envelope in Phase Diagram
Hourglass Behavior in Phase Diagrams
Molecular Architecture

Partially Miscible Blends
Commercial Blends That Are Partially Miscible
Entropy Difference Model (ΔΔSm)
Estimates of Change in Entropy of Mixing at Glass Transition, ΔΔSm
Copolymer and Homopolymer Blend
Sequence Distribution Effects on Miscibility

Polymer Nanocomposites
Commercial Products
Thermodynamic Stability
Vision and Realities
Carbon Nanotubes (CNT)
Morphology of CNTs
Nanostructuring Operations
Polymer Thin Films
Nanostructuring from Self-Assembly of Block Copolymers
Intercalated and Exfoliated Nanocomposites

Polymer Alloys
PC/ABS Alloys
Nylon/ABS Alloys
PVC Alloys
Polyolefin Alloys
Natural Polymer Alloy

Binary Diffusion in Polymer Blends
Diffusion Phenomena
Fick’s First and Second Laws of Diffusion
Skylab Diffusion Demonstration Experiments
Bulk Motion, Molecular Motion, and Total Molar Flux
Stokes–Einstein Equation for Dilute Solutions
Diffusion in Solids
Diffusion Coefficient in Polymers
Transient Diffusion
Damped Wave Diffusion and Relaxation
Periodic Boundary Condition

Copolymer Composition
Composition for Random Copolymers
Composition of Random Terpolymers
Reactivity Ratios
Multicomponent Copolymerization—n Monomers

Sequence Distribution of Copolymers
Dyad and Triad Probabilities in Copolymer
Dyad and Triad Probabilities in Terpolymers
Sequence Alignment in DNA and Protein Sequences

Reversible Polymerization
Heat Effects during Polymerization
Ceiling Temperature during Reversible Polymerization
Subcritical Oscillations during Thermal Polymerization
Thermal Terpolymerization of Alphamethyl Styrene, Acrylonitrile, and Styrene
Reversible Copolymerization

Appendix A: Maxwell’s Relations
Appendix B: Five Laws of Thermodynamics
Appendix C: Glass Transition Temperature
Appendix D: Statistical Distributions


A Summary and References appear at the end of each chapter.

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Kal Renganathan Sharma, PE, is an adjunct professor in the Department of Chemical Engineering at Prairie View A&M University in Texas. He earned his Ph.D. in chemical engineering from West Virginia University. Dr. Sharma has published numerous journal articles and conference papers and is listed in Who’s Who in America.


The morphology of materials is a fascinating field and structure-related properties are of key interest in product development and process engineering, resulting in materials with advanced performance in sustainable, environmentally friendly applications. … This text is a welcome and highly effective response to this challenge that must be met if we are to develop the sustainable technologies we shall certainly need to survive into the next century.
—From the Foreword by Harold Kroto, Department of Chemistry and Biochemistry, Florida State University, Tallahassee, USA