1st Edition

Polymer Thermodynamics Blends, Copolymers and Reversible Polymerization

By Kal Renganathan Sharma Copyright 2012
    371 Pages 62 B/W Illustrations
    by CRC Press

    372 Pages 62 B/W Illustrations
    by CRC Press

    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.

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

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

    Binary Diffusion in Polymer Blends
    Introduction
    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
    Introduction
    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

    Index

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

    Biography

    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