Polymer Thermodynamics Blends, Copolymers and Reversible Polymerization

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 BlendsHistory of Polymer BlendsFlory–Huggin’s Solution Theory—and BeyondMiscible Polymer BlendsPartially Miscible Polymer BlendsNatural PolymersPolymer Alloy Equation of State Theories for PolymersSmall Molecules and Large MoleculesPVT Relations for Polymeric LiquidsTait EquationFlory, Orwoll, and Vrij ModelPrigogine Square-Well Cell ModelLattice Fluid Model of Sanchez and Lacombe Negative Coefficient of Thermal Expansion Binary Interaction ModelIntroductionCompositional Window of Miscibility: Copolymer–HomopolymerCompositional Window of Miscibility: Copolymers with Common MonomersCompositional Window of Miscibility: Terpolymer System with Common MonomersCompositional Window of Miscibility: Terpolymer and Homopolymer System without Common MonomersSpinodal Curve from B Values and EOSCopolymer/Homopolymer Blends of AMS–AN/PVCCopolymer/Homopolymer Blends of AMS–AN with Other CopolymersIntramolecular Repulsion as Driving Force for Miscibility–Mean Field Approach Keesom Forces and Group Solubility Parameter ApproachHildebrandt Solubility ParameterHansen Three-Dimensional Solubility ParameterSpecific Interactions Phase BehaviorIntroductionLCST and UCSTCircular Envelope in Phase DiagramHourglass Behavior in Phase DiagramsMolecular Architecture Partially Miscible BlendsCommercial Blends That Are Partially MiscibleEntropy Difference Model (??Sm) Estimates of Change in Entropy of Mixing at Glass Transition, ??SmCopolymer and Homopolymer BlendSequence Distribution Effects on Miscibility Polymer NanocompositesIntroductionCommercial ProductsThermodynamic StabilityVision and RealitiesFullerenesCarbon Nanotubes (CNT)Morphology of CNTsNanostructuring OperationsPolymer Thin FilmsNanostructuring from Self-Assembly of Block CopolymersIntercalated and Exfoliated Nanocomposites Polymer AlloysIntroductionPC/ABS AlloysNylon/ABS AlloysPVC AlloysPolyolefin AlloysNatural Polymer Alloy Binary Diffusion in Polymer BlendsIntroductionDiffusion PhenomenaFick’s First and Second Laws of DiffusionSkylab Diffusion Demonstration ExperimentsBulk Motion, Molecular Motion, and Total Molar FluxStokes–Einstein Equation for Dilute SolutionsDiffusion in SolidsDiffusion Coefficient in PolymersTransient DiffusionDamped Wave Diffusion and RelaxationPeriodic Boundary Condition Copolymer CompositionIntroductionComposition for Random CopolymersComposition of Random TerpolymersReactivity RatiosMulticomponent Copolymerization—n Monomers Sequence Distribution of CopolymersDyad and Triad Probabilities in CopolymerDyad and Triad Probabilities in TerpolymersSequence Alignment in DNA and Protein Sequences Reversible PolymerizationHeat Effects during PolymerizationCeiling Temperature during Reversible PolymerizationSubcritical Oscillations during Thermal PolymerizationThermal Terpolymerization of Alphamethyl Styrene, Acrylonitrile, and StyreneReversible Copolymerization Appendix A: Maxwell’s RelationsAppendix B: Five Laws of ThermodynamicsAppendix C: Glass Transition TemperatureAppendix D: Statistical Distributions Index A Summary and References appear at the end of each chapter.

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.