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Table of Contents:

• Machine generated contents note: 1. Glass Transitions in Amorphous Polymers: Basic Concepts
• 1.1. Phase Transitions in Amorphous Materials
• 1.2. Volume[–]Temperature and Enthalpy[–]Temperature Relations in the Vicinity of First-Order and Second-Order Phase Transitions: Discontinuous Thermophysical Properties at Tff, and Tg
• 1.3. Equilibrium Glassy State
• 1.4. Physical Aging, Densification, and Volume and Enthalpy Relaxation
• 1.5. Temperature[–]Pressure Differential Phase Equilibrium Relations for First-Order Processes: The Clapeyron Equation
• 1.6. Temperature[–]Pressure Differential Phase Equilibrium Relations for Second-Order Processes: The Ehrenfest Equations
• 1.7. Compositional Dependence of Tg via Entropy Continuity
• 1.8. Compositional Dependence of Tg via Volume Continuity
• 1.9. Linear Least Squares Analysis of the Gordon[–]Taylor Equation and Other Tg[–]Composition Relations for Binary Mixtures
• 1.10. Free Volume Concepts
• 1.11. Temperature Dependence of Fractional Free Volume
• 1.12. Compositional Dependence of Fractional Free Volume and Plasticizer Efficiency for Binary Mixtures
• 1.13. Fractional Free Volume Analysis of Multicomponent Mixtures: Compositional Dependence of the Glass Transition Temperature
• 1.14. Molecular Weight Dependence of Fractional Free Volume
• 1.15. Experimental Design to Test the Molecular Weight Dependence of Fractional Free Volume and Tg
• 1.16. Pressure Dependence of Fractional Free Volume
• 1.17. Effect of Particle Size or Film Thickness on the Glass Transition Temperature
• 1.18. Effect of the Glass Transition on Surface Tension
• References

• Problems
• 2. Diffusion in Amorphous Polymers Near the Glass Transition Temperature
• 2.1. Diffusion on a Lattice
• 2.2. Overview of the Relation Between Fractional Free Volume and Diffusive Motion of Liquids and Gases Through Polymeric Membranes
• 2.3. Free Volume Theory of Cohen and Turnbull for Diffusion in Liquids and Glasses
• 2.4. Free Volume Theory of Vrentas and Duda for Solvent Diffusion in Polymers Above the Glass Transition Temperature
• 2.5. Influence of the Glass Transition on Diffusion in Amorphous Polymers
• 2.6. Analysis of Half-Times and Lag Times via the Unsteady State Diffusion Equation
• 2.7. Example Problem: Effect of Molecular Weight Distribution Functions on Average Diffusivities
• References
• 3. Lattice Theories for Polymer[–]Small-Molecule Mixtures and the Conformational Entropy Description of the Glass Transition Temperature
• 3.1. Lattice Models in Thermodynamics
• 3.2. Membrane Osmometry and the Osmotic Pressure Expansion
• 3.3. Lattice Models for Athermal Mixtures with Excluded Volume
• 3.4. Flory[–]Huggins Lattice Theory for Flexible Polymer Solutions
• 3.5. Chemical Stability of Binary Mixtures
• 3.6. Guggenheim's Lattice Theory of Athermal Mixtures
• 3.7. Gibbs[–]DiMarzio Conformational Entropy Description of the Glass Transition for Tetrahedral Lattices
• 3.8. Lattice Cluster Theory Analysis of Conformational Entropy and the Glass Transition in Amorphous Polymers
• 3.9. Sanchez[–]Lacombe Statistical Thermodynamic Lattice Fluid Theory of Polymer[–]Solvent Mixtures
• Appendix: The Connection Between Exothermic Energetics and Volume Contraction of the Mixture
• References
• Problems
• 4. dc Electric Field Effects on First- and Second-Order Phase Transitions in Pure Materials and Binary Mixtures
• 4.1. Electric-Field-Induced Alignment and Phase Separation
• 4.2. Overview
• 4.3. Electric Field Effects on Low-Molecular-Weight Molecules and Their Mixtures
• 4.4. Electric Field Effects on Polymers and Their Mixtures
• 4.5. Motivation for Analysis of Electric Field Effects on Phase Transitions
• 4.6. Theoretical Considerations
• 4.7. Summary
• Appendix: Nomenclature
• References
• 5. Order Parameters for Glasses: Pressure and Compositional Dependence of the Glass Transition Temperature
• 5.1. Thermodynamic Order Parameters
• 5.2. Ehrenfest Inequalities: Two Independent Internal Order Parameters Identify an Inequality Between the Two Predictions for the Pressure Dependence of the Glass Transition Temperature
• 5.3. Compositional Dependence of the Glass Transition Temperature
• 5.4. Diluent Concentration Dependence of the Glass Transition Temperature via Classical Thermodynamics
• 5.5. Compositional Dependence of the Glass Transition Temperature via Lattice Theory Models
• 5.6. Comparison with Other Theories
• 5.7. Model Calculations
• 5.8. Limitations of the Theory
• References
• Problem
• 6. Macromolecule[–]Metal Complexes: Ligand Field Stabilization and Glass Transition Temperature Enhancement
• 6.1. Ligand Field Stabilization
• 6.2. Overview
• 6.3. Methodology of Transition-Metal Coordination in Polymeric Complexes
• 6.4. Pseudo-Octahedral d8 Nickel Complexes with Poly(4-vinylpyridine)
• 6.5. d6 Molybdenum Carbonyl Complexes with Poly(vinylamine) that I. Reduced Symmetry Above the Glass Transition Temperature .)
• 6.6. Cobalt, Nickel, and Ruthenium Complexes with Poly(4-vinylpyridine) and Poly(L-histidine) that Exhibit Reduced Symmetry in the Molten State
• 6.7. Total Energetic Requirements to Induce the Glass Transition via Consideration of the First-Shell Coordination Sphere in Transition Metal and Lanthanide Complexes
• 6.8. Summary
• 6.9. Epilogue
• Appendix: Physical Interpretation of the Parameters in the Kwei Equation for Synergistic Enhancement of the Glass Transition Temperature in Binary Mixtures
• References
• 7. Basic Concepts and Molecular Optical Anisotropy in Semicrystalline Polymers
• 7.1. Spherulitic Superstructure
• 7.2. Comments about Crystallization
• 7.3. Spherulitic Superstructures that Exhibit Molecular Optical Anisotropy
• 7.4. Interaction of a Birefringent Spherulite with Polarized Light
• 7.5. Interaction of Disordered Lamellae with Polarized Light
• 7.6. Interaction of Disordered Lamellae with Unpolarized Light
• 7.7. Molecular Optical Anisotropy of Random Coils and Rigid Rod-Like Polymers
• 7.8. Birefringence of Rubbery Polymers Subjected to External Force Fields
• 7.9. Chain Folding, Interspherulitic Connectivity, and Mechanical Properties of Semicrystalline Polymers
• References
• Problems
• 8. Crystallization Kinetics via Spherulitic Growth
• 8.1. Nucleation and Growth
• 8.2. Heterogeneous Nucleation and Growth Prior to Impingement
• 8.3. Avrami Equation for Heterogeneous Nucleation that Accounts for Impingement of Spherulites
• 8.4. Crystallization Kinetics and the Avrami Equation for Homogeneous Nucleation of Spherulites
• 8.5. Linear Least Squares Analysis of the Kinetics of Crystallization via the Generalized Avrami Equation
• 8.6. Half-Time Analysis of Crystallization Isotherms
• 8.7. Maximum Rate of Isothermal Crystallization
• 8.8. Thermodynamics and Kinetics of Homogeneous Nucleation
• 8.9. Temperature Dependence of the Crystallization Rate Constant
• 8.10. Optimum Crystallization Temperatures: Comparison Between Theory and Experiment
• 8.11. Energetics of Chain Folding in Semicrystalline Polymer[–]Polymer Blends that Exhibit Multiple Melting Endotherms
• 8.12. Melting Point Depression in Polymer[–]Polymer and Polymer[–]Diluent Blends that Contain a High-Molecular-Weight Semicrystalline Component
• References
• Problems
• 9. Experimental Analysis of Semicrystalline Polymers
• 9.1. Semicrystallinity
• 9.2. Differential Scanning Calorimetry: Thermograms of Small Molecules that Exhibit Liquid Crystalline Phase Transitions Below the Melting Point
• 9.3. Isothermal Analysis of Crystallization Exotherms via Differential Scanning Calorimetry
• 9.4. Kinetic Analysis of the Mass Fraction of Crystallinity via the Generalized Avrami Equation
• 9.5. Measurements of Crystallinity via Differential Scanning Calorimetry
• 9.6. Analysis of Crystallinity via Density Measurements
• 9.7. Pychnometry: Density and Thermal Expansion Coefficient
• Measurements of Liquids and Solids
• References
• Problems
• 10. Mechanical Properties of Viscoelastic Materials: Basic Concepts in Linear Viscoelasticity
• 10.1. Mathematical Models of
• Linear Viscoelasticity
• 10.2. Objectives
• 10.3. Simple Definitions of Stress, Strain, and Poisson's Ratio
• 10.4. Stress Tensor
• 10.5. Strain and Rate-of-Strain Tensors
• 10.6. Hooke's Law of Elasticity
• 10.7. Newton's Law of Viscosity
• 10.8. Simple Analogies Between Mechanical and Electrical Response
• 10.9. Phase Angle Difference Between Stress and Strain and Voltage and Current in Dynamic Mechanical and Dielectric Experiments
• 10.10. Maxwell's Viscoelastic Constitutive Equation
• 10.11. Integral Forms of Maxwell's Viscoelastic Constitutive Equation
• 10.12. Mechanical Model of Maxwell's Viscoelastic Constitutive Equation
• 10.13. Four Well-Defined Mechanical Experiments
• 10.14. Linear Response of the Maxwell Model during Creep Experiments
• 10.15. Creep Recovery of the Maxwell Model
• 10.16. Linear Response of the Maxwell Model during Stress Relaxation
• 10.17. Temperature Dependence of the Stress Relaxation Modulus and Definition of the Deborah Number
• 10.18. Other Combinations of Springs and Dashpots
• 10.19. Equation of Motion for the Voigt Model
• 10.20. Linear Response of the Voigt Model in Creep Experiments
• 10.21. Creep Recovery of the Voigt Model
• 10.22. Creep and Stress Relaxation for a Series Combination of Maxwell and Voigt Elements
• 10.23. Principle of Time-Temperature Superposition
• Contents note continued: 10.24. Stress Relaxation via the Equivalence Between Time and Temperature
• 10.25. Semi Theoretical Justification for the Empirical Form of the WLF Shift Factor aT(T; Teference)
• 10.26. Temperature Dependence of the Zero-Shear-Rate Polymer Viscosity via Fractional Free Volume and the Doolittle Equation
• 10.27. Apparent Activation Energy for aT and the Zero-Shear-Rate Polymer Viscosity
• 10.28. Comparison of the WLF Shift Factor aT at Different Reference Temperatures
• 10.29. Vogel's Equation for the Time-Temperature Shift Factor
• 10.30. Effect of Diluent Concentration on the WLF Shift Factor ac in Concentrated Polymer Solutions
• 10.31. Stress Relaxation Moduli via the Distribution of Viscoelastic Time Constants
• 10.32. Stress Relaxation Moduli and Terminal Relaxation Times
• 10.33. Critical Molecular Weight Required for Entanglement Formation
• 10.34. Zero-Shear-Rate Viscosity via the Distribution of Viscoelastic Relaxation Times
• 10.35. Boltzmann Superposition Integral for Linear Viscoelastic Response
• 10.36. Alternate Forms of the Boltzmann Superposition Integral for o- (t)
• 10.37. Linear Viscoelastic Application of the Boltzmann Superposition Principle: Elastic Free Recovery
• 10.38. Dynamic Mechanical Testing of Viscoelastic Solids via Forced Vibration Analysis of Time-Dependent Stress and Dynamic Modulus E* (t ; co)
• 10.39. Phasor Analysis of Dynamic Viscoelastic Experiments via Complex Variables
• 10.40. Fourier Transformation of the Stress Relaxation Modulus Yields Dynamic Moduli via Complex Variable Analysis
• 10.41. Energy Dissipation and Storage During Forced Vibration Dynamic Mechanical Experiments
• 10.42. Free Vibration Dynamic Measurements via the Torsion Pendulum
• Appendix A: Linear Viscoelasticity
• Appendix B: Finite Strain Concepts for Elastic Materials
• Appendix C: Distribution of Linear Viscoelastic Relaxation Times
• Further Reading
• References
• Problems
• 11. Nonlinear Stress Relaxation in Macromolecule[—]Metal Complexes
• 11.1. Nonlinear Viscoelasticity
• 11.2. Overview
• 11.3. Relevant Background Information about Palladium Complexes with Macromolecules that Contain Alkene Functional Groups
• 11.4. Effect of Palladium Chloride on the Stress[—]Strain Behavior of Triblock Copolymers Containing Styrene and Butadiene
• 11.5. Crosslinked Polymers and Limited Chain Extensibility
• 11.6. Nonlinear Stress Relaxation
• 11.7. Results from Stress Relaxation Experiments on Triblock Copolymers
• 11.8. Effect of Strain on Stress Relaxation
• 11.9. Time[—]Strain Separability of the Relaxation Function
• 11.10. Characteristic Length Scales for Cooperative Reorganization and the Effect of Strain on Viscoelastic Relaxation Times
• 11.11. Summary
• References
• 12. Kinetic Analysis of Molecular Weight Distribution Functions in Linear Polymers
• 12.1. All Chains Do Not Contain the Same Number of Repeat Units
• 12.2. "Most Probable Distribution" for Polycondensation Reactions: Statistical Considerations
• 12.3. Discrete versus Continuous Distributions for Condensation Polymerization
• 12.4. Degree of Polymerization for Polycondensation Reactions
• 12.5. Moments-Generating Functions for Discrete Distributions via z-Transforms
• 12.6. Kinetics, Molecular Weight Distributions, and Moments-Generating Functions for Free Radical Polymerizations
• 12.7. Anionic "Living" Polymerizations and the Poisson Distribution
• 12.8. Connection Between Laplace Transforms and the Moments-Generating Function for any Distribution in the Continuous Limit
• 12.9. Expansion of Continuous Distribution Functions via Orthogonal Laguerre Polynomials
• Appendix A: Unsteady State Batch Reactor Analysis of the Most Probable Distribution Function
• Appendix B: Mechanism and Kinetics of Alkene Hydrogenation Reactions via Transition-Metal Catalysts
• Appendix C: Alkene Dimerization and Transition-Metal Compatibilization of 1,2-Polybutadiene and cis-polybutadiene via Palladium(II) Catalysis: Organometallic Mechanism and Kinetics
• References
• Problems
• 13. Gaussian Statistics of Linear Chain Molecules and Crosslinked Elastomers
• 13.1. Gaussian Chains and Entropy Elasticity
• 13.2. Summary of Three-Dimensional Gaussian Chain Statistics
• 13.3. Vector Analysis of the Mean-Square End-to-End Chain Distance
• 13.4. One-Dimensional Random Walk Statistics via Bernoulli Trials and the Binomial Distribution
• 13.5. Extrapolation of One-Dimensional Gaussian Statistics to Three Dimensions
• 13.6. Properties of Three-Dimensional Gaussian Distributions and Their Moments-Generating Function
• 13.7. Mean-Square Radius of Gyration of Freely Jointed Chains
• 13.8. Mean-Square End-to-End Distance of Freely Rotating Chains
• 13.9. Characteristic Ratios and Statistical Segment Length
• 13.10. Excluded Volume and the Expansion Factor a for Real Chains in "Good" Solvents: Athermal Solutions
• 13.11. deGennes Scaling Analysis of Flory's Law for Real Chains in "Good" Solvents
• 13.12. Intrinsic Viscosity of Dilute Polymer Solutions and Universal Calibration Curves for Gel Permeation Chromatography
• 13.13. Scaling Laws for Intrinsic Viscosity and the Mark[–]Houwink Equation
• 13.14. Intrinsic Viscosities of Polystyrene and Poly(ethylene oxide)
• 13.15. Effect of pH During Dilute-Aqueous-Solution Preparation of Solid Films on the Glass Transition
• 13.16. deGennes Scaling Analysis of the Threshold Overlap Molar Density c* in Concentrated Polymer Solutions and the Concept of "Blobs"
• 13.17. Entropically Elastic Retractive Forces via Statistical Thermodynamics of Gaussian Chains
• Appendix: Capillary Viscometry
• References
• Problems
• 14. Classical and Statistical Thermodynamics of Rubber-Like Materials
• 14.1. Affine Deformation
• 14.2. Overview
• 14.3. Analogies
• 14.4. Classical Thermodynamic Analysis of the Ideal Equation of State for Retractive Force from Chapter 13
• 14.5. Analogous Development for the Effect of Sample Length on Internal Energy: The Concept of Ideal Rubber-Like Solids
• 14.6. Thermoelastic Inversion
• 14.7. Temperature Dependence of Retractive Forces that Accounts for Thermal Expansion
• 14.8. Derivation of Flory's Approximation for Isotropic Rubber-Like Materials that Exhibit No Volume Change upon Deformation
• 14.9. Statistical Thermodynamic Analysis of the Equation of State for Ideal Rubber-Like Materials
• 14.10. Effect of Biaxial Deformation at Constant Volume on Boltzmann's Entropy and Stress versus Strain
• 14.11. Effect of Isotropic Chain Expansion in "Good" Solvents on the Conformational Entropy of Linear Macromolecules due to Excluded Volume
• 14.12. Effect of Polymer[–]Solvent Energetics on Chain Expansion via the Flory[–]Huggins Lattice Model
• 14.13. Gibbs Free Energy Minimization Yields the Equilibrium Chain Expansion Factor
• Appendix A: Chemical or Diffusional Stability of Polymer[–]Solvent Mixtures
• Appendix B: Generalized Linear Least Squares Analysis for Second-Order Polynomials with One Independent Variable
• Appendix C: Linear versus Nonlinear Least Squares Dilemma
• References
• Problems
• 15. Molecular Dynamics via Magnetic Resonance, Viscoelastic, and Dielectric Relaxation Phenomena
• 15.1. Fluctuation[–]Dissipation
• 15.2. Overview
• 15.3. Brief Introduction to Quantum Statistical Mechanics
• 15.4. Ergodic Problem of Statistical Thermodynamics
• 15.5. NMR Relaxation via Spin Temperature Equilibration with the Lattice
• 15.6. Analysis of Spin[–]Lattice Relaxation Rates via Time-Dependent Perturbation Theory and the Density Matrix
• 15.7. Classical Description of Stress Relaxation via Autocorrelation of the End-to-End Chain Vector and the Fluctuation[–]Dissipation Theorem
• 15.8. Comparisons Among NMR, Mechanical, and Dielectric Relaxation via Molecular Motion in Polymeric Materials: Activated Rate Processes
• 15.9. Activation Energies for the Aging Process in Bisphenol-A Polycarbonate
• 15.10. Complex Impedance Analysis of Dielectric Relaxation Measurements via Electrical Analogs of the Maxwell and Voigt Models of Linear Viscoelastic Response
• 15.11. Thermally Stimulated Discharge
• Currents in Polarized Dielectric Materials
• 15.12. Summary
• References
• 16. Magnetic Spin Diffusion at the Nanoscale in Multiphase Polymers and Molecular Complexes
• 16.1. Magnetic Resonance
• 16.2. Overview
• 16.3. Spin-Diffusion Problem
• 16.4. Interdomain Communication via Magnetic Spin Diffusion: Description of the Modified Goldman[–]Shen Experiment
• 16.5. Materials
• 16.6. Magnetic Spin-Diffusion Experiments on Random Copolymers that Contain Disorganized Lamellae
• 16.7. Magnetic Spin-Diffusion Experiments on Triblock Copolymers that Contain Spherically Dispersed Hard Segments
• 16.8. Phenomenological Transient Diffusion Models for Two-Phase Systems with Spherical Polystyrene Domains in a Polybutadiene Matrix
• 16.9. Solid State NMR Analysis of Molecular Complexes
• 16.10. High-Resolution Solid State NMR Spectroscopy of PEO Molecular Complexes: Correlations with Phase Behavior
• 16.11. Carbon-13 Solid State NMR Spectroscopy: Laboratory Experiments and Data Analysis
• 16.12. Summary
• References.

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Author/Creator:

Belfiore, Laurence A.

Languages:

English

Language Notes:

Item content: English

Main Work:

Physical properties of macromolecules [by Belfiore, L.A.]

Subjects:

Polymers

Chemistry, Physical and theoretical

Genres:

Electronic book

General Notes:

Description based on print version record.
Includes bibliographical references and index.
Electronic reproduction. Palo Alto, Calif. Available via World Wide Web.

Physical Description:

1 online resource.

Digital Characteristics:

text file

Call Numbers:

QC173.4.P65 B45 2010eb

ISBNs:

0470551593 (electronic bk.)
9780470551592 (electronic bk.)

OCLC Numbers:

676969148

Other Control Numbers:

EBC698694 (source: MiAaPQ)