Introduction to Physical Polymer Science

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; and 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.

 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. 1.2.1. Effect on Tensile Strength. 1.2.2. Molecular Weight Averages. 1.3. Major Polymer Transitions. 1.4. Polymer Synthesis and Structure. 1.4.1. Chain Polymerization. 1.4.1.1. Free Radical Polymerization. 1.4.1.2. Initiation. 1.4.1.3. Propagation. 1.4.1.4. Termination. 1.4.1.5. Structure and Nomenclature. 1.4.2. Step Polymerization. 1.4.2.1. A Polyester Condensation Reaction. 1.4.2.2. Stepwise Nomenclature and Structures. 1.4.2.3. Natural Product Polymers. 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. 2.1.1. Head-to-Head and Head-to-Tail Configurations. 2.1.2. Trans-Gauche Conformations. 2.2. Theory and Instruments. 2.2.1. Chemical Methods of Determining Microstructure. 2.2.2. General Physical Methods. 2.2.3. Infrared and Raman Spectroscopic Characterization. 2.2.4. Nuclear Magnetic Resonance Methods. 2.3. Stereochemistry of Repeating Units. 2.3.1. Chiral Centers. 2.3.2. Tacticity in Polymers. 2.3.3. Meso- and Racemic Placements. 2.3.4. Proton Spectra by NMR. 2.4. Repeating Unit Isomerism. 2.4.1. Optical Isomerism. 2.4.2. Geometric Isomerism. 2.4.3. Substitutional Isomerism. 2.4.4. Infrared and Raman Spectroscopic Characterization. 2.5. Common Types of Copolymers. 2.5.1. Unspecified Copolymers. 2.5.2. Statistical Copolymers. 2.5.3. Random copolymers. 2.5.4. Alternating Copolymers. 2.5.5. Periodic Copolymers. 2.6. NMR in Modern Research. 2.6.1. Dilute Solution Studies: Mer Distribution. 2.6.2. High-Resolution NMR in the Solid State. 2.7. Multicomponent Polymers. 2.7.1. Block Copolymers. 2.7.2. Graft Copolymers. 2.7.3. AB-Cross-linked Copolymers. 2.7.4. Interpenetrating Polymer Networks. 2.7.5. Other Polymer-Polymer Combinations. 2.7.6. Separation and Identification of Multicomponent Polymers. 2.8. Conformational States in Polymers. 2.9. Analysis of Polymers during Mechanical Strain. 2.10. Photophysics of Polymers. 2.10.1. Quenching Phenomena. 2.10.2. Excimer Formation. 2.10.3. Experimental Studies. 2.10.3.1. Microstructure of Polystyrene. 2.10.3.2. Excimer Stability. 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. 3.1.1. Polymer Size and Shape. 3.1.2. How Does a Polymer Dissolve?. 3.2. The Solubility Parameter. 3.2.1. Solubility Parameter Tables. 3.2.2. Experimental Determination. 3.2.3. Theoretical Calculation: An Example. 3.3. Thermodynamics of Mixing. 3.3.1. Types of Solutions. 3.3.1.1. The Ideal Solution. 3.3.1.2. Statistical Thermodynamics of Mixing. 3.3.1.3. Other Types of Solutions. 3.3.2. Dilute Solutions. 3.3.3. Values of the Flory-Huggins c1 Parameter. 3.3.4. A Worked Example for the Free Energy of Mixing. 3.4. Molecular Weight Averages. 3.5. Determination of the Number-Average Molecular Weight. 3.5.1. End-Group Analyses. 3.5.2 Colligative Properties. 3.5.3. Osmotic Pressure. 3.5.3.1. Thermodynamic Basis. 3.5.3.2. Instrumentation. 3.5.3.3. The Flory q-Temperature. 3.6. Weight-Average Molecular Weights and Radii of Gyration. 3.6.1. Scattering Theory and Formulations. 3.6.2. The Appropriate Angular Range. 3.6.3. The Zimm Plot. 3.6.4. Polymer Chain Dimensions and Random Coils. 3.6.5. Scattering Data. 3.6.6. Dynamic Light-Scattering. 3.7. Molecular Weights of Polymers. 3.7.1. Molecular Weights of Polymers. 3.7.2. Thermodynamics and Kinetics of Polymerization. 3.7.2.1. Thermodynamics of Chain Polymerization. 3.7.2.2. Kinetics of Chain Polymerization. 3.7.2.3. Thermodynamics of Step Polymerization. 3.7.2.4. Kinetics of Step Polymerizations. 3.7.3. Molecular Weight Distributions. 3.7.4. Gelation and Network Formation. 3.8. Intrinsic Viscosity. 3.8.1. Definition of Terms. 3.8.2. The Equivalent Sphere Model. 3.8.3. The Mark-Houwink Sakurada Relationship. 3.8.4. Intrinsic Viscosity Experiments. 3.8.5. Example Calculation Involving Intrinsic Viscosity. 3.9. Gel Permeation Chromatography. 3.9.1. Theory of Gel Permeation Chromatography. 3.9.2. Utilization of Distribution Coefficients in GPC and HPLC. 3.9.3. Types of Chromatography. 3.9.4. GPC Instrumentation. 3.9.5. Calibration. 3.9.6. Selected Current Research Problems. 3.9.7. The Universal Calibration. 3.9.8. Properties of Cyclic Polymers. 3.10. Mass Spectrometry. 3.10.1. High Molecular Weight Studies. 3.10.2. Advances Using MALDI Techniques. 3.10.2.1. Small Sample Size. 3.10.2.2. Oligomer and Telomer-Type Studies. 3.10.2.3. Calibration of Results. 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. 4.1.1. Motor Oil Viscosity Example. 4.1.2. Polymer-Solvent Systems. 4.1.3. Vitrification Effects. 4.2. Regions of the Polymer-Solvent Phase Diagram. 4.3. Polymer-Polymer Phase Separation. 4.3.1. Phase Diagrams. 4.3.2. Thermodynamics of Phase Separation. 4.3.3. An Example Calculation: Molecular Weight Miscibility Limit. 4.3.4. Equation of State Theories. 4.3.5. Kinetics of Phase Separation. 4.3.6. Miscibility in Statistical Copolymer Blends. 4.3.7. Polymer Blend Characterization. 4.3.8. Graft Copolymers and IPNs. 4.3.9. Block Copolymers. 4.3.10. Example Calculations with Block Copolymers. 4.3.11. Ionomers. 4.4. Diffusion and Permeability in Polymers. 4.4.1. Swelling Phenomena. 4.4.2. Fick's Laws. 4.4.3. Permeability Units. 4.4.4. Permeability Data. 4.4.5. Effect of Permeant Size. 4.4.6. Permselectivity of Polymeric Membranes and Separations. 4.4.6.1. Types of Membranes. 4.4.6.2. Gas Separations. 4.4.7. Gas Permeability in Polymer Blends. 4.4.8. Fickian and Non-Fickian Diffusion. 4.4.9. Controlled Drug Delivery via Diffusion. 4.4.9.1. Methods of Incorporating Drugs into Polymers. 4.4.9.2. Drug Diffusion Kinetics. 4.4.9.3. Design of Transdermal Delivery Systems. 4.5. Latexes and Suspensions. 4.5.1. Natural Rubber Latex. 4.5.2. Colloidal stability and Film Formation. 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. 5.1.1. Solids and Liquids. 5.1.2. Possible Residual Order in Amorphous Polymers?. 5.2. Experimental Evidence Regarding Amorphous Polymers. 5.2.1. Short-Range Interactions in Amorphous Polymers. 5.2.2. Long-Range Interactions in Amorphous Polymers. 5.2.2.1. Small-Angle Neutron Scattering. 5.2.2.2. Electron and X-Ray Diffraction. 5.2.2.3. General Properties. 5.3. Conformation of the Polymer Chain. 5.3.1. Models and Ideas. 5.3.1.1. The Freely Jointed Chain. 5.3.1.2. Kuhn Segments. 5.3.2. The Random Coil. 5.3.3. Models of Polymer Chains in the Bulk Amorphous State. 5.4. Macromolecular Dynamics. 5.4.1. The Rouse-Bueche Theory. 5.4.2. Reptation and Chain Motion. 5.4.2.1. The de Gennes Reptation Theory. 5.4.2.2. Fickian and Non-Fickian Diffusion. 5.4.3. Nonlinear Chains. 5.4.4. Experimental Methods of Determining Diffusion Coefficients. 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. 6.1.1. Historical Aspects. 6.1.2. Melting Phenomena. 6.1.3. Example Calculation of Percent Crystallinity. 6.2. Methods of Determining Crystal Structure. 6.2.1. A Review of Crystal Structure. 6.2.2. X-Ray methods. 6.2.3. Electron Diffraction of Single Crystals. 6.2.4. Infrared Absorption. 6.2.5. Raman Spectra. 6.3. The Unit Cell of Crystalline Polymers. 6.3.1. Polyethylene. 6.3.2. Other Polyolefin Polymers. 6.3.3. Polar Polymers and Hydrogen Bonding. 6.3.4. Polymorphic Forms of Cellulose. 6.3.5. Principles of Crystal Structure Determination. 6.4. Structure of Crystalline Polymers. 6.4.1. The Fringed Micelle Model. 6.4.2. Polymer Single Crystals. 6.4.2.1. The Folded-Chain Model. 6.4.2.2. The Switchboard Model. 6.5. Crystallization from the Melt. 6.5.1. Spherulitic Morphology. 6.5.2. Mechanism of Spherulite Formation. 6.5.3. Spherulites in Polymer Blends and Block Copolymers. 6.5.4. Percent Crystallinity in Polymers. 6.6. Kinetics of Crystallization. 6.6.1. Experimental Observations of Crystallization Kinetics. 6.6.2. Theories of Crystallization Kinetics. 6.6.2.1. The Avrami Equation. 6.6.2.2. Keith-Padden Kinetics of Spherulitic Crystallization. 6.6.2.3. Hoffman's Nucleation Theory. 6.6.2.4. Example Calculation of the Fold Surface Free Energy. 6.6.2.5. Three Regimes of Crystallization Kinetics. 6.6.3. Analysis of the Three Crystallization Regimes. 6.6.3.1. Kinetics of Crystallization. 6.6.3.2. Experimental Data on Regimes I, II, and III. 6.6.3.3. Changes in Crystal Growth Habit. 6.6.4. The Entropic Barrier Theory. 6.7. The Reentry Problem in Lamellae. 6.7.1. Infrared Spectroscopy. 6.7.2. Carbon-13 NMR. 6.7.3. Small-Angle Neutron Scattering. 6.7.3.1. Single-Crystal Studies. 6.7.3.2. Melt-Crystallized Polymers. 6.7.4. Extended Chain Crystals. 6.8. Thermodynamics of Fusion. 6.8.1. Theory of Melting Point Depression. 6.8.2. Example Calculation of Melting Point Depression. 6.8.3. Experimental Thermodynamic Parameters. 6.8.4. Entropy of Melting. 6.8.5. The Hoffman-Weeks Equilibrium Melting Temperature. 6.9. Effect of Chemical Structure on the Melting Temperature. 6.10. Fiber Formation and Structure. 6.10.1. X-Ray Fiber Diagrams. 6.10.2. Natural Fibers. 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. 7.3.1. Mesophase Topologies. 7.3.2. Phase Diagrams. 7.3.3. First-Order Transitions. 7.4. Liquid Crystal Classification. 7.4.1. Lyotropic Liquid Crystalline Chemical Structures. 7.4.2. Thermotropic Liquid Crystalline Chemical Structures. 7.4.3. Side-Chain Liquid Crystalline Chemical Structures. 7.5. Thermodynamics and Phase Diagrams. 7.5.1. Historical Aspects. 7.5.2. Importance of the c1 Parameter. 7.6. Mesophase Identification in Thermotropic Polymers. 7.7. Fiber Formation. 7.7.1. Viscosity of Lyotropic Solutions. 7.7.2. Molecular Orientation. 7.8. Comparison of Major Polymer Types. 7.8.1. Molecular Conformation. 7.8.2. Properties in bulk. 7.9. Basic Requirements for Liquid Crystal Formation. References. General Reading. Study Problems. 8. Glass-Rubber Transition Behavior. 8.1. Simple Mechanical Relationships. 8.1.1. Modulus. 8.1.1.1. Young's Modulus. 8.1.1.2. Shear Modulus. 8.1.2. Newton's Law. 8.1.3. Poisson's Ratio. 8.1.4. The Bulk Modulus and Compressibility. 8.1.5. Relationships among E, G, B, and n. 8.1.6. Compliance versus Modulus. 8.1.7. Numerical Values for E. 8.1.8. Storage and Loss Moduli. 8.1.9. Elongational Viscosity. 8.2. Five Regions of Viscoelastic Behavior. 8.2.1. The Glassy Region. 8.2.2. The Glass Transition Region. 8.2.3. The Rubbery Plateau Region. 8.2.4. The Rubbery Flow Region. 8.2.5. The Liquid flow Region. 8.2.6. Effect of Plasticizers. 8.2.7. Definitions of the Terms "Transition," "Relaxation," and "Dispersion". 8.2.8. Melt Viscosity Relationships Near TG. 8.2.9. Dynamic Mechanical Behavior through the Five Regions. 8.3. Methods of Measuring Transitions in Polymers. 8.3.1. Dilatometry Studies. 8.3.2. Thermal Methods. 8.3.3. Mechanical Methods. 8.3.4. Dielectric and Magnetic Methods. 8.3.5. A Comparison of the Methods. 8.3.6. The Cole-Cole Plot. 8.4. Other Transitions and Relaxations. 8.4.1. The Schatzki Crankshaft Mechanism. 8.4.1.1. The Main-Chain Motions. 8.4.1.2. Side-Chain Motions. 8.4.2. The Tll Transition. 8.5. Time and Frequency Effects on Relaxation Processes. 8.5.1. Time Dependence in Dilatometric Studies. 8.5.2. Time Dependence in Mechanical Relaxation Studies. 8.5.3. Frequency Effects in Dynamic Experiments. 8.6. Theories of the Glass Transition. 8.6.1. The Free-Volume Theory. 8.6.1.1. TG as an ISO-Free-Volume State. 8.6.1.2. The WLF Equation. 8.6.1.3. An Example of WLF Calculations. 8.6.2. The Kinetic Theory of the Glass Transition. 8.6.2.1. Estimations of the Free-Volume Hole Size in Polymers. 8.6.2.2. Positron Annihilation Lifetime Spectroscopy. 8.6.3. Thermodynamic Theory of TG. 8.6.3.1. The Gibbs and DiMarzio Theory. 8.6.3.2. Effect of Cross-Link Density on TG. 8.6.3.3. A Summary of the Glass Transition Theories. 8.6.3.4. A Unifying Treatment. 8.7. Effect of Molecular Weight on TG. 8.7.1. Linear Polymers. 8.7.2. Effect of TG on Polymerization. 8.8. Effect of Copolymeriza