Introduction to Physical Polymer Science
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"Anyone in need of a basic text on polymer science would find this to be a very good choice, and it is highly recommended." (IEEE Electrical Insulation Magazine, January/February 2007)More details
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Content
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.
1.3. Major Polymer Transitions.
1.4. Polymer Synthesis and Structure.
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.
2.2. Theory and Instruments.
2.3. Stereochemistry of Repeating Units.
2.4. Repeating Unit Isomerism.
2.5. Common Types of Copolymers.
2.6. NMR in Modern Research.
2.7. Multicomponent Polymers.
2.8. Conformational States in Polymers.
2.9. Analysis of Polymers during Mechanical Strain.
2.10. Photophysics of Polymers.
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.
3.2. The Solubility Parameter.
3.3. Thermodynamics of Mixing.
3.4. Molecular Weight Averages.
3.5. Determination of the Number-Average Molecular Weight.
3.6. Weight-Average Molecular Weights and Radii of Gyration.
3.7. Molecular Weights of Polymers.
3.8. Intrinsic Viscosity.
3.9. Gel Permeation Chromatography.
3.10. Mass Spectrometry.
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.
4.2. Regions of the Polymer-Solvent Phase Diagram.
4.3. Polymer-Polymer Phase Separation.
4.4. Diffusion and Permeability in Polymers.
4.5. Latexes and Suspensions.
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.
5.2. Experimental Evidence Regarding Amorphous Polymers.
5.3. Conformation of the Polymer Chain.
5.4. Macromolecular Dynamics.
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.
6.2. Methods of Determining Crystal Structure.
6.3. The Unit Cell of Crystalline Polymers.
6.4. Structure of Crystalline Polymers.
6.5. Crystallization from the Melt.
6.6. Kinetics of Crystallization.
6.7. The Reentry Problem in Lamellae.
6.8. Thermodynamics of Fusion.
6.9. Effect of Chemical Structure on the Melting Temperature.
6.10. Fiber Formation and Structure.
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.
7.4. Liquid Crystal Classification.
7.5. Thermodynamics and Phase Diagrams.
7.6. Mesophase Identification in Thermotropic Polymers.
7.7. Fiber Formation.
7.8. Comparison of Major Polymer Types.
7.9. Basic Requirements for Liquid Crystal Formation.
References.
General Reading.
Study Problems.
8. Glass-Rubber Transition Behavior.
8.1. Simple Mechanical Relationships.
8.2. Five Regions of Viscoelastic Behavior.
8.3. Methods of Measuring Transitions in Polymers.
8.4. Other Transitions and Relaxations.
8.5. Time and Frequency Effects on Relaxation Processes.
8.6. Theories of the Glass Transition.
8.7. Effect of Molecular Weight on TG.
8.8. Effect of Copolymerization on TG.
8.9. Effect of Crystallinity on TG.
8.10. Dependence of TG on Chemical Structure.
8.11. Effect of Pressure on TG.
8.12. Damping and Dynamic Mechanical Behavior.
8.13. Definitions of Elastomers, Plastics, Adhesives, and Fibers.
References.
General Reading.
Study Problems.
Appendix 8.1. Molecular Motion near the Glass Transition.
9. Cross-linked Polymers and Rubber Elasticity.
9.1. Cross-links and Networks.
9.2. Historical Development of Rubber.
9.3. Rubber Network Structure.
9.4. Rubber Elasticity Concepts.
9.5. Thermodynamic Equation of State.
9.6. Equation of State for Gases.
9.7. Statistical Thermodynamics of Rubber Elasticity.
9.8. The "Carnot Cycle" for Elastomers.
9.9. Continuum Theories of Rubber Elasticity.
9.10. Some Refinements to Rubber Elasticity.
9.11. Internal Energy Effects.
9.12. The Flory-Rehner Equation.
9.13. Gelation Phenomena in Polymers.
9.14. Gels and Gelation.
9.15. Effects of Strain on the Melting Temperature.
9.16. Elastomers in Current Use.
9.17. Summary of Rubber Elasticity Behavior.
References.
General Reading.
Study Problems.
Appendix 9.1. Gelatin as a Physically Cross-linked Elastomer.
Appendix 9.2. Elastic Behavior of a Rubber Band.
Appendix 9.3. Determination of the Cross-link Density of Rubber by Swelling to Equilibrium.
10. Polymer Viscoelasticity and Rheology.
10.1. Stress Relaxation and Creep.
10.2. Relaxation and Retardation Times.
10.3. The Time-Temperature Superposition Principle.
10.4. Polymer Melt Viscosity.
10.5. Polymer Rheology.
10.6. Overview of Viscoelasticity and Rheology.
References.
General Reading.
Study Problems.
Appendix 10.1. Energy of Activation from Chemical Stress Relaxation Times.
Appendix 10.2. Viscoelasticity of Cheese.
11. Mechanical Behavior of Polymers.
11.1. An Energy Balance for Deformation and Fracture.
11.2. Deformation and Fracture in Polymers.
11.3. Crack Growth.
11.4. Cyclic Deformations.
11.5. Molecular Aspects of Fracture and Healing in Polymers.
11.6. Friction and Wear in Polymers.
11.7. Mechanical Behavior of Biomedical Polymers.
11.8. Summary.
References.
General Reading.
Study Problems.
12. Polymer Surfaces and Interfaces.
12.1. Polymer Surfaces.
12.2. Thermodynamics of Surfaces and Interfaces.
12.3. Instrumental Methods of Characterization.
12.4. Conformation of Polymer Chains in a Polymer Blend Interphase.
12.5. The Dilute Solution-Solid Interface.
12.6. Instrumental Methods for Analyzing Polymer Solution Interfaces.
12.7. Theoretical aspects of the Organization of Chains at Walls.
12.8. Adhesion at Interfaces.
12.9. Interfaces of Polymeric Biomaterials with Living Organisms.
12.10. Overview of Polymer Surface and Interface Science.
References.
General Reading.
Study Problems.
Appendix 12.1. Estimation of Fractal Dimensions.
13. Multicomponent Polymeric Materials.
13.1. Classification Schemes for Multicomponent Polymeric Materials.
13.2. Miscible and Immiscible Polymer Pairs.
13.3. The Glass Transition Behavior of Multicomponent Polymer Materials.
13.4. The Modulus of Multicomponent Polymeric Materials.
13.5. The Morphology of Multiphase Polymeric Materials.
13.6. Phase Diagrams in Polymer Blends (Broad Definition).
13.7. Morphology of Composite Materials.
13.8. Nanotechnology-Based Materials.
13.9. Montmorillonite Clays.
13.10. Fracture Behavior of Multiphase Polymeric Materials.
13.11. Processing and Applications of Polymer Blends and Composites.
References.
General Reading.
Study Problems.
14. Modern Polymer Topics.
14.1. Polyolefins.
14.2. Thermoset Polymer Materials.
14.3. Polymer and Polymer Blend Aspects of Bread Doughs.
14.4. Natural Product Polymers.
14.5. Dendritic Polymers and Other Novel Polymeric Structures.
14.6. Polymers in Supercritical Fluids.
14.7. Electrical Behavior of Polymers.
14.8. Polymers for Nonlinear Optics.
14.9. Light-Emitting Polymers and Electroactive Materials.
14.10. Optical Tweezers in Biopolymer Research.
14.11. The 3-D Structure and Function of Biopolymers.
14.12. Fire Retardancy in Polymers.
14.13. Polymer Solution-Induced Drag Reduction.
14.14. Modern engineering Plastics.
14.15. Major Advances in Polymer Science and Engineering.
References.
General Reading.
Study Problems.
Index.
SYMBOLS AND DEFINITIONS
SYMBOL DEFINITION SECTION English Alphabet A A2 = second virial coefficient 3.3.2 A1 = first virial coefficient 3.5.3.3 A3 = third virial coefficient 3.5.3.3 A4 = fourth virial coefficient 3.5.3.3 A (with various subscripts) = area under a Bragg diffraction line 6.5.4 Angular amplitude 8.3.3 AT = reduced variables shift factor 8.6.1.2 Surface area (with various subscripts) 12.2.3 B Bulk modulus 8.1.1.2, 8.1.4 C C* = chiral center, optically active carbon 2.3.2, 2.4.1 Cm = constant 3.3.2 CN = neutron scatting equivalent of H 5.2.2.1 C8 = characteristic ratio 5.3.1.1 ?Cp = change in heat capacity 6.1 CI = crystallinity index 6.5.4 Cp = heat capacity 8.2.9 C1, C2 = Mooney-Rivlin constants 9.9.1 C100, C010, C200, C400, C, C´, C", = generalized strain energy constants 9.9.2 C1´, C2´ = WLF constants 10.4.1 CA = concentration of A A10.1 Cp, Cv = capacitance of polymer and vacuum 14.7.1 D Diffusion coefficient 3.6.6, 4.4.2, 5.4.2.1 Disk diameter 13.9.3 De = Deborah number 10.2.4 D´ = fractal dimension 12.7.3 D2 = IPN phase domain size 13.5.4 D = Tensile compliance 8.1.6 E Young's modulus 1.3, 8.1.1.1 ?E = change in energy 2.2.4 Eact = energy of activation 2.8, 8.6.1.2 E* = complex Young's (tensile) modulus 8.1.8 E´ = storage modulus 8.1.8 E" = loss modulus 8.1.8 E1, E2, etc. = spring moduli 10.1.2.1 Elongational compliance 8.1.6 F Helmholtz free energy 9.5 G Gibbs's free energy 3.2 Group molar attraction constant 3.2.3 ?GM = change in free energy on mixing 3.2 GN0 = steady-state rubbery shear modulus 5.4.2.1 Radial growth rate of crystal 6.6.2.2 Shear modulus 8.1.1.1 G* = complex shear modulus 8.1.8 G´ = shear storage modulus 8.2.9 G" = shear loss modulus 8.2.9 = fracture energy 11.1.2 = critical energy of crack growth 11.1.2 = critical energy of crack growth on extension 11.5.2.4 Gs = surface free energy 12.2.1 H H0 = magnetic field 2.2.4 Optical constant 3.6 ?Hf = enthalpy of fusion 6.1 dH = NMR absorption line width 8.3.4 Heat energy per unit volume per cycle 8.12 Wool's general function 11.5.3 Hs = surface enthalpy 12.2.1 I ID = dimer emission intensity 2.10.3.1 IM = single mer emission intensity 2.10.3.1 I I1, I2, I3 = strain invarients 9.9.2 Current 14.7.1 J Flux 4.4.2 Jn = de Gennes defect current 5.4.2.1 Compliance (with various subscripts) 5.4.2.1, 8.1.1.2 Shear compliance 8.1.1, 8.1.6 J* = complex compliance 8.1.6 J´, J" = storage and loss compliance 10.2.4 K = constant 3.6.1 Wave vector 3.6.1, 5.2.2.1, 12.3.8.1 Equilibrium constant of polymerization 3.7.2.1 Constant in the Mark-Houwink-Sakurada equation 3.8.3 Kd = distribution coefficient 3.9.2 = constant relating end-to-end distance to molecular weight 4.3.9 K1, K2 = measures of free volume 8.6.1.1 KL, KH = constants in melt viscosity 10.4.2.1 K = stress intensity factor 11.2.4.1, 11.3.2 K1c, K2c, K3c = critical stress intensity factor in the extension, shear, and tearing modes 11.2.4.1, 11.3.2 ?K = stress intensity factor range 11.4.2 L Sample length 9.4 L(x), L(ß) = inverse Langevin function 9.10.1 L1, L2 = transverse lengths 12.3.8.1 2L0 = separation length 12.6.1 M Molecular weight Mn = number-average molecular weight 1.2.1, 3.4 Mw = weight-average molecular weight 3.4 Mz = z-average molecular weight 3.4 Mv = viscosity-average molecular weight 3.4 M1, M2 = mass fractions 8.8.1 Mc = number-average molecular weight between cross-links 9.4 M Me = molecular weight between entanglements 9.4 M´c = entanglement molecular weight 9.4,...