Polymer Science

Contents of Volume 2

Chapter 13 Adhesion


1. General Introduction


2. Factors Affecting Adhesion


2.1. Introduction


2.2. Viscosity


2.3. Surface Energy


2.4. Weak Boundary Layers


2.5. Surface Pre-Treatments


2.6. Stress Concentrations


2.7. Conditions of Joint Formation and Testing


2.8. Conclusions


3. Theories of Adhesion


3.1. Mechanical Theory


3.2. Adsorption Theory


3.3. Diffusion Theory


3.4. Electrostatic Theory


3.5. Conclusions


4. Forces Operating at the Interface


5. Interfacial and Cohesive Failure


6. Individual Polymers


6.1. Introduction


6.2. Polyolefins


6.3. Fluorinated Polymers


6.4. Poly(Ethylene Terephthalate)


6.5. Poly(Vinylchloride)


6.6. Poly(Hexamethylene Adipamide)


6.7. Elastomers


6.8. Acrylonitrile-Butadiene-Styrene Terpolymers


6.9. Poly(Phenylene Oxide)


7. Conclusions

References

Chapter 14 Friction and Wear


1. Introduction


2. Friction


2.1. Elastic Deformation—Single Contacts


2.2. Multiple Contacts


2.3. Rolling Friction


2.4. Sliding Friction of Rubbers


2.5. Sliding Friction of Rigid Polymers


2.6. Lubrication by Fluids


3. Wear


3.1. Classification of Wear


3.2. Wear Testing


3.3. Abrasive Wear


3.4. Erosive Wear


3.5. Fatigue


3.6. Adhesive Wear


3.7. Composites


3.8. Design Considerations


4. Areas of Uncertainty

References

Chapter 15 Polymer Solutions and Fractionation


1. Introduction


2. Free Enthalpy Functions and Related Equations


2.1. Free Enthalpy of Mixing


2.2. Consolute State and Spinodal


2.3. Equilibrium Conditions and the Fractionation Equation


3. Phase Diagrams


3.1. General Considerations


3.2. Cloud-Point Curves


3.3. Coexistence Curves


3.4. Separation Into Three Liquid Phases


3.5. The Influence of Pressure


4. The Free Enthalpy Function


4.1. Determination of the G Function


4.2. The Shultz-Flory Method (Determination of the Θ Temperture)


5. Polymer Fractionation


5.1. Preparative Fractionation


5.2. Analytical Fractionation


5.3. Alternative Analytical Approach


6. Conclusions


7. Appendices


7.1. Molecular Weight Distributions and Average Molecular Weights


7.2. Criteria of Fractionation Efficiency

References

Chapter 16 Polyelectrolytes


1. Introduction


2. Preparation of Polyelectrolytes


3. Solubility of Polyelectrolytes


4. The Thermodynamics of Polyelectrolyte Solutions


5. The Electrostatic Free Energy of Polyelectrolytes


6. Molecular Models For Polyelectrolyte Molecules in Solution


6.1. The Rigid, Impenetrable Spherical Molecule


6.2. The Rigid, Rod-Like Molecule


6.3. The Electrostatic Free Energy of Flexible-Chain Molecules


7. The Potentiometric Titration of Polyelectrolytes


7.1. The Titration Equation


7.2. Treatment of Experimental Titration Data


8.


8.1. Irreversible Processes in Polyelectrolyte Solutions


8.2. The Molecular Expansion of Flexible Polyelectrolytes


9. Electrophoresis


10. Electrolytic Conductance


11. The Sedimentation Rate


12. Diffusion


13. The Effect of Polyelectrolytes On Small Ions


13.1. Ion Binding


14. Catalytic and Inhibitory Effect of Polyelectrolytes


14.1. Reaction With The Poly-Ions


14.2. Reactions Between Two Small Molecular Weight Ionic Species


14.3. Kinetic Effect of Polyelectrolyte Molecules Containing Catalytic Substituents


15. Some Dielectric Properties of Polyelectrolyte Solutions


16. Cross-Linked Polyelectrolyte Networks and Ion Exchangers


16.1. Bulk Properties of Polyelectrolytes

References

Chapter 17 Electrical Properties of Polymers


1. Introduction


1.1. Parameters Involved


1.2. Experimental Techniques


2. The Charge Carriers


2.1. Intrinsic Generation


2.2. Impurity Conduction


2.3. Injection Processes


2.4. Photoconductivity


2.5. Space-Charge-Limited Currents


2.6. Thermally Stimulated Currents


3. Charge-Carrier Mobility


4. Ionic Conduction


5. Conductivity of Polymers


5.1. Types of Polymer


5.2. Morphology and Similar Effects


5.3. Polymethylenes


5.4. Polymers Containing Conjugated Double Bonds


5.5. Charge-Transfer Complexes


5.6. Polymeric Salts of the Tetracyanoquinodimethane Radical Anion


5.7. Polymers Containing Metal Atoms


6. Contact Electrification


7. Electrets


8. Dielectric Breakdown

References

Chapter 18 Dielectric Properties of Polymers, I


1. Introduction


2. General Relations


3. Nonpolar Polymers


4. Polar Polymers

Chapter 19 Dielectric Properties of Polymers, II


1. Basic Theory of Dielectric Behaviour of Small Molecules


1.1. Introduction


1.2. Permittivity in A Static Field


1.3. Permittivity in An Alternating Field


2. Complexity Arising From Chain Structure of Polymers


2.1. Dipole Moment of An Isolated Polymer Molecule


2.2. Dipole Moment of Non-Isolated Polymer Chains


2.3. Polymer Chains in An Alternating Field


3. A.C. Effects Arising From The Mobility of Charge Carriers


3.1. Effects Arising From Bulk Conduction


3.2. Interfacial Polarization


4. Molecular Theories of Relaxation in Polymers


4.1. Amorphous Polymers


4.2. Crystalline Polymers


4.3. Steric Hindrance and Plasticization


4.4. Stereospecificity


5. Dielectric Relaxation in Polymer Solutions


6. Dielectric Behaviour of Specific Polymers


6.1. Non-Polar Polymers


6.2. Polar Polymers

References

Chapter 20 Far Infrared Spectra of Polymers


1. General Introduction


2. Theory of the Absorption and Dispersion of Electromagnetic Waves in Condensed Media


3. Absorption Spectroscopy in the Far Infrared


4. Far Infrared Refractometry


4.1. Basic Theory


4.2. Measurements of Real Refractive Index


4.3. Experimental Determination of N Using the 337 µm HCN Laser


4.4. Complex Refractive Index Measurements With Broad-Band Radiation. Fourier Refractometry


4.5. Experimental Apparatus For Broad-Band Fourier Refractometry of Polymers


4.6. The Uses of the Refraction Spectrum


5. Experimental Results


5.1. Introduction


5.2. Polyethylene


5.3. Polypropylene


5.4. TPX


5.5. Polytetrafluorethylene


5.6. Polymethylmethacrylate and Polystyrene


5.7. Miscellaneous Polymers

References

Chapter 21 Nuclear Magnetic Resonance


1. Introduction


2. Principles of High-Resolution NMR


2.1. Properties of Nuclei


2.2. The NMR Experiment


2.3. Nuclei in Molecules


2.4. Chemical Shifts


2.5. Coupling Constants


2.6. Quadrupole Effects


2.7. Summary


2.8. Solvents


2.9. Signal-to-Noise Ratio


2.10. Double Resonance


2.11. Deuteriation


3. High-Resolution NMR Spectra of Polymers


3.1. Poly (Methylmethacrylate)


3.2. Poly(Vinylchloride)


3.3. Polyethylene


3.4. Polyisoprene


3.5. Vinylidene Chloride-Isobutylene Copolymer


4. Broad-Line NMR Spectra


4.1. Line Shapes in A Rigid Lattice


4.2. Motional Narrowing


4.3. Degree of Crystallinity


4.4. Second Moments of NMR Lines


4.5. Studies of Relaxation Times


4.6. Polyisobutylene


4.7. Poly(Methylmethacrylate)


4.8. Polyethylene


4.9. Other Studies

References

Chapter 22 Degradation


1. Introduction


2. Thermal Degradation


2.1. Introduction


2.2. Depolymerization


2.3. Substituent Reactions


3. Mechanical Degradation


4. Photodegradation


4.1. Introduction


4.2. Acrylic and Methacrylic Ester Polymers


4.3. Poly(A-Methylstyrene)


4.4. Poly(Methyl Isopropenyl Ketone) and Poly(Methyl Vinyl Ketone)


4.5. Polystyrene


4.5. Polyacrylonitrile


5. Oxidation


5.1. Introduction


5.2. Unsaturated Polymers


5.3. Saturated Polymers

References

Chapter 23 Radiation Effects in Polymers


1. Introduction


2. Radiation Doses


3. Radiation Sources


4. Basic Processes


5. Main Chain Scission—Degradation


6. Cross-Linking and Network Formation


7. Memory Effect


8. Reinforcement


9. Electrical Effects


10. Graft Copolymers


11. Effect of 02


12. Some Practical Applications


13. Polyester Cure

Chapter 24 Identification and Analysis of Plastic Materials


1. Introduction


1.1. Components of A Plastic Composition


1.2. Plasticizers, Stabilizers, Anti-Oxidants, Slip Agents, Surface-Active Agents and Antistatic Additives


1.3. Special Tests On Plastics Compositions


2. Qualitative Elemental Analysis


2.1. Preparation of the Test Solution


2.2. Nitrogen


2.3. Sulphur


2.4. Phosphorus


2.5. Fluorine


2.6. Halogens (Chlorine, Bromine Or Iodine)


2.7. Fluorescein Test (Bromine and Iodine Only)


2.8. Starch Test (Iodine Only)


3. Simple Identification Tests For Plastics


3.1. Surface Character of the Specimen


3.2. Flotation in Water


3.3. Transparent Samples


3.4. Translucent Samples


3.5. Heating and Burning Tests


3.6. Solubility Tests


3.7. Qualitative Tests For Elements


3.8. Colour Tests


3.9. Tests With The Microscope


3.10. General Observations


4. Methods of Separating Compositions


4.1. Solvent Extraction


4.2. Solution and Precipitation


4.3. Coagulation of Latices


4.4. Vacuum Distillation


4.5. Pyrolysis in Nitrogen


4.6. Chromatography


5. Identification of Polymers and Monomers


5.1. Identification of Polymeric Constituents by IR Spectroscopy


5.2. Identification of Polymers by High-Resolution N M R Spectroscopy


5.3. Identification of Polymers by Pyrolysis/Gas-Liquid Chromatography


5.4. ATR (Attenuated Total Reflection) IR Spectroscopy in the Examination of Polymers


5.5. Identification of Polymers by Chemical Methods


5.6. Identification of Monomeric Constituents by IR Spectroscopy


5.7. Identification of Monomeric Organic Substances by N M R Spectroscopy


5.8. Identification of Additives To Polymer Compositions by UV Spectroscopy


5.9. The Identification of Additives To Polymers by Mass Spectroscopy


5.10. Identification of Constituents From Polymer Compositions by Gas Chromatography


5.11. Identification of Gas-Chromatographic Fractions by IR Analysis


5.12. Gas Chromatography/Mass Spectrometry


5.13. Preliminary Examination of Inorganic Materials


5.14. Identification of Inorganic Constitutents by IR Spectroscopy


5.15. Identification of Inorganic Constituents From Polymer Compositions by X-Ray Diffraction


6. Quantitative Analytical Methods


6.1. Elemental Organic Analysis


6.2. Elemental Inorganic Analysis


6.3. Quantitative Spectroscopic Methods of Analysis in the Polymer Field


6.4. Applications of Non-Aqueous Titrimetry To Polymer Analyses


6.5. Quantitative Applications of Gas Chromatography


6.6. Elemental Analysis by X-Ray Fluorescence Spectrometry


6.7. Determination of Residual Monomers in Polymer Compositions


6.8. Moisture Content of Polymer Compositions

References

Chapter 25 Polymers For Use At High and Low Temperatures


1. Introduction


2. Polymers For Use At High Temperatures


2.1. The Chemical Stability of Polymers At High Temperatures


2.2. Physical Properties of High-Temperature Polymers


2.3. High-Temperature, High Tg Polymers


2.4. High-Temperature, Low Tg Polymers


2.5. Summary


3. Polymers For Use At Low Temperatures


3.1. Physical Properties of Low-Temperature Polymers


3.2. Low-Temperature Polymers

References

Chapter 26 Composites


1. Scope


2. Early History


3. Techniques in Fabrication


3.1. Glass-Fibre Techniques


3.2. Vacuum-Bag Moulding


3.3. Spray-Up Technique


3.4. Filament-Winding


3.5. Compression Moulding


3.6. Phenolic/Asbestos Techniques


3.7. Carbon Fibre-Reinforced Plastics


4. Design Considerations


4.1. Mechanism


4.2. Relative Properties of Fibre and Matrix


4.3. Volume Fractions


4.4. Orientation


5. Uses

References

Chapter 27 Neutron Spectroscopy of Polymers


1. Introduction


2. General Theory of Neutron Scattering


2.1. The Effect of Atomic Motions


3. Incoherent Scattering Spectroscopy and Molecular Forces in Polymers


3.1. Time-Of-Flight Spectroscopy For Incoherent Scattering Spectroscopy


3.2. Methyl Torsions and Other Side-Group Motions—Isotopic Substitution Method


3.3. Practical Applications


3.4. Vibrational Modes of the Polymer Chain—Density of States Spectra


4. Coherent Neutron Scattering Spectroscopy—Determination of Dispersion Curves


4.1. Experimental Methods


4.2. Dispersion Curves and Force Fields


4.3. Dispersion Curves in Long-Chain Polymers


4.4. Conclusions On Polymer Forces


5. General Conclusions

References

Subject Index

Author Index