Thermophysical Properties of Polymers

ISBN-13: 9783642516726 / Angielski / Miękka / 2012 / 300 str.

Yuli K. Godovsky

Opis

Among various branches of polymer physics an important position is occupied by that vast area, which deals with the thermal behav ior and thermal properties of polymers and which is normally called the thermal physics of polymers. Historically it began when the un usual thermo-mechanical behavior of natural rubber under stretch ing, which had been discovered by Gough at the very beginning of the last century, was studied 50 years later experimentally by Joule and theoretically by Lord Kelvin. This made it possible even at that time to distinguish polymers from other subjects of physical investigations. These investigation laid down the basic principles of solving the key problem of polymer physics - rubberlike elasticity - which was solved in the middle of our century by means of the statistical thermodynamics applied to chain molecules. At approx imately the same time it was demonstrated, by using the methods of solid state physics, that the low temperature dependence of heat capacity and thermal expansivity of linear polymers should fol low dependencies different from that characteristic of nonpolymeric solids. Finally, new ideas about the structure and morphology of polymers arised at the end of the 1950s stimulated the development of new thermal methods (differential scanning calorimetry, defor mation calorimetry), which have become very powerful instruments for studying the nature of various states of polymers and the struc tural heterogeneity."

Spis treści

One: Thermal Properties of Polymers.- 1 Heat Capacity.- 1.1 Basic Concepts of the Heat Capacity of Solids.- 1.2 Temperature Dependence of Heat Capacity of Polymers.- 1.2.1 Theoretical Frameworks.- 1.2.2 Experimental Results and Comparison with Theoretical Concepts.- 1.3 Temperature Transitions and Heat Capacity.- 1.3.1 Amorphous Polymers.- 1.3.2 Crystalline Polymers.- References.- 2 Thermal Conductivity.- 2.1 Basic Concepts of Thermal Conductivity of Solids.- 2.2 Temperature Dependence of Thermal Conductivity of Polymers.- 2.2.1 Amorphous Polymers.- 2.2.2 Crystalline Polymers.- 2.3 Effect of Molecular Parameters.- 2.4 Anisotropy of Thermal Conductivity — Effect of Orientation.- 2.5 Effect of Radiation.- 2.6 Effect of Pressure.- 2.7 Thermal Conductivity of Filled Polymer Materials.- 2.8 Thermal (Temperature) Diffusivity.- References.- 3 Thermal Expansion.- 3.1 Basic Concepts of Thermal Expansion of Solids.- 3.2 Equation of State of Polymers.- 3.3 Gruneisen Parameters of Polymers.- 3.4 Thermal Expansion of Polymeric Crystals.- 3.5 Thermal Expansion of Drawn Polymers.- 3.5.1 Negative Thermal Expansion of Drawn Crystalline Polymers.- 3.5.2 Anisotropy of Thermal Expansion.- 3.6 Thermal Expansion of Filled Polymers and Polymer-Matrix Composites.- References.- 4 Experimental Methods and Instrumentation.- 4.1 Heat Capacity.- 4.1.1 Adiabatic Calorimetry.- 4.1.2 Differential Scanning Calorimetry (DSC).- 4.2 Thermal Conductivity and Diffusivity.- 4.2.1 Steady-State Methods.- 4.2.2 Unsteady-State Methods.- 4.3 Thermal Expansion.- References.- Two: Thermal Behavior of Polymers under Mechanical Deformation and Fracture.- 5 Thermomechanics of Glassy and Crystalline Polymers.- 5.1 Phenomenological Aspects of Thermomechanics of Elastic Materials.- 5.2 Linear Thermomechanics of Quasi-Isotropic Hookean Solids.- 5.2.1 Uniform (Volume) Dilatation and Compression.- 5.2.2 Simple Elongation and Compression.- 5.2.3 Shear Torsion.- 5.3 The Thermoelastic Effect in Glassy and Crystalline Polymers.- 5.4 Thermomechanics of the Undrawn Glassy and Crystalline Polymers.- 5.5 Thermomechanics of Drawn Polymers.- 5.5.1 Drawn Amorphous Polymers.- 5.5.2 Drawn Crystalline Polymers.- 5.6 Microphase-Separated Block Copolymers with a Solid Matrix.- 5.7 Filled Solid Polymers.- 5.8 Biopolymers.- References.- 6 Thermomechanics of Molecular Networks and Rubberlike Materials.- 6.1 Thermomechanics of Molecular Networks (Theory).- 6.1.1 Thermomechanics of Gaussian Networks.- 6.1.2 Thermomechanics of Non-Gaussian Networks.- 6.1.3 Phenomenological Equations of State.- 6.1.4 Thermoelasticity of Liquid Crystalline Networks.- 6.2 Thermomechanical Behavior of Molecular Networks.- 6.2.1 Entropy and Energy Effects at Small and Moderate Deformations.- 6.2.2 Thermomechanics at Large Deformations.- 6.2.3 The Thermoelasticity of Mesophase Networks.- 6.3 Thermomechanical Behavior of Rubberlike Materials.- 6.3.1 Stress Softening: Thermomechanics and Mechanism.- 6.3.2 Energy Contribution.- 6.3.3 Mesophase Block Copolymers.- 6.3.4 Random Copolymers.- 6.3.5 Elastomer Blends.- 6.3.6 Bioelastomer Materials.- Appendix Thermomechanics of the New Models of Rubber Elasticity.- References.- 7 Thermodynamic Behavior of Solid Polymers in Plastic Deformation and Cold Drawing.- 7.1 Temperature Effects During Plastic Deformation and Cold Drawing of Glassy and Crystalline Polymers.- 7.1.1 Uniform Neck Propagation.- 7.1.2 Self-Oscillated Neck Propagation.- 7.2 Thermodynamics of Plastic Deformation and Cold Drawing of Glassy and Crystalline Polymers.- 7.2.1 Plastic Deformation at Uniaxial Extension (Cold Drawing).- 7.2.2 Plastic Deformation at Simple Compression.- 7.3 Thermal Behavior of Cold Drawn and Plastically Deformed Glassy and Crystalline Polymers and the Nature of the Stored Energy.- 7.3.1 Amorphous Polymers.- 7.3.2 Crystalline Polymers.- 7.4 Thermomechanical Behavior of Hard Elastic Fibers and Films.- References.- 8 Thermal Behavior of Solid Polymers Under Fracture.- 8.1 Thermal and Temperature Effects Resulting from the Formation and Growth of Cracks in Solid Polymers.- 8.1.1 Estimation of Temperature Rise at the tip of Propagating Cracks.- 8.1.2 The Local Thermal Processes During the Crack Growth in Solid Polymers.- 8.2 Energetics of Chain Rupture in Stressed Polymers.- 8.2.1 Energetics of Elementary Scissions of Stressed Macromolecules.- 8.2.2 Experimental Data on the Energetic Effects Resulting from the Degradation of Macromolecules in Stressed Polymers.- 8.3 Self-Heating During Cyclic Deformation and Thermal Fatigue Failure.- References.- 9 Experimental Methods and Instrumentation.- 9.1 Measurements of the Temperature Changes During Deformation.- 9.1.1 Elastic Deformation (Isoentropic Measurements).- 9.1.2 Temperature Rise in the Necking of Polymers.- 9.1.3 Temperature Rise in the Zone of Rupture of Polymers.- 9.2 Temperature Dependence of Stresses (Isometric Measurements).- 9.3 Deformation Calorimetry (Isothermal Measurements).- 9.3.1 Gas Calorimeters.- 9.3.2 Heat-Conducted Deformation Calorimeters (Tian-Calvet Type).- 9.4 Calorimetric Methods for Investigating the Energy State of Deformed Polymers.- 9.4.1 Dissolution Calorimetry.- 9.4.2 DSC Measurements.- References.