This book deals with the problems of the thermodynamics of systems containing flexible-chain polymers as the basis of polymer material science. The main thermodynamic quantities and concepts are introduced and discussed in the order of the objects getting more and more complicated: gases, magnets, low-molecular-weight substances and mixtures, and finally, polymers and polymer blends.

All topics are considered in a common clue, using the principle of universality. The stability conditions for the one-phase state of multi-component systems are given. Phase separation is regarded as a result of loss in stability. The critical state of a system, with the one-phase state being close to the boundary of stability conditions breaking, is discussed in detail. The effects of both light scattering (elastic and dynamic) and diffusion, as directly depending on the thermodynamic parameters characterizing the one-phase state stability, are considered in detail. One of the versions of colloid scattering, namely, the turbidity spectrum method, is described as useful for the characterization of various heterogeneous structures and for the phase analysis of polymer systems. In the approximation of mean field theories and advanced field theory, formalisms expound the following divisions of the thermodynamics of binary and polynary systems with flexible-chain polymers: conformation of the polymer coil, composition fluctuations, elastic and dynamic light scattering, diffusion in the one-phase state (including the critical range), phase separation, polymer fractionation, the coil-globule transition, phase equilibrium and separation in the system network polymer + low-molecular-weight liquid, polymer blends and multiphase separation.

Table of Contents

1. Stability and Phase Separation. Stability conditions of the one-phase multicomponent system. Conditions for equilibrium and stability of the multiphase multicomponent system. Phase separation of regular mixtures. Stability and fluctuations. Loss of stability and phase transitions (phase separation). Landau's phenomenological theory. Elements of statistical physics and phase transitions. State equation of real gas. Chapter summary. 2. Fluctuations, Light Scattering and Diffusion. Light scattering in matter. Main concepts and definitions. Light scattering in gases and vapours. Light scattering in one-component liquids. Concentration fluctuations, light scattering and diffusion in solutions. Correlation of the order parameter fluctuations in the critical region. Hypothesis of similarity. Hypothesis of universality. Lagrangian formalism of the field theory. Chapter summary. 3. Polymer + Low-Molecular-Liquid System. Mean Field Approaches. Liquid-Liquid Phase Separation. Binary systems. Polynary systems. Composition fluctuations, light scattering and diffusion. Random coil-globule transition. Phase equilibrium in the crosslinked polymer + low-molecular-weight liquid system. Improvement of Flory-Huggins' lattice theory. Polymer mixtures. Theory of corresponding states. Relaxational thermodynamics. Multiphase separation. Chapter summary. 4. Universality Principle. Scaling Ideas.


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© 1999
Elsevier Science
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About the author

V.J. Klenin

Affiliations and Expertise

Saratov State University, Chemistry Department, Saratov, Russia