Thermodynamics and kinetics of the glass transition: A generic geometric approach
- Institute of Physical Chemistry, Bulgarian Academy of Sciences, 1113, Sofia, (Bulgaria)
- Department of Physics and Astronomy, Michigan State University, East Lansing, Michigan 48824 (United States)
- Argonne National Laboratory, Materials Science Division, Argonne, Illinois 60439 (United States)
A generic phenomenological theory of the glass transition is developed in the framework of a quasilinear formulation of the thermodynamics of irreversible processes. Starting from one of the basic principles of this science in its approximate form given by de Donder's equation, after a change of variables the temperature dependence of the structural parameter {xi}(T), the thermodynamic potentials {delta}G(tilde sign)(T), the thermodynamic functions and the time of molecular relaxation {tau} of vitrifying systems is constructed. In doing so, a new effect in the {delta}G(tilde sign)(T) course is observed. The analysis of the higher derivatives of the thermodynamic potential, and especially the nullification of the second derivative of the configurational specific heats {delta}C(tilde sign){sub p}(T) of the vitrifying liquid defines glass transition temperature T(tilde sign){sub g} and leads directly to the basic dependence of glass transition kinetics: the Frenkel-Kobeko-Reiner equation. The conditions guaranteeing the fulfillment of this equation specify the temperature dependence of the activation energy U(T,{xi}(tilde sign)) for viscous flow and give a natural differentiation of glass formers into fragile and strong liquids. The effect of thermal prehistory on the temperature dependence of both thermodynamic functions and kinetic coefficients is established by an appropriate separation of de Donder's equation. (c) 2000 American Institute of Physics.
- OSTI ID:
- 20216753
- Journal Information:
- Journal of Chemical Physics, Vol. 112, Issue 24; Other Information: PBD: 22 Jun 2000; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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