Glass Transition, Crystallization of Glass-Forming Melts, and Entropy

A critical analysis of possible (including some newly proposed) definitions of the vitreous state and the glass transition is performed and an overview of kinetic criteria of vitrification is presented. On the basis of these results, recent controversial discussions on the possible values of the residual entropy of glasses are reviewed. Our conclusion is that the treatment of vitrification as a process of continuously breaking ergodicity with entropy loss and a residual entropy tending to zero in the limit of zero absolute temperature is in disagreement with the absolute majority of experimental and theoretical investigations of this process and the nature of the vitreous state. This conclusion is illustrated by model computations. In addition to the main conclusion derived from these computations, they are employed as a test for several suggestions concerning the behavior of thermodynamic coefficients in the glass transition range. Further, a brief review is given on possible ways of resolving the Kauzmann paradox and its implications with respect to the validity of the third law of thermodynamics. It is shown that neither in its primary formulations nor in its consequences does the Kauzmann paradox result in contradictions with any basic laws of nature. Such contradictions are excluded by either crystallization (not associated with a pseudospinodal as suggested by Kauzmann) or a conventional (and not an ideal) glass transition. Some further so far widely unexplored directions of research on the interplay between crystallization and glass transition are anticipated, in which entropy may play—beyond the topics widely discussed and reviewed here—a major role.