The Role of the Communal Entropy and Free Volume for the Viscosity Divergence near the Glass Transition: A New Conceptual Approach

TL;DR

This paper introduces a new conceptual framework linking communal entropy and free volume to explain the divergence of viscosity near the glass transition, unifying existing phenomenologies and clarifying the nature of the ideal glass transition.

Contribution

It proposes replacing excess entropy with communal entropy and shows both vanish simultaneously at the ideal glass transition, unifying different approaches.

Findings

Communal entropy and free volume vanish together at IG.

The approach unifies existing phenomenologies of glass transition.

No thermodynamic singularities exist at the ideal glass transition.

Abstract

The conventional approach to study glasses either requires considering the rapid drop in the excess entropy {\Delta}S_ex or the free volume V_f. As the two quantities are not directly related to each other, the viscosity in the two approaches do not diverge at the same temperature, which casts doubt on the physical significance of the divergence and of the ideal glass transition (IG). By invoking a recently developed nonequilibrium thermodynamics, we identify the instantaneous temperature, pressure, entropy, etc. and discover the way they relax. We show that by replacing {\Delta}S_ex by a properly defined communal entropy S^comm (not to be confused with the configurational entropy) and V_f vanish simultaneously at IG, where the glass is jammed with no free volume and communal entropy. By exploiting the fact that there are no thermodynamic singularities in the entropy of the supercooled liquid at IG, we show that various currently existing phenomenologies become unified.