A macroscopic model that connects the molar excess entropy of a deeply supercooled liquid near its glass transition temperature to its viscosity

TL;DR

This paper proposes a macroscopic model linking the molar excess entropy to viscosity in supercooled liquids near the glass transition, using a mixture of micro regions and their collective activated motion.

Contribution

It introduces a novel macroscopic model connecting excess entropy and viscosity without microscopic assumptions, applicable to glass formers near Tg.

Findings

Model accurately predicts viscosity near Tg using excess entropy data.

Viscosity follows Vogel-Fulcher-Tamman behavior close to Tg.

Parameters estimated for specific glass formers match experimental data.

Abstract

For a deeply supercooled liquid near its glass transition temperature, we suggest a possible way to connect the temperature dependence of its molar excess entropy to that of its viscosity by constructing a macroscopic model, where the deeply supercooled liquid is assumed to be a mixture of solid-like and liquid-like micro regions. In this model, we assume that the mole fraction x of the liquid-like micro regions tends to zero as the temperature T of the liquid is decreased and extrapolated to a temperature Tg*, which we assume to be below but close to the lowest glass transition temperature Tg attainable with the slowest possible cooling rate for the liquid. Without referring to any specific microscopic nature of the solid-like and liquid-like micro regions, we also assume that near Tg, the molar enthalpy of the solid-like micro regions is lower than that of the liquid-like micro regions. We then show that the temperature dependence of x is directly related to that of the molar excess entropy. Close to Tg, we assume that an activated motion of the solid-like micro regions controls the viscosity and that this activated motion is a collective motion involving practically all of the solid-like micro-regions so that the molar activation free energy for the activated motion is proportional to the mole fraction, 1-x, of the solid-like micro regions. The temperature dependence of the viscosity is thus connected to that of the molar excess entropy through the temperature dependence of the mole fraction x. As an example, we apply our model to a class of glass formers for which the molar excess entropy at temperatures near Tg is proportional to 1-T/TK with TK < Tg \sim Tg* and find their viscosities to be well approximated by the Vogel-Fulcher-Tamman equation for temperatures very close to Tg. We estimate the values of three parameters in our model for three glass formers in this class.