Thermodynamic approach to viscosity in the glass transition

Abstract

The glass transition is re-investigated by means of the formahsm of linear nonequilibrium thermodynamics. The process is treated for melts cooled down below their liquidus temperatures in terms of three events. These events are, in the order of decreasing temperature: by-passing of crystallization, freezing-in of stress relaxation, and freezing-in o f near-range structural relaxation. Conditions for the viscosity levels are derived at which each of these events is accomplished. The model is tested against data of five one-component, three simple binary and ternary, and three multicomponent systems. Within the scope of this test, it is confirmed that the model correctly describes the viscosity levels typical of the glass transition, as well as their dependence on the cooling rate. An explanation for the 10¹³dPa*s rule at Tg is included.