Arrhenian to non-Arrhenian crossover in glass melt viscosity

Abstract

The activation energy for glass melt viscosity is a function of temperature, i.e., non-Arrhenian, within a middle range of viscosity values (typically, between 102 and 1010 Pa s) and constant, i.e., Arrhenian, outside this range. At the low-viscosity end, the Arrhenian to non-Arrhenian transition (termed the crossover) falls within the glass processing range: glass melting and fining occur within the Arrhenian range while glass forming occurs within the non-Arrhenian range. By the Adam-Gibbs equation, the configuration entropy is nearly constant at high temperatures, where the glass melt turns into a simple liquid, and decreases with decreasing temperature as the glass is increasingly polymerized. It appears that the limited range of the configuration entropy of the fully depolymerized melt imposes a restriction on the crossover viscosity; for well-defined glass families, such as float glasses or nuclear waste glasses, the crossover point can be defined using a fixed, i.e., composition-independent, viscosity value.