Is the Structural Relaxation of Glasses Controlled by Equilibrium Shear Viscosity?

TL;DR

This study investigates whether the structural relaxation time of glasses correlates with equilibrium shear viscosity, finding that viscosity provides only a lower boundary and is not the controlling factor.

Contribution

The paper provides experimental evidence that structural relaxation in glasses is not directly controlled by equilibrium shear viscosity, challenging previous assumptions.

Findings

Structural relaxation times are longer than viscosity-based predictions.

Relaxation times are less than an order of magnitude higher than Maxwell equation estimates.

Equilibrium shear viscosity sets a lower boundary for relaxation kinetics.

Abstract

Knowledge of relaxation processes is fundamental in glass science and technology because relaxation is intrinsically related to vitrification, tempering as well as to annealing and sev-eral applications of glasses. However, there are conflicting reports -- summarized here for different glasses -- on whether the structural relaxation time of glass can be calculated using the Maxwell equation, which relates relaxation time with shear viscosity and shear modulus. Hence, this study aimed to verify whether these two relaxation times are comparable. The structural relaxation kinetics of a lead metasilicate glass were studied by measuring the re-fractive index variation over time at temperatures between 5 and 25 K below the fictive temperature, which was initially set 5 K below the glass transition temperature. Equilibrium shear viscosity was measured above and below the glass transition range, expanding the current knowledge by one order of magnitude. The Kohlrausch equation described very well the experimental structural relaxation kinetics throughout the investigated temperature range and the Kohlrausch exponent increased with temperature, in agreement with studies on other glasses. The experimental average structural relaxation times were much longer than the values computed from isostructural viscosity, as expected. Still, they were less than one order of magnitude higher than the average relaxation time computed through the Maxwell equation, which relies on equilibrium shear viscosity. Thus, these results demon-strate that the structural relaxation process is not controlled by isostructural viscosity, and that equilibrium shear viscosity only provides a lower boundary for structural relaxation kinetics.