Is the structural relaxation of glasses controlled by equilibrium shear viscosity?

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 several 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 refractive 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 demonstrate 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.

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Predicting Dielectric and Shear-Rheology Properties of Glass-Forming Pharmaceutical Liquids from Each Other: Applications and Limitations

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