Rheology of a sodium-molybdenum borosilicate melt undergoing phase separation

Abstract

During glass production, phase separation can result in the formation of suspended liquid droplets, which can cause changes in the system rheology. In nuclear waste vitrification context, some new glassy matrices may present this phase separation matter, but the mechanisms controlling the viscosity changes have not yet been determined. Here, we measure the viscosity of a sodium-borosilicate melt containing dissolved MoO₃ at different temperatures and subject to different applied shear strain rates. We observe that (i) the viscosity increases sharply as the temperature decreases and (ii) at any constant temperature below 1000°C, the system presents non-Newtonian response. Using transmission electron microscope observations coupled with viscosity calculations, we interpret the cause of the observed changes as the result of phase separation. We show that the viscosity increase on cooling is in excess of the predicted temperature dependence for a homogeneous melt of the starting composition. The increase is due to the formation of a second phase and is controlled by chemical and structural modifications of the matrix during the loss of the elements that form the droplets. This work provides insights into the rheology of a system composed of two composition sets due to a miscibility gap.