Influence of cerium addition and redox state on silicate structure and viscosity

Abstract

The viscosities of Ce-free and Ce-bearing (∼1.3 mol%, ∼6.5 wt.% Ce₂O₃) soda lime silicate (window glass) melts were measured with respect to oxidation state. Experiments were performed isothermally using a concentric-cylinder viscometer on melts equilibrated with successively reducing CO–CO₂ gas mixtures within a gas tight vertical tube furnace at 1 atm. Viscosity measurement and sampling were performed at the end of each melt reduction step. Further, viscosities in the glass transition temperature range were estimated using the shift factor method applied to glass transition temperature values determined using differential scanning calorimetry (DSC) measurements on quenched glasses. The Ce speciation at each stepwise melt reduction was probed using Ce L₃-edge X-ray absorption near-edge structure (XANES) spectroscopy, while structural information upon Ce addition and reduction was provided by Raman spectroscopy. The viscosities of these materials remain constant at this level of Ce addition and do not vary significantly with redox state at high temperature. Conversely, viscosity values in the glass transition temperature range increase upon both Ce addition and reduction. Our analysis, based on the glass composition analyses obtained via electron probe microanalyzer (EPMA), viscosity calculations, and observations of silicate structural changes, leads to the conclusion that the observed viscosity increase around the glass transition temperature is explained by the high ionic field strength of Ce ions as well as the polymerization behavior of the silicate matrix occurring during reduction of Ce. Because of its low concentration, resulting from its low solubility, Ce redox changes exert only minimal effects on the viscosity of this melt.