The Effects of Mixing Multi-Component HLW Glasses on Spinel Crystal Size

Abstract The Hanford Waste Treatment and Immobilization Plant will vitrify radioactive waste into borosilicate glass. The high-level waste (HLW) glass formulations are constrained by processing and property requirements, including restrictions aimed at avoiding detrimental impacts of spinel crystallization in the melter. To understand the impact of glass chemistry on crystallization, two HLW glasses precipitating small (∼5 μm) spinel crystals were individually mixed and melted with a glass that precipitated large (∼45 μm) spinel crystals in ratios of 25, 50, and 75 wt%. The size of spinel crystals in the mixed glasses varied from 5 to 20 μm. Small crystal size was attributed to: (1) high concentrations of nuclei due to the presence of ruthenium oxide and (2) chromium oxide aiding high rates of nucleation. Results from this study indicate that the spinel crystal size can be controlled using chromium oxide and/or noble metal concentrations in the melt, even in complex mixtures like HLW glasses. Smaller crystals tend to settle more slowly than larger crystals, therefore smaller crystals would be more acceptable in the melter without a risk of failure. Allowing higher concentrations of spinel-forming waste components in the waste glass enables glass compositions with higher waste loading, thus increasing plant operational flexibility. An additional benefit to the presence of chromium oxide in the glass composition is the potential for the oxide to protect melter walls against corrosion.