The Effects Of Mixing Multi-component HLW Glasses On Spinel Crystal Size

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

Micron-sized Spinel Crystals In High Level Waste Glass Compositions: Determination Of Crystal Size And Crystal Fraction

The compositions utilized for immobilization of high-level nuclear wastes (HLW) are controlled using glass property models to avoid the deleterious effects of crystallization in the high-level waste (HLW) vitrification melters. The type and size of the crystals that precipitate during melter operations (typically at 1150 °C) and idling (∼1000 °C) are significantly impacted by glass composition and thermal history. This study was conducted to measure the impact of melt composition and heat treatment temperature on crystal size and fraction. A matrix of 31 multi-component glasses canvasing the expected Hanford HLW compositional space was developed and the glasses fabricated, and heat treated at 850, 900, and 950 °C. The crystal amounts, as determined by X-ray diffraction, varied from 0.2 to 41.0 wt.%. Spinel concentrations ranged from 0.0 to 13.8 wt.%. One glass of the matrix did not precipitate spinel and contained 0.2 wt.% RuO2, which was assumed to be undissolved from the melting process. All compositions contained crystals in the as-quenched glass. All of the spinel-based crystals present in the glasses were less than 10 μm in diameter, as determined by scanning electron microscopy with image analysis. Composition and temperature dependent models were generated using the resulting data and the best model fit was obtained by only considering spinel concentrations (R2 = 0.87). Two glasses were unable to be characterized because of an inability to process the glass under the conditions of this study. Those glasses were utilized to give insight into a potential multi-component constraint to aid in future statistical composition designs

Measuring Accurate Optical Constants Of Uranium Minerals For Use In Optical Modeling Of Infrared Spectra

Knowledge of the bulk optical constants n and k of solids or liquids allows researchers to accurately predict the absorption, reflection, and scattering properties of materials for different physical forms. Indeed, chemically complex materials such as minerals can have an almost limitless variety of morphologies, particle sizes, shapes, and compositions, and the optical properties of such species can be predicted if the optical constants are known. For species such as minerals, there can be additional challenges due to e.g. hydration or dehydration during the course of the optical constants measurement. Here, we describe the protocols to obtain the bulk optical constants n and k of uranium-bearing minerals and ores such as uraninite or autunite. If quality n and k data are at hand, the (infrared) reflectance spectra can be predicted for different particle sizes and morphologies and the modeling results for various scenarios can be derived