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Precipitation of Mixed-Alkali Molybdates During HLW Vitrification

  • Scott Kroeker (a1), Carolyn Higman (a2), Vladimir K Michaelis (a3), Nicholas B Svenda (a4) and Sophie Schuller (a5)...

Crystalline precipitates from molybdenum-containing nuclear waste glasses are complex, often containing multiple cations which confound routine structural techniques. A simplified mixed-alkali borosilicate model glass was found to have minor crystalline phases which could not be identified by x-ray diffraction. Multinuclear magnetic resonance (NMR) spectroscopy revealed sharp peaks characteristic of crystallinity superimposed on the broader glass signals, but were unattributable to any known molybdate phases. When a comprehensive range of cesium molybdates failed to reveal any matches with the observed 133Cs magic-angle spinning (MAS) NMR peaks in the composite glass/crystalline material, a series of mixed-alkali sodium-cesium molybdate phases was synthesized. 23Na, 133Cs and 95Mo MAS NMR revealed the formation of two mixed-cation molybdates which correlate with the observed NMR peaks for the phase-separated model glass. This work highlights the prominence of multiple crystalline phases in Mo-bearing nuclear waste glasses, and demonstrates the unique utility of solid-state NMR as a fingerprinting approach to identifying complex phases, especially where x-ray diffraction is limited by multiple phases, low concentrations or substitutionally disordered precipitates.

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MRS Online Proceedings Library (OPL)
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  • EISSN: 1946-4274
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