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Precipitation of Mixed-Alkali Molybdates During HLW Vitrification

Published online by Cambridge University Press:  01 February 2011

Scott Kroeker
Affiliation:
[email protected], University of Manitoba, Chemistry, Department of Chemistry, 458 Parker Building, Winnipeg, R3T 2N2, Canada
Carolyn Higman
Affiliation:
[email protected], University of Manitoba, Chemistry, Winnipeg, Canada
Vladimir K Michaelis
Affiliation:
[email protected], University of Manitoba, Chemistry, Winnipeg, Canada
Nicholas B Svenda
Affiliation:
[email protected], University of Manitoba, Chemistry, Winnipeg, Canada
Sophie Schuller
Affiliation:
[email protected], CEA-Marcoule, DEN/DTCD/SECM/LDMC, Bagnols/Céze, France
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Abstract

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.

Type
Research Article
Copyright
Copyright © Materials Research Society 2010

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