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Precipitation of Mixed-Alkali Molybdates During HLW Vitrification

Published online by Cambridge University Press:  01 February 2011

Scott Kroeker ,
Carolyn Higman ,
Vladimir K Michaelis ,
Nicholas B Svenda  and
Sophie Schuller
Scott Kroeker
Affiliation:
scott_kroeker@umanitoba.ca, University of Manitoba, Chemistry, Department of Chemistry, 458 Parker Building, Winnipeg, R3T 2N2, Canada
Carolyn Higman
Affiliation:
carolynhigman@gmail.com, University of Manitoba, Chemistry, Winnipeg, Canada
Vladimir K Michaelis
Affiliation:
ummichae@cc.umanitoba.ca, University of Manitoba, Chemistry, Winnipeg, Canada
Nicholas B Svenda
Affiliation:
nick.svenda@gmail.com, University of Manitoba, Chemistry, Winnipeg, Canada
Sophie Schuller
Affiliation:
sophie.schuller@cea.fr, 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.

Keywords

nuclear materialsnuclear magnetic resonance (NMR)amorphous
Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 1265: Symposium AA – Scientific Basis for Nuclear Waste Management XXXIV , 2010 , 1265-AA03-03
Copyright
Copyright © Materials Research Society 2010

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References

1 Hand, R.J. Short, R.J. Morgan, S. Hyatt, N.C., Möbus, G. and Lee, W.E., European Society of Glass Science and Technology, 46(2), 121–124, (2005).Google Scholar
2 Schuller, S. Pinet, O. Grandjean, A. and Blisson, T. J. Non –Cryst. Solids 354, 296–300 (2008).Google Scholar
3 Kroeker, S. Schuller, S. Farnan, I. manuscript in preparatio preparation. n.Google Scholar
4 Enjalbert, R. Guinneton, F. and Galy, J. Acta Cryst., C55, 273–276 (1999).Google Scholar
5 Gatehouse, B.M. and Miskin, B.K. Acta Cryst. Cryst., B31, 1293–99 (1975).Google Scholar
6 Marrot, J. and Savariault, J. Acta Cryst., C51, 2201–2205 (1999).Google Scholar
7 Solodovnikova, Z.A. and Solodovnikov, S.F. Acta C Cryst., C62, i53–i56 (2006).Google Scholar
8 Skibsted, J. and Jakobsen, H.J. Solid State Nuclear Magnetic Resonance Resonance, 3, 29–38 (1994).Google Scholar
9 Kroeker, S. Farnan, I. Schuller, S. and Advocat, T. Mater. Res. Soc. Symp. Proc., 1124, Q03–06, (2009).Google Scholar
10 Lacaillerie, J.B.E. Barberon, F., Romanenko, K.V. Lapina, O.B. Polles, L. Gautier, R. and Gan, Z., J. Phys. Chem. B 109, 14033–14042 (2005).Google Scholar
11 Macicek, J. Bulgarian Academy of Sciences, Sofia, Bulgaria, ICDD, (1992).Google Scholar
12 Klevtsov, P.V. Glinskaya, L.A. Klevtova, R.F. and Aleksandrov, K.S. Zh. Str Strukt. Khim., 38, 739 (1997).Google Scholar