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Title: Coordination Environments of Highly Charged Cations (Ti, Cr, and Light REE's) in Borosilicate Glass/Melts to 1120 deg. C

Journal Article · · AIP Conference Proceedings
DOI:https://doi.org/10.1063/1.2644476· OSTI ID:21054596
 [1];  [2]
  1. USM 201 Mineralogie, Museum National d'Histoire Naturelle, CNRS UMR 7160, Paris (France)
  2. Dept. of Geological and Environmental Sciences, Stanford University, Stanford, CA 94305-2115 (United States)

The local environments around Ti, Cr, and several light rare-earth elements (La, Ce, and Nd) were investigated by in-situ XANES spectroscopy in a number of complex borosilicate glasses and melts (to 1120 deg. C) that are used for nuclear waste storage. Examination of the high-resolution XANES spectra at the Ti K-edge shows that the average coordination of Ti changes from {approx}5 to {approx}4.5. Cr is dominantly trivalent in the melts studied. However, its average coordination is probably lower in the melt (tetrahedral ?) as revealed by the more intense Cr-K pre-edge feature. Ce also changes its average valence from dominantly +4 to +3.5 upon glass melting. These changes are reversible at Tg, the glass transition temperature ({approx}500-550 deg. C for these glasses). In contrast, the local environments of Nd, Pr, and La are unaffected by melting. Therefore, structural reorganization of these borosilicate glass/melts above Tg is variable, not only in terms of valence (as for Ce) but also speciation (Ti and Cr). Both the ability of B to adopt various coordination geometries (triangular and tetrahedral) and the chemical complexity of the glass/melts explain these changes.

OSTI ID:
21054596
Journal Information:
AIP Conference Proceedings, Vol. 882, Issue 1; Conference: XAFS13: 13. international conference on X-ray absorption fine structure, Stanford, CA (United States), 9-14 Jul 2006; Other Information: DOI: 10.1063/1.2644476; (c) 2007 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0094-243X
Country of Publication:
United States
Language:
English