Journal
JOURNAL OF NON-CRYSTALLINE SOLIDS
Volume 355, Issue 16-17, Pages 932-937Publisher
ELSEVIER SCIENCE BV
DOI: 10.1016/j.jnoncrysol.2009.04.023
Keywords
Raman scattering; Optical spectroscopy; Absorption; Optical spectroscopy; FTIR measurements; Raman spectroscopy; Phosphates; Short-range order; Glass transition; Water; Water in glass
Funding
- US Department of Energy [DE-AC02-05CH11231]
- Max Planck Institute in Stuttgart
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The structure of La-based metaphosphate glasses modified with aliovalent alkaline earth elements (M = Ba, Ca, Sr), with P:(M + La) ratio kept approximately at 3, were analyzed using Raman and IR spectroscopy. Increasing the concentration of the alkaline earths monotonically decreased the glass density and glass transition temperature, and shifted some vibrational modes by as much as 40 wavenumbers. The Raman frequencies of the symmetric POP and the P=O vibrations depended on the M/La ratio, but not on the type of alkaline earth addition; however, the type of alkaline earth cation significantly changed the symmetric PO2 vibration. The average cation-oxygen coordination number remained near similar to 7 except for a slight decrease for high concentrations of Ca and Sr substitutions. The POP/PO2 intensity ratio increased with increasing alkaline earth content. The replacement of divalent elements for trivalent La in a metaphosphate glass structure was partially accommodated by incorporation of protons as charge compensating defects. The protons were found to be in close proximity to the divalent cations. (C) 2009 Elsevier B.V. All rights reserved.
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