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A multinuclear MAS NMR study of the short-range structure of fluorophosphate glass

Published online by Cambridge University Press:  31 January 2011

R.K. Brow ,
Z.A. Osborne  and
R.J. Kirkpatrick
R.K. Brow
Affiliation:
Glass and Ceramics Science & Technology Division, Sandia National Laboratories, Albuquerque, New Mexico 87185
Z.A. Osborne*
Affiliation:
Glass and Ceramics Science & Technology Division, Sandia National Laboratories, Albuquerque, New Mexico 87185
R.J. Kirkpatrick
Affiliation:
Department of Geology, University of Illinois at Urbana–Champaign, Urbana, Illinois 61801
*
a)Current address: Arizona Materials Lab, Tucson, Arizona.
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Abstract

We have examined the bonding arrangements in Na–P–O–F and Na–Al–P–O–F glasses using 19F, 27Al, and 31P solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. For the Al-free series of glasses, the 19F NMR spectra are dominated by peaks near +90 ppm, representative of F terminating P-chains. The formation of these bonds has little effect on the 31P chemical shifts, indicating that F preferentially replaces bridging oxygen on the phosphate tetrahedra, consistent with previous NMR studies of crystalline fluorophosphates and other spectroscopic studies of fluorophosphate glass. For the Na–Al–P–O–F glasses, 27Al NMR detects only octahedral Al-sites, the 19F NMR spectra include a second peak near −12 ppm due to F bonded to Al, and the 31P NMR spectra contain signals due to Q1-sites with one or more Al next-nearest neighbors. The relative intensity of the two 19F peaks correlates well with previous spectroscopic studies and shows that a greater fraction of F–P bonds forms when the base glass is remelted in NH4HF2.

Type
Articles
Information
Journal of Materials Research , Volume 7 , Issue 7 , July 1992 , pp. 1892 - 1899
Copyright
Copyright © Materials Research Society 1992

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