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

Journal Article · · Journal of Materials Research; (United States)
;  [1];  [2]
  1. Glass and Ceramics Science and Technology Division, Sandia National Laboratories, Albuquerque, New Mexico 87185 (United States)
  2. Department of Geology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States)

We have examined the bonding arrangements in Na--P--O--F and Na--Al--P--O--F glasses using {sup 19}F, {sup 27}Al, and {sup 31}P solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. For the Al-free series of glasses, the {sup 19}F 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 {sup 31}P 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, {sup 27}Al NMR detects only octahedral Al-sites, the {sup 19}F NMR spectra include a second peak near {minus}12 ppm due to F bonded to Al, and the {sup 31}P NMR spectra contain signals due to Q{sup 1}-sites with one or more Al next-nearest neighbors. The relative intensity of the two {sup 19}F 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 NH{sub 4}HF{sub 2}.

DOE Contract Number:
AC04-76DP00789
OSTI ID:
7164521
Journal Information:
Journal of Materials Research; (United States), Journal Name: Journal of Materials Research; (United States) Vol. 7:7; ISSN JMREE; ISSN 0884-2914
Country of Publication:
United States
Language:
English