High resolution 17O MAS and triple-quantum MAS NMR studies of gallosilicate glasses

Gallosilicate (or ‘galliosilicate’) glasses have been widely studied as analogs of aluminosilicates, and the variations with composition in properties are known to be similar in both systems. We have applied 17O MAS and triple-quantum MAS (3QMAS) NMR spectroscopy to investigate the oxygen local environments in Na-, Li-, Ca- and Y-gallosilicate glasses. Signals due to several different oxygen species can be resolved and their concentrations quantified and NMR parameters determined. The NMR spectra generally resemble those of aluminosilicate glasses, indicating that the current model of gallium ions occupying the same types of sites as aluminum ions is a good first approximation. Quadrupolar coupling constants for the various oxygen sites tend to be larger than those for aluminosilicates, however, and vary less among different types of sites. Broader 17O spectra at low to medium external magnetic fields result. In detail, several types of differences between the observed oxygen species populations for gallosilicate and aluminosilicate are consistent with the larger radius of Ga3+ in comparison to Al3+, and possibly with a somewhat greater tendency for the former to form groups with oxygen coordination numbers greater than four. These include more Si–Ga disorder than Si–Al disorder in corresponding sodium gallo- vs. aluminosilicates, and more ‘non-stoichiometric’ non-bridging oxygen in a calcium gallosilicate than in a calcium aluminosilicate glass.