Structural characterization of fluorophosphate glasses using NMR methodologies

MOREIRA, R.J.S. Structural characterization of fluorophosphate glasses using NMR methodologies 2014. 84 p. Dissertation (Master in Science) Instituto de Física de São Carlos, Universidade de São Paulo, São Carlos, 2014. In this work was studied the development of structure/property correlations for new fluorophosphate glasses compositions: [80Ba(PO3)2 – 20Al(PO3)3]1-x[80BaF2 – 20AlF3]x(0 ≤ x ≤ 40 mol%). Most suitable techniques for the structural analysis in case of disordered and amorphous material are Nuclear Magnetic Resonance (NMR) Spectroscopy and Raman scattering. Results from X-ray diffraction (XRD) and differential thermal analysis (DTA) reveal that amorphous samples were obtained for all glass compositions up to x ≤ 30. However, the fluorine quantification via F MAS NMR suggests significant fluoride loss and/or fluoride/oxide replacement. Both P and Raman results indicate gradual conversion of Qm units to Q 1 m units with increasing the fluorine concentration. F MAS NMR spectra indicate fluorine atoms in two different chemical environments bonded wither covalently to P-atoms or located in a mixed Al/Ba environment. The P-F assignment is confirmed by F{P}REDOR experiments. Al NMR spectra shows dominantly six-coordinated aluminium, and the Al{P}-REDOR data suggest nearly exclusive coordination of Al with phosphate species. The dipolar coupling constant obtained by P{P}-DRENAR are roughly consistent with P spectral deconvolution suggesting the presence of Qand Q species.

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