Solid-State 19F NMR On Cao-SiO2-CaF2 Glasses

Chemical states of fluorine in CaO-SiO2-CaF2glasses in a composition range of CaO/SiO2=0.5?1.3 and 5?25 mol%CaF2have been investigated by 19F solid-state NMR with and without MAS. The isotropic chemical shifts of the glasses are close to those of cuspidine crystal (59.4 and64.3 ppm with respect to C6F6) and CaF2crystal (58.6 ppm). The fluoride ions are coordinated with four or less than four calcium ions in this composition range. The chemical shifts move to the lower frequency with an increase in the CaF2content, whereas those are not affected by theCaO/SiO2ratio. The ionic distance between calcium and fluoride ions increases with an increase in the CaF2content. The chemical state of fluorine is not disturbed by the degree of polymerization of the silicate network. Comparing the MAS and static NMR spectra, the second moment attributed to 19F-19F dipole-dipole interaction has been estimated. The values of the glasses range over 3.1?7.3107Hz2andthose are larger than the calculated value of cuspidine crystal. This indicates that fluoride ions form Ca-F clusters in the glasses and that the size of clusters increases with increasing the CaF2content. Keywords: chemical state of fluoride ion, CaO-SiO2-CaF2glass, solid state 19F NMR spectroscopy