Nuclear magnetic resonance studies of alkaline earth phosphosilicate and aluminoborosilicate glasses

The 11B, 27Al, 29Si and 31P magic angle spinning (MAS) NMR spectra of MO–P2O5, MO–SiO2–P2O5 and MO(M′2O)–SiO2–Al2O3–B2O3 (M=Mg, Ca, Sr and Ba, M′=Na) glasses were examined. In binary MO–P2O5 (M=Ca and Mg) glasses, the distributions of the phosphate sites, P(Qn), can be expressed by a theoretical prediction that P2O5 reacts quantitatively with MO. In the ternary 0.30MO–0.05SiO2–0.65P2O5 glasses, the 6-coordinated silicon sites were detected, whose population increases in the order of MgO<CaO<SrO≒BaO. In xCaO–0.05SiO2–(0.95−x)P2O5 glasses, its population increases with an increase in f (=([P2O5]−[MO]−[B2O3]−[Na2O])/[SiO2]) and has maximum at f=9. The signal due to the 5-coordinated silicon atoms is also observed when x is smaller than 0.45. When three network-forming oxides such as SiO2, Al2O3 and B2O3 coexist, Al2O3 reacts preferably with MO. The populations of 4-coordinated boron atoms, N4, are expressed well with r/(1−r), where r=([Na2O]−[Al2O3])/([Na2O]−[Al2O3]+[B2O3]). The correlation of the Raman signal at 1210 and 1350 cm−1 with the NMR signal of Si(Q6) at −215 ppm is also seen.