• Journal of the Mineralogical Society of Korea
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• v.32 no.1
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• pp.41-49
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• 2019

Probing the Na environments in Na silicate and aluminosilicate glasses is essential to the macroscopic properties of melts in the Earth. In particular, exploring the atomic structure of Na silicate and aluminosilicate glasses reveals Na-O distance, which plays an important role in transport properties of melts. Here we report the local environment around Na using $^{23}Na$ magic angle spinning (MAS) NMR. We also obtain $^{23}Na$ isotropic chemical shift (${\delta}_{iso}$) of Na silicate and aluminosilicate glasses with varying composition using Dmfit program. The Q mas 1/2 model simulates the experimental results with three simulated peaks while the CzSimple model simulates with one peak. The ${\delta}_{iso}$ decreases with increasing $SiO_2$ content in Na silicate and aluminosilicate glasses. The ${\delta}_{iso}$ increases with increasing $Na_2O$ content in Na-Ca silicate and Na aluminosilicate glasses when the $SiO_2$ content is fixed. Considering the ${\delta}_{iso}$ of Na aluminosilicate glasses available in the previous studies, together with the current simulation results, we confirm that the ${\delta}_{iso}$ has positive correlation with Al / (Al + Si). Those experimental results were reproduced better using Q mas 1/2 model. The disorder of Na in Na silicate and aluminosilicate glasses can be revealed through the simulation of 1D $^{23}Na$ MAS NMR spectra using Dmfit program in a short time.

• Journal of the Mineralogical Society of Korea
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• v.19 no.4 s.50
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• pp.347-353
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• 2006

The atomic-nano scale structures of multi-component aluminosilicate glasses have not been well understood in spite of its implications fur dynamics and generation of magma in the natural system due to lack of suitable spectroscopic and scattering experiments. Here, we report O-17 MAS and isotropic projection of 3QMAS NMR spectra for quaternary Na-Ca silicate glasses $[(CaO)_x(Na_2O)_{1-x}]\;(A1_2O_3)_{0.5}(SiO_2)_6,\;CNAS)$ at 14.1 Tesla where atomic configurations around bridging oxygen (Si-O-Si, Si-O-Al) and non bridging oxygen (Na-O-Si, Ca-O-Si, (Na, Ca)-O-Si) are partially resolved. With increasing Na content, the fraction of Na-O-Si increases while those for bridging oxygens remain constant. The Na/Ca ratio apparently affects the peak widths of bridging oxygen peaks (e.g., Si-O-Si)) and thus the topological entropy as well as chemical shifts of the bridging oxygen peaks, implying that both BOs and NBOs are strongly interacting with network modifying cations The effect of cation field strength on the degree of Al-avoidance was also discussed.

• Journal of the Mineralogical Society of Korea
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• v.29 no.3
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• pp.155-165
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• 2016

Understanding the effect of boron content on atomic structures of boron-bearing multicomponent silicate melts is essential to reveal the atomistic origins of diverse geochemical processes involving silica-rich magmas, such as explosive volcanic eruption. The detailed atomic environments around B and Al in boron-bearing complex aluminosilicate glasses yield atomistic insights into reactivity of nuclear waste glasses in contact with aqueous solutions. We report experimental results on the effect of boron content on the atomic structures of sodium borate glasses and boron-bearing multicomponent silicate melts [malinkoite ($NaBSiO_4$)-nepheline ($NaAlSiO_4$) pseudo-binary glasses] using the high-resolution solid-state NMR ($^{11}B$ and $^{27}Al$). The $^{11}B$ MAS NMR spectra of sodium borate glasses show that three-coodrinated boron ($^{[3]}B$) increases with increasing $B_2O_3$ content. While the spectra imply that the fraction of non-ring species decreases with decreasing boron content, peak position of the species is expected to vary with Na content. Therefore, the quantitative estimation of the fractions of the ring/non-ring species remains to be explored. The $^{11}B$ MAS NMR spectra of the glasses in the malinkoite-nepheline join show that four-coordinated boron ($^{[4]}B$) increases as $X_{Ma}$ [$=NaBSiO_4/(NaBSiO_4+NaAlSiO_4)$] increases while $^{[3]}B$ decreases. $^{27}Al$ MAS NMR spectra of the multicomponent glasses confirm that four-coordinated aluminum ($^{[4]}Al$) is dominant. It is also observed that a drastic decrease in the peak widths (full-width at half-maximum, FWHM) of $^{[4]}Al$ with an addition of boron ($X_{Ma}=0.25$) in nepheline glasses. This indicates a decrease in structural and topological disorder around $^{[4]}Al$ in the glasses with increasing boron content. The quantitative atomic environments around boron of both binary and multicomponent glasses were estimated from the simulation results of $^{11}B$ MAS NMR spectra, revealing complex-nonlinear variation of boron topology with varying composition. The current results can be potentially used to account for the structural origins of the change in macroscopic properties of boron-bearing oxide melts with varying boron content.