• Journal of the Mineralogical Society of Korea
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• v.31 no.4
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• pp.295-306
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• 2018

Despite the utility of solid-state NMR, NMR studies of iron-bearing silicate glasses remain a challenge because the variations in the peak position and width with increasing iron content reflect both paramagnetic effect and iron-induced structural changes. Therefore, it is essential to elucidate the effect of temperature on the NMR signal for iron-bearing silicate glasses. Here, we report the $^{29}Si$ and $^{27}Al$ MAS NMR spectra for $(Mg_{0.95}Fe_{0.05})SiO_3$ and $Fe_2O_3$-bearing $CaAl_2Si_2O_8$ (anorthite) glasses with varying spinning speed to interpret the NMR spectra for iron-bearing silicate glasses. The increase in the spinning speed results in an increase in the sample temperature. The current NMR results allow us to understand the origins of the changes in NMR signal with increasing iron content and to provide information on the dipolar interaction between nuclear spins. The $^{29}Si$ NMR spectra for $(Mg_{0.95}Fe_{0.05})SiO_3$ glass and $^{27}Al$ NMR spectra for $Fe_2O_3$-bearing $CaAl_2Si_2O_8$ glasses show that the peak shape and position of iron-bearing glasses do not change with increasing spinning speed up to 30 kHz. These results suggest that the NMR signal in the Fe-bearing glasses may stem from the 'survived nuclear spins' beyond the cutoff radius from the Fe, not from the paramagnetic shift. Based on the current results, the observed apparent shifts toward lower frequency of Al peak for $Fe_2O_3$-bearing $CaAl_2Si_2O_8$ glasses with increasing $Fe_2O_3$ at all spinning speed (15 kHz to 30 kHz) indicate the increase in the fraction of ${Q^4}_{Al}$(nSi) with lower n (i.e., 1 or 2) with increasing $Fe_2O_3$ and the spatial proximity between Fe and ${Q^4}_{Al}$(nSi) with higher n (i.e., 3 or 4). The present results show that changes in the NMR signal for iron-bearing silicate glasses reflect the actual iron-induced structural changes. Thus, it is clear that the applications of solid-state NMR for iron-bearing silicate glasses hold strong promise for unraveling the atomic structure of natural silicate glasses.

• Journal of the Mineralogical Society of Korea
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• v.24 no.4
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• pp.301-312
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• 2011

The study on the atomic structure of iron-bearing silicate glasses has significant geological implications for both diverse igneous processes on Earth surface and ultra-low velocity zones at the core-mantle boundary. Here, we report experimental results on the effect of iron content on the atomic structure in iron-bearing alkali silicate glasses ($Na_2O-Fe_2O_3-SiO_2$ glasses, up to 16.07 wt% $Fe_2O_3$) using $^{29}Si$ and $^{17}O$ solid-state NMR spectroscopy. $^{29}Si$ spin-lattice ($T_1$) relaxation time for the glasses decreases with increasing iron content due to an enhanced interaction between nuclear spin and unpaired electron in iron. $^{29}Si$ MAS NMR spectra for the glasses show a decrease in signal intensity and an increase in peak width with increasing iron content. However, the heterogeneous peak broa-dening in $^{29}Si$ MAS NMR spectra suggests the heterogeneous distribution of $Q^n$ species around iron in iron-bearing silicate glasses. While nonbridging oxygen ($Na-O-Si$) and bridging oxygen (Si-O-Si) peaks are partially resolved in $^{17}O$ MAS NMR spectrum for iron-free silicate glass, it is difficult to distinguish the oxygen clusters in iron-bearing silicate glass. The Lorentzian peak shape for $^{29}Si$ and $^{17}O$ MAS NMR spectra may reflect life-time broadening due to spin-electron interaction. These results demonstrate that solid-state NMR can be an effective probe of the detailed structure in iron-bearing silicate glasses.