• Journal of the Mineralogical Society of Korea
• /
• v.28 no.1
• /
• pp.61-69
• /
• 2015

While the macroscopic properties and eruption style of basaltic and phonolitic melts are different, the microscopic origins including atomic structures are not well understood. Here we report the atomic structure differences of glass in diopside-anorthite eutectic composition (basaltic glass) and phonolitic glass using high-resolution 1D and 2D solid-state Nuclear Magnetic Resonance (NMR). The $^{27}Al$ MAS NMR spectra for basaltic glass and phonolitic glass show that the full width at half maximum (FWHM) of Al for basaltic glass is about twice than phonolitic glass, suggesting the topological disorder of basaltic magma is larger than that of phonolitic magma. The $^{27}Al$ 3QMAS NMR spectra for basaltic glass and phonolite glass show much improved resolution than the 1D MAS NMR, resolving Al and Al. Approximately 3.3% of Al is observed for basaltic glass, demonstrating the configurational disorder of basaltic magma is larger than phonolitic magma. This result confirms that the topological disorder of Al in basaltic glass is larger than that of phonolitic glass. The observed structural differences between basaltic glass and phonolitic glass can provide an atomistic origin for change of the macroscopic properties with composition including viscosity.

• Journal of the Mineralogical Society of Korea
• /
• v.18 no.1
• /
• pp.45-52
• /
• 2005

The recent development and advances in 2 dimensional solid-state NMR, particularly, triple quantum (3Q) MAS NMR yield much improved resolution compared with conventional 1 dimensional MAS NMR, allowing us to study the distributions of cations and anions in the non-crystalline silicate glasses and melts. Here, we present the recent progress made by 3QMAS NMR spectra of silicate glasses quenched from melts at pressures up to 10 GPa in a multi-anvil apparatus, revealing previously unknown details of structures of covalent oxide glasses and melts at high pressure.

• Journal of the Mineralogical Society of Korea
• /
• v.21 no.3
• /
• pp.321-329
• /
• 2008

Amorphous silica nanoparticles are among the most fundamental $SiO_2$ compounds, having implications in diverse geological processes and technological applications. Here, we explore structural details of amorphous silica nanoparticles with varying particle sizes (7 and 14 nm) using $^{29}Si$ and $^{1}H$ MAS NMR spectroscopy together with quantum chemical calculations to have better prospect for their size-dependent atomic structures. $^{29}Si$ MAS NMR spectra at 9.4 T resolve $Q^2,\;Q^3$ and $Q^4$ species at -93 ppm, -101 ppm, -110 ppm, respectively. The fractions of $Q^2,\;Q^3,\;O^4$ species are $7{\pm}1%,\;27{\pm}2%$, and $66{\pm}2%$ for 7 nm amorphous silica nanoparticles and $6{\pm}1%,\;21{\pm}2%$, and $73{\pm}2%$ for 14 nm amorphous silica nanoparticles. Whereas it has been suggested that $Q^2$ and $Q^3$ species exist on particles surfaces, the difference in $Q^{2}\;+\;Q^{3}$ fraction in both 7 and 14 nm particles is not significant, suggesting that $Q^2$ and $Q^3$ species could exist inside particles. $^{1}H$ MAS NMR spectra at 11.7 T shows diverse hydrogen environments, including physisorbed water, hydrogen bonded silanol, and non-hydrogen bonded silanol with varying hydrogen bond strength. The hydrogen contents in the 7nm silica nanoparticles (including water and hydroxyl groups) are about 3 times of that of 14 nm particles. The larger chemical shills for proton environments in the former suggest stronger hydrogen bond strength. The fractions of non-hydrogen bonded silanols in the 14 nm amorphous silica nanoparticles are larger than those in 7 nm amorphous silica nanoparticles. This observation suggests closer proximity among hydrogen atoms in the nanoparticles with smaller diameter. The current results with high-resolution solid-state NMR reveal previously unknown structural details in amorphous silica nanoparticles with particle size.

• Korean Journal of Mineralogy and Petrology
• /
• v.34 no.3
• /
• pp.157-167
• /
• 2021

Lead (Pb) is one of the key trace elements, exhibiting a peculiar partitioning behavior into silicate melts in contact with minerals. Partitioning behaviors of Pb between silicate mineral and melt have been known to depend on melt composition and thus, the atomic structures of corresponding silicate liquids. Despite the importance, detailed structural studies of Pb-bearing silicate melts are still lacking due to experimental difficulties. Here, we explored the effect of lead content on the atomic structures, particularly the evolution of silicate networks in Pb-bearing sodium metasilicate ([(PbO)_x(Na₂O)_1-x]·SiO₂) glasses as a model system for trace metal bearing natural silicate melts, using ²⁹Si solid-state nuclear magnetic resonance (NMR) spectroscopy. As the PbO content increases, the ²⁹Si peak widths increase, and the maximum peak positions shift from -76.2, -77.8, -80.3, -81.5, -84.6, to -87.7 ppm with increasing PbO contents of 0, 0.25, 0.5, 0.67, 0.86, and 1, respectively. The ²⁹Si MAS NMR spectra for the glasses were simulated with Gaussian functions for Qⁿ species (SiO₄ tetrahedra with n BOs) for providing quantitative resolution. The simulation results reveal the evolution of each Qⁿ species with varying PbO content. Na-endmember Na₂SiO₃ glass consists of predominant Q² species together with equal proportions of Q¹ and Q³. As Pb replaces Na, the fraction of Q² species tends to decrease, while those for Q¹ and Q³ species increase indicating an increase in disproportionation among Qⁿ species. Simulation results on the ²⁹Si NMR spectrum showed increases in structural disorder and chemical disorder as evidenced by an increase in disproportionation factor with an increase in average cation field strengths of the network modifying cations. Changes in the topological and configurational disorder of the model silicate melt by Pb imply an intrinsic origin of macroscopic properties such as element partitioning behavior.

• Journal of the Mineralogical Society of Korea
• /
• v.22 no.4
• /
• pp.343-352
• /
• 2009

High-resolution Solid-state NMR provides element specific and quantitative information and also resolves, otherwise overlapping atomic configurations in multi-component non-crystalline silicates. Here we report the preliminary results on the effect of composition on the structure of CMAS (CaO-MgO-$Al_2O_3-SiO_2$) silicate glasses, as a model system for basaltic magmas, using the high-resolution 1D and 2D solid-state NMR. The $^{27}Al$ MAS NMR spectra for the CMAS silicate glasses show that four-coordinated Al is predominant, demonstrating that $Al^{3+}$ is network forming cation. The peak position moves toward lower frequency about 4.7 ppm with increasing $X_{MgO}$ due to an increase in $Q^4$(4Si) fraction with increasing Si content, indicating that Al are surrounded only by bridging oxygen. $^{17}O$ MAS NMR spectra for $CaAl_2SiO_6$ and $CaMgSi_2O_6$ glasses qualitatively suggest that NBO fraction in the former is smaller than that in $CaMgSi_2O_6$ glasses. As $^{17}O$ 3QMAS NMR spectrum of model quaternary aluminosilicate glass resolved distinct bridging and non-bridging oxygen environments, atomic structure for natural magmas can also be potentially probed using high-resolution 3QMAS NMR.

• Journal of Astronomy and Space Sciences
• /
• v.23 no.1
• /
• pp.11-18
• /
• 2006

We have modeled dust envelopes around silicate carbon stars using optical properties for a mixture of amorphous carbon and silicate dust grains paying close attention to the infrared observations of the stars. The 4 stars show various properties in chemistry and location of the dust shell. We expect that the objects that fit a simple detached silicate dust shell model could be in the transition phase of the stellar chemistry. For binary system objects, we find that a mixed dust chemistry model would be necessary.

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

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

• Korean Journal of Mineralogy and Petrology
• /
• v.34 no.1
• /
• pp.31-40
• /
• 2021

The hydrogen in nominally anhydrous mineral is known to be associated with lattice defects, but it also can exist in the form of water and hydroxyl groups on the large surface of the nanoscale particles. In this study, we investigate the effectiveness of 1H solid-state nuclear magnetic resonance (NMR) spectroscopy as a robust experimental method to quantify the hydrogen atomic environments of amorphous silica nanoparticles with varying relative humidity. Amorphous silica nanoparticles were packed into NMR rotors in a temperature-humidity controlled glove box, then stored in different atmospheric conditions with 25% and 70% relative humidity for 2~10 days until 1H NMR experiments, and a slight difference was observed in 1H NMR spectra. These results indicate that amount of hydrous species in the sample packed in the NMR rotor is rarely changed by the external atmosphere. The amount of hydrogen atom, especially the amount of physisorbed water may vary in the range of ~10% due to the temporal and spatial inhomogeneity of relative humidity in the glove box. The quantitative analysis of 1H NMR spectra shows that the amount of hydrogen atom in amorphous silica nanoparticles linearly increases as the relative humidity increases. These results imply that the sample sealing capability of the NMR rotor is sufficient to preserve the hydrous environments of samples, and is suitable for the quantitative measurement of water content of ultrafine nominally anhydrous minerals depending on the atmospheric relative humidity. We expect that 1H solid-state NMR method is suitable to investigate systematically the effect of surface area and crystallinity on the water content of diverse nano-sized nominally anhydrous minerals with varying relative humidity.

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