• The Journal of the Petrological Society of Korea
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• v.10 no.3
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• pp.233-245
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• 2001

With the advent of super-conducting magnet, NMR spectroscopy becomes a very important tool in geology as well as in chemistry. $^{29}Si$ and $^{27}Al$ which are the main components of minerals and contain structural informations, are useful major targets for the NMR study in geology, but some other elements including alkali cations such as $^{23}Na$ are also one of them. NMR can be applied to many different fields. For example, it can be applied to study smaller range of structure (in molecular level) than XRD and TEM. NMR provides us with structural informations such as order-disorder in Al and Si distribution, oxygen coordination number, and distribution of other cations. Another important information that we can obtain from NMR is not only the static structural informations, but also the molecular dynamics. This dynamic informations of molecules also enable us to figure out the frequency of molecular motion and activation energy. Structure of amorphous minerals and chemistry and structure of natural organic materials are also studied by NMR.

• 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.

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

• Bulletin of the Korean Chemical Society
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• v.17 no.8
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• pp.696-699
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• 1996

Silicate and borosilicate gels were prepared by the sol-gel process and thermally treated in the 150-850 ℃ temperature range. Solid-state 1H MAS and 29Si CP/MAS NMR spectroscopy were used to investigate the effects of heat treatments on the silicate gel to glass conversion process. The 1H NMR isotropic chemical shifts and the relative intensities of hydrogen bonded and isolated silanol groups have been used to access the information concerning the dehydration process on the silicate gel surface. The 29Si NMR isotropic chemical shifts affected by the local silicon environment have been used to determine the degree of crosslinking, i.e. the number of siloxane bonds. These NMR results suggest that the silicate gel to glass conversion process is occurred by two stages which are dependent on the temperature; (1) the formation of particles up to 450 ℃ and (2) the formation of large particles by aggregation of each separated single particle above 450 ℃. In addition, the effects of B atom on the formation of borosiloxane bonds in borosilicates have been discussed.

• 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 Korean Chemical Society
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• v.40 no.10
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• pp.656-662
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• 1996

Using low temperature and atmospheric pressure method, we synthesized Na, TPA-ZSM-5 with Si/Al ratio of about 100. We employed 27Al and 29Si MAS NMR spectroscopy and FT-IR to investigate the crystallization process as a function of time. The chemical shift depends on the initial composition of reactants and changes during the course of synthesis different from those reported by others earlier. However, the chemical shift of our final product showed in the range of typical ZSM-5. And the defect site was removed by the calcine. From XRD and SEM data, the formation of ZSM-5 was also confirmed.

• Bulletin of the Korean Chemical Society
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• v.32 no.10
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• pp.3644-3649
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• 2011

Multinuclear solid-state nuclear magnetic resonance (NMR) experiments were performed to investigate the local structure changes of nanoporous silica during hydrothermal treatment and surface modification with 3-aminopropyltriethoxysilane (3-APTES). The nanoporous silica was prepared by sol-gel polymerization using inexpensive sodium silicate as a silica precursor. Using $^1H$ magic angle spinning (MAS) NMR spectra, the hydroxyl groups, which play an important role in surface reactions, were probed. Various silicon sites such as $Q^2$, $Q^3$, $Q^4$, $T^2$, and $T^3$ were identified with $^{29}Si$ cross polarization (CP) MAS NMR spectra and quantified with $^{29}Si$ MAS NMR spectra. The results indicated that about 25% of the silica surface was modified. $^1H$ and $^{29}Si$ NMR data proved that the hydrothermal treatment induced dehydration and dehyroxylation. The $^{13}C$ CP MAS and $^1H$ MAS NMR spectra of 3-APTES attached on the surface of nanoporous silica revealed that the amines of the 3-aminopropyl groups were in the chemical state of ${NH_3}^+$ rather than $NH_2$.

• Analytical Science and Technology
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• v.18 no.1
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• pp.1-4
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• 2005

The stable $Ti(OPr^i)_2(OAc)_2$ sol which reacts with a solution of prehydrolysed $Si(OEt)_4$ was made by addition of acetic acid. The structure evolution of the reaction mixture was monitered by $^1H$, $^{29}Si$ NMR and FT-IR spectroscopy.

• Journal of the Korean Chemical Society
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• v.38 no.3
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• pp.241-245
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• 1994

The oxidative addition reaction has been employed to synthesize heteropolynuclear compounds containing Si-M bonding interaction between the silicon atom of silatrane, pentacoordinate silicon derivative with transannular Si-N dative bond, and the main group element. The reaction of $SnBr_2 with 1-bromosilatrane(1a) in acetonitrile gives the mixture of yellow(2a) and white(2b) solids which were isolated and charaterized by ^1H-NMR, ^{29}Si-NMR, ^{119}Sn-NMR and Mass spectroscopy. The yellow compound was characterized as 1-tribromotinsilatrane which had Si-Sn bonding interaction. The reaction of SnBr2 with 1-bromo-3,7,10-trimethylsilatrane(1b) in methanol gives the Sn(Ⅳ) complex, N[CH_2CH(CH_3)O]_3SiSnBr_3(CH_3OH)_2(3),$ which was characterized by various means.

• Korean Journal of Materials Research
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• v.11 no.7
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• pp.603-608
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• 2001

$MO-SiO_2$ (M = Zn, Sn, In, Ag, Ni) binary silica gels were synthesized by sol-gel method and their structural change with the kind of metal ions was characterized by XRD, FT- IR and $^{29}$Si-NMR. Although X-ray analysis showed partial recrystallization of $AgNO_3$ in $Ag-SiO_2$gel, crystalline phase formed by the bonding between metal ion and the silica matrix didn't appear in all $MO-SiO_2$ gels. The FT-IR analysis showed that Zn, Sn and in partially formed Si-O-M bonding in silica matrix and made an shift of absorption peak to by Si-O-Si symmetrical vibration. In addition, $^{29}Si-NMR$ studies showed that Zn, Sn and In didn't affect sol-gel process of silica and were linked with non-bridging oxygen of the linear silica structure, which formed imperfect network because of low temperature sol-gel process. Ag and Ni make a role of catalysis on sol-gel process, resulting in densifying the silica network structure.