• Bulletin of the Korean Chemical Society
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• v.20 no.10
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• pp.1205-1208
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• 1999

27Al NMR chemical shielding, quadrupolar coupling, and dipolar coupling interactions for corundum (α-Al2O3) are determined from the single-crystal 27 Al NMR spectra according to the rotation about three orthogonal axis. 27 Al NMR parameters obtained in this work with high accuracy are as follows: δiso = 7.4(4) ppm, QCC = 2.30(4) MHz, h = 0.08(3), and R = 2.0(3) kHz. This work appears to be the first NMR measurement of an aluminum-aluminum dipolar coupling interaction in α-Al2O3 crystals.

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

• 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 Korean Magnetic Resonance Society
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• v.11 no.1
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• pp.42-47
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• 2007

Several hydrotalcite compounds calcined with different temperature for applications in a chlorine resistant textile were prepared, and its structural changes in dependence on the temperature were studied by using $^{27}Al$ solid-state nuclear magnetic resonance(NMR) spectroscopy. We found that the Al coordination was partly lowered from octahedral to tetrahedral site as the calcined temperature goes up. And we also investigated the hydrotalcite-treated textile for chlorine resistance by using $^{27}Al$ solid-state NMR spectroscopy.

• Journal of the Korean Magnetic Resonance Society
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• v.16 no.2
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• pp.111-121
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• 2012

The spin-lattice relaxation times, $T_1$, and spin-spin relaxation times, $T_2$, of the $^{27}Al$ and $^{87}Rb$ nuclei in $RbAl(CrO_4)_2{\cdot}2H_2O$ crystals were investigated. The presence of only one resonance line for the $^{27}Al$ nuclei indicates that the results in a dynamical averaging of the crystal electric field that produces a cubic symmetry field. The changes in the temperature dependence of $T_1$ are related to variations in the symmetry of the octahedra of water molecules surrounding $Al^+$ and $Rb^+$. The $T_1$ values for the $^{27}Al$ and $^{87}Rb$ nuclei are different due to differences in the local environments of these ions. We also compared these $^{27}Al$ and $^{87}Rb$ NMR results with those obtained for $RbAl(CrO_4)_2{\cdot}2H_2O$ crystals. The relaxation mechanisms of $RbAl(XO_4)_2{\cdot}nH_2O$ (X=Cr and S) crystals are characterized by completely different NMR behaviors.

• 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 Magnetic Resonance Society
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• v.4 no.1
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• pp.12-18
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• 2000

Metakaolinite produced by thermal transformation from kaolinite was studied by 27Al multiple quantum magic angel spinning (MQMAS) NMR technique in addition to 1-dimensional 27Al and 29Si MAS NMR. Our results confirm that 4-, 5-, 6- coordinated aluminum sites co-exit with some distribution of isotropic chemical shifts. This is consistent with amorphous character of metakaolinite observed with X-ray diffraction. In addition, characterization with MQMAS is briefly discussed in comparison with other NMR techniques to identify different aluminum sites especially when peaks are severely overlapped in 1-dimensional 27Al MAS NMR spectra.

• 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.

• Journal of the Mineralogical Society of Korea
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• v.25 no.4
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• pp.283-293
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• 2012

In order to have better insights into the chemical differentiation of Earth from its magma ocean phase to the current stratified structure, detailed information of crystallization kinetics of silicate melts consisting of the magma ocean is essential. The structural transitions in oxide glasses and melts upon crystallization provide improved prospects for a systematic and quantitative understanding of the crystallization processes. Here, we report the $^{27}Al$ 3QMAS NMR spectra for sol-gel synthesized $Al_2O_3$ glass with varying temperature and annealing time. The NMR spectra for the amorphous $Al_2O_3$ show well-resolved Al coordination environments, characterized with mostly $^{[4,5]}Al$ and a minor fraction of $^{[6]}Al$. The fraction of $^{[5]}Al$ in the alumina phase decreases with increasing annealing time at constant temperature. The NMR results of $Al_2O_3$ phases also imply that multiple processes (e.g., crystallization and/or changes in structural disorder within glasses) could involve upon its phase transition. The current results and method can be useful to understand crystallization kinetics of diverse natural and multi-component silicate glasses and melts. The potential result may yield atomic-level understanding of Earth's chemical evolution and differentiation from the magma ocean.

• Bulletin of the Korean Chemical Society
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• v.30 no.1
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• pp.149-152
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• 2009

Hydrotalcites are anionic clays that are quite prevalent in nature and their importance is growing more and more because of their very wide range of potential applications and uses. Understanding the structural and compositional changes that occur on the molecular scale during the thermal decomposition of hydrotalcite compounds is essential for the basic prediction and comprehensive understanding of the behavior and technical application of these materials. In this study, several hydrotalcite compounds calcined at different temperatures for applications in a chlorine resistant textile were prepared and 27-Aluminm solid-state nuclear magnetic resonance (NMR) spectroscopy was used as a tool to study their local structure and behavior. The changes in the Al coordination of the hydrotalcite compounds were investigated with one dimensional (1D) solid-state magic angle spinning (MAS) NMR spectroscopy. The two broad resonances arising from the structurally different Al coordinations of these compounds were clearly resolved by two dimensional (2D) triple quantum magic angle spinning (3QMAS) NMR spectroscopy.