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

• 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 the Korean Crystal Growth and Crystal Technology
• /
• v.8 no.2
• /
• pp.332-341
• /
• 1998

Reaction kinetics for the solid - state reaction of ${\alpha}-Al_2O_3$with amorphous $SiO_2$to produce mullite ($3Al_2O_3;{cdot};2SiO_2$) was studied in the temperature range of 1450~$1480^{\circ}C$. Rate of kinetic reaction were determined by using $SiO_2$- coated $Al_2O_3$ compact containing 28.16 wt.% $SiO_2$and heating the reactant mixtures in MgO at definite temperature for various times. Amount of products and unreacted reactants were determined by X-ray diffractometry. Data from the volume fraction and ratio of peak intensities of mullite indicated that the reaction of ${\alpha}-;Al_2O_3$ with $SiO_2$to form $3Al_2O_3\;{\cdot}\;2SiO_2$ start between 1450 and $1480^{\circ}C$. The activation energy for solid-state reaction was determined by using the Arrhenius equation; The activation energy was 31.9 kJ/mol.

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

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

• New & Renewable Energy
• /
• v.2 no.3
• /
• pp.31-36
• /
• 2006

Superstrate pin amorphous silicon thin-film(a-Si:H) solar cells are prepared on $SnO_2:F$ and ZnO:Al transparent conducting oxides(TCO) in order to see the effect of TCO/p-layers on a-Si:H solar cell operation. The solar cells prepared on textured ZnO:Al have higher open circuit voltage VOC than cells prepared on $SnO_2:F$. Presence of thin microcrystalline p-type silicon layer(${\mu}c-Si:H$) between ZnO:Al and p a-SiC:H plays a major role by causing improvement in fill factor as well as $V_{OC}$ of a-Si:H solar cells prepared on ZnO:Al TCO. Without any treatment of pi interface, we could obtain high $V_{OC}$ of 994mV while keeping fill factor(72.7%) and short circuit current density $J_{SC}$ at the same level as for the cells on $SnO_2:F$ TCO. This high $V_{OC}$ value can be attributed to modification in the current transport in this region due to creation of a potential barrier.

• Journal of the Korean Crystal Growth and Crystal Technology
• /
• v.7 no.2
• /
• pp.259-270
• /
• 1997

Reaction kinetics for the solid-state reaction of $\alpha-Al_2O_3$ with amorphous $TiO_2$ to produce $Al_2TiO_5$ (Tialite) was studied in the temperature range of $1200~1300^{\circ}C$. Rate of kinetic reaction were determined by using $TiO_2$-coated $Al_2O_3$ compact containing 50 mol% $TiO_2$ and heating the reactant mixtures in MgO at definite temperature for various times. Amount of products and unreacted reactants were determined by X-ray diffractometry. Data from the volume fraction and ratio of peak intensities of $\beta-Al_2TiO_5$ indicated that the reaction of $\alpha-Al_2O_3$ with $TiO_2$ to form pseudobrookite starts between 1280 and $1300^{\circ}C$. The activation energy for solid-state reaction was determined by using the Arrhenius equation ; The activation energy was 622.4 kJ/mol.

• Proceedings of the Korean Ceranic Society Conference
• /
• 2003.04a
• /
• pp.38.1-38
• /
• 2003

• Journal of the Korean Ceramic Society
• /
• v.25 no.3
• /
• pp.193-200
• /
• 1988

The starting materials were aluminum hydroxide prepared by precipitation method at the conditions of pH values; 7, 9, 10 and 11. The properties of alumina powder on heat-treatment were studied. After dehydrating structural water from amorphous aluminum hydroxide, the first formed phase was amorphous alumina and its specific surface are was decreased. The specific surface area was increased by dehydration of structural water from aluminum hydroxides except amorphous aluminum hydroxide. The specific surface area was increased with increase of the ratio of A1OOH to $A1(OH)_3$ in the region of transition aluminas. The rate of transition from aluminum hydroxide to alpha alumina occurred in the order of 7, 10, 9 and 11 of pH values. The morphology of alpha alumina powders was skeleton particles remaining outer shape of aluminum hydroxide. Both the elevation of heat-treatment temperature and the transition toalpha alumina decreased specific surface area and brought about the growth of particles.