• Ceramist
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• v.23 no.2
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• pp.211-230
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• 2020

Perovskite-type oxides with the nominal composition of ABO₃ can exsolve the B-site transition metal upon the controlled reduction. In this exsolution process, the transition metal emerges from the oxide lattice and migrates to the surface at which it forms catalytically active nanoparticles. The exsolved nanoparticles can recover back to the bulk lattice under oxidation treatment. This unique regeneration character by the redox treatment provides uniformly dispersed noble metal nanoparticles. Therefore, the conventional problem of traditional impregnated metal/support, i.e., sintering during reaction, can be effectively avoided by using the exsolution phenomenon. In this regard, the catalysts using the exsolution strategy have been well studied for a wide range of applications in energy conversion and storage devices such as solid oxide fuel cells and electrolysis cells (SOFCs and SOECs) because of its high thermal and chemical stability. On the other hand, although this exsolution strategy can also be applied to gas phase reaction catalysts, it has seldomly been reviewed. Here, we thus review recent applications of the exsolution catalysts to the gas phase reactions from the aspects of experimental measurements, where various functions of the exsolved particles were utilized. We also review non-perovskite type metal oxides that might have exolution phenomenon to provide more possibilities to develop higher efficient catalysts.

• Journal of the Korean Ceramic Society
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• v.53 no.5
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• pp.469-477
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• 2016

The application of nanomaterials for electrodes of intermediate temperature solid oxide fuel cells (SOFC) is introduced. In conventional SOFCs, the operating temperature is higher than 1073 K, and so application of nanomaterials is not suitable because of the high degradation rate that results from sintering, aggregation, or reactions. However, by allowing a decrease of the operating temperature, nanomaterials are attracting much interest. In this review, nanocomposite films with columnar morphology, called double columnar or vertically aligned nanocomposites and prepared by pulsed laser ablation method, are introduced. For anodes, metal nano particles prepared by exsolution from perovskite lattice are also applied. By using dissolution and exsolution into and from the perovskite matrix, performed by changing $P_{O2}$ in the gas phase at each interval, recovery of the power density can be achieved by keeping the metal particle size small. Therefore, it is expected that the application of nanomaterials will become more popular in future SOFC development.

• Proceedings of the Petrological Society of Korea Conference
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• 2009.05a
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• pp.104-107
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• 2009

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.402.1-402.1
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• 2016

The performance of solid oxide fuel cells (SOFCs) is directly related to the electrocatalytic activity of composite electrodes in which triple phase boundaries (TPBs) of metallic catalyst, oxygen ion conducting support, and gas should be three-dimensionally maximized. The distribution morphology of catalytic nanoparticle dispersed on external surfaces is of key importance for maximized TPBs. Herein in situ grown nickel nanoparticle onto the surface of fluorite oxide is demonstrated employing gadolium-nickel co-doped ceria ($Gd0.2-xNixCe0.8O2-{\delta}$, GNDC) by reductive annealing. GNDC powders were synthesized via a Pechini-type sol-gel process while maximum doping ratio of Ni into the cerium oxide was defined by X-ray diffraction. Subsequently, NiO-GNDC composite were screen printed on the both sides of yttrium-stabilized zirconia (YSZ) pellet to fabricate the symmetrical half cells. Electrochemical impedance spectroscopy (EIS) showed that the polarization resistance was decreased when it was compared to conventional Ni-GDC anode and this effect became greater at lower temperature. Ex situ microstructural analysis using scanning electron microscopy after the reductive annealing exhibited the exsolution of Ni nanoparticles on the fluorite phases. The influence of Ni contents in GNDC on polarization characteristics of anodes were examined by EIS under H2/H2O atmosphere. Finally, the addition of optimized GNDC into the anode functional layer (AFL) dramatically enhanced cell performance of anode-supported coin cells.

• Journal of the Mineralogical Society of Korea
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• v.27 no.4
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• pp.197-205
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• 2014

Study area (Jikjeon-ri) is located in south end of the Hadong anorthositic rocks. And along the south-western boundary, diorite intruded the Hadong anorthosite. Ilmenite ore bodies are extended in both anorthosite and diorite. And their occurrence in the diorite are not studied yet. While no particular textures are found in the ilmenite within the anorthosite, the ilmenite within the diorite shows characteristic exsolution texture, that is, ilmenite phases are separated into rutile and Fe-oxide and the ilmenite and Fe-oxide. MnO composition in ilmenite ratios are 2.14~3.74wt%, it has higher composition in diorite than that in anorthosite. The plagioclase composition display andesine ($An_{28.7-42.9}$) in the diorite and labradorite ($An_{57.1-72.8}$) in the anorthosite in composition. The exsolution of ilmenite has been developed during the cooling of partly melted ilmenite into rutile and Fe-oxides which is related to the intrusion of the diorite.

• Journal of the Mineralogical Society of Korea
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• v.24 no.3
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• pp.195-204
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• 2011

Exsolution intergrowth of ilmenite and hematite was studied by the Rietveld refinement method. According to the analysis on these two structural analog minerals, it was found that octahedron (M2) of Ti in ilmenite is in the least deformation, then that (M1) of Fe in ilmenite is deformed next, and octaheron deformation of Fe in hematite is between M1 and M2. High pressure compression experiment was performed up to 5.8 GPa, where two minerals' XRD peaks merged completely. Ilmenite shows normal compression behavior, whereas hematite shrinks in very small amount. This kind of abnormal behavior might be due to the differential response to the applied pressure corresponding to the different compressibilities of the minerals each other.

• Economic and Environmental Geology
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• v.20 no.4
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• pp.213-221
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• 1987

The Donghae mine locates at Jangjoari, Koseongun, Kyongsang-nam-do. The geology of the mine consists of the upper part of Chin dong Formation conformably overlain by tuffaceous Koseong Formation. These formations are intruded by the granodiorite and the basic dikes. The ore mineralization occurs in the fault breccia pipe at the center of a granodiorite stock. The estimated dimension of the breccia pipe is $7m{\times}70m{\times}200m$. The host rock has distinctive hydrothermal alteration halos consisting hematite zone, chlorite zone, epidote zone and sericite zone from outer zone to the ore vein. The ore mineralization occurred in the three distinctive stages. The ore minerals formed in the first stage are pyrite, sphalerite, chalcopyrite, stannite and tetrahedrite. Galena and arsenopyrite are formed in the second stage. Some sphalerite grains include exsolution dots of the chalcopyrite. It is suggested that the ore mineralization occurred by a boiling of a hydrothermal fluid during its initial stage and subsequent cooling and $CO_2$ fugacity drop of remaining hydrothermal fluid by a ground water mixing aided vertical zoning of the ore minerals.

• Journal of the Korean Ceramic Society
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• v.28 no.12
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• pp.981-988
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• 1991

Various crystal defects such as voids, inclusions dislocations, stacking faults and precipitates were observed in the Czochralski-grown Bi12GeO20 crystals. Particularly, precipitates were found in the whole crystals. The phase of these precipitates was identified as Bi4Ge3O12 by EPMA and transmission electron microscopy. The precipitates were produced by pulling rapidly from a non-stoichiometric charge. During the pulling of Bi12GeO20 crystals, the melt composition of stoichiometric charge was changed Bi-deficent with gradual volatilization of Bi2O3. Precipition of the second phase may have been affected by an abrube thermal stress. By adding excess Bi2O3 into the stoichiometric batch, the precipitation of Bi4Ge3O12 was suppressed. At a pulling speed of 2 mm/hr, clear and precipitate from crystals of Bi12GeO20 were grown from the melt of the Bi2O3 excess charge.

• The Journal of the Petrological Society of Korea
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• v.18 no.3
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• pp.223-236
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• 2009

Ultramafic xenoliths from southeastern part of Jeju Island can be grouped into two types: Type I and Type II. Type I xenoliths are magnesian and olivine-rich peridotite (mg#=89-91), which are commonly found at the outcrop. Most previous works have been focused on Type I xenoliths. Type II xenoliths, consisting of olivine, orthopyroxene and clinopyroxene with higher Fe and Ti components (mg#=77-83) and lower Mg, Ni, Cr, are reported in this study. They are less common with a more extensive compositional range. The studied Type II xenoliths are wehrlite, olivine-clinopyroxenite, olivine websterite, and websterite. They sometimes show ophitic textures in outcrops indicating cumulate natures. The textural characteristics, such as kink banding and more straight grain boundaries with triple junctions, are interpreted as the result of recrystallization and annealing. Large pyroxene grains have exsolution textures and show almost the same major compositions as small exsolution-free pyroxenes. Although the exsolution texture indicates a previous high-temperature history, all mineral phases are completely reequilibrated to some lower temperature. Orthopyroxenes replacing clinopyroxene margin or olivine indicate an orthopyroxene enrichment event. Mineral phases of Type II are compared with Type I xenoliths, gabbroic xenoliths, and the host basalts. Those from Type II xenoliths show a distinct discontinuity with those from Type I mantle xenoliths, whereas they show a continuous or overlapping relation with those from gabbroic xenoliths and the host basalts. Our petrographic and geochemical results suggest that the studied type II xenoliths appear to be cumulates derived from the host magma-related system, being formed by early fractional crystallization, although these xenoliths may not be directly linked to the host basalt.

• Journal of the Mineralogical Society of Korea
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• v.19 no.3 s.49
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• pp.153-162
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• 2006

Fluid inclusions in amethyst from the Samcheonpo amethyst deposit of the Waryongsan area, Kyongnam generally grouped into four different types: Type I (liquid-rich and $10{\sim}23wt%$ NaCl, $Th=289{\sim}359^{\circ}C$), Type II (vapor-rich and $2{\sim}10wt%$ NaCl, $Th=304{\sim}365^{\circ}C;$), Type III (halite-bearing, $31{\sim}54wt%$ NaCl, $Th=259{\sim}510^{\circ}C;$), and Type IV ($CO_{2}-bearing\;9{\sim}13wt%\;NaCl,\;126{\sim}277^{\circ}$). Type I, II, and III inclusions are confined in the lower part of the amethyst and Type IV in the upper, which indicates significant hydrothermal activity during the earliest stage of the amethyst growth or the solidus condition of granitic rocks. The earliest fluid exsolved from the crystallizing granitic magma formed Type IIIa which is spatially associated with silicate melt inclusions. The homogenization behavior of Type IIIa inclusions by dissolution of the halite crystal after the bubble disappearance indicates that Type IIIa inclusions were trapped at some relatively elevated pressure. Exsolution of Type IIIb, I, II forming fluids with gradual decrease in their salinity was followed. The last fluid was $CO_{2}-bearing$ fluid (Type IV), which is assumed to be derived by decarbonization reactions with the surrounding sedimentary rocks. It suggests that the fine-grained granitic rocks containing the Samcheonpo amethyst crystallized at the sub-solvus condition saturated with water and exsolved abundant water.