• Proceedings of the Korean Magnestics Society Conference
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• 2012.05a
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• pp.151-151
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• 2012

• Proceedings of the Materials Research Society of Korea Conference
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• 2011.10a
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• pp.33.1-33.1
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• 2011

Strontium doped lanthanum manganite (LSM) with perovskite structure for SOFC cathode material shows high electrical conductivity and good chemical stability, whereas the electrical conductivity at intermediate temperature below $800^{\circ}C$ is not sufficient due to low oxygen ion conductivity. The approach to improve electrical conductivity is to make more oxygen vacancies by substituting alkaline earths (such as Ca, Sr and Ba) for La and/or a transition metal (such as Fe, Co and Cu) for Mn. Among various cathode materials, $LaSrMnCuO_3$ has recently been suggested as the potential cathode materials for solid oxide fuel cells (SOFCs). As for the Cu doping at the B-site, it has been reported that the valence change of Mn ions is occurred by substituting Cu ions and it leads to formation of oxygen vacancies. The electrical conductivity is also affected by doping element at the A-site and the co-doping effect between A-site and B-site should be described. In this study, the $La_{1-x}Sr_xMn_{0.8}Cu_{0.2}O_{3{\pm}{\delta}}$ ($0{\leq}x{\leq}0.4$) systems were synthesized by a combined EDTA-citrate complexing process. The crystal structure, morphology, thermal expansion and electrical conductivity with different Sr contents were studied and their co-doping effects were also investigated.

• Proceedings of the Korea Association of Crystal Growth Conference
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• 1996.06b
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• pp.219-222
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• 1996

수열법은 밀폐용기중에서 10$0^{\circ}C$이상의 가열, 가압된 수용액이 반응에 관여하는 것으로써, 수정, CaCO3, AlPO4, GaPO4 등과 같은 단결정의 육성 뿐만 아니라 균일분산계로부터 균일한 결정성의 미립자 합성에도 폭넓게 이용되고 있다. 세라믹분말의 합성에 있어서, 이 방법은 특히 형상, 입자크기의 제어가 용이할 뿐만 아니라 고상법, 졸-겔법, 공침법에서와 같은 열처리, 분쇄과정이 필요없기 때문에 고순도의 초미립자를 얻을 수 있는 장점이 있다. 근년 미국, 일본에서는 수열법을 이용한 유전, 압전체 등 세라믹분말의 일부가 공업적인 규모로 대량 생산되고 있다. 그러나 이에 대한 국내 기술은 아직 초기단계에 이르고 있는 실정이다. 따라서 본 연구실에서는 수열법에 의한 단결정 육성 (예; 자수정, CaCO3, AlPO4, GaPO4, KTP, Emerald 등), 박막제조 (예; GaP, PbTiO3, BaTiO3 등), 정제 (고령토, 장석, 도석 등), 원석처리 (진주, 인공 emerald, 비취 등) 그리고 각종 세라믹분말의 합성 등과 같은 다양한 기반기술의 축적과 동시에 공업화에 대응한 수열장치를 위하여 반응용기의 대형화, 엄밀한 밀폐방식, 실용적인 수열조건 등을 개발해 오고 있다. 본 발표에서는 현재까지의 연구개발 내용 중에서 결정성 미립자에 관련한 세라믹분말의 합성에 대한 일부의 결과들을 보고한다. 일반적으로 수열장치는 전기로, 반응용기, 온도 및 압력제어계 등을 기본으로 하고 있으며 시판용의 대부분이 교반기가 부착된 수직형 (vertical type)이다. 이와 같은 방식에 있어서는 엄밀한 밀폐가 곤란, 반응온도의 한계성 (25$0^{\circ}C$ 이하), 증진율의 한계성 (소량생산) 등과 같은 점이 있기 때문에 본 연구실에서는 개폐식 전기로내에 엄밀한 밀폐가 가능한 수평식(horizontal type)의 반응용기를 채택한 뒤 이를 회전 또는 시이소(seesaw)식으로 움직일 수 있도록 하여 연속공정화, 온도구배의 자율조절 그리고 보다 저온에서도 인위적인 이온의 확산을 효율적으로 유도할 수 있도록 하였다. 이와 같은 방식은 기존의 방식과 비교하여 반응용기 내에 응집현상과 미반응물이 존재하지 않으며 또한 단분산으로 결정성 미립자를 대량적으로 얻을 수 있는 장점이 있었다. 다음은 이상과 같이 본 연구실에서 자체 개발한 수열장치를 이용하여 PbTiO3, (Pb,La)TiO3Mn, BaTiO3, ZnSiO4:Mn, CaWO4 등과 같은 세라믹분말에 대한 합성 실험의 결과이다. 압전성, 초전성이 우수한 PbTiO3 및 (Pb,La)TiO3:Mn 분말의 수열합성은 PbO, TiO2, La2O3 등의 분말을 출발원료로 하여 합성도도 25$0^{\circ}C$부근의 알카리성 용액중에서 결정성 PbTiO3 및 (Pb,La)TiO3:Mn 미립자를 단상으로 얻었으며 입자의 형상 및 크기는 합성온도와 수열용매의 종류에 의존하였다. 유전체로서 폭넓게 응용되고 있는 BaTiO3 분말은 Ba(OH)2.8H2O, TiO2와 같은 최적의 출발원료를 선택함으로써 15$0^{\circ}C$ 부근의 저온영역에서도 용이하게 합성할 수 있었다. 특히 본 연구에서는 수용성인 Ba(OH)2.8H2O를 사용함으로써 host-guest적인 반응을 유도시키는데 있어 물의 가장 실용적이고 효과적인 수열용매임도 알았다. ZnSiO4:Mn, CaWO4, MgWO4와 같은 형광체 분말은 공업적으로 고상반응 또는 습식법에 의해 얻어지고 있으나 이들 방법에 있어서는 분쇄공정으로 인한 형광특성의 저하와 같은 문제점이 있다. 따라서 본 연구에서는 수열법을 이용하여 이들 화합물의 합성을 시도하였으며 그 결과 합성온도 30$0^{\circ}C$ 부근의 알칼리성 용액중에서 수열적으로 얻어짐을 알았다. 여기서의 합성분말을 이용하여 실제 조명램프로 제조한 결과 녹색, 청색 발광용 형광체로서 우수한 형광특성을 나타내었다. 천연에서 소량 산출되고 있는 고가의 (Li,Al)MnO2(OH)2:Co 분말은 도자기의 전사지용 청색안료로써 이용되고 있다. 본 연구실에서는 LiOH.H2O, Al(OH)3, MnO2 등의 분말을 출발원료로 하고 24$0^{\circ}C$ 온도 부근 그리고 물을 수열용매로 하여 천연산에 필적하는 (Li,Al)MnO2(OH)2:Co 분말을 인공적으로 합성하였다.

• Proceedings of the Korean Vacuum Society Conference
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• 2002.02a
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• pp.75-75
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• 2002

• Proceedings of the Korean Magnestics Society Conference
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• 2008.12a
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• pp.120.2-120.2
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• 2008

• Economic and Environmental Geology
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• v.45 no.6
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• pp.643-659
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• 2012

The Chungju Fe-REE deposit is located in the Kyemyeongsan Formation of the Ogcheon Group. The Kyemyeongsan Formation includes meta-volcanic rocks and pegmatite hosted REE deposit which show different kind of REE-containing minerals. The meta-volcanic rocks hosted REE deposits' main REE minerals are allanite, zircon, apatite, and sphene, whereas the pegmatite hosted REE deposits is mainly composed of fergusonite, and karnasurtite, zircon, thorite. The meta-volcanic rock hosted major REE mineral is allanite as the form of aggregation and contains 23.89-29.19 wt% TREO (Total Rare Earth Oxide), 4.71-9.92 wt% $La_2O_3$, 11.30-14.33 wt% $Ce_2O_3$, 0.11-0.29 wt% $Y_2O_3$, 0.15-0.94 wt% $ThO_2$, as a formula of (Ca, Y, REE, Th)$_{2.095}$(Mg, Al, Ti, Mn, $Fe^{3+})_{2.770}(SiO_4)_{2.975}(OH)$. Accompanying REE in a coupled substitution for $Ca^{2+}$ (M1 site) and $Al^{3+}-Fe^{2+}$ (M2 site) leads to a large chemical variety. Due to the allanite's high contents of Fe, it belongs to Ferrialanite. The pegmatite hosted deposit's domi-nant REE mineral is fergusonite as prismatic or subhedral grains associated with zircon, fluorite and karnasurtite. Geochemical composition of the fergusonite($YNbO_4$) suggests substitution of Y-REE and Y-Th in A-site, and Nb-Ta-Ti in B-site, furthermore the proportion of $Y_2O_3$ and $Nb_2O_5$ is oddly 1:1.5 comparing to the ideal ratio 1:1 and Nb is higher than Y, also A-site Y actively substitutes with REE. Karnasurtite in pegmatite variously ranges 9.16-22.88 wt% $Ce_2O_3$, 2.15-9.16 wt% and $La_2O_3$, 0.44-10.8 wt% $ThO_2$, as a calculated formula (Y, REE, Th, K, Na, Ca)$_{1.478}(Ti, Nb)_{1.304}$(Mg, Al, Mn, $Fe^{3+})_{0.988}$(Si, P)$_{1.431}O_7(OH)_4{\cdot}3H_2O$. Firstly the 870-860 Ma is the initial age of the supercontinent Rhodinia dispersal and subsequent A-1 type volcanism, which contains Fe, REE, and HFS(High Field Strength elements; Nb, Zr, Y etc.) elements in Fe-rich meta-volcanic rocks dominant Kyemyeongsan Formation, might mineralized allanite. Another synthesis is that regional metamorphism at late Paleozoic 300-280 Ma(Cho et al., 2002) might cause allanite mineralization. Also pegmatite REE mineralization highly related to the granite intrusion over the Chungju area in Jurassic(190 Ma; Koh et al., 2012). Otherwise above all, A-1 type volcanism at the same time of the Kyemyeongsan Formation development, regional metamorphism and pegmatite, might have caused REE mineralization. Although REE ore bodies display a close spatial association, each ore bodies display temporal distinction, different mineral assemblage and environment of ore formation.

• The Journal of the Petrological Society of Korea
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• v.6 no.1
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• pp.19-33
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• 1997

This study reports the results about the petrography and geochemical characteristics of 10 representative volacanic rocks. The Cretaceous volcanic rocks distributed in the vicinity of the Kageo island composed of andesitic rocks, dacitic welded tuff, and rhyolitic rocks in ascending order. Sedimentary rock is the basement in the study area covered with volcanic rocks. Andesitic rocks composed of pyroclastic volcanic breccia, lithic lapilli tuff and cryptocrystallin lava-flow. Most dacitic rocks are lapilli ash-flow welded tuff. Rhyolitic rocks consists of rhyolite tuff and rhyolite lava flow. Rhyolite tuff are lithic crystal ash-flow tuff and crystal vitric ash-flow tuff with somewhat accidental fragments of andesitic rocks, but dacitic rocks. The variation of major and trace element of the volcanic rocks show that contents of $Al_2O_3$, FeO, CaO, MgO, $TiO_2$ decrease with increasing of $SiO_2$. On the basis of Variation diagrams such as $Al_2O_3$ vs. CaO, Th/Yb vs. Ta/Yb, and $Ce_N/YB_N$ vs. $Ce_N$, these rocks represent mainly differentiation trend of calc-alkaline rock series. On the discriminant diagrams such as Ba/La and La/Th ratio, Rb vs. Y + Nb, the volcanic rocks in study area belongs to high-K Orogenic suites, with abundances of trace element and ternary diagram of K, Na, Ca. According to the tectonic discriminant diagram by Wood, these rocks falls into the diestructructive continental margin. K-Ar ages of whole rocks are from andesite to rhyolite $97.0{\pm}6.8~94.5{\pm}6.6,\68.9{\pm}4.8,\61.5{\pm}4.9~60.7{\pm}4.2$ Ma, repectively. Volcanic rocks in study area show well correlation to the Yucheon Group in terms of rock age dating and geochemcial data, and derived from andesitic calc-alkaline magma that undergone low pressure fractional crystallization dominated plagioclase at <30km.

• Economic and Environmental Geology
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• v.32 no.6
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• pp.611-631
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• 1999

Enviromental geochemisty and heary metal contamination at the Kongjueil mine creek were underaken on the basis of physicohemical properties and mineralogy for various kinds of water (surface, mine and ground water),soil, precipitate and sediment collected of April and December in 1998. Hydrgeochemical composition of the water samples are characterized by relatively significant enricant of Ca+Na, alkiali ions $NO_3$ and Cl inground and surfore water, wheras the mine waters are relatively eneripheral water of the mining creek have the characteristics of the (Ca+Mg)-$(HCO_3+SO_4)$type. The pH of the mine water is high acidity (3.24)and high EC (613$\mu$S/cm)compared with those of surface and ground water. The range of $\delta$D and $\delta^{18}O$ values (relative to SMOW) in the waters are shpwn in -50.2 to -61.6% and -7.0 to -8.6$\textperthousand$(d value=5.8 to 8.7). Using computer program, saturation index of albite, calcite, dolomite in mine water are nearly saturated. The gibbiste, kaolinite and smectite are superaturated in the surface and ground water, respectively. Calculated water-mineral reaction and stabilities suggest that weathing of silicate minerals may be stable kaolinite owing to the continuous water-rock reaction. Geochemical modeling showed that mostly toxic heavy metals may exist larfely in the from of metal-sulfate $(MSO_4\;^2)$and free metal $(M^{2+})$ in nmine water. These metals in the ground and surface water could be formed of $CO_3$ and OH complex ions. The average enrichment indices of water samples are 2.72 of the groundwater, 2.26 of the surface water and 14.15 of the acid mine water, normalizing by surface water composition at the non-mining creek, repectively. Characteristics of some major, minor and rate earth elements (Al/Na, K/Na, V/Ni, Cr/V, Ni/Co, La/Ce, Th/Yb, $La_N/Yb_N$, Co/Th, La/Sc and Sc/Th) in soil and sediment are revealed a narrow range and homogeneous compositions may be explained by acidic to intermediate igneous rocks. And these suggested that sediment source of host granitic gneiss colud be due to rocks of high grade metamorphism originated by sedimentary rocks. Maximum concentrations of environmentally toxic elements in sediment and soil are Fe=53.80 wt.% As=660, Cd=4, Cr=175, Cu=158, Mn=1010, Pb=2933, Sb=4 and Zn=3740 ppm, and extremely high concentrations are found are found in the subsurface soil near the ore dump and precipitates. Normalizing by composition of host granitic gneiss, the average enerichment indices are 3.72 of the sediments, 3.48 of the soils, 10.40 of the precipitates of acid mine drainage and 6.25 of the soils near the main adit. The level of enerichment was very severe in mining drainage sediments, while it was not so great in the soils. mineral composition of soil and sediment near the mining area were partly variable being composed of quartz, mica, feldspar, chlorite, vermiculite, bethierin and clay minerals. reddish variable being composed of quartz, mica, feldspar, chlorite, vermiculite, bethierin and clay minerals. Reddish brown precipitation mineral in the acid mine drainage identifies by schwertmanite. From the separated mineralgy, soil and sediment are composed of some pyrite, arsenopyite, chalcopyrite, sphalerite, galena, malachite, goethite and various kinds of hydroxied minerals.