• Economic and Environmental Geology
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• v.19 no.4
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• pp.243-264
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• 1986

This work is a metallogeny on gold-silver deposits in South Korea based on the close examination of the author's own data and a broad review of existing literature available. The metallogenic epochs in Korea are temporarily connected with the history of tectonism and igneous activities, and are identified as the Precambrian, Paleozoic, Jurassic to early Cretaceous, late Cretaceous to early Tertiary, and Quaternary epochs, whereas the metallogenic provinces are spatially associated with some of the felsic to intermediate igneous rocks, lacking mineralization related to basic and ultrabasic rocks. The metallogeny on the gold-silver deposits is mostly related to the granitic rocks intrusives. Epigenetic gold-silver mineralization in South Korea ranges in metallogenic epochs from Precambrian through Triassic, Jurassic and Cretaceous to Eocene (?), in genetic types from hypothermal through mesothermal and epithermal quartz-sulfide veins to volcanogenic stockworks, with some disseminated types. Reporting on metallic association from gold without silver, gold-silver, silver-gold, silver without gold, and gold or silver as a by-product from other metallic ores. The most representative genetic types and metal associations of gold-silver deposits are hydrothermal quartz veins associated with the Daebo and Bulgugsa granitic magmatism. The most closely associated paragenetic metallic minerals in gold-silver hydrothermal quartz-sulfide vein type deposits are: copper, lead, zinc, pyrite and arsenopyrite. More than 560 gold-silver mines are plotted in the distribution map grouped within the 10 different metallogenic provinces of South Korea. Specific mineralizations with related mineral association in both sulfides and gangues observed selected from 18 Korean and 8 Japanese Au-Ag deposits. The 7 selected individual gold-silver mines representing specific mineralization types are described in this report.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.368-370
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• 2013

투명 전극은 전기전도도를 갖는 동시에 가시광선을 투과하는 소재를 말하며, 구체적으로는 빛의 파장이 400~700 nm 영역대의 가시광선을 80% 이상 투과하며 전기전도도가 비저항으로 $10^{-3}{\Omega}cm$이하이거나 면저항이 $10^3{\Omega}$/${\Box}$소재를 의미한다. 투명 전극은 전기전도도에 따라 사용되는 용도가 다양하다. LCD, PDP, OLED 와 같은 평판디스플레이 및 3D 디스플레이의 투명전극으로 사용되는 핵심재료일 뿐만 아니라 터치스크린, 투명필름, 대전방지막, 열반사막, EMI 방지막, 태양전지 분야에 광범위하게 이용되고 있다. 일반적으로, 투명전극 박막에 가장 많이 사용되고 있는 소재는 ITO (indium tin oxide)이나, 주성분인 In의 사용량 증가로 상용 ITO 타겟 가격이 급등하고 있음으며, 고가의 ITO 타겟을 대체하기 위한 저가의 투명전극 소재 개발이 절대적으로 요구되며, 신규 소재 개발을 통한 기술력 우위 선점이 필수적으로 요구되는 상황이다. 본 연구에서는 기존에 디스플레이 분야에서 널리 활용되는 고가의 ITO를 대체하기 위한 다성분 금속산화물 투명전극 스퍼터링 타겟 제조기술을 개발하기 위한 연구로서, Metal이 첨가된 In-Ga-Zn-O기반의 3성분계 투명도전성 소재를 조성설계, 고밀도 균질 타겟 제조 및 투명전극 박막을 형성하는 연구를 실시하였다. 고체산화물 산화인듐(In2O3)분말, 산화갈륨(Ga2O3) 분말그리고 산화아연(ZnO)분말과 Metal을 몰비로 칭량한 후 분말을 폴리에틸렌제 포트에 넣고 에탄올을 충분히 채운 후 지르코니아(ZrO2) 볼(ball)을 이용하여 24 h 동안 볼 밀링(ball milling) 방법으로 혼합한 뒤, $120^{\circ}C$의 플레이트위에서 마그네틱 바로 stirring하면서 건조하였다. 이 분말을 건조기에서 완전히 건조한 후 알루미나 유발을 이용해서 pulverizing한 후 sieving기를 이용하여 분말의 조립화를 하였다. 이 분말을 금형에 넣고 300 kg/$cm^2$의 압력으로 press하여 성형한 뒤 대기중에서 소결하였다 소결을 위한 승온 온도는 $10^{\circ}C$/min이었고 소결은 $1,450^{\circ}C$에서 6 h 동안 하였다. IGZO target의 조성 비율은 1:1:12 (mol%)를 사용하였으며, 첨가한 Metal은 Boron (B), Germanium (Ge), Barium (Ba)을 사용하여 타겟을 제작하였다. M-IGZO 박막은RF magnetron Sputter를 이용하여 증착하였으며, 앞선 실험에서 제작한 타겟을 사용하여 M-IGZO박막을 투명전극으로 사용하기 위한 각각의 특성을 파악하였다. 모든 박막은 상온에서 증착을 하였으며, 증착된 박막두께를 측정하기 위해 ${\alpha}$-step IQ를 사용하였고, 광학적 특성을 분석하기 위해 UV-Visible spectrophotometer 로 투과율을 측정하였다. 그리고 전기적 특성을 측정하기 위해 Hall effect measurement 및 4-probe를 사용하였으며, 결정성 분석을 위하여 XRD를 이용하여 분석하였다. 표1은 M-IGZO타겟을 사용하여 증착시간에 따른 면저항 특성을 나타내었다. Ge, B, Ba이 첨가된 IGZO 박막은 증착시간이 증가할수록 면저항이 낮아짐을 알 수 있었다. 또한, Ge이 첨가된 IGZO 박막이 다른 금속이 첨가된 IGZO 박막의 면저항보다 현저히 낮음을 알 수 있었다. Fig. 1(a), (b), (c)는 각 타겟을 동일한 조건으로 증착을 하여 광학적특성을 나타내는 그래프이다. GZO 박막의 광학적 특성을 보면 가시광 영역에서 평균 투과율은 모두 80% 이상으로 우수한 광투과 특성을 보여 투명전자소자로 사용가능하다. 특히, 자외선 영역을 모두 차단하는 UV cut 능력이 우수함을 알 수 있었다. 따라서, 금속이 첨가된 IGZO 박막을 태양전지용 투명전극으로 사용할 경우, 자외선에 의하여 수명이 단축되는 현상을 줄여줄 수 있음을 기대할 수 있으며 내구성 향상에 크게 기여할 것으로 보인다. Fig. 2는 Ge=0, 0.5, 5%인 IGZO 투명전극을 총 40회 반복하여 증착을 실시한 후 각각의 면저항을 측정한 결과이다. 실험결과에 따르면 Ge가 0%, 5%인 IGZO 투명전극은 증착을 거듭할수록 면저항이 증가하는 결과를 나타내었으며, 0.5%인 IGZO 투명전극은 점차 안정화되어가는 결과를 나타내었다. 따라서 안정화 되었을 때 평균 면저항은 26ohm/sq.로 나타났으며, 광투과율은 Fig. 3과 같이 가시광영역에서 평균 80%이상의 결과를 보였으며, 550 nm에서는 86.36%의 우수한 특성을 나타내었다. 본 연구에서는 Metal이 첨가된 In-Ga-Zn-O기반의 3성분계 투명도전성 소재 target을 제작하여 RF magnetron sputter로 박막을 형성한 후 특성을 비교하였다. M-IGZO target 중 Ge (0.5%)을 첨가한 IGZO 타겟을 사용한 투명전극이 가장 우수한 특성을 보였으며, 제작된 M-target의 In 비율이 30% 정도로 기존의 ITO (90%) 대비하여 투명전극 제작 단가를 절감할 수 있다.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.5 no.3
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• pp.171-177
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• 2007

This study suggested a new method to stabilize molten salt wastes generated from the pyre-process for the spent fuel treatment. Using conventional sol-gel process, $SiO_2-Al_2O_3-P_2O_5$ (SAP) inorganic material that is reactive to metal chlorides were prepared. In this paper, the reactivity of SAP with the metal chlorides at $650{\sim}850$, the thermal stability of reaction products and their leach-resistance under the PCT-A test method were investigated. Alkali metal chlorides were converted into metal aluminosilicate($LixAlxSi1-_xO_{2-x}$) and metal phosphate($Li_3PO_4\;and\;Cs_2AlP_3O_{10}$) While alkali earth and rare earth chlorides were changed into only metal phosphates ($Sr_5(PO_4)_3Cl\;and\;CePO_4$). The conversion rate was about $96{\sim}99%$ at a salt waste/SAP weight ratio of 0.5 and a weight loss up to $1100^{\circ}C$ measured by thermogravimetric analysis were below 1wt%. The leach rates of Cs and Sr under the PCT-A test condition were about $10^{-2}g/m^2\;day\;and\;10^{-4}g/m^2\;day$. From these results, it could be concluded that SAP can be considered as an effective stabilizer for metal chlorides and the method using SAP will give a chance to reduce the volume of salt wasteform for the final disposal through further researches.

• Economic and Environmental Geology
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• v.36 no.4
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• pp.285-293
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• 2003

Tailings of Dukum mine in the vadose and saturated zone were investigated to reveal the mobility of metal elements and the condition of mineralogical solubility according to redox environments throughout the geochemical analysis, thermodynamic modelling, and mineralogical study for solid-samples and water samples(vadose zone; distilled water: tailings=5 : 1 reacted, saturated zone; pore-water extracted). In the vadose zone, sulfide oxidation has generated low-pH(2.72∼6.91) condition and high concentration levels of S $O_4$$^{2-}$(561∼1430mg/L) and other metals(Zn : 0.12∼l57 mg/L, Pb : 0.06∼0.83 mg/L, Cd : 0.06∼l.35 mg/L). Jarosite$(KFe_3(SO_4)_2(OH)_6)$ and gypsum$(CaSO_4{\cdot}2H_2O$) were identified on XRD patterns and thermodynamics modelling. In the saturated zone, concentration of metal ions decreased because pH values were neutral(7.25∼8.10). But Fe and Mn susceptible to redox potential increased by low-pe values(7.40∼3.40) as the depth increased. Rhodochrosite$(MnCO_3)$ identified by XRD and thermodynamics modelling suggested that $Mn^{4+}$ or $Mn^{3+}$ was reduced to $Mn^{2+}$. Along pH conditions, concentrations of dissolved metal ions has been most abundant in vadose zone throughout borehole samples. It was observed that pH had more effect on metal solubilities than redox potential. How-ever, the release of co-precipitated heavy metals following the dissolution of Fe-Mn oxyhydroxides could be the mechanism by which reduced condition affected heavy metal solubility considering the decrease of pe as depth increased in tile saturated zone.

• Economic and Environmental Geology
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• v.40 no.5
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• pp.517-535
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• 2007

Two distinctive Mesozoic hydrothermal systems occurred in South Korea: the Jurassic/Early Cretaceous(ca. $200{\sim}130$ Ma) deep-level ones during the Daebo orogeny and the Late Cretaceous/Tertiary(ca. $110{\sim}45$ Ma) shallow hydrothermal ones during the Bulgugsa event. The Mesozoic hydrothermal system and the metallic mineralization in the Korean Peninsula document a close spatial and temporal relationship with syn- to post-tectonic magmatism. The calculated ${\delta}^{18}O_{H2O}$ values of the ore-forming fluids from the Mesozoic metallic mineral deposits show limited range for the Jurassic ones but variable range for the Late Cretaceous ones. The orogenic mineral deposits were formed at relatively high temperatures and deep-crustal levels. The mineralizing fluids that were responsible for the formation of theses deposits are characterized by the reasonably homogeneous and similar ranges of ${\delta}^{18}O_{H2O}$ values. This implies that the ore-forming fluids were principally derived from spatially associated Jurassic granitoids and related pegmatite. On the contrary, the Late Cretaceous ferroalloy, base-metal and precious-metal deposits in the Taebaeksan, Okcheon and Gyeongsang basins occurred as vein, replacement, breccia-pipe, porphyry-style and skarn deposits. Diverse mineralization styles represent a spatial and temporal distinction between the proximal environment of subvolcanic activity and the distal to transitional condition derived from volcanic environments. The Cu(-Au) or Fe-Mo-W deposits are proximal to a magmatic source, whereas the polymetallic or the precious-metal deposits are more distal to transitional. On the basis of the overall ${\delta}^{18}O_{H2O}$ values of various ore deposits in these areas, it can be briefed that the ore fluids show very extensive oxygen isotope exchange with country rocks, though the ${\delta}D_{H2O}$ values are relatively homogeneous and similarly restricted.

• Korean Chemical Engineering Research
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• v.51 no.4
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• pp.418-425
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• 2013

The catalytic conversion of ethanol to aromatic compounds ETA was studied over ZSM-5 heterogeneous catalysts. The effect of reaction temperature, weight hourly space velocity (WHSV), and addition of water and methanol, which are the potential impurities of bio-ethanol, on the catalytic performance was investigated in a fixed bed reactor. Commercial ZSM-5 catalysts having different Si/$Al_2$ ratios of 23 to 280 and modified ZSM-5 catalysts by addition of metal (Zn, La, Cu, and Ga) were used for the activity and stability tests in ETA reaction. The catalysts were characterized with ammonia temperature programmed desorption ($NH_3$-TPD) and nitrogen adsorption-desorption techniques. The results of catalytic performance revealed that the optimal Si/$Al_2$ ratio of ZSM-5 is about 50~80 and the selectivity to aromatic compounds decreases in the order of Zn/La > Zn > La > Cu > Ga for the modified ZSM-5 catalysts. Among these catalysts from the ETA reaction, Zn-La/ZSM-5 showed the best catalytic performance for the ETA reaction. The selectivity to aromatic compounds was 72% initially and 56% after 30 h over the catalysts at reaction temperature of $437^{\circ}C$ and WHSV of $0.8h^{-1}$.

• Korean Chemical Engineering Research
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• v.43 no.2
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• pp.206-214
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• 2005

Heterogeneously-catalyzed oxidation of aqueous phase trichloroethylene (TCE) over supported metal oxides has been conducted to establish an approach to eliminate ppm levels of organic compounds in water. A continuous flow reactor system was designed to effect predominant reaction parameters in determining catalytic activity of the catalysts for wet TCE decomposition as a model reaction. 5 wt.% $CoO_x/TiO_2$ catalyst exhibited a transient period in activity vs. on-stream time behavior, suggesting that the surface structure of the $CoO_x$ might be altered with on-stream hours; regardless, it is probable to be the most promising catalyst. Not only could the bare support be inactive for the wet decomposition reaction at $36^{\circ}C$, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. Very low TCE conversion appeared for $TiO_2$-supported $NiO_x$ and $CrO_x$ catalysts. Wet oxidation performance of supported Cu and Fe catalysts, obtained through an incipient wetness and ion exchange technique, was dependent primarily on the kinds of the metal oxides, in addition to the acidic solid supports and the preparation routes. 5 wt.% $FeO_x/TiO_2$ catalyst gave no activity in the oxidation reaction at $36^{\circ}C$, while 1.2 wt.% Fe-MFI was active for the wet decomposition depending on time on-stream. The noticeable difference in activity of the both catalysts suggests that the Fe oxidation states involved to catalytic redox cycle during the course of reaction play a significant role in catalyzing the wet decomposition as well as in maintaining the time on-stream activity. Based on the results of different $CoO_x$ loadings and reaction temperatures for the decomposition reaction at $36^{\circ}C$ with $CoO_x/TiO_2$, the catalyst possessed an optimal $CoO_x$ amount at which higher reaction temperatures facilitated the catalytic TCE conversion. Small amounts of the active ingredient could be dissolved by acidic leaching but such a process gave no appreciable activity loss of the $CoO_x$ catalyst.

• Clean Technology
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• v.24 no.1
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• pp.55-62
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• 2018

The adsorbent used in water-adsorption cooling system utilizing low-temperature heat of below $90^{\circ}C$ is required to exhibit high water uptake capacity at a relative humidity ($P/P_0$) between 0.1 and 0.3. Mesoporous silica (MCM-41) and MOF(MIL-101) exhibit quite large water adsorption capacity under saturated water vapor at $35^{\circ}C$. However, these adsorbents show small water adsorption capacity ($0.027{g_{water}\;g_{ads}}^{-1}$, $0.074{g_{water}\;g_{ads}}^{-1}$, respectively) in the relative humidity ($P/P_0$) range of 0.1 to 0.3. In this study, the surface properties of mesoporous silica and MOF were modified by simple methods to develop an adsorbent having a higher water uptake than the conventional water adsorbents at a relative humidity ($P/P_0$) of 0.1 ~ 0.3. In the case of mesoporous silica (MCM-41) exhibiting mainly water adsorption at $P/P_0=0.5{\sim}0.7$, aluminum species was functionalized on the mesopore walls and then cations existing near the aluminum were exchanged with various cations (e.g., $Na^+$, ${NH_4}^+$, and $(C_2H_5)_4N^+$). In addition, 20 wt% (to total weight of the composites) of hygroscopic inorganic salt ($CaCl_2$) was impregnated on the MCM-41. In the case of the MIL-101 (MOF), 20 wt% of hygroscopic inorganic salt ($CaCl_2$) was impregnated on the MIL-101. The MCM-41 which was ion-exchanged with various cations has main adsorption branch around 0.5 of $P/P_0$ which was slightly shifted with low-pressure direction in comparison with pristine MCM-41. However, tiny increases were observed on the adsorption in the range of $P/P_0$ between 0.1 and 0.3. After salt impregnation on the MCM-41, the adsorption capacity under $P/P_0=0.1{\sim}0.3$ at $35^{\circ}C$ was increased from $0.027{g_{water}\;g_{ads}}^{-1}$ to $0.152{g_{water}\;g_{ads}}^{-1}$. In the case of MIL-101, the amount of water adsorption at $35^{\circ}C$ under $P/P_0=0.1{\sim}0.3$ was increased from $0.074{g_{water}\;g_{ads}}^{-1}$ to $0.330{g_{water}\;g_{ads}}^{-1}$ after the salt impregnation.

• Economic and Environmental Geology
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• v.52 no.1
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• pp.1-12
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• 2019

Batch experiments for the soil washing coupled with the magnetic separation process were performed to remediate the soil contaminated with metal and oil wastes. The soil was seriously contaminated by Zn and TPH (total petroleum hydrocarbon), of which concentrations were 1743.3 mg/kg and 3558.9 mg/kg, respectively, and initial concentrations of Zn, Pb, Cu, and TPH were higher than the 2nd SPWL (soil pollution warning limit: remediation goal). The soil washing with acidic solution was performed to remove heavy metals from the soil, but Pb and Zn concentration of the soil maintained higher than the 2nd SWPL even after the soil washing with acidic solution. The 2nd soil washing was repeated to increase the Pb and Zn removal efficiency and the Zn and Pb removal efficiencies additionally increased by only 8 % and 5 %, respectively, by the 2nd soil washing (> 2nd SPWL). The small particle separation from the soil was conducted to decrease the initial concentration of heavy metals and to increase the washing effectiveness before the soil washing and 4.1 % of the soil were separated as small particles (< 0.075 mm in diameter). The small particle separation lowered down Zn and Pb concentrations of soil to 1256.3 mg/kg (27.9 % decrease) and 325.8 mg/kg (56.3 % decrease). However, the Zn concentration of soil without small particles still was higher than the 2nd SPWL even after the soil washing, suggesting that the additional process is necessary to lower Zn concentration to below the 2nd SPWL after the treatment process. As an alternative process, the magnetic separation process was performed for the soil and 16.4 % of soil mass were removed, because the soil contamination was originated from unreasonable dumping of metal wastes. The Zn and Pb concentrations of soil were lowered down to 637.2 mg/kg (63.4 % decrease) and 139.6 mg/kg (81.5 % decrease) by the magnetic separation, which were much higher than the removal efficiency of the soil washing and the particle separation. The 1st soil washing after the magnetic separation lowered concentration of both TPH and heavy metals to below 2nd SPWL, suggesting that the soil washing conjugated with the magnetic separation can be applied for the heavy metal and TPH contaminated soil including high content of metal wastes.

• Resources Recycling
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• v.31 no.1
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• pp.65-77
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• 2022

A study was conducted in Korea on the leaching behavior and possibility of recovery of vanadium and other valuable metals from domestic vanadium titanomagnetite (VTM) by direct acid leaching. In this study, a VTM concentrate containing 0.8% V₂O₅ was used, and the ratio of magnetite to ilmenite was calculated as 1.9:1 by using the HSC program. The leaching behavior of vanadium from the VTM was similar to that of iron, and it was affected by the concentration of sulfuric acid and temperature. Further, titanium could be leached in the form of TiOSO₄ at a temperature higher than 75℃. To improve the leaching efficiency of V, Fe, and Ti in VTM, reductive sulfuric acid and oxidative sulfuric acid leaching were performed. When Na₂SO₃ was used as a reducing agent, the leaching rate of vanadium was 80% of that in that case of leaching by sulfuric acid. Similarly, the leaching rate of titanium increased from 20% to 50%. When Na₂S₂O₈ was used as an oxidation agent, most of the vanadium was leached, and the main residue found by XRD analysis was ilmenite. In studies on the possibility of recovering valuable metals, the selective extraction of metals is hardly achieved by solvent extraction from oxidation leaching solutions; however, in this study, Cyanex 923, a solvation extractant from reductive leaching solutions, could selectively extract Ti.