• Applied Biological Chemistry
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• v.41 no.1
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• pp.89-94
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• 1998

Various Mn-oxides can oxidize Cr(III) to Cr(VI). Behaviors of chromium species in the oxidation system, especially on the oxide surface, are expected to control the reaction. During Cr(III) oxidation by birnessite and pyrolusite, Cr species in the reaction system were determined to elucidate their effects on the oxidation. Capacities of Cr oxidation of the two Mn-oxides were quite different. Solution pH and initial Cr(III) concentration also had significant effects on the Cr(III) oxidation by Mn-oxides. Chromium oxidation by pyrolusite was less than 5% of the oxidation by birnessite. The high crystallinity of pyrolusite could be one of the reasons and the difficulty of Cr (III) diffusion to the positive pyrolusite surface and Cr(VI) and Cr(III) adsorption seems to be other controlling factors. At pH 3, adsorption or precipitation of Cr species on the surface of birnessite were not found. Small amount of Cr(VI) adsorption was found on the surface of pyrolusite, but arty Cr precipitation on the oxide surface was not found. Therefore Cr(III) oxidation at pH 3 seems to be controlled mainly by the characteristics of Mn-oxides. Chromiun oxidation by Mn-oxides is thermodynamically more favorable at higher solution pH. However as solution pH increased Cr oxidation by birnessite was significantly inhibited. For Cr oxidation by pyrolusite, as pH increased the oxidation increased, but as Cr(III) addition increased the reaction was inhibited. Under these conditions some unidentified fraction of Cr species was found and this fraction is considered to be Cr(III) precipitation an the oxide surface. Chromium(III) precipitation on the oxide surface seems to play an important role in limiting Cr(III) oxidation by armoring the reaction surface on Mn-oxides as well as lowering Cr(III) concentration available for the oxidation reaction.

• Applied Biological Chemistry
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• v.37 no.5
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• pp.414-420
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• 1994

Birnessite, pyrolusite and hausmannite were synthesized and tested for the ability to oxidize Cr(III) to Cr(VI). These oxides differed in zero point of charge, surface area, and crystallinity. The kinetic study showed that Cr(III) oxidation on the Mn-oxide surface is a first-order reaction. The reaction rate was various for different oxide at different conditions. Generally the reaction by hausmannite, containing Mn(III), was faster than the others, and oxidation by pyrolusite was much slower. Solution pH and initial Cr(III) concentration had a significant effect on the reaction. Inhibited oxidation at higher pH and initial Cr(III) concentration could be due to the chance of Cr(III) precipitation or complexing on the oxide surface. Oxidations by birnessite and hausmannite were faster at lower pH, but pyrolusite exhibited increased oxidation capacity at higher pH in the range between 3.0 and 5.0. Reactions were also temperature sensitive. Although calculated activation energies for the oxidation reactions at pH 3.0 were higher than the general activation energy for diffusion, there is no experimental evidence to suggest which reaction is the rate limiting step.

• Journal of the Korean Ceramic Society
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• v.37 no.9
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• pp.879-886
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• 2000

고온용 전기.열 절연재의 유리모재로 사용하기 위한 산화크롬함유 인산염 유리 복합체의 소결거동, 물성, 그리고 미세구조변화를 연구하였다. 단미의 유리는 점성유동에 의한 1단계 소결수축을 보이나 복합체는 점성유동 및 반응 액상소결에 의한 2단계 수축을 보였다. 단미 유리는 소결온도 증가에 따라 재기공율이 감소하고 기공크기가 작아지지만 93$0^{\circ}C$ 이사에서는 폐기공이 생성되면서 기공이 성장함을 보였다. 복합체 소결밀도는 산화크롬 증가에 따라 감소하였으며, 특히 산화크롬 40% 이상에서는 percolation에 의해 소결수축율이 급격히 저하하였다. 복합체의 곡강도는 산화크롬 증가에 따라 거의 직선적으로 감소한 반면 열팽창율은 오히려 급속히 증가함을 보였다.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.104.1-104.1
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• 2013

스테인레스강 진공용기의 기체방출률을 낮추기 위해 구연산을 사용하여 화학세척한 후 진공 중 산화처리(VTO)하였다. 1E-11 mbar 이하의 극고진공에 도달하기 위해서는 진공펌프의 성능 뿐 아니라 진공 용기 자체로부터 지속적으로 방출되는 수소의 양을 줄이는 것이 중요하다. 스테인레스 강의 경우 잘 형성된 표면의 크롬산화막이 수소 방출을 억제하는데 효과가 있다고 알려져 있다. 구연산은 스테인레스 강의 표면 철 성분을 감소시키므로 상대적으로 크롬 비율을 증가한다. 이렇게 표면의 크롬 비율이 증가한 상태로 VTO 처리하면 보다 순수하고 균일한 크롬산화막이 형성될 것으로 기대할 수 있다. 본 발표에서는 구연산 +VTO 처리한 스테인레스 강(SST304) 진공 용기의 기체방출률 측정결과에 대해 논의하고자 한다.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.111.1-111.1
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• 2016

진공 중 산화처리 방법으로 스테인레스강 표면에 형성한 크롬 산화막에 의한 수소 기체방출 저감 효과를 수치해석 방법으로 분석하였다. 스테인레스 강 진공 용기를 진공 중 산화처리하면 표면의 확산 방지막 효과에 의하여 수소 기체방출률을 낮출 수 있다고 알려져 있으나 그 구체적인 원리는 명확하지 않다. 표면 크롬 산화막의 수소 확산계수가 스테인레스 강 내부의 확산계수보다 작으므로 수소의 확산을 지연시켜 기체방출을 낮춘다는 설명이 가능하지만, 크롬 산화막의 두께 및 확산계수가 미치는 영향을 정량적으로 분석한 예는 없었다. 본 발표에서는 스테인레스강 진공용기의 크롬산화막과 모재 내부에 서로 다른 확산계수를 부여한 후 기체방출에 관여하는 확산 방정식을 수치해석으로 풂으로써, 표면의 확산 방지막에 의한 기체방출 저감 효과를 설명하고자 한다.

• Resources Recycling
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• v.13 no.2
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• pp.9-15
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• 2004

A large tons of spent iron oxide catalyst come from the Styrene Monomer(SM) production company. It is caused to pollute the land and underground water due to the high alkali contents in the catalyst by burying them in the landfill. In order to recycle the spent catalyst, a basic study on the recovery of chromium ion from metal plating wastewater with the spent catalyst was carried out. The iron oxide catalyst adsorbed physically $Cr^{+6}$ in the lower pH 3.0, that is the isoelectric point of the spent catalyst. It was found that the iron oxide catalyst reduced the $Cr^{+6}$ into Cr+3 by the oxidation of ferrous ion into ferric ion on the surface of catalyst, and precipitated as $Cr(OH)_3$ in the higher than pH 3.0. The $Cr^{+6}$ was recovered 2.0∼2.3g/L catalyst in the range of pH 0.5∼2.0, but it was recovered 1.5 g/L catalyst at pH 3.0 of wastewater. The recovery of Cr was increased as the higher concentration in the continuous process, but the flowrates were nearly affected on the Cr recovery.

• Journal of Convergence for Information Technology
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• v.11 no.9
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• pp.109-114
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• 2021

Cr(VI)-quinoline compound[(C₉H₇NH)₂Cr₂O₇] was synthesized by the reaction between of quinoline and chromium(VI) trioxide, and structure was FT-IR, elemental analysis. The oxidation ability of benzyl alcohol greatly depends upon the dielectric constant of the used organic solvent, where carbon tetrachloride was worst and N,N'-dimethylformamide was best solvent. Noticeably, in N,N'-dimethylformamide solvent, Cr(VI)-quinoline compound oxidized substituted benzyl alcohols. The Hammett reaction constant(ρ)=-0.69(303K). As a resuit, Cr(VI)-quinoline compound was found as efficicent oxidizing agent that converted benzyl alcohol, allyl alcohol, primary alcohol and secondary alcohols to the corresponding aldehydes or ketones. Cr(VI)-quinoline compound was selective oxidizing agent of benzyl alcohol, allyl alcohol and primary alcohol in the presence of secondary alcohol ones.

• Analytical Science and Technology
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• v.12 no.5
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• pp.447-459
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• 1999

A study was conducted to compare three analytical methods for determination of hexavalent chromium in the welding fume. Precision and accuracy arc documented for colorimetric, ion chromatographic, and inductively coupled plasma-optical emission spectroscopic method. Evidence is presented that welding fume can affect the oxidation of trivalent chromium. A simple sonication extraction method, proposed in this study, instead of hot alkaline extraction has the advantage of minimizing the potential for chromium oxidation.

• 한국신재생에너지학회:학술대회논문집
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• 2010.11a
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• pp.83.2-83.2
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• 2010

평판형 고체산화물 연료전지(planar SOFC : Solid oxide Fuelcell)는 높은 전류 효율 및 출력밀도를 가지는 중,대형 발전용 전기소자이다. SOFC 스택을 600~800도에서 작동할 경우, 금속 분리판에서 휘발된 크롬에 의한 열화현상과 금속의 산화에 의한 표면 저항의 증가가 큰 문제점으로 알려져 있으며, 이를 개선하기 위한 많은 연구가 진행되고 있다. 본 연구에서는 금속 분리판의 열화를 억제하기 위한 여러 보호코팅의 특성을 밝히고, 특성차이의 원인을 분석하고자 하였다. 모재는 상용 STS444합금 (Nisshin steel 생산) 2.0mmt 박판을 사용하였으며, 표면 상태를 균일하게 하기 위하여 표면은 동일한 #1200 번 사포로 연마후 코팅하였다. 적용한 코팅은 전기도금 Ni 코팅, (MnCo)3O4 wet powder spray 코팅, (MnCo)3O4 ADM코팅 3종이었으며, 코팅층의 두께는 최적 공정조건에 따라 달리 하였다. 산화후 형성되는 표면 산화물의 전기적 특성을 평가하기 위하여 시험편의 비면적 저항 (ASR : area specific resistance)을 장시간 측정하였다. 측정편의 크기는 가로 4cm ${\times}$ 세로 4cm였으며, 100시간 공기중 산화후 측정하였다. 표면 접촉을 높이기 위하여 Pt paste를 40~50um도포하였으며, 1~0.1A인가된 전류에 대한 저항을 4전극법 (4-probe)으로 측정하였다. 표면 코팅층이 크롬 휘발을 억제하는 정도를 평가하기 위하여 크롬 휘발량을 측정하였다. 시편은 가로 1.5cm ${\times}$ 세로 1cm 였으며, 공급된 공기와 수분의 혼합가스와 응축기 표면에 흡착된 크롬의 양을 ICP-MASS법으로 측정하였다.

• Proceedings of the KSEEG Conference
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• 2007.04a
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• pp.346-348
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• 2007