• Title/Summary/Keyword: CrO

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Cr(III)-Tetraaza Macrocyclic Complexes Containing Auxiliary Ligands (Part IV); Synthesis and Characterization of Cr(III)-Acetylacetonato, -Malonato and -Oxalato Macrocyclic Complexes

  • Byun, Jong-Chul;Han, Chung-Hun
    • Bulletin of the Korean Chemical Society
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    • v.26 no.9
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    • pp.1395-1402
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    • 2005
  • The reaction of cis-[Cr([14]-decane)$(OH)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = acetylacetonate (acac), oxalate (ox) or malonate (mal)} leads to a new cis-[Cr([14]-decane)(acac)]$(ClO_4)_2{\cdot}(1/2)H_2O\;(1),\;cis-[Cr([14]-decane)(ox)]ClO_4{\cdot}(1/2)H_2O\;(2)\;or\;cis-[Cr([14]-decane)(mal)]ClO_4{\cdot}(1/4)H_2O\;(3)$. These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[Cr([14]-decane)(acac)]$(ClO_4)_2{\cdot}(1/2)H_2O$ reveals that central chromium(III) has a distorted octahedral coordination environment and two acetylacetonate-oxygen atoms are bonded to the chromium(III) ion in the cis positions. The angle $N_{axial}-Cr-N_{axial}$ deviates by $11^{\circ}$ from the ideal value of $180^{\circ}$ for a perfect octahedron. The bond angle O-Cr-O between the chromium(III) ion and the two acetylacetonate-oxygen atoms is close to $90^{\circ}$. The bond lengths of Cr-O between the chromium and the acetylacetonate-oxygen atoms are 1.950(3) and 1.954(2) $\AA$. They are shorter than those between chromium and nitrogen atoms of the macrocycle. The IR spectra of 1, 2 and 3 display bands at 1560 {ν (C=O)}, 1710 {${\nu}_{as}$(OCO)} and 1660 $cm^{-1}$ {${\nu}_{as}$(OCO)} attributed to the acac, ox and mal auxiliary ligands stretching vibrations, respectively.

Synthesis of $CaCrO_4$Powders for the Cathode Material of Thermal Battery by GNP and Electrochemical Properties of Ca/LiCl-KCl/$CaCrO_4$Thermal Battery System (GNP 방법에 의한 Thermal Battery용 양극 재료 $CaCrO_4$분말 합성 및 Ca/LiCl-KCl/$CaCrO_4$전지계의 전기 화학적인 특성 평가)

  • 이현주;김영석;김선재;이창규;김홍회;김길무
    • Journal of the Korean Ceramic Society
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    • v.38 no.2
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    • pp.143-151
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    • 2001
  • Ca/LiCl-KCl/CaCrO$_4$열 전지계의 양극재료로서 BCT(Body-Centered Tetragonal) 결정구조를 갖는 CaCrO$_4$분말을 GNP로 합성하고, SEM, TEM, XRD를 이용하여 그 미세구조를 분석하였다. GNP 공정에 의한 CaCrO$_4$분말은 단일상으로 0.5$mu extrm{m}$ 이하의 입자 크기를 가지며 균일하게 분포한 반면, 기존의 분말 혼합법은 높은 하수 온도 및 장시간의 하소 조건을 필요하므로 미세한 분말 합성이 어렵고 pellet 형태로 만들었을 때 GNP 분말에 비해 비표면적이 현저하게 작기 때문에 전극 재료로써 유리하지 못하다. Ca/LiCl-KCl/CaCrO$_4$계의 전기 화학적인 특성을 평가해본 결과 전지셀을 Ca/DEB(LiCl-KCl+CaCrO$_4$+SiO$_2$)와 같은 DEB 형태로 만들었을 때 $600^{\circ}C$의 온도에서 2.0 V이상 (<100 mA/㎤)의 안정한 전압이 5분 이상 유지되었다. 그러나 3층 전극 셀(Ca/LiCl/KCl/ CaCrO$_4$)에서는 동일한 온도에서 2.0 V이상 (<100 mA/㎤)의 전압이 7분 이상 유지되었으나 불안정한 전압 변동 및 낮은 peak voltage로 인해 DEB 셀의 전지 특성이 더 우수한 것으로 생각된다. 양극 재료의 제조 방법의 관점에서 볼 때, 동일한 DEB(Depolarizer : Electrolyte : Binder=25 : 70 : 5 wt%) 조성의 셀 구성시, GNP 분말은 분말 혼합법에 의한 분말보다 반응 표면적이 훨씬 크기 때문에 GNP 양극 활 물질의 DEB 셀에서의 전지 수명이 더 길었다.

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Oxidative Decomposition of TCE over TiO2-Supported Metal Oxide Catalysts (TiO2에 담지된 금속 산화물 촉매상에서 TCE 산화분해반응)

  • Yang Won-Ho;Kim Moon-Hyeon
    • Journal of Environmental Science International
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    • v.15 no.3
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    • pp.221-227
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    • 2006
  • Oxidative TCE decomposition over $TiO_2$-supported single and complex metal oxide catalysts has been conducted using a continuous flow type fixed-bed reactor system. Different types of commercial $TiO_2$ were used for obtaining the supported catalysts via an incipient wetness technique. Among a variety of titanias and metal oxides used, a DT51D $TiO_2\;and\;CrO_x$ would be the respective promising support and active ingredient for the oxidative TCE decomposition. The $TiO_2-based\;CrO_x$ catalyst gave a significant dependence of the catalytic activity in TCE oxidation reaction on the metal loadings. The use of high $CrO_x$ contents for preparing $CrO_x/TiO_2$ catalysts might produce $Cr_2O_3$ crystallites on the surface of $TiO_2$, thereby decreasing catalytic performance in the oxidative decomposition at low reaction temperatures. Supported $CrO_x$-based bimetallic oxide systems offered a very useful approach to lower the $CrO_x$ amounts without any loss in their catalytic activity for the catalytic TCE oxidation and to minimize the formation of Cl-containing organic products in the course of the catalytic reaction.

Mössbauer Studies of Changed Interaction on Cr Ions in Chromite (Chromite 물질의 자기상호작용에 관한 뫼스바우어 분광연구)

  • Choi, Kang-Ryong;Kim, Chul-Sung
    • Journal of the Korean Magnetics Society
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    • v.17 no.1
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    • pp.47-50
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    • 2007
  • [ $ZnCr_2O_4$ ] shows geometrically frustrated magnet. Recently, $CoCr_2O_4$ has been investigated for multiferroic property and dielectric anomalies by spin-current model. Polycrystalline $CoCr_2O_4$ and $CoCrFeO_4$ compounds was prepared by wet-chemical process. Crystallographic and magnetic properties of $CoCr_2O_4$ and $CoCrFeO_4$ were investigate by using the x-ray diffractometer(XRD), vibrating sample magnetometer(VSM), superconducting quantum interference device magnetometer(SQUID), and $M\"{o}ssbauer$ spectroscopy. The crystal structure was found to be single-phase cubic spinel with space group of Fd3m. The lattice constants of $CoCr_2O_4$ and $CoCrFeO_4$ $a_0$ were determined to be 8.340 and 8.377 ${\AA}$, respectively. The ferrimagnetic transition temperature for the both samples were observed at 97 K and 320 K. The $M\"{o}ssbauer$ absorption spectra at 4.2 K show that the well developed two sextets are superposed with small difference of hyperfine field($H_{hf1}=507\;and\;H_{hf2}=492\;kOe$). Isomer shift values($\delta$) of the two sextets are found to be 0.33 and 0.34 mm/s relative to the Fe metal, respectively, which are consistent with the high spin $Fe^{3+}$ charge state.

Effect of Fe2O3 Concentration in Coal Slag on the Formation of (Fe,Cr)3O4 in Chromia Refractory (크롬계 내화물에서 슬래그의 산화철 농도가 (Fe,Cr)3O4 형성에 미치는 영향)

  • Park, Woo Sung;Oh, Myongsook S.
    • Applied Chemistry for Engineering
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    • v.18 no.5
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    • pp.495-500
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    • 2007
  • The inside wall of a coal gasifier is lined with refractory, and the corrosion of the refractory is an important factor affecting the refractory lifetime and the replacement period. This paper examines the changes in microstructure of a chromia refractory due to chemical reactions with slag having varying amounts of $Fe_2O_3$. Slag samples were prepared by adding $Fe_2O_3$ to KIDECO slag, and static corrosion experiments were carried out at $1550^{\circ}C$. The layer of $(Fe,Cr)_3O_4$ formation and the depth of Fe depletion in the infiltrating slag were determined. In addition, FactSage equilibrium calculations were carried out in order to determine the conditions of formation, and to compare with the experimental observations. In the sample exposed to KIDECO slag, which has about 10 wt% $Fe_2O_3$, the formation of $(Fe,Cr)_3O_4$ was not observed. As the $Fe_2O_3$ concentration in slag increased, $(Fe,Cr)_3O_4$ formation and Fe depletion depth increased. Increasing $Fe_2O_3$ concentration also made the slag/refractory interface indistinguishable. Equilibrium calculations predicted that higher $Fe_2O_3$ concentrations favor chromite formation at gasification temperatures. The chromite formation was most favorable when the amount of $Cr_2O_3$ was limited, as in the case of dissolved $Cr_2O_3$ in slag. When the concentration of $Fe_2O_3$ in slag was less than 20%, the formation of chromite was least favorable in the system with equal amounts of slag and refractory.

The Dielectric Properties of the Cr added BiNbO$_4$Ceramics (Cr이 첨가된 BiNbO$_4$유전체 세라믹스의 유전 특성)

  • 심규진;박정흠;윤광희;윤현상;박용욱;박창엽
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 1995.11a
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    • pp.14-17
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    • 1995
  • In this study, fur the use of portable communication multilayer devices. 0.15wt% V$_2$O$\_$5/ added BiNbO$_4$which is low-fire microwave dielectric ceramic as able to co-fire with high conductors was made into specimens with the additions of Cr$_2$O$_3$0.04, 0.2, 0.4, 0.8, 1.2wt%. These specimens were sintered at 930, 960. 990, 1030$^{\circ}C$ respectively to make the microwave dielectric resonators. These resonators were investigated by measuring the structure and dielectric properties. The density of the specimens was increased by the amounts of the Cr$_2$O$_3$and increased by increasing the temperature. 0.8wt% Cr$_2$O$_3$added and sintered at 960$^{\circ}C$ specimen skewed 49 dielectric constant. Q$.$f values were increased by the amounts of Cr$_2$O$_3$. And Q value was deteriorated by the additions of Cr$_2$O$_3$at sufficiently sintered temperatures. Negative resonant temperature coefficients were moved to positive by the amounts of Cr$_2$O$_3$and returned negative again at 1.2wt%. Temperature characteristics were deteriorated at 1030$^{\circ}C$.

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High temperature air-oxidation of CrAlSiN thin films (CrAlSiN 박막의 대기중 고온산화)

  • Hwang, Yeon-Sang;Won, Seong-Bin;Chunyu, Xu;Kim, Seon-Gyu;Lee, Dong-Bok
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2013.05a
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    • pp.53-54
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    • 2013
  • Nano-multilayered CrAlSiN films consisting of crystalline CrN nanolayers and amorphous AlSiN nanolayers were deposited by cathodic arc plasma deposition. Their oxidation characteristics were studied between 600 and $1000^{\circ}C$ for up to 70 h in air. During their oxidation, the amorphous AlSiN nanolayers crystallized. The formed oxides consisted primarily of $Cr_2O_3$, ${\alpha}-Al_2O_3$, $SiO_2$. The outer $Al_2O_3$ layer formed by outward diffusion of Al ions. Simultaneously, an inner ($Al_2O_3$, $Cr_2O_3$)-mixed layer formed by the inward diffusion of oxygen ions. $SiO_2$ was present mainly in the lower part of the oxide layer due to its immobility. The CrAlSiN films displayed good oxidation resistance, owing to the formation of oxide crystallites of $Cr_2O_3$, ${\alpha}-Al_2O_3$, and amorphous $SiO_2$.

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Synthesis of Cobalt Oxide Free Black Color Spinel Pigment (CoO가 첨가되지 않은 스피넬계 흑색안료의 합성)

  • Kim, Jun-Ho;Lee, Seong-Ho;Suh, Man-Chul;Lee, Byung-Ha
    • Journal of the Korean Ceramic Society
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    • v.44 no.11
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    • pp.639-644
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    • 2007
  • Spinel pigments, developing black color in high temperature glazes at oxidation or reduction atmosphere, without CoO because of its high price were synthesized by solid solution method. Ten mixed compositions consisted of NiO, MnO, $Fe_2O_3 and $Mn_2O_3$ were fired at $1250^{\circ}C$ for 1h. The resulting pigments were characterized by using XRD, FT-IR, SEM and UV-vis spectrometer. Structure of the pigments are spinel and particles' shape are spherical or cubic. Glazed tiles containing 5 wt% pigments were fired at $1260^{\circ}C$ and $1240^{\circ}C$ in reduction atmosphere. Color in glazes were analyzed by UV-vis spectrometer. Colors of NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.4875{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0125 mole% and NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.3875{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.1125 mole% in lime glaze showed black in oxidation, in reduction NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.4875{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0125 mole% and NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.4375{\cdot}Cr_2O_3$ $0.55{\cdot}Mn_2O_3$ 0.0125 mole% showed black. In case of lime-barium glaze, NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.3875{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.1125 mole%, NiO 0.975 MnO $0.075{\cdot}Fe_2O_3$ $0.4375{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0625 mole% and NiO 0.925 MnO $0.075{\cdot}Fe_2O_3$ $0.4375{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0625 mole% showed black color in oxidation and NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.3875{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.1125 mole%, NiO 0.925 MnO $0.075{\cdot}Fe_2O_3$ $0.4375{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0625 mole% and NiO 0.725 MnO $0.275{\cdot}Fe_2O_3$ $0.4375{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0625 mole% showed black one in reduction.

Mechanical Behavior of $Al_2O_3/Cr_2O_3-ZrO_2/HfO_2$ System ($Al_2O_3/Cr_2O_3-ZrO_2/HfO_2$ 계의 기계적 거동)

  • 신동우;오근호;이종근
    • Journal of the Korean Ceramic Society
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    • v.22 no.6
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    • pp.42-52
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    • 1985
  • Several $Al_2O_3$-based polycrystalline which had different dopant ratio in the range of 0.5mol% were prepared by doping pure $Cr_2O_3$ $HfO_2$. Single crystalline which had same composition with above polycrystalline were made by means of floating zone method. This study examined the role of each dopant for enhancing the mechanical properties of $Al_2O_3$-based Ceramics. Optical micrographs $({ imes}200)$ of $Al_2O_3-Cr_2O_3$ single crystal showing not only radial crack (rc) on the specimen surface but median crack(mc) and lateral crack(lc) under surface at the edge of indentation mark. Fracture toughness of Al2O3-based Ceramics was increased with $ZrO_2$ content. Alloying effect of $Cr_2O_3$ contributed to the hardness of $Al_2O_3$ based ceramics.

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Catalysis Reaction for the Formation of Hydrogen Cyanide from Metal Complex (금속착물로부터 HCN 생성에 대한 촉매반응연구)

  • 박흥재
    • Journal of Environmental Science International
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    • v.3 no.4
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    • pp.439-443
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    • 1994
  • In aqueous acid solution ${[Cr(CN)_6]}^{3-}$ aquates via a series of stepwise stereospecific reactions to give ${[Cr{(H_2O)}_6]}^{3+}$as the final product.Some of the intermediate cyanoaquo complexes in the sequence have been isolated.These complexes aquate by both acid independent and acid denpendent pathways, the latter involving protonation of the cyano ligands followed by aquation of the singly protonated species. The kinetic data for the aquation of {[CrCN{(H_2O)}_5]}^{2+}$ are consistent with the transition state structure ${[{(H_2O)}_4Cr(CN)-OH-Cr{(H_2O)}_5]}^{3+}$. Addition of $Cr^{2+}$ to solutions of cyanocobalt(III) complexes produces the metastable intermediate${[CrNC{(H_2O)}_5]}^{2+}$ This isomerizes to in a $Cr^{2+}$-catalyzed reaction which occurs by a ligand-bridged electron-change mechnism. From acid catalysis on these aquation reactions, it product HCN. Especially, $HSO_3$-ions do the role of catalyst in the formation of HCN from $CrCN^{3-}$

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