• Title/Summary/Keyword: spinel

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Phase Transitions of $LiMn_2O_4$ on $CO_2$ Decomposition (($CO_2$ 분해시 $LiMn_2O_4$의 상변화)

  • Kwoen, Tae-Hwan;Yang, Chun-Mo;Park, Young-Goo;Cho, Young-Koo;Rim, Byung-O
    • Journal of the Korean Applied Science and Technology
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    • v.20 no.1
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    • pp.33-43
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    • 2003
  • $LiMn_2O_4$ catalyst for $CO_2$ decomposition was synthesized by oxidation method for 30 min at 600$^{\circ}C$ in an electric furnace under air condition using manganese(II) nitrate $(Mn(NO_3)_2{\cdot}6H_2O)$, Lithium nitrate ($LiNO_3$) and Urea $(CO(NH_2)_2)$. The synthesized catalyst was reduced by $H_2$ at various temperatures for 3 hr. The reduction degree of the reduced catalysts were measured using the TGA. And then $CO_2$ decomposition rate was measured using the reduced catalysts. Phase-transitions of the catalysts were observed after $CO_2$ decomposition reaction at an optimal decomposition temperature. As the result of X-ray powder diffraction analysis, the synthesized catalyst was confirmed that the catalyst has the spinel structure, and also confirmed that when it was reduced by $H_2$, the phase of $LiMn_2O_4$ catalyst was transformed into $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase. After $CO_2$ decomposition reaction, it was confirmed that the peak of $LiMn_2O_4$ of spinel phase. The optimal reduction temperature of the catalyst with $H_2$ was confirmed to be 450$^{\circ}C$(maximum weight-increasing ratio 9.47%) in the case of $LiMn_2O_4$ through the TGA analysis. Decomposition rate(%) using the $LiMn_2O_4$ catalyst showed the 67%. The crystal structure of the synthesized $LiMn_2O_4$ observed with a scanning electron microscope(SEM) shows cubic form. After reduction, $LiMn_2O_4$ catalyst became condensed each other to form interface. It was confirmed that after $CO_2$ decomposition, crystal structure of $LiMn_2O_4$ catalyst showed that its particle grew up more than that of reduction. Phase-transition by reduction and $CO_2$ decomposition ; $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase at the first time of $CO_2$ decomposition appear like the same as the above contents. Phase-transition at $2{\sim}5$ time ; $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase by reduction and $LiMn_2O_4$ of spinel phase after $CO_2$ decomposition appear like the same as the first time case. The result of the TGA analysis by catalyst reduction ; The first time, weight of reduced catalyst increased by 9.47%, for 2${\sim}$5 times, weight of reduced catalyst increased by average 2.3% But, in any time, there is little difference in the decomposition ratio of $CO_2$. That is to say, at the first time, it showed 67% in $CO_2$ decomposition rate and after 5 times reaction of $CO_2$ decomposition, it showed 67% nearly the same as the first time.

A Geochemical Indicator in Exploration for the Kalaymyo Chromitite Deposit, Myanmar (미얀마 깔레이미요 크롬철석광상 탐사의 지구화학적 인자)

  • Park, Jung-Woo;Park, Gyuseung;Heo, Chul-Ho;Kim, Jihyuk
    • Economic and Environmental Geology
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    • v.50 no.6
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    • pp.423-433
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    • 2017
  • Korea Institute of Geoscience and Mineral Resources and Department of Geological Survey and Mineral Exploration in Myanmar have explored the Kalaymyo chromitite deposit, Myanmar since 2013. It is now necessary to find a geochemical indicator for efficient mineral exploration in the future and building a 3D geological model for this ore deposit. Mantle podiform chromitite is a major type of Cr ore in this region, which is considered to be formed by mantle-melt interaction beneath the mantle-crust boundary of oceanic lithosphere. In this study we measured major element composition of spinels in harzburgite, dunite and chromitite, and examined the hypothesis that spinel Cr#(molar Cr/(Cr+Al)${\times}$100) can be used as a geochemical indicator in exploration for the Kalaymyo chromitite. The results show that there is a clear correlation between spinel Cr# and distribution of chromitite. The spinel Cr# of harzburgite increases with decreasing the distance from the chromitite bodies. The spinel composition is also closely associated with texture and occurrence of spinels. The high Cr# spinels (30-48) are subhedral to euhedral and enclosed by olivine whereas the low Cr# spinels (16-27) are anhedral and commonly associated with pyroxenes. Often the low Cr# spinels show symplectite intergrowths with pyroxenes, indicating their residual nature. These petrological and geochemical results suggest that the high Cr# spinels have resulted from mantle-melt interaction. We suggest that spinel Cr# can be used as a geochemical indicator for Cr ore exploration and as one of critical factors in 3D geological model in the Kalaymyo chromitite deposit.

Phase Evolution in LiMO2(M=Co,Ni) Cathode Materials for Secondary Lithium Ion Batteries : Effect of Temperature and Oxygen Partial Pressure (리튬 2차 전지용 양극활물질 LiMO2(M=Co,Ni)의 온도와 산소 분압에 따른 상전이 거동)

  • Huang, Cheng-Zhu;Kim, Ho-Jin;Jeong, Yeon-Uk;Lee, Joon-Hyung;Kim, Jeong-Joo
    • Journal of the Korean Ceramic Society
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    • v.42 no.4
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    • pp.292-297
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    • 2005
  • $LiMO_{2}(M=Co,Ni)$ samples were synthesized with $Li_{2}CO_{3},\;Co_{3}O_{4}$, and NiO by the solid-state reaction method. In the case of $LiCoO_{2}$, at low temperature$(T=400^{\circ}C)$ spinel structure was synthesized and the obtained spinel phase was transformed to layered phase at high temperature$(T\ge600^{\circ}C)$. The phase transition behaviors of $LiCoO_{2}$ were investigated with various heating temperature and time. The rate of transition was directly proportional to the concentrations of reactant, and activation energy of reaction was around 6.76 kcal/mol. When CoO(rock salt structure) was used as a starting material instead of $Co_{3}O_{4}$(spinel structure), layered structure of $LiCoO_{2}$ was obtained at low temperature. In the case of $LiNiO_{2}$ the transition from layered structure to rock salt structure occurred easily by disordering/ordering reaction, but did not occur in $LiCoO_{2}$. The difference in metal ion radii in $LiCoO_{2}$ and $LiNiO_{2}$ results in different behaviors of phase transitions.

Annealing Effects on Al0.2CoFe1.8O4 Ferrite Film and Powder (Sol Gel 방법으로 제조한 Al0.2CoFe1.8O4 분말과 박막의 열처리 효과)

  • Chae, Kwang-Pyo;Lee, Jae-Gwang;Kweon, Hyuck-Su;Kim, Jung-Hoon;Lee, Young-Bae
    • Journal of the Korean Magnetics Society
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    • v.15 no.3
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    • pp.186-190
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    • 2005
  • The $Al_{0.2}CoFe_{1.8}O_4$ ferrite films and powders were prepared by the sol-gel method. The crystallographic and magnetic properties of the samples were examined with annealing temperature by X-ray diffraction, $M\ddot{o}ssbauer$ spetroscopy and vibrating sample magnetometry. The powder samples showed the presence of spinel structure at annealing temperatures above 673 K, while the film samples indicated the spinel structure above 873 K, also the particle size increased with rising annealing temperatures. The $M\ddot{o}ssbauer$ spectra of $Al_{0.2}CoFe_{1.8}O_4$ powder annealed above 873 K could be fitted as the superposition of two Zeeman sextets due to ferrimagnetic phase. And the spectra of annealed at 673 K exhibited the superposition of ferrimanetic and paramagnetic phase and those of annealed at 473 K showed only a paramagnetic phase. The magnetic behaviour of powders appeared that the coercivity increased until annealed at 673 K but decreased above this temperature. The coercivity of the film samples decreased from 1.084 kOe at 873 K to 0.540 kOe at 1073 K with increasing annealing temperatures.

Investigation of Electronic Structures of TCr2O4 (T = Fe, Co, Ni) Spinel Oxides by Employing Soft X ray Synchrotron Radiation Spectroscopy (연 X선 방사광 분광법을 이용한 TCr2O4(T = Fe, Co, Ni) 스피넬 산화물의 전자구조 연구)

  • Kim, Hyun Woo;Hwang, Jihoon;Kim, D.H.;Lee, Eunsook;Kang, J.S.
    • Journal of the Korean Magnetics Society
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    • v.23 no.5
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    • pp.149-153
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    • 2013
  • The electronic structures of $TCr_2O_4$ (T = Fe, Co, Ni) spinel oxides have been investigated by employing synchrotron radiation-based soft X ray absorption spectroscopy (XAS). The measured 2p XAS spectra of transition-metal ions reveal that Cr ions are trivalent ($Cr^{3+}$), and all the T (T = Fe, Co, Ni) ions are divalent ($Fe^{2+}$, $Co^{2+}$, $Ni^{2+}$). It is also found that most of T (T = Fe, Co, Ni) ions occupy the A sites under the tetrahedral symmetry, while Cr ions occupy mainly the B sites under the octahedral symmetry. These findings show that the structures of $TCr_2O_4$ (T = Fe, Co, Ni) are very close to the normal spinel structures. Based on these findings, it is expected that Jahn-Teller (JT) effects are important in $FeCr_2O_4$ and $NiCr_2O_4$. In contrast, $CoCr_2O_4$ maintains the cubic structure without having the JT distortion since both $Cr^{3+}$ and $Co^{2+}$ ions are non-JT ions. This work suggests that the antiferromagnetic interaction between $Cr^{3+}$ and $T^{2+}$ ions plays an important role in determining the magnetic properties of $TCr_2O_4$ (T = Fe, Co, Ni).

Electrochemical Properties of Spinel LiMn2O4 Prepared Through Different Synthesis Routes (스피넬형 양극활물질 LiMn2O4의 합성방법에 따른 전기화학적 특성 비교)

  • Lee, Ki-Soo;Bang, Hyun-Joo;Sun, Yang-Kook
    • Journal of the Korean Electrochemical Society
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    • v.10 no.1
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    • pp.48-51
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    • 2007
  • In order to investigate the effects of particle size and specific surface area(BET area) of spinel powder, $LiMn_2O_4$ were synthesized using metal oxide precursor by co-precipitation method(CoP) and solid state reaction (SSR) .X-ray diffraction(XRD) patterns revealed that the both prepared powder has a well developed spinel structure with Fd3m space group. The $LiMn_2O_4$ prepared by co-precipitation showed spherical morphology with narrow size distribution. However, the $LiMn_2O_4$ prepared by solid state reaction showed relatively smaller particles with irregular shape. The measured BET areas of the powers are $0.8m^2g^{-1}$ (CoP) and $3.6m^2g^{-1}$(SSR). The electrochemical performance of the Prepared $LiMn_2O_4$ powders was evaluated using coin type cells(CR2032) at elevated temperature ($55^{\circ}C$). The $LiMn_2O_4$ prepared by co-precipitation showed the better cycling performance(82.3%capacity retention at $50^{th}$ cycle) than that of the $LiMn_2O_4$(68.3%) prepared by solid state reaction at elevated temperature.

Mössbauer Study of Al0.2CoFe1.8O4 Ferrite Powders (Mössbauer 분광법에 의한 Al0.2CoFe1.8O4분말의 자기적 특성 연구)

  • Chae, Kwang-Pyo;Lee, Jae-Gwang;Kweon, Hyuck-Su;Lee, Young-Bae
    • Journal of the Korean Magnetics Society
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    • v.13 no.6
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    • pp.231-236
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    • 2003
  • The $Al_{0.2}$CoF $e_{1.8}$ $O_4$ferrite powders have been prepared by the sol-gel method. The crystallographic and magnetic properties of the sample depending on annealing temperature have been investigated by means of x-ray diffraction, FE SEM, Mossbauer spetroscopy and vibrating sample magnetometry. The x-ray diffractions of all samples annealing temperature above 873 K clearly indicate the presence of spinel structure, the lattice constant decrease from 8.425 $\AA$ at 873 K to 8.321 $\AA$ at 1073 K, whereas the particle size rapidly increase from about 39 nm at 673 K to about 108 nm at 1073 K. The Mossbauer spectra annealed above 873 K could be fitted as the superposition of two sextets due to F $e^{3+}$ at A-site and B-site. The isomer shift (IS) and quadruple splitting (QS) values nearly constant with annealing temperature, whereas magnetic hyperfine field ( $H_{hf}$) of A-site slowly in crease and that of B-site fastly increases with increasing annealing temperature. The magnetic behaviour of powders shows that the saturation magnetization increase from 0.7 emu/g at 473 K to 72.1 emu/g at 1073 K while the coercivity decrease from 0.951 kOe at 673 K to 0.374 kOe at 1073 K with increasing annealing temperature.

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.

Crystal structure and microstructure of Z-type hexaferrite (Ba, La)Co2Fe24O41 by molten salt synthesis (용융염 합성법에 의한 Z형 육방정 페라이트 (Ba, La)Co2Fe24O41계의 결정구조와 미세구조)

  • Lee, Do Hyeok;Kwon, Chae-Yeon;Moon, Kyoung-Seok
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.31 no.5
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    • pp.197-202
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    • 2021
  • Synthesis of Z-type hexaferrite Ba3Co2Fe24O41 (Ba3Z) and Ba1.5La1.5Co2Fe24O41 (Ba1.5La1.5Z) powders were tried using molten salt synthesis after primary calcination. Ba3Z calcined at 1000℃ was formed with both M-type and Y-type hexaferrite, and then Z-type was obtained when sintered with molten salt at 1150℃ and 1200℃. In the case of Ba1.5La1.5Z calcined at 1000℃, however, M-type hexaferrite, CoFe2O4 (Spinel phase), and LaFeO3 were synthesized. As a result, Z-type hexaferrite was not synthesized after sintering with molten salt. In addition, the aspect ratio of the particles decreased as the sintering temperature increased with molten salt synthesis. To obtain a single-phase Ba1.5La1.5Z with a high aspect ratio, it is expected the raw materials have to calcine below the temperature of a spinel phase formation before sintering with molten salt.