• Title/Summary/Keyword: perovskite$LaCoO_3$

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Short-range magnetic order in La1-xBaxCoO3 cobaltites

  • Long, Phan The;Petrov, Dimitar N.;Cwik, J.;Dang, N.T.;Dongquoc, Viet
    • Current Applied Physics
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    • v.18 no.11
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    • pp.1248-1254
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    • 2018
  • Magnetization versus temperature and magnetic-field measurements, M(T, $H_a$), have been carried out to study the magnetic and critical properties of polycrystalline $La_{1-x}Ba_xCoO_3$ (x = 0.3 and 0.5) cobaltites. These compounds with the density of ${\sim}6.2g/cm^3$ crystallized in the $R{\bar{3}}c$ rhombohedral and $Pm{\bar{3}}m$ cubic structures, respectively. With an applied field $H_a=200Oe$, M(T) data have revealed that the samples with x = 0.3 and 0.5 exhibit the ferromagnetic-paramagnetic (FM-PM) phase transition at the Curie temperature points $T_C=202$ and 157 K, respectively. At 4.2 K, the saturation magnetization ($M_{sat}$) decreases from 35.9 emu/g for x = 0.3-26.1 emu/g for x = 0.5. Particularly, the critical-behavior analyses in the vicinity of $T_C$ reveal all samples undergoing a second-order phase transition, with critical exponent values (${\beta}=0.328$ and ${\gamma}=1.251$ for x = 0.3, and ${\beta}=0.331$ and ${\gamma}=1.246$ for x = 0.5) close to those expected for the 3D Ising model. This proves short-range magnetic order existing in $La_{1-x}Ba_xCoO_3$. We believe that magnetic inhomogeneities due to the mixture of hole-rich FM regions (confined in the trivalent-cobalt hole-poor anti-FM matrix) and uniaxial anisotropy prevent long-range order in $La_{1-x}Ba_xCoO_3$.

Kinetic Investigation of CO2-CH4 Reaction over Ni/La2O3 Catalyst using Photoacoustic Spectroscopy

  • Oh, Hyun-Jin;Kang, Jin-Gyu;Heo, Eil;Lee, Sung-Han;Choi, Joong-Gill
    • Bulletin of the Korean Chemical Society
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    • v.35 no.9
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    • pp.2615-2620
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    • 2014
  • Ni/$La_2O_3$ with a high dispersion was prepared by reduction of $La_2O_3$ perovskite oxide to examine the catalytic activity for the $CO_2-CH_4$ reaction. The Ni/$La_2O_3$ catalyst was found to be highly active for the reaction. The ratios of $H_2$/CO were measured in a flow of the reaction mixture containing $CO_2/CH_4$/Ar using an on-line gas chromatography system operated at 1 atm and found to be varied with temperature between 0.66 and 1 in the temperature range of $500-800^{\circ}C$. A kinetic study of the catalytic reaction was performed in a static reactor at 40 Torr total pressure of $CO_2/CH_4/N_2$ by using a photoacoustic spectroscopy technique. The $CO_2$ photoacoustic signal varying with the concentration of $CO_2$ during the catalytic reaction was recorded as a function of time. Rates of $CO_2$ disappearance in the temperature range of $550-700^{\circ}C$ were obtained from the changes in the $CO_2$ photoacoustic signal at early reaction stage. The plot of ln rate vs. 1/T showed linear lines below and above $610^{\circ}C$. Apparent activation energies were determined to be 10.4 kcal/mol in the temperature range of $550-610^{\circ}C$ and 14.6 kcal/mol in the temperature range of $610-700^{\circ}C$. From the initial rates measured at $640^{\circ}C$ under various partial pressures of $CO_2$ and $CH_4$, the reaction orders were determined to be 0.43 with respect to $CO_2$ and 0.33 with respect to $CH_4$. The kinetic results were compared with those reported previously and used to infer a reaction mechanism for the Ni/$La_2O_3$-catalyzed $CO_2-CH_4$ reaction.

Synthesis and Characterization of LSCF/CGO Composite Used as SOFC Cathode Materials (SOFC 용 LSCF/CGO 공기극의 제조 및 특성연구)

  • Park, Jae-Layng;Lim, Tak-Hyoung;Lee, Seung-Bok;Park, Seok-Joo;Shin, Dong-Ryul;Song, Rak-Hyun
    • 한국신재생에너지학회:학술대회논문집
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    • 2009.11a
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    • pp.184-186
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    • 2009
  • Composites of LSCF($La_{0.6}Sr_{0.4}Co_{0.2}Fe_{0.8}O_{3-\delta}$ and CGO(gadolinium doped ceria) is an efficient candidate cathode material with CGO electrolytes. In this study, LSCF with exact perovskite structure was synthesized by using solid state reaction(SSR) method. The optimized temperature to synthesize $La_{0.6}Sr_{0.4}Co_{0.2}Fe_{0.8}O_{3-\delta}$ with rhombohedral structure. was $1100^{\circ}C$. The polarization resistance of the LSCF/CGO(50:50 wt.%) was smaller than those of other composite cathodes. The analysis of the EIS data of LSCF/CGO suggests that the diffusion and adsorption-desorption of oxygen can be the key process in the cathodic reaction of SOFC using LSCF/CGO as cathode material.

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Oxygen Permeation Properties of $La_{0.6}Sr_{0.4}Co_{0.2}Fe_{0.8}O_{3-{\delta}}$ Mixed-conducting Membrane (혼합전도성 $La_{0.6}Sr_{0.4}Co_{0.2}Fe_{0.8}O_{3-{\delta}}$ 분리막의 산소투과 특성)

  • Lim, Kyoung-Tae;Cho, Tong-Lae;Lee, Kee-Sung;Woo, Sang-Kuk;Park, Kee-Bae;Kim, Jong-Won
    • Journal of the Korean Ceramic Society
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    • v.38 no.9
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    • pp.787-793
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    • 2001
  • $La_{0.6}Sr_{0.4}Co_{0.2}Fe_{0.8}O_{3-{\delta}}$ membranes were fabricated by solid-state reaction. We investigated sintering behavior and oxygen permeation flux as a function of time-on-stream, temperature and upstream oxygen partial pressure. The oxygen was permeated at temperatures form 750$^{\circ}$C to 950$^{\circ}$C by mixed conducting through oxygen vacancy diffusion in the dense membrane. The oxygen permeation flux through the membrane were about 0.1ml/$cm^3{\cdot}$min at 850$^{\circ}$C. A constant time was required for reaching stable oxygen flux, and oxygen partial pressure affected the oxygen permeation fluxes.

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Characterization and Preparation of Ceramic Interconnect of SOFC by Thermal Plasma Spray Coating Process (열 플라스마 용사법에 의해 코팅된 고체산화물 연료전지용 세라믹 연결재 특성 연구)

  • Park, Kwang-Yeon;Lim, Tak-Hyoung;Lee, Seung-Bok;Park, Seok-Joo;Shin, Dong-Ryul;Song, Rak-Hyun
    • 한국신재생에너지학회:학술대회논문집
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    • 2009.11a
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    • pp.187-190
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    • 2009
  • $LaCrO_3$ series are the most common candidate materials for a ceramic interconnect for SOFC and the thermal expansion coefficient of these matches very well with that of YSZ electrolyte. In this study, characteristics of the coated films on the anode-support, which were formed by using $La_{0.8}Ca_{0.2}CrO_3$, $La_{0.8}Sr_{0.2}CrO_3$, $La_{0.8}Ca_{0.2}Co_{0.1}Cr_{0.9}O_3$ for ceramic interconnet for SOFC, were investigated. All powders showed single perovskite phase and the precursors had spherical shapes of $2{\mu}m{\sim}30{\mu}m$. According to SEM analysis, coated film of LCC on pretreated anode-support was more thicker, whereas the coated film on untreated anode-support was densely formed. As the results of electrical conductivity of anode-support coated with the ceramic interconnects, LCCC exhibited the most excellent electrical conductivity of 0.15S/cm at $750^{\circ}C$.

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Cathode materials advance in solid oxide fuel cells (고체산화물연료전지 공기극의 재료개발동향)

  • Son, Young-Mok;Cho, Mann;Nah, Do-Baek;Kil, Sang-Cheol;Kim, Sang-Woo
    • Journal of Energy Engineering
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    • v.19 no.2
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    • pp.73-80
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    • 2010
  • A solid oxide fuel cells(SOFC) is a clean energy technology which directly converts chemical energy to electric energy. When the SOFC is used in cogeneration then the efficiency can reach higher than 80%. Also, it has flexibility in using various fuels like natural gases and bio gases, so it has an advantage over polymer electrolyte membrane fuel cells in terms of fuel selection. A typical cathode material of the SOFC in conjunction with yttria stabilized zirconia(YSZ) electrolyte is still Sr-doped $LaMnO_3$(LSM). Recently, application of mixed electronic and ionic conducting perovskites such as Sr-doped $LaCoO_3$(LSCo), $LaFeO_3$(LSF), and $LaFe_{0.8}Co_{0.2}O_3$(LSCF) has drawn much attention because these materials exhibit lower electrode impedance than LSM. However, chemical reaction occurs at the manufacturing temperature of the cathode when these materials directly contact with YSZ. In addition, thermal expansion coefficient(TEC) mismatch with YSZ is also a significant issue. It is important, therefore, to develop cathode materials with good chemical stability and matched TEC with the SOFC electrolyte, as well as with high electrochemical activity.

Preparation of the Hollow Fiber Type Perovskite Catalyst for Methane Complete Oxidation (메탄의 완전산화 반응을 위한 중공사형 페롭스카이트 촉매 제조)

  • Lee, Seong Woon;Kim, Eun Ju;Lee, Hong Joo;Park, Jung Hoon
    • Korean Chemical Engineering Research
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    • v.56 no.3
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    • pp.297-302
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    • 2018
  • Bead type and hollow fiber type catalyst (HFC, Hollow Fiber type Catalyst) was prepared by $La_{0.1}Sr_{0.9}Co_{0.2}Fe_{0.8}O_{3-{\delta}}$ (LSCF1928) perovskite powder catalyst which showed excellent methane complete oxidation characteristics through previous studies. The HFC have a cylindrical shape with an empty interior, and pores can be formed through Phase inversion method so the specific surface area can be remarkably improved. In the case of the bead type catalyst prepared by adding Methyl Cellulose (MC), $SrCO_3$ was produced in addition to the original catalyst composition of LSCF1928 due to the reaction of $CO_2$ emitted from MC and Sr of the catalyst. In the case of the HFC, a single phase perovskite structure was obtained without impurities. The HFC calcined at $700{\sim}900^{\circ}C$ showed pore structure of finger-sponge-finger structure, and 99.9% oxygen conversion rate was achieved through complete oxidation of methane at $475^{\circ}C$. Air gap and spinning pressure condition were changed to control the HFC pore. 2 cm air gap and 7 bar spinning pressure showed the best catalytic performance and achieved oxygen conversion rates of more than 70.65%, 93.01%, and 99.99% at $425^{\circ}C$, $450^{\circ}C$ and $475^{\circ}C$, respectively.

Application of Bond Valence Method to Estimate the Valence Charge Distributi on in the Metal-to-Oxygen Bonding Spheres in Perovskites

  • Nhat, Hoang Nam;Chau, Dinh Van;Thuong, Dinh Van;Hang, Nguyen Thi
    • International Journal of Internet, Broadcasting and Communication
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    • v.7 no.1
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    • pp.75-92
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    • 2015
  • This paper presents the application of the bond valence method to estimate the valence charge distribution in several perovskite systems: $La_{{\tilde{1}}x}Pb_xMnO_3$ (x=0.1-0.5), $La_{0.6}Sr_{0.{\tilde{4}}x}Ti_xMnO_3$ (x=0.0-0.25) and $La_{{\tilde{1}}x}Sr_xCoO_3$ (x=0.1-0.5); the reviewing of their crystal structures is also incorporated. The results showed the failure of the elastic bonding mechanism in all studied systems and revealed the general deficit of the valence charge in their unit cells. This valence deficit was not associated with the structural defects and was not equally localized in all coordination spheres. As the content of substitution increased, the charge deficit declined systematically from balanced level, signifying the transfer of valence charge from the ${\tilde{B}}O_6$ to ${\tilde{A}}O_{12}$ spheres. This transfer depended on the valence deviation of spheres and the average reached near 2 electron per unit cell. The possible impact of the limitted accuracy of the available structural data on the bond valence results has also been considered.

Mössbauer Study of Silver Nanoparticle Coated Perovskites La0.7Sr0.3Co0.3Fe0.7O3-δ (LSCF) (은(Ag) 나노입자가 코팅된 페롭스카이트 La0.7Sr0.3Co0.3Fe0.7O3-δ의 Mössbauer 분광연구)

  • Uhm, Young-Rang;Rhee, Chang-Kyu;Kim, Chul-Sung
    • Journal of the Korean Magnetics Society
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    • v.22 no.2
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    • pp.37-41
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    • 2012
  • The Ag nanoparticles attached $La_{0.7}Sr_{0.3}Co_{0.3}Fe_{0.7}O_{3-{\delta}}$ (LSCF) perovskites were prepared by plasma method. The Ag nanoparticles with size of several nanometers deposited from the Ag target were coated on the surface of LSCF powders with size range from 0.2 to 3 ${\mu}m$. The agglomeration of Ag particles annealed at $800^{\circ}C$ under inert gas of Ar were rarely observed. The inter-diffusion between surface Ag and core LSCF is effectively strong to prevent aggregation of Ag nanoparticles. The wave number of FT-IR spectra for LSCF were largely shifted as the concentration of Ag on LSCF up to 2.11 wt.%. The ionic states of irons in LSCF were measured by M$\ddot{o}$ssbauer spectroscopy. The small amount of $Fe^{4+}$ ions are converted to $Fe^{3+}$ ions after Ag nanopartcles were coated on LSCF.

Effects of Ca-Source on the Sintering and Electrical Properties of La0.7Ca0.3Cr0.9Co0.1O3-δ for Solid Oxide Fuel Cell Interconnects (고체산화물연료전지 연결재용 La0.7Ca0.3Cr0.9Co0.1O3-δ 조성계에 Ca Source 변화에 따른 소결 및 전기적 특성에 관한 연구)

  • Park, Sung-Tae;Choi, Byung-Hyun;Ji, Mi-Jung;An, Yong-Tae;Choi, Heon-Jin
    • Journal of the Korean Ceramic Society
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    • v.48 no.3
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    • pp.246-250
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    • 2011
  • Effects on sintering and electrical properties of $La_{0.7}Ca_{0.3}Cr_{0.9}Co_{0.1}O_{3-{\delta}}$ system, a interconnect material for cylindrical and flat tubular solid oxide fuel cells (SOFC), have been investigated by Ca-source when using $CaCO_3$ and $CaF_2$. When using $CaCO_3$ and $CaF_2$ was mixing as Ca-source, single phased perovskite solid solution was observed for each sample. The sintering temperature was decreased by $CaF_2$ contents was increased. When using 0.1 mole $CaF_2$ was densely sintered at $1400^{\circ}C$ and relative density was 93.8%. Also, electrical conductivity in oxidation and reducing atmosphere was 47, 4.3 S/cm, respectively, due to $F^-$ ion enhance the electrical conductivity in reducing atmosphere.