• Title/Summary/Keyword: nonstoichiometry

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Defect Structure, Nonstoichiometry and Nonstoichiometry Relaxation of Complex Oxides

  • Yoo, Han-Ill
    • Journal of the Korean Ceramic Society
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    • v.44 no.12
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    • pp.660-682
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    • 2007
  • An SOFC consists of all ceramic complex oxides each with different electrochemical-property requirements. These requirements, in principle, can be made met to a great extent by controlling or tailoring the defect structure of the oxide. This paper reviews the defect structure, nonstoichiometry as a measure of the total defect concentration, and the defect relaxation kinetics of complex oxides that are currently involved in a variety of growing applications today.

Measurement of Nonstoichiometry (x) of $UO_{2+x}$ and $(Er_{0.06}U_{0.94})O_{2+x}$ by a Coulometric Titration Method (전하 적정법에 의한 $UO_{2+x}$$(Er_{0.06}U_{0.94})O_{2+x}$ 의 Nonstoichiometry (x) 측정)

  • 강선호;이종호;유한일;김한수;이영우
    • Journal of the Korean Ceramic Society
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    • v.34 no.7
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    • pp.722-730
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    • 1997
  • The nonstoichiometry (x) of UO2+x and (Er0.06U0.94)O2+x has been in-situ measure against oxygen activity (Po2) at elevated temperatures by a coulometric titration method. From the dependence of the oxygen excess (x) of UO2+x on Po2 at 1000℃, it has been concluded that (2Vo2Oia2Oib)〃〃and (2Vo2Oia2Oib)' clusters are prevailing at low oxygen partial pressure [log(Po2/atm) -10.6] and at high oxygen partial pressure [log(Po2/atm) -10.6], respectively. The nonstoichiometry is found to be reduced with the addition of Er, which is ascribed to the fact that the fixed-valent Er3+ reduces the oxidation capacities of UO2+x. The enthalpy of oxygen incorporation in (Er0.06li0.94)O2+x has been evaluated from the mean valences of U-ion as -180±70 kJ/mole.

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Interface Migration lnduced by Nonstoichiometry and Dielectric Property of Nb-doped $SrTiO_3$ (Nonstoichiometry에 의한 Nb-doped $SrTiO_3$의 계면 이동과 유전 성질)

  • Jeon, Jae-Ho;Gang, Seok-Jung
    • 연구논문집
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    • s.25
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    • pp.185-192
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    • 1995
  • The solid/liquid interface migration in Nb-doped $SrTiO_3$ and its effect on dielectric properties have been investigated. The specimen sintered in air shows no migration during oxide infiltration treatment in air, whereas the specimen sintered in $5H_2-95N_2$ shows appreciable migration during similar infiltration. In the migrated layers of the specimen sintered in a reducing atmosphere, no cations of the infiltrants are detected by wavelength dispersive spectroscopy. These results show that nonstoichiometry due to the atmosphere change can induce the interface migration as in the case of frequently observed migrations due to solute concentration change. The driving force for the migration is discussed in terms of the coherency strain energy in a thin diffusional oxidized layer of the receding grain. The interface migration caused by nonstoichiometry could be suppressed by preoxidizing grain surfaces before oxide infiltration treatment. The suppression of migration increased the effective dielectric constant of the material.

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Coulometric Titration for the Determination of Nonstoichiometry in Ni1-XO (전하량적정법에 의한 Ni1-XO의 Nonstoichiometry 측정)

  • Suh, Sang-hyuk;Oh, Seung-Mo
    • Applied Chemistry for Engineering
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    • v.2 no.4
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    • pp.385-392
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    • 1991
  • Nonstoichiometry and defect model for $Ni_{1-x}O$ were determined by coulometric titration method. In the temperature range of 1123-1198K and oxygen partial pressure of 0.21-0.1 atm, the nonstoichiometry was found to be proportional to the fourth root of the oxygen partial pressure. This pressure dependence can be explained by the fact that nonstoichiometric $Ni_{1-x}O$ contains singly ionized metal vacancies as the predominant point defects. At T=1173K and $Po_2=0.21atm$, the nonstoichiometry, x was $1.21{\times}10^{-4}$. The standard formation enthalpy of defects in $Ni_{1-x}O$ was found, on the basis of this defect model, to be 0.95 eV. Also the result indicates that both of singly and doubly ionized metal vacancies are simultaneously present at above 1248K.

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Determination of Nonstoichiometry$(\delta)$and Phase Stability Region of $(Mg_{0.29}Fe_{0.71})_{3-}\deltaO_4$ by a Coulometric Titration Method (전하적정법에 의한 $(Mg_{0.29}Fe_{0.71})_{3-}\deltaO_4$ 훼라이트의 Nonstoichiometry$(\delta)$와 상안정 영역 결정)

  • 강선호;유한일;강대석;유병두
    • Journal of the Korean Ceramic Society
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    • v.31 no.12
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    • pp.1491-1500
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    • 1994
  • Nonstoichiometry($\delta$) and the phase stability region of a ferrite spinel (Mg0.29Fe0.71)3-$\delta$O4 have been investigated by a coulometric titration method as a function of temperature(T) and oxygen partial pressure(Po2). It has been found that the spinel is thermodynamically stable in the ranges -8.0$\leq$log(PO2/atm)$\leq$-2.4, -7.0$\leq$log(PO2/atm)$\leq$-1.7 respectvely at 100$0^{\circ}C$. The nonstoichiometry extends over the ranges of -0.004$\leq$$\delta$$\leq$0.007, -0.008$\leq$$\delta$$\leq$0.006, -0.033$\leq$$\delta$$\leq$0.004 at 100$0^{\circ}C$, 120$0^{\circ}C$, respectvely. The observed PO2-dependence of $\delta$ suggests that the majority ionic defects are cation interstitials in the low PO2 region and cation vacancies in the high PO2 region.

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Morphology and Characteristic change of $LiMn_2O_4$ Powder Prepared by Precipitation-Evaporation Method (침전-증발법에 의해 제조된 $LiMn_2O_4$ 분말의 특성과 형태 변화)

  • Kim, Guk-Tae;Shim, Young-Jae
    • Korean Journal of Crystallography
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    • v.15 no.1
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    • pp.44-50
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    • 2004
  • Spinel structured lithium managanese oxide $(LiMn_2O_4)$ powder with well defined facetted morphology was prepared by precipitation-evaporation method. {111}, {110}, and {100} planes are mainly observed in the $LiMn_2O_4$ powder. And powder shape of tetradecahedron and octahedron was observed depending on the calcinations temperature. The observed powder morphology observed seemed to be related to the nonstoichiometry of the oxygen in the $LiMn_2O_4$ spinel structure. Oxygen nonstoichiometry might be responsible for the Jahn-teller effect and structure transition which in turn affects the surface energy of the {111}, {110}, and {100} planes. Powder shape transition from tetradecahedron to octahedron seemed to be related to the surface energy of the {111}, {110}, and {100} planes with oxygen nonstoichiometry.

Variation of Oxygen Nonstoichiometry of Porous $La_{0.6}Ca_{0.4}MnO_{3-{\delta}}$ SOFC-Cathode under Polarization

  • Mizusaki, Junichiro;Harita, Hideki;Mori, Naoya;Dokiya, Masayuki;Tagawa, Hiroaki
    • The Korean Journal of Ceramics
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    • v.6 no.2
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    • pp.177-182
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    • 2000
  • At the porous $La_{0.6}Ca_{0.4}MnO_{3-{\delta}}$(LCM)/YSZ electrodes of solid oxide fuel cells (SOFC), the electrochemical redox reaction of oxygen proceeds via the triple boundary (TPB) of gas/LCM/YSZ. The surface diffusion of adsorbed oxygen on LCM has been proposed as the rate determining process, assuming the gradient of oxygen chemical potential from the outer surface of porous layer to TPB. Along with the formation of this gradient, oxygen nonstoichiometry in the bulk of LCM may varies. In this paper, an electrochemical technique was described precisely to determine the variation of oxygen content in LCM of porous LCM/YSZ under polarization. It was shown that the oxygen potential in LCM layer under large cathodic polarization is much lower than that in the gas phase, being determined from the electrode potential and Nernst equation.

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Nonstoichimetry (x) of Nuclear Materials UO2+x and $(Ce_yU_{1-y})O_{2+x}$ at High Temperatures as a Function of Oxygen Activity$(a_o_2)$

  • Kang, Sun-Ho;Yoo, Han-Ill;Kim, Han-Soo;Lee, Young-Woo
    • The Korean Journal of Ceramics
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    • v.4 no.2
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    • pp.78-82
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    • 1998
  • The oxygen nonstoichiometry (x) of UO$_{2+x}$ and $(Ce_yU_{1-y})O_{2+x}$ (y=0.05, 0.25) has been measured as a function of oxygen activity (a02) at 100$0^{\circ}C$ by a solid state coulometri titration technique. The results for UO$_{2+x}$ are in a good agreement with literature data and the ao2-dependence of the nonstoichimetry has been well explained with (2:2:2) cluster model. The equilibrium oxygen activity of $(Ce_yU_{1-y})O_{2+x}$ increases with Ce-content (y) for given nonstoichiometry (x), which is ascribed to the fact that Ce is present as Ce$^{3+}\; and\; Ce^{4+}$, and, therefore, the addition of Ce reduces the oxidation capacity of UO$_{2+x}$. From the oxygen activity dependence of x in $(Ce_yU_{1-y})O_{2+x}$ the defect structure of $(Ce_yU_{1-y})O_{2+x}$ is discussed.

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