• Title/Summary/Keyword: ionic defect

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Electrical Conduction in $SrZr_{0.95}Y_{0.05}O_{2.975}$ Ceramics

  • Baek, Hyun-Deok;Noh, Jin-Hyo
    • The Korean Journal of Ceramics
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    • v.5 no.3
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    • pp.288-295
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    • 1999
  • Partial conductivities contributed by electron holes, oxygen ions, and protons were caluclated in $SrZr_{0.95}Y_{0.05}O_{2.975}$, using the reported formulae derived from the defect chemistry of HTPCs. Required parameters were obtained from the graphical analysis of total conductivity variation against partial pressure of water vapor and oxygen. Predicted overall conductivities showed a reasonable agreement with experimental measurements. The conductivity of the material showed a linear increase with square root of the water vapor pressure. This increase was due to proton conduction in an almost pure ionic conductivity. The calculation of partial conductivities at $800^{\circ}C$ resulted in an almost pure ionic conductivity at $P_{02}=10^{-10}$ atm and a predominant hole conductivity at $P_{02}=10^{-10}$ atm. Pure proton conduction was not expected at this temperature, contrary to the earlier reports. Discussions were made in relation with reported thermodynamic data and defect structure of the material. It was shown that from the total conductivity dependence on water vapor pressure, the pure ionic conductivity at low oxygen partial pressures could be separated into protonic and oxygen ionic conductivity in $ZrO_2$-based HTPCs.

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Defect Chemistry of the Mixed Conducting Cage Compound Ca12Al14O33

  • Janek, J.;Lee, D.K.
    • Journal of the Korean Ceramic Society
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    • v.47 no.2
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    • pp.99-105
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    • 2010
  • The electrical transport properties of mayenite ($Ca_{12}Al_{14}O_{33}$ or $12CaO{\cdot}7Al_2O_3$; mostly abbreviated as $C_{12}A_7$) can be controlled in a wide range by varying the oxygen deficiency: At high temperatures mayenite becomes either an oxygen solid electrolyte, a mixed ionic/electronic conductor or an inorganic electride with metal-like properties upon chemical reduction (removing oxygen). The underlying defect chemistry can be understood on the basis of a relatively simple model-despite the complex cage structure: A point defect model based on the assumption that the framework $[Ca_{12}Al_{14}O_{32}]^{2+}$ acts as a pseudo-donor describes well the high temperature transport properties. It accounts for the observed conductivity plateau at higher oxygen activities and also describes the experimentally observed oxygen activity dependence of the electronic conductivity with -1/4 slope at temperatures between 800 and $1000^{\circ}C$. Doping effects in mayenite are still not well explored, and we review briefly the existing data on doping by different elements. Hydration of mayenite plays a crucial role, as Mayenite is hygroscopic, which may be a major obstacle for technical applications.

Investigation of High Temperature Electrical Conductivity of CaO-partially Stabilized $ZrO_2$ (CaO에 의하여 부분 안정화된 $ZrO_2$의 고온 전기 전도도에 대한 연구)

  • 변수일
    • Journal of the Korean Ceramic Society
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    • v.16 no.4
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    • pp.213-224
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    • 1979
  • The present work was undertaken: (1) to determine if CaO-partially stabilized $ZrO_2$ prepared by Hot Petroleum Drying Method would show better ionic conductor as an oxygen sensor in molten metals than that prepared by Oxide Wet Mixing Method and than CaO-fully stabilized $ZrO_2$, and (2) to understand the nature of conduction mechanism of CaO-partially stabilized $ZrO_2$ by a comparison of measured electrical conductivity data with theory on defect structure of pure monoclinic $ZrO_2$ and fully stabilized cubic $ZrO_2$. The DC electrical conductivity was measured by 3-probe technique and the AC electrical conductivity by 2-probe technique as a function of temperature in the range 973-1373 K and oxygen partial pressure in the range 10-1-10-25Mpa. The results of the experiments were as follows: 1. CaO-partially stabilized $ZrO_2$ prepared by Hot petroleum Drying Method showed at T=1094-1285 K and $Po_2$=10-7-10-25 MPa a nearly ionic conduction with 4 times higher conductivity than that prepared by Oxide Wet Mixing Method. 2. High-oxygen pressure conductivity tends toward a Po_2^{+1/5}-Po_2^{+1/6}$dependence. An analysis of possible defect structures suggests that CaO-partially stabilized $ZrO_2$ has an anti-Frenkel defect in which singly or doubly ionized oxygen interstitials and defect electrons predominate at T=1094-1285 K and $Po_2$=10-1-10-7MPa. 3. The activation energy for pure electron hole-conduction and ionic conduction of CaO-partially stabilized $ZrO_2$ was found to be 130 KJ/mol at T=973-1373 K, $Po_2$=2, 127 10-2 MPa(air) and 153KJ/mol at T=1094-1285 K respectively.

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Void Formation Induced by the Divergence of the Diffusive Ionic Fluxes in Metal Oxides Under Chemical Potential Gradients

  • Maruyama, Toshio;Ueda, Mitsutoshi
    • Journal of the Korean Ceramic Society
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    • v.47 no.1
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    • pp.8-18
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    • 2010
  • When metal oxides are exposed to chemical potential gradients, ions are driven to diffusive mass transport. During this transport process, the divergence of ionic fluxes offers the formation/annihilation of oxides. Therefore, the divergence of ionic flux may play an important role in the void formation in oxides. Kinetic equations were derived for describing chemical potential distribution, ionic fluxes and their divergence in oxides. The divergence was found to be the measure of void formation. Defect chemistry in scales is directly related to the sign of divergence and gives an indication of the void formation behavior. The quantitative estimation on the void formation was successfully applied to a growing magnetite scale in high temperature oxidation of iron at 823 K.

Function through Defects: Thermodynamic and Kinetics of Point Defects in Ionic Solids

  • Ko, Taegyung;Bang, Gyusuk;Shin, Jungmuk
    • The Korean Journal of Ceramics
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    • v.4 no.2
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    • pp.61-67
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    • 1998
  • The significance of point defects as relevant centers concerning electrochemical function is highlighted. Starting from the most simple case of dilute equilibrium bulk defect chemistry, influence of defect interaction and in particular the impact of interfaces on point defect redistribution are considered. Then recent progress in the field of kinetics in bulk and at boundaries is discussed. Finally, selected applications with emphasis on battery and sensor technology are presented.

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Partial Conductivities, Nonstoichiometry and Defect Structure of a New Cathode Candidate $Y_{1-x}Ca_xFeO_{3-\delta}$

  • Kim, Chan-Soo;Yoo, Han-Ill
    • The Korean Journal of Ceramics
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    • v.4 no.2
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    • pp.151-155
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    • 1998
  • The total electrical conductivity, ionic conductivity, and nonstoichimetry of a new cathode material $Y_{1-x}Ca_xFeO_{3-\delta}$ (x=0.1) were measured as functions of temperature ($900\leqT/^{\circ}C\leq1100$) and oxygen partial pressure $(10^{-6}\leqPo_2/atm\leq0.21$). Isothermal variations of these properties with $Po_2$ support that the majority type of ionic defects are anti-Frenkel disorder which, however, has seldom been considered for perovskite-based oxides. The results are discussed in comparison with those reported on similar oxides.

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On Electric Field Induced Processes in Ionic Compounds

  • Schmalzried, H.
    • Journal of the Korean Ceramic Society
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    • v.38 no.6
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    • pp.499-505
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    • 2001
  • The behaviour of ionic compound crystals under combined chemical and externally applied electrical potential gradients is discussed. Firstly, a systematic overview is given. Then a formal analysis follows. The transport equations of the ions and the electric defects predict that even with reversible electrodes demixing, and in particular decomposition of the compound will occur if the applied d.c. current density is sufficiently high. These predictions are illustrated by appropriate experiments. With the help of the solid solution (Me, Fe)O, where Fe-ions are the dilute species, we investigate experimentally the behaviour of a ternary ionic crystal under a d.c. electric current load. All the compounds were placed in a galvanic cell, and the internal reactions which then could be observed were driven by the electric field in this cell. In addition, we discuss the influence of the electric field on the classical solid state reaction AX+BX=ABX$_2$, if again the reaction couple is placed in a galvanic cell.

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Hologram Fixing in Photorefractive Crystal (광굴절 결정에서의 홀로그램 Fixing에 관한 연구)

  • Hwang, Seong-Mo;Lee, Hyuk
    • Proceedings of the KIEE Conference
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    • 1994.11a
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    • pp.379-381
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    • 1994
  • Volume holograms recorded in photorefractive materials can find important applications in optical memories and optical computing systems. One problem with a photorefractive hologram is that it gets erased by the readout light. Nondestructive readout can be achieved by hologram fixing, and several fixing methods have been reported. Fixing is accomplished by thermally activated motion of an unknown ionic defect, which neutralizes the electronic space-charge patterns. At room temperature the ionic patterns are stabilized. When the electrons are partially redistributed by light, a net space-charge pattern appears, and tile fixed hologram can be read out. In this paper, theoretical modeling and some experimental results are presented for thermal fixing of volume phase holograms in photorefractive $LiNbO_3$:Fe. Thermal fixing can be done during or after recording and depends on fixing temperature ($100{\sim}200^{\circ}C$ range) and grating length. Fixed Slating can be erased completely at the temperature over $300^{\circ}C$. Theoretical modeling shows weil the compensation of electronic Slating by ionic grating and is in good agreement with experimental results. In experiments the dependence of thermal fixing on temperatures and grating lengths is investigated.

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Electrical Conductivities of [(ZrO2)$_{1-x}$(CeO2)$_x$]$_{0.92}$(Y$_2$O$_3$)$_{0.08}$ Solid Solution ([(ZrO2)$_{1-x}$(CeO2)$_x$$_{0.92}$(Y$_2$O$_3$)$_{0.08}$ 고용체의 전기전도도)

  • 이창호;최경만
    • Journal of the Korean Ceramic Society
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    • v.35 no.12
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    • pp.1323-1328
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    • 1998
  • The electrical conductivities of the yttria (8mol%) stabilizedzirconia-ceria solid solutions were measured as a function of oxygen partial between 80$0^{\circ}C$ and 100$0^{\circ}C$ using 4-probe d.c. method Under pure oxygen atmosphere the oxygen ionic conductivity of CeO2-ZrO2 decreased with the concentration of CeO2 Under reducing condition electronic conduction due to the redox equilibrium of Ce ion was observed. Total ionic and electronic conductivities fitted by a defect model enabled to determine the electronic transference number(tei) which increased with the concentration of CeO2 and with the degree of reduction.

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Oxygen Interstitial Defects and Ion Hopping Conduction of $X ThO_2 + (1-X) Gd_2O_3 $Solid Solutions: $O.O8{\le}X{\le}0.12$

  • Park, Sung-Ho;Kim, Yoo-Young;Kim, Keu-Hong
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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    • pp.339-342
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    • 1990
  • $Gd_2O_3-ThO_2$ solid solutions containing 8,10 and 12 mol % $ThO_2$ were synthesized with spectroscopically pure $Gd_2O_3,$ and $ThO_2$ polycrystalline powders. X-ray diffraction revealed that all synthesized specimens have the modified fluorite structure, and the lattice parameter of $Gd_2O_3$ is nearly unchanged with increasing $ThO_2$ mol %. Both ac and dc conductivities were measured in the temperature range $500-1100^{\circ}C$ under $Po_2's$ from $10^{-6}$ to $10^{-1}$ atm. The dc conductivities are nearly independent of $Po_2,$ and agree with the ac values. This implies that the solid solutions are ionic conductors. The conductivity increases with increasing $ThO_2$ mol % with an average activation energy of 1.23 eV. An oxygen interstitial defect and ionic hopping conduction are suggested.