• 한국재료학회:학술대회논문집
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• 한국재료학회 1994년도 춘계 학술발표 강연 및 논문 개요집
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• pp.26-26
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• 1994

• 한국세라믹학회지
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• 제37권8호
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• pp.799-804
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• 2000

Coulometric titration experiments have been done for copper doped cobaltous oxide (Co1-xCux)1-$\delta$ O with various dopant concentrations. We present the obtained experimental data and compare our results to those of previous thermogravimetric investigation. The experimental data are fitted by theoretical calculations based on various defect models. For this modeling, we considered different types fo major defects like copper in substitutional and interstitial lattice sites as well as copper vacancy. We also introduced the copper evaporation effect during titration experiment into our consideration.

• 한국세라믹학회지
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• 제34권7호
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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.

• The Korean Journal of Ceramics
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• 제4권2호
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• pp.103-113
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• 1998

By using a gas-tight electrochemical cell, we can perform high-temperature coulometric titration and measure electronic transport properties to determine the elecronic defect structure of metal oxides. This technique reduces the time and expense required for conventional thermogravimetric measurements. The components of the gas-tight coulometric titration cell are an oxygen sensor, Pt/yttria stabilitized zirconia(YSZ)/Pt, and an encapsulated metal oxide sample. Based on cell design, both transport and thermodynamic measurements can be performed over a wide range of oxygen partial pressure ($pO_2=10^{-35}$ to 1 atm). This paper describes the high-temperature gas-tight electrochemical cells used to determine electronic defect structures and transport properties for pure and doped-oxide systems, such as YSZ, doped and pure ceria $(Ca-CeO_2 \;and\; CeO_2)$, copper oxides and copper-oxide-based ceramic superconductors, transition metal oxides, $SrFeCo_{0.5}O_x,\; and \;BaTiO_2$.

• 한국세라믹학회지
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• 제31권12호
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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.

• 대한화학회지
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• 제44권6호
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• pp.581-586
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• 2000

가압경수로형 사용후핵연료에 포함된 플루토늄을 분리하여 전기량 적정방벙으로 정량하였다. 플루토늄은 음이온 교환수지(AG MP-1)를 이용하여 분리하였으며 플루토늄의 정량은 조절전위전기량 적정방법을 이용하였다. 본 연구에서는 플루토늄 분리와 관련된 산화상태 조절, 분리 회수율 및 정량과 관련된 몇 가지 전기량 적정조건들에 대해 검토하였다. 실험결과 플루토늄은 산화상태를 조절하여 분리하는 것이 정량결과에 대한 정확도를 높였으며, 플루토늄의 전기량 적정결과에 미치는 몇 가지 금속이온들에 의한 영향은 나타나지 않았다. 플루토늄 표준용액을 이용하여 측정한 전기량 정량결과에 대한 정확도는 회수율로 나타냈을 경우 0.230∼3.02 mg 범위에서 99.36%이었다. 가압경수로형 사용후핵연료 용해용액들에 포함된 0.250∼0.450 mg의 플루토늄을 적정하여 얻은 전기량 정량결과에 대한 평균 정밀도(상대표준편차, RSD)는 0.38%이었다.

• 공업화학
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• 제2권4호
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• pp.385-392
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• 1991

전하량적정법에 의해 $Ni_{1-x}O$의 비화학양(nonstoichiometry)를 측정하였고 결함모델을 확인하였다. 0.1-0.21atm의 산소분압과 1123-1198K의 온도범위에서 $Ni_{1-x}O$의 비화학양은 $Po_2{^{1/4}}$에 비례하였다. 이러한 산소분압의 의존성으로부터 $Ni_{1-x}O$의 주 결함은 singly 이온화한 Ni 빈자리임을 확인할 수 있었다. T=1173K와 $Po_2=0.21atm$인 조건에서 $x=1.21{\times}10^{-4}$의 값을 가졌다. 제안된 결함모델로 부터 결함의 표준생성엔탈피를 계산하였는데 0.95 eV의 값을 가졌다. 1248K 이상의 온도에서는 doubly 이온화된 빈자리로의 전이가 나타나기 시작하였다.

• The Korean Journal of Ceramics
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• 제4권2호
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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.