• 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.

• Proceedings of the Korean Nuclear Society Conference
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• 1996.05c
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• pp.231-237
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• 1996

Defect equilibrium equations were modelled, and the relations of P $o_2$, venus x were derived using the mass action law. The dominant defect species active in a specified region were determined by fitting the curve of experimental data to the calculated curve of log P $o_2$, versus log x for each theoretical model. The calculated curve for (2:1:2) and (Er')$^{x}$ in the hyperstoichiometric $U_{1-y}$E $r_{y}$ $O_{2＋x}$ and that for (2Er'quot;)$^{x}$ $_{dec}$ in the hypostoichiometric $U_{1-y}$E $r_{y}$ $O_{2－x}$ are in good agreement with the present experimental results. The sintering behavior of Er-doped U $O_2$ is observed with erbium content in oxidizing and reducing atmospheres. For sintering in oxidizing atmosphere, sintered density decreases as increasing y in $U_{1-y}$E $r_{y}$ $O_{2＋x}$. However, in hydrogen atmosphere, sintered density decreases as increasing y at lower erbium content but the density increases again above y=0.10. In oxidizing sintering conditions, the formation of (Er'U')$^{x}$ clusters hinders the diffusion of cations, and hence the sinterability of Er-doped U $O_2$ decreases. In reducing atmosphere of Er-doped U $O_2$ for higher Er concent, the oxygen vacancies make (Er')$^{x}$ cluster decompose by charge compensation and the concentration of mobile cations increases, thereby improving the sinterability.ntration of mobile cations increases, thereby improving the sinterability.ability.