Electrical conductivity of the system Y2O3CeO2

The electrical conductivity of the system Y₂O₃CeO₂ was measured in the temperature range 500–1100°C and P_o2 range 10^–7?10^?1 atm. Possible defect models were suggested on the basis of conductivity data, which were investigated as a function of temperature and of P_o2. The observed activation energies were 0.40 eV and 1.79 eV in the low- and high-temperature regions, respectively. The observed conductivity dependences on P_o2 were in the temperature range 500–750°C and at temperatures from 750–1100°C. It is suggested that the system Y₂O₃CeO₂ shows a mixed ionic plus hole conduction due to an O^″_i defect and an electronic hole conduction due to a V^'''_Y defect in the low- and high-temperature regions, respectively.     

A thermodynamic study of nonstoichiometric cerium dioxide

Thermogravimetric measurements were performed on nonstoichiometric CeO_2?x in the temperature range 750–1500°C and from oxygen pressures of 10^?2 to 10^?26 atm. From this data the deviation from stoichiometry x = x(T, P_o2) was determined. The thermodynamic quantities Δ$\text{H}$_o2 and Δ$\text{S}$_o2 were calculated in the region 0.001? x ? 0.3 and found to be independent of temperature.In the composition region 0.001< x < 0.006, the variation of Δ$\text{S}$_o2 with x is consistent with a defect model involving randomly distributed doubly ionized oxygen vacancies. The experimental dependence of x and σ (electrical conductivity) is shown to be consistent with this model as Δ$\text{H}$_o2 (≈ -10 eV) exhibits a slight dependence on x. It is postulated that the variation in Δ$\text{H}$_o2 may result from lattice parameter increases with x, while the defects remain essentially randomly distributed.In the composition region 0.006 < x < 0.1, x ∝ with 1 < n < 5, and in the region 0.1 < x < 0.3, x ∝ with n increasing rapidly with x to n? 30. This behavior is believed to result from increasing defect interaction with increasing departures from stoichiometry. It is interesting to note that the ordered phase observed by Bevan and Kordis between CeO_1·72 and CeO_1·70 was not observed in this study at temperatures between 1300° and 1500°C.     

Metal-nonmetal transition in solid argon-lanthanum mixtures

A continuous metal-nonmetal transition is observed in solid ArLa mixtures. The d.c. conductivity σ starts at a La atomic fraction c_La ? 0.15 with $\text{σ = 2 × 10}{}^{-2}\text{[Ω-cm]}{}^{-1}$ and increases exponentially with c_La until σ reaches the minimum metallic conductivity $\text{σ}{}_{\min }\text{= 300 ± 100[Ω-cm]}{}^{-1}$ at c_La ? 0.4. The temperature dependence of σ shows variable range hopping between localized states for c>_La ? 0.4 and metallic behaviour for $\text{c}{}_{\mathrm{<mtext>La</mtext>}}\text{? 0.4.}$