Direct-Current Conductivity of Y2O3 as a Function of Water Vapor Pressure

The dc conductivity of a sintered sample of Y₂O₃ containing an excess of lower-valent metal (Ml) impurities has been measured at 600° to 1100°C in air as a function of the water vapor pressure (0.4 to 3000 Pa). The logarithm of the p -type conductivity vs log P _H2o has a slope of – 1/2 in certain regions of F _H2o and temperature. This reflects a defect situation where interstitial protons from water vapor balance the excess of lower-valent cation impurities: [H_˙] = [M1_']. The activation energy for the p -type conductivity under these conditions is evaluated and interpreted in terms of the enthalpy needed to dissolve interstitial protons in yttria.     

Electrical Conductivity and Defect Structure of Y2O3 as a Function of Water Vapor Pressure

The electrical conductivity of several sintered yttria ceramics with different levels of lower valent cation impurities was studied as a function of the partial pressure of water vapor (3 to 1600 Pa) at 500° to 1300°C in oxygen or air. At the higher temperatures yttria is a P -type conductor, but at the lowest temperatures and highest water vapor pressures, an ionic contribution becomes significant. The p -type conductivity decreases with increasing water vapor pressure. This is interpreted in terms of a model involving dissolution of hydrogen as interstitial protons and which counterbalance the effective charges of the lower valent impurities. At the higher water vapor pressures and lower impurity levels excess protons are probably compensated by interstitial hydroxide or oxygen ions. Indications of grain boundary segregation of impurities are reported.     

Electrical Conductivity of Y2O3 as a Function of Oxygen Partial Pressure in Wet and Dry Atmospheres

The electrical conductivity of polycrystalline Y₂O₃ has been studied as a function of the partial pressure of oxygen (10^–14 to 10⁵ Pa) at 900° to 1500°C in atmospheres saturated with water vapor at 12°C or dried with P₂O₅. Yttria is a p -conductor at high oxygen activities. The p -conductivity increases with increasing P _O2 and decreases with increasing P_H2O. At low oxygen activities the oxide is a mixed ionic/electronic conductor. The ionic conductivity is approximately independent of P _O2 and increases with increasing P _H2O. In the Y₂O₃ samples, excesses of lower-valent cation impurities (in the 10 to 100 mol-ppm range) are the dominating negatively charged defects, and in the presence of water vapor they are compensated by interstitial protons. At high P _H2O levels additional protons are probably compensated by interstitial oxygen ions. At high temperatures (±1100°C) and for high P _O2 and low P _H2O, the protons are no longer dominant, and the lower-valent cations are mainly compensated by electron holes. The electrical conductivity exhibits hysteresis-like effects which are interpreted in terms of segregation/desegregation of impurities at grain boundaries. The mobility of electron holes in yttria at 1500°C is estimated to be of the order of magnitude of 0.05 cm². s^–1. V^–1