Effect of the Phase Composition and Local Crystal Structure on the Transport Properties of the ZrO2–Y2O3 and ZrO2–Gd2O3 Solid Solutions

Abstract

The results of investigating the crystal structure, ionic conductivity, and local structure of the (ZrO2)1 –x(Gd2O3)x and (ZrO2)1 –x(Y2O3)x (x = 0.04, 0.08, 0.10, 0.12, and 0.14) solid solutions are reported. The crystals are grown by directional crystallization of the melt in a cold container. The phase composition of the crystals is investigated by X-ray diffractometry and transmission electron microscopy. The transport characteristics are studied by impedance spectroscopy in the temperature range of 400 to 900°C. The local crystal structure is examined by optical spectroscopy. Eu3+ ions were used as a spectroscopic probe. The study of the local structure of the ZrO2–Y2O3 and ZrO2–Gd2O3 solid solutions revealed the features in the formation of optical centers, which reflect the character of localization of oxygen vacancies in the crystal lattice depending on the stabilizing oxide concentration. It is established that the local crystal environment of Eu3+ ions in the (ZrO2)1 –x(Y2O3)x and (ZrO2)1 –x(Gd2O3)x solid solutions is determined by the stabilizing oxide concentration and is practically independent of the stabilizing oxide type (Y2O3 or Gd2O3). The maximum conductivity at a temperature of 900°C is observed in the crystals with 10 mol % of Gd2O3 and 8 mol % of Y2O3. These compositions correspond to the t'' phase and are close to the interface between the cubic and tetragonal phase regions. It is found that in the ZrO2–Y2O3 system the highly symmetric phase is stabilized at a lower stabilizing oxide concentration than in the ZrO2–Gd2O3 system. The analysis of the data obtained makes it possible to conclude that, in this composition range, the concentration dependence of the ionic conductivity is mainly affected by the phase composition rather than the character of the localization of oxygen vacancies in the crystal lattice.