Mechanochemical synthesis and ionic conductivity in the Gd2(Sn1–yZry)2O7 (0⩽y⩽10⩽y⩽1) solid solution

Several compositions within the Gd2(Sn1−yZry)2O7 solid solution with a pyrochlore-type of structure, have been prepared at room temperature in a planetary ball mill starting from stoichiometric mixtures of the constituent oxides, SnO2, ZrO2 and Gd2O3. Phase evolution in the powder mixtures as a function of composition and milling time was followed by X-ray diffraction (XRD) finding out that after 18 h, every mixture consist of a single phase. Mechanically activated chemical reaction takes place after an intial step of particle size refinement and polymorphic transformation of C-Gd2O3. We have performed Impedance Spectroscopy measurements to investigate oxygen ion dynamics in the series and conclude that Zr substitution for Sn hardly modifies the importance of ion–ion correlations in the oxygen diffusion process. We also estimate from conductivity measurements the value of the microscopic activation energy needed for independent ion hopping, which is found to be 0.56±0.06 eV, independent of Zr content.

Macroscopic (Edc, empty squares) and microscopic (Ea, solid squares) activation energies for oxygen ion migration as a function of Zr content, for the Gd2(Sn(1−y)Zry)2O7 solid solution. Inset: DRX patterns of several compositions in the title solid solution with different Sn/Zr ratio.Figure optionsDownload as PowerPoint slide