Lanthanum pyrochlores and the effect of yttrium addition in the systems La2−xYxZr2O7 and La2−xYxHf2O7

The crystal structures of the compounds La2−xYxZr2O7 and La2−xYxHf2O7 with x=0.0, 0.4, 0.8, 1.2, 1.6, and 2.0 have been studied using neutron powder diffraction and electron microscopy to determine the stability fields of the pyrochlore and fluorite solid solutions. The limits of pyrochlore stability in these solid solutions are found to be close to La0.8Y1.2Zr2O7 and La0.4Y1.6Hf2O7, respectively. In both systems the unit cell parameter is found to vary linearly with Y content across those compositions where the pyrochlore phase is stable, as does the x-coordinate of the oxygen atoms on the 48f (x  ,38,38) sites. In both systems, linear extrapolations of the pyrochlore data suggest that the disordering is accompanied by a small decrease in the lattice parameter of approximately 0.4%. After the pyrochlore solid solution limit is reached, a sharp change is observed from x∼0.41 to 0.375 as the disordered defect fluorite structure is favoured. Electron diffraction patterns illustrate that some short-range order remains in the disordered defect fluorite phases.

Short-range ordering has been seen in the defect fluorites Y2Zr2O7 and Y2Hf2O7, where they previously were thought to be entirely disordered. Evidence suggests the correlation length changes with composition, but is not commensurate with unit cell sizes.Figure optionsDownload as PowerPoint slide