Influence of disorder-to-order transition on lattice thermal expansion and oxide ion conductivity in (Ca_xGd_(1-x))_2(Zr _(1-x)M_x)_2O_7 pyrochlore solid solutions

摘要

The effect of simultaneous substitutions of Ca at A site and Nb or Ta at B site in pyrochlore-type solid solutions: (Ca_xGd_(1-x)) _2(Zr_(1-x)M_x)_2 O_7 (x = 0.1, 0.2, 0.3, 0.4, 0.5 and M = Nb or Ta) were studied by powder X-ray diffraction (XRD), FT NIR Raman spectroscopic techniques and transmission electron microscopy. The solid solutions were prepared by the conventional high-temperature ceramic route. The XRD results and Rietveld analysis revealed that the defect fluorite structure of Gd_2Zr_2O_7 progressively changed to a more ordered pyrochlore phase by simultaneous substitutions at A and B sites. Raman spectroscopy reveals the progressive ordering in the anion sublattice with simultaneous doping. High-resolution images and selected-area electron diffraction patterns obtained from TEM confirms the XRD and Raman spectroscopic results. High-temperature XRD studies show that the lattice expansion coefficient in these pyrochlore oxides is of the order of 10~(-6) K~(-1). Lattice thermal expansion coefficient increases with increase of disorder in pyrochlore oxides, and hence the variation of thermal expansion coefficient with composition is also a good indicator of disordering in pyrochlore-type oxides. The ionic conducting properties of the samples were characterised by impedance spectroscopy, and it was found that Nb-doped compositions show a considerable change in conductivity near the phase boundary of disordered pyrochlore and defect fluorite phases.