Quaternary pyrochlore-type solid solutions, CaGdZrNb(1-x)Ta(x)O(7) (x = 0, 0.2, 0.4, 0.6, 0.8, 1), were prepared by a high-temperature ceramic route. The pyrochlore phases of the compounds were confirmed by powder X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy. The crystallographic parameters of the pyrochlore compounds were accurately determined by Rietveld analysis of the powder XRD data. The isovalent substitution of Ta in place of Nb at the B site can reveal the effect of chemical bonding on lattice thermal expansion and oxide ion conductivity because both Nb and Ta have the same ionic radius (0.64 Å). Lattice thermal expansion coefficients of the samples were calculated from high-temperature XRD measurements, and it was found that the thermal expansion coefficient decreases with substitution of Ta. Oxide ion conductivity measured by a two-probe method also shows the same trend with substitution of Ta, and this can be attributed to the high bond strength of the Ta-O bond compared to that of the Nb-O bond. Microstructural characterization using scanning electron microscopy proves that the size of the grains has a small effect on the oxide ion conductivity. Our studies established the role of chemical bonding in deciding the conductivity of pyrochlore oxides and confirmed that the 48f-48f mechanism of oxide ion conduction is dominant in pyrochlore oxides.

Fluorite-type zirconate compositions: Gd2(Zr1−xMx)2O7−δ (M = Sc, Y; x = 0, 0.1, 0.2, 0.3, 0.4) were prepared and the influence of aliovalent cation substitution on the structural and electrical properties were investigated in detail and correlated.

No abstract

No abstract