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Phase Equilibria, Crystal Structures, and Dielectric Anomaly in the BaZrO3-CaZrO3 System



Igor Levin, T G. Amos, S M. Bell, L Farber, Robert S. Roth, Terrell A. Vanderah, B H. Toby


Phase equilibria in the (1-x)BaZrO3-xCaZrO3 system were analyzed using a combination of X-ray and neutron powder diffraction, and transmission electron microscopy. The proposed phase diagram features two extended two-phase fields containing mixtures of a Ba-rich cubic phase and a tetragonal, or orthorhombic Ca-rich phase, all having perovskite-related structures. The symmetry differences in the Ca-rich phases are caused by different tilting patterns of the [ZrO6] octahedra. In specimens quenched from 1650 C, CaZrO3 dissolves only a few percent of Ba, whereas the atom fraction solubility of Ca in BaZrO3 is approximately 30%. The BaZrO3-CaZrO3 system features at least two tilting phase transitions, Pm3m--> I4/mcm and I4/mcm-->Pbnm. Rietveld refinements of the Ba0.8Ca0.2ZrO3 structure using variable-temperature neutron powder diffraction data confirmed that the Pm3m--->I4/mcm transition corresponds to a rotation of octahedra about one of the cubic axes; successive octahedra along this axis rotate in opposite directions. In situ variable-temperature electron diffraction studies indicates formation the transition temperature increases with increasing Ca-substitution on the A-sites, from approximately 120 C at 5% atom fraction Ca to 225 C at 20 % Ca. Dielectric measurements revealed that the permittivity increases monotonically from 36 for BaZrO3 to 53 for Ba0.9Ca0.1ZrO3, and then decreases to 50 for Ba0.8Ca0.2ZrO3. This latter specimen was the Ca-richest composition for which pellets could be quenched from the single-phase cubic field with presently available equipment.
Journal of Solid State Chemistry
No. 2


Bond strain, crystal structure, dielectric properties, octahedral tilting, perovskites, zirconates


Levin, I. , Amos, T. , Bell, S. , Farber, L. , Roth, R. , Vanderah, T. and Toby, B. (2003), Phase Equilibria, Crystal Structures, and Dielectric Anomaly in the BaZrO<sub>3</sub>-CaZrO<sub>3</sub> System, Journal of Solid State Chemistry (Accessed September 23, 2023)
Created November 1, 2003, Updated February 19, 2017