Enthalpy of formation and thermodynamic insights into yttrium doped BaZrO3

Journal of Materials Chemistry A Volume: 2 Issue: 42 Pages: 17840-17847 Published: 2014

Enthalpies of drop solution (left, solid squares) and formation from the oxides at 25 ºC (right, solid circles) as a function of yttrium content in BZ and YBZx solid solutions, x. The experimental uncertainties are indicated.

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Writers: M. D. Gonçalves, P. S. Maram, R. Muccillo, A. Navrotsky 

Keywords: enthalpy; exothermic; endothermic; thermodynamic

Abstract: The enthalpies of formation from binary oxide components at 25 °C of Ba(Zr1−xYx)O3−δ, x = 0.1 to 0.5 solid solutions are measured by high temperature oxide melt solution calorimetry in a molten solvent, 3Na2O·4MoO3at 702 °C. The enthalpy of formation is exothermic for all the compositions and becomes less negative when increasing yttrium content from undoped (−115.12 ± 3.69 kJ mol−1) to x = 0.5 (−77.09 ± 4.31 kJ mol−1). The endothermic contribution to the enthalpy of formation with doping content can be attributed to lattice distortions related to the large ionic radius difference of yttrium and zirconium and vacancy formation. For 0.3 ≤ x ≤ 0.5, the enthalpy of formation appears to level off, consistent with an exothermic contribution from defect clustering. Raman spectra indicate changes in short range structural features as a function of dopant content and, suggests that from x = 0.3 to 0.5 the defects begins to cluster significantly in the solid solution, which corroborates with the thermodynamic data and the drop-off in proton conductivity from x > 0.3.

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