Pyrochlore and perovskite potassium tantalate: enthalpies of formation and phase transformation.

Alkali niobates and tantalates are currently important lead-free functional oxides. The formation and decomposition energetics of potassium tantalum oxide compounds (K2 O-Ta2 O5 ) were measured by high-temperature oxide melt solution calorimetry. The enthalpies of formation from oxides of KTaO3 perovskite and defect pyrochlores with K/Ta ratio of less than 1 stoichiometry-K0.873 Ta2.226 O6 , K1.128 Ta2.175 O6 , and K1.291 Ta2.142 O6 -were experimentally determined, and the values are (-203.63 ± 2.92) kJ mol(-1) for KTaO3 perovskite, and (-339.54 ± 5.03) kJ mol(-1) , (-369.71 ± 4.84) kJ mol(-1) , and (-364.78 ± 4.24) kJ mol(-1) , respectively, for non-stoichiometric pyrochlores. That of stoichiometric defect K2 Ta2 O6 pyrochlore, by extrapolation, is (-409.87 ± 6.89) kJ mol(-1) . Thus, the enthalpy of the stoichiometric pyrochlore and perovskite at K/Ta=1 stoichiometry are equal in energy within experimental error. By providing data on the thermodynamic stability of each phase, this work supplies knowledge on the phase-formation process and phase stability within the K2 O-Ta2 O5 system, thus assisting in the synthesis of materials with reproducible properties based on controlled processing. Additionally, the relation of stoichiometric and non-stoichiometric pyrochlore with perovskite structure in potassium tantalum oxide system is discussed.