Oxygen order–disorder phase transition in layered GdBaCo2O5+δ perovskite: Thermodynamic and transport properties

L. MOGNI; F. PRADO; C.JIMENEZ; A. CANEIRO

SOLID STATE IONICS

ELSEVIER SCIENCE BV

Lugar: Amsterdam; Año: 2013 vol. 240 p. 19 - 28

0167-2738

The effects of the orthorhombic (O) to tetragonal (T) phase transition around 450/500 °C on the thermodynamic and transport properties of the layered cobaltite GdBaCo2O5+δ have been investigated in detail using complementary techniques such as thermo-gravimetry (TG), differential scanning calorimetry (DSC), dilatometry, angle dispersive as well as energy dispersive high temperature X-ray diffraction (HT-XRD and ED-XRD). Experimental data show that the O/T transition temperature shifts to higher values when the pO2 of the experiment increases. The equilibrium pO2 data shows the presence of a narrow two-phase field around 5 + δ ≈ 5.42. The presence of a two-phase field together with an enthalpy change (ΔH ≈ 4 J/g) and HT-XRD data showing coexistence of both phases confirms that this phase transition is first-order type. Oxygen partial molar enthalpy and entropy of both phases, the ?ordered? O and the ?disordered? T, are obtained from TG under controlled pO2, and yield lower entropy and enthalpy values for the ordered O phase. The O/T phase transition at constant temperature involves a volume contraction and a density change of 0.3%. Isotherms of electrical conductivity as a function of pO2 show that this compound exhibits itinerant charge carrier behavior regardless of the crystal symmetry. The charge carrier mobility decreases for the T phase, which might be due to the shortening of Co\O\Co distance along a-direction.