Oxygen order-disorder phase transition in layered GdBaCo2O 5+δ perovskite: Thermodynamic and transport properties

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...

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Detalhes bibliográficos
Autores: Mogni, Liliana Verónica, Prado, Fernando Daniel, Jimenez, Catalina, Caneiro, Alberto
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2013
País:Argentina
Recursos:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/2067
Acesso em linha:http://hdl.handle.net/11336/2067
Access Level:acceso abierto
Palavra-chave:ELECTRON-HOLE TRANSPORT
GDBACO2O5+Δ
LAYERED PEROVSKITES
ORDER-DISORDER
PHASE TRANSITION
THERMODYNAMIC PROPERTIES
https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
https://purl.org/becyt/ford/1.4
Descrição
Resumo: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 (â̂†H ≈ 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 pO 2, 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 CoOCo distance along a-direction.