Oxygen stoichiometry, phase stability, and thermodynamic behavior of the lead-doped and lead-free Bi-2212 systems

Electromotive-force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made on lead-doped and lead-free Bi 2− z Pb z Sr 2Ca 1Cu 2O x superconducting ceramics in the temperature range ≈ 700–815°C by means of an oxygen-titration techique that employs an yttria-stabilized zirconia electrolyte. Equations for the variation of oxygen partial pressure with composition and temperature have been derived from our EMF measurements. Thermodynamic assessments of the partial molar quantities Δ H (O 2) and Δ S (O 2) for lead-doped Bi-2212 and lead-free Bi-2212 indicate that the solid-state decomposition of these bismuth cuprates at low oxygen partial pressure can be represented by the diphasic CuOCu 2O system.