Papers by Keyword: Oxygen Stoichiometry

Abstract: This work investigates the influence of initial compound synthesis prehistory on the phase sequence during formation of single-phase Sr2FeMoO6 (SFMO). Analytical-grade SrCO3, Fe2O3 and MoO3 (sample No.1) and partially reduced precursors of SrFeO3-x (SFO) and SrMoO4-y (SMO) (sample No.2) were used as initial reagents. In the latter case, kinetic limitations of SFMO phase formation are resolved by increasing the diffusivity of both of Fe3+ and Mo5+ and decreasing diffusion lengths to the reaction zone. This enhances the double-perovskite growth rate, lowers synthesis temperature and increases the intensity of X-ray reflections of (011) and (013) planes suggesting a superstructural ordering of Fe3+ and Mo5+ cations. Samples No.1 and No.2 have both a Тс ~ 420K while the magnetization value at 77 K in the sample No.2 is higher by a factor 2.3 compared to that of sample No.1. A decrease of the oxygen vacancy concentration by annealing Sr2FeMoO5.82 lowered magnetization of the samples and promoted the formation of a second magnetic phase with Тс = 700 К. We suppose that an increase of oxygen partial pressure during annealing causes formation of clusters with antiferromagnetic coupling in Fe3+-О2--Fe3+ chains. In order to increase the magnetoresistive effect at temperatures relevant for technical application, weak intergrain bonds should be formed.

Abstract: The p(O2)-T- diagrams of La2Ni1-xMxO4+ (M=Co and Cu, x= 0-0.20), determined by the coulometric titration technique at 923-1223 K in the oxygen partial pressure range 10-4 to 0.6 atm, can be adequately described by equilibrium processes of oxygen intercalation into the rock-salt type layers and hole localization on B-site cations forming 3+ oxidation states. For the hole activity, a non-ideal solution model taking into account the repulsion of p-type electronic charge carriers can be used. The electrostatic repulsion excludes occupation of nearest neighboring sites and leads to splitting of the energy levels for more distant sites. The affinity of Ni and Cu cations with respect to the hole localization is similar and cannot be statistically separated analyzing the oxygen nonstoichiometry data only. On the contrary, cobalt cations tend to remain in the trivalent state and Co3+ should be treated as a separate type of charged point defect. Oxygen vacancies formed in the perovskite-like layers due to intrinsic Frenkel disorder have no essential effect on the oxygen thermodynamics. As expected, the thermodynamic functions governing the intercalation-related processes are independent of defect concentrations.