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Mixed ionic electronic conducting perovskite materials have been receiving considerable attention for the application of oxygen separation membranes. These membranes have potential to be integrated in industrial processes that require pure oxygen and to provide advantages considering economical and environmental aspects. The used perovskite materials can accommodate a high concentration of disordered oxygen vacancies and provide high oxygen permeation flux in the presence of an oxygen partial pressure gradient. However, the materials with high oxygen flux are observed to have low chemical and mechanical stability, originating from oxygen vacancy formation and reduction of the B-site transition metal ion. Based on the fact that the stability of the materials at reducing pO2 is dependent on the redox stability of the B-site cation, a partial substitution of the B-site transition metal with a more stable cation is considered in this thesis to improve the stability of the base perovskite oxide. The approach used for the identification of the suitable material based on the host composition La0.5Sr0.5FeO3-δ (LSF) was to first explore the B-site substituting elements in terms of their effect on the thermal expansion and the isothermal expansion measured during the atmosphere change from air to argon. The elements Al, Cr, Zr, Ga, Ti, Sn, Ta, In, V, and Mg were used for 10 or 20% substitution of Fe. The isothermal expansion of the host material was decreased by substitution, which was attributed to decreased amount of oxygen vacancy formation as it was evidenced later by TGA of chosen compositions. As a result, the compositions substituted with higher valence ions (particularly, 20% Ti4+, LSFTi2, and 10% Ta5+, LSFTa1) were identified as the least expanding materials in isothermal conditions. The effect of substitution was further characterized extensively including structural, mechanical, and oxygen transport properties. The oxygen vacancy (VO••) concentration changes induced by substitution of Fe were reflected in unit cell sizes of heat-treated samples under argon atmosphere. The increase in the unit cell size was attributed to the isothermal expansion due to B-site reduction and lowered to half in case of substituted LSFTi2 and LSFTa1 compared to the host material LSF. Similar trends were observed for interrelated properties such as the coefficient of thermal expansion, isothermal expansion, and the actual amount of oxygen vacancies formed under argon at 900°C, all of which were higher for LSF. The mechanical properties of LSF, LSFTi2, and LSFTa1 were characterized at room temperature. The Young's modulus and the bending strength of the materials were in the same range (141-147 GPa and ∼120 MPa, respectively) while the fracture toughness of the LSF sample was improved by Ti and especially Ta substitution. The fractography of the samples provided evidence that the several LSF samples showed extended cracks possibly related to residual stresses forming during cooling, due to non-equilibrated oxygen stoichiometry across the sample. The potential step measurements showed that the chemical diffusion and the surface exchange coefficients measured during oxidation of the samples were higher than the ones measured during reduction of the samples. The tendency was reversed at lowered pO2 along with the decrease of both coefficients. The influence of B-site substitution on both coefficients was not substantial. The oxygen permeation flux of LSF, LSFTi2, and LSFTa1 was measured under air/argon gradient on planar membranes. The permeation rates of the membranes with thicknesses close to 1 mm were considered to be limited by surface exchange kinetics at temperatures above 875°C. The permeation rate of LSF was decreased (from 0.2 µmolcm-2s-1) to its third by Ti and Ta additions. The permeation rate of Ti and Ta-substituted samples showed a drop around 875°C, keeping a similar activation energy at lower and higher temperature regions. Oxygen vacancy ordering in the perovskite structure was given as a possible explanation, which provided explanation for the slow equilibrium in the lower temperature region. Tubular membranes of LSF and LSFTi2 (0.47 mm and 0.36 mm thick, respectively) and a planar LSFTa1 membrane were characterized using an air/(Ar-CH4) gradient. The measurements conducted using pure Ar on the lean-side provided the possibility to compare the thickness dependence of the permeation. In agreement with the previous observations, the permeation of the materials at and above 900°C was independent of the thickness, therefore, surface exchange limited. Stability under reducing atmospheres was increased by substitution. The LSF membrane failed shortly after the introduction of CH4 to the system, while LSFTi2 survived 5% CH4 and its oxygen permeation was improved substantially by a factor of 14. LSFTa1 membrane was measured with pure CH4 and the permeation was increased by a factor of 9, reaching 0.7 µmolcm-2s-1 at 900°C. The membrane operated stably over 2000h with pure CH4, 1000h. A slow degradation of 3.7% per 1000h was observed at 1000°C, most probably due to cation migration. The compositions identified as a result of B-site substitution screening were effective in improving the stability of the materials without extensive loss of the oxygen permeation rate. Ta-substituted material was shown to be promising with its long-term stability as a partial oxidation membrane.