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Selected compositions of the Ba–Sr–Co–Fe–O system were synthesized from powders by the solid-state reaction method. Samples were equilibrated at 1273 K for 36 000 s in air. The resulting powders were characterized by X-ray diffraction (XRD) at room temperature and by high-temperature in situ XRD. The phases present in the BaxSr1−xCoyFe1−yO3−δ system are outlined for 1273 K in air. For most of the quaternary compositions, the cubic perovskite is formed, except for the compositions with x = 1 (excluding y = 0.4), y = 1 and x, y = 0.8, where the phases mainly show hexagonal distortions, and x, y = 0, for which a predominant cubic phase is mixed with other phases.

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