Synthesis and characterization of perovskite-type SrxY1−xFeO3−δ (0.63≤x<1.0) and Sr0.75Y0.25Fe1−yMyO3−δ (M=Cr, Mn, Ni), (y=0.2, 0.33, 0.5)

Oxygen-deficient ferrates with the cubic perovskite structure SrxY1−xFeO3−δ were prepared in air (0.71≤x≤0.91) as well as in N2 (x=0.75 and 0.79) at 1573 K. The oxygen content of the compounds prepared in air increases with increasing strontium content from 3−δ=2.79(2) for x=0.75 to 3−δ=2.83(2) for x=0.91. Refinement of the crystal structure of Sr0.75Y0.25FeO2.79 using TOF neutron powder diffraction (NPD) data shows high anisotropic atomic displacement parameter (ADP) for the oxygen atom resulting from a substantial cation and anion disorder. Electron diffraction (ED) and high-resolution electron microscopy (HREM) studies of Sr0.75Y0.25FeO2.79 reveal a modulation along 〈1 0 0〉p with G± ∼0.4〈1 0 0〉p indicating a local ordering of oxygen vacancies. Magnetic susceptibility measurements at 5–390 K show spin-glass behaviour with dominating antiferromagnetic coupling between the magnetic moments of Fe cations. Among the studied compositions, Sr0.75Y0.25FeO2.79 shows the lowest thermal expansion coefficient (TEC) of 10.5 ppm/K in air at 298–673 K. At 773–1173 K TEC increases up to 17.2 ppm/K due to substantial reduction of oxygen content. The latter also results in a dramatic decrease of the electrical conductivity in air above 673 K. Partial substitution of Fe by Cr, Mn and Ni according to the formula Sr0.75Y0.25Fe1−yMyO3−δ (y=0.2, 0.33, 0.5) leads to cubic perovskites for all substituents with y=0.2. Their TECs are higher in comparison with un-doped Sr0.75Y0.25FeO2.79. Only M=Ni has increased electrical conductivity compared to un-doped Sr0.75Y0.25FeO2.79.

Graphical abstractOxygen-deficient ferrates with the cubic perovskite structure SrxY1−xFeO3−δ were prepared both in air (0.71≤x≤0.91) and N2 (x=0.75 and 0.79) at 1573 K. Refinement of the crystal structure of Sr0.75Y0.25FeO2.79 using TOF neutron powder diffraction (NPD) data (S.G. Pm-3m, a=3.86455(3) Å; χ2=6.71, Rp=0.03; Rwp=0.04) confirmed the cubic perovskite structure. The observed high anisotropic atomic displacement parameter for the oxygen atom indicates a substantial anion sublattice disorder. Electron diffraction (ED) and high-resolution electron microscopy (HREM) studies of Sr0.75Y0.25FeO2.79 show compositional modulation along 〈1 0 0〉p with G± ∼0.4〈1 0 0〉p indicating ordering of oxygen vacancies at the local scale. Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Cubic perovskites SrxY1−xFeO3−δ (0.71≤x<0.91) were synthesized. ► Sr0.75Y0.25Fe1−yMyO3−δ, M=Cr, Mn, Ni were prepared. ► High-temperature conductivity properties and crystal structure were studied. ► High-temperature thermal expansion behavior was investigated.