Phase equilibria, crystal structure and oxygen nonstoichiometry of complex oxides formed in the system GdCoO3–SrCoO3–δ–SrFeO3–δ–GdFeO3

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Abstract

The phase equilibria in the quasi-quaternary GdCoO3–SrCoO3–δ–SrFeO3–δ–GdFeO3 system have been studied at 1373 K in air. The homogeneity ranges and crystal structure of solid solutions of general composition Gd1–xSrxCo1–yFeyO3–δ have been determined. Depending on the concentration of introduced strontium and iron, the Gd1–xSrxCo1–yFeyO3–δ oxides crystallize in orthorhombic (x = 0.1 and 0.4 ≤ y ≤ 1.0; x = 0.2 and y = 0.9, sp. gr. Pbnm), tetragonal (0.6 ≤ x ≤ 0.8 and 0.1 ≤ y ≤ 0.5, sp. gr. I4/mmm) or cubic (x = 0.9 and 0.1 ≤ y ≤ 0.9; 0.6 ≤ x ≤ 0.8 and 0.6 ≤ y ≤ 0.9, sp. gr. Pm-3m) perovskite structure. Structural parameters were determined for all single-phase samples. An increase in the concentration of strontium and iron leads to an increase in the unit cell parameters of the Gd1–xSrxCo1–yFeyO3–δ oxides. It has been shown that the oxygen content in Gd1–xSrxCo1–yFeyO3–δ cobaltites, determined by thermogravimetric analysis, decreases with increasing temperature and strontium content in the samples. An isobaric-isothermal phase diagram of the GdCoO3 – SrCoO3–δ–SrFeO3–δ–GdFeO3 system at 1373 K in air was constructed.

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Т. V. Aksenova

Yeltsin Ural Federal University

Author for correspondence.
Email: TV.Aksenova@urfu.ru
Russian Federation, Ekaterinburg, 620002

E. E. Solomakhina

Yeltsin Ural Federal University

Email: TV.Aksenova@urfu.ru
Russian Federation, Ekaterinburg, 620002

A. S. Urusova

Yeltsin Ural Federal University

Email: TV.Aksenova@urfu.ru
Russian Federation, Ekaterinburg, 620002

V. A. Cherepanov

Yeltsin Ural Federal University

Email: TV.Aksenova@urfu.ru
Russian Federation, Ekaterinburg, 620002

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2. Fig. 1. X-ray data for Gd1-xSrxCo0.2Fe0.8O3-δ, where x = 0.0 (a), x = 0.1 (b), processed using the Rietveld method. Dots - experimental data, 1 - theoretical spectrum; 2 - location of maxima with a resolved set of Miller indices (hkl); 3 - difference between experimental data and theoretical curve

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3. Fig. 2. Concentration dependences of unit cell parameters of Gd1-xSrxCo1-yFeyO3-δ solid solutions, where x = 0.0, 0.0 ≤ y ≤ 1.0 are closed symbols; x = 0.1, 0.4 ≤ y ≤ 0.9 are open symbols

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4. Fig. 3. X-ray data for Gd0.3Sr0.7Co1-yFeyO3-δ, where y = 0.2 (a) and y = 0.7 (b), processed using the Rietveld method. Dots are experimental data, 1 - theoretical spectrum; 2 - location of maxima with Miller index set resolved (hkl); 3 - difference between experimental data and theoretical curve. Arrows indicate superstructural reflections for the 2ap × 2ap × 4ap tetragonal cell

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5. Fig. 4. Dependences of unit cell parameters on the composition of solid solution Gd1-xSrxCo1-yFeyO3-δ, where x = 0.6 are closed symbols, x = 0.7 are open symbols

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6. Fig. 5. Dependences of the pseudocubic cell parameters on the composition of the solid solution Gd1-xSrxCo1-yFeyO3-δ

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7. Fig. 6. Dependences of oxygen content in oxides Gd1-xSrxCo0.3Fe0.7O3-δ (0.6 ≤ x ≤ 0.9) on temperature in air

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8. Fig. 7. Isobaric-isothermal diagram of the state of the system GdCoO3-SrCoO3-δ-SrFeO3-δ-GdFeO3 at 1373 K in air. Green dots correspond to the orthorhombic structure of Gd1-xSrxCo1-yFeyO3-δ (pr. gr. Pbnm), blue dots to the cubic structure (pr. gr. Pm3m), and red dots to the tetragonal ordered structure (pr. gr. I4/mmm). Purple dots correspond to the two-phase region of coexistence of orthorhombic and tetragonal (or cubic) structures

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