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- Biendicho, J. J., et al.
(författare)
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Synthesis and characterization of perovskite-type Sr(x)Y1-xFeO(3-delta) (0.63 <= x < 1.0) and Sr0.75Y0.25Fe1-yMyO3-delta (M=Cr, Mn, Ni), (y=0.2, 0.33, 0.5)
- 2013
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Ingår i: Journal of Solid State Chemistry. - : Elsevier BV. - 0022-4596 .- 1095-726X. ; 200, s. 30-38
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Tidskriftsartikel (refereegranskat)abstract
- Oxygen-deficient ferrates with the cubic perovskite structure SrxY1-xFeO3-delta were prepared in air (0.71 <= x <= 0.91) as well as in N-2 (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-delta=2.79(2) for x=0.75 to 3-delta=2.83(2) for x=0.91. Refinement of the crystal structure of Sr0.25Y0.25FeO2.29 using TOP 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 highresolution electron microscopy (HREM) studies of Sr0.75Y0.25FeO2.79 reveal a modulation along (1 0 0)(p) with G +/- similar to 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, Sr0.75Y0.25Fe02.79 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-delta (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 Sr0.75Y0.25Fe02.79. Only M=Ni has increased electrical conductivity compared to un-doped Sr0.75Y0.25Fe02.79.
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| 2. |
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| 3. |
- Shafeie, Samrand, 1984-, et al.
(författare)
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Phase formation, crystal structures and magnetic properties of perovskite-type phases in the system La2Co1+z(MgxTi1-x)1-zO6
- 2011
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Ingår i: Journal of Solid State Chemistry. - : Elsevier BV. - 0022-4596 .- 1095-726X. ; 184:1, s. 177-190
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Tidskriftsartikel (refereegranskat)abstract
- Perovskite-type cobaltates in the system La(2)Co(1+z) (Mg(x)Ti(1-x))(1-z)O(6) were studied for z=0 <= x <= 0.6 and 0 <= x <= 0.9, using X-ray and neutron powder diffraction, electron diffraction (ED), magnetic susceptibility measurements and X-ray absorption near-edge structure (XANES) spectroscopy. The samples were synthesised using the citrate route in air at 1350 degrees C. The space group symmetry of the structure changes from P2(1)/n via Pbnm to R (3) over barc with both increasing Mg content and increasing Co content. The La(2)Co(Mg(x)Ti(1-x))O(6) (z=0) compounds show anti-ferromagnetic couplings of the magnetic moments for the Co below 15 K for x=0, 0.1 and 0.2. XANES spectra show for the compositions 0 <= x <= 0.5 a linear decrease in the L(3)/(L(3)+ L(2))Co-L(2.3) edge branching ratio with x, in agreement with a decrease of the average Co ion spin-state, from a high-spin to a lower-spin-state, with decreasing nominal Co(2+) ion content.
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| 4. |
- Shafeie, Samrand, 1984-, et al.
(författare)
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Tracking of high-temperature thermal expansion and transport properties vs. oxidation state of cobalt between +2 and +3 in the La2Co1+z(Ti1-xMgx)(1-z)O-6-system
- 2012
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Ingår i: Journal of Materials Chemistry. - : Royal Society of Chemistry (RSC). - 0959-9428 .- 1364-5501. ; 22:32, s. 16269-16276
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Tidskriftsartikel (refereegranskat)abstract
- The high-temperature thermal expansion and electronic transport properties of the B-site substituted LaCoO3 with both variable oxidation state of cobalt between +2 and +3 (La2Co(Ti1-xMgx)O-6, 0 <= x <= 0.5) and variable Co3+-content relative to the other B-cations (La2Co1+z(Ti0.5Mg0.5)(1-z)O-6, 0.2 <= z <= 0.6) have been investigated. Based on the temperature dependence of the thermal expansion, electronic transport properties and Seebeck coefficient, three different groups of compositions according to their symmetries can be allocated. It was found that the thermal expansion coefficients (TECs) of the studied compounds are mainly dependent on the proportion of Co2+/Co3+. For La2Co(Ti1-xMgx)O-6, the TEC increases from similar to 9 (x = 0) to similar to 19 ppm K-1 (x = 0.5) with an increase of the oxidation state of cobalt from +2 to +3, respectively. The TECs of La2Co1+z(Ti0.5Mg0.5)(1-z)O-6, z = 0.2-0.6 with Co3+-only, remain constant at similar to 21 ppm K-1 independent of the cobalt content. Thermoelectric measurements of the system indicate that all samples in the system, except La2Co1.6(Ti0.5Mg0.5)(0.4)O-6, are p-type conductors over the whole temperature range, 300 < T < 1175 K. The conductivities were found to increase with an increase of both Co3+ and total cobalt content and are described with a small polaron hopping model. Due to an insignificant number of oxygen vacancies of La2Co1+z(Ti1-xMgx)(1-z)O-6 samples prepared in air at elevated temperatures, the investigated system is proposed as an excellent model system for the investigation of the influence of the Co oxidation state and stoichiometry on different properties in perovskite cobalt oxides.
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