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The K2NiF4 type diluted solid solutio Y0.9Ca1.1Al1-yCryO 4-δ (y ≤ 0.10) has been prepared by solid state reaction at 1430°C in air and studied to obtain evidence for the oxygen non-stoichiometry phenomena, depending on the partial Y3+ → Ca2+ replacement and to some extent of Cr3+ → Cr4+ oxidation. The structural characterization by X-ray diffraction for the composition y = 0 points to the simultaneous existence of an oxygen deficiency and supplementary oxygen which is located in the rock-salt layer of the perovskite-rock-salt intergrowth structure, as in La2NiO4.18. The effective magnetic moment which is calculated from the measured magnetic susceptibility for six compositions shows a systematic decrease over the whole temperature range 80-300 K, as a result of the decrease of the Y3+/Ca2+ ratio. The partial occurrence of Cr4+ oxidized species is considered for the modelling of the temperature dependence of μeff: the amount of Cr4+ is found to be in the range 55-60% of the total chromium amount, as deduced from the calculation of the distribution of the monomer and dimer Cr species in the perovskite layer. The electrical conductivity measured in the range 1100-1400°C for T and 10-13-105 Pa for po2 indicates a significant increase of the anionic contribution, due firstly to the decrease of the Y3+/Ca2+ ratio and secondly to the increase of Cr content y in the oxygen defective solid solution; such an effect agrees well with the favourable role of the oxygen defects, namely both vacancies and interstitial positions. Finally, the overall crystallochemical, magnetic and electrical data are consistent with a partial Cr3+ → Cr4+ oxidation which is coupled to the partial Y3+ → Ca2+ replacement: this creates oxygen non-stoichiometry phenomena very similar to those observed for the isotypic nickelates and cuprates.
Original language | English |
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Pages (from-to) | 103-110 |
Number of pages | 8 |
Journal | Materials Chemistry and Physics |
Volume | 48 |
Issue number | 2 |
DOIs | |
State | Published - Apr 1997 |
ID: 88614521