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Structural features, nonstoichiometry and high-temperature transport in SrFe1−xMoxO3−δ

✍ Scribed by A.A. Markov; O.A. Savinskaya; M.V. Patrakeev; A.P. Nemudry; I.A. Leonidov; Yu.T. Pavlyukhin; A.V. Ishchenko; V.L. Kozhevnikov


Book ID
104030299
Publisher
Elsevier Science
Year
2009
Tongue
English
Weight
853 KB
Volume
182
Category
Article
ISSN
0022-4596

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✦ Synopsis


The oxide solid solutions SrFe 1Àx Mo x O 3Àd , where x ¼ 0.05, 0.1 and 0.2, are studied in this work. It is shown that substitution of iron for molybdenum results in stabilization of a cubic quasi-perovskite locally inhomogeneous structure, which is evidenced by HREM and Mo ¨ssbauer spectroscopy. The coulometric titration is used in order to determine changes of oxygen nonstoichiometry in the obtained solutions with temperature and ambient oxygen partial pressure. Partial molar thermodynamic functions of the labile oxygen are calculated from the measured data. The variations of partial molar entropy with oxygen content follow the ideal gas model reasonably well thus demonstrating approximately random distribution of oxygen vacancies in the doped ferrite at high temperatures. The partial molar enthalpy is found to increase with doping, which is indicative of a progressive decrease in average values of the bonding energy of labile oxygen ions. The measurements of total conductivity are used in order to determine partial contributions of charge carriers. The oxygen ion component is shown to increase at small level of doping, x ¼ 0.05 while further increase in molybdenum content is accompanied with the decline in the ion conductivity. The electron contribution in reducing conditions tends to increase with molybdenum content, which is interpreted as a manifestation of involvement of Mo 5+ cations in electron transport. Concentration and mobility of electron carriers are calculated. Some increase in mobility of electron holes at small doping is explained as related to the filling of oxygen vacancies.


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