Synthesis and characterisation of metal oxides and fluorinated perovskite-related oxides

Ren, Xiaolin (2005). Synthesis and characterisation of metal oxides and fluorinated perovskite-related oxides. PhD thesis The Open University.

DOI: https://doi.org/10.21954/ou.ro.0000d3b8

Abstract

Perovskite-related materials of composition LaFe1-xCoxO3 prepared by conventional calcination methods and mechanical milling are shown by temperature programmed reduction to be more susceptible to reduction in a flowing mixture of hydrogen and nitrogen by the incorporation of cobalt. X-ray powder diffraction and Mossbauer spectroscopy show that in iron-rich systems the limited reduction of iron and cobalt leads to the segregation of discrete metallic phases without destruction of the perovskite structure. In cobalt-rich systems, the reduction of Co3+ to Coo precedes complete reduction of Fe3+ and the segregation of alloy and metal phases is accompanied by destruction of the perovskite structure. Phases made by milling techniques were of smaller particle size and are more susceptible to hydrogen reduction than their counterparts made by conventional techniques. Materials of the type La0.5Sr0.5MO3 (M= Fe, Co) made by calcination methods are more susceptible to reduction when the transition metal M is cobalt as compared to iron.

Perovskite-related oxides of composition La1-xSrxFe1-yCoyO3 have been fluorinated by reaction with poly(vinylidene fluoride). The materials have been characterised by X-ray powder diffraction and Mossbauer spectroscopy. Fluorination induces a reduction in the oxidation state of iron from Fe4+ to Fe3+. The fluorinated materials were magnetically ordered at 298 K.

Compounds of the type SrFe1-xSnxO3 were found to contain Fe5+ and Fe3+. Fluorination resulted in reduction of the transition metal to Fe3+ and, in iron-rich systems, magnetic order. The compound Ba2SnO4 which adopts the K2NiF4-type structure has also been fluorinated by reaction with zinc fluoride. X-ray powder diffraction shows an enlargement of the unit cell of the fluorinated phase along the c-axis. Small particle iron- and vanadium- antimonate have been prepared by mechanical milling methods. The phases have been examined by M6ssbauer spectroscopy and can be formulated M3+Sb5+O4 (M = Fe, V). Thermal analysis suggests that the vanadium animonate formed by milling V2O5 and Sb2O3 in an inert atmosphere may be oxygen deficient. X-ray powder diffraction shows that milling also induces the phase transformation of the cubic senarmontite Sb2O3 form to the orthorhombic valentinite Sb2O3 form and of a-Sb2O4 to B-Sb2O4.

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