0000000000300489
AUTHOR
Abel Rousset
Mixed-Valence Defect Ferrites : a New Family of Fine Powders and Thin Films of Spinel Ferrites
When highly divided spinel ferrites become reactive enough with oxygen, to allow the oxidation of the Fe 2+ ions at low temperature and of substitute cations too, when these cations are capable of different valence states. We prepared fine particles of spinel ferrites substituted by Mn, Mo, Cu, by chimie douce, especially from oxalate precursors and used them to reveal and to study the oxido-reduction phenomena occurring in these finely divided materials. It was shown that the oxidation created a new family of spinel ferrites : the mixed-valence defect ferrites, having specific characteristics and properties. The ferrites of this type can be fine powders prepared at low temperature, or grou…
Valence states of copper in copper ferrite spinels CuxFe3−xO4 (0 < x ≤ 1) fine powders: Evidence of copper insertion
Abstract The oxidation in cation deficient spinels of copper iron spinels Cu x Fe 3− x O 4 (0 x ≤ 1) synthesized by soft chemistry with a grain size x per mole of ferrite, three oxidation phenomena corresponding to Cu + at B-sites (130°C), Fe 2+ at B-sites (180°C) and Cu + at A-sites (240°C) have been found in close relation with the cation-oxygen distance of each oxidizable cation. For nonstoichiometric synthesized spinels Cu x Fe 3− x O 4+ δ with δ x , the presence of additional interstitial Cu + ions has been envisaged. The oxidation temperature of these interstitial ions (> 300°C) is higher than that for Cu + ions at Asites suggesting that interstitial copper ions also essentially resid…
Thermal stability and reactivity in oxygen of potassium ferrites with spinel structure
The potassium content really incorporated in the spinel lattice of the magnetite determined by thermogravimetric analysis in vacuum or in oxygen was about 2.45 wt%. In spite of this low content, the potassium strongly stabilises the defect spinel structure resulted by the potassium-substituted magnetite oxidation and increases the transformation temperature of the defect phases into α-Fe2O3 or KFe11O17.
Correlation between oxidation states of transition metal ions and variation of the coercivity in mixed-valence defect spinel ferrites
Abstract Due to the very high dispersion of mixed-valence spinel ferrites prepared by ‘soft chemistry’ it becomes possible to oxidize in the spinel lattice, not only ferrous ions but also different transition metal ions (Cr 3+ , Mn 2+ , Mn 3+ , Mo 3+ , Mo 4+ V 2+ , V 3+ , Cu + ), by ‘soft’ oxidation between 150 and 500°C, under formation of non-stoichiometric spinels cation vacancies. The oxidation state with the coordination and the oxidation temperature of the cations have been determined in coppermanganese ferrites by derivative thermogravimetry (DTG), based on the specific solid-state reactivity of cations in the redox reaction. For Co-modified non-stoichiometric spinels, which present…