0000000000311995
AUTHOR
Ph. Tailhades
Analysis of the oxidation process and mechanical evolution in nanosized copper spinel ferrites. Role of stresses on the coercivity
Isothermal oxidations of the iron(II) and copper(I) cations in nanosized copper spinel ferrites which were oxidized in cation-deficient spinels have been studied by thermogravimetric analysis. The low temperature kinetics of oxidation of each oxidizable cation has been explained on the basis of a diffusion-induced stress effect, these stresses being generated in the ferrite particles by the chemical gradient induced during the oxidation process where the cations at the surface are more oxidized than those in the bulk. A reaction mechanism coupling the chemical and the mechanical effects has been proposed. When the Cu-ferrites contain some Co-cations, it has also been revealed that the stres…
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…
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…