0000000000300487
AUTHOR
B. Gillot
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…
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…
Cation Distribution in a Titanium Ferrite Fe2.75Ti0.25O4Measured byin-SituAnomalous Powder Diffraction Using Rietveld Refinement
Many ferrites contain different cations with various valence states and location in the spinel structure. In compounds such as these, only a combination of different techniques such as Mussbauer spectroscopy, IR analysis, and thermogravimetry allows the distribution of cations to be obtained. For very complicated distributions, the mathematical decomposition of derivative thermogravimetric curves (DTG) leading to quantitative distribution is uncertain. In this paper, we present an alternative technique based on resonant diffraction. The anomalous scattering of each cation in the crystalline material is used to determine its amount and position by Rietveld refinement. Since the energy for su…
Synthesis and Stability Region of Stoichiometric Nanocrystalline Vanadium−Iron Spinel Powders
Vanadium-iron spinels with nanometric sizes have been synthesized by a soft chemistry route. This way of elaboration consists of a coprecipitation followed by thermal treatments at low temperatures. The last thermal annealing is performed under a reducing atmosphere in order to obtain the exact oxygen stoichiometry (four oxygen atoms for three metal atoms in AB 2 O 4 ). Because of the low temperatures used, very low oxygen partial pressures (between 10 -20 and 10 -30 Pa) have to be applied. For this purpose, a reducing setup has been used. It consists of H 2 /N 2 /H 2 O gas mixtures, creating a reducing atmosphere with low oxygen partial pressure. This atmosphere can be applied to a sample …
Analysis of the Diffusion-Induced Stress Effect on the Oxidation in Finely Divided Vanadium Ferrites
L'oxydation isotherme des cations fer(II), vanadium(II) et vanadium(III) pour les ferrites spinelles finement divises, lesquels sont oxydes en phases deficitaires en cations, a ete etudiee par thermogravimetrie. La faible temperature de cinetique d'oxydation de chaque cation oxydable a ete expliquee en considerant que l'oxydation genere des contraintes qui en modifie la cinetique ou les cations a la surface sont plus oxydes que dans le volume. Pour cela, il at ete considere que le coefficient de diffusion chimique est donne par la relation D = D 0 exp [-(E' a + pV a )/RT] ou D 0 represente le facteur pre-exponentiel, E' a l'energie d'activation, V a le volume d'activation et p la pression i…
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…
Fine–grained spinel ferrites: From the reactivity to magnetic properties
The oxidation at low temperature of fine-grained ferrites containing oxidizable cations such as Cu + , Fe 2+ , Mn 2+ , Mo 3+ , V 3+ , has led to new mixed-valent cation deficient ferrites with a large number of vacancies. It has been demonstrated by DTG analysis that each cation oxidizes at a specific temperature in close relation with the cation-oxygen distance. The kinetics oxidation of each oxidizable cation has been explained on the basis of a diffusion-induced stress effect when these stresses are generated by the chemical gradient induced during the oxidation process. When fine-grained ferrites contain some Co-cations, it has been revealed that the stresses have a significant influenc…
Experimental set up for determining the temperature-oxygen partial pressure conditions during synthesis of spinel oxide nanoparticles
Abstract Nanometric spinel oxide powders, Fe 3− x M x O 4 , where M is a transition element, have been synthetized by soft chemistry. This method generally leads to a non-stoichiometric phase, Fe 3− x M x O 4+δ where δ is the deviation from stoichiometry so that further annealing at low temperatures around 450°C and low oxygen partial pressure around 10 −25 Pa given by N 2 /H 2 /H 2 O gas mixtures is required: this enables a stoichiometric compound to be obtained and a nanometric size to be maintained. The complete set up consisting of a gas mixer, a thermogravimetric apparatus and a preparative furnace is described. Some results concerning the conditions of temperature and oxygen partial p…
Intermediate valencies of vanadium cations appearing during oxidation of vanadium–iron spinels
Abstract The oxidation state of vanadium cations in nanosized vanadium–iron spinels at stoichiometry and at oxidative nonstoichiometry has been investigated by associating X-ray diffraction, thermal analysis (DSC), infrared and X-ray photoelectron spectroscopies. It has been established that, during oxidation, the V3+ cations present several intermediate valencies before to realize the final oxidation state +5. A comparison was made with the oxidation of V2O3.
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.
Réactivité vis-à-vis de l'oxygène de spinelles de fer-vanadium de taille nanométrique et distribution cationique
Resume L'etat de division des spinelles de fer-vanadium nanometriques V x Fe 3− x O 4 (0 ⩽ x ⩽ 2 ) permet d'oxyder au sein-meme de la structure spinelle les ions du fer et du vanadium. Les analyses calorimetriques et thermogravimetriques, ainsi que la spectroscopie infrarouge, montrent que les ions Fe B 2+ ,V B 3+ et Fe A 2+ sont oxydes successivement en ions Fe 3+ et V 5+ a des temperatures inferieures a 450 °C. Les spinelles lacunaires a valence mixte qui en resultent, ont un taux en lacunes croissant avec x, qui peut etre superieur a ceux determines jusqu'alors pour ce type d'oxydes.
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…
Temperature dependence of oxidation behavior and coercivity evolution in fine-grained spinel ferrites
Abstract The present paper reviews for a series of fine-grained MxCoyFe(3−x−y)O4 spinel ferrites (M=Mn, Mo, Cu, V) which oxidize into mixed-valence defect ferrites, a systematic study of the correlation between the oxidation temperature and the variation of coercivity. An increase of the coercivity is observed as often as the oxidation reactions Fe2+→Fe3+ and Mn+→M(n+m)+ (1⩽m⩽3) occur. This enhancement of coercivity has been explained by stresses generated during each specific oxidation reaction. The well-known property of cobalt to strongly magnify the magnetostrictive effects has been used to support this interpretation.
Mechanical activation conditions of the Fe2O3 and V2O3 mixture powders in order to obtain a nanometric vanadium spinel ferrite
Abstract Co-milling of iron and vanadium oxides allows to obtain an intimate oxides mixture at a nanoscale, similar to a coprecipitate elaborated by soft chemistry. Reduction of such a mixture in the same temperature and oxygen partial pressure conditions (500°C and 10−25 Pa) as the soft chemistry products leads to a nanometric vanadium ferrite with the only spinel phase. The characterization of the powders is achieved by X-ray diffraction (XRD), scanning electron microscopy, infrared (IR) spectrometry, thermogravimetry and calorimetry. Homogeneity of grain size and chemical composition is reached if the initial oxides have similar grain size.
"Reactivity of Cu3Si of different genesis towards copper(I) chloride"
Abstract A comparative study of the reactivity between copper(I) chloride and three types of Cu 3 Si obtained in a molten medium (Cu 3 Si-Ref) and from mechanical activation following an annealing process (Cu 3 Si-M2AP) or a self-propagating high-temperature synthesis (Cu 3 Si-MASHS) was performed by thermogravimetry under vacuum using non-isothermal and isothermal methods of kinetic measurement. It was established that for the three Cu 3 Si/CuCl systems, the acceleration and decay stages in the temperature range 145–215°C are very closely approximated by an equation of the Prout–Tompkins type where an autocatalytic process was proposed. The lower apparent activation energy obtained for the…
Effect of the preparation method and grinding time of some mixed valency ferrite spinels on their cationic distribution and thermal stability toward oxygen
Abstract The reactivity in oxygen of several mixed valency ferrite spinels, namely Fe3O4, FeCr2O4, Fe3 − xTixO4 and Fe3 − xMoxO4 was investigated by derivative thermogravimetry (DTG) analysis as a function of the conditions of preparation and grinding. For all these compounds, low temperature preparation or prolonged grinding time enables small particles ( 0.5 μm), it was observed that oxidation was starting at higher temperature and that the defect spinel phases could not be retained during oxidation. This behaviour was attributed to the presence of stresses induced by the lattice parameter gradient and promoting the formation of nuclei of the α-rhombohedral phase from the superficial γ-de…