Effects of γ-radiation on the thermal stability of cobalt oxides

Pure cobaltic oxide, prepared by thermal decomposition of pure basic cobalt carbonate in air at 500°C, was subjected to different doses of γ-radiation varying between 5 and 50 M rad. The influence of γ-radiation on the thermal decomposition of cobaltic oxide to cobaltous oxide and the re-oxidation of CoO to Co₃O₄ was studied using DTA, with a controlled rate of heating and cooling. The effects of γ-radiation on the specific surface area (S_BET) and oxidation character of Co₃O₄ were also investigated.The DTA investigation revealed that γ-radiation effectively decreased the thermal stability of cobaltic oxide to an extent proportional to the dose employed. The maximum decrease in the thermal stability of 60% was attained by exposing Co₃O₄ solid to 30 M rad. γ-Irradiation, however, exerted no detectable effect on the re-oxidation of CoO by O₂ to Co₃O₄.The S_BET measurements showed that the small dose (5 M rad) of γ-radiation effected a decrease of 15% in the surface area of Co₃O₄, the higher doses (10–50 M rad) caused a further slight decrease of 18% in its surface area.γ-Irradiation was found to decrease the oxidation character of Co₃O₄ to an extent proportional to the dose employed.The decrease in the thermal stability of Co₃O₄ due to radiation is explained in terms of the decrease in the oxidation character of cobaltic oxide observed after subjecting the solid to γ-radiation.     

Thermal behaviour of cobalt oxides doped with ZrO2 and ThO2 and the possible cubic phase stabilization of zirconia

The effects of doping cobalt oxides with different amounts of ZrO₂ and ThO₂ (1.5–9 mol%) on the thermal stability of Co₃O₄ and the re-oxidation of CoO by O₂ to Co₃O₄ were investigated. The techniques employed were DTA, with a controlled rate of heating and cooling, X-ray diffraction, and IR spectrometry.The results obtained by DTA revealed that the addition of both Th⁴⁺ and Zr⁴⁺ (up to 6 mol%) exerted no appreciable effect on the thermal stability of Co₃O₄. Increasing the amount of the dopant ions to 9% resulted in no further change in the thermal stability of Co₃O₄ in the case of Th⁴⁺, and an increase of 16% in case of Zr⁴⁺-doping. However, ThO₂-doping of cobalt oxide was accompanied by an enhancement in the reactivity of CoO towards re-oxidation by O₂ to Co₃O₄ to an extent proportional to the amount of dopant oxide.The X-ray investigation of ZrO₂-doped cobalt oxides calcined in air at 1000°C revealed the presence of highly crystalline and stable zirconia in the cubic form. Such a stable phase could not be obtained at temperatures below 2370°C in the absence of stabilizing agents.X-ray and IR investigations of different solids showed the presence of free thoria and zirconia together with new thorium—cobalt and zirconium—cobalt compounds. However, the slow cooling of Zr-treated cobalt oxides from 1000°C to room temperature led to the decomposition of the newly formed compound. The d-spacings and absorption bands of the newly formed compounds were determined.     

Investigation of Solid-Solid Interactions between Pure and Li2O-Doped Magnesium and Ferric Oxides

The results obtained showed that the addition of small amounts of LiNO₃ to the reacting mixed solids, consisting of equimolar proportion of Fe₂O₃ and basic MgCO₃ much enhanced the thermal decomposition of magnesium carbonate. The addition of 12 mol% LiNO₃ (6 mol% Li₂O) decreased the decomposition temperature of MgCO₃ from 525.5 to362°C. MgO underwent solid–solid interaction with Fe2O3 at temperatures starting from800°C yielding MgFe₂O₄. The amount of ferrite produced increased by increasing the precalcination temperature of the mixed solids. However, the completion of this reaction required prolonged heating at elevated temperature above 1100°C. Doping with Li₂O much enhanced the solid–solid interaction between the mixed oxides leading to the formation of MgFe₂O₄ phase at temperatures starting from 700°C. The addition of 6 mol% Li₂O to the mixed solids followed by precalcination at 1050°C for 4 h resulted in complete conversion of the reacting oxides into magnesium ferrite. The heat treatment of pure and doped solids at 900–1050°C effected the disappearance of most of IR transmission bands of the free oxides with subsequent appearance of new bands characteristic for MgFe₂O₄ structure. The promotion effect of Li2O towards the ferrite formation was attributed to an effective increase in the mobility of the various reacting cations. The activation energy of formation (ΔE) of magnesium ferrite was determined for pure and variously doped solids and the values obtained were 203, 126, 95 and 61 kJ mol⁻¹ for pure mixed solids and those treated with 1.5, 3.0 and 6.0 mol% Li₂O, respectively. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis and Thermal Decomposition of Cobalt(II) bis (Tartrato) Cobaltate(II) Trihydrate

The paper describes the synthesis and characterization of cobalt(II) bis (tartrato) cobaltate(II) trihydrate Co[Co[C₄O₆H₄)₂]·3H₂O. The complex was characterized on the basis of elemental analysis, infrared, electronic, e.s.r. spectra and X-ray powder diffraction studies. The thermal decomposition of the complex led to a mixture of Co₂O₃and Co₃O₄in air at about 400°C, whereas in nitrogen it was decomposed to a mixture of CoO and C at about 384°C. A tentative reaction mechanism is suggested for the thermal decomposition of the complex in air and nitrogen. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal processes in the systems with Li-battery cathode materials and LiPF6 -based organic solutions

Thermodynamic instability of positive electrodes (cathodes) in Li-ion batteries in humid air and battery solutions results in capacity fading and batteries degradation, especially at elevated temperatures. In this work, we studied thermal interactions between cathode materials Li₂MnO₃, xLi₂MnO₃ ^.(1???x)Li(MnNiCo)O₂,LiNi_0.33Mn_0.33Co_0.33O₂, LiNi_0.4Mn_0.4Co_0.2O₂, LiNi_0.8Co_0.15Al_0.05O₂ LiMn_1.5Ni_0.5O₄, LiMn(or Fe)PO₄, and battery solutions containing ethylene carbonate (EC) or propylene carbonate (PC), dimethyl carbonate (DMC) or ethylmethyl carbonate (EMC) and LiPF₆ salt in the temperature range of 40–400 °C. It was found that these materials are stable chemically and well performing in LiPF₆-based solutions up to 60 °C. The thermal decomposition of the electrolyte solutions starts >180 °C. The macro-structural transformations of cathode materials upon exothermic reactions were studied by transmission electron microscopy (TEM), X-ray difraction (XRD) and Raman spectroscopy. Differential scanning calorimetry (DSC) studies have shown that the exothermic reactions in the temperature range of 60–140 °C lead to partial decomposition of both the cathode material and electrolyte solution. The systems thus formed consisted of partially decomposed solutions and partially chemically delithiated cathode materials covered by reactions products. Thermal reactions terminate and this system reaches equilibrium at about 120 °C. It remains stable up to the beginning of the solution decomposition at about 180 °C. The increased content of surface Li₂CO₃ is found to significantly affect the thermal processes at high temperature range due to extensive exothermic decomposition at low temperatures.     

Synthesis,structural characterization and thermal analysis of the cobalt(II) oxalate obtained through the reaction of 1,2-ethanediol with Co(NO<Subscript>3</Subscript>)<Subscript>2</Subscript> · 6H<Subscript>2</Subscript>O

The homopolynuclear coordination compound [CoL · 2.5H₂O]_n with L=C₂O₄ ²⁻ was synthesized by a new unconventional method. It consist in the redox reaction between 1,2-ethanediol and cobalt nitrate in presence of nitric acid. The coordination compound was characterized by chemical analysis, electronic and vibrational spectra respectively, thermal analysis. In the coordination compound the Co(II) ion exists in a high spin octahedral configuration and oxalate anion acts as double-bridge ligand, tetradentate, similar as in CoC₂O₄ · 2H₂O obtained by the classical method. Nonstoichiometric oxide, Co₃O_4+0.25 with deficit in cobalt and normal spinel Co₃O₄ where identified as thermal decomposition intermediates. As final product of decomposition, the oxide CoO was obtained.     

Thermogravimetric studies on catalytic effect of metal oxide nanoparticles on asphaltene pyrolysis under inert conditions

This study investigated the catalytic effect of NiO, Co₃O₄ and Fe₃O₄ nanoparticles toward asphaltene thermal decomposition (pyrolysis) under inert conditions. Asphaltene adsorbed onto the selected nanoparticles were subjected to thermal decomposition up to 800?°C in a thermogravimetric analyzer. The presence of nanoparticles caused a significant decrease in the asphaltene decomposition temperature and activation energy. Activation energies for the process were calculated using the Ozawa?CFlynn?CWall method. All the selected metal oxide nanoparticles showed high catalytic activity toward asphaltene decomposition in the following order NiO?>?Co₃O₄?>?Fe₃O₄. This study confirms that metal oxide nanoparticles can significantly enhance the thermal decomposition of heavy hydrocarbons, like asphaltenes.     

Thermal behaviour of cobaltic and cobaltous oxides as influenced by doping with some alkali metal oxides

The role of Na₂O- and Li₂O-doping on the thermal decomposition of Co₃O₄ to CoO and the re-oxidation of cobaltous to cobaltic oxide has been investigated using DTA, with controlled rates of heating and cooling, IR and X-ray diffraction spectrometry techniques.

The DTA investigation revealed that both Li₂O and Na₂O increased the thermal stability of Co₃O₄. However, the effect was much more pronounced in the case of lithium oxide. Doping Co₃O₄ with 1.5 mole% Li₂O was found to prevent any thermal decomposition of cobaltic oxide even by heating at 1100°C. The maximum thermal stabilization effect induced by doping with sodium oxide (4.5 mole%) was 30%. The sodium oxide- and lithium oxide-doping enhanced the reactivity of the produced CoO towards the re-oxidation by O₂ yielding Co₃O₄.

The X-ray diffraction and IR spectrometric investigations showed that part of Li₂O and Na₂O was effectively incorporated in the Co₃O₄ lattice, affecting the thermal stabilization of the solid, and another part of the dopant oxide interacted with the produced CoO and also with Co₃O₄ giving a new sodium cobalt compound, and with Co₃O₄ producing, also, a new lithium cobalt oxide phase. However, the amount of Li₂O dissolved in the Co₃O₄ lattice was greater than that of Na₂O. The sudden cooling of doped solids, from 1000°C to room temperature, favoured the formation of the new sodium cobalt oxide compound, and exerted no effect on the production of the new lithium cobalt oxide phase. The characteristic d spacings and IR absorption bands of these new compounds have been determined.

The possible mechanisms of dissolution of Li₂O and Na₂O in cobaltic oxide lattice are discussed.     

CO oxidation with oxygen of the catalyst and gas-phase oxygen over (0.5−15)%СоО/СеО<Subscript>2</Subscript>

The CO adsorption species on Co₃O₄ and (0.5-15%)CoO/CeO₂ catalysts have been investigated by temperature-programmed desorption and IR spectroscopy. At 20°C, the largest amount of CO is adsorbed on the 5%CoO/CeO₂ sample to form, on Co_m²⁺O_n²⁺ clusters, hydrogen-containing, bidentate, and monodentate carbonate complexes, whose decomposition is accompanied by CO₂ desorption at 300 and 450°C (1.1 × 10²⁰ g^–1). The formation of the carbonates is accompanied by the formation of Co⁺ cations and Co⁰, on which carbonyls form. The latter decompose at 20, 90, and 170°C to release CO (2.7 × 10¹⁹ g^–1). Part of the carbonyls oxidizes to CO₂ upon oxygen adsorption, and the CO₂ undergoes desorption at 20°C. Adsorbed oxygen decreases the decomposition temperature of the H-containing and bidentate carbonates from 300 to 100-170°C and maintains the sample in the oxidized state, which is active in subsequent CO adsorption and oxidation. CO oxidation by oxygen of the catalyst diminishes the activity of the sample in these processes and increases the decomposition temperature of the carbonate complexes. Taking into account the properties of the adsorption complexes, we concluded that the H-containing and bidentate carbonates are involved in CO oxidation by oxygen of the catalyst at ~170°C under isothermal conditions. The rate limiting step is the decomposition of the carbonates, a process whose activation energy is 65-74 kJ/mol.     

An investigation on the solid state pyrolytic decomposition of bimetallic oxalate precursors of Ca,Sr and Ba with cobalt: A mechanistic approach

The mixed metal oxalate precursors, calcium(II)bis(oxalato)cobaltate(II)hydrate (COC), strontium(II)bis(oxalato)cobaltate(II)pentahydrate (SOC) and barium(II)bis(oxalato)cobaltate(II)octahydrate (BOC) have been synthesized and their thermal stability was investigated. The complexes were characterized by elemental analysis, IR spectral and X-ray powder diffraction studies. Thermal decomposition studies (TG, DTG and DTA) in air showed that the compound COC decomposed mainly to CaC₂O₄ and Co₃O₄ at 340 °C, and a mixture of CaCO₃ and Co₃O₄ identified at 510 °C. A mixture of CaCO₃ and Ca₃Co₂O₆ along with the oxides and carbides of both the cobalt and calcium were attributed at 1000 °C as end products. DSC study in nitrogen ascertained the formation of a mixture of CaO and CoO along with a trace of carbon at 550 °C. The mixture species, SrC₂O₄, CoC₂O₄ and Co₃O₄ were generated at 255 °C in case of SOC in air, which ultimately changed to CoSrO₃, SrCO₃ and oxides of strontium and cobalt at 1000 °C. The several mixture species also generated as intermediate at 332 and 532 °C. The DSC study in nitrogen indicated the formation of CoSrO_x (0.5 < x < 1) as end product. In case of BOC in air, a mixture of BaCoO₂, BaO, CoO and carbides are identified as end product at 1000 °C through the generation of several intermediate species at 350 and 530 °C. A mixture of BaO and CoO is identified as end product in DSC study in nitrogen. The kinetic parameters have been evaluated for all the dehydration and decomposition steps of all the three compounds using four non-mechanistic equations. Using seven mechanistic equations, the kind of dominance of kinetic control mechanism of the dehydration and decomposition steps are also inferred. The kinetic parameters, ΔH and ΔS of all the steps are explored from the DSC studies. Some of the decomposition products are identified by IR and X-ray powder diffraction studies.     

Neue Oxoterbate(IV) mit Lithium Rb2Li14[Tb3O14] und Li6Tb2O7

New Oxoterbates(IV) with Lithium: On Rb₂Li₁₄[Tb₃O₁₄] and Li₆Tb₂O₇ For the first time we prepared Rb₂Li₁₄[Tb₃O₁₄] as yellow single crystals from Li₈TbO₆ and Rb₂O (Tb:Rb = 1:2) [Ag-cylinder, 500°C, 30 d, then Au-tube, 700°C, 27 d]. The structure refinement [652 I₀ (h kl), four circle diffractometer Philips PW 1100, ω-scan, MoKα, R = 4.69%, R_w = 3.24%, absorption considered, Immm with a = 1 283.07(10), b = 790.87(7), c = 736.87(7)pm, Z = 2, d_x = 4.30 g · cm^?3] confirms that it is isotypic with K₂Li₁₄[Pb₃O₁₄]. Furthermore we got for the first time Li₆Tb₂O₇ as a bright yellow compound from Li₂O₂ and “Tb₄O₇*” [(Li:Tb = 3.4:1), Au-ube, 750°C, 13 d (powder), 850°C 22 d (single crystals)] and by thermal decomposition of Rb₂Li₁₄[Tb₃O₁₄] (Au-tube, 850°C, 25 d). Powder and single crystal data [1 327 I₀ (h kl), four circle diffractometer PW 1100, ω-scan, AgKα, R = 9.38%, R_w = 5.23%, absorption not considered, P2₁/a, a = 1 056.30(10), b = 613.50(4), c = 546.56(5) pm, β = 109.668(7)°, Z = 2, d_x = 4.67 g · cm^?3 d_pyc = 4.53 g · cm^?3] reveal a new type of structure that may be deduced by the NaCl-type of structure. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.     

Carboxylate clusters with the M<Subscript>4</Subscript>O<Subscript>4</Subscript> cubane-like core: pivalate cocrystal containing Co<Superscript>II</Superscript> and Ni<Superscript>II</Superscript>

Joint thermolysis of the dinuclear pivalate complexes M₂(μ-H₂O)(μ-Piv)₂(Piv)₂(HPiv)₄ (M = Co (1) and Ni (2), Piv^- is the pivalate anion), in decane at 174 °C at the reactant ratio 1: 1 followed by treatment of the dry thermolysis product with methanol afforded crystals of a new cocrystallization product of the molecules containing the heterometallic cubane-like core M₄(Co,Ni)O₄. According to the X-ray diffraction data and the results of magnetic measurements, inductively coupled plasma atomic emission spectrometry (ICP-AES), and investigations of the solid-state thermal decomposition products, the isolated cocrystallization product has the general formula [Co_1.6Ni_2.4(μ₃-OMe)₄(μ₂-Piv)₂(pg² -Piv)₂(MeOH)₄] ·4MeOH (3·4MeOH). Thermolysis of the crystals of the solvate 3·4MeOH is a destructive process accompanied by the intramolecular redox reaction. A mixture of metallic Ni and cobalt oxide (CoO) are the final solid decomposition products of 3 · 4MeOH in an argon atmosphere, whereas a mixture of the phases NiO, Co₃O₄, and NiCo₂O₄ is formed in air.     

Oxidation of magnesium in the systems NaClO4-Mg-Metal oxide (peroxide)

Oxidation of magnesium in mixtures NaClO₄ + Mg + metal oxide or peroxide has been investigated using differential thermal analysis (DTA). In the systems with peroxides Na₂O₂, Li₂O₂, BaO₂, CaO₂ or ZnO, magnesium oxidizes simultaneously with decomposition of NaClO₄ in the region 380–520°C, which is 100–200°C below the oxidation temperature of magnesium in air. In the ternary systems with transition-metal oxides NiO, CuO, FeO, and Fe₂O₃, magnesium transforms into oxide at above 600°C after sodium perchlorate had been decomposed completely. The low-temperature oxidation of magnesium occurs in the systems in which sodium chlorate is accumulated during the catalytic decomposition of NaClO₄.     

Thermische Analyse eines chloridhaltigen basischen Cobaltcarbonates

The thermal decomposition of a chloride and water-containing basic cobalt carbonate was studied. As a first step, crystal water is lost without change of structure. The following decomposition steps overlap and proceed in different ways, depending on the atmosphere over the sample: under nitrogen, chloride volatilizes as HCl and CoCl₂; in air, oxidation occurs. CoO and Co₃O₄, respectively, are the final solid products at 700–800°.     

Kinetics of thermal decomposition of Co3O4 powder and single crystals

Kinetics of thermal decomposition in vacuum of Co₃O₄ powder as well as single crystals has been investigated. Discrepancies with the results of previous authors have been discussed. Decomposition of Co₃O₄ proceeds through formation of a compact layer of CoO and hence diffusion is the rate-limiting factor. The experimental curves α(t) be described for 0.05 < α < 0.85 using a modified Ginstling-Brounshtein equation: 1 ? 2α/3 ? (1 ? α)^2/3 = ktⁿ where the activation energy varies with the degree of decomposition.     

Studies on the thermal decomposition of the silver group of alkali metal nitritocobaltates(III)

The thermal decomposition of nitritocobaltate(III) of the silver group of general formula M₂Ag[Co(NO₂)₆] (where M = K⁺, NH⁺₄, Rb⁺ or Cs⁺) has been investigated. Based on the thermal curves of the investigated compounds and chemical and diffractometric analysis, the mechanism of thermal decomposition has been determined. The results obtained indicate that the decomposition proceeds in three stages. As a result of decomposition in the first stage (300°C), nitrates of alkali metals, metallic silver and Co₃O₄ are formed. In the second stage (500°C), a partial decomposition of nitrates to alkali metal oxides occurs, and in the third stage the products are alkali metal oxides, silver and Co₃O₄. This paper also presents the dependence of the decomposition temperature of nitritocobaltates(III) of the silver group on the ionic radius of the outer-sphere cation.     

Thermal decomposition of nickel aluminium mixed hydroxides and formation of nickel aluminate spinel

Various nickel aluminium mixed hydroxide samples of different compositions were prepared by co-precipitation from their nitrate solutions using dilute NH₄OH. Additional samples were prepared by impregnation of hydrated Al₂O₃, preheated at 600 and 900°C, with nickel nitrate solution in an equimolar ratio. The thermal decomposition of different mixed solids was studied using DTA. The X-ray investigation of thermal products of the mixed solids was also studied.The results obtained revealed that the presence of NiO up to 33.3 mole % with aluminium oxide much enhanced the degree of crystallinity of the γ-Al₂O₃ phase. In contrast, the presence of Al₂O₃ much retarded the crystallization process of the NiO phase. With the exception of samples containing 20 mole% NiO, all the mixed hydroxide samples, when heated in air at 900°C, led to the formation of well-crystalline Ni Al₂O₄ spinel, alone, or together with either NiO or γ-Al₂O₃, depending on the composition of the mixed oxide samples. The solid containing 20% NiO and heated at 900°C was constituted of amorphous NiO dispersed in γ-Al₂O₃. Heating the nickel nitrate-impregnated Al₂O₃ in air at 800–1000°C led to the formation of Ni Al₂O₄ together with non-reacted NiO and γ-Al₂O₃. The degree of crystallinity of the spinel was found to increase by increasing the calcination temperature of the impregnated solids from 800 to 1000°C and by increasing the preheating temperature of the hydrated Al₂O₃ employed from 600 to 900°C.     

Thermal Characterization and Physico-Chemical Properties of Fe2O3−Mn2O3/Al2O3 Systems

The effect of ferric and manganese oxides dopants on thermal and physicochemical properties of Mn-oxide/Al₂O₃ and Fe₂O₃/Al₂O₃ systems has been studied separately. The pure and doped mixed solids were thermally treated at 400–1000°C. Pyrolysis of pure and doped mixed solids was investigated via thermal analysis (TG-DTG) techniques. The thermal products were characterized using XRD-analysis. The results revealed that pure ferric nitrate decomposes into Fe₂O₃ at 350°C and shows thermal stability up to1000°C. Crystalline Fe₃O₄ and Mn₃O₄phases were detected for some doped solids precalcined at 1000°C. Crystalline γ-Al₂O₃ phase was detected for all solids preheated up to 800°C. Ferric and manganese oxides enhanced the formation of α-Al₂O₃ phase at1000°C. Crystalline MnAl₂O₄ and MnFe₂O₄ phases were formed at 1000°C as a result of solid–solid interaction processes. The catalytic behavior of the thermal products was tested using the decomposition of H₂O₂ reaction. This revised version was published online in August 2006 with corrections to the Cover Date.     

ZnO/Co3O4 Porous Nanocomposites Derived from MOFs: Room‐Temperature Ferromagnetism and High Catalytic Oxidation of CO

ZnO/Co₃O₄ porous nanocomposites were successfully fabricated by the thermal decomposition of Prussian Blue analogue (PBA) Zn₃[Co(CN)₆]₂ nanospheres obtained at room temperature. Interestingly, ZnO/Co₃O₄ porous nanocomposites exhibit room‐temperature ferromagnetism. Moreover, the ZnO/Co₃O₄ porous nanocomposites show good catalytic activity for CO oxidation, and the CO conversion rate reaches 100 % at 250 °C. It is suggested that the synergistic effect of each component, relative high surface area (32 m² g^?1) and porous structure lead to the promising catalytic properties.     

Studies regarding the formation from metal nitrates and diol of NiM 2 III O4 spinels, inside a silica matrix

The present study deals with preparation and characterization of spinel mixed oxide systems NiM ₂ ^III O₄, where M^III?=?Fe^III, Cr^III. In order to obtain 50% NiFe₂O₄/50% SiO₂ and 50% NiCr₂O₄/50% SiO₂ nanocomposite, we have used a versatile route based on the thermal decomposition inside the SiO₂ matrix, of some particular precursors, coordination compounds of the involved M^II and M^III cations with dicarboxylate ligands. The ligands form in the redox reaction between metal nitrates mixture and 1,3-propanediol at the heating around 140?°C of the gels (tetraethylorthosilicate?Cmetal nitrates?C1,3-propanediol?Cwater). The as-obtained precursors, embedded in silica gels, have been characterized by FT-IR spectrometry and thermal analysis. Both precursors thermally decompose up to 350?°C leading to the formation of the corresponding metal oxides inside the silica matrix. X-ray diffraction of the annealed powders have evidenced the formation of NiFe₂O₄ starting with 600?°C, and NiCr₂O₄ starting with 400?°C. This behavior can be explained by the fact that, by thermal decomposition of the Fe(III) carboxylate at 300?°C, the spinelic phase ??-Fe₂O₃ is formed, which interacts with the NiO, forming the ferrite nuclei. By thermal decomposition of chromium carboxylate, a nonstoichiometric chromium oxide (Cr₂O_3+x ) is formed. In the range 380?C400?°C, Cr₂O_3+x turns into Cr₂O₃ which immediately interacts with NiO leading to the formation of nickel chromites nuclei inside the pores of silica matrix. Both spinels have been obtained as nanocrystalites homogenously dispersed as resulted from XRD and TEM data.