CoFe2O4 nanocrystalline powders prepared by citrate-gel methods: Synthesis, structure and magnetic properties

Nanocrystalline CoFe₂O₄ powders were prepared by decomposition of metal ion citrate precursors. Four samples were synthesized from precursor solutions having different pH values in the range <1–7.0. The powders were characterized by X-ray Diffraction, Thermogravimetry, Differential Thermal Analysis, N₂ physisorption and Transmission Electron Microscopy. Magnetic properties were explored by a SQUID magnetometer. Three out of the four samples, coming from solutions of pH 2, 4 and 7, were produced by an autocombustion reaction and are very similar as regards average size of the nanoparticles (about 20 nm), their morphology and the magnetic properties, while the fourth sample was produced by a slower thermal decomposition and is composed of smaller nanoparticles (about 10 nm).     

X-Ray Diffraction Study Of Aqueous [Cr(H2O)6]Cl3

A [Cr(H₂O)₆]Cl₃ aqueous solution, 0.25 M at T=20°C, is investigated by X-ray diffraction. The calculated radial distribution function shows, in spite of the low Cr³⁺ concentration, a well resolved peak centred around 1.90 A, a distance coincident with the Cr³⁺-H₂O distance found in crystalline [Cr(H₂O)₆]Cl₃. It can reasonably be stated that the [Cr(H₂O)₆]³⁺ ions pass relatively undisturbed into solutions where they constitute quite stable units.     

An X-ray diffraction study of sodium borate glasses

X-ray diffraction measurements have been performed on two pairs of sodium borate glasses of differing compositions. Glasses of given composition were obtained with two different thermal histories. The radial distribution functions of samples of the same composition appear similar. The short range order is not affected by the range of quenching rates explored.     

Non-Stoichiometric CoFe2O4 Nanoparticles Supported on an Amorphous Silica Matrix

Non-Stoichiometric CoFe₂O₄ nanoparticles dispersed in an silica matrix with a silica content of 87 wt% and Co/Fe molar ratio of 1:1, were prepared by the sol-gel method using an ethanolic solution of tetraethoxysilane and either iron(III) and cobalt(II) nitrates or iron(II) and cobalt(II) acetates. The influence of different metal precursors on the xerogels were examined by X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and N₂ physisorption measurements at 77 K. Magnetic properties of the samples were investigated by field cooled FC and zero field cooled ZFC measurements.Depending on the metal precursor, different spinel oxides of a few nanometers were observed in the samples treated at 350°C. After heating at 900°C non-stoichiometric CoFe₂O₄ was formed in both samples, whose average particle size was only slightly larger than in samples treated at 350°C.     

Mechanochemical Route for the Synthesis of Cobalt Ferrite–Silica and Iron–Cobalt Alloy–Silica Nanocomposites

CoFe₂O₄–SiO₂ and Fe–Co alloy–SiO₂ nanocomposites were prepared by high energy ball milling of Si, -Fe₂O₃, Co₃O₄ and SiO₂ mixtures, followed by thermal treatment under appropriate oxidative/reductive conditions. XRD and TEM measurements carried out after 50 h of milling show highly dispersed unidentified reaction products. Further thermal treatment at 900°C in air leads to spherical CoFe₂O₄ nanocrystals (NCs) with a narrow size distribution centered around 2.5 nm, uniformly dispersed in the amorphous SiO₂ matrix. Reduction of this sample in a H₂ flow at 800°C produces a mixture of dispersed metallic cobalt and iron silicate with traces of Fe–Co alloy NCs. Reduction of the as-milled sample, on the contrary, leads almost completely to Fe–Co alloy NCs uniformly dispersed in the SiO₂ matrix and with an average particles size around 11.2 nm.     

Advances in the structure and microstructure determination of yttrium silicates using the Rietveld method

The Y₂O₃-SiO₂ 1:1 composition doped with a weak concentration of europium ions was prepared with the sol-gel technique and the products studied by X-ray diffraction as a function of temperature in the range from 900 to 1300 °C, using the method of Rietveld for quantitative evaluation of amorphous and crystalline evolving phases. The amorphous profile of the yttrium oxyorthosilicate glasses has been described following the “Rietveld for Disordered Materials” method and subsequently included in the patterns of semicrystalline samples that have been heat-treated for temperatures above 900 °C at 1000, 1100, 1150, 1200 and 1300 °C. The quantitative evaluation of the amorphous phase is obtainable from the Rietveld approach equivalent to the method after Ruland. This enabled us to study in fine detail the structural rearrangements and growth mechanisms that take place during the crystal-to-amorphous transformation in terms of coordination numbers, average interatomic distances, average crystallite size and microstrain and to identify the polymorphous transformation involving the Y₂SiO₅ phase from low-to-high-temperature forms, as well as some minor quantities of other phases namely α-Y₂Si₂O₇ phase, Y₂O₃ and Y_4.67(SiO₄)₃O.     

New Synthesis of Ferrite–Silica Nanocomposites by a Sol–Gel Auto-Combustion

A sol–gel autocombustion method was used to synthesize nanometric metal-oxide powders, and was extended for the first time to prepare ferrite–silica nanocomposites. The gels obtained by mixing suitable amounts of citric acid, metal nitrates, ammonia (pure phases) and tetraethylortosilicate (nanocomposites) were converted directly to ferrite (either γ-Fe₂O₃ or CoFe₂O₄) or ferrite–silica composites through a rapid autocombustion reaction. The combustion involves a thermally induced autocatalytic oxidation–reduction reaction between the nitrate and the citrate ions. The sample characterization by X-ray diffraction, transmission electron microscopy and N₂ physisorption measurements revealed nanosized pure phase powders and nanocomposites in which small spherical nanoparticles (mean size 3.5 and 5.0nm, respectively for the γ-Fe₂O₃and CoFe₂O₄) are homogeneously dispersed over a mesoporous silica matrix.     

Exafs study of Ni2+ coordination in concentrated aqueous solutions

EXAFS measurements are reported for NiCl₂ and Ni(N0₃)₂ aqueous solutions with molar concentrations of about 4, and for crystalline Ni(N0₃)₂·6H₂O. A comparative analysis of the Fourier filtered spectra confirms that the first coordination sphere essentially consists of water molecules. No evidence was found for outer-sphere Cl^? ions approaching closely the inner sphere in NiCI₂ solution.     

Spin-canting and magnetic anisotropy in ultrasmall CoFe2O4 nanoparticles

The magnetic properties of cobalt ferrite nanoparticles dispersed in a silica matrix in samples with different concentrations (5 and 10 wt% CoFe2O 4) and same particle size (3 nm) were studied by magnetization, DC and AC susceptibility, and Mossbauer spectroscopy measurements. The results indicate that the particles are very weakly interacting. The magnetic properties (saturation magnetization, anisotropy constant, and spin-canting) are discussed in relation to the cation distribution.