Structural,electrical and magnetic properties of Zr–Mg cobalt ferrite

Spinel cobalt ferrite, CoFe_2−xM_xO₄ has been synthesized by substitution of the combination of metallic elements M=Zr–Mg by the microemulsion method using polyethylene glycol as a surfactant. Powder X-ray diffraction analysis reveals that the substitution results in shrinkage of the unit cell of cobalt ferrite due to higher binding energy of the synthesized samples. The energy-dispersive X-ray fluorescence analysis confirms the stoichiometric ratios of the elements present. The thermogravimetric analysis shows that the minimum temperature required for the synthesis of these substituted compounds is 700 °C. A two-point probe method was employed for the measurement of the electrical resistivity in a temperature range of 293±5 to 673±5 K. It appears that there is a decrease in the number of Fe²⁺/Fe³⁺ pairs at the octahedral sites due to the substitution and corresponding migration of some of the Fe³⁺ ions to tetrahedral sites, consequently increasing the resistivity and the activation energy of hopping of electron at the octahedral sites. The susceptibility data also suggest migration of Fe³⁺ to tetrahedral site in the initial stage, which results in an increase in A–B interactions leading to large increase in the blocking temperature (T_B) as observed in samples having dopant content x=0.1.     

56,57,60CoFe NMR/ON,hyperfine anomalies and γ-factors of cobalt isotopes

The results of NMR/ON measurements on^56'57'60Co isotopes in iron are presented. To avoid the uncertainties caused by local demagnetizing field inhomogenities the measurements on two cobalt isotopes in one sample have been carried out. The values of nuclear-factor ratios ⁵⁷/ ⁶⁰ = 1.805 (20), ⁶⁰/ ⁵⁶ = 0.761 (20), ⁵⁶/ ⁵⁷ = 0.726 (20) and hyperfine anomalies⁵⁶⁶⁰ = -0.036 (10),^{60 57} = 0.017 (10) and⁵⁷⁵⁶ = 0.018 (10) have been calculated from the experimental results.     

Structure and magnetism in compressed iron–cobalt alloys

Combined Co K-edge XANES-XMCD and XRD measurements were used to shed light on the magnetic and structural phase diagram of the Fe_1?x Co _x alloy under HP in the Co-rich region (x≥0.5). At 0.5≤x≤0.75, the alloy shows a pressure-induced structural/magnetic phase transition from bcc-FM to hcp-non-FM phase just like pure iron but at higher pressures. The x=0.9 sample has an fcc structure in the pressure range investigated but presents an FM to non-FM transition at P=64 GPa, a significantly lower pressure compared with pure Co (predicted ≈120 GPa), showing that Fe impurities strongly affect the HP Co response.     

Fe57 Mössbauer study in cobalt substituted magnetite

The Mössbauer effect has been studied in the mixed ferrites Co _x Fe_3–x O₄ (forx=0.8, 0.9 and 1) with the spinel structure in the temperature range between 78 and 380 K. The composition withx=1, showed an expected Zeeman spectrum with two overlapping magnetic hyperfine patterns related to the Fe³⁺ ions in tetrahedral and octahedral sites. While for samples withx=0.8 and 0.9 the Mössbauer spectrum for each compound was successfully analysed into three different patterns corresponding to the ferric ions placed at the tetrahedral and octahedral sites and ferrous ions at the octahedral sites, indicating no electron transfer between Fe³⁺ and Fe²⁺, where the quantity of cobalt is sufficiently large to be located at the six nearest neighbours to ferrous ions. The Mössbauer effect parameters were calculated for these observed sites and their variation with temperature reported. The reduced hyperfine magnetic fields of the Fe³⁺ (B) ions were found to follow the Brillouin curve forS=5/2 and one third power law. The magnetic ordering temperature was determined to be 815 K and the possible magnetic interactions were discussed.     

Ion-Exchange selectivity coefficients in the exchange of calcium,strontium, cobalt,nickel, zinc,and cadmium ions with hydrogen ion in variously cross-linked polystyrene sulfonate cation exchangers at 25°C

The ion-exchange selectivity parameters for the exchange of trace calcium, strontium, cobalt, nickel, zinc, and cadmium ions with hydrogen ion in cross-linked polystyrene-sulfonic acid cation exchangers have been determined from equilibrium ionic distribution measurements at 25°C in dilute solutions of perchloric acid and polystyrene-sulfonic acid. The selectivity behavior in perchloric acid solutions shows that the divalent ion is always preferred by the resin phase. The selectivity coefficients are a smooth function of resin phase concentration, increasing with concentration for Sr²⁺ more than for Ca²⁺ and Cd²⁺ and being practically independent of resin phase concentration for Co²⁺, Ni²⁺, and Zn²⁺. The selectivity coefficients measured in salt-free solutions of polystyrene-sulfonic acid show a marked dependence on the polyelectrolyte concentration, the divalent ion being preferred by the aqueous phase. This preference diminishes with the concentration of polyelectrolyte. These results are interpreted by resort to the Gibbs-Duhem equation. This thermodynamic analysis has been facilitated by the availability of osmotic coefficient data for the pure polyelectrolyte ion forms over a large concentration range. Ion-exchange selectivity predictions by using this approach accurately reflect the observed ion-exchange selectivity behavior.     

Grain boundary wetting phase transitions in peritectic copper—cobalt alloys

The transition from incomplete to complete grain boundary wetting in copper alloys with 2.2 and 4.9 wt % Co has been studied. These alloys with peritectic phase diagrams differ from previously studied systems with eutectic transformation by the fact that the melt layer separating grains from each other is not enriched, but is depleted by the second component (cobalt in this case). The fraction of completely wetted grain boundaries increases with temperature, as in eutectic systems, from zero at a temperature of 1098°C to ~80% at 1096°C. For symmetric twin boundaries, the temperature dependence of the contact angle with melt drops is constructed. As in the eutectic systems, the contact angle decreases with increasing temperature (although not to zero due to the extremely low energy of symmetric twin boundaries).     

Inverse magnetocaloric effect in sol–gel derived nanosized cobalt ferrite

The magnetocaloric properties of cobalt ferrite nanoparticles were investigated to evaluate the potential of these materials as magnetic refrigerants. Nanosized cobalt ferrites were synthesized by the method of sol–gel combustion. The nanoparticles were found to be spherical with an average crystallite size of 14 nm. The magnetic entropy change (ΔS _m) calculated indirectly from magnetization isotherms in the temperature region 170–320 K was found to be negative, signifying an inverse magnetocaloric effect in the nanoparticles. The magnitudes of the ΔS _m values were found to be larger when compared to the reported values in the literature for the corresponding ferrite materials in the nanoregime.     

Mössbauer and magnetic study of silicon substituted cobalt ferrite

Silicon substituted cobalt ferrites have been investigated for improved performance as stress sensing materials. A series of samples with the formulae CoSi _x Fe_2???x O₄ were prepared using conventional powder ceramic technique. X-ray diffraction patterns were taken to examine spinel crystal structures and energy dispersive spectrometry was done to confirm Si segregations at the grain boundaries. Magnetic and magneto-strictive measurements were carried out to evaluate the material performance. Mössbauer spectra were taken on selective samples to understand the cationic distribution responsible for the modification of properties. The variations are explained on the basis of the strength of the exchange interactions between cations, and anisotropy contributions of cobalt ions. The results demonstrate the possibility of controlling magnetic and magneto-mechanical properties such as Curie temperature and strain derivative through Co and Si substitutions.     

Structural analysis of cobalt titanate nanoparticles obtained by sol–gel process

In this work we report the synthesis of nanocomposites based on nanoparticles of cobalt titanate and titanium dioxide in their anatase crystalline phase by a sol–gel process. The synthesized nanoparticles of titanate vary from 1 to 6 nm in size. They are embedded in the anatase matrix, and they were obtained from TiO₂ monoliths doped with Co²⁺. The formation of cobalt titanate nanoparticles showed a linear dependence on the cobalt concentration. The cobalt titanate nanocrystals are very stable even at temperatures higher than 1000 °C. The crystalline structures of the samples were examined using high-resolution transmission electron microscopy and X-ray diffraction. Molecular simulation methods were utilized for a better understanding and for improving the analytical data interpretation of the experimental results. PACS 61.16.Bg; 79.60.Jv; 61.46.+w; 61.50.Ah     

Heterodiffusion rapide du cobalt dans le plutonium δ cubique a faces centrees

The serial sectioning method, used to study solute diffusion of ⁶⁰Co in f.c.c. δ plutonium, gives the following results:

$\text{D = 1,2.10}{}^{\mathrm{?2}}\text{exp(}\text{?12700}\text{RT}\text{)}\text{cm}{}^2\text{s}$

in the temperature range 344–426°C.Cobalt is a very fast solute in δ plutonium. It diffuses most likely by a dissociative interstitial mechanism in a matrix where self diffusion takes place by a vacancy mechanism.     

Nickel–cobalt oxide/activated carbon composite electrodes for electrochemical capacitors

Nanostructured synthesis of nickel–cobalt oxide/activated carbon composite by adapting a co-precipitation protocol was revealed by transmission electron microscopy. X-ray diffraction analysis confirmed that nickel–cobalt oxide spinel phase was maintained in the pure and composite phases. Cyclic voltammetry, galvanostatic charge–discharge tests and ac impedance spectroscopy were employed to elucidate the electrochemical properties of the composite electrodes in 1.0 M KCl. The specific capacitance which was the sum of double-layer capacitance of the activated carbon and pseudocapacitance of the metal oxide increased with the composition of nickel–cobalt oxide before showing a decrement for heavily-loaded electrodes. Utilisation of nickel–cobalt oxide component in the composite with 50 wt. % loading displayed a capacitance value of ～59 F g^?1. The prepared composite electrodes exhibited good electrochemical stability.     

Kinetics of copper,nickel, cobalt and iron sulfidation by a modified “pellet” method. The effect of reaction at the metal/scale interface

This paper presents the results of studies on sulfidation of copper at temperature 600–700 K, nickel at 870–890 K, cobalt at 1060–1140 K and iron at 970–1170 K in sulfur vapor at 101 kPa with the use of a modified Wagner's pellet method. It has been stated that in the case of copper and nickel the initial heating of metal samples with a corresponding sulfide greatly influences the formation of hexagonal Cu₂S or Ni_{3 ± y}S₂ which are the thermodynamically stable phases under the reaction conditions. If these sulfides are lacking the scale morphology, the sulfidation rates are different. In the case of cobalt and iron the process of sulfure dissolution does not affect the sulfidation rate. The modified pellet method permits the measurement of the sulfidation kinetics of these metals which has not been possible with the use of the classical one.     

Structural and Mössbauer investigation on barium titanate–cobalt ferrite composites

Perovskite and spinels oxides have received renewed attention due to the possibility of combining both structures in di-phase composites to obtain multifunctional materials. In this work, barium titanate (perovskite)-cobalt ferrite (spinel) composite powders with different microstructures were obtained from thermal treatment of amorphous precursors at 500–1100 °C. The precursors were prepared by combining coprecipitation and sol–gel routes. Lyophilization of ferrite prior to mixing was used as a strategy to control interphase reaction. Mössbauer spectroscopy showed that the dispersion of coprecipitated ferrite in a viscous BaTiO₃ precursor gel resulted in superparamagnetic behavior and reduction of the local magnetic field of site [B].     

Synthesis of monolayers and bilayers of cobalt oxyhydrates (Na,K) x (H2O) y CoO2− δ

Potassium sodium cobalt oxyhydrates (Na,K)_x(H₂O)_yCoO_{2? δ} were synthesized from γ-Na_0.7CoO₂ by using aqueous KMnO₄ solution in a one-pot process. Chemical and structural analyses revealed that a partial or even almost complete replacement of K⁺ for Na⁺ in the alkaline layers occurs. Direct formation of the c ≈ 13.9 Å phase is apparently associated with the larger size of K⁺ (～1.4 Å) as compared to Na⁺ (～1.0 Å). Formation of (Na,K) _x (H₂O) _y CoO_{2? δ} not only involves de-intercalation, oxidation and hydration processes, but also an ion exchange reaction. Based on a systematic study, the phase formation of (Na,K) _x (H₂O) _y CoO_{2? δ} with c ≈ 19.6 Å is a slow process, particularly when using aqueous KMnO₄ solution with low molar ratio of KMnO₄/Na. When comparing the Co K-edge X-ray absorption spectra of (Na,K) _x (H₂O) _y CoO_{2? δ} with those of Na _x (H₂O) _y CoO₂ obtained from Br₂/CH₃CN solution, the edge energy of the main peak of the bilayered hydrate is found to be 3.5 eV higher than that of the monolayered hydrate for (Na,K) _x (H₂O) _y CoO_{2? δ}. In contrast, the edge energy of the main peak of the bilayered hydrate is 0.4 eV lower than that of the monolayered hydrate for Na _x (H₂O) _y CoO₂. In addition, the hydration behavior of monolayered of (Na,K) _x (H₂O) _y CoO_{2? δ} is different from that of Na _x (H₂O) _y CoO₂. These results seem to suggest that they are two different systems.     

Lattice dynamics and electronic structure of cobalt–titanium spinel Co2TiO4

Physics of the Solid State - The results are presented on phonon excitations and the electronic structure of Co2TiO4 inverse spinel in which magnetically ordered cobalt ions Co2+ (3d 7) are in...     

Chromium and cobalt diffusion in a ZnSe1 ? x S x solid solution

ZnSe_{1 ? x} S _x (1 ?? x ?? 0) crystals are grown from the vapor of binary components in a closed horizontal system. The ZnSe_{1 ? x} S _x crystals doped with chromium and cobalt are prepared by post-growth diffusion. Their absorption spectra are studied depending on the composition of the solid solution and the doping level. The diffusion coefficients of chromium and cobalt at the temperature 1040°C and their dependence on composition are determined.     

Temperature and composition dependence of magnetic properties of cobalt–chromium co-substituted magnesium ferrite nanomaterials

The temperature and composition dependence of magnetic properties of Co–Cr co-substituted magnesium ferrite, Mg_1−xCo_xCr_xFe_2−xO₄ (x=0.0–0.5), prepared by novel polyethylene glycol assisted microemulsion method, are studied. The synthesized materials are characterized by the Mössbauer spectrometer and standard magnetic measurements. Major hysteresis loops are measured up to the magnetic field of 50 kOe at 300, 200 and 100 K. The high field regimes of these loops are modeled using the Law of Approach to saturation to determine the first-order cubic anisotropy coefficient and saturation magnetization. Both the saturation magnetization and the anisotropy coefficient are observed to increase with the decrease in temperature for all Co–Cr co-substitution levels. Also, both the saturation magnetization and the anisotropy coefficient achieved maximum value at x=0.3 and x=0.2, respectively. Explanation of the observed behavior is proposed in terms of the site occupancy of the co-substituent, Co²⁺ and Cr³⁺ in the cubic spinel lattice.     

Structural studies on the yttrium-doped cobalt ferrite powders synthesized by sol–gel combustion method

Y_0.2CoFe_1.8O₄ nanopowders were prepared using a sol–gel combustion method. Metal nitrates, such as yttrium nitrate, cobalt nitrate and ferric nitrate, were used as the source materials. Citric acid and polyvinyl alcohol were used as the burning agent and agglomeration reducing agent, respectively. The pH of the precursor was maintained at 7. The mean crystallite size of the prepared ferrite was in the range of ∼20–70 nm. The inverse spinel structure, cubic morphology, and the identification of functional groups of the yttrium-doped cobalt ferrite were analyzed systematically using several analytical tools.