Studies on Structural, Magnetic and Thermal Properties of xFe2TiO4-(1−x)Fe3O4 (0≤x≤1) Pseudo-binary System

The xFe₂TiO₄-(1−x)Fe₃O₄ pseudo-binary systems (0≤x≤1) of ulvöspinel component were synthesized by solid-state reaction between ulvöspinel Fe₂TiO₄ precursors and commercial Fe₃O₄ powders in stochiometric proportions. Crystalline structures were determined by X-ray powder diffraction (XRD) and it was found that the as-obtained titanomagnetites maintain an inverse spinel structure. The lattice parameter a of synthesized titanomagnetite increases linearly with the increase in the ulvöspinel component. ⁵⁷Fe room temperature Mössbauer spectra were employed to evaluate the magnetic properties and cation distribution. The hyperfine magnetic field is observed to decrease with increasing Fe₂TiO₄ component. The fraction of Fe²⁺ in both tetrahedral and octahedral sites increases with the increase in Ti⁴⁺ content, due to the substitution and reduction of Fe³⁺ by Ti⁴⁺ that maintains the charge balance in the spinel structure. For x in the range of 0 ≤x≤0.4, the solid solution is ferrimagnetic at room temperature. However, it shows weak ferrimagnetic and paramagnetic behavior for x in the range of 0.4<x≤0.7. When x>0.70, it only shows paramagnetic behavior, with the appearance of quadrupole doublets in the Mössbauer spectra. Simultaneous differential scanning calorimetry and thermogravimetric analysis (DSC-TGA) studies showed that magnetite is not stable, and thermal decomposition of magnetite occurs with weight losses accompanying with exothermic processes under heat treatment in inert atmosphere.     

Lattice vibrations of MgAl2O4 spinel

Raman spectra have been measured on oriented single crystals of MgAl₂O₄ spinel. The fundamental frequencies are A_1g = 772, E_g = 410, and T_2g = 671, 492 and 311 cm^?1. A Kramers-Kronig analysis of the reflectance spectrum of spinel yields the i. r. -active vibrations T_1u = 670, 485, 428 and 305 cm^?1.     

Mössbauer effect measurement in ferromagnetic CuCr2Te3I

Mössbauer effect measurement of the internal fields at ¹²⁹I impurities in the ferromagnetic halo-chalcogenide spinel CuCr₂Te₃I was performed. The magnetic hyperfine field was found to be |34±2| kOe. The results are compared with those measured in the spinel CuCr₂Te₄.     

Structural and transport properties of cubic spinel ZnCo2O4 thin films grown by reactive magnetron sputtering

We report on the growth of cubic spinel ZnCo₂O₄ thin films by reactive magnetron sputtering and bipolarity of their conduction type by tuning of oxygen partial pressure ratio in the sputtering gas mixture. Crystal structure of zinc cobalt oxide films sputtered in an oxygen partial pressure ratio of 90% was found to change from wurtzite Zn_1−xCo_xO to spinel ZnCo₂O₄ with an increase of the sputtering power ratio between the Co and Zn metal targets, D_Co/D_Zn, from 0.1 to 2.2. For a fixed D_Co/D_Zn of 2.0 yielding single-phase spinel ZnCo₂O₄ films, the conduction type was found to be dependent on the oxygen partial pressure ratio: n-type and p-type for the oxygen partial pressure ratio below ∼70% and above ∼85%, respectively. The electron and hole concentrations for the ZnCo₂O₄ films at 300 K were as high as 1.37×10²⁰ and 2.81×10²⁰ cm⁻³, respectively, with a mobility of more than 0.2 cm²/V s and a conductivity of more than 1.8 S cm⁻¹.     

Novel approach to preparation of LiMn2O4 core/LiNixMn2−xO4 shell composite

Combining two methods, coating and doping, to modify spinel LiMn₂O₄, is a novel approach we used to synthesize active material. First we coated the LiMn₂O₄ particles with the nickel oxide particles by means of homogenous precipitation, and then the nickel oxide-coated LiMn₂O₄ was calcined at 750 °C to form a LiNi_xMn_2−xO₄ shell on the surface of spinel LiMn₂O₄ particles. Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), cyclic voltammetry (CV) and charge-discharge test were performed to characterize the spinel LiMn₂O₄ before and after modification. The experimental results indicated that a spinel LiMn₂O₄ core is surrounded by a LiNi_xMn_2−xO₄ shell. The resulting composite showed excellent electrochemical cycling performance with an average fading rate of 0.014% per cycle. This improved cycle stability is greatly attributed to the suppression of Jahn-Teller distortion on the surface of spinel LiMn₂O₄ particles during cycling.     

Synthesis and electrochemical performances of Li4Ti4.95Al0.05O12/C as anode material for lithium-ion batteries

Spinel compounds Li₄Ti_5−xAl_xO₁₂/C (x=0, 0.05) were synthesized via solid state reaction in an Ar atmosphere, and the electrochemical properties were investigated by means of electronic conductivity, cyclic voltammetry, and charge-discharge tests at different discharge voltage ranges (0-2.5 V and 1-2.5 V). The results indicated that Al³⁺ doping of the compound did not affect the spinel structure but considerably improved the initial capacity and cycling performance, implying the spinel structure of Li₄Ti₅O₁₂ was more stable when Ti⁴⁺ was substituted by Al³⁺, and Al³⁺ doping was beneficial to the reversible intercalation and deintercalation of Li⁺. Al³⁺ doping improved the reversible capacity and cycling performance effectively especially when it was discharged to 0 V.     

Electrochemical behaviour of nano-sized spinel LiMn2O4 and LiAlxMn2−xO4 (x=Al: 0.00-0.40) synthesized via fumaric acid-assisted sol-gel synthesis for use in lithium rechargeable batteries

Pristine spinel LiMn₂O₄ and LiAl_xMn_2−xO₄ (x=Al: 0.00-0.40) with sub-micron sized particles have been synthesized using fumaric acid as chelating agent by sol-gel method. The synthesized samples were subjected to thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and cyclic voltammetry (CV) and galvanostatic cycling studies. The TGA curve of the gel shows several weight-loss regions stepwise amounting to 55% till 800 °C attributed to the decomposition of the precursors. Calcination to higher temperatures (800 °C) yields pure-phase spinel (LiAl_xMn_2−xO₄), as it is evident from the high-intensity XRD reflections matching to the standard pattern. SEM and TEM studies confirm that the synthesized grains are of uniform regular surface morphology. FT-IR studies show stretching and bending vibration bands of Li-O, Li-Al-Mn-O. LiAl_0.1Mn_1.90O₄ spinel was found to deliver discharge capacity of 139 mA h/g during the first cycle with columbic efficiency of 97%. LiAl_0.1Mn_1.90O₄ spinel exhibits the high cathodic peak current indicating better electrochemical performance. Low doping (x=0.1) of Al is found to be beneficial in stabilizing the spinel structure.     

EPR powder spectra of Co(II) in ZnRh2O4 spinel matrix

The EPR powder spectra of spinel solid solutions Co_xZn_1-xRh₂O₄ (x ? 0.10) have been studied in the temperature range 6–77 K. The spectra show that Co²⁺ ions occupy distorted tetrahedral sites. As the cobalt concentration increases, the spectrum of the isolated ions is gradually replaced by a strong absorption produced by antiferromagnetic exchange coupled clusters of Co²⁺ ions.     

Effect of calcination temperature on the structure and hydroxylation activity of Ni0.5Cu0.5Fe2O4 nanoparticles

Nanocrystalline Ni_0.5Cu_0.5Fe₂O₄ was synthesized by sol-gel method with varying calcination temperature over the range of 500-1000. The powders obtained were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). In addition, thermal analysis (TG-DTG-DTA) of the precursor was carried out. The study reveals the simultaneous decomposition and ferritization process at rather low temperature (280-350). For the crystalline structure investigated, single cubic spinel is gained when the precursor was decomposed at 800-1000, whereas separated crystal CuO formed when calcination temperature is below 800. The increase of calcination temperature favors the appearance of Fe_B³⁺, Cu_A²⁺ and O on the spinel surface. The hydroxylation activity is relative to the amount of Cu_B²⁺ species on the spinel surface. The lattice oxygen species on the spinel surface are favorable for the deep oxidation of phenol.     

Jahn-Teller transition in Al doped LiMn2O4 spinel

Al-doped lithium manganese spinels, with starting composition Li_1.02Al_xMn_1.98−xO₄ (0.00<x≤0.06), are investigated to determine the influence of the Al³⁺ doping on the Jahn-Teller (J-T) cooperative transition temperature T_J-T. X-ray powder diffraction (XRPD), nuclear magnetic resonance, electron paramagnetic resonance, conductivity and magnetic susceptibility data are put into relation with the tetrahedral and octahedral occupancy fraction of the spinel sites and with the homogeneous distribution of the Al³⁺ ions in the spinel phase. It is observed that Al³⁺ may distribute between the two cationic sublattices. The J-T distortion, associated with a drop of conductivity near room temperature in the undoped sample, is shifted towards lower temperature by very low substitution. However, for x>0.04 T_J-T it increases with increasing x, as clearly evidenced in low temperature XRPD observations. A charge distribution model in the cationic sublattice, for Al substitution, is proposed to explain this peculiar behavior.     

Mössbauer study of the re-entrant spin-glass behaviour in the mixed spinel ferrites Mg(0.9+x)Fe2(1−x)Ni0.1TixO4 (x=0.5 and 0.6)

Samples of the mixed spinel ferrite series Mg_(0.9+x)Fe_2(1−x)Ni_0.1Ti_xO₄ with x=0.5 and 0.6, prepared by solid state reaction of the appropriate oxides, have been investigated with ⁵⁷Fe Mössbauer spectroscopy. The as-prepared samples are found to be mainly superparamagnetic due to magnetic cluster formation. Samples after at least three times reheated exhibit spectra, which can be rather interpreted by a transversal relaxation of the spin above and spin-glass behaviour below the respective freezing temperatures T_f. External-field spectra reveal the canting to occur only on the octahedral sites. From the derived transition temperatures and thresholds together with data from earlier investigated sample with x=0.7 a compositional magnetic phase diagram for this spinel series is obtained.     

The synthesis and the magnetic properties of Gd-doped FexCo1−x/CoyFe3−yO4 micro-octahedrons composites

Gd³⁺-substituted micro-octahedron composites (Fe_xCo_1−x/Co_yGd_zFe_3−y−zO₄) in which the Fe-Co alloy has either a bcc or fcc structure and the oxide is a spinel phase were fabricated by the hydrothermal method. The X-ray diffraction (XRD) patterns indicate that the as-synthesized Gd³⁺-substituted micro-octahedron composites are well crystallized. Scanning electron microscopy (SEM) images show that the final product consists of larger numbers of micro-octahedrons with the size ranging from 1.3 to 5 μm, and the size of products are increased with increasing the concentration of KOH. The effect of the Co²⁺/Fe²⁺ ratio (0?Co²⁺/Fe²⁺?1) and substitution Fe³⁺ ions by Gd³⁺ ions on structure, magnetic properties of the micro-octahedrons composites were investigated, and a possible growth mechanism is suggested to explain the formation of micro-octahedrons composites. The magnetic properties of the structure show the maximal saturation magnetization (107 emu/g) and the maximal coercivity (1192 Oe) detected by a vibrating sample magnetometer.     

Immiscibility in the Fe3O4-FeCr2O4 spinel binary

A recent thermodynamic model of mixing in spinel binaries, based on changes in cation disordering (x) between tetrahedral and octahedral sites [Am. Mineral. 68 (1983) 18, 69 (1984) 733], is investigated for applicability to the Fe₃O₄-FeCr₂O₄ system under conditions where incomplete mixing occurs. Poor agreement with measured consolute solution temperature and solvus [N. Jb. Miner. Abh. 111 (1969) 184] is attributed to neglect of: (1) ordering of magnetic moments of cations in the tetrahedral sublattice antiparallel to the moments of those in the octahedral sublattice and (2) pair-wise electron hopping between octahedral site Fe³⁺ and Fe²⁺ ions. Disordering free energies (ΔG_D), from which free energies of mixing are calculated, are modeled by

     

Investigations on magnetically-dilute CoxZn1−x Rh2O4 spinel solid solution

Magnetic measurements have been performed on polycrystalline solid solutions Co_xZn_1?xRh₂O₄ with a spinel structure. The samples with 0.50? x ? 1.00 are antiferromagnets. The samples with x?0.40 do not show a magnetic order, and their magnetic behavior can be explained taking into account the presence of finite clusters of Co²⁺ ions and paramagnetic isolated ions.     

Enhancement of microstructure and initial permeability due to Cu substitution in Ni0.50−xCuxZn0.50Fe2O4 ferrites

Structural and magnetic properties of Cu substituted Ni_0.50−xCu_xZn_0.50Fe₂O₄ ferrites (where x=0.0-0.25) prepared by an auto combustion method have been investigated. The X-ray diffraction patterns of these compositions confirmed the formation of the single phase spinel structure. The lattice parameter increases with the increase in Cu²⁺ content obeying Vegard's law. The particle size of the starting powder compositions varied from 22 to 72 nm. The theoretical density increases with increase in copper content whereas the Néel temperature decreases. The bulk density, grain size and permeability increases up to a certain level of Cu²⁺ substitution, beyond that all these properties decrease with increase in Cu²⁺ content. The bulk density increases with increase in sintering temperatures up to 1250 °C for the parent composition, while for substituted compositions it increases up to 1200 °C. Due to substitution of Cu²⁺, the real part of the initial permeability increases from 97 to ∼390 for the sample sintered at 1100 °C and from 450 to 920 for the sample sintered at 1300 °C. The ferrites with higher initial permeability have a relatively lower resonance frequency, which obey Snoek's law. The initial permeability strongly depends on average grain size and intragranular porosity. The saturation magnetization, M_s, and the number of Bohr magneton, n(μ_B)_, decreases up to x=0.15 due to the reduction of the A-B interaction in the AB₂O₄ spinel type ferrites. Beyond that value of x, the M_s and the n(μ_B) values are enhanced. The substitution of Cu²⁺ influences the magnetic parameters due to modification of the cation distribution.     

Spin-glass like behaviour in a concentrated chromium spinel: Zn0.5Cd0.5Cr2S4

Low field d.c. and a.c. susceptibility measurements are reported for the non magnetically diluted spinel Zn_0.5Cd_0.5Cr₂S₄. A spin-glass like behaviour is observed at low temperature (T_F = 15.4Katv = 198 Hz).This is the result of the presence of competing interactions (ferromagnetic between nearest-neighbours and antiferromagnetic between higher order neighbours) and of the disorder of their distribution due to the substitution between non-magnetic zinc and cadmium ions in the tetrahedral sites of the spinel lattice.     

Measurement of the branching ratios for Kμ2+, Kπ2+, Ke3+ and Ke3+ decays using a magnetic spectrometer with streamer chambers

The momenta of ～30 000 charged particles from K⁺ decays were measured using a magnetic spectrometer with streamer chambers. The ratio R = Γ(K_π2⁺)/Γ(K_μ2⁺) = 0.3355 ± 0.0057 was obtained. Our values for the branching ratios are: (63.18±0.43)% for K_μ2⁺, (21.18±0.33)% for K_π2⁺, (3.33±0.51)% for K_μ3⁺, (4.99±0.54)% for K_e3⁺.     

Transport properties and conduction mechanisms in CuFe2O4 and Cu1−xZnxGa0.3Fe1.7O4 compounds

Single-phase structure of CuFe₂O₄ and Cu_1−xZn_xGa_0.3Fe_1.7O₄; with (0.0≤x≤0.5) are synthesized. Electrical conductivity measurements as a function of temperature are carried out in the frequency range (10²-10⁵ Hz) for the prepared samples. The obtained results of these materials reveal a metallic-like behavior in the low range of frequency. At high frequency regime metallic-to-semiconductor transition has been observed as the compositional parameter x increases. Metallic-like behavior is accompanied with samples having low Zn content, where cation-cation [Cu-Cu] interaction is major at the octahedral B-sites and semiconductor behavior is associated with compounds having high Zn content, where cation-anion-cation [Fe-O-Fe] interaction is most predominant at B-sites in these spinel oxides. All studied compositions exhibit a transition with change in the slope of conductivity versus temperature curve. This transition temperature is found to decrease linearly with increasing Zn concentration x. The relation of the universal exponent s with temperature indicates the presence of two hopping conduction mechanisms; the correlated barrier hopping CBH at low Zn content x≤0.2 and small polaron (SP) at Zn content x≥0.3.     

Resonance paramagnetique electronique du manganese divalent dans ZnAl2O4

The electron paramagnetic resonance spectrum of a single crystal of ZnAl₂O₄ (spinel structure) doped with manganese displays a fine structure characteristic of a purely cubic crystal field. Contrary to MgAl₂O₄: Mn²⁺, where the degree of inversion is sizable, ZnAl₂O₄ therefore is a normal spinel.     

The ESR study of single crystal spinel ZnCr2Se4 diluted with Sb and V

The single crystal of Sb³⁺ and V³⁺ doped zinc chromium selenide spinel ZnCr₂Se₄ were prepared by a chemical transport method and characterized by ESR spectroscopy in order to examine the effect of nonmagnetic antimony and magnetic vanadium on properties of the system. For antimony admixtures the Neel temperature is very similar to that of the parent spinel ZnCr₂Se₄ (22 K). However, upon incorporating vanadium ions, the T_N temperature decreases down to 17.5 K, determined for the maximum vanadium content (x=0.06). The temperature dependence of the ESR linewidth over paramagnetic region is interpreted by an occurrence of spin-phonon interaction. The strong broadening linewidth together with its strong temperature dependence for vanadium doped ZnCr₂Se₄ is explained by the complex paramagnetic relaxation model.