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.     

New ferrimagnetic spinel compositions in the system MCr2S4−xSex where M=Fe,Co, Mn

Phase relationship between ferrimagnetic semiconducting spinels of the type MCr₂S₄ and defect NiAs compositions of the type MCr₂Se₄ (where M=Mn, Fe, Co) are established. It was found that the amount of Se which can be substituted, with retention of the spinel structure, decreases from MnCr₂S_4?xSe_x (x=0 to x=2) to FeCr₂S_4?xSe_x (x=0 to x=1·25) to CoCr₂S_4?xSe_x (x=0 to x=1). This phenomena is accounted for on the basis of sulfide spinel stability and unit cell size. The Curie temperatures of the spinel compositions decrease slowly with increasing Se content. This is presumably caused by weakening of the spinel A-B superexchange interaction.     

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.     

Influence of vacancies on the electrical properties of the ZnCr2−xNixSe4 spinels

The effect of vacancies on the electronic transport in the ZnCr_2−xNi_xSe₄ paramagnetic single crystals is considered. For this purpose, the structure refinements, the high temperature electrical conductivity and the thermoelectric power measurements as well as the calculations of the vacancy model parameters were used. The electrical measurements have been done in the temperature range from 290 to 520 K for single crystals with x=0.001, 0.05, and 0.065. The above investigations provide evidence for polaron conduction in defective spinel materials. In particular: (1) at high temperatures a linear dependence between thermopower S and the electrical resistivity (ln ρ), a characteristic of small polarons, was observed, (2) an origin of small polarons in this case could be associated with a crystalline distortion, which is characterized by larger values of the anion parameter than u=0.375, which describes an ideal spinel structure, and (3) a large defectiveness, which is identified by the large value of the vacancy parameter of about β=11.5%. These effects are explained in terms of a polaron mechanism of the electrical conductivity including structural defects.     

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.     

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.     

Phase relationships and magnetic phase diagram in the system Mn1−xCuxCr2S4

Ternary spinel compounds have been found in the system Mn_1?xCu_xCr₂S₄ for x < 0.4 and x ? 0.8. The unit cell parameter does not follow a Vegard law. Magnetization measurements up to 150 kOe for Mn_0.95Cu_0.05Cr₂S₄ show three magnetic structures: Néel ferrimagnet, Yafet-Kittel and tridimensional. The magnetic phase diagram has been calculated within the molecular field approximation. There is strong evidence for the non-existence of Mn³⁺. Our findings are in conformity with a model proposed by Goodenough.     

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.     

Thermodynamic and kinetic properties of Ho1−xTixCo2-hydrogen system

The hydrogen absorption behavior of Laves phase Ho_1−xTi_xCo₂ (x=0.1-0.6) alloys has been investigated by pressure-concentration (PC) isotherms and cyclic-, temperature- and pressure-dependent absorption kinetics. The PC isotherms and kinetics of hydrogen absorption have been studied in the pressure range 0.01-1 bar and temperature range 50-200 °C using Sievert's-type apparatus. The drastic changes in the induction period and particle size during the activation process have been discussed based on the kinetics of repeated hydrogenation cycles and scanning electron microscopy (SEM) images of the hydrides at different hydriding cycles, respectively. The experimental results of kinetic curves are interpreted using the Johnson-Mehl-Avrami (JMA) model, and the reaction order and reaction rate have been determined. The α-, (α+β)- and β-phase regions in Ho_1−xTi_xCo₂-H have been identified from the different slope regions of the first-order-type kinetic plots. The dependence of the reaction rate parameter on hydriding pressure and temperature in the (α+β)-phase region has been discussed.     

‘Soft’ optical phonons and the morphotropic phase transition of the Pb(Ti1−x, Zrx)O3 system

Room temperature Raman scattering results for the Pb(Ti_1?x, Zr_x)O₃ system in its tetragonal ferroelectric phase are analyzed. For x ≤ 0.25, the square of the frequency of the ‘soft’ E(TO) phonon is linear in the Zr concentration. In addition, we find that the morphotropic phase transition at x = 0.535 may be associated with an instability of this ‘soft’ phonon. It is shown that changes in the short-range harmonic forces play an important role in the x-dependence of the ‘soft’ E(TO) phonon frequency.     

Spin alignment of yrast levels populated by pre-equilibrium (α, xnγ) reactions

Angular momenta of yrast levels following pre-equilibrium (α, xnγ) reactions at E_α, = 110 MeV were found to be aligned as well as those following the equilibrium (compound) (α, xnγ) reactions at E_α = 20–50 MeV. They are uniform against the neutron multiplicity x. The degrees of the spin (angular momentum) alignment with rank 2 for the yrast levels with spins 8–12 average about α₂ ≈ 0.87 ± 0.05. The good spin alignment indicates that both the neutron emission and the γ-emission are stretched in angular momentum space. This supports the pre-equilibrium neutron emission process, where the momenta carried away by the neutrons are not in random directions but rather in the beam direction. The result is well reproduced by the pre-equilibrium neutron emission process followed by neutron evaporation and the K-band γ-deexcitation process.     

Alloying effects on Kβ/Kα intensity ratios and electrical properties in Cd1−xZnxS semi-conductor alloys

The alloying effect on K_β/K_α intensity ratio in Cd_1−xZn_xS semi-conductor alloys and on structural, electrical and optical properties of these alloys were investigated. The sample was excited by gamma rays with energy 59.5 keV photons from an Am-241 radioisotope source. K X-rays emitted by the sample were counted with a Si(Li) detector. We found that the K_β/K_α intensity ratio is changed by the alloying effect in Cd_1−xZn_xS semi-conductor alloys for different compositions x. We compared our results with the theoretical values.     

Phase transition and extended X-ray absorption fine structure of melt-spun amorphous Fe100−xYx alloys

The phase diagram and local structure of melt-spun amorphous (a-) Fe_100−xY_x (22?x?62) alloys were investigated using AC and DC magnetic and extended X-ray absorption fine structure (EXAFS) measurements. The a-Fe–Y system shows reentrant spin glass (RSG) behavior for 42?x?58 and spin glass (SG) behavior for 60?x. Two SG transition temperatures, T_g and T_f, were obtained in the RSG state. The T_g, T_f and Curie temperature T_C decrease with increasing x, and the T_C and T_g vanish at x=60. A new magnetic phase diagram for the melt-spun a-Fe_100−xY_x alloys was obtained from magnetic measurements for higher Y concentration. The magnetic states of the a-Fe_100−xY_x alloys change remarkably around x=60 and an EXAFS study revealed that the average atomic distance between nearest-neighboring Fe atoms changes at approximately x=60.     

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.     

EXAFS of the superconducting oxide BaPb1−xBixO3

The two-valence state Bi³⁺ and Bi⁵⁺ of Bi in the semiconductor BaBiO₃ and in the BaPb_1?xBi_xO₃ (x = 0, 0.25, 0.6 and 1) system has been determined from the EXAFS spectra above the L_III-edges of Ba, Pb and Bi. Peaks in the radial distribution function up to 5 Å from the absorber have been identified through a model calculation using theoretical amplitudes and phase shifts and the interatomic distances from neutron diffraction measurements. We found indication of local disorder in the Pb-Bi sublattice for the mixed compound.     

Infrared and structural studies of Mg1-xZnxFe2O4 ferrites

Compositions of polycrystalline Mg-Zn mixed ferrites with the general formula Mg_1−xZn_xFe₂O₄ (0≤x≤1) were prepared by the standard double sintering ceramic method. The structural properties of these ferrites have been investigated using X-ray diffraction and infrared absorption spectroscopy. The lattice parameter, particle size, bonds length, force constants, density, porosity, shrinkage and cation distribution of these samples have been estimated and compared with those predicted theoretically. Most of these values were found to increase with increasing Zn content. The energy dispersive (EDS) analysis confirmed the proposed sample composition. The scanning electron microscope (SEM) and transmission electron microscope (TEM) micrographs showed aggregates of stacked crystallites of about 200-800 nm in diameter. Far infrared absorption spectra showed two significant absorption bands. The wave number of the first band, ν₁, decreases with increasing Zn content, while the band, ν₂ shifts linearly towards higher wave numbers with Zn contents, over the whole composition range. The room temperature electrical resistivity was found to decrease as Zn-content increases. Values of the vacancy model parameters showed that the packing factors P_a and P_b decrease, the fulfillment coefficient, α, remains almost constant and the vacancy parameter, β, strongly increases with increasing Zn content in the sample. The small values of P_a, P_b, α and the strong increase of the vacancy parameter, β, indicate the presence of cation or anion vacancies and the partial participation of the Zn²⁺ vacancies in the improvement of the electrical conductivity in the Mg-Zn ferrites.     

Structural characterization and magnetization of Mg0.7Zn0.3SmxFe2−xO4 ferrites

Mg_0.7Zn_0.3Sm_xFe_2−xO₄ ferrites were prepared by the solid-state reaction method and were characterized by X-ray diffraction and magnetization measurements. A single spinel phase was obtained in the range 0.00?x?0.03$0.00?x?0.03$. The lattice parameter was found to increase at x=0.01$x=0.01$ and then decreases up to x=0.03$x=0.03$, which may indicate a distortion in the spinel lattice. The saturation magnetization was found to decrease with the increase in x up to 0.04, due to the replacement of the Fe³⁺ ions by the Sm³⁺ ions.     

Hydrothermal synthesis and structural characterization of (1−x)α-Fe2O3-xSnO2 nanoparticles

Structural and morphological characteristics of (1−x)α-Fe₂O₃-xSnO₂ (x=0.0-1.0) nanoparticles obtained under hydrothermal conditions have been investigated by X-ray diffraction (XRD), transmission Mössbauer spectroscopy, scanning and transmission electron microscopy as well as energy dispersive X-ray analysis. On the basis of the Rietveld structure refinements of the XRD spectra at low tin concentrations, it was found that Sn⁴⁺ ions partially substitute for Fe³⁺ at the octahedral sites and also occupy the interstitial octahedral sites which are vacant in α-Fe₂O₃ corundum structure. A phase separation of α-Fe₂O₃ and SnO₂ was observed for x≥0.4: the α-Fe₂O₃ structure containing tin decreases simultaneously with the increase of the SnO₂ phase containing substitutional iron ions. The mean particle dimension decreases from 70 to 6 nm, as the molar fraction x increases up to x=1.0. The estimated solubility limits in the nanoparticle system (1−x)α-Fe₂O₃-xSnO₂ synthesized under hydrothermal conditions are: x≤0.2 for Sn⁴⁺ in α-Fe₂O₃ and x≥0.7 for Fe³⁺ in SnO₂.     

Epr study of CoxZn1−xRh2O4 spinel solid solution

The EPR powder spectra of Co_xZn_1?xRh₂O₄ spinel solid solutions have been studied in the temperature range, 6–300 K for x ? 0.10. The principal features of the spectrum have been examined as a function of the temperature and of the composition. Evidence is presented that the solid solutions are antiferromagnetically ordered for x ? 0.40.