The magnetic behaviour of the magnetically diluted spinel compound Fe0.6Mg1.6Ni0.1Ti0.7O4 studied by Mössbauer spectroscopy

From a new magnetically diluted spinel oxide with composition Fe_0.6Mg_1.6Ni_0.1Ti_0.7O₄ an as-prepared sample and one after reheating three times have been investigated with Mössbauer spectroscopy. The spectra of the as-prepared sample clearly show a typical superparamagnetic behaviour of magnetic clusters with diverging sizes. On the other hand, the reheated sample exhibits a sharp magnetic transition at 16 K. External-field Mössbauer measurements of the latter reveal spin canting to be exclusively present on the octahedral sites which disappears at the magnetic transition temperature. These results show that this spinel compound exhibits a transition to a spin-glass for which the random freezing only occurs on the octahedral sites.     

Estimating the cation distributions in the spinel ferrites Cu0.5−xNi0.5ZnxFe2O4 (0.0≤x≤0.5)

Ferrite samples of the composition Cu_0.5−xNi_0.5Zn_xFe₂O₄ (0.0≤x≤0.5) were synthesized by chemical co-precipitation. The samples exhibited a single phase cubic spinel structure, and the saturation magnetization of the samples was found to increase with increasing Zn content. Using a quantum mechanical method proposed by our group, the cation distributions in the samples were estimated. Estimated cation distributions obtained by fitting the magnetic moments of the samples were then used to perform Rietveld fitting for X-ray diffraction patterns. The acceptable error parameters in the Rietveld fitting indicate that the estimated cation distributions in the samples are reasonable.     

XRD,magnetic and Mössbauer spectral studies of nano size aluminum substituted cobalt ferrites (CoAlxFe2−xO4)

Aluminum substituted cobalt ferrites having particle size ∼10 nm were prepared using aerosol route, which increases with annealing temperature. The unit cell parameter ‘a’ and saturation magnetization decreases linearly with the increase of aluminum concentration. This is due to the smaller ionic radius and the diamagnetic nature of the Al³⁺, respectively. Room temperature Mössbauer spectra of the samples annealed at 1200 °C show broad sextets, which were fitted with different sextets, indicating different local environment of both tetrahedrally and octahedrally coordinated iron cation. Further, hyperfine field of the samples decreases with the increase of Al³⁺ concentration due to the fact that the Al³⁺ diamagnetic species reduce the magnetic interactions. Cations distribution indicated a increase in Fe³⁺(oct.)/Fe³⁺(tet.) ratio on increasing the Al³⁺ concentration.     

Influence of frequency, temperature and composition on electrical properties of polycrystalline Co0.5CdxFe2.5−xO4 ferrites

Polycrystalline ferrites with general formula Co_0.5Cd_xFe_2.5−xO₄ (0.0?x?0.5) were prepared by sol-gel method. The dielectric properties ε′, ε″, loss tangent tan δ and ac conductivity σ_ac have been studied as a function of frequency, temperature and composition. The experimental results indicate that ε′, ε″, tan δ and σ_ac decrease as the frequency increases; whereas they increase as the temperature increases. These parameters are found to increase by increasing the concentration of Cd content up to x=0.2, after which they start to decrease with further increase in concentration of Cd ion. The dielectric properties and ac conductivity in studied samples have been explained on the basis of space charge polarization according to Maxwell and Wagner's two-layer model and the hoping between adjacent Fe²⁺ and Fe³⁺ as well as the hole hopping between Co³⁺and Co²⁺ ions at B-sites. The values of activation energies E_f for conduction process are determined from Arrhenius plots, and the variations in these activation energies as a function of Cd content are discussed. The complex impedance analysis is used to separate the grain and grain boundary of the system Co_0.5Cd_xFe_2.5−xO₄. The variations of both grain boundary and grain resistances with temperature and composition are evaluated in the frequency range 42 Hz-5 MHz.     

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.     

A magnetic, magnetostrictive and Mössbauer study of Tb0.3Dy0.7−xPrx(Fe0.9Al0.1)1.95 alloys

The effect of Pr substitution for Dy on the magnetization, magnetostriction, anisotropy and spin reorientation of a series of Tb_0.3Dy_0.7−xPr_x(Fe_0.9Al_0.1)_1.95 alloys (x=0, 0.1, 0.20, 0.25, 0.30, 0.35) at room temperature has been investigated. It was found that the magnetization and magnetostriction of the homogenized Tb_0.3Dy_0.7−xPr_x(Fe_0.9Al_0.1)_1.95 alloys decreases drastically with increasing x and the magnetostrictive effect disappears for x>0.2, but the spontaneous magnetostriction λ₁₁₁ increases approximately linearly with increasing x. Moreover, the magnetostriction exhibits slightly bigger value at x=0.1 than the free alloys and is saturated more easily with the magnetic field H, showing that a small amount of Pr substitution is beneficial to a decrease in the magnetocrystalline anisotropy. The analysis of the Mössbauer spectra indicated that the easy magnetization direction in the {1 1 0} plane deviates slightly from the main axis of symmetry with Pr concentration x, namely spin reorientation. Comparing with the Al substitution, the effect of Pr substitution for Dy on the spin reorientation is smaller.     

Effect of In ions doping on the structural and magnetic properties of Mg0.2Mn0.5Ni0.3InxFe2−xO4 spinel ferrites

Effect of substitution of diamagnetic trivalent indium ions on the composition Mg_0.2Mn_0.5Ni_0.3In_xFe_2−xO₄ with x varying from 0.1 to 0.3 in steps of 0.1 using citrate precursor techniques has been investigated. Single-phase cubic spinel structure of these samples has been confirmed from X-ray diffraction analyses. Micro structural features were examined by TEM images. Lattice constant ‘a’ initially increases up to x = 0.1 and thereafter it decreases with further increase in x. This indicates that variation of ‘a’ with x do not obey Vegard's law. Nonlinear behavior of ‘a’ with x may be due to substitutional effect of larger In³⁺ ions (0.91Å) with smaller Fe³⁺ ions (0.67Å) in Mg-Mn-Ni ferrite. Ferrites have been investigated for their structural and magnetic properties such as variations in lattice constant, saturation magnetization, coercivity, retentivity, initial permeability, magnetic loss and relative loss factor (RLF). Fairly constant value of initial permeability over a wide frequency range (0.075–10 MHz) and low values of relative loss factor of order of 10⁻⁶–10⁻⁵ in same frequency range are main achievement of present investigations. RLF has been reduced by three orders of magnitude as compared to those samples prepared by conventional method. Low values of relative loss factor even at a high frequency indicate that prepared materials may have great potential for use in microwave devices. Possible mechanisms contributing to these properties have been discussed in this paper.     

Finite size effect on Gd doped CoGdxFe2−xO4 (0.0≤x≤0.5) particles

Nanoparticles of CoGd_xFe_2−xO₄ (where x=0.0, 0.1, 0.3, 0.5) series have been prepared by chemical co-precipitation. The effect of Gd³⁺ ion concentration on crystalline phase, crystallinity, crystallite size, molecular vibrations and magnetic resonance has been investigated in detail. The crystallinity decreases with an increase in Gd³⁺ ion concentration and changes the structural parameters. The spin lattice relaxation has been correlated with the doping ion concentration. Similarly, the superparamagnetic behavior of these particles has been observed with EPR spectroscopy.     

Oxygen nonstoichiometry, Mössbauer spectra and mixed conductivity of Pr0.5Sr0.5FeO3−δ

The oxygen deficiency of perovskite-type Pr_0.5Sr_0.5FeO_3−δ, studied by coulometric titration, thermogravimetry and Mössbauer spectroscopy, is significantly higher than that in La_0.5Sr_0.5FeO_3−δ at 973-1223 K. The variations of hole mobility and Seebeck coefficient in oxidizing atmospheres, where the total conductivity of praseodymium-strontium ferrite is predominantly p-type electronic, suggest progressive delocalization of the p-type charge carriers on increasing oxygen chemical potential. As for other perovskite-type ferrites, reduction leads to the co-existence of vacancy-ordered and disordered domains. The n-type electronic conductivity of Pr_0.5Sr_0.5FeO_3−δ at reduced p(O₂) and the hole transport under oxidizing conditions are both lower compared to the La-containing analogue. Analogous conclusion was drawn for the ionic conductivity, calculated from the steady-state oxygen permeation data under oxidizing conditions and from the p(O₂)-dependencies of total conductivity in the vicinity of electron-hole equilibrium points where the average iron oxidation state is 3+. The similar activation energies for partial ionic and electronic conductivities in Ln_0.5Sr_0.5FeO_3−δ (Ln=La, Pr) indicate that the presence of praseodymium does not alter any of the conduction mechanisms but decreases the charge-carrier mobility due to the smaller radius of Pr³⁺ cations stabilized in the perovskite lattice.     

Cr-doping effect on the structural, magnetic, transport properties and Raman spectroscopy of La(2+x)/3Sr(1−x)/3Mn1−xCrxO3 perovskites

A series of the double-doping samples La_(2+x)/3Sr_(1−4x)/3Mn_1−xCr_xO₃ (0?x?0.25) with the Mn³⁺/Mn⁴⁺ ratio fixed at 2:1 have been fabricated. The structural, magnetic, transport properties and Raman spectroscopy have been investigated, and no apparent crystal structure change is introduced by Cr doping up to x=0.25. But the Curie temperature T_C and metal-insulator transition temperature T_MI are strongly affected by Cr substitution. The room temperature Raman spectra start exhibiting some new features following the increasing concentration of Cr substitutions. Moreover, it is worth noting that the frequency of the A_1g phonon mode can also be well correlated with the A-site mismatch effect (σ²), which is influenced mainly by the variety of the Sr content.     

Microstructure characterization and magnetic behavior of NiAlxFe2−xO4 and Ni1−yMnyAl0.2Fe1.8O4 ferrites

NiAl_xFe_2−xO₄ and Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites were prepared by the conventional ceramic method and were characterized by X-ray diffraction, scanning electron microscopy, and magnetic measurements. The single spinel phase was confirmed for all prepared samples. A proper explanation of data is possible if the Al³⁺ ions are assumed to replace Fe³⁺ ions in the A and B sites simultaneously for NiAl_xFe_2−xO₄ ferrites, and if the Mn²⁺ ions are assumed to replace Ni²⁺ ions in the B sites for Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites. Microstructural factors play an important role in the magnetic behavior of Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites with large Mn²⁺ content.     

Magnetic properties of (Ce1−xLax)PdIn2

We report on results of X-ray powder diffraction, magnetization and specific heat measurements of the pseudo-ternary (Ce_1−xLa_x)PdIn₂ system with x=0; 0.2; 0.4 and 0.6. The results show a linear increase of the unit cell volume and a reduction of the ferromagnetic transition as La content increases. The Debye temperature, Sommerfeld coefficient and crystal field parameters were estimated from specific heat data, and are found to be weakly dependent of the Ce concentration. Also, the variation of magnetic entropy at T_C is only weakly dependent on x (ΔS≅0.92Rln2) indicating that T_K/T_C is approximately constant along the series. The T_C and T_K behaviors are explained by the variation of the exchange parameter due to the volume change when Ce is replaced by La. Our results indicate that the chemical pressure is the dominant effect rather than the chemical disorder for determining the physical proprieties of the (Ce_1−xLa_x)PdIn₂ system.     

High-frequency permeability and permittivity of NixZn(1−x)Fe2O4 thick film

Magnetic materials such as Ni_xZn_(1−x)Fe₂O₄ have resonant frequency in high frequency; therefore, they are more useful especially in microwaves. The Ni_xZn_(1−x)Fe₂O₄ was prepared by the chemical coprecipitation method using citrate precursors, and the fritless thick film was screen printed on alumina substrates. The composition-dependent permeability and permittivity in the high frequency 8–12 GHz are investigated. Using the overlay technique on Ag-thick-film patch antenna, the change in reflectance and transmittance has been measured. The Ni_xZn_(1−x)Fe₂O₄ thick film, when used as overlay on Ag-thick-film patch antenna, changes the resonance characteristics. The changes in resonance frequency, reflectance and transmittance have been used to calculate the permeability and permittivity of the thick film. Zinc-concentration-dependent changes are obtained.     

Effect of Ga doping on magneto-transport properties in colossal magnetoresistive La0.7Ca0.3Mn1−xGaxO3 (0<x<0.1)

Samples of La_0.7Ca_0.3Mn_1−xGa_xO₃ with x=0, 0.025, 0.05 and 0.10 were prepared by standard solid-state reaction. They were first characterized chemically, including the microstructure. The magnetic properties and various transport properties, i.e. the electrical resistivity, magnetoresistivity (for a field below 8 T), thermoelectric power and thermal conductivity measured each time on the same sample, are reported. The markedly different behaviour of the x=0.1 sample from those with a smaller Ga content, is discussed. The dilution of the Mn³⁺/Mn⁴⁺ interactions with Ga doping considerably reduces the ferromagnetic double exchange interaction within the manganese lattice leading to a decrease of the Curie temperature. The polaron binding energy varies from 224 to 243 meV with increased Ga doping.     

Magnetic properties of magnetic Co1−xMgxFe2O4 spinel by HTSE method

Magnetic properties and exchange-coupling interactions of diluted magnetic spinels A_1−xA′_xB₂X₄, where A and B are magnetic ions, namely Co_1−xMg_xFe₂O₄, were investigated using the high-temperature series expansion method (HTSE) and the distribution method of magnetic cations in the range 0≤x≤1. The magnetic phase diagram and transition temperature versus dilution x were determined using the Padé approximants method along with HTSE. The critical exponent associated with the magnetic susceptibility γ was then deduced. The obtained results are in good agreement with experimental results and critical exponent values are consistent with those suggested by the universality hypothesis.     

Effects of simultaneous carrier doping in the charge reservoir and conducting layers of superconducting CeO0.9F0.1Fe1−xCoxAs

Electron-doping of the semimetal (CeOFeAs) by either fluorine (max T_c ∼ 43 K) or cobalt (max T_c ∼ 11 K) leads to superconductivity. Here we show the effect of transition metal (Co) substitution at the iron site on the superconducting properties of CeO_0.9F_0.1FeAs (T_c ∼ 38 K) to understand the interplay of charge carriers in both the rare earth-oxygen and Fe–As layers. Simultaneous doping of equivalent number of charge carriers in both layers leads to a T_c of 9.8 K which is lower than the T_c obtained when either the conducting layer (FeAs) or charge reservoir layer (CeO) is individually doped. This suggests a clear interplay between the two layers to control the superconductivity. Resistivity upturn and negative magnetoresistance are observed with Co doping that is interpreted in the gamut of Kondo effect. Hall coefficient and thermoelectric power indicate increased carrier concentration with cobalt doping in CeO_0.9F_0.1FeAs. The rf penetration depth both for CeO_0.9F_0.1Fe_0.95Co_0.05As and CeO_0.9F_0.1FeAs show an exponential temperature dependence with gap values of ∼1.6 and 1.9 meV respectively.     

Magnetic and magnetocaloric properties of Gd1−xScxNi2 solid solutions

Magnetic and heat capacity measurements have been carried out on the polycrystalline Gd_1−xSc_xNi₂ solid solutions (0≤x≤1), which crystallize in the cubic C15 Laves phases superstructure (space group F4?3m). These solid solutions are ferromagnetic with a Curie temperature below 76 K. Their Curie temperature decreases from 75.4 K for GdNi₂ to 13.6 K for Gd_0.2Sc_0.8Ni₂. At high temperatures, all solid solutions, except ScNi₂, are Curie-Weiss paramagnets. The Debye temperature as well as phonon, conduction electron and magnetic contributions to the heat capacity have been determined from heat capacity measurements. The magnetocaloric effect has been estimated both in terms of isothermal magnetic entropy change and adiabatic temperature change for selected solid solutions in magnetic fields up to 3 T.     

Structural and magnetic properties of sol-gel Co2xNi0.5−x Zn0.5−xFe2O4 thin films

Nanocrystalline Co_2xNi_0.5−xZn_0.5−xFe₂O₄ (x=0−0.5) thin films have been synthesized with various grain sizes by a sol-gel method on polycrystalline silicon substrates. The morphology as well as magnetic and microwave absorption properties of the films calcined at 1073 K were studied using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and vibrating sample magnetometry. All films were uniform without microcracks. The Co content in the Co-Ni-Zn films resulted in a grain size ranging from 15 to 32 nm while it ranged from 33 to 49 nm in the corresponding powders. Saturation and remnant magnetization increased with increase in grain size, while coercivity demonstrated a drop due to multidomain behavior of crystallites for a given value of x. Saturation magnetization increased and remnant magnetization had a maximum as a function of grain size independent of x. In turn, coercivity increased with x independent of grain size. Complex permittivity of the Co-Ni-Zn ferrite films was measured in the frequency range 2-15 GHz. The highest hysteretic heating rate in the temperature range 315-355 K was observed in CoFe₂O₄. The maximum absorption band shifted from 13 to 11 GHz as cobalt content increased from x=0.1 to 0.2.     

Oxygen non-stoichiometry and defect thermodynamics in La2Ni0.9Fe0.1O4+δ

The oxygen hyperstoichiometry of K₂NiF₄-type La₂Ni_0.9Fe_0.1O_4+δ, studied by thermogravimetric analysis and coulometric titration in the oxygen partial pressure range 6×10⁻⁵-0.7 atm at 923-1223 K, is considerably higher than that of undoped lanthanum nickelate. The p(O₂)-T-δ diagram of iron-doped lanthanum nickelate can be adequately described by introducing point-defect interaction energy in the concentration-dependent part of defect chemical potentials and accounting for the site-exclusion effects. The critical factors affecting the equilibrium oxygen incorporation process include coulombic repulsion of interstitial anions, trapping of the p-type electronic charge carriers by iron, and interaction between Fe³⁺ and holes localized on nickel cations. Due to low chemical expansion of La₂Ni_0.9Fe_0.1O_4+δ lattice, the thermodynamic functions governing oxygen intercalation, site-blocking factors and hole mobility are all independent of the defect concentrations. The predominant 3+ state of iron cations under oxidizing conditions was confirmed by the Mössbauer spectroscopy. The stability of La₂NiO₄-based phase in reducing atmospheres is essentially unaffected by doping.     

Effects of composition on phase structure and electrical properties of (K0.5Na0.5)0.90Li0.06Sr0.02Nb(1−x)SbxO3 ceramics

Lead-free (K_0.5Na_0.5)_0.90Li_0.06Sr_0.02Nb_(1−x)Sb_xO₃ (KNLSN-Sb_x) ceramics were synthesized by ordinary sintering technique. The compositional dependence of phase structure and electrical properties of the ceramics was systematically investigated. All samples possessed pure perovskite structure, showing room temperature symmetries of orthorhombic at x<0.01, coexistence of orthorhombic and tetragonal phases at x=0.01, and tetragonal at 0.02≤x≤0.05. The temperature of the polymorphic phase transition (PPT) was shifted to lower temperature and dielectric relaxor behavior was induced by increasing Sb content. The samples near the coexistence region (x=0.01) exhibited enhanced electrical properties: d₃₃∼145 pC/N, k_p∼38% and P_r∼20.4 μC/cm².