Structural,transport and spectroscopic properties of Ti substituted magnetite: Fe3−xTixO4

The effect of Ti⁴⁺ ion on the formation of magnetite, which were prepared by solid-state route reaction method, were studied by resistivity, Raman and ⁵⁷Fe Mössbauer spectrometry. Resistivity measured in the range of 10 < T < 300 K for Ti⁴⁺ magnetite Fe_3−xTi_xO₄ exhibit first order phase transformations at the Verwey transition T_v for Fe₃O₄, Fe_2.98Ti_0.02O₄ and Fe_2.97Ti_0.03O₄ at 123 K, 121 K and 118 K, respectively. No first order phase transition was observed for Fe_2.9Ti_0.1O₄ and small polaron model retraces the semiconducting resistivity behavior with activation energy of about 72 meV. The changes in Raman spectra as a function of doping show that the changes are gradual for samples with higher Ti doping. The Raman active mode for Fe_2.9Ti_0.1O₄ at ≅634.4 cm⁻¹ is shifted as compared to parent Fe₃O₄ at ≅670 cm⁻¹, inferring that Mn²⁺ ions are located mostly on the octahedral sites. ⁵⁷Fe Mössbauer spectroscopy probes the site preference of the substitutions and their effect on the hyperfine magnetic fields confirms that Ti⁴⁺ ions are located mostly on the octahedral sites of the Fe_3−xTi_xO₄ spinel structure.     

Synthesis and characterization of Ni1−xZnxFe2O4 spinel ferrites from tailored layered double hydroxide precursors

In this paper, a series of pure Ni_1 − xZn_xFe₂O₄ (0 ≤ x ≤ 1) spinel ferrites have been synthesized successfully using a novel route through calcination of tailored hydrotalcite-like layered double hydroxide molecular precursors of the type [(Ni + Zn)_{1 − x − y}Fe_y²⁺Fe_x³⁺(OH)₂]^x+(SO₄²⁻)_x/2·mH₂O at 900 °C for 2 h, in which the molar ratio of (Ni²⁺ + Zn²⁺)/(Fe²⁺ + Fe³⁺) was adjusted to the same value as that in single spinel ferrite itself. The physico-chemical characteristics of the LDHs and their resulting calcined products were investigated by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and Mössbauer spectroscopy. The results indicate that calcination of the as-synthesized LDH precursor affords a pure single Ni_1 − xZn_xFe₂O₄ (0 ≤ x ≤ 1) spinel ferrite phase. Moreover, formation of pure ferrites starting from LDHs precursors requires a much lower temperature and shorter time, leading to a lower chance of side-reactions occurring, because all metal cations on the brucite-like layers of LDHs can be uniformly distributed at an atomic level.     

Microscopic and Macroscopic Magnetic Properties of the MgAl x Cr x Fe2 − 2x O4 Spinel Ferrite System

To determine the influence of the substitution of Al³⁺ and Cr³⁺ for Fe³⁺ in MgFe₂O₄ ferrites on the structural and magnetic properties, the MgAl _x Cr _x Fe_{2 – 2x} O₄ (x = 0.0–0.8) spinel systems were studied by using the X-ray diffraction analysis, magnetization in strong fields, magnetic susceptibility in weakly variable electric fields, and Mössbauer spectroscopy. Unlike previous investigations, it was discovered that a half of Al³⁺ occupies tetragonal positions. The system forms a noncollinear spin structure and a central paramagnetic doublet is superimposed over the magnetic sextet in the Mössbauer spectrum (0.5 > x > 0.2). The dependence of the magnetic susceptibility on temperature reveals the normal ferromagnetic properties of the material.     

NiMn2−xFexO4 prepared by a reverse micelles method as conversion anode materials for Li-ion batteries

Synthesis by reverse micelles was used to produce NiMn_2−xFe_xO₄ with nanometric particle sizes for their use as conversion anode materials for lithium ion batteries. The hydroxide precursor was characterized by infrared spectroscopy and the decomposition was followed by thermal analysis. Cation distribution in the spinel structure of pristine samples was evaluated by Mössbauer spectroscopy evidencing that octahedral Fe³⁺ is substituted by Mn³⁺ ions in NiMnFeO₄. Capacity values of 750 mA h g⁻¹ were retained for 50 cycles for NiMnFeO₄ and NiFe₂O₄, respectively. A good kinetic response was observed in NiMnFeO₄ at 2C.     

Structural and transport properties of stoichiometric Mn-doped magnetite: Fe3−xMnxO4

The polycrystalline samples of Fe_3−xMn_xO₄ (0.10 ≤ x ≤ 0.50) were prepared by a solid-state route reaction method. X-ray diffraction pattern shows that Mn²⁺ doped magnetites are in single phase and possess cubic inverse spinel structure. The resistivity measurements (10 < T < 300 K) for x = 0.0 and 0.01 confirms the first order phase transition at the Verwey transition T_V = 123 K and 117 K, respectively. No first order phase transition was evidenced for Fe_3−xMn_xO₄ (0.10 ≤ x ≤ 0.50). Small polaron model has been used to fit the semiconducting resistivity behavior and the activation energy ?_a, for samples x = 0.10 and 0.50 is about 72.41 meV and 77.39 meV, respectively. The Raman spectra of Fe_3−xMn_xO₄ at room temperature reveal five phonons modes for Fe_3−xMn_xO₄ (0.01 ≤ x ≤ 0.50) as expected for the magnetite (Fe₃O₄). Increased Mn²⁺ doping at Fe site leads to a gradual changes in phonon modes. The Raman active mode for Fe_3−xMn_xO₄ (x = 0.50) at ≅641.5 cm⁻¹ is shifted as compared to parent Fe₃O₄ at ≅669.7 cm⁻¹, inferring that Mn⁺² ions are located mostly on the octahedral sites. The laser power is fixed to 5 mW causes the bands to broaden and to undergo a small shift to lower wave numbers as well as increase in the full width half maxima for A_1g phonon mode with the enhancement of Mn²⁺ doping. Mössbauer spectroscopy probes the site preference of the substitutions and their effect on the hyperfine magnetic fields confirms that Mn⁺² ions are located mostly on the octahedral sites of the Fe_3−xMn_xO₄ spinel structure.     

Substitutional effect on structural and dielectric properties of Ni1−xAxFe2O4 (A = Mg,Zn) mixed spinel ferrites

The Ni_1−xA_xFe₂O₄ (A = Zn, Mg; x = 0.0, 0.5) ferrites synthesized by chemical co-precipitation method. X-ray diffraction and Raman spectroscopy reveals that all the ferrite samples are in single-phase cubic spinel structure with Fd3m space group. The lattice parameter enhances with Mg and Zn substitution. Raman spectroscopy identifies a doublet like nature of A_1g mode for all the three ferrites. A blue shift in Mg doped ferrite and a red shift in Zn doped ferrite has been observed as compared to parent NiFe₂O₄. Frequency dependent dielectric response confirms the dielectric polarization and electrical conduction mechanism. The minimum value of loss tangent (∼0.03) at 5 KHz suggests that Ni_1−xA_xFe₂O₄ is effective material for microwave application. The activation energy for NiFe₂O₄, Ni_0.5Mg_0.5Fe₂O₄ and Ni_0.5Zn_0.5Fe₂O₄ are found to be 0.28 eV, 0.29 eV and 0.31 eV, respectively.     

Mössbauer effect and dielectric behavior of NixCu0.8−xZn0.2Fe2O4 compound

The ferrite system Ni_xCu_0.8−xZn_0.2Fe₂O₄ with 0.0 ≤ x ≤ 0.8 was synthesized. XRD measurement confirmed the presence of single-phase spinel structure. The area ratio of Fe³⁺ at the tetrahedral A- and octahedral B-sites was deduced from the spectral analysis of Mössbauer measurements. The results give evidence that Ni²⁺ replaces Cu at B-site in the present unit cell. The dielectric properties ?′, ?″, loss tangent tan(δ) and ac conductivity σ_ac have been studied for the prepared samples in the temperature range (300-600 K) and over the frequency range (10² to 10⁵ Hz). The electrical conductivity results revealed a semiconductor behavior with increasing nickel concentration with a change in the slope at the transition temperature T_c. The variation of the dielectric parameters (?′, ?″ and tan(δ)) with frequency and temperature displayed a strong dependence on nickel concentration. Dielectric anomaly at the transition temperature T_c was pronounced in the relations of ?′ and ?″ with temperature. The determined T_c was found to increase with increasing Ni content. The relation of tan(δ) with frequency at different temperatures showed two relaxation processes where the relaxation time and maximum frequency of the hopping conduction mechanism were determined. The results are explained in the light of cation-anion-cation and cation-cation interactions over the octahedral site in the spinel structure.     

AC conductivity, density related and magnetic properties of Ni1 − xZnxFe2O4 ferrites with the variation of zinc concentration

AC conductivity, density related and magnetic properties are reported for Ni_1 − xZn_xFe₂O₄ ferrites with the variation of zinc concentration prepared by the standard solid state reaction technique. X-ray powder diffraction patterns confirmed the spinel structure of the prepared compounds. AC conductivity (lnσ_ac) increases from − 10.045 (S/m) to − 3.781 (S/m) with the increase in zinc concentration from 0.0 to 1.0 at the frequency of 1 kHz. Lattice parameters, sintered density and grain size increase whereas X-ray density and porosity decrease with the increase in zinc concentration. Saturation magnetization increases with the increase in zinc concentration up to x = 0.4 and after that it decreases with the increase in zinc concentration. Remanence magnetization and magnetic moment almost have the similar trend as that of saturation magnetization. Yafet-Kittel angles increase with the increase in zinc concentration. The possible reasons responsible for these changes are undertaken.     

Investigation of phase separation in the Ge x Cu1–x Fe2O4 system

The spinel series Ge _x Cu_1–x Fe₂O₄ (x=0.0 to 0.9) has been studied in detail by means of Mössbauer spectroscopy, X-ray diffraction and magnetization measurements at room temperature (298 K). Analysis of X-ray diffraction intensity data and Mössbauer intensity data suggest that this system remains in single phase up tox=0.4 then it phase separates into two different phases forx=0.5 to 0.9. Lattice constants of this system deviate from Vegard's law. Mössbauer spectra for x=0.0 to 0.4 suggest the existence of two hyperfine fields, one due to the Fe³⁺ tetrahedral ions (A-sites) and the other due to the Fe³⁺ octrahedral ions (B-sites), while forx=0.5 to 0.9 it gives Mössbauer patterns corresponding to two separate phases. The systematic composition dependence of quadrupole interactions and nuclear hyperfine fields of⁵⁷Fe³⁺ ions also support the concept of phase separation forx=0.5 to 0.9. The observed variation of⁵⁷Fe³⁺ hyperfine field on A- and B-sites withx forx=0.0 to 0.4 can be explained qualitatively on the basis of supertransferred hyperfine interactions.     

Decomposition of (Ti2xFe1−xSb1−x)O4 solid solutions below 1673 K

The pseudo-binary TiO₂-FeSbO₄ system was investigated by means of thermogravimetric analysis below 1673 K in O₂. Rutile-type solid solutions were synthesised at 1373 K in O₂ by means of a solid state reaction between the two pure end members TiO₂ (rutile) and FeSbO₄ mixed in stoichiometric amounts. Thermal stability of the (Ti_2xFe_1−xSb_1−x)O₄ solid solution increases with rutile content; equimolar (Ti_1.00Fe_0.50Sb_0.50)O₄ solid solutions decompose at about 1673 K forming a TiO₂-enriched solid solution and FeSbO₄, that subsequently decomposes into Fe₂O₃ (hematite) and a volatile Sb oxide, probably Sb₄O₆. For compositions characterised by higher Ti content the decomposition temperature is higher than 1673 K.     

X-ray Rietveld analysis and Fourier transform infrared spectra of the solid solutions [Eu2−xMx][Sn2−xMx]O7−3x/2 (M = Mg or Zn)

Two series of mixed oxides with formula [Eu_2−xM_x][Sn_2−xM_x]O_7−3x/2 (M = Mg or Zn) have been synthesized. The study by X-ray diffraction and Fourier transform infrared spectroscopy shows that the solids obtained are new non-stoichiometric solid solutions with the pyrochlore type structure. For both series a decrease of the cell parameter is observed when the degree of substitution, x, increases. The structural refinements (X-ray studies) were achieved in the space group Fd-3m, no. 227 (origin at center -3m) by using the Fullprof software. The Rietveld refinements show that the divalent cations M²⁺ (Mg²⁺, Zn²⁺) substitute isomorphically for Eu³⁺ and Sn⁴⁺ ions producing vacancies in the anionic sublattice.     

Magnetic and electrical properties of hot-pressed Ni-Zn-Li ferrites

The magnetic properties of Ni-Zn ferrites have been upgraded by preparing hot-pressed Ni_0.4Zn_0.6–2xLi_xFe_2+xO₄ ferrites wherein 2xZn²⁺ ions have been substituted byxLi¹⁺ andxFe³⁺ ions. This results in an increase of saturation magnetization, Curie temperature and dielectric constant, whereas resistivity and initial permeability are reduced. The values of saturation magnetization, Curie temperature and dielectric constant are improved due to hot pressing in which grain growth and densification are controlled simultaneously. The variations of saturation magnetization and Curie temperature can be explained by the preferential site occupancy of Li¹⁺ and Ni²⁺ ions at the tetrahedral site, sublattice magnetization with canted spin structure, and magnetic exchange interactions. The inferences drawn from the bulk magnetic properties of these ferrites conform with the conclusions drawn from variations of internal magnetic field, obtained from Mössbauer studies of these samples. The decrease in d.c. resistivity due to substitution of Li¹⁺ ions is attributed to increased hopping due to formation of Fe²⁺ and Ni³⁺ ions.     

Impact of transition metal doping on Mössbauer,electrical and dielectric parameters of structurally modified lithium ferrite nanomaterials

Zr–Mn doped spinel lithium ferrites Li_0.5Fe_2.5−2xZr_xMn_xO₄ (0.0 ≤ x ≤ 0.5) are synthesized using the citrate precursor method. The spinel ferrite is formed at a relatively lower annealing temperature (873 K) compared to those synthesized by other conformist methods. Powder X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis are carried out to determine the cell parameters, crystallite size and grain growth. Cation distribution and site preferences for the doped ions are determined by Mössbauer spectroscopy at room temperature. The impact of doping of Li_0.5Fe_2.5O₄ with the binary mixtures of transition metals (Mn, Zr) on hyperfine interaction parameters (δ, Δ and H_int), electrical resistivity (ρ), dielectric constant (?) and dielectric loss tangent (tan δ) over the frequency range of 100 Hz to 3 MHz is discussed in details. Zr–Mn doping enhanced the DC electrical resistivity and decreased the loss tangent value which is considered useful for technological application in microwave and telecommunication devices.     

Induced ferromagnetic metallic state and Griffiths phase in La1/2Ca1/2Mn1−xMoxO3 compounds

We have investigated the magnetic and transport properties of the La_0.5Ca_0.5Mn_1−xMo_xO₃ (0.0 ≤ x ≤ 0.1) compounds. Partial substitution of Mn by Mo destroys the charge-ordering (CO) phase and induces the ferromagnetic (FM) metallic transition at low temperatures in the samples. The thermo-magnetic irreversibility observed in both resistivity ρ (T) and magnetization M (T) curves suggest a competing scenario due to the coexistence of different phases in the Mo doped samples. In addition, a deviation from the Curie–Weiss behavior in the inverse susceptibility far above the Curie temperature (T_C) indicates the existence of Griffiths phase (GP) in the Mo-doped compounds. The above results can be interpreted based on the induced Mn²⁺ species by Mo substitution in the La_0.5Ca_0.5Mn_1−xMo_xO₃ system.     

SrSn1−xFexO3−δ (0≤x≤1) perovskites: a novel mixed oxide ion and electronic conductor

The electrical conductivity of SrSn_1−xFe_xO_3−δ increases with the Fe content and reaches a value of ∼10⁻¹ S/cm at 25°C at x=1. Compounds with low Fe content exhibit both ionic and electronic conductivity, while the higher Fe content perovskites are mainly electronic conductors with a conductivity independent of the oxygen partial pressure over a wide range from 0.21 to 10⁻²² atm.     

Dependence of optical properties on the composition of (Ba1−x−ySrxEuy)Si2O2N2 phosphors for white light emitting diodes

BaSi₂O₂N₂: Eu²⁺ is an efficient phosphor because of its high quantum yield and quenching temperature. Partial substitution of Ba²⁺ by Sr²⁺ is the most promising approach to tune the color of phosphors. In this study, a series of (Ba_1−x−ySr_xEu_y)Si₂O₂N₂ (x = 0.0–0.97, y = 0.00–0.10) phosphors are synthesized via high-temperature solid-state reactions. Intense green to yellow phosphors can be obtained by the partial substitution of the host lattice cation Ba²⁺ by either Sr²⁺ or Eu²⁺. The luminescent properties and the relationships among the lowest 5d absorption bands, Stokes shifts, centroid shifts, and the splitting of Eu²⁺ are studied systematically. Then, based on (Ba_1−x−ySr_xEu_y)Si₂O₂N₂ phosphors and near-ultraviolet (∼395 nm)/blue (460 nm) InGaN chips, intense green–yellow light emitting diodes (LEDs) and white LEDs are fabricated. (Ba_0.37Sr_0.60)Si₂O₂N₂: 0.03Eu²⁺ phosphors present the highest efficiency, and the luminous efficiency of white LEDs can reach 17 lm/w. These results indicate that (Ba_1−x−ySr_xEu_y)Si₂O₂N₂ phosphors are promising candidates for solid-state lighting.     

Synthesis and characterization of pyrochlore-type solid solutions Y2−xLaxRu2O7

New pyrochlore-type solid solutions Y_2−xLa_xRu₂O₇ have been synthesized for x=0.0, 0.1, 0.2, 0.3, 0.4, 0.5, and 0.6 as single-phase materials. The lattice parameters for these solid solutions are linear with x and range from 1.0140 nm (x=0.0) to 1.0257 nm (x=0.6). All the samples show semiconducting behavior with an activation energy of about 0.1 eV. They show the spin-glass-like magnetic transition at low temperatures. Its transition temperature T_G decreases from 77 K for Y₂Ru₂O₇ with increasing the La³⁺ content.     

Low temperature step magnetization and magnetodielectric study in Bi0.95La0.05Fe1−xZrxO3 ceramics

Single-phase, co-doped (La³⁺, Zr⁴⁺) in polycrystalline Bi_0.95La_0.05Fe_1−xZr_xO₃ (with x = 0, 0.02, 0.04 and 0.06) ceramics (particle size ∼650 nm; tolerance factor ∼0.883) were prepared by solid state reaction of oxides, followed by rapid quenching of samples. Enhanced magnetization was observed in co-doped (La³⁺, Zr⁴⁺) BiFeO₃ which may be ascribed to the collapse of the spiral spin structure. Step magnetization was observed in zero field cooled (ZFC) and field cooled (FC) curves. The coexistence of ferromagnetism and ferroelectricity has been confirmed in the co-doped (La³⁺, Zr⁴⁺) in BiFeO₃ ceramics by means of (M–H) and (P–E) loops measurements. Magnetodielectric properties have been observed at room temperature.     

Composition dependent thermoelectric properties of sintered Mg2Si1−xGex (x = 0 to 1) initiated from a melt-grown polycrystalline source

Fabrication of Mg₂Si_1−xGe_x (x = 0-1.0) was carried out using a spark plasma sintering technique initiated from melt-grown polycrystalline Mg₂Si_1−xGe_x powder. The thermoelectric properties were evaluated from RT to 873 K. The power factor of Mg₂Si_1−xGe_x with higher Ge content (x = 0.6-1.0) tends to decrease at higher temperatures, and the maximum value of about 2.2 × 10^− 5 Wcm^− 1K^− 2 was observed at 420 K for Mg₂Si and Mg₂Si_0.6Ge_0.4. The coexistence of Si and Ge gave rise to a decrease in the thermal conductivity in the Mg₂Si_1−xGe_x. The values close to 0.02 Wcm^− 1K^− 1 were obtained for Mg₂Si_1−xGe_x (x = 0.4-0.6) over the temperature range from 573 to 773 K, with the minimum value being about 0.018 Wcm^− 1K^− 1 at 773 K for Mg₂Si_0.4Ge_0.6. The maximum dimensionless figure of merit was estimated to be 0.67 at 750 K for samples of Mg₂Si_0.6Ge_0.4.     

Order-disorder phase transitions and high-temperature oxide ion conductivity of Er2+xTi2−xO7−δ (x = 0, 0.096)

The Er_2+xTi_2−xO_7−δ (x = 0.096; 35.5 mol% Er₂O₃) solid solution and the stoichiometric pyrochlore-structured compound Er₂Ti₂O₇ (x = 0; 33.3 mol% Er₂O₃) are characterized by X-ray diffraction (phase analysis and Rietveld method), thermal analysis and optical spectroscopy. Both oxides were synthesized by thermal sintering of co-precipitated powders. The synthesis study was performed in the temperature range 650-1690 °C. The amorphous phase exists below 700 °C. The crystallization of the ordered pyrochlore phase (P) in the range 800-1000 °C is accompanied by oxygen release. The ordered pyrochlore phase (P) exists in the range 1000−1200 °C. Heat-treatment at T ≥ 1600 °C leads to the formation of an oxide ion-conducting phase with a distorted pyrochlore structure (P2) and an ionic conductivity of about 10⁻³ S/cm at 740 °C. Complex impedance spectra are used to separately assess the bulk and grain-boundary conductivity of the samples. At 700 °C and oxygen pressures above 10⁻¹⁰ Pa, the Er_2+xTi_2−xO_7−δ (x = 0, 0.096) samples are purely ionic conductors.