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.     

XRD and Sn Mössbauer spectroscopy characterization of SnSe obtained from a simple chemical route

Crystalline tin selenide semiconductor was synthesized by a chemical route. Selenium powder reacted with potassium boronhydride, giving a soluble selenium species potassium seleniumhydride. The reaction of potassium seleniumhydride with tin chloride produced crystalline tin selenide, which was characterized by X-ray diffraction, ¹¹⁹Sn Mössbauer spectroscopy and scanning electronic microscopy. The material was thermally treated, in nitrogen flow, at 300 and 600 °C for 2 h and the particle size evolution was studied by X-ray diffraction. The X-ray diffraction and ¹¹⁹Sn Mössbauer results showed that a mixture of tin oxides and orthorhombic tin selenide was obtained.     

Transport properties and Mössbauer spectra of Fe-substituted La10−x(Si,Al)6O26 apatites

Increasing iron content in apatite-type La_9.83Si_4.5Al_1.5−yFe_yO_26+δ (y=0.5-1.5) leads to increasing unit cell volume, fraction of Fe⁴⁺, partial oxygen ionic and p-type electronic conductivities, and ceramics sinterability. The oxygen ion transference numbers, determined by Faradaic efficiency (FE) measurements at 973-1223 K in air, are in the range 0.986-0.994. Data on total conductivity and Seebeck coefficient as functions of the oxygen partial pressure, varying in the range 10⁻² Pa to 70 kPa, confirm that under oxidizing conditions the ionic conduction in Fe-substituted La_9.83(Si,Al)₆O_26+δ apatites is dominant. Due to stabilization of Fe³⁺, substantially worse transport properties are observed for A-site stoichiometric La₁₀Si₄Fe₂O₂₆, having activation energy for ionic conductivity of 107 kJ/mol and electron transference numbers close to 0.03. The correlation between partial ionic and electron-hole conductivities suggests a significant role of Fe⁴⁺ formation compensated by extra oxygen incorporation into the vacant sites, which are formed due to Frenkel-type disorder induced by La vacancies. The average thermal expansion coefficients of Fe-doped La_10−x(Si,Al)₆O_26+δ ceramics, calculated from dilatometric data in air, are 8.9×10⁻⁶ to 9.9×10⁻⁶ K⁻¹ at 300-1250 K.     

Mössbauer and magnetic studies of Mg1+2xSbxFe2−3xO4 spinel ferrites

Spinel-related Mg_1+2xSb_xFe_2−3xO₄ samples (x = 0.0, 0.05, 0.10, 0.15, 0.20, and 0.30) prepared using the conventional double sintering technique were investigated using ⁵⁷Fe Mössbauer spectroscopy and magnetic measurements. Mössbauer spectra favor a cationic distribution of the form (Mg_δFe_1−δ)^A[Mg_1+2x−δSb_xFe_1+δ−3x]^BO₄ among the tetrahedral-A and octahedral-B sites of the spinel structure. The cation distribution parameter (δ) was found to vary with the Sb⁵⁺ concentration (x). The Mössbauer hyperfine magnetic fields at both sites and the Curie temperatures of the ferrites decrease as x increases. This was attributed to gradual weakening in the magnetic exchange interaction as more Fe³⁺ ions are substituted by diamagnetic Sb⁵⁺ and Mg²⁺ ones. The sample with x = 0.30 exhibits short range magnetic order due to cationic clustering and/or superparamagnetism. The magnetization of all samples was found to be temperature-dependent implying that δ depends on temperature in addition to x. At low temperatures the substituted ferrites (x ≠ 0.0) unexpectedly exhibit higher magnetization values relative to that of the pure ferrite MgFe₂O₄. This behavior, while at variance with the Néel's model for ferrimagnetism, is explicable in terms of the spin canting mechanism proposed in the Yafet–Kittel model.     

Influence of structural transformations on functional properties of Fe75Ni2Si8B13C2 amorphous alloy

The influence of thermal treatment on functional properties of Fe₇₅Ni₂Si₈B₁₃C₂ amorphous alloy was investigated, showing the change that resulted from thermally induced structural transformations. Thermal history of the sample was found to have a significant effect on magnetic properties. Structural transformations were identified using DSC and thermomagnetic curve and characterized using Mössbauer spectroscopy and X-ray diffraction. Further investigation of magnetic and electrical properties of the alloy showed that structural relaxation prior to crystallization affected both magnetic susceptibility and electrical resistivity of the alloy, leading to an increase in both. This was caused by a confluence of stress relieving and a decrease in number of defects and an increase in free volume in the alloy sample, not only enabling greater mobility of magnetic domain walls, but also decreasing electron density of states at the Fermi level. Annealing at temperatures below crystallization caused an increase in magnetic susceptibility of the alloy at room temperature, however, a shift in Curie temperature was not observed. The alloy also exhibits a wide supercooled liquid region before crystallization, where its functional properties remained relatively constant, exhibiting the low values of both magnetic susceptibility and electrical conductivity.     

Mössbauer and magnetic study of Mn, Zr and Cd substituted W-type hexaferrites prepared by co-precipitation

BaCo_2−xMn_xFe_16−2y(Zr–Cd)_yO₂₇ (x = 0–0.5 and y = 0–1.0) hexaferrite nanocrystallites of average sizes in the range of 33–42 nm are synthesized by the chemical co-precipitation method. The synthesized materials are characterized using different techniques including X-ray diffraction (XRD), energy dispersive X-ray florescence (ED-XRF), scanning electron microscope (SEM), Mössbauer spectrometer and vibrating-sample magnetometer (VSM). Based on analysis of the data obtained from Mössbauer spectral studies, doping is believed to have occurred preferably in the vicinity of 12k sub-lattice, i.e. f_IV (4e, 4f_IV), 2b (6g, 4f) and 2d site. Variations in the saturation magnetization (77.1–60.9 emu g⁻¹), remanent magnetization (22.08–31.23 emu g⁻¹) and coercivity (1570.1–674.7 Oe) exhibit tunable behavior with dopant content and therefore can be useful for application in various magnetic devices.     

Mössbauer spectrometry study of early stage spinodal decomposition in Fe-Cr-Co alloy under high magnetic field

Local structure in a low-cobalt-type Fe-25Cr-12Co-1Si ferromagnetic alloy spinodal decomposed under an external magnetic field up to 120 kOe was investigated by Mössbauer spectrometry. The high magnetic field was found to significantly affect the local structure in the alloy formed at the early stage of phase decomposition. It was found that high magnetic field favors the acceleration of phase decomposition of ferromagnetic alloy at the early stage, resulting in the enhancement of average hyperfine field. The effect of high magnetic field on spinodal decomposition in ferromagnetic alloy was initially interpreted based on the free energy analyses.     

Synthesis, structure and magnetic properties of a new iron phosphonate-oxalate with 3D framework: [Fe(O3PCH3)(C2O4)0.5(H2O)]

A new iron phosphonate-oxalate [Fe(O₃PCH₃)(C₂O₄)_0.5(H₂O)] (1), has been synthesized under hydrothermal condition. The single-crystal X-ray diffraction studies reveal that 1 consists of layers of vertex-linked FeO₆ octahedra and O₃PC tetrahedra, which are further connected by bis-chelate oxalate bridges, giving to a 3D structure with 10-membered channels. Crystal data: monoclinic, P2₁/n (no. 14), a = 4.851(2) Å, b = 16.803(7) Å, c = 7.941(4) Å, β = 107.516(6)°, V = 617.2(5) Å³, Z = 4, R₁ = 0.0337 and wR₂=0.0874 for 1251 reflections [I > 2σ(I)]. Mössbauer spectroscopy measurement confirms the existence of high-spin Fe(III) in 1. Magnetic studies show that 1 exhibits weak ferromagnetism with T_N = 30 K due to a weak spin canting.     

A study of the influence of crystallite size on the electrical and magnetic properties of CuFe2O4

An attempt has been made to clarify the fundamental assumption that the properties of materials change as the crystallite size of the material is reduced below 100 nm. CuFe₂O₄ samples of different crystallite sizes were prepared by the sol–gel and combustion methods and then analyzed by X-ray diffraction (XRD), thermal analyses (TGA/DTG) and scanning electron microscopy (SEM) techniques. The magnetic properties were studied by measuring the AC magnetic susceptibility (χ) and the Mössbauer spectroscopy. The DC electrical resistivity, dielectric constant, dielectric loss tangent, Curie temperature and hyperfine splitting of the samples change with the crystallite size. The change in the electrical properties is attributed to the formation of discrete energy levels instead of the bands. However, the magnetic parameters change due to the existence of non magnetic surface layers. The isomer shift and the hyperfine splitting show gradual increase with the increase in crystallite sizes.     

Structural and magnetic properties of a mechanochemically activated Ti-Fe2O3 solid mixture

The mechanochemical effects on the reactivity and properties of a titanium/hematite powder mixture with molar ratio of 1/2 are investigated. Crystalline-phase structure, composition, hyperfine and magnetic behaviors were analyzed as a function of activation time by means of X-ray diffraction, scanning electron microscopy, Mössbauer spectroscopy and vibrating sample magnetometry. The results showed that at relatively short activation times metallic Ti reduces part of the ferric ions, yielding a complex product formed mainly by a mix of two solid solutions Fe_3−xTi_xO₄ (titanomagnetites), both with very different x values (0 < x < 1). Also metallic iron and superparamagnetic hematite particles were detected by Mössbauer spectroscopy. As the mechanical treatment extends the composition of the reactive mixture changes, prevailing in the end the solid solution with higher x value. In contrast, when these activated samples are thermally treated the fraction of the solid solution which is richer in Ti diminishes. This fact produces a significant variation of the saturation magnetization of the obtained material.     

Assessment of the optimum degree of Sr3Fe2MoO9 electron-doping through oxygen removal: An X-ray powder diffraction and Fe Mössbauer spectroscopy study

We describe the preparation and structural characterization by X-ray powder diffraction (XRPD) and Mössbauer spectroscopy of three electron-doped perovskites Sr₃Fe₂MoO_9−δ with Fe/Mo = 2 obtained from Sr₃Fe₂MoO₉. The compounds were synthesized by topotactic reduction with H₂/N₂ (5/95) at 600, 700 and 800 °C. Above 800 °C the Fe/Mo ratio changes from Fe/Mo = 2-1 < Fe/Mo < 2. The structural refinements of the XRPD data for the reduced perovskites were carried out by the Rietveld profile analysis method. The crystal structure of these phases is cubic, space group , with cationic disorder at the two different B sites that can be populated in variable proportions by the Fe atoms. The Mössbauer spectra allowed determining the evolution of the different species formed after the treatments at different temperatures and confirm that Fe ions in the samples reduced at 600, 700 and 800 °C are only in the high-spin Fe³⁺ electronic state.     

Eu-Mössbauer spectroscopic and X-ray diffraction study on EuyM1−yO2−x (0 ≤ y ≤ 1.0) (M = Th, U)

¹⁵¹Eu-Mössbauer spectroscopic and powder X-ray diffraction (XRD) study has been performed for the Eu_yM_1−yO_2−x (M = Th and U) systems over the entire composition range of 0 ≤ y ≤ 1.0. The XRD results of the Eu-Th system showed that a very wide defect-fluorite (DF) type phase in which oxygen vacancies (V_O) are disordered (x = y/2) is formed for 0 ≤ y < 0.5 and that two-phase regions sandwitching a narrow C-type (C) single phase around y ≈ 0.8 appear for 0.5 < y < 0.8 (DF + C) and 0.82 < y < 1.0 (C + B-type (monoclinic) Eu₂O₃). The Mössbauer results show that the isomer shifts (ISs) of Eu³⁺ in this system smoothly increase with Eu composition, y. The decrease of average coordination number (CN) of O²⁻ around Eu³⁺ with increasing y (CN = 8 − 2y) (x = y/2) results in the decrease of the average EuO bond length, which is due to the decrease of repulsion force between O²⁻ anions. This result confirms that the IS of Eu³⁺ correlates well with the average EuO bond length in oxide systems. For the Eu-U system, the lattice parameter, a₀, of the system decreases almost linearly with y, in accordance with the calculated a₀ versus y curve for the oxygen-stoichiometric (i.e. x = 0) fluorite-type dioxide (CN = 8). The ISs of Eu³⁺ in this composition range remain almost constant around 0.5 mm/s, which is comparable to those of pyrochlore oxides (Eu₂Zr₂O₇ and Eu₂Hf₂O₇ (y = 0.5)) with O²⁻-eight-fold coordinated Eu³⁺(CN = 8).     

Structural, thermal, magnetic and electrical studies of the iron oxophosphate Rb7Fe7(PO4)8O2·2H2O

A new iron oxophosphate of composition Rb₇Fe₇(PO₄)₈O₂·2H₂O has been synthesized and studied by X-ray diffraction, TG and DTA analysis, magnetic susceptibility, neutron diffraction, Mössbauer spectroscopy and ionic conductivity. This compound crystallizes in the monoclinic system with the P2₁/c space group and the unit cell parameters a = 8.224(8) Å, b = 22.162(6) Å, c = 9.962(6) Å and β = 109.41(8)°. Its structure is built up from Fe₇O₃₂ clusters of edge- and corner-sharing FeO₅ and FeO₆ polyhedra. Neighboring clusters are connected by the phosphate tetrahedra to form a three-dimensional framework. The Rb⁺ cations and the water molecules are occupying intersecting tunnels parallel to a and c. The presence of water molecules was confirmed by TG and DTA analysis. The magnetic susceptibility measurements have shown the existence of antiferromagnetic ordering below 22 K with a weak ferromagnetic component. Additionally, these measurements show evidence for a strong magnetic frustration characterized by |θ/T_N| ≈ 12. Powder neutron diffraction study confirms the presence of a long range antiferromagnetic order coupled to a weak ferromagnetic component along the b-axis. The strongly reduced magnetic moments extracted from the refinement support the existence of a magnetically frustrated ground state. The Mössbauer spectroscopy results confirmed the presence of only Fe³⁺ ions in both five and six coordination. The ionic conductivity measurements led to activation energy of 0.81 eV, a value that agrees with the obtained for other rubidium phosphates.     

Structural properties and Mössbauer spectra of metastable NdFe12B6

Metastable ternary NdFe₁₂B₆ compound was prepared by the annealing of the amorphous Nd-Fe-B ribbons and has a main phase of NdFe₁₂B₆ with some impurities of α-Fe and Nd₅Fe₁₈B₁₈. The NdFe₁₂B₆ was found to have a SrNi₁₂B₆ structure with space group R3¯m. Mössbauer spectra of the sample were measured between 300 K and 20 K. The result indicated that an abrupt drop with increasing temperature took place at about 205 K for the hyperfine field at both Fe(18 g) and Fe(18 h) sites. The corresponding hyperfine fields were found nearly constant at ferromagnetic state about 16.9(6) T and 19.3(5) T for Fe(18 g) and Fe(18 h) sites, respectively. Accordingly, the relative size of the Fe moments was deduced.     

Synthesis and electrical properties of ordered perovskite oxide Cd3−x−yCuxAyTeO6 (A = Li, Na; 0.00 ≤ x, y ≤ 0.15)

Polycrystalline Cd_3−x−yCu_xA_yTeO₆ (A = Li, Na) samples were prepared by solid-state reaction, and their crystal structure and electrical properties were investigated. In Cd_3−xCu_xTeO₆ and Cd_3−yA_yTeO₆ (A = Li, Na), the maxim solubility of x and y was 0.15 and 0.15 for A = Li, 0.05 for A = Na, respectively. For co-substituted samples Cd_2.9−yCu_0.1Li_yTeO₆ and Cd_2.9−yCu_0.1Na_yTeO₆, the maxim solubility of x was the same as single substitution above-mentioned. The alkali-metal substituted samples Cd_3−yA_yTeO₆ (A = Li, Na) showed a negative Seebeck coefficient, which indicates that the major conduction carriers are electron. On the other hand, the co-substituted samples Cd_2.9−yCu_0.1A_yTeO₆ (A = Li, Na) represented a positive Seebeck coefficient, and major conduction carriers were hole through substitution by copper ions.     

Mechanosynthesis and magnetic properties of nanocrystalline LaFeO3 using different iron oxides

The synthesis of the orthoferrite LaFeO₃ using high-energy ball-milling of La₂O₃ and Fe₃O₄ or α-Fe₂O₃ oxides and subsequent thermal treatments of resulting powders was studied. The phase evolution during the mechanical treatment was analyzed by X-ray diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy (SEM). Also, magnetic properties of the obtained materials were measured at room temperature by vibrating sample magnetometry (VSM). From 30 min of mechanochemical activation the gradual disappearance of reactants and the formation of LaFeO₃ were observed. For both reactive mixtures the reaction was completed after 3 h of milling. Magnetic hysteresis loops of these mechanoactivated samples showed a significant ferromagnetic component in LaFeO₃. This behavior was interpreted on the basis of a spin-canting effect induced by the mechanochemical treatment. Thermal treatments allowed the relaxation of the distorted structure, resulting in the formation of the conventional antiferromagnetic LaFeO₃ phase.     

Nanocrystallization kinetics of amorphous Fe81B13.5Si3.5C2 magnetic ribbons

The kinetics of the nanocrystallization of amorphous Fe₈₁B_13.5Si_3.5C₂ ribbon is studied. The changes in the microstructures and magnetic properties of ribbons annealed at 425 and 495 °C for 0.5-10 h were investigated using an X-ray diffractometer (XRD), Mössbauer spectroscopy (MS), differential scanning calorimeter (DSC) and vibrating sample magnetometer (VSM). The changes in the surface morphology were observed by a changed atomic force microscope (AFM). The XRD patterns and the Mössbauer spectrums show the formation of nanocrystallites of α-Fe(Si), Fe-B, Fe₃C and Fe₃Si of different grain sizes when annealed at different temperatures. The nanocrystallization kinetics of the Fe₈₁B_13.5Si_3.5C₂ ribbon are described by an Avrami growth curve with an exponent values of 1.34 and 1.01 for the isothermal annealing at 425 and 495 °C, respectively. AFM topography pictures and surface image show that the density of the microstructure and the size of the grain increase as higher annealing temperatures are used.     

Structural and magnetic properties of glass-ceramics containing silver and iron oxide

Glass-ceramics with a nominal composition of 25SiO₂–(50 − x)CaO–15P₂O₅–8Fe₂O₃–2ZnO–xAg (where x = 0, 2 and 4 mol%) have been prepared. Structural features of glass-ceramics have been investigated using X-ray diffraction (XRD) and scanning electron microscope (SEM) techniques. Magnetic properties were studied using vibrating sample magnetometer and Mössbauer spectroscopy. Ca₃(PO₄)₂, hematite and magnetite are formed as major crystalline phases. The microstructure reveals the formation of 25–30 nm size particles. Mössbauer spectroscopy has shown the relaxation of magnetic particles. Saturation magnetization value is increased with an increase of Ag content up to 4 mol%, which has been attributed to the formation of magnetically ordered particles. The antibacterial response was found to depend on Ag ions concentration in the glass matrix and samples with 4 mol% Ag in glass matrix have shown effective antibacterial activity against Escherichia coli.     

Pyrochlore type semiconducting ceramic oxides in Ca-Ce-Ti-M-O system (M = Nb or Ta)—Structure, microstructure and electrical properties

A new series of pyrochlore type ceramic semiconducting oxides in Ca-Ce-Ti-M-O (M = Nb or Ta) system has been synthesized by the conventional ceramic route. The electrical conductivity measurements show that these oxides exhibit semiconducting behavior and the conductivity increases with the Ce content in the compound. Activation energy of the current carriers is in the range of 0.5-1.6 eV. The electrical conductivity in these oxides is due to the presence of Ce³⁺, which remains in the reduced state without being oxidized to Ce⁴⁺ by structural stabilization. The photoluminescence and X-ray photoelectron spectroscopy analysis corroborate the presence of Ce in the 3+ state. Impedance spectral analysis is carried out to evaluate the transport properties and indicates that the conduction in these compounds is mainly due to electronic contribution. The X-ray powder diffraction and Raman spectroscopy analysis establishes that these oxides belong to a cubic pyrochlore type structure.     

The Morin transition in nanostructured pseudocubic hematite: Effect of the intercrystallite magnetic exchange

The Morin transition in α-Fe₂O₃ particles with homogeneous pseudocubic morphology of about 1.8 μm side has been studied by different techniques. The particles are made up of nanometric crystallites with a narrow size distribution. Samples annealed at 673, 773 and 873 K, yielded Morin transition temperatures, T_M, of about 230, 241, and 245 K, respectively, which are lower than the bulk value, T_M ≈ 263 K. In addition, the temperature range ΔT_M through which these samples undergo the transition is very narrow with respect to the values reported in the literature. Ranges of 20, 10 and 8 K, were obtained for the samples annealed at 673, 773 and 873 K. In this work, through the estimation of the exchange magnetic energy, we demonstrate that the existence of the Morin transition, and its shift and breadth are related to the presence of intercrystallite interactions within the pseudocubic particles. These intercrystallite interactions are modified by the annealing treatments, which help to remove non-stoichiometric hydroxyl groups and incorporated water molecules.