Analysis of magnetic disaccommodation in La-Co-substituted strontium ferrites

M-type strontium ferrites substituted by La³⁺-Co²⁺(Sr_1−xLa_xFe_12−xCo_xO₁₉) were prepared by ceramic process. Effects of the substituted amount of La³⁺ and Co²⁺ on structure and magnetic properties of Sr_1−xLa_xFe_12−xCo_xO₁₉ compounds have systematically been investigated by X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and magnetic disaccommodation. In the measurement range from 80 to 500 K, the magnetic disaccommodation is represented by means of isochronal curves. It is well known that magnetic disaccommodation cannot be obviously found in the M-type of pure strontium ferrites. However, three peaks were observed in Sr_1−xLa_xFe_12−xCo_xO₁₉, and this behavior is explained in terms of the presence of Fe²⁺ cation and to the site occupation by the magnetic Co²⁺ ionic within the hexagonal structure.     

Research on La–Co-substituted strontium ferrite magnets for high intrinsic coercive force

M-type strontium ferrites with substitution of Sr²⁺ by rare-earth La³⁺, and a little amount of Fe³⁺ by Co²⁺ according to the formula Sr_1−xLa_xFe_12−xCo_xO₁₉, are prepared by the ceramic process. Effects of the substituted amount of La³⁺ and Co²⁺ on structure and magnetic properties of Sr_1−xLa_xFe_12−xCo_xO₁₉ compounds have systematically been investigated by X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and B–H hysteresis curve measurements. In our results, the suitable amount of La³⁺–Co²⁺ substitution may remarkably increase saturation magnetization. Intrinsic coercive force (H_cj) of Sr ferrite magnets is evidently increased without significant decrease in residual flux density (B_r) by La³⁺–Co²⁺ substitution.     

Synthesis and magnetic properties of La-substituted M-type Sr hexaferrites

Single-phase M-type hexagonal ferrites Sr_1−xLa_xFe₁₂O₁₉ (0≤x≤1) were prepared by a ceramic route. The stability limits of the ferrite phases were determined with a combination of various microscopy techniques, electron-probe micro-analysis, powder X-ray diffraction and thermal analysis. SrFe₁₂O₁₉ (x=0) is stable up to 1420 °C, whereas LaFe₁₂O₁₉ (x=1) exists between 1360 and 1400 °C only. The lattice parameters of Sr_1−xLa_xFe₁₂O₁₉ exhibit a linear variation with x, i.e. a₀ slightly increases and c₀ decreases with x, leading to a decrease of the unit cell volume with x. The saturation magnetization at T=5 K decreases with increasing La concentration. Room temperature Mössbauer analysis shows that the Fe³⁺/Fe²⁺ valence change occurs in the 2a sites for the whole composition range.     

Complex permittivity and complex permeability of Sr ions substituted Ba ferrite at X-band

M-type hexagonal ferrite composition, Ba_(1−x)Sr_xFe₁₂O₁₉ (x=0.0, 0.2, 0.4, 0.6, 0.8 and 1.0), was prepared by a two route ceramic method. Complex permittivity (ε′−jε″) and complex permeability (μ′−jμ″) have been measured using a network analyzer from 8.2 to 12.4 GHz X-ray diffraction confirmed the M-type hexagonal structure and a scanned electron micrograph was used to analyze the grain size distribution of ferrite. Substitution of Sr²⁺ ions causes an increase in porosity that deteriorates the electromagnetic and microstructural properties in the doped samples. Both dielectric constant and dielectric loss are enhanced in comparison to the permeability and magnetic loss over the entire frequency region. This is due to a resistivity variation and the formation of Fe²⁺ ions, which increases the hopping mechanism between Fe²⁺ and Fe³⁺ ions.     

Electrical conductivity and structural stability of SrCo1−xFexO3−δ

Perovskite compounds in the system of SrCo_1−xFe_xO_3−δ (x=0.2, 0.4 and 0.6) were synthesized by solid state reaction. SrCo_1−xFe_xO_3−δ shows the p-type small polaron conduction behavior. Electrical conductivity and oxygen vacancy content decrease with increase in Fe content. The incorporation of Fe increases the structural stability of SrCo_1−xFe_xO_3−δ at low temperatures, while decreasing the structural stability at high temperatures. Oxygen partial pressure has a strong influence on electrical conductivity. At low oxygen partial pressure, SrCo_0.8Fe_0.2O_3−δ will transform from cubic to orthorhombic structure. This structure can remain in 5%H₂/Ar only for a short time and then dissociates into Sr₃Fe₂O_6.64 and Co due to the reduction of B-site elements.     

High temperature ferromagnetism of the vacuum-annealed (In1−xFex)2O3 powders

(In_1−xFe_x)₂O₃ (x = 0.02, 0.05, 0.2) powders were prepared by a solid state reaction method and a vacuum annealing process. A systematic study was done on the structural and magnetic properties of (In_1−xFe_x)₂O₃ powders as a function of Fe concentration and annealing temperature. The X-ray diffraction and high-resolution transmission electron microscopy results confirmed that there were not any Fe or Fe oxide secondary phases in vacuum-annealed (In_1−xFe_x)₂O₃ samples and the Fe element was incorporated into the indium oxide lattice by substituting the position of indium atoms. The X-ray photoelectron spectroscopy revealed that both Fe²⁺ and Fe³⁺ ions existed in the samples. Magnetic measurements indicated that all samples were ferromagnetic with the magnetic moment of 0.49-1.73 μ_B/Fe and the Curie temperature around 783 K. The appearance of ferromagnetism was attributed to the ferromagnetic coupling of Fe²⁺ and Fe³⁺ ions via an electron trapped in a bridging oxygen vacancy.     

Magnetic properties of La-Co substituted M-type strontium hexaferrites prepared by polymerizable complex method

Magnetic properties of La-Co substituted M-type strontium hexaferrites were studied. The samples were prepared by polymerizable complex method. Crystal structure of samples has been investigated by powder X-ray diffraction (XRD). Single-phase M-type strontium hexaferrites with chemical composition of Sr_1.05−xLa_xFe_12−xCo_xO₁₉ (x=0-0.4) were formed by heating at 1173 K for 24 h in air. Magnetic properties were discussed by measurements of M-H curves with vibrating sample magnetometer (VSM). La-Co substituted M-type strontium hexaferrites prepared by polymerizable complex method showed typical magnetic hysteresis of hard ferrite. The coercive force increased significantly by La-Co substitution with polymerizable complex method. Maximum coercive force achieved in this study is 8.0 kOe (640 kA/m). Scanning electron microscopy revealed that the prepared ferrite particles have plate-like shape of diameter range between 20 and 500 nm.     

The influence of Nd-Co substitution on the magnetic properties of non-stoichiometric strontium hexaferrite nanoparticles

Non-stoichiometric Nd-Co substituted hexaferrites of composition Sr_1−xNd_xFe_12(1−x)Co_xO₁₉ (x=0-0.4) were prepared by the self-propagating combustion method and subsequent heat treatments. Structural characterization of samples showed that the M-type hexagonal structure can be maintained for substitutions x<0.4 without the segregation of secondary phases on samples calcined at 1100 °C. The crystallites sizes range between 50 and 70 nm. Mössbauer spectroscopy results indicate that the iron vacancies are not evenly distributed over the lattice and that Co/Fe substitution mainly takes place in site 4f2. Magnetic measurements reveal that values of saturation magnetization M_S increased from 72 to 76 Am²/kg (x=0-0.2), while coercivity H_c increased from 26.40 to 58.70 A/m (x=0-0.3). Nd-Co substitutions enhance magnetic properties in deficient iron Sr hexaferrites.     

An investigation on microstructural,spectral and magnetic properties of Pr–Cu double-substituted M-type Ba–Sr hexaferrites

This is first report on Pr–Cu double-substituted M-type Ba–Sr hexaferrites with nominal compositions Ba_0.3Sr_0.7−xPr_xFe_12.0−xCu_xO₁₉ (x = 0.00–0.35) fabricated by the solid-state reaction route. X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FE-SEM) and Hysteresis graph meter were used to characterize the synthesized M-type Ba–Sr hexaferrites. XRD results show that the hexaferrites with x ≤ 0.21 exhibited single M-type phase, while the hexaferrites with x ≥ 0.28 exhibited the M-type phase and impurity phases. FE-SEM images proposed that all particles with hexagonal platelet-like shape were homogeneously dispersed. The remanence (B_r) first increased with Pr–Cu content (x) from 0.00 to 0.14, and then decreased when x ≥ 0.14. The intrinsic coercivity (H_cj) and magnetic induction coercivity (H_cb) first decreased with x from 0.00 to 0.14, and then increased when x ≥ 0.14. Maximum energy product [(BH)_max] reached the maximum value at x = 0.14.     

Changes of microstructure and magnetic properties of Nd-Fe-B sintered magnets by doping Al-Cu

The microstructural and magnetic properties of Al_100−xCu_x (15at%≤x≤45 at%) doped Nd-Fe-B magnets were studied. The distribution and alloying effects of Cu or Al on the intergranular microstructure were investigated by thermodynamic analysis, differential scanning calorimetery and microscopy techniques. It was observed that when the Cu content of Al_100xCu_x exceeds to 25 at%, the (Pr, Nd)Cu and CuAl₂ phases form in these magnets. The formation of (Pr, Nd)Cu phase depends on the negative formation enthalpy of (Pr, Nd)Cu and the exclusive distribution of Cu in the intergranular regions. The eutectic reaction between (Pr, Nd)Cu phase and (Pr, Nd) occurs at 480 °C, which forms the liquid phase that dissolves the (Pr, Nd)₂Fe₁₄B surface irregularities and thus increases the quantities of (Pr, Nd)-rich phase at the grain boundaries. These changes benefit the grain boundary microstructure, especially the distribution of (Pr, Nd)-rich phase, which effectively improves the intrinsic coercivity _iH_c due to the decreases of exchange coupling between the (Pr, Nd)₂Fe₁₄B grains.     

Influences of La3+ substitution on the structure and magnetic properties of M-type strontium ferrites

M-type strontium ferrites with substitution of Sr²⁺ by rare-earth La³⁺, according to the formula Sr_1−xLa_xFe₁₂O₁₉, are prepared by the ceramic process. Influences of the substituted amount of La³⁺ on structure and magnetic properties of Sr_1−xLa_xFe₁₂O₁₉ compounds have systematically been investigated by XRD, VSM and Mössbauer spectrum. When the substituted amount x is below 0.30, X-ray diffraction shows that the samples are single M-type hexagonal ferrites. It is found that the suitable amount of La³⁺ substitution may remarkably increase saturation magnetization σ_s and intrinsic coercivity H_cJ. With the La³⁺ addition for the same sintering temperature, σ_s and H_cJ increase at first, then decrease gradually. However, the substituted amount x at the maximum value of H_cJ is bigger than that of σ_s. Mössbauer spectroscopy of ⁵⁷Fe in Sr_1−xLa_xFe₁₂O₁₉ has shown that the substitution of Sr²⁺ by La³⁺ is associated with a valence change of Fe³⁺ to Fe²⁺ at 2a or 4f₂ site. The magnetic properties are reflected in the Mössbauer spectra which indicate that the magnetic hyperfine field (H_hf) is detected with the highest value at x=0.20. The different exchange paths between the iron sublattices are discussed according to the increased hyperfine fields of the 12k- and 2b-site. The Curie temperature of Sr_1−xLa_xFe₁₂O₁₉ decreases linearly with increasing La³⁺ substitution.     

Magnetic and Microwave Absorbing Properties of Electrospun Ba(1−x)LaxFe12O19 Nanofibers

Ba_(1−x)La_xFe₁₂O₁₉ (0.00≤x≤0.10) nanofibers were fabricated via the electrospinning technique followed by heat treatment at different temperatures for 2 h. Various characterization methods including scanning electron microscopy (SEM), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), and microwave vector network analyzer were employed to investigate the morphologies, crystalline phases, magnetic properties, and complex electromagnetic parameters of nanofibers. The SEM images indicate that samples with various values of x are of a continuous fiber-like morphology with an average diameter of 110±20 nm. The XRD patterns show that the main phase is M-type barium hexaferrite without other impurity phases when calcined at 1100 °C. The VSM results show that coercive force (H_c) decreases first and then increases, while saturation magnetization (M_s) reveals an increase at first and then decreases with La³⁺ ions content increase. Both the magnetic and dielectric losses are significantly enhanced by partial substitution of La³⁺ for Ba²⁺ in the M-type barium hexaferrites. The microwave absorption performance of Ba_0.95La_0.05Fe₁₂O₁₉ nanofibers gets significant improvement: The bandwidth below −10 dB expands from 0 GHz to 12.6 GHz, and the peak value of reflection loss decreases from −9.65 dB to −23.02 dB with the layer thickness of 2.0 mm.     

Preparation and properties of disordered NaBi(XO4)2, X=W or Mo, crystals doped with rare earths

NaBi_1−xRE_x(XO₄)₂, X=W or Mo and RE=Pr, Nd, Ho, Er and Yb single crystals have been grown by the Czochralski technique. Rare earth concentrations about 3.5×10²⁰ cm⁻³ have been achieved in crystals with good optical quality. Melt stability is obtained by synthesising NaBi(XO₄)₂ from the precursor Na₂X₄O₁₃ phase and minimising Mo volatility. The strength of W and Mo compounds to chemical attack and thermal annealing in several atmospheres is reported. Mo compound is etched by inorganic acids and becomes coloured after vacuum annealing. The optical absorption, photoluminescence and refractive indices of the hosts are characterised and show a dichroic character. The lattice disorder induces broadening of the 10 K optical absorption of the rare earth impurities.     

Improving magnetic properties of barium hexaferrites by La or Pr substitution

La or Pr substituted barium hexaferrites, Ba_1−x(La or Pr)_xFe₁₂O₁₉, x=0.00-0.20, were successfully prepared by a citrate combustion process. The sintered bodies were structurally and magnetically studied by powder X-ray diffraction (XRD) and vibrating sample magnetometry (VSM). All XRD patterns show the single phase of the magnetoplumbite barium ferrite without other intermediate phases. Magnetization (M_S) and coercive field (H_C) could be improved by substitutions of La or Pr ions on Ba ion basis sites. The M_S reveal magnetic behavior with respect to La or Pr ions content, showing an increase at first and then a decrease. The H_C increases remarkably with increasing La or Pr ions content.     

Li0.5Fe2.5−xMnxO4 ferrite sintered from microwave-induced combustion

Li_0.5Fe_2.5−xMn_xO₄ (0≦x≦1.0) powders with small and uniformly sized particles were successfully synthesized by microwave-induced combustion, using lithium nitrate, ferric nitrate, manganese nitrate and carbohydrazide as the starting materials. The process takes only a few minutes to obtain as-received Mn-substituted lithium ferrite powders. The resultant powders annealed at 650 ^°C for 2 h and were investigated by thermogravimeter/differential thermal analyzer (TG/DTA), X-ray diffractometer (XRD), transmission electron microscopy (TEM), vibrating sample magnetometer (VSM), and thermomagnetic analysis (TMA). The results revealed that the Mn content were strongly influenced the magnetic properties and Curie temperature of Mn-substituted lithium ferrite powder. As for sintered Li_0.5Fe_2.5−xMn_xO₄ specimens, substituting an appropriate amount of Mn for Fe in the Li_0.5Fe_2.5−xMn_xO₄ specimens markedly improved the complex permeability and loss tangent.     

Synthesis and characterization of room-temperature ferromagnetism in Fe- and Ni-co-doped In2O3

Observation of room-temperature ferromagnetism in Fe- and Ni-co-doped In₂O₃ samples (In_0.9Fe_0.1−xNi_x)₂O₃ (0?x?0.1) prepared by citric acid sol-gel auto-igniting method is reported. All of the samples with intermediate x values are ferromagnetic at room-temperature. The highest saturation magnetization (0.453 μ_B/Fe+Ni ions) moment is reached in the sample with x=0.04. The highest solubility of Fe and Ni ions in the In₂O₃ lattice is around 10 and 4 at%, respectively. The 10 at% Fe-doped sample is found to be weakly ferromagnetic, while the 10 at% Ni-doped sample is paramagnetic. Extensive structure including Extended X-ray absorption fine structure (EXAFS), magnetic and magneto-transport including Hall effects studies on the samples indicate the observed ferromagnetism is intrinsic rather than from the secondary impurity phases.     

Occurrence of re-entrant ferromagnetic transitions in rare-earth manganates on cooling the charge-ordered states

Some of the compositions of the half-doped rare-earth manganates, La_0.5−xLn_xCa_0.5MnO₃ (Ln=Nd, Pr) and Nd_0.5Ca_0.5−xSr_xMnO₃ with relatively small A-cation radii, 〈r_A〉, show an unusual behavior wherein they become ferromagnetic (FM) on cooling the charge ordered (CO) state (T_CO>T_C). With increase in 〈r_A〉, however, the T_C becomes greater than T_CO. Thus, plots of T_C and T_CO against 〈r_A〉 for La_0.5−xLn_xCa_0.5MnO₃ (Ln=Nd, Pr) and Nd_0.5Ca_0.5−xSr_xMnO₃ show cross-over from the T_CO>T_C regime to the T_C>T_CO regime around 〈r_A〉 values of 1.195±0.003 and 1.200±0.005 Å, respectively. Between T_C and T_CO, the CO and FM phases are likely to coexist. In Nd_0.5Ca_0.5Mn_1−xM_xO₃ (M=Cr, Ru), T_CO>T_C when x≤0.10, suggesting the re-entrant nature of the FM transition.     

Fluorination of perovskite-related phases of composition La1−xSrxFe1−yCoyO3−δ

We report here on the fluorination of the perovskite-related phases La_1−xSr_xFe_1−yCo_yO_3−δ. The introduction of fluorine in place of oxygen is achieved through a low-temperature (400 °C) reaction with poly(vinylidene fluoride). X-ray powder diffraction data show that in all cases the fluorination leads to an expansion in the unit cell, which is consistent with partial replacement of oxygen by fluorine and consequent reduction in the oxidation state of iron and/or cobalt. This reduction in oxidation state is confirmed by X-ray absorption- and Mössbauer-spectroscopy. The Mössbauer spectra show complex magnetically split hyperfine patterns for the fluorinated samples, reflecting the interactions between Fe³⁺ ions, which are not possible in oxides containing Fe⁴⁺.     

The effect of La-substitution on magnetic properties of nanosized Sr1−xLaxTi0.05Zn0.2(Fe)11.75−δ(Fe)δO19 powders

A series of La-substituted M-type Sr hexaferrite powders Sr_1−xLa_xTi_0.05Zn_0.2Fe³⁺_11.75O₁₉, wherein x ranges from 0.1 to 0.5 with a step of 0.1, have been prepared by the conventional ceramic method and were then milled in a high energy mill to prepare nanosized powders. XRD investigation of the calcined and the milled powders shows that single phase hexaferrite structure has been formed after calcining and has not changed after milling. The lattice parameters and the mean crystallite sizes of the samples have been determined from the XRD data and Scherrer's formula. The results show that the lattice parameters (“а” and “c”) decrease with increase in La-substitution and the mean crystallite size of the milled powders is about 17 nm. Coercivities and magnetizations of the samples in a magnetic field of 16 kOe have been determined from the room temperature hysteresis loops. It was found that both parameters increase with La substitutions up to 0.3 and then decrease for higher substitutions. These variations were attributed to the enhancement of hyperfine field and spin-canting magnetic structure when La content increases. In addition, the magnetizations were smaller for the nanosized samples in comparison with those of bulk ones, which were discussed according to the core-shell model. Also the results show that annealing of the nanosized samples up to 500 °C can enhance coercivity and magnetization of the samples, which is discussed based on crystallite size growth.     

Structure and magnetic properties of (Nd,Dy)16(Fe,Co)76−xTixB8 powders prepared by mechanical alloying

Nanocrystalline (Nd,Dy)₁₆(Fe,Co)_76−xTi_xB₈ magnets were prepared by mechanical alloying and respective heat treatment at 973–1073 K/30–60 min. An addition of 0.5 at % of Ti results in an increase of coercivity from 796 to 1115 kA m⁻¹. Partial substitution of Nd by Dy results in an additional increase of coercivity up to 1234 kA m⁻¹. Mössbauer investigations shows that for x?1 the (Nd,Dy)₁₆(Fe,Co)_76−xTi_xB₈ powders are single phase. For higher Ti contents (x>1) the mechanically alloyed powders heat treated at 973 K are no more single phase, and the coercivity decreases due to the presence of an amorphous phase. A heat treatment at a higher temperature (1073 K) for longer time (1 h) results in the full recrystallisation of powders. The mean hyperfine field of the Nd₂Fe₁₄B phase decreases for titanium contents of 0?x?1, and remains constant for x>1. This indicates that the Ti content in the Nd₂Fe₁₄B phase reaches its maximum value.