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.     

Effects of In-substitution on the structure and magnetic properties of multi-doped YIG ferrites with low saturation magnetizations

Multi-doped YIG ferrites {Y_1.7Gd_0.5Ca_0.8}[Fe_2−xIn_x](Fe_2.15V_0.4Mn_0.05Al_0.4)O₁₂ (x=0, 0.3, 0.6, 0.7, 0.8 and 0.9) with low saturation magnetizations (4πM_s=400-600 G at 298 K) were prepared by a conventional ceramic technology and the effects of In³⁺-substitution on their structures and magnetic properties were systematically investigated using XRD, SEM and VSM. It has been found that as-synthesized powders and sintered ferrites showed a single-phase of garnet structure with a cell parameter (a) that increased linearly with increase in In³⁺ concentration from x=0 up to 0.9. Apparent relative densities of sintered samples were all over 98%, but no remarkable influences of In³⁺-substitution were observed by SEM on the refinement of crystal grains and the enhancement of sintering of ferrites. In addition, the Curie temperature T_c decreased almost linearly as In³⁺concentration increased, while the corresponding saturation magnetization at room temperature presented a variation characterized by a gradual increase first and then a rapid plunge. On the basis of quantitative analysis of XRD data and the theory on super-exchange interactions, it has been established that the incorporated In³⁺ ions via doping were exclusively located at the sites with octahedral coordinations in the crystal structure and the aforementioned magnetic properties can be simply attributed to weakening super-exchange interactions between neighboring magnetic ions through oxygen ions due to the “dilution effect” of added non-magnetic In³⁺ ions.     

Indium doping effect on the magnetic properties of Y-type hexaferrite Ba0.5Sr1.5Zn2(Fe1-xInx)12O22

The effect of indium doping on structural and magnetic properties of Y-type hexaferrite Ba_0.5Sr_1.5Zn₂(Fe_1-xIn_x)₁₂O₂₂ (x = 0, 0.02, 0.04, 0.06, 0.08 and 0.1) prepared by the solid state reaction method was investigated. The Rietveld refinement method was used to analyze the X-ray diffraction patterns. The magnetic transition temperatures associated with the proper-screw spin phase to the collinear ferrimagnetic spin phase transition can be efficiently modulated by varying indium content. The magnetic transition temperature increases to a maximum with indium content x = 0.04 and then decreases with x, suggesting the possibility that electrically controlled magnetization reversal can be can be effectively tailored by varying indium content. The saturation magnetization at room temperature was decreased as increasing indium content, which can be explained as the metal ions occupation. It is worthy to note that the coercivity of In-doped samples was decreased drastically compared that of undoped sample, which is probably resulted from the reduction in anisotropy field with substitution of In³⁺ for Fe³⁺. The In-doped hexaferrite Ba_0.5Sr_1.5Zn₂(Fe_1-xIn_x)₁₂O₂₂ may be potential candidates for application in magnetoelectric devices.     

Modifications in magnetic anisotropy of M—type strontium hexaferrite crystals by swift heavy ion irradiation.

Using vibrating sample magnetometery (VSM) 50 MeV Li³⁺ ion irradiation effects on magnetic properties of single crystals of SrGa_xIn_yFe_12−(x+y)O₁₉ (where x=0, 5, 7, 9; y=0, 0.8, 1.3, 1.0), are reported. The substitution of Ga and In in strontium hexaferrite crystals decreases the value of magnetization sharply, which is attributed to shifting of collinear magnetic order to a non-collinear one. Reduction of magnetization is also explained to be as a result of the occupation of the crystallographic sites of Fe³⁺ by Ga³⁺ and In³⁺. The Li³⁺ ion irradiation decreases the value of magnetization, irrespective of whether the crystals are Ga–In substituted or unsubstituted crystals of SrFe₁₂O₁₉. The result is interpreted in terms of the occurrence of a paramagnetic doublet in crystals replacing magnetic sextuplet as a result of irradiation. Substitution of Ga–In in Strontium hexaferrite decreases the value of anisotropy constant. Irradiation with Li³⁺ ions increases the values of anisotropy field for both substituted as well as unsubstituted crystals. Substitution with Ga–In also decreases the Curie temperature (T_c) but the irradiation with Li³⁺ ions does not affect the curie temperature of either Ga–In substituted or pure SrFe₁₂O₁₉ crystals.     

Magnetic behavior of the oxide spinels: Li0.5Fe2.5−2x Al x Cr x O4

In order to study the effect of substitution of Fe³⁺ by Al³⁺ and Cr³⁺ in Li_0.5Fe_2.5O₄ on its structural and magnetic properties, the spinel system Li_0.5Al _x Cr _x Fe_2.5?2x O₄ (x=0.0, 0.2, 0.4, 0.5, 0.6 and 0.8) has been characterized by X-ray diffraction, high field magnetization, low field ac susceptibility and ⁵⁷Fe Mossbauer spectroscopy. Contrary to the earlier reports, about 50% of Al³⁺ is found to occupy the tetrahedral sites. The system exhibits canted spin structure and a central paramagnetic doublet was found superimposed on magnetic sextet in the Mössbauer spectra (x>0.5).     

Synthesis and characterization of indium oxide-hematite magnetic ceramic solid solution

Indium oxide-doped hematite xIn₂O_3*(1-x)??-Fe₂O₃ (molar concentration x = 0.1?C0.7) solid solutions were synthesized using mechanochemical activation by ball milling. XRD patterns yield the dependence of lattice parameters and grain size as function of milling time. After 12 h of milling, the completion of In^3?+? substitution of Fe^3?+? in hematite lattice occurs for x = 0.1. For x = 0.3, 0.5 and 0.7, the substitutions between In^3?+? and Fe^3?+? into hematite and respectively, In₂O₃ lattices occur simultaneously. The lattice parameters of ??-Fe₂O₃ (a and c) and In₂O₃ (a) vary with milling time. For x = 0.1, Mössbauer spectra were fitted with one, two, or three sextets versus milling time, corresponding to gradual substitution of In^3?+? for Fe^3?+? in hematite lattice. For x = 0.3, Mössbauer spectra after milling were fitted with three sextets and two quadrupole-split doublets, representing In^3?+? substitution of Fe^3?+? in hematite lattice and Fe^3?+? substitution of In^3?+? in two different sites of In₂O₃ lattice. For x = 0.5 and 0.7, Mössbauer spectra fitting required two sextets and one quadrupole-split doublet, representing coexistence of In^3?+? substitution of Fe^3?+? in hematite lattice and Fe^3?+? substitution of In^3?+? in indium oxide lattice. The recoilless fraction studied versus milling time for each molar concentration exhibited low values, consistent with the occurrence of nanoparticles in the system. SEM/EDS measurements revealed that the mechanochemical activation by ball milling produced xIn₂O_3*(1-x)??-Fe₂O₃ solid solution system with a wide range of particle size distribution, from nanometer to micrometer, but with a uniform distribution of Fe, In, and O elements.     

Structural and magnetic properties of Mg(In2−xMnx)O4 system

We synthesized the Mn-doped Mg(In_2−xMn_x)O₄ oxides with 0.03?x?0.55 using a solid-state reaction method. The X-ray diffraction patterns of the samples were in a good agreement with that of a distorted orthorhombic spinel phase. Their lattice parameters and unit-cell volumes decrease with x due to the substitution of the smaller Mn³⁺ ions to the larger In³⁺ ions. The undoped MgIn₂O₄ oxide presents diamagnetic signals for 5 K?T?300 K. The M(H) at T=300 K reveals a fairly negative-sloped linear relationship. Neither magnetic hysteresis nor saturation behavior was observed in this parent sample. For the Mn-doped samples, however, positive magnetization were observed between 5 and 300 K even if the x value is as low as 0.03. The mass susceptibility enhances with Mn content and it reaches the highest value of 1.4×10⁻³ emu/g Oe (at T=300 K) at x=0.45. Furthermore, the Mn-doped oxides with x=0.06 and 0.2, respectively, exhibit nonlinear magnetization curves and small hysteretic loops in low magnetic fields. Susceptibilities of the Mn-doped samples are much higher than those of MnO₂, Mn₂O₃ oxides, and Mn metals. These results show that the oxides have potential to be magnetic semiconductors.     

Effects of In-substitution on the microstructure and magnetic properties of Bi-CVG ferrite with low temperature sintering

[Y_1.05Bi_0.75Ca_1.2](Fe_4.4−xIn_xV_0.6)O₁₂(In_x:Bi-CVG) ferrite material has been prepared successfully by a solid-state reaction method. The effects of In³⁺ substitution and sintering temperatures on the bulk density, microstructure and magnetic properties are performed by X-ray diffraction (XRD), scanning electron microscopy (SEM), materials automatic test system (MATS) and microwave ferrite parameters meter. The results show that In³⁺ can lower the sintering temperatures and enhance the magnetic properties of Bi-CVG ferrite. Besides, all sintered specimens with different In³⁺ contents show a single garnet crystal structure. The specimen of [Y_1.05Bi_0.75Ca_1.2](Fe₄In_0.4V_0.6)O₁₂ sintered at 1075 °C shows homogenous distribution of grain size and densified microstructures. The ferromagnetic resonance linewidth (ΔH) has an increase with In³⁺ contents. Additionally, the sample has the optimum magnetic properties: ρ=5.23 g/cm³, B_r=31.3 mT, H_c=378.8 A/m, 4πM_s=506.2×10⁻⁴ T.     

Temperature dependent Mössbauer and neutron diffraction studies of Cu x Fe1−x Cr2S4 compounds

The cation distribution and magnetic structure of Cu _x Fe_1?x Cr₂S₄ (x?=?0.1, 0.2, 0.3, 0.4, and 0.5) has been studied by X-ray and neutron diffraction, vibrating sample magnetometer (VSM), and Mössbauer spectroscopy. The charge state of Fe is found to be ferrous (Fe²⁺) for the x?=?0.1 sample; ferric (Fe³⁺) for the x?=?0.5 sample; mixed state (Fe²⁺, Fe³⁺) for the x?=?0.2, 0.3, and 0.4 samples. The Mössbauer spectra of the x?=?0.1 sample show asymmetric line broadening, which is considered to be due to the Jahn–Teller effect of Cu²⁺ ions, and a symmetrical six-line pattern is shown for the x?=?0.5 sample. The valence state of the Cu ions for the x?=?0.1 and 0.5 samples is found to be divalent and monovalent, respectively. The magnetic structure of the samples was determined to be a ferrimagnetic structure with antiparallel alignment of the Fe and Cr ion magnetic moments.     

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.     

Effect of Fe substitution on magnetocaloric effect in La0.7Sr0.3Mn1−xFexO3 (0.05≤x≤0.20)

We have studied the effect of Fe substitution on magnetic and magnetocaloric properties in La_0.7Sr_0.3Mn_1−xFe_xO₃ (x=0.05, 0.07, 0.10, 0.15, and 0.20) over a wide temperature range (T=10-400 K). It is shown that substitution by Fe gradually decreases the ferromagnetic Curie temperature (T_C) and saturation magnetization up to x=0.15 but a dramatic change occurs for x=0.2. The x=0.2 sample can be considered as a phase separated compound in which both short-range ordered ferromagnetic and antiferromagnetic phases coexist. The magnetic entropy change (−ΔS_m) was estimated from isothermal magnetization curves and it decreases with increase of Fe content from 4.4 J kg⁻¹ K⁻¹ at 343 K (x=0.05) to 1.3 J kg⁻¹ K⁻¹ at 105 K (x=0.2), under ΔH=5 T. The La_0.7Sr_0.3Mn_0.93Fe_0.07O₃ sample shows negligible hysteresis loss, operating temperature range over 60 K around room temperature with refrigerant capacity of 225 J kg⁻¹, and magnetic entropy of 4 J kg⁻¹ K⁻¹ which will be an interesting compound for application in room temperature refrigeration.     

Physical and magnetic properties of highly aluminum doped strontium ferrite nanoparticles prepared by auto-combustion route

Highly Al³⁺ ion doped nanocrystalline SrFe_12−xAl_xO₁₉ (0≤x≤12), were prepared by the auto-combustion method and heat treated in air at 1100 °C for 12 h. The phase identification of the powders performed using x-ray diffraction show presence of high-purity hexaferrite phase and absence of any secondary phases. With Al³⁺ doping, the lattice parameters decrease due to smaller Al³⁺ ion replacing Fe³⁺ ions. Morphological analysis performed using transmission electron microscope show growth of needle shaped ferrites with high aspect ratio at Al³⁺ ion content exceeding x≥2. Al³⁺ substitution modifies saturation magnetization (M_S) and coercivity (H_C). The room temperature M_S values continuously reduced while H_C value increased to a maximum value of 18,100 Oe at x=4, which is an unprecedented increase (∼321%) in the coercivity as compared to pure Sr-Ferrite. However, at higher Al³⁺ content x>4, a decline in magnetization and coercivity has been observed. The magnetic results indicate that the best results for applications of this ferrite will be obtained with an iron deficiency in the stoichiometric formulation.     

Magnetism, magnetocaloric effect and positive magnetoresistance in Fe-doped antipervoskite compounds SnCMn3−xFex (x=0.05-0.20)

The effects of Fe substitution on the structure, magnetic properties, magnetocaloric effect and positive magnetoresistance (MR) effect in antipervoskite compounds SnCMn_3−xFe_x (x=0.05-0.20) have been investigated systematically. Partial substitution of Fe for Mn leads to the monotonic reduction in both the Curie temperature T_C and saturated magnetization (M_S). It can be attributed to the reduction of electronic density of state at the Fermi energy by Fe-doping. The maximum values of magnetic entropy change (−ΔS_M) and positive MR gradually decrease as x increases, due to the broadening of magnetic phase transition. The refrigerant capacity increases initially with x≤0.05, then decreases gradually as x increases further, which is suggested to originate from the competition between the decreasing −ΔS_M and broadening temperature span. Our result indicates that the chemical doping on Mn site is an effective method for manipulating the properties of antiperovskite compounds AXMn₃.     

Entropy changes accompanying the magnetic phase transitions in low Si-doped Ce2Fe17−xSix Alloy

A summary of the results of ac susceptibility and isothermal magnetization measurements on polycrystalline samples of Ce₂Fe_17−xSi_x with nominal composition of x=0.0, 0.1, 0.2 and 1.0 is presented. These data reveal that the substitution of small amounts of Si for Fe produce a significant increase in temperature at which ferromagnetism appears, to the extent that, at x=1, characteristics of the anti ferromagnetic to paramagnetic transition (at temperature T_N) have disappeared completely. The nature of the various magnetic phase transitions — identified through the use of Arrott plots — and the accompanying magnetic entropy change, ΔSm, are both affected significantly by small amounts of Si substitution. In particular, while the peak entropy change is modest (occurring at x=0.1), the temperature interval over which a substantial entropy change occures is significant, approaching 150 K, an important criterion for improving the overall effectiveness of such materials for magnetic refrigeration.     

Spectral studies of Co substituted Ni-Zn ferrites

The spinel ferrites Zn_0.35Ni_0.65−xCo_xFe₂O₄, 0≤x≤1, have been prepared using the standard ceramic technique. Room temperature Mössbauer, X-ray and infrared IR spectra were used for carrying out this study. X-ray patterns reveal that all the samples have single-phase cubic spinel structure. The Mössbauer spectra of the samples show a paramagnetic phase for x=0 and a six-line magnetic pattern and a central paramagnetic phase for x≥0.1. They are analyzed and attributed to two magnetic subpatterns and two quadrupole doublets due to Fe³⁺ ions at the tetrahedral A-sites and octahedral B-sites. Four absorption bands are observed in IR spectra. They confirm the spinel structure of the samples and existence of Fe³⁺ ions in the sample sublattices. The deduced hyperfine interactions, lattice parameters, absorption band positions and intensities and force constant are found to be dependent on the substitution factor x, where the cation distribution is estimated. The hyperfine magnetic fields, magnetization and lattice resonant frequency are found to be dependent on the interionic distance.     

Magnetic properties of rare earth ion (Sm) added nanocrystalline Mg-Cd ferrites, prepared by oxalate co-precipitation method

Nanocrystalline ferrite powder having the general formula Mg_1−xCd_xFe₂O₄+5% Sm³⁺ (x=0, 0.2, 0.4, 0.6, 0.8 and 1.0) was synthesized by chemical oxalate co-precipitation technique. The synthesized powder was characterized by X-ray, IR and SEM techniques. The XRD analysis confirms cubic spinel phase with orthoferrite secondary phase. The lattice constant increases with increase in Cd²⁺ content (x). It is smaller than that for pure Mg-Cd ferrites. The average crystallite size lies in the range 28.69-32.66 nm. Saturation magnetization and magnetic moment increase with cadmium content up to x=0.4 and decrease thereafter. This is attributed to the existence of localized canted spin. The decrease in saturation magnetization and magnetic moment beyond x=0.4 is due to the presence of triangular spin arrangement on B-site. Coercivity and remanent magnetization decrease while Y-K angles increase with Cd²⁺ content. The Sm³⁺ addition improves the magnetic properties.     

Site occupancy and magnetic study of Al and Cr co-substituted Y3Fe5O12

Single-phased polycrystalline Y₃Fe_5−2xAl_xCr_xO₁₂ garnet samples (x=0, 0.2, 0.4 and 0.6) have been prepared by the conventional ceramic technique. Rietveld refinement of X-ray diffraction patterns of the samples shows them to crystallize in the Ia3d space group and the corresponding lattice constant to decrease with increasing Al³⁺ and Cr³⁺ contents (x). Mössbauer results indicate that Cr³⁺ substitutes for Fe³⁺ at the octahedral sites whilst Al³⁺ essentially replaces Fe³⁺ at the tetrahedral sites. This result indicates that co-doping of Y₃Fe₅O₁₂ does not affect the preferential site occupancy for separate individual substitution of either Cr³⁺ or Al³⁺. The magnetization measurements reveal that the Curie temperature (T_c) monotonically decreases with increasing x while the magnetic moment per unit formula decreases up to x=0.4 and then slightly increases for x=0.6. This reflects a progressive weakening of the ferrimagnetic exchange interaction between the Fe³⁺ ions at octahedral and tetrahedral sites due to co-substitution. The magnetic moment was calculated using the cations distribution inferred from the Mössbauer data and the collinear ferrimagnetic model, and was found to agree reasonably with the experimentally measured value. The phenomenological amplitude crossover, characterized by the temperature T*, has also been observed in the doped YIG and briefly discussed.     

Structure, electric and dielectric studies of indium-substituted magnesium copper manganese ferrites

The structure, electric and dielectric properties of In-substituted Mg-Cu-Mn ferrites having the general formula of Mg_0.9Cu_0.1Mn_0.1In_xFe_1.9−xO₄ with 0.0≤x≤0.4 have been studied. X-ray diffraction (XRD) patterns of the samples indicated the formation of single-phase cubic spinel structure up to 0.2 and mixed phase (cubic and tetragonal phase) for samples x≥0.3. The relation of conductivity with temperature revealed a semiconductor to semimetal behavior as In⁺³ concentration increases. Variation in the universal exponent s with temperature indicates the presence of two hopping conduction mechanisms: the correlated barrier hopping (CHB) at low In⁺³ content x≤0.1 and small-polaron (SP) hopping at In⁺³ content x≥0.2. The variation in dielectric permittivity (ε′, ε″) with temperature at different frequencies shows a normal behavior for the studied compounds, while the variation in dielectric loss tangent with frequency at different temperatures shows abnormal behavior with more than relaxation peak. The conduction mechanism used in the present study has been discussed in the light of electron exchange between Fe³⁺ and Fe²⁺ ions and hole hopping between Mn²⁺ and Mn³⁺ ions at the octahedral B-sites.     

Structural and magnetic properties of holmium substituted cobalt ferrites synthesized by chemical co-precipitation method

CoHo_xFe_2−xO₄ ferrites (x=0.00–0.1) were prepared by the co-precipitation technique and the effect of holmium substitution on the magnetic properties was investigated. X-ray diffraction reveals that the substituted samples show a second phase of HoFeO₃ along with the spinel phase. The magnetic properties such as the saturation magnetization (M_s), coercivity (H_c) and remanence (M_r) are obtained from the hysteresis loops. It is observed that the M_s decreases while H_c increases with Ho³⁺ substitution. The decrease of saturation magnetization is attributed to the weakening of exchange interactions. The coercivity increases with increase of the Ho³⁺ concentration, which is attributed to the presence of an ultra-thin layer at the grain boundaries that impedes the domain wall motion. Low field AC susceptibility was also measured over the temperature range 300–600 K at the frequency of 200 Hz. It decreases with the increase of temperature following the Curie–Weiss law up to the Curie temperature. Above the Curie temperature it shows paramagnetic behavior. The increase in coercivity suggests that the material can be used for applications in perpendicular recording media.     

代In的BCVIG单晶的磁光克尔旋转

我们测量了分子式为{Bi_3-2xCa_2x}[Fc_2-yIn_y](Fe_{(3x)Vx)O12的铁石榴石单晶(简记为代In的BCVIG)在0.45—0.80μm内的饱和极向磁光克尔旋转谱。在0.47μm附近观察到一个强的旋转峰值。通过改变In,V(Bi)的替代量获得了室温下磁矩抵消点附近0.47μm磁光旋转值与成份的关系。发现当替代量的变化通过磁矩抵消点时,克尔旋转的符号突然由正变负,但其绝对值并不依替代量趋近磁矩抵消点(总4πMs下降)而逐渐下降。还发现In的代入使磁光旋转有所增强,在y≈0.15时增强最大。借助总磁光旋转为Bi增强了的次点阵磁光旋转迭加的模型解释了代In引起的旋转增强。按此拟合实验结果导出了0.47μm下四、八面体次晶格旋转系数之比为α4/α8≈1.5即单位Fe³⁺在四面体比在八面体对磁光旋转的贡献大。实验结果还表明,在x<1.0的配方区,并有小量In代入(y<0.15)时可望得到大磁光旋转材料。考虑到低而可变的4πMs,高的居里点和相当大的磁光旋转,该配方区的代In的BCVIG在磁光各种应用中将是强有力的竞争者。 关键词：}