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.     

Preparation of substituted barium ferrite BaFe12−x(Ti0.5Co0.5)xO19 by citrate precursor method and compositional dependence of their magnetic properties

As a possible candidate for the left-handed metamaterial with negative permeability, a series of Ti, Co-substituted M-type barium hexaferrite BaFe_12−x(Ti_0.5Co_0.5)_xO₁₉ (x=0, 1, 2, 3, 4 and 5) was prepared by citrate precursor method. The formation processes of the substituted barium hexaferrite compounds from the precursors were followed by the measurements of powder X-ray diffraction (XRD), Infrared absorption spectra (FT-IR), and thermogravimetry and differential thermal analysis (TG/DTA) coupled with mass spectroscopy (MS). In the case of the non-substituted sample, the formation of the barium hexaferrite is regulated by the thermal decomposition of BaCO₃ and the solid-state reactions of BaO and Fe₂O₃ in the temperature range from 800 to 1100 K. The formation temperature of the substituted BaFe_12−x(Ti_0.5Co_0.5)_xO₁₉ is higher than that for the non-substituted sample and increases with the value of x, due to the effects of carbonate ions incorporated by the partial substitution of Fe³⁺ by (Ti_0.5Co_0.5)³⁺. On heating up to ca. 1200 K, all the substituted samples transform into the magenetoplumbite phase as is the non-substituted sample. The compositional dependence of the magnetic properties of the substituted barium hexaferrite was investigated by the magnetization measurement. The decrease in the magnetic anisotropy was confirmed by the change in the magnetization curve and coercivity H_C with the composition x. A negative permeability spectrum was observed in the BaFe₉(Ti_0.5Co_0.5)₃O₁₉ in the frequency range from 2 to 4 GHz.     

Structural and magnetic study of the Ti-doped barium hexaferrite ceramic samples: Theoretical and experimental results

We present a theoretical and experimental study of the structural and magnetic properties of M-type Ti⁴⁺-doped barium hexaferrite BaFe_{(12−(4/3)x)}Ti_xO₁₉ with x=0, 0.1, 0.2, 0.3, 0.5, 0.7 and 1.3. The XRD patterns and magnetic measurements show appreciable variations in the values of the saturation magnetization and the magnetic anisotropy field, H_an, with increasing Ti⁴⁺ content. We did not observe significant changes in the Lotgering factor along the (0 0 l) direction and in the texture coefficient, C_ex, which was estimated from the torque curves. The magnetic properties of these materials are explained by the combined effect of the coherent rotation of the magnetic domains and the replacements of Fe³⁺ by Ti⁴⁺ ions in the octahedral and tetrahedral sites. The influence of the Ti⁴⁺ content on the samples was studied theoretically by using a statistical phenomenological model. The main purpose of the model is to make preliminary predictions of the distribution of any dopant cation in the Fe³⁺ sites. As a result, we are able to analyze both structural and magnetic features of M-type barium hexaferrite.     

Mössbauer study of substituted barium ferrite BaFe11−x−y Co0.5Ti0.5Ni x ZnyO19−r

Substituted barium ferrite BaFe_11–x–y Co_0.5Ti_0.5Ni _x Zn_yO_19–r powders were prepared using a coprecipitation method and investigated by X-ray diffraction (XRD) and⁵⁷Fe Mössbauer spectroscopy. The results show that the as-prepared magnetic powders possess the typical hexagonal structure and demonstrate both a good dispersibility and a narrow particle size distribution. The hyperfine fields for all sites decrease slightly asx (ory) increases. The Ni²⁺ ions prefer to occupy the 2a and 12k sites, and Zn²⁺ ions occupy the 4f_IV site.     

Effect of allied and alien ions on the EPR spectrum of Mn-containing lithium-manganese spinel oxides

Electron paramagnetic resonance spectroscopy was used for studying the effect of allied and alien ions on the EPR spectrum of Mn⁴⁺-containing lithium-manganese spinel oxides. Manganese spinel oxides with paramagnetic Mn⁴⁺ and diamagnetic substituents in the 16d spinel sites were studied: Li[Mg_0.5Mn_1.5]O₄, Li[Mg_0.5−xCo_2xMn_1.5−x]O₄, 0<x≤0.5, and Li[Li_1/3Mn_5/3]O₄. Ni²⁺-ions with integer-spin-ground state (S=1) were selected as alien ions: Li[Mg_0.5−xNi_xMn_1.5]O₄ (0≤x≤0.5), Li[Li_(1−2x)/3Ni_xMn_(5−x)/3]O₄ (0≤x≤0.5), and Li[Ni_0.5Mn_1.5−yTi_y]O₄ (0≤y≤1.0). It was shown that in Ni-substituted oxides the low temperature EPR response comes from magnetically correlated Ni-Mn spins, while at high registration temperature Mn⁴⁺ ions give rise to the EPR profile. Analysis of the EPR line width allows differentiating between the contributions of the density of paramagnetic species and the strength of the exchange interactions in magnetically concentrated systems. The density of allied and alien paramagnetic species has no effect on the EPR line width in cases when the strengths of antiferro- and ferromagnetic interactions on an atomic site are close. On the contrary, when antiferro- or ferromagnetic interactions on an atomic site are dominant, the EPR line width increases with the density of paramagnetic species.     

Electrochemical behavior of Li intercalation processes into a Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 cathode

Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ (X=0.17, 0.25, 0.33, 0.5) compounds are prepared by a simple combustion method. The Rietvelt analysis shows that these compounds could be classified as having the α-NaFeO₂ structure. The initial charge-discharge and irreversible capacity increases with the decrease of x in Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂. Indeed, Li[Ni_0.50Mn_0.50]O₂ compound shows relatively low initial discharge capacity of 200 mAh/g and large capacity loss during cycling, with Li[Ni_0.17Li_0.22Mn_0.61]O₂ and Li[Ni_0.25Li_0.17Mn₀.₅₈]O₂ compounds exhibit high initial discharge capacity over 245 mAh/g and stable cycle performance in the voltage range of 4.8 -2.0 V. On the other hand, XANES analysis shows that the oxidation state of Ni ion reversibly changes between Ni²⁺ and about Ni³⁺, while the oxidation state of Mn ion sustains Mn⁴⁺ during charge-discharge process. This result does not agree with the previously reported ‘electrochemistry model’ of Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂, in which Ni ion changes between Ni²⁺ and NI⁴⁺. Based on these results, we modified oxidation-state change of Mn and Ni ion during charge-discharge process.     

Structural and magnetic behaviour of aluminium doped barium hexaferrite nanoparticles synthesized by solution combustion technique

Nanocrystalline M-type Al³⁺ substituted barium hexaferrite samples having generic formula BaFe_12−xAl_xO₁₉ (where x=0.00, 0.25, 0.50, 0.75, 1.00) were synthesized by the solution combustion technique. The precursors were prepared using stoichiometric amounts of Ba²⁺, Fe³⁺ and Al³⁺ nitrate solutions with citric acid as a chelating agent. The barium nitrate to citric acid ratio was taken as 1:2 and pH of the solution was kept at 8. The sintered samples were characterized by XRD, EDAX, SEM, TEM and VSM techniques. Pure barium hexaferrite shows only single phase hexagonal structure while samples at 0.25≤x≥1.00 show α-Fe₂O₃ peaks with M-phase of barium hexaferrite in the X-ray diffraction pattern. The lattice parameters (a and c) obtained from XRD data decreases with increase in aluminium content x. The particle size obtained from X-ray diffraction data is in the nanometer range. The magnetic behaviour of the samples was studied using vibrating sample magnetometer technique. The saturation magnetization (M_s) and magneton number (n_B) decrease from 38.567 to 21.732 emu/g and from 7.6752 to 4.2126μ_B, respectively, with increase in Al³⁺ substitution x from x=0.0 to 1.0.     

Mn-doped (Ba,Y)Fe12O19 hexaferrites: Crystal structure and oxidation states of Mn and Fe

We have fabricated Ba_0.95Y_0.05Fe_12-xMn_xO₁₉ samples with large Mn-doping amounts of x = 4 and 6, using the mechanical milling and heat treatment. X-ray diffraction analysis indicated the samples crystallized in the M-type hexaferrite structure. The Mn doping caused the modification, shift and broadening of some characteristic phonon-vibration modes, which were recorded by Raman spectroscopy. This is due to an incorporation of Mn ions into the M-type structure that disorders the periodic lattice and changes symmetry. Basing on X-ray absorption spectroscopy, we have found Fe in all samples stable with an oxidation state 3+ (Fe³⁺). Though Mn²⁺ and Mn³⁺ ions coexist, the concentration of Mn²⁺ in x = 4 is larger than that in x = 6. The analysis of Fourier-transform spectra have demonstrated the replacement of Mn^2+,3+ ions for Fe³⁺ in the M-type structure. The sites of Mn^2+,3+ ions in this structure have been discussed.     

Structural and some magnetic properties of manganese-substituted lithium ferrites

The structural and magnetic properties of Mn-substituted lithium ferrites having the general formula Li_0.5−0.5xMn_xFe_2.5−0.5xO₄ (where x=0.0–1.0) prepared by the standard ceramic technique have been studied. Single phase cubic structure is confirmed by X-ray diffractometer. This result demonstrates that the samples are homogeneous, and the sharp peaks reveal that the samples are in crystalline form. The lattice parameter ‘a’ and average grain diameter ‘D’ increase with increasing Mn²⁺ ion substitution. The saturation magnetization and the experimental magnetic moment are found to increase with manganese up to x=0.5 and then tends to decrease for x>0.5. The increase in magnetic moment with manganese is attributed to Neel's two sublattice model according to which the magnetic moment is the vector sum of lattice magnetic moment. The decrease in magnetization for x>0.5 obeys the Yafet–Kittel (Y–K) model. The increase in Y–K angles for x≥0.5 indicates the increased favor for triangle spin arrangements on B-sites. This suggests the existence of canted spin structure in the ferrite system with higher content of Mn. Hystersis loops were measured. The initial permeability μ_i was measured as a function of temperature.     

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.     

Static and dynamic magnetic characteristics of BaCo0.5Mn0.5Ti1.0Fe10O19

The effect of Mn²⁺Co²⁺Ti⁴⁺ substitution on microwave absorption has been studied for BaCo_0.5Mn_0.5Ti_1.0Fe₁₀O₁₉ ferrite-acrylic resin composites in frequency range from 12 to 20 GHz. X-ray diffraction (XRD), scanning electron microscope (SEM), vibrating sample magnetometer, AC susceptometer and vector network analyzer were used to analyze the structural, magnetic and microwave absorption properties. The results showed that the magnetoplumbite structures for all samples have been formed. Based on microwave measurement on reflectivity, BaCo_0.5Mn_0.5Ti_1.0Fe₁₀O₁₉ may be a good candidate for electromagnetic compatibility and other practical applications at high frequency.     

Optical characterization of Mn, Ni and Co ions doped zinc lead borate glasses

This paper reports on the development and optical characterization of heavy metal oxide (HMO)-based transparent glasses in the chemical composition of 15PbO-40B₂O₃-(45−x) ZnO−x TM²⁺ (=Mn²⁺ or Ni²⁺ or Co²⁺) (where x=0.2, 0.5 mol%). For these glasses both absorption and emission spectra have been measured, in order to understand their optical performances. The XRD profiles have confirmed their glassy nature and the FTIR spectral features have been analyzed. From the emission spectra, a bright green emission (538 nm) from Mn²⁺-glasses, an intense red emission (670 nm) from Ni²⁺ and from Co²⁺ (625 nm) glasses have been noticed very clearly. Based on the UV-absorption spectra of these materials, both direct and indirect bond gaps have been computed. Apart from the spectral analysis, different physical properties of these glasses have also been carried out. Due to the presence of both PbO and ZnO, these glasses are found to be good moisture-resistant optical systems. Both optical and physical properties have been found to be more encouraging towards their use as novel luminescent optical materials.     

Synthesis and characterization of La0.7Sr0.3Mn1−x TixO3 manganites

The structural, electrical and magnetic properties of the La_0.7Sr_0.3Mn_1?x Ti_xO₃ system characterized by rhombohedral lattice distortions are studied. Substitution of titanium for manganese weakens ferromagnetism and leads to an increased resistivity. Using x-ray Rietveld full-profile refinement data and ferromagnetic resonance spectra, it is demonstrated that titanium substitution for manganese occurs with charge compensation according to the equation Mn⁴⁺ → Ti⁴⁺ and with a simultaneous decrease in the oxygen nonstoichiometry as the value of x increases.     

Structure and magnetic properties of Ni0.5Zn0.5Mn0.5-xMoxFe1.5O4 ferrites prepared by sol-gel auto-combustion method

A series of Mo doped Ni-Mn-Zn ferrites compounds with the formula Ni_0.5Zn_0.5Mn_0.5-xMo_xFe_1.5O₄ (x = 0, 0.025, 0.05, 0.075 and 0.1) were first synthesized by sol-gel auto-combustion method. The X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), and vibrating sample magnetometer (VSM) analysis were carried out to characterize the microstructural and magnetic properties of ferrites. Rietveld refinement of X-ray diffraction data confirmed the formation of cubic spinel structure and the emergence of FeMoO₄ phase with the substitution of Mo⁶⁺ contents. The grain size increased remarkably due to the formation of the liquid phase. The saturation magnetization (M_s) increased while the coercivity (H_c) decreased from 67.3 to 12.1 Oe due to the decrease of magneto-crystalline anisotropy constant. The initial permeability (μ_i) increased significantly from 34 (x = 0) to 114 (x = 0.075) and later decreased for x = 0.1. In our experiment, Ni_0.5Zn_0.5Mn_0.425Mo_0.075Fe_1.5O₄ ferrite presented the best microstructure and soft magnetic properties.     

Spinel-type solid solutions involving Mn and Ti:Crystal chemistry, magnetic and electrochemical properties

This study reports the structural and magnetic properties of spinel systems Li₄Mn_5−xTi_xO₁₂ (“4-5-12” series) and LiNi_0.5Mn_1.5−xTi_xO₄ (“LNMTO” series), both based on Mn⁴⁺ substitution by Ti⁴⁺. Intermediate compositions covering the whole range of compositions (0≤x≤5 and 0≤x≤1.5, respectively) were prepared by solid state reaction. The 4-5-12 system forms a continuous spinel solid solution, whereas the spinel phase range in LNMTO stops before the end member “LiNi_0.5Ti_1.5O₄”, which is multi-phased with a major hexagonal phase component. Cell parameters and (Mn,Ti)-O distances increase monotonically with titanium content in both series. In the LNMTO series, the end member LiNi_0.5Mn_1.5O₄ is known to form a superstructure with Ni/Mn cation ordering. Neutron diffraction and Raman spectroscopy show that this order is lost when Ti is substituted, even at low level (x=0.15). The LNMTO crystal chemistry is also complicated by the presence of partial cation inversion, and the presence of a secondary rocksalt-type phase that modifies the spinel stoichiometry. Magnetic properties are characterized by a competition between ferromagnetic and antiferromagnetic interactions; no magnetic ordering is achieved, in agreement with B-site cation frustration and disorder. Electrochemical measurements show that the Ti^3+/4+ and Mn^3+/4+ redox couples behave independently in the 4-5-12 series, and that titanium decreases the high-potential electrochemical redox activity of LNMTO because of its blocking character for electron transfer to and from the nickel sites in the spinel structure.     

Mössbauer and magnetic study of Mn2+- and Cr3+-substituted spinel magnesioferrites of the composition Mg1−xMnxFe2−2xCr2xO4

Chromium and manganese co-substituted spinel magnesioferrites of the composition Mg_1?x Mn _x Fe_2?2x Cr_2x O₄ (x?=?0.0, 0.1, 0.2, 0.3, and 0.5) were investigated with X-ray diffraction (XRD), Mössbauer spectroscopy and magnetic measurements. The cation distribution inferred suggests that Mn²⁺ and Cr³⁺ ions dominantly occupy the A- and B-sites respectively. The gradual decrease of the hyperfine fields and Curie temperatures with increasing x reflects a gradual weakening in the AB exchange interaction. Mössbauer data of the sample with x = 0.5 is suggestive of cation clustering and/or superparamagnetism. The magnetization data is suggestive of Yafet-Kittel-type canted magnetism.     

Investigation of magnetic properties of Al substituted nickel ferrite nanopowders, synthesized by the sol-gel method

NiFe_2−xAl_xO₄ nanopowders, where x is from 0 to 1.5 with a step of 0.5, have been synthesized by the sol-gel method and the effect of non-magnetic aluminum content on their structural and magnetic properties were investigated. The X-ray diffraction (XRD) patterns revealed that the synthesized nanopowders are single phase with a spinel structure. Mean crystallite sizes of the samples were calculated by Scherrer's formula and were in the range 20-31 nm. The morphology of the nanopowders was investigated by TEM and the mean particle sizes of the samples were in the range 55-80 nm. Magnetic hysteresis loops were recorded at room temperature in a maximum applied field of 3000 Oe. The results show that by increasing the aluminum content, the magnetizations of the nanopowders are decreased. This reduction is caused by non-magnetic Al³⁺ ions, which by their substitutions the super exchange interactions between different sites will be reduced. It is also seen that the magnetizations of the nanopowders are lower than those related to their bulk counterparts. This reduction was found to be as a consequence of surface spin disorder. M-T curves of the samples were obtained using a Faraday balance and by which the Curie temperatures of the powders were determined. The results that are obtained show that the Curie temperatures of the nanopowders are higher than those of their bulk counterparts.     

Electronic structure and magnetic properties of BaTi1-xMnxO3

The electronic structure and magnetic properties of polycrystalline BaTi_1-xMn_xO₃ (x = 0–0.1) compounds prepared by solid-state reactions were studied. The results revealed that the increase in Mn content (x) did not change the oxidation numbers of Ba (+2) and Ti (+4) in BaTi_1-xMn_xO₃. However, there is the change in Mn valence that Mn^3+,4+ ions coexist in the samples with x = 0.01–0.04 while Mn⁴⁺ ions are almost dominant in the samples with x = 0.06–0.1. We also point out that Mn³⁺ and Mn⁴⁺ ions substitute for Ti⁴⁺ and prefer locating in the tetragonal and hexagonal BaTiO₃ structures, respectively, in which the hexagonal phase constitutes soon as x = 0.01. Particularly, all the samples exhibit room-temperature ferromagnetism. Ferromagnetic order increases with increasing x from 0 to 0.02, but decreases as x ≥ 0.04. We think that ferromagnetism in BaTi_1-xMn_xO₃ is related to lattice defects and/or exchange interactions between Mn³⁺ and Mn⁴⁺ ions.     

A comparison of the magnetic and microwave absorption properties of Mn–Sn–Ti substituted strontium ferrite with and without multi-walled carbon nanotube

In this work, a comparison of magnetic and microwave properties between Mn–Sn–Ti substituted SrM ferrite and nanocomposite of Mn–Sn–Ti substituted SrM ferrite–20% volume multi-walled carbon nanotube (MWCNT) has been done. Phase characterization and crystal structure of the synthesized nanoparticles were tested by X-ray diffraction (XRD). Field emission scanning electron microscopy (FESEM), Fourier transform infrared spectrometry (FTIR) analysis approved that the SrFe_12−x(MnSn_0.5Ti_0.5)_x/2O₁₉ nanoparticles were attached on the external surfaces of the MWCNTs. Mӧssbauer spectroscopy (M_S) showed the occupancy by non-magnetic Mn²⁺–Sn⁴⁺–Ti⁴⁺ cations into the hexagonal lattice structure. Magnetic properties were evaluated by a vibrating sample magnetometer (VSM). The results also indicated that saturation magnetization and coercivity were decreased with an increase in x content and also MWCNTs addition. Microwave absorption properties were investigated by a vector network analyzer (VNA). It was found that with an addition of 20 volume percentage of MWCNTs, the saturation magnetization coupled with coercivity decrease, but reflection loss (RL) increase broadly. Also it proved that with an increase in the thickness of absorption the frequency band shifts from K_u (12–18 GHz) to X (8–12 GHz) band.     

Tuning of electromagnetic wave absorbing properties in Fe-deficient SrFe9.6-xCo1.2Ti1.2O19 hexaferrite-epoxy composites

We report the tunable electromagnetic (EM) wave absorption properties of Fe-deficient SrFe_9.6-xCo_1.2Ti_1.2O₁₉ hexaferrite–epoxy composites. SrFe_9.6-xCo_1.2Ti_1.2O₁₉ hexaferrite powders were prepared via solid-state reaction routes. It was observed that Sr–Ti-rich second phases were formed as x increased, i.e., the Fe content decreased. The ferromagnetic resonance (FMR) frequency of the composites gradually decreased from 8.8 GHz to 4.8 GHz with increasing x, and accordingly, the EM absorption frequency range also gradually changed. The gradual FMR frequency shift was attributed to the compositional shift in the mother phase. It is predicted that the Fe deficiency caused a decrease in the magnetocrystalline anisotropy, and in turn, it shifted the FMR frequency and modified the corresponding EM absorbing properties. All the samples demonstrated a high EM absorption performance with the lowest reflection loss of < −40 dB at the optimized frequency and thickness.