Iron-based soft magnetic composites with Mn–Zn ferrite nanoparticles coating obtained by sol–gel method

This paper focuses on iron-based soft magnetic composites which were synthesized by utilizing Mn–Zn ferrite nanoparticles to coat iron powder. The nanocrystalline iron powders, with an average particle diameter of 20 nm, were obtained via the sol–gel method. Scanning electron microscopy, energy dispersive X-ray spectroscopy and distribution maps show that the iron particle surface is covered with a thin layer of Mn–Zn ferrites. Mn–Zn ferrite uniformly coated the surface of the powder particles, resulting in a reduced imaginary permeability, increased electrical resistivity and a higher operating frequency of the synthesized magnets. Mn–Zn ferrite coated samples have higher permeability and lower magnetic loss when compared with the non-magnetic epoxy resin coated compacts. The real part of permeability increases by 33.5% when compared with the epoxy resin coated samples at 10 kHz. The effects of heat treatment temperature on crystalline phase formation and on the magnetic properties of the Mn–Zn ferrite were investigated via X-ray diffraction and a vibrating sample magnetometer. Ferrites decomposed to FeO and MnO after annealing above 400 °C in nitrogen; thus it is the optimum annealing temperature to attain the desired permeability.     

In situ observations of domain wall motion in Mn–Zn and Ni–Zn ferrites by Lorentz microscopy and electron holography

Domain wall motion in Mn–Zn and Ni–Zn ferrites with applied magnetic fields is investigated by in situ observations with Lorentz microscopy and electron holography. It is found that both Mn–Zn and Ni–Zn ferrites have a mean grain size of approximately 10 μm and several pores with sizes ranging from 0.2 to 1.1 μm. In situ observations by Lorentz microscopy with an applied magnetic field reveals that in Mn–Zn ferrite, the domain walls move easily across the grain boundary, while in Ni–Zn ferrite, the domain walls move along the grain boundary but are pinned at the grain boundary and pores. From in situ observations of Ni–Zn ferrite by electron holography, it is clarified that domain wall pinning at the grain boundary retards a sensitive increase in magnetic flux parallel to the applied field direction, which is considered to result in high hysteresis loss.     

Magnetic and structural studies of the Mn-doped Mg–Zn ferrite nanoparticles synthesized by the glycine nitrate process

In this study, Nanocrystalline Mn–Mg–Zn ferrite with the chemical formula Mn_xMg_0.5−xZn_0.5Fe₂O₄ (x=0, 0.1, 0.2, 0.3, 0.4, 0.5) was successfully synthesized by the glycine-nitrate autocombustion process using glycine as a fuel and nitrates as oxidants. The as-synthesized powders were characterized by the X-ray diffraction analysis, field emission scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometer. The X-ray diffraction data was used to determine the lattice constant, cation distribution and the oxygen position parameter. The results reveal that the nanocrystalline Mn–Mg–Zn ferrite has an average crystallite size of 35–67 nm and particle size of 40 nm. The lattice parameter increases linearly with an increase in the Mn content. The FTIR analysis confirms the intrinsic vibrational frequencies of the tetrahedral and octahedral of the spinel structure. The magnetic measurements indicate that the coercivity decreases, and the magnetization increases by increasing the Mn content.     

Anomalous magnetic behaviour of zinc and chromium ferrites without any hyperfine splitting

Two groups of ferrite namely zinc ferrite and chromium ferrite were synthesized by citrate precursor route in the size range of 8 to 35 nm. We have studied the structural and magnetic behaviour of these ferrites using X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and Mössbauer spectroscopic techniques. Our studies show that the nanocrystalline ferrites interact with the hand magnet strongly and give large magnetization in the VSM measurement. The maximum magnetization in the samples sensitively depends on the particle size of synthesized ferrites. We observed as large as 28 Am²/kg of magnetization in the zinc ferrite nanoparticles while that in chromium ferrite is around 11 Am²/kg. In spite of the large magnetization in the zinc ferrite nanoparticles we did not observe any hyperfine splitting even down to 12 K of temperature. Similar behaviour is also observed for chromium ferrite down to 16 K.     

Influence of manganese substitution and annealing temperature on the formation,microstructure and magnetic properties of Mn–Zn ferrites

The effects of annealing temperature and manganese substitution on the formation, microstructure and magnetic properties of Mn_xZn_1−xFe₂O₄ (with x varying from 0.3 to 0.9) through a solid-state method have been investigated. The correlation of the microstructure and the grain size with the magnetic properties of Mn–Zn ferrite powders was also reported. X-ray diffraction (XRD), a scanning electron microscope (SEM) and a vibrating sample magnetometer (VSM) were utilized in order to study the effect of variation of manganese substitution and its impact on crystal structure, crystalline size, microstructure and magnetic properties of the ferrite powders formed. The XRD analysis showed that pure single phases of Mn–Zn ferrites were obtained by increasing the annealing temperature to 1200–1300 °C. Increasing the annealing temperature to ?1300 °C led to abnormal grain growth with inter-granular pores and this led to a decrease in the saturation magnetization. Moreover, an increase in the Mn²⁺ ion substitution up to x=0.8 increased the lattice parameter of the formed powders due to the high ionic radii of the Mn²⁺ ion. Mn–Zn ferrites phases were formed and the positions of peaks were shifted by substituting manganese. The average crystalline size was increased by increasing the annealing temperature and decreased by increasing the substitution by manganese up to 0.8. The average crystalline size was in the range 95–137.3 nm. The saturation magnetization of the Mn–Zn-substituted ferrite powders increased continuously with an increase in the Mn concentration up to 0.8 at annealing temperatures of 1200–1300 °C. Further increase of Mn substitution up to 0.9 led to a decrease of saturation magnetization. The saturation magnetization increased from 17.3 emu/g for the Mn_0.3Zn_0.7Fe₂O₄ phase particles produced to 59.08 emu/g for Mn_0.8Mn_0.2Fe₂O₄ particles.     

Synthesis and magnetic properties of Mn–Zn ferrite nanoparticles

Mn–Zn ferrite nanoparticles (Mn_1−xZn_xFe₂O₄) are synthesized by a hydrothermal precipitation approach using metal sulfate solution and aqueous ammonia. The analysis methods of XRPD, TEM, TGA, and VSM are used to characterize the magnetic nanoparticles. Through the characterization of the precipitated nanoparticles, the effects of the reacting component proportions and preparation techniques on the Curie temperature, the magnetization, and the size distribution of Mn–Zn ferrite nanoparticles are discussed. Furthermore, the Mn–Zn ferrite nanoparticles are used to prepare ferrofluid. Variation of the magnetic properties of the ferrite nanoparticles with the composition content x of Zn and the magnetic moment of the nanoparticles are discussed.     

Effects of cobalt doping on the microstructure and magnetic properties of Mn-Zn ferrites prepared by the co-precipitation method

Mn-Zn ferrite nanoparticles with various amounts of cobalt doping have been synthesized by the co-precipitation method. The structure and morphology of the nanoparticles have been characterized by X-ray diffraction and transmission electron microscopy. The effects of cobalt ions on the crystallization behavior, lattice parameters and magnetic properties of Mn-Zn ferrites have been investigated. All the Co-doped ferrite nanoparticles calcined at 1150 °C possess a simple spinel structure and have an approximately spherical shape. The lattice parameters increase almost linearly with increasing Co content. The studies of magnetic properties show that the saturation magnetization M_s strongly depends on the Co content, having a maximum M_s value of 73 emu/g at a Co content of 1.0 at%, and all the Co-doped ferrites, with the average crystallite sizes ranging from 24.5 to 27.0 nm, exhibit superparamagnetism at room temperature.     

Synthesis of nanocrystalline spinel CoFe2O4 via a polymer-pyrolysis route

Nanocrystalline CoFe₂O₄ spinel ferrites were synthesized via the pyrolysis of polyacrylate salt precursors prepared by in situ polymerization of metal salts and acrylic acid. The pyrolytic behaviors of the polymeric precursors were analyzed by use of simultaneous thermogravimetric and differential thermal analysis (TG-DTA). The structural characteristics of the calcined products were obtained by powder X-ray diffraction (XRD), infrared spectroscopy (IR) and transmission electron microscope (TEM). The results revealed that cobalt ferrites had nano-sized morphology and good crystallinity even if calcined at moderate temperature like 500 °C for 3 h. The average size of nanocrystalline cobalt ferrites ranged from 20 to 30 nm with a narrow size distribution, while the particle size increased with the increase of the calcination temperature. Magnetic properties were obtained at room temperature using a vibrating sample magnetometer. The samples exhibited hysteresis loop typical of magnetic behaviors, indicating that the presence of an ordered magnetic structure could exist in the mixed spinel system. The as-calcined cobalt ferrites at 500 °C exhibited the highest magnetization value of 77.4 emu/g at 10 kOe, while the highest remanence and coercivity of 35.6 emu/g and 1445 Oe, respectively, for those calcined at 700 °C were obtained.     

Fine structure of vibratory spectra and cation distribution in nonstoichiometric Mn-Zn ferrites

We have studied vibratory spectra in the range 200–700 cm⁻¹ of Mn−Zn ferrite crystal lattices containing both an iron excess or an iron deficit of up to 8 mole% relative to the stoichiometric compound. We performed a Kramers-Kronig analysis of the reflectance spectra, and a dispersion analysis of the spectra of the dielectric functions. The vibratory spectral band is quite complex. The compositional dependence of the individual component intensities is explained by a cation distribution model. According to this model the manganese cations in the octahedral sites are +3 valence in both iron-poor and iron-rich ferrites. Kazanskii State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 34–40, October, 1996.     

Influence of environment and grain size on magnetic properties of nanocrystalline Mn–Zn ferrite

Nanocrystalline Mn_1−xZn_xFe₂O₄ (0.2?x?0.9) was prepared by mechanical alloying of the concerned oxide precursors and subsequent annealing in air and Ar atmosphere, respectively. Milling and annealing in air produces Zn-ferrites (ZnFe₂O₄) instead of Mn–Zn ferrites as MnO converts to higher oxides at higher oxygen partial pressure and fails to dissolve in the spinel phase. This is confirmed by careful quantitative X-ray diffraction analysis using Rietvelt profile matching and also by the non-saturating paramagnetic nature of the magnetization response with very low saturation level of these spinels milled and annealed in air. On the other hand, single-phase Mn–Zn ferrite results from the identical precursor oxide blend when milling and annealing are carried out under controlled (Ar) atmosphere. The average grain size of the as-milled and annealed powders, measured by Rietvelt refinement, varies between 6–8 and 14–18 nm, respectively. Further investigations performed with Mn_0.6Zn_0.4Fe₂O₄ reveal that a careful selection of annealing parameters may lead to an early superparamagnetic relaxation. Therefore, the blocking temperature can be significantly reduced through proper heat treatment schedule to ensure superparamagnetism and negligible hysteresis at low temperature.     

镍锰铁氧体纳米线阵列的制备与表征

采用真空负压灌注技术, 结合溶胶-凝胶法在多孔氧化铝模板的纳米孔洞中成功制备了平均直径为80 nm左右的Ni_{1- x}Mn_xFe₂O₄(x=0, 0.25, 0.5, 0.75) 纳米线阵列. XRD结果显示所制备的纳米线阵列为立方尖晶石结构, SEM和TEM的结果表明纳米线是由大量不同晶体取向的亚微晶粒联接组成. 磁测量结果显示, 随着Mn掺杂浓度的增加, 饱和磁化强度先增加而后减小, 这种变化与离子在尖晶石结构中的替代、占位变化有关. 相比于块体材料的NiFe₂O₄, 由于非线性磁结构比例的增加, 导致了线体NiFe₂O₄的饱和磁化强度降低.     

Abnormal morphology of nanocrystalline Mn–Zn ferrite sintered by pulse electric current sintering

Nanocrystalline manganese–zinc (Mn–Zn) ferrite powders prepared by the sol–gel auto-combustion method are sintered to form bulk ferrite by pulse electric current sintering technique. The sample phase, before sintering and after sintering, is carried out by X-ray diffraction (XRD). The morphology of the sample is observed by scanning electron microscopy (SEM). The results indicate that the bulk ferrite obtained has a pure spinel structure. With special graphite die, a special morphology is observed, which is explained by pressure, temperature and induced electromagnetic field.     

Magnetic and Gas Sensing Property of Nanosized NiFe2O4 Powders Synthesized by Pulsed Wire Discharge

Nickel ferrite (NiFe₂O₄) powders were synthesized by pulsed wire discharge method. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses show that only nickel ferrite spinel and no other phase was observed in the powders. Mean size of the obtained particles strongly depended on the oxygen pressure: the higher oxygen pressure corresponds to larger powder size, as determined by Brunauer–Emmet–Teller (BET). The room temperature saturation magnetization of the synthesized powders was 42–46 emu/g depending on the powder size. These powders also showed high chlorine sensitivity at about 280–360°C, and a good linear sensitivity with chlorine concentration.     

Electronic structure at rubrene metal interfaces

Many studies have been done on low energy (1–200 keV) and high dose (10¹⁶–10¹⁷) implantation of Mn in GaAs. This study is an attempt to incorporate Mn ions in GaAs through implantation of 1 MeV Mn⁺¹ ions in semi-insulating GaAs substrates at doses of 3×10¹⁵/cm² and subsequent annealing. This was done to find out if any alloy of Mn–Ga–As, or binary compounds of Mn–Ga or Mn–As form due to annealing of Mn⁺¹ ions implanted in GaAs substrates. High Resolution XRD (HRXRD) performed before annealing shows a possibility of Ga–Mn–As alloy formation, and after annealing at 800°C, except for GaAs main peaks no other phase peaks were detected. Scanning electron microscopy (SEM) shows nanostructures of various dimensions which are thought to be formed due to the defects generated due to implantation. Fourier Transform Infrared (FTIR) study shows the shift in bandgap due to Mn doping. Raman spectroscopy shows the red shift in LO and TO peak positions of GaAs after annealing, which indicates the presence of disorder and damage due to implantation. Resistivity measurement shows a thermally activated semiconductor character of charge conduction with an activation energy of 51 meV and this activation may have occurred through the transitions from impurity band to valence band. Large positive (∼25%) magnetoresistance and a mixture of ferromagnetic and paramagnetic behavior obtained in the magnetization measurement indicate the presence of ferromagnetic MnAs nanoclusters embedded in paramagnetic GaAs:Mn matrix.     

Inverse magnetocaloric effect in sol–gel derived nanosized cobalt ferrite

The magnetocaloric properties of cobalt ferrite nanoparticles were investigated to evaluate the potential of these materials as magnetic refrigerants. Nanosized cobalt ferrites were synthesized by the method of sol–gel combustion. The nanoparticles were found to be spherical with an average crystallite size of 14 nm. The magnetic entropy change (ΔS _m) calculated indirectly from magnetization isotherms in the temperature region 170–320 K was found to be negative, signifying an inverse magnetocaloric effect in the nanoparticles. The magnitudes of the ΔS _m values were found to be larger when compared to the reported values in the literature for the corresponding ferrite materials in the nanoregime.     

Sol–gel auto-combustion synthesis,structural and enhanced magnetic properties of Ni substituted nanocrystalline Mg–Zn spinel ferrite

Nanocrystalline arrays of Ni²⁺ substituted Mg–Zn spinel ferrite having a generic formula Mg_0.7−xNi_xZn_0.3Fe₂O₄ (x=0.0, 0.2, 0.4 and 0.6) were successfully synthesized by sol–gel auto-combustion technique. The fuel used in the synthesis process was citric acid and the metal nitrate-to-citric acid ratio was taken as 1:3. The phase, crystal structure and morphology of Mg–Ni–Zn ferrites were investigated by X-ray diffraction, scanning electron microscopy, and Fourier transformer infrared spectroscopy techniques. The lattice constant, crystallite size, porosity and cation distribution were determined from the X-ray diffraction data method. The FTIR spectroscopy is used to deduce the structural investigation and redistribution of cations between octahedral and tetrahedral sites of Mg–Ni–Zn spinel structured material. Morphological investigation suggests the formation of grain growth as the Ni²⁺ content x increases. The saturation magnetization and magneton number were determined from hysteresis loop technique. The saturation magnetization increases with increasing Ni²⁺ concentration ‘x’ in Mg–Zn ferrite.     

Mn–ferrite nanoparticles via reverse microemulsions: synthesis and characterization

Mn–ferrite nanoparticles were synthesized by thermal treatment at 800 °C of manganese and iron oxo-hydroxides obtained via water-in-oil microemulsions consisting of n-hexanol as continuous phase, cetyl trimethyl ammonium bromide (CTAB) as the cationic surfactant and aqueous solutions of metal salts and precipitant agent (tetramethyl ammonium hydroxide) as reagents. Nanoparticles were synthesized using a multi-microemulsion approach. Two different co-precipitation routes are described depending on the Fe(II) or Fe(III) precursor salts. The influence of salt concentration and digestion process on the final products was examined. The nanoparticles were characterized by X-ray diffraction accompanied by Rietveld analysis, transmission electron microscopy, thermal analysis, infrared spectroscopy, and SQUID magnetometry. In all the synthesis reported in this study MnFe₂O₄ was observed only after thermal treatment at 800 °C of the as-prepared precursors. Almost spherical nanocrystalline MnFe₂O₄ ranging from 12 to 39 nm was obtained starting from chlorides or mixed chloride–sulfate salts as precursors. Low values of reduced remanent magnetization (M _r/M _s) and coercive field (H _c) induce to believe that a fraction of superparamagnetic particle is present at room temperature.     

Effect of zinc substitution on magnetic and electrical properties of nanocrystalline nickel ferrite synthesized by refluxing method

Nanocrystalline Nickel ferrite (NiFe₂O₄) and Zn substituted nickel ferrite (NiZnFe₂O₄) have been synthesized by the refluxing method. These ferrites were characterized by XRD, TEM, Mossbauer spectroscopy and VSM in order to study the effect of zinc substitution in nickel ferrite. XRD diffraction results confirm the spinel structure for the prepared nanocrystalline ferrites with an average crystallite size of 14-16 nm. Lattice parameter was found to increase with the substitution of Zn²⁺ ions from 8.40 Å to 8.42 Å. TEM images confirmed average particle size of about 20 nm and indicates nanocrystalline nature of the compounds. A shift in isomeric deviation with the doublet was observed due to the influence of Zn substitution in the nickel ferrite. The Zn content has a significant influence on the magnetic behavior and electrical conductivity of NiFe₂O₄. Saturation magnetization drastically increased whereas room temperature electrical conductivity decreased due to the addition of Zn content in NiFe₂O₄, indicating super magnetic material with lesser coercivity.     

Micro Raman,Mossbauer and magnetic studies of manganese substituted zinc ferrite nanoparticles: Role of Mn

A series of Mn–Zn Ferrite nanoparticles (<15 nm) with formula Mn_xZn_1−xFe₂O₄ (where x=0.00, 0.35, 0.50, 0.65) were successfully prepared by citrate-gel method at low temperature (400 °C). X-ray diffraction analysis confirmed the formation of single cubic spinel phase in these nanoparticles. The FESEM and TEM micrographs revealed the nanoparticles to be nearly spherical in shape and of fairly uniform size. The fractions of Mn²⁺, Zn²⁺ and Fe³⁺ cations occupying tetrahedral sites along with Fe occupying octahedral sites within the unit cell of different ferrite samples are estimated by room temperature micro-Raman spectroscopy. Low temperature Mossbauer measurement on Mn_0.5Zn_0.5Fe₂O₄ has reconfirmed the mixed spinel phase of these nanoparticles. Room temperature magnetization studies (PPMS) of Mn substituted samples showed superparamagnetic behavior. Manganese substitution for Zn in the ferrite caused the magnetization to increase from 04 to18 emu/g and Lande's g factor (estimated from ferromagnetic resonance measurement) from 2.02 to 2.12 when x was increased up to 0.50. The FMR has shown that higher Mn cationic substitution leads to increase in dipolar interaction and decrease in super exchange interaction. Thermomagnetic (M–T) and magnetization (M–H) measurements have shown that the increase in Mn concentration (up to x=0.50) enhances the spin ordering temperature up to 150 K (blocking temperature). Magnetocrystalline anisotropy in the nanoparticles was established by Mossbauer, ferromagnetic resonance and thermomagnetic measurements. The optimized substitution of manganese for zinc improves the magnetic properties and makes these nanoparticles a potential candidate for their applications in microwave region and biomedical field.     

Influence of copper cations on the magnetic properties of NiCuZn ferrite nanoparticles

Ni_0.6−xCu_xZn_0.4Fe₂O₄ (x=0-0.5) ferrite nanoparticles were prepared, employing a reverse micelle process. X-ray diffraction and transmission electron microscopy evaluations demonstrated that single phase spinel ferrites with narrow size distribution were obtained. Vibrating sample magnetometer was employed to probe the magnetic properties of the samples. It was found that with an increase in copper content, the saturation magnetization decreases. Magnetic dynamics of the samples was studied by measuring a.c. magnetic susceptibility versus temperature at different frequencies. The phenomenological Néel-Brown and Vogel-Fulcher models were employed to distinguish between the interacting or non-interacting systems. The system exhibits that there is strong interaction among fine particles.