Synthesis of cobalt ferrite nano-particles and their magnetic characterization

Cobalt ferrite nano-particles (CoFe₂O₄) were synthesized by the co-precipitation method with ammonium hydroxide as an alkaline solution. The reactions were carried out at different temperatures between 20 and 80 °C. The nano-particles have been investigated by magnetic measurements, X-ray powder diffraction and transmission electron microscopy. The average crystallite size of the synthesized samples was between 11 and 45 nm, which was found to be dependent on both pH value of the reaction and annealing temperatures. However, lattice parameters, interplane spacing and grain size were controlled by varying the annealing temperature. Magnetic characterization of the nano-samples were carried out using a vibrating sample magnetometer at room temperature. The saturation magnetization was computed and found to lie between 5 and 67 emu/g depending on the particle size of the studied sample. The coercivity was found to exhibit non-monotonic behavior with the particle size. Such behavior can be accounted for by the combination between surface anisotropy and thermal energies. The ratio of remanence magnetization to saturation magnetization was found to exhibit almost linear dependence on the particle size.     

Composition and magnetic properties of cobalt ferrite nano-particles prepared by the co-precipitation method

Cobalt ferrite nano-particles were prepared using the co-precipitation method followed by annealing treatment. The formation of nano-particles with different composition, microstructure and sizes were confirmed by X-ray diffraction, Raman, thermogravimetric-differential thermal analysis and transmission electron microscope. The magnetic hysteresis loops measured at room temperature revealed smaller effective magnetic anisotropy constant, coercivity and remanence ratio for the samples prepared by adding the NaOH solutions into the mixed solutions of Co²⁺ and Fe³⁺ ions due to the formation of Co³⁺ ions. A small saturation magnetization and an enhanced coercivity were observed for the nano-particles prepared by adding the mixed solutions of Co²⁺ and Fe³⁺ ions into the NaOH solutions, which was related to the formation of outer layers with poor crystallization on the surfaces of the cobalt ferrite nano-crystals. Furthermore, the existence of these outer layers induced the oxidation of Co²⁺ ions in cobalt ferrite nano-crystals at 200 and 300 °C, and led to a large change on the composition and magnetic properties.     

Temperature dependence of magnetic anisotropy constant in cobalt ferrite nanoparticles

The temperature dependence of the effective magnetic anisotropy constant K(T) of CoFe₂O₄ nanoparticles is obtained based on the SQUID magnetometry measurements and Mössbauer spectroscopy. The variation of the blocking temperature T_B as a function of particle radius r is first determined by associating the particle size distribution and the anisotropy energy barrier distribution deduced from the hysteresis curve and the magnetization decay curve, respectively. Finally, the magnetic anisotropy constant at each temperature is calculated from the relation between r and T_B. The resultant effective magnetic anisotropy constant K(T) decreases markedly with increasing temperature from 1.1×10⁷ J/m³ at 5 K to 0.6×10⁵ J/m³ at 280 K. The attempt time τ₀ is also determined to be 6.1×10⁻¹² s which together with the K(T) best explains the temperature dependence of superparamagnetic fraction in Mössbauer spectra.     

Ionic magnetic fluid based on cobalt ferrite nanoparticles: Influence of hydrothermal treatment on the nanoparticle size

Magnetic fluid based on cobalt ferrite nanoparticles was obtained using a hydrothermal treatment added to the Massart procedure. This treatment increases the average size of the nanoparticles from 11.9 to 18.7 nm and also improves the dispersity and crystallinity of the cobalt ferrite particles. The nanoparticles obtained after the hydrothermal treatment were dispersed in aqueous solvent by the classical procedure for ionic magnetic fluids. The ferrofluid thus obtained is stable at pH 7 and may be useful for hyperthermia applications.     

Effect of aluminum substitution on the structural and magnetic properties of cobalt ferrite synthesized by sol-gel auto combustion process

Aluminum substituted cobalt ferrite powders (CoFe_2−xAl_xO₄) with varying composition from 0.0 to 1.0 in the step of 0.2 have been obtained by sol-gel auto combustion technique using citric acid as a fuel. The metal nitrate to fuel ratio was maintained 1:4 throughout the synthesis of CoFe_2−xAl_xO₄. The thermal analysis of as prepared samples is done by TGA technique. The compositional stoichiometry of the prepared samples is confirmed by Energy dispersive X-ray analysis technique. Single phase cubic spinel structure and nano phase structure of the synthesized powders were confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The crystallite size of 16-26 nm was obtained using Scherrer formula. SEM analysis shows the formation of uniform grain growth. The grain size obtained from SEM results is of the order of 30 nm. Maximum specific surface area was observed to be of the order of 52 m²/gm. The highest value of saturation magnetization and coercivity was observed for pure cobalt ferrite sample and it decreases as the aluminum content x increases. A strong co-relation between the saturation magnetization and aluminum content was observed. The decrease in magnetic properties is due to the substitution of aluminum ions in place of Fe³⁺.     

Microstructure characterization and cation distribution of nanocrystalline cobalt ferrite

Nanocrystalline cobalt ferrite has been synthesized using two different methods: ceramic and co-precipitation techniques. The nanocrystalline ferrite phase has been formed after 3 h of sintering at 1000 °C. The structural and microstructural evolutions of the nanophase have been studied using X-ray powder diffraction and the Rietveld method. The refinement result showed that the type of the cationic distribution over the tetrahedral and octahedral sites in the nanocrystalline lattice is partially an inverse spinel. The transmission electronic microscope analysis confirmed the X-ray results. The magnetic properties of the samples were characterized using a vibrating sample magnetometer.     

Investigations on structural and magnetic properties of cobalt ferrite/silica nanocomposites prepared by the coprecipitation method

Magnetic nanocomposites consisting of cobalt ferrite nanoparticles embedded in silica matrix were prepared by the coprecipitation method using metallic chlorides as precursors for ferrite. Subsequently composites were annealed at 100, 200 and 300 °C for 2 h. The samples were structurally characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The magnetic properties were measured in the temperature range of 10-300 K using vibrating sample magnetometer (VSM). The effects of thermal treatment on structural and magnetic properties of nanocomposites were investigated. When the samples were annealed, CoFe₂O₄ nanocrystallites were observed in the SiO₂ matrix, whose size increases with increase in annealing temperature. The coercivity and saturation magnetization of nanocomposite (annealed at 300 °C for 2 h) are much higher than that of bulk cobalt ferrite. The realization of adjustable particle sizes and controllable magnetic properties makes the applicability of the CoFe₂O₄ nanocomposite more versatile.     

Structure and magnetic properties of nanocrystalline cobalt ferrite powders synthesized using organic acid precursor method

Nanocrystalline octahedra of cobalt ferrite CoFe₂O₄ powders were synthesized using the organic acid precursor route. The effect of the calcination temperature, Fe³⁺/Co²⁺ molar ratio, calcination time and type of organic acid (oxalic, benzoic and tartaric acids) on the formation, crystallite size, microstructure and magnetic properties was studied systematically. The Fe³⁺/Co²⁺ molar ratio was varied from 2 to 1.739 while the annealing temperature was controlled from 400 to 1000 °C for various periods from 0.5 to 2 h. The resulting powders were investigated using X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). XRD results indicate that a well crystallized, single spinel cobalt ferrite phase was formed for the precursors annealed at 600-800 °C for 2 h, using oxalic and tartaric acids as precursors for Fe³⁺/Co²⁺ molar ratio 1.818. The crystallite size of as-formed powders was in the range of 38.0-92.6 nm at different operating conditions. The calcination temperature and Fe³⁺/Co²⁺ molar ratio have a significant effect on the microstructure of the produced cobalt ferrite. The microstructure of the produced powders was found to be octahedra-shaped. The crystalline, pure cobalt ferrite powders with magnetic properties having a maximum saturation magnetization (76.1 emu/g) was achieved for the single phase at Fe³⁺/Co²⁺ molar ratio 1.818 and annealing temperature of 600 °C for 2 h using tartaric acid precursor.     

High magnetostriction coefficient of Mn substituted cobalt ferrite sintered from nanocrystalline powders and after magnetic field annealing

Magnetostriction characteristics of Mn substituted cobalt ferrite, CoFe_2?xMn_xO₄ (0 ≤ x ≤ 0.3), sintered from nanocrystalline powders of average particle size of ～4 nm have been studied. Larger value of magnetostriction at lower magnetic field is achieved after substitution of Mn for Fe. The maximum value of magnetostriction coefficient is not much affected and the slope of the magnetostriction is increased with increasing Mn content. Higher maximum value of magnetostriction coefficient (λ) of 234 ppm comparable to that of the unsubstituted composition with larger strain derivative (dλ/dH) is obtained for x = 0.2 in CoFe_2?xMn_xO₄. The magnetostriction coefficient is increased to 262 ppm with further enhancement in the strain derivative after annealing the sintered compact at 300 °C in a magnetic field of 400 kA/m for 30 min.     

Tape casting of cobalt ferrite from nonaqueous slurry

This paper describes the fabrication of CoFe₂O₄ thick films using the tape casting method from nonaqueous slurry. CoFe₂O₄ particles with average size of ∼800 nm were prepared by the solid-state reaction method. Sediment volumes and viscosity were tested to study the effects of dispersant in reducing aggregations in slurry. Slurry with 0.25 wt% dispersant amounts and 41.3 wt% solid content showed the optimal stability and rheological properties. A tape velocity of 8 cm/s was used in this study considering the non-Newtonian flow behavior at low shear rate. CoFe₂O₄ ceramic films sintered at 1150 °C for 2 h have dense structure (relative density of 94%) and exhibited ferromagnetic properties with in-plane saturation magnetization of ∼324 emu/cm³.     

Dielectric,electrical transport and magnetic properties of Er3+substituted nanocrystalline cobalt ferrite

Erbium substituted cobalt ferrite (CoFe_2−xEr_xO₄; x=0.0–0.2, referred to CFEO) materials were synthesized by sol-gel auto-combustion method. The effect of erbium (Er³⁺) substitution on the crystal structure, dielectric, electrical transport and magnetic properties of cobalt ferrite is evaluated. CoFe_2−xEr_xO₄ ceramics exhibit the spinel cubic structure without any impurity phase for x≤0.10 whereas formation of the ErFeO₃ orthoferrite secondary phase was observed for x≥0.15. All the CFEO samples demonstrate the typical hysteresis (M–H) behavior with a decrease in magnetization as a function of Er content due to weak superexchange interaction. The frequency (f) dependent dielectric constant (ε′) revealed the usual dielectric dispersion. The ε′–f dispersion (f=20 Hz to 1 MHz) fits to the modified Debye's function with more than one ion contributing to the relaxation. The relaxation time and spread factor derived are ∼10⁻⁴ s and ∼0.61(±0.04), respectively. Electrical and dielectric studies indicate that ε′ increases and the dc electrical resistivity decreases as a function of Er content (x≤0.15). Complex impedance analyses confirm only the grain interior contribution to the conduction process. Temperature dependent electrical transport and room temperature ac conductivity (σ_ac) analyses indicate the semiconducting nature and small polaron hopping.     

Reduced conductivity and enhancement of Debye orientational polarization in lanthanum doped cobalt ferrite nanoparticles

In this work we have investigated the conductivity and dielectric properties of CoLa_xFe_2−xO₄ (x=0.0, 0.03, 0.05, and 0.07) nanoparticles synthesized by chemical co-precipitation route. X-ray diffraction analysis confirms the inverse spinal structure of nanoparticles with slight increase in the lattice constant as La concentration increases. Transmission electron microscopy shows spherical nanoparticles with sizes of ∼20 nm. Impedance spectroscopy of the samples was performed in the frequency range 20 Hz-2 MHz at room temperature. The resistance of the grains and grain boundaries was found to increase with lanthanum concentration while the AC conductivity of the samples was observed to decrease with increasing La concentration. Dipolar orientational polarization was found to play an important role in determining dielectric properties of the samples.     

Influence of vacuum sintering on microstructure and magnetic properties of magnetostrictive cobalt ferrite

Differences in the microstructure and magnetic properties of highly magnetostrictive cobalt ferrite resulting from the effects of different vacuum sintering temperatures and times have been investigated. A vacuum environment was chosen to allow direct comparison of results with air-sintered samples which are more often reported in the literature. It was found that vacuum sintering resulted in the development of a solid solution second phase with composition Co_1−xFe_xO₄ (x∼0.33). There was a decrease in magnetostriction as a result of the formation of the second phase. Furthermore, differences in sintering temperatures were found to have a greater effect on the magnetostriction than differences in sintering times. It was found that the first order cubic anisotropy coefficient initially increased with both sintering temperature and time, before peaking and decreasing to its lowest measured value. The lowest anisotropy was therefore achieved with samples sintered at higher temperatures and longer times.     

Structural and magnetic properties of nanocrystalline stannic substituted cobalt ferrite

The structural and magnetic properties of the spinel ferrite system Co_1+xFe_2−2xSn_xO₄ (x=0.0–1.0) have been studied. Samples in the series were prepared by the ceramic technique. The structural and microstructural evolutions of the nanophase have been studied using X-ray powder diffraction and the Rietveld method. The refinement result showed that the type of the cationic distribution over the tetrahedral and octahedral sites in the nanocrystalline lattice is partially an inverse spinel. Far infrared absorption spectra show two significant absorption bands, around 600 cm⁻¹ and 425 cm⁻¹, which are respectively attributed to tetrahedral (A) and octahedral [B] vibrations of the spinel. Scanning Electron Microscopy (SEM) was used to study surface morphology. SEM images reveal particles in the nanosize range. The transmission electronic microscope (TEM) reveals that the grains are spherical in shape. TEM analysis confirmed the X-ray results. The magnetic properties of the prepared samples were characterized by using a vibrating sample magnetometer.     

Effect of heat treatment on the magnetic and magnetoelastic properties of cobalt ferrite

The influence of different heat treatments on the magnetic and magnetoelastic properties of highly magnetostrictive CoFe₂O₄ has been investigated. The first order cubic anisotropy coefficient, coercive field, magnetostriction and high strain sensitivity were observed to decrease as the heat treatment temperature increased. The saturation magnetization of the samples on the other hand increased with increase in heat treatment temperature. These changes were not accompanied by any observable changes in crystal structure or composition and are indicative of migration of Co²⁺ from the octahedral sites (B-sites) to the tetrahedral sites (A-sites) and Fe³⁺ from the A-sites to the B-sites of the spinel structure. Different distributions of the cations at the two distinct lattice sites can strongly affect the magnetic and magnetoelastic properties of these materials.     

Thermal activation of magnetization in Pr_2Fe_(14)B ribbons

The aftereffect field of thermal activation,which corresponds to the fluctuation field of a domain wall,is investigated via specific measurements of the magnetization behavior in Pr2Fe14B nanocrystalline magnets.The thermal activation is a magnetization reversal arising from thermal fluctuation over an energy barrier to an equilibrate state.According to the magnetic viscosity and the field sweep rate dependence of the coercivity,the calculated values of the fluctuation field are lower than the aftereffect field and in a range between those of domain walls and individual grains.Based on these results,we propose that the magnetization reversal occurs in multiple ways involving grain activation and domain wall activation in thermal activation,and the thermal activation decreases the coercivity by~0.2 kOe in the Pr2Fe14B ribbons.     

Dependence of the magnetic and magnetoelastic properties of cobalt ferrite on processing parameters

The dependence of the magnetic and magnetoelastic properties of highly magnetostrictive cobalt ferrite on processing parameters has been investigated. The cobalt ferrite samples used in this study were prepared via conventional ceramic processing methods. The processing parameters of interest were sintering temperature, holding time at the sintering temperature and powder compaction pressure. It was observed that the crystal structure, composition and saturation magnetization of the samples studied did not vary with changes in processing parameters but coercive field decreased with increasing sintering temperature. The amplitude of peak to peak magnetostriction was dependent on the holding time and powder compaction pressure. The strain derivative on the other hand was found to depend on powder compaction pressure at any given sintering temperature or holding time. The results show how the magnetoelastic properties of cobalt ferrite can be varied by changing the processing parameters.     

Cobalt ferrite nanoparticles: The control of the particle size and surface state and their effects on magnetic properties

In order to improve the efficacy of magnetic fluid hyperthermia (MFH) mediators, we synthesised cobalt ferrite nanoparticles with different sizes (between 5 and 7 nm) via successive polyol synthesis. The static and dynamic magnetic properties of the prepared particles, dispersed in a solid matrix, were investigated in order to evaluate the possibility of applying cobalt ferrite as magnetic susceptors in MFH. The effect on magnetic properties coming from the surface anchoring of the model molecule cetyl phosphate, was also investigated.     

Magnetostatic interactions in cylindrical nanostructures with non-uniform magnetization

Cylindrical magnetic nanostructures, like nanowires or nanotubes, should be used for the new generation of magnetic devices. Therefore, the investigation of inter-element interaction is an intense area of research. In this paper we investigated cylindrical nanostructures with non-uniform magnetization field. We focus on particles with a periodic magnetization function and using Fourier series we reduced the problem to a single integral expression. Analytical expressions for both, the self and the interaction magnetostatic energy, are given. These expressions are used to analyze multisegmented tubes, as a function of the number of segments and the distance between particles.     

Combined effect of demagnetizing field and induced magnetic anisotropy on the magnetic properties of manganese-zinc ferrite composites

This work is devoted to the analysis of factors responsible for the high-frequency shift of the complex permeability (μ^?) dispersion region in polymer composites of manganese-zinc (MnZn) ferrite, as well as to the increase in their thermomagnetic stability. The magnetic spectra of the ferrite and its composites with polyurethane (MnZn-PU) and polyaniline (MnZn-PANI) are measured in the frequency range from 1 MHz to 3 GHz in a longitudinal magnetization field of up to 700 Ое and in the temperature interval from −20 °С to +150 °С. The approximation of the magnetic spectra by a model, which takes into account the role of domain wall motion and magnetization rotation, allows one to determine the specific contribution of resonance processes associated with domain wall motion and the natural ferromagnetic resonance to the μ^?. It is established that, at high frequencies, the μ^? of the MnZn ferrite is determined solely by magnetization rotation, which occurs in the region of natural ferromagnetic resonance when the ferrite is in the “single domain” state. In the polymer composites of the MnZn ferrite, the high-frequency permeability is also determined mainly by the magnetization rotation; however, up to high values of magnetizing fields, there is a contribution of domain wall motion, thus the “single domain” state in ferrite is not reached. The frequency and temperature dependence of μ^? in polymer composites are governed by demagnetizing field and the induced magnetic anisotropy. The contribution of the induced magnetic anisotropy is crucial for MnZn-PANI. It is attributed to the elastic stresses that arise due to the domain wall pinning by a polyaniline film adsorbed on the surface of the ferrite during in-situ polymerization.