Synthesis and magnetic properties of cobalt ferrite (CoFe2O4) nanoparticles prepared by wet chemical route

Magnetic nanoparticles of cobalt ferrite have been synthesized by wet chemical method using stable ferric and cobalt salts with oleic acid as the surfactant. X-ray Diffraction (XRD) and Transmission Electron Microscope (TEM) confirmed the formation of single-phase cobalt ferrite nanoparticles in the range 15–48 nm depending on the annealing temperature and time. The size of the particles increases with annealing temperature and time while the coercivity goes through a maximum, peaking at around 28 nm. A very large coercivity (10.5 kOe) is observed on cooling down to 77 K while typical blocking effects are observed below about 260 K. The high field moment is observed to be small for smaller particles and approaches the bulk value for large particles.     

The effect of solution temperature on crystallite size and magnetic properties of Zn substituted Co ferrite nanoparticles

In this work zinc substituted cobalt ferrite nanoparticles (Co_0.5Zn_0.5Fe₂O₄) have been synthesized by the coprecipitation method, using stable ferric, zinc and cobalt salts with sodium hydroxide, at different solution temperatures, from room temperature to 363 K. The cobalt-zinc ferrite crystalline phase, the particle size and the morphology of the resulting nanoparticles were studied by X-ray diffraction and transmission electron microscopy. The average crystallite size of each sample was calculated from the broadening of the most intense peak (3 1 1), using Scherrer's formula and the results show crystallite sizes increased from 6 to 8 nm by increasing the solution temperature from room temperature to 363 K respectively. Room temperature VSM measurements show that the prepared nanoparticles have superparamagnetic behavior and did not saturate at maximum field of 800 kA/m. The variation of AC-susceptibility of the samples with respect to temperature was measured and it was found that the blocking temperature increased from 198 to 270 K by increasing the solution temperature from room temperature to 363 K respectively. FTIR spectra of the samples have been analyzed in the frequency range 400-4000 cm⁻¹, which also confirms the results of XRD.     

Order-disorder transformation in FePt nanoparticles studied by ferromagnetic resonance

We have investigated the ferromagnetic resonance (FMR) response of as-made and temperature annealed FePt magnetic nanoparticles. The as-made nanoparticles, which have been fabricated by a chemical route, crystallize in the low magnetic anisotropy fcc phase and have a diameter in the range of 2-4 nm. The annealing of the particles at high temperatures (T_A=550, 650 and C) in an inert Ar atmosphere produces a partial transformation to the high magnetocrystalline anisotropy L1₀ phase, with a significant increase in particle size and size distribution. FMR measurements at X-band (9.5 GHz) and Q-band (34 GHz) show a single relatively narrow line for the as-synthesized particles and a structure of two superimposed lines for the three annealed samples. The origin of this line shape has been attributed to the presence of the disordered fcc phase. Assuming that the system consists of a collection of identical particles with a random distribution of easy axes, we have been able to estimate a mean value for the magnetic anisotropy constant of the particles in the fcc phase, K∼2×10⁶ erg/cm³. The measured line shape in the annealed samples can be explained if we consider that the magnetic anisotropy of the particles has a gaussian distribution with a relatively broad width.     

Temperature dependence of magnetic properties of NiFe2O4 nanoparticles embeded in SiO2 matrix

Spinel ferrite NiFe₂O₄ nanoparticles (?25 nm) in SiO₂ matrix were prepared by sol–gel method. The phase and average crystallite size of the samples were determined by X-ray diffraction method and the particle size distributions were studied by a transmission electron microscope. Magnetic properties of the samples were investigated with different ferrite particle sizes and at various temperatures down to 10 K. Superparamagnetic properties were observed at room temperature when the particle size is less than 10 nm.In superparamagnetic state, the field dependence of magnetization follows Langevin function which was originally developed for paramagnetism. The effective anisotropy constant K_eff is found to increase significantly with the decrease in particle volume and an order of magnitude higher than that of the bulk samples when the particle size is below 5 nm due to the dominance of surface anisotropy. In case of nanosized systems, the effect of size reduction on the law of approach to saturation has also been studied in detail.     

Synthesis and magnetic characterization of Zn0.6Ni0.4Fe2O4 nanoparticles via a polyethylene glycol-assisted hydrothermal route

Zn-doped nickel ferrite nanoparticles (Zn_0.6Ni_0.4Fe₂O₄) have been prepared via a surfactant, polyethylene glycol assisted hydrothermal route. X-ray powder diffractometry (XRD), Fourier transform infrared spectroscopy, transmission electron microscopy (TEM), and vibrating scanning magnetometry (VSM) were used for the structural, morphological, and magnetic characterizations of the product, respectively. TEM analysis revealed that the nanoparticles have a narrow size distribution, with average particle size of 15±1 nm, which agrees well with the XRD based estimate of 14±2 nm. The absence of saturation and remanent magnetization, and coercivity in the high temperature region of the M-H curve and non-zero magnetic moments indicate superparamagnetism of the nanoparticles with a canted spin structure. The appearance of a peak on the temperature-dependent zero-field cooling magnetization curve at ∼190 K indicates the blocking temperature of the sample.     

Microstructural,dielectric and magnetic behavior of spin-deposited nanocrystalline nickel–zinc ferrite thin films for microwave applications

Nanocrystalline nickel ferrite and zinc doped nickel ferrite thin films with general composition Ni_1−xZn_xFe₂O₄; x=0.0, 0.2 and 0.5 were fabricated by the spin-deposition technique. Citrate precursor method was adopted to prepare coating solution used for film deposition. This method resulted in single phase, transparent, homogeneous and crack-free nanocrystalline ferrite thin films at annealing temperature as low as 400 °C. The substrates used for film deposition were ITO-coated 7059 glass, fused quartz and Si (1 0 0). The thickness of films was found to be in the range ∼1000–5500 Å. The surface microstructure and morphology investigated by atomic force microscopy (AFM) confirmed the grain size of nickel–zinc ferrite films to be in nanometer range indicating nanocrystalline nature of the films. Dielectric properties such as the real (∈′) and imaginary parts (∈″) of complex permittivity were measured in the X-band microwave frequency region (8–12 GHz) by employing extended cavity perturbation technique. The M–H hysteresis measurements on the films annealed at 650 °C revealed narrow hysteresis curves with H_c and M_s varying for different compositions.     

Particle size effect on phase and magnetic properties of polymer-coated magnetic nanoparticles

Polymer-coated magnetic nanoparticles are hi-tech materials with ample applications in the field of biomedicine for the treatment of cancer and targeted drug delivery. In this study, magnetic nanoparticles were synthesized by chemical reduction of FeCl₂ solution with sodium borohydride and coated with amine-terminated polyethylene glycol (aPEG). By varying the concentration of the reactants, the particle size and the crystallinity of the particles were varied. The particle size was found to increase from 6 to 20 nm and the structure becomes amorphous-like with increase in the molar concentration of the reactant. The magnetization at 1 T field (M_1T) for all samples is > 45 emu/g while the coercivity is in the range of 100-350 Oe. When the ethanol-suspended particles are subjected to an alternating magnetic field of 4 Oe at 500 kHz, the temperature is increased to a maximum normalized temperature (3.8 °C/mg) with decreasing particle size.     

Ferromagnetic resonance observation of a phase transition in magnetic field-aligned Fe2O3 nanoparticles

Fe₂O₃ hematite (alpha) nanoparticles suspended in the liquid phase of the liquid crystal 4,4-azoxyanlsole (PAA) are cooled below the freezing temperature (397 K) in a 4000 G dc magnetic field. The in field solidification locks the direction of maximum magnetization of the particles parallel to the direction of the applied dc magnetic field removing the effects of dynamical fluctuations of the nanoparticles on the magnetic properties allowing a study of the intrinsic magnetic properties of the nanoparticles as well as the anisotropic behavior of the ferromagnetic resonance (FMR) signal. Freezing in PAA allows temperature-dependent measurements to be made at much higher temperature than previous measurements. The field position, line width and intensity of the FMR signal as a function of temperature as well as the magnetization show anomalies in the vicinity of 200 K indicative of a magnetic transition, likely the previously observed Morin transition shifted to lower temperature due to the small particle size. Weak ferromagnetism is observed below T_c in contrast to the bulk material where it is antiferromagnetic below T_c. The Raman spectrum above and below 200 K shows no evidence of a change in lattice symmetry associated with the magnetic transition.     

Mechanical alloyed Ho doping in CoFe2O4 spinel ferrite and understanding of magnetic nanodomains

We doped Ho³⁺ in CoFe_1.95Ho_0.05O₄ spinel ferrite by mechanical alloying and subsequent annealing at different temperatures (600-1200 °C). We understood the structural and magnetic properties of the samples using X-ray diffraction, SEM, Thermal analysis (TGA and DTA), and VSM measurement. The samples have shown structural stabilization within cubic spinel phase for the annealing temperature (T_AN)≥800 °C. Thermal activated grain growth kinetics has been accompanied with the substantial decrease in lattice strain. The gain size dependent magnetism is evident from the variation of magnetic moment, remanent magnetization and coercivity of the material. The paramagnetic to ferrimagnetic transition temperature T_C (∼805 K) seems to be grain size independent in the present material. The magnetic nanograins, either single domain/pseudo-single domain (50-64 nm) or multi-domain (above 64 nm) regime, showed superparamagnetic blocking below T_m, which is below T_C (805 K) and also well above the room temperature.     

Synthesis of magnetite nanoparticles via a solvent-free thermal decomposition route

Superparamagnetic nanoparticles have been widely applied in various bio-medical applications. To date, it is still a challenge to synthesize nanosized Fe₃O₄ particles with controlled size and distribution. In this paper, a novel solvent-free thermal decomposition method is reported for synthesizing Fe₃O₄ nanoparticles. Size and morphology of the nanoparticles are determined by TEM while the structure of the nanoparticles is identified by FTIR, XPS and TGA measurements. Magnetic properties of the obtained particles are determined using VSM and SQUID measurement. The particle size of the Fe₃O₄ can be tailored by adjusting either reaction temperature or time. When the reaction temperature is increased to 330 °C and the reaction time is extended to 4 h, the average particle size of the obtained nanoparticles is ∼9 nm, while Ms value reaches ∼76 emu/g. The as synthesized Fe₃O₄ nanoparticles show well-established superparamagnetic properties with the blocking temperature at around 100 K.     

Surface effects in maghemite nanoparticles

A consistent model is presented for the variation of saturation magnetization with particle size in maghemite nanoparticles, based on the existence of a magnetically disordered layer with a constant thickness of 1 nm. For particles smaller than 3 nm, layer thickness increases rapidly, and M_S is already zero for 2.5 nm particle size. Magnetization measurements have been performed on maghemite–polymer nanocomposites with low size dispersion and a regular distribution of particles in the matrix. A representative number of samples have been studied with a diameter size in the range from 1.5 to 15 nm and ±10% of size dispersion.     

High concentration of hematite nanoparticles in a silica matrix: Structural and magnetic properties

The α-Fe₂O₃/SiO₂ nanocomposite containing 45 wt% of hematite was prepared by the sol-gel method followed by heating in air at 200 °C. The so-obtained composite of iron(III) nanoparticles dissolved in glassy silica matrix was investigated by X-ray powder diffraction (XRPD), transmission electron microscopy (TEM), and superconducting quantum interference device (SQUID) magnetometry. XRPD confirms the formation of a single-phase hematite sample, whereas TEM reveals spherical particles in a silica matrix with an average diameter of 10 nm. DC magnetization shows bifurcation of the zero-field-cooled (ZFC) and field-cooled (FC) branches up to the room temperature with a blocking temperature T_B=65 K. Isothermal M(H) dependence displays significant hysteretic behaviour below T_B, whereas the room temperature data were successfully fitted to a weighted Langevin function. The average particle size obtained from this fit is in agreement with the TEM findings. The small shift of the T_B value with the magnetic field strength, narrowing of the hysteresis loop at low applied field, and the frequency dependence of the AC susceptibility data point to the presence of inter-particle interactions. The analysis of the results suggests that the system consists of single-domain nanoparticles with intermediate strength interactions.     

Tailoring the exchange bias of Ni/NiO nanogranular samples by the structure control

The exchange bias (EB) effect has been studied in Ni/NiO nanogranular samples obtained by annealing in H₂, at selected temperatures (200≤T_ann≤300 °C), NiO powder previously milled for 5, 10, 20 and 30 h. Both the as-milled NiO powders and the Ni/NiO samples have been analyzed by X-ray diffraction and the exchange bias properties have been investigated in the 5-200 K temperature range. The structure and the composition of the Ni/NiO samples can be satisfactorily controlled during the synthesis procedure by varying both T_ann and the milling time of the precursor NiO powders. In particular, by increasing this last parameter, the mean grain size of the NiO phase reduces down to the final value of 16 nm and the microstrain increases, which is consistent with an enhancement of the structural disorder. The structure of the milled NiO matrix strongly affects the process of nucleation and growth of the Ni nanocrystallites induced by the H₂ treatments, so that, T_ann being equal, the amount and the mean grain size D_Ni of the Ni phase vary substantially in samples having different milling times. Such features of the Ni phase determine the extent of the Ni/NiO interface and consequently the magnitude of the exchange field H_ex: the highest value (∼940 Oe) has been measured at T=5 K in a sample containing ∼7 wt% Ni and with D_Ni=19 nm. However, in Ni/NiO samples with very different structural characteristics and different values of H_ex at T=5 K, the EB effect vanishes at the same temperature (∼200 K) and the same thermal dependence of H_ex is observed. We consider that the evolution of the EB effect with temperature is ultimately determined by the microstructure of the Ni/NiO interface, which cannot be substantially modified by changing the synthesis parameters, milling time and T_ann.     

Synthesis and magnetic characterization of cobalt-substituted ferrite (CoxFe3−xO4) nanoparticles

Cobalt-substituted ferrite nanoparticles were synthesized with a narrow size distribution using reverse micelles formed in the system water/AOT/isooctane. Fe:Co ratios of 3:1, 4:1, and 5:1 were used in the synthesis, obtaining cobalt-substituted ferrites (Co_xFe_3−xO₄) and some indication of γ-Fe₃O₄ when 4:1 and 5:1 Fe:Co ratios were used. Inductively coupled plasma mass spectroscopy (ICP-MS) verified the presence of cobalt in all samples. Fourier transform infrared (FTIR) showed bands at ∼560 and ∼400 cm⁻¹, characteristic of the metal–oxygen bond in ferrites. Transmission electron microscopy showed that the number median diameter of the particles was ∼3 nm with a geometric deviation of ∼0.2. X-ray diffraction (XRD) confirmed the inverse spinel structure typical of ferrites with a lattice parameter of a=8.388 Å for Co_0.61Fe_0.39O₄, which is near that of CoFe₂O₄ (a=8.394 Å). Magnetic properties were determined using a superconducting quantum interference device (SQUID). Coercivities higher than 8 kOe were observed at 5 K, whereas at 300 K the particles showed superparamagnetic behavior. The anisotropy constant was determined based on the Debye model for a magnetic dipole in an oscillating field and an expression relating χ′ and the temperature of the in-phase susceptibility peak. Anisotropy constant values in the order of ∼10⁶ erg/cm³ were determined using the Debye model, whereas anisotropy constants in the order of ∼10⁷ erg/cm³ were calculated assuming Ωτ=1 at the temperature peak of the in-phase component of the susceptibility curve as commonly done in the literature. Our analysis demonstrates that the assumption Ωτ=1 at the temperature peak of χ′ is rigorously incorrect.     

Exchange bias in Co nanoparticles embedded in an Mn matrix

Magnetic properties of Co nanoparticles of 1.8 nm diameter embedded in Mn and Ag matrices have been studied as a function of the volume fraction (VFF). While the Co nanoparticles in the Ag matrix show superparamagnetic behavior with T_B=9.5 K (1.5% VFF) and T_B=18.5 K (8.9% VFF), the Co nanoparticles in the antiferromagnetic Mn matrix show a transition peak at ∼65 K in the ZFC/FC susceptibility measurements, and an increase of the coercive fields at low temperature with respect to the Ag matrix. Exchange bias due to the interface exchange coupling between Co particles and the antiferromagnetic Mn matrix has also been studied. The exchange bias field (H_eb), observed for all Co/Mn samples below 40 K, decreases with decreasing volume fraction and with increasing temperature and depends on the field of cooling (H_fc). Exchange bias is accompanied by an increase of coercivity.     

Magnetic properties and microstructure of cobalt nanoparticles in a polymer film

Superparamagnetic properties of self-aggregated cobalt nanoparticles in the perfluorinated sulfo-cation membrane (MF-4SK) prepared by ion-exchange method were investigated by transmission electron microscopy (TEM) and superconducting quantum interference device (SQUID) magnetometry at various temperatures. Our experimental results show that cobalt nanoparticles in MF-4SK exhibit superparamagnetic properties above the blocking temperature (T_B), which varies from ∼80 to ∼300 K depending on the cobalt concentration at 100 Oe applied field. The average particle radius of 3.8 nm inferred from Langevin function fit for the concentration of 7.8×10¹⁹ cobalt atoms per 1 g of polymer film is in good agreement with TEM observation. This experimental evidence suggests that cobalt nanoparticles in the polymer film obey a single-domain theory. The results are discussed in the light of current theory for the superparamagnetic behavior of magnetic nanoparticles.     

Magnetic resonance study of Ce and Gd doped NiFe2O4 nanoparticles

Present work is a study of temperature dependent electron paramagnetic resonance spectra of Ce and Gd doped nickel ferrite nanoparticles. The samples, synthesised by chemical route were characterised by X-ray diffractometer, electron paramagnetic resonance spectroscopy (EPR) and vibrating sample magnetometer (VSM). The average crystallite size of pure nickel ferrite is ∼64 nm and for Gd and Ce doped samples it is ∼20 nm and ∼14 nm, respectively. The EPR spectra were recorded from 120 to 300 K. Doping with Gd and Ce reduces the line width and g-value in comparison to that of pure nickel ferrite. Ce doped samples have the lowest values of both these parameters at room temperature. This indicates that Ce doped samples show lowest loss and is suitable for high frequency devices. EPR spin numbers are reduced while the spin relaxation time is increased after doping with rare earth ions. Gd doped samples have higher values of relaxation time and lower spin numbers in comparison to that of Ce doped samples. VSM results show that the magnetisation and coercivity are reduced after doping with both Ce and Gd rare earth ions.     

Structural,magnetic and Mössbauer spectral studies of nanosize aluminum substituted nickel zinc ferrites

Nanosize aluminum substituted nickel zinc ferrites were prepared through aerosol route and characterized using TEM, XRD, magnetic measurements and Mössbauer spectroscopy. The particle size of as obtained samples was found to be ∼10 nm which increases up to ∼85 nm upon annealing at 1200 °C. The unit cell parameter ‘a’ decreases linearly with concentration of aluminum due to the small ionic radius of aluminum. The saturation magnetization for all the samples after annealing at 1200 °C lies in the range 12.9–72.6 emu/g and decreases linearly with concentration of aluminum. Room temperature Mössbauer spectra of all as obtained samples of ferrite compositions exhibited a broad doublet suggesting super paramagnetic nature. This doublet is further resolved into two doublets and assigned to the surface region and internal region atoms of the particles. The samples annealed at 1200 °C show broad sextets, which were fitted with five sextets, indicating different local environment of both tetrahedrally and octahedrally coordinated Fe cation.     

Magnetic properties of nanocrystalline Co1−xZnxFe2O4 prepared by forced hydrolysis method

Nanocrystalline zinc-substituted cobalt ferrite powders, Co_1−xZn_xFe₂O₄ (x=0, 0.2, 0.4), were for the first time prepared by forced hydrolysis method. Magnetic and structural properties in these specimens were investigated. The average crystallite size is about 3.0 nm. When the zinc substitution increases from x=0 to x=0.4, at 4.2 K, the saturation magnetization increases from 72.1 to 99.7 emu/g and the coercive field decreases from 1.22 to 0.71 T. All samples are superparamagnetic at room temperature and ferrimagnetic at temperatures below the blocking temperature. The high value of the saturation magnetization and the very thin thickness of the disorder surface layer of all samples suggests that this forced hydrolysis method is suitable not only for preparing two metal element systems but also for three or more ones.