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.     

Effect of high magnetic field annealing on the microstructure and magnetic properties of Co-Fe layered double hydroxide

The effects of high magnetic field (10 T) on the products obtained by calcination of Co-Fe LDH precursors at different temperatures were investigated. The XRD results indicated that Fe^III substituted for Co^III in Co₃O₄ to yield Co^IICo^IIIFe^IIIO₄ under the calcination of Co-Fe LDH precursors at 400 °C. The products obtained by magnetic field annealing at 400 °C had a porous plate-like morphology, whereas the products without magnetic field annealing were composed of nanoparticles. It was seen that CoFe₂O₄ phase could be formed at low temperature (about 500 °C) under the magnetic field annealing. The grain size of products obtained by magnetic field annealing at 800 °C was larger than that of zero magnetic field. It was found that the saturation magnetization was significantly enhanced after magnetic field annealing, especially at lower temperature (≤600 °C). The possible reason for the effects on the microstructure and magnetic properties of products obtained by magnetic field annealing was discussed.     

Heat generation of aqueously dispersed CoFe2O4 nanoparticles as heating agents for magnetically activated drug delivery and hyperthermia

Self-heating from magnetic nanoparticles under AC magnetic field can be used either for hyperthermia or to trigger the release of an anti-cancer drug, using thermo-responsive polymers. The heat generated by applying an AC magnetic field depends on the properties of magnetic nanoparticles (composition, size, crystal structure) as well as the frequency and amplitude of the magnetic field. Before these systems can be efficiently applied for in vitro or in vivo studies, a thorough analysis of the magnetically induced heating is required. In this study, CoFe₂O₄ nanoparticles were synthesized, dispersed in water, and investigated as heating agents for magnetic thermo-drug delivery and hyperthermia. The temperature profiles and infrared (IR) camera images of heat generation of CoFe₂O₄ nanoparticles under various AC magnetic fields of 127–700 Oe at 195, 231, and 266 kHz were measured using an IR thermacam, excluding the external AC magnetic field interruption. The CoFe₂O₄ nanoparticles were successfully dispersed in water using an 11-mercaptoundecanoic acid ligand exchange method to exchange the solvent used for synthesis of hexane for water. During the heating experiments, each of CoFe₂O₄ nanoparticle solutions reached a steady state where the temperature rose between 0.1 and 42.9 °C above ambient conditions when a magnetic field of 127–634 Oe was applied at 231 or 266 kHz. The heat generation was found to be dependent on the intensity of AC magnetic field and applied frequency. Therefore, the desired heating for magnetically triggered drug delivery or hyperthermia could be achieved in water-dispersed CoFe₂O₄ nanoparticles by adjusting the AC magnetic field and frequency.     

Morphology and magnetic properties of FeCo nanocrystalline powder produced by modified mechanochemical procedure

Properties of FeCo nanocrystalline intermetallic powders prepared by salt-matrix hydrogen reduction of a milled Fe₂O₃-Co₃O₄ mixture were investigated. The product of 72 ks ball-milling at 350 rpm was CoFe₂O₄ nanopowder. Reduction of this powder for 3.6 ks by hydrogen at 750 °C resulted in the formation of Fe_0.67Co_0.33 stoichiometric compound. Scanning electron microscopy, electron dispersive spectrometry, X-ray diffraction and vibrating sample magnetometry were used to characterize the nanopowder. Using a salt-matrix (NaCl as a dispersion medium) resulted in the decrease of the reduction temperature and improvement of the morphology and magnetic properties of the nanopowder. Dispersion of the ball-milled product in Hexan resulted in further improvements of the magnetic properties.     

Preparation of silica coated cobalt ferrite magnetic nanoparticles for the purification of histidine-tagged proteins

Surface modified cobalt ferrite (CoFe₂O₄) nanoparticles containing Ni–NTA affinity group were synthesized and used for the separation of histidine tag proteins from the complex matrices through the use of imidazole side chains of histidine molecules. Firstly, CoFe₂O₄ nanoparticles with a narrow size distribution were prepared in an aqueous solution using the controlled co-precipitation method. In order to obtain small CoFe₂O₄ agglomerates, oleic acid and sodium chloride were used as dispersants. The CoFe₂O₄ particles were coated with silica and subsequently the surface of these silica coated particles (SiO₂–CoFe₂O₄) was modified by amine (NH₂) groups in order to add further functional groups on the silica shell. Then, carboxyl (–COOH) functional groups were added to the SiO₂–CoFe₂O₄ magnetic nanoparticles through the NH₂ groups. After that Nα,Nα–Bis(carboxymethyl)-l-lysine hydrate (NTA) was attached to carboxyl ends of the structure. Finally, the surface modified nanoparticles were labeled with nickel (Ni) (II) ions. Furthermore, the modified SiO₂–CoFe₂O₄ magnetic nanoparticles were utilized as a new system that allows purification of the N-terminal His-tagged recombinant small heat shock protein, Tpv-sHSP 14.3.     

Particles size effects of single domain CoFe2O4 on suspensions stability

Single domain magnetic CoFe₂O₄ nanoparticles with spinel structure were prepared by the coprecipitation method. Particles with size of 16, 20, 40 and 60 nm were synthesized by sintering the precursor at 500, 600, 800 and 900 °C, respectively. The magnetic hysteresis measurement of CoFe₂O₄ particles showed that particles were single domain particles with similar saturation magnetization (∼300 emu/cm³) at room temperature. The zeta potential study of suspensions (CoFe₂O₄-acetylacetone system) with various particle sizes showed the suspension systems had similar zeta potential values (∼40 mV). The effects of magnetic particle size on the suspension stability characterized by electrophoretic deposition yields and sediment volumes were studied. The suspension stability decreased with an increase in particle size and a flocculation threshold of particle radius a was found at 30 nm. A suspension stability theory approaching to the phenomenon was established. The theory based on the DLVO theory was developed by introducing an extra magnetic interaction force. Dormann model was adopted, in which the magnetic interactions of two spherical nanoparticles were investigated in terms of dipole-dipole interactions. Compared to DLVO, suspension's physical parameters not only zeta potential ζ and the Debye length 1/κ, but also particles' radius a brought about stable to flocculation transition in the theory.     

Sol-gel preparation and characterization of CoFe2O4-SiO2 nanocomposites

Magnetic nanocomposites formed by cobalt ferrite particles dispersed in a silica matrix were prepared by a sol-gel process. The effects of the thermal treatment temperature and the salt concentration on the structural and magnetic properties of the composites were investigated. By controlling these parameters, CoFe₂O₄/SiO₂ nanocomposites with different crystallite size and magnetic properties were obtained. By increasing the annealing temperature and salt concentration, composites with a progressive increase in the coercive field and of the density of magnetization were produced. In particular, a nanocomposite, with a Fe/Si molar concentration of 21%, obtained by drying the gel at 150 °C and further annealing at 800 °C, has a coercivity of 2000 Oe, which is more than twice higher than the coercivity of bulk cobalt ferrite.     

Synthesis and magnetic properties of hard magnetic (CoFe2O4)-soft magnetic (Fe3O4) nano-composite ceramics by SPS technology

CoFe₂O₄/Fe₃O₄ nano-composite ceramics were synthesized by Spark Plasma Sintering. The X-ray diffraction patterns show that all samples are composed of CoFe₂O₄ and Fe₃O₄ phases when the sintering temperature is below 900 °C. It is found that the magnetic properties strongly depend on the sintering temperature. The two-step hysteresis loops for samples sintered below 500 °C are observed, but when sintering temperature reaches 500 °C, the step disappears, which indicates that the CoFe₂O₄ and Fe₃O₄ are well exchange coupled. As the sintering temperature increases from 500 to 800 °C, the results of X-ray diffractometer indicate the constriction of crystalline regions due to the ion diffusion at the interfaces of CoFe₂O₄/Fe₃O₄ phases, which have great impact on the magnetic properties.     

Templated synthesis of monodisperse mesoporous maghemite/silica microspheres for magnetic separation of genomic DNA

A novel method is described for the preparation of superparamagnetic mesoporous maghemite (γ-Fe₂O₃)/silica (SiO₂) composite microspheres to allow rapid magnetic separation of DNA from biological samples. With magnetite (Fe₃O₄) and silica nanoparticles as starting materials, such microspheres were synthesized by the following two consecutive steps: (1) formation of monodispersed organic/inorganic hybrid microspheres through urea-formaldedyde (UF) polymerization and (2) removal of the organic template and phase transformation of Fe₃O₄ to γ-Fe₂O₃ by calcination at elevated temperatures. The as-synthesized particles obtained by heating at temperature 300 °C feature spherical shape and uniform particle size (d_particle=1.72 μm), high saturation magnetization (M_s=17.22 emu/g), superparamagnetism (M_r/M_s=0.023), high surface area (S_BET=240 m²/g), and mesoporosity (d_pore=6.62 nm). The composite microsphere consists of interlocked amorphous SiO₂ nanoparticles, in which cubic γ-Fe₂O₃ nanocrystals are homogeneously dispersed and thermally stable against γ- to α-phase transformation at temperatures up to 600 °C. With the exposed iron oxide nanoparticles coated with a thin layer of silica shell, the magnetic microspheres were used as a solid-phase adsorbent for rapid extraction of genomic DNA from plant samples. The results show that the DNA templates isolated from pea and green pepper displayed single bands with molecular weights greater than 8 kb and A₂₆₀/A₂₈₀ values of 1.60-1.72. The PCR amplification of a fragment encoding the endogenous chloroplast ndhB gene confirmed that the DNA templates obtained were inhibitor-free and amenable to sensitive amplification-based DNA technologies.     

Solid state reaction synthesis of NiFe2O4 nanoparticles

Ni-ferrite (NiFe₂O₄) nanoparticles have been synthesized via a solid state reaction process. Ni and Fe bi-metallic nanoparticles in the form of Ni₃₃Fe₆₇ alloy nanopowder are first synthesized by simultaneous evaporation of the required amounts of pure Ni and Fe metals followed by rapid condensation of the evaporated metal flux into solid state by means of an inert gas, helium, using the process of inert gas condensation (IGC). In order to form the NiFe₂O₄ structure, as-synthesized samples (Ni₃₃Fe₆₇) are annealed for 12 h in ambient conditions at different annealing temperatures. Structural analyses show that NiFe₂O₄ starts to form at around 450 °C and gets progressively well defined with increasing annealing temperatures yielding particle with size ranging between 15 and 50 nm. Besides successfully forming NiFe₂O₄, NiO/Fe₃O₄ core/shell nanoparticles have also been synthesized by adjusting the annealing conditions. Three different structures, Ni₃₃Fe₆₇, NiO/Fe₃O₄, and NiFe₂O₄, obtained in this study are compared with respect to their structural and magnetic properties.     

Infrared and Raman spectroscopic studies on iron oxide magnetic nano-particles and their surface modifications

Iron oxide magnetic nano-particles (MNPs) have been prepared in aqueous solution by a modified co-precipitation method. Surface modifications have been carried out using tetraethoxysilane (TEOS), triethoxysilane (TES) and 3-aminopropyltrimethoxysilane (APTMS). The uncoated and coated particle products have been characterized with transmission electron microscope (TEM), energy dispersive X-ray (EDX) spectroscopy, infrared (IR) and Raman spectroscopy, and thermal gravimetric analysis (TGA). The particle sizes were determined from TEM images and found to have mean diameters of 13, 16 and 14 nm for Fe₃O₄, TES/Fe₃O₄ and APTMS/Fe₃O₄, respectively. IR and Raman spectroscopy has been applied to study the effect of thermal annealing on the uncoated and coated particles. The results have shown that magnetite nano-particles are converted to maghemite at 109 °C and then to hematite by 500 °C. In contrast, the study of the effect of thermal annealing of micro-crystalline magnetite by IR spectroscopy revealed that the conversion to hematite began by 300 °C and that no maghemite could be identified as an intermediate phase. IR spectra and TGA measurements revealed that the Si-H and 3-aminopropyl functional groups in TES and APTMS coated magnetite nano-particles decomposed below 500 °C while the silica layer around the iron oxide core remained unchanged. The molecular ratio of APTMS coating to iron oxide core was determined to be 1:7 from the TGA data. Raman scattering signals have indicated that MNPs could be converted to maghemite and then to hematite using increasing power of laser irradiation in a manner similar to that observed for thermal annealing.     

Synthesis of nearly monodisperse nanoparticles in alcohol: A pressure and solvent-induced low-temperature strategy

Nearly monodisperse nanoparticles were synthesized by an environmentally benign low-temperature (140-180 °C) method involving pressure-induced decomposition of metal oleates in alcohol. XRD and TEM were employed in the characterization of the samples. In this study, Fe₃O₄, CoO, MnO, CoFe₂O₄, MnFe₂O₄, and a mixture of Ni, NiO, Ni₂O₃ nanoparticles, exhibiting various shapes and assemblies, were obtained.     

Magnetic behavior of core–shell particles

We have prepared composite magnetic core–shell particles using the process of soap-free emulsion polymerization and the co-precipitation method. The shell of the synthesized composite sphere is cobalt ferrite (CoFe₂O₄) nanoparticles and the core consists of poly(styrene-co-methacrylic acid) polymer. The mean crystallite sizes of the coated CoFe₂O₄ nanoparticles were controlled in the range of 2.4–6.7 nm by the concentration of [NH₄⁺] and heated temperature. The magnetic properties of the core–shell spherical particles can go from superparamagnetic to ferromagnetic behavior depending on the crystalline sizes of CoFe₂O₄.     

Effects of synthesis variables on the magnetic properties of CoFe2O4 nanoparticles

Cobalt ferrite nanoparticles (CoFe₂O₄) have been synthesized using precipitation in water solution with polyethylene glycol as surfactant. Influence of various synthesis variables included pH, reaction time and annealing temperature on the magnetic properties and particle sizes has also been studied. Structural identification of the samples was carried out using Thermogravimetric and Differential thermal analysis, X-ray diffraction, Fourier transform infrared spectroscopy, Scanning electron microscopy, High resolution transmission electron microscopy. Vibrating sample magnetometer was used for the magnetic investigation of the samples. Magnetic properties of nanoparticles show strong dependence on the particle size. The magnetic properties increase with pH of the precipitating medium and annealing temperature while the coercivity goes through a maximum, peaking at around 25 nm.     

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.     

Magnetic properties in Fe-doped NiO synthesized by co-precipitation

The magnetic properties of 1.5 at% Fe-doped NiO bulk samples were investigated. The samples were prepared by sintering the corresponding precursor in air at temperatures between 400 and 800 °C for 6 h. The synthesis was by a chemical co-precipitation and post-thermal decomposition method. In order to allow a comparison, a NiO/0.76 at% NiFe₂O₄ mixture was also prepared. The X-ray diffraction pattern shows that the samples that were sintered at 400 and 600 °C remain single phase. As the sintering temperature increased to 800 °C, however, the sample becomes a mixture of NiO and NiFe₂O₄ ferrite phases. The samples were investigated by measuring their magnetization as a function of magnetic field. The samples sintered between 400 and 800 °C and the one mixed directly with NiFe₂O₄ nanoparticles show a coercivity value of H_c≈200, 325, 350 and 110 Oe, respectively. The magnetic properties of the samples depend strongly on the sintering temperature. Simultaneously, the field-cooling hysteresis loop shift also observed after cooling the sample sintered at 600 °C to low temperature suggests the possibility of the existence of a ferromagnetic/antiferromagnetic exchange coupling.     

Structural characterization and magnetic properties of superparamagnetic zinc ferrite nanoparticles synthesized by the coprecipitation method

Single phase zinc ferrite (ZnFe₂O₄) nanoparticles have been prepared by the coprecipitation method without any subsequent calcination. The effects of precipitation temperature in the range 20–80 °C on the structural and the magnetic properties of zinc ferrite nanoparticles were investigated. The crystallite size, microstructure and magnetic properties of the prepared nanoparticles were studied using X-ray diffraction (XRD), Fourier transmission infrared spectrum, transmission electron microscope (TEM), energy dispersive X-ray spectrometer and vibrating sample magnetometer. The XRD results showed that the coprecipitated nanoparticles were single phase zinc ferrite with mixture of normal and inverse spinel structures. Furthermore, ZnFe₂O₄ nanoparticles have the crystallite size in the range 5–10 nm, as confirmed by TEM. The magnetic measurements exhibited that the zinc ferrite nanoparticles synthesized at 40 °C were superparamagnetic with the maximum magnetization of 7.3 emu/g at 10 kOe.     

Superparamagnetic silica nanoparticles with immobilized metal affinity ligands for protein adsorption

Superparamagnetic silica-coated magnetite (Fe₃O₄) nanoparticles with immobilized metal affinity ligands were prepared for protein adsorption. First, magnetite nanoparticles were synthesized by co-precipitating Fe²⁺ and Fe³⁺ in an ammonia solution. Then silica was coated on the Fe₃O₄ nanoparticles using a sol–gel method to obtain magnetic silica nanoparticles. The condensation product of 3-Glycidoxypropyltrimethoxysilane (GLYMO) and iminodiacetic acid (IDA) was immobilized on them and after charged with Cu²⁺, the magnetic silica nanoparticles with immobilized Cu²⁺ were applied for the adsorption of bovine serum albumin (BSA). Scanning electron micrograph showed that the magnetic silica nanoparticles with an average size of 190 nm were well dispersed without aggregation. X-ray diffraction showed the spinel structure for the magnetite particles coated with silica. Magnetic measurement revealed the magnetic silica nanoparticles were superparamagnetic and the saturation magnetization was about 15.0 emu/g. Protein adsorption results showed that the nanoparticles had high adsorption capacity for BSA (73 mg/g) and low nonspecific adsorption. The regeneration of these nanoparticles was also studied.     

Dependence of structural and magnetic properties of CoFe2O4/SiO2 nanocomposites on annealing temperature and component ratio

Cobalt ferrite (CoFe₂O₄) nanoparticles embedded in amorphous silica can be synthesized by using tetraethylorthosilicate (TEOS) and metallic nitrates as precursors. A well-established silica matrix network provides nucleation locations for CoFe₂O₄ nanoparticles, thus confining their growth and aggregation. The structural and magnetic properties show strong dependence on the variation of particle size caused by annealing temperature and CoFe₂O₄ ratio, resulting in higher crystallization, saturation magnetization M_s and remanent magnetization M_r as the annealing temperature and CoFe₂O₄ ratio increase. But the variation of coercivity H_c is not in accordance with that of M_s and M_r, indicating that H_c is not determined by the size of CoFe₂O₄ nanoparticles only. The realization of the adjustable particle sizes and the controllable magnetic properties makes the applicability of CoFe₂O₄ even more versatile.     

Preparation and characterization of multi-functional CoFe2O4-ZnO nanocomposites

Multi-functional magnetic, photoluminescent and photocatalytic CoFe₂O₄-ZnO nanocomposites were successfully synthesized by a collosol method. The average diameter of the prepared CoFe₂O₄-ZnO nanocomposites was 30±5 nm, and a diffusion layer was formed to link CoFe₂O₄ and ZnO. The saturation magnetization of the CoFe₂O₄-ZnO nanocomposites was 8.99 emu/g. Generation of ZnO from Zn(OH)₂ collosol was nearly complete after thermal decomposition at about 380 °C. A photoluminescence emission peak was observed at 443 nm when excitated at 350 nm. Degradation of methyl orange is performed by CoFe₂O₄-ZnO nanocomposites under ultraviolet radiation, with a degradation rate of up to 93.9%.