Cation distribution dependence of magnetic properties of sol-gel prepared MnFe2O4 spinel ferrite nanoparticles

MnFe₂O₄ nanoparticles have been synthesized with a sol-gel method. Both differential thermal and thermo-gravimetric analyses indicate that MnFe₂O₄ nanoparticles form at 400 °C. Samples treated at 450 and 500 °C exhibit superparamagnetism at room temperature as implied from vibrating sample magnetometry. Mössbauer results indicate that as Mn²⁺ ions enter into the octahedral sites, Fe³⁺ ions transfer from octahedral to tetrahedral sites. When the calcination temperature increases from 450 to 700 °C, the occupation ratio of Fe³⁺ ions at the octahedral sites decreases from 43% to 39%. Susceptibility measurements versus magnetic field are reported for various temperatures (from 450 to 700 °C) and interpreted within the Stoner-Wohlfarth model.     

High pressure Raman spectroscopy of spinel-type ferrite ZnFe2O4

An in-situ Raman spectroscopic study was conducted to explore the pressure induced phase transformation of spinel-type ferrite ZnFe₂O₄. Results indicate that ferrite ZnFe₂O₄ initially transforms to an orthorhombic structure phase (CaFe₂O₄-polymorph) at a pressure of 24.6 GPa. Such a phase transformation is complete at 34.2 GPa, and continuously remains stable to the peak pressure of 61.9 GPa. The coexistence of the two phases over a wide range of pressure implies a sluggish mechanism upon the spinel-to-orthorhombic phase transition. Upon release of pressure, the high pressure ZnFe₂O₄ polymorph is quenchable at ambient conditions.     

Superspin glass state in MnFe2O4 nanoparticles

Nanosized MnFe₂O₄ ferrites were synthesized by a simple method, which is based on the solid state ball-milling and calcinations of nitrate precursors and citric acid. The samples were characterized by using different methods. The results indicate that the products mainly consist of MnFe₂O₄ nanoparticles. The effect of different annealing temperatures on particle sizes and crystallinity of the samples was also studied. By increasing the particle size, the coercivity and magnetization of the samples increase. The increase of magnetization by increasing the crystallite size could be attributed to the lower surface spin canting and surface spin disorder of the larger magnetic nanoparticles. Our analysis of ac susceptibility measurements shows that the interparticle magnetic interaction leads to the superspin glass-like behavior in these nanoparticle samples.     

Effect of substitution elements on magnetization of monodispersed MFe2O4 particles

The monodispersed hydrophilic magnetic fluids with nanometric M_xFe_3−xO₄ (M = Cu, Co, Ca and Ni) particles were prepared by sonochemical method. The substituted M amounts were analyzed with different x values by ICP-AES quantitatively. The excellent substitutability and magnetic property for Co, Ni was observed compared to those for Cu and Ca relatively. In particular, the applicability of Co was confirmed for novel radiotherapy.     

Synthesis of ZnFe2O4 nanocrystallites by mechanochemical reaction

Mechanochemical reaction of ZnO and α-Fe₂O₃ in a planetary mill formed an amorphous precursor, which was subsequently heated to successfully produce zinc ferrite (ZnFe₂O₄) nanocrystallites. The amorphous precursor and nanocrystallites were characterized by differential thermal analysis (DTA), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and transmission electron microscopy (TEM). Calcination of the precursor powder at 600 °C led to the formation of ZnFe₂O₄ nanocrystallites of about 22 nm in crystal size, and most of particle was about 10-50 nm in diameter. Effect of calcination temperature on the crystal size of the nanoparticles was investigated. The mechanism of nanocrystallite growth was primarily investigated. The activation energy of ZnFe₂O₄ nanocrystallite formation during thermal treatment was calculated to be 18.5 kJ/mol.     

A study of modified Fe3O4 nanoparticles for the synthesis of ionic ferrofluids

XRD and XPS analyses revealed that a Fe(NO₃)₃·9H₂O layer formed outside γ-Fe₂O₃ particles when Fe₃O₄ nanoparticles were treated with ferric nitrate. The particle density differed for untreated and treated particles and was not uniform for the latter. The specific saturation magnetization of both treated and untreated particles was used to estimate the thickness of the Fe(NO₃)₃·9H₂O layer and the average density of the treated particles. The density of the treated particles was used to calculate the density of ferrofluids of different particle volume fractions. These values are in agreement with measured results. Therefore, the particle volume fraction can be designed to synthesize acid ionic ferrofluids based on Fe₃O₄ nanoparticles using Massart's method.     

Magnetic and structural studies on CoFe2O4 nanoparticles synthesized by co-precipitation,normal micelles and reverse micelles methods

Cobalt ferrite nanoparticles were synthesized by the chemical co-precipitation, normal micelles and reverse micelles methods of iron and cobalt chlorides. X-ray diffraction analysis, Fourier Transform Infrared (FTIR) and Vibrating Sample Magnetometer were carried out at room temperature to study the structural and magnetic properties. X-ray patterns revealed the production of a broad single cubic phase with the average particle sizes of ∼12 nm, 5 nm and 8 nm for co-precipitation, normal micelles and reverse micelles methods, respectively. The FTIR measurements between 400 and 4000 cm⁻¹ confirmed the intrinsic cation vibrations of spinel structure for each one of the three methods. Moreover, the average particle sizes were lower than the single domain size (128 nm) and higher than the super-paramagnetic size (2–3 nm) at room temperature. The results revealed that the magnetic properties depend on the particle size and cation distribution, whereas the role of particle size is more significant.     

The effect of cation distribution on magnetization of ZnFe2O4 nanoparticles

In this work zinc ferrite (ZnFe₂O₄) nanoparticles have been prepared by sol-gel method in two different media, one acidic and another one basic and then annealed at different temperatures from 350 to 800 °C. XRD investigations show that both samples have a single phase spinel structure. Mean crystallite sizes of the samples were calculated, using Scherrer’s formula, which are 13 and 16 nm for the samples prepared in acidic and basic media, respectively. The variation of cation distribution in the samples was estimated by the ratio of (2 2 0) and (2 2 2) intensity diffraction peaks and the results show that as-prepared nanoparticles have different ionic distributions in comparison with that of bulk zinc ferrite. Also the results show that by increasing annealing temperature the ionic distribution of the zinc ferrite nanoparticles tends to that of bulk sample. The magnetic properties of the samples were studied by VSM and the results show that zinc ferrite nanoparticles have a ferrimagnetic behavior. Also the morphology of the powders was examined by TEM.     

Structural and magnetic characteristics of Co1−xNix/2Srx/2Fe2O4 nanoparticles

Co_1−xNi_x/2Sr_x/2Fe₂O₄ (x=0–0.5 in steps of 0.1) ferrite nanoparticles have been synthesized at room temperature, without calcination, using a reverse micelle process. The site preference was determined by Mössbauer spectroscopy at 300 K. The hyperfine parameters were obtained, for the whole series of solid solutions. For the X≤0.20 samples, the spectra were fitted with two discrete sextets and for the X>0.20 samples, a magnetic hyperfine field distribution and a doublet were also imposed in the fit procedure. Hysteresis loops were measured using a superconducting quantum interference device magnetometer at 2 K and 300 K. The results indicate that the relative decrease in saturation magnetization of nanoparticles compared to the submicron particles could be attributed to a surface spin termination and disorder. Magnetic dynamics of the nanoparticles was studied by the measurement of ac magnetic susceptibility versus temperature at different frequencies and it is found that the results are well described by the Vogel–Fulcher model.     

Synthesis, structural, magnetic and optical properties of nanocrystalline ZnFe2O4

Nanocrystalline zinc ferrite (ZnFe₂O₄) is synthesized by high-energy ball-milling after 12 h from a powders mixture of zinc oxide (ZnO) and hematite (α-Fe₂O₃) with balls to powders mass ratio of 20:1. X-ray diffraction, vibrating sample magnetometer (VSM), the Mössbauer spectrometry and photoluminescence (PL) are used to characterize the samples. Rietveld analysis and VSM measurements show that the powder has an average crystallites size of 10 nm and a ferrimagnetic behavior with a saturation magnetization of 30 emu/g. After annealing at 700 °C, the lattice parameter reduces from 8.448 to 8.427 Å and the sample transforms into a superparamagnetic behavior, which was confirmed as well by the room temperature Mössbauer spectrometry. Different mechanisms to explain the obtained results and the correlation between magnetism and structure are discussed. Finally, the broadband visible emission band is observed in the entire PL spectrum and the estimated energy band gap is about 2.13 eV.     

Studies on polyethylene glycol coating on NiFe2O4 nanoparticles for biomedical applications

The NiFe₂O₄ nanoparticles were prepared by the combustion method and these nanoparticles were successfully coated with polyethylene glycol (PEG) for the possible biomedical applications such as magnetic resonance imaging, drug delivery, tissue repair, magnetic fluid hyperthermia etc. The structural and magnetic characterizations of NiFe₂O₄ nanoparticles were carried out by x-ray diffraction and vibrating sample magnetometry techniques, respectively. The morphology of the uncoated and coated nanoparticles was studied by scanning electron microscopy. The existence of PEG layer on NiFe₂O₄ nanoparticles was confirmed by fourier transform infrared spectroscopy technique.     

Magnetic response of NiFe2O4 nanoparticles in polymer matrix

We report the magnetic properties of magnetic nano-composite, consisting of different quantity of NiFe₂O₄ nanoparticles in polymer matrix. The nanoparticles exhibited a typical magnetization blocking, which is sensitive on the variation of magnetic field, mode of zero-field-cooled/field-cooled experiments and particle quantity in the matrix. The samples with lower particle quantity showed an upturn of magnetization down to 5 K, whereas the blocking of magnetization dominates at lower temperatures as the particle quantity increases in the polymer. We examine such magnetic behaviour in terms of the competitive magnetic ordering between core and surface spins of nanoparticles, taking into account the effect of inter-particle (dipole-dipole) interactions on nanoparticle magnetic dynamics.     

Magnetic field synthesis of Fe3O4 nanoparticles used as a precursor of ferrofluids

Methods to synthesize magnetic Fe₃O₄ nanoparticles and to modify the nanoparticle surface are presented in this paper. In these methods, Fe₃O₄ nanoparticles were prepared by co-precipitation, and the aging of nanoparticles was improved by applied magnetic field. The obtained nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and vibrating sample magnetometer (VSM). Thereafter, to enhance the compatibility between nanoparticles and water, an effective surface modification method was developed by grafting acrylic acid onto the nanoparticle surface. FT-IR, XRD, transmission electron microscopy (TEM), and thermogravimetry (TG) were used to characterize the resultant sample. The testing results indicated that the polyacrylic acid chains have been covalently bonded to the surface of magnetic Fe₃O₄ nanoparticles. The effects of initiator dosage, monomer concentration, and reaction temperature on the characteristics of surface-modified Fe₃O₄ nanoparticles were investigated. Moreover, the Fe₃O₄-g-PAA hybrid nanoparticles were dispersed in water to form ferrofluids (FFs). The obtained FFs were characterized by UV–vis spectrophotometer, Gouy magnetic balance and laser particle-size analyzer. The testing results showed that the high-concentration FF had excellent stability, with high susceptibility and high saturation magnetization. The rheological properties of the FFs were also investigated using a rotating rheometer.     

Synthesis and characterization of MnFe2O4-BiFeO3 multiferroic composites

The mixed spinel-perovskite composites of xMnFe₂O₄-(1-x)BiFeO₃ with x=0, 0.1, 0.2, 0.3 and 0.4 were prepared by solid state reaction method. The structure and grain size were examined by means of X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM), respectively. The XRD results showed that the composites consisted of spinel MnFe₂O₄ and perovskite BiFeO₃ phases after being calcined at the temperature 950 °C for 2 h. The grain size ranged from 0.8 to 1 μm. Magnetization was found to increase with increasing concentration of ferrite content. The variation of dielectric constant and dielectric loss with frequency showed dispersion in the low frequency range. Magnetocapacitance was also observed in the prepared composites, which may be the sign of magnetoelectric coupling in the synthesized composites at room temperature.     

Electrical transport properties of Fe3−xCrxO4 ferrite films on MgO (0 0 1) grown by molecular beam epitaxy

In this report, we fabricated a series of Fe_3−xCr_xO₄(0≦x≦2) films by plasma-oxygen-assisted molecular beam epitaxy (MBE) and did structural and electrical characterizations of these films. These films show textured single phase quality and the lattice parameters are consistent with those of the bulk at low Cr composition (x<0.9). However, the lattice parameters show severe deviation from the bulk value in the intermediate region of 0.9≦x≦1.5 and no diffraction can be resolved at x∼2. These discrepancies may be attributed to the cation distributions and the instability of spinal structure as Cr concentration becomes dominant. The resistivity presents a typical Arrhenius temperature dependence with ρ=ρ₀ exp (E_p/k_BT) indicating that the transport is due to a hopping mechanism. The prefactor ρ₀ increases in Fe_3−xCr_xO₄, at smaller x but tends to level out for x>1, suggesting that Cr³⁺ ions may start to replace Fe³⁺ ions at the A site in the high x region. The activation energy of electrical hopping gradually increases at low Cr concentration but abruptly rises to ∼110 meV at x>0.9, suggesting a crossover from electron-hopping mediated transport to a thermally activated band gap excitation.     

Magnetic anisotropic properties in Fe3O4 and CoFe2O4 ferrite epitaxy thin films

Epitaxial thin films of Fe₃O₄ and CoFe₂O₄ on MgO (0 0 1) substrates were grown by molecular beam epitaxy at low temperature growth process. Magnetization and hysteresis loop of both films were measured to investigate magnetic anisotropic properties at various temperatures. Anomalous magnetic properties are found to be correlated with crystalline, shape, and stress anisotropies. The Fe₃O₄ film below Verwey structural transition has a change in crystal structure, thus causing many anomalous magnetic properties. Crystalline anisotropy and anomalous magnetic properties are affected substantially by Co ions. The saturation magnetization of Co–ferrite film becomes much lower than that of Fe₃O₄ film, being very different from the bulks. It indicates that the low temperature growth process could not provide enough energy to have the lowest energy state.     

Magnetic properties of ZnFe2O4 nanoparticles produced by a low-temperature solid-state reaction method

ZnFe₂O₄ nanoparticles with average grain size ranging from 40 to 60 nm behaving superparamagnetic at room temperature have been produced using a low-temperature solid-state reaction (LTSSR) method without ball-milling process. Abnormal magnetic properties such as S-shape hysteresis loops and non-zero magnetic moments were observed. ZnFe₂O₄ nanoparticles were also synthesized using a NaOH coprecipitation method and a PVA sol-gel method to study the relationship between the preparation processes and the magnetic properties. Spin-glass behavior was observed in the low temperature solid-state reaction produced Zn ferrite in the zero-field cooled (ZFC) measurement. Our work proves that the various preparation methods will to some extent determine the properties of magnetic nanoparticles.     

Synthesis of Co-Cu-Zn doped Fe3O4 nanoparticles with tunable morphology and magnetic properties

Co-Cu-Zn doped Fe₃O₄ nanoparticles can be successfully synthesized using a simple method. The particles in the size range 20−400 nm with different regular shapes i.e. sphere-like, regular hexane and tetrahedron are controllably achieved by changing the metal ion concentration. Compared to pure Fe₃O₄ without dopants, Co-Cu-Zn doped Fe₃O₄ nanoparticles exhibit better microwave absorbing properties at 2−18 GHz. Among three Co-Cu-Zn doped Fe₃O₄ nanoparticles with different morphologies, tetrahedral Co-Cu-Zn doped Fe₃O₄ nanoparticles represent a better dielectric loss in high frequency range. This work is believed the first known report of Co-Cu-Zn doped Fe₃O₄ nanoparticles with tunable morphology and magnetic properties through the hydrothermal process without using any organic solvents, organic metal salts or surfactants.     

Synthesis and characterization of CoFe2O4 octahedrons via an EDTA-assisted route

Octahedral-like CoFe₂O₄ ferrite was fabricated using an ethylenediaminetetraacetic acid (EDTA)-assisted route under mild conditions. EDTA plays important roles in the formation of the products in the process. Also, the magnetic properties of the samples were characterized on a vibrating sample magnetometer (VSM).     

Heat dissipation and magnetic properties of surface-coated Fe3O4 nanoparticles for biomedical applications

In this study, the influence of surface coating on the magnetic and heat dissipation properties of Fe₃O₄ nanoparticles was investigated. Fe₃O₄ nanoparticles that ranged in size between (particle sizes of 20 and 30 nm) were coated with polyethylenimine (PEI), oleic acid, and Pluronic F-127. Surface coatings that were composed of thick layers of oleic acid and Pluronic F-127 reduced dipole interactions between the particles, and resulted in reduced coercivity and decreased Néel relaxation times. The ac magnetization measurements revealed that the heat dissipation of the PEI-coated Fe₃O₄ nanoparticles was induced by hysteresis loss and Brownian relaxation loss and that of the oleic-acid-coated Fe₃O₄ nanoparticles was mainly induced by hysteresis loss and Néel relaxation loss.