Microwave resonant and zero-field absorption study of pure and doped ferrite nanoparticles

Microwave absorption was studied for magnetic nanoparticles of Fe₃O₄ (A) prepared by co-precipitation and Ni_0.35Cu_0.15Zn_0.5Fe₂O₄ (B) nanoparticles prepared by the sol-gel combustion method at different temperature. In all cases only one ferromagnetic resonance line was observed which indicated that the materials were magnetically uniform. The linewidths were large mainly because of the wide variations in particle sizes, shapes and orientations. As expected, A type nanoparticles showed no absorption at zero-field. However, B type nanoparticles exhibited a sizable loss at a zero-field and the effect increases with the increase of reaction temperature. Mechanical crushing of the sample further enhanced the absorption.     

Biocompatibility of various ferrite nanoparticles evaluated by in vitro cytotoxicity assays using HeLa cells

Magnetic nanoparticles for thermotherapy must be biocompatible and possess high thermal efficiency as heating elements. The biocompatibility of Fe₃O₄ (20-30 nm), ZnFe₂O₄ (15-30 nm) and NiFe₂O₄ (20-30 nm) nanoparticles was studied using a cytotoxicity colony formation assay and a cell viability assay. The Fe₃O₄ sample was found to be biocompatible on HeLa cells. While ZnFe₂O₄ and NiFe₂O₄ were non-toxic at low concentrations, HeLa cells exhibited cytotoxic effects when exposed to concentrations of 100 μg/ml nanoparticles.     

Ferromagnetic resonance of nonstoichiometric zinc ferrite and cobalt-doped zinc ferrite nanoparticles

Ferromagnetic resonance spectra of zinc ferrite and cobalt doped zinc ferrite nanoparticles, measured at various temperatures, exhibit an invariant point at a given field. This makes it possible to determine the equation relating the resonance field shift to the peak-to-peak linewidth. When particles are frozen in a matrix in a magnetic field, the anisotropy constant of the material can be derived from the angular variation of the resonance field. This procedure is useful to determine the thermal dependence of the anisotropy constant, but is shown to require various freezing temperatures experiments to estimate the accuracy of the deduced anisotropy constant values. It is also shown that the angular dependence of the resonance field is similar for a uniaxial (zinc ferrite) and cubic (zinc ferrite containing 40% cobalt ions) anisotropy. This unexpected result is explained by the weakness of the texturation, leading to a distribution in easy axes directions.     

Polar Kerr rotation spectra in yttrium iron garnet and lithium ferrite: A comparative study

Polar Kerr rotation (PKR) spectra in the range 2.0–5.7 eV at 295 K of lithium ferrite and yttrium iron garnet (YIG) single crystals are reported. The spectra show more details and cover a more extended energy region than those published so far. The interpretation of the spectra is based on the assumptions that 1) PKR is an odd function of the sublattice magnetic moments 2) the origin of PKR in both compounds is of similar nature, the differences due to the different crystal structures (garnet and spinel) being less important. The calculated PKR sublattice components show some similarities in their energy dependences, the magnitude of the tetrahedral sublattice component being higher than that of the octahedral one. The components were used in the calculation of the PKR spectra in diamagnetically substituted yttrium iron garnet (J. Appl. Phys.49, 2212, 1978). The results correctly predict the trends observed experimentally.     

Pegylated silica nanoparticles: cytotoxicity and macrophage uptake

Here, we present a thorough study of pegylated silica nanoparticle (SNP) interaction with different biological environments. The SNPs have a mean diameter of about 40 nm and are coated with polyethylene glycol (PEG) of different molecular weights. The physicochemical characterization of SNPs allowed the confirmation of the binding of PEG chains to the silica surface, the reproducibility of the synthesis and the narrow size-dispersion. In view of clarifying the SNP interaction with biological environments, we first assessed the SNP reactivity after the incubation with two cell lines (macrophages RAW 264.7 and primary human fibroblasts), observing a reduced toxicity of pegylated SNPs compared to the bare ones. Then, we investigated the effect of the protein adsorption on the SNP surface using the model serum protein, bovine serum albumin (BSA). We found that the protein adsorption takes place more heavily on poorly pegylated SNPs, promoting the uptake of the latter by macrophages and leading to an increased mortality of these cells. To better understand this mechanism by means of flow cytometry, the dye Ru(bpy)₃Cl₂ was incorporated in the SNPs. The overall results highlight the SNP potentialities as a drug delivery system, thanks to the low interactions with the macrophages.     

Synthesis and characterization of Ni-Zn ferrite nanoparticles

Nickel zinc ferrite nanoparticles Ni_xZn_1−xFe₂O₄ (x=0.1, 0.3, 0.5) have been synthesized by a chemical co-precipitation method. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, electron paramagnetic resonance, dc magnetization and ac susceptibility measurements. The X-ray diffraction patterns confirm the synthesis of single crystalline Ni_xZn_1−xFe₂O₄ nanoparticles. The lattice parameter decreases with increase in Ni content resulting in a reduction in lattice strain. Similarly crystallite size increases with the concentration of Ni. The magnetic measurements show the superparamagnetic nature of the samples for x=0.1 and 0.3 whereas for x=0.5 the material is ferromagnetic. The saturation magnetization is 23.95 emu/g and increases with increase in Ni content. The superparamagnetic nature of the samples is supported by the EPR and ac susceptibility measurement studies. The blocking temperature increases with Ni concentration. The increase in blocking temperature is explained by the redistribution of the cations on tetrahedral (A) and octahedral (B) sites.     

Preparation and characterization of complex ferrite nanoparticles by a polymer-pyrolysis route

The polymer-pyrolysis route used in this work was to synthesize the copolymeric precursor of the mixed metallic ions and then to pyrolyze the precursor into complex spinel ferrite nanoparticles. Thermogravimetric analysis (TGA) showed that the complex ferrite nanoparticles could be obtained by calcination of their precursors at 500°C. The structures, elemental analyses and particle morphology of the as-calcined products were characterized by powder X-ray diffraction (XRD), ICP-AES, transmission electron microscope (TEM) and electron diffraction (ED) pattern. The results revealed that the as-calcined powders were complex spinel ferrites and the size of those nanoparticles ranged from 10 to 20 nm. Magnetic measurements were carried out at room temperature using a vibrating sample magnetometer (VSM). The saturation magnetization of the Mn–Zn ferrites was related to the molar ratio of Mn to Zn and increased with the increase of Mn. The complex Co–Mn–Zn ferrite nanoparticles showed a high magnetization of 58 emu/g at the applied field of 10 kOe and a low coercivity of 30 Oe, which indicated that this materials exhibited characteristics of soft ferromagnetism.     

Silica-coated Y2O3:Eu nanoparticles and their luminescence properties

Crystalline Y₂O₃:Eu is of paramount significance in rare earth materials and research on luminescence spectra. In this work, the nanocrystalline Y₂O₃:Eu was coated with silica by a facile solid state reaction method at room temperature. The transmission electron microscope (TEM) photographs showed that the prepared Y₂O₃:Eu particle is polycrystalline with the size of 20 nm, the size of silica-coated particle is about 25 nm. The XPS spectra indicated that the silica layer is likely to interact with Y₂O₃:Eu by a Si-O-Y chemical bond. The luminescence spectra showed that the intensity of ground samples is lower than that of unground ones, the intensity of silica-coated phosphors is higher than that of the ground samples, while almost the same as that of the unground ones. Therefore, the silica coating decreases the surface defects of nanoparticles of the nanocrystalline Y₂O₃:Eu, thus increasing their luminescent intensity.     

One-pot production of copper ferrite nanoparticles using a chemical method

Copper ferrite nanoparticles were synthesized via the oxidation of precipitates obtained from the reaction of FeCl₂, CuSO₄ and N₂H₄ in the presence of gelatin. These copper ferrite particles were subsequently examined using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and Mössbauer spectroscopy. The average size of the copper ferrite nanoparticles was less than 5 nm, and they exhibited superparamagnetic behavior as a result of their small size. The low temperature Mössbauer spectrum exhibited three sets of sextets, two corresponding to the tetrahedral and octahedral sites of the copper spinel structure and one with small hyperfine magnetic field corresponding to the surface or defects of the nanoparticles. When the ratio of copper salt was increased, the tetrahedral site became preferable for copper, and metallic copper and copper ferrite were both present in a single nanoparticle.     

A comparative study of magnetic transferability of superparamagnetic nanoparticles

The aspect of magnetic transferability was established using an automated magnetic particle transfer workstation. Maghemite (γ-Fe₂O₃) nanoparticles were synthesized via conventional co-precipitation procedure. Their transferability was determined in addition to several commercial nanoparticles that ranged in diameter, surface functionality, and composition. Transmission and scanning electron micrographs and infrared spectrum, respectively, provided size and surface information on the synthesized particles for comparison to commercially available magnetic nanoparticles.     

Temperature dependent coercivity and magnetization of nickel ferrite nanoparticles

Magnetic nanoparticles of nickel ferrite (size: 24±4 nm) have been synthesized by chemical coprecipitation method using stable ferric and nickel salts. Coercivity of nanoparticles has been found to increase with decrease in temperature of the samples. It has been observed that the coercivity follows a simple model of thermal activation of particle’s moment over the anisotropy barrier in the temperature range (10-300 K), in accordance with Kneller’s law for ferromagnetic materials. Saturation magnetization follows the modified Bloch’s law in the temperature range from 300 to 50 K. However, below 50 K, an abrupt increase in magnetization of nanoparticles was observed. This increase in magnetization at lower temperatures was explained with reference to the presence of freezed surface-spins and some paramagnetic impurities at the shell of nanoparticles that are activated at lower temperatures in core-shell nickel ferrite nanoparticles.     

ZnO microparticles,ZnO nanoparticles and Zn0.9Cu0.1O nanoparticles toward ethanol vapor sensing: A comparative study

ZnO and Zn_0.9Cu_0.1O nanoparticles were synthesized by the sonochemical method. Structural and morphological properties of the synthesized nanoparticles were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive analysis of X-ray (EDAX). The results revealed the formation of ZnO and Zn_0.9Cu_0.1O nanoparticles in wurtzite phase with average crystallite diameter of 30–40 nm calculated from Debye–Scherrer equation. Moreover, the ethanol vapor sensing properties of ZnO and Zn_0.9Cu_0.1O nanoparticles were investigated at different operating temperatures and they were compared with commercial ZnO microparticles. Comparative results demonstrated that Zn_0.9Cu_0.1O nanoparticles exhibit highest and fastest response to 250 ppm of ethanol at 300 °C. Results on response/recovery time, sensing mechanism, conductance variation and thermodynamics/kinetics of ethanol sensing is also studied and discussed.     

Electron spin resonance studies on quantum tunneling in spinel ferrite nanoparticles

The electron spin resonance (ESR) spectrometer, a very sensitive instrument with fast detecting window to explore quantum phase transitions for magnetic nanoparticles, was exploited to study the fascinating interplay between thermal and quantum fluctuations in the vicinity of a quantum critical point. We have measured ESR in ferrofluid samples containing nanosize particles of Fe₂O₃. The evolution of the ESR spectrum with temperature suggests that quantum tunneling of spins occurs in single domain magnetic particles in the low temperature regime. The effects of various microwave fields, particle sizes, and temperatures on the magnetic states of single domain spinel ferrite nanoparticles are investigated. We can consistently explain experimental data assuming that, as the temperature decreases, the spectrum changes from superparamagnetic (SPR) to blocked SPR and finally evolves quantum superparamagnetic behaviour as the temperature lowers down further. A nanoparticle system of a highly anisotropic magnetic material can be qualitatively specified by a simple quantum spin model, or by the Heisenberg model with strong easy-plane anisotropy.Received: 29 August 2003, Published online: 15 October 2003PACS: 76.30.-v Electron paramagnetic resonance and relaxation - 75.40.Cx Static properties (order parameter, static susceptibility, heat capacities, critical exponents, etc.) - 05.30.-d Quantum statistical mechanics - 75.50.Dd Nonmetallic ferromagnetic materials     

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.     

Magnetic properties of substituted strontium ferrite nanoparticles and thin films

SrFe_12−x(Zr_0.5Mg_0.5)_xO₁₉ nanoparticles and thin films with x=0-2.5 were synthesized by a sol-gel method on thermally oxidized silicon wafer (Si/SiO₂). Structural and magnetic characteristics of synthesized samples were studied employing x-rays diffraction (XRD), transmission electron microscopy (TEM), magnetic susceptometer, atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM), and vibrating sample magnetometer (VSM). TEM micrographs display that the narrow size distribution of ferrite nanoparticles with average particle size of 50 nm were fabricated. Fitting obtained data of effective magnetic susceptibility by Vogel-Fulcher law confirms the existence of strong magnetic interaction among fine particles. XRD patterns and FE-SEM micrographs demonstrated that single phase c-axis hexagonal ferrite films with rather narrow grain size distribution were obtained. AFM micrographs exhibited that the surface roughness increases with an increase in Zr-Mg content. It was found from the VSM graphs that with an increase in substitution contents the coercivity decreases, while the saturation of magnetization increases. The Henkle plots confirms the existence of exchange coupling among nano-grain in ferrite thin films.     

Size and compositionally controlled manganese ferrite nanoparticles with enhanced magnetization

The effects of solvents on the anatase crystallite size prepared by sol–gel microwave-assisted solvothermal method were investigated in this study. Eight different alcohol solvents classified into two groups, i.e. primary and secondary/ternary alcohols, were used as reaction media and the effects of solvent properties, such as dielectric constant, boiling point, and internal pressure during the solvothermal process, on the crystallite size and shape were analyzed. According to the experimental results, selecting the solvent type allowed not only the alteration of the crystallite size but also the crystallite shape without the need of any additives. The boiling point of solvent was determined as the major factor influencing the crystallite size. Among the solvents with similar boiling points, the solvent with a higher carbon number produced the smaller crystallite size because of steric hindrance effect. In addition, the carboxyl groups dissociated from the alcohol solvent can play a role as a structural capping agent to retard the anatase crystal growth along the [001] direction and led to a rectangular crystallite shape with preferred development in {001} facets. On the other hand, the alcoholysis reaction was found easily occurred between the primary alcohol and isopropoxide that effectively limited the hydrolysis and condensation processes but also suppressed the structural capping effect. Therefore, the anatase crystals prepared in the primary alcohols became exceptionally small and showed spherical shape. Finally, the anatase crystals prepared using isopropanol demonstrated the highest photocatalytic activity due to its evident preferred crystallization in the {001} facets.     

A cellular uptake and cytotoxicity properties study of gallic acid-loaded mesoporous silica nanoparticles on Caco-2 cells

In this study, the effects of intracellular delivery of various concentrations of gallic acid (GA) as a semistable antioxidant, gallic acid-loaded mesoporous silica nanoparticles (MSNs-GA), and cellular uptake of nanoparticles into Caco-2 cells were investigated. MSNs were synthesized and loaded with GA, then characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy, N₂ adsorption isotherms, X-ray diffraction, and thermal gravimetric analysis. The cytotoxicity of MSNs and MSNs-GA at low and high concentrations were studied by means of 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide (MTT) test and flow cytometry. MSNs did not show significant toxicity in various concentrations (0–500 μg/ml) on Caco-2 cells. For MSNs-GA, cell viability was reduced as a function of incubation time and different concentrations of nanoparticles. The in vitro GA release from MSNs-GA exhibited the same antitumor properties as free GA on Caco-2 cells. Flow cytometry results confirmed those obtained using MTT assay. TEM and fluorescent microscopy confirmed the internalization of MSNs by Caco-2 cells through nonspecific cellular uptake. MSNs can easily internalize into Caco-2 cells without deleterious effects on cell viability. The cell viability of Caco-2 cells was affected during MSNs-GA uptake. MSNs could be designed as suitable nanocarriers for antioxidants delivery.     

Study of magnetic and structural properties of ferrofluids based on cobalt-zinc ferrite nanoparticles

Ferrofluids are colloidal systems composed of a single domain of magnetic nanoparticles with a mean diameter around 30 nm, dispersed in a liquid carrier. Magnetic Co_(1−x)Zn_xFe₂O₄ (x=0.25, 0.50, 0.75) ferrite nanoparticles were prepared via co-precipitation method from aqueous salt solutions in an alkaline medium. The composition and structure of the samples were characterized through Energy Dispersive X-ray Spectroscopy and X-ray diffraction, respectively. Transmission Electron Microscopy (TEM) studies permitted determining nanoparticle size; grain size of nanoparticle conglomerates was established via Atomic Force Microscopy. The magnetic behavior of ferrofluids was characterized by Vibrating Sample Magnetometer (VSM); and finally, a magnetic force microscope was used to visualize the magnetic domains of Co_(1−x)Zn_xFe₂O₄ nanoparticles. X-ray diffraction patterns of Co_(1−x)Zn_xFe₂O₄ show the presence of the most intense peak corresponding to the (311) crystallographic orientation of the spinel phase of CoFe₂O₄. Fourier Transform Infrared Spectroscopy confirmed the presence of the bonds associated to the spinel structures; particularly for ferrites. The mean size of the crystallite of nanoparticles determined from the full-width at half maximum of the strongest reflection of the (311) peak by using the Scherrer approximation diminished from (9.5±0.3) nm to (5.4±0.2) nm when the Zn concentration increases from 0.21 to 0.75. The size of the Co-Zn ferrite nanoparticles obtained by TEM is in good agreement with the crystallite size calculated from X-ray diffraction patterns, using Scherer's formula. The magnetic properties investigated with the aid of a VSM at room temperature presented super-paramagnetic behavior, determined by the shape of the hysteresis loop. In this study, we established that the coercive field of Co_(1−x)Zn_xFe₂O₄ magnetic nanoparticles, the crystal and nanoparticle sizes determined by X-ray Diffraction and TEM, respectively, decrease with the increase of the Zn at%. Finally, our magnetic nanoparticles are not very hard magnetic materials given that the hysteresis loop is small and for this reason Co_(1−x)Zn_xFe₂O₄ nanoparticles are considered as soft magnetic material.     

Influence of synthesis method on structural and magnetic properties of cobalt ferrite nanoparticles

The Co–ferrite nanoparticles having a relatively uniform size distribution around 8 nm were synthesized by three different methods. A simple co-precipitation from aqueous solutions and a co-precipitation in an environment of microemulsions are low temperature methods (50 °C), whereas a thermal decomposition of organo-metallic complexes was performed at elevated temperature of 290 °C. The X-ray diffractometry (XRD) showed spinel structure, and the high-resolution transmission electron microscopy (HRTEM) a good crystallinity of all the nanoparticles. Energy-dispersive X-ray spectroscopy (EDS) showed the composition close to stoichiometric (~CoFe₂O₄) for both co-precipitated nanoparticles, whereas the nanoparticles prepared by the thermal decomposition were Co-deficient (~Co_0.6Fe_2.4O₄). The X-ray absorption near-edge structure (XANES) analysis showed Co valence of 2+ in all the samples, Fe valence 3+ in both co-precipitated samples, but average Fe valence of 2.7+ in the sample synthesized by thermal decomposition. The variations in cation distribution within the spinel lattice were observed by structural refinement of X-ray absorption fine structure (EXAFS). Like the bulk CoFe₂O₄, the nanoparticles synthesized at elevated temperature using thermal decomposition displayed inverse spinel structure with the Co ions occupying predominantly octahedral lattice sites, whereas co-precipitated samples showed considerable proportion of cobalt ions occupying tetrahedral sites (nearly 1/3 for the nanoparticles synthesized by co-precipitation from aqueous solutions and almost 1/4 for the nanoparticles synthesized in microemulsions). Magnetic measurements performed at room temperature and at 10 K were in good agreement with the nanoparticles’ composition and the cation distribution in their structure. The presented study clearly shows that the distribution of the cations within the spinel lattice of the ferrite nanoparticles, and consequently their magnetic properties are strongly affected by the synthesis method used.