Effects of crystalline grain size and packing ratio of self-forming core/shell nanoparticles on magnetic properties at up to GHz bands

Self-forming core/shell nanoparticles of magnetic metal/oxide with crystalline grain size of less than 40 nm were synthesized. The nanoparticles were highly concentrated in an insulating matrix to fabricate a nanocomposite, whose magnetic properties were investigated. The crystalline grain size of the nanoparticles strongly influenced the magnetic anisotropy field, magnetic coercivity, relative permeability, and loss factor (tan δ=μ″/μ′) at high frequency. The packing ratio of the magnetic metallic phase in the nanocomposite also influenced those properties. High permeability with low tan δ of less than 1.5% at up to 1 GHz was obtained in the case of the nanoparticles with crystalline grain size of around 15 nm with large packing ratio of the nanoparticles.     

Fabrication and characterization of iron oxide nanoparticles filled polypyrrole nanocomposites

The effect of iron oxide nanoparticle addition on the physicochemical properties of the polypyrrole (PPy) was investigated. In the presence of iron oxide nanoparticles, PPy was observed in the form of discrete nanoparticles, not the usual network structure. PPy showed crystalline structure in the nanocomposites and pure PPy formed without iron oxide nanoparticles. PPy exhibited amorphous structure and nanoparticles were completely etched away in the nanocomposites formed with mechanical stirring over a 7-h reaction. The thermal stability of the PPy in the nanocomposites was enhanced under the thermo-gravimetric analysis (TGA). The electrical conductivity of the nanocomposites increased greatly upon the initial addition (20 wt%) of iron oxide nanoparticles. However, a higher nanoparticle loading (50 wt%) decreased the conductivity as a result of the dominance of the insulating iron oxide nanoparticles. Standard four-probe measurements indicated a three-dimensional variable-range-hopping conductivity mechanism. The magnetic properties of the fabricated nanocomposites were dependent on the particle loading. Ultrasonic stirring was observed to have a favorable effect on the protection of iron oxide nanoparticles from dissolution in acid. A tight polymer structure surrounds the magnetic nanoparticles, as compared to a complete loss of the magnetic iron oxide nanoparticles during conventional mechanical stirring for the micron-sized iron oxide particles filled PPy composite fabrication.     

Surface morphology and optical and magnetic properties of polyelectrolyte/magnetite nanoparticles nanofilms

Polyelectrolyte/iron oxide nanoparticles composite nanocoatings are fabricated by polyionic assembly. They are characterized by atomic force microscopy, electron magnetic resonance, ellipsometry, and secondary-ion mass spectrometry. The results obtained indicate that the number of magnetite nanoparticle layers in a film is related to its refractive index, thickness, and surface roughness. The electron magnetic resonance signal intensity is found to nonlinearly depend on the number of magnetic nanoparticle layers in a film.     

The role of copper ions on the structural and magnetic characteristics of MgZn ferrite nanoparticles and thin films

In this study Cu_xMg_0.5−xZn_0.5Fe₂O₄ (x=0-0.5) nanoparticles and thin films were prepared by sol-gel processing. The morphologies of nanoparticles were observed by transmission electron microscope (TEM). The Mössbauer spectroscopy (MS) was employed to determine the site preference of the constitutive elements. Magnetic dynamics of the nanoparticles was studied by the measurement of AC magnetic susceptibility versus temperature at different frequencies. The phenomenological Néel-Brown and Vogel-Fulcher models were employed to distinguish between interacting or non-interacting system. Results exhibited that there is strong interaction between fine particles. X-ray diffraction (XRD) patterns of the thin films indicate the formation of single-phase cubic spinel structure. Atomic force microscope (AFM) was employed to evaluate the surface morphologies of the prepared thin films. Vibrating sample magnetometer (VSM) was employed to probe magnetic properties of samples. It was found that with an increase in the amount of copper, the saturation of magnetization and initial permeability increase.     

Water-soluble magnetic nanoparticles with biologically active stabilizers

We present the results of the interaction of iron oxide nanoparticles with some biologically active surfactants, namely, oleic acid and cytotoxic alkanolamine derivatives. Physico-chemical properties, as magnetization, magnetite concentration and particle diameter, of the prepared magnetic samples were studied. The nanoparticle size of 11 nm for toluene magnetic fluid determined by TEM is in good agreement with the data obtained by the method of magnetogranulometry. In vitro cytotoxic effect of water-soluble nanoparticles with different iron oxide:oleic acid molar ratio were revealed against human fibrosarcoma and mouse hepatoma cells. In vivo results using a sarcoma mouse model showed observable antitumor action.     

The detection of HBV DNA with gold-coated iron oxide nanoparticle gene probes

Gold-coated iron oxide nanoparticle Hepatitis B virus (HBV) DNA probes were prepared, and their application for HBV DNA measurement was studied. Gold-coated iron oxide nanoparticles were prepared by the citrate reduction of tetra-chloroauric acid in the presence of iron oxide nanoparticles which were added as seeds. With a fluorescence-based method, the maximal surface coverage of hexaethiol 30-mer oligonucleotides and the maximal percentage of hybridization strands on gold-coated iron oxide nanoparticles were (120 ± 8) oligonucleotides per nanoparticle, and (14 ± 2%), respectively, which were comparable with those of (132 ± 10) and (22 ± 3%) in Au nanoparticle groups. Large network aggregates were formed when gold-coated iron oxide nanoparticle HBV DNA gene probe was applied to detect HBV DNA molecules as evidenced by transmission electron microscopy and the high specificity was verified by blot hybridization. Our results further suggested that detecting DNA with iron oxide nanoparticles and magnetic separator was feasible and might be an alternative effective method.     

Magnetic behavior of iron and iron-oxide nanoparticle/polymer composites

An inert gas condensation technique was used to prepare nanometer-sized particles of metallic iron and iron oxide. The particles were passivated by the controlled oxidation of the particle surface leading to an Fe-oxide shell-Fe core structure. Nanoparticle–polymer composites were obtained by spin casting mixtures of nanoparticles and polymethylmethacrylate films. The magnetic properties of the nanoparticles compressed into pellets and dispersed in the composites were both studied. The particles were observed to exhibit increased coercivity and exchange bias. The exchange bias was observed to increase with oxide shell thickness. The magnetism in the nanoparticle composites was studied as a function of nanoparticle loading. It was observed that when the particles were dispersed into the nanocomposite the coercivity was increased, suggesting a heightened anisotropy barrier. Similarly, the magnetic relaxation results indicate that the composites exhibit significantly reduced relaxations through the entire temperature range, as compared to the compressed pellet. This observation supports the possibility of heightened anisotropy barriers due to reduced dipolar interactions.     

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.     

Application of factor analysis to XPS valence band of superparamagnetic iron oxide nanoparticles

X-Ray photoelectron spectra of nano-sized superparamagnetic iron oxide nanoparticles were examined with the aim to discriminate the different degree of iron oxidation. Careful analysis of the valence band regions reveals the presence of both Fe₃O₄ and Fe₂O₃. The application of factor analysis enabled us to extract the relative molar concentrations of these oxides in the nanoparticles. This is of particular interest in improving the magnetic properties of iron oxide nanoparticles whose superparamagnetic character can be optimized to obtain better contrast in images from nuclear magnetic resonance. As a result, the factor analysis allows tuning the nanoparticle synthesis conditions in order to obtain the optimal magnetic properties for imaging. Results obtained by the XPS valence band analysis were compared to the transmission electron microscopy, X-ray diffraction and Raman measurements.     

Mössbauer investigation of maghemite-based glycolic acid nanocomposite

Transmission electron microscopy, X-ray diffraction and Mössbauer spectroscopy were used in the characterization of a nanocomposite containing magnetic nanoparticles dispersed in a glycolic acid-based template. Maghemite nanoparticles were identified as the iron oxide phase dispersed in the polymeric template. From the low-temperature Mössbauer data the amount of the iron-based, non-magnetic material at the nanoparticle surface was estimated as roughly one monolayer in thickness.     

Stability of the magnetic domain structure of nanoparticle thin films against external fields

We investigate the effect of external magnetic fields on the magnetic structure of thin films from magnetic nanoparticles (MNP) with dipolar interaction. Such fields are present, for example, if samples are scanned with magnetic probes. Numerical simulations and experimental magnetic force microscopy (MFM) studies are presented. Numerically, we have calculated the magnetization pattern of single-layer and multilayer MNP thin films. The calculations show that unperturbed single-layer MNP films have an in-plane orientation of the magnetization with a flux-closure-domain pattern. An external field generated by a point dipole above the film induces locally an out-of-plane configuration of the magnetization. In the corresponding MFM images, the domain pattern in the film is erased and a stripe-like contrast enhancement at the edges appears. Multilayer films are found to be more robust against external fields than monolayers.     

Structure and magnetic properties of the oxide layers on iron ultrafine particles

5 . The γ-Fe particles, because of their paramagnetic nature, are very convenient for investigation on the attributes of iron oxide layers formed on the particle surfaces. Structures, morphologies and magnetic properties of the oxide layers covering the iron ultrafine particles have been studied using transmission electron microscopy observation, magnetic property measurement, X-ray diffraction and annealing treatment. Convincing evidences established that the iron oxide layers are not continuous and consist of very fine crystallites, and that these layers are non-ferromagnetic and have no contribution to the saturation magnetization of the iron particles. The iron oxide layers formed at room temperature was determined to be Fe₃O₄. Additionally, a brief annealing of the iron particles in air were performed to examine magnetic properties of the formed iron oxide layers and ultrafine oxide particles. Received: 30 April 1996/Accepted: 5 November 1996     

Effect of pH value on the structural and magnetic properties of nanocrystalline strontium hexaferrite thin films

Strontium hexaferrite SrFe₁₂O₁₉ thin films have been synthesized at different pH, adjusted by NH₄OH, on the Si (1 0 0) substrate using a spin coating sol-gel process. Fourier transform infrared spectroscopy analysis and theoretical calculations were conducted for determination and controlling metal citrates in solution precursors. X-ray diffraction, scanning electron microscopy and vibrating sample magnetometer were applied to evaluate the composition, microstructure, crystallite size and magnetic properties of the SrFe₁₂O₁₉ thin films. Using the solution with pH 7, the approximately single phase strontium hexaferrite thin films with optimum physical properties can be obtained at calcination temperature of 800 °C. The SrFe₁₂O₁₉ thin films derived from the solution with pH 7 after calcination at 800 °C exhibited crystallite size of 42 nm and magnetic properties of M_s=267 emu/cm³ (at 10 kOe), M_r=134 emu/cm³ and H_c=4290 Oe.     

Thiol‐immobilized silver nanoparticle aggregate films for surface enhanced Raman scattering

We report a novel method for the fabrication of films of silver nanoparticle aggregates that are strongly attached to Si substrates (Thiol‐immobilized silver nanoparticle aggregates or TISNA). The attachment is achieved by chemically modifying the surface of a Si(100) surface in order to provide SH groups covalently linked to the substrate and then aggregating silver nanoparticles on these thiol covered surfaces. The transmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM) characterization show a high coverage with single nanoparticles or small clusters and a partial coverage with fractal aggregates that provide potential hot spots for surface enhanced Raman scattering (SERS). We have confirmed the SERS activity of these films by adsorbing rhodamine 6G and recording the Raman spectra at several concentrations. By using the silver‐chloride stretching band as an internal standard, the adsorbate bands can be normalized in order to correct for the effects of focusing and aggregate size, which determine the number of SERS active sites in the focal area. This allows a quantitative use of SERS to be done. The adsorption–desorption of rhodamine 6G on TISNA films is reversible. These features make our TISNA films potential candidates for their use in chemical sensors based on the SERS effect. Copyright © 2008 John Wiley & Sons, Ltd.     

Iron oxide nanoparticles and VOx/Hexadecylamine nanotubes composite

In this work, we present the synthesis and characterization of a hybrid nanocomposite constituted by iron oxide nanoparticles and vanadium oxide/Hexadecylamine (VO_x/Hexa) nanotubes. Transmission Electron Microscopy (TEM) images show small particles (around 20 nm) in contact with the external wall of the multiwall tubes, which consist of alternate layers of VO_x and Hexa. By Energy Dispersive Spectroscopy (EDS), we detected iron ions within the tube walls and we have also established that the nanoparticles are composed of segregated iron oxide. The samples were studied by Electron Paramagnetic Resonances (EPR) and dc-magnetization as a function of the magnetic field. The analysis of the magnetization and EPR data confirms that a fraction of the V atoms are in the V⁴⁺ electronic state and that the nanoparticles exhibit a superparamagnetic behavior. The percentage of V and Fe present in the nanocomposite was determined using Instrumental Neutron Activation Analysis (INAA).     

Optical properties of ZnO and ZnO:Ce layers grown by spray pyrolysis

In this paper, zinc oxide (ZnO) and cerium-doped zinc oxide (ZnO:Ce) films were deposited by reactive chemical pulverization spray pyrolysis technique using zinc and cerium chlorides as precursors. The effects of Ce concentration on the structural and optical properties of ZnO thin films were investigated in detail. These films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL) measurements. All deposited ZnO layers at the temperature 450 °C are polycrystalline and indicate highly c-axis oriented structure. The dimension of crystallites depends on incorporation of Ce atoms into the ZnO films. The photoluminescence spectra of the films have been studied as a function of the deposition parameters such as doping concentrations and post grows annealing. Photoluminescence spectra were measured at the temperature range from 13 K to 320 K.     

Synthesis and magnetic properties of Cu-coated Fe composite nanoparticles

The Fe/Cu nanocomposites with iron as core and copper as shell have been successfully synthesized by a two-step reduction method. A spherical nanoparticle of γ-Fe was first fabricated by the reduction of ferrous chloride, and then the Fe particle was coated by nanocrystalline Cu through the reduction of copper sulfate. The thickness of copper shell has been tuned by varying the initial concentration of copper sulfate. The morphology, crystalline structure, chemical composition and magnetic properties of the products were investigated by using transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS) and vibrating sample magnetometer (VSM). It was found that the saturation magnetization (M_s) values of the Fe/Cu core–shell particles are varied owing to the different thickness of copper layer. Though the M_s value of the Fe/Cu nanocomposite is lower than that of pure iron nanoparticles, the higher M_s value (22.411 emu/g) of the Fe/Cu composites is also investigated. The result of the thermogravimetric analysis (TGA) showed the enhanced antioxidation capacity of the Fe/Cu nanocomposites. This kind of nanocomposites combined the excellent magnetism of iron and the electronic, thermal conductivity of copper, suggesting potential application as a novel electromagnetic material.     

Synthesis of ZnO nanoparticles using nanosecond pulsed laser ablation in aqueous media and their self-assembly towards spindle-like ZnO aggregates

ZnO nanoparticles were fabricated by pulsed laser ablation (PLA) of a Zn metal in aqueous media, and aging effects on the morphology and photoluminescence properties of ZnO nanoparticles were investigated. The crystalline phase and particle morphology were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). It was found that small, well-defined ZnO nanoparticles were obtained by PLA of a Zn plate in aqueous media, and subsequent aging of the obtained ZnO nanoparticle suspension produced in cetyltrimethylammonium bromide (CTAB) solution led to the formation of spindle-like ZnO aggregates. However, in deionized water not the spindle-like ZnO aggregates but fluffy round aggregates were obtained. High-resolution transmission electron microscopic (HRTEM) observation indicated that the spindle-like ZnO aggregates were composed of many well-defined nanoparticles. Spindle-like aggregates exhibited strong exciton emission, while green emission could be suppressed via an aging process in the presence of CTAB. Moreover, thin films prepared by electrophoretic deposition (EPD) of ZnO nanoparticles after PLA in the presence of CTAB also possessed highly elongated aggregate structures that were possibly formed by surrounding the ZnO nanoparticles with double layers of CTAB molecules.     

Morphology of cobalt ferrite nanoparticle-polyelectrolyte multilayered nanocomposites

Novel magnetic nanocomposite films with controlled morphology were produced via the electrostatic layer-by-layer assembly of cationic CoFe₂O₄ nanoparticles and anionic poly(3,4-ethylenedioxy thiophene)/poly(styrene sulfonic acid) (PEDOT:PSS) complex. The electrostatic interaction between nanoparticle and the polyelectrolyte complex ensured a stepwise growth of the nanocomposite film with virtually identical amounts of materials being adsorbed at each deposition cycle as observed by UV-vis spectroscopy. AFM images acquired under the tapping mode revealed a globular morphology with dense and continuous layers of nanoparticles with voids being filled with polymeric material.     

Preparation,structural and magnetic characterization of synthetic anti-ferromagnetic (SAF) nanoparticles

Synthetic anti-ferromagnetic nanoparticles (SAFs) are a novel type of magnetic nanoparticle (MNP) fabricated using nanoimprint lithography, direct deposition of multilayer films and retrieval in liquid phase via an ‘etching’ release process. Such physical fabrication techniques enable accurate control of particle shape, size and composition. We systematically varied the processing conditions to produce different configurations of SAF nanoparticles and performed extensive characterization using transmission electron microscopy (TEM) and alternating gradient magnetometry (AGM) to study their corresponding structural and magnetic behavior. A key focus of this paper is the preparation of TEM cross-section specimens of SAF nanoparticles for their structural characterization. This is not a trivial task, but is useful and revealing in terms of structural features. A major finding from our study shows that the introduction of oxygen during deposition of the copper release layer gives significantly improved flatness of the multilayer structure but no significant change in the magnetic properties. Magnetic measurements show that these nanoparticles have nearly zero magnetic remanence, a linear response of magnetization and more than twice the saturation magnetization compared to iron oxide nanoparticles.