Synthesis of Fe3O4 nanoparticles without inert gas protection used as precursors of magnetic fluids

Fe₃O₄ nanoparticles were hydrothermally synthesized under continuous microwave irradiation from FeCl₃·6H₂O and FeSO₄·7H₂O aqueous solutions, using NH₄OH as precipitating reagent and N₂H₄·H₂O as oxidation-resistant reagent. The results of X-ray powder diffraction (XRD), FT–IR spectroscopy and scanning electron microscopy (SEM) measurements showed that the synthesized magnetite (Fe₃O₄) nanoparticles had an average diameter of 10 nm. The magnetic properties of the Fe₃O₄ nanoparticles were measured using a vibrating sample magnetometer (VSM), indicating that the nanoparticles possessed high saturation magnetization at room temperature. The Fe₃O₄ nanoparticles were used to prepare magnetic fluids (MFs) based on water, and the properties of the MFs were characterized by a Gouy magnetic balance, a capillary rheometer and a rotating rheometer, respectively.     

Synthesis and characterization of spherical and narrow size distribution indium oxide nanoparticles

This work reports the synthesis of indium oxide nanoparticles and their thermal, structural, microstructural and optical characterization. The preparation method is based on a surfactant-free room temperature soft chemistry route. Spherical indium oxide nanoparticles (about 8 nm in diameter) were obtained after thermal treatment of gels at 400 °C for 2 h, as shown by X-ray diffraction experiments and nitrogen adsorption measurements. Transmission electron microscopy observations confirm the single-crystalline nature of the produced nanoparticles. The photoluminescence emission spectrum at room temperature shows a broad peak with onset at approximately 315 nm as a result of quantum size effect as revealed by small-angle X-ray scattering.     

Synthesis of magnetic hollow silica using polystyrene bead as a template

In this paper, we report a new route to synthesize novel magnetic hollow silica nanospheres (MHSNs) using polystyrene particles as sacrificial templates, and TEOS and Fe₃O₄ as precursors. TEM, EDS, XRD, and SQUID were applied to characterize MHSNs. TEM and EDS results show that the MHSNs consist of about 200 nm of hollow cores and ∼35 nm shells with ∼10 nm of Fe₃O₄ nanoparticles embedded. The polystyrene beads were successfully removed by immersing the as-prepared silica nanocomposite in a toluene solution. XRD results demonstrate that the Fe₃O₄ magnetic nanoparticles still keep spinel structure even heated at low temperature. The surface status of the polystyrene beads and Fe₃O₄ nanoparticles has an important effect on the formation of the MHSNs. The MHSNs present a superparamagnetism at room temperature by SQUID measurement. The MHSNs have potential applications in biosystem and nanomedicine.     

Magnetic properties of self-assembled nanostructure films on the base of amorphous Ni granules

We report on structural and magnetic properties of granular films consisting of 2.5 nm Ni nanoparticles. The films are fabricated by the original laser electrodispersion technique, which allows producing nearly monodisperse and amorphous particles. Atomic force microscopy (AFM) study shows that in 8 nm thickness films the particles are self-assembled in clusters with the lateral size 100-150 nm and the height of about 8 nm. Performed by SQUID, the films magnetization measurements reveal superparamagnetic behaviour, characteristic for an ensemble of non-interacting single domain magnetic particulates. It is found that the magnetic moment of the particulate is equal to that of about 3000 individual Ni nanoparticles and the blocking temperature is close to room temperature. Defined from magnetic measurements, the size of single domain particulates correlates well with the size of the clusters determined from AFM images. We propose that exchange interaction plays an important role in the formation of the particulates by aligning the magnetic moments of the individual Ni nanoparticles inside the clusters. Presence of magnetic clusters with high blocking temperature makes the fabricated films potentially useful for high-density magnetic data storage applications.     

High-resolution X-ray diffraction studies of combinatorial epitaxial Ge (0 0 1) thin-films on Ge (0 0 1) substrates

We report high-resolution X-ray diffraction studies of combinatorial epitaxial Ge (0 0 1) thin-films with varying doping concentrations of Co and Mn grown on Ge (0 0 1) substrates. The crystalline structure of the epitaxial thin-film has been determined using crystal-truncation rod (CTR) measurements and fitting analysis. By analyzing the fine interference fringes in the CTR intensity profile, strain sensitivity of ∼0.003% has been achieved. Using this method, the evolution of interfacial structures has been quantified as a function of doping concentration.     

Structural and magnetic properties of evaporated Fe thin films on Si(1 1 1), Si(1 0 0) and glass substrates

We present experimental results on the structural and magnetic properties of series of Fe thin films evaporated onto Si(1 1 1), Si(1 0 0) and glass substrates. The Fe thickness, t, ranges from 6 to110 nm. X-ray diffraction (XRD) and atomic force microscopy (AFM) have been used to study the structure and surface morphology of these films. The magnetic properties were investigated by means of the Brillouin light scattering (BLS) and magnetic force microscopy (MFM) techniques. The Fe films grow with (1 1 0) texture; as t increases, this (1 1 0) texture becomes weaker for Fe/Si, while for Fe/glass, the texture changes from (1 1 0) to (2 1 1). Grains are larger in Fe/Si than in Fe/glass. The effective magnetization, 4πM_eff, inferred from BLS was found to be lower than the 4πM_S bulk value. Stress induced anisotropy might be in part responsible for this difference. MFM images reveal stripe domain structure for the 110 nm thick Fe/Si(1 0 0) only.     

Details of crystalline growth in co-deposited electroplated nickel films with hard (nano)particles

Electroplated nickel dispersion films with incorporated hard particles, primarily titanium oxide, were studied. A sufficient dispersion of nanometre-scaled particles in Watts solution was reached by application of ultrasonic energy to the galvanic bath. Crystal morphology, mean grain size and formation of textures were examined by electron backscattering diffraction (EBSD), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The typical columnar structure of pure Ni films was refined by means of ultrasound. Incorporation of micron-sized TiO₂ particles generates additional nucleation surfaces in contrast to SiC particles. Textures of the subsequent columnar nickel crystals change from 〈2 1 1〉 (silent condition) or 〈1 1 0〉 (ultrasonic condition) fibre textures in growth direction to 〈1 0 0〉 and 〈1 1 1〉 textures under the influence of nanoparticle incorporation. Moreover, nanoparticles remarkably decrease the grain size and grain aspect ratio. Their incorporation takes place inside the crystals as well as between grains.     

Oleic acid coating on the monodisperse magnetite nanoparticles

Monodisperse magnetite nanoparticles provide a more factual model to study the interface interactions between the surfactants and magnetic nanoparticles. Monodisperse magnetite nanoparticles of 7 and 19 nm coated with oleic acid (OA) were prepared by the seed-mediated high temperature thermal decomposition of iron(III) acetylacetonate (Fe(acac)₃) precursor method. Fourier transform infrared spectra (FTIR) and X-ray photoelectron spectroscopy (XPS) reveal that the OA molecules were adsorbed on the magnetic nanoparticles by chemisorption way. Analyses of transmission electron microscopy (TEM) shows the OA provided the particles with better isolation and dispersibility. Thermogravimetric analysis (TGA) measurement results suggest that there were two kinds of different binding energies between the OA molecules and the magnetic nanoparticles. The cover density of OA molecules on the particle surface was significantly various with the size of magnetite nanoparticles. Magnetic measurements of the magnetite nanoparticles show the surface coating reduced the interactions among the nanoparticles.     

Improved biological performance of low modulus Ti-24Nb-4Zr-7.9Sn implants due to surface modification by anodic oxidation

Dental implants are usually made from commercially pure titanium or titanium alloys. The purpose of this study was to evaluate the influence of surface treatment to low modulus Ti-24Nb-4Zr-7.9Sn (TNZS) on cell and bone responses. The TNZS alloy samples were modified using anodic oxidation (AD). Surface oxide properties were characterized by using various surface analytic techniques, involving scanning electron microscopy (SEM) equipped with energy dispersive spectrometer (EDS), X-ray diffractometry (XRD) and surface profilometer. During the AD treatment, porous titanium oxide layer was formed and Ca ions were incorporated into the oxide layer. The viability and morphology of osteoblasts on Ca-incorporated TNZS were studied. The bone responses of Ca-incorporated TNZS were evaluated by pull-out tests and morphological analysis after implantation in rabbit tibiae. The non-treated Ti and TNZS samples were used as the control. Significant increases in cell viability and pull-out forces (p < 0.05) were observed for Ca-incorporated TNZS implants compared with those for the control groups. Porous structures supplied positive guidance cues for osteoblasts to attach. The enhanced cell and bone responses to Ca-incorporated TNZS implants could be explained by the surface chemistry and microtopography.     

Polarized angular dependence of three-dimensional light-scattering for nanoparticles on thin film wafer

Bidirectional ellipsometry has been developed as a technique for distinguishing among various scattering features near surfaces. The polarized angular dependence of three-dimensional light-scattering by the nanoparticles on thin film wafer is calculated and measured. These calculations and measurements yield angular dependence of bidirectional ellipsometric parameters for out-of-plane light-scattering. The experimental data show good agreement with theoretical predictions for different nanoparticle diameters and thin film thicknesses when bidirectional ellipsometry was employed to measure nanoparticles (60 nm, 100 nm, and 200 nm) on Si wafers with different film thicknesses of 2 nm, 5 nm, and 10 nm. Not only are the diameters of the nanoparticles determined, but also the film thicknesses can be calculated and distinguished from the measurement results. Additionally, the results indicate that improved accuracy is possible for measurements of scattering features from nanoparticles and thin films.     

3000% high-field magnetoresistance in super-lattices of CoFe nanoparticles

We report on magnetotransport measurements on millimeter-large super-lattices of CoFe nanoparticles surrounded by an organic layer. Electrical properties are typical of Coulomb blockade in three-dimensional arrays of nanoparticles. A large high-field magnetoresistance, reaching up to 3000%, is measured between 1.8 and 10 K. This exceeds by two orders of magnitude magnetoresistance values generally measured in arrays of 3d transition metal ferromagnetic nanoparticles. The magnetoresistance amplitude scales with the magnetic field/temperature ratio and displays an unusual exponential dependency with the applied voltage. The magnetoresistance abruptly disappears below 1.8 K. We propose that the magnetoresistance is due to some individual paramagnetic moments localized between the metallic cores of the nanoparticles, the origin of which is discussed.     

Growth research of Sn nanoparticles deposited on Si(0 0 1) substrate by solid phase epitaxy

High density of Sn nanoparticles (NPs) had been obtained directly on Si(0 0 1) substrate by solid phase epitaxy. The dependence of the morphology and crystallinity of Sn NPs on Sn coverage, annealing temperature and annealing time was investigated by atomic force microscope (AFM) and X-ray diffraction (XRD). Uniform and densely packed (∼10¹⁰ cm⁻²) Sn NPs were obtained at low Sn coverage, low annealing temperature and short annealing time, respectively. The XRD results showed that, the formed Sn NPs were in the form of crystalline β-Sn, with a distinct orientation of Sn(1 1 0)//Si(0 0 1). The nucleation activation energy of Sn adatoms on Si(0 0 1) surface was estimated to be 0.41 ± 0.05 eV.     

Growth of thin Fe(0 0 1) films for terahertz emission experiments

The electrical and magnetic properties of thin iron (Fe) films have sparked significant scientific interest. Our interest, however, is in the fundamental interactions between light and matter. We have discovered a novel application for thin Fe films. These films are sources of terahertz (THz) radiation when stimulated by an incident laser pulse. After intense femtosecond pulse excitation by a Ti:sapphire laser, these films emit picosecond, broadband THz frequencies. The terahertz emission provides a direct measure of the induced ultrafast change in magnetization within the Fe film. The THz generation experiments and the growth of appropriate thin Fe films for these experiments are discussed. Several criteria are used to select the substrate and film growth conditions, including that the substrate must permit the epitaxial growth of a continuous, monocrystalline or single crystal film, yet must also be transparent to the emitted THz radiation. An Fe(0 0 1) film grown on the (0 0 1) surface of a magnesium oxide (MgO) substrate makes an ideal sample. The Fe films are grown by physical vapor deposition (PVD) in an ultrahigh vacuum (UHV) system. Low energy electron diffraction (LEED) and Auger electron spectroscopy (AES) are used to characterize the Fe(0 0 1) films. Two substrate surface preparation methods are investigated. Fe(0 0 1) films grown on MgO(0 0 1) substrates that are used as-received and films grown on MgO(0 0 1) substrates that have been UV/ozone-cleaned ex vacuo and annealed in vacuo produce the same results in the THz generation experiments. Either substrate preparation method permits the growth of samples suitable for the THz emission experiments.     

Half Ca-doped LaMnO3 films on (0 0 1) SLAO and STO substrate studied by magnetization and transport measurements

In this study, La_0.5Ca_0.5MnO₃ (LCMO) films, at the boundary between ferromagnetic metallic and charge-ordered antiferromagnetic insulator according to the bulk phase diagram, were epitaxially grown on (0 0 1) SrTiO₃ (STO) and SrLaAlO₄ (SLAO) substrates by pulsed laser deposition technique. The films were analyzed by X-ray diffraction, magnetization and magnetoresistance measurements. A considerably higher magnetization was measured for 290-nm-thick film on SLAO substrate compared to the film on STO substrate, although both films have the same chemical composition, thickness and epitaxial orientation. The film on SLAO shows a metal-insulator (MI) transition, which occurs at higher temperatures with increasing applied magnetic field, whereas only insulating behavior was observed for the 290-nm-thick film on STO except for the highest applied magnetic field (7 T). In addition, transport measurements were performed and analyzed by Mott's variable range hopping (VRH) model to correlate the resistivity of the films with the Jahn-Teller strain (ε_J−T) in the structure.     

Magnetic resonances spectroscopy of nanosize particles La0.7Sr0.3MnO3

Using a co-precipitation method, perovskite-type manganese oxide La_0.7Sr_0.3MnO₃ nanoparticles (NPs) with particle size 12 nm were prepared. Detailed studies of both ⁵⁵Mn nuclear magnetic resonance and superparamagnetic resonance spectrum, completed by magnetic measurements, have been performed to obtain microscopic information on the local magnetic structure of the NP. Our results on nuclear dynamics provide direct evidence of formation of a magnetically dead layer, of the thickness ≈2 nm, at the particle surface. Temperature dependences of the magnetic resonance spectra have been measured to obtain information about complex magnetic properties of La_0.7Sr_0.3MnO₃ fine-particle ensembles. In particular, electron paramagnetic resonance spectrum at 300 K shows a relatively narrow sharp line, but as the temperature decreases to 5 K, the apparent resonance field decreases and the line width considerably increases. The low-temperature blocking of the NPs magnetic moments has been clearly observed in the electron paramagnetic resonances. The blocking temperature depends on the measuring frequency and for the ensemble of 12 nm NPs at 9.244 GHz has been evaluated as 110 K.     

Synthesis of ZnS nanorods by annealing precursor ZnS nanoparticles in NaCl flux

ZnS nanorods were fabricated by annealing precursor ZnS nanoparticles, which were prepared by one-step, solid-state reaction of ZnCl₂ and Na₂S through grinding by hand at ambient temperature, in NaCl flux. The as-prepared ZnS nanorods have diameters of 40-80 nm, and lengths up to several micrometers. The structural features and chemical composition of the nanorods were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), high-resolution transmission electron microscopy (HRTEM), and Raman spectra.     

Ordered mesoporous silica materials (SBA-15) with good heat-resistant magnetism

A series of highly ordered mesoporous materials (CF-SBA-15) with heat-resistant magnetism have been successfully prepared from impregnation of cobalt salt, iron salt, and citric acid with as-synthesized SBA-15. XRD and N₂ isotherms indicate that these materials have highly ordered hexagonal mesoporous symmetry and open pore systems. The measurement of magnetic property shows that these materials are ferromagnetic even if calcined at 550 °C for 10 h in air, indicating their good heat-resistant magnetism. These results would be very important for recycle and regeneration of adsorbents and catalysts in practical applications. Moreover, this method may be useful for other mesoporous materials with thermally stable magnetism from a combination of other mesoporous materials such as MCM-41 with magnetic nanoparticles of MnFe₂O₄ and NiFe₂O₄.     

Inter-particle spin-polarized tunneling in arrays of magnetite nanocrystals

Inter-particle spin-polarized tunneling was measured in an organically capped magnetite nanocrystal (NC) array deposited between 30 nm spaced gold electrodes. Magnetoresistance (MR) measurements performed around the blocking temperature (T_b) of the magnetic moments of the particles in the array, which was relatively high (220 K), yielded negative MR values of the order of 10-25% under moderate magnetic fields of several kOe. The field dependence of the MR followed closely the square of the film's magnetization and its voltage dependence indicated maximal spin polarization around the Fermi level. These findings suggested that the measured MR is the result of spin-polarized tunneling between individual magnetite NCs acting as superparamagnetic spin polarizers.     

Textural and electronic characteristics of mechanochemically activated composites with nanosilica and activated carbon

Nanosilicas (A-50, A-300, A-500)/activated carbon (AC, S_BET = 1520 m²/g) composites were prepared using short-term (5 min) mechanochemical activation (MCA) of powder mixtures in a microbreaker. Smaller silica nanoparticles of A-500 (average diameter d_av = 5.5 nm) can more easily penetrate into broad mesopores and macropores of AC microparticles than larger nanoparticles of A-50 (d_av = 52.4 nm) or A-300 (d_av = 8.1 nm). After MCA of silica/AC, nanopores of non-broken AC nanoparticles remained accessible for adsorbed N₂ molecules. According to ultra-soft X-ray emission spectra (USXES), MCA of silica/AC caused formation of chemical bonds Si-O-C; however, Si-C and Si-Si bonds were practically not formed. A decrease in intensity of OK_α band in respect to CK_α band of silica/AC composites with diminishing sizes of silica nanoparticles is due to both changes in the surface structure of particles and penetration of a greater number of silica nanoparticles into broad pores of AC microparticles and restriction of penetration depth of exciting electron beam into the AC particles.     

The study of novel Fe3O4@γ-Fe2O3 core/shell nanomaterials with improved properties

The surface structure of the iron oxide nanoparticles obtained by the co-precipitation method has been investigated, and a thin layer of α-FeOOH absorbed on surface of the nanoparticle is confirmed by analyses of Fourier transform infrared (FTIR), X-ray photoelectron spectra (XPS) and surface photovoltage spectroscopy (SPS). After annealed at 400 °C, the α-FeOOH can be converted to γ-Fe₂O₃. The simple-annealed procedure resulted in the formation of Fe₃O₄@γ-Fe₂O₃ core/shell structure with improved stability and a higher magnetic saturation value, and also the simple method can be used to obtain core/shell structure in other similar system.