Laser-driven synthesis and magnetic properties of iron nanoparticles

Nanoparticles of iron have been prepared by laser-driven decomposition of iron pentacarbonyl vapor. In this method, an infrared laser rapidly heats a dilute mixture of precursor vapors to decompose the precursor and initiate particle nucleation. It was found that when using SF₆ as a photosensitizer during the synthesis, ferrous fluoride (FeF₂) was produced as an undesired byproduct in the product powder. The particle size, composition, and crystalline structure have been characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and X-ray photoelectron spectroscopy (XPS). Results of magnetization measurements for small iron nanoparticles (about 5 nm diameter) are also presented, showing superparamagnetic behavior at room temperature, and a blocking temperature near 125 K.     

Preparation of magnetic nanoparticles by pulsed plasma chemical vapor synthesis

FePt nanoparticle is expected as a candidate for the magnetic material of the high density recording media. We attempted to synthesize FePt alloy nanoparticles using 13.56 MHz glow discharge plasma with the pulse operation of a square-wave on/off cycle of plasma discharge to control the size of nanoparticles. Vapors of metal organics, Biscyclopentadienyl iron (ferrocene) for Fe and (Methylcyclopentadienyl) trimethyl platinum for Pt, were introduced into the capacitively coupled flow-through plasma chamber, which consisted of shower head RF electrode and grounded mesh electrode. Synthesis experiments were conducted at room temperature under the conditions of pressure 0.27 Pa, source gas concentration 0.005 Pa, gas residence time 0.5 s and plasma powers 60 watts. Pulse width for plasma duration was chosen from 0.5 to 30 s and plasma off period was 4 s to each pulse operation. Visual observations during the particle growth showed plasma emission in the bulk region was increased with the particle growth. These were theoretically explained by using the model for both transient particle charging in the plasma and single particle behavior in the stationary plasma as well as assuming the similarity between the negative charged particle and negative gas containing plasma. Synthesized nanoparticles were directly collected onto TEM grid, which was placed just below the grounded mesh electrode in the plasma reactor downstream. TEM pictures showed two kinds of particles in size, one of which was nanometer size and isolated with crystal structures and the other appeared agglomerate of nanometer size particles. The size of agglomerated particle was controlled in the 10–120 nm range by varying the plasma-on time from 0.5 to 30 s, although the nanometer size particles did not change. The composition of FePt alloy particles could be altered by adjusting the source gas feed ratio. Also magnetization of FePt nanoparticles was measured by use of SQUID (superconducting quantum interference device) magnetometry measurements. As-synthesized FePt nanoparticles did not exhibit loop-shape characteristic, which indicated superpamagnetic property. Annealed nanoparticles with the composition of Fe₅₈Pt₄₂ at 650°C in atmospheric hydrogen showed clear hysterisis loop with the coercivity as large as 10 KOe.     

Large-scale synthesis and magnetic properties of cubic CoO nanoparticles

We present the synthesis, microstructural and magnetic characterization of cubic CoO nanoparticles with well-controlled size and shape. The as-synthesized CoO nanoparticles are stable because of the organic coating that occurred in situ. The Néel temperature is 225 and 280 K for the 42 and 74 nm CoO particles, respectively. The CoO nanoparticles exhibit anomalous magnetic properties, such as large moments, coercivities and loop shifts. These results provide evidence for the formation of spin compensated random system in CoO. The structurally distorted and magnetically disordered surface layer ferromagnetic phase played an important role in the magnetic behavior of CoO nanoparticles. The smaller is the particle size, the stronger is the contribution of the ferromagnetic phase and the more is the surface layer helpful to enhance the observed coercivity and the exchange bias.     

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.     

Laser synthesis and magnetic properties of monodispersed core–shell nanoparticles

This paper presents a method for fabricating size-selected nickel nanoparticles coated with oxide shells (shell thickness of about 2 nm). The size of the generated particles was controlled by a low-pressure differential mobility analyzer. The total mass of the deposited particles was estimated on the basis of their measured electric current. A high-resolution transmission electron microscope was used to observe the morphologies of the particles. We successfully synthesized a series of monodispersed (geometric standard deviation <1.2) core–shell particles with oxidized surface layers of 2 nm and analyzed their magnetic properties. PACS 75.50.Te; 75.30.Gw; 75.70.Cn     

Chemical synthesis and magnetic properties of HCP and FCC nickel nanoparticles

In this study, we successfully synthesized single-phase hexagonal closed packed (HCP) and face-centered cubic (FCC) nickel nanoparticles via reduction of nickel nitrate hexahydrate and nickel acetate tetrahydrate, respectively, in polyethylene glycol-200. Structural information of the as-synthesized nickel nanoparticles are studied by X-ray diffraction (XRD) as a function of the molar concentration of the nickel precursor. XRD results reveal that low concentrations of nickel precursor (0.005?M and below) favor the HCP, while high concentrations favor the mixture of HCP and FCC crystal structures. Particle size of HCP structure is found in the range of ～15?nm via transmission electron microscope analysis. Vibratory sample magnetometer is employed to study its magnetic behavior and the results reveal that FCC crystalline phase shows ferromagnetic nature with high saturation magnetization (M _s?～?39.6?emu?gm^?1) as compared to metastable HCP crystalline structure (M _s?～?2?emu?gm^?1). The surfactants bonding on the surface of nickel nanoparticles are studied.     

Solid state synthesis and room temperature magnetic properties of iron phosphide nanoparticles

Room temperature magnetic properties have been achieved for nano-crystalline iron phosphide synthesized from the direct solid state reaction of iron chloride and tri-octylphosphine (TOP). The magnetization continuously increased with higher magnetic fields, indicating a super-paramagnetic behavior. It is observed that room temperature magnetism is possible for the material showing antiferromagnetic nature at low temperatures. In the present synthesis, TOP acted as a source of phosphorus as well as a surfactant. X-ray diffraction (XRD) studies revealed that the black powder is a mixture of FeP and Fe₂P. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed elongated as well spherical particles. Energy dispersion X-ray analysis (EDAX) confirmed a non-stoichiometric iron phosphide. Presence of TOP was confirmed by infra-red (IR) spectroscopy, and thermo-gravimetric analysis (TGA) indicated about 6% wt. loss due to presence of organics.     

Investigations of crystal and magnetic properties of Dy-Fe intermetallic compounds

The crystal and magnetic properties of Dy₂Fe₁₇, Dy₆Fe₂₃, DyFe₃ and DyFe₂ intermetallic compounds are investigated with X-ray, magnetometric, ⁵⁷Fe and ¹⁶¹Dy Mössbauer effect methods. The X-ray analysis shows that investigated compounds are single phases with Th₂Ni₁₇, Th₆Mn₂₃, PuNi₃ and NgCu₂ type crystal structures, respectively. The magnetometric measurements prove their ferrimagnetic behaviour, localization of Fe magnetic moments and long range Fe-Fe exchange magnetic interactions. The crystal field effects induce magnetic anisotropy which results in local magnetic symmetry or iron atoms lower than the crystal one. This is observed by the Mössbauer effect method. The values of ¹⁶¹Dy hyperfine magnetic fields measured for investigated compounds exceed that found in metallic dysprosium due to polarization of conduction electrons by 3d-electrons of iron atoms. The weighted average value of ⁵⁷Fe hyperfine magnetic field decreases with the increase of Dy content in the compounds.     

Doping effects on the magnetic properties of NdRhIn5 intermetallic antiferromagnet

We report temperature dependent heat capacity and magnetization measurements on single crystals of Nd_1-xLa_xRhIn₅ (x=0.15, 0.4 and 0.5) and NdRhIn_5-xSn_x (x=0.08, 0.12 and 0.24). NdRhIn₅ is an antiferromagnetic (AFM) compound with T_N≈ 11 K which crystallizes in the same layered tetragonal structure of the CeMIn₅ family (M=Rh, Co and Ir), where different ground states can be found by tuning the interplay among different microscopic interactions such as the Kondo effect, crystal field (CEF) effects and the Ruderman-Kittel-Kasuya-Yoshida (RKKY) magnetic interaction. Here, we explore the evolution of the AFM correlations in this Nd-based (non-Kondo) compound while perturbing the RKKY exchange by using two different substitutions: (i) replacing Nd³⁺ by non-magnetic La³⁺ within NdIn₃ atomic planes (dilution) and (ii) substituting In by Sn in the In-sites (electronic tuning). For both types of doping, our results show the suppression of the AFM state as the La- or Sn-content is increased. This doping induced suppression of the AFM order is discussed considering the effects of dilution and effects in the tetragonal CEF using a mean-field model applied to the observed data. Our results are compared to the properties of other members of the RRhIn₅ family considering the role of dimensionality in the magnetic interactions.     

Shape-influenced magnetic properties of CoO nanoparticles

Despite uncertainty about the potential human health and environmental risks of nanotechnology, major stakeholders such as regulatory agencies and the nanotechnology industry are already negotiating the emerging regulatory framework for nanotechnology. Because of a relative lack of nano-specific regulations, the future of nanotechnology development will depend greatly on the views held by the nanotechnology industry. This study fills the research gap in understanding how the nanotechnology industry perceives the risks of nanotechnology. This is the first interview-based study of the nanotechnology industry in the United States. Semi-structured, open-ended phone interviews were conducted with 17 individuals involved in the commercialization of nanotechnology in the United States. Results indicate that while the industry acknowledges uncertainty about the potential risks of nanotechnology and takes significant precaution in ensuring the safety of their products, they do not see nanotechnology as novel or risky. They do not believe that uncertainty over risk ought to delay the further development of nanotechnology. The industry sees itself as the primary agent in ensuring consumer safety and believes that consumers are adequately protected. They are also largely benefit-centric and view product labeling as inefficacious.     

Design and synthesis of plasmonic magnetic nanoparticles

Core–shell nanoparticles containing both iron oxide and gold are proposed for bioseparation applications. The surface plasmon resonance of gold makes it possible to track the positions of individual particles, even when they are smaller than the optical diffraction limit. The synthesis of water-dispersible iron oxide-gold nanoparticles is described. Absorption spectra show the plasmon peaks for Au shells on silica particles, suggesting that thin shells may be sufficient to impart a strong surface plasmon resonance to iron oxide-gold nanoparticles. Dark field optical microscopy illustrates the feasibility of single-particle detection. Calculations of magnetophoretic and drag forces for particles of different sizes reveal design requirements for effective separation of these small particles.     

Carbon-encapsulated cobalt nanoparticles: synthesis,properties, and magnetic particle hyperthermia efficiency

A facile and low-cost method for structuring carbon-encapsulated cobalt nanoparticles (Co@C) is presented. Three samples were solvothermally prepared in one step at 220 °C and one in two steps at 200 °C. Three different polyols such as propylene glycol, triethylene glycol, and tetraethylene glycol were used as carbon sources, solvents, and reducing agents. The samples were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and Raman spectroscopy. Concerning the crystal structure of the particles, a mixture of hcp/fcc Co phases was obtained in three of the samples, independently of the polyol used. The coexistence of cubic and hexagonal phases was revealed both from XRD and high-resolution TEM (HRTEM). The formation of the cubic fcc structure, despite the relatively low reaction temperature, is attributed to the role of the interface between carbon coating and metallic core. The presence of carbon coating was demonstrated by Raman spectrometry, exhibiting the characteristic D and G graphitic bands, and by HRTEM observations. All samples showed ferromagnetic behavior with saturation magnetization up to 158 emu/g and coercivity up to 206 Oe. From the magnetic particle hyperthermia measurements recorded at a frequency of 765 kHz, a maximum SLP value of 241 W/g was obtained.     

The influence of Nd-Co substitution on the magnetic properties of non-stoichiometric strontium hexaferrite nanoparticles

Non-stoichiometric Nd-Co substituted hexaferrites of composition Sr_1−xNd_xFe_12(1−x)Co_xO₁₉ (x=0-0.4) were prepared by the self-propagating combustion method and subsequent heat treatments. Structural characterization of samples showed that the M-type hexagonal structure can be maintained for substitutions x<0.4 without the segregation of secondary phases on samples calcined at 1100 °C. The crystallites sizes range between 50 and 70 nm. Mössbauer spectroscopy results indicate that the iron vacancies are not evenly distributed over the lattice and that Co/Fe substitution mainly takes place in site 4f2. Magnetic measurements reveal that values of saturation magnetization M_S increased from 72 to 76 Am²/kg (x=0-0.2), while coercivity H_c increased from 26.40 to 58.70 A/m (x=0-0.3). Nd-Co substitutions enhance magnetic properties in deficient iron Sr hexaferrites.     

The influence of thermal annealing on the structural and magnetic properties of gold nanoparticles

In the past few years ferromagnetic-like behavior has been reported in metal gold nanoparticles coated with diverse organic surfactants. In this work we report on the effect of thermal annealing on the ferromagnetic-like behavior of oleic acid and oleylamine coated gold nanoparticles of about 7 nm size. The magnetic moment of the “as prepared” sample is about 3×10⁻² emu/g and the coercive field is 200 Oe at 10 kOe and 5 K, after the annealing the behavior changes from ferromagnetic-like to paramagnetic and the magnetization at 10 kOe decreases at a factor of 10. These results are compared with those obtained for oleylamine coated gold nanoparticles, which are diamagnetic at room temperature.     

Particle size effect on phase and magnetic properties of polymer-coated magnetic nanoparticles

Polymer-coated magnetic nanoparticles are hi-tech materials with ample applications in the field of biomedicine for the treatment of cancer and targeted drug delivery. In this study, magnetic nanoparticles were synthesized by chemical reduction of FeCl₂ solution with sodium borohydride and coated with amine-terminated polyethylene glycol (aPEG). By varying the concentration of the reactants, the particle size and the crystallinity of the particles were varied. The particle size was found to increase from 6 to 20 nm and the structure becomes amorphous-like with increase in the molar concentration of the reactant. The magnetization at 1 T field (M_1T) for all samples is > 45 emu/g while the coercivity is in the range of 100-350 Oe. When the ethanol-suspended particles are subjected to an alternating magnetic field of 4 Oe at 500 kHz, the temperature is increased to a maximum normalized temperature (3.8 °C/mg) with decreasing particle size.     

Annealing effects on magnetic properties of acicular hematite nanoparticles

The effect of transformation on the structure and magnetic properties of -Fe₂O₃ acicular nanoparticles (major axis, 330 nm; minor axis, 70 nm) has been investigated. The particles were prepared by hydrolysis and polymerization in an aqueous solution of FeCl₃. Particles in the as-prepared sample are constituted by sub-units of 3–5 nm. The results indicate that the changes in the magnetic properties of the samples under thermal treatments (e.g. Morin transition, superparamagnetic behaviour) are mainly caused by the coalesce of the sub-units and by the variation of the crystallinity of nanoparticles.     

Size effects on the magnetic and optical properties of CuO nanoparticles

Optical and magnetic studies on CuO nanoparticles prepared by a chemical route are reported and the effect of size variation on these properties is discussed. SEM images show that the nanoparticles are interlinked into microspheres with the cages containing visible nanoscale holes. Diffuse reflectance spectroscopy indicates a consistent red shift in the fundamental band gap (indirect band gap) from 1.23 to 1 eV as the size decreases from 29 to 11 nm. This observed red shift is attributed to the presence of defect states within the band gap. A clear blue shift is observed in the direct band gap of these nanoparticles presumably due to the quantum confinement effects. Air-annealed samples show a paramagnetic response whereas particles annealed in a reducing atmosphere show additionally a weak ferromagnetic component at room temperature. For both types of particles, the paramagnetic and ferromagnetic moments, respectively, increase with decreasing size. The role of oxygen vacancies is understood to relate to the generation of free carriers mediating ferromagnetism between Cu spins. AC susceptibility measurements show both the antiferromagnetic transitions of CuO including the one at 231 K which is associated with the onset of the spiral antiferromagnetic phase transition.     

Influence of annealing treatment on microstructure and soft magnetic properties of Fe-B-P nanoparticles prepared by aqueous chemical reduction

During the recovery of base metals from the Bushveld Igneous Complex ores, South Africa, a two-stage process is used to ensure complete recovery of nickel from the ore. A nickel flash smelting furnace is initially used to obtain the valuable metal but the loss of nickel in the slag amounts to about 4 % and thus an electric slag-cleaning furnace has to be subsequently used to reduce the loss of the valuable metal to less than 0.5 % nickel oxide in the slag. The Fe^2?+?/Fe^3?+? ratio and mineralogy in the two different furnaces differ and can be used as a tool to determine the efficiency of the nickel recovered in the two-stage process. By means of XRD, SEM/EDS and Mössbauer spectroscopy the Fe^2?+?/Fe^3?+? ratio and the amount of magnetite was determined in each furnace, which was then used as an indicator of the effectiveness of the whole process.