The role of synthetic parameters in the magnetic behavior of relative large hcp Ni nanoparticles

The controllable synthesis of relatively large nickel nanoparticles via thermal decomposition of nickel acetate tetrahydrate in oleylamine in the presence of 1-adamantane carboxylic acid (ACA) and trioctylphosphine oxide (TOPO) is reported. High crystalline hcp nanoparticles of different sizes have been prepared at 290 °C, whereas at relative lower temperatures fcc are favored. The particle size was varying between 50 and 150 nm by properly adjusting the proportion of the capping ligands. TOPO-to-ACA ratio was also found to have an influence on the magnetic properties through the potential formation of a NiO shell. Pure hcp Ni nanoparticles over 50 nm in size served as models to illuminate the magnetic behavior of this metastable hexagonal Ni phase. Contrary to the net ferromagnetic characteristics of fcc Ni nanoparticles in the same size range, hexagonal structured particles exhibit superparamagnetic behavior at room temperature and a weak ferromagnetic contribution below 15 K.     

Superparamagnetic nickel nanoparticles obtained by an organometallic approach

Nickel nanoparticles were prepared by decomposition of the organometallic precursor Ni(COD)₂ (COD=cycloocta-1,5-diene) dissolved in organic media in the presence of anthranilic acid as stabilizer. Transmission electron microscopy revealed nickel nanoparticles with a mean size of 4.2 ± 1.1 nm and selected area electron diffraction showed the formation of fcc nickel. FTIR spectroscopy confirmed the presence of modified anthranilic acid on the surface of the Ni nanoparticles suggesting that it is able to interact with the metal particles. The magnetic response of the nanoparticles was established as being of superparmagnetic character, for which a detailed quantitative analysis resulted in a mean magnetic moment of 2652 μ_B per particle together with a blocking temperature of 32 K.     

离子注入金红石单晶生成的金属Ni纳米晶的磁学性能研究

 研究了能量为64keV、注量1×10¹⁷cm^-2的Ni离子注入金红石TiO₂单晶制备的植入金属纳米晶的微观结构和磁学性能。注入层的结构和磁学性能采用透射电子显微分析（TEM）和超导量子干涉磁强计（SQUID）进行分析。结果表明，金红石单晶中有尺寸为3～18nm的金属Ni纳米晶生成，注入区域基体明显非晶化。10K温度下金属Ni纳米晶的矫顽力约为16.8kA·m^-1，比Ni块材的矫顽力大。样品的零场冷却/有场冷却（ZFC/FC）曲线表明，金属Ni纳米晶的截止温度约为85K。     

On the origin of the substrate-induced oxidation of Ni/NiO(001) studied by X-ray Photoelectron Spectroscopy and Molecular Dynamics Simulations

Metallic Ni, vapor-deposited on NiO(001) near room temperature, could be gradually oxidised upon annealing between 800 K and 940 K in Ultra High Vacuum (UHV), as evidenced by X-ray Photoelectron Spectroscopy for initial Ni coverage of 1.6, 3.8 and 7.5 equivalent monolayers (ML). The time dependence of the oxidation process was consistent with a diffusion mechanism, supplying oxygen via the NiO crystal to a coalesced particulate deposit and resulting in an oxide shell, which grew over the entire surface and enclosed a shrinking metallic core. Similar to the well known behaviour upon gas phase oxidation, the process was fast within a depth of two atomic layers of Ni, limited by the diffusive supply of oxygen from the substrate. Molecular Dynamics Simulations for 0.06, 0.11 and 0.22 ML of Ni ions deposited on a model NiO(001) substrate indicated the formation of NiO islands via oxygen ions transferred from the surface and near-surface layers of the crystal. A significant atomic concentration of oxygen vacancies of the order of 10 to 20% could be created in each underneath layer, before the next one started donating lattice anions. This suggests a possible explanation for the aforementioned NiO-substrate-induced oxidation of deposited Ni, whereby the formation of oxygen vacancies inside the crystal supplies the necessary oxygen.     

Nanostructural and magnetic studies of virtually monodispersed NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanocrystals synthesized by a liquid–solid-solution assisted hydrothermal route

This study presents a comprehensively and systematically structural, chemical and magnetic characterization of ~9.5 nm virtually monodispersed nickel ferrite (NiFe₂O₄) nanoparticles prepared using a modified liquid–solid-solution (LSS) assisted hydrothermal method. Lattice-resolution scanning transmission electron microscope (STEM) and converged beam electron diffraction pattern (CBED) techniques are adapted to characterize the detailed spatial morphology and crystal structure of individual NiFe₂O₄ particles at nano scale for the first time. It is found that each NiFe₂O₄ nanoparticle is single crystal with an fcc structure. The morphology investigation reveals that the prepared NiFe₂O₄ nanoparticles of which the surfaces are decorated by oleic acid are dispersed individually in hexane. The chemical composition of nickel ferrite nanoparticles is measured to be 1:2 atomic ratio of Ni:Fe, indicating a pure NiFe₂O₄ composition. Magnetic measurements reveal that the as-synthesized nanocrystals displayed superparamagnetic behavior at room temperature and were ferromagnetic at 10 K. The nanoscale characterization and magnetic investigation of monodispersed NiFe₂O₄ nanoparticles should be significant for its potential applications in the field of biomedicine and magnetic fluid using them as magnetic materials.     

Optical properties of sol-gel fabricated Ni/SiO2 glass nanocomposites

Nickel nanoparticles were grown in silica glass by annealing of the sol-gel prepared silicate matrices doped with nickel nitrate. TEM characterization of Ni/SiO₂ glass proves the formation of isolated spherical nickel nanoparticles with mean sizes 6.7 and 20 nm depending on annealing conditions. The absorption and photoluminescence spectra of Ni/SiO₂ glasses were measured. In the absorption spectra, we observed the band related to the surface plasmon resonance (SPR) in Ni nanoparticles. The broadening of SPR was observed with decrease of Ni nanoparticle size. The width of the surface plasmon band decreases 1.5 times at the lowering of temperature from 293 to 2 K because of strong electron-phonon interaction. The spectra proved the creation of nickel oxide NiO clusters and Ni²⁺ ions in silica glass as well.     

FORC analysis of Ni(SiO2) nanogranular film in the blocked regime

In this work the magnetic and structural properties of granular Ni(SiO₂) films are studied by means of FORCs diagrams and microscopy. Transmission electron microscopy images show that the sample is composed of a fine dispersion of Ni nanoparticles with 3.7 nm in average sizes. Magnetic measurements as function of temperature show that the nanoparticles are superparamagnetic at room temperature and are blocked at 5 K. The FORCs diagrams obtained below the blocking temperature allow us to determine the average size of the nanoparticles and the distribution of sizes in a very good agreement with TEM images.     

Evidence for the interfacial reaction between Ni adatoms and H-Si(001) surface

Hydrogen termination of Si surfaces (H-Si) does not stop the interfacial reaction between Ni adatoms and H-Si(001) surface at room temperature. At low Ni coverage of 0.1% (equivalent to 0.02 ML), X-ray photoelectron spectroscopy (XPS) reveals a binding energy shift of Ni 2p_3/2 to 854.0 eV, which corresponds to the formation a NiSi-like environment. As the coverage of Ni increases, the Ni 2p_3/2 eventually shifts to 852.8 eV, indicative of formation of metallic Ni. XPS intensity vs Ni coverage analysis reveals a growth process akin to pseudo-layer-by-layer growth mode, thereby suggesting the formation of bulk-Si(001)/NiSi-like/Ni-rich-silicide-like/metallic Ni structure as growth proceeds. For Ni coverage not more that 33% (equivalent to 12.68 ML), Ni remains protected by the silicide environment and no oxidation of Ni to form Ni-oxides was observed even after exposing the samples to air for 400 days. For samples with Ni coverage above 41%, oxidation of Ni is observed by presence of NiO and NiSiO₃ peaks at 854.5 and 857.0 eV, respectively. The current studies suggest that there is reaction between Ni adatoms and Si at the growth front on H-Si(001) surfaces upon Ni deposition at room temperature and hydrogen termination does not suppress the interface reaction between Ni and Si.     

Eco-friendly combustion-based synthesis of metal aluminates MAl<Subscript>2</Subscript>O<Subscript>4</Subscript> (M = Ni,Co)

Nanosized metal aluminates, MAl₂O₄ (M = Ni, Co), have been prepared following a nonpolluting, low temperature, and self-sustaining starch single-fuel combustion synthesis. The mixed fuel-coordinating actions of starch have given rise to an intermediary precursor which afforded monodisperse metal aluminate nanoparticles. The thermal analysis of the [M(II), Al(III)]-starch precursors indicates a similar thermochemical reactivity for the two compounds, displaying a sequence of well-defined decomposition stages associated with three endothermic effects and three/four (nickel/cobalt) exothermic ones. The XRD data confirm the formation of spinelic phase and a continuous growth of particle sizes with the increase of calcination temperatures. The mechanisms proposed for the formation of metal aluminates essentially consist in a combination of solid-state reactions of amorphous NiO/Co₃O₄ and Al₂O₃ simple oxides. The evaluation criterion of Ni(II) cations into the spinelic lattice is original and is based on the distinct occupancy degree of tetrahedral and octahedral sites in NiAl₂O₄ and γ-Al₂O₃. TEM/HRTEM investigations performed on the cobalt(II) and nickel(II) aluminate oxide powders resulted after calcination at 800 and 900 °C, respectively, for 1 h show the formation of irregular and isolated plate-like particles for Co(II)-based spinelic oxides (the average particle size is 16.6 nm) and submicron aggregates of small, bimodal, and almost uniform (as shape and size) of NiAl₂O₄ mixed oxide (the mean particle size is 33.6 nm). The NIR–UV–Vis spectra for the resulted MAl₂O₄ (M = Co, Ni) mixed oxides reveal a massive presence of tetrahedral divalent cations both for short- and long-time calcined samples. NiO impurities are detected using FTIR and electronic spectra for all NiAl₂O₄ samples.     

Magnetic properties of Fe nanoparticles trapped at the tips of the aligned carbon nanotubes

The magnetic properties of iron nanoparticles partially encapsulated at the tips of aligned carbon nanotubes have been studied. The carbon nanotube wall not only protects the metallic particles from oxidization, but also reduces the inter-particle dipolar interaction by non-magnetic separation. Magnetic characterizations performed in the temperature range of 5–350 K with magnetic field up to 3 T show that these carbon-nanotube-supported iron particles are good candidates for high-density magnetic recording media.     

Preparation of NiO and CoO nanoparticles using M2+-oleate (M = Ni,Co) as precursor

The preparation of NiO and CoO nanoparticles was reported. The dot-like NiO and flower-like CoO nanoparticles were obtained using M²⁺-oleate (M = Ni, Co) as precursor via thermal decomposition method. Transmission electron microscopic (TEM) images monitored the growth of NiO and CoO nanoparticles. When the reaction complex including M²⁺-oleate (M = Ni, Co) precursor, oleic acid and 1-octadecene was heated to the refluxing temperature (320 °C), the formed NiO and CoO nanoparticles were needle-like and very small, indicating low growth speed. However, when the reaction complex was kept refluxing for 30 min, dot-like NiO and flower-like CoO nanoparticles were observed, suggesting the accelerated growth at this refluxing stage. The difference of the morphology of the resultant NiO and CoO nanoparticles resulted from the difference of their growth mode. Selected-area electron diffraction (SAED) patterns showed the face-centered cubic structures of NiO and CoO nanoparticles. The magnetic property of the nanoparticles was studied using vibrating sample magnetometer (VSM).     

Effect of Ni doping on the structural and magnetic properties of FePt nanoparticles

A serial of FePtNi nanoparticles were investigated on their crystal structure and magnetic properties. The FePtNi nanoparticles were synthesized simultaneously by the reduction of iron (III) acetylacetonate, platinum (II) acetylacetonate and nickel (II) acetylacetonate with 1,2-hexadecanediol as the reducing agent. The X-ray diffraction patterns indicate that the addition of 8, 12, 17 at% Ni in FePt nanoparticles suppressed the transformation of the particles from disorder face-centered cubic to order face-centered tetragonal L1₀-phase under annealing treatment. However, further increasing Ni contents to 21 at%, the nanoparticle transformed to L1₂ phase. Doping of Ni into the FePt compound system may decrease coercivity and crystal anisotropy energy. A maximum coercivity of 7 KOe at room temperature was obtained for (Fe₅₂Pt₄₈)₉₂Ni₈ nanoparticles after annealing at 600 °C for 30 min.     

FMR and TEM Studies of Co and Ni Nanoparticles Implanted in the SiO<Subscript>2</Subscript> Matrix

Fused silica plates have been implanted with 40 keV Co⁺ or Ni⁺ ions to high doses in the range of (0.25–1.0) × 10¹⁷ ions/cm², and magnetic properties of the implanted samples have been studied with ferromagnetic resonance (FMR) technique supplemented by transmission electron microscopy, electron diffraction and energy dispersive X-ray spectroscopy. The high-dose implantation with 3d-ions results in the formation of cobalt and nickel metal nanoparticles in the irradiated subsurface layer of the SiO₂ matrix. Co and Ni nanocrystals with hexagonal close packing and face-centered cubic structures have a spherical shape and the sizes of 4–5 nm (for cobalt) and 6–14 nm (for nickel) in diameter. Room-temperature FMR signals from ensembles of Co and Ni nanoparticles implanted in the SiO₂ matrix exhibit an out-of-plane uniaxial magnetic anisotropy that is typical for thin magnetic films. The dose and temperature dependences of FMR spectra have been analyzed using the Kittel formalism, and the effective magnetization and g-factor values have been obtained for Co- and Ni-implanted samples. Nonsymmetric FMR line shapes have been fitted by a sum of two symmetrical curves. The dependences of the magnetic parameters of each curve on the implantation dose and temperature are presented.     

Magnetic properties of Ni/NiO nanocomposites synthesized by one step solution combustion method

Ni/NiO nanocomposites were synthesized using solution combustion method and characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDAX) and carbon, hydrogen, nitrogen (CHN) analyser. The Ni or NiO content in Ni/NiO nanocomposites vary with the quantity of HNO₃ used for the synthesis. Magnetic coercivity (H_c) of Ni/NiO nanocomposites is found to be 413 Oe which can be used in magnetic applications. A feeble exchange bias of 7 Oe is seen from the NiO rich Ni/NiO.     

A new nano-structured Ni(II) Schiff base complex: synthesis,characterization, optical band gaps,and biological activity

New Ni(II) Schiff base complexes [{Ni(L)(H₂O)Cl} where HL = 2-((pyridin-3-ylmethylene)amino)phenol] have been synthesized using the reflux and sonochemical methods. The nickel oxide NiO nanopowder was obtained from the metal complexes after calcination at 650 °C for 2 h. The Schiff base complexes and NiO powders were characterized in detail. The HL and its metal complexes were depicted high activity towards microorganism and breast carcinoma cells. The inhibitory activity against breast carcinoma (MCF-7) were detected with IC₅₀ = 5.5, 12.5 and 9.6 for HL, complex (1) and complex (2), respectively. The optical band gap energy was 3.6, 3.0 and 2.37 eV for Ni complexes (1), (2) and NiO, respectively. The microstructure of the formed NiO powders appeared as cubic-like structure. Furthermore, magnetic properties of NiO sample were identified and paramagnetic property was found at a room temperature. The saturation magnetization and coercive force for the NiO sample were 0.47 emu/g and 42.68 Oe, respectively.     

Synthesis,structure stability and magnetic properties of nanocrystalline Ag–Ni alloy

Silver–nickel alloy nanoparticles with an average size of 30–40 nm were synthesized by chemically reducing the mixture of silver and nickel salts using sodium borohydride. The structure and the magnetic properties of the alloy samples with different compositions were investigated. The phase stability of the material was analysed after annealing the sample in vacuum at various temperatures. The material exhibits single fcc phase which is stable up to 400 °C and Ni precipitation sets in when the sample is annealed to 500 °C. The thermal analysis using DSC was carried out to confirm the same. The alloy compositions are found to be in close correlation with the metal salt ratios in the precursors. The synthesized samples exhibit weak paramagnetic to ferromagnetic behaviour. The magnetic measurements reveal that by adjusting the precursor ratio, the Ni content in the material can be altered and hence its magnetic properties tailored to suit specific requirements. The formation of Ag–Ni alloy is confirmed by the observed Curie temperature from the magneto thermogram. Annealing the sample helps to produce significant enhancement in the magnetization of the material.     

Room temperature ferromagnetism in nanocrystalline Ni-doped ZnO synthesized by co-precipitation

Ni-doped ZnO powder was synthesized by thermal co-decomposition of a mixture of bis(acetylacetonato) zinc(II)hydrate and bis(dimethylglyoximato)nickel(II) complexes. The samples were characterised by X-ray diffraction (XRD), Energy dispersion X-ray fluorescence (EDXRF), and FT-IR spectroscopy. The atomic ratio Ni/Zn of the samples was determined by the EDXRF method to be 1%, 4.3%, 7.4% and 22.5 wt%. The XRD studies show the formation of nanocrystalline (14-18 nm) of Ni-doped ZnO along with nanoparticles of NiO. By magnetic measurements, it was observed that powder contains 1%Ni, 4.3%Ni, 7.4%Ni exhibits superparamagnetic behaviour while the sample of 22.5%Ni prepared in closed atmospheric environment shows clear ferromagnetic (FM) loop at room temperature due to the formation of solid solution Zn_1−xNi_xO.     

Magnetotransport in core-shell Fe–Fe oxide nanostructures

Magnetic and magnetotransport measurements were performed on gas-phase synthesized Fe nanoparticles subjected to surface oxidation and cold consolidation. Two samples were investigated with α-Fe volume fraction of 0.15 and 0.60. The sample with smaller metallic fraction is below the percolation threshold for metallic conduction and the conduction mechanism is dominated by thermally activated processes across the oxide. In this case, by lowering the temperature, an increase of the negative magnetoresistance is observed up to 5% at 50 K in a magnetic field of 70 kOe. The magnetoresistance dependence on the sample magnetization, temperature and sample composition is discussed considering the magnetic correlations present in these nanostrucuterd systems.     

Controlling the crystal structure of Ni nanoparticles by the use of alkylamines

Ni nanoparticles were prepared via thermal decomposition of nickel acetate tetrahydrate in the presence of long-chain amines, which acted as both solvents and reducing agents. By tuning the reaction temperature, Ni nanostructures with either hcp or fcc crystal structure were obtained. In principle, higher temperatures favored the formation of hcp nanoparticles. The employment of additional surfactants such as 1-adamantanecarboxylic acid and trioctylphosphine-oxide facilitated the tuning of the particles’ growth limit. The size of the particles varied between 5 and 120 nm. The magnetic features of fcc-Ni nanoparticles were quite similar to the corresponding ‘bulk’ ones. On the other hand, the hcp-Ni particles showed weak magnetic features, reflected by low magnetization values, the absence of saturation magnetization and by blocking temperatures far below room temperature.     

Structural analysis of nickel doped cobalt ferrite nanoparticles prepared by coprecipitation route

Magnetic nanoparticles of nickel substituted cobalt ferrite (Ni_xCo_1−xFe₂O₄:0≤x≤1) have been synthesized by co-precipitation route. Particles size as estimated by the full width half maximum (FWHM) of the strongest X-ray diffraction (XRD) peak and transmission electron microscopy (TEM) techniques was found in the range 18–28±4 nm. Energy dispersive X-ray (EDX) analysis confirms the presence of Co, Ni, Fe and oxygen as well as the desired phases in the prepared nanoparticles. The selective area electron diffraction (SAED) analysis confirms the crystalline nature of the prepared nanoparticles. Data collected from the magnetization hysteresis loops of the samples show that the prepared nanoparticles are highly magnetic at room temperature. Both coercivity and saturation magnetization of the samples were found to decrease linearly with increasing Ni-concentration in cobalt ferrite. Superparamagnetic blocking temperature as determined from the zero field cooled (ZFC) magnetization curve shows a decreasing trend with increasing Ni-concentration in cobalt ferrite nanoparticles.