Synthesis and characterisation of metal oxides nanoparticles entrapped in cyclodextrin

A new technique to prepare very small metal oxide (γ-Fe₂O₃, NiO and CoO) magnetic nanoparticles is presented. Nanoparticles are prepared by addition of NaOH to a ferrous chloride solution in the presence of γ-cyclodextrin and once formed are entrapped in the pseudo-single crystals of the oligosaccharide. The resulting crystals give diffraction pattern which looks like those of pure γ-cyclodextrin crystals. Evidences of nanosized particles embedded in the organic crystals were obtained by HREM. The magnetic properties, investigated by ZFC-FC magnetisations, hysteresis loops and ac susceptibility measurements, deviate from those predicted on the basis of the classic single domain particles model due to the complex properties of the surface which for such small sizes, plays the major role in the total magnetic behaviour.     

Microstructural properties and local atomic structures of cobalt oxide nanoparticles synthesised by mechanical ball-milling process

In this study, facile preparation of pure and nano-sized cobalt oxides particles was achieved using low-cost mechanical ball-milling synthesis route. Microstructural and morphological properties of synthesised products were characterised by X-ray diffraction (XRD) and transmission electron microscopy (TEM) techniques. XRD results indicated that the fabricated samples composed of cubic pure phase CoO and Co₃O₄ nanocrystalline particles with an average crystallite size of 37.2 and 31.8 nm, respectively. TEM images showed that the resulting samples consisted of agglomerates of particles with average diameter of about 37.6 nm for CoO and 31.9 nm for Co₃O₄. Phase purity of the prepared samples was further investigated due to their promising technological applications. Local atomic structure properties of the prepared nanoparticles were probed using synchrotron radiation-based X-ray absorption spectroscopy (XAS) including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). EXAFS data analysis further confirmed the formation of single-phase CoO and Co₃O₄ nanoparticles. In addition, structural properties of cobalt oxide nanoparticles were investigated by performing density functional theory calculations at B3LYP/TZVP level and Born–Oppenheimer molecular dynamics. Theoretical calculations for both prepared samples were found to be consistent with the experimental results derived from EXAFS analysis. Obtained results herein reveals that highly crystalline and pure phase CoO and Co₃O₄ nanoparticles can be synthesised using simple, inexpensive and eco-friendly ball-milling method for renewable energy applications involving fuel cells and water splitting devices.     

Eggshell‐Assisted Preparation of Mixed Nanoparticles Simultaneously Encapsulated in Carbon Microcubes for Reversible Lithium Storage

Nanoparticle‐based electrodes often suffer from poor electrical properties due to high interparticle resistance, as well as low Coulombic efficiency attributed to large surface area induced parasitic reactions. In order to address this issue, a strategy of encapsulating two kinds of nanoparticles of both metal oxide and metallic nanoparticles is attempted, simultaneously, in microscale carbon cubic shells for highly reversible lithium storage. The unique structure is synthesized by simultaneous reactions of (1) decomposition of crystalline Co₂(OH)₃Cl microparticle precursor, synthesized in unique eggshell reactor systems, into nanoparticles, (2) partial reduction of CoO into metallic Co by eggshell membrane, (3) carbon coating by chemical vapor deposition facilitated by presence of catalytic Co with carbon released from the eggshell membrane, and (4) microscale carbon shell formed using the Co₂(OH)₃Cl particles as microtemplates. The carbon shells can prevent the encapsulated mixed nanoparticles from direct contact with electrolyte and reduce undesirable parasitic reactions, and accommodate volumetric variation during cycling. The introduction of metallic Co nanoparticles can reduce interparticle resistance. When evaluated for lithium storage, the unique structures of CoO–Co@C demonstrate superior electrochemical performances in terms of electrode stability and rate performance, as compared to that of pure CoO.     

Amphiphilic Core–Shell Nanocomposite Particles for Enhanced Magnetic Resonance Imaging

A scalable synthesis of magnetic core–shell nanocomposite particles, acting as a novel class of magnetic resonance (MR) contrast agents, has been developed. Each nanocomposite particle consists of a biocompatible chitosan shell and a poly(methyl methacrylate) (PMMA) core where multiple aggregated γ‐Fe₂O₃ nanoparticles are confined within the hydrophobic core. Properties of the nanocomposite particles including their chemical structure, particle size, size distribution, and morphology, as well as crystallinity of the magnetic nanoparticles and magnetic properties were systematically characterized. Their potential application as an MR contrast agent has been evaluated. Results show that the nanocomposite particles have good stability in biological media and very low cytotoxicity in both L929 mouse fibroblasts (normal cells) and HeLa cells (cervical cancer cells). They also exhibited excellent MR imaging performance with a T₂ relaxivity of up to 364 mM_Fe^?1 s^?1. An in vivo MR test performed on a naked mouse bearing breast tumor indicates that the nanocomposite particles can localize in both normal liver and tumor tissues. These results suggest that the magnetic core–shell nanocomposite particles are an efficient, inexpensive and safe T₂‐weighted MR contrast agent for both liver and tumor MR imaging in cancer therapy.     

Ferromagnetic/antiferromagnetic exchange coupling in SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript>/CoO composites

The surface of SrFe₁₂O₁₉ coated with a CoO layer reveals a strong exchange bias characterized by magnetic hysteresis loops. The low-temperature coercivity, H_C, and the squareness, M_R/M_S, of a permanent magnet of SrFe₁₂O₁₉/CoO powder prepared by the sol–gel method are enhanced after field cooling through the Néel temperature (T_N=290 K) when compared to those after zero-field cooling. The existence of loop shifts and the enhancement of H_C indicate that exchange-bias effects, which are induced by the ferromagnetic/antiferromagnetic (FM/AFM) exchange-coupling interactions, are responsible for these behaviors. According to our experimental results, some of the factors controlling the exchange bias, such as FM/AFM interfaces and the CoO amount of the antiferromagnetic layer, are discussed. PACS 75.30.Et; 75.50.Ee; 75.60.Ej; 75.60.Gm; 75.70.Cn     

Preparation and Characterization of Polypyrrole/Ferrospinel Nanocomposite by W/O Microemulsion Pathway

A polypyrrole/ferrospinel(NiFe₂O₄) nanocomposite was prepared by the in situ chemical oxidizing of pyrrole in the presence of NiFe₂O₄ nanoparticles in water-in-oil (w/o) microemulsion. The structural, morphological, and magnetic properties of the as-prepared polypyrrole/NiFe₂O₄ nanocomposite were characterized by X-ray diffraction (XRD), Fourier transform infrared spectra, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and magnetic measurements. XRD and FTIR revealed the presence of NiFe₂O₄ in the nanocomposite. SEM and TEM images illustrated that polypyrrole was coated on the NiFe₂O₄ surface. The electromagnetic parameters, such as conductivity, saturation magnetization, and coercivity of NiFe₂O₄ nanoparticles varied after coating with polypyrrole.     

Synthesis and characterization of carbon coated nanoparticles produced by a continuous low-pressure plasma process

Core–shell nanoparticles coated with carbon have been synthesized in a single chamber using a continuous and entirely low-pressure plasma-based process. Nanoparticles are formed in an argon plasma using iron pentacarbonyl Fe(CO)₅ as a precursor. These particles are trapped in a pure argon plasma by shutting off the precursor and then coated with carbon by passing acetylene along with argon as the main background gas. Characterization of the particles was carried out using TEM for morphology, XPS for elemental composition and PPMS for magnetic properties. Iron nanoparticles obtained were a mixture of FeO and Fe₃O₄. TEM analysis shows an average size of 7–14 nm for uncoated particles and 15–24 nm for coated particles. The effect of the carbon coating on magnetic properties of the nanoparticles is studied in detail.     

Preparation of Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles for superthermites by the detonation of an explosive nanocomposite material

This article reports on the preparation of chromium(III) oxide nanoparticles by detonation. For this purpose, a high explosive—hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX)—has been solidified from a solution infiltrated into the macro- and mesoporosity of Cr₂O₃ powder obtained by the combustion of ammonium dichromate. The resulting Cr₂O₃/RDX nanocomposite material was embedded in a cylindrical charge of pure explosive and detonated in order to fragment the metallic oxide into nanoparticles. The resulting soot contains Cr₂O₃ nanoparticles, nanodiamonds, amorphous carbon species and inorganic particles resulting from the erosion by the blast of the detonation tank wall. The purification process consists in (i) removing the carbonaceous species by an oxidative treatment at 500 °C and (ii) dissolving the mineral particles by a chemical treatment with hydrofluoric acid. Contrary to what could be expected, the Cr₂O₃ particles formed during the detonation are twice larger than those of initial Cr₂O₃. The detonation causes the fragmentation of the porous oxide and the melting of resulting particles. Nanometric droplets of molten Cr₂O₃ are ejected and quenched by the water in which the charge is fired. Despite their larger size, the Cr₂O₃ nanoparticles prepared by detonation were found to be less aggregated than those of the initial oxide used as precursor. Finally, the Cr₂O₃ synthesized by detonation was used to prepare a superthermite with aluminium nanoparticles. This material possesses a lower sensitivity and a more regular combustion compared to the one made of initial Cr₂O₃.     

Co–CoO nanoparticles prepared by reactive gas-phase aggregation

The technique of gas-phase aggregation has been used to prepare partially oxidized Co nanoparticles films by allowing a controlled flow of oxygen gas into the aggregation zone. This method differs from those previously reported, that is, the passivation of a beam of preformed particles in a secondary chamber and the conventional (low Ar pressure) reactive sputtering of Co to produce Co–CoO composite films. Transmission electron microscopy shows that the mean size of the particles is about 6 nm. For sufficiently high oxygen pressures, the nanoparticles films become super-paramagnetic at room temperature. X-ray diffraction patterns display reflections corresponding to fcc Co and fcc CoO phases, with an increasing dominance of the latter upon increasing the oxygen pressure in the aggregation zone, which is consistent with the observed reduction in saturation magnetization. The cluster films assembled with particles grown under oxygen in the condensation zone exhibit exchange-bias fields (about 8 kOe at 20 K) systematically higher than those measured for Co–CoO core-shell nanoparticles prepared by oxidizing preformed particles in the deposition chamber, which we attribute, in the light of results from annealing experiments, to a higher ferromagnetic–antiferromagnetic (Co–CoO) interface density.     

Exchange coupling behavior in bimagnetic CoFe2O4/CoFe2 nanocomposite

In this work we report a study of the magnetic behavior of ferrimagnetic oxide CoFe₂O₄ and ferrimagnetic oxide/ferromagnetic metal CoFe₂O₄/CoFe₂ nanocomposite. The latter compound is a good system to study hard ferrimagnet/soft ferromagnet exchange coupled. Two steps were followed to synthesize the bimagnetic CoFe₂O₄/CoFe₂ nanocomposite: (i) first, preparation of CoFe₂O₄ nanoparticles using a simple hydrothermal method, and (ii) second, reduction reaction of cobalt ferrite nanoparticles using activated charcoal in inert atmosphere and high temperature. The phase structures, particle sizes, morphology, and magnetic properties of CoFe₂O₄ nanoparticles were investigated by X-Ray diffraction (XRD), Mossbauer spectroscopy (MS), transmission electron microscopy (TEM), and vibrating sample magnetometer (VSM) with applied field up to 3.0 kOe at room temperature and 50 K. The mean diameter of CoFe₂O₄ particles is about 16 nm. Mossbauer spectra revealed two sites for Fe³⁺. One site is related to Fe in an octahedral coordination and the other one to the Fe³⁺ in a tetrahedral coordination, as expected for a spinel crystal structure of CoFe₂O₄. TEM measurements of nanocomposite showed the formation of a thin shell of CoFe₂ on the cobalt ferrite and indicate that the nanoparticles increase to about 100 nm. The magnetization of the nanocomposite showed a hysteresis loop that is characteristic of exchange coupled systems. A maximum energy product (BH)_max of 1.22 MGOe was achieved at room temperature for CoFe₂O₄/CoFe₂ nanocomposites, which is about 115% higher than the value obtained for CoFe₂O₄ precursor. The exchange coupling interaction and the enhancement of product (BH)_max in nanocomposite CoFe₂O₄/CoFe₂ are discussed.     

Microwave synthesis of magnetic Fe3O4 nanoparticles used as a precursor of nanocomposites and ferrofluids

Methods to synthesize magnetic Fe₃O₄ nanoparticles and to modify the surface of particles are presented in the present investigation. Fe₃O₄ magnetic nanoparticles were prepared by the co-precipitation of Fe³⁺ and Fe²⁺, NH₃·H₂O was used as the precipitating agent to adjust the pH value, and the aging of Fe₃O₄ magnetic nanoparticles was accelerated by microwave (MW) irradiation. The obtained Fe₃O₄ magnetic nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and vibrating sample magnetometer (VSM). The average size of Fe₃O₄ crystallites was found to be around 8–9 nm. Thereafter, the surface of Fe₃O₄ magnetic nanoparticles was modified by stearic acid. The resultant sample was characterized by FT-IR, scanning electron microscopy (SEM), XRD, lipophilic degree (LD) and sedimentation test. The FT-IR results indicated that a covalent bond was formed by chemical reaction between the hydroxyl groups on the surface of Fe₃O₄ nanoparticles and carboxyl groups of stearic acid, which changed the polarity of Fe₃O₄ nanoparticles. The dispersion of Fe₃O₄ in organic solvent was greatly improved. Effects of reaction time, reaction temperature and concentration of stearic acid on particle surface modification were investigated. In addition, Fe₃O₄/polystyrene (PS) nanocomposite was synthesized by adding surface modified Fe₃O₄ magnetic nanoparticles into styrene monomer, followed by the radical polymerization. The obtained nanocomposite was tested by thermogravimetry (TG), differential scanning calorimetry (DSC) and XRD. Results revealed that the thermal stability of PS was not significantly changed after adding Fe₃O₄ nanoparticles. The Fe₃O₄ magnetic fluid was characterized using UV–vis spectrophotometer, Gouy magnetic balance and laser particle-size analyzer. The testing results showed that the magnetic fluid had excellent stability, and had susceptibility of 4.46×10⁻⁸ and saturated magnetization of 6.56 emu/g. In addition, the mean size d (0.99) of magnetic Fe₃O₄ nanoparticles in the fluid was 36.19 nm.     

Preparation and Properties of Iron and Iron Oxide Nanocrystals in MgO Matrix

We have prepared α-iron and magnetite (Fe₃O₄) nanoparticles in MgO matrix from a mixture of nanocrystalline Fe₂O₃ with Mg(H,O) powders calcinated in hydrogen. This procedure yielded spherical magnetic nanoparticles embedded in MgO. Transmission electron microscopy and Mössbauer spectroscopy were used for structure and phase analysis. The measurements of magnetic properties showed increased coercivity of the nanocomposite samples.     

Sonochemical synthesis and characterization of Co3O4 nanocrystals in the presence of the ionic liquid [EMIM][BF4]

For the first time, a sonochemical process has been used to synthesis cobalt oxide Co₃O₄ nanoflowers and nanorods morphology in the presence of the ionic liquid 1-Ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF₄] as reaction media and morphology template. Different sonication time periods and different molar ratios of the ionic liquid (IL) were used to investigate their effects on the structural, optical, chemical and magnetic properties of the produced Co₃O₄ nanoparticles. During synthesis process brown powder contains cobalt hydroxide Co(OH)₂ and cobalt oxyhydroxide (Cobalt hydroxide oxide) CoO(OH) was formed, after calcination in air for 4 h at 400 °C a black powder of Co₃O₄ nanoparticles was produced. The produced Co₃O₄ nanoparticles properties were characterized by X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), transmission electron microscopy (TEM), FTIR spectroscopy, UV–vis spectroscopy, and Vibrating Sample Magnetometer (VSM). To explain the formation mechanism of Co₃O₄ NPs some investigations were carried on the brown powder before calcination.     

Mechanosynthesis,magnetic and Mössbauer characterization of pure and Ti4+-doped cubic phase BiFeO3 nanocrystalline particles

The mechanosynthesis of cubic γ-phase pure BiFeO₃ and Ti⁴⁺-doped BiFeO₃ nanocrystalline particles and their preliminary characterization with magnetic measurements and Mössbauer spectroscopy are reported. The BiFeO₃ nanoparticles (5–40 nm) were prepared by heating a 48 h pre-milled 1:1 molar mixture of α-Bi₂O₃ and α-Fe₂O₃ at 400 °C for (1 h). Doping α-Fe₂O₃ in the initial mixture of reactants with Ti⁴⁺ was found to lead to the formation of Ti⁴⁺-doped BiFeO₃ nanoparticles by milling the reactants for 32 h. The magnetization of the BiFeO₃ nanoparticles is found to be tripled under a maximum external field of 1.35 T and their magnetic hardness increases by ～15 times relative to those of the corresponding bulk. The Ti⁴⁺-doped BiFeO₃ nanoparticles exhibit higher magnetization relative to the pure ones. These observations are related to the spiral modulated spin structure of the compound. The Mössbauer data show ～12 % of the BiFeO₃ nanocrystalline particles to be superparamagnetic having blocking temperatures of less than 78 K. The quadrupole shift values of the magnetic spectral component favor the cubic structural symmetry. These observations were mainly associated with possible collective magnetic excitations as well as transverse relaxation of canted surface spins. The Ti-doped BiFeO₃ nanoparticles gave statistically-poor Mössbauer spectra with no signs of a superparamagnetic behavior.     

Effect of the dispersibility of ZrO2 nanoparticles in Ni-ZrO2 electroplated nanocomposite coatings on the mechanical properties of nanocomposite coatings

ZrO₂ nanoparticles was uniformly co-deposited into a nickel matrix by electroplating of nickel from a Watts bath containing particles in suspension which were monodispersed with dispersant under DC electrodeposition condition. It was found that morphology, orientation and hardness of the nanocomposite coatings with monodispersed ZrO₂ nanoparticles had lots of difference from the nanocomposite coatings with agglomerated ZrO₂ nanoparticles and pure nickel coatings. Especially, the result of hardness showed that only a very low volume percent (less than 1 wt.%) of monodispered ZrO₂ nanoparticles in Ni-ZrO₂ nanocomposite coatings would result in higher hardness of the coatings. The hardness of Ni-ZrO₂ nanocomposite coatings with monodispersed and agglomerated ZrO₂ nanoparticles were 529 and 393 HV, respectively. The hardness value of the former composite coatings was over 1.3 times higher than that of the later. All these composite coatings were two-three times higher than that of pure nickel plating (207 HV) prepared under the same condition. The strengthening mechanisms of the Ni-ZrO₂ nanocomposite coatings based on a combination of grain refinement strengthening from nickel matrix grain refining and dispersion strengthening from dispersion state of ZrO₂ nanoparticles in the coatings.     

Physical and chemical properties of nanostructured CoO-AlOx granular films

A series of nano CoO-AlO_x granular films were prepared by Ar-O₂ reactive rf sputtering and their resistive and magnetoresistive properties were measured for studying the spin-dependent properties. Transmission electron microscopy and X-ray photoelectron spectroscopy are also utilized to investigate the structures and chemical states of these samples. Based on our results, the particles of CoO with radius around 2 nm could be magnetic at room temperature and provide a large tunneling magnetoreststance of −6% through the AlO_x barrier.     

Synthesis of Co-Cu-Zn doped Fe3O4 nanoparticles with tunable morphology and magnetic properties

Co-Cu-Zn doped Fe₃O₄ nanoparticles can be successfully synthesized using a simple method. The particles in the size range 20−400 nm with different regular shapes i.e. sphere-like, regular hexane and tetrahedron are controllably achieved by changing the metal ion concentration. Compared to pure Fe₃O₄ without dopants, Co-Cu-Zn doped Fe₃O₄ nanoparticles exhibit better microwave absorbing properties at 2−18 GHz. Among three Co-Cu-Zn doped Fe₃O₄ nanoparticles with different morphologies, tetrahedral Co-Cu-Zn doped Fe₃O₄ nanoparticles represent a better dielectric loss in high frequency range. This work is believed the first known report of Co-Cu-Zn doped Fe₃O₄ nanoparticles with tunable morphology and magnetic properties through the hydrothermal process without using any organic solvents, organic metal salts or surfactants.     

Microemulsion-mediated in-situ synthesis and magnetic characterization of polyaniline/Zn<Subscript>0.5</Subscript>Cu<Subscript>0.5</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanocomposite

Polyaniline/Zn_0.5Cu_0.5Fe₂O₄ nanocomposite was synthesized by a simple, general and inexpensive in-situ polymerization method in w/o microemulsion. The effects of polyaniline coating on the magnetic properties of Zn_0.5Cu_0.5Fe₂O₄ nanoparticles were investigated. The structural, morphological and magnetic properties of as-prepared samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectra, scanning electron microscopy (SEM) and magnetic measurements. The morphology analysis confirmed that polyaniline was deposited on the porous surface of magnetic Zn_0.5Cu_0.5Fe₂O₄. It was shown that the saturation magnetization and coercivity of Zn_0.5Cu_0.5Fe₂O₄ decreased after polyaniline coating, which can be interpreted by the interparticle dipole–dipole interactions that contributed to magnetic anisotropy and changed the magnetic properties of the nanoparticles. PACS  74.25.Ha; 81.05.-t; 81.05.Lg     

Structural and Magnetic Characteristics of Nanogranular Co–Al2O3 Single- and Multilayer Films Formed by the Solid-State Synthesis

The results of structural and magnetic investigations of nanogranular Co–Al₂O₃ films formed from Co₃O₄/Al thin-film layered structures upon vacuum annealing are reported. The Co₃O₄/Al films have been obtained by sequential reactive magnetron sputtering of a metallic cobalt target in a medium consisting of the Ar + O₂ gas mixture and magnetron sputtering of an aluminum target in the pure argon atmosphere. It is shown that such a technique makes it possible to obtain nanogranular Co–Al₂O₃ single- and multilayer thin films with a well-controlled size of magnetic grains and their distribution over the film thickness.

     

Magnetic properties of xCoO.(1-x)[2B2O3.K2O] glasses

The results of magnetic investigations onxCoO.(1-x)[2B₂O₃.K₂O] glasses are reported. The magnetic properties of these glasses are dependent on the CoO content. For glasses withx > > 10 mol% CoO, the Co²⁺ ions are coupled antiferromagnetically.