Akaganeite polymer nanocomposites

An “in situ” method for the production of akaganeite polymer nanocomposites is described. A controlled precipitation is achieved by using a polymer matrix, polyvinylpyridine, containing N-base functional groups that form coordination bonds with iron ions. The resulting materials have permitted the observation of two sources of magnetic moment in akaganeite nanoparticles: (1) finite size effects with a characteristic blocking temperature below 2 K; and (2) a deficient Cl⁻ occupancy, with a characteristic blocking temperature around 18 K. Moreover, the nanocomposites can be dissolved in slightly acidic media to obtain stable aqueous nanoparticle dispersions that could be useful in biomedical applications.     

Size Controlling of L1<Subscript>0</Subscript>-FePt Nanoparticles During High Temperature Annealing on the Surface of Carbon Nanotubes

Mono-size FePt nanoparticles with particles size about 2.5 nm have been prepared by polyol method on the surface of carbon nanotubes (CNTs). The CNTs functinalization time and the mass ratio of nanoparticles to CNTs affects on the CNTs surface coating. The as-synthesis nanocomposites have a superparamagnetic behavior with chemically disordered fcc structure at room temperature and they can be transformed into chemically ordered fct structure after thermal annealing above 600 °C. Their magnetic behavior changes from the superparamagnetic to the ferromagnetic with a large coercivity up to 0.83 T for the nanocomposites which annealed at 800 °C. The CNTs surfaces as a substrate prevent the agglomeration of nanoparticles during high temperature annealing and the FePt nanoparticles after annealing at 800 °C have finite size with an average about 10 nm. The structure, composition and magnetic properties of nanocomposite were characterized by X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy and vibrating sample magnetometer.     

Simple synthesis of mesoporous carbon with magnetic nanoparticles embedded in carbon rods

Magnetically separable ordered mesoporous carbon containing magnetic nanoparticles embedded in the carbon walls was synthesized using a simple synthetic procedure. The resulting magnetically separable mesoporous carbon was denoted as M-OMC (magnetically separable ordered mesoporous carbon) poly(pyrrole) with residual Fe²⁺ ions in the mesoporous channel was converted to carbon material containing superparamagnetic nanoparticles. The size of the magnetic nanoparticles obtained was restricted by the channel size of the SBA-15 silica template, which resulted in the generation of superparamagnetic nanoparticles embedded in the carbon rods. The blocking temperature of M-OMC is 110 K. Pore size and textural property of M-OMC is similar to that of hexagonally ordered mesoporous carbon fabricated using SBA-15 silica as a template. The saturation magnetization of M-OMC is ca. 30.0 emu/g at 300 K, high enough for magnetic separation.     

Variable blocking temperature of a porous silicon/Fe3O4 composite due to different interactions of the magnetic nanoparticles

ABSTRACT: In the frame of this work, the aim was to create a superparamagnetic nanocomposite system with a maximized magnetic moment when magnetized by an external field and a blocking temperature far below room temperature. For this purpose, iron oxide nanoparticles of 3.8-, 5- and 8-nm size have been infiltrated into the pores of porous silicon. To fabricate tailored magnetic properties of the system, the particle size and the magnetic interactions among the particles play a crucial role. Different concentrations of the particles dispersed in hexane have been used for the infiltration to vary the blocking temperature TB, which indicates the transition between the superparamagnetic behavior and blocked state. TB is not only dependent on the particle size but also on the magnetic interactions between them, which can be varied by the particle-particle distance. Thus, a modification of the pore loading on the one hand and of the porous silicon morphology on the other hand results in a composite material with a desired blocking temperature. Because both materials, the mesoporous silicon matrices as well as the Fe3O4 nanoparticles, offer low toxicity, the system is a promising candidate for biomedical applications.     

表面活性剂调节高矫顽力FePt纳米颗粒的合成

在表面活性剂聚乙烯吡咯烷酮(PVP)存在的体系中,通过NaBH4还原前驱体Fe(acac)3和H2PtCl6·6H2O,制备出了单分散的尺寸在3.0 nm左右的FePt纳米颗粒。XRD和TEM表征结果显示,表面活性剂PVP的用量影响FePt纳米颗粒相变,但对颗粒的尺寸无明显作用。由此推测,PVP对FePt纳米颗粒的相变起"催化"作用,适量的PVP诱导纳米颗粒的相变,可以通过改变表面活性剂的用量来调节FePt纳米颗粒的磁性能,当表面活性剂PVP单体与FePt前驱体的摩尔比(PVP/FePt)为7时,制得的FePt纳米颗粒经过500℃保温30 min热处理后,矫顽力高达5.2 kOe。     

Low temperature synthesis of monolithic mesoporous magnetite nanoparticles

Magnetite nanoparticles are commonly used for drug delivery, as MRI contrast agents, and as adsorbents for the removal of heavy metal cations from waste water. The smaller the particle sizes the higher the efficiency of these particles in these applications. Different methods have been explored for the preparation of magnetic nanoparticles with this size limitation. Co-precipitation is one of the most versatile methods in this regard, and is characterized by the ability of preparation of a high yield of nanoparticles. Control of the particle size distribution, phase purity and type of porosity of the formed magnetite nanoparticles has been always considered a challenge. In the current study, magnetite mesoporous nanoparticles with an average particle size of 55 nm were prepared in pre-adjusted highly alkaline aqueous media at relatively low temperatures. Phase purity of the deposited magnetite was confirmed by X-ray diffraction (XRD) and thermogravimetric analysis (TGA). Scanning (SEM) and transmission electron microscopy (TEM) graphs showed homogenously dispersion of spherical magnetite nanoparticles. Agglomeration of the mesoporous nanoparticles took place forming clusters with unified pore size distribution due to the homogenous particle size distribution. Magnetic susceptibility measurements at room temperature confirmed the magnetization characteristics of the nanoparticles.     

Magnetic Properties of FePt Nanoparticles Prepared by a Micellar Method

FePt nanoparticles with average size of 9 nm were synthesized using a diblock polymer micellar method combined with plasma treatment. To prevent from oxidation under ambient conditions, immediately after plasma treatment, the FePt nanoparticle arrays were in situ transferred into the film-growth chamber where they were covered by an SiO₂ overlayer. A nearly complete transformation of L1₀ FePt was achieved for samples annealed at temperatures above 700 °C. The well control on the FePt stoichiometry and avoidance from surface oxidation largely enhanced the coercivity, and a value as high as 10 kOe was obtained in this study. An evaluation of magnetic interactions was made using the so-called isothermal remanence (IRM) and dc-demagnetization (DCD) remanence curves and Kelly–Henkel plots (ΔM measurement). The ΔM measurement reveals that the resultant FePt nanoparticles exhibit a rather weak interparticle dipolar coupling, and the absence of interparticle exchange interaction suggests no significant particle agglomeration occurred during the post-annealing. Additionally, a slight parallel magnetic anisotropy was also observed. The results indicate the micellar method has a high potential in preparing FePt nanoparticle arrays used for ultrahigh density recording media.     

Study on Composition Distribution and Ferromagnetism of Monodisperse FePt Nanoparticles

Monodisperse FePt nanoparticles with size of 4.5 and 6.0 nm were prepared by simultaneous reduction of platinum acetylacetonate and thermal decomposition of iron pentacarbonyl in benzylether. The crystallography structure, size, and composition of the FePt nanoparticles were examined by X-ray diffraction and transmission electron microscopy. Energy dispersive X-ray spectrometry measurements of individual particles indicate a broad compositional distribution in both the 4.5 and 6 nm FePt nanoparticles. The effects of compositional distribution on the phase-transition and magnetic properties of the FePt nanoparticles were investigated.     

New Trends in Nanoparticles: Syntheses and Their Applications to Fuel Cells,Health Care,and Magnetic Storage

This paper reviews important research on chemical and electrochemical synthesis and application of nanoparticles, especially our recent results in this field: (i) catalytic metal nanoparticles for micro-fuel cells, (ii) magnetic oxide nanoparticles for drug delivery systems, and (iii) magnetic metal nanoparticles for magnetic recording media. To fulfill the requirements of each application, we chose and modified those synthetic methods for obtaining suitable properties, e.g., morphology, catalytic activity, and magnetic properties. (i) For micro-fuel cells, electrodeposition is attractive because of its selective deposition onto current collectors and possible elimination of an annealing process. As a result, we have successfully synthesized Pt, PtRu alloy, and PdCo alloy, which consisted of dendritic structures macroscopically and of interconnected nanoparticles microscopically. (ii) For drug delivery systems, since magnetic nanoparticles should possess ferromagnetism, be dispersible in water, and be nontoxic, Fe₃O₄ nanoparticles synthesized by hydrolysis in aqueous media are suitable. As a result, we have successfully controlled the size (10–40 nm in diameter) and the magnetic properties of Fe₃O₄ nanoparticles by means of adjusting the molar ratio of ferrous to ferric ions in the precursor solution. (iii) For magnetic recording materials, since magnetic nanoparticles should possess high coercivity, a controlled shape, and a uniform small size, we have modified a chemical method for synthesizing FePt by adjusting the growth temperature. As a result, we have succeeded in synthesizing FePt nanoparticles with a controlled shape (cubic) and a uniform size (ca. 5.6 nm).     

Nanoscaling laws of magnetic nanoparticles and their applicabilities in biomedical sciences

Magnetic nanoparticles, which exhibit a variety of unique magnetic phenomena that are drastically different from those of their bulk counterparts, are garnering significant interest since these properties can be advantageous for utilization in a variety of applications ranging from storage media for magnetic memory devices to probes and vectors in the biomedical sciences. In this Account, we discuss the nanoscaling laws of magnetic nanoparticles including metals, metal ferrites, and metal alloys, while focusing on their size, shape, and composition effects. Their fundamental magnetic properties such as blocking temperature (Tb), spin life time (tau), coercivity (Hc), and susceptibility (chi) are strongly influenced by the nanoscaling laws, and as a result, these scaling relationships can be leveraged to control magnetism from the ferromagnetic to the superparamagnetic regimes. At the same time, they can be used in order to tune magnetic values including Hc, chi, and remanence (Mr). For example, life time of magnetic spin is directly related to the magnetic anisotropy energy (KuV) and also the size and volume of nanoparticles. The blocking temperature (Tb) changes from room temperature to 10 K as the size of cobalt nanoparticles is reduced from 13 to 2 nm. Similarly, H c is highly susceptible to the anisotropy of nanoparticles, while saturation magnetization is directly related to the canting effects of the disordered surface magnetic spins and follows a linear relationship upon plotting of ms (1/3) vs r(-1). Therefore, the nanoscaling laws of magnetic nanoparticles are important not only for understanding the behavior of existing materials but also for developing novel nanomaterials with superior properties. Since magnetic nanoparticles can be easily conjugated with biologically important constituents such as DNA, peptides, and antibodies, it is possible to construct versatile nano-bio hybrid particles, which simultaneously possess magnetic and biological functions for biomedical diagnostics and therapeutics. As demonstrated in this Account, nanoscaling laws for magnetic components are found to be critical to the design of optimized magnetic characteristics of hybrid nanoparticles and their enhanced applicability in the biomedical sciences including their utilizations as contrast enhancement agents for magnetic resonance imaging (MRI), ferromagnetic components for nano-bio hybrid structures, and translational vectors for magnetophoretic sensing of biological species. In particular, systematic modulation of saturation magnetization of nanoparticle probes is important to maximize MR contrast effects and magnetic separation of biological targets.     

Syntheses of Fe-Ni Magnetic Nanoparticles and Their Applications on Biologic Labeling

In this study, we compared FeNi alloy magnetic nanoparticles (MNPs) prepared by either combustion or chemical precipitation methods. We found that the FeNi MNPs generated by combustion method have a rather high saturation magnetization Ms of～180 emu/g and a coercivity field Hc of near zero. However, the alloy nanoparticles are easily aggregated and are not well dispersive such that size distribution of the nanoparticle clusters is wide and clusters are rather big (around 50～700 nm). To prepare a better quality and well dispersed Fe-Ni MNPs, we also developed a thermal reflux chemical precipitation method to synthesize FeNi3 alloy MNPs. The precursor chemicals of Fe(acac)3 and Ni(acac)2 in a molecular ratio 1,2-hexadecandiol and tri-n-octylphosphine oxide (TOPO) were used as reducer and surfactant, respectively. The chemically precipitated FeNi3 MNPs are well dispersed and have well-controlled particle sizes around 10～20 nm with a very narrow size distribution (±1.2 nm). The highly monodispersive FeNi3 MNPs present good uniformity in particle shape and crystallinity on particle surfaces. The MNPs exhibit well soft magnetism with saturation magnetization of ～61 emu/g and Hc～0. The biomedically compatible FeNi MNPs which were coated with biocompatible polyethyleneimine (PEI) polymer were also synthesized. We demonstrated that the PEI coated FeNi MNPs can enter the mammalian cells in vitro and can be used as a magnetic resonance imagine (MRI) contrast agent. The results demonstrated that FeNi MNPs potentially could be applied in the biomedical field. The functionalized magnetic beads with biocompatible polymer coated on MNPs are also completed for biomedical applications.     

Synthesis and Characterization of FePt/NiO Core–Shell Nanoparticles

Monodisperse FePt nanoparticles were successfully synthesized using the chemical polyol process. Annealing at the high temperatures is required to achieve the hard ferromagnetic behavior with L1₀ phase. Annealing causes the surfactant surrounding particles to be decomposed. Under such circumstances, FePt particles are agglomerated, and their size increases. In this research, NiO oxide particle with a high melting point was used for the first time as the shell around FePt core particles to prevent agglomeration. As a result, coercivity, H_c, of FePt and FePt/NiO nanoparticles after annealing at 750?°C are equal to 10 and 7?kOe, respectively.     

Synthesis of Bio-Compatible SPION-based Aqueous Ferrofluids and Evaluation of RadioFrequency Power Loss for Magnetic Hyperthermia

Bio-compatible magnetic fluids having high saturation magnetization find immense applications in various biomedical fields. Aqueous ferrofluids of superparamagnetic iron oxide nanoparticles with narrow size distribution, high shelf life and good stability is realized by controlled chemical co-precipitation process. The crystal structure is verified by X-ray diffraction technique. Particle sizes are evaluated by employing Transmission electron microscopy. Room temperature and low-temperature magnetic measurements were carried out with Superconducting Quantum Interference Device. The fluid exhibits good magnetic response even at very high dilution (6.28 mg/cc). This is an advantage for biomedical applications, since only a small amount of iron is to be metabolised by body organs. Magnetic field induced transmission measurements carried out at photon energy of diode laser (670 nm) exhibited excellent linear dichroism. Based on the structural and magnetic measurements, the power loss for the magnetic nanoparticles under study is evaluated over a range of radiofrequencies.     

Temperature induced evolution of structure/microstructure parameters and their correlations with electric/magnetic properties of nanocrystalline Nickel ferrite

Nickel ferrite nanoparticles were annealed in order to find dependence of electric/magnetic properties on crystallite size. The following correlations of crystallite size with physical parameters were found: (a) lattice parameter decreases with the increase in size and it reaches value for bulk counterpart approximately for crystallites bigger than 7 nm, (b) ac electrical resistivity at room temperature increases with the increase in crystallite size, (c) for crystallites of ~7 nm or smaller electrical resistivity have maximum value at 50 °C, (d) the real part of permittivity at selected frequency generally decreases with the increase in crystallite size and (e) magnetization increases with the increase in crystallite size. Deviation of stoichiometry, cation polyvalence, and cation redistribution with annealing are the main factors that influence physical properties of Nickel ferrite nanoparticles.     

Low-temperature sol–gel synthesis of magnetite superparamagnetic nanoparticles: Influence of heat treatment and citrate–nitrate equivalence ratio

Spinel ferrite nanoparticles are a remarkably versatile group of metal oxides with unique magnetic and electronic properties, making them promising candidates for certain electronic, biomedical, and environmental applications. Magnetite nanoparticles are obtained using complex synthesis methodologies that require inert atmospheres, additives to induce pH changes, expensive or toxic reagents, or complex equipment. In this work, a new approach to obtain superparamagnetic magnetite nanoparticles using citrate–nitrate sol–gel synthesis followed by heat treatment is presented. Iron nitrate and citric acid were added in different equivalence ratios (χ) (citrate/nitrate = 0.30, 0.85, and 1.40). The thermal behaviour of the xerogels was evaluated using thermal analysis techniques, and the results indicated that decreasing the equivalence ratio decreased the temperature required for magnetite formation, and the different release rates of reducing gases influenced the properties of the final material formed. The heat-treatment temperatures for the synthesis with the optimal χ were 130, 150, and 170 °C for 2, 4, and 8 h. Each condition was characterised in terms of the structure and magnetic properties of the product. The results showed that the prepared iron oxide nanoparticles were in the magnetite phase (Fe₃O₄) and possessed a crystallite size of 4.5–6.0 nm and average particle size of <10 nm. The magnetite nanoparticles displayed superparamagnetic behaviour, with a saturation magnetisation of up to 26.24 emu/g and remanent magnetisation of almost zero. Therefore, these superparamagnetic magnetite nanoparticles have excellent potential for biomedical and environmental applications.     

Influence of carbon chain length on the synthesis and yield of fatty amine-coated iron-platinum nanoparticles

Iron oxide nanoparticles are among the most widely used and characterized magnetic nanoparticles. However, metal alloys such as superparamagnetic iron-platinum particles (SIPPs), which have better magnetic properties, are receiving increased attention. Scalable techniques to routinely synthesize SIPPs in bulk need further study. Here, we focus on the role played by the fatty amine ligand in the formation of the bimetallic FePt nanocrystal. More specifically, we compare the effect of varying lengths of fatty amine ligands on the shape, structure, uniformity, composition, and magnetic properties of the SIPPs. We synthesized SIPPs by employing a ‘green’ thermal decomposition reaction using fatty amine ligands containing 12 to 18 carbons in length. Greater fatty amine chain length increased the polydispersity, particle concentration, iron concentration, and the stability of the SIPPs. Additionally, longer reflux times increased the diameter of the particles, but decreased the iron concentration, suggesting that shorter reaction times are preferable. Fourier transform infrared spectroscopy of the SIPPs indicates that the ligands are successfully bound to the FePt cores through the amine group. Superconducting quantum interference device magnetometry measurements suggest that all of the SIPPs were superparamagnetic at room temperature and that SIPPs synthesized using tetradecylamine had the highest saturation magnetization. Our findings indicate that the octadecylamine ligand, which is currently used for the routine synthesis of SIPPs, may not be optimal. Overall, we found that using tetradecylamine and a 30-min reflux reaction resulted in optimal particles with the highest degree of monodispersity, iron content, stability, and saturation magnetization.

PACS

81.07.-b; 75.75.Fk; 61.46.Df     

Radiolytic synthesis of Pd-M (M=Ag and Ni) and Pt-M (M=Ru and Ni) alloy colloids

Pd-M (M=Ag and Ni) and Pt-M (Ru and Ni) alloy colloids were successfully prepared in aqueous solution by γ-irradiation using poly(vinylpyrrolidone), PVP, as stabilizer. The PVP-stabilized Pd-M and Pt-M nanoparticles were characterized by UV-Vis spectroscopy, Transmission Electron Microscopy (TEM) and Electrophoretic Light Scattering (ELS) analysis. The influence of molecular size of the PVP on the size and size distribution of the alloy nanoparticles was followed. Pd-Ag nanoparticles were formed by employing PVP with different molecular weights. The size of Pd-Ag alloy nanoparticles was determined by TEM photograph and ELS spectra, respectively. From the TEM photographs, the average diameter of Pd-Ag nanoparticles does not show strong dependence on the molecular weight of the PVP. On the other hand, the average diameter of Pd-Ag alloy colloids prepared by PVP with Mw=40,000 was consistently larger than that of Pd-Ag alloy colloids prepared by PVP with Mw=10,000. A plausible scheme is given to explaining this. The size and size distribution of Pt-M (Ru and Ni) alloy colloids are presented.     

Rietveld structure refinement,cations distribution and magnetic features of CoFe2O4 nanoparticles synthesized by co-precipitation,hydrothermal, and combustion methods

Cobalt ferrite nanoparticles were synthesized by chemical co-precipitation, hydrothermal and sol gel auto-combustion methods. X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FTIR), field-emission scanning electron microscopy (FE-SEM) and vibrating sample magnetometer (VSM) were used to investigate the structural characteristics and magnetic properties of cobalt ferrite nanocrystals. X-ray patterns revealed the production of a broad single cubic phase with the average crystallite size of 16, 18 and 178 nm for co-precipitation, hydrothermal and combustion methods, respectively. The FTIR measurements between 400 and 4000 cm⁻¹ confirmed the intrinsic cation vibrations of spinel structure. The FE-SEM micrographs of the synthesized samples indicated the presence of two distinct groups of grains exhibiting different sizes and, different shapes for hydrothermal route. The results of magnetic hysteresis at a room temperature showed that the magnetic properties depend on the particle size and shape of particles, whereas the role of particle size is more significant.     

The heating effect of iron-cobalt magnetic nanofluids in an alternating magnetic field: application in magnetic hyperthermia treatment

In this research, FeCo alloy magnetic nanofluids were prepared by reducing iron(III) chloride hexahydrate and cobalt(II) sulfate heptahydrate with sodium borohydride in a water/CTAB/hexanol reverse micelle system for application in magnetic hyperthermia treatment. X-ray diffraction, electron microscopy, selected area electron diffraction, and energy-dispersive analysis indicate the formation of bcc-structured iron-cobalt alloy. Magnetic property assessment of nanoparticles reveals that some samples are single-domain superparamagnetic, while others are single- or multi-domain ferromagnetic. The stability of the magnetic fluids was achieved by using a CTAB/1-butanol surfactant bilayer. Results of Gouy magnetic susceptibility balance experiments indicate good stability of FeCo nanoparticles even after dilution. The inductive properties of corresponding magnetic fluids including temperature rise and specific absorption rate were determined. Results show that with increasing of the nanoparticle size in the single-domain size regime, the generated heat increases, indicating the significant effect of the hysteresis loss. Finally, the central parameter controlling the specific absorption rate of nanoparticles was introduced, the experimental results were compared with those of the Stoner-Wohlfarth model and linear response theory, and the best sample for magnetic hyperthermia treatment was specified.     

Research progress on magnetic nanoparticles for magnetic induction hyperthermia of malignant tumor

As a new malignant tumor therapy method with low side effect, high safety and efficiency, magnetic induction hyperthermia (MIH) has attracted great attention in recent years. As magnetic induction heating media, magnetic nanoparticles (MNPs) are critical for the development of MIH. For clinical safety, the MNPs need a high heating efficiency to reduce the applied dose, minimizing the risk of side effect. Increasing the saturation magnetization and initial susceptibility, adjusting the magnetocrystalline anisotropy constant and particle size to the optimal values are the effective methods of improving heating efficiency. On the other hand, a suitable Curie temperature is desired to realize the self-regulation of the therapy temperature, avoiding the use of clumsy and expensive temperature monitoring and control devices. Substituting the magnetic ions in tetrahedral (A) site of the spinel ferrite with nonmagnetic ions or magnetic ions with smaller magnetic moments can effectively reduce the superexchange interaction between the A and B (octahedral) sites, decreasing Curie temperature. Yet, the reduction of the Curie temperature by ion doping usually reduces the saturation magnetization, decreasing heating efficiency. Increasing the fraction of heat generated by relaxation loss and increasing the saturation magnetization may be used to improve the heating efficiency.