Magnetic field synthesis of Fe3O4 nanoparticles used as a precursor of ferrofluids

Methods to synthesize magnetic Fe₃O₄ nanoparticles and to modify the nanoparticle surface are presented in this paper. In these methods, Fe₃O₄ nanoparticles were prepared by co-precipitation, and the aging of nanoparticles was improved by applied magnetic field. The obtained nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and vibrating sample magnetometer (VSM). Thereafter, to enhance the compatibility between nanoparticles and water, an effective surface modification method was developed by grafting acrylic acid onto the nanoparticle surface. FT-IR, XRD, transmission electron microscopy (TEM), and thermogravimetry (TG) were used to characterize the resultant sample. The testing results indicated that the polyacrylic acid chains have been covalently bonded to the surface of magnetic Fe₃O₄ nanoparticles. The effects of initiator dosage, monomer concentration, and reaction temperature on the characteristics of surface-modified Fe₃O₄ nanoparticles were investigated. Moreover, the Fe₃O₄-g-PAA hybrid nanoparticles were dispersed in water to form ferrofluids (FFs). The obtained FFs were characterized by UV–vis spectrophotometer, Gouy magnetic balance and laser particle-size analyzer. The testing results showed that the high-concentration FF had excellent stability, with high susceptibility and high saturation magnetization. The rheological properties of the FFs were also investigated using a rotating rheometer.     

Superspin glass state in MnFe2O4 nanoparticles

Nanosized MnFe₂O₄ ferrites were synthesized by a simple method, which is based on the solid state ball-milling and calcinations of nitrate precursors and citric acid. The samples were characterized by using different methods. The results indicate that the products mainly consist of MnFe₂O₄ nanoparticles. The effect of different annealing temperatures on particle sizes and crystallinity of the samples was also studied. By increasing the particle size, the coercivity and magnetization of the samples increase. The increase of magnetization by increasing the crystallite size could be attributed to the lower surface spin canting and surface spin disorder of the larger magnetic nanoparticles. Our analysis of ac susceptibility measurements shows that the interparticle magnetic interaction leads to the superspin glass-like behavior in these nanoparticle samples.     

Thermomagnetic determination of Fe3O4 magnetic nanoparticle diameters for biomedical applications

The utility and promise of magnetic nanoparticles (MagNPs) for biomedicine rely heavily on accurate determination of the particle diameter attributes. While the average functional size and size distribution of the magnetic nanoparticles directly impact the implementation and optimization of nanobiotechnology applications in which they are employed, the determination of these attributes using electron microscopy techniques can be time-consuming and misrepresentative of the full nanoparticle population. In this work the average particle diameter and distribution of an ensemble of Fe₃O₄ ferrimagnetic nanoparticles are determined solely from temperature-dependent magnetization measurements; the results compare favorably to those obtained from extensive electron microscopy observations. The attributes of a population of biocompatible Fe₃O₄ nanoparticles synthesized by a thermal decomposition method are obtained from quantitative evaluation of a model that incorporates the distribution of superparamagnetic blocking temperatures represented through thermomagnetization data. The average size and size distributions are determined from magnetization data via temperature-dependent zero-field-cooled magnetization. The current work is unique from existing approaches based on magnetic measurement for the characterization of a nanoparticle ensemble as it provides both the average particle size as well as the particle size distribution.     

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.     

Magnetic and rheological properties of monodisperse Fe3O4 nanoparticle/organic hybrid

Fe₃O₄ nanoparticle/organic hybrids were synthesized via hydrolysis using iron (III) acetylacetonate at ∼80 °C. The synthesis of Fe₃O₄ was confirmed by X-ray diffraction, selected-area diffraction, and X-ray photoelectron spectroscopy. Fe₃O₄ nanoparticles in the organic matrix had diameters ranging from 7 to 13 nm depending on the conditions of hydrolysis. The saturation magnetization of the hybrid increased with an increase in the particle size. When the hybrid contained Fe₃O₄ particles with a size of less than 10 nm, it exhibited superparamagnetic behavior. The blocking temperature of the hybrid containing Fe₃O₄ particles with a size of 7.3 nm was 200 K, and it increased to 310 K as the particle size increased to 9.1 nm. A hybrid containing Fe₃O₄ particles of size greater than 10 nm was ferrimagnetic, and underwent Verwey transition at 130 K. Under a magnetic field, a suspension of the hybrid in silicone oil revealed the magnetorheological effect. The yield stress of the fluid was dependent on the saturation magnetization of Fe₃O₄ nanoparticles in the hybrid, the strength of the magnetic field, and the amount of the hybrid.     

Strongly interacting superspins in Fe3O4 nanoparticles

In this paper we report structural and magnetic properties of Fe₃O₄ nanoparticles synthesized by thermal decomposition of ball milled iron nitrate and citric acid in N₂ and air ambient. The XRD pattern of samples which are prepared in air shows some impurity phases, while the samples synthesized in the N₂ atmosphere are almost pure Fe₃O₄ phase. The result shows that by increasing the particle size, the magnetization of the samples increases. The increase of magnetization by increasing the particle size could be attributed to the lower surface spin canting and surface spin disorder of the larger magnetic nanoparticles. The results of ac magnetic susceptibility measurements show that the susceptibility data are not in accordance with the Néel -Brown model for superparamagnetic relaxation, but fit well with conventional critical slowing down model which indicates that the dipole-dipole interactions are strong enough to cause superspin-glass like phase in these samples.     

Grafting poly(ethylene glycol) monomethacrylate onto Fe3O4 nanoparticles to resist nonspecific protein adsorption

Magnetic nanoparticles grafted with poly(poly(ethylene glycol) monomethacrylate) (P(PEGMA)) were prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization. In this approach, S-benzyl S′-trimethoxysilylpropyltrithiocarbonate, used as a chain transfer agent for RAFT, was first immobilized onto the magnetic nanoparticle surface, and then PEGMA was grafted onto the surface of magnetic nanoparticle via RAFT polymerization. The results showed that P(PEGMA) chains grew from magnetic nanoparticles by surface-induced RAFT polymerization. The grafted P(PEGMA) chains can decrease the nonspecific adsorption of proteins on the surface of Fe₃O₄ nanoparticles.     

The structure and magnetic properties of Zn1−xNixFe2O4 ferrite nanoparticles prepared by sol–gel auto-combustion

Zn_1−xNi_xFe₂O₄ ferrite nanoparticles were prepared by sol–gel auto-combustion and then annealed at 700 °C for 4 h. The results of differential thermal analysis indicate that the thermal decomposition temperature is about 210 °C and Ni–Zn ferrite nanoparticles could be synthesized in the self-propagating combustion process. The microstructure and magnetic properties were investigated by means of X-ray diffraction, scanning electron microscope, and Vibrating sample magnetometer. It is observed that all the spherical nanoparticles with an average grain size of about 35 nm are of pure spinel cubic structure. The crystal lattice constant declines gradually with increasing x from 0.8435 nm (x=0.20) to 0.8352 nm (x=1.00). Different from the composition of Zn_0.5Ni_0.5Fe₂O₄ for the bulk, the maximum M_s is found in the composition of Zn_0.3Ni_0.7Fe₂O₄ for nanoparticles. The H_c of samples is much larger than the bulk ferrites and increases with the enlarging x. The results of Zn_0.3Ni_0.7Fe₂O₄ annealed at different temperatures indicate that the maximum M_s (83.2 emu/g) appears in the sample annealed at 900 °C. The H_c of Zn_0.3Ni_0.7Fe₂O₄ firstly increases slightly as the grain size increases, and presents a maximum value of 115 Oe when the grains grow up to about 30 nm, and then declines rapidly with the grains further growing. The critical diameter (under the critical diameter, the grain is of single domain) of Zn_0.3Ni_0.7Fe₂O₄ nanoparticles is found to be about 30 nm.     

Low-temperature synthesis and growth of superparamagnetic Zn0.5Ni0.5Fe2O4 nanosized particles

Mono-disperse spinel Ni_0.5Zn_0.5Fe₂O₄ nanosized particles have been synthesized via a hydrothermal method at low temperature. X-ray diffraction (XRD), transmission electron microscope (TEM) and high-resolution transmission electron microscope (HRTEM) analysis indicated that the synthesized nanocrystals were of pure cubic spinel structure with the size about 6-20 nm. The activation energy of grain growth is 35.06 kJ/mol experimented by the Arrhenius equation. A primary experimental model was put forward to shed light on the growth mechanism of crystallined spinel Ni-Zn ferrite nanosized particles under hydrothermal conditions. The magnetic measurements shows that the prepared Ni_0.5Zn_0.5Fe₂O₄ nanoparticle possess good superparamagnetic behavior.     

Magnetic properties of the novel nanocomposite (Zn0.15Ni0.85Fe2O4)0.15/(SiO2)0.85 at room temperature

The value of the effective magnetic anisotropy constant of the ferrimagnetic nanoparticles Zn_0.15Ni_0.85Fe₂O₄ embedded in a SiO₂ silica matrix, determined through ferromagnetic resonance (FMR), is much higher than the magnetocrystalline anisotropy constant. The higher value of the anisotropy constant is due to the existence of surface anisotropy. However, even if the magnetic anisotropy is high, the ferrimagnetic nanoparticles with a 15% concentration, which are isolated in a SiO₂ matrix, display a superparamagnetic (SPM) behavior at room temperature and at a frequency of the magnetization field equal to 50 Hz. The FMR spectrum of the novel nanocomposite (Zn_0.15Ni_0.85Fe₂O₄)_0.15/(SiO₂)_0.85, recorded at room temperature and a frequency of 9.060 GHz, is observed at a resonance field (B_0r) of 0.2285 T, which is substantially lower than the field corresponding to free electron resonance (ESR) (0.3236 T). Apart from the line corresponding to the resonance of the nanoparticle system, the spectrum also contains an additional weaker line, identified for a resonance field of ∼0.12 T, which is appreciably lower than B_0r. This line was attributed to magnetic ions complex that is in a disordered structure in the layer that has an average thickness of 1.4 nm, this layer being situated on the surface of the Zn_0.15Ni_0.85Fe₂O₄ nanoparticles that have a mean magnetic diameter of 8.9 nm.     

Synthesis and magnetic characterization of Zn0.7Ni0.3Fe2O4 nanoparticles via microwave-assisted combustion route

We report on the synthesis of Zn_0.7Ni_0.3Fe₂O₄ nanoparticles via microwave assisted combustion route by using urea as fuel. XRD and FT-IR analyses confirm the composition and structure as spinel ferrite. The crystallite size estimated from XRD (16.4 nm) and the magnetic core size (15.04 nm) estimated from VSM agree well, while a slightly smaller magnetic diameter reflects a very thin magnetically dead layer on the surface of the nanoparticles. Morphological investigation of the products was done by TEM which revealed the existence of irregular shapes such spherical, spherodial and polygon. Magnetization measurements performed on Zn_0.7Ni_0.3Fe₂O₄ nanoparticles showed that saturation was not attained at even in the high magnetic field. The sample shows superparamagnetic behavior at around the room temperature and ferromagnetic behavior below the blocking temperature which is measured as 284 K.     

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.     

压力对纳米CoFe2O4/SiO2复合材料结构的影响

 采用溶胶-凝胶工艺和高温高压实验技术,制备了纳米CoFe₂O₄/SiO₂复合材料。利用X射线衍射仪、扫描电子显微镜和振动样品磁强计,对样品的结构、微观形貌和磁性进行了研究,并对CoFe₂O₄中阳离子的占位情况进行了讨论。结果表明,随着处理压力的升高,样品的晶粒尺寸增大,晶格常数减小,比饱和磁化强度增大。通过计算结果可以推断,压力的升高导致CoFe₂O₄中的部分Fe³⁺从A位移向了B位,而部分Co²⁺则从B位移向了A位。     

Heat dissipation and magnetic properties of surface-coated Fe3O4 nanoparticles for biomedical applications

In this study, the influence of surface coating on the magnetic and heat dissipation properties of Fe₃O₄ nanoparticles was investigated. Fe₃O₄ nanoparticles that ranged in size between (particle sizes of 20 and 30 nm) were coated with polyethylenimine (PEI), oleic acid, and Pluronic F-127. Surface coatings that were composed of thick layers of oleic acid and Pluronic F-127 reduced dipole interactions between the particles, and resulted in reduced coercivity and decreased Néel relaxation times. The ac magnetization measurements revealed that the heat dissipation of the PEI-coated Fe₃O₄ nanoparticles was induced by hysteresis loss and Brownian relaxation loss and that of the oleic-acid-coated Fe₃O₄ nanoparticles was mainly induced by hysteresis loss and Néel relaxation loss.     

海藻酸改性的空心Fe3O4纳米颗粒的制备与应用

不使用任何模板一步制得空心Fe₃O₄纳米颗粒,然后将海藻酸钠嫁接在氨基化的空心Fe₃O₄表面,再利用海藻酸盐与钙离子的作用,在空心Fe₃O₄表面形成一个凝胶化层,制得海藻酸盐凝胶化的空心Fe₃O₄纳米颗粒,粒径约为400～500 nm．采用TEM、XRD、XPS、VSM等手段对纳米微球进行表征．VSM表征结果表明在室温下样品磁性材料为超顺磁性．改性Fe₃O₄纳米颗粒成功地用于柔红霉素的载负和缓释,最大载负率和载药量分别为28.4%和14.2%．缓释结果表明,海藻酸盐凝胶化层的存在,能更有效控制柔红霉素缓慢地释放．     

Enhancement of low-field magnetoresistance in Fe3O4 particles induced by ball milling

A series of Fe₃O₄ particles with different size have been obtained by mechanical ball milling from t=0-450 h. Crystal structure and microstructure of the samples are analyzed by XRD and SEM. An emphasis has been placed on magnetic and transport properties. The experimental results indicate that the sample t=350 exhibits an enhancement of magnetoresistance (MR) comparing with initial powder compress sample (t=0). The low-field magnetoresistance reaches MR=−6.04% at Verwey temperature 120 K and MR=−2.54% at 290 K. Thermal behavior TGA analysis and investigation of magnetic properties have revealed that there is an oxide layer on surface of Fe₃O₄ particles. It is considered that the enhanced magnetoresistance can be taken into account in terms of spin-dependent tunneling effect between Fe₃O₄ particles.Temperature dependence of magnetization and resistivity are measured in order to study electrical and magnetic behavior near Verwey transition. In addition, we also discuss ball milling time dependence of coercivity H_c and specific magnetization M_s of these samples.     

Solid state reaction synthesis of NiFe2O4 nanoparticles

Ni-ferrite (NiFe₂O₄) nanoparticles have been synthesized via a solid state reaction process. Ni and Fe bi-metallic nanoparticles in the form of Ni₃₃Fe₆₇ alloy nanopowder are first synthesized by simultaneous evaporation of the required amounts of pure Ni and Fe metals followed by rapid condensation of the evaporated metal flux into solid state by means of an inert gas, helium, using the process of inert gas condensation (IGC). In order to form the NiFe₂O₄ structure, as-synthesized samples (Ni₃₃Fe₆₇) are annealed for 12 h in ambient conditions at different annealing temperatures. Structural analyses show that NiFe₂O₄ starts to form at around 450 °C and gets progressively well defined with increasing annealing temperatures yielding particle with size ranging between 15 and 50 nm. Besides successfully forming NiFe₂O₄, NiO/Fe₃O₄ core/shell nanoparticles have also been synthesized by adjusting the annealing conditions. Three different structures, Ni₃₃Fe₆₇, NiO/Fe₃O₄, and NiFe₂O₄, obtained in this study are compared with respect to their structural and magnetic properties.     

低温固相反应法制备的NiFe2O4纳米颗粒的结构与磁性

采用低温固相反应法制备了晶粒尺寸在8—47nm之间的NiFe₂O₄纳米颗粒系列样品，用X射线衍射仪(XRD)、高分辨中子粉末衍射谱仪、振动样品磁强计和超导量子干涉仪等对样品的晶体结构、宏观磁性和纳米颗粒的表面各向异性进行了分析研究.XRD和中子衍射测量结果显示纳米颗粒的晶格常数略高于块体材料，样品的氧参量表明纳米颗粒的晶格畸变程度没有块体材料严重.相对块体材料，纳米颗粒具有较小的磁化强度、较大的矫顽力和各向异性能密度.纳米颗粒从多畴转变为单畴的临界尺寸约为40nm，超顺磁性临界尺寸约为16nm.     

Enzymes immobilization on Fe3O4-gold nanoparticles

In the present study Fe₃O₄ magnetic nanoparticles were synthesized by coprecipitation of Fe²⁺ and Fe³⁺ from chlorides. In the next step magnetite-gold core-shell nanoparticles were synthesized from HAuCl₄ using an ethanol as a reducing agent. Finally, magnetic nanoparticles were functionalized by hexadecanethiol. The immobilization of biological molecules (trypsin and glucose oxidase) to the thiol-modified and unmodified magnetite-gold nanoparticles surface was tested. The resulting nanoparticles were characterized by infrared spectroscopy, differential scanning calorimetry, Mössbauer spectroscopy and transmission electron microscopy.     

Magnetic properties of prussian blue modified Fe3O4 nanocubes

Size controlled cubic Fe₃O₄ nanoparticles in the size range 90–10 nm were synthesized by varying the ferric ion concentration using the oxidation method. A bimodal size distribution was found without ferric ion concentration and the monodispersity increased with higher concentration. The saturation magnetization decreased from 90 to 62 emu/g when the particle size is reduced to 10 nm. The Fe₃O₄ nanoparticles with average particle sizes 10 and 90 nm were surface modified with prussian blue. The attachment of prussian blue with Fe₃O₄ was found to depend on the concentration of HCl and the particle size. The saturation magnetization of prussian blue modified Fe₃O₄ varied from 10 to 80 emu/g depending on the particle size. The increased tendency for the attachment of prussian blue with smaller particle size was explained based on the surface charge. The prussian blue modified magnetite nanoparticles could be used as a radiotoxin remover in detoxification applications.