Electrical and magnetic properties of polyaniline/Fe3O4 nanostructures

We report on electrical and magnetic properties of polyaniline (PANI) nanotubes (150 nm in diameter) and PANI/Fe₃O₄ nanowires (140 nm in diameter) containing Fe₃O₄ nanoparticles with a typical size of 12 nm. These systems were prepared by a template-free method. The conductivity of the nanostructures is 10⁻¹–10⁻² S/cm; and the temperature dependent resistivity follows a ln ρT^−1/2 law. The composites (6 and 20 wt% of Fe₃O₄) show a large negative magnetoresistance compared with that of pure PANI nanotubes and a considerably lower saturated magnetization (M_s=3.45 emu/g at 300 K and 4.21 emu/g at 4 K) compared with the values measured from bulk magnetite (M_s=84 emu/g) and pure Fe₃O₄ nanoparticles (M_s=65 emu/g). AC magnetic susceptibility was also measured. It is found that the peak position of the AC susceptibility of the nanocomposites shifts to a higher temperature (>245 K) compared with that of pure Fe₃O₄ nanoparticles (190–200 K). These results suggest that interactions between the polymer matrix and nanoparticles take place in these nanocomposites.     

Preparation and microwave absorption properties of Fe-phthalocyanine oligomer/Fe3O4 hybrid microspheres

The novel nano-scale Fe-phthalocyanine oligomer/Fe₃O₄ hybrid microspheres were synthesized from bis-phthalonitrile and FeCl₃·6H₂O through a simple solvent-thermal route. The morphology and structure of the hybrid microspheres were characterized by FTIR, XRD, SEM and TEM. These results showed that the hybrids were monodispersed solid microspheres and the morphology can be adjusted by controlling the addition of bis-phthalonitrile. On the basis of these results, the formation process was discussed. Magnetization measurement indicated that saturation magnetizations decreased linearly with increasing the addition of bis-phthalonitrile, while coercivities increased. The microwave absorption properties were measured by a vector network analyzer. The dielectric loss of the hybrid microspheres was larger and a new magnetic loss peak appeared at high frequency. The microwave absorbing properties enhanced with increasing the addition of bis-phthalonitrile and a maximum reflection loss of −31.1 dB was obtained at 8.6 GHz with 1 g bis-phthalonitrile when the matching thickness was 3.0 mm. The novel hybrid materials are believed to have potential applications in the microwave absorbing performances.     

空心Fe_3O_4纳米微球的制备及超顺磁性

采用水热控制合成法,以六水三氯化铁、柠檬酸三钠和尿素为原料,聚丙烯酰胺为稳定剂, 200?C下反应12 h制备得到了超顺磁性空心Fe_3O_4纳米微球.通过X射线衍射仪、扫描电子显微镜、透射电子显微镜对样品的结构和形貌进行表征,并采用振动样品磁强计测试了样品的磁性能.结果表明:所得样品为具有尖晶石结构的Fe_3O_4纳米微球,尺寸为160 nm左右,呈分等级结构,即整个微球由粒径约18 nm的初级晶粒自组装堆叠而成;室温下表现为典型的超顺磁性,且饱和磁化强度为73.3 emu/g (1 emu/g=1 A·m~2/kg),这种高饱和磁化强度可以由其初级晶粒晶化程度高且粒径较大以及这种特殊的二次自组装结构进行解释.这种Fe_3O_4纳米微球为疏松多孔的空心球状结构,具有粒径分布均匀、分散性良好和超顺磁性的特点,在药物靶向输运和肿瘤热疗中有潜在的应用.     

Synthesis of Fe3O4 magnetic fluid used for magnetic resonance imaging and hyperthermia

Fe₃O₄ magnetic nanoparticles were prepared by co-precipitation from FeSO₄·7H₂O and FeCl₃·6H₂O aqueous solutions using NaOH as precipitating reagent. The nanoparticles have an average size of 12 nm and exhibit superparamagnetism at room temperature. The nanoparticles were used to prepare a water-based magnetic fluid using oleic acid and Tween 80 as surfactants. The stability and magnetic properties of the magnetic fluid were characterized by Gouy magnetic balance. The experimental results imply that the hydrophilic block of Tween 80 can make the Fe₃O₄ nanoparticles suspending in water stable even after dilution and autoclaving. The magnetic fluid demonstrates excellent stability and fast magneto-temperature response, which can be used both in magnetic resonance imaging and magnetic fluid hyperthermia.     

Synthesis, infrared and microwave absorbing properties of (BaFe12O19+BaTiO3)/polyaniline composite

The (BaFe₁₂O₁₉+BaTiO₃)/polyaniline composite was synthesized by in situ polymerization and introduced into epoxy resin and polyethylene to be a microwave and infrared absorber. The spectroscopic characterizations of the formation processes of (BaFe₁₂O₁₉+BaTiO₃)/polyaniline composite were examined using Fourier transform infrared, ultraviolet-visible spectrophotometer, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and electron spin resonance. Microwave absorbing properties were investigated by measuring reflection loss in 2-18 and 18-40 GHz microwave frequency range using the free space method. Thermal extinction measurements in the 3-5 and 8-12 μm were done to evaluate the shielding effectivity of infrared. The results showed that a significant absorption frequency range shifting and thermal extinction could be obtained by adding polyaniline to the BaFe₁₂O₁₉+BaTiO₃ blend.     

Magnetoresistance of Fe3O4/Au/Fe3O4 and Fe3O4/Au/Fe spin-valve structures

A detailed study of the in-plane magnetotransport properties of spin valves with one and two Fe₃O₄ electrodes is presented. Fe₃O₄/Au/Fe₃O₄ spin valves exhibit a clear anisotropic magnetoresistance in small magnetic fields but no giant magnetoresistance (GMR). The absence of GMR in these structures is due to simultaneous magnetization reversal in the two Fe₃O₄ layers. By contrast, a negative GMR effect is measured on Fe₃O₄/Au/Fe spin valves. The negative GMR is attributed to an electron spin scattering asymmetry at the Fe₃O₄/Au interface or an induced spin scattering asymmetry in the Au interfacial layers.     

Magnetically directed self-assembly of submicron spheres with a Fe3O4 nanoparticle shell

A grid of micrometer-sized core-shell particles was fabricated by magnetophoretic deposition using a water-based colloidal solution. The core-shell particles consist of a 640 nm diameter polystyrene spherical core covered with a shell of five layers of 12 nm diameter Fe₃O₄ nanocrystals. The separation and the length of the individual chains can be tuned by the magnetic field strength and the concentration of the particle solution. The magnetic properties were characterized by angular-dependent ferromagnetic resonance and SQUID magnetometry.     

Biosynthesis and magnetic properties of mesoporous Fe3O4 composites

Magnetic Fe₃O₄ materials with mesoporous structure are synthesized by co-precipitation method using yeast cells as a template. The X-ray diffraction (XRD) pattern indicates that the as-synthesized mesoporous hybrid Fe₃O₄ is well crystallized. The Barrett-Joyner-Halenda (BJH) models reveal the existence of mesostructure in the dried sample which has a specific surface area of 96.31 m²/g and a pore size distribution of 8-14 nm. Transmission electron microscopy (TEM) measurements confirm the wormhole-like structure of the resulting samples. The composition and chemical bonds of the Fe₃O₄/cells composites are studied by Fourier transform infrared (FT-IR) spectroscopy. Preliminary magnetic properties of the mesoporous hybrid Fe₃O₄ are characterized by a vibrating sample magnetometer (VSM). The magnetic Fe₃O₄/cells composites with mesoporous structure have potential applications in biomedical areas, such as drug delivery.     

Electromagnetic and microwave absorption properties of Fe3O4 magnetic films plated on hollow glass spheres

Magnetic hollow spheres of low density were prepared by plating Fe₃O₄ magnetic films on hollow glass spheres using ferrite plating. The complex permeability and permittivity of spheres–wax composites were measured in the range of 2–18 GHz. The complex permeability and permittivity increased, and the dielectric and magnetic losses were improved as the volume fraction of the magnetic spheres in the composites increased from 60% to 80%, which also resulted in a great improvement of microwave absorption properties. For composites with volume fraction 80%, its magnetic resonance frequency was at about 13 GHz and it appeared three loss peaks in the calculated reflection loss curves; the bandwidth less than −10 dB was almost 4 GHz which was just in the Ku-band frequencies (12–18 GHz) and a minimum reflection loss of −20 dB was obtained when the thickness was 2.6 mm; the microwave absorbing properties were mainly due to the magnetic loss. The results showed that the magnetic spheres composites were good and light microwave absorbers in the Ku-band frequencies.     

One-step preparation of organometal/Fe3O4 hybrid microspheres and their electromagnetic properties

Novel organometal/Fe₃O₄ hybrid microspheres were prepared from bisphthalonitrile-benzoxine resin containing ferrocene (FPNBZ) and FeCl₃·6H₂O via a one-step solvent-thermal method. The phase structure, composition and morphology of as-prepared hybrid microspheres were characterized by X-ray powder diffraction, Fourier transform infrared spectrophotometer and scanning electron microscopy. The results revealed that crystallinity, dispersity and size of hybrid microspheres can be controlled by altering the reaction parameters. Density measurement showed that the density is decreased with increasing FPNBZ concentration in the hybrid materials. Electromagnetic properties of the FPNBZ/Fe₃O₄ hybrid microspheres were measured at 2-18 GHz. The electromagnetic measurement indicated that the resonance peaks of complex permittivity, complex permeability, dielectric loss and magnetic loss were shifted to the high frequencies, with the increasing amount of FPNBZ. The as-prepared hybrid materials are believed to have broad applications both in microwave absorption materials in a wide frequency range and in biomedical fields.     

Preparation of poly(styrene-glucidylmethacrylate)/Fe3O4 composite microspheres with high magnetite contents

Magnetic polymer composite microspheres with high magnetite contents were prepared by dispersion polymerization of styrene (St) and glucidylmethacrylate (GMA), in which Fe₃O₄ nanoparticles were co-stabilized by oleic acid and silane surfactants. The microstructure of the composite microspheres was characterized by Fourier transform infrared (FTIR) spectrometry, X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results demonstrated the presence of a hybrid morphology with organic polymer-encapsulated inorganic particles. Subsequently, thermogravimetric analysis (TGA) and vibrating sample magnetometry (VSM) were used to evaluate the magnetite content of the microspheres. It was found that an accordant magnetite content of about 70 wt%, could be obtained for the magnetic polymer microspheres, a value significantly higher than those reported thus far. The possible mechanism for the formation of the microspheres was proposed.     

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.     

Synthesis and properties of Au-Fe3O4 and Ag-Fe3O4 heterodimeric nanoparticles

Monodisperse Au-Fe 3 O 4 heterodimeric nanoparticles (NPs) were prepared by injecting precursors into a hot reaction solution.The size of Au and Fe 3 O 4 particles can be controlled by changing the injection temperature.UV-Vis spectra show that the surface plasma resonance band of Au-Fe 3 O 4 heterodimeric NPs was evidently red-shifted compared with the resonance band of Au NPs of similar size.The as-prepared heterodimeric Au-Fe 3 O 4 NPs exhibited superparamagnetic properties at room temperature.The Ag-Fe 3 O 4 heterodimeric NPs were also prepared by this synthetic method simply using AgNO 3 as precursor instead of HAuCl 4.It is indicated that the reported method can be readily extended to the synthesis of other noble metal conjugated heterodimeric NPs.     

Effect of ferrofluid concentration on electrical and magnetic properties of the Fe3O4/PANI nanocomposites

Magnetic nanocomposites can be controlled and tailored to provide the desired mechanical, physical, chemical, and biomedical properties depending on the final applications. The coating of ferrite nanoparticles with polymers affords the possibility of minimizing agglomeration in large-scale commercial synthesis of nanocomposite materials. The process of coating not only provides effective encapsulation of individual nanoparticles, but also controls the growth in size, thus, yielding a better overall size distribution. In this paper, in-situ polymerization of aniline was carried out in different concentration of the ferrofluid with the aim to obtain agglomerate free nanocomposites. The role of the ferrite concentration was investigated by the spectral, morphological, conductivity, and magnetic properties of Fe₃O₄/polyaniline (PANI) nanocomposites. XRD revealed the presence of spinel phase of Fe₃O₄ and the particle size was calculated to be 14.3 nm. Spectral analysis confirmed the formation of PANI encapsulated Fe₃O₄ nanocomposite. Conductivity of the nanocomposites was found to be in the range of 0.001–0.003 S/cm. Higher saturation magnetization of 3.2 emu/g was observed at 300 K, revealing a super paramagnetic behavior of this nanocomposite.     

Electro-precipitation of Fe3O4 nanoparticles in ethanol

The preparation of superparamagnetic magnetite (Fe₃O₄) nanoparticles by electro-precipitation in ethanol is proposed. Particle average size can be set from 4.4 to 9 nm with a standard deviation around 20%. Combination of wide-angle X-ray scattering (WAXS), Electron energy loss spectroscopy (EELS) and Mössbauer spectroscopy characterizations clearly identifies the particles as magnetite single-crystals (Fe₃O₄).     

Fabrication and characterization of magnetic Fe3O4-CNT composites

Carbon nanotubes (CNTs) decorated with magnetite nanoparticles on their external surface have been fabricated by in situ solvothermal method, which was conducted in benzene at 500 °C with ferrocene and CNTs as starting reagents. The as-prepared composites were characterized using XRD, FTIR, SEM and TEM. It has been found that the amount of magnetite nanoparticles deposited on the CNTs can be controlled by adjusting the initial mass ratio of ferrocene to CNTs. The Fe₃O₄-CNT composites display good ferromagnetic property at room temperature, with a saturation magnetization value (M_s) of 32.5 emu g⁻¹ and a coercivity (H_c) of 110 Oe.     

Field-induced microwave absorption in Fe3O4 nanoparticles and Fe3O4/polyaniline composites synthesized by different methods

Three kinds of nanoscale powders containing Fe₃O₄ nanoparticles (NPs) have been studied by ferromagnetic resonance (FMR): (i) Fe₃O₄ NPs grown and then covered with polyaniline (PANI), (ii) unclad Fe₃O₄ NPs, and (iii) Fe₃O₄ NPs grown “in situ” with the PANI. In every case, there is no low field microwave absorption, rather a single FMR line is observed. However, the half-power widths are of order of 1 kOe presumably due to a distribution of internal fields. For type I particles with a low concentration (below 40%) of Fe₃O₄, the observed resonance fields (H_r) are close to those expected for spheres with negligible magnetocrystalline anisotropy. For all other cases, H_r values are significantly lower. Such shortfalls can be roughly understood by invoking dipolar interactions between the grains, stresses frozen in grains during manufacture (method III), as well as anisotropy fields when the specimens are prepared in an aligning field.     

Synthesis of fluorinated TiO2 hollow microspheres and their photocatalytic activity under visible light

Fluorinated TiO₂ hollow microspheres with three-dimensional hierarchical architecture were prepared by solvothermally treatment using solid microspheres as precursor. The obtained solid and hollow TiO₂ microspheres were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), UV-Vis diffuse reflectance spectrum (DRS) and photoluminescence (PL) spectra. The photocatalytic activity of as-prepared solid and hollow TiO₂ microspheres was determined by degradation of methyl orange (MO) under visible light irradiation. The results showed that the surface fluorination, the existence of accessible mesopores channels, and the increased light harvesting abilities could remarkably improve the photocatalytic activity of TiO₂ hollow microspheres.     

Structural and magnetic studies of Fe2O3/SiO2 granular nanocomposites

Fe₂O₃/SiO₂ nanocomposites were synthesized by mechanical alloying, using Fe and SiO₂ powders as precursors. After 340 h milling, the sample essentially consists of hematite and amorphous silica. TEM images show hematite particles embedded in and surrounded by an amorphous silica matrix. A broad size distribution—5–50 nm—of hematite particles is found, and other group of very small—2–3 nm—unidentified particles are observed. Room temperature Mössbauer spectra show a paramagnetic doublet, which may correspond to a non-crystalline phase in the sample (probably the small unidentified particles), and a sextet corresponding to hematite. Magnetic properties were investigated by measuring hysteresis curves at different temperatures (5–300 K) and by zero-field-cooled (ZFC) and field-cooled (FC) magnetization curves (10 mT). The hysteresis loops were well fitted by a ferromagnetic contribution. No evidence of Morin transition is found down to 5 K.     

Iron phthalocyanine oligomer/Fe3O4 hybrid microspheres and their microwave absorption property

The novel nano-scale iron phthalocyanine oligomer/Fe₃O₄ (FePc/Fe₃O₄) hybrid microspheres were synthesized from iron phthalocyanine oligomer and FeCl₃·6H₂O via a solvent-thermal crystallization route. The morphology and structure of the hybrid microspheres were characterized by Fourier transform infrared spectrophotometer, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. These results showed that the hybrids were monodisperse microspheres and the morphology can be adjusted by controlling pre-polymerization time. The saturation magnetization increased with increase in the pre-polymerization time, while the coercivities decreased. The FePc/Fe₃O₄ hybrid microspheres exhibited novel microwave electromagnetic properties: the dielectric loss was enhanced when the pre-polymerization time increased and a new microwave loss peak appeared at high frequency. The microwave absorbing properties enhanced with increase in the pre-polymerization time and a maximum reflection loss of −29.7 dB was obtained at 11.7 GHz with 6 h of pre-polymerization time when the matching thickness was 3.0 mm. The novel hybrid materials are believed to have potential applications as microwave absorbing materials.