有机-无机杂化一维磁性自组装聚合物纳米链的研究进展

随着纳米科技的发展,有机-无机杂化一维磁性自组装聚合物纳米链的设计合成与应用成为新的研究热点。综述了有机-无机杂化一维磁性自组装聚合物纳米链的磁场诱导自组装、模板诱导自组装和偶极诱导自组装等制备方法,并介绍了其在光学、生物医学和水处理等领域的应用。最后指出有机-无机杂化一维磁性自组装聚合物纳米材料制备技术存在的不足,并对其应用前景进行展望。     

Magnetic chains of Co spheres synthesized by hydrothermal process under magnetic field

Hydrothermal process under magnetic fields is successfully used to synthesize Co chains using reduction approach by carefully controlling the reaction conditions. The formation of the chain structure might be that magnetic fields drive the nanoscale crystals of Co to form chains. The Co sphere size and chain length are analyzed by X-ray diffraction (XRD) and scan electron microscopy (SEM). The result of the vibrating sample magnetometer (VSM) shows that the magnetic chains possess the saturation magnetization of 102 emu/g. The factors on the magnetic properties of the magnetic nanochains are discussed.     

Three‐dimensional modelling and simulation of magnetorheological fluids

A magnetorheological fluid (MR fluid) is a type of smart fluid composed of micrometer‐sized magnetizable particles suspended in a carrier fluid. The rheological properties of an MR fluid can be greatly altered upon application of an external magnetic field. This paper presents a computational framework for the numerical study of MR fluids, in which a two‐stage modelling and simulation strategy is proposed to achieve reasonable accuracy and computational efficiency. At the first stage for simulating the particle chain formation, the particle dynamics plays a major role whereas the hydrodynamics of the fluid flow is of secondary importance. Thus an MR fluid is modelled in the context of the discrete element method and the simple Stokes formula is adopted for the hydrodynamic interaction. At the second stage, the formulated particle chains are applied as the initial configuration for simulating the rheological properties of the fluid under different shear loading conditions. A combined lattice Boltzmann and discrete element approach is employed to fully resolve the fluid field and the hydrodynamic interactions between the fluid and the particles. Some relevant magnetic models are comprehensively reviewed and the mutual dipole model is employed in this work to account for the magnetic interactions between the particles. The proposed solution procedure is illustrated via a set of numerical simulations for a representative volume element of an MR fluid. Copyright © 2010 John Wiley & Sons, Ltd.     

DNA- and Field-Mediated Assembly of Magnetic Nanoparticles into High-Aspect Ratio Crystals

Under an applied magnetic field, superparamagnetic Fe₃O₄ nanoparticles with complementary DNA strands assemble into crystalline, pseudo-1D elongated superlattice structures. The assembly process is driven through a combination of DNA hybridization and particle dipolar coupling, a property dependent on particle composition, size, and interparticle distance. The DNA controls interparticle distance and crystal symmetry, while the magnetic field leads to anisotropic crystal growth. Increasing the dipole interaction between particles by increasing particle size or external field strength leads to a preference for a particular crystal morphology (e.g., rhombic dodecahedra, stacked clusters, and smooth rods). Molecular dynamics simulations show that an understanding of both DNA hybridization energetic and magnetic interactions is required to predict the resulting crystal morphology. Taken together, the data show that applied magnetic fields with magnetic nanoparticles can be deliberately used to access nanostructures beyond what is possible with DNA hybridization alone.     

Microstructure and Magnetic Properties of Bulk FeCo Alloys Fabricated from Mechanically Alloying and Chemically Synthesized Powders

Three different methods of fabrication of FeCo soft magnetic material using ferromagnetic powders are compared: (i) simple sintering of elemental powders of Fe and Co, (ii) sintering of mechanically alloying FeCo powder, and (iii) sintering of chemically synthesized FeCo powder. The microstructure of ferromagnetic powders and bulk sintered alloys is characterized using scanning electron microscopy and energy-dispersive X-ray spectroscopy analysis. The best magnetic properties with high saturation magnetization, M _s = 211.3 emu/g, are obtained for bulk FeCo alloy sintered from chemically synthesized powder. It consists of nearly spherical FeCo particles with diameters from 5 to 15 μ m. The mean particle size of chemically synthesized FeCo powder can be controlled by changing the melt composition, temperature, and process duration. The relatively large size of FeCo particles reduces the influence of surface oxidation on the particle magnetic properties. The low-cost chemical technology developed is promising for a large-scale production of small FeCo magnetic components of arbitrary shapes with high-dimensional precision.     

Kinetically driven self assembly of highly ordered nanoparticle monolayers

When a drop of a colloidal solution of nanoparticles dries on a surface, it leaves behind coffee-stain-like rings of material with lace-like patterns or clumps of particles in the interior. These non-uniform mass distributions are manifestations of far-from-equilibrium effects, such as fluid flows and solvent fluctuations during late-stage drying. However, recently a strikingly different drying regime promising highly uniform, long-range-ordered nanocrystal monolayers has been found. Here we make direct, real-time and real-space observations of nanocrystal self-assembly to reveal the mechanism. We show how the morphology of drop-deposited nanoparticle films is controlled by evaporation kinetics and particle interactions with the liquid-air interface. In the presence of an attractive particle-interface interaction, rapid early-stage evaporation dynamically produces a two-dimensional solution of nanoparticles at the liquid-air interface, from which nanoparticle islands nucleate and grow. This self-assembly mechanism produces monolayers with exceptional long-range ordering that are compact over macroscopic areas, despite the far-from-equilibrium evaporation process. This new drop-drying regime is simple, robust and scalable, is insensitive to the substrate material and topography, and has a strong preference for forming monolayer films. As such, it stands out as an excellent candidate for the fabrication of technologically important ultra thin film materials for sensors, optical devices and magnetic storage media.     

Template-free synthesis and self-assembly of aligned nickel nanochains under magnetic fields

Well-aligned and uniform Nickel nanochains with diameters ranging from 20 to 110 nm have been synthesized using a simple template-free solution-phase method using environment friendly reagents under diverse temperature and magnetic field. Our results indicate that the size and morphology of as-prepared nanochains can be controlled by adjusting the reaction temperature and the applied magnetic fields, respectively. The formation of the aligned chains can be explained by the interactions of magnetic dipoles in the presence of magnetic field. Systematical magnetic measurements demonstrate that the saturation magnetization of the synthesized samples depends crucially on the particle size. Furthermore, the magnetic anisotropy of the well-aligned nickel nanochains is dominated by the shape anisotropy.     

Magnetic forces on monocomponent toner

The magnetic field strengths and magnetizations of an assembly of magnetic (monocomponent) particles in a constant external field has been calculated. Due to the equilibrium configuration of the particles, forming chains or treelike structures, a one-dimensional approach has been employed. Using the dipole approximation, the problem can be cast as an eigenvalue problem, whose solution yields the magnetizations and field strengths, where the nonlinear interaction between particles has been explicitly accounted for in the formalism.     

Facile synthesis and characterization of hydroxylapatite nanoparticle chains

The hydroxylapatite nanoparticle chains were firstly synthesized by self-assembly with sodium polymethacrylic acid as the template. These high-quality HAP nanoparticle chains showed well-defined nanoscaled structures and regular morphology. The nanoparticle chains were 1.4-2 μm in length and the nanoparticles were about 45 nm in diameter. The structure of products has been studied with XRD and FT-IR spectrum. The forming conditions and mechanism of the products have been investigated. This synthesis method is facile and effective. The products will have potential applications in many fields such as biosensor, and biomimetic bone materials etc. The experimental outcomes present here will have potential values in crystal engineering research and practical applications.     

Rheological Tunable Magnetic Fluids with Long-Term Stability

Magnetic fluids have advantages such as flow ability and solid-like property in strong magnetic fields, but have to suffer from the tradeoff between suspension stability and flow resistance. In this work, a thermal/photo/magnetorheological water-based magnetic fluid is fabricated by using oleic acid-coated Fe₃O₄ (Fe₃O₄@OA) nanoparticles as the magnetic particles and the amphiphilic penta block copolymer (PTMC-F127-PTMC)-based aqueous solution as the carrier fluid. Due to the hydrophobic self-assembly between Fe₃O₄@OA and PTMC-F127-PTMC, the Newtonian-like magnetic fluid has outstanding long-term stability and reversible rheological changes between the low-viscosity flow state and the 3D gel structure. In the linear viscoelastic region, the viscosity exhibits an abrupt increase from below 0.10 Pa s at 20 °C to ≈1.3 × 10⁴ Pa s at 40 °C. Benefitting from the photothermal and magnetocaloric effects of the Fe₃O₄@OA nanoparticles, the rheological change process also can be controlled by near infrared light and alternating magnetic field, which endows the magnetic fluid with the applications in the fields of mobile valves, moveable switches, buffer or damping materials in sealed devices, etc.     

Magnetic carbonyl iron nanoparticle based magnetorheological suspension and its characteristics

Magnetic nano-sized carbonyl iron (CI) particle was prepared and adopted as an additive for micron-sized CI based magnetorheological (MR) fluid, in which the magnetic nanoparticle was fabricated via decomposition of pentacarbonyl iron (Fe(CO)₅). Magnetic property and morphology of the nanoparticle were confirmed via vibration sample magnetometer (VSM) and transmission electron microscopy (TEM), respectively. MR fluids, consisting of micron-sized CI and carrier fluid, were investigated under different external magnetic field strengths via a rotational rheometer. Their flow behaviors at a steady shear mode were examined with and without a nano-sized magnetic additive under magnetic field strength. The MR fluid with magnetic CI nanoparticle added demonstrated slightly higher yield behaviors, suggesting that micron-sized CI and magnetic CI nanoparticle particle were being oriented in magnetic field direction under applied magnetic field and with strengthened structure.     

Nematic‐like Organization of Magnetic Mesogen‐Hybridized Nanoparticles

A fluid nematic‐like phase is induced in monodisperse iron oxide nanoparticles with a diameter of 3.3 nm. This supramolecular arrangement is governed by the covalent functionalization of the nanoparticle surface with cyanobiphenyl‐based ligands as mesogenic promoters. The design and synthesis of these hybrid materials and the study of their mesogenic properties are reported. In addition, the modifications of the magnetic properties of the hybridized nanoparticles are investigated as a function of the different grafted ligands. Owing to the rather large interparticular distances (about 7 nm), the dipolar interaction between nanoparticles is shown to play only a minor role. Conversely, the surface magnetic anisotropy of the particles is significantly affected by the surface derivatization.     

Production and characterization of single-crystal FeCo nanowires inside carbon nanotubes

We describe the synthesis of novel monocrystalline FeCo nanowires encapsulated inside multiwalled carbon nanotubes (MWNTs). These FeCo nanowires exhibit homogeneous Fe and Co concentrations and do not contain an external oxide layer due to the presence of insulating nanotube layers. The method involves the aerosol thermolysis of toluene-ferrocene-cobaltocene solutions in inert atmospheres. The materials have been carefully characterized using state-of-the-art high-resolution transmission electron microscopy (HRTEM), electron-energy-loss spectroscopy (EELS), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), electron diffraction, HREELS-STM elemental mapping, X-ray powder diffraction, and SQUID magnetometry. We noted that the formation of FeCo alloys occurs at relatively low pyrolytic temperatures (e.g., 650-750 degrees C). These single-crystal nanowires, which have not been reported hitherto, always exhibit the FeCo (110) plane parallel to the carbon nanotube axis. The FeCo nanomaterials have shown large coercive fields at room temperature (e.g., 900 Oe). We envisage that these aligned ferromagnetic nanowires could be used in the fabrication of high-density magnetic storage devices and magnetic composites.     

Measurement of the Viscosity of Dilute Magnetic Fluids

The capillary tube viscometer is used to measure the viscosity of aqueous magnetic fluids under the influence of parallel and perpendicular magnetic fields. The effects of the volume fraction of the suspended magnetic particles, the concentration of surfactants, and the external magnetic field strength, as well as the orientation, on the viscosity of the magnetic fluid are analyzed. The experimental results show that the viscosity of the sample magnetic fluids increases with increases in the concentrations of suspended magnetic particles and surfactants. The external magnetic field is also an important factor that affects the viscosity of the magnetic fluid. The viscosity first increases with the magnetic field and finally approaches a constant as the magnetization attains a saturation state. For the same magnetic fluid, the viscosity in a perpendicular magnetic field is larger than that in a parallel magnetic field for the same magnetic field.Paper presented at the Seventh Asian Thermophysical Properties Conference, August 23–28, 2004, Hefei and Huangshan, Anhui, P. R. China     

交流电化学沉积FeCo合金纳米线阵列及其磁性能研究

采用二步阳极氧化法制备孔结构高度有序的多孔氧化铝(AAO)模板。在不同Fe2+/Co2+摩尔比的电解液中,利用交流电化学沉积,在模板孔内成功制备了FeCo合金纳米线阵列。分别采用透射电子显微镜(TEM),场发射扫描电子显微镜(FE-SEM),X射线衍射仪(XRD)和震动样品磁强计(VSM)对样品的形貌,结构及磁学性能进行了表征。结果表明,制备的FeCo合金纳米线排列有序,粗细均匀;其直径与模板孔径一致,填充率较高,且具有明显的[110]择优取向。VSM测试结果表明,不同溶液浓度下制备的FeCo合金纳米线阵列均具有良好的垂直磁各向异性,易磁化轴沿着纳米线轴线方向。随着电解液Fe2+/Co2+摩尔比的不同,可在一定范围内对FeCo合金纳米线阵列的磁性进行调控,并对其原因进行了讨论。     

Functional crosslinked nanostructures from block copolymers

Nanostructure fabrication from block copolymers in my group normally involves polymer design, synthesis, self-assembly, selective domain crosslinking and sometimes degradation. The preparation of thin film with nanochannels was used to illustrate the strategy we took. The nanochannels generated in thin films functioned as chemical valves. The nanochannels also served as templates for semiconductor or magnetic nanoparticle preparation.     

磁性液体纳米磁性颗粒磁场诱导链状结构研究

研究了磁性液体在有、无外加磁场作用时磁性液体中纳米磁性颗粒的微观排列结构, 发现无外加磁场作用时磁性颗粒随机均匀分布在载液中, 有外加均匀磁场作用时, 磁性颗粒沿磁场方向排列成均匀链状结构。当外加均匀磁场强度为11.1 kA/m, TEM照片清晰显示磁性颗粒排列成一条链状结构, 随着外加均匀磁场强度逐渐增强到28.6 kA/m, 更多磁性颗粒沿磁场方向紧密排列成链状结构。在外加梯度磁场作用下, 铁芯中心处磁场强度为28.7 kA/m时, 大量磁性颗粒聚集于线圈中心轴附近形成复杂链状团簇结构; 沿r轴方向磁场强度较弱的地方, 较少磁性颗粒排列成链状结构。当磁场梯度从1.73 kA/m²逐渐增加到5.11 kA/m²时, 磁场梯度轴线上的磁性颗粒团簇结构由稀疏逐渐变成为密集。磁场诱导磁性颗粒链状排列结构的研究对磁性液体在机械工程、生物工程、热力工程等领域的应用有重要意义。     

Magnetic field-induced solvothermal synthesis of one-dimensional assemblies of Ni-Co alloy microstructures

One-dimensional magnetic Ni-Co alloy microwires with different microstructures and differently shaped building blocks including spherical particles, multilayer stacked alloy plates, and alloy flowers, have been synthesized by an external magnetic field-assisted solvothermal reaction of mixtures of cobalt(II) chloride and nickel(II) chloride in 1, 2-propanediol with different NaOH concentrations. By adjusting the experimental parameters, such as precursor concentration and Ni/Co ratio, Ni-Co alloy chains with uniform diameters in the range 500 nm to 1.3 μm and lengths ranging from several micrometers to hundreds of micrometers can be obtained. A mechanism of formation of the one-dimensional assemblies of magnetic Ni-Co microparticles in a weak external magnetic field is proposed. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. This article is published with open access at Springerlink.com     

Magnetostatic interactions in planar ring-like nanoparticle structures

Numerical calculations of equilibrium state energies and local magnetic fields in planar ring-like nanoparticle structures were performed. The dipole–dipole, Zeeman and magnetic anisotropy interactions were included into the model. The result of their competition depends on the value of the external magnetic field, magnetic parameters of an individual nanoparticle, size and shape of the structures. Flux-closed vortexes, single domain, two-domain “onion”-like, “hedgehog”-like and more complex spin structures can be realized. The critical field, providing a sharp transition from the flux-closed vortex to the “onion”-like state, can be regulated by a variation of the particle magnetization and anisotropy constant, their easy directions, and particle space arrangement.     

Thermally and Magnetically Programmable Hydrogel Microactuators

The rapid development in micro-machinery enabled the investigation of smart materials that can embody fast response, programmable actuation, and flexibility to perform mechanical work. Soft magnetic actuators represent an interesting platform toward combining those properties. This study focuses on the synthesis of micro-actuators that respond to thermal and magnetic stimuli using micro-molding with a soft template as a fabrication technique. These microsystems consist of a hydrogel matrix loaded with anisotropic magnetic nanospindles. When a homogeneous magnetic field is applied, the nanospindles initially dispersed in monomer solution, align and assemble into dipolar chains. The ensuing UV-polymerization creates a network and conveniently arrests these nanostructures. Consequently, the magnetic dipole moment is coplanar with the microgel. Varying the shape, volume, and composition of the micro-actuators during synthesis provides a temperature-dependent control over the magnetic response and the polarizability. Beyond isotropic swelling, shaping the hydrogel as long thin ribbons with a passive layer on one side allows for differential swelling leading to bending and twisting deformations, for example, 2D- or 3D-spiral. These deformations involve a reversible amplification of the magnetic response and orientation of the hydrogels under magnetic field. Temperature control herewith determines the conformation and simultaneously the magnetic response of the micro-actuators.