Atom transfer radical polymerization synthesis and magnetic characterization of MnFe2O4/polystyrene core/shell nanoparticles

An atom transfer radical polymerization route is developed for the coating of MnFe2O4 nanoparticles with polystyrene yielding the core-shell nanoparticles with size <15 nm. Magnetic studies show a decrease in coercivity after the formation of polystyrene shell, which is considered due to the reduction of magnetic surface anisotropy upon polymer coating. The MnFe2O4 nanoparticles as the magnetic core were separately prepared by a reverse micelle microemulsion method. Polymerization initiators are chemically attached onto the surface of nanoparticles. The modified nanoparticles are then used as macro-initiators in the subsequent polymerization reaction. This approach provides great flexibility in the selection of magnetic core. Consequently, magnetic tunability is able to be introduced into these core/shell nanoparticulate systems to achieve the desired superparamagnetic response.     

Correlation between spin-orbital coupling and the superparamagnetic properties in magnetite and cobalt ferrite spinel nanocrystals

The superparamagnetic properties of CoFe2O4 and Fe3O4 nanocrystals have been systematically investigated. The observed blocking temperature of CoFe2O4 nanocrystals is at least 100 deg higher than that of the same sized Fe3O4 nanocrystals. The coercivity of CoFe2O4 nanocrystals at 5 K is over 50 times higher than the same sized Fe3O4 nanocrystals. The drastic difference in superparamagnetic properties between the similar sized spherical CoFe2O4 and Fe3O4 (or FeFe2O4) spinel ferrite nanocrystals was correlated to the coupling strength between electron spin and orbital angular momentum (L-S) in magnetic cations. Compared to the Fe2+ ion, the effect of much stronger spin-orbital coupling at Co2+ lattice sites leads to a higher magnetic anisotropy and results in the dramatic discrepancy of superparamagnetic properties between CoFe2O4 and Fe3O4 nanocrystals. These results provide some insight to the fundamental understanding of the quantum origin of superparamagnetic properties. Furthermore, they suggest that it is possible to control the superparamagnetic properties through magnetic coupling at the atomic level in spinel ferrite nanocrystals for various applications.     

铁酸钴纳米晶的低温合成、谱学表征及磁性

以十六烷基三甲基溴化铵（CTAB）为模板,Fe(NO3)3·9H2O和Co(NO3)2·6H2O为前躯体,NaOH为沉淀剂,低温回流合成了磁性铁酸钴纳米晶。利用X射线衍射、透射电子显微镜、红外光谱、拉曼光谱等测试技术对产品的结构进行了表征,借助振动样品磁强计测定了样品的室温磁性能。结果表明,铁酸钴纳米晶为单相立方尖晶石结构,纳米晶的平均粒径为15-20 nm。铁酸钴纳米晶在室温外加磁场下表现出明显的磁滞现象,饱和比磁化强度MS=36.5 A.m2/kg,矫顽力HC=5.89×104 A/m。     

Monodispersed core-shell Fe3O4@Au nanoparticles

The ability to synthesize and assemble monodispersed core-shell nanoparticles is important for exploring the unique properties of nanoscale core, shell, or their combinations in technological applications. This paper describes findings of an investigation of the synthesis and assembly of core (Fe(3)O(4))-shell (Au) nanoparticles with high monodispersity. Fe(3)O(4) nanoparticles of selected sizes were used as seeding materials for the reduction of gold precursors to produce gold-coated Fe(3)O(4) nanoparticles (Fe(3)O(4)@Au). Experimental data from both physical and chemical determinations of the changes in particle size, surface plasmon resonance optical band, core-shell composition, surface reactivity, and magnetic properties have confirmed the formation of the core-shell nanostructure. The interfacial reactivity of a combination of ligand-exchanging and interparticle cross-linking was exploited for molecularly mediated thin film assembly of the core-shell nanoparticles. The SQUID data reveal a decrease in magnetization and blocking temperature and an increase in coercivity for Fe(3)O(4)@Au, reflecting the decreased coupling of the magnetic moments as a result of the increased interparticle spacing by both gold and capping shells. Implications of the findings to the design of interfacial reactivities via core-shell nanocomposites for magnetic, catalytic, and biological applications are also briefly discussed.     

Synthesis and size-dependent exchange bias in inverted core-shell MnO|Mn3O4 nanoparticles

Core-shell nanoparticles of MnO|Mn3O4 with average particle sizes of 5-60 nm, composed of an antiferromagnetic (AFM) core and a ferrimagnetic (FiM) shell, have been synthesized and their magnetic properties investigated. The core-shell structure has been generated by the passivation of the MnO cores, yielding an inverted AFM-core|FiM-shell system, as opposed to the typical FM-core|AFM-shell. The exchange-coupling between AFM and FiM gives rise to an enhanced coercivity of approximately 8 kOe and a loop shift of approximately 2 kOe at 10 K, i.e., exchange bias. The coercivity and loop shift show a non-monotonic variation with the core diameter. The large coercivity and the loop shift are ascribed to the highly anisotropic Mn3O4 and size effects of the AFM (i.e., uncompensated spins, AFM domains, and size-dependent transition temperature).     

均匀共沉淀法制备BaTiO3 -Nix Zn1-x Fe2 O4 核-壳粒子及其性能

以尿素为沉淀剂, 在无后续热处理的情况下, 采用均匀共沉淀法制备了BaTiO3-NixZn1-xFe2O4核-壳粒子. 采用透射电子显微镜(TEM)、 X射线衍射仪(XRD)、 能谱仪(EDS)及振动样品磁强计(VSM)对BaTiO3-NixZn1-xFe2O4核-壳粒子的形貌、 结构、 成分和磁性能进行了表征. 结果表明, 制备的核-壳结构粒子中NixZn1-xFe2O4壳层在BaTiO3颗粒的表面包覆完整. 通过控制共沉淀中NiCl2·6H2O与ZnCl2的摩尔比可以调控BaTiO3-NixZn1-xFe2O4核-壳粒子的磁性; 加入的NiCl2·6H2O与ZnCl2摩尔比为7∶3时制得的核-壳粒子具有较好的磁性能, 其饱和磁化强度和矫顽力分别为26.999 A·m2/kg和902.787 A/m.     

Shape control and associated magnetic properties of spinel cobalt ferrite nanocrystals

By combining nonhydrolytic reaction with seed-mediated growth, high-quality and monodisperse spinel cobalt ferrite, CoFe(2)O(4), nanocrystals can be synthesized with a highly controllable shape of nearly spherical or almost perfectly cubic. The shape of the nanocrystals can also be reversibly interchanged between spherical and cubic morphology through controlling nanocrystal growth rate. Furthermore, the magnetic studies show that the blocking temperature, saturation, and remanent magnetization of nanocrystals are solely determined by the size regardless the spherical or cubic shape. However, the shape of the nanocrystals is a dominating factor for the coercivity of nanocrystals due to the effect of surface anisotropy. Such magnetic nanocrystals with distinct shapes possess tremendous potentials in fundamental understanding of magnetism and in technological applications of magnetic nanocrystals for high-density information storage.     

导电聚苯胺与磁性CoFe2O4纳米复合物的制备与表征

在利用HNO3酸化处理CoFe2O4磁性纳米粒子使其表面离子化、分散性得到改善的基础上, 采用原位聚合法制备了具有电磁功能的聚苯胺/CoFe2O4 (PANI/CoFe2O4)纳米复合物. 借助TEM, XRD, FT-IR, TG, 四探针电导率仪、VSM(振动样品磁强计)等分析手段研究了复合物的形貌、结构、热稳定性及电磁性能. 结果表明, 处理过的CoFe2O4磁性纳米粒子可形成分散均匀的PANI/CoFe2O4纳米复合物, CoFe2O4以25 nm左右的粒子分散于聚苯胺基体中; PANI与CoFe2O4之间存在化学键合作用, 正是这种作用使复合物热稳定性得以提高; 复合物同时具有导电性和磁性能, 且随CoFe2O4含量变化而变化.     

CoFe2O4-TiO2 and CoFe2O4-ZnO thin film nanostructures elaborated from colloidal chemistry and atomic layer deposition

CoFe(2)O(4)-TiO(2) and CoFe(2)O(4)-ZnO nanoparticles/film composites were prepared from directed assembly of colloidal CoFe(2)O(4) in a Langmuir-Blodgett monolayer and atomic layer deposition (ALD) of an oxide (TiO(2) or ZnO). The combination of these two methods permits the use of well-defined nanoparticles from colloidal chemistry, their assembly on a large scale, and the control over the interface between a ferrimagnetic material (CoFe(2)O(4)) and a semiconductor (TiO(2) or ZnO). Using this approach, architectures can be assembled with a precise control from the Angstrom scale (ALD) to the micrometer scale (Langmuir-Blodgett film). The resulting heterostructures present well-calibrated thicknesses. Electron microscopy and magnetic measurement studies give evidence that the size of the nanoparticles and their intrinsic magnetic properties are not altered by the various steps involved in the synthesis process. Therefore, the approach is suitable to obtain a layered composite with a quasi-monodisperse layer of ferrimagnetic nanoparticles embedded in an ultrathin film of semiconducting material.     

Core-shell-structured magnetic ternary nanocubes

We report a novel core-shell-structured ternary nanocube of MnZn ferrite synthesized by controlling the reaction temperature and composition in the absence of conventionally used reducing agents. The highly monodispersed core-shell structure consists of an Fe(3)O(4) core and an MnZn Ferrite shell. The observation of a Moire? pattern indicates that the core and the shell are two highly crystalline materials with slightly different lattice constants that are rotated relative to each other by a small angle. The ternary core-shell nanocubes display magnetic properties regulated by a combination of the core-shell composition and exhibit an increased coercivity and field-cooled/zero-field-cooled characteristics drastically different from those of regular MnZn ferrite nanoparticles. The ability to engineer the spatial nanostructures of ternary magnetic nanoparticles in terms of shape and composition offers atomic-level versatility in fine-tuning the nanoscale magnetic properties.     

Monodisperse MFe2O4 (M = Fe, Co, Mn) nanoparticles

High-temperature solution phase reaction of iron(III) acetylacetonate, Fe(acac)(3), with 1,2-hexadecanediol in the presence of oleic acid and oleylamine leads to monodisperse magnetite (Fe(3)O(4)) nanoparticles. Similarly, reaction of Fe(acac)(3) and Co(acac)(2) or Mn(acac)(2) with the same diol results in monodisperse CoFe(2)O(4) or MnFe(2)O(4) nanoparticles. Particle diameter can be tuned from 3 to 20 nm by varying reaction conditions or by seed-mediated growth. The as-synthesized iron oxide nanoparticles have a cubic spinel structure as characterized by HRTEM, SAED, and XRD. Further, Fe(3)O(4) can be oxidized to Fe(2)O(3), as evidenced by XRD, NEXAFS spectroscopy, and SQUID magnetometry. The hydrophobic nanoparticles can be transformed into hydrophilic ones by adding bipolar surfactants, and aqueous nanoparticle dispersion is readily made. These iron oxide nanoparticles and their dispersions in various media have great potential in magnetic nanodevice and biomagnetic applications.     

Exchange‐Coupled fct‐FePd/α‐Fe Nanocomposite Magnets Converted from Pd/Fe3O4 Core/Shell Nanoparticles

We report the controlled synthesis of exchange‐coupled face‐centered tetragonal (fct) FePd/α‐Fe nanocomposite magnets with variable Fe concentration. The composite was converted from Pd/Fe₃O₄ core/shell nanoparticles through a high‐temperature annealing process in a reducing atmosphere. The shell thickness of core/shell Pd/Fe₃O₄ nanoparticles could be readily tuned, and subsequently the concentration of Fe in nanocomposite magnets was controlled. Upon annealing reduction, the hard magnetic fct‐FePd phase was formed by the interdiffusion between reduced α‐Fe and face‐centered cubic (fcc) Pd, whereas the excessive α‐Fe remained around the fct‐FePd grains, realizing exchange coupling between the soft magnetic α‐Fe and hard magnetic fct‐FePd phases. Magnetic measurements showed variation in the magnetic properties of the nanocomposite magnets with different compositions, indicating distinct exchange coupling at the interfaces. The coercivity of the exchange‐coupled nanocomposites could be tuned from 0.7 to 2.8 kOe and the saturation magnetization could be controlled from 93 to 160 emu g^?1. This work provides a bottom‐up approach using exchange‐coupled nanocomposites for engineering advanced permanent magnets with controllable magnetic properties.     

Effects of surface coordination chemistry on the magnetic properties of MnFe(2)O(4) spinel ferrite nanoparticles

To understand the influence of surface interactions upon the magnetic properties of magnetic nanoparticles, the surface of manganese ferrite, MnFe(2)O(4), nanoparticles have been systematically modified with a series of para-substituted benzoic acid ligands (HOOC-C(6)H(4)-R; R = H, CH(3), Cl, NO(2), OH) and substituted benzene ligands (Y-C(6)H(5), Y = COOH, SH, NH(2), OH, SO(3)H). The coercivity of magnetic nanoparticles decreases up to almost 50% upon the coordination of the ligands on the nanoparticle surface, whereas the saturation magnetization has increased. The percentage coercivity decrease of the modified nanoparticles with respect to the native nanoparticles strongly correlates with the crystal field splitting energy (CFSE) Delta evoked by the coordination ligands. The ligand inducing largest CFSE results in the strongest effect on the coercivity of magnetic nanoparticles. The change in magnetic properties of nanoparticles also correlates with the specific coordinating functional group bound onto the nanoparticle surface. The correlations suggest the decrease in spin-orbital couplings and surface anisotropy of magnetic nanoparticles due to the surface coordination. Such surface effects clearly show the dependence on the size of nanoparticles.     

Building Nanocomposite Magnets by Coating a Hard Magnetic Core with a Soft Magnetic Shell

Controlling exchange coupling between hard magnetic and soft magnetic phases is the key to the fabrication of advanced magnets with tunable magnetism and high energy density. Using FePt as an example, control over the magnetism in exchange‐coupled nanocomposites of hard magnetic face‐centered tetragonal (fct) FePt and soft magnetic Co (or Ni, Fe₂C) is shown. The dispersible hard magnetic fct‐FePt nanoparticles are first prepared with their coercivity (H_c) reaching 33 kOe. Then core/shell fct‐FePt/Co (or Ni, Fe₂C) nanoparticles are synthesized by reductive thermal decomposition of the proper metal precursors in the presence of fct‐FePt nanoparticles. These core/shell nanoparticles are strongly coupled by exchange interactions and their magnetic properties can be rationally tuned by the shell thickness of the soft phase. This work provides an ideal model system for the study of exchange coupling at the nanoscale, which will be essential for building superstrong magnets for various permanent magnet applications in the future.     

Controlling phase formation in solids: rational synthesis of phase separated Co@Fe2O3 heteroparticles and CoFe2O4 nanoparticles

A wet chemical approach from organometallic reactants allowed the targeted synthesis of Co@Fe(2)O(3) heterodimer and CoFe(2)O(4) ferrite nanoparticles. They display magnetic properties that are useful for magnetic MRI detection.     

The Role of Frozen Spins in the Exchange Anisotropy of Core-Shell Fe@Fe(3)O(4) Nanoparticles

Core-shell Fe@Fe(3)O(4) nanoparticles exhibit substantial exchange bias at low temperatures, mediated by unidirectionally aligned moments at the core-shell interface. These spins are frozen into magnetic alignment with field cooling, and are depinned in a temperature-dependent manner. The population of such frozen spins has a direct impact on both coercivity (H(C)) and the exchange-bias field (H(E)), which are modulated by external physical parameters such as the strength of the applied cooling field and the cycling history of magnetic field sweeps (training effect). Aging of the core-shell nanoparticles under ambient conditions results in a gradual decrease in magnetization but overall retention of H(C) and H(E), as well as a large increase in the population of frozen spins. These changes are accompanied by a structural evolution from well-defined core-shell structures to particles containing multiple voids, attributable to the Kirkendall effect. Energy-filtered and high-resolution transmission electron microscopy both indicate further oxidation of the shell layer, but the Fe core is remarkably well preserved. The increase in frozen spin population with age is responsible for the overall retention of exchange bias, despite void formation and other oxidation-dependent changes. The exchange-bias field becomes negligible upon deliberate oxidation of Fe@Fe(3)O(4) nanoparticles into yolk-shell particles, with a nearly complete physical separation of core and shell.     

Fe3O4@Al2O3 magnetic core-shell microspheres for rapid and highly specific capture of phosphopeptides with mass spectrometry analysis

Selective detection of phosphopeptides from complex biological samples is a challenging and highly relevant task in many proteomics applications. In this study, a novel phosphopeptide enrichment approach based on the strong interaction of Fe(3)O(4)@Al(2)O(3) magnetic core-shell microspheres with phosphopeptides has been developed. With a well-defined core-shell structure, the Fe(3)O(4)@Al(2)O(3) magnetic core-shell microspheres not only have a shell of aluminum oxide, giving them a high-trapping capacity for the phosphopeptides, but also have magnetic property that enables easy isolation by positioning an external magnetic field. The prepared Fe(3)O(4)@Al(2)O(3) magnetic core-shell microspheres have been successfully applied to the enrichment of phosphopeptides from the tryptic digest of standard phosphoproteins beta-casein and ovalbumin. The excellent selectivity of this approach was demonstrated by analyzing phosphopeptides in the digest mixture of beta-casein and bovine serum albumin with molar ratio of 1:50 as well as tryptic digest product of casein and five protein mixtures. The results also proved a stronger selective ability of Fe(3)O(4)@Al(2)O(3) magnetic core-shell microspheres over Fe(3+)-immobilized magnetic silica microspheres, commercial Fe(3+)-IMAC (immobilized metal affinity chromatography) resin, and TiO(2) beads. Finally, the Al(2)O(3) coated Fe(3)O(4) microspheres were successfully utilized for enrichment of phosphopeptides from digestion products of rat liver extract. These results show that Fe(3)O(4)@Al(2)O(3) magnetic core-shell microspheres are very good materials for rapid and selective separation and enrichment of phosphopeptides.     

纳米复合材料CoFe2O4/SiO2的制备和表征

采用溶胶-凝胶法制备了(CoFe2O4)x/(SiO2)1-x纳米复合材料. 利用TG/DTA, XRD和Mssbauer效应研究了热处理过程中干凝胶的变化及样品的结构、晶粒尺寸和磁性. 结果表明, 随着SiO2含量的增加, 样品中CoFe2O4的晶粒尺寸和内磁场逐渐变小, 并从磁有序状态转变为超顺磁状态.     

导电聚苯胺与磁性CoFe2O4纳米复合物的合成及其电磁性能

在利用HNO3处理CoFe2O4磁性纳米粒子使其表面离子化、分散性得到改善的基础上, 采用苯胺在其表面原位聚合, 制备了具有电磁功能的聚苯胺(PANI)/CoFe2O4纳米复合物. 借助TEM、XRD、FT-IR、四探针电导率仪和VSM(振动样品磁强计)等分析手段研究了复合物的形貌、结构及其电磁性能. 结果表明, CoFe2O4以25 nm左右的粒子分散于聚苯胺基体中, 被其完全包覆, CoFe2O4与PANI之间存在化学键合作用; 复合物同时具有电性能和磁性能, 其导电率随CoFe2O4含量增加而降低, 饱和磁化强度随之升高, 而矫顽力在所研究的范围内则先增大而后又减小, 且均高于CoFe2O4的矫顽力.     

Facile synthesis and properties of ZnFe2O4 and ZnFe2O4/polypyrrole core-shell nanoparticles

We demonstrated that ZnFe₂O₄/polypyrrole core-shell nanoparticles could be facilely synthesized via in situ chemical oxidative polymerization of pyrrole monomers on the surface of ZnFe₂O₄ nanoparticles. The shell thickness of core-shell nanoparticles could be easily controlled by adjusting the amount of pyrrole monomers. The phase structures, morphologies and properties of the as-prepared products were investigated by XRD, TEM, SEM, VSM, and FTIR spectra. Magnetic studies revealed that the saturation magnetization (M_s) and coercivity (H_c) of ZnFe₂O₄/PPy core-shell nanoparticles is 17.8 emu/g and 130 Oe, respectively. The electromagnetic characteristics of products showed that ZnFe₂O₄/PPy core-shell nanoparticles exhibit excellent microwave absorption performance than ZnFe₂O₄ nanoparticles, such as more powerful absorbing property and wider electromagnetic wave absorbing frequency band due to the proper matching of the permittivity and the permeability of ZnFe₂O₄/PPy core-shell nanoparticles.