Non-equilibrium cation distribution and enhanced spin disorder in hollow CoFe2O4 nanoparticles

We present magnetic properties of hollow and solid CoFe(2)O(4) nanoparticles that were obtained by annealing of Co(33)Fe(67)/CoFe(2)O(4) (core/shell) nanoparticles. Hollow nanoparticles were polycrystalline whereas the solid nanoparticles were mostly single crystal. Electronic structure studies were performed by photoemission which revealed that particles with hollow morphology have a higher degree of inversion compared to solid nanoparticles and the bulk counterpart. Electronic structure and the magnetic measurements show that particles have uncompensated spins. Quantitative comparison of saturation magnetization (M(S )), assuming bulk Néel type spin structure with cationic distribution, calculated from quantitative XPS analysis, is presented. The thickness of uncompensated spins is calculated to be significantly large for particles with hollow morphology compared to solid nanoparticles. Both morphologies show a lack of saturation up to 7 T. Moreover magnetic irreversibility exists up to 7 T of cooling fields for the entire temperature range (10-300 K). These effects are due to the large bulk anisotropy constant of CoFe(2)O(4) which is the highest among the cubic spinel ferrites. The effect of the uncompensated spins for hollow nanoparticles was investigated by cooling the sample in large fields of up to 9 T. The magnitude of horizontal shift resulting from the unidirectional anisotropy was more than three times larger than that of solid nanoparticles. As an indication signature of uncompensated spin structure, 11% vertical shift for hollow nanoparticles is observed, whereas solid nanoparticles do not show a similar shift. Deconvolution of the hysteresis response recorded at 300 K reveals the presence of a significant paramagnetic component for particles with hollow morphology which further confirms enhanced spin disorder.     

Magnetic response of NiFe2O4 nanoparticles in polymer matrix

We report the magnetic properties of magnetic nano-composite, consisting of different quantity of NiFe₂O₄ nanoparticles in polymer matrix. The nanoparticles exhibited a typical magnetization blocking, which is sensitive on the variation of magnetic field, mode of zero-field-cooled/field-cooled experiments and particle quantity in the matrix. The samples with lower particle quantity showed an upturn of magnetization down to 5 K, whereas the blocking of magnetization dominates at lower temperatures as the particle quantity increases in the polymer. We examine such magnetic behaviour in terms of the competitive magnetic ordering between core and surface spins of nanoparticles, taking into account the effect of inter-particle (dipole-dipole) interactions on nanoparticle magnetic dynamics.     

磁性聚苯胺纳米微球的合成与表征

报道了具有核壳结构的Fe3 O4 聚苯胺磁性纳米微球的合成方法和表征结果 .微球同时具有导电性和磁性能 .在优化的实验条件下 ,可得到饱和磁化强度Ms 为 5 5 .4emu/g ,矫顽力Hc 为 6 2Oe的磁性微球 .微球的导电性随着微球中Fe含量的增加而下降 .微球的磁性能则随着Fe含量的增加而增大 .Fe3 O4 磁流体的粒径和磁性聚苯胺微球的粒径均在纳米量级 .纳米Fe3 O4 粒子能够提高复合物的热性能 .实验表明 ,磁流体和聚苯胺之间可能存在着一定的相互作用 ,但这种相互作用较为复杂 ,难于研究 .     

Evidence of a core–shell structure in the antiferromagnetic La0.2Ce0.8CrO3 nanoparticles by neutron scattering

We report the evidence of a core?Cshell structure in the antiferromagnetic La_0.2Ce_0.8CrO₃ nanoparticles by using a combination of neutron diffraction, polarized neutron small angle scattering (SANSPOL), and dc magnetization techniques. The neutron diffraction study establishes that the present nanoparticles are antiferromagnetic in nature. The magnetic scattering in the SANSPOL study arises from the shell part of the nanoparticles due to the disordered surface spins. The analysis of the SANSPOL data shows that these nanoparticles have a mean core diameter of 12.3±1.1?nm, and a shell thickness of 2.8±0.4?nm, giving a core?Cshell structure with an antiferromagnetic core, and a shell with a net magnetic moment under an applied magnetic field.     

Synthesis and characterization of hard magnetic composites—Hollow microsphere/titania/barium ferrite

Hard magnetic composites—hollow microsphere (core)/titania (intermediate layer)/barium ferrite (magnetic shell) (M/T/B) were prepared by wet-chemical method. Barium ferrite nanoparticles were directly coated on the rutile titania-coated hollow microsphere forming light hard magnetic composites using sol-gel technique. The prepared composites were characterized with FESEM, EDS, XRD and vibrating sample magnetometry. The composites are composed of barium ferrite, hematite, titania and mullite. For the samples with 40 wt.% barium ferrite, its specific saturation magnetization with titania is increased to 17.88 emu/g in comparison with 9.6 emu/g without titania. The function of titania in the composites is also discussed.     

Nanostructures of gold coated iron core-shell nanoparticles and the nanobands assembled under magnetic field

Pure metal iron nanoparticles are unstable in the air. By a coating iron on nanoparticle surface with a stable noble metal, these air-stable nanoparticles are protected from the oxidation and retain most of the favorable magnetic properties, which possess the potential application in high density memory device by forming self-assembling nanoarrays. Gold-coated iron core-shell structure nanoparticles (Fe/Au) synthesized using reverse micelles were characterized by transmission electron microscopy (TEM). The average nanoparticle size of the core-shell structure is about 8 nm, with about 6 nm diameter core and 1∼2 nm shell. Since the gold shell is not epitaxial growth related to the iron core, the morié pattern can be seen from the overlapping of iron core and gold shell. However, the gold shell lattice can be seen by changing the defocus of TEM. An energy dispersive X-ray spectrum (EDS) also shows the nanoparticles are air-stable. The magnetic measurement of the nanoparticles also proved successful synthesis of gold coated iron core-shell structure. The nanoparticles were then assembled under 0.5 T magnetic field and formed parallel nanobands with about 10 μm long. Assembling two dimensional ordered nanoarrays are still under going. Received 29 November 2000     

Air stability and magnetic properties of GdN, TiN, and (Gd,Ti)N nanoparticles

GdN, TiN, and (Gd,Ti)N nanoparticles were prepared by arc evaporating Gd, Ti, and Gd-Ti alloys in N₂, respectively. Most of these nanoparticles show narrow size distribution with average diameter of 20 nm. Shell/core structure was observed in the (Gd,Ti)N nanoparticles, in which the shell was formed by surface reaction with air. (Gd,Ti)N nanoparticles are more stable than GdN nanoparticles in air due partially to the formation of the protective shell. The Curie temperature of GdN nanoparticles is lower than that of the bulk GdN. Both GdN and (Gd, Ti)N nanoparticles are difficult to reach magnetic saturation and show zero coercivity.     

MnZnFe nanoparticles for self-controlled magnetic hyperthermia

Manganese zinc iron magnetic nanoparticles were synthesized by a co-precipitation method for application as hyperthermia inducing agents. The structure, morphology and magnetic properties of the nanoparticles are characterized using scanning electron microscopy, X-ray diffraction, and a superconducting quantum interference device. The magnetic properties being investigated include Curie temperature, saturation magnetization, remnant magnetization, coercive field, and hysteresis. The study showed that adjusting the Mn contribution to the particles contributed to the adjustment of all magnetic properties of the complex.     

Structural and magnetic properties of polymer-stabilized tetragonal Ni nanoparticles

Ni nanoparticles (Ni-NPs), with diameter (D) ranging 5–30 nm, were synthesized by reducing nickel chloride with NaBH₄ in the presence of polymer molecules of poly-vinyl alcohol (PVA) in cold water. Nickel chloride was dispersed in the PVA molecules which stabilized the resulting Ni-NPs. Experiments were carried out with and without PVA to elucidate the effect of PVA molecules on the structural and magnetic properties of Ni-NPs. It was found that both uncoated (uc) and PVA-coated (pc) Ni-NPs exhibit a tetragonal (t) crystal structure, i.e. different from the cubic (fcc) structure of bulk nickel. pc Ni-NPs (paramagnetic in nature) converted to fcc Ni (spherical shape, D ～ 12 nm) on annealing at 573 K in air, exhibiting a saturation magnetization M _s = 20.5 emu/g, squareness ratio M _r /M _s = 0.48 and coercivity H _c = 248 Oe, which is higher than the bulk Ni (0.7 Oe). uc Ni-NPs showed little improvement in M _s and H _c on air annealing. The core–shell structure resulted in a high H _c value in stable pc Ni-NPs in air. Electron magnetic resonance revealed exchange interaction between the core and shell, which changes on annealing in air.     

Controlling the crystal structure of Ni nanoparticles by the use of alkylamines

Ni nanoparticles were prepared via thermal decomposition of nickel acetate tetrahydrate in the presence of long-chain amines, which acted as both solvents and reducing agents. By tuning the reaction temperature, Ni nanostructures with either hcp or fcc crystal structure were obtained. In principle, higher temperatures favored the formation of hcp nanoparticles. The employment of additional surfactants such as 1-adamantanecarboxylic acid and trioctylphosphine-oxide facilitated the tuning of the particles’ growth limit. The size of the particles varied between 5 and 120 nm. The magnetic features of fcc-Ni nanoparticles were quite similar to the corresponding ‘bulk’ ones. On the other hand, the hcp-Ni particles showed weak magnetic features, reflected by low magnetization values, the absence of saturation magnetization and by blocking temperatures far below room temperature.     

Tuning Carbon Content and Morphology of FeCo/Graphitic Carbon Core–Shell Nanoparticles using a Salt‐Matrix‐Assisted CVD Process

Large‐scale and tunable synthesis of FeCo/graphitic carbon (FeCo/GC) core–shell nanoparticles as a promising material for multipurpose biomedical applications is reported. The high‐quality graphitic structure of the carbon shells is demonstrated through high‐resolution transmission electron microscopy (HRTEM), X‐ray diffraction (XRD), and Raman spectroscopy. A saturation magnetization of 80.2 emu g^?1 is reached for the pure FeCo/GC core–shell nanoparticles. A decrease in the saturation magnetization of the samples is observed with an increase in their carbon content with different carbon morphologies evolved in the process. It is also shown how hybrid nanostructures, including mixtures of the FeCo/GC nanoparticles and multi‐walled carbon nanotubes (MWNTs) or carbon nanorods (CNRs), can be obtained only by manipulation of the carbon‐bearing gas flow rate.     

Effect of the number of iron oxide nanoparticle layers on the magnetic properties of nanocomposite LbL assemblies

Aqueous colloidal suspension of iron oxide nanoparticles has been synthesized. Z-potential of iron oxide nanoparticles stabilized by citric acid was −35±3 mV. Iron oxide nanoparticles have been characterized by the light scattering method and transmission electron microscopy. The polyelectrolyte/iron oxide nanoparticle thin films with different numbers of iron oxide nanoparticle layers have been prepared on the surface of silicon substrates via the layer-by-layer assembly technique. The physical properties and chemical composition of nanocomposite thin films have been studied by atomic force microscopy, magnetic force microscopy, magnetization measurements, Raman spectroscopy. Using the analysis of experimental data it was established, that the magnetic properties of nanocomposite films depended on the number of iron oxide nanoparticle layers, the size of iron oxide nanoparticle aggregates, the distance between aggregates, and the chemical composition of iron oxide nanoparticles embedded into the nanocomposite films. The magnetic permeability of nanocomposite coatings has been calculated. The magnetic permeability values depend on the number of iron oxide nanoparticle layers in nanocomposite film.     

Formation and strain distribution of Ni/NiO core/shell magnetic nanoparticles fabricated by pulsed laser deposition

Nucleation and growth lead to substantial strain in nanoparticles embedded in a host matrix.The distribution of strain field plays an important role in the physical properties of nanoparticles.Magnetic Ni/NiO core/shell nanoparticles embedded in the amorphous Al2O3 matrix were fabricated by pulsed laser deposition.The results from a high-resolution transmission electron microscope also revealed that the core/shell nanoparticles consist of a single crystal Ni core with a faced-centered cubic structure(Space ...     

Comparative analysis of the 1H NMR relaxation enhancement produced by iron oxide and core-shell iron-iron oxide nanoparticles

Physicochemical and magnetorelaxometric characterization of the colloidal suspensions consisting of Fe-based nanoparticles coated with dextran have been carried out. Iron oxide and iron core/iron oxide shell nanoparticles were obtained by laser-induced pyrolysis of Fe(CO)₅ vapours. Under different magnetic field strengths, the colloidal suspension formed by iron oxide nanoparticles showed longitudinal (R₁) and transverse (R₂) nuclear magnetic relaxation suspension (NMRD) profiles, similar to those previously reported for other commercial magnetic resonance imaging (MRI) contrast agents. However, colloidal suspension formed by ferromagnetic iron-core nanoparticles showed a strong increase of the R₁ values at low applied magnetic fields and a strong increase of the R₂ measured at high applied magnetic field. This behaviour was explained considering the larger magnetic aggregate size and saturation magnetization values measured for this sample, 92 nm and 31 emu/g Fe, respectively, with respect to those measured for the colloidal suspensions of iron oxide nanoparticles (61 nm and 23 emu/g Fe). This suspension can be used both as T₁ and T₂ contrast agent.     

Preparation and photocatalytic properties of magnetically reusable Fe3O4@ZnO core/shell nanoparticles

Fe₃O₄@ZnO binary nanoparticles were synthesized by a simple two-step chemical method and characterized using various analytical instruments. TEM result proved the binary nanoparticles have core/shell structures and average particle size is 60 nm. Photocatalytic investigation of Fe₃O₄@ZnO core/shell nanoparticles was carried out using rhodamine B (RhB) solution under UV light. Fe₃O₄@ZnO core/shell nanoparticles showed enhanced photocatalytic performance in comparison with the as prepared ZnO nanoparticles. The enhanced photocatalytic activity for Fe₃O₄@ZnO might be resulting from the higher concentration of surface oxygen vacancies and the suppressing effect of the Fe³⁺ ions on the recombination of photoinduced electron–hole pairs. Magnetization saturation value (5.96 emu/g) of Fe₃O₄@ZnO core/shell nanoparticles is high enough to be magnetically removed by applying a magnetic field. The core/shell photocatalyst can be easily separated by using a commercial magnet and almost no decrease in photocatalytic efficiency was observed even after recycling six times.     

Structural, static and dynamic magnetic properties of dextran coated γ-Fe(2)O(3) nanoparticles studied by (57)Fe NMR, M?ssbauer, TEM and magnetization measurements

The structural and magnetic properties and spin dynamics of dextran coated and uncoated γ-Fe(2)O(3) (maghemite) nanoparticles have been investigated using high resolution transmission electron microscopy (HRTEM), (57)Fe nuclear magnetic resonance (NMR), M?ssbauer spectroscopy and dc magnetization measurements. The HRTEM observations indicated a well-crystallized system of ellipsoid-shaped nanoparticles, with an average size of 10 nm. The combined M?ssbauer and magnetic study suggested the existence of significant interparticle interactions not only in the uncoated but also in the dextran coated nanoparticle assemblies. The zero-field NMR spectra of the nanoparticles at low temperatures are very similar to those of the bulk material, indicating the same hyperfine field values at saturation in accord with the performed M?ssbauer measurements. The T(2) NMR spin-spin relaxation time of the nanoparticles has also been measured as a function of temperature and found to be two orders of magnitude shorter than that of the bulk material. It is shown that the thermal fluctuations in the longitudinal magnetization of the nanoparticles in the low temperature limit may account for the shortening and the temperature dependence of the T(2) relaxation time. Thus, the low temperature NMR results are in accord with the mechanism of collective magnetic excitations, due to the precession of the magnetization around the easy direction of the magnetization at an energy minimum, a mechanism originally proposed to interpret M?ssbauer experiments in magnetic nanoparticles. The effect of the surface spins on the NMR relaxation mechanisms is also discussed.     

离子型钴铁氧体磁流体的稀土改性与机理研究

采用化学共沉淀法以柠檬酸三钠为表面改性剂制备了离子型稀土复合钴铁氧体磁流体.利用X衍射仪和透射电镜对磁粒子的组成、结构及粒径进行了分析.利用古埃磁天平和分光光度计研究了稀土离子改性对磁流体饱和磁化强度和磁感应的影响,实验结果表明:合成过程中添加稀土离子能明显降低磁性纳米粒子的粒径,制得的磁粒子均呈球形,钴铁氧体磁粒子的粒径为12～15nm,稀土钴铁氧体磁粒子的粒径为6～8nm.利用稀土改性的微观模型解释了粒径的降低.添加Dy3+能提高饱和磁化强度和磁感应,添加Y3+则能提高磁感应,却降低了饱和磁化强度.并从理论上对其改性机理进行了详细的分析.     

In situ synthesis and characterization of LiNi0.5La0.08Fe1.92O4-polyaniline core-shell nanocomposites

Core-shell-structured LiNi_0.5La_0.08Fe_1.92O₄-polyaniline (PANI) nanocomposites with magnetic behavior were synthesized by in situ polymerization of aniline in the presence of LiNi_0.5La_0.08Fe_1.92O₄ nanoparticles. The structure, morphology and magnetic properties of samples were characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FTIR), UV-vis absorption, transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM) technique. The results of spectroanalysis indicated that there was interaction between PANI chains and ferrite particles. TEM study showed that LiNi_0.5La_0.08Fe_1.92O₄-PANI nanocomposites presented a core-shell structure with a magnetic core of 30-50 nm diameter and an amorphous shell of 10-20 nm thickness. The nanocomposites under applied magnetic field exhibited the hysteresis loops of the ferromagnetic nature. The saturation magnetization and coercivity of nanocomposites decreased with decreasing content of LiNi_0.5La_0.08Fe_1.92O₄. The polymerization mechanism and bonding interaction in the nanocomposites have been discussed.     

Structural, magnetic and electrical properties of NiCuZn ferrites prepared by microwave sintering method suitable for MLCI applications

Polycrystalline NiCuZn soft ferrites with stoichiometric iron were prepared by a novel microwave sintering method. The powders were calcined, compacted and sintered at 950 °C for 30 min in a microwave sintering furnace. X-ray diffraction patterns confirm the formation of single phase cubic spinel structure. The grain size was estimated using SEM micrographs. The lattice constant is found to increase with increase in zinc concentration. The sintered ferrites have been investigated for their physical, magnetic and electrical properties such as bulk density, X-ray density, porosity, anisotropy constant, initial permeability, saturation magnetization, DC resistivity, dielectric constant and dielectric loss as a function of zinc concentration. Permeability, saturation magnetization, dielectric constant and dielectric loss were found to increase while DC resistivity was found to decrease with the replacement of Zn with Ni. The present series of ferrites are found to posses properties that are suitable for the core materials in multilayer chip inductors.     

Atomic physics at the planned new RIKEN facility

Combining Mössbauer spectroscopy with magnetic property measurement, we have studied Fe-N and (Fe, Ni)-N powders for magnetic recording. The typical particles of the core (α-Fe)/shell (γ′-Fe₄N) structure have been successfully prepared. All the products are stabilized in a multi-organic solution. It has been found that the coercivity can be changed from 300 to 800 Oe by adjusting the shape of the particles. The special saturation magnetization of the particles can be adjusted from 120 to 180emu/g and their chemical stability is improved by substituting nickel for iron in γ′-Fe₄N. Following experiments for corrosion resistance, it is expected that (Fe, Ni)-N and the core/shell particles will be applied as recording media in the near future.