Exchange bias in iron oxide nanoclusters

Iron oxide nanoclusters have been prepared by the gas-phase aggregation technique to form thin film structures with very high exchange bias values (up to 3000?Oe at low temperatures). Composition has been analysed by x-ray absorption and M?ssbauer spectroscopies in order to elucidate the actual origin of the observed magnetic behaviour. The formation of a metal-oxide core-shell arrangement to explain the observed exchange bias has to be discarded since results show no metallic iron content and the main presence of α-Fe(2)O(3). The observed weak ferromagnetism and exchange bias are in agreement with the obtained size of α-Fe(2)O(3) nanoparticles: weak ferromagnetism because of the well-known spin canting in this antiferromagnetic structure and exchange bias because of the interaction between different spin sublattice configurations promoted by the modification of iron coordination in α-Fe(2)O(3) nanoparticles. Moreover, the preparation method is proposed for tuning both magnetization and exchange bias values by modification of the preparation conditions of α-Fe(2)O(3) nanoparticles, which open new possibilities in the design of new materials with required properties.     

Magnetic iron oxide nanoclusters with tunable optical response

We have developed a modified synthetic protocol for the growth of monodispersed, superparamagnetic, flower-like colloidal nanoclusters (CNCs), which are consisted of smaller iron oxide nanocrystals with adjustable size. We show that their optical properties can be tuned by applying an external magnetic field. The latter controls the subtle balance of the CNCs’ mutual interactions (magnetic versus electrostatic) and drives their assembly in aqueous media. Spectrophotometric measurements reveal that a diffuse reflectance maximum, in the visible range, is related to the CNCs organization. As the strength of the external magnetic field increases, in the range 160–600 G, the spectral weight of this feature shifts towards the blue region of the spectrum. The induced photonic crystal-like response entails a remarkable magneto-optical behavior, closely associated with the size-dependent characteristics of the CNCs ensemble. Such materials pave the way for promising technological implementations in photonics.     

Iron/iron oxide core-shell nanoclusters for biomedical applications

Biocompatible magnetic nanoparticles have been found promising in several biomedical applications for tagging, imaging, sensing and separation in recent years. Most magnetic particles or beads currently used in biomedical applications are based on ferromagnetic iron oxides with very low specific magnetic moments of about 20–30 emu/g. Here we report a new approach to synthesize monodispersed core-shell nanostructured clusters with high specific magnetic moments above 200 emu/g. Iron nanoclusters with monodispersive size of diameters from 2 nm to 100 nm are produced by our newly developed nanocluster source and go to a deposition chamber, where a chemical reaction starts, and the nanoclusters are coated with iron oxides. HRTEM Images show the coatings are very uniform and stable. The core-shell nanoclusters are superparamagnetic at room temperature for sizes less than 15 nm, and then become ferromagnetic when the cluster size increases. The specific magnetic moment of core-shell nanoclusters is size dependent, and increases rapidly from about 80 emu/g at the cluster size of around 3 nm to over 200 emu/g up to the size of 100 nm. The use of high magnetic moment nanoclusters for biomedical applications could dramatically enhance the contrast for MRI, reduce the concentration of magnetic particle needs for cell separation, or make drug delivery possible with much lower magnetic field gradients     

纳米多晶铁的冲击相变研究

利用分子动力学方法研究了不同晶粒度的纳米多晶铁在冲击压缩下的结构相变过程,模拟结果表明:纳米多晶铁的冲击结构相变(由体心立方(bcc)结构 α 相到六角密排(hcp)结构 ε 相)发生的临界冲击应力在15 GPa左右.纳米多晶铁在经过弹性压缩变形后,晶界导致的塑性变形开始发生,然后大多数相变从晶界成核并最终发展为大规模相变.不同变形过程在应力和粒子速度剖面上能得到清晰的体现,并通过微观原子结构分析分辨.冲击压缩后的微观结构以晶界原子和以fcc结构原子充当孪晶界的hcp原子为主.晶粒度明显影响晶界变形及相变 关键词： 冲击相变 纳米多晶铁 冲击波 分子动力学     

Starch vermicelli template for synthesis of magnetic iron oxide nanoclusters

A novel method for fabricating magnetic iron oxide nanoparticles was achieved by using transparent vermicelli template as a new stabilizing material. The morphology of the as-prepared magnetic iron oxide deposited on the surface of vermicelli was observed as nanoclusters. The magnetization of the magnetic iron oxide nanoparticles at room temperature was decreased after carbonization at 200 °C. Therefore the thermal decomposition of iron oxide nanoparticles stabilized by starch vermicelli template yielded iron oxide/carbon nanocomposites with the soft magnetic behavior which are useful for biomedical applications.     

Quantum spins in Mackay icosahedral gold nanoparticles

We report on the direct observation of the intrinsic magnetization behavior of Mackay icosahedral Au nanoparticles. The spin arrangements in 3.5-nm icosahedral Au particles are found to be ferrimagnetic-like, where the core and surface moments point in opposite directions, with a net spontaneous magnetic moment of 16 μ_B per particle. The unpaired spins behave as J = 1/2 quantum spins. The average level separation is found to be a factor of ~1.53 larger than that estimated according to the Kubo formula for spherical Au particles. This reflects the fact that there are considerably fewer atoms packed in a particle with an icosahedral geometry than with a spherical one.     

Importance of shear in the bcc-to-hcp transformation in iron

Iron shows a pressure-induced martensitic phase transformation from the ground state ferromagnetic bcc phase to a nonmagnetic hcp phase at approximately 13 GPa. The exact transformation pressure (TP) and pathway are not known. Here we present a multiscale model containing a quantum-mechanics-based multiwell energy function accounting for the bcc and hcp phases of Fe and a construction of kinematically compatible and equilibrated mixed phases. This model suggests that shear stresses have a significant influence on the bcc<-->hcp transformation. In particular, the presence of modest shear accounts for the scatter in measured TPs. The formation of mixed phases also provides an explanation for the observed hysteresis in TP.     

铁冲击相变的晶向效应

采用基于火炮加载的三样品精细波剖面对比测量,研究了晶向效应对铁弹-塑性转变及体心立方结构(bcc,α相)至六角密排结构(hcp,ε相)相变特性的影响.观测到单晶铁异常的弹-塑性转变行为,这与基于位错密度描述的黏塑性本构模型计算结果相符,对应的Hugoniot弹性极限δ_(HEL)均大于6 GPa,且具有晶向相关性,即δ(111)/(HEL)δ(110)/(HEL)δ(100)/(HEL);系统获取了相变起始压力P_(PT)晶向相关性的实验数据,[100],[110]和[111]晶向的PPT实测值分别为13.89±0.57 GPa,14.53±0.53 GPa,16.05±0.67 GPa,其变化规律与非平衡分子动力学计算结果相符.上述结果揭示出冲击压缩下单晶铁存在塑性与相变微观机理的强耦合,为完善用于冲击实验描述的相场动力学模型提供了重要的实验支撑.     

EXAFS measurement of iron bcc-to-hcp phase transformation in nanosecond-laser shocks

Extended x-ray absorption fine structure (EXAFS) measurements have demonstrated the phase transformation from body-centered-cubic (bcc) to hexagonal-close-packed (hcp) iron due to nanosecond, laser-generated shocks. The EXAFS spectra are also used to determine the compression and temperature in the shocked iron, which are consistent with hydrodynamic simulations and with the compression inferred from velocity interferometry. This is a direct, atomic-level, and in situ proof of shock-induced transformation in iron, as opposed to the previous indirect proof based on shock-wave splitting.     

Cooperative superfluorescence in nanoclusters

The features of superfluorescence (SF) in nanoclusters, which consist of a few neighboring particles interacting with each other by exchange or/and electrostatic forces, are investigated theoretically. It is shown that there are two types of cooperatively SF depending on the ratio between the linear size of a nanocluster and the cooperative interaction range. Experiments on cooperative luminescence in Ytterbium-doped silica fibers are analyzed. It is shown that the intensity of cooperative SF in such a system should be proportional to the fourth degree of Ytterbium concentration.     

Abnormal austenite–ferrite transformation behaviour of pure iron

The isochronal and isothermal austenite (γ) → ferrite (α) transformation of pure iron was measured by high-resolution dilatometry and differential thermal analysis. Both abnormal and normal transformation kinetics were recognized for the first time in pure iron according to the variation in the ferrite formation rate. The occurrence of the type of γ?→α transformation strongly depends on the grain size; the transformation type changes from abnormal to normal with decreasing grain size. The abnormal transformation process involves the occurrence of additional peaks in the transformation rate for the first stage of the transformation. A phase transformation model, involving repeated nucleation (autocatalytic nucleation), interface-controlled continuous growth and incorporating correction for impingement, has been employed successfully to describe the observed kinetics of the abnormal transformation.     

The transformation and the catalytic activity of iron sulfide in lignite liquefaction

The Mössbauer effect was used to study the decomposition of pyrite in the presence of tetralin and hydrogen atmosphere. Iron sulfide catalysts with different amounts of sulphur are prepared and their transformations and catalytic activities in coal hydroliquefaction are examined.     

The structure and photochemical transformation of chloride complexes of iron in polyethylenglycol

The investigation of (C₂H₅)₄NFeCl₄-polyethylenglycol (PEG) system was carried out by means of optical spectroscopy, electron spin resonance (ESR) and Mössbauer spectroscopy. We also tried to connect kinetic parameters of photoreduction process with the structure of the complex and polymer surrounding.     

Horizontal low gradient magnetophoresis behaviour of iron oxide nanoclusters at the different steps of the synthesis route

In this study, the use of horizontal low gradient magnetic field (HLGMF) (<100 T/m) for filtration, control and separation of synthesized magnetic nanoparticles (NPs) is investigated. The characteristics of the suspension, size and type of the NPs are considered and discussed. For these purposes, Fe₂O₃ silica-coated nanoclusters of about 150 nm are synthesized by co-precipitation, monodispersion and silica coating. Superconducting quantum interference device, TEM, XRD and ζ potential techniques were used to characterize the synthesized nanoclusters. An extensive magnetophoresis study was performed at different magnetophoretical conditions. Different reversible aggregation times were observed at different HLGMF, at each step of the synthesis route. In particular, differences of several orders of magnitude were observed when comparing citric acid-modified NPs with silica-coated nanoclusters. Reversible aggregation times are correlated to the properties of the NPs at different steps of synthesis route.     

Copper nanoclusters in amorphous hydrogenated carbon

A study of the geometric characteristics of copper nanoclusters incorporated in an amorphous hydrogenated carbon matrix is reported. It makes use of small-angle x-ray scattering and transmission electron microscopy (100 keV). The fractal dimension and nanocluster diameter have been determined from the x-ray scattering indicatrix for different copper concentrations. TEM images of copper nanoclusters have been analyzed, and a cluster distribution function in size constructed. The shape of the distribution function is discussed in terms of the theory of nucleation of a new phase. Fiz. Tverd. Tela (St. Petersburg) 40, 568–572 (March 1998)     

Novel magnetism in 3He nanoclusters

The magnetic susceptibility of 3He nanoclusters embedded in a 4He matrix has been measured from 0.5 to 10 mK at pressures from 2.88 to 3.54 MPa. Even the lowest pressure clusters have a solid fraction in the region of the phase diagram where bulk solid is unstable. At 3.54 MPa, straight theta = -250 microK, equal to that of bulk 3He for v = 21.3 cm3/mole. For 2.88 MPa, straight theta = 140 microK, indicating a ferromagnetic tendency, similar to 2D films at some coverages. At intermediate pressures, chi has a peak near 1.05 mK, but with no discontinuity. Magnetic ordering in nanoclusters appears to be different than the U2D2 phase of bulk 3He.     

Phase stresses induced by the γ → α transformation in an iron polycrystal

The evolution of the phase stresses induced in the course of the γ ? α transformation in polycrystalline iron is analyzed in the framework of the elastoplastic model of a spherical inclusion. The isolated regions of the α phase (ferrite) and the γ phase (austenite) are treated as inclusions at the initial and final stages of the transformation, respectively. The stresses are calculated with due regard for the plastic flow in a spherical layer (matrix) around these inclusions. The calculated dependence of the hydrostatic phase stresses on the volume fraction of ferrite suggests that these stresses retard the initial stage and promote the final stage of the transformation.     

Chemical transformation of iron compounds during the process of coal pyrolysis in steam

When the content of sulphur in hard coal is higher than 1.5% weight, such coal cannot be used as fuel in thermal-electric power stations due to environmental protection. Such coal can be used as a raw product in various chemical processes in which many valuable substances are obtained. This study is a small part of a major project looking for improved ways of utilizing sulphur-rich coals. Mössbauer measurements were carried out for semi-cokes obtained from sulphur-rich coal in the pyrolysis process in a steam atmosphere in the temperature range of 300–800 °C. Results of these measurements showed that during the pyrolysis process, pyrite transformed completely into iron oxides (magnetite and hematite), whereas illite transformed only partly even at the highest temperatures. Unfortunately, it was not possible to identify some products of the illite transformation.