Magnetically Induced Anomalous Dichroism of Atomic Transitions of the Cesium D<Subscript>2</Subscript> Line

An alternative treatment of the well-known effect of a decrease in the Morin transition temperature in hematite with a decrease in the size of crystallites to the complete disappearance of the transition for nanoparticles smaller than 20 nm is proposed. In contrast to the standard speculative explanation of this effect in terms of the effect of surface and defectiveness of grains, we suggest that the decisive factor is an increase in the contribution of the shape anisotropy of particles with a decrease in their size, which is responsible for the spread of orientations of the axes of the resulting magnetic anisotropy with respect to the crystallographic axes. Our reasons are confirmed by a numerical analysis of Mössbauer spectra of hematite nanoparticles within the continuous model of magnetic dynamics of an ensemble of antiferromagnetic nanoparticles in the two-sublattice approximation generalized to the existence of weak ferromagnetism (Dzyaloshinskii interaction).     

Structure and magnetic properties of Fe/Fe oxide clusters

Fe clusters have been synthesised in ultra-high-vacuum chamber using a gas-stabilized cluster aggregation method that ensures good control of the cluster size and naturally oxidized in order to obtain Fe/Fe oxide core-shell nanoparticles. The morphology of an individual nanoparticle, as revealed by transmission electron microscopy, consists of a Fe core of an average diameter of 4.4 nm surrounded by an oxide shell of uniform thickness of about 1.2 nm in average. The nanoparticles may be assimilated with a ferro-/antiferromagnetic (FM/AF) system. The morpho-structural features have been correlated with magnetic measurements on the core-shell nanoparticles. A significant exchange bias effect has been measured, when the sample was field-cooled under an applied field of 3 T. As the morphology of core-shell nanoclusters is much more complicated than in FM/AF bilayers of regular thickness due to the particular geometry of the coronal AF layer, the shape and surface anisotropy have to be taken into account for a correct interpretation of the magnetic data.     

Magnetic anisotropy and magnetization dynamics of Fe nanoparticles embedded in Cr and Ag matrices

Static and dynamical magnetic properties of Fe nanoparticles (NPs) embedded in non-magnetic (Ag) and antiferromagnetic (Cr) matrices with a volume filling fraction (VFF) of 10% have been investigated. In both Fe@Ag and Fe@Cr nanocomposites, the Fe NPs have a narrow size distribution, with a mean particle diameter around 2 nm. In both samples, the saturation magnetization reaches that of Fe bulk bcc, suggesting the absence of alloying with the matrices. The coercivity at 5 K is much larger in Fe@Cr than in Fe@Ag as a result of the strong interaction between the Fe NPs and the Cr matrix. Temperature-dependent magnetization and ac-susceptibility measurements point out further evidence of the enhanced interparticle interaction in the Fe@Cr system. While the behaviour of Fe@Ag indicates the presence of weakly interacting magnetic monodomain particles with a wide distribution of blocking temperatures, Fe@Cr behaves like a superspin glass produced by the magnetic interactions between NPs.     

Mössbauer and magnetization studies of iron oxide nanocrystals

Monodisperse iron oxide nanocrystals have been produced following non-hydrolytic, thermal decomposition routes. Spherically shaped particles with diameter of 4 and 12 nm and cubic shaped particles with an edge length of 9 nm have been studied. The particles have been shown to consist of mainly maghemite. A reduction of the saturation magnetic hyperfine field is observed for the 4 nm particles as compared to the corresponding bulk value. The anisotropy energy determined from the temperature variation of the magnetic hyperfine field was strongly enhanced for the 4 nm particles.     

On the influence of anisotropy on the magnetic small-angle neutron scattering of superparamagnetic particles

This paper presents a calculation of the magnetic small-angle neutron scattering cross-section resulting from a dilute ensemble of superparamagnetic particles exhibiting uniaxial magnetic anisotropy. We focus on the two experimentally relevant scattering geometries in which the incident neutron beam is perpendicular or parallel to an applied magnetic field, and we discuss several orientations of the anisotropy axes with respect to the field. Magnetic anisotropy has no influence on the magnetic small-angle neutron scattering when the particles are mobile, as is the case e.g. in ferrofluids, but, when the particles are embedded in a rigid non-magnetic matrix and the orientations of the anisotropy axes are fixed, significant deviations compared to the case of negligible anisotropy are expected. For the particluar situation in which the anisotropy axes are parallel to the applied field, closed-form expressions suggest that an effective anisotropy energy or anisotropy-energy distribution can be determined from experimental scattering data. Received 8 November 2001     

Mechanochemical and magnetomechanical synthesis of hematite nanoparticles

Samples of hematite were exposed to mechanochemical activation by high energy ball milling for 0–27 h. The milling-induced changes to the structural and magnetic properties of hematite were characterized by X-ray diffraction (XRD) and Mössbauer spectroscopy. The particle size was found to decrease from 80 to 16.5 nm after 8 h of ball milling time, followed by a small increase to 19.8 nm at the end of the milling period. An overall expansion of the crystalline lattice parameters a and c with the milling time was deduced. The magnetic hyperfine field decreased with the ball milling time, from 51.46 down to 50.68 T after 27 h of grinding. Magnetite and traces of iron were observed at the longest milling time employed. The recoilless fraction (f ) was measured simultaneously using a dual Mössbauer absorber consisting of hematite and a stainless steel etalon. The f factor first decreased with the milling time due to occurrence of nanoparticles in the system, had a maximum at 12 h due to agglomerations of nanoparticles and exhibited a second maximum at 27 h, due to the appearance of magnetite in the system. More samples of hematite were subjected to magnetomechanical activation by magnetic ball milling for 52 and 134 h. A phase mixture of hematite and magnetite was observed.     

Synthesis and investigation of precipitated ensembles of magnetic nanoparticles with controlled easy axis orientation

Two samples with immobilized magnetic nanoparticles are synthesized and investigated. The first sample has randomly oriented easy axes of magnetic anisotropy; the second sample has preferentially aligned easy axes, produced via the precipitation of a colloid of ferromagnetic particles in the presence of a magnetic field. It is shown that the precipitation of an aqueous suspension of nanoparticles in the presence of a magnetic field greatly changes the anisotropy of a sample, compared to one prepared by precipitation without a magnetic field. The second sample exhibits a preferential direction of the easy axes of magnetic anisotropy that coincides with the direction of the external magnetic field applied in the drying process of sample preparation.     

Order-disorder transformation in FePt nanoparticles studied by ferromagnetic resonance

We have investigated the ferromagnetic resonance (FMR) response of as-made and temperature annealed FePt magnetic nanoparticles. The as-made nanoparticles, which have been fabricated by a chemical route, crystallize in the low magnetic anisotropy fcc phase and have a diameter in the range of 2-4 nm. The annealing of the particles at high temperatures (T_A=550, 650 and C) in an inert Ar atmosphere produces a partial transformation to the high magnetocrystalline anisotropy L1₀ phase, with a significant increase in particle size and size distribution. FMR measurements at X-band (9.5 GHz) and Q-band (34 GHz) show a single relatively narrow line for the as-synthesized particles and a structure of two superimposed lines for the three annealed samples. The origin of this line shape has been attributed to the presence of the disordered fcc phase. Assuming that the system consists of a collection of identical particles with a random distribution of easy axes, we have been able to estimate a mean value for the magnetic anisotropy constant of the particles in the fcc phase, K∼2×10⁶ erg/cm³. The measured line shape in the annealed samples can be explained if we consider that the magnetic anisotropy of the particles has a gaussian distribution with a relatively broad width.     

Specific features of magnetic properties of ferrihydrite nanoparticles of bacterial origin: A shift of the hysteresis loop

The results of the experimental investigation into the magnetic hysteresis of systems of superparamagnetic ferrihydrite nanoparticles of bacterial origin have been presented. The hysteresis properties of these objects are determined by the presence of an uncompensated magnetic moment in antiferromagnetic nanoparticles. It has been revealed that, under the conditions of cooling in an external magnetic field, there is a shift of the hysteresis loop with respect to the origin of the coordinates. These features are associated with the exchange coupling of the uncompensated magnetic moment and the antiferromagnetic “core” of the particles, as well as with processes similar to those responsible for the behavior of minor hysteresis loops due to strong local anisotropy fields of the ferrihydrite nanoparticles.     

Simultaneous SWAXS study of metallic and oxide nanostructured particles

In this work we investigate the magnetic properties of iron oxide nanoparticles obtained by two-step synthesis (seeded-growth route) with sizes that range from 6 to 18 nm. The initial seeds result monocrystalline and exhibit ferromagnetic behavior with low saturation field. The subsequent growth of a shell enhances the anisotropy inducing magnetic frustration, and, consequently, reducing its magnetization. This increase in anisotropy occurs suddenly at a certain size (~10 nm). Electronic and structural analysis with X-ray absorption spectroscopy indicates a step reduction in the oxidation state as the particle reaches 10 nm size while keeping its overall structure in spite of the magnetic polydispersity. The formation of antiphase magnetic boundaries due to island percolation in the growing shells is hypothesized to be the mechanism responsible of the magnetic behavior, as a direct consequence of the two-step synthesis route of the nanoparticles.     

Mobility of inorganic nanoparticles in soft matter

The 100 nm hematite Fe₂O₃ particles in gelatin gel, dense water solution of sugar, commercial paints, foam, cosmetic cream and friable powder exhibit the mobility in the range of mm/s which was determined from the analysis of the resonance absorption line shape. In the solution of sugar the movement is correlated for particle–particle distance less then 300 nm. The Mössbauer spectroscopy of the iron bearing nanoparticles is proposed as a novel experimental technique for the investigation of the dynamical and structural properties of the soft matter at the mesoscoipic scale.     

Resultant exchange bias and coercivity on rotatable antiferromagnetic anisotropy in ellipsoidal core/shell nanoparticles

A special consideration has been conducted on the dependencies of exchange bias and coercivity on rotatable antiferromagnetic anisotropy with respect to the collinear ferromagnetic anisotropy and field-cooling directions in ellipsoidal core/shell nanoparticles. With increasing the angle between antiferromagnetic and ferromagnetic easy axes, exchange bias field and coercivity both exhibit biaxial symmetries about the ferromagnetic easy and hard axes. Moreover, the variations of the antiferromagnetic anisotropy constant cannot change the trends of these novel behaviors, but only control their occurrences by dominating the coercive field behaviors. This new exchange-biased feature obtained by means of the special nanoparticle shape and the relative angle between anisotropies is of technological importance for maximizing exchange bias, in order to optimize the designs of the involved devices.     

Decoration of carbon nanotube with size-controlled L10-FePt nanoparticles for storage media

In this work, first multi-wall carbon nanotubes (MWCNTs) with outer diameter about 20–30 nm are synthesized by a CVD method; they have been purified and functionalized with a two-step process. The approach consists of thermal oxidation and subsequent chemical oxidation. Then, monosize FePt nanoparticles along carbon nanotubes surface are synthesized by a Polyol process. The synthesized FePt nanoparticles are about 2.5 nm in size and they have superparamagnetic behavior with fcc structure. The CNTs surfaces as a substrate prevent the coalescence of particles during thermal annealing. Annealing at the temperature higher than 600 ^°C for 2 h under a reducing atmosphere (90 % Ar + 10 % H₂) leads to phase transition from fcc to fct-L1₀ structure. So, the magnetic behavior changes from the superparamagnetic to the ferromagnetic. Furthermore, after the phase transition, the FePt nanoparticles have finite size with an average of about 3.5 nm and the coercivity of particles reaches 5.1 kOe.     

Uniform spin wave modes in antiferromagnetic nanoparticles with uncompensated moments

In magnetic nanoparticles the uniform precession (q = 0 spin wave) mode gives the predominant contribution to the magnetic excitations. We have calculated the energy of the uniform mode in antiferromagnetic nanoparticles with uncompensated magnetic moments, using the coherent potential approximation. In the presence of uncompensated moments, an antiferromagnetic nanoparticle must be considered as a kind of a ferrimagnet. Two magnetic anisotropy terms are considered, a planar term confining the spins to the basal plane, and an axial term determining an easy axis in this plane. Excitation energies are calculated for various combinations of these two anisotropy terms, ranging from the simple uniaxial case to the planar case with a strong out-of-plane anisotropy. In the simple uniaxial case, the uncompensated moment has a large influence on the excitation energy, but in the planar case it is much less important. The calculations explain recent neutron scattering measurements on nanoparticles of antiferromagnetic α-Fe₂O₃ and NiO.     

Role of the oxygen partial pressure in the formation of composite Co-CoO nanoparticles by reactive aggregation

The magnetic properties of diluted films composed of nanocomposite Co-CoO nanoparticles (of ~8 nm diameter) dispersed in a Cu matrix have been investigated. The nanoparticles were formed in an aggregation chamber by sputtering at different Ar/O₂ partial pressures (0?C0.015). The exchange-bias properties appear to be insensitive to the amount of O₂ during their formation. However, the temperature dependence of the magnetization, M(T), exhibits two different contributions with relative intensities that correlate with the amount of O₂. The magnetic results imply that two types of particles are formed, nanocomposite Co-CoO (determining the exchange-bias) and pure CoO, as confirmed by transmission electron microscopy observations. Importantly, as the O₂ partial pressure during the sputtering is raised the number of nanocomposite Co-CoO nanoparticles (exhibiting exchange-bias properties) is reduced and, consequently, there is an increase in the relative amount of pure, antiferromagnetic CoO particles.     

Magnetic nanoparticles as building blocks for high-performance magnetic materials

We report on the magnetic behaviour of films of Fe nanoparticles deposited from the gas phase with sizes in the range 2–3 nm embedded in Ag and Co matrices and Co nanoparticles of the same size embedded in Ag matrices. Magnetometry measurements, using a VSM, of very low volume fraction (1–2%) assemblies of Fe and Co in Ag show perfect superparamagnetism and enable us to confirm that the size distribution of the particles in the matrix is the same as that of the free particles prior to deposition. The hysteresis loops at 2 K, which is below the blocking temperature, show that the particles have a uniaxial anisotropy that is randomly oriented in three dimensions with the Co nanoparticles having a much higher anisotropy than the Fe particles. The soft magnetic behaviour of pure Fe and Co nanoparticle films with no matrix is well described by a random anisotropy model and is consistent with the formation of a correlated super-spin glass (CSSG) characteristic of amorphous materials. The Co nanoparticle films appear to have a lower random anisotropy than the Fe ones in contrast to the behaviour observed for the isolated particles. Films of Fe nanoparticles embedded in Co matrices, whose saturation magnetization exceeds the Slater–Pauling curve, also show magnetic behaviour consistent with a CSSG. At high volume fractions, the films of Fe nanoparticles embedded in Co matrices behave almost identically to films of pure Co nanoparticles.     

Macroscopic quantum effects observed in Mössbauer spectra of antiferromagnetic nanoparticles

The ⁵⁷Fe Mössbauer spectra of antiferromagnetic nanoparticles have been measured for almost half a century and often displayed a specific (non-superparamagnetic) temperature evolution of the spectral shape which looks like a quantum superposition of well-resolved magnetic hyperfine structure and single line or quadrupolar doublet of lines with the temperature-dependent partial spectral areas. We have developed a quantum-mechanical model for describing thermodynamic characteristics of an ensemble of ideal and “uncompensated” antiferromagnetic nanoparticles with uniaxial magnetic anisotropy in the first approximation of slowly relaxing macrospins of magnetic sublattices. This model allows one to qualitatively describe the macroscopic quantum effects observed in the Mössbauer spectra and to clarify principally the difference in thermodynamic properties of ferromagnetic and antiferromagnetic particles revealed in spectroscopic measurements.     

Growth and magnetic behavior of bismuth substituted yttrium iron garnet nanoparticles

Crystal growth and the magnetic properties of bismuth substituted yttrium iron garnet (Bi-YIG) nanoparticles were studied with particular focus on the bismuth composition dependence of the magnetic properties of the particles and the effects of annealing on the garnet phase formation. The Bi-YIG nanoparticles of 47–67 nm in size can be chemically synthesized when they are annealed at 650–850 °C. Both the lattice constant and the magnetization of the garnet nanoparticles linearly increase when the bismuth composition in the Bi-YIG particles increases. We have found that chemically synthesized nanoparticles transform from the amorphous to the garnet phase when annealed at temperatures below 650 °C, while the onset of magnetic moment of iron in the garnet nanoparticles is observed slightly above 650 °C. According to Mössbauer effect measurements, the hyperfine fields of ⁵⁷Fe at the tetrahedral and octahedral sites in the garnet are 39 and 48 T, respectively.     

Individual-collective crossover driven by particle size in dense assemblies of superparamagnetic nanoparticles

Prussian blue analogues (PBA) ferromagnetic nanoparticles Cs ^I _x Ni ^II [Cr ^III (CN)₆ ] _z ·3(H₂O) embedded in CTA⁺ (cetyltrimethylammonium) matrix have been investigated by magnetometry and magnetic small-angle neutron scattering (SANS). Choosing particle sizes (diameter D = 4.8 and 8.6 nm) well below the single-domain radius and comparable volume fraction of particle, we show that the expected superparamagnetic regime for weakly anisotropic isolated magnetic particles is drastically affected due to the interplay of surface/volume anisotropies and dipolar interactions. For the smallest particles (D = 4.8 nm), magnetocrystalline anisotropy is enhanced by surface spins and drives the system into a regime of ferromagnetically correlated clusters characterized by a temperature-dependent magnetic correlation length L _mag which is experimentally accessible using magnetic SANS. For D = 8.6 nm particles, a superparamagnetic regime is recovered in a wide temperature range. We propose a model of interacting single-domain particles with axial anisotropy that accounts quantitatively for the observed behaviors in both magnetic regimes.     

Mechanism of the formation of an uncompensated magnetic moment in bacterial ferrihydrite nanoparticles

The magnetic properties of antiferromagnetic nanoparticles of FeOOH · nH₂O with sizes of 3–7 nm, which are products of vital functions of Klebsiella oxytoca bacteria, have been studied. Particles exhibit a superparamagnetic behavior. The characteristic blocking temperature is 23 K. Analysis of the magnetization curves shows that the mechanism of the formation of the uncompensated magnetic moment of particles is the random decompensation of magnetic moments of Fe³⁺ ions both on the surface and in the bulk of the antiferromagnetic particle. In this mechanism, the exchange coupling between the uncompensated magnetic moment of the particle and its antiferromagnetic “core” is implemented. It has been found that the temperature dependence of the uncompensated magnetic moment has the form 1 — constT ².