Magnetic order and disorder environments in superantiferromagnetic [Formula: see text] nanoparticles.

Magnetic nanoparticles exhibit two different local symmetry environments, one ascribed to the core and one corresponding to the nanoparticle surface. This implies the existence of a dual spin dynamics, leading to the presence of two different magnetic arrangements governed by different correlation lengths. In this work, two ensembles of [Formula: see text] nanoparticles with mean sizes of 18 nm and 13 nm have been produced to unravel the magnetic couplings established among the magnetic moments located within the core and at the nanoparticle surface. To this end, we have combined neutron diffraction measurements, appropriate to investigate magnetically-ordered spin arrangements, with time-dependent macroscopic AC susceptibility measurements to reveal memory and aging effects. The observation of the latter phenomena are indicative of magnetically-frustrated states. The obtained results indicate that, while the [Formula: see text] magnetic moments located within the nanoparticle core keep the bulk antiferromagnetic commensurate structure in the whole magnetic state, the correlations among the surface spins give rise to a collective frustrated spin-glass phase. The interpretation of the magnetic structure of the nanoparticles is complemented by specific-heat measurements, which further support the lack of incommensurability in the nanoparticle state.

Configuration of the magnetosome chain: a natural magnetic nanoarchitecture.

Magnetospirillum gryphiswaldense is a microorganism with the ability to biomineralize magnetite nanoparticles, called magnetosomes, and arrange them into a chain that behaves like a magnetic compass. Rather than straight lines, magnetosome chains are slightly bent, as evidenced by electron cryotomography. Our experimental and theoretical results suggest that due to the competition between the magnetocrystalline and shape anisotropies, the effective magnetic moment of individual magnetosomes is tilted out of the [111] crystallographic easy axis of magnetite. This tilt does not affect the direction of the chain net magnetic moment, which remains along the [111] axis, but explains the arrangement of magnetosomes in helical-like shaped chains. Indeed, we demonstrate that the chain shape can be reproduced by considering an interplay between the magnetic dipolar interactions between magnetosomes, ruled by the orientation of the magnetosome magnetic moment, and a lipid/protein-based mechanism, modeled as an elastic recovery force exerted on the magnetosomes.

Breakdown of the coherence effects and Fermi liquid behavior in YbAl3 nanoparticles.

A change in the Kondo lattice behavior of bulk YbAl3 has been observed when the alloy is shaped into nanoparticles (≈12 nm). Measurements of the electrical resistivity show inhibited coherence effects and deviation from the standard Fermi liquid behavior (T 2-dependence). These results are interpreted as being due to the effect of the disruption of the periodicity of the array of Kondo ions provoked by the size reduction process. Additionally, the ensemble of randomly placed nanoparticles also triggers an extra source of electronic scattering at very low temperatures (≈15 K) due to quantum interference effects.

Magnetization reversal in circular vortex dots of small radius.

We present a detailed study of the magnetic behavior of Permalloy (Ni80Fe20 alloy) circular nanodots with small radii (30 nm and 70 nm) and different thicknesses (30 nm or 50 nm). Despite the small size of the dots, the measured hysteresis loops manifestly display the features of classical vortex behavior with zero remanence and lobes at high magnetic fields. This is remarkable because the size of the magnetic vortex core is comparable to the dot diameter, as revealed by magnetic force microscopy and micromagnetic simulations. The dot ground states are close to the border of the vortex stability and, depending on the dot size, the magnetization distribution combines attributes of the typical vortex, single domain states or even presents features resembling magnetic skyrmions. An analytical model of the dot magnetization reversal, accounting for the large vortex core size, is developed to explain the observed behavior, providing a rather good agreement with the experimental results. The study extends the understanding of magnetic nanodots beyond the classical vortex concept (where the vortex core spins have a negligible influence on the magnetic behavior) and can therefore be useful for improving emerging spintronic applications, such as spin-torque nano-oscillators. It also delimits the feasibility of producing a well-defined vortex configuration in sub-100 nm dots, enabling the intracellular magneto-mechanical actuation for biomedical applications.

Influence of the bacterial growth phase on the magnetic properties of magnetosomes synthesized by Magnetospirillum gryphiswaldense.

BACKGROUND: The magnetosome biosynthesis is a genetically controlled process but the physical properties of the magnetosomes can be slightly tuned by modifying the bacterial growth conditions. METHODS: We designed two time-resolved experiments in which iron-starved bacteria at the mid-logarithmic phase are transferred to Fe-supplemented medium to induce the magnetosomes biogenesis along the exponential growth or at the stationary phase. We used flow cytometry to determine the cell concentration, transmission electron microscopy to image the magnetosomes, DC and AC magnetometry methods for the magnetic characterization, and X-ray absorption spectroscopy to analyze the magnetosome structure. RESULTS: When the magnetosomes synthesis occurs during the exponential growth phase, they reach larger sizes and higher monodispersity, displaying a stoichiometric magnetite structure, as fingerprinted by the well defined Verwey temperature. On the contrary, the magnetosomes synthesized at the stationary phase reach smaller sizes and display a smeared Verwey transition, that suggests that these magnetosomes may deviate slightly from the perfect stoichiometry. CONCLUSIONS: Magnetosomes magnetically closer to stoichiometric magnetite are obtained when bacteria start synthesizing them at the exponential growth phase rather than at the stationary phase. GENERAL SIGNIFICANCE: The growth conditions influence the final properties of the biosynthesized magnetosomes. This article is part of a Special Issue entitled "Recent Advances in Bionanomaterials" Guest Editors: Dr. Marie-Louise Saboungi and Dr. Samuel D. Bader.

Interacting Superparamagnetic Iron(II) Oxide Nanoparticles: Synthesis and Characterization in Ionic Liquids.

Interacting superparamagnetic iron(II) oxide nanoparticles (NPs) with sizes of 5.3 ± 1.6 nm were prepared by simple decomposition of [Fe(COT)2] (COT = 1,3,5,7-cyclooctatetraene) with 5 bar of H2 in 1-n-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMI·NTf2) ionic liquid (IL). The static and dynamic magnetic characterization revealed a superparamagnetic behavior with weak dipolar interactions of these NPs. In situ structural studies by X-ray absorption spectroscopy demonstrated that they consist of nanostructured FeO. This approach is an appropriate method to prepare and stabilize nanostructured FeO particles, where the presence of an IL proved to be fundamental to suppress the aggregation and usual overoxidation of the FeO NPs.

Magnetic phase diagram of superantiferromagnetic TbCu2 nanoparticles.

The structural state and static and dynamic magnetic properties of TbCu2 nanoparticles are reported to be produced by mechanical milling under inert atmosphere. The randomly dispersed nanoparticles as detected by TEM retain the bulk symmetry with an orthorhombic Imma lattice and Tb and Cu in the 4e and 8h positions, respectively. Rietveld refinements confirm that the milling produces a controlled reduction of particle sizes reaching ≃6 nm and an increase of the microstrain up to ≃0.6%. The electrical resistivity indicates a metallic behavior and the presence of a magnetic contribution to the electronic scattering which decreases with milling times. The dc-susceptibility shows a reduction of the Néel transition (from 49 K to 43 K) and a progressive increase of a peak (from 9 K to 15 K) in the zero-field-cooled magnetization with size reduction. The exchange anisotropy is very weak (a bias field of ≃30 Oe) and is due to the presence of a disordered (thin) shell coupled to the antiferromagnetic core. The dynamic susceptibility evidences a critical slowing down in the spin-disordered state for the lowest temperature peak associated with a spin glass-like freezing with a tendency of zv and ß exponents to increase when the size becomes 6 nm (zv ≃ 6.6 and ß ≃ 0.85). A Rietveld analysis of the neutron diffraction patterns 1.8 ≤ T ≤ 60 K, including the magnetic structure determination, reveals that there is a reduction of the expected moment (≃80%), which must be connected to the presence of the disordered particle shell. The core magnetic structure retains the bulk antiferromagnetic arrangement. The overall interpretation is based on a superantiferromagnetic behavior which at low temperatures coexists with a canting of surface moments and a mismatch of the antiferromagnetic sublattices of the nanoparticles. We propose a novel magnetic phase diagram where changes are provoked by a combination of the decrease of size and the increase of microstrain.

Interplay between microstructure and magnetism in NiO nanoparticles: breakdown of the antiferromagnetic order.

The possibility of tuning the magnetic behaviour of nanostructured 3d transition metal oxides has opened up the path for extensive research activity in the nanoscale world. In this work we report on how the antiferromagnetism of a bulk material can be broken when reducing its size under a given threshold. We combined X-ray diffraction, high-resolution transmission electron microscopy, extended X-ray absorption fine structure and magnetic measurements in order to describe the influence of the microstructure and morphology on the magnetic behaviour of NiO nanoparticles (NPs) with sizes ranging from 2.5 to 9 nm. The present findings reveal that size effects induce surface spin frustration which competes with the expected antiferromagnetic (AFM) order, typical of bulk NiO, giving rise to a threshold size for the AFM phase to nucleate. Ni(2+) magnetic moments in 2.5 nm NPs seem to be in a spin glass (SG) state, whereas larger NPs are formed by an uncompensated AFM core with a net magnetic moment surrounded by a SG shell. The coupling at the core-shell interface leads to an exchange bias effect manifested at low temperature as horizontal shifts of the hysteresis loop (~1 kOe) and a coercivity enhancement (~0.2 kOe).

Magnetic disorder in diluted FexM100-x granular thin films (M=Au, Ag, Cu; x < 10 at.%).

Nanogranular thin films of Fe7Au93, Fe7Ag93 and Fe9Cu91 have been sputtered onto Si(100) substrates with the aim of studying the magnetic interactions. X-ray diffraction shows a major noble metal matrix with broad peaks stemming from (111) textured fcc-Au, Ag and Cu. The noble metal forms a nanogranular environment, as confirmed by transmission electron microscopy, with mean particle sizes below 10 nm. The high magnetoresistance (>6%) reveals the existence of Fe nanoparticles. X-ray absorption near edge spectroscopy confirms the presence of a bcc-Fe atom arrangement and some dissolved Fe atoms in the matrix, and XMCD shows the polarization of Au by the Fe nanoparticles. DC-magnetization displays a field-dependent irreversibility produced by the freezing of magnetic nanoparticles into a superspin-glass state. The hysteresis loops remain unsaturated at 5 K and 45 kOe. The coercivity displays a sharp temperature decrease towards a minimum below 50 K, levelling off at higher values, reaching Hc = 200 Oe at 300 K. Annealing of FeAu results in a double-peak zero field cooled magnetization and a slight decrease of the coercivity. The interpretation of the results supports the presence of Fe nanoparticles embedded in the major noble matrix, with some diluted Fe atoms/clusters.

Magnetic properties of TbAl2 nanometric alloys.

The magnetic properties of nanometric TbAI2 alloys have been investigated. The Curie temperature (T(c)) of these nanometric alloys is strongly size dependent and decreases from 103 K for the bulk alloy down to 98 K for the 14 nm alloy, as the particle volume is reduced. This reduction of T(c) has been explained by a finite-size scaling law of type [T(c)(D) -T(c)(infinity)]/T(c)(infinity) = -(D/D0)-(1/vp), with v = 0.7 and D0 = 2.2a (a, the lattice parameter), in agreement with the three-dimensional Heisenberg model. The size dependence of the coercivity has also been established. An increase of the coercivity from 0.08 kOe (bulk) to 1 kOe for 10 h milled alloy, indicates the crossover from multidomain to single domain behavior around 85 nm, as expected from the estimate of the critical size of monodomain particles. The field dependence of the magnetization indicates a faster thermal reduction of the magnetization of the nanosized alloys (17% in 300 h milled alloy with mean particle size of 14 nm) related to the bulk (3%), in the temperature range between 5 K and 30 K. The results can be explained as a direct consequence of the competing effects of the surface and the purely finite-size effects, in an ensemble of nanometric particles suffering interactions.

Poly(methyl methacrylate) coating of soft magnetic amorphous and crystalline Fe,Co-B nanoparticles by chemical reduction.

The structural and magnetic properties of a collection of nanoparticles coated by Poly(methyl methacrylate) through a wet chemical synthesis have been investigated. The particles display either an amorphous (M = Fe, Co) M-B arrangement or a mixed structure bcc-Fe and fcc-Co + amorphous M-B. Both show the presence of a metal oxi-hydroxide formed in aqueous reduction. The organic coating facilitates technological handling. The cost-effective synthesis involves a reduction in a Poly(methyl methacrylate) aqueous solution of iron(II) or cobalt(II) sulphates (< 0.5 M) by sodium borohydride (< 0.5 M). The particles present an oxidized component, as deduced from X-ray diffraction, Mössbauer and Fe- and Co K-edge X-ray absorption spectroscopy and electron microscopy. For the ferrous alloys, this Fe-oxide is alpha-goethite, favoured by the aqueous solution. The Poly(methyl methacrylate) coating is confirmed by Fourier transform infrared spectroscopy. In pure amorphous core alloys there is a drastic change of the coercivity from bulk to around 30 Oe in the nanoparticles. The mixed structured alloys also lie in the soft magnetic regime. Magnetisation values at room temperature range around 100 emu/g. The coercivity stems from multidomain particles and their agglomeration, triggering the dipolar interactions.

Interfacial magnetic coupling between Fe nanoparticles in Fe­Ag granular alloys.

The role of the interface in mediating interparticle magnetic interactions has been analysed in Fe50Ag50 and Fe55Ag45 granular thin films deposited by the pulsed laser deposition technique (PLD). These samples are composed of crystalline bcc Fe (2­4 nm) nanoparticles and fcc Ag (10­12 nm) nanoparticles, separated by an amorphous Fe50Ag50 interface, occupying around 20% of the sample volume, as determined by x-ray diffraction (XRD), x-ray absorption spectroscopy (XAS), and high resolution transmission electron microscopy (HRTEM). Interfacial magnetic coupling between Fe nanoparticles is studied by dc magnetization and x-ray magnetic circular dichroism (XMCD) measurements at the Fe K and Ag L2,3 edges. This paper reveals that these thin films present two magnetic transitions, at low and high temperatures, which are strongly related to the magnetic state of the amorphous interface, which acts as a barrier for interparticle magnetic coupling.

Phonon softening on the specific heat of nanocrystalline metals.

Specific heat enhancement in several common nanocrystalline metals is established by comparison with their bulk counterparts. Measurements were carried out in Fe, Cu, Ni and binary alloy LaAl(2). The excess specific heat is evidenced as a low temperature peak below 65 K and a high temperature slope above 150 K. The experimental data are in good agreement with a model which considers contributions from the grain boundary and core atoms in the nanoparticles. This model is supported by Raman spectroscopy measurements, showing a softening of the frequency phonon modes associated with a size reduction and increase of the atomic disorder.

Size effects in the magnetic behaviour of TbAl(2) milled alloys.

The study of the magnetic properties depending upon mechanical milling of the ferromagnetic polycrystalline TbAl(2) material is reported. Rietveld analysis of the x-ray diffraction data reveals a decrease in the grain size down to 14 nm and a -0.15% variation in the lattice parameter, after 300 h of milling time. Irreversibility in the zero field cooled-field cooled (ZFC-FC) dc susceptibility and clear peaks in the ac susceptibility between 5 and 300 K show that the long-range ferromagnetic structure is inhibited in favour of a disordered spin arrangement below 45 K. This glassy behaviour is also deduced from the variation of the irreversibility transition with the field (H(2/3)) and frequency. The magnetization process of the bulk TbAl(2) is governed by domain-wall thermal activation processes. In contrast, in the milled samples, cluster-glass properties arise as a result of cooperative interactions due to the substitutional disorder. The interactions are also influenced by the nanograin structure of the milled alloys, showing a variation in coercivity with the grain size, below the crossover between the multi- and single-domain behaviours.