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Hypothesis Some of the most promising fields of application of ionic liquid-based colloids imply elevated temperatures. Their careful design and analysis is therefore essential. We assume that tuning the structure of the nanoparticle-ionic liquid interface through its composition can ensure colloidal stability for a wide temperature range, from room temperature up to 200 °C. Experiments The system under study consists of iron oxide nanoparticles (NPs) dispersed in ethylmethylimidazolium bistriflimide (EMIM TFSI). The key parameters of the solid-liquid interface, tuned at room temperature, are the surface charge density and the nature of the counterions. The thermal stability of these nanoparticle dispersions is then analysed on the short and long term up to 200 °C. A multiscale analysis is performed combining dynamic light scattering (DLS), small angle X-ray/neutron scattering (SAXS/SANS) and thermogravimetric analysis (TGA). Findings Following the proposed approach with a careful choice of the species at the solid-liquid interface, ionic liquid-based colloidal dispersions of iron oxide NPs in EMIM TFSI stable over years at room temperature can be obtained, also stable at least over days up to 200 °C and NPs concentrations up to 12 vol% ( ≈ 30 wt%) thanks to few near-surface ionic layers.

Amesoscopic scale approach and the Monte Carlo (MC)method have been employed to study the exchange bias behaviour of MnFe2O4 (soft)/maghemite (soft) and CoFe2O4 (hard)/maghemite (soft) nanoparticles (NPs) of size ~ 3nm in dense and diluted assemblies at low temperatures. The analysis of our MC results clearly shows that in the powder samples the contribution to the exchange bias field (Hex) and the coercivity (Hc) comes mainly from the intraparticle core/shell structure in the hard/soft sample and that the interplay between the internal characteristics and the interparticle interactions is more important in the soft/soft samples where the dipolar strength is enhanced. In the diluted frozen ferrofluid samples where interparticle exchange interactions are absent and the role of the dipolar interactions is not significant the exchange bias effects are reduced, and they come from the intra particle structure. The variation of Hex and Hc with the applied cooling field well reproduces the experimental findings and sheds light on the key mechanisms of the observed magnetic behaviour. Our results demonstrate the possibility to control the magnetic behaviour of nanostructures by using properly chosen core/shell bimagnetic nanoparticles.

Dispersions of charged maghemite nanoparticles (NPs) in EAN (ethylammonium nitrate) a reference Ionic Liquid (IL), are here studied using a number of static and dynamical experimental techniques; Small Angle Scattering (SAS) of X-rays and of Neutrons, Dynamical Light Scattering and Forced Rayleigh Scattering. A particular insight is given to the importance of tuning the ionic species present at the interface NP /IL; In this work we compare the effect of Na+, Rb+ or Li+ ions. The nature of these species have here an influence on the short-range spatial organization of the ions at the interface and thus on the colloidal stability of the dispersions. They govern both the NP/NP and the NP/IL interaction, which are here both characterized. The short-range global NP/NP interaction is either attractive or repulsive. It is characterized by the determination of the second virial coefficient A2 thanks to the SAS techniques and which is found independent of temperature. The NP/IL interaction is characterized by the dynamical effective charge ξoeff of the NPs and by their entropy of transfer SˆNP determined here thanks to thermoelectric and thermodiffusive measurements. For repulsive systems, a temperature dependence through an activated process is obtained for these two latter quantities.

The effect of an excess of surfactant on the thermophoresis of a sterically stabilized ferrofluid is investigated experimentally by forced Rayleigh scattering (FRS). The experiments are performed with a stable magnetic fluid sample to which controlled amounts of surfactant are added. A decrease in the thermally induced transport of magnetic nanoparticles is observed while increasing the temperature T. The positive Soret coefficient [Formula: see text] decreases by adding 2 vol% of surfactant at room temperature. As shown by FRS relaxation, this decreasing is mainly associated with a reduction of the interaction between the carrier fluid and individual nanoparticles. No significant effect of extra surfactant on the sign of [Formula: see text] is observed at higher T's (up to [Formula: see text]C). Dynamic light scattering at room temperature reveals the presence of a small amount of clusters/aggregates in the samples, which are hardly detectable by FRS relaxation. The presence of these small clusters/aggregates is confirmed by a rheological probing of the fluid properties. Whatever T, a small amount of added surfactant first causes a decrease of the ferrofluid viscosity, associated with a 10% decreasing of the flow activation energy. Further on, viscosity and activation energy both recover at higher excess surfactant concentrations. These results are analyzed in terms of saturation of the surfactant layer, concentration of free surfactant chains and heat of transport of the nanoparticles.

We investigate the local structure of nanoparticles based on cobalt ferrite core with and without a hydrothermal surface treatment of variable duration of time that promotes a coating shell by crossing information obtained from atomic absorption spectroscopy (AAS), X-ray powder diffraction (XRD), neutron powder diffraction (NPD), and X-ray absorption spectroscopy (XAS) measurements. Chemical titration results show that the surface layer thickness increases as the duration of the surface treatment increases. The cation distribution obtained by Rietveld refinement of NPD patterns allows splitting the core and shell structural parameters obtained from Rietveld refinement of XRD data of the samples well described in a core-shell model. We follow the local structural evolution with the surface treatment time analyzing both XANES and EXAFS regions of the absorption spectrum. As a result, we observe that the surface treatment is not energetically strong enough to provoke changes on the mean oxidation states of the cations in the spinel structure; indeed, the interatomic distances are similar to those found in bulk materials and the inversion degree remains the same after the surface treatment, in good accordance with the cation distribution obtained by Rietveld refinement of NPD data.

The use of ionic liquid-based colloids at elevated temperatures is one of their most promising fields of application. However long term stability on the whole range of temperature is mandatory. First a detailed study on colloidal dispersions of iron oxide nanoparticles in EMIM TFSI is performed at room temperature in order to determine the best solid/liquid interface. The previously identified key parameters are tuned: the surface charge density and the nature of the counterions. Here a sulfonate based imidazolium ion is chosen. In a second step, the thermal stability of these nanoparticle dispersions is analysed on the short and long term up to 473 K (200◦C) combining dynamic light scattering (DLS), small angle X-ray/neutron scattering (SAXS/SANS) and thermogravimetric analysis (TGA). Ionic liquid-based colloidal dispersions of iron oxide nanoparticles in EMIM TFSI stable in the long term can be obtained at least up to 473 K and nanoparticle concentrations of 12 vol% (≈30wt%)

Exchange bias properties of MnFe$$_2$$ 2 O$$_4$$ 4 @$$\gamma$$ γ –Fe$$_2$$ 2 O$$_3$$ 3 core–shell nanoparticles are investigated. The measured field and temperature dependencies of the magnetization point out a well-ordered ferrimagnetic core surrounded by a layer with spin glass-like arrangement. Quasi-static SQUID magnetization measurements are presented along with high-amplitude pulse ones and are cross-analyzed by comparison against ferromagnetic resonance experiments at 9 GHz. These measurements allow one to discern three types of magnetic anisotropies affecting the dynamics of the magnetic moment of the well-ordered ferrimagnetic NP’s core viz. the easy-axis (uniaxial) anisotropy, the unidirectional exchange-bias anisotropy and the rotatable anisotropy. The uniaxial anisotropy originates from the structural core–shell interface. The unidirectional exchange-bias anisotropy is associated with the spin-coupling at the ferrimagnetic/spin glass-like interface; it is observable only at low temperatures after a field-cooling process. The rotatable anisotropy is caused by partially-pinned spins at the core/shell interface; it manifests itself as an intrinsic field always parallel to the external applied magnetic field. The whole set of experimental results is interpreted in the framework of superparamagnetic theory, i.e., essentially taking into account the effect of thermal fluctuations on the magnetic moment of the particle core. In particular, it is found that the rotatable anisotropy of our system is of a uniaxial type.

International audience; Ferrofluids based on maghemite nanoparticles (NPs), typically 10 nm in diameter, are dispersed in an ionic liquid (1-ethyl 3-methylimidazolium bistriflimide - EMIM-TFSI). The average interparticle interaction is found to be repulsive by small angle scattering of X-rays and of neutrons, with a second virial coefficient A2 = 7.3. A moderately concentrated sample at Φ = 5.95 vol% is probed by forced Rayleigh scattering under an applied magnetic field (up to H = 100 kA m-1) from room temperature up to T = 460 K. Irrespective of the values of H and T, the NPs in this study are always found to migrate towards the cold region. The in-field anisotropy of the mass diffusion coefficient Dm and that of the (always positive) Soret coefficient ST are well described by the presented model in the whole range of H and T. The main origin of anisotropy is the spatial inhomogeneities of concentration in the ferrofluid along the direction of the applied field. Since this effect originates from the magnetic dipolar interparticle interaction, the anisotropy of thermodiffusion progressively vanishes when temperature and thermal motion increase.

Stimuli-responsive compartments are attracting more and more attention through the years motivated by their wide applications in different fields including encapsulation, manipulation, and triggering of chemical reactions on demand. Among others, magnetic responsive compartments are particularly attractive due to the numerous advantages of magnetic fields compared to other external stimuli. In this article, we used an oil-based ferrofluid where the magnetic nanoparticles have been coated with different polymers to increase their amphiphilic character and surface activity, consequently rendering the interface magnetically responsive. Microliter aqueous nonmagnetic droplets dispersed in the oil-based ferrofluid were used as a model of microreactors. A comprehensive experimental and theoretical study of the deformation, attraction, and coalescence processes of the nonmagnetic water droplets coated with the magnetic nanoparticles under an applied magnetic field in the continuous oil-based ferrofluid phase is provided. To manipulate the packing of the nanoparticles at the water/oil interface, the ionic strength of the aqueous droplets was varied using different NaCl concentrations, and its effect on modulating the coalescence of the droplets was probed. Our results show that the water droplets deform along the magnetic field depending on the magnetic properties of the ferrofluid itself and on the surface properties of the interface, attract in pairs under the action of the magnetic dipole force, and coalesce by the action of the same force with a stochastic behavior. We have studied all of these phenomena as a function of the magnetic field applied, evaluating in each case the forces and/or pressures acting on the droplets with particular attention to roles of magnetic attraction, interface properties, and viscosity in the system. This work offers an overall set of tools to understand and predict the behavior of multiple water droplets in an oil-based ferrofluid for lab-on-a-chip applications.

International audience; The mixture of choline chloride and ethyleneglycol ((1:3) on the molar scale) is first characterized using density, viscosimetry and refractive index measurements, in the temperature range 20–45°C, with controlled amounts of water. Thermodynamic parameters such as the activation entropy, enthalpy and Gibbs energy for the viscous flow are deduced from the data and show that the solvent is highly structured. A protocol to disperse in this solvent 10 nm maghemite nanoparticles previously synthesized in water is described. The good quality of the dispersion is assessed by visual observations, optical microscopy, small angle X-ray scattering (SAXS), magnetization measurements, viscosimetry, and light scattering. The results lead to the description of a local viscosity around the particles, lower than the macroscopic one, that could be the result of the solvent segregation with ethyleneglycol being mostly present in the close vicinity of the particles.

We report on the suitability of core/shell nanoparticles (NPs) for magnetic fluid hyperthermia in a self-regulated and theranostic approach. Aqueous magnetic colloids based on core/shell ZnxMnyFezO4@γ-Fe2O3 and ZnxCoyFezO4@γ-Fe2O3 NPs were produced by a three-step chemical synthesis. Systematic deviations from stoichiometry were observed with increasing Zn substitution for both series of samples. We investigated how the chemical composition affects the saturation magnetization, magnetic anisotropy, and thermomagnetic properties of these core/shell NPs. The heating efficiency through specific power absorption (SPA) was analyzed in the framework of the linear response theory. SPA values obtained for NPs present a different contrast of anisotropy between the core and shell materials, indicating no evidence of the contribution of enhanced exchange coupling to the heating efficiency.

We focus here on the relationship between the physicochemical properties of electrostatically stabilized colloidal dispersions and the nanoparticles/solvent interface. Dispersions of maghemite (γ-Fe2O3) in polar solvents, here water and dimethyl sulfoxide (DMSO), are prepared with a new process that enables tuning easily this interface. Departing from the point of zero charge (PZC), the nanoparticles (NPs) are charged in a controlled way by adding acid or base. This pathway enables control of the surface state of the nanoparticles, i.e., the NP’s charge and the nature of the counterions, as well as the amount of free electrolyte in the dispersion. Stable dispersions are obtained because of electrostatic repulsion, in water and in DMSO, with electrolyte concentrations up to 20–40 mM. Small angle X-ray scattering (SAXS) and dynamic light scattering (DLS) techniques are here applied to concentrated dispersions in order to understand the nanostructure and quantify the interparticle interactions. Specific ioni...

International audience; The combination of ionic liquid and nanoparticle properties is highly appealing for a number of applications. However, thus far there has been limited systematic exploration of colloidal stabilisation in these solvents, which provides an initial direction towards their employment. Here, we present a new and comprehensive study of the key parameters affecting the colloidal stability in dispersions of oxide nanoparticles in ionic liquids. Twelve diverse and representative ionic liquids are used to disperse iron oxide nanoparticles. The liquid interface of these nanoparticles has been carefully tuned in a molecular solvent before transferring into an ionic liquid, without passing through the powder state. Multiscale-characterisation is applied, on both the micro and the nano scale, incorporating both small angle X-ray scattering and dynamic light scattering. The results show the surface charge of the nanoparticles to be a crucial parameter, controlling the layering of the surrounding ionic liquid, and hence producing repulsion allowing efficient counterbalancing of the attractive interactions. For intermediate charges the strength of the repulsion depends on the specific system causing varying levels of aggregation or even none at all. Several samples consist of sufficiently repulsive systems leading to single dispersed nanoparticles, stable in the long term. Thanks to the magnetic properties of the chosen iron oxide nanoparticles, true ferrofluids are produced, appropriate for applications using magnetic fields. The strength and breadth of the observed trends suggests that the key parameters identified here can be generalised to most ionic liquids.

We have studied the charge distribution in the γ-Fe2O3interface with H2O, for two different structures (films and spherical nanoparticles) with Density functional (DFT) molecular dynamics calculations. Our results show that the adsorption energy depends on the shape of the surface and in the case of the films also on the orientation of the crystal and that the ionic state of iron atoms increases with the addition of water in both structures while the magnetic moments of the structures do not show any significant change. The mean displacement of the charge with temperature is significant only in the spherical nanoparticles. The average electrostatic potential decreases with the addition of water and shows an oscillatory behavior near the surface.

The influence of the magnetic field on the Seebeck coefficient (Se) was investigated in dilute magnetic nanofluids (ferrofluids) composed of maghemite magnetic nanoparticles dispersed in dimethyl-sulfoxide (DMSO). A 25% increase in the Se value was found when the external magnetic field was applied perpendicularly to the temperature gradient, reminiscent of an increase in the Soret coefficient (ST, concentration gradient) observed in the same fluids. In-depth analysis of experimental data, however, revealed that different mechanisms are responsible for the observed magneto-thermoelectric and -thermodiffusive phenomena. Possible physical and physico-chemical origins leading to the enhancement of the fluids' Seebeck coefficient are discussed.

Thermodiffusion properties at room temperature of colloidal dispersions of hydroxyl-coated nanoparticles (NPs) are probed in water, in dimethyl sulfoxide (DMSO) and in mixtures of water and DMSO at various proportions of water, [Formula: see text]. In these polar solvents, the positive NPs superficial charge imparts the systems with a strong electrostatic interparticle repulsion, slightly decreasing from water to DMSO, which is here probed by Small Angle Neutron Scattering and Dynamic Light Scattering. However if submitted to a gradient of temperature, the NPs dispersed in water with ClO4- counterions present a thermophilic behavior, the same NPs dispersed in DMSO with the same counterions present a thermophobic behavior. Mass diffusion coefficient [Formula: see text] and Ludwig-Soret coefficient [Formula: see text] are measured as a function of NP volume fraction [Formula: see text] at various [Formula: see text]. The [Formula: see text]-dependence of [Formula: see text] is analyzed in terms of thermoelectric and thermophoretic contributions as a function of [Formula: see text]. Using two different models for evaluating the Eastman entropy of transfer of the co- and counterions in the mixtures, the single-particle thermophoretic contribution (the NP's Eastman entropy of transfer) is deduced. It is found to evolve from negative in water to positive in DMSO. It is close to zero on a large range of [Formula: see text] values, meaning that in this [Formula: see text]-range [Formula: see text] largely depends on the thermoelectric effect of free co- and counterions.

International audience; Under a temperature gradient, the direction of thermodiffusion of charged g Fe 2 O 3 nanoparticles (NPs) depends on the nature of the counter-ions present in the dispersion, resulting in either positive or negative Soret coefficient. Various counter-ions are probed in finely tuned and well characterized dispersions of citrate-coated NPs at comparable concentrations of free ionic species. The Soret coefficient S T is measured in stationary conditions together with the mass-diffusion coefficient D m using a Forced Rayleigh Scattering method. The strong interparticle repulsion, determined by SAXS, is also attested by the increase of D m with NP's volume fraction F. The F-dependence of S T is analyzed in terms of thermophoretic and thermoelectric contributions of the various ionic species. The obtained single-particle thermophoretic contribution of the NPs (the Eastman entropy of transferŜ NP) varies linearly with the entropy of transfer of the counter-ions. This is understood in terms of electrostatic contribution and of hydration of the ionic shell surrounding the NPs. Two aqueous dispersions, respectively with S T > 0 and with S T < 0 are then probed under an applied fieldH, an anisotropy of D m and of S T is induced while the in-field system remains monophasic. Whatever theH-direction (parallel or perpendicular to the gradients-T and-F), the Soret coefficient is modulated keeping the same sign as in zero applied field. In-field experimental determinations are well described using a mean field model of the interparticle magnetic interaction.

Ensembles of elongated magnetic droplets in a rotating field are studied experimentally. In a given range of field strength and frequency the droplets form rotating structures with a triangular order - rotating crystals. A model is developed to describe ensembles of several droplets, taking into account the hydrodynamic interactions between the rotating droplets in the presence of a solid wall below the rotating ensemble. A good agreement with the experimentally observed periodic dynamics for an ensemble of four droplets is obtained. During the rotation, the tips of the elongated magnetic droplets approach close to one another. An expression is derived that gives the magnetic interaction between such droplets by taking into account the coulombian forces between magnetic charges on the droplet tips., Comment: Submitted to JMMM for ICMF2019 special issue

Energy input by under-field rotation of particles drives the systems to emergent non-equilibrium states. Here we investigate the suspension of rotating magnetic cubes. Micron-sized hematite cubes are synthesized and observed microscopically. When exposed to a rotating magnetic field, they form rotating swarms that interact with each other like liquid droplets. We describe the swarming behaviour and its limits and characterize swarm size and angular velocity dependence on magnetic field strength and frequency. A quantitative agreement with a theoretical model is found for the angular velocity of swarms as a function of field frequency. It is interesting to note that hematite particles with peanut or ellipsoidal shapes do not form swarms., Comment: submitted to JMMM for ICMF2019 special issue. Uses Elsevier template

Ultrasmall magnetic particles are notorious for exhibiting a magnetization increase even at quite intense applied fields, behavior which can be interpreted as a non-saturation of the magnetic disordered shell even if the nanoparticle magnetization is reversible. In this work we study two kinds of ultrasmall core@shell nanoparticles (3 nm) with contrasting core anisotropy, composed of MnFe2O4 and CoFe2O4 cores covered by a thin maghemite layer. In order to investigate the saturation criterion associated to the closure of major loops (in contrast to minor loops), we use several procedures to determine, at moderate fields, if the effective anisotropy energy barrier is overcome or not. Firstly, we carefully evaluate the closure field of the hysteresis loop, interpreted as the effective anisotropy field, correspondent to two different contributions. One, arising from the nanoparticle core, is related to the coercivity and the other one is associated to pinned spins of the nanoparticle shell. Secondly, the ZFC-FC magnetization measurements taken at different fields give us information about both the anisotropy energy barrier distribution and the thermal dependence of effective anisotropy field. Thirdly, forced minor loops are performed, measured after either ZFC or FC processes, to counter-check the effective magnetic anisotropy at low temperature of both samples. Finally, we perform major hysteresis loop calculations in order to better understand the magnetization processes involved. To go further, we propose in this study a procedure to extract information about the two contributions which composes the effective magnetic anisotropy field.

An analytical model describing the thermoelectric potential production in magnetic nanofluids (dispersions of magnetic and charged colloidal particles in liquid media) is presented. The two major entropy sources, the thermogalvanic and thermodiffusion processes are considered. The thermodiffusion term is described in terms of three physical parameters; the diffusion coefficient, the Eastman entropy of transfer and the electrophoretic charge number of colloidal particles, which all depend on the particle concentration and the applied magnetic field strength and direction. The results are combined with well-known formulation of thermoelectric potential in thermogalvanic cells and compared to the recent observation of Seebeck coefficient enhancement/diminution in magnetic nanofluids in polar media.

International audience; Thermodiffusion of different ferrite nanoparticles (NPs), ∼10 nm in diameter, is explored in tailor-made aqueous dispersions stabilized by electrostatic interparticle interactions. In the dispersions, electrosteric repulsion is the dominant force, which is tuned by an osmotic-stress technique, i.e. controlling of osmotic pressure Π, pH and ionic strength. It is then possible to map Π and the NPs’ osmotic compressibility χ in the dispersion with a Carnahan–Starling formalism of effective hard spheres (larger than the NPs’ core). The NPs are here dispersed with two different surface ionic species, either at pH ∼ 2 or 7, leading to a surface charge, either positive or negative. Their Ludwig–Soret $S_{T}$ coefficient together with their mass diffusion $D_{m}$ coefficient are determined experimentally by forced Rayleigh scattering. All probed NPs display a thermophilic behavior ($S_{T}$ < 0) regardless of the ionic species used to cover the surface. We determine the NPs’ Eastman entropy of transfer and the Seebeck (thermoelectric) contribution to the measured Ludwig–Soret coefficient in these ionic dispersions. The NPs’ Eastman entropy of transfer $Ŝ_{NP}$ is interpreted through the electrostatic and hydration contributions of the ionic shell surrounding the NPs.

Currently, liquid thermocells are receiving increasing attention as an inexpensive alternative to conventional solid-state thermoelectrics for low-grade waste heat recovery applications. Here we present a novel path to increase the Seebeck coefficient of liquid thermoelectric materials using charged colloidal suspensions; namely, ionically stabilized magnetic nanoparticles (ferrofluids) dispersed in aqueous potassium ferro-/ferri-cyanide electrolytes. The dependency of thermoelectric potential on experimental parameters such as nanoparticle concentration and types of solute ions (lithium citrate and tetrabutylammonium citrate) is examined to reveal the relative contributions from the thermogalvanic potential of redox couples and the entropy of transfer of nanoparticles and ions. The results show that under specific ionic conditions, the inclusion of magnetic nanoparticles can lead to an enhancement of the ferrofluid's initial Seebeck coefficient by 15% (at a nanoparticle volume fraction of ∼1%). Based on these observations, some practical directions are given on which ionic and colloidal parameters to adjust for improving the Seebeck coefficients of liquid thermoelectric materials.

Magnetic droplets obtained by induced phase separation in a magnetic colloid show a large variety of shapes when exposed to an external field. However, the description of shapes is often limited. Here we formulate an algorithm based on three dimensional boundary-integral equations for strongly magnetic droplets in a high-frequency rotating magnetic field, allowing us to find their figures of equilibrium in three dimensions. The algorithm is justified by a series of comparisons with known analytical results. We compare the calculated equilibrium shapes with experimental observations and find a good agreement. The main features of these observations are the oblate-prolate transition, the flattening of prolate shapes with the increase of magnetic field strength and the formation of star-fish like equilibrium shapes. We show both numerically and in experiments that the magnetic droplet behaviour may be described with a tri-axial ellipsoid approximation. Directions for further research are mentioned, including the dipolar interaction contribution to the surface tension of the magnetic droplets, account for the large viscosity contrast between the magnetic droplet and the surrounding fluid., This is a first revision of the article, submitted to the Journal of Fluid Mechanics (cambridge.org/core/journals/journal-of-fluid-mechanics)

International audience; We investigate the local structure of nanoparticles based on a manganese ferrite core surrounded or not by a maghemite layer obtained after hydrothermal surface treatment. Results of X-ray powder diffraction (XRD) and neutron powder diffraction (NPD) measurements are crossed with those of in-field Mö ssbauer spectroscopy and X-ray absorption spectroscopy (XANES/EXAFS) to study the valence state of Mn ions and the cation distribution at interstitial sites of the core−shell nano-particle structure. Linear combination fitting of XANES data clearly indicates the existence of mixed valence states of Mn cations in the Mn ferrite phase. As a direct consequence, it induces nonequilibrium cation distributions in the nanoparticle core with the presence of a large amount of Mn cations at octahedral sites. The quantitative results of the inversion degree given by NPD, Mö ssbauer spectroscopy measurements, and EXAFS are in good accordance. It is also shown that both the proportions of each oxidation degree of Mn ions and their location at tetrahedral or octahedral sites of the spinel nanocrystal core can be modified by increasing the duration of the surface treatment.

We compare here exchange bias (EB) properties of chemically synthesized core-shell nanoparticles (NPs), based either on a core of soft ferrite (MnFe2O4) or hard ferrite (CoFe2O4) protected by a maghemite shell (γ-Fe2O3). These NPs dispersed in acidic solutions are electrostatically stabilized, yielding to stable colloidal dispersions with a strong interparticle repulsion and negligible dipolar interactions in the probed range of temperatures. Field cooled (FC) magnetic hysteresis loops of non-textured frozen dispersions (with magnetic anisotropy axis of NPs distributed at random) and those of a powder based on the same NPs present a shift along the H-axis, expressing the coupling between the spin-ordered cores and the disordered surface layer of the NPs. The bias field is found to present a maximum, larger for NPs based on harder ferrite core. It is obtained for a cooling field of the order of one half of the anisotropy field, which is much larger for the CoFe2O4 cores than for MnFe2O4 ones. In powders, particles are in contact leading to an interparticle exchange which is not present in the dilute solutions where exchange bias properties are only due to an intraparticle exchange between core and surface. The thermal dependence of the bias field is well described by a reduced exponential behavior with a characteristic freezing temperature of about 8 K.

The aim of the present study is to propose a new reproducible method for preparing colloidal dispersions of electrostatically charged nanoparticles (NPs) in polar solvents with different kinds of counter-ions. Maghemite NPs are here dispersed in solvents of different dielectric constant, namely water, dimethylsulfoxide (DMSO) and an ionic liquid, ethylammonium nitrate (EAN). If the existence of a NP superficial charge happens to be necessary for the colloidal stability of the dispersions in these three solvents, the standard DLVO theory cannot be used any more to describe the colloidal stability in EAN. The structure of the dispersions and the strength of the interparticle repulsion are investigated by small angle X-ray scattering measurements, in association with Ludwig–Soret coefficient determinations. Specificities, associated to the nature of the counter-ions are identified in this work on the colloidal stability, on the interparticle repulsion and on the Ludwig–Soret coefficient.

We synthesize Zn-substituted cobalt ferrite (Zn x Co1−x Fe2O4, with 0 ≤ x ≤ 1) magnetic nanoparticles by a hydrothermal co-precipitation method in alkaline medium. The chemical composition is evaluated by atomic absorption spectroscopy and energy-dispersive X-ray spectroscopy techniques. The structure and morphology of the nanopaticles are investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. XRD Rietveld refinements reveal the cation distribution among the tetrahedral (A) and octahedral (B) sites. It shows that up to x ~0.5 zinc ions occupy preferably A-sites, above which Zn ions begin also a gradual occupancy of B-sites. TEM images show nanoparticles with different shapes varying from spheres, cubes, to octahedrons. Hysteresis loop properties are studied at 300 and 5 K. These properties are strongly influenced by the Zn and Co proportion in the nanoparticle composition. At 300 K, only samples with high Co content present hysteresis. At 5 K, the reduced remanent magnetization ratio (M R/M S) and the coercivity (H C) suggest that nanoparticles with x

A new magnetorheological cell is implemented to perform measurements of temperature-controlled flows and determine viscoelastic properties in magnetic complex fluids under applied continuous magnetic fields. The flow properties of water-based and oil-based ferrofluids with volume fractions up to 10 % are investigated here in various situations of interparticle interaction, leading also to various microstructures already known from previous works. Shear flow behaviors under magnetic fields resulting in a competition between magnetic and hydrodynamic forces are directly related to the microscopic structure of the probed magnetic fluids.

We investigate here the internal structure of zinc ferrite nanoparticles designed and prepared by a soft chemistry method to elaborate magnetic nanocolloids. The strategy used to avoid acid dissolu...

The Monte Carlo method, which is a powerful tool for finding equilibrium states (and/or their corresponding characteristics) in systems of a different nature in many cases allows one to also describe the course of kinetic processes. This work presents the Monte Carlo modeling of magnetic relaxation and dynamics of induced magnetization of an ensemble of ferromagnetic nanoparticles. It is shown by comparison with the exact solution that in both problems there is a proportionality between the number of calculation steps and the physical duration of the transition or periodic process. On this basis, relationships are proposed making it possible to estimate the time interval corresponding to a single Monte Carlo step. For the process of magnetic relaxation the obtained result is a generalization of the well-known Nowak-Chantrell-Kennedy formula for the case of particles with finite magnetic anisotropy.

A soft-chemistry method is used to synthesize zinc ferrite nanoparticles to prepare a magnetic fluid. We investigate here their internal structure by X-ray Absorption Near Edge Spectroscopy (XANES) and X-Ray Diffraction (XRD). A cross analysis of XANES and Rietveld refinement of XRD spectra shows non-equilibrium site occupancy with respect to bulk zinc ferrite, suggesting a cation redistribution that enhances the magnetic and magneto-optical responses of the nanoparticles.

Monte Carlo method with a variable number of calculation steps is used for simulations of the magnetization dynamics in a microsphere consisting of a non-magnetic core coated with a layer of magnetic nanograins. Namely, the dynamic magnetic hysteresis under an AC field in such a core-shell microsphere is considered for the cases of non-interacting particles and with allowance for the interparticle dipole-dipole interaction. The time portions corresponding to one calculation step are estimated from comparison of the Monte Carlo-Metropolis results and a numerically-exact solution of the kinetic equation.

Structure analysis of a magnetic fluid (nanoparticles of maghemite dispersed in water with charge stabilization and without surfactant) by means of small-angle neutron scattering is presented. A combination of the contrast variation technique and scattering of polarized neutrons was applied. In the first case, the scattering curves obtained for the unmagnetized fluid with variation of the heavy water content in the carrier are treated in terms of the basic functions approach. The almost homogeneous character of the nanoparticles with respect to the nuclear scattering length density makes it possible to separate information about their characteristic nuclear and magnetic radii. Polarized neutrons are then used to separate and analyze independently the nuclear and magnetic scattering contributions for the fully magnetized fluid. Both methods reveal a significant excess of the apparent nuclear size over the magnetic one, which is explained by a difference in the nonmagnetic and magnetic interactions in the system. The results indicate that from the viewpoint of magnetic interaction the studied fluid behaves under a magnetic field as a purely superparamagnetic system of independent particles. The magnetic scattering length density of the maghemite nanoparticles is found to be ∼25% less than the bulk value, which is in agreement with the data of the magnetization analysis.

The ground magnetic state of systems of finite number N of single-domain particles confined in a spherical monolayer is investigated by numeric simulations. Two model situations are considered. In the first, the particle positions are imposed and fixed, in the second, the particles are able to move freely within the layer; in the latter case the excluded volume effect is taken into account. It is found that in all the range studied ( N ⩽200) the ground state of the system retains a considerable extent of magnetic vorticity (toroid moment). Moreover, the magnetic and toroid moments are correlated: they are approximately perpendicular to one another.

The magnetic structure of NiFe2O4 nanoparticles has been investigated by means of Mossbauer spectra at T = 4.2 K in applied fields up to 12 T. Four samples were studied, with mean particle diameters ranging from 4.3 to 8.9 nm. All spectra could be decomposed into three sextets, two corresponding to the ferrimagnetic sublattices of Fe ions in the spinel structure (core) and the third one to randomly frozen spins near the particle surface (shell). The shell thickness, calculated from the fraction of disordered spins, was found to be about one-third of the particle radius at H app = 0 and to decrease with the applied field toward a common limit of ~0.4 nm. The mean canting angle relative to the field was also found to decrease for increasing fields, at a rate inversely correlated to the particle size.

A chemical core−shell strategy is developed here for the synthesis of ferrofluids based on nanoparticles of different ferrites with different mean sizes. A heterogeneity of chemical composition, associated with a superficial enrichment of iron, allows to obtain chemically stable ionic colloids. We propose here a core−shell model to describe the synthesized nanoparticles, which is tested by chemical and magnetic measurements performed at the various steps of the synthesis. The thickness of the superficial layer, rich in iron, is ranging between 0.4 and 1.3 nm, depending on the nanoparticle size and on the underlying ferrite. Its density is found close to that of maghemite, and its magnetization depends on the core ferrite. It is low with a cobalt ferrite core and larger for the three other ferrites investigated here (NiFe2O4, CuFe2O4, and ZnFe2O4). Magnetic measurements prove that there is a strong redistribution of Zn2+ ions inside the core of the synthesized nanoparticles based on ZnFe2O4.

International audience; The Seebeck and Soret coefficients of ionically stabilized suspension of maghemite nanoparticles in dimethyl sulfoxide are experimentally studied as a function of nanoparticle volume fraction. In the presence of a temperature gradient, the charged colloidal nanoparticles experience both thermal drift due to their interactions with the solvent and electric forces proportional to the internal thermoelectric field. The resulting thermodiffusion of nanoparticles is observed through forced Rayleigh scattering measurements, while the thermoelectric field is accessed through voltage measurements in a thermocell. Both techniques provide independent estimates of nanoparticle’s entropy of transfer as high as 82 meV K$_{−1}$. Such a property may be used to improve the thermoelectric coefficients in liquid thermocells.

We present a structural and a multi-scale rheophysical investigation of magneto-sensitive materials based on biopolymers, namely aqueous solutions of sodium alginate incorporating magnetic maghemite nanoparticles, functionalized with adsorbed negative citrate ions. The large alginate ionic strength impacts the structure and the rheology of these nanocomposites in zero magnetic field. In given physico-chemical conditions, the system is fluid and homogeneous on macroscopic scales while it is diphasic on microscopic ones, containing micro-droplets coming from the demixion of the system. These micro-droplets are liquid and deformable under magnetic field. Their under-field elongation and their zero-field relaxation are directly observed by optical microscopy to determine their interfacial tension, their magnetic susceptibility and their internal viscosity. A structural analysis of the solutions of alginate chains and of the phase-separated mixtures of alginate and nanoparticles by Small Angle Scattering completes the local description of the system.

Javier Reguera, Christophe Petit, Leonardo Scarabelli, Xiaoying Liu, Edward Malachosky, Matthew Martin, Bruce Law, Xiao-Min Lin, Helmuth Moehwald, Peter Schurtenberger, Heiko Wolf, Vicki Meli, Damien Faivre, Eser Metin Akinoglu, Dhanavel Ganeshan, Fernando Bresme, Yangwei Liu, Casper Kunstmann-Olsen, Christopher Sorensen, Suvojit Ghosh, Asanka Yapa, Asaph WidmerCooper, M. Fernanda Cardinal, Almudena Gallego, Ozgur Tarhan, Gunadhor Okram, Andreas Fery, Emanuela Del Gado, Lucio Isa, Regine Perzynski and Brian Korgel

International audience; The micro-convection caused by the ponderomotive forces of the self-magnetic field in a magnetic fluid is studied here both numerically and experimentally. The theoretical approach based on the general Brinkman model substantially improves the description with respect to the previously proposed Darcy model. The predictions of both models are here compared to finely controlled experiments. The Brinkman model, in contrast to the Darcy model, allows us to describe the formation of mushrooms on the plumes of the micro-convective flow and the width of the fingers. In the Brinkman approach, excellent quantitative agreement is also obtained for the finger velocity dynamics and the velocity maximal values as a function of the magnetic Rayleigh number. The diffusion coefficient of particles of the water-based magnetic colloid determined by the threshold field strength value of the micro-convection is significantly larger than the diffusion coefficient of individual particles. This result is confirmed by independent measurements of the diffusion coefficient at the smearing of the diffusion front.

International audience; In this paper we discuss the magnetic micro-convection phenomenon as a tool for mixing enhancement in microfluidics systems in cases when one of the mis-cible fluids is a magnetic particle colloid. A system of a water-based magnetic fluid and water is investigated experimentally under homogeneous magnetic field in a Hele-Shaw cell. Subsequent image analysis both qualitatively and quan-titatively reveals the high enhancement of mixing efficiency provided by this method. The mixing efficiency dependence on the magnetic field and the phys-ical limits is discussed. A suitable model for a continuous-flow microfluidics setup for mixing with magnetic micro-convection is also proposed and justified with an experiment. In addition, possible applications in improving the speed of ferrohydrodynamic sorting and magnetic label or selected tracer mixing in lab on a chip systems are noted.

Maghemite (γ-Fe2O3) nanoparticles (NPs) can be successfully dispersed in a protic ionic liquid, ethylammonium nitrate (EAN), by transfer from aqueous dispersions into EAN. As the aqueous systems are well controlled, several parameters can be tuned. Their crucial role towards the interparticle potential and the structure of the dispersions is evidenced: (i) the size of the NPs tunes the interparticle attraction monitoring dispersions to be either monophasic or gas–liquid-like phase separated; (ii) the nature of the initial counterion in water (here sodium, lithium or ethylammonium) and the amount of added water (

International audience; The translational dynamics of a repulsive colloidal glass-former is probed by time-resolved X-ray Photon Correlation Spectroscopy. In this dense dispersion of charge-stabilized and magnetic nanoparticles, the interaction potential can be tuned, from quasi-isotropic to anisotropic by applying an external magnetic field. This powerful control parameter finely tunes the anisotropy of the intricate energy landscape in the colloidal glass-former, which is seen here as a new tunable model-system to probe the dynamical heterogeneities at the approach of the glass transition. Both structural and dynamical anisotropies are reported on interparticle lengthscales associated with highly anisotropic cooperativity, almost two orders of magnitude larger in the field direction than in the perpendicular direction and in zero field.

Yugang Sun, Leonardo Scarabelli, Nicholas Kotov, Moritz Tebbe, Xiao-Min Lin, Ward Brullot, Lucio Isa, Peter Schurtenberger, Helmuth Moehwald, Igor Fedin, Orlin Velev, Damien Faivre, Christopher Sorensen, Regine Perzynski, Munish Chanana, Zhihai Li, Fernando Bresme, Petr Kral, Emre Firlar, David Schiffrin, Joao Batista Souza Junior, Andreas Fery, Elena Shevchenko, Ozgur Tarhan, Armand Paul Alivisatos, Sabrina Disch, Rafal Klajn and Suvojit Ghosh

Theory of Brownian motion of a fine particle in a viscoelastic fluid continuum is developed. The rheology of the embedding medium is described in terms of classical structure (spring-and-damper) schemes. It is shown that a great variety of conceivable ramifications of such structures could be reduced to an effective Jeffreys model: a Maxwell chain shunted by a damper. This scheme comprises just three material parameters: two for viscosities (fast and slow) and one for elasticity. For the thermal motion of a particle in such a fluid, the set of Langevin equations is derived. In the cases of 1D translational and 2D orientational (rotation about fixed axis) motions, the time dependencies of mean-square displacements are found analytically. It is shown that in a Jeffreys fluid, the Brownian motion has three regimes: fast diffusion (short times), slow diffusion (long times) and a crossover of those resulting in virtual localization (dynamic confinement) of the particle. Experimental evidence for that taken from the literature is presented. The developed formalism is applied to the particles with “frozen-in” dipole moments, whose orientational motion is a combination of Brownian diffusion and regular excitation by an AC field. The dynamic susceptibilities are calculated for the ensembles of particles liable for either 2D or 3D rotations. Comparison shows that the out-of-phase part of the susceptibility χ ′′(ω ) in 3D case differs considerably from that of 2D case. Function χ (ω ) for the forced 3D rotary diffusion in a Jeffreys fluid is found for the first time. In our view, it would be useful for realistic theoretical interpretation of microrheology data and the more so for estimating the particle-mediated AC field-induced heating (magnetic hyperthermia) in viscoelastic fluid media.

X-ray Photon Correlation Spectroscopy is used here to probe for the first time a glass-forming dispersion of repulsive particles spherical and 10 nm sized. The highly concentrated colloidal system is based on the magnetic and charge-stabilized nanoparticles of a ferrofluid. Their out-of-equilibrium translational dynamics capture on nanoscale generic features usually observed on microscale: namely i) stretched exponential α relaxation with an exponent around 1.5 and ii) age-dependent characteristic time τ evolving from exponential at young ages to a slower behavior at large ages. τ is here scaling as Q−1 in the whole experimental Q-range, below, on and above the scale of the interparticle distance, the driving force for aging in this glass-forming nanosystem being associated to larger scale rearrangements.