Effect of an excess of surfactant on thermophoresis, mass diffusion and viscosity in an oily surfactant-stabilized ferrofluid.

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.

Thermoelectricity and Thermodiffusion in Magnetic Nanofluids: Entropic Analysis.

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.

Can charged colloidal particles increase the thermoelectric energy conversion efficiency?

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.

Structural and multi-scale rheophysical investigation of diphasic magneto-sensitive materials based on biopolymers.

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.

A numerical study on the interplay between the intra-particle and interparticle characteristics in bimagnetic soft/soft and hard/soft ultrasmall nanoparticle assemblies.

A mesoscopic 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 ∼ 3 nm 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 (H ex) and the coercivity (H c) 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 H ex and H c 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.

Experimental evidence for violation of the fluctuation-dissipation theorem in a superspin glass.

We present the experimental observation of the fluctuation-dissipation theorem violation in an assembly of interacting magnetic nanoparticles in the low temperature superspin-glass phase. The magnetic noise is measured with a two-dimension electron gas Hall probe and compared to the out of phase ac susceptibility of the same ferrofluid. For "intermediate" aging times of the order of 1 h, the ratio of the effective temperature T(eff) to the bath temperature T grows from 1 to 6.5 when T is lowered from T(g) to 0.3 T(g), regardless of the noise frequency. These values are comparable to those measured in an atomic spin glass as well as those calculated for a Heisenberg spin glass.

Magnetically enhancing the Seebeck coefficient in ferrofluids.

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 (S T, 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.

What tunes the structural anisotropy of magnetic fluids under a magnetic field?

In the present study, the structure of monophasic ionic magnetic fluids under a static magnetic field is explored. In these aqueous electrostatically stabilized ferrofluids, we vary both the isotropic interparticle interactions and the anisotropic dipolar magnetic interaction by tuning the ionic strength and the size of the nanoparticles. Small angle neutron scattering measurements carried out on nanoparticles dispersed in light water exhibit miscellaneous 2D nuclear patterns under a magnetic field with various q-dependent anisotropies. In this nondeuterated solvent where the magnetic scattering is negligible, this anisotropy originates from an anisotropy of the structure of the dispersions. Both the low q region and the peak of the structure factor can be anisotropic. On the scale of the interparticle distance, the structure is better defined in the direction perpendicular to the field. In the thermodynamic limit (q-->0), the model previously described in ref 10 matches the data without any fitting parameters: the interparticle interaction is more repulsive in the direction parallel to the magnetic field. At low q, the amplitude of the anisotropy of the pattern is governed by the ratio of two interaction parameters: the reduced parameter of the anisotropic magnetic dipolar interaction, gamma/Phi, over the isotropic interaction parameter, , in zero field, which is proportional to the second virial coefficient.

Concentrated assemblies of magnetic nanoparticles in ionic liquids.

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 (<20 vol%) modulate the interparticle repulsion. Very concentrated dispersions with a volume fraction of around 25% are obtained thanks to the gas-liquid-like phase separations. Such conclusions are derived from a fine structural and dynamical study of the dispersions on a large range of spatial scales by coupling several techniques: chemical analyses, optical microscopy, dynamic light scattering, magneto-optic birefringence and small angle scattering.

Liquid-liquid phase-transfer of magnetic nanoparticles in organic solvents.

We report a novel route for the preparation of well-defined colloidal dispersions of magnetic nanoparticles stabilized by steric repulsion in organic solvents. The usual methods standardly lead to the surfaction of multiparticle aggregates, incompatible with our long-term aim of studying and modeling the influence of magnetic dipolar interactions in colloidal dispersions which are free of aggregates, all other interactions being perfectly defined. A new and reproducible method based on a surfactant-mediated liquid-liquid phase transfer of individually dispersed gamma-Fe(2)O(3) nanoparticles from an aqueous colloidal dispersion to an organic phase is developed. The choice of the reagent and the preparation techniques is discussed. Among several solvent/surfactant pairs, the cyclohexane/dimethyldidodecylammonium bromide (DDAB) system is found to fulfill the colloidal stability criterion: aggregation does not appear, even upon aging. A complete transfer of isolated particles is observed above a threshold in DDAB concentration. The nanoparticle surface is then fully covered with adsorbed DDAB molecules, each surfactant head occupying a surface of 0.57+/-0.05 nm(2). The volume fraction of the cyclohexane-based organosols is easily tunable up to a volume fraction of 12% by modifying the volume ratio of the organic and of the aqueous phases during the liquid-liquid phase transfer.

Lipid bilayer elasticity measurements in giant liposomes in contact with a solubilizing surfactant.

A new method to probe the modification of the elasticity of phospholipid bilayers is presented. The purpose here concerns the action of a solubilizing surfactant on a vesicle bilayer. This method is based on the measure of the under-field elongation of giant magnetic-fluid-loaded liposomes. The addition of the nonionic surfactant octyl-beta-d-glucopyranoside (OG) to vesicles at sublytic levels increases the elasticity of the membrane, as shown by the value of the bending modulus K(b), which decreases. K(b) measured around 20 kT for a pure 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) bilayer indeed reaches a few kT in the case of the mixed OG-DOPC bilayer. The purpose and interest of this study are to allow the determination of the membrane bending modulus before and after the addition of OG on the same magnetic liposome. Moreover, the experimental conditions used in this work allow the control of lipid and surfactant molar fractions in the mixed aggregates. Then, optical microscopy observation can be performed on samples in well-defined regions of the OG-phospholipid state diagram.