Ion specific tuning of nanoparticle dispersion in an ionic liquid: a structural, thermoelectric and thermo-diffusive investigation.

Dispersions of charged maghemite nanoparticles (NPs) in EAN (ethylammonium nitrate) a reference Ionic Liquid (IL) are studied here 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. Particular insight is provided regarding the importance of tuning the ionic species present at the NP/IL interface. In this work we compare the effect of Li+, Na+ or Rb+ ions. Here, the nature of these species has a clear influence on the short-range spatial organisation of the ions at the interface and thus on the colloidal stability of the dispersions, governing both the NP/NP and NP/IL interactions, which are both evaluated here. The overall NP/NP interaction is either attractive or repulsive. It is characterised by determining, thanks to the SAS techniques, the second virial coefficient A2, which is found to be independent of temperature. The NP/IL interaction is featured by the dynamical effective charge ξeff0 of the NPs and by their entropy of transfer SNP (or equivalently their heat of transport ) determined here thanks to thermoelectric and thermodiffusive measurements. For repulsive systems, an activated process rules the temperature dependence of these two latter quantities.

Nonlinear behavior of the impedance spectrum of a kerosene based ferrofluid.

We investigate the nonlinear behavior of the electric impedance of a kerosene-based ferrofluid (FF) sample subjected to an ac electric voltage of amplitude ranging from 10 mV to 3 V in the frequency range 6.3 mHz, 100 kHz. The FF sample was inserted between two parallel gold electrodes separated by 127 µm distance. The results show that even a sinusoidal voltage of amplitude low as 80 mV can give origin to nonlinear effects for frequency of the applied voltage smaller than 100 mHz. Our experimental data confirm the results obtained by solving numerically the equations of the Poisson-Nernst-Planck model. From this agreement it follows that the model based on the equation of continuity for the mobile ions, and the equation of Poisson for the actual potential across the sample, works well also in its non-linear version.

Design of concentrated colloidal dispersions of iron oxide nanoparticles in ionic liquids: Structure and thermal stability from 25 to 200 °C.

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.

Thermodiffusion anisotropy under a magnetic field in ionic liquid-based ferrofluids.

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.

Exchange-bias and magnetic anisotropy fields in core-shell ferrite nanoparticles.

Exchange bias properties of MnFe[Formula: see text]O[Formula: see text]@[Formula: see text]-Fe[Formula: see text]O[Formula: see text] 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.

Structural and Magnetic Properties of Spinel Ferrite Nanoparticles.

In this paper we review the magnetic properties of spinel ferrite nanoparticles pointing out the primary role of the crystalline structure besides finite size and surface/interface effects. The details of the spinel crystal structure of bulk spinel ferrite materials and their influence on both the magnetization and magnetocrystalline anisotropy are recalled. Moreover, we review some results published in the literature over the last years about how the structure of magnetic nanoparticles influences their magnetic features. Perspectives about the challenges to improve the applications in several fields are finally reported.

Blocking and remanence properties of weakly and highly interactive cobalt ferrite based nanoparticles.

We compare both magnetic blocking properties and remanence curves for dilute ferrofluid and powder samples of ferrite magnetic nanoparticles. Low field DC magnetization, AC susceptibility, isothermal remanent magnetization and DC demagnetization techniques are employed to investigate the role of interparticle magnetic interactions on the superparamagnetic relaxation, the magnetic anisotropy and on the super-spin-glass state in closely packed particles. The samples used herein are 3 nm sized spinel-type nanocrystals made of a cobalt ferrite core covered by a layer of maghemite on its outermost surface and can be obtained as aqueous colloidal dispersions thanks to this core-shell strategy. They show large anisotropy attributed to an enhanced surface contribution and the blocking temperature is shifted towards higher values as interparticle distance decreases. For all investigated diluted liquids and powder samples the frequency dependency of the peak temperature is well accounted by a Vogel-Fulcher law, with the insertion of a phenomenological temperature associated to the magnitude of interparticle dipolar interactions. The fractional change of the peak temperature per decade of frequency enlights the presence of interactions between particles in dilute liquids and of a spin-glass-like state in powder samples. The remanence curves always show global demagnetizing behavior, attributed to the combination of both spin surface disorder and interparticle dipolar interactions, the former being predominant in isolated nanoparticles and the latter in powder samples. However, in the most compacted powder, exchange interaction between surface ions of different particles becomes more pronounced and promotes an additive magnetizing effect.

Thermodiffusion of citrate-coated γ-Fe2O3 nanoparticles in aqueous dispersions with tuned counter-ions - anisotropy of the Soret coefficient under a magnetic field.

Under a temperature gradient, the direction of thermodiffusion of charged γ-Fe2O3 nanoparticles (NPs) depends on the nature of the counter-ions present in the dispersion, resulting in either a 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 ST is measured in stationary conditions together with the mass-diffusion coefficient Dm using a forced Rayleigh scattering method. The strong interparticle repulsion, determined by SAXS, is also attested by the increase of Dm with NP volume fraction Φ. The Φ-dependence of ST 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 transfer sNP) 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 ST > 0 and with ST < 0 are then probed under an applied field H[combining right harpoon above], and an anisotropy of Dm and of ST is induced while the in-field system remains monophasic. Whatever the H[combining right harpoon above]-direction (parallel or perpendicular to the gradients and ), 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.

Thermodiffusion of repulsive charged nanoparticles - the interplay between single-particle and thermoelectric contributions.

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 ST coefficient together with their mass diffusion Dm coefficient are determined experimentally by forced Rayleigh scattering. All probed NPs display a thermophilic behavior (ST < 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 sNP is interpreted through the electrostatic and hydration contributions of the ionic shell surrounding the NPs.

Temperature dependence of the Soret coefficient of ionic colloids.

The temperature dependence of the Soret coefficient S(T)(T) in electrostatically charged magnetic colloids is investigated. Two different ferrofluids, with different particles' mean dimensions, are studied. In both cases we obtain a thermophilic behavior of the Soret effect. The temperature dependence of the Soret coefficient is described assuming that the nanoparticles migrate along the ionic thermoelectric field created by the thermal gradient. A model based on the contributions from the thermoelectrophoresis and variation of the double-layer energy, without fitting parameters, is used to describe the experimental results of the colloid with the bigger particles. To do so, independent measurements of the ζ potential, mass diffusion coefficient, and Seebeck coefficient are performed. The agreement of the theory and the experimental results is rather good. In the case of the ferrofluid with smaller particles, it is not possible to get experimentally reliable values of the ζ potential and the model described is used to evaluate this parameter and its temperature dependence.

Thermoelectricity and thermodiffusion in charged colloids.

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.

Magnetic and structural study of electric double-layered ferrofluid with MnFe(2)O(4)@γ-Fe(2)O(3) nanoparticles of different mean diameters: Determination of the magnetic correlation distance.

Magnetic fluids based on manganese ferrite nanoparticles were studied from the structural point of view through small angle x-rays scattering (SAXS) and from the magnetic point of view through zero-field cooling and field cooling (ZFC-FC) and ac susceptibility measurements (MS). Three different colloids with particles mean diameters of 2.78,3.42, and 6.15 nm were investigated. The size distribution obtained from SAXS measurements follows a log-normal behavior. The ZFC-FC and MS results revealed the presence of an important magnetic interaction between the nanoparticles, characterized by a magnetic correlation distance Λ. The colloidal medium can be pictures as composed by magnetic cluster constituted by N interacting particles. These magnetic clusters are not characterized by a physical aggregation of particles. The energy barrier energy obtained is consistent with the existence of this magnetic clusters. Besides the magnetic interaction between particles, confinement effects must be included to account for the experimental values of the magnetic energy barrier encountered.

Thermodiffusion in positively charged magnetic colloids: influence of the particle diameter.

The Soret coefficient (ST) of positively charged magnetic colloids was measured as a function of the nanoparticles' diameter. The Z-scan technique and the generalization of the thermal lens model proved to be a reliable technique to measure ST. We show that ST is negative and increases with the particle's diameter, being best described by a functional dependence of the type ST∝d0. Potentiometric and conductometric experiments show that the particle's surface charge decreases as the temperature increases, changing the electrostatic interaction between the nanoparticles. The temperature gradient imposed in the ferrofluid by the Gaussian laser beam leads to the formation of the particle's concentration gradient. The origin of this phenomenon is discussed in terms of the decrease of the particle's surface charge in the hottest region of the sample and the thermoelectric field due to the inhomogeneous distribution of hydrogenous ions present in the colloidal suspension.

Influence of the spatial confinement at nanoscale on the structural surface charging in magnetic nanocolloids.

In this work we focus on the surface charging properties of core shell ferrite nanoparticles dispersed in water, namely magnetic nanocolloids. This structural charge results from the Brönsted acid-base behavior of the particles surface sites and is achieved through hydrolysis reactions. It can be modeled by considering identical charged sites behaving as weak diprotic acids. Then, electrochemical techniques could be implemented to study the acid-base equilibrium between the particle surface and the colloid bulk solution. Simultaneous potentio-conductimetric titrations are therefore performed to determine the thermodynamical constants of the p H-dependent reactions and to obtain the p H variations of the surface charge density. The results reveal that the saturation value of the structural charge strongly depends on the nanoparticle mean size. For large particles, the surface tends to be fully ionized whereas for smaller particles the saturated structural charge decreases drastically. This surface charge reduction is attributed to the existence in smaller particles of metallic surface sites, which cannot be accessible to the proton charge. The existence of such dead sites would be related to hydroxo-bonded sites with very low acidity combined with a quantum size effect, which would affect the charging/discharging process at the surface of the semiconductor ferrite quantum dot.