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 coreshell 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 (NiFe 2 O 4 , CuFe 2 O 4 , and ZnFe 2 O 4 ). Magnetic measurements prove that there is a strong redistribution of Zn 2+ ions inside the core of the synthesized nanoparticles based on ZnFe 2 O 4 .
We report on stable colloidal aqueous suspensions of magnetic nanostructures made of copper, nickel, and zinc ferrites. These magnetic fluids could represent a new alternative for biological applications. The basic steps of the nanoparticles synthesis, their chemical surface treatment, and their peptization in a stable colloidal sol are given. Their chemical composition is carefully checked, and X-ray diffraction patterns provide both their mean size and a structural characterization. Magnetization results obtained at 300 K are presented and discussed.
We report on the suitability of core/shell nanoparticles (NPs) for magnetic fluid hyperthermia in a selfregulated and theranostic approach. Aqueous magnetic colloids based on core/shell ZnxMnyFezO4@γ-Fe2O3 and ZnxCoyFe-zO4@γ-Fe2O3 NPs were produced by a three-step chemical synthesis. Systematic deviations from stoichiometry was observed with increasing Zn substitution for both series of samples. We investigated how the chemical composition affects 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 presenting different contrast of anisotropy between the core and shell materials indicate no evidence of enhanced exchange coupling contribution to the heating efficiency.
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.
Soret coefficient is modulated in sign by the counterion nature and in magnitude by volume fraction and applied magnetic field; single-particle and thermoelectric contributions are sorted out.
New ionic ferrofluids containing NiFe2O4 nanoparticles of size ⩽10 nm are investigated. The crystalline structure of the particles is probed by transmission electron microscopy and x-ray scattering. Static magnetization and field-induced birefringence measurements are performed on three samples differing by particle volume fraction. Cross analyzing of the results of those two types of macroscopic tests completely rejects a simple single-domain particle model but readily supports the two-component scheme of a particle as consisting of a core with a uniform magnetization and a surface layer of comparable thickness stowed with a spin-glass-like arrangement.
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 ŝNP is interpreted through the electrostatic and hydration contributions of the ionic shell surrounding the NPs.
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