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Homogeneous Dispersion of Magnetic Nanoparticles Aggregates in a PS Nanocomposite: Highly Reproducible Hierarchical Structure Tuned by the Nanoparticles’ Size

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journal contribution
posted on 13.07.2010, 00:00 by Anne-Sophie Robbes, Jacques Jestin, Florian Meneau, Florent Dalmas, Olivier Sandre, Javier Perez, François Boué, Fabrice Cousin
We present here the synthesis and structural characterization of new nanocomposites made of spherical magnetic nanoparticles of maghemite (γ-Fe2O3) dispersed in a polystyrene (PS) matrix. The γ-Fe2O3 nanoparticles, synthesized in aqueous media, were first gently transferred by dialysis in dimethylacetamide (DMAc), a polar solvent which is a good solvent for PS. Electrostatic repulsions enable to keep colloidal stability in DMAc. The nanocomposites were then processed by a controlled evaporation of DMAc of binary mixtures of γ-Fe2O3 nanoparticles and PS chains. The size of the nanoparticles ranges from 3.5 to 6.5 nm and can be changed without any modification of the nanoparticles’ surface. The structural organization of the nanoparticles inside the polymer was determined as a function of the nanoparticles’ size. It was performed by combining very high resolution SAXS measurements which permit to decrease the nanoparticles content down to very low values (Φmag ∼ 10−5) and TEM microscopy. Whatever the size, the nanoparticles are organized with a hierarchical structure that shows that their aggregation has been driven by a two-step process. At low spatial scale, dense primary aggregates composed of some tens of nanoparticles are formed whatever Φmag, resulting from the first aggregation step. For Φmag > 10−4, these primary aggregates underwent a second aggregation step and are organized at larger scale in fractal aggregates of finite size of ∼200 nm of radius, with a dimension of 1.7. The size of the dense primary aggregates is almost constant when changing the nanoparticles radius; i.e., the mean aggregation number of primary aggregates decreases with an increase of the radius.

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