Résumé:

Composite materials, comprising nanoparticles (NPs) dispersed in a matrix, are of great interest, since the NPs can enhance the matrix properties or impart new functionalities and because the matrix can act as a template that structures the particles at the nanometer scale. However, controlling the spatial distribution of NPs remains a challenging task, as it usually depends crucially on the particles surface chemistry. We present here a general approach to confine NPs in colloidal materials in a controlled fashion. We design nanocomposite material obtained by dispersing small quantities of NPs (at most 2%) in a colloidal crystalline matrix composed of thermosensitive copolymer micelles. The volume fraction of the micelles increases with temperature T, until crystallization occurs due to entropic reasons. Hence our system allows crystallization to be induced at the desired rate simply by varying T. By analogy with atomic crystals, we expect the NPs, which act as impurities, to be partially expulsed from the growing lattice and to segregate in the grain boundaries. We use scattering techniques and confocal microscopy to probe the microscopic and mesoscopic structures of the composite materials. We show that the NPs do not perturb the crystalline structure of the micelles but that different crystallization rates lead to different NPs rearrangements. We show that the NPs segregate in the grain-boundaries of the copolymer polycrystal. We demonstrate that the texture of the polycrystal can be tuned by varying independently the nanoparticle volume fraction and the crystallization rate, and quantify our findings using classical nucleation theory. Remarkably, we find that the efficiency of the segregation of the NPs in the grain-boundaries is determined solely by the typical size of the crystalline grains.