The adsorption of small silica particles onto large sterically stabilized poly(2-vinylpyridine) [P2VP] latex particles in aqueous solution is assessed as a potential route to nanocomposite particles with a "core-shell" morphology. Geometric considerations allow the packing efficiency, P, to be related to the number of adsorbed silica particles per latex particle, N. Making no assumptions about the packing structure, this approach leads to a theoretical estimate for P of 86 +/- 4%. Experimentally, dynamic light scattering is used to obtain a plot of hydrodynamic diameter against N, which indicates the conditions required for monolayer coverage of the latex by the silica particles. Transmission electron microscopy confirmed that, at approximately monolayer coverage, calcination of these nanocomposite particles led to the formation of well-defined hollow silica shells. This is interpreted as strong evidence for a contiguous monolayer of silica particles surrounding the latex cores. On this basis, an experimental value for P of 69 +/- 4% was estimated for nanocomposite particles prepared by the heteroflocculation of a 20 nm silica sol with near-monodisperse P2VP latexes of either 463 or 616 nm diameter at approximately pH 10. X-ray photoelectron spectroscopy was used to quantify the extent of latex surface coverage by the silica particles. This technique gave good agreement with the silica packing efficiencies estimated from calcination studies.

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Addition of excess sterically stabilized P2VP latex to a colloidal dispersion of P2VP-silica nanocomposite particles (with silica shells at full monolayer coverage) leads to the facile redistribution of the silica nanoparticles such that partial coverage of all the P2VP latex particles is achieved. This silica exchange, which is complete within 1 h at 20 degrees C as judged by small-angle x-ray scattering, is observed for nanocomposite particles prepared by heteroflocculation, but not for nanocomposite particles prepared by in situ copolymerization. These observations are expected to have important implications for the optimization of nanocomposite formulations in the coatings industry.

Small angle X-ray scattering (SAXS) is a powerful characterization technique for the analysis of polymer-silica nanocomposite particles due to their relatively narrow particle size distributions and high electron density contrast between the polymer core and the silica shell. Time-resolved SAXS is used to follow the kinetics of both nanocomposite particle formation (via silica nanoparticle adsorption onto sterically stabilized poly(2-vinylpyridine) (P2VP) latex in dilute aqueous solution) and also the spontaneous redistribution of silica that occurs when such P2VP-silica nanocomposite particles are challenged by the addition of sterically stabilized P2VP latex. Silica adsorption is complete within a few seconds at 20 °C and the rate of adsorption strongly dependent on the extent of silica surface coverage. Similar very short time scales for silica redistribution are consistent with facile silica exchange occurring as a result of rapid interparticle collisions due to Brownian motion; this interpretation is consistent with a zeroth-order Smoluchowski-type calculation.