Structure of alumina-silica nanoparticles grafted with alkylphosphonic acids in poly(ethylacrylate) nanocomposites

Alumina-coated silica nanoparticles (NPs) grafted with phosphonic acids of different hydrophobicity were used as filler in poly(ethylacrylate) nanocomposites. Phosphonic acids bearing short alkyl chains or a diethylene glycol group have been grafted at densities up to 3.2 P/nm2 on NPs (20 nm) dispersed in water. Nanocomposites at particle fractions up to 10 vol% have been formulated by casting from the colloidal mixtures of modified NPs and nanolatex in water. The dispersion of the NPs in the polymer matrix has been studied by TEM combined with small-angle scattering, evidencing aggregation of NPs. TEM shows micrometer-scale inhomogeneities depending on the surface/polymer matrix compatibility. For the local interparticle correlations, a quantitative analysis of the intensity based on the mapping onto the effective structure factor of polydisperse hard spheres is developed. This mapping allows the model-free determination of the internal volume fraction of aggregates, termed compacity κ, to between 10% and 30%, compatible with the TEM analysis. κ is found to increase for the higher particle volume fractions, to decrease with grafting density, and to be mostly independent of the nature and mass of the graft. Preliminary evidence for an improved compatibility of grafted with respect to bare NPs is found, as opposed to their aqueous precursor suspensions where some pre-aggregation is induced by grafting. [Display omitted] •Nanocomposite formulation is based on an original surface modification in water.•A correlation hole analysis of the scattered intensity leads to aggregate compacity.•Grafting phosphonic acids on nanoparticles is found to decrease the local compacity.•Hydrophobic grafting improves local-scale compatibility with the hydrophobic matrix.