Structure and thermodynamics of grafted silica/polystyrene dilute nanocomposites investigated through self-consistent field theory.

Polymer/matrix nanocomposites (PNCs) are materials with exceptional properties. They offer a plethora of promising applications in key industrial sectors. In most cases, it is preferable to disperse the nanoparticles (NPs) homogeneously across the matrix phase. However, under certain conditions NPs might lump together and lead to a composite material with undesirable properties. A common strategy to stabilize the NPs is to graft on their surface polymer chains of the same chemical constitution as the matrix chains. There are several unresolved issues concerning the optimal molar mass and areal density of grafted chains that would ensure best dispersion, given the nanoparticles and the polymer matrix. We propose a model for the prediction of key structural and thermodynamic properties of PNC and apply it to a single spherical silica (SiO2) nanoparticle or planar surface grafted with polystyrene chains embedded at low concentration in a matrix phase of the same chemical constitution. Our model is based on self-consistent field theory, formulated in terms of the Edwards diffusion equation. The properties of the PNC are explored across a broad parameter space, spanning the mushroom regime (low grafting densities, small NPs and chain lengths), the dense brush regime, and the crowding regime (large grafting densities, NP diameters, and chain lengths). We extract several key quantities regarding the distributions and the configurations of the polymer chains, such as the radial density profiles and their decomposition into contributions of adsorbed and free chains, the chains/area profiles, and the tendency of end segments to segregate at the interfaces. Based on our predictions concerning the brush thickness, we revisit the scaling behaviors proposed in the literature and we compare our findings with experiment, relevant simulations, and analytic models, such as Alexander's model for incompressible brushes.