Dispersion morphology of poly(methyl acrylate)/silica nanocomposites

Nearly monodisperse poly(methyl acrylate) (PMA) and spherical SiO ₂ nanoparticles (NP, d = 14 ± 4 nm) were co-cast from 2-butanone, a mutually good solvent and a displacer of adsorbed PMA from silica. The effects of NP content and post-casting sample history on the dispersion morphology were found by small-angle X-ray scattering supplemented by transmission electron microscopy. Analysis of the X-ray results show that cast and thermally annealed samples exhibited a nearly random particle dispersion. That the same samples, prior to annealing, were not well-dispersed is indicative of thermodynamic miscibility during thermal annealing over the range of NP loadings studied. A simple mean-field thermodynamic model suggests that miscibility results primarily from favorable polymer segment/NP surface interactions. The model also indicates, and experiments confirm, that subsequent exposure of the composites to the likely displacer ethyl acetate results in entropic destabilization and demixing into NP-rich and NP-lean phases.