Location of Imbibed Solvent in Polymer-Grafted Nanoparticle Membranes

Membranes made purely from nanoparticles (NPs) grafted with polymer chains show increased gas permeability relative to the analogous neat polymer films, with this effect apparently being tunable with systematic variations in polymer graft density and molecular weight. To explore the structural origins of these unusual transport results, we use small angle scattering (neutron, X-ray) on the dry nanocomposite film and to critically examine in situ the structural effects of absorbed solvent. The relatively low diffusion coefficients of typical solvents (∼10^-12 m²/s) restricts us to thin films (≈1 μm in thickness) if solute concentration profiles are to equilibrate on the 1 s time scale. The use of such thin films, however, renders them as weak scatterers. Inspired by our nearly two decades old previous work, we address these conflicting requirements through the use of a custom designed flow cell, where stacks of 10 individual ≈1 μm thick supported films are used, while ensuring that each film is individually exposed to solvent vapor. By using isotopically labeled solvents, we study the solvent distribution within the film and show surprisingly that the solvent homogeneously swells the polymer under all conditions that we examined. These results are not anticipated by current theories, but they suggest that, at least under some conditions, the free volume increases due to the grafting of chains to nanoparticles is apparently distributed isotropically in these materials.