Local Structure of Polymer-Grafted Nanoparticle Melts

Polymer-grafted nanoparticle (GNP) membranes show unexpected gas transport enhancements relative to the neat polymer, with a maximum as a function of graft molecular weight (MW_g ≈ 100 kDa) for sufficiently high grafting densities. The structural origins of this behavior are unclear. Simulations suggest that polymer segments are stretched near the nanoparticle (NP) surface and form a dry layer, while more distal chain fragments are in their undeformed Gaussian states and interpenetrate with segments from neighboring NPs. This theoretical basis is derived by considering the behavior of two adjacent NPs; how this behavior is modified by multi-NP effects relevant to gas separation membranes is unexplored. Here, we measure and interpret SAXS data for poly(methyl acrylate)-grafted silica NPs and find that for very low MW_gs, contact between GNPs obeys the two-NP theory─namely that the NPs act like hard spheres, with radii that are linear combinations of the NP core sizes and the dry zone dimensions; thus, the interpenetration zones relax into the interstitial spaces. For chains with MW_g > 100 kDa, the interpenetration zones are in the contact regions between two NPs. These results suggest that for MW_gs below the transition, gas primarily moves through a series of dry zones with favorable transport, with the interpenetration zone with less favorable transport properties in parallel. For higher MW_gs, the dry and interpenetration zones are in series, resulting in a decrease in transport enhancement. The MW_g at the transport maximum then corresponds to the chain length with the largest, unfavorable stretching free energy.