High-Frequency Mechanical Behavior of Pure Polymer-Grafted Nanoparticle Constructs.

Polymer-grafted nanoparticle (GNP) membranes show increased gas permeability relative to pure polymer analogs, with this effect evidently tunable through systematic variations in the grafted polymer chain length and grafting density. Additionally, these materials show less deleterious aging effects relative to the pure polymer. To better understand these issues, we explore the solid-state mechanical properties of GNP layers using quartz crystal microbalance (QCM) spectroscopy, which operates under conditions (≈5 MHz) that we believe are relevant to gas transport. The GNP's high-frequency storage moduli exhibit a characteristic increase with increasing nanoparticle (NP) core loading, consistent with past work on the reinforcement of polymers physically well mixed with bare NPs. However, these GNPs show a substantial, nonmonotonic decrease in loss as a function of chain length (at fixed grafting density), with the loss minimum corresponding to the chain length with the maximum gas permeability. We speculate that this feature corresponds to a dynamical transition, where the GNP membranes go from a jammed solid (colloid-like) to liquid-like (polymer-controlled) behavior with increasing chain length.