Gas Transport in Interacting Planar Brushes

[Image: see text] Recent experiments on melts of spherical nanoparticles (NPs) densely grafted with polymer chains show enhanced gas transport relative to the neat polymer (without NPs). Simulations on such systems do not reproduce these experimental trends. As a means of understanding this unexpected behavior, here we consider the simpler case of two interacting planar brushes, under conditions representing a polymer melt far below its critical point (i.e., where the “free volume” or holes act akin to a poor solvent). Computer simulations illustrate, in agreement with mean-field ideas, that the density profile far away from the walls is flat but with a value that is marginally larger than that of the corresponding polymer melt under identical state conditions. We find that tracer particles, which represent the gas of interest, segregate preferentially to the grafting surface, with this result being relatively insensitive to the nature of polymer–surface interactions. These brush layers therefore correspond to heterogeneous transport media: gas molecules near the grafting surface have accelerated dynamics (presumably parallel to the wall) relative to the corresponding polymer melt, but they have slower dynamics in the central region of the brush. We therefore find that gas molecules perform hop-like motions—they spend a significant part of their time in the regions of fast transport, separated by motions where they “hop” from one surface to the other. These phenomena in combination lead to an overall speedup in gas dynamics in these brush layers relative to a polymer melt, in good agreement with the experimental data.