Capillary filling dynamics of polymer melts in a bicontinuous nanoporous scaffold

Polymer infiltrated nanoporous gold is prepared by infiltrating polymer melts into a bicontinuous, nanoporous gold (NPG) scaffold. Polystyrene (PS) films with molecular weights (M-w) from 424 to 1133 kDa are infiltrated into a NPG scaffold (similar to 120 nm), with a pore radius (R-p) and pore volume fraction of 37.5 nm and 50%, respectively. The confinement ratios (Gamma=(R) g/R-p) range from 0.47 to 0.77, suggesting that the polymers inside the pores are moderately confined. The time for PS to achieve 80% infiltration (tau 80%) is determined using in situ spectroscopic ellipsometry at 150 degrees C. The kinetics of infiltration scales weaker with Mw, tau 80%proportional to M(w)1.30 +/- 0.20, than expected from bulk viscosity M-w(3.4). Furthermore, the effective viscosity of the PS melt inside NPG, inferred from the Lucas-Washburn model, is reduced by more than one order of magnitude compared to the bulk. Molecular dynamics simulation results are in good agreement with experiments predicting scaling as M-w(1.4). The reduced dependence of M-w and the enhanced kinetics of infiltration are attributed to a reduction in chain entanglement density during infiltration and a reduction in polymer-wall friction with increasing polymer molecular weight. Compared to the traditional approach involving adding discrete particles into the polymer matrix, these studies show that nanocomposites with higher loading can be readily prepared, and that kinetics of infiltration are faster due to polymer confinement inside pores. These films have potential as actuators when filled with stimuli-responsive polymers as well as polymer electrolyte and fuel cell membranes.