Thermodynamics of Polymers in Nanoparticle Films

Many polymer membranes are amorphous solids where the microscopic packing dictates the performance of the membrane. One strategy to improve the performance of membranes has been to blend them with nanoparticles, though it is often challenging to design systems with a high volume fraction of nanoparticles. In this talk, I will describe our recent work studying the dynamics and thermodynamics of polymer blends infiltrated into nanoparticle films. Capillary forces can be readily used to cause the polymer to infiltrate the nanoparticle films, where there is an extraordinarily high surface-to-volume ratio that we find modulates the polymer dynamics and thermodynamics. I will describe our recent work using polymer field theory that predicts large increases in the miscibility window for polymer blends under confinement, which is widened further when one of the polymers wets the nanoparticle surface. I will also show results from our simulations of phase separation kinetics of a polymer blend in nanoparticle films as well as some recent simulations and experiments on the kinetics of infiltration in block and statistical copolymers in nanoparticle packings. Overall, our work presents several novel methods for designing novel, amorphous materials with structure on a variety of length scales and provides fundamental insights into the thermodynamics of highly confined polymers.