Stable polydisperse free-standing porous films made by mechanical deformation

Using molecular dynamics simulations, we show that the methodology of making thin stable nanoporous monodisperse films by biaxial mechanical expansion and subsequent cooling into the glassy state, also works for polydisperse films. To test this, a bidisperse polymer system of an equal number of very long (≈72 entanglements) and short (≤4 entanglements) chains with a polydispersity index of 1.80 is considered. The void formation and the development of the local morphology upon expansion, relaxation, and cooling are investigated. As for the monodisperse case, long chains in thin porous polydisperse films extend over several pores, stabilizing the whole morphology. The short chains do not fill up the pores but tend to aggregate inside the polymer matrix and to avoid surface areas and reduce conformational constraints imposed by the surrounding, a scenario very similar to strain-induced segregation between the strained long and relaxed short chains.