Entanglement-Stabilized Nanoporous Polymer Films Made by Mechanical Deformation.

We present a new simulation-guided process to create nanoporous materials, which does not require specific chemical treatment and solely relies on mechanical deformation of pure highly entangled homopolymer films. Starting from fully equilibrated freestanding thick polymer melt films, we apply a simple "biaxial expansion" deformation. Upon expansion holes form, which are prevented from growing and coalescing beyond a characteristic size due to the entanglement structure of the melt. We investigate the local morphology, the void formation upon expansion, and their stabilization. The dependence of the average void (pore) size and void fraction (porosity) on the total strain and subsequent relaxation is investigated. Furthermore, the stabilization of the porous structure of the thin expanded films through cooling below the glass transition temperature is discussed.