We demonstrate with molecular simulation that the acceleration of structural relaxation, also known as physical aging, commonly experimentally observed in thin polymer films slows down at extremely small thicknesses. This phenomenon can be attributed to an inversed free volume diffusion process caused by the sliding motion of chain molecules. Our findings provide direct evidence of the relationship between the sliding motion of short chain fragments and the structural relaxation of ultrathin polymer films, and also verify the existence of a new confinement effect at the nanoscale.

• Received 8 November 2013

DOI:https://doi.org/10.1103/PhysRevLett.112.148306