Slowing down of accelerated structural relaxation in ultrathin polymer films.
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.
Department of Polymer Science and Engineering, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, 210093 Nanjing, China.
Qiyun
Q
Tang
Wenbing
W
Hu
Laboratory of Polymer and Soft Matter Dynamics, Faculté des Sciences, Université Libre de Bruxelles (ULB), Boulevard du Triomphe, Bâtiment NO, Bruxelles 1050, Belgium.
Simone
S
Napolitano