Calculations of free energy of surface interactions in crystalline polyethylene

The surface free energy of the crystalline polyethylene (PE) is an important property related with wettability, adhesion, and crystal growth. We investigated the profiles of free energy of surface interactions in the fully thermalized crystalline PE during debonding and shearing with atomistic molecular dynamics simulations using steered molecular dynamics and umbrella sampling techniques. The stress profiles during debonding and shearing processes were also estimated and compared with those obtained from analogous deformation simulations. We estimated the vacuum surface free energies of two different crystallographic surfaces (100) and (010) of the crystalline PE from the free energy changes during the debonding process. The estimated surface free energies were insensitive to the choice of simulation protocols after combining estimates from both forward and backward processes and were in excellent agreement with those obtained from an experiment on PE single crystal aggregates, which underscores the importance of the inclusion of the entropic contribution in the free energy calculated with the fully flexible interface adopted in this study.