Molecular scale simulation of homopolymer wall slip.

The first molecular scale simulation of highly entangled polydisperse homopolymers that is capable of capturing all three regions--no slip, weak slip, and strong slip--of the hydrodynamic boundary condition is presented. An on-lattice dynamic Monte Carlo technique capable of correctly capturing both unentangled and entangled polymer dynamics is used to study the molecular details of wall slip phenomena for homopolymers and energetically neutral walls. For unentangled chains (those exhibiting Rouse dynamics) weak slip is not present but evidence of strong slip is manifest at very high shear rates. For entangled chains (of sufficient length to exhibit reptation dynamics), both weak and strong slip are observed. Consistent with numerous experimental studies, disentanglement and cohesive failure occur at high shear rates. Disentanglement is clearly evidenced in a nonlinear velocity profile that exhibits shear banding, in an excess of chain ends at the slip plane, and perhaps most importantly in a nonmonotonic stress versus shear rate response. The chain end density exhibits a pretransitional periodicity prior to disentanglement. Unentangled Rouse chains do not show this pretransitional response or a bifurcation in their stress versus shear rate response. Finally, it is shown that when polydispersity is introduced, slip phenomena are severely reduced and the inherent constitutive bifurcation is limited to a small region. Predictions are in post facto agreement with many experiments, are distinct from existing results obtained using molecular dynamics simulation techniques, and shed light on fundamental mechanisms of polymer wall slip.