Reduced Interfacial Entanglement Density Affects the Boundary Conditions of Polymer Flow

Hydrodynamic boundary conditions play a crucial role in the flow dynamics of thin films and can be probed by the analysis of liquid front profiles. For long-chained polymer films it was reported that a deviation from a symmetric profile is a result of viscoelastic effects. In this Letter, however, evidence is given that merely a slip-boundary condition at the solid-liquid interface can lead to an asymmetric profile. Variation of molecular weight shows that slippage is directly linked to chain entanglements. We find a reduced entanglement density at the solid-liquid interface (factors 3 to 4), which stresses the importance of considering nonbulk polymer properties in the vicinity of an interface.