Temperature-Controlled Slip of Polymer Melts on Ideal Substrates

Abstract

The temperature dependence of the hydrodynamic boundary condition between a polydimethylsiloxane melt and two different nonattractive surfaces made of either an octadecyltrichlorosilane self-assembled monolayer or a grafted layer of short polydimethylsiloxane chains has been characterized. We observe a slip length proportional to the fluid viscosity. The temperature dependence is deeply influenced by the surfaces. The viscous stress exerted by the polymer liquid on the surface is observed to follow exactly the same temperature dependences as the friction stress of a cross-linked elastomer sliding on the same surfaces. Far above the glass transition temperature, these observations are rationalized in the framework of a molecular model based on activation energies: increase or decrease of the slip length with increasing temperatures can be observed depending on how the activation energy of the bulk viscosity compares to that of the interfacial Navier's friction coefficient.