Arm Retraction Dynamics in Dense Polymer Brushes

Large scale Monte Carlo simulations of dense layers of grafted polymer chains in good solvent conditions are used to explore the relaxation of a polymer brush. Monomer displacements are analyzed for the directions parallel and perpendicular to the grafting plane. Autocorrelation functions of individual segments or chain sections are monitored as a function of time. We demonstrate that the terminal relaxation time τ of grafted layers well in the brush regime grows exponentially with degree of polymerization N of the chains, τ ∝ N3 exp(N/Ne), with Ne the entanglement degree of polymerization in the brush. One specific feature of entangled polymer brushes is that the late time relaxation of the perpendicular component coincides for all segments. We use this observation to extract the terminal relaxation time of an entangled brush.