Structural and Dynamical Coupling in Solvent-Free Polymer Brushes Elucidated by Molecular Dynamics Simulations.

Abstract

We investigate the chain configuration and segmental dynamics in interacting solvent-free polymer brushes using molecular dynamics simulations. The brush systems are designed to mimic the interstitial space between a pair of neighboring polymer-grafted nanoparticles in solvent-free nanoparticle-organic hybrid materials. Each brush consists of uniformly grafted chains formed by a given number of monomer beads. In monodisperse systems, two opposing brushes have the same chain length and grafting density. In mixed conditions, we consider binary systems with two surfaces being separately grafted with polymers of distinct chain lengths at different grafting densities as well as bidisperse systems with polymers of two different lengths being tethered to the surfaces at a fixed grafting density. We demonstrate that the brush configuration and interpenetration are both governed by the need that monomer beads have to uniformly fill the space. For systems with longer chain lengths and/or higher grafting densities, the larger interwall separation yields more stretched brush conformations and reduced extents of interbrush mixing. As a result, the polymer configurational entropy is generally decreased and the segment-to-segment relaxation dynamics is slowed down accordingly. The grafting of chains at a high density not only makes the relaxation dynamics deviate from the standard Rouse prediction but also leads to distinct relaxation times for the free and tethered segments. The more slowly relaxing tethered segments play a more important role in determining the overall end-to-end fluctuations. Moreover, the two distinct relaxation processes are consistent with the two-stage decay in the Rouse mode fluctuation autocorrelation function. In the presence of brush bidispersity, the collaboration between polymers of different lengths is evidently observed in the brush profiles. The variations of the chain configuration for the two polymers are complementary, and the associated relaxation dynamics of the two species are significantly coupled.