Coupling between Polymer Conformations and Dynamics Near Amorphous Silica Surfaces: A Direct Insight from Atomistic Simulations

The dynamics of polymer chains in the polymer/solid interphase region have been a point of debate in recent years. Its understanding is the first step towards the description and the prediction of the properties of a wide family of commercially used polymeric-based nanostructured materials. Here, we present a detailed investigation of the conformational and dynamical features of unentangled and mildly entangled cis-1,4-polybutadiene melts in the vicinity of amorphous silica surface via atomistic simulations. Accounting for the roughness of the surface, we analyze the properties of the polymer chains as a function of their distance from the silica slab, their conformations and the chain molecular weight. Unlike the case of perfectly flat and homogeneous surfaces, the monomeric translational motion parallel to the surface was affected by the presence of the silica slab up to distances comparable with the extension of the density fluctuations. In addition, the intramolecular dynamical heterogeneities in adsorbed chains were revealed by linking the conformations and the structure of the adsorbed chains with their dynamical properties. Strong dynamical heterogeneities within the adsorbed layer are found, with the chains possessing longer sequences of adsorbed segments (“trains”) exhibiting slower dynamics than the adsorbed chains with short ones. Our results suggest that, apart from the density-dynamics correlation, the configurational entropy plays an important role in the dynamical response of the polymers confined between the silica slabs.