From Rouse dynamics to local relaxation: A neutron spin echo study on polyisobutylene melts

Abstract

We investigated the single chain motions of monodisperse polyisobutylene chains in the melt by neutron spin echo spectroscopy. Thereby a wide range in momentum space over a large dynamic range was covered. Motional processes from the center of mass diffusion, the Rouse dynamics to the more local relaxation processes which limit the validity of the standard Rouse model, were elucidated. The observed dynamic structure factors were analyzed in terms of relevant theoretical approaches addressing the limiting factors of the Rouse model. We found that other than claimed in the literature effects of local chain stiffness—they were treated in terms of the all rotational states model and a bending force model—cannot account for the experimental observations. It appears that additional damping effects related to an internal viscosity of the chain have to be involved, in order to explain the experimental results.