(670g) Interrelations between Segmental and Chain Dynamics in the Glass Formation Range of Bulk and Nanoconfined Polymers

Canonical theories of polymer chain dynamics predict that segmental and chain motion should share a common temperature dependence. It has long been known that this prediction can fail for polymers in the glass formation range; however, the origin of this failure has been unresolved. Here we describe how the introduction of dynamic heterogeneity to the Rouse model leads to a quantitative prediction for the decoupling between segmental and chain translational dynamics near the glass transition. We further discuss the extension of these findings to other relaxation functions and to nanoconfined polymers, where interfaces can lead to substantial alterations in dynamical properties and their interrelations.