Self-diffusion of multiarm star polymers in solution far from and near the ordering transition

The self-diffusion of three 128-arm polybutadiene star solutions in toluene was investigated over a broad concentration range from dilute to the ordering region with pulsed field gradient NMR (PFG-NMR). The strong concentration dependence of the self-diffusion coefficient in the fluid state is distinguished clearly from that of linear chains and can be described by a non-Arrhenius VFT-like equation with the concentration playing the role of inverse temperature. In the concentrated regime, the observation of two dynamic phases reflects the coexistence of crystalline and liquid phases over a limited concentration region. The concentration dependences of both the ordinary (fluid-like) diffusion and the completely restricted in-cage motion of these hyper stars are in agreement with the behavior of concentrated colloidal suspensions.