Macromolecules, Vol.27, No.25, 7437-7446, 1994
Polymer Motion at the Crossover from Rouse to Reptation Dynamics
Employing neutron spin-echo spectroscopy we have studied the dynamic structure factors for the relaxation of a single. chain;in polymer melts. We have varied the molecular weights through the transition region from unrestricted Rouse dynamics to entanglement controlled behavior. Investigating the dependence of the dynamic structure factor on the momentum transfer and, it is possible to access the different relaxation modes separately. We found that, depending on their spatial extension in relation to the entanglement distance, larger scale relaxations are successively slowed down compared to Rouse relaxation. A comparison with macroscopic diffusion and viscosity data yields excellent internal consistency. Furthermore, we solve explicitly the generalized Rouse model by Hess(12) and compare its. predictions to our data. Fitting only two parameters, all the Q and molecular weight dependent structure factors can be well reproduced.