A modified tube dilatation theory for the relaxation of entangled linear polymer melts

In this paper, the “tube dilatation” or “tube Enlargement” concept introduced by Marrucci, is revisited in the case of broad entangled linear polymer melts. Using the tube fluctuation relaxation function of Doi and a linear mixing rule, the model implicitly contains both the features of double reptation and time modification by tube renewal. It has been shown that theoretical arguments of both double reptation with tube renewal and tube dilatation can be used to take into account the effect of polydispersity on the distribution of relaxation times. The model has been tested for some polymers with various N/Ne values. However, experiments indicate that the loss of only one entanglement does not systematically induce a change of the relaxation times through a constraint release and tube renewal process. The freeing of a critical volume, larger than the volume of a tube segment, is required to induce an efficient dilution effect on relaxation times.