Do Deviations from Reptation Scaling of Entangled Polymer Melts Result from Single- or Many-Chain Effects?

Abstract

By studying the relaxation of small amounts of short entangled "probe" chains in a high molecular weight matrix, we show that the deviations from reptation scaling of the longest relaxation time are not as much dominated by single-chain effects (usually referred to as contour length fluctuations or CLF) as assumed by current mesoscopic models but also originate to a very significant extent from mutual chain relaxation effects. This result is in fact consistent with literature data on tracer and self-diffusion. Moreover, tube theories also overpredict the influence of CLF on the plateau modulus. Improved theories, simulations, and careful experiments are urgently needed to resolve this important question.