Molecular observation of contour-length fluctuations limiting topological confinement in polymer melts

Phys Rev Lett. 2002 Feb 4;88(5):058301. doi: 10.1103/PhysRevLett.88.058301. Epub 2002 Jan 17.

Abstract

In order to study the mechanisms limiting the topological chain confinement in polymer melts, we have performed neutron-spin-echo investigations of the single-chain dynamic-structure factor from polyethylene melts over a large range of chain lengths. While at high molecular weight the reptation model is corroborated, a systematic loosening of the confinement with decreasing chain length is found. The dynamic-structure factors are quantitatively described by the effect of contour-length fluctuations on the confining tube, establishing this mechanism on a molecular level in space and time.