Non-ideality of polymer melts confined to nanotubes

Corrections to chain ideality have been demonstrated recently for polymer melts in the bulk and in ultrathin films. It has been shown that the effect of incomplete screening is stronger in the latter. We show here that the deviation from ideality is even stronger in thin capillaries. Describing the crossover from the free bulk to the confined regime as the radius of the capillary decreases below the typical coil radius we make connection to the so far disconnected work by Brochard and de Gennes (J. Phys. ( Paris), Lett., 40 ( 1979) 399) predicting chain segregation in very thin capillaries. Due to the generalized Porod scattering of the segregated chains, the Kratky representation of the intrachain structure factor reveals a plateau for all regimes although the chains become swollen with increasing confinement. Copyright (C) EPLA, 2011