Molecular dynamics of shear banding flow in associative polymers solutions: effect of sticker groups location.

Non-equilibrium molecular dynamics are used in a coarse-grained scale to simulate the simple shear flow of telechelic and non-telechelic associative polymer solutions. The work includes the study of inception of flow and stress relaxation in transient flows and the constitutive curve at steady state. The instabilities (plateau stress, stress maxima) and the formation of bands with different velocity gradient and concentration depend on the location of the hydrophobic sites (sticker sites, SS) in the chain. Results allow to shed light on the origin of banded flow within the transient state, related to depletion of bridges between aggregates. This situation induces instabilities in the velocity profiles and concentration inhomogeneities along the velocity gradient during the stress overshoot. As the steady state is reached, instabilities disappear for systems where the SS are in the middle of the chain. The conformation relaxation occurs during a time scale larger than that of the stress, but this is not sufficient condition for the presence of banded flow in telechelic polymer solutions, as it holds in polymer melts. The difference in concentration among the bands suggests the existence of a shear-gradient concentration coupling mechanism under banded flow conditions, such as spatial non-homogeneities in the network density, induces chain diffusivity in the gradient direction and increasing normal stresses, especially in telechelic chains. The role of normal stresses on the flow-concentration coupling instability is analyzed in detail. [ABSTRACT FROM AUTHOR]