Revisit the Stress-Optical Rule for Entangled Flexible Chains: Overshoot of Stress, Segmental Orientation, and Chain Stretch on Start-up of Flow

Abstract

For flexible polymers, the deviatoric parts of the stress and optical anisotropy tensors, with the latter reflecting the orientational anisotropy of the monomeric segments, are proportional to each other. This proportionality, known as the stress-optical rule (SOR), is valid not only in the linear viscoelastic regime but also in the moderately nonlinear regime, given that the chain is not highly stretched and is free from the finite extensible nonlinear elasticity (FENE) effect. On start-up of flow in such a moderately nonlinear regime, the chain exhibits an overshoot of the shear stress and thus of the shear component of the segmental orientational anisotropy. Nevertheless, it was not clearly understood whether this overshoot is associated with an overshoot of chain stretch. This study revisited SOR to conduct a simple analysis for this problem. It turned out that the orientational anisotropy of subchains overshoots but the subchain stretch (identical to the chain stretch) does not when the shear stress overshoots in the moderately nonlinear regime.