The effect of rotationality on nonlinear shear flow of polymer melts and solutions

By considering the rotationality of shear flow, we distinguish between tube segments created by reptation before the inception of shear flow and those created during flow. Tube segments created before inception of shear flow experience both stretch and orientation, while tube segments created after inception of flow are not stretched, but are only aligned in the flow direction. Based on this idea, the Rotation Zero Stretch (RZS) model allows for a quantitative description of the start-up of shear flow and stress relaxation after step-shear strain experiments, in agreement with data of polystyrene long/short blends and corresponding polystyrene 3-arm star polymers investigated by Liu et al. (Polymer 2023, 281:126125), as well as the shear viscosity data of poly(propylene carbonate) melts reported by Yang et al. (Nihon Reoroji Gakkaishi 2022, 50:127–135). In the limit of steady-state shear flow, the RZS model converges to the Doi-Edwards IA model, which quantitatively describes the steady-state shear viscosity of linear polymer melts and long/short blends. The assumption of “non-stretching” of tube segments created during rotational flow is therefore in agreement with the available experimental evidence. Three-arm star polymers behave in a similar way as corresponding blends of long and short polymers confirming the solution effect of the short arm in asymmetric stars. The analysis of step-shear strain experiments reveals that stress relaxation is at first dominated by stretch relaxation, followed at times larger than the Rouse stretch relaxation time by relaxation of orientation as described by the damping function of the Doi-Edwards IA model. The RZS model does not require any nonlinear-viscoelastic parameter, but relies solely on the linear-viscoelastic relaxation modulus and the Rouse stretch relaxation time.

Graphical Abstract