Linear and Nonlinear Shear Rheology of a Marginally Entangled Ring Polymer

We present systematic, unique linear and nonlinear shear rheology data of an experimentally pure ring polystyrene and its linear precursor. This polymer was synthesized anionically and characterized by interaction chromatography and fractionation at the critical condition. Its weight-average molar mass is 84 kg/mol; i.e., it is marginally entangled (entanglement number <i>Z</i> ≈ 5). Its linear viscoelastic response appears to be better described by the Rouse model (accounting for ring closure) rather than the lattice-animal-based model, suggesting a transition from unentangled to entangled ring dynamics. The failure of both models in the terminal region may reflect the remaining unlinked linear contaminants and/or ring–ring interpenetration. The viscosity evolution at different shear rates was measured using a homemade cone-partitioned plate fixture in order to avoid edge fracture instabilities. Our findings suggest that rings are much less shear thinning compared to their linear counterparts, whereas both obey the Cox–Merz rule. The shear stress (or viscosity) overshoot is much weaker for rings compared to linear chains, pointing to the fact that their effective deformation is smaller. Finally, step strain experiments indicate that the damping function data of ring polymers clearly depart from the Doi–Edwards prediction for entangled linear chains, exhibiting a weak thinning response. These findings indicate that these marginally entangled rings behave like effectively unentangled chains with finite extensibility and deform much less in shear flow compared to linear polymers. They can serve as guideline for further investigation of the nonlinear dynamics of ring polymers and the development of constitutive equations