New experiments for improved theoretical description of nonlinear rheology of entangled polymers

The present work discusses four types of new experiments that can improve the current theoretical description of nonlinear rheology of entangled polymers. First, a slowly imposed strain is found to result in nonmonotonic evolution of the state of chain entanglement during quiescent relaxation, consistent with the idea of chain disentanglement after step shear. Second, the stress relaxation upon a sizable step strain is found to be identical to that for small step strain, consistent with a molecular scenario that a strained entangled melt has an entropic barrier to resist chain retraction. Third, the ability of a step-strained polymer to undergo elastic recovery is found to be the same up to strain amplitude of unity, and a sample sheared for a period much longer than the Rouse time is shown to still undergo nearly full elastic recovery. Fourth, an entangled melt, stretched at a rate significantly lower than the Rouse relaxation rate, undergoes full elastic recovery until the point of tensile force maximum. We have discussed an alternative conceptual framework to describe these nonlinear responses of entangled polymers despite the possibility that the tube model might be further remedied to characterize the new rheometric measurements presented in this work.