Recovery of shear-modified polybutadiene solutions

We have investigated the recovery of the overshoot in the transient viscosity, the first normal stress coefficient, and the dynamic modulus for entangled polybutadiene solutions subjected to nonlinear shear flow. The molecular-weight dependences of the various time scales (linear viscoelastic relaxation time, entanglement recovery time, and timescale for decay of stress following cessation of shearing) are all consistent with the usual 3.4 power law. Nevertheless, the time for recovery of the stress overshoot and plateau value of the dynamic modulus were substantially longer (by as much as two orders of magnitude) than the linear viscoelastic relaxation time calculated from the Newtonian viscosity and the equilibrium recoverable compliance. These results indicate that complete entanglement recovery requires cooperative chain motions over a length scale exceeding that associated with linear relaxation. This persistence of a disentangled state means that a state of low viscosity and reduced elasticity is retained for an extended time, suggesting that shear modification can be used to facilitate the processing of polymers.