RESUMEN

In a recent reformulation of the Marrucci-Ianniruberto constitutive equation for the rheology of entangled polymer melts in the context of nonequilibrium thermodynamics, rather large values of the convective constraint release parameter ßccr had to be used in order for the model not to violate the second law of thermodynamics. In this work, we present an appropriate modification of the model, which avoids the splitting of the evolution equation for the conformation tensor into an orientation and a stretching part. Then, thermodynamic admissibility simply dictates that ßccr ≥ 0, thus allowing for more realistic values of ßccr to be chosen. Moreover, and in view of recent experimental evidence for a transient stress undershoot (following the overshoot) at high shear rates, whose origin may be traced back to molecular tumbling, we have incorporated additional terms into the model accounting, at least in an approximate way, for non-affine deformation through a slip parameter ξ. Use of the new model to describe available experimental data for the transient and steady-state shear and elongational rheology of entangled polystyrene melts and concentrated solutions shows close agreement. Overall, the modified model proposed here combines simplicity with accuracy, which renders it an excellent choice for managing complex viscoelastic fluid flows in large-scale numerical calculations.