Nonlinear rheology of polymer melts: a new perspective on finite chain extensibility effects

Measurements by Luap et al. (2005) of elongational viscosity and birefringence of two nearly monodisperse polystyrene melts with molar masses $M_{w}$ of $206,000g{\cdot}mol^{-1}$ (PS206k) and $465,000g{\cdot}mol^{-1}$ (PS465k) respectively are reconsidered. At higher elongational stresses, the samples showed clearly deviations from the stress optical rule (SOR). The elongational viscosity data of both melts can be modeled quantitatively by the MSF model of Wagner et al. (2005), which is based on the assumption of a strain-dependent tube diameter and the interchain pressure term of Marrucci and Ianniruberto (2004). The only nonlinear parameter of the model, the tube diameter relaxation time, scales with $M_{w}^{2}$. In order to get agreement with the birefringence data, finite chain extensibility effects are taken into account by use of the $Pad\ approximation of the inverse Langevin function, and the interchain pressure term is modified accordingly. Due to a selfregulating limitation of chain stretch by the FENE interchain pressure term, the transient elongational viscosity shows a small dependence on finite extensibility only, while the predicted steady-state elongational viscosity is not affected by non-Gaussian effects in agreement with experimental evidence. However, deviations from the SOR are described quantitatively by the MSF model by taking into account finite chain extensibility, and within the experimental window investigated, deviations from the SOR are predicted to be strain rate, temperature, and molar mass independent for the two nearly monodisperse polystyrene melts in good agreement with experimental data.