A relationship between steady-state shear melt viscosity and molecular weight distribution in polystyrene



A model that relates to the molecular weight distribution (MWD) of high-density polyethylene to the steady-state shear melt viscosity has been applied to polystyrene melts. Relations are developed for predicting the rheological flow curve from the molecular weight distribution. Relationships are also developed to predict the MWD from the flow curve, although practical limitations to this procedure are given. From a consideration of predictions of the model and experimental data, it is concluded that the transition for a given molecular species from Newtonian to non-Newtonian flow is sharp. Additionally, the calculated empirical parameter that partitions the MWD into molecules that act in a Newtonian fashion and those that do not is shown to be equivalent to the largest molecular weight homolog that can still undergo Newtonian flow at a given shear rate for monodisperse fractions. The temperature dependence of the relaxation times is found to be somewhat higher than that predicted by the Rouse theory. An activation energy of 30 kcal/mole for η0 was used to fit the experimental viscosity data adequately at 190° and 225°C. The terminal relaxation spectrum for a narrow-MWD polystyrene standard is calculated and found to agree well for long relaxation times with that reported in the literature.