A convenient way of interpreting steady shear rheo-optical data of semi-dilute polymer solutions

Abstract

Rheo-mechanical and rheo-optical investigations were carried out with the aim of determining the influence of deformation and orientation or disentangling of polymer coils on the flow behavior in the non-Newtonian region of the flow curve, for a moderately concentrated network solution. To avoid the influence of polydispersity this was done on a series of narrowly distributed polystyrene standards (dissolved in toluene). By using steady state shear flow measurements it was possible to detect qualitatively a reduction in the entanglement density within the non-Newtonian flow region. Birefringence experiments were able to show that deformation of the polymer coils also occurs in the Newtonian flow region, which has no effect on the flow behavior in this range, whereas in the non-Newtonian flow region the increase in deformation is lower than in the Newtonian range. The flow birefringence and its orientation can be described over the whole range of the flow curve with a newly developed equation system (Eq. 8 and 14) derived from the stress states of a sheared solution using the stress-optical rule. Starting from these equations, it could be shown, that in the Newtonian flow region a mastercurve in form of a reduced birefringence Δn′/η0=f(γ˙) and a reduced orientation φ= f(γ˙/γ˙crit) can be plotted, independent from concentration and molar mass. A comparison of the experimentally determined orientation angle and birefringence curve form with theoretical deformations and orientations of polymer coils in a solution state, without intermolecular interactions, was able to demonstrate that the flow behavior of a moderately concentrated network solution is determined decisively (approximately to 85%) by the disentanglement.