Rheological studies of moderately concentrated polystyrene solutions. I. A new method for the extrapolation of the zero-shear viscosity

Measurements of the viscosity coefficient η of solutions of polystyrene (Mw = 6.0 × 105 and 1.77 × 106) in trans-decalin (TD, θ solvent) and toluene (TL, good solvent) as function of shear rate (11−104 s−1), concentration (4.24−11.21 wt %), and temperature (10–50°C) are reported. As a new theoretically grounded method for the determination of the zero-shear viscosity η0 it is proposed to plot η as a function of . The intercepts of the straight lines obtained by this procedure give η0 in good agreement with directly measured values.

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Rheological studies of moderately concentrated polystyrene solutions in the vicinity of the θ temperature. II. Shear-rate dependence for different thermodynamic conditions

The viscosity data of moderately concentrated polystyrene solutions in trans-decalin (TD) (θ solvent, θ temperature 21°C) and toluene (TL) (good solvent) reported in Part I are discussed in terms of Graessley's entanglement theory. Under good solvent conditions, Graessley's master curve provides an excellent fit up to high shear rates, whereas in the vicinity of the θ conditions the data have to be modified by a parameter ηfric introduced by Ito and Shishido. The characteristic time of mechanical response to flow of chains approximately given by the shift factor τ0 is found in good solvents to be on the order of the Rouse relaxation time. In poor solvents, close to demixing, τ0 tends to muc…

Phase separation of flowing polymer solutions studied by viscosity and by turbidity