Viscoelastic characterization of moderately concentrated polystyrene solutions by dynamic light scattering

The dynamic light scattering measurements were performed for moderately concentrated entangled solutions of atactic polystyrene in benzene (BZ) at 25.0 °C, in cyclohexane (CH) at 34.5 °C (Θ), and in diethyl malonate (DEM) at 35.0 °C (Θ) to characterize their viscoelastic properties. The results have shown that while the mutual diffusion coefficient D increases in the BZ solutions and decreases in the CH and DEM solutions with increasing polymer mass concentration c, the friction coefficient ζ for the three solutions increases with c showing the same power-law behavior irrespective of the weight-average molecular weight M_w and solvent quality. It has been found that the instantaneous longitudinal modulus L₀ for the CH and DEM solutions increases in proportion to c², obeying the familiar relation for the plateau value (4/3)G_N of the longitudinal stress relaxation modulus, but the L₀ values for these solutions are somewhat smaller than the values predicted from the relation. The terminal relaxation time τ_m for the two Θ solvent systems has been found to follow the power-law τ_m∝c^2.7, showing good correspondence to the relation established by rheological measurements.