Journal of Polymer Science Part B: Polymer Physics, Vol.39, No.2, 211-217, 2001
Viscoelastic properties of dilute polymer solutions: The effect of varying the concentration
Dynamic viscoelastic behavior was investigated for solutions of polystyrene in tricresyl phosphate, a good solvent, at concentrations, c, less than the coil-overlapping concentration, c*. At the infinite dilution limit, the behavior was in accord with the theory of Doi and Edwards involving the excluded volume potential and hydrodynamic interaction (HDI). Thus, the viscoelastic functions were completely derived from the intrinsic viscosity-molecular weight relation. At finite c, the complex modulus was represented by the sum of two terms. One was a Rouse-Zimm (RZ) term conveniently represented by the Zimm theory with an arbitrarily chosen value of the HDI parameter. The other was a term with a single relaxation time, longer than the longest RZ relaxation time, and with a high-frequency modulus proportional to the square of c [the long-time (LT) term]. The behavior of the RZ term indicated the stronger screening of HDI with increasing c. Using the experimental c dependence of the longest RZ relaxation time to get the relevant parameter, we compared the RZ viscoelastic function with the Muthukumar-Freed theory. The agreement was good at low concentrations, c < c* The contribution of the LT term, which was not included in the theory, was quite significant at low frequencies; about 60% of the Huggins coefficient was attributable to this term. (C) 2000 John Wiley & Sons, Inc.
Keywords:dilute polymer solution;viscoelasticity;Rouse model;hydrodynamic interaction;Huggins coefficient