The Steady-State Compliance of Polymer Solutions

Abstract
The steady-state compliance (Je) has been derived from low-frequency dynamic viscoelastic measurements on solutions of several sample of polystyrene, poly-α-methyl styrene, polyvinyl acetate, and cellulose tributyrate in several different solvents including a Θ solvent for polystyrene. The molecular weight (M) distributions were reasonably sharp. Maximum concentrations (c) ranged from 0.17 g/ml (M=860,000) to 0.55 g/ml (M=19,800). In general, Je changes with increasing concentration from a value close to the Zimm theory prediction to a value close to the Rouse theory prediction, the transition occurring in the neighborhood of c[η]=3, where [η] is the intrinsic viscosity. However, for polystyrenes of molecular weights 19,800 and 51,000, values of Je were abnormally small, and some of those for cellulose tributyrate appeared to be abnormally large. Otherwise, there is no marked influence of the chemical nature of either polymer or solvent. The change in behavior with increasing concentration near c[η]=3 is attributed to an overlapping of molecular domains which is sufficient to alter the hydrodynamic interaction. A further change, observed by other investigators at higher concentrations, where the dependence of Je on c and M becomes quite different, is attributed to domination of the behavior by entanglements which develop at a higher degree of overlapping.