Dynamics of critical fluctuations in polymer solutions

Abstract

Using dynamic light scattering we have investigated the time dependence of fluctuations near the critical point of phase separation in solutions of polystyrene in cyclohexane with polymer molecular weights ranging from 196,000 to 11.4 x 10(6) g mol(-1). At the lowest polymer molecular weight the dynamic correlation function follows a single-exponential decay with a decay rate that can be represented by the mode-coupling theory of critical dynamics but with a mesoscopic viscosity that characterizes the hydrodynamic environment of the polymers in the solution. At all higher polymer molecular weights two distinct dynamic modes are observed, a slow and a fast mode, that originate from a coupling of the critical concentration fluctuations with viscoelastic relaxation of the polymer chain in solutions. This coupling causes an additional slowing down of the fluctuations on top of the well-known critical slowing down expected in the absence of a coupling between the two modes. From an analysis of the time dependence of the experimental dynamic correlation functions in terms of a theory of coupling of dynamic modes we are able to determine the viscoelastic properties of the polymers in the solution. These viscoelastic properties diverge in the theta-point limit of infinite polymer molecular weight.