Dynamic crossover to tricriticality and anomalous slowdown of critical fluctuations by entanglements in polymer solutions.

Abstract

We have performed accurate dynamic light-scattering measurements near critical demixing points of solutions of polystyrene in cyclohexane with polymer molecular weight ranging from 200 000 to 11.4 x 10(6). Two dynamic modes have been observed, "slow" and "fast," which result from a coupling between diffusive relaxation of critical fluctuations of the concentration and viscoelastic relaxation associated with the entanglement network of the polymer chains. The coupling with the viscoelastic mode causes an additional slowdown of the critical mode on top of the uncoupled diffusion mode. By implementing crossover from the critical to the theta-point tricritical behavior for both static and dynamic properties, we are able to present a quantitative description of the phenomenon and obtain a scaling of the viscoelastic parameters as a function of the molecular weight.