Dynamic Crossover to Tricriticality and Anomalous Slowdown of Critical Fluctuations by Entanglements in Polymer Solutions

TL;DR

This study investigates how entanglements in polymer solutions influence critical fluctuations, revealing a crossover to tricritical behavior and an anomalous slowdown of dynamics through detailed light-scattering experiments.

Contribution

It provides a quantitative description of the crossover from critical to tricritical behavior and links visco-elastic parameters to polymer molecular weight.

Findings

Observation of slow and fast dynamic modes due to coupling effects

Identification of slowdown in critical fluctuations caused by visco-elastic coupling

Scaling laws for visco-elastic parameters with molecular weight

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 million. Two dynamic modes have been observed, ''slow'' and ''fast'', that result from a coupling between diffusive relaxation of critical fluctuations of the concentration and visco-elastic relaxation associated with the entanglement network of the polymer chains. The coupling with the visco-elastic mode causes an additional slowdown of the critical mode on top of the uncoupled diffusion mode. By implementing crossover from critical to theta-point tricritical behavior for both static and dynamic properties, we are able to present a quantitative description of the phenomenon and to obtain a scaling of the visco-elastic parameters as a function of the molecular weight.