Shear-Induced Phase Separation of Chemically-Responsive Polymer Solutions
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Chemically-responsive polymers are macromolecules that respond to local variations of the chemical composition of the solution by changing their conformation, with notable examples including polyelectrolytes, proteins and DNA. The polymer conformation changes can occur in response to changes to the pH, the ionic strength or to the concentration of a generic solute that interacts with the polymer. In many situations, the spatial distribution of the chemical stimuli can be highly inhomogeneous, which can lead to large spatial variations of polymer conformation and of the rheological properties of the mixture. Here, we develop a theory for the flow of a mixture of a solute and chemically-responsive polymers. To model the polymer conformation changes introduced by the interactions with the solute, we consider the polymers as linear elastic dumbbells whose spring stiffness depends on the solute concentration. We use the Onsager's variational formalism to derive the equations governing the evolution of the variables, which unveils novel couplings between the distribution of dumbbells and that of the solute. By using a linear stability analysis, we find a shear-induced phase separation whereby a homogeneous distribution of solute and dumbbells spontaneously demix. Similar phase transitions have been observed in previous experiments and may play an important role in living systems.