Strongly Compressed Polyelectrolyte Brushes under Shear

By means of molecular dynamics simulations we provide evidence for pronounced counterion immobilization in strongly compressed polyelectrolyte-brush bilayers, where the counterions represent the vast majority of mobile solvent particles. As a consequence, hydrodynamic effects are strongly suppressed and semidilute bilayers can respond to shear motion like electrically neutral bilayers at melt density. For large, time-independent shear rates, γ̇, the shear force scales as f(γ̇) ∼ γ̇^0.69, in agreement with scaling theory. In this regime, polyelectrolyte-brush bilayers can stabilize highly nonstationary processes, such as the instantaneous inversion of the shear direction. The absence of hydrodynamic flow leads to a suppression of the overshoot for the shear force, which is found for electrically neutral bilayers with the same molecular parameters. We suggest that nature uses this mechanism to optimize biolubrication, for instance in synovial joints.