Comparison of the kinetic friction of planar neutral and polyelectrolyte polymer brushes using molecular dynamics simulations

Abstract

We have simulated the relative shear motion of both neutral and polyelectrolyte end-grafted polymer brushes using molecular dynamics. The flexible neutral polymer brush is treated as a bead-spring model, and the polyelectrolyte brush is treated the same way except that each bead is charged and there are counterions present to neutralize the charge. We investigated the friction coefficient, monomer density, and brush penetration for both polyelectrolyte and neutral brushes with both equal grafting density and equal normal force under good solvent conditions. We found that polyelectrolyte brushes had a smaller friction coefficient and monomer penetration than neutral polymer brushes with the identical grafting density and chain length, and the polyelectrolyte brushes supported a much higher normal load than the neutral brushes for the same degree of compression. Charged and neutral brushes with their grafting densities chosen so that they support the same load exhibited approximately the same degree of interpenetration, but the polyelectrolyte brush exhibited a significantly lower friction coefficient. We present evidence that the reason for this is that the extra normal force contribution provided by the counterion osmotic pressure that exists for polyelectrolyte brushes permits them to support the same load as an identical neutral polymer brush of higher grafting density. Because of the resulting lower monomer density for the charged brushes, fewer monomer collisions take place per unit time, resulting in a lower friction coefficient.