Surface morphologies of spherical polyelectrolyte brushes induced by trivalent salt ions

The surface morphologies of spherical polyelectrolyte brushes in salt solutions with opposite trivalent ions are studied using molecular dynamics (MD) simulations. The impact of salt concentration, grafting density, and charge fraction on brush morphologies is investigated systematically. A variety of surface patterns are predicted and the phase diagrams are presented. Both lateral and radial microphase separated structures in the brushes are observed upon varying the salt concentration. With low grafting density the spherical brush is separated into several patches, the number of which decreases with the addition of salt. At high grafting density, the polymer brush changes its morphology from an extended micelle to a 'carpet + brush' to the collapsed state upon increasing the salt concentration. Especially, the 'carpet + brush' structure consists of a core formed by partially collapsed brush chains and a corona formed by other stretched chains. The inter-chain 'bridging' interactions mediated by trivalent ions and the curvature effect play important roles in determining the chain conformations and brush structures.