Nonelectrostatic Adsorption of Polyelectrolytes and Mediated Interactions between Solid Surfaces

Polymer-mediated interaction between two solid surfaces is directly connected to the properties of the adsorbed polymer layers. Nonelectrostatic interactions with a surface can significantly impact the adsorption of polyelectrolytes to charged surfaces. We use a classical density functional theory to study the effect of various polyelectrolyte solution properties on the adsorption and interaction between two like-charged surfaces. Our results show that nonelectrostatic interactions not only enhance polyelectrolyte adsorption but can also result in qualitatively different salt effects with respect to the adsorbed amount. In particular, we observe decreasing, increasing, and a previously unreported nonmonotonic behavior in the adsorbed amount of polymer with added salt under the conditions studied, although the nonmonotonic regime only occurs for a narrow range in the parameter space. With sufficient nonelectrostatic adsorption, the adsorbed polymer layers produce a long-range repulsive barrier that is strong enough to overcome dispersive interactions that cause surfaces to attract. Concurrently, a short-range bridging attraction is observed when the two polyelectrolyte layers span both the surfaces. Both the repulsive barrier and bridging attraction depend on the charge density of the polymer backbone and the bulk salt concentration but not on the chain length in the semidilute regime studied.

Automated summary

The study found that nonelectrostatic interactions with a surface have a significant impact on the adsorption of polyelectrolytes, potentially resulting in qualitatively different salt effects than the charge effects. Under certain conditions, the adsorbed polymer layers produce a long-range repulsive barrier that can overcome dispersive interactions causing surfaces to attract, and a short-range bridging attraction is observed when two polyelectrolyte layers span both surfaces. These phenomena depend on the charge density of the polymer backbone and the bulk salt concentration, rather than the chain length in the semidilute regime studied.