Statics of polymer droplets on deformable surfaces

TL;DR

This study uses molecular dynamics simulations to explore how polymer droplets interact with soft, deformable surfaces, revealing how surface softness influences wetting behavior and the transition between classical and coupled adhesion-elastic regimes.

Contribution

It introduces a detailed simulation approach to analyze the equilibrium and wetting properties of polymer droplets on deformable surfaces, including a comparison with phenomenological free-energy models.

Findings

Wetting ridge formation under certain conditions.

Transition between classical Young-Dupré and coupled regimes.

Surface softness affects droplet shape and adhesion.

Abstract

The equilibrium properties of polymer droplets on a soft deformable surface are investigated by molecular dynamics simulations of a bead-spring model. The surface consists of a polymer brush with irreversibly end-tethered linear homopolymer chains onto a flat solid substrate. We tune the softness of the surface by varying the grafting density. Droplets are comprised of bead-spring polymers of various chain lengths. First, both systems, brush and polymer liquid, are studied independently in order to determine their static and dynamic properties. In particular, using a numerical implementation of an AFM experiment, we measure the shear modulus of the brush surface and compare the results to theoretical predictions. Then, we study the wetting behavior of polymer droplets with different contact angles and on substrates that differ in softness. Density profiles reveal, under certain conditions, the formation of a wetting ridge beneath the three-phase contact line. Cap-shaped droplets and cylindrical droplets are also compared to estimate the effect of the line tension with respect to the droplet size. Finally, the results of the simulations are compared to a phenomenological free-energy calculation that accounts for the surface tensions and the compliance of the soft substrate. Depending on the surface/drop compatibility, surface softness and drop size, a transition between two regimes is observed: from one where the drop surface energy balances the adhesion with the surface, which is the classical Young-Dupr\'e wetting regime, to another one where a coupling occurs between adhesion, droplet and surface elastic energies.