Adhesion of nanoparticles to polymer brushes studied with the ghost tweezers method

Mechanisms of interactions between nanoparticles (NPs) and polymer brushes (PBs) are explored using dissipative particle dynamics simulations and an original "ghost tweezers" method that emulates lab experiments performed with optical or magnetic tweezers. The ghost tweezers method is employed to calculate the free energy of adhesion. Ghost tweezers represents a virtual harmonic potential, which tethers NP with a spring to a given anchor point. The average spring force represents the effective force of NP-PB interaction as a function of the NP coordinate. The free energy landscape of NP-PB interactions is calculated as the mechanical work needed to transfer NP from the solvent bulk to a particular distance from the substrate surface. With this technique, we explore the adhesion of bare and ligand-functionalized spherical NPs to polyisoprene natural rubber brush in acetone-benzene binary solvent. We examine two basic mechanisms of NP-PB interactions, NP adhesion at PB exterior and NP immersion into PB, which are governed by interplay between entropic repulsive forces and enthalpic attractive forces caused by polymer adsorption at the NP surface and ligand adsorption at the substrate. The relative free energies of the equilibrium adhesion states and the potential barriers separating these states are calculated at varying grafting density, NP size, and solvent composition.