Nanoparticles insertion and dimerization in polymer brushes

Molecular dynamics simulations are conducted to systematically investigate the insertion of spherical nanoparticles (NPs) in polymer brushes as a function of their size, strength of their interaction with the polymers, polymer grafting density, and polymer chain length. For attractive interactions between the NPs and the polymers, the depth of NPs' penetration in the brush results from a competition between the enthalpic gain due to the favorable polymer-NP interaction and the effect of osmotic pressure resulting from displaced polymers by the NP's volume. A large number of simulations show that the average depth of the NPs increases by increasing the strength of the interaction strength. However, it decreases by increasing the NPs' diameter or increasing the polymer grafting density. While the NPs' effect on the polymer density is local, their effect on their conformations is long-ranged and extends laterally over length scales larger than the NP's size. This effect is manifested by the emergence of laterally damped oscillations in the normal component of the chains' radius of gyration. Interestingly, we found that for high enough interaction strength, two NPs dimerize in the polymer brush. The dimer is parallel to the substrate if the NPs' depth in the brush is shallow. However, the dimer is perpendicular to the substrate if the NPs' are deep in the brush. These results imply that polymer brushes can be used as a tool to localize and self-assemble NPs in polymer brushes.