Unveiling the Mechanism of the Location of the Grafted Nanoparticles in a Lamellar-Forming Block Copolymer

Through coarse-grained molecular dynamics simulation of polymer-grafted nanoparticles (NPs) in a lamellar-forming diblock copolymer (BCP), we systematically study the effects of the grafting density (N_g), the compatibility between the grafted chains and the A-block of BCPs (ϵ_gA), and the NP number (N) on the distance (D) of the NPs from the interface by proposing novel characterization parameters of the orientation and distribution of the grafted chains. The NP gradually migrates away from the interface and into the A-block region with the increase of ϵ_gA for all studied N_g, while slightly returning toward the interface at high ϵ_gA and great N_g, which is the first observation of nonmonotonic migration at the molecular level. We ascribe the reason of this to the behavior of the grafted chains that are near the interface. Furthermore, we classify the grafted chains into three types along the normal direction of the interface and the migration process is illustrated by the distribution and orientation of the different types of grafted chains, together with the radial distribution function between the NP and the A-block chains. We observe the formation of the NP layers parallel to the interface for N < 20, and a similar nonmonotonic migration of the layers is as well observed. The D is the largest for a small N because of the excluded volume effects between the NPs. Increasing N_g and N pushes the neighboring NP layers toward the interface due to the mutual repulsion. Generally, this study may shed some light on how to better understand and design high-performance polymer nanocomposites with a tunable location of NPs.