Computational investigation of the effects of polymer grafting on the effective interaction between silica nanoparticles in water†

Understanding and control of the effective interaction between nanoscale building blocks (colloids or nanoparticles) dispersed in a solvent is an important prerequisite for the development of bottom-up design strategies for soft functional materials. Here, we have employed all-atom molecular dynamics simulations to investigate the impact of polymer grafting on the solvent-mediated effective interaction between the silica nanoparticles (Si-NPs) in water, and in turn, on its bulk structural and thermodynamic properties. We found that the nature of the short grafting polymers [characterized by their interaction with water (hydrophobicity or hydrophilicity) and molecular weight] has a profound effect on the range and strength of the effective interaction between the Si-NPs. The hydrophobic polymer [such as polyethylene (PE)]-grafting of Si-NP gives rise to a more attractive interaction between the Si-NPs compared to the hydrophilic polymer [such as polyethylene glycol (PEG)] and non-grafted cases. This study further provides fundamental insights into the molecular origin of the observed behavior of the effective pair interactions between the grafted Si-NPs. For PE-grafted Si-NPs, the confined water (water inside the cavity formed by a pair of Si-NPs) undergoes a partial dewetting transition on approaching below a critical inter-particle separation leading to a stronger attractive interaction. Furthermore, we report that the effective attraction between the PE-grafted Si-NPs can be reliably controlled by changing the grafting PE density. We have also investigated the bulk structural and thermodynamic behavior of the coarse-grained Si-NP system where the particles interact via effective interaction in the absence of water. We believe that the insights gained from this work are important prerequisites for formulating rational bottom-up design strategies for functional materials where nano- (or, colloidal) particles are the building blocks.