Interdependent Roles of Electrostatics and Surface Functionalization on the Adhesion Strengths of Nanodiamonds to Gold in Aqueous Environments Revealed by Molecular Dynamics Simulations

Molecular dynamics simulations demonstrate that adhesion strengths as a function of charge for aqueous nanodiamonds (NDs) interacting with a gold substrate result from an interdependence of electrostatics and surface functionalization. The simulations reveal a water layer containing Na+ counterions between a negative ND with surface −COO– functional groups that is not present for a positively charged ND with −NH3+ functional groups. The closer proximity of the positive ND to the gold surface and the lack of cancelation of electrostatic interactions due to counterions and the water layer lead to an electrostatic adhesion force for the positive ND that is nearly three times larger than that of the negative ND. Prior interpretations of experimental tribological studies of ND–gold systems suggested that electrostatics or surface functionalization could be responsible for observed adhesion strength differences. The present work demonstrates how these two effects work together in determining adhesion for this system.