Relating Dry Friction to Interdigitation of Surface Passivation Species: A Molecular Dynamics Study on Amorphous Carbon.

Friction in boundary lubrication is strongly influenced by the atomic structure of the sliding surfaces. In this work, friction between dry amorphous carbon (a-C) surfaces with chemisorbed fragments of lubricant molecules is investigated employing molecular dynamic simulations. The influence of length, grafting density and polarity of the fragments on the shear stress is studied for linear alkanes and alcohols. We find that the shear stress of chain-passivated a-C surfaces is independent of the a-C density. Among all considered chain-passivated systems, those with a high density of chains of equal length exhibit the lowest shear stress. However, shear stress in chain-passivated a-C is consistently higher than in a-C surfaces with atomic passivation. Finally, surface passivation species with OH head groups generally lead to higher friction than their non-polar analogs. Beyond these qualitative trends, the shear stress behavior for all atomic- and chain-passivated, non-polar systems can be explained semi-quantitatively by steric interactions between the two surfaces that cause resistance to the sliding motion. For polar passivation species electrostatic interactions play an additional role. A corresponding descriptor that properly captures the interlocking of the two surfaces along the sliding direction is developed based on the maximum overlap between atoms of the two contacting surfaces.