How Polytetrafluoroethylene Lubricates Iron: An Atomistic View by Reactive Molecular Dynamics

The tribochemistry and transfer film formation at the metal/polymer interface plays an essential role in surface protection, wear reduction, and lubrication. Although the topic has been studied for decades, challenges persist in clarifying the nanoscale mechanism and dynamic evolution of tribochemical reactions. To investigate the tribochemistry between iron and polytetrafluoroethylene (PTFE) in ambient and cryogenic environments, we have trained and expanded a ReaxFF reactive force field to describe iron-oxygen-water-PTFE systems (C/H/O/F/Fe). Using ReaxFF molecular dynamics simulations, we find that mechanical shearing of single asperity induced the degradation of PTFE molecules and radicals, showing subsequent oxidation and hydroxylation reactions of the radicals initiated by C-C bond cleavage, in agreement with previous experimental observations. Furthermore, we studied mechanisms of interfacial tribochemical reactions and formation of transfer films. We found that tribochemical wear and Fe-C and Fe-F bonding networks are important mechanisms for anchoring molecular chains to form a transfer film on the iron countersurface. Hydroxyl groups can dehydrogenate to form short and strong chelation bonds with the Fe₂O₃ countersurface. A friction-induced oriented molecular layer plays a key role in reducing friction, which is responsible for the excellent lubrication property. By varying temperatures in the range of 10-300 K, we found a nonmonotonic change in friction with a maxima at 100 K. At cryogenic temperatures, the molecular mobility was obviously suppressed, while the chain rigidity was enhanced, resulting in the less oriented interface and brittle-like shear interface, which is responsible for nonmonotonic friction. This work elucidates mechanisms of tribochemical reactions and transfer film formation between iron and PTFE at the atomistic level, facilitating design and development of self-lubricating materials, especially under harsh conditions.