We performed for the first time to our knowledge fully ab initio molecular dynamics simulations of additive tribochemistry in boundary lubrication conditions. We consider an organophosphourus additive that has been experimentally shown to reduce friction in steel-on-steel sliding contacts thanks to the tribologically-induced formation of an iron phosphide tribofilm. The simulations allow us to observe in real time the molecular dissociation at the sliding iron interface under pressure and to understand the mechanism of iron phosphide formation. We discuss the role played by the mechanical stress by comparing the activation times for molecular dissociation observed in the tribological simulations at different applied loads with that expected on the basis of the dissociation barrier.

Dynamic tribochemical processes for dicationic ionic liquid containing a germinal imidazolium cation head groups bridged by a poly(ethylene glycol) and bis(trifluoromethylsulfonyl)imide anion were studied using time-resolved Mechanically Stimulated Gas Emission Mass-Spectrometry (MSGE-MS). In comparison with similar monocationic imidazolium ionic liquids with short alkylic or long polyether side chains the dicationic ionic liquid had lower coefficient of friction on Ti6Al4V alloy and smoother behaviour. The analysis of volatile decomposition products suggested multiple tribochemical reactions in which both anionic and cationic moieties are involved. Tribochemical degradation of cations was mainly through detachment of the side and bridging chains from the imidazolium head groups. Absence of volatile products containing nitrogen implies that imidazole group remained unchanged. Hydrogen and water desorption were attributed to the reactions of hydrogen fluoride being a product of anion degradation with titanium and titanium oxide.