Shear and thermal effects in boundary film formation during sliding

A prerequisite for understanding mechano- and tribochemical reaction pathways is that the interface be in thermodynamic equilibrium and that the temperature be well defined. It is suggested that this occurs in two regimes: when the surfaces are only slightly perturbed during sliding, leading to negligible frictional heating, and when the surface temperatures are very high (∼1000 K), in the so-called extreme pressure regime. The tribochemistry occurring in each regime is discussed in terms of the elementary steps leading to tribofilm formation, namely (i) a reaction of the additive or gas-phase lubricant on the surface to form an adsorbed precursor, (ii) decomposition of the molecular precursor, (iii) a process that causes the formation of a tribofilm that (iv) regenerates a clean surface that allows this tribochemical cycle to continue to form a thicker film. These steps are thermally driven in the extreme-pressure regime, while under milder conditions, they are induced by interfacial shear. In intermediate situations, the processes are likely to be a combination of those occurring at the extrema.