Tribochemical processes have profound consequences on tribological performance. In the present paper, the tribochemical mechanism of low friction state in the silica/phosphoric acid system is elucidated by reactive molecular dynamics (ReaxFF) simulations. The friction coefficient is found having strong positive correlation with the number of interfacial hydrogen bonds, which suggests that a weaker interfacial hydrogen bond network would favor a lower friction. The friction reduction mechanisms have been analyzed in two temperature regimes: For 300 ≤ T ≤ 600 K, no indication of tribochemical reaction is observed, and the friction coefficient decreases because of the accelerated molecular rotational and translational motion and the corresponding weakened hydrogen bond network. For 800 K ≤ T ≤ 1400 K, the occurrence of tribochemical reactions leads to a clustering and polymerization of the phosphoric acid molecules and generation of a considerable quantity of water molecules distributed mainly in the sliding interface which could act as lubricant, and a low friction state is reached with a friction coefficient of 0.02.

Reactive molecular dynamics (ReaxFF) simulations are used to explore the atomic-level tribochemical mechanism of amorphous silica (a-SiO2) in a nanoscale, single-asperity contact in an aqueous environment. These sliding simulations are performed in both a phosphoric acid solution and in pure water under different normal pressures. The results show that tribochemical processes have profound consequences on tribological performance. Water molecules could help avoid direct adhesive interaction between a-SiO2 surfaces in pure water under low normal load. However, formation and rupture of interfacial siloxane bonds are obviously observed under higher normal load. In phosphoric acid solution, polymerization of phosphoric acid molecules occurs, yielding oligomers under lower load, and tribochemical reactions between the molecules and the sliding surfaces could enhance wear under higher load. The bridging oxygen atoms in silica play an important role in the formation of interfacial covalent bonds, and hydrogen is found to have a weakening effect on these bonds, resulting in the rupture during shear-related loading. This work sheds light on tribochemical reactions as a mechanism for lubrication and wear in water-based or other tribological systems.