Is more always better? Tribofilm evolution and tribological behavior impacted by the concentration of ZDDP, ionic liquid, and ZDDP-Ionic liquid combination

Anti-wear additives (AWs), like zinc dialkyldithiophosphates (ZDDPs), have been used in lubricants for more than a half-century, and more effective candidate AWs, like oil-soluble ionic liquids (ILs), are emerging. However, there is a lack of fundamental understanding of how the AW concentration impacts the tribochemical activities at the contact interface. This study systematically investigated the friction and wear behavior in correlation to the tribofilm morphology and composition as a function of the concentration of a ZDDP, a phosphonium-alkylphosphate IL, and an IL+ZDDP combination. The ZDDP concentration rising from 0.4 to 6.4 wt% caused a proportionally increased friction coefficient, which was well correlated to a thicker, rougher, and more brittle tribofilm. This was further understood by the decreasing phosphates but increasing sulfur compounds in the ZDDP tribofilm. In contrast, the IL and IL+ZDDP maintained a low and stable friction coefficient at 0.5 wt% or above. There was no sulfur in the IL tribofilm, and the sulfur compounds were maintained at a low level in the tribofilm for IL+ZDDP even at high concentrations. Results suggested minimizing the sulfur content in the tribofilm would be an effective way to control the friction. An interesting V-shape relationship between the AW concentration and the wear loss was observed for both the IL-containing AWs, with an optimum at 2 wt% for the IL alone and 0.46–0.92 wt% for the IL+ZDDP, respectively. A unique heat map was created using the phosphorus binding energy distribution to reveal the phosphate polymerization at different depths of the tribofilms, which provided additional insight for the tribofilm evolution.