Zinc dialkyldithiophosphate (ZDDP) is added to engine lubricants to reduce wear and ensure reliable operation. ZDDP reacts under rubbing conditions to form protective zinc/iron phosphate tribofilms on steel surfaces. Recently, it has been demonstrated that this process can be promoted by applied stresses in lubricated contacts, as well as temperature, and is thus mechanochemical in origin. In this study, a tribology test rig, capable of applying very high loads, has been developed to generate ZDDP tribofilms under full-film elastohydrodynamic lubrication (EHL) conditions in steel/steel ball-on-disk contacts. This provides a well-defined temperature and stress environment with negligible direct asperity contact in which to study mechanochemical processes. ZDDPs with branched primary and secondary alkyl substituents have been studied in three base oils, two with high EHL friction and one with low EHL friction. In the high EHL friction base oils, the tribofilm growth rate increases exponentially with shear stress and temperature for both ZDDPs, as predicted by a stress-augmented thermal activation model. Conversely, under otherwise identical conditions, negligible ZDDP tribofilm formation takes place in the low EHL friction base oil. This confirms that the ZDDP reaction is driven by macroscopic shear stress rather than hydrostatic pressure. The secondary ZDDP forms tribofilms considerably faster than the primary ZDDP under equivalent conditions, suggesting that the initial decomposition reaction is the rate-determining step for tribofilm formation. The rate of tribofilm growth is independent of ZDDP concentration over the range studied, indicating that this process follows zero-order kinetics. Under full-film EHL conditions, ZDDP tribofilm formation is promoted by macroscopic shear stress applied through the base oil molecules, which induces asymmetric stress on adsorbed ZDDP molecules to promote their decomposition and initiate rapid phosphate polymerization.
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