Studies on ZDDP Anti-Wear Films Formed Under Different Conditions by XANES Spectroscopy, Atomic Force Microscopy and 31P NMR

Antiwear (AW) films, generated from a mineral base oil containing a zinc dialkyl dithiophosphate (ZDDP) additive, were studied as a function of formation temperature, load and rubbing time. The surface morphology of these films was investigated using atomic force microscopy (AFM), and surface roughness calculated for the observed differing surface morphologies. The morphology of the films is heterogeneous for all the tested conditions, but the surface roughness is dependent on the rubbing condition. X-ray absorption near edge structure (XANES) spectroscopy has been used to characterize the chemistry of these films, and the intensity of the phosphorus K-edge was also used to monitor their thickness. The thickness of these films is in the range of 10–90 nm depending on the running conditions. Phosphorus L-edge spectra show that these films have a similar chemical nature with variable polyphosphate chain-lengths. 31P NMR was used to study the decomposition of ZDDP in the residual oils. The spectra show that the primary and secondary ZDDP react differently under the various conditions. The tribological characteristics of these AW films were probed by measuring the coefficients of friction (μ) and the wear scar width (WSW) of the counter faces. μ is highly related to the applied load and the results of WSW measurements show that the wear performance is related to all the tested parameters, temperature, load and rubbing time.