Tribochemical Behavior of Ashless Dialkyl Dithiophosphate Ester as an EP/AW Additive in Mineral Oil for Steel–Aluminum Contact

Dialkyl dithiophosphate ester (DDPE) used as an extreme pressure/antiwear (EP/AW) additive in mineral base oil (BO) was introduced to a steel–aluminum contact in this study. The tribological performance of DDPE was explored by means of a universal tribotester under different loads and durations. The worn aluminum surface topographies were observed and photographed via laser scanning confocal microscopy (LSCM) and scanning electron microscopy (SEM). Tribochemical interactions between the additive and aluminum surface were investigated using energy-dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The distinction of chemical structure between lubricant untapped and the counterpart retrieved after a 3-h sliding process was detected by Fourier transform infrared spectroscopy (FTIR). The friction coefficient of a BO + DDPE-lubricated friction pair under 300 N shows the lowest value. LSCM and SEM images show that the aluminum surface lubricated with BO + DDPE was well protected under a high loading condition of 300 N, and the 3-h sliding process deteriorated the surface topography. However, DDPE was not able to offer an effective lubricating film under a mild condition of 50 N. EDS results of S and P elements on the worn surface indicate that a tribochemical film was generated under 300 N in the sliding process. XPS results further show that the chemical compounds in the tribochemical film included Al₂S₃, Al₂(SO₄)₃, AlPO₄, and Al₂O₃. The P-containing compound in the tribofilm acted as a sacrificial layer, whereas the S-containing compounds were more durable. FTIR analyses demonstrate that the phosphorus–sulfur double bond was broken up due to the tribochemical interactions.