The Correlation of Microchemical Properties to Antiwear (AW) Performance in Ashless Thiophosphate Oil Additives

X-ray absorption near-edge structure (XANES) spectroscopy at macro-scale (mm2) and X-ray photoelectron emissions microscopy (X-PEEM) at micro-scale (μm2) have been used to investigate the chemistry and spatial distributions of chemical species in tribochemical films generated from ashless thiophosphate oil additives on steel. Two different ashless thiophosphate additives were used: a triaryl monothiophosphate (MTP) and a dialkyldithiophosphate (DTP). Atomic force microscopy (AFM) and secondary electron microscopy (SEM) were also used to investigate the thickness and the topography of the tribofilms. Macro-scale XANES analysis showed that both ashless thiophosphates reacted with the steel surface to produce short to medium chain polyphosphates as the main constituent and sulfur species as minor component. From the PEEM experiment, it was found that the DTP tribofilm was microchemically heterogeneous, with areas of varying degrees of polyphosphate chain length. Conversely, MTP formed a tribofilm microchemically homogeneous, with areas comprised of only short chain polyphosphates. From, the different areas of polyphosphate chain length within the DTP tribofilm, colour-coded polyphosphate distribution map was generated. AFM, X-PEEM and SEM revealed that the DTP film was thicker and was composed of AW pads that were wider in area than MTP. This resulted in a smaller wear scar width (WSW) value for DTP. This is the first time that all these analytical techniques have been combined to better understand the nature of the tribofilms from ashless additives. We have concluded that an ideal AW film is comprised of a thick film with pad-like structures that are wider in area and microchemically heterogeneous, with areas of varying polyphosphate chain length.