An ESCA study of the effectiveness of antiwear and extreme‐pressure additives based on substituted phosphorodithioate derivatives,and a comparison with ZDDP

Ashless substituted dithiophosphoric acid derivatives (ADPs) are a new generation of multifunctional additives with promising antiwear (AW) and extreme‐pressure (EP) characteristics. Three such additives synthesised in the authors' laboratory have been evaluated for their AW and EP properties by standard four‐ball friction and wear tests. The friction‐reducing properties of these additives were compared with those of a commercial zinc dialkyldithiophosphate (ZDDP). It was found that the phosphorodithioate compounds studied here possessed excellent AW/EP properties. Their AW characteristics were found to be comparable to those of ZDDP at low loads. However, at higher loads they show inferior AW characteristics in comparison to ZDDP. Nevertheless, ADP derived from cashew nut shell oil had a higher load‐carrying capacity than ZDDP. The mechanism of the AW and EP behaviour exhibited by the different additives was investigated using X‐ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and scanning electron microscopy (SEM) of the worn surfaces formed during friction. XPS and AES analyses of the worn surfaces reveal that the tribochemical film formed on the ADP‐tested surfaces consisted mainly of metal phosphates and only a small amount of metal sulphides, even though the ADPs contained twice the number of sulphur atoms than phosphorus atoms. The ZDDP‐tested surface showed a mixture of metal sulphides and metal phosphates. Alkylamino substitution appeared to have no significant effect on the AW/EP properties of the additive. XPS and AES analyses also revealed that the tribochemical film formed on an ADP‐tested surface was thicker than that present on the ZDDP‐tested surface at low loads, whereas at higher loads the reverse was true. The higher weld load obtained for the blend containing cashew nut shell oil‐derived ADP is attributed to the thicker adsorbed reaction film formed on the surface due to the long alkyl groups present in the original additive structure. Short‐chain alkyl groups, however, form only a thin adsorbed layer, which may get rubbed off during the friction at high load. The low sulphide formation on ADP‐tested surfaces was attributed to the absence of any metal atom in the additive, which would help in the formation of metal sulphides during tribofragmentation and further tribochemical reactions.