Understanding the effect of water on the transient decomposition of zinc dialkyldithiophosphate (ZDDP)

The effect of water on the transient kinetics of the decomposition reaction of zinc dialkyldithiophosphate (ZDDP) additive has been investigated using X-ray photoelectron spectroscopy (XPS). Water was found to have a long-lasting detrimental effect on ZDDP triboreactive film layers by changing their composition depending on their proximity to the metal surface. Particularly, water impeded the polymerisation reaction in the top layers, which results in the formation of short zinc (thio)phosphate chains. The most probable explanation for this was related to the formation of a single or multiple bridges between water molecules and PO2 groups of the decomposed ZDDP. This caging effect, which does not fade away as water evaporates, can suppress the chemical reactivity of these groups to a great extent, which in turn can hinder their polymerisation into long phosphate chains.