Green Alternatives to Zinc Dialkyldithiophosphates: Vanadium Oxide-Based Additives

[Image: see text] A functionalized vanadyl(IV) acetylacetonate (acac) complex has been found to be a superior and highly effective antiwear agent, affording remarkable wear protection, compared to the current industry standard, zinc dialkyldithiophosphates (ZDDPs). Analysis of vanadium speciation and the depth profile of the active tribofilms by a combination of X-ray absorption near-edge structure (XANES), X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure (NEXAFS) analyses indicated a mixed-valence oxide composite, comprising V(III), V(IV), and V(V) species. A marked difference in composition between the bulk and the surfaces of the tribofilms was found. The vanadyl(VI) acac precursor has the potential to reduce or even replace ZDDP, which would represent a paradigm shift in the antiwear agent design. A major benefit relative to ZDDPs is the absence of S and P moieties, eliminating the potential for forming noxious and environmentally harmful byproducts of these elements.