X-ray absorption near edge structure (XANES) spectroscopy was used to monitor the products formed during the breakdown of the engine additive ZDDP during its action as a protective tribochemical agent. This investigation examines the film formed under various physical conditions on a near hypereutectic Al-Si alloy. For the first time, tribochemical films (tribofilms) formed on a high silicon weight content alloy, with virtually no ferrous component have been studied. Phosphorus K-and L-edge spectroscopies show that under typical engine operating conditions, the tribofilms have similar chemical composition over a range of different test conditions. X-ray photoelectron emission microscopy (X-PEEM) reveals that the polyphosphate glasses formed vary in chain length within localized regions. The mechanical properties of the substrate and the tribofilms were acquired using a Triboscope Ò from Hysitron Inc. The elastic moduli can be extracted from the indentation curves and show that the tribofilms' mechanical properties are similar to those of the tribofilms which form on steel under similar conditions.
Understanding the lubrication of aluminum-silicon (Al-Si) alloys (>18% Si) under conditions similar to those in the cylinder/bore system is vital to determining their applicability to current engine designs. A novel investigation of the location of zinc-dialkyl-dithiophosphate (ZDDPs) antiwear (AW) film formation on an Al-Si alloy has been performed using X-ray absorption near edge structure (XANES) analysis, X-ray photoelectron emission spectroscopy (X-PEEM), and imaging nanoindentation techniques. A study of the initial stages of wear (10 min) to prolonged rubbing (60 min) was performed. The findings show that the film forms primarily on the raised silicon grains and is consistent with a zinc polyphosphate glass. The film has an elastic modulus of $70 GPa and a similar elastic response to a ZDDP AW film formed on steel under the same conditions. This provides the first direct observation and characterization of a ZDDP antiwear film on Al-Si alloys using spatially resolved chemical and mechanical techniques at the nanoscale.
X-ray absorption near edge structure spectroscopy (XANES) analysis has been routinely used to study the complex chemical interactions between additives in engine oil and metallic surfaces during high-temperature and pressure reciprocating wear conditions. XANES analysis provides detailed chemical and structural information on the resultant antiwear and tribo films formed on metallic surfaces. The following review will illustrate how XANES analysis on the macro scale can provide the information required to elucidate complex film formation mechanisms, then describes the use of emerging XANES spectromicroscopy to such systems, and concludes by showing the complementary nature of the macro and micro scale spatially resolved XANES analysis; Professor Bancroft has utilized the combination of these to stay at the forefront of XANES research in the field of tribology and in spectroscopy science in general.Key words: tribology, XANES, X-ray absorption near edge structure spectroscopy, metals, thiophosphates, spectromicroscopy, tribochemistry.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.