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Hardness as a function of indentation depth for tribofilms formed from ZDDP and N_DEHP ionic liquid. Superimposed on the data is the corresponding phosphate chain length information acquired from XANES.

The aim of this study was to investigate the utility of ion trap mass spectrometry (ITMS) in combination with the two desorption/ionization methods, electrospray (ESI) and atmospheric pressure matrix-assisted laser desorption/ionization (AP-MALDI), for the detection of antioxidants which are applied in lubricants. These experiments should form the base for future investigations of antioxidants in tribologically formed thin layers on the surface of frictional systems. Seventeen different antioxidants were selected out of the group of hindered phenolic and aromatic aminic compounds. Practically all antioxidants could be characterized by positive ion ESI- and AP-MALDI-ITMS, forming various types/species of molecular ions (e.g. [M]+*, [M+H]+, [M+Na]+ or [M-2H+H]+). A few compounds could be analyzed by negative ion ESI-MS, too, but none by negative ion AP-MALDI-MS. The influence of target materials in AP-MALDI-MS (gold- and titanium nitride (TiN)-covered stainless steel, micro-diamond-covered hard metal, hand-polished and sand-blasted stainless steel targets) with respect to the molecular ion intensity and type of molecular ion of two selected antioxidants was evaluated. The surface properties are of particular interest because in friction tests different materials with different surface characteristics are used. However, the MS results indicate that optimal target surfaces have to be found for individual antioxidants in AP-MALDI-MS but in general smooth surfaces were superior to rough surfaces. Finally the gold-covered stainless steel MALDI target provided the best mass spectra and was selected for all the antioxidants investigated.

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The combined methods allow qualitative and quantitative determination of a wide variety of different antioxidants including aminic/phenolic compounds applied in lubricant engineering. These data show that the developed methods will be versatile tools for further research on identification and characterization of the thermo-oxidative degradation products of antioxidants in lubricants.