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Studies on ZDDP Thermal Film Formation by XANES Spectroscopy, Atomic Force Microscopy, FIB/SEM and 31P NMR

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Abstract

X-ray absorption near edge structure (XANES) spectroscopy has been used to characterize the chemistry of thermal films on steel samples, which were generated from a mineral base oil containing a zinc dialkyl dithiophosphate (ZDDP) additive. These films were formed at 150 °C by immersing steel coupons in ZDDP oil solutions. The phosphorus L-edge XANES spectra show that these films are composed of polyphosphates, unreacted ZDDP and other thiophosphate intermediates. Phosphorus K-edge FY XANES was used to monitor the thickness of these films, and the data are consistent with thickness derived by focussed ion beam (FIB) milling and SEM imaging. The sulphur K-edge TEY and FY XANES spectra show that these films are composed of different sulphur components, which depend upon the formation times. The surface morphology of these films was investigated using atomic force microscopy (AFM). These images show that the surface morphology of the thermal films changes with the formation time. 31P NMR spectra show that both primary and secondary ZDDP decomposes gradually at 150 °C.

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Acknowledgments

The authors are grateful to Dr. Astrid Jürgensen from Canadian Synchrotron Radiation Facility (CSRF) and to the staff of the Synchrotron Radiation Centre (SRC), University of Wisconsin, Madison, for their technical support. The National Science Foundation (NSF) is acknowledged for supporting the SRC under Award #NMR-0537588. The authors also thank Imperial Oil, Canada for the ZDDP concentrate. The authors would like to thank University Machine Shop and Kyle Pollard in NMR facility center in the University of Western Ontario. This work was financially supported by the National Research Council of Canada (NRC), the Natural Sciences and Engineering Research Council of Canada (NSERC) and General Motors of Canada Ltd.

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  1. Department of Chemistry, The University of Western Ontario, London, ON, Canada, N6A 5B7

    Yue-Rong Li, Gavin Pereira, Andreas Lachenwitzer, Masoud Kasrai & Peter R. Norton

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  1. Yue-Rong Li
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Correspondence to Peter R. Norton.

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Li, YR., Pereira, G., Lachenwitzer, A. et al. Studies on ZDDP Thermal Film Formation by XANES Spectroscopy, Atomic Force Microscopy, FIB/SEM and 31P NMR. Tribol Lett 29, 11–22 (2008). https://doi.org/10.1007/s11249-007-9277-y

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