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Surface reactivity of tributyl thiophosphate: effects of temperature and mechanical stress

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Abstract

The surface reactivity of tributyl thiophosphate on iron surfaces has been studied in situ by attenuated total reflection Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy and temperature-programmed reaction and desorption spectroscopies. The results show that at temperatures lower than 373 K the molecule forms a physisorbed layer on the iron substrate. At 373 K a reaction takes place with the formation of an organic layer, together with iron polyphosphate and sulfate. At higher temperatures temperature-programmed desorption results suggest that the mechanism involves P–O bond scission to yield butoxy groups. This could be preceded by P=S bond scission to give tributyl phosphite, which then, in turn, undergoes P–O bond scission to produce butoxy groups. The results obtained following tribological testing are in agreement with those of thermal tests: evidence of polyphosphate and sulfate formation is found.

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Acknowledgments

The authors would like to thank Dr. H. Camenzind (Ciba Specialty Chemicals, Switzerland) for supplying the purified tributyl thiophosphate and tributyl phosphate, and Mr. M. Horisberger (PSI, Villigen, Switzerland) for preparing the iron coatings by magnetron sputtering. AJG and DK acknowledge support from NSF grant no. CMS0408574.

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Authors and Affiliations

  1. Department of Materials, Laboratory for Surface Science and Technology, ETH Zurich, Wolfgang-Pauli-Strasse 10, CH-8093, Zurich, Switzerland

    A. Rossi, F.M. Piras & N.D. Spencer

  2. Dipartimento di Chimica Inorganica ed Analitica, Università degli Studi di Cagliari, Cittadella Universitaria di Monserrato, 09100, Cagliari, Italy

    A. Rossi

  3. Department of Chemical Engineering, Carnegie Mellon University, 5000 Forbes Ave., Pittsburgh, PA, 15213, USA

    D. Kim & A.J. Gellman

  4. Department of Chemical and Biosystems Science and Technology, University of Siena, Via Aldo Moro 2, I-53100, Siena, Italy

    F.M. Piras

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  1. A. Rossi
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Correspondence to N.D. Spencer.

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Rossi, A., Piras, F., Kim, D. et al. Surface reactivity of tributyl thiophosphate: effects of temperature and mechanical stress. Tribol Lett 23, 197–208 (2006). https://doi.org/10.1007/s11249-006-9051-6

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