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

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 373K the molecule forms a physisorbed layer on the iron substrate. At 373K 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 foun

Nanofriction mechanisms derived from the dependence of friction on load and sliding velocity from air to UHV on hydrophilic silicon

This paper examines friction as a function of the sliding velocity and applied normal load from air to UHV in a scanning force microscope (SFM) experiment in which a sharp silicon tip slides against a flat Si(100) sample. Under ambient conditions, both surfaces are covered by a native oxide, which is hydrophilic. During pump-down in the vacuum chamber housing the SFM, the behavior of friction as a function of the applied normal load and the sliding velocity undergoes a change. By analyzing these changes it is possible to identify three distinct friction regimes with corresponding contact properties: (a) friction dominated by the additional normal forces induced by capillarity due to the presence of thick water films, (b) higher drag force from ordering effects present in thin water layers and (c) low friction due to direct solid-solid contact for the sample with the counterbody. Depending on environmental conditions and the applied normal load, all three mechanisms may be present at one time. Their individual contributions can be identified by investigating the dependence of friction on the applied normal load as well as on the sliding velocity in different pressure regimes, thus providing information about nanoscale friction mechanisms