The surface chemistry of a model lubricant additive, tributyl phosphite (TBPi), is investigated on Fe3O4 in ultrahigh vacuum. A portion of the TBPi desorbs molecularly following adsorption at approximately 200 K, the remainder decomposing either by C-O bond scission to form 1-butyl species or by P-O bond cleavage to form butoxy species. Adsorbed butyl species either undergo beta-hydride elimination to desorb 1-butene or decompose to deposit carbon and hydrogen on the surface. The resulting adsorbed hydrogen reacts with the oxide to desorb water or with the butoxy species to form 1-butanol. Butoxy species are stable up to approximately 600 K at which temperature they also undergo beta-hydride elimination to form butanal and the released hydrogen reacts with other butoxy species to form 1-butanol. Only a small amount of carbon is deposited onto the surface following adsorption at approximately 200 K, which then desorbs as CO above approximately 750 K. Adsorbing TBPi at 300 K results in the deposition of more carbon and an Auger depth profile reveals that the carbon is located predominantly on the surface, while the phosphorus is rather uniformly distributed throughout the oxide film. This result is in accord with previous near-edge X-ray absorption fine structure measurements, which show the formation of phosphates and polyphosphate glasses. The resulting tribological film appears to be composed of a relatively hard polyphosphate glass formed by rapid diffusion of POx species into the oxide, covered by a low shear strength graphitic layer.

The chemistry of tributyl phosphate on Fe 3 O 4 was studied in ultrahigh vacuum using temperature-programmed desorption (TPD) and Auger spectroscopy. A portion of the tributyl phosphate desorbs intact with an activation energy of $120 kJ/mol. The remainder decomposes either by PAO bond scission to deposit surface butoxy species or appears to dehydrogenate desorbing C 2 or C 3 compounds and depositing hydrogen and carbon on the surface. The resulting hydrogen reacts either with the oxide to desorb water or with butoxy species yielding 1-butanol. The remaining butoxy species are stable up to $600 K where they decompose to desorb butanal via hydride elimination where again the hydrogen reacts with butoxy species to form 1-butanol or with the oxide to form water. The carbon deposited onto the surface further reduces the oxide to desorb as CO above $750 K, although a small amount of carbon is detected on the surface using Auger spectroscopy. Substantially larger amounts of carbon are deposited onto the surface when Fe 3 O 4 is exposed to tributyl phosphate at 300 K, where an Auger depth profile reveals that the carbon is located at the surface while the PO x species formed by tributyl phosphate decomposition diffuse rapidly into the oxide layer, leading to a film structure in which graphitic carbon is deposited onto a phosphorus-containing oxide layer.

The frictional properties of a sliding copper-copper interface exposed to dimethyl disulfide (DMDS) are measured in UHV under conditions at which the interfacial temperature rise is <1 K. A significant reduction in friction is found from the clean-surface values and sulfur is found on the surface and below the surface in the wear scar region by Auger spectroscopy. Because the interfacial temperature rise under the experimental conditions used to measure friction is very small, tribofilm formation is not thermally induced. The novel, low-temperature tribofilm formation observed here is ascribed to a shear-induced intermixing of the surface layer(s) with the subsurface region as suggested using previous molecular dynamics simulations. Although the tribofilm contains predominantly sulfur, a small amount of carbon is also found in the film.

The growth kinetics of a film formed by the thermal decomposition of dimethyl disulfide on an iron foil are measured using a microbalance where the growth kinetics are parabolic (film thickness X varies with time as X 2 ∝ t) at high reaction temperatures and pressures, indicating that it is limited by diffusion through the film. The activation energy for this process is 54.5 ( 0.5 kcal/mol. The growth rate becomes linear as the reaction temperature and/or reactant pressure is lowered, indicating that, under these circumstances, the reaction rate is limited by thermal decomposition of dimethyl disulfide at the growing interface. The activation energy for thermal decomposition at the interface is found to be 37.6 ( 0.7 kcal/mol, and a half-order kinetics pressure dependence for the surface reaction rate is found consistent with a reaction limited by the rate of dimethyl disulfide dissociation. Analysis of the resulting film using Raman and X-ray photoelectron spectroscopies as well as X-ray diffraction reveal the formation of FeS, which may be slightly nonstoichiometric. This film is similar to that formed by methanethiol, suggesting that they may both initially form a surface thiolate species that further reacts to form FeS. The half-order reaction kinetics noted above are consistent with this. Measurement of dimethyl disulfide as an extreme-pressure (antiseizure) additive reveals a plateau at an applied load of ∼4000 N in the seizure load versus additive concentration curve. It has previously been suggested that the plateau corresponds to the load at which the interface reaches the melting point of the solid lubricant layer (in this case proposed to be FeS). Estimation of the interfacial temperature using a method developed previously yields an interfacial temperature of ∼1480 K, in good agreement with the melting point of FeS.

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