The surface chemistry of dimethyl disulfide (DMDS) is studied on a Cu(111) single crystal and a polished copper foil in ultrahigh vacuum as a basis for understanding its tribological chemistry using a combination of temperature-programmed desorption (TPD), reflection-absorption infrared spectroscopy (RAIRS), and X-ray photoelectron spectroscopy (XPS). Low-energy electron diffraction reveals that the polished foil becomes ordered on heating in vacuo and displays identical surface chemistry to that found on the Cu(111) surface. Dimethyl disulfide reacts with the copper surface at 80 K to form thiolate species. Heating the surface to ∼230 K causes a small portion of the thiolate species to decompose to form methyl groups adsorbed on the surface. Further heating results in methane and C(2) hydrocarbon desorption at ∼426 K, due to a reaction of adsorbed methyl species, to completely remove carbon from the surface and to deposit atomic sulfur.
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.
Predictions from molecular dynamics (MD) simulations, that sliding at a metal-metal interface causes vortices in the near-surface region that transport atoms from the surface into the subsurface region, is tested experimentally. This is accomplished by rubbing a methyl thiolate overlayer grown on a clean copper foil by exposure to dimethyl disulfide at room temperature. Repeatedly rubbing a 1.27 9 10 -2 m diameter pin over a thiolatecovered copper surface at an applied load of 0.44 N and sliding speed of 4 9 10 -3 m/s in an ultrahigh vacuum tribometer, results in the removal of sulfur from the wear track as measured using spatially resolved Auger spectroscopy. Any remaining surface species, in particular, outside the wear track, are removed by argon ion bombardment. Since sulfur is more thermodynamically stable at the surface, heating the sample causes the sulfur to resegregate to the surface only inside the wear track, thereby directly confirming the predictions from MD simulations.
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