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.
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.
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 mechanochemical reaction between copper and dimethyl disulfide is studied under well-controlled conditions in ultrahigh vacuum (UHV). Reaction is initiated by fast S-S bond scission to form adsorbed methyl thiolate species, and the reaction kinetics are reproduced by two subsequent elementary mechanochemical reaction steps, namely a mechanochemical decomposition of methyl thiolate to deposit sulfur on the surface and evolve small, gas-phase hydrocarbons, and sliding-induced oxidation of the copper by sulfur that regenerates vacant reaction sites. The steady-state reaction kinetics are monitored in situ from the variation in the friction force as the reaction proceeds and modeled using the elementary-step reaction rate constants found for monolayer adsorbates. The analysis yields excellent agreement between the experiment and the kinetic model, as well as correctly predicting the total amount of subsurface sulfur in the film measured using Auger spectroscopy and the sulfur depth distribution measured by angle-resolved X-ray photoelectron spectroscopy.
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