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Protective coatings are important for enhancing tribological behavior, preventing surface degradation, and reducing friction-induced energy losses during the operation of mechanical systems. Recently, tribocatalytically driven formation of protective carbon films at the contact interface has been demonstrated as a viable approach for repairing and extending the lifetime of protective coatings. Here, we study the effect of catalytic metals, specifically their composition and amount, on the tribocatalysis process. To achieve this, we test the tribological performance of electro-deposited amorphous CoNiP and CoCuP coatings in different hydrocarbon-rich environments. Our results indicate that the tribocatalytic repair of wear-induced damage is optimal when Ni and Cu are included in the Co-P matrix at 5 wt% Ni and 7 wt% Cu, respectively. Characterization of the wear tracks suggests that among the considered samples, the tribofilms formed on the surface of Co7CuP have the highest concentration of graphitic carbon, leading to a more significant reduction in the COF and wear rate. The carbon tribofilm formation was more pronounced in decane and synthetic oil than in ethanol, which is attributed to the difference in the length of the hydrocarbon molecules affecting viscosity and the lubricant film thickness during boundary lubrication sliding. 

Abstract High-contact stresses generated at the sliding interfaces during their relative movement provide a unique combination of local heating and shear- and load-induced compression conditions. These conditions, when involving the sliding of surfaces with certain material characteristics, may facilitate tribochemical reactions with the environment, leading to the formation of a protective, damage-suppressing tribofilm directly at the contact. Here, we employ the electrodeposition process to design a coating composed of a hard cobalt-phosphorous matrix with the inclusion of tribocatalytically-active nickel clusters. The coating is optimized in terms of its relative composition and mechanical characteristics. We demonstrate the excellent tribological performance of the coating in the presence of a hydrocarbon environment, both in the form of a liquid lubricant and as a hydrocarbon-saturated vapor. Characterization of the wear track indicates that the origin of such performance lies in the formation of a protective carbon-based tribofilm on the surface of the coating during sliding. These results contribute to the advancement of knowledge on material transformations in the contact, thus providing a robust and versatile approach to addressing tribological challenges in mechanical systems.