Adsorption properties of molybdenum based FMs on boron-doped DLC

Development of low friction surface materials matched with low friction lubricants is an important route to improving engine efficiency and reducing emissions. Diamond-like carbon (DLC) is a material of interest because it combines the durability of diamond with the low friction properties of graphite. Consequently, various forms of DLC have been studied as durable, low friction surface coatings. At the same time, friction modifiers (FMs) are often used in engine lubricants to produce low friction surface layers. Molybdenum-based friction modifiers are commonly used additives that mechanochemically decompose to cover surfaces with MoS2, a solid lubricant. FMs can also reduce friction on DLC surfaces. However, molybdenum can be harmful to DLC and cause rapid degradation and breakthrough of the DLC surface layer. We have found that the wear debit of molybdenum FMs trends with surface affinity of the additive. The adsorption isotherms of 4 Mo-based FMs on boron-doped diamond-like carbon (BDLC) were measured with a quartz crystal microbalance (QCM). The strongest adsorbate, Mo dithiophosphate (MoDTP), which also forms the thickest film, protects the BDLC surface enabling low friction while keeping wear low. Theoretical predictions based on molecular dynamics simulations combined with molecular-thermodynamic theory (MD-MTT) show that adsorption of MoDTP on BDLC deviates significantly from Langmuir behavior and free energy of adsorption for the first monolayer is significantly more negative than the multilayer adsorption free energy observed experimentally. The relationship between wear and adsorption behavior is consistent with experimental observations in the literature. These results also suggest that additive performance in a fully formulated lubricant is related to fundamental adsorption properties measured on the neat additive.