Nanometer-Scale Distribution of a Lubricant Modifier on Iron Films: A Frequency-Modulation Atomic Force Microscopy...

Liquid lubricants used in mechanical applications are low-vapor-pressure hydrocarbons modified with a small quantity of polar compounds. The polar modifiers adsorbed on the surface of sliding solids dominate the friction properties when the sliding surfaces are in close proximity. However, a few methods are available for the characterization of the adsorbed modifiers of a nanometer-scale thickness. In this study, we applied frequency-modulation atomic force microscopy to evaluate the vertical and lateral density distributions of the adsorbed modifier in a real lubricant, namely, poly-α-olefin (PAO) modified with an orthophosphoric acid oleyl ester. The liquid-induced force on the probing tip was mapped on a plane that was perpendicular to the lubricant-iron interface with a force sensitivity on the order of 10 pN. The PAO in the absence of the ester modifier was directly exposed to the film, which produced a few liquid layers parallel to the film surface with layer-to-layer distances of 0.6-0.7 nm. A monomolecular layer of the modifier was intermittently adsorbed with increasing ester concentration in the bulk lubricant, with complete coverage seen at 20 ppm. The C₁₈H₃₅ chains of the oleyl esters fluctuating in the lubricant produced a repulsive force on the tip, which monotonically decayed with the tip-to-surface distance. The dynamic friction coefficient of sliding steel-lubricant-steel interfaces, which was separately determined using a friction tester, was compared with the force map determined on the iron film immersed in the corresponding lubricant. The complete monomolecular layer of the ester modifier on the static lubricant-iron boundary is a requirement for achieving smooth and stable friction at the sliding interface.