Adsorption of Stearic Acid at the Iron Oxide/Oil Interface: Theory, Experiments, and Modeling.

Improved friction performance is an important objective of equipment manufacturers for meeting improved energy efficiency demands. The addition of friction-reducing additives, or friction modifiers (FMs), to lubricants is a key part of the strategy. The performance of these additives is related to their surface activity and their ability to form adsorbed layers on the metal surface. However, the extent of surface coverage (mass per unit area) required for effective friction reduction is currently unknown. In this article, we show that full coverage is not necessary for significant friction reduction. We first highlight various features of surface adsorption that can influence the surface coverage, packing, and free energy of adsorption of organic FMs on iron oxide surfaces. Using stearic acid in heptane and hexadecane as model lubricant formulations, we employ a combination of experiments and molecular dynamics (MD) simulations to show how the dimerization of acid molecules in the bulk solvent and the crystallographic orientation of the surface modifies surface adsorption. In addition, we show that the solvent can strongly influence the adsorption kinetics, and MD simulations reveal that hexadecane tends to align on the surface, increasing the energy barrier for the adsorption of stearic acid to the surface. Furthermore, we present a combined approach using MD and molecular thermodynamic theory to calculate adsorption isotherms for stearic acid on iron oxide surfaces, which agrees well with experimental data obtained with a quartz crystal microbalance (QCM). Our results suggest that while the friction of systems lubricated with organic FMs decreases with increasing coverage, complete coverage of the surface is neither practically achievable nor necessary for effective friction reduction for the systems and conditions studied here.