AbstractIt is widely acknowledged that the process of surface film formation by tribological additives is very complex, because even saturated hydrocarbons — as major components of lubricating oils — undergo chemical changes under boundary lubrication conditions. To gain a better understanding of the tribochemical changes of paraffinic hydrocarbons, research was carried out using n‐hexadecane, which is widely used as a low‐viscosity model base oil. It has been hypothesised that the interactions between the products of n‐hexadecane triboreactions and steel surfaces are mostly initiated by the mechanical action of the system. Wear tests were performed, using a pin‐on‐disc machine. Fourier transform infrared microspectrophotometry and X‐ray photoelectron spectroscopy were used to analyse the wear tracks on the steel discs. Based on the analytical data obtained, a model of boundary film formation from aliphatic hydrocarb