The Effect of the Chemical Structures of Synthetic Hydrocarbon Oils on Their Tribochemical Decomposition

Under boundary lubrication conditions, the formation of a highly active nascent surface can catalyze the decomposition of lubricant oils. Extreme pressure additives can reduce this decomposition but have undesirable environmental impacts, and so it is necessary to develop eco-friendly lubricants. The following study investigated the effects of the chemical structures of hydrocarbon oils on their tribochemical decomposition by comparing an alkyldiphenylether (ADE) to a multialkylated cyclopentane. The analysis of gaseous decomposition products via mass spectrometry during the application of friction showed that the multialkylated cyclopentane decomposed after an induction period of 1.95 km while the ADE did not degrade, even at a distance of 57.5 km, under the same mechanical contact conditions, and exhibited superior anti-wear properties. However, a high concentration of the ADE was necessary to extend the induction period for lubricant decomposition when it was used as an additive. Although the ADE showed high stability in response to friction, it was prone to decomposition once a nascent steel surface was formed. These decomposition characteristics of the ADE are closely related to its chemical structure, because the ether group in the ADE molecule preferentially adsorbs on metal oxide surfaces, forming a dense and robust film. In contrast, the weak bonding between adjacent alkyl groups reduces the shear strength at the interface. Both the benzene and alkyl groups of ADE molecules were found to detach, followed by the further rupture of C–C, C–H, and C–O bonds, catalyzed by active sites on the nascent surface such as surface defects.