Temperature dependence of molybdenum dialkyl dithiocarbamate (MoDTC) tribofilms via time-resolved Raman spectroscopy.

Molybdenum dialkyl dithiocarbamate (MoDTC) is a friction reducing additive commonly used in lubricants. MoDTC works by forming a low-friction molybdenum disulphide (MoS2) film (tribofilm) on rubbed surfaces. MoDTC-induced MoS2 tribofilms have been studied extensively ex-situ; however, there is no consensus on the chemical mechanism of its formation process. By combining Raman spectroscopy with a tribometer, effects of temperature and shear stress on MoS2 tribofilm formation in steel-steel contacts were examined. Time-resolved Raman spectra of the tribofilm were acquired, together with the instantaneous friction coefficient. The tribofilm is constantly being formed and removed mechanically during rubbing. Increasing shear stress promotes MoS2 formation. The nature of the tribofilm is temperature-dependent, with high-temperature tribofilms giving a higher friction than lower temperature films. Below a critical temperature Tc, a small amount of MoS2 gives significant friction reduction. Above Tc, a patchy film with more MoS2, together with a substantial amount of amorphous carbon attributed to base oil degradation, forms. The composition of this tribofilm evolves during rubbing and a temporal correlation is found between carbon signal intensity and friction. Our results highlight the mechanochemical nature of tribofilm formation process and the role of oil degradation in the effectiveness of friction modifier MoDTC.