Emulsion lubrication is widely used in metal forming operations and has potential applications in the biomedical field, yet the emulsion lubrication mechanism is not well understood. This work explores the possibilities of three different oil-in-water (O/W) emulsions containing dibutyl octadecylphosphoramidate (DBOP), 6-octadecyl-1,3,6,2-dioxazaborocan-2-ol calcium salt (ODOC) and 2-(4-dodecylphenoxy)-6-octadecyl-1,3,6,2-dioxazaborocane (DOB) to generate boundary films on stainless steel AISI 316 and CoCrMo alloy surfaces. Experimental results show lower friction values for the emulsions in combination with CoCrMo compared to AISI 316. The different performance of the additives is related to the composition of the adsorption and reaction film on the interacting surfaces, which was shown to be dependent on the active elements and molecular structure of the additives. The friction profile of the emulsions indicates that the emulsion appears to be broken during the rubbing process, then the additives adsorb onto the metal surface to form protecting boundary layers. The XPS analysis shows that for boundary lubrication conditions, the additive molecules in the emulsion first adsorb on the metal surface after the droplet is broken, and then decompose and react with the metal surface during the rubbing process to form stable lubricating films on the rubbed surfaces. (C) 2014 Elsevier B.V. All rights reserved.