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Deep eutectic solvents (DESs) are acknowledged as a novel class of functional liquid. DESs share similar physical properties with ionic liquids (ILs) and have the potential to be a novel class of lubricants. In this study, two DESs, namely tetrabutylammonium chloride-decanoic acid DES (C4-DES) and methyl tricaprylmethylammonium chloride-decanoic acid DES (C8-DES), were synthesized, and their physico-chemical properties and tribological performances were evaluated. Post-analysis of the rubbing surfaces used multiple techniques to gain insights into the lubrication mechanisms. Results show that the coefficient of friction (COF) and wear were reduced by approximately 29% and 91% for the C4-DES, and 36% and 94% for the C8-DES, compared to an ester base oil. The friction reduction behavior of the DESs is attributed to the monolayer adsorption of the polar group in the decanoic acid (DEAC), whose effectiveness is affected by the component of the ammonium salts in the DESs and the operating temperatures. In addition to the adsorbed film, worn surface analysis revealed that an ultra-thin tribochemical film with a thickness of 3–7 nm was formed on the surfaces lubricated with the C8-DES. The composition of the film was studied, and the lubrication mechanisms of the two DESs were discussed.

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