Ionic liquids are expected to become increasingly popular lubricants as they feature a number of attractive properties. This investigation focused on sulfate and phosphate anion-based ionic liquids and the improvement in lubricating performance with the addition of these anions. However, the detailed lubricating mechanism and effect of alkyl chain length on tribochemical reactions are unclear. This study investigates tribochemical reaction processes using a quadrupole mass spectrometer (Q-MS) and X-ray photoelectron spectroscopy. Seven types of ionic liquids: 1-ethyl-3-methylimidazolium hydrogensulfate ([EMIM][HSO4]), 1-ethyl-3-methylimidazolium methylsulfate ([EMIM][MSU]), 1-ethyl-3-methylimidazolium ethylsulfate ([EMIM][ESU]), 1-ethyl-3-methylimidazolium n-octylsulfate ([EMIM][OSU]), 1-ethyl-3-methylimidazolium dimethyl phosphate ([EMIM][DMP]), 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIM][DEP]), and 1-ethyl-3-methylimidazolium dibutyl phosphate ([EMIM][DBP]), were selected as lubricants. The friction coefficient of sulfate anion-based ionic liquids increased as their alkyl chain lengthened. However, wear scar diameter in this case showed the opposite tendency. The friction coefficient and wear scar diameter of phosphate anion-based ionic liquids increased with an increase in the alkyl chain length. Q-MS results indicated that the main outgassing components during sliding were the cation components, whereas the anion remained on the sliding surface and formed a tribofilm. The ionic liquids with short alkyl chains reacted with the sliding surface easily and led to very low friction. However, corrosive wear occurred in the case of the sulfate anion. On the other hand, anions with long alkyl chains underwent gradual tribochemical reactions because that led the mitigation of contact with nascent surface. The phosphate-based ionic liquids with long alkyl chains were unable to cause the lubricating effect due to low reactivity.

The friction coefficients of ionic liquids were evaluated by many investigations. Most investigations used fluorine-based ionic liquids as lubricants. However, these ionic liquids produce the corrosion wear. This investigation focuses on the use of cyano-based ionic liquids as lubricants. Compared to fluorine-based ionic liquids, cyano-based ionic liquids exhibit high friction coefficients against steel material. This work examines how the friction coefficients of cyano-based ionic liquids are influenced by the type of sliding material used (AISI 52100, TiO2, and tetrahedral amorphous carbon). TiO2 lubricated with 1-ethyl-3-methylimidazolium tricyanomethanide, and ta-C lubricated with 1-butyl-1methylpyrrolidinium tetracyanoborate exhibited very low friction coefficients, smaller than fluorine-based ionic liquids. Time-of-Flight Secondary Ion Mass Spectrometry analysis showed that anions adsorb onto the worn surface, suggesting that anion adsorption is a critical parameter influencing friction coefficients. Quadrupole Mass Spectrometry measurements revealed that cations decompose on the nascent surface, preventing adsorption on the worn surface. These results suggest that low friction coefficients require the decomposition of cations and adsorption of anions. The reactivity of nascent surface changes with the sliding material used due to varying catalytic activity of the nascent surfaces.

This study investigates the lubricating mechanism of cyano-based ionic liquids on steel surfaces using Q-MS, ToF-SIMS, and TGA. [EMIM][DCN], [EMIM][TCC], [EMIM][TCB], [BMPL][DCN], [BMPL][TCC], and [BMPL][TCB] were selected as lubricants. [EMIM][TCB] exhibited the highest friction coefficient. The others exhibited very low friction coefficients of less than 0.08. Q-MS analysis indicated that the cation components were detected in outgassing during sliding tests. However, anion components were not detected. ToF-SIMS results showed that the anions remained on the worn surfaces which would lead low friction coefficients. To achieve low friction coefficient, the tribo-decomposition of the ionic liquids and adsorption of anion were required. TGA indicated thermal stability was an index for tribo-decomposition on the nascent steel surface.

Ionic liquids are expected to be used as a new lubricants and lubricant additives because of their unique properties. However, cyano-based ionic liquids have exhibited poor lubricating property with steel/steel contacts. We evaluated the lubricating properties of cyano-based ionic liquids with steel/hard materials contacts. TiO2, Al2O3, and tetrahedral amorphous carbon (ta-C) DLC were used as hard materials. Six types of ionic liquids, as combination of two types of cations ([EMIM], [BMPL]) and three types of cyanide anions ([DCN], [TCC] and [TCB]), were selected. In sliding tests of steel/TiO2 and steel/Al2O3 lubricated with [EMIM][DCN], [BMPL][DCN], [EMIM][TCC], [BMPL][TCC] exhibited low friction coefficients of less than 0.1. In addition, steel/Al2O3 and steel/ta-C DLC lubricated with [BMPL][TCB] exhibited very low friction coefficients less than 0.05. On the other hand, high friction coefficients were observed at steel/TiO2 and steel/Al2O3 contacts lubricated with [EMIM][TCB] and steel/ta-C DLC contact lubricated with [EMIM] cation group. Peeling of the ta-C DLC was observed when [EMIM] cation group was used. ToF-SIMS analysis indicated that the anion was adsorbed on the worn surfaces in the case of low frictional conditions. However, both ions were hardly observed in the case of high frictional conditions. It is considered that the ionic liquids underwent tribo-decomposition on the worn surfaces at low friction coefficient. To evaluate the degree of tribo-decomposition, Thermogravimetric analysis (TGA) was used. TGA results indicated that [EMIM][TCB], which exhibited high friction coefficient, had the most highest stability among all ionic liquids. Low stability ionic liquids, however, showed a tendency for low friction coefficient. These results suggest that lubricating properties are related to the stability of ionic liquids.