Shouhei Kawada

Tribochemical Reactions of Ionic Liquids Under Vacuum Conditions

Abstract Ionic liquids are expected to function as novel lubricants owing to their attractive characteristics such as high thermal stability and low vapor pressure. In order for ionic liquids to be used as lubricants, knowledge of their corrosion and lubricating properties must be obtained. However, the reaction mechanism and decomposition of ionic liquids have not yet been sufficiently clarified. In this study, we elucidate the tribological properties and tribochemical reaction mechanism by analyzing outgassing generated by the decomposition or reaction of ionic liquids [EMIM][DCN], [EMIM][TCB], and [BMPL][TCB] on a sliding surface. From our results, [BMPL][TCB] showed the lowest friction coefficient and [EMIM][DCN] had a lower friction coefficient than [EMIM][TCB]. In all cases, outgassing from the ionic liquid was confirmed, and main outgassing products were derived from the cation. [BMPL][TCB] had the largest amount of outgassing. Time-of-flight secondary ion mass spectroscopy analysis showed that tribochemical reactions involving the anion occurred. From sliding tests and experimental analyses, it is revealed that the [DCN] anion showed superior lubricating properties to the [TCB] anion.

Effects of Alkyl Chain Length of Sulfate and Phosphate Anion-Based Ionic Liquids on Tribochemical Reactions

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.